WO2018163514A1

WO2018163514A1 - All-solid state battery and manufacturing method therefor, and electronic device and electronic card

Info

Publication number: WO2018163514A1
Application number: PCT/JP2017/041199
Authority: WO
Inventors: 友裕加藤; 鈴木　正光; 圭輔清水
Original assignee: 株式会社村田製作所
Priority date: 2017-03-10
Filing date: 2017-11-16
Publication date: 2018-09-13

Abstract

This all-solid state battery is provided with: a battery element containing Li; an outer packaging material for covering the battery element; and a protective layer which is provided between the battery element and the outer packaging material, and contains Li.

Description

All-solid battery and method for manufacturing the same, electronic device and electronic card

This technology relates to an all-solid-state battery, a manufacturing method thereof, an electronic device, and an electronic card.

Since all-solid-state batteries are greatly deteriorated by moisture, a technique has been proposed in which all-solid-state batteries are covered with an exterior material containing glass to suppress moisture intrusion into all-solid-state batteries (see, for example, Patent Documents 1 to 3). .

Japanese Patent Laid-Open No. 2016-1601 JP2015-220106A Japanese Patent Laid-Open No. 2015-220099

However, there is a possibility that Li ions diffuse from the all solid state battery to the exterior material, and the irreversible capacity of the all solid state battery increases.

The purpose of the present technology is to provide an all-solid-state battery capable of suppressing an increase in irreversible capacity, a manufacturing method thereof, an electronic device, and an electronic card.

In order to solve the above-described problem, the first technique includes a battery element including Li, an exterior material that covers the battery element, and a protective layer that is provided between the battery element and the exterior material and includes Li. It is an all-solid-state battery.

The second technology is an electronic device that receives power from the all-solid-state battery of the first technology.

The third technology is an electronic card that receives power from the all-solid-state battery of the first technology.

In the fourth technique, a battery element containing Li conductivity is covered with a protective layer containing Li, an exterior material is formed on the protective layer, a layer containing crystal particles is formed on the exterior material, and the exterior material is sintered. Then, it is a manufacturing method of an all-solid-state battery including removing the layer containing crystal particles.

In the first technique, since a protective layer containing Li is provided between a battery element containing Li and an exterior material covering the battery element, the diffusion of Li from the battery element to the exterior material is suppressed. Can do.

In the second technique, after covering a battery element including Li conductivity with a protective layer containing Li, an exterior material is formed on the protective layer, so that diffusion of Li from the battery element to the exterior material is suppressed. be able to. In addition, since the layer containing crystal particles is formed on the exterior material and the exterior material is sintered and then the layer containing the crystal particles is removed, the shrinkage of the exterior material during the sintering of the exterior material is suppressed. Can do. Therefore, it can suppress that a crack generate | occur | produces in an exterior material at the time of sintering of an exterior material.

According to this technology, an increase in the irreversible capacity of the all solid state battery can be suppressed. Note that the effects described here are not necessarily limited, and may be any of the effects described in the present disclosure or effects different from those.

It is a perspective view showing an example of appearance of a battery concerning a 1st embodiment of this art. 2A is a cross-sectional view taken along the line IIA-IIA in FIG. 2B is a cross-sectional view taken along the line IIB-IIB in FIG. FIG. 3A is a perspective view showing an example of the appearance of the battery with the positive electrode terminal removed. FIG. 3B is a perspective view showing an example of the appearance of the battery with the negative electrode terminal removed. 4A and 4B are process diagrams for explaining an example of the method for manufacturing the battery according to the first embodiment of the present technology. FIG. 5A and FIG. 5B are process diagrams for explaining an example of the battery manufacturing method according to the first embodiment of the present technology. 6A and 6B are process diagrams for explaining an example of the method for manufacturing the battery according to the first embodiment of the present technology. FIG. 7A and FIG. 7B are process diagrams for explaining an example of the battery manufacturing method according to the first embodiment of the present technology. It is sectional drawing which shows an example of a structure of the battery which concerns on the modification of 1st Embodiment of this technique. It is sectional drawing which shows an example of a structure of the battery which concerns on the modification of 1st Embodiment of this technique. It is a perspective view showing an example of appearance of a battery concerning a 2nd embodiment of this art. FIG. 11A is a cross-sectional view taken along line XIA-XIA in FIG. 11B is a cross-sectional view taken along line XIB-XIB in FIG. FIG. 12A and FIG. 12B are process diagrams for explaining an example of a battery manufacturing method according to the second embodiment of the present technology. FIG. 13A and FIG. 13B are process diagrams for explaining an example of a battery manufacturing method according to the second embodiment of the present technology. FIG. 14A and FIG. 14B are process diagrams for explaining an example of a battery manufacturing method according to the second embodiment of the present technology. FIG. 15A and FIG. 15B are process diagrams for explaining an example of a battery manufacturing method according to the second embodiment of the present technology. It is a perspective view which shows an example of a structure of the printed circuit board as an application example. It is a top view which shows an example of the external appearance of the universal credit card as an application example. It is a block diagram of an example of a structure of the wireless sensor node as an application example. It is a perspective view which shows an example of the external appearance of the wristband type electronic device as an application example. It is a block diagram which shows an example of a structure of the wristband type electronic device as an application example. It is a perspective view which shows an example of the whole structure of the smart watch as an application example. It is a block diagram which shows an example of the circuit structure of the smart watch as an application example. It is a perspective view which shows an example of the external appearance of the glasses-type terminal as an application example. It is a conceptual diagram of an example of a structure of the image display apparatus of the glasses-type terminal as an application example. It is the schematic which shows an example of a structure of the electrical storage system in the vehicle as an application example. It is the schematic which shows an example of a structure of the electrical storage system in the house as an application example.

Embodiments of the present technology will be described in the following order.
1 1st Embodiment (example of all-solid-state battery)
2 Second Embodiment (Example of all-solid battery)
3 Application examples

<1 First Embodiment>
[Battery configuration]
The battery according to the first embodiment of the present technology is a so-called bulk type all-solid-state battery, and as illustrated in FIGS. 1, 2A, and 2B, the first end surface 11SA and the second end opposite to the first end surface 11SA are provided. A thin plate-shaped external battery element 11 having an end face 11SB, a positive terminal 12 provided on the first end face 11SA, and a negative terminal 13 provided on the second end face 11SB are provided. Although 1st Embodiment demonstrates the case where the main surface of the exterior battery element 11 has a rectangle, the shape of the main surface of the exterior battery element 11 is not limited to this. Hereinafter, the two end faces located between the first and second end faces 11SA and 11SB are referred to as third and fourth end faces 11SC and 11SD, respectively.

This battery is a secondary battery obtained by repeatedly receiving and transferring Li, which is an electrode reactant, and may be a lithium ion secondary battery in which the capacity of the negative electrode is obtained by occlusion and release of lithium ions, It may be a lithium metal secondary battery in which the capacity of the negative electrode is obtained by precipitation dissolution of lithium metal.

(Positive electrode, negative electrode terminal)
The positive electrode and the

negative electrode terminals

12 and 13 include, for example, conductive particle powder. The conductive particles may be sintered. The positive electrode and the

negative electrode terminals

12 and 13 may further contain glass or glass ceramics as necessary. Glass or glass ceramics may be sintered.

The glass transition temperature of the glass contained in the positive and

negative electrode terminals

12 and 13 is preferably equal to or lower than the sintering temperature of the exterior material 15. When the glass transition temperature is equal to or lower than the sintering temperature of the exterior material 15, the positive electrode and the

negative electrode terminals

12 and 13 can be simultaneously sintered when the exterior material 15 is sintered.

Examples of the shape of the conductive particles include a spherical shape, an ellipsoidal shape, a needle shape, a plate shape, a scale shape, a tube shape, a wire shape, a rod shape (rod shape), and an indefinite shape, but are not particularly limited thereto. It is not something. Two or more kinds of particles having the above shapes may be used in combination.

The conductive particles are metal particles, metal oxide particles, or carbon particles. Here, the metal is defined to include a semi-metal. Examples of the metal particles include Ag (silver), Pt (platinum), Au (gold), Ni (nickel), Cu (copper), Pd (palladium), Al (aluminum), and Fe (iron). Although what contains 1 type is mentioned, it is not limited to this.

Examples of the metal oxide particles include indium tin oxide (ITO), zinc oxide, indium oxide, antimony-added tin oxide, fluorine-added tin oxide, aluminum-added zinc oxide, gallium-added zinc oxide, silicon-added zinc oxide, and zinc oxide. Examples thereof include, but are not limited to, a tin oxide system, an indium oxide-tin oxide system, and a zinc oxide-indium oxide-magnesium oxide system.

Examples of the carbon particles include, but are not limited to, carbon black, porous carbon, carbon fiber, fullerene, graphene, carbon nanotube, carbon microcoil, and nanohorn. The glass is, for example, oxide glass. Glass ceramics are oxide glass ceramics, for example.

(External battery element)
As shown in FIGS. 2A and 2B, the exterior battery element 11 is provided between the battery element 20 including the laminated battery element 20 including Li, the exterior material 15 that covers the surface of the battery element 20, and the battery element 20 and the exterior material 15. And a protective layer 14 containing Li.

The battery element 20 is a laminate including two positive electrode layers 21, one negative electrode layer 22, and two solid electrolyte layers 23. A negative electrode layer 22 is provided between the two positive electrode layers 21, and a solid electrolyte layer 23 is provided between the positive electrode layer 21 and the negative electrode layer 22. The positive electrode layer 21 includes a positive electrode current collecting layer 21A and a positive electrode active material layer 21B provided on a main surface on the side facing the negative electrode layer 22 among both main surfaces of the positive electrode current collecting layer 21A. The negative electrode layer 22 includes a negative electrode current collecting layer 22A and a negative electrode active material layer 22B provided on both surfaces of the negative electrode current collecting layer 22A.

(Protective layer)
4A and 4B, the protective layer 14 has one end of the positive electrode current collecting layer 21A exposed from the first end face 11SA, one end of the negative electrode current collecting layer 22A exposed from the second end face 11SB, and the solid electrolyte layer 23. The surface of the battery element 20 is covered so that the peripheral edge of the battery element is exposed from the first to fourth end faces 11SA to 11SD. The protective layer 14 may cover the surface of the battery element 20 so that the peripheral edge of the solid electrolyte layer 23 is not exposed from the first to fourth end faces 11SA to 11SD.

The protective layer 14 includes a Li-containing solid electrolyte having Li ion conductivity. The protective layer 14 may contain at least one of Li-free glass, glass ceramics, and crystals having non-Li ion conductivity. The solid electrolyte is the same as that contained in the solid electrolyte layer 23 described later. However, the composition (type of material) or composition ratio of the solid electrolytes contained in the solid electrolyte layer 23 and the protective layer 14 may be the same or different.

The volume occupancy of the solid electrolyte in the protective layer 14 is preferably 10 vol% or more, more preferably 20 vol% or more, and even more preferably 30 vol% or more. When the volume occupancy is 10 vol% or more, the diffusion of Li ions from the battery element 20 to the protective layer 14 can be further reduced, so that an increase in irreversible capacity of the battery can be further suppressed. The upper limit value of the volume occupation rate is not particularly limited, and may be 100 vol%.

The volume occupancy of the above solid electrolyte is obtained as follows. First, a cross section of the battery is prepared by ion milling or the like, and a procedure for photographing a cross-sectional SEM (Scanning / Electron / Microscope) image of the exterior material 15 is repeated to obtain a three-dimensional SEM image. Thereafter, from the acquired three-dimensional SEM image, the volume occupancy rate of the solid electrolyte in the cube having a height about the thickness of the protective layer 14 is obtained.

