WO2018212120A1

WO2018212120A1 - Solid-state battery, battery pack, vehicle, electricity storage system, electric tool and electronic device

Info

Publication number: WO2018212120A1
Application number: PCT/JP2018/018471
Authority: WO
Inventors: 晴美柴田; 圭輔清水
Original assignee: 株式会社村田製作所
Priority date: 2017-05-16
Filing date: 2018-05-14
Publication date: 2018-11-22

Abstract

The present invention provides a solid-state battery which is capable of achieving further improved battery characteristics and reliability. Provided is a solid-state battery which comprises at least an electrode layer, an electrolyte layer, and a buffer layer that is arranged between the electrode layer and the electrolyte layer, and which is configured such that: the electrode layer contains electrode particles; the buffer layer contains buffer particles; the electrode particles contain a first electrode active material; the buffer particles contain a second electrode active material and/or at least one kind of atom that constitutes the second electrode active material; and the average particle diameter (D50) of the buffer particles is smaller than the average particle diameter (D50) of the electrode particles.

Description

Solid battery, battery pack, vehicle, power storage system, electric tool and electronic device

This technology relates to solid state batteries. More specifically, the present technology relates to a solid battery, a battery pack, a vehicle, a power storage system, a power tool, and an electronic device.

In recent years, with the development of portable devices such as PCs (personal computers) and mobile phones, the demand for batteries has been rapidly expanding. In addition, the spread of electric vehicles is accelerating, and the need for batteries is increasing. Among them, research and development of solid batteries in which the electrolyte is changed from a liquid system to a solid system are actively performed.

For example, a forming step of forming an intermediate layer made of a metal and / or a compound containing one or more of Co, Ni and Mn on the surface of the first layer containing a garnet-type oxide containing at least Li, La and Zr; A second layer comprising a composite oxide particle containing one or more elements of Co, Ni and Mn contained in the intermediate layer and a flux containing Li and formed on the intermediate layer. And a method for producing a composite laminate including a firing step of firing the laminate (see Patent Document 1), and a current collector and at least a part of the surface of the current collector An electrode plate for a non-aqueous electrolyte secondary battery comprising an electrode active material layer formed on the electrode active material layer, wherein the electrode active material layer contains active material particles and binder material particles, and the binder The metal particles show a lithium ion insertion / extraction reaction An electrode plate for a non-aqueous electrolyte secondary battery is proposed in which the average particle size of the binder material particles is smaller than the average particle size of the active material particles (Patent Document). 2).

Further, for example, a lithium ion secondary battery including a positive electrode current collector, a positive electrode layer, a negative electrode current collector, a negative electrode layer, and a solid electrolyte layer, the solid electrolyte being made of a lithium ion conductive inorganic substance. A thin-film solid electrolyte having a thickness of 20 μm or less containing powder, and at the interface between the positive electrode layer and / or the negative electrode layer and the solid electrolyte layer, the positive electrode layer and / or the negative electrode layer and the solid electrolyte. A lithium ion secondary battery in which a layer is mixed is proposed (see Patent Document 3). In a lithium ion secondary battery including a positive electrode, a negative electrode, and a solid electrolyte, a solid electrolyte-positive electrode interface and / or a solid There has been proposed a lithium ion secondary battery characterized in that a fiber layer is formed at the electrolyte-negative electrode interface (see Patent Document 4).

Furthermore, for example, a positive electrode current collector, a positive electrode body formed on the positive electrode current collector and having a positive electrode active material layer containing a positive electrode active material and a solid electrolyte material, a negative electrode current collector, and the negative electrode current collector An all-solid battery comprising a negative electrode body having a negative electrode active material layer formed on a body and containing a negative electrode active material and a solid electrolyte material; and a solid electrolyte layer formed between the positive electrode body and the negative electrode body. The electrode active material layer of at least one of the positive electrode body and the negative electrode body has the electrode active material relative to the volume (V _e (partial)) of the solid electrolyte material contained in a part of the electrode active material layer. local content volume ratio expressed by volume of the electrode active material contained in said portion of the layer _(V a _(partial)) ratio _{_{(V a (partial) / V}} e (partial)) is, before The electrode active material layer has a composition distribution that increases as the thickness direction of the electrode active material layer approaches the current collector interface side from the solid electrolyte layer interface side, and the porosity of the electrode active material layer is solid in the thickness direction of the electrode active material layer. An all-solid battery characterized in that it becomes larger as it approaches the current collector interface side from the electrolyte layer interface side (see Patent Document 5), between the electrode layers in which the active material is bound with low-melting glass, In a lithium battery having a solid electrolyte layer in which a solid electrolyte is bound with a low-melting glass, a powder mixture of the active material and the solid electrolyte is bound with the low-melting glass between the electrode layer and the solid electrolyte layer. There has been proposed a lithium battery characterized in that an attached mixed layer is provided (see Patent Document 6).

JP 2016-15213 A JP 2012-79447 A JP 2010-56093 A JP 2003-346901 A JP 2012-104270 A JP 2001-126758 A

However, the techniques proposed in Patent Documents 1 to 6 may not be able to further improve battery characteristics and reliability.

Therefore, the present technology has been made in view of such circumstances, and a solid battery capable of further improving battery characteristics and reliability, and a battery pack, vehicle, power storage system, and electric tool including the solid battery. The main purpose is to provide electronic devices.

As a result of intensive studies to solve the above-mentioned object, the present inventors have surprisingly improved battery characteristics and reliability by paying attention to the interface between the electrode layer and the electrolyte layer. We have succeeded in making this technology complete.

That is, the present technology includes at least an electrode layer, an electrolyte layer, and a buffer layer disposed between the electrode layer and the electrolyte layer,
The electrode layer comprises electrode particles, the buffer layer comprises buffer particles;
The electrode particles contain a first electrode active material;
The buffer particles contain the second electrode active material and / or at least one atom constituting the second electrode active material;
Provided is a solid state battery in which the average particle size (D50) of the buffer particles is smaller than the average particle size (D50) of the electrode particles.

In the solid state battery according to the present technology, the ratio of the average particle diameter (D50) of the electrode particles to the average particle diameter (D50) of the buffer particles (average particle diameter of electrode particles (D50) / average particle diameter of buffer particles (D50 )) May be from 4 to 450.

In the solid state battery according to the present technology, the first electrode active material includes Co, Mn, Fe, Ni. It may contain at least one atom selected from the group consisting of C, Si, Li, Mg, Al and Ti.
In the solid state battery according to the present technology, the second electrode active material includes Co, Mn, Fe, Ni. It may contain at least one atom selected from the group consisting of C, Si, Li, Mg, Al and Ti.

In the solid state battery according to the present technology, the electrode layer may be a positive electrode layer.
In the solid state battery according to the present technology, the electrode layer may be a negative electrode layer.
The solid state battery according to the present technology may include the two electrode layers, and each of the two electrode layers may be a positive electrode layer and a negative electrode layer.

In this technology,
Providing a battery pack comprising a solid state battery according to the present technology;
A solid state battery according to the present technology; a control unit that controls a use state of the solid state battery;
A battery pack comprising: a switch unit that switches a use state of the solid state battery according to an instruction of the control unit;
A solid state battery according to the present technology, a driving force conversion device that receives power supplied from the solid state battery and converts the power into a driving force of the vehicle, a driving unit that drives according to the driving force, and a vehicle control device. Provide vehicles,
A power storage device having a solid battery according to the present technology, a power consuming device to which power is supplied from the solid battery, a control device for controlling power supply from the solid battery to the power consuming device, and charging the solid battery Providing a power storage system comprising:
Providing a power tool comprising a solid state battery according to the present technology and a movable part to which power is supplied from the solid state battery,
Provided is an electronic device that includes the solid state battery according to the present technology and receives power supply from the solid state battery.

According to the present technology, battery characteristics and reliability can be improved. Note that the effects described herein are not necessarily limited, and may be any of the effects described in the present disclosure, or effects different from those.

It is a figure showing an example of composition of a solid battery of a 1st embodiment concerning this art. It is a block diagram showing the structure of the example of application (battery pack) of the solid battery which concerns on this technique. It is a block diagram showing the composition of the example of application (vehicle) of the solid battery concerning this art. It is a block diagram showing the composition of the example of application (electric storage system) of the solid battery concerning this art. It is a block diagram showing the composition of the example of application (electric tool) of the solid battery concerning this art. It is a block diagram showing the structure of the application example (electronic device) of the solid battery which concerns on this technique. It is a figure showing the structure of the application example 1 (printed circuit board) of the solid battery which concerns on this technique. It is a figure showing an example of composition of application example 2 (universal credit card) of a solid battery concerning this art. It is a figure showing an example of composition of application example 3 (wristband type activity meter) of a solid battery concerning this art. It is a figure showing an example of composition of application example 3 (wristband type activity meter) of a solid battery concerning this art. It is a figure showing the structure of the application example 3 (wristband type electronic device) of the solid battery which concerns on this technique. It is a disassembled perspective view showing the structure of the application example 4 (smart watch) of the solid battery which concerns on this technique. It is a figure showing a part of internal structure of the application example 4 (band type electronic device) of the solid battery which concerns on this technique. It is a block diagram which shows the circuit structure of the application example 4 (band type electronic device) of the solid battery which concerns on this technique. It is a figure showing the specific example of a structure of the application example 5 (glasses type terminal) of the solid battery which concerns on this technique.

Hereinafter, preferred embodiments for implementing the present technology will be described. The embodiment described below shows an example of a typical embodiment of the present technology, and the scope of the present technology is not interpreted narrowly.

The description will be given in the following order.
1. Overview of this technology First Embodiment (Example of Solid Battery)
2-1. Solid battery 2-2. Electrode layer (positive electrode layer and negative electrode layer)
2-3. Buffer layer 2-4. Electrolyte layer 2-5. Current collecting layer 2-6. Insulating layer 2-7. Protective layer 2-8. Terminal layer 2-9. 2. Solid battery manufacturing method 3. Use of solid battery 3-1. Overview of solid battery applications 3-2. Second embodiment (example of battery pack)
3-3. Third embodiment (example of vehicle)
3-4. Fourth embodiment (an example of a power storage system)
3-5. Fifth embodiment (example of electric tool)
3-6. Sixth Embodiment (Example of electronic device)

<1. Overview of this technology>
First, an outline of the present technology will be described.

In the manufacturing process of a solid battery, the difference in thermal expansion coefficient between the electrode layer and the electrolyte layer may be large during sintering, and the interface between the electrode layer and the electrolyte layer may peel off. Further, if the interface does not contact well, an increase in resistance value, a decrease in charge / discharge efficiency, a decrease in cycle characteristics and the like may occur. Furthermore, when the electrolyte is thinned, if large particles are present at the interface, a short circuit may occur. Therefore, in the present technical field, there is a demand for a solid battery with improved battery characteristics and reliability.