The Li ion conductivity of the protective layer 14 is preferably 1.0 × 10 ⁻¹⁰ S / cm or more. When the Li ion conductivity is 1.0 × 10 ⁻¹⁰ S / cm or more, the diffusion of Li ions from the battery element 20 to the protective layer 14 can be further reduced, so that an increase in the irreversible capacity of the battery can be further suppressed. . The Li ion conductivity of the protective layer 14 is determined by the AC impedance method as follows. First, a part of the protective layer 14 is taken out as a rectangular plate-shaped piece from the all-solid battery by ion milling or polishing. Next, an electrode made of gold (Au) is formed on both ends of the taken out small piece to prepare a sample. Next, AC impedance measurement (frequency: 10 ⁺⁶ Hz to 10 ⁻¹ Hz, voltage: 100 mV, 1000 mV) is performed on the sample at room temperature (25 ° C.) using an impedance measuring device (manufactured by Toyo Technica). -Create a call plot. Subsequently, the ionic conductivity is obtained from the Cole-Cole plot.

(Exterior material)
As shown in FIGS. 3A and 3B, the exterior material 15 has a protective layer such that one end of the positive electrode current collecting layer 21A is exposed from the first end surface 11SA and one end of the negative electrode current collecting layer 22A is exposed from the second end surface 11SB. The surface of the battery element 20 covered with 14 is covered. One end of the positive electrode current collecting layer 21 A exposed from the first end face 11 SA is electrically connected to the positive electrode terminal 12. One end of the negative electrode current collecting layer 22 A exposed from the second end surface 11 SB is electrically connected to the negative electrode terminal 13. All the surfaces of the exterior battery element 11 other than the first and second end surfaces 11SA and 11SB are covered with the exterior material 15.

The exterior material 15 includes Li-containing glass having non-Li ion conductivity and powder of crystal particles 16. The crystal particles 16 are included in at least one of the surface and the inside of the exterior material 15. The exterior material 15 is, for example, a green sheet sintered body as an exterior material precursor.

The exterior material 15 is, for example, at least one of B (boron), Bi (bismuth), Te (tellurium), P (phosphorus), V (vanadium), Sn (tin), Pb (lead), and Si (silicon). Contains one species. More specifically, an oxide containing at least one of B, Bi, Te, P, V, Sn, Pb, and Si is included.

The moisture permeability of the outer package 15 is preferably 1.0 g / m ² / day or less, more preferably 0.75 g / m ² / day or less, and even more preferably, from the viewpoint of improving the atmospheric stability of the all-solid battery. Is 0.5 g / m ² / day or less. The moisture permeability of the exterior material 15 is obtained as follows. First, a part of the outer packaging material 15 is taken out from the all-solid battery element as a rectangular plate-shaped piece by ion milling or polishing. Next, the water vapor transmission rate (23 ° C., 90% RH) of the exterior material 15 is measured according to JIS K7129-C (ISO 15106-4).

The Li ion conductivity of the outer package 15 is preferably 1 × 10 ⁻⁸ S / cm or less from the viewpoint of suppressing self-discharge of the all-solid battery. The Li ion conductivity of the packaging material 15 is obtained by taking a part of the packaging material 15 as a rectangular plate-shaped piece from an all-solid battery by ion milling or polishing, and using this to produce a measurement sample. It is obtained in the same manner as the method for measuring the Li ion conductivity of the protective layer 14 described above.

From the viewpoint of suppressing self-discharge of the all-solid-state battery, it is preferable that the electrical conductivity (electronic conductivity) of the packaging material 15 is 1 × 10 ⁻⁸ S / cm or less. The electrical conductivity of the exterior material 15 is obtained as follows. First, a sample is prepared in the same manner as the method for measuring the Li ion conductivity of the exterior material 15 described above. Next, electrical conductivity is calculated | required at room temperature (25 degreeC) by the 2 terminal method using the produced sample.

The average thickness of the outer package 15 is preferably 100 μm or less, more preferably 75 μm or less, and even more preferably 50 μm or less, from the viewpoint of improving the energy density of the all solid state battery. The average thickness of the exterior material 15 is obtained as follows. First, a cross section of the exterior material 15 is produced by ion milling or the like, and a cross-sectional SEM image is taken. Next, 10 points are randomly selected from the cross-sectional SEM image, the thickness of the exterior material 15 is measured at each point, and the measured values are simply averaged (arithmetic average) to obtain the exterior material 15. The average thickness of is determined.

The crystal particles 16 preferably contain crystals that do not melt at the glass transition temperature of the glass contained in the exterior material 15. By including such crystals in the crystal particles 16, in the process of sintering the glass contained in the exterior material 15, the exterior material 15 is thermally contracted in the in-plane direction, and cracking of the exterior material 15 is suppressed. it can. Here, the “in-plane direction” means the in-plane direction of the main surface of the external battery element 11.

Crystal grain 16 contains at least one of metal oxide, metal nitride, and metal carbide. Here, the metal is defined to include a semi-metal. More specifically, the crystal particles 16 are made of Al ₂ O ₃ (aluminum oxide: alumina), SiO ₂ (silicon oxide: quartz), SiN (silicon nitride), AlN (aluminum nitride), and SiC (silicon carbide). Of at least one of the following.

The average particle diameter (average diameter) of the crystal particles 16 is preferably 10 μm or less. If the average particle size of the crystal particles 16 exceeds 10 μm, the effect of suppressing the thermal shrinkage of the exterior material 15 in the in-plane direction may be reduced in the step of sintering the glass contained in the exterior material 15. That is, there is a possibility that the exterior material 15 may be cracked.

The average particle size of the crystal particles 16 is determined as follows. First, a surface SEM image of the exterior material 15 is taken. Next, 100 crystal particles 16 are selected at random from the surface SEM image, the particle diameters (diameters) of these crystal particles 16 are measured, and simply averaged (arithmetic average). Obtain the average particle size. Here, when the crystal particle 16 is not spherical, the maximum distance (so-called maximum ferret diameter) among the distances between two parallel lines drawn from all angles so as to contact the contour of the crystal particle 16 is selected. The particle size (diameter) is 16. However, when the crystal particles 16 are embedded in the exterior material 15 and the particle size of the crystal particles 16 cannot be measured from the surface SEM image of the exterior material 15, the average of the crystal particles 16 from the cross-sectional SEM image of the exterior material 15 The particle size shall be determined.

(Solid electrolyte layer)
The solid electrolyte layer 23 includes a solid electrolyte containing Li. The solid electrolyte is at least one of an oxide glass and an oxide glass ceramic that are lithium ion conductors, and is preferably an oxide glass ceramic from the viewpoint of improving Li ion conductivity. When the solid electrolyte is at least one of oxide glass and oxide glass ceramics, the stability of the solid electrolyte layer 23 against the atmosphere (moisture) can be improved. The solid electrolyte layer 23 is a sintered body of a green sheet as a solid electrolyte layer precursor, for example.

Here, the glass means a crystallographically amorphous material such as halo observed in X-ray diffraction or electron beam diffraction. Glass ceramics (crystallized glass) refers to a crystallographic mixture of amorphous and crystalline materials, such as peaks and halos observed in X-ray diffraction, electron beam diffraction, and the like.

The Li ion conductivity of the solid electrolyte is preferably 10 ⁻⁷ S / cm or more from the viewpoint of improving battery performance. The Li ion conductivity of the solid electrolyte is the same as that of the protective layer 14 described above except that the solid electrolyte layer 23 is taken out from the all-solid battery element by ion milling or polishing, and a measurement sample is produced using this. It is obtained in the same manner as the rate measurement method.

The solid electrolyte contained in the solid electrolyte layer 23 is sintered. The sintering temperature of the oxide glass and the oxide glass ceramic that is a solid electrolyte is preferably 550 ° C. or lower, more preferably 300 ° C. or higher and 550 ° C. or lower, and even more preferably 300 ° C. or higher and 500 ° C. or lower.

When the sintering temperature is 550 ° C. or lower, the carbon material can be prevented from being burned out in the sintering process, so that the carbon material can be used as the negative electrode active material. Therefore, the energy density of the battery can be further improved. Further, when the positive electrode active material layer 21B includes a conductive agent, a carbon material can be used as the conductive agent. Therefore, a favorable electron conduction path can be formed in the positive electrode active material layer 21B, and the conductivity of the positive electrode active material layer 21B can be improved. Even when the negative electrode layer 22 contains a conductive agent, a carbon material can be used as the conductive agent, so that the conductivity of the negative electrode layer 22 can be improved.

Also, when the sintering temperature is 550 ° C. or lower, it is possible to suppress the formation of by-products such as a passive state due to the reaction between the solid electrolyte and the electrode active material in the sintering process. Accordingly, it is possible to suppress a decrease in battery characteristics. Further, when the sintering temperature is as low as 550 ° C. or less, the range of selection of the type of electrode active material is widened, so that the degree of freedom in battery design can be improved.

On the other hand, when the sintering temperature is 300 ° C. or higher, a general organic binder such as an acrylic resin contained in the electrode precursor and / or the solid electrolyte layer precursor can be burned out in the sintering step. .

Oxide glass and oxide glass ceramics preferably have a sintering temperature of 550 ° C. or lower, a high heat shrinkage rate, and high fluidity. This is because the following effects can be obtained. That is, the reaction between the solid electrolyte layer 23 and the positive electrode active material layer 21B and the reaction between the solid electrolyte layer 23 and the negative electrode layer 22 can be suppressed. Further, good interfaces are formed between the positive electrode active material layer 21B and the solid electrolyte layer 23, and between the negative electrode layer 22 and the solid electrolyte layer 23, and between the positive electrode active material layer 21B and the solid electrolyte layer 23, and the negative electrode layer. The interface resistance between 22 and the solid electrolyte layer 23 can be reduced.

As oxide glass and oxide glass ceramic, at least one of Ge (germanium), Si (silicon), B (boron), and P (phosphorus), Li (lithium), and O (oxygen) Those containing Si, B, Li and O are more preferable. Specifically, at least one of germanium oxide (GeO ₂ ), silicon oxide (SiO ₂ ), boron oxide (B ₂ O ₃ ) and phosphorus oxide (P ₂ O ₅ ), and lithium oxide (Li ₂ O). ) Are preferred, and those containing SiO ₂ , B ₂ O ₃ and Li ₂ O are more preferred. As described above, the oxide glass and oxide glass ceramic containing at least one of Ge, Si, B, and P, Li, and O have a sintering temperature of 300 ° C. or higher and 550 ° C. or lower, Since it has a high heat shrinkage ratio and is rich in fluidity, it is advantageous from the viewpoint of reducing interfacial resistance and improving the energy density of the battery.

The content of Li ₂ O is preferably 20 mol% or more and 75 mol% or less, more preferably 30 mol% or more and 75 mol% or less, still more preferably 40 mol% or more and 75 mol% or less, from the viewpoint of lowering the sintering temperature of the solid electrolyte. Especially preferably, they are 50 mol% or more and 75 mol% or less.

When a solid electrolyte containing GeO _2, the content of the GeO ₂ is preferably less greater 80 mol% than 0 mol%. When a solid electrolyte containing SiO _2, the content of the SiO ₂ is preferably from greater than 0 mol% 70 mol%. When a solid electrolyte comprising a B ₂ O _3, the content of the B ₂ O ₃ is preferably not more than greater than 0 mol% 60 mol%. When a solid electrolyte comprising a P ₂ O _5, the content of the P ₂ O ₅ is preferably from greater than 0 mol% 50 mol%.

The content of each oxide is the content of each oxide in the solid electrolyte, and specifically, one or more of GeO ₂ , SiO ₂ , B ₂ O ₃ and P ₂ O ₅ , The ratio of the content (mol) of each oxide to the total amount (mol) with Li ₂ O is shown as a percentage (mol%). The content of each oxide can be measured using inductively coupled plasma emission spectroscopy (ICP-AES) or the like.