For example, an intermediate layer made of a metal and / or compound containing at least one of Co, Ni and Mn is formed on the surface of the electrolyte layer containing a garnet-type oxide, and the Co, Ni and Mn contained in the intermediate layer A technique related to a laminate in which an active material layer containing composite oxide particles containing one or more elements and a flux containing Li is formed on an intermediate layer, and the intermediate layer disappears and becomes an interface when fired. There is. This technique is effective for preventing separation at the interface with a garnet-type oxide having a low expansion coefficient, but may not be effective with a glass electrolyte having a large thermal expansion coefficient. The electrode active material layer contains active material particles and binder material particles, and the binder material particles are metal oxide particles that exhibit a lithium ion insertion / release reaction, and the average particle size of the binder material particles However, there is a technique relating to a nonaqueous electrolyte secondary battery that is smaller than the average particle diameter of the active material particles. Since this technique does not use binder particles at the interface between the electrode layer and the electrolyte layer, there is a possibility that peeling of the interface cannot be prevented.

The solid electrolyte is made of a thin-film solid electrolyte having a thickness of 20 μm or less containing a powder made of a lithium ion conductive inorganic substance. At the interface between the positive electrode layer and / or the negative electrode layer and the solid electrolyte layer, the positive electrode There is a technology related to a lithium ion secondary battery in which a layer and / or a negative electrode layer and a solid electrolyte layer are mixed. This technique is a lithium ion secondary battery in which organic and inorganic materials are mixed, and it may be difficult to further improve battery characteristics and reliability.

There is a technology related to a lithium ion secondary battery in which a fiber layer is formed at a solid electrolyte-positive electrode interface and / or a solid electrolyte-negative electrode interface. However, when a fiber layer is used in a lithium ion secondary battery, the adhesion at the interface is lowered, which may work in a disadvantageous direction for the interface formation. There is a battery technology regarding a structure in which the porosity of the active material layer is distributed in the thickness direction and an electrolyte having a mixed layer between the electrode and the solid electrolyte and having a smaller particle size than the electrode layer. Focusing on the diameter, there is a possibility that further improvement of battery characteristics and reliability cannot be achieved.

Under the circumstances as described above, the present technology has been made as a result of extensive research conducted by the present inventors. According to the present technology, it is possible to improve and maintain the battery characteristics and reliability of the solid state battery. More specifically, according to the present technology, the electrode layer and the electrolyte layer are prevented from being separated or short-circuited to improve reliability, and the resistance value is increased, charging / discharging efficiency is decreased, and cycle characteristics are decreased. The battery characteristics are improved.

The solid state battery according to the present technology is, for example, an all solid state battery, and is a lithium ion secondary battery that is obtained by repeatedly receiving and receiving lithium (Li) and / or lithium ions (Li ⁺ ) that are electrode reactants. Can be mentioned. In the solid state battery according to the present technology, for example, during charging, lithium ions released from the positive electrode layer are taken into the negative electrode layer through the solid electrolyte layer, and during discharge, lithium ions released from the negative electrode layer are solid. It is taken into the positive electrode layer through the electrolyte layer.

As described above, the use of lithium (Li) and / or lithium ions (Li ⁺ ) as the electrode reactant has been described. However, the solid state battery according to the present technology may include lithium (Li) and / or lithium ions (Li ⁺ ). As an electrode reactant, for example, other alkali metals such as sodium (Na) or potassium (K), alkaline earth metals such as magnesium (Mg) or calcium (Ca), or aluminum ( Other metals such as Al) or silver (Ag) may be applied to the solid state battery according to the present technology.

The solid state battery according to the present technology can be applied to, for example, a battery pack, a vehicle, a power storage system, a power tool, an electronic device, and the like.

<2. First Embodiment (Example of Solid Battery)>
[2-1. Solid battery]
The solid state battery according to the first embodiment of the present technology includes at least an electrode layer, an electrolyte layer, and a buffer layer disposed between the electrode layer and the electrolyte layer, and the electrode layer includes electrode particles. The buffer layer includes buffer particles, the electrode particles contain a first electrode active material, the buffer particles contain at least one atom constituting the second electrode active material and / or the second electrode active material, and the buffer particles Is a solid battery in which the average particle size (D50) is smaller than the average particle size (D50) of the electrode particles.

The solid battery according to the first embodiment of the present technology exhibits excellent battery characteristics and excellent reliability effects. In addition, according to the solid state battery of the first embodiment according to the present technology, both the excellent battery characteristics and the excellent reliability are achieved, and both the battery characteristics and the reliability can be achieved. Become.

More specifically, according to the solid state battery of the first embodiment of the present technology, the introduction of the buffer layer increases the contact area at the interface between the electrode layer and the electrolyte layer, and the electrode layer and the electrolyte layer are separated. Can be prevented, and the resistance of the interface can be reduced. Further, according to the solid state battery of the first embodiment according to the present technology, the difference in the expansion coefficient between the electrode layer and the electrolyte layer is reduced, and the effect of suppressing peeling is exhibited.

Furthermore, the solid state battery according to the first embodiment of the present technology can improve load characteristics and yield. The solid state battery of the first embodiment according to the present technology can suppress a short circuit even when the electrolyte layer is thinned.

In the solid state battery according to the first embodiment of the present technology, a layer in which electrode particles are present (electrode layer) is formed, and a layer in which buffer particles are present (buffer layer) is formed. In the solid state battery according to the first embodiment of the present technology, the electrode particles are large particles from the viewpoint of shape retention and side reaction suppression, and the buffer particles are small particles from the viewpoint of improving the contact area and preventing short circuit, It has a structure that uses large particles and small particles separately. That is, in the solid state battery according to the first embodiment of the present technology, the average particle diameter (D50) of the buffer particles is smaller than the average particle diameter (D50) of the electrode particles.

As described above, if the average particle diameter (D50) of the buffer particles is smaller than the average particle diameter (D50) of the electrode particles, the ratio of the average particle diameter (D50) of the electrode particles to the average particle diameter (D50) of the buffer particles (Average particle diameter of electrode particles (D50) / average particle diameter of buffer particles (D50)) may be an arbitrary value (however, a value larger than 1), preferably 4 to 450, and preferably 5 to 420. It is more preferable that With this preferable aspect and a more preferable aspect, battery characteristics such as charge / discharge characteristics and reliability such as prevention of separation between the electrode layer and the electrolyte layer can be further improved.

The average particle diameter (D50) of the electrode particles may be any value, but is preferably 1 to 30 μm, more preferably 1 to 9 μm, and even more preferably 2.5 to 4.2 μm. . According to this preferable aspect, a more preferable aspect, and a further preferable aspect, battery characteristics such as charge / discharge characteristics and reliability such as prevention of peeling between the electrode layer and the electrolyte layer can be further improved.

On the other hand, the average particle diameter (D50) of the buffer particles may be any value, but is preferably 1 nm to 7.5 μm, more preferably 1 nm to 5 μm, and even more preferably 10 to 500 nm. . According to this preferable aspect, a more preferable aspect, and a further preferable aspect, battery characteristics such as charge / discharge characteristics and reliability such as prevention of peeling between the electrode layer and the electrolyte layer can be further improved.

The electrode particles contain a first electrode active material. The first electrode active material is not particularly limited and may be any material, but Co, Mn, Fe, Ni. It preferably contains at least one atom selected from the group consisting of C, Si, Li, Mg, Al and Ti. According to this preferred embodiment, battery characteristics such as charge / discharge characteristics and reliability such as prevention of peeling between the electrode layer and the electrolyte layer can be further improved.

The buffer particles contain at least one atom constituting the second electrode active material and / or the second electrode active material. The buffer particles may contain at least one of atoms constituting the second electrode active material and the second electrode active material, or at least constitute the second electrode active material and the second electrode active material. May also contain both of one atom. For example, the buffer particles may be a mixture of Co particles and LiCoO ₂ particles, or may be composite particles composed of a plurality of atoms. The second electrode active material is not particularly limited and may be any material, but Co, Mn, Fe, Ni. It preferably contains at least one atom selected from the group consisting of C, Si, Li, Mg, Al and Ti. According to this preferred embodiment, battery characteristics such as charge / discharge characteristics and reliability such as prevention of peeling between the electrode layer and the electrolyte layer can be further improved.

The relationship between the thickness of the electrode layer and the thickness of the buffer layer will be described. The thickness of the buffer layer may be substantially equal to the thickness of the electrode layer, and may be larger or smaller than the thickness of the electrode layer, but is preferably small. That is, the ratio of the electrode layer thickness to the buffer layer thickness (electrode layer thickness / buffer layer thickness) is preferably more than 1, more preferably 1 to 20000, and even more preferably 2 to 4000. According to this preferable aspect, a more preferable aspect, and a further preferable aspect, battery characteristics such as charge / discharge characteristics and reliability such as prevention of peeling between the electrode layer and the electrolyte layer can be further improved. In addition, the thickness of an electrode layer and the thickness of a buffer layer can be measured using a scanning electron microscope.

The thickness of the electrode layer may be any value, but is preferably 1 to 100 μm, and more preferably 3 to 20 μm. With this preferable aspect and a more preferable aspect, battery characteristics such as charge / discharge characteristics and reliability such as prevention of separation between the electrode layer and the electrolyte layer can be further improved.

The thickness of the buffer layer may be any value, but is preferably 1 nm to 20 μm, and more preferably 5 nm to 10 μm. With this preferable aspect and a more preferable aspect, battery characteristics such as charge / discharge characteristics and reliability such as prevention of separation between the electrode layer and the electrolyte layer can be further improved.

Next, the solid state battery according to the first embodiment of the present technology will be described in more detail with reference to FIG. FIG. 1 is a schematic cross-sectional view showing a solid state battery 10 according to a first embodiment of the present technology.

The solid battery 10 includes an electrode layer 1, a buffer layer 2, and an electrolyte layer 3, and the buffer layer 2 is provided between the electrode layer 1 and the electrolyte layer 3. The electrode layer 1 includes electrode particles 4, and the buffer layer 2 includes buffer particles 5.

The electrode layer 1 may be a positive electrode layer or a negative electrode layer. In the solid battery 10, when the electrode layer 1 is a positive electrode layer, a negative electrode layer (not shown) may be laminated on the other surface opposite to the one surface of the electrolyte layer 3 on which the positive electrode layer is laminated. . The negative electrode layer (not shown) may also be an electrode layer. In this case, in the solid battery 10, a buffer layer (not shown) may be provided between the electrolyte layer 3 and the negative electrode layer (not shown).

In the solid battery 10, when the electrode layer 1 is a negative electrode layer, a positive electrode layer (not shown) is laminated on the other surface opposite to the one surface of the electrolyte layer 3 on which the negative electrode layer is laminated. Good. The positive electrode layer (not shown) may be an electrode layer. In this case, in the solid battery 10, a buffer layer (not shown) may be provided between the electrolyte layer 3 and the positive electrode layer (not shown).

The solid battery 10 may include a current collecting layer (not shown). In this case, the current collecting layer may be provided outside the positive electrode layer and / or the negative electrode layer. Further, the solid battery 10 may include an insulating layer (not shown). In that case, the insulating layer may be provided outside the current collecting layer.

[2-2. Electrode layer]
The solid state battery of the first embodiment according to the present technology includes an electrode layer. As described above, the electrode layer may be a positive electrode layer or a negative electrode layer. Further, when the solid state battery according to the first embodiment of the present technology includes two electrode layers, the two electrode layers are a positive electrode layer and a negative electrode layer, respectively. Hereinafter, the positive electrode layer and the negative electrode layer will be described in detail.

(Positive electrode layer)
The positive electrode layer includes one type or two or more types of positive electrode active materials, and may further include an additive such as a binder and a conductive agent, and an electrolyte (for example, a solid electrolyte) as necessary. When the positive electrode layer is an electrode layer, the positive electrode active material is the first electrode active material.

The positive electrode active material includes 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 cobalt (Co), nickel (Ni), manganese (Mn), and iron (Fe). This is because a higher voltage can be obtained.

The chemical formula of the lithium transition metal composite oxide is represented by, for example, Li _x M1O ₂ or Li _y M2O _4, and the chemical formula of the lithium transition metal phosphate compound is represented by, for example, Li _z M3PO ₄ . However, M1 to M3 are one kind or two or more kinds of transition metal elements, and the values of x to z are arbitrary.

Examples of the lithium transition metal composite oxide include LiCoO ₂ , LiNiO ₂ , LiVO ₂ , LiCrO _{2, and} LiMn ₂ O ₄ . The lithium transition metal phosphate compound is, for example, LiFePO ₄ or LiCoPO ₄ .

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 sulfur, polyaniline, and polythiophene.

The positive electrode active material may contain a powder of positive electrode active material particles. The surface of the positive electrode active material particles may be coated with a coating agent. Here, the coating is not limited to the entire surface of the positive electrode active material particles, and may be a part of the surface of the positive electrode active material particles. The coating agent is at least one of a solid electrolyte and a conductive agent, for example. By covering the surfaces of the positive electrode active material particles with a coating agent, the interface resistance between the positive electrode active material and the solid electrolyte can be reduced. In addition, since the collapse of the structure of the positive electrode active material can be suppressed, the sweep potential width can be widened so that more lithium can be used for the reaction, and the cycle characteristics can be improved.

The binder is, for example, any one kind or two kinds or more of synthetic rubber or polymer material. Examples of the synthetic rubber include styrene butadiene rubber, fluorine rubber, and ethylene propylene diene. The polymer material is, for example, polyvinylidene fluoride or polyimide. The binder is used for binding particles such as a positive electrode active material. However, when the positive electrode is sufficiently bound by a glass material described later, the positive electrode does not contain the binder. It does not have to be.

The conductive agent includes, for example, a carbon material, a metal, a metal oxide, a conductive polymer, or the like alone or in combination. Examples of the carbon material include graphite, carbon black, acetylene black, ketjen black, and carbon fiber. An example of the metal oxide is SnO ₂ . Note that the conductive agent may be any material having conductivity, and is not limited to the above example.

(Negative electrode layer)
The negative electrode layer includes one type or two or more types of negative electrode active materials, and may further include additives such as a binder and a conductive agent, and the above-described solid electrolyte as necessary. When the negative electrode layer is an electrode layer, the negative electrode active material is the first electrode active material.

The negative electrode active material includes 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, the metal-based material is, for example, silicon (Si), tin (Sn), aluminum (Al), indium (In), magnesium (Mg), boron (B), gallium (Ga), germanium ( Ge), lead (Pb), bismuth (Bi), cadmium (Cd), silver (Ag), zinc (Zn), hafnium (Hf), zirconium (Zr), yttrium (Y), palladium (Pd) or platinum ( Any one or more of simple substance such as Pt), alloy or compound. However, the simple substance is not limited to 100% purity, and may contain a small amount of impurities. Examples of the metal-based material include Si, Sn, SiB ₄ , TiSi ₂ , SiC, Si ₃ N ₄ , SiOv (0 <v ≦ 2), LiSiO, SnO _w (0 <w ≦ 2), SnSiO ₃ , LiSnO. Or Mg ₂ Sn.

In addition, the metal-based material may be a lithium-containing compound or lithium metal (lithium simple substance). This lithium-containing compound is a complex oxide (lithium transition metal complex oxide) containing lithium and a transition metal element as constituent elements, such as Li ₄ Ti ₅ O ₁₂ .

The negative electrode active material may contain a powder of negative electrode active material particles. The surface of the negative electrode active material particles may be coated with a coating agent. Here, the coating is not limited to the entire surface of the negative electrode active material particles, and may be a part of the surface of the negative electrode active material particles. The coating agent is at least one of a solid electrolyte and a conductive agent, for example. By covering the surfaces of the negative electrode active material particles with a coating agent, the interface resistance between the negative electrode active material and the solid electrolyte can be reduced. In addition, since the collapse of the structure of the negative electrode active material can be suppressed, the sweep potential width can be widened, and a large amount of lithium can be used for the reaction, and the cycle characteristics can be improved.

The binder and conductive agent are as described above.

The electrode layer may include a glass material. Below, a glass material is demonstrated in detail.

The glass material is preferably a lithium ion conductive oxide crystallized glass containing Li (lithium), Si (silicon) and B (boron), and Li (lithium), Si (silicon) and B A lithium ion conductive oxide crystallized glass containing at least one selected from (boron) is also preferable.

The glass material may be a material having a glass transition point at 500 ° C. or lower, that is, a so-called low-melting glass material. The low-melting glass material has, for example, a glass transition point at 500 ° C. or lower, but preferably has a glass transition point at 300 ° C. to 500 ° C.

Furthermore, the glass material preferably contains an oxide containing lithium (Li), silicon (Si), and boron (B). More specifically, the glass material contains Li ₂ O, SiO ₂ and B ₂ O ₃ . The content of Li ₂ O with respect to the total amount of Li ₂ O, SiO ₂ and B ₂ O ₃ is preferably 40 mol% or more and 73 mol% or less. The content of SiO ₂ with respect to the total amount of Li ₂ O, SiO ₂ and B ₂ O ₃ is preferably 8 mol% or more and 40 mol% or less. The content of B ₂ O ₃ with respect to the total amount of Li ₂ O, SiO ₂ and B ₂ O ₃ is preferably 10 mol% or more and 50 mol% or less. Still further, the glass material includes an oxide containing lithium (Li) (eg, Li ₂ O), an oxide containing silicon (Si) (eg, SiO ₂ ), and an oxide containing boron (B) (eg, B It is also preferable that at least one oxide selected from ₂ O ₃ ) is included. Note that these contents can be measured using inductively coupled plasma optical emission spectrometry (ICP-AES) or the like.

As the glass material, oxide glass (Li ₂ O: SiO ₂ : B ₂ O ₃ = 54: 11: 35) or oxide glass (Bi ₂ O ₃ · B ₂ O ₃ ) is preferably used.

The glass material may further contain an additive element as necessary. Examples of the additive element include Na (sodium), Mg (magnesium), Al (aluminum), P (phosphorus), K (potassium), Ca (calcium), Ti (titanium), V (vanadium), and Cr (chromium). ), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Ga (gallium), Ge (germanium), 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 1 or more members selected from the group consisting of (europium), and the like.

Hereinafter, an example of a method for producing a glass material will be described.

First, a plurality of types of amorphous materials are mixed as raw materials. As the amorphous material, a network-forming oxide, a modified oxide, and, if necessary, an intermediate oxide are used. As the network forming oxide, SiO ₂ and B ₂ O ₃ are used. Li ₂ O is used as the modified oxide. Examples of the intermediate oxide include Na, Mg, Al, P, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Se, Rb, S, Y, One or more oxides selected from the group consisting of Zr, Nb, Mo, Ag, In, Sn, Sb, Cs, Ba, Hf, Ta, W, Pb, Bi, Au, La, Nd, and Eu are used. .

The blending amount of Li ₂ O with respect to the total amount of Li ₂ O, SiO ₂ and B ₂ O ₃ is preferably 40 mol% or more and 73 mol% or less. The blending amount of Li ₂ O with respect to the total amount of Li ₂ O, SiO ₂ and B ₂ O ₃ is preferably 8 mol% or more and 40 mol% or less. The blending amount of B ₂ O ₃ with respect to the total amount of Li ₂ O, SiO ₂ and B ₂ O ₃ is preferably 10 mol% or more and 50 mol% or less.

When an intermediate oxide is used as the amorphous material, the amount of the intermediate oxide is preferably 10 mol% or less with respect to the total amount of the network forming oxide, the modified oxide, and the intermediate oxide.

In general, the amorphous material is a network forming oxide (Network WF), a modified oxide (Network modifier), or an intermediate oxide (Intermediate). The network forming oxide (Network Former: NWF) can be vitrified by itself such as SiO ₂ , B ₂ O ₃ , P ₂ O ₅ , GeO ₂ . The modified oxide (Network modifier) cannot be amorphized by itself, but can be amorphized within the network structure formed by the network oxide, that is, the network can be modified. . The modified oxide contains, for example, alkali metals or alkaline earth metals, and is known to have an effect of improving the fluidity by cutting the glass network structure. The intermediate oxide (Intermediate) is a raw material having an intermediate property between the network-forming oxide and the modified oxide, and has an effect of, for example, reducing the thermal expansion coefficient among the thermal characteristics of the glass.

Finally, a glass material can be produced by vitrifying the raw material. As a method for vitrifying the raw material, for example, a method in which the raw material is melted to a melt and allowed to cool, a method in which the melt is pressed with a metal plate, a method in which the melt is dropped into mercury, a strip furnace, a splat quench, a roll method ( In addition to single and twin), mechanical milling method, sol-gel method, vapor deposition method, sputtering method, laser ablation method, PLD (pulse laser deposition) method, plasma method and the like can be mentioned.

The glass transition point of the low-melting glass material can be measured by a known method, but can be measured, for example, by a TG measurement (thermogravimetric measurement) method.

[2-3. Buffer layer]
The solid state battery according to the first embodiment of the present technology includes a buffer layer containing buffer particles. The buffer layer may include the glass material described above.