The solid electrolyte may further contain an additive element as necessary. As an additive element, for example, Na (sodium), Mg (magnesium), Al (aluminum), K (potassium), Ca (calcium), Ti (titanium), V (vanadium), Cr (chromium), Mn (manganese) ), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Ga (gallium), Se (selenium), Rb (rubidium), S (sulfur), Y (yttrium) ), Zr (zirconium), Nb (niobium), Mo (molybdenum), Ag (silver), In (indium), Sn (tin), Sb (antimony), Cs (cesium), Ba (vanadium), Hf (hafnium) ), Ta (tantalum), W (tungsten), Pb (lead), Bi (bismuth), Au (gold), La (lanthanum), Nd (neodymium) and Eu (you) At least one type selected from the group consisting of Piumu). The solid electrolyte may contain at least one selected from the group consisting of these additive elements as an oxide.

(Positive electrode current collector layer)
The positive electrode current collecting layer 21A includes conductive particles and a solid electrolyte. The conductive particles are the same as those contained in the positive electrode and

negative electrode terminals

12 and 13 described above. The solid electrolyte is the same as that included in the solid electrolyte layer 23 described above. However, the composition (kind of materials) or composition ratio of the solid electrolyte contained in the solid electrolyte layer 23 and the positive electrode current collecting layer 21A may be the same or different.

The positive electrode current collecting layer 21A may be a metal layer containing, for example, Al, Ni, stainless steel, or the like. The shape of the metal layer is, for example, a foil shape, a plate shape, or a mesh shape.

(Positive electrode active material layer)
The positive electrode active material layer 21B includes a positive electrode active material and a solid electrolyte. The solid electrolyte may have a function as a binder. The positive electrode active material layer 21B may further contain a conductive agent as necessary.

The positive electrode active material includes, for example, a positive electrode material capable of occluding and releasing lithium ions that are electrode reactants. The positive electrode material is preferably a lithium-containing compound or the like from the viewpoint of obtaining a high energy density, but is not limited thereto. This lithium-containing compound is, for example, a composite oxide (lithium transition metal composite oxide) containing lithium and a transition metal element as constituent elements, or a phosphate compound (lithium transition metal) containing lithium and a transition metal element as constituent elements. Phosphate compounds). Among these, the transition metal element is preferably one or more of Co, Ni, Mn, and Fe. Thereby, when a higher voltage is obtained and the voltage of the battery can be increased, the energy (Wh) of the battery having the same capacity (mAh) can be increased.

The lithium transition metal composite oxide is represented by, for example, Li _x M1O ₂ or Li _y M2O ₄ . More specifically, for example, the lithium transition metal composite oxide is LiCoO ₂ , LiNiO ₂ , LiVO ₂ , LiCrO _2, or LiMn ₂ O ₄ . Further, the lithium transition metal phosphate compound is represented by, for example, Li _z M3PO ₄ . More specifically, for example, the lithium transition metal phosphate compound is LiFePO ₄ or LiCoPO ₄ . However, M1 to M3 are one or more transition metal elements, and the values of x to z are arbitrary.

In addition, the positive electrode active material may be, for example, an oxide, disulfide, chalcogenide, or conductive polymer. Examples of the oxide include titanium oxide, vanadium oxide, and manganese dioxide. Examples of the disulfide include titanium disulfide and molybdenum sulfide. An example of the chalcogenide is niobium selenide. Examples of the conductive polymer include disulfide, polypyrrole, polyaniline, polythiophene, polyparastyrene, polyacetylene, and polyacene.

The solid electrolyte is the same as that included in the solid electrolyte layer 23 described above. However, the composition (kind of materials) or composition ratio of the solid electrolyte contained in the solid electrolyte layer 23 and the positive electrode active material layer 21B may be the same or different.

The conductive agent is, for example, at least one of a carbon material, a metal, a metal oxide, a conductive polymer, and the like. As the carbon material, for example, at least one of graphite, carbon fiber, carbon black, carbon nanotube, and the like can be used. As the carbon fiber, for example, vapor growth carbon fiber (VGCF) can be used. As the carbon black, for example, at least one of acetylene black and ketjen black can be used. As the carbon nanotube, for example, a multi-wall carbon nanotube (MWCNT) such as a single wall carbon nanotube (SWCNT) or a double wall carbon nanotube (DWCNT) can be used. As the metal, for example, Ni powder can be used. For example, SnO ₂ can be used as the metal oxide. As the conductive polymer, for example, at least one of substituted or unsubstituted polyaniline, polypyrrole, polythiophene, and one or two (co) polymers selected from these can be used. Note that the conductive agent may be any material having conductivity, and is not limited to the above example.

(Negative electrode current collector layer)
The anode current collecting layer 22A includes conductive particles and a solid electrolyte. The conductive particles are the same as those contained in the positive electrode and

negative electrode terminals

12 and 13 described above. The solid electrolyte is the same as that included in the solid electrolyte layer 23 described above. However, the composition (kind of materials) or composition ratio of the solid electrolyte contained in the solid electrolyte layer 23 and the anode current collecting layer 22A may be the same or different.

The negative electrode current collecting layer 22A may be a metal layer containing, for example, Cu or stainless steel. The shape of the metal layer is, for example, a foil shape, a plate shape, or a mesh shape.

(Negative electrode active material layer)
The negative electrode active material layer 22B includes a negative electrode active material and a solid electrolyte. The solid electrolyte may have a function as a binder. The negative electrode layer 22 may further contain a conductive agent as necessary. The negative electrode layer 22 is, for example, a green sheet sintered body as a negative electrode layer precursor.

The negative electrode active material includes, for example, a negative electrode material capable of occluding and releasing lithium ions that are electrode reactants. The negative electrode material is preferably a carbon material or a metal-based material from the viewpoint of obtaining a high energy density, but is not limited thereto.

Examples of the carbon material include graphitizable carbon, non-graphitizable carbon, graphite, mesocarbon microbeads (MCMB), and highly oriented graphite (HOPG).

The metal-based material is a material containing, for example, a metal element or a metalloid element capable of forming an alloy with lithium as a constituent element. More specifically, for example, the metal materials are Si (silicon), Sn (tin), Al (aluminum), In (indium), Mg (magnesium), B (boron), Ga (gallium), Ge (germanium). ), Pb (lead), Bi (bismuth), Cd (cadmium), Ag (silver), Zn (zinc), Hf (hafnium), Zr (zirconium), Y (yttrium), Pd (palladium) or Pt (platinum) ) And the like, any one kind or two or more kinds of alloys or compounds. However, the simple substance is not limited to 100% purity, and may contain a small amount of impurities. Examples of the alloy or compound include SiB ₄ , TiSi ₂ , SiC, Si ₃ N ₄ , SiO _v (0 <v ≦ 2), LiSiO, SnO _w (0 <w ≦ 2), SnSiO ₃ , LiSnO, Mg _2. Sn etc. are mentioned.

The metal-based material may be a lithium-containing compound or lithium metal (lithium simple substance). The lithium-containing compound is a composite oxide (lithium transition metal composite oxide) containing lithium and a transition metal element as constituent elements. Examples of this composite oxide include Li ₄ Ti ₅ O ₁₂ .

The solid electrolyte is the same as that included in the solid electrolyte layer 23 described above. However, the composition (kind of materials) or composition ratio of the solid electrolyte contained in the solid electrolyte layer 23 and the negative electrode active material layer 22B may be the same or different.

The conductive agent is the same as the conductive agent in the positive electrode active material layer 21B described above.

[Battery operation]
In this battery, for example, at the time of charging, lithium ions released from the positive electrode active material layer 21B are taken into the negative electrode active material layer 22B via the solid electrolyte layer 23, and discharged from the negative electrode active material layer 22B during discharge. The lithium ions thus taken are taken into the positive electrode active material layer 21 B through the solid electrolyte layer 23.

[Battery manufacturing method]
Hereinafter, an example of a battery manufacturing method according to the first embodiment of the present technology will be described with reference to FIGS. 4A to 7B. 4A, 5A, 6A, and 7A are perspective views when the battery element 20 is viewed from the first end face 11SA side, and FIGS. 4B, 5B, 6B, and 7B show the battery element 20 from the second end face 11SB side. It is a perspective view when seen.

(Production process of solid electrolyte layer forming paste)
A solid electrolyte and an organic binder are mixed to prepare a mixture powder, and then the mixture powder is dispersed in a solvent to obtain a solid electrolyte layer forming paste.

As the organic binder, for example, an acrylic resin can be used. The solvent is not particularly limited as long as it can disperse the mixture powder, but is preferably one that burns away in a temperature range lower than the sintering temperature of the solid electrolyte layer forming paste. Examples of the solvent include lower alcohols having 4 or less carbon atoms such as methanol, ethanol, isopropanol, n-butanol, sec-butanol, t-butanol, ethylene glycol, propylene glycol (1,3-propanediol), 1, Aliphatic glycols such as 3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, ketones such as methyl ethyl ketone, dimethylethylamine Amines such as alicyclic alcohols such as terpineol can be used alone or in admixture of two or more, but the invention is not particularly limited thereto. Examples of the dispersion method include stirring treatment, ultrasonic dispersion treatment, bead dispersion treatment, kneading treatment, and homogenizer treatment. Positive electrode current collecting layer forming paste, positive electrode active material layer forming paste, negative electrode current collecting layer forming paste, negative electrode active material layer forming paste, protective layer forming paste, exterior material forming paste and conductivity described below Also in the paste production process, examples of the organic binder and the solvent include the same materials as the solid electrolyte layer forming paste.

(Preparation process of positive electrode current collector layer forming paste)
A powder of conductive particles, a Li-containing solid electrolyte having Li conductivity, and an organic binder are mixed to prepare a mixture powder, and then the mixture powder is dispersed in a solvent to form a positive electrode. A paste for forming a current collecting layer is obtained.

(Preparation process of positive electrode active material layer forming paste)
A mixture powder is prepared by mixing a positive electrode active material, a Li-containing solid electrolyte having Li conductivity, an organic binder, and, if necessary, a conductive agent. To obtain a paste for forming a positive electrode active material layer.

(Preparation process of paste for forming negative electrode current collector layer)
A powder of conductive particles, a Li-containing solid electrolyte having Li conductivity, and an organic binder are mixed to prepare a mixture powder, and then the mixture powder is dispersed in a solvent to form a positive electrode. A paste for forming a current collecting layer is obtained.

(Process for producing negative electrode active material layer forming paste)
A mixture powder is prepared by mixing a negative electrode active material, a Li-containing solid electrolyte having Li conductivity, an organic binder, and, if necessary, a conductive agent. To obtain a paste for forming a negative electrode active material.

(Process for producing protective layer forming paste)
A Li-containing solid electrolyte having Li conductivity, an organic binder, and, if necessary, at least one of glass, glass ceramics, and powder of crystal particles having non-Li ion conductivity are mixed together. After preparing the agent powder, the mixture powder is dispersed in a solvent to obtain a protective layer forming paste.

(Process for producing exterior material forming paste)
A non-Li-containing glass having non-Li ion conductivity and a glass transition temperature of 500 ° C. or lower is mixed with an organic binder to prepare a mixture powder, which is then used as a solvent. To obtain a paste as a composition for forming an exterior material.

(Process for producing conductive paste)
The powder of conductive particles, glass having a glass transition temperature of 500 ° C. or lower, and an organic binder are mixed to prepare a mixture powder. A conductive paste (a paste for forming a positive electrode terminal and a negative electrode terminal) is obtained.

(Production process of solid electrolyte layer)
First, a paste layer is shape | molded by apply | coating or printing a paste uniformly on the surface of a support base material. As the support substrate, for example, a polymer resin film such as a polyethylene terephthalate (PET) film can be used. As a method for coating and printing, it is preferable to use a simple and suitable method for mass production. Examples of coating methods include die coating, micro gravure coating, wire bar coating, direct gravure coating, reverse roll coating, comma coating, knife coating, spray coating, curtain coating, dipping, and spin. A coating method or the like can be used, but is not particularly limited thereto. As a printing method, for example, a relief printing method, an offset printing method, a gravure printing method, an intaglio printing method, a rubber plate printing method, a screen printing method, and the like can be used, but the invention is not particularly limited thereto.

In order to make it easier to peel off the green sheet from the surface of the supporting base material in a later step, it is preferable to perform a peeling treatment on the surface of the supporting base material in advance. As a peeling process, the method of apply | coating or printing in advance on the surface of a support base material is mentioned, for example. Examples of the composition imparting releasability include a paint containing a binder as a main component and added with wax or fluorine, or a silicone resin.

Next, the paste layer is dried to form a green sheet on the surface of the support substrate. Examples of the drying method include natural drying, blow drying with hot air, heating drying with infrared rays or far infrared rays, vacuum drying, and the like. These drying methods may be used alone or in combination of two or more. Next, the green sheet is peeled off from the support substrate and cut into a predetermined size and shape. Thereby, the unsintered solid electrolyte layer 23 as a green sheet is obtained.

(Protective layer manufacturing process)
Except for using the protective layer forming paste, the green protective layer 14 as a green sheet is obtained in the same manner as in the above-described “solid electrolyte preparation step”.

(Exterior material manufacturing process)
Except for using the packaging material forming paste, an unsintered packaging material 15 as a green sheet is obtained in the same manner as in the above-described “solid electrolyte production step”.

(Battery element manufacturing process)
The first laminate is produced as follows. First, the positive electrode layer forming paste is applied to one surface of the solid electrolyte layer 23 as a green sheet so that a loop-shaped uncoated portion is formed on the peripheral portion of the surface, and is dried. The active material layer 21B is formed. Subsequently, the protective layer forming paste is applied to the uncoated portion of the loop shape and dried to form the protective layer 14 having substantially the same thickness as the positive electrode active material layer 21B. Thereafter, the paste for forming the positive electrode current collecting layer is applied to the surface formed by the positive electrode active material layer 21B and the protective layer 14 so that a U-shaped uncoated portion is formed at the peripheral portion of the surface and dried. Thus, the positive electrode current collecting layer 21A is formed. Finally, the protective layer forming paste is applied to the U-shaped unapplied portion and dried to form the protective layer 14 having substantially the same thickness as the positive electrode current collecting layer 21A. Thus, the first laminate is obtained.

The second laminate is produced as follows. First, a solid electrolyte layer 23 as a green sheet is prepared separately from the first laminate. Then, the negative electrode layer forming paste is applied to one surface of the solid electrolyte layer 23 so that a loop-shaped uncoated portion is formed on the peripheral portion of the surface, and is dried, whereby the negative electrode active material layer 22B. Form. Subsequently, the protective layer forming paste is applied to the loop-shaped uncoated portion and dried, thereby forming the protective layer 14 having substantially the same thickness as the negative electrode active material layer 22B. Thereafter, the paste for forming the negative electrode current collecting layer is applied to the surface formed by the negative electrode active material layer 22B and the protective layer 14 so that a U-shaped uncoated portion is formed at the peripheral portion of the surface and dried. Thus, the negative electrode current collecting layer 22A is formed.

Next, the protective layer forming paste is applied to the U-shaped uncoated portion and dried to form the protective layer 14 having substantially the same thickness as the negative electrode current collecting layer 22A. Thereafter, the negative electrode active material layer forming paste is applied to the surface formed by the negative electrode current collecting layer 22A and the protective layer 14 so that a loop-shaped uncoated portion is formed at the peripheral portion of the surface, and is dried. Thus, the negative electrode active material layer 22B is formed. Subsequently, a protective layer forming paste having the same thickness as that of the negative electrode active material layer 22 B is formed by applying the protective layer forming paste to the loop-shaped uncoated portion and drying the paste. Further, the positive electrode active material layer 21 B, the positive electrode current collecting layer 21 A, and the protective layer 14 are formed on the other surface of the solid electrolyte layer 23 in the same manner as in the first laminate manufacturing process.
Thus, the second laminate is obtained.

The first laminated body, the second laminated body, and the two protective layers 14 as green sheets obtained as described above, the positive electrode active material layer 21B and the negative electrode active material layer 22B are interposed via the solid electrolyte layer 23. Then, the protective layer 14, the second stacked body, the first stacked body, and the protective layer 14 are stacked in this order so as to face each other. As a result, an unsintered laminated battery element 20 covered with the unsintered protective layer 14 shown in FIGS. 4A and 4B is obtained. Subsequently, the protective layer 14 and the battery element 20 are simultaneously sintered.

(Exterior material manufacturing process)
Next, as shown in FIGS. 5A and 5B, the surface of the battery element 20 excluding the first and second end faces 11SA and 11SB is made of glass having a glass transition temperature of 500 ° C. or lower (that is, glass that melts at 500 ° C. or lower). ) Including an exterior material (green sheet) 15. After coating, as shown in FIGS. 6A and 6B, a crystalline powder layer having a thickness of 50 μm including crystal particles that do not melt at the glass transition temperature of the glass contained in the packaging material 15 is formed on the surface of the packaging material 15.

(Sintering process for exterior materials)
Next, the glass contained in the exterior material 15 is sintered at 500 ° C. or lower. At this time, the crystal particles contained in the crystalline powder layer are held in a particle state. Further, the powder of crystal particles existing at the interface between the exterior material 15 and the crystalline powder layer 16 A is bound to the surface of the exterior material 15. In addition, by adjusting the sintering temperature of the exterior material 15 or pressing the exterior material 15 when the exterior material 15 is sintered, the powder of crystal particles may be embedded in the interior of the exterior material 15, It may be bound to the surface of the exterior material 15 and embedded in the exterior material 15. After cooling, the crystalline powder layer is removed as shown in FIGS. 7A and 7B. At this time, among the powders of crystal particles included in the crystalline powder layer 16 A, those bound to the surface of the exterior material 15 remain on the protective layer 14. For this reason, whether or not the battery is manufactured using the battery manufacturing method according to the first embodiment depends on whether or not the crystal particles 16 are present on the protective layer 14 by, for example, SEM and X-ray diffraction. This can be confirmed by analyzing the above.

(Preparation process of positive terminal and negative terminal)
After the removal, the first and second end faces 11SA and 11SB are dip-coated with a conductive paste and dried to form the positive and

negative terminals

12 and 13, respectively. Thereafter, after burning (degreasing) the organic binder contained in the positive electrode and the

negative electrode terminals

12 and 13, the glass contained in them is sintered at a sintering temperature or lower (that is, 500 ° C. or lower) of the exterior material 15. Let Thereby, the all-solid-state battery shown in FIG. 1 is obtained.

[effect]
In the battery according to the first embodiment, since the protective layer 14 contains Li from the beginning, Li ion diffusion from the battery element 20 to the protective layer 14 can be suppressed. Therefore, an increase in irreversible capacity can be suppressed.

Since the protective layer 14 containing a solid electrolyte is provided between the battery element 20 having a laminated structure and the exterior material 15 that suppresses moisture permeation, the battery element 20 and the exterior material 15 are electrically and chemically insulated. can do. Therefore, a stable charge / discharge cycle is possible.

Since the battery element 20 is covered with the dense exterior material 15, moisture permeation to the battery element 20 can be suppressed even if the average thickness of the exterior material 15 is 100 μm or less. Therefore, a stable charge / discharge operation can be realized.

In the battery manufacturing method according to the first embodiment, after forming the crystalline powder layer 16A including the powder of the crystal particles 16 that does not melt at the sintering temperature of the exterior material 15 on the exterior material 15 including glass, the exterior Since the material 15 is sintered, the exterior material 15 can be prevented from shrinking in the in-plane direction of the main surface of the battery element 20 during sintering. Therefore, generation | occurrence | production of the crack of the exterior material 15 can be suppressed. That is, the dense exterior material 15 can be formed on the surface of the battery element 20. Moreover, since the crystalline powder layer 16A is removed after the exterior material 15 is sintered, cracking of the exterior material 15 can be suppressed without increasing the battery volume. On the other hand, when the exterior material 15 is sintered without forming the crystalline powder layer 16A on the exterior material 15, the exterior material 15 may be cracked due to shrinkage during sintering. .

Since the crystalline powder layer 16A containing the powder of the crystal particles 16 that does not melt at the sintering temperature of the exterior material 15 is provided on the surface of the exterior battery element 11, the exterior material 15 is used as a support base (susceptor) for the exterior battery element 11. The exterior material 15 can be sintered without being in close contact. Therefore, since it can suppress that the exterior battery element 11 adheres to a support stand, workability | operativity and a yield can be improved.

[Modification]
(Modification 1)
In the first embodiment, the configuration in which the battery includes the negative electrode layer 22 having the two-layer structure including the negative electrode current collecting layer 22A and the negative electrode active material layer 22B has been described. Instead of the negative electrode layer 22, FIG. As shown, a configuration including a single-layered negative electrode layer 24 may be employed.

The negative electrode layer 24 is a negative electrode active material layer containing a negative electrode active material and a solid electrolyte. The solid electrolyte may have a function as a binder. The negative electrode layer 24 may further contain a conductive agent as necessary. The negative electrode active material is the same as that included in the negative electrode active material layer 22B in the first embodiment. In addition, it may replace with the positive electrode layer 21 of a two-layer structure, and the structure provided with the positive electrode layer of a single layer structure may be employ | adopted.

(Modification 2)
In the first embodiment, the configuration in which the battery element 20 includes the two positive electrode layers 21, the one negative electrode layer 22, and the two solid electrolyte layers 23 has been described. The number of layers of the positive electrode layer 21, the negative electrode layer 22, and the solid electrolyte layer 23 is not particularly limited as long as the positive electrode layer 21 and the negative electrode layer 22 are stacked via the solid electrolyte layer 23.

FIG. 9 shows an example of a configuration in which the battery element 20 includes four positive electrode layers 21, four negative electrode layers 22, and seven solid electrolyte layers 23. The positive electrode layers 21 and the negative electrode layers 22 are alternately stacked with the solid electrolyte layers 23 interposed therebetween. A positive electrode layer 21 is provided at one end of the battery element 20, and a negative electrode layer 22 is provided at the other end. Of the four positive electrode layers 21, the positive electrode layer 21 located at one end of the battery element 20 is the main electrode on the side facing the negative electrode layer 22 of both main surfaces of the positive electrode current collector layer 21 A and the positive electrode current collector layer 21 A. And a positive electrode active material layer 21B provided on the surface. Among the four positive electrode layers 21, the positive electrode layer 21 located at a position other than one end of the battery element 20 includes a positive electrode current collecting layer 21 A and a positive electrode active material layer 21 B provided on both main surfaces of the positive electrode current collecting layer 21 A. Is provided.

Of the four negative electrode layers 22, the negative electrode layer 22 located at the other end of the battery element 20 is on the side facing the positive electrode layer 21 of both main surfaces of the negative electrode current collector layer 22 A and the negative electrode current collector layer 22 A. A negative electrode active material layer 22B provided on the main surface. Of the four negative electrode layers 22, the negative electrode layer 22 positioned other than the other end of the battery element 20 includes a negative electrode current collecting layer 22 A and a negative electrode active material layer 22 B provided on both main surfaces of the negative electrode current collecting layer 22 A. With.

One end of the four positive electrode current collecting layers 21A is exposed from the first end face 11SA. The positive electrode terminal 12 is electrically connected to one end of the exposed four positive electrode current collecting layers 21A. On the other hand, one end of the four negative electrode current collecting layers 22A is exposed from the second end face 11SB. A negative electrode terminal 13 is electrically connected to one end of the exposed negative electrode current collecting layer 22A.

(Modification 3)
In the battery of the first embodiment, the configuration in which the exterior material 15 includes the powder of the crystal particles 16 has been described, but the exterior material 15 may not include the crystal particles 16. In the battery element manufacturing method according to the first embodiment, the case where the step of forming the crystalline powder layer 16 A on the exterior material 15 has been described, but the above step may be omitted. However, in order to suppress the occurrence of cracks in the exterior material 15, it is preferable that the above process is provided.