When the electrode layer is a positive electrode layer, the second electrode active material contained in the buffer layer is not particularly limited, but is preferably a positive electrode active material or particles containing a component of the positive electrode active material. The first electrode active material included in the positive electrode layer (electrode layer) and the second electrode active material included in the buffer layer may be the same type of positive electrode active material or different types of positive electrode active materials. When the electrode layer is a negative electrode layer, the second electrode active material contained in the buffer layer is not particularly limited, but is preferably a particle containing a negative electrode active material or a component of the negative electrode active material. The first electrode active material contained in the negative electrode layer (electrode layer) and the second electrode active material contained in the buffer layer may be the same type of negative electrode active material or different types of negative electrode active materials.

[2-4. Electrolyte layer]
The solid state battery according to the first embodiment of the present technology includes an electrolyte layer. The electrolyte layer may be a solid electrolyte layer.

The glass material described above may be included in the solid electrolyte layer. The solid electrolyte layer may further contain a solid electrolyte, and may contain a binder described later as necessary.

Examples of the solid electrolyte include one type or two or more types of crystalline solid electrolytes. The type of the crystalline solid electrolyte is not particularly limited as long as it is a crystalline solid electrolyte capable of conducting lithium ions, and examples thereof include inorganic materials and polymer materials. Inorganic materials include, for example, 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 Sulfides such as 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 An oxide such as Ti _2-x (PO ₄ ) ₃ or La _{2 / 3-x} Li _3x TiO ₃ . Examples of the polymer material include polyethylene oxide (PEO).

[2-5. Current collecting layer]
The solid state battery of the first embodiment according to the present technology may further include a current collecting layer. In the above, as described with reference to FIG. 1, in the solid state battery according to the first embodiment of the present technology, the current collecting layer is disposed outside the positive electrode layer (electrode layer) and the negative electrode layer (electrode layer). can do.

The current collecting layer may contain the glass material described above. The current collecting layer may include a material having high conductivity in addition to the glass material. Examples of the material included in the current collecting layer for the positive electrode include general carbon-based materials such as carbon, graphite, and carbon nanotubes, Cu, Mg, Ti, Fe, Co, Ni, Zn, Al, Ge, and In. , Au, Pt, Ag, Pd, or an alloy containing any of these. As the material contained in the current collecting layer for the negative electrode, the same material as that for the current collecting layer for the positive electrode can be used.

Further, the material constituting the positive electrode current collecting layer may be the same as or different from the material constituting the positive electrode layer. Furthermore, the material constituting the negative electrode current collecting layer may be the same as or different from the material constituting the negative electrode layer.

Further, the current collecting layer for the positive electrode and the current collecting layer for the negative electrode may include a positive electrode active material and a negative electrode active material, respectively. For example, a conductive carbon material (graphite) that is a negative electrode active material may be included in the negative electrode current collecting layer. The content ratio is not particularly limited as long as it functions as a current collecting layer, but the volume ratio of the positive electrode current collector / positive electrode active material or the negative electrode current collector / negative electrode active material is in the range of 90/10 to 70/30. It is preferable. The positive electrode current collecting layer and the negative electrode current collecting layer contain a positive electrode active material and a negative electrode active material, respectively, so that the positive electrode current collector layer and the positive electrode active material layer, and the negative electrode current collector layer and the negative electrode active material This is desirable because adhesion to the material layer is improved.

The current collecting layer may further contain an additive such as a binder as necessary.

[2-6. Insulation layer]
The solid state battery of the first embodiment according to the present technology may further include an insulating layer. In the above, as demonstrated using FIG. 1, the solid state battery of 1st Embodiment which concerns on this technique can distribute | arrange an insulating layer on the outer side of a current collection layer. Moreover, it can arrange | position between an electrolyte layer and a positive electrode layer (electrode layer) and / or between an electrolyte layer and a negative electrode layer (electrode layer).

The insulating layer may include the glass material described above. The insulating layer may include an inorganic insulating material and / or an organic insulating material in addition to the glass material. Examples of the inorganic insulating material include aluminum oxide (Al ₂ O ₃ ), silicon oxide (SiO ₂ ), magnesium oxide (MgO), titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), and the like. Examples of the insulating material include polyvinylidene fluoride, a copolymer of vinylidene fluoride and hexafluoropropylene, and the like.

The insulating layer may further contain an additive such as a binder as necessary.

[2-7. Protective layer]
The solid state battery according to the first embodiment of the present technology may further include a protective layer. The protective layer may be disposed as the outermost layer of the solid state battery according to the first embodiment of the present technology.

The protective layer may include the glass material described above. For example, the glass material content of the protective layer may be greater or less than the glass material content of each of the positive electrode layer, the negative electrode layer, the current collecting layer, and the insulating layer.

The protective layer is for electrical, physical, and chemical protection, and can improve the reliability of the solid state battery. In addition to the glass material, the protective layer may include a material that is excellent in insulation, durability, and moisture resistance and is environmentally safe. For example, a thermosetting resin and a photocurable resin are mentioned.

The protective layer may further contain an additive such as a binder as necessary.

[2-8. Terminal layer]
The solid state battery of the first embodiment according to the present technology may further include a terminal layer. You may arrange | position in the electrode extraction part of an electrode layer, ie, a positive electrode layer, and / or a negative electrode layer.

The terminal layer may include the glass material described above. For example, the content of the glass material of the terminal layer may be larger or smaller than the content of the glass material of each layer of the positive electrode layer, the negative electrode layer, the current collecting layer, and the insulating layer, for example.

The terminal layer may include a material having a high conductivity, for example, silver, gold, platinum, aluminum, copper, tin, nickel, in addition to the glass material.

The terminal layer may further contain an additive such as a binder as necessary.

[2-9. Solid battery manufacturing method]
A method for manufacturing the solid state battery according to the first embodiment of the present technology will be described. This manufacturing method uses a coating method to form a positive electrode layer (electrode layer), a negative electrode layer (electrode layer), a buffer layer and an electrolyte layer, and, if necessary, a current collecting layer, an insulating layer, a protective layer, and a terminal layer. A step of forming, and a step of stacking and heating these layers. The positive electrode layer (electrode layer), the negative electrode layer (electrode layer), the buffer layer and the electrolyte layer, and the current collecting layer, insulating layer, protective layer and terminal layer may all be green sheets, or the positive electrode At least one of the layer (electrode layer), the negative electrode layer (electrode layer), the buffer layer and the electrolyte layer, and the current collecting layer, insulating layer, protective layer and terminal layer may be a green sheet. When at least one of a positive electrode layer (electrode layer), a negative electrode layer (electrode layer), a buffer layer and an electrolyte layer, and a current collecting layer, an insulating layer, a protective layer and a terminal layer is a green sheet, at least one green A layer (for example, slurry) other than the green sheet may be formed on the sheet by, for example, a screen printing method or the like.

Further, the solid state battery according to the first embodiment of the present technology may be manufactured by a method other than the coating method. As a method other than the coating method, for example, a method of press-molding a powder of an electrode mixture containing an active material and a glass material using a press machine or the like may be used. The shape of the compact after the pressure molding is not particularly limited, and may be, for example, a pellet shape (coin shape).

<3. Applications of solid batteries>
The use of the solid battery will be described in detail below.

<3-1. Overview of solid battery applications>
The solid battery can be used as a machine, device, instrument, device, and system (an assembly of a plurality of devices) that can be used as a power source for driving or a power storage source for storing power. There is no particular limitation. The solid battery used as a power source may be a main power source (a power source used preferentially) or an auxiliary power source (a power source used in place of or switched from the main power source). When a solid battery is used as an auxiliary power source, the type of main power source is not limited to a solid battery.

The usage of the solid battery is as follows, for example. Notebook personal computers, tablet computers, mobile phones (for example, smart phones), personal digital assistants (PDAs), imaging devices (for example, digital still cameras, digital video cameras), audio devices (for example, portable audio players) , Game devices, cordless phones, electronic books, electronic dictionaries, radios, headphones, navigation systems, memory cards, pacemakers, hearing aids, lighting devices, toys, medical devices, robots, and other electronic devices (including portable electronic devices) It is. It is a portable living device such as an electric shaver. Storage devices such as backup power supplies and memory cards. Electric tools such as electric drills and electric saws. It is a battery pack used for a notebook computer or the like as a detachable power source. Medical electronic devices such as pacemakers and hearing aids. It is a vehicle used for an electric vehicle (including a hybrid vehicle). It is a power storage system such as a home battery system that stores electric power in case of an emergency. Of course, other uses may be used.

Especially, it is effective that the solid battery is applied to a battery pack, a vehicle, a power storage system, a power tool, and an electronic device. This is because, since excellent battery characteristics are required, performance can be effectively improved by using the solid battery of the present technology. The battery pack is a power source using a solid battery, and is a so-called assembled battery. The vehicle is a vehicle that operates (runs) using a solid battery as a driving power source, and may be an automobile (such as a hybrid automobile) that includes a drive source other than the solid battery as described above. The power storage system is, for example, a residential power storage system and uses a solid battery as a power storage source. In the power storage system, since power is stored in a solid state battery that is a power storage source, a power consuming device, for example, a household electric product can be used by using the power. An electric power tool is a tool in which a movable part (for example, a drill etc.) moves, using a solid battery as a driving power source. An electronic device is a device that exhibits various functions using a solid state battery as a driving power source (power supply source).

Here, some application examples of the solid state battery will be specifically described. In addition, since the structure of each application example demonstrated below is an example to the last, it can change suitably.

<3-2. Second Embodiment (Battery Pack)>
The battery pack according to the second embodiment of the present technology includes the solid state battery according to the first embodiment of the present technology. For example, the battery pack according to the second embodiment according to the present technology includes the solid state battery according to the first embodiment according to the present technology, a control unit that controls a use state of the solid state battery, and an instruction from the control unit. And a switch unit that switches a use state of the solid state battery. The battery pack of the second embodiment according to the present technology includes the solid state battery of the first embodiment according to the present technology having excellent battery characteristics and excellent reliability. Leads to improvement.

Hereinafter, an example of the battery pack according to the second embodiment of the present technology will be described with reference to the drawings.

FIG. 2 shows a block configuration of the battery pack. This battery pack includes, for example, a control unit 61, a power source 62, a switch unit 63, a current measurement unit 64, a temperature detection unit 65, and a voltage detection unit inside a housing 60 formed of a plastic material or the like. 66, a switch control unit 67, a memory 68, a temperature detection element 69, a current detection resistor 70, a positive terminal 71 and a negative terminal 72.

The control unit 61 controls the operation of the entire battery pack (including the usage state of the power supply 62), and includes, for example, a central processing unit (CPU). The power source 62 includes one or more solid batteries (not shown). The power source 62 is, for example, an assembled battery including two or more solid batteries, and the connection form of these solid batteries may be in series, in parallel, or a mixture of both. As an example, the power source 62 includes six solid state batteries connected in two parallel three series.