(Modification 4)
In the first embodiment, the case where the shape of the main surface of the external battery element 11 is a square has been described, but the shape of the main surface of the external battery element 11 is not particularly limited. For example, a circle, an ellipse, a polygon other than a quadrangle, an indefinite shape, or the like can be given. The shape of the external battery element 11 is not limited to a plate shape, and may be a sheet shape or a block shape. Moreover, the exterior battery element 11 may be curved or bent.

(Modification 5)
In the first embodiment described above, an example in which the present technology is applied to a battery using lithium as an electrode reactant has been described, but the present technology is not limited to this example. For example, the present technology may be applied to a battery using another alkali metal such as Na or K, an alkaline earth metal such as Mg or Ca, or another metal such as Al or Ag as an electrode reactant.

(Modification 6)
In the first embodiment described above, the case where all the layers of the positive electrode current collecting layer 21A, the positive electrode active material layer 21B, the negative electrode current collecting layer 22A, and the negative electrode active material layer 22B contain a solid electrolyte has been described. At least one of the layer 21A, the positive electrode active material layer 21B, the negative electrode current collecting layer 22A, and the negative electrode active material layer 22B may not contain a solid electrolyte. In this case, the layer not including the solid electrolyte may be a thin film formed by a vapor deposition method such as a vapor deposition method or a sputtering method.

(Modification 7)
The solid electrolyte contained in 21 A of positive electrode current collection layers, 21 B of positive electrode active material layers, the negative electrode layer 22, and the solid electrolyte layer 23 is not specifically limited. Examples of the solid electrolyte other than the solid electrolyte of the first embodiment include a perovskite oxide crystal composed of La—Li—Ti—O and the like, and a garnet oxidation composed of Li—La—Zr—O and the like. A phosphoric acid compound (LATP) containing constituent crystals, lithium, aluminum and titanium as constituent elements, a phosphoric acid compound (LAGP) containing lithium, aluminum and germanium as constituent elements can be used.

Further, sulfides such as Li ₂ S—P ₂ S ₅ , Li ₂ S—SiS ₂ —Li ₃ PO ₄ , Li ₇ P ₃ S ₁₁ , Li _3.25 Ge _0.25 P _0.75 S, or Li ₁₀ GeP ₂ S ₁₂ , Li ₇ La ₃ Zr ₂ O ₁₂ , Li _6.75 La ₃ Zr _1.75 Nb _0.25 O ₁₂ , Li ₆ BaLa ₂ Ta ₂ O ₁₂ , Li _{1 + x} Al _x Ti _2-x (PO ₄ ) ₃ or La _2/3 An oxide such as _-x Li _3x TiO ₃ can also be used.

(Modification 8)
In the first embodiment, the configuration in which the peripheral edge portion of the solid electrolyte layer 23 is exposed from the peripheral edge portion (first to fourth end faces 11SA to 11SD) of the battery element 20 without being covered with the protective layer 14 has been described. However, a configuration in which the peripheral portion of the solid electrolyte layer 23 is covered with the protective layer 14 may be adopted.

(Other variations)
The structure of the battery element 20 is not particularly limited, and may have a bipolar stacked structure. Further, at least one of the positive electrode current collecting layer 21A, the positive electrode active material layer 21B, the negative electrode current collecting layer 22A, and the negative electrode active material layer 22B may be a green sheet sintered body. Further, at least one of positive electrode current collecting layer 21A, positive electrode active material layer 21B, negative electrode current collecting layer 22A, negative electrode active material layer 22B, and solid electrolyte layer 23 may be a green compact. The green compact does not need to contain an organic binder.

<2 Second Embodiment>
[Battery configuration]
In the battery according to the second embodiment of the present technology, as shown in FIGS. 10, 11 A, and 11 B, the exterior material 15 includes powder of crystal particles 16 in portions corresponding to the third and fourth end surfaces 11 SC and 11 SD. This is different from the battery according to the first embodiment.

[Battery manufacturing method]
Hereinafter, an example of a method for manufacturing a battery according to the second embodiment of the present technology will be described with reference to FIGS. 4 and 12A to 15B. 4A, 12A, 13A, 14A, and 15A are perspective views when the battery element 20 is viewed from the first end surface 11SA side, and FIGS. 4B, 12B, 13B, 14B, and 15B are from the second end surface 11SB side. It is a perspective view when the battery element 20 and the exterior battery element 31 are seen.

First, similarly to the manufacturing method of the first embodiment, as shown in FIGS. 4A and 4B, a Li-containing battery element 20 covered with a Li-containing protective layer 14 having Li ion conductivity is manufactured. Next, as shown in FIGS. 12A and 12B, both main surfaces of the battery element 20 covered with the protective layer 14 include glass having a glass transition temperature of 500 ° C. or lower (that is, glass that melts at 500 ° C. or lower). Cover with exterior material 15. Subsequently, as illustrated in FIGS. 13A and 13B, a crystalline powder layer 16 A having a thickness of 50 μm including crystals that do not melt at the glass transition temperature of the glass included in the exterior material 15 is formed on the exterior material 15. Then, after burning (degreasing) the organic binder (binder) contained in the unsintered battery element 20, the protective layer 14, and the exterior material 15 at the same time, the solid electrolyte contained in the battery element 20 and the protective layer 14. (For example, oxide glass) and the glass contained in the exterior material 15 are simultaneously sintered at 500 ° C. or lower. At this time, the powder of crystal particles existing at the interface between the exterior material 15 and the crystalline powder layer 16 A is bound to the surface of the exterior material 15.

After sintering, the crystalline powder layer 16A is removed from the protective layer 14 as shown in FIGS. 14A and 14B. At this time, among the powders of crystal particles included in the crystalline powder layer 16 A, those bound to the surface of the exterior material 15 remain on the protective layer 14. Next, as shown in FIGS. 15A and 15B, the packaging material forming paste is dip coated on the third and fourth end surfaces 11SC and 11SD and dried, so that the packaging material 15 is applied to the third and fourth end surfaces 11SC and 11SD. Form.

Subsequently, the first and second end faces 11SA and 11SB of the exterior battery element 31 are dip-coated with a conductive paste and dried to form the positive and

negative terminals

12 and 13. Thereafter, the exterior binder 15 formed on the third and fourth end faces 11SC and 11SD and the organic binder contained in the positive electrode and the

negative electrode terminals

12 and 13 are simultaneously burned (degreased) and then included. The glass is simultaneously sintered at a temperature equal to or lower than the sintering temperature of the outer package 15 (that is, 500 ° C. or lower). Thereby, the battery shown in FIG. 10 is obtained.

[effect]
In the battery according to the second embodiment, the same effect as that of the battery according to the first embodiment can be obtained. The battery manufacturing method according to the second embodiment can achieve the same effects as the battery manufacturing method according to the first embodiment.

<3 Application example>
"Printed circuit boards as application examples"
Hereinafter, application examples in which the present disclosure is applied to a printed circuit board will be described.
The battery described above can be mounted on a printed circuit board together with a charging circuit or the like. For example, an electronic circuit such as an all-solid battery and a charging circuit can be mounted on a printed circuit board by a reflow process. The printed circuit board is an example of a battery module, and may be a portable card type mobile battery.

FIG. 16 shows an example of the configuration of the printed circuit board 1201. The printed circuit board 1201 includes a board 1202, an all solid state battery 1203 provided on one side of the board 1202, a charge / discharge control IC (Integrated Circuit) 1204, a battery protection IC 1205, a battery remaining amount monitoring IC 1206, and a USB (Universal Serial Bus). And an interface 1207. Although an example in which the printed circuit board 1201 is a single-sided board is described here, a double-sided board may be used. Moreover, a multilayer board | substrate may be sufficient and a buildup board | substrate may be sufficient.

The substrate 1202 is, for example, a rigid substrate. The all-solid-state battery 1203 is a battery according to any one of the first and second embodiments and modifications thereof. The charge / discharge control IC 1204 is a control unit that controls the charge / discharge operation for the all-solid battery 1203. The battery protection IC 1205 is a control unit that controls the charging / discharging operation so that the charging voltage does not become excessive at the time of charging / discharging, the overcurrent flows due to the load short circuit, and the overdischarging does not occur. The battery remaining amount monitoring IC 1206 is a monitoring unit that monitors the remaining battery amount of the all-solid-state battery 1203 and notifies the load (for example, host device) 1209 to the remaining battery amount.

The all-solid-state battery 1203 is charged by the power supplied from the external power source or the like via the USB interface 1207. Predetermined power (for example, a voltage of 4.2 V) is supplied from the all solid state battery 1203 to the load 1209 via the load connection terminals 1208a and 1208b. Note that the USB interface 1207 may be used for connection with a load.

Specific examples of the load 1209 include wearable devices (sports watches, watches, hearing aids, etc.), IoT terminals (sensor network terminals, etc.), amusement devices (portable game terminals, game controllers), IC board embedded batteries (real-time clock ICs), Examples include energy harvesting devices (storage elements for power generation elements such as solar power generation, thermoelectric power generation, and vibration power generation).

"Universal credit card as an application"
Hereinafter, application examples in which the present disclosure is applied to a universal credit card will be described.
The universal credit card is a card in which functions such as a plurality of credit cards and point cards are integrated into one card. For example, information such as the number and expiration date of various credit cards and point cards can be taken into this card, so if you put one card in your wallet, you can use it whenever you want. You can select and use the correct card.

FIG. 17 shows an example of the configuration of the universal credit card 1301. The universal credit card 1301 has a card shape and includes an IC chip (not shown) and an all-solid battery inside. The universal credit card 1301 includes a display 1302 with low power consumption on one side,

direction keys

1303a and 1303b as operation units, and a charging terminal 1304. The all-solid-state battery is a battery according to any one of the first and second embodiments and modifications thereof.

For example, the user can designate a desired one from a plurality of credit cards loaded in advance on the universal credit card 1301 by operating the

direction keys

1303a and 1303b while looking at the display 1302. After designation, it can be used like a conventional credit card. Note that the above is an example, and it goes without saying that the battery according to any of the first and second embodiments and the modifications thereof can be applied to any electronic card other than the universal credit card 1301.

"Sensor network terminal as an application example"
Hereinafter, an application example in which the present disclosure is applied to a sensor network terminal will be described.
A wireless terminal in a wireless sensor network is called a sensor node, and includes one or more wireless chips, a microprocessor, a power source (battery), and the like. Specific examples of sensor networks are used to monitor energy saving management, health management, industrial measurement, traffic conditions, agriculture, and the like. As the type of sensor, voltage, temperature, gas, illuminance and the like are used.

In the case of energy saving management, a power monitor node, a temperature / humidity node, an illuminance node, a CO ₂ node, a human sensor node, a remote control node, a router (relay machine), and the like are used as sensor nodes. These sensor nodes are provided so as to constitute a wireless network in homes, office buildings, factories, stores, amusement facilities, and the like.

Data such as temperature, humidity, illuminance, CO ₂ concentration, and electric energy is displayed so that the energy saving status of the environment can be seen. Furthermore, on / off control of lighting, air-conditioning facilities, ventilation facilities, etc. is performed according to commands from the control station.

ZigBee (registered trademark) can be used as one of the wireless interfaces of the sensor network. This wireless interface is one of the short-range wireless communication standards, and has a feature that it is inexpensive and consumes less power, instead of having a short transferable distance and a low transfer speed. Therefore, it is suitable for mounting on a battery-driven device. The basic part of this communication standard is standardized as IEEE 802.15.4. The ZigBee (Registered Trademark) Alliance has formulated specifications for communication protocols between devices above the logical layer.

FIG. 18 shows an example of the configuration of the wireless sensor node 1401. A detection signal of the sensor 1402 is supplied to an AD conversion circuit 1404 of a microprocessor (MPU) 1403. The various sensors described above can be used as the sensor 1402. A memory 1406 is provided in association with the microprocessor 1403. Further, the output of the battery 1407 is supplied to the power supply control unit 1408, and the power supply of the sensor node 1401 is managed. The battery 1407 is a battery according to any one of the first and second embodiments and the modifications thereof.

The program is installed in the microprocessor 1403. The microprocessor 1403 processes the detection result data of the sensor 1402 output from the AD conversion circuit 1404 according to the program. A wireless communication unit 1409 is connected to the communication control unit 1405 of the microprocessor 1403, and detection result data is transmitted from the wireless communication unit 1409 to a network terminal (not shown) using, for example, ZigBee (registered trademark). And connected to the network via a network terminal. A predetermined number of wireless sensor nodes can be connected to one network terminal. In addition to the star type, the network type may be a tree type, a mesh type, a linear type, or the like.

"Wristband electronic devices as application examples"
Hereinafter, application examples in which the present disclosure is applied to a wristband type electronic device will be described.
Wristband electronic devices, also called smartbands, can acquire data related to human activities such as the number of steps, distance traveled, calories burned, amount of sleep, heart rate, etc. just by wrapping around the wrist. . Furthermore, the acquired data can also be managed with a smartphone. Furthermore, a mail transmission / reception function can be provided. For example, an incoming mail can be notified to the user by an LED (Light Emitting Diode) lamp and / or vibration.

FIG. 19 shows an example of the appearance of the wristband type electronic device 1601. The electronic device 1601 is a so-called wearable device that is detachable from the human body. The electronic device 1601 includes a band portion 1611 attached to the arm, a display device 1612 that displays numbers, characters, symbols, and the like, and operation buttons 1613. The band portion 1611 is formed with a plurality of hole portions 1611a and protrusions 1611b provided on the inner peripheral surface (the surface that comes into contact with the arm when the electronic device 1601 is attached).

In the state of use, the electronic device 1601 is bent so that the band portion 1611 is substantially circular as shown in FIG. 19, and the protrusion 1611b is inserted into the hole portion 1611a and attached to the arm. By adjusting the position of the hole 1611a into which the protrusion 1611b is inserted, the diameter can be adjusted corresponding to the thickness of the arm. When the electronic device 1601 is not used, the protrusion 1611b is removed from the hole 1611a, and the band 1611 is stored in a substantially flat state. Inside the band part 1611, a sensor (not shown) is provided over almost the entire band part 1611.

FIG. 20 shows an example of the configuration of the electronic device 1601. In addition to the display device 1612 described above, the electronic device 1601 includes a controller IC 1615 as a drive control unit, a sensor 1620, a host device 1616, a battery 1617 as a power source, and a charge / discharge control unit 1618. Sensor 1620 may include a controller IC 1615.

The sensor 1620 can detect both pressing and bending. The sensor 1620 detects a change in capacitance according to the pressing, and outputs an output signal corresponding to the change to the controller IC 1615. Further, the sensor 1620 detects a change in resistance value (resistance change) according to bending, and outputs an output signal corresponding to the change to the controller IC 1615. The controller IC 1615 detects pressing and bending of the sensor 1620 based on the output signal from the sensor 1620 and outputs information corresponding to the detection result to the host device 1616.

The host device 1616 executes various processes based on information supplied from the controller IC 1615. For example, processing such as displaying character information and image information on the display device 1612, moving the cursor displayed on the display device 1612, scrolling the screen, and the like is executed.

The display device 1612 is, for example, a flexible display device, and displays a video (screen) based on a video signal, a control signal, or the like supplied from the host device 1616. Examples of the display device 1612 include, but are not limited to, a liquid crystal display, an electroluminescence (EL) display, and electronic paper.

The battery 1617 is a battery according to any one of the first and second embodiments and the modifications thereof. The charge / discharge control unit 1618 controls the charge / discharge operation of the battery 1617. Specifically, charging of the battery 1617 from an external power source or the like is controlled. Further, power supply from the battery 1617 to the host device 1616 is controlled.

"Smart watch as an application"
Hereinafter, an application example in which the present disclosure is applied to a smart watch will be described.
This smart watch has the same or similar appearance as the design of an existing wristwatch, and is worn on the user's wrist in the same way as a wristwatch. The information displayed on the display is used for telephone and e-mail. It has a function of notifying the user of various messages such as incoming calls. Further, it may have a function such as an electronic money function and an activity meter, or may have a function of performing short-range wireless communication such as Bluetooth (registered trademark) with a communication terminal (smartphone or the like).

(Overall configuration of smart watch)
FIG. 21 shows an example of the overall configuration of the smart watch 2000. The smart watch 2000 includes a watch body 3000 and a band type electronic device 2100. The watch body 3000 includes a dial 3100 for displaying time. The watch body 3000 may display the time electronically on a liquid crystal display or the like instead of the dial 3100.

The band-type electronic device 2100 is a metal band attached to the watch body 3000, and is attached to the user's arm. The band-type electronic device 2100 has a configuration in which a plurality of segments 2110 to 2230 are connected. The segment 2110 is attached to one band attachment hole of the watch body 3000, and the segment 2230 is attached to the other band attachment hole of the watch body 3000. Each of the segments 2110 to 2230 is made of metal.

FIG. 21 shows a state in which the watch main body 3000 and the segment 2230 are separated in order to describe an example of the configuration of the band-type electronic device 2100, but the segment 2230 is attached to the watch main body 3000 in actual use. . By attaching the segment 2230 to the watch main body 3000, the smart watch 2000 can be mounted on the user's arm in the same manner as a normal wristwatch. The connection location of each segment 2110 to 2230 can be moved. Since the connection part of the segment is movable, the band-type electronic device 2100 can be fitted to the user's arm.

Between the segment 2170 and the segment 2160, a buckle portion 2300 is disposed. The buckle portion 2300 extends long when unlocked and shortens when locked. Each segment 2110 to 2230 has a plurality of sizes.

(Smart watch circuit configuration)
FIG. 22 illustrates an example of a circuit configuration of the band-type electronic device 2100. The circuit inside the band-type electronic device 2100 has a configuration independent of the watch main body 3000. The watch main body 3000 includes a movement unit 3200 that rotates hands arranged on the dial 3100. A battery 3300 is connected to the movement unit 3200. The movement unit 3200 and the battery 3300 are built in the casing of the watch main body 3000. The battery 3300 is a battery according to any of the first and second embodiments and the modifications thereof.

Among the segments 2110 to 2230, the three

segments

2170, 2190, and 2210 are arranged with electronic components and the like. In the segment 2170, a data processing unit 4101, a wireless communication unit 4102, an NFC communication unit 4104, and a GPS unit 4106 are arranged.

Antennas

4103, 4105, and 4107 are connected to the wireless communication unit 4102, the NFC communication unit 4104, and the GPS unit 4106, respectively. Each

antenna

4103, 4105, and 4107 is arrange | positioned in the vicinity of the slit (not shown) which the segment 2170 has.

The wireless communication unit 4102 performs short-range wireless communication with other terminals based on, for example, Bluetooth (registered trademark) standards. The NFC communication unit 4104 performs wireless communication with an adjacent reader / writer according to the NFC standard. The GPS unit 4106 is a positioning unit that receives radio waves from a satellite of a system called GPS (Global Positioning System) and measures the current position. Data obtained by the wireless communication unit 4102, NFC communication unit 4104, and GPS unit 4106 is supplied to the data processing unit 4101.

In the segment 2170, a display 4108, a vibrator 4109, a motion sensor 4110, and an audio processing unit 4111 are arranged. The display 4108 and the vibrator 4109 function as a notification unit that notifies the wearer of the band-type electronic device 2100. The display 4108 includes a plurality of light emitting diodes, and notifies the user by lighting or blinking of the light emitting diodes. The plurality of light-emitting diodes are disposed, for example, in a slit (not shown) included in the segment 2170, and notification of incoming calls, reception of e-mails, and the like is made by lighting or blinking. As the display 4108, a display that displays characters, numbers, and the like may be used. Vibrator 4109 is a member that vibrates segment 2170. The band-type electronic device 2100 notifies an incoming call, an e-mail, or the like by the vibration of the segment 2170 by the vibrator 4109.

Motion sensor 4110 detects the movement of the user wearing smart watch 2000. As the motion sensor 4110, an acceleration sensor, a gyro sensor, an electronic compass, an atmospheric pressure sensor, or the like is used. The segment 2170 may incorporate a sensor other than the motion sensor 4110. For example, a biosensor that detects the pulse of the user wearing the smart watch 2000 may be incorporated. A microphone 4112 and a speaker 4113 are connected to the audio processing unit 4111, and the audio processing unit 4111 performs a call process with the other party connected by wireless communication in the wireless communication unit 4102. The voice processing unit 4111 can also perform processing for voice input operation.

In the segment 2190, a battery 2411 is incorporated, and in the segment 2210, a battery 2421 is incorporated. The batteries 2411 and 2421 supply driving power to the circuits in the segment 2170. The circuit in the segment 2170 and the batteries 2411 and 2421 are connected by a flexible circuit board (not shown). Note that, although not shown in FIG. 22, the segment 2170 includes terminals for charging the batteries 2411 and 2421. Further, electronic components other than the batteries 2411 and 2421 may be disposed in the

segments

2190 and 2210. For example, the

segments

2190 and 2210 may include a circuit that controls charging and discharging of the batteries 2411 and 2421. The batteries 2411 and 2421 are batteries according to any one of the first and second embodiments and modifications thereof.

“Glasses type terminal as an application example”
Hereinafter, an application example in which the present disclosure is applied to a glasses-type terminal represented by a kind of head-mounted display (head-mounted display (HMD)) will be described.
The glasses-type terminal described below can display information such as text, symbols, and images superimposed on the scenery in front of you. That is, a light-weight and thin image display device display module dedicated to a transmissive glasses-type terminal is mounted.

This image display device comprises an optical engine and a hologram light guide plate. The optical engine emits image light such as an image and text using a micro display lens. This image light is incident on the hologram light guide plate. A hologram light guide plate has hologram optical elements incorporated at both ends of a transparent plate, and propagates image light from an optical engine through a very thin transparent plate having a thickness of 1 mm to the eyes of an observer. deliver. With such a configuration, a lens having a transmittance of, for example, 85% and a thickness of 3 mm (including protective plates before and after the light guide plate) is realized. With such a glasses-type terminal, it is possible to see the results of players and teams in real time while watching sports, and to display a tourist guide at a destination.

As a specific example of the glasses-type terminal, as shown in FIG. 23, the image display unit has a glasses-type configuration. That is, as with normal glasses, the frame 5003 for holding the right image display unit 5001 and the left image display unit 5002 is provided in front of the eyes. The frame 5003 includes a front portion 5004 disposed in front of the observer, and two

temple portions

5005 and 5006 that are rotatably attached to both ends of the front portion 5004 via hinges. The frame 5003 is made of the same material as that of normal glasses, such as metal, alloy, plastic, or a combination thereof. A headphone unit may be provided.

The right image display unit 5001 and the left image display unit 5002 are arranged so as to be positioned in front of the user's right eye and in front of the left eye, respectively.

Temple units

5005 and 5006 hold a right image display unit 5001 and a left image display unit 5002 on the user's head. A right display driving unit 5007 is disposed inside the temple unit 5005 at a connection portion between the front unit 5004 and the temple unit 5005. A left display driving unit 5008 is arranged inside the temple unit 5006 at a connection portion between the front unit 5004 and the temple unit 5006.

The frame 5003 is provided with batteries 5009 and 5010. Batteries 5009 and 5010 are batteries according to any one of the first and second embodiments and modifications thereof. Although omitted in FIG. 23, the frame 5003 is provided with an acceleration sensor, a gyro, an electronic compass, a microphone / speaker, and the like. Further, the frame 5003 is provided with an imaging device so that still images / moving images can be taken. Further, the frame 5003 is provided with a controller connected to the glasses unit by, for example, a wireless or wired interface. The controller is provided with a touch sensor, various buttons, a speaker, a microphone, and the like. Further, the frame 5003 has a cooperation function with a smartphone. For example, it is possible to provide information according to the user's situation by utilizing the GPS function of a smartphone. Hereinafter, the image display device (the right image display unit 5001 or the left image display unit 5002) will be mainly described.