The switch unit 63 switches the usage state of the power source 62 (whether or not the power source 62 can be connected to an external device) according to an instruction from the control unit 61. The switch unit 63 includes, for example, a charge control switch, a discharge control switch, a charging diode, a discharging diode (all not shown), and the like. The charge control switch and the discharge control switch are semiconductor switches such as a field effect transistor (MOSFET) using a metal oxide semiconductor, for example.

The current measurement unit 64 measures current using the current detection resistor 70 and outputs the measurement result to the control unit 61. The temperature detection unit 65 measures the temperature using the temperature detection element 69 and outputs the measurement result to the control unit 61. This temperature measurement result is used, for example, when the control unit 61 performs charge / discharge control during abnormal heat generation, or when the control unit 61 performs correction processing when calculating the remaining capacity. The voltage detection unit 66 measures the voltage of the solid state battery in the power source 62, converts the measured voltage from analog to digital, and supplies the converted voltage to the control unit 61.

The switch control unit 67 controls the operation of the switch unit 63 in accordance with signals input from the current measurement unit 64 and the voltage detection unit 66.

For example, when the battery voltage reaches the overcharge detection voltage, the switch control unit 67 disconnects the switch unit 63 (charge control switch) and controls the charging current not to flow through the current path of the power source 62. . As a result, the power source 62 can only discharge through the discharging diode. The switch control unit 67 is configured to cut off the charging current when a large current flows during charging, for example.

Further, the switch control unit 67 disconnects the switch unit 63 (discharge control switch) so that the discharge current does not flow in the current path of the power source 62 when the battery voltage reaches the overdischarge detection voltage, for example. . As a result, the power source 62 can only be charged via the charging diode. For example, the switch control unit 67 is configured to cut off the discharge current when a large current flows during discharging.

In the solid state battery, for example, the overcharge detection voltage is 4.2V ± 0.05V, and the overdischarge detection voltage is 2.4V ± 0.1V.

The memory 68 is, for example, an EEPROM which is a nonvolatile memory. The memory 68 stores, for example, numerical values calculated by the control unit 61 and information (for example, internal resistance in an initial state) of the solid battery measured in the manufacturing process stage. If the full charge capacity of the solid battery is stored in the memory 68, the control unit 61 can grasp information such as the remaining capacity.

The temperature detection element 69 measures the temperature of the power supply 62 and outputs the measurement result to the control unit 61, and is, for example, a thermistor.

The positive electrode terminal 71 and the negative electrode terminal 72 are connected to an external device (for example, a notebook personal computer) operated using a battery pack, an external device (for example, a charger) used to charge the battery pack, or the like. Terminal. Charging / discharging of the power source 62 is performed via the positive terminal 71 and the negative terminal 72.

<3-3. Third Embodiment (Vehicle)>
The vehicle according to the third embodiment of the present technology includes a solid state battery according to the first embodiment of the present technology, a driving force conversion device that converts electric power supplied from the solid state battery into driving force, and a driving force. And a vehicle control device. The vehicle according to the third embodiment according to the present technology includes the solid state battery according to the first embodiment according to the present technology having excellent battery characteristics and excellent reliability. Therefore, the performance and reliability of the vehicle are improved. Leads to.

Hereinafter, a vehicle according to a third embodiment of the present technology will be described with reference to FIG.

FIG. 3 schematically shows an example of the configuration of a hybrid vehicle that employs a series hybrid system to which the present technology 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. A power storage device (not shown) 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 device 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, the series hybrid vehicle that runs on the motor using the power generated by the generator driven by the engine or the power stored once in the battery has been described as an example. However, the present disclosure is also effective for a parallel hybrid vehicle that uses both engine and motor outputs as drive sources, 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 technology can be effectively applied to a so-called electric vehicle that travels only by a drive motor without using an engine.

<3-4. Fourth Embodiment (Power Storage System)>
The power storage system according to the fourth embodiment of the present technology includes a power storage device including the solid state battery according to the first embodiment of the present technology, a power consuming device supplied with power from the solid state battery, and the solid state battery. A power storage system includes a control device that controls power supply to a power consuming device and a power generation device that charges a solid state battery. The power storage system of the fourth embodiment according to the present technology includes the solid state battery of the first embodiment according to the present technology having excellent battery characteristics and excellent reliability. Leads to improvement.

Hereinafter, a residential power storage system that is an example of the power storage system according to the fourth embodiment of the present technology will be described with reference to FIG. 4.

For example, in a power storage system 9100 for a house 9001, electric power is supplied from a centralized power system 9002 such as a thermal power generation 9002a, a nuclear power generation 9002b, and a hydropower generation 9002c via a power network 9009, an information network 9012, a smart meter 9007, a power hub 9008, and the like. The power is supplied to the power storage 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 according to the present technology (solid battery according to the present technology) 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.

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 regarding 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. Communication methods of the information network 9012 connected to the control device 9010 include a method using a communication interface such as UART (Universal Asynchronous Receiver-Transmitter), Bluetooth (registered trademark), ZigBee, Wi-Fi. There is a method of using a sensor network based on a wireless communication standard such as. The Bluetooth (registered trademark) system is applied to multimedia communication and can perform one-to-many connection communication. ZigBee uses the physical layer of IEEE (Institut-of-Electrical-and-Electronics-Engineers) -802.15.4. IEEE 802.15.4 is the 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, such as a television receiver, a mobile phone, a personal digital assistant (PDA), or the like.

The control device 9010 that controls each unit includes a CPU, 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, the various sensors 9011, the server 9013, and the information network 9012. For example, the control device 9010 functions to adjust 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 example in which the control device 9010 is stored in the power storage device 9003 has been described. 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.

<3-5. Fifth Embodiment (Electric Tool)>
The power tool of the fifth embodiment according to the present technology is a power tool including the solid state battery of the first embodiment according to the present technology and a movable part to which power is supplied from the solid state battery. Since the power tool of the fifth embodiment according to the present technology includes the solid state battery of the first embodiment according to the present technology having excellent battery characteristics and excellent reliability, the performance and reliability of the power tool. Leads to improvement.

Hereinafter, a power tool according to a fifth embodiment of the present technology will be described with reference to FIG.

FIG. 5 shows a block configuration of the electric tool. This electric tool is, for example, an electric drill, and includes a control unit 99 and a power supply 100 inside a tool main body 98 formed of a plastic material or the like. For example, a drill portion 101 which is a movable portion is attached to the tool body 98 so as to be operable (rotatable).

The control unit 99 controls the operation of the entire power tool (including the usage state of the power supply 100), and includes, for example, a CPU. The power supply 100 includes one or more solid batteries (not shown). The control unit 99 supplies power from the power supply 100 to the drill unit 101 in response to an operation switch (not shown).

<3-6. Sixth Embodiment (Electronic Device)>
The electronic device according to the sixth embodiment of the present technology is an electronic device that includes the solid state battery according to the first embodiment of the present technology and receives power supply from the solid state battery. As described above, the electronic device according to the sixth embodiment of the present technology is a device that exhibits various functions using a solid battery as a driving power source (power supply source). Since the electronic device of the sixth embodiment according to the present technology includes the solid state battery of the first embodiment according to the present technology having excellent battery characteristics and excellent reliability, the performance and reliability of the electronic device. Leads to improvement.

Hereinafter, an electronic apparatus according to a sixth embodiment of the present technology will be described with reference to FIG.

An example of the configuration of the electronic device 400 according to the sixth embodiment of the present technology will be described. The electronic device 400 includes an electronic circuit 401 of the electronic device body and a battery pack 300. The battery pack 300 is electrically connected to the electronic circuit 401 via the positive terminal 331a and the negative terminal 331b. For example, the electronic device 400 has a configuration in which the battery pack 300 is detachable by a user. The configuration of the electronic device 400 is not limited to this, and the battery pack 300 is built in the electronic device 400 so that the user cannot remove the battery pack 300 from the electronic device 400. May be.

When charging the battery pack 300, the positive terminal 331a and the negative terminal 331b of the battery pack 300 are connected to the positive terminal and the negative terminal of a charger (not shown), respectively. On the other hand, when the battery pack 300 is discharged (when the electronic apparatus 400 is used), the positive terminal 331a and the negative terminal 331b of the battery pack 300 are connected to the positive terminal and the negative terminal of the electronic circuit 401, respectively.

Examples of the electronic device 400 include a notebook personal computer, a tablet computer, a mobile phone (for example, a smartphone), a personal digital assistant (PDA), an imaging device (for example, a digital still camera, a digital video camera), and an audio device (for example, Portable audio players), game devices, cordless phones, electronic books, electronic dictionaries, radio, headphones, navigation systems, memory cards, pacemakers, hearing aids, lighting equipment, toys, medical equipment, robots, etc. It is not limited. As a specific example, a head-mounted display and a band-type electronic device will be described. The head-mounted display includes an image display device, a mounting device for mounting the image display device on an observer's head, and the image display device. The electronic device includes a mounting member for attaching the battery to a mounting device, and uses the solid state battery of the first embodiment according to the present technology or the solid state battery of the second embodiment according to the present technology as a driving power source. Type electronic devices connect a plurality of segments connected in a band shape, a plurality of electronic components arranged in the plurality of segments, and a plurality of electronic components in the plurality of segments, and meander in at least one segment A flexible circuit board arranged in a shape, for example, as the electronic component, for example, the solid state battery of the first embodiment according to the present technology or the second embodiment according to the present technology. Body cell is an electronic device that is disposed above the segment.

The electronic circuit 401 includes, for example, a CPU, a peripheral logic unit, an interface unit, a storage unit, and the like, and controls the entire electronic device 400.

The battery pack 300 includes an assembled battery 301 and a charge / discharge circuit 302. The assembled battery 301 is configured by connecting a plurality of secondary batteries 301a in series and / or in parallel. The plurality of secondary batteries 301a are connected, for example, in n parallel m series (n and m are positive integers). FIG. 6 shows an example in which six secondary batteries 301a are connected in two parallel three series (2P3S). As the secondary battery 301a, the secondary battery according to the first embodiment or its modification is used.

At the time of charging, the charging / discharging circuit 302 controls charging of the assembled battery 301. On the other hand, at the time of discharging (that is, when the electronic device 400 is used), the charging / discharging circuit 302 controls the discharging of the electronic device 400.

Hereinafter, the effects of the present technology will be described in detail with examples. Note that the scope of the present technology is not limited to the examples.

<Example 1>
A solid battery A according to Example 1 was manufactured according to the following experimental method.

[experimental method]
(Measurement of average particle diameter (D50) of electrode particles for positive electrode)
First, the average particle diameter (D50) and D90 of lithium cobalt oxide (LiCoO ₂ ) manufactured by Aldrich, which are electrode particles for the positive electrode (first electrode active material) used in the solid battery A, were measured with a microtrack particle size analyzer. (Nikkiso) was used for measurement. The average particle diameter (D50) of lithium cobaltate (LiCoO ₂ ) was 4.2 μm. Moreover, D90 was 13.3 micrometers.