FIG. 24 shows an example of the configuration of an image display device (right image display unit 5001 or left image display unit 5002) of a glasses-type terminal. The image display device 5100 includes an image generation device 5110 and an optical device (light guide unit) 5120 that receives the light emitted from the image generation device 5110 and is guided toward the observer's pupil 5041. Has been. The optical device 5120 is attached to the image generation device 5110.

The optical device 5120 includes the optical device having the first configuration, and the light incident from the image generation device 5110 propagates through the interior by total reflection, and then is emitted toward the observer's pupil 5041. The first light deflecting unit 5130 that deflects the light incident on the light guide plate 5121 and the light guide plate 5121 are propagated by total reflection so that the light incident on the light guide plate 5121 is totally reflected inside the light guide plate 5121. In order to emit the emitted light from the light guide plate 5121, second deflection means 5140 is provided that deflects the light propagated through the light guide plate 5121 by total reflection over a plurality of times.

The first deflecting unit 5130 and the second deflecting unit 5140 are disposed inside the light guide plate 5121. The first deflecting unit 5130 reflects the light incident on the light guide plate 5121, and the second deflecting unit 5140 transmits the light propagating through the light guide plate 5121 by total reflection, and transmits and reflects the light. To do. That is, the first deflecting unit 5130 functions as a reflecting mirror, and the second deflecting unit 5140 functions as a semi-transmissive mirror. More specifically, the first deflecting means 5130 provided inside the light guide plate 5121 is made of aluminum, and is composed of a light reflecting film (a kind of mirror) that reflects light incident on the light guide plate 5121. . On the other hand, the second deflecting means 5140 provided inside the light guide plate 5121 is composed of a multilayer laminated structure in which a large number of dielectric laminated films are laminated. The dielectric laminated film is composed of, for example, a TiO ₂ film as a high dielectric constant material and an SiO ₂ film as a low dielectric constant material.

A thin piece made of the same material as that constituting the light guide plate 5121 is sandwiched between the dielectric laminated film and the dielectric laminated film. In the first deflecting unit 5130, the parallel light incident on the light guide plate 5121 is reflected (or diffracted) so that the parallel light incident on the light guide plate 5121 is totally reflected inside the light guide plate 5121. . On the other hand, in the second deflecting unit 5140, the parallel light propagated through the light guide plate 5121 by total reflection is reflected (or diffracted) a plurality of times and is emitted from the light guide plate 5121 in the state of parallel light.

The first deflecting unit 5130 cuts out a portion 5124 of the light guide plate 5121 where the first deflecting unit 5130 is provided, thereby providing the light guide plate 5121 with an inclined surface on which the first deflecting unit 5130 is to be formed, and vacuuming the light reflecting film on the inclined surface. After vapor deposition, the cut-out portion 5124 of the light guide plate 5121 may be bonded to the first deflecting means 5130. In addition, the second deflecting unit 5140 is formed by laminating a large number of the same material (for example, glass) as the material constituting the light guide plate 5121 and a dielectric laminated film (for example, it can be formed by a vacuum deposition method). A multilayer laminated structure is manufactured, and a portion 5125 provided with the second deflecting means 5140 of the light guide plate 5121 is cut out to form a slope, and the multilayer laminated structure is bonded to the slope and polished to adjust the outer shape. That's fine. In this way, an optical device 5120 in which the first deflection unit 5130 and the second deflection unit 5140 are provided inside the light guide plate 5121 can be obtained.

The light guide plate 5121 made of optical glass or plastic material has two parallel surfaces (a first surface 5122 and a second surface 5123) extending in parallel with the axis of the light guide plate 5121. The first surface 5122 and the second surface 5123 are opposed to each other. Then, parallel light enters from the first surface 5122 corresponding to the light incident surface, propagates through the interior by total reflection, and then exits from the first surface 5122 corresponding to the light exit surface.

The image generation device 5110 includes the first configuration image generation device, the image formation device 5111 having a plurality of pixels arranged in a two-dimensional matrix, and the pixels of the image formation device 5111. A collimating optical system 5112 for emitting light as parallel light is provided.

Here, the image forming apparatus 5111 includes a reflective spatial light modulator 5150 and a light source 5153 including a light emitting diode that emits white light. More specifically, the reflective spatial light modulator 5150 reflects a part of light from a liquid crystal display (LCD) 5151 composed of LCOS (Liquid Crystal On On Silicon) as a light valve and a light source 5153. The polarizing beam splitter 5152 is guided to the liquid crystal display device 5151, and part of the light reflected by the liquid crystal display device 5151 is transmitted to the collimating optical system 5112. The LCD is not limited to the LCOS type.

The liquid crystal display device 5151 includes a plurality of (for example, 320 × 240) pixels arranged in a two-dimensional matrix. The polarization beam splitter 5152 has a known configuration and structure. Non-polarized light emitted from the light source 5153 collides with the polarization beam splitter 5152. In the polarization beam splitter 5152, the P-polarized component passes and is emitted out of the system. On the other hand, the S-polarized component is reflected by the polarization beam splitter 5152, enters the liquid crystal display device 5151, is reflected inside the liquid crystal display device 5151, and is emitted from the liquid crystal display device 5151. Here, among the light emitted from the liquid crystal display device 5151, the light emitted from the pixel displaying “white” contains a lot of P-polarized light components, and the light emitted from the pixel displaying “black” is S-polarized light. Contains many ingredients. Therefore, among the light emitted from the liquid crystal display device 5151 and colliding with the polarization beam splitter 5152, the P-polarized component passes through the polarization beam splitter 5152 and is guided to the collimating optical system 5112.

On the other hand, the S-polarized light component is reflected by the polarization beam splitter 5152 and returned to the light source 5153. The liquid crystal display device 5151 includes, for example, a plurality of (for example, 320 × 240) pixels (the number of liquid crystal cells is three times the number of pixels) arranged in a two-dimensional matrix. The collimating optical system 112 is composed of, for example, a convex lens, and in order to generate parallel light, the image forming apparatus 5111 (more specifically, the liquid crystal display device 5151) is located at the focal position (position) in the collimating optical system 5112. Is arranged. One pixel is composed of a red light emitting subpixel that emits red, a green light emitting subpixel that emits green, and a blue light emitting subpixel that emits blue.

"Vehicle power storage system as an application example"
An example in which the present disclosure is applied to a power storage system for a vehicle will be described with reference to FIG. FIG. 25 schematically illustrates an example of a configuration of a hybrid vehicle that employs a series hybrid system to which the present disclosure is applied. A series hybrid system is a car that runs on an electric power driving force conversion device using electric power generated by a generator driven by an engine or electric power once stored in a battery.

The hybrid vehicle 7200 includes an engine 7201, a generator 7202, a power driving force conversion device 7203, a driving wheel 7204a, a driving wheel 7204b, a wheel 7205a, a wheel 7205b, a battery 7208, a vehicle control device 7209, various sensors 7210, and a charging port 7211. Is installed. The above-described power storage device of the present disclosure is applied to the battery 7208.

Hybrid vehicle 7200 travels using power driving force conversion device 7203 as a power source. An example of the power driving force conversion device 7203 is a motor. The electric power / driving force conversion device 7203 is operated by the electric power of the battery 7208, and the rotational force of the electric power / driving force conversion device 7203 is transmitted to the

driving wheels

7204a and 7204b. Note that the power driving force conversion device 7203 can be applied to either an AC motor or a DC motor by using DC-AC (DC-AC) or reverse conversion (AC-DC conversion) where necessary. Various sensors 7210 control the engine speed through the vehicle control device 7209 and control the opening of a throttle valve (throttle opening) (not shown). Various sensors 7210 include a speed sensor, an acceleration sensor, an engine speed sensor, and the like.

The rotational force of the engine 7201 is transmitted to the generator 7202, and the electric power generated by the generator 7202 by the rotational force can be stored in the battery 7208.

When the hybrid vehicle decelerates by a braking mechanism (not shown), the resistance force at the time of deceleration is applied as a rotational force to the power driving force conversion device 7203, and the regenerative power generated by the power driving force conversion device 7203 by this rotational force is applied to the battery 7208. Accumulated.

The battery 7208 is connected to an external power source of the hybrid vehicle, so that the battery 7208 can receive power from the external power source using the charging port 211 as an input port and store the received power.

Although not shown, an information processing apparatus that performs information processing related to vehicle control based on information related to the secondary battery may be provided. As such an information processing apparatus, for example, there is an information processing apparatus that displays a remaining battery level based on information on the remaining battery level.

In the above description, a series hybrid vehicle that runs on a motor using electric power generated by a generator driven by an engine or electric power stored once in a battery has been described as an example. However, the present disclosure is also effective for a parallel hybrid vehicle that uses both the engine and motor outputs as the drive source, and switches between the three modes of running with the engine alone, running with the motor alone, and engine and motor running as appropriate. Applicable. Furthermore, the present disclosure can be effectively applied to a so-called electric vehicle that travels only by a drive motor without using an engine.

Heretofore, an example of the hybrid vehicle 7200 to which the technology according to the present disclosure can be applied has been described. The technology according to the present disclosure can be suitably applied to the battery 7208 among the configurations described above.

"Storage system in a house as an application example"
An example in which the present disclosure is applied to a residential power storage system will be described with reference to FIG. For example, in a power storage system 9100 for a house 9001, power is stored from a centralized power system 9002 such as a thermal power generation 9002a, a nuclear power generation 9002b, and a hydropower generation 9002c through a power network 9009, an information network 9012, a smart meter 9007, a power hub 9008, and the like. Supplied to the device 9003. At the same time, power is supplied to the power storage device 9003 from an independent power source such as the home power generation device 9004. The electric power supplied to the power storage device 9003 is stored. Electric power used in the house 9001 is supplied using the power storage device 9003. The same power storage system can be used not only for the house 9001 but also for buildings.

The house 9001 is provided with a power generation device 9004, a power consumption device 9005, a power storage device 9003, a control device 9010 that controls each device, a smart meter 9007, and a sensor 9011 that acquires various types of information. Each device is connected by a power network 9009 and an information network 9012. As the power generation device 9004, a solar cell, a fuel cell, or the like is used, and the generated power is supplied to the power consumption device 9005 and / or the power storage device 9003. The power consuming apparatus 9005 is a refrigerator 9005a, an air conditioner 9005b, a television receiver 9005c, a bath 9005d, or the like. Furthermore, the electric power consumption device 9005 includes an electric vehicle 9006. The electric vehicle 9006 is an electric vehicle 9006a, a hybrid car 9006b, and an electric motorcycle 9006c.

The battery unit of the present disclosure described above is applied to the power storage device 9003. The power storage device 9003 is composed of a secondary battery or a capacitor. For example, a lithium ion battery is used. The lithium ion battery may be a stationary type or used in the electric vehicle 9006. The smart meter 9007 has a function of measuring the usage amount of commercial power and transmitting the measured usage amount to an electric power company. The power network 9009 may be any one or a combination of DC power supply, AC power supply, and non-contact power supply.

The various sensors 9011 are, for example, human sensors, illuminance sensors, object detection sensors, power consumption sensors, vibration sensors, contact sensors, temperature sensors, infrared sensors, and the like. Information acquired by the various sensors 9011 is transmitted to the control device 9010. Based on the information from the sensor 9011, the weather condition, the condition of the person, and the like can be grasped, and the power consumption device 9005 can be automatically controlled to minimize the energy consumption. Furthermore, the control device 9010 can transmit information on the house 9001 to an external power company or the like via the Internet.

The power hub 9008 performs processing such as branching of power lines and DC / AC conversion. As a communication method of the information network 9012 connected to the control device 9010, a method using a communication interface such as UART (Universal Asynchronous Receiver-Transmitter), Bluetooth (registered trademark), ZigBee (registered trademark), or the like. There is a method of using a sensor network based on a wireless communication standard such as Wi-Fi. The Bluetooth method is applied to multimedia communication and can perform one-to-many connection communication. ZigBee uses the physical layer of IEEE (Institute of Electrical and Electronics Electronics) (802.15.4). IEEE802.15.4 is a name of a short-range wireless network standard called PAN (Personal Area Network) or W (Wireless) PAN.

The control device 9010 is connected to an external server 9013. The server 9013 may be managed by any one of the house 9001, the electric power company, and the service provider. Information transmitted / received by the server 9013 is, for example, information on power consumption information, life pattern information, power charges, weather information, natural disaster information, and power transactions. These pieces of information may be transmitted / received from a power consuming device (for example, a television receiver) in the home, or may be transmitted / received from a device outside the home (for example, a mobile phone). Such information may be displayed on a device having a display function, for example, a television receiver, a mobile phone, a PDA (Personal Digital Assistant) or the like.

A control device 9010 that controls each unit includes a CPU (Central Processing Unit), a RAM (Random Access Memory), a ROM (Read Only Memory), and the like, and is stored in the power storage device 9003 in this example. The control device 9010 is connected to the power storage device 9003, the home power generation device 9004, the power consumption device 9005, various sensors 9011, the server 9013 and the information network 9012, for example, a function of adjusting the amount of commercial power used and the amount of power generation have. In addition, you may provide the function etc. which carry out an electric power transaction in an electric power market.

As described above, electric power can be stored not only in the centralized power system 9002 such as the thermal power 9002a, the nuclear power 9002b, and the hydropower 9002c but also in the power storage device 9003 in the power generation device 9004 (solar power generation, wind power generation). it can. Therefore, even if the generated power of the home power generation apparatus 9004 fluctuates, it is possible to perform control such that the amount of power to be sent to the outside is constant or discharge is performed as necessary. For example, the power obtained by solar power generation is stored in the power storage device 9003, and midnight power with a low charge is stored in the power storage device 9003 at night, and the power stored by the power storage device 9003 is discharged during a high daytime charge. You can also use it.

In this example, the control device 9010 is stored in the power storage device 9003. However, the control device 9010 may be stored in the smart meter 9007, or may be configured independently. Furthermore, the power storage system 9100 may be used for a plurality of homes in an apartment house, or may be used for a plurality of detached houses.

Heretofore, an example of the power storage system 9100 to which the technology according to the present disclosure can be applied has been described. The technology according to the present disclosure can be suitably applied to the secondary battery included in the power storage device 9003 among the configurations described above.

As mentioned above, although embodiment of this art, its modification, and an example were explained concretely, this art is not limited to the above-mentioned embodiment, its modification, and an example. Various modifications based on technical ideas are possible.

For example, the configurations, methods, processes, shapes, materials, numerical values, and the like given in the above-described embodiment and its modified examples and examples are merely examples, and different configurations, methods, processes, and shapes are necessary as necessary. , Materials and numerical values may be used. In addition, chemical formulas of compounds and the like are representative and are not limited to the described valences and the like as long as they are general names of the same compounds.

In addition, the above-described embodiment and its modified examples, and the configurations, methods, processes, shapes, materials, numerical values, and the like of the examples can be combined with each other without departing from the gist of the present technology.

In addition, the present technology can be applied to various electronic devices including a battery, and is not limited to the electronic devices described in the above application examples. Examples of electronic devices other than the application examples described above include notebook personal computers, tablet computers, mobile phones (for example, smartphones), personal digital assistants (PDAs), display devices (LCD, EL displays, electronic devices). Paper), imaging devices (eg digital still cameras, digital video cameras, etc.), audio equipment (eg portable audio players), game machines, cordless phones, electronic books, electronic dictionaries, radios, headphones, navigation systems, memory cards , Pacemaker, hearing aid, electric tool, electric shaver, refrigerator, air conditioner, TV, stereo, water heater, microwave, dishwasher, washing machine, dryer, lighting equipment, toy, medical equipment, robot, road conditioner, communication Although aircraft and the like, without such limited thereto.

The present technology can also employ the following configurations.
(1)
A battery element containing Li;
An exterior material covering the battery element;
An all-solid-state battery comprising: a protective layer provided between the battery element and the exterior material and including Li.
(2)
The all-solid battery according to (1), wherein the exterior material includes crystal particles.
(3)
The all-solid-state battery according to (2), wherein the crystal particles include at least one of aluminum oxide, silicon oxide, silicon nitride, aluminum nitride, and silicon carbide.
(4)
The average particle size of the crystal particles is the all solid state battery according to (2) or (3), which is 10 μm or less.
(5)
The exterior material includes glass,
The all-solid-state battery according to any one of (2) to (4), wherein the crystal particles include crystals that do not melt at the glass transition temperature of the glass.
(6)
The protective layer includes a solid electrolyte containing Li,
The all-solid-state battery according to any one of (1) to (5), wherein a volume occupation ratio of the solid electrolyte in the protective layer is 10 vol% or more.
(7)
The all-solid-state battery according to any one of (1) to (6), wherein the protective layer has a Li ion conductivity of 1.0 × 10 ⁻¹⁰ S / cm or more.
(8)
The all-solid battery according to any one of (1) to (7), wherein the exterior material includes glass having non-Li ion conductivity.
(9)
The average thickness of the said exterior material is an all-solid-state battery in any one of (1) to (8) which is 100 micrometers or less.
(10)
Li ion conductivity of the exterior material is 1 × 10 ⁻⁸ S / cm or less,
The all-solid-state battery in any one of (1) to (9) whose electrical conductivity of the said exterior material is 1 * 10 < ^-8 > S / cm or less.
(11)
The all-solid-state battery according to any one of (1) to (10), wherein the exterior material has a moisture permeability of 1.0 g / m ² / day or less.
(12)
The exterior material includes glass,
The all-solid-state battery according to any one of (1) to (11), wherein the glass includes at least one of B, Bi, Te, P, V, Sn, Pb, and Si.
(13)
The battery element includes a positive electrode layer, a negative electrode layer, and a solid electrolyte layer,
The all-solid-state battery in any one of (1) to (12) in which the said positive electrode layer, the said negative electrode layer, and the said solid electrolyte layer contain the solid electrolyte containing Li.
(14)
A positive electrode terminal provided at a portion where the positive electrode layer is exposed from the exterior material and the protective layer;
The all-solid-state battery according to (13), further comprising: a negative electrode terminal provided at a portion where the negative electrode layer is exposed from the exterior material and the protective layer.
(15)
The positive electrode layer includes a positive electrode current collecting layer and a positive electrode active material layer,
The negative electrode layer includes a negative electrode current collecting layer and a negative electrode active material layer,
A positive electrode terminal provided on a portion where the positive electrode current collecting layer is exposed from the exterior material and the protective layer;
The all-solid-state battery according to (13), further comprising: a negative electrode terminal provided at a portion where the negative electrode current collecting layer is exposed from the exterior material and the protective layer.
(16)
The positive terminal and the negative terminal include glass and metal,
The glass transition temperature of the glass is the all solid state battery according to (14) or (15), which is equal to or lower than a sintering temperature of the exterior material.
(17)
The all-solid-state battery according to (14) or (15), wherein each of the positive electrode terminal and the negative electrode terminal independently contains at least one of Ag, Pt, Au, Ni, Cu, Pd, Al, and Fe.
(18)
(1) Electronic equipment which receives supply of electric power from the all-solid-state battery in any one of (17).
(19)
(1) The electronic card which receives supply of electric power from the all-solid-state battery in any one of (17).
(20)
Covering a battery element containing Li with a protective layer containing Li, forming an exterior material on the protective layer,
A method for producing an all-solid-state battery, comprising: forming a layer containing crystal particles on the exterior material; sintering the exterior material; and removing the layer containing the crystal particles.

DESCRIPTION OF SYMBOLS 11 Exterior battery element 11SA 1st end surface 11SB 2nd end surface 11SB 3rd end surface 11SC 4th end surface 12 Positive electrode terminal 13 Negative electrode terminal 14 Protective layer 15 Exterior material 16 Crystal particle 16A Crystal powder layer 20 Battery element 21 Positive electrode 21A Positive electrode current collection layer 21B Positive electrode active material layer 22, 24 Negative electrode 22A Negative electrode current collecting layer 22B Negative electrode active material layer 23 Solid electrolyte layer

Claims

A battery element containing Li;
An exterior material covering the battery element;
An all-solid-state battery comprising: a protective layer provided between the battery element and the exterior material and including Li.
The all-solid-state battery according to claim 1, wherein the exterior material includes crystal particles.
The all-solid-state battery according to claim 2, wherein the crystal particles include at least one of aluminum oxide, silicon oxide, silicon nitride, aluminum nitride, and silicon carbide.
The all-solid-state battery according to claim 2, wherein the average particle diameter of the crystal particles is 10 μm or less.
The exterior material includes glass,
The all-solid-state battery according to claim 2, wherein the crystal particles include crystals that do not melt at the glass transition temperature of the glass.
The protective layer includes a solid electrolyte containing Li,
2. The all-solid-state battery according to claim 1, wherein a volume occupation ratio of the solid electrolyte in the protective layer is 10 vol% or more.
The all-solid-state battery according to claim 1, wherein the protective layer has a Li ion conductivity of 1.0 × 10 −10 S / cm or more.
The all-solid-state battery according to claim 1, wherein the exterior material includes glass having non-Li ion conductivity.
The all-solid-state battery according to claim 1, wherein an average thickness of the exterior material is 100 μm or less.
Li ion conductivity of the exterior material is 1 × 10 −8 S / cm or less,
The all-solid-state battery according to claim 1, wherein the exterior material has an electric conductivity of 1 × 10 −8 S / cm or less.
The all-solid-state battery according to claim 1, wherein the exterior material has a moisture permeability of 1.0 g / m 2 / day or less.
The exterior material includes glass,
The all-solid-state battery according to claim 1, wherein the glass contains at least one of B, Bi, Te, P, V, Sn, Pb, and Si.
The battery element includes a positive electrode layer, a negative electrode layer, and a solid electrolyte layer,
The all-solid-state battery of Claim 1 in which the said positive electrode layer, the said negative electrode layer, and the said solid electrolyte layer contain the solid electrolyte containing Li.
A positive electrode terminal provided at a portion where the positive electrode layer is exposed from the exterior material and the protective layer;
The all-solid-state battery according to claim 13, further comprising: a negative electrode terminal provided at a portion where the negative electrode layer is exposed from the exterior material and the protective layer.
The positive electrode layer includes a positive electrode current collecting layer and a positive electrode active material layer,
The negative electrode layer includes a negative electrode current collecting layer and a negative electrode active material layer,
A positive electrode terminal provided on a portion where the positive electrode current collecting layer is exposed from the exterior material and the protective layer;
The all-solid-state battery according to claim 13, further comprising: a negative electrode terminal provided at a portion where the negative electrode current collecting layer is exposed from the exterior material and the protective layer.
The positive terminal and the negative terminal include glass and metal,
The all-solid-state battery according to claim 14, wherein a glass transition temperature of the glass is equal to or lower than a sintering temperature of the exterior material.
The all-solid-state battery according to claim 14, wherein the positive electrode terminal and the negative electrode terminal independently include at least one of Ag, Pt, Au, Ni, Cu, Pd, Al, and Fe.
An electronic device that receives power supply from the all-solid-state battery according to claim 1.
An electronic card that receives power from the all-solid-state battery according to claim 1.
Covering a battery element containing Li with a protective layer containing Li, forming an exterior material on the protective layer,
A method for producing an all-solid-state battery, comprising: forming a layer containing crystal particles on the exterior material; sintering the exterior material; and removing the layer containing the crystal particles.