(Measurement of average particle diameter (D50) of buffer particles)
The average particle diameter (D50) of Co particles, which are buffer particles used in the solid battery A, was measured using a scanning electron microscope. The average particle diameter (D50) of the Co particles was 10 nm.

(Calculation of particle size ratio)
Using the measurement result of the average particle diameter (D50) of the electrode particles for positive electrodes and the measurement result of the average particle diameter (D50) of the buffer particles, the particle diameter ratio (average particle diameter of electrode particles (D50) / buffer particles) Average particle diameter (D50)) was calculated. As a calculation result, the particle size ratio was 420 (4.2 μm / 10 nm).

(Preparation of positive electrode layer)
Lithium cobaltate (LiCoO ₂ ) whose average particle diameter (D50) was measured as described above, and oxide glass (Li ₂ O: SiO ₂ : B ₂ O ₃ = 54: 11: 35, glass transition temperature: 380 ° C. ) At a predetermined mass ratio (for example, lithium cobaltate: oxide glass = 80: 20 mass ratio (volume ratio 60:40 vol%)), and then the mixture and the acrylic binder are (cobalt acid) Lithium + oxide glass): Acrylic binder = 70: 30 and mixed, and the mixture was mixed with butyl acetate so that the solid content was 30% by mass, together with 5 mmφ zirconia balls for 4 hours. Stir. It was coated on a release film and dried at 80 ° C. for 10 minutes to produce a positive electrode layer of solid battery A according to Example 1.

(Preparation of buffer layer)
Co particles whose average particle diameter (D50) was measured as described above, and oxide glass (Li ₂ O: SiO ₂ : B ₂ O ₃ = 54: 11: 35, glass transition temperature: 380 ° C.) were predetermined. (For example, lithium cobaltate: oxide glass = 80: 20 mass ratio (volume ratio 60:40 vol%)), and then the mixture and the acrylic binder are (lithium cobaltate + oxide glass). ): Acrylic binder = 70: 30 The mass ratio was mixed, and the mixture was mixed with butyl acetate so that the solid content was 30% by mass, and stirred with 5 mmφ zirconia balls for 4 hours. It was applied onto a release film and dried at 80 ° C. for 10 minutes to produce a buffer layer of solid battery A according to Example 1.

(Preparation of solid electrolyte layer)
Garnet-type oxide crystal electrolyte (Li ₆ BaLa ₂ Ta ₂ O ₁₂ ) and oxide glass (Li ₂ O: SiO ₂ : B ₂ O ₃ = 54: 11: 35, glass transition temperature: 380 ° C.) are predetermined. (For example, garnet-type oxide crystal electrolyte: oxide glass = 70: 30 mass ratio (volume ratio 50:50 vol%)), and then the mixture and the acrylic binder are mixed with (garnet-type oxide). (Crystal electrolyte + oxide glass): Acrylic binder = 70: 30 The mass ratio was mixed, and the mixture was mixed with butyl acetate so that the solid content was 30% by mass, together with 5 mmφ zirconia balls for 4 hours. Stir. It was coated on a release film and dried at 80 ° C. for 10 minutes to produce a solid electrolyte layer of the solid battery A according to Example 1.

(Preparation of negative electrode layer)
Spherical natural graphite and oxide glass (Li ₂ O: SiO ₂ : B ₂ O ₃ = 54: 11: 35, glass transition temperature: 380 ° C.) and a predetermined mass ratio (for example, spherical natural graphite: oxide) After mixing at a mass ratio of glass = 80: 20 (volume ratio 80:20 vol%)), the mixture and the acrylic binder were (spherical natural graphite + oxide glass): acryl binder = 70: 30 in a mass ratio. The mixture was mixed with butyl acetate so that the solid content was 30% by mass, and stirred with 5 mmφ zirconia balls for 4 hours. It was coated on a release film and dried at 80 ° C. for 10 minutes to produce a negative electrode layer of the solid battery A according to Example 1.

(Preparation of current collecting layer)
TIMCAL KS6 and oxide glass (Li ₂ O: SiO ₂ : B ₂ O ₃ = 54: 11: 35, glass transition temperature: 380 ° C.) in a predetermined mass ratio (for example, KS6: oxide glass) = 70: 30 mass ratio (volume ratio 70:30 vol%)), the mixture and the acrylic binder were mixed at a mass ratio of (KS6 + oxide glass): acrylic binder = 70: 30, The mixture was mixed with butyl acetate so that the solid content was 30% by mass, and stirred with 5 mmφ zirconia balls for 4 hours. It was coated on a release film and dried at 80 ° C. for 10 minutes to produce a current collecting layer of the solid battery A according to Example 1.

(Preparation of insulating layer)
Alumina particles (AHP300 Nippon Light Metal) and oxide glass (Li ₂ O: SiO ₂ : B ₂ O ₃ = 54: 11: 35) are mixed at a predetermined mass ratio (for example, alumina particles: oxide glass = 75: After mixing at a mass ratio of 25 (volume ratio 60:40 vol%), the mixture and the acrylic binder were mixed at a mass ratio of (alumina particles + oxide glass): acrylic binder = 70: 30, The mixture was mixed with butyl acetate so that the solid content was 30% by mass, and stirred with 5 mmφ zirconia balls for 4 hours. It was applied onto a release film and dried at 80 ° C. for 10 minutes to produce an insulating layer of the solid battery A according to Example 1.

(Preparation of protective layer)
Alumina particles (AHP300 Nippon Light Metal) and oxide glass (Li ₂ O: SiO ₂ : B ₂ O ₃ = 54: 11: 35) were used for volume fractions (volume% (vol%) shown in Table 1 below. )) After mixing at a predetermined mass ratio (for example, when the alumina particles: oxide glass = 65: 35 mass ratio (volume ratio 50:50 vol%)), the mixture and the acrylic binder are (Alumina particles + oxide glass): Acrylic binder = 70:30 mixed at a mass ratio, and the mixture was mixed with butyl acetate so that the solid content was 30% by mass, along with 5 mmφ zirconia balls, Stir for 4 hours. It was coated on a release film and dried at 80 ° C. for 10 minutes to produce a protective layer for the solid battery A according to Example 1.

(Production of solid battery)
Each positive electrode layer, buffer layer, solid electrolyte layer, negative electrode layer, current collecting layer, insulating layer and protective layer obtained above are processed into a predetermined shape, and then released from the release film, After laminating a protective layer, an insulating layer, a current collecting layer, a negative electrode layer, a solid electrolyte layer, a buffer layer, a positive electrode layer, a current collecting layer, an insulating layer and a protective layer (9 layers in total) in this order, 100 ° C. for 10 minutes The laminated structure used in Example 1 (solid battery A) was obtained by pressure bonding. Note that the stacked structure may be stacked in a bipolar type. Also, the positive electrode layer, the buffer layer, the solid electrolyte layer, the negative electrode layer, the current collecting layer, the insulating layer, and the protective layer are not all green sheets, but directly on a specific green sheet layer by printing, etc. A laminated structure may be formed.

After pressure bonding at 100 ° C. for 10 minutes, the laminated structure of the positive electrode layer, the buffer layer, the solid electrolyte layer, the negative electrode layer, the current collecting layer, the insulating layer, and the protective layer was heated at 300 ° C. for 10 hours to remove the acrylic binder. Thereafter, the laminated structure was sintered at 400 ° C. for 30 minutes.

(Preparation of terminal layer)
Ag powder (Daiken Chemical Co., Ltd.) and oxide glass (Bi-B glass ASF1096 manufactured by Asahi Glass Co., Ltd.) have a predetermined mass ratio (for example, Ag powder: oxide glass = 60: 40 mass ratio (volume ratio 50). : 50 vol%)), and the mixture and the acrylic binder were mixed at a mass ratio of (Ag powder + oxide glass): acrylic binder = 70: 30, and the mixture was mixed with terpineol as a solid content. Was mixed so as to be 50% by mass, and stirred with 5 mmφ zirconia balls for 4 hours. After coating it on a release film, the end face where the electrode was exposed was attached to the above laminated structure and sintered at 400 ° C. for 1 hour to form a terminal electrode.

Current leads were placed on the terminal layer (terminal electrode) obtained above to obtain a solid battery A according to Example 1.

<Example 2>
A solid battery B according to Example 2 was produced according to the following experimental method.

[experimental method]
(Measurement of average particle diameter (D50) of electrode particles for positive electrode)
First, an average particle diameter (D50) of lithium cobaltate (LiCoO ₂ ) manufactured by Aldrich, which is a positive electrode particle (first electrode active material) used in the solid battery B, was measured with a microtrack particle size analyzer (Nikkiso). ). The average particle diameter (D50) of lithium cobaltate (LiCoO ₂ ) was 2.5 μm.

(Measurement of average particle diameter (D50) of buffer particles)
The average particle diameter (D50) of LiCoO ₂ particles, which are buffer particles used in the solid battery A, was measured using a Microtrac particle size analyzer (Nikkiso). The average particle diameter (D50) of the LiCoO ₂ particles was 500 nm.

(Calculation of particle size ratio)
Using the measurement result of the average particle diameter (D50) of the electrode particles for positive electrodes and the measurement result of the average particle diameter (D50) of the buffer particles, the particle diameter ratio (average particle diameter of electrode particles (D50) / buffer particles) Average particle diameter (D50)) was calculated. As a calculation result, the particle size ratio was 5 (2.5 μm / 500 nm).

(Preparation of positive electrode layer)
Lithium cobaltate (LiCoO ₂ ) whose average particle diameter (D50) was measured as described above, and oxide glass (Li ₂ O: SiO ₂ : B ₂ O ₃ = 54: 11: 35, glass transition temperature: 380 ° C. ) At a predetermined mass ratio (for example, lithium cobaltate: oxide glass = 80: 20 mass ratio (volume ratio 60:40 vol%)), and then the mixture and the acrylic binder are (cobalt acid) Lithium + oxide glass): Acrylic binder = 70: 30 and mixed, and the mixture was mixed with butyl acetate so that the solid content was 30% by mass, together with 5 mmφ zirconia balls for 4 hours. Stir. It was coated on a release film and dried at 80 ° C. for 10 minutes to produce a positive electrode layer of solid battery B according to Example 2.

(Preparation of buffer layer)
LiCoO ₂ particles whose average particle diameter (D50) was measured as described above and oxide glass (Li ₂ O: SiO ₂ : B ₂ O ₃ = 54: 11: 35, glass transition temperature: 380 ° C.) After mixing at a predetermined mass ratio (for example, lithium cobalt oxide: oxide glass = 80: 20 mass ratio (volume ratio 60:40 vol%)), the mixture and the acrylic binder are combined with (lithium cobalt oxide + oxide). Glass): Acrylic binder = 70: 30 The mass ratio was mixed, and the mixture was mixed with butyl acetate so that the solid content was 30% by mass, and stirred with 5 mmφ zirconia balls for 4 hours. It was coated on a release film and dried at 80 ° C. for 10 minutes to produce a buffer layer of solid battery B according to Example 2.

The solid electrolyte layer, the negative electrode layer, the current collecting layer, the insulating layer, and the protective layer of the solid battery B according to Example 2 are the solid electrolyte layer, the negative electrode layer, the current collecting layer, the insulating layer, and the solid battery A according to Example 1. It was produced by the same method as the production method of the protective layer.

Subsequently, the solid battery B according to Example 2 was produced by the same method as the production method of the solid battery A according to Example 1, and the terminal layer of the solid battery B according to Example 2 was A solid battery B according to Example 2 was obtained in the same manner as the terminal layer of the solid battery A according to 1.

<Comparative Example 1>
The solid battery a according to Comparative Example 1 was produced by the same method as the production method of the solid battery A according to Example 1 except that the buffer layer was not produced. That is, the positive electrode layer, the solid electrolyte layer, the negative electrode layer, the current collecting layer, the insulating layer, and the protective layer of the solid battery a according to Comparative Example 1 are the positive electrode layer, the solid electrolyte layer, and the negative electrode layer of the solid battery A according to Example 1. The current collecting layer, the insulating layer, and the protective layer were produced in the same manner as the production method.

Subsequently, the solid battery a according to Comparative Example 1 was produced by the same method as the production method of the solid battery A according to Example 1, and the terminal layer of the solid battery a according to Comparative Example 1 was The solid battery A according to Comparative Example 1 was obtained in the same manner as the terminal layer of the solid battery A according to Comparative Example 1.

[Charge / discharge evaluation and results]
Charging / discharging evaluation was performed using the solid battery A, the solid battery B, and the solid battery a produced as described above. The solid battery A, the solid battery B, and the solid battery a were each produced 3 cells, and charge / discharge measurement (charge: 0.1C4.2Vcccc, discharge: 0.1C2Vcc) was performed at room temperature.

The evaluation result of charging / discharging is shown by the average value of 3 cells of each of solid battery A, solid battery B, and solid battery a. The solid battery a according to Comparative Example 1 was 101.1 mAh / g, whereas the solid battery A according to Example 1 was 143.0 mAh / g. It was confirmed that the performance of the solid battery A was greatly improved with respect to the performance of the solid battery a. Moreover, the solid battery B according to Example 2 was 135.4 mAh / g. It was confirmed that the performance of the solid battery B was greatly improved with respect to the performance of the solid battery a. In Example 1 (solid battery A) and Example 2 (solid battery B), at least one atom constituting electrode particles (first electrode active material) and buffer particles (second electrode active material or second electrode active material) Co) was used for the above, but for example, Mn, Fe, Ni. C, Si, Li, Mg, Al or Ti, or Co, Mn, Fe, Ni. Even if at least two selected from the group consisting of C, Si, Li, Mg, Al and Ti are used, charging / discharging of Example 1 (solid battery A) and Example 2 (solid battery B) described above is possible. Results similar to the evaluation results are obtained.

In the following, the present technology will be described more specifically with application examples 1 to 5.

<Application Example 1: Printed Circuit Board>
As shown in FIG. 7, the above-described solid battery can be mounted on a printed circuit board 1202 (print circuit board, hereinafter referred to as “PCB”) together with a charging circuit or the like. For example, a solid battery 1203 and an electronic circuit such as a charging circuit can be mounted on the PCB 1202 by a reflow process. A battery module 1201 in which an electronic circuit such as a solid battery 1203 and a charging circuit is mounted on a PCB 1202 is referred to as a battery module 1201. The battery module 1201 has a card type configuration as necessary, and can be configured as a portable card type mobile battery.

On the PCB 1202, a charge control IC (IntegratedIntegrCircuit) 1204, a battery protection IC 1205, and a battery remaining amount monitoring IC 1206 are also formed. The battery protection IC 1205 controls the charging / discharging operation so that the charging voltage does not become excessive at the time of charging / discharging, an overcurrent flows due to a load short circuit, and no overdischarging occurs.

A USB (Universal Serial Bus) interface 1207 is attached to the PCB 1202. The solid state battery 1203 is charged by the power supplied through the USB interface 1207. In this case, the charging operation is controlled by the charging control IC 1204. Furthermore, predetermined power (for example, a voltage of 4.2 V) is supplied to the load 1209 from the load connection terminals 1208a and 1208b attached to the PCB 1202. The remaining battery level of the solid battery 1203 is monitored by the remaining battery level monitoring IC 1206 so that a display (not shown) indicating the remaining battery level can be seen from the outside. Note that the USB interface 1207 may be used for load connection.

A specific example of the load 1209 described above is as follows.
A. Wearable devices (sports watches, watches, hearing aids, etc.)
B. IoT terminals (sensor network terminals, etc.)
C. Amusement equipment (portable game terminals, game controllers),
D. IC board embedded battery (real-time clock IC),
E. Energy harvesting equipment (storage elements for power generation elements such as solar power generation, thermoelectric power generation, vibration power generation).

<Application Example 2: Universal Credit Card>
Currently, many people carry multiple credit cards. However, there is a problem that the risk of loss, theft, etc. increases as the number of credit cards increases. Therefore, a card called a universal credit card in which functions such as a plurality of credit cards and point cards are integrated into one card has been put into practical use. 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. 8 shows an example of the configuration of the universal credit card 1301. It has a card type shape and contains an IC chip and a solid battery (not shown) according to the present technology. Further, a display 1302 that consumes less power and an operation unit such as

direction keys

1303a and 1303b are provided. Further, a charging terminal 1304 is provided on the surface of the universal credit card 1301.

For example, the user can specify a credit card or the like loaded in advance on the universal credit card 1301 by operating the

direction keys

1303a and 1303b while looking at the display 1302. When a plurality of credit cards are loaded in advance, information indicating each credit card is displayed on the display 1302, and the user can designate a desired credit card by operating the

direction keys

1303a and 1303b. After that, it can be used like a conventional credit card. Note that the above is an example, and it goes without saying that the solid battery according to the present technology can be applied to any electronic card other than the universal credit card 1301.

<Application Example 3: Wristband Electronic Device>
An example of a wearable terminal is a wristband type electronic device. Among them, the wristband type activity meter is also called a smart band, and it is possible to obtain data on human activities such as the number of steps, distance traveled, calories burned, sleep amount, heart rate, etc. just by wrapping around the wrist. It can be done. Furthermore, the acquired data can also be managed with a smartphone. Further, a mail transmission / reception function can be provided. For example, a mail notification function that notifies a user of an incoming mail by an LED (Light Emitting Diode) lamp and / or vibration is used.

9 and 10 show an example of a wristband type activity meter that measures, for example, a pulse. FIG. 9 shows an example of the external configuration of the wristband type activity meter 1501. FIG. 10 shows a configuration example of the main body 1502 of the wristband type activity meter 1501.

The wristband type activity meter 1501 is a wristband type measuring device that measures, for example, a pulse of a subject by an optical method. As shown in FIG. 9, the wristband type active mass meter 1501 includes a main body 1502 and a band 1503, and the band 1503 is attached to the arm (wrist) 1504 of the subject like a wristwatch. And the main-body part 1502 irradiates the measurement light of a predetermined wavelength to the part containing the pulse of a test subject's arm 1504, and measures a test subject's pulse based on the intensity | strength of the returned light.

The main body 1502 is configured to include a substrate 1521, an LED 1522, a light receiving IC 1523, a light shield 1524, an operation unit 1525, an arithmetic processing unit 1526, a display unit 1527, and a wireless device 1528. The LED 1522, the light receiving IC 1523, and the light shield 1524 are provided over the substrate 1521. The LED 1522 irradiates a portion including the pulse of the arm 1504 of the subject under measurement light of a predetermined wavelength under the control of the light receiving IC 1523.

The light receiving IC 1523 receives light that has returned after the measurement light is applied to the arm 1504. The light receiving IC 1523 generates a digital measurement signal indicating the intensity of the returned light, and supplies the generated measurement signal to the arithmetic processing unit 1526.

The light shield 1524 is provided between the LED 1522 and the light receiving IC 1523 on the substrate 1521. The light shield 1524 prevents measurement light from the LED 1522 from directly entering the light receiving IC 1523.

The operation unit 1525 is composed of various operation members such as buttons and switches, and is provided on the surface of the main body 1502 or the like. The operation unit 1525 is used to operate the wristband type activity meter 1501 and supplies a signal indicating the operation content to the arithmetic processing unit 1526.

The arithmetic processing unit 1526 performs arithmetic processing for measuring the pulse of the subject based on the measurement signal supplied from the light receiving IC 1523. The arithmetic processing unit 1526 supplies the pulse measurement result to the display unit 1527 and the wireless device 1528.

The display unit 1527 is configured by a display device such as an LCD (Liquid Crystal Display), and is provided on the surface of the main body unit 1502. The display unit 1527 displays the measurement result of the subject's pulse and the like.

The wireless device 1528 transmits the measurement result of the subject's pulse to an external device by wireless communication of a predetermined method. For example, as illustrated in FIG. 10, the wireless device 1528 transmits the measurement result of the subject's pulse to the smartphone 1505 and causes the screen 1506 of the smartphone 1505 to display the measurement result. Furthermore, the measurement result data is managed by the smartphone 1505, and the measurement result can be browsed by the smartphone 1505 or stored in a server on the network. Note that any method can be adopted as a communication method of the wireless device 1528. The light receiving IC 1523 can also be used when measuring a pulse in a part other than the subject's arm 1504 (eg, finger, earlobe, etc.).

The wristband type active mass meter 1501 described above can accurately measure the pulse wave and pulse of the subject by removing the influence of body movement by the signal processing in the light receiving IC 1523. For example, even if the subject performs intense exercise such as running, the pulse wave and pulse of the subject can be accurately measured. In addition, for example, even when the subject wears the wristband type activity meter 1501 for a long time and performs measurement, the influence of the subject's body movement can be removed and the pulse wave and the pulse can be accurately measured. .

Moreover, the power consumption of the wristband type activity meter 1501 can be reduced by reducing the amount of calculation. As a result, for example, it is possible to perform measurement by wearing the wristband type activity meter 1501 on the subject for a long time without performing charging or battery replacement.

Note that, for example, a thin battery is housed in the band 1503 as a power source. The wristband type activity meter 1501 includes an electronic circuit of the main body and a battery pack. For example, the battery pack is detachable by the user. The electronic circuit is a circuit included in the main body 1502 described above. The present technology can be applied when using an all-solid battery as a battery.

FIG. 11 shows a structural example of the appearance of a wristband type electronic device 1601 (hereinafter simply referred to as “electronic device 1601”).

The electronic device 1601 is, for example, a watch-type so-called wearable device that is detachable from the human body. The electronic device 1601 includes, for example, 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 formed on the inner peripheral surface (the surface that comes into contact with the arm when the electronic device 1601 is attached).

In the use state, the electronic device 1601 is bent so that the band portion 1611 is substantially circular as shown in FIG. 11, 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. For example, the sensor according to the embodiment of the present technology is provided over the entire band portion 1611.

<Application example 4: Smart watch>
Smart watches have the same or similar appearance as existing wristwatch designs, and are worn on the user's wrist in the same way as wristwatches. Information displayed on the display is used to receive incoming calls and e-mails. A function for notifying the user of various messages such as. Further, smart watches having functions such as an electronic money function and an activity meter have been proposed. In the smart watch, a display is incorporated on the surface of the main body portion of the electronic device, and various information is displayed on the display. In addition, the smart watch can also cooperate with functions, contents, and the like of the communication terminal by performing short-range wireless communication such as Bluetooth (registered trademark) with a communication terminal (smart phone or the like).

As one of the smart watches, a plurality of segments connected in a band, a plurality of electronic components arranged in the plurality of segments, and a plurality of electronic components in the plurality of segments are connected to each other in at least one segment. A device including a flexible circuit board arranged in a meandering shape has been proposed. By having such a meandering shape, the flexible circuit board is not stressed even when the band is bent, and the circuit is prevented from being cut. In addition, it is possible to incorporate electronic circuit components in the band-side segment attached to the watch body instead of the chassis that makes up the watch body, eliminating the need to make changes on the watch body side. It is possible to construct a smart watch having the same design as the watch. In addition, the smart watch of this application example can perform notifications such as e-mails and incoming calls, log recording of user action history, telephone calls, and the like. In addition, the smart watch has a function as a non-contact IC card, and can perform settlement, authentication, and the like in a non-contact manner.

The smart watch of this application example has built-in circuit components that perform communication processing and notification processing in a metal band. In order to function as an electronic device while reducing the thickness of a metal band, the band is configured by connecting a plurality of segments, and a circuit board, a vibration motor, a battery, and an acceleration sensor are accommodated in each segment. Components such as circuit boards, vibration motors, batteries, and acceleration sensors in each segment are connected by a flexible printed circuit board (FPC).

Fig. 12 shows the overall structure (disassembled perspective view) of the smart watch. The band-type electronic device 2000 is a metal band attached to the watch main body 3000 and is attached to the user's arm. 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 2000 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. In this example, each of the segments 2110 to 2230 is made of metal.

(Segment internal overview)
FIG. 13 shows a part of the internal configuration of the band-type electronic apparatus 2000. For example, the inside of three

segments

2170, 2180, 2190, 2200, and 2210 is shown. In the band-type electronic device 2000, a flexible circuit board 2400 is arranged inside five continuous segments 2170 to 2210. Various electronic components are disposed in the segment 2170, and

batteries

2411 and 2421 according to the present technology are disposed in the

segments

2190 and 2210, and these components are electrically connected by the flexible circuit board 2400. A segment 2180 between the segment 2170 and the segment 2190 has a relatively small size, and the flexible circuit board 2400 in a meandering state is disposed. Inside the segment 2180, the flexible circuit board 2400 is disposed in a state of being sandwiched between waterproofing members. The inside of the segments 2170 to 2210 has a waterproof structure.

(Smart watch circuit configuration)
FIG. 14 is a block diagram showing a circuit configuration of the band-type electronic apparatus 2000. The circuit inside the band-type electronic device 2000 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.

In the band-type electronic device 2000 connected to the watch body 3000, electronic components are arranged in the three

segments

2170, 2190, and 2210. 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, 4107 is arranged in the vicinity of a slit 2173 described later of the segment 2170.

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, the NFC communication unit 4104, and the 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 2000. 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 2173 described later of the segment 2170, and notification of incoming calls or reception of e-mails is made by lighting or blinking. The display 4108 may be a type that displays characters, numbers, and the like. Vibrator 4109 is a member that vibrates segment 2170. The band-type electronic device 2000 notifies the incoming call or the reception of an e-mail by the vibration of the segment 2170 by the vibrator 4109.

The motion sensor 4110 detects the movement of the user wearing the band-type electronic device 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 band-type electronic device 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.

The segment 2190 has a built-in battery 2411, and the segment 2210 has a built-in battery 2421. The

batteries

2411 and 2421 can be configured by a solid state battery according to the present technology, and 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 2400 (FIG. 13). Although not shown in FIG. 14, the segment 2170 includes terminals for charging the

batteries

2411 and 2421. Further, electronic components other than the

batteries

2411 and 2421 may be arranged 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.

<Application Example 5: Eyeglass Type Terminal>
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. A typical example is a head-mounted display (head mounted display (HMD)).

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, the image display unit has a glasses-type configuration as shown in FIG. 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 the

image display units

5001 and 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.

Although omitted in FIG. 15, a solid battery, an acceleration sensor, a gyroscope, an electronic compass, a microphone / speaker, and the like according to the present technology are mounted on the frame 5003. Further, an image pickup apparatus is attached, and still images / moving images can be taken. In addition, a controller connected to the glasses unit via, for example, a wireless or wired interface is provided. The controller is provided with a touch sensor, various buttons, a speaker, a microphone, and the like. Furthermore, it has a linkage 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.

The present technology is not limited to the above-described embodiments, examples, and application examples, and can be changed without departing from the gist of the present technology.

In addition, since the effect of this technique should be obtained without depending on the type of the electrode reactant if it is an electrode reactant used in a solid state battery, the same effect can be obtained even if the type of the electrode reactant is changed. Can be obtained. 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 present technology may have the following configurations.
[1]
At least an electrode layer, an electrolyte layer, and a buffer layer disposed between the electrode layer and the electrolyte layer,
The electrode layer comprises electrode particles, the buffer layer comprises buffer particles;
The electrode particles contain a first electrode active material;
The buffer particles contain the second electrode active material and / or at least one atom constituting the second electrode active material;
A solid battery in which an average particle diameter (D50) of the buffer particles is smaller than an average particle diameter (D50) of the electrode particles.
[2]
The ratio of the average particle diameter (D50) of the electrode particles to the average particle diameter (D50) of the buffer particles (the average particle diameter of the electrode particles (D50) / the average particle diameter of the buffer particles (D50)) is 4 to 450 The solid battery according to [1].
[3]
The first electrode active material is Co, Mn, Fe, Ni. The solid battery according to [1] or [2], comprising at least one atom selected from the group consisting of C, Si, Li, Mg, Al and Ti.
[4]
The second electrode active material is made of Co, Mn, Fe, Ni. The solid battery according to any one of [1] to [3], including at least one atom selected from the group consisting of C, Si, Li, Mg, Al, and Ti.
[5]
The solid battery according to any one of [1] to [4], wherein the electrode layer is a positive electrode layer.
[6]
The solid battery according to any one of [1] to [4], wherein the electrode layer is a negative electrode layer.
[7]
The solid battery according to any one of [1] to [4], including the two electrode layers, each of the two electrode layers being a positive electrode layer and a negative electrode layer.
[8]
A battery pack comprising the solid battery according to any one of [1] to [7].
[9]
[1] to [7] any one of the solid state batteries,
A control unit for controlling the use state of the solid state battery;
A battery pack comprising: a switch unit that switches a use state of the solid state battery in accordance with an instruction from the control unit.
[10]
[1] to [7] any one of the solid state batteries,
A driving force conversion device that receives supply of electric power from the solid state battery and converts it into driving force of a vehicle;
A vehicle comprising: a drive unit that drives according to the drive force; and a vehicle control device.
[11]
[1] to [7] A power storage device having the solid state battery according to any one of
A power consuming device to which power is supplied from the solid state battery;
A control device for controlling power supply from the solid state battery to the power consuming device;
A power storage system comprising: a power generation device that charges the solid state battery.
[12]
[1] to [7] any one of the solid state batteries,
And a movable part to which electric power is supplied from the solid state battery.
[13]
The solid battery according to any one of [1] to [7] is provided,
An electronic device that is supplied with power from the solid state battery.

1 ... electrode layer, 2 ... buffer layer, 3 ... electrolyte layer, 4 ... electrode particles, 5 ... buffer particles, 10 ... solid battery

Claims

At least an electrode layer, an electrolyte layer, and a buffer layer disposed between the electrode layer and the electrolyte layer,
The electrode layer comprises electrode particles, the buffer layer comprises buffer particles;
The electrode particles contain a first electrode active material;
The buffer particles contain the second electrode active material and / or at least one atom constituting the second electrode active material;
A solid battery in which an average particle diameter (D50) of the buffer particles is smaller than an average particle diameter (D50) of the electrode particles.
The ratio of the average particle diameter (D50) of the electrode particles to the average particle diameter (D50) of the buffer particles (the average particle diameter of the electrode particles (D50) / the average particle diameter of the buffer particles (D50)) is 4 to 450 The solid battery according to claim 1.
The first electrode active material is Co, Mn, Fe, Ni. The solid state battery according to claim 1, comprising at least one atom selected from the group consisting of C, Si, Li, Mg, Al and Ti.
The second electrode active material is Co, Mn, Fe, Ni. The solid state battery according to claim 1, comprising at least one atom selected from the group consisting of C, Si, Li, Mg, Al and Ti.
The solid state battery according to claim 1, wherein the electrode layer is a positive electrode layer.
The solid state battery according to claim 1, wherein the electrode layer is a negative electrode layer.
The solid state battery according to claim 1, comprising two electrode layers, each of the two electrode layers being a positive electrode layer and a negative electrode layer.
A battery pack comprising the solid state battery according to claim 1.
A solid state battery according to claim 1;
A control unit for controlling the use state of the solid state battery;
A battery pack comprising: a switch unit that switches a use state of the solid state battery in accordance with an instruction from the control unit.
A solid state battery according to claim 1;
A driving force conversion device that receives supply of electric power from the solid state battery and converts it into driving force of a vehicle;
A vehicle comprising: a drive unit that drives according to the drive force; and a vehicle control device.
A power storage device having the solid state battery according to claim 1;
A power consuming device to which power is supplied from the solid state battery;
A control device for controlling power supply from the solid state battery to the power consuming device;
A power storage system comprising: a power generation device that charges the solid state battery.
A solid state battery according to claim 1;
And a movable part to which electric power is supplied from the solid state battery.
A solid battery according to claim 1 is provided,
An electronic device that is supplied with power from the solid state battery.