JP6768398B2 - Electrodes for power storage devices, power storage devices, air batteries and all-solid-state batteries - Google Patents

Description

The present invention relates to electrodes for power storage devices, power storage devices, air batteries and all-solid-state batteries.

Energy storage devices using metals with high ionization tendency such as lithium are used in many fields because they can store a large amount of energy.
Lithium is a dangerous material that easily ignites when used in the state of metallic lithium, but safety is enhanced by using graphite as the active material for the negative electrode and intercalating lithium ions between the layers of graphite, and secondary batteries. It has become possible to use it safely.
However, since intercalation is used, when graphite is used as the active material, the lithium ion occlusion has a theoretical upper limit of 372 mAh / g, which cannot be exceeded. Therefore, studies are being conducted on active materials that can occlude more lithium ions than graphite.

Examples of the negative electrode material capable of achieving a high capacity include silicon that occludes lithium ions by chemical bonding instead of intercalation between layers. The negative electrode using silicon has a large amount of lithium ions occluded and released per unit volume and has a high capacity, but when lithium ions are occluded and released, the electrode active material itself expands and contracts greatly, so that pulverization progresses. The irreversible capacity in the initial charge / discharge is large, and there is a portion on the positive electrode side that is not used for charge / discharge. There is also a problem that the charge / discharge cycle life is short.
Patent Document 1 proposes a method of using silicon oxide as a negative electrode active material as a measure for reducing the initial irreversible capacity using silicon and improving the charge / discharge cycle life. In Patent Document 1, it is confirmed that the cycle characteristics are improved because the volume expansion / contraction per unit mass of the active material can be reduced by using the silicon oxide as the negative electrode active material. On the other hand, since the oxide has low conductivity, it has a problem that the current collecting property is lowered and the irreversible capacitance in charge / discharge is large.
Patent Document 1 describes a negative electrode active material containing at least one selected from the group consisting of silicon, silicon oxide, and carbon as a negative electrode for a non-aqueous electrolyte secondary battery having a high capacity for solving such a problem. Described is a negative electrode having a layer, wherein the negative electrode is doped with lithium by contacting the negative electrode active material layer with a lithium source and performing a heat treatment in the presence of an ionic liquid. There is. According to such a negative electrode, it is possible to provide a negative electrode for a non-aqueous electrolyte secondary battery having a high capacity, and further, it is described that the manufacturing time of the negative electrode can be shortened.

Republished Patent WO 2013/183524

However, since the invention described in Patent Document 1 contains a substance that occludes lithium ions in the crystal structure such as silicon oxide and carbon, the amount of lithium ions occluded per weight is reduced, and the weight of the power storage device is reduced. The charge / discharge capacity per unit decreases. That is, it was difficult to increase the occluded amount of lithium ions by using silicon oxide, carbon, or the like.

The present invention has been made to solve the above problems, and an object of the present invention is to provide an electrode for a power storage device having a sufficiently large amount of metal ions occluded per weight.

(1) The electrode for a power storage device of the present invention is a current collector plate made of a metal having a first main surface and a second main surface opposite to the first main surface, and the first main surface and / or the first main surface. The electrode layer is composed of an electrode layer provided on two main surfaces, and the electrode layer is characterized by being composed of an active material composed of only silicon and a binder for binding the active material.

Since the electrode for the power storage device of the present invention contains only silicon as the active material, the amount of metal ions occluded per weight of the active material can be increased. Therefore, the electrode for the power storage device can be miniaturized.
Further, since the active material is bound by a binder, even if the volume of the active material changes due to the occlusion and release of metal ions, it is possible to make it difficult for the electrode layer to be separated from the current collector plate.

Further, the electrode for a power storage device of the present invention preferably has the following aspects.
(2) In the electrode for a power storage device of the present invention, it is preferable that the active material occludes the metal ions by chemically bonding with the metal ions.
Silicon, which forms an active material, can occlude metal ions by chemically bonding with metal ions.
Therefore, for example, more metal ions can be occluded than a substance such as carbon that occludes metal ions by intercalation.
The electrode for a power storage device of the present invention in which metal ions are occluded in this way can be suitably used as an electrode for a power storage device.

(3) In the electrode for a power storage device of the present invention, the metal ion is preferably an ion of an alkali metal and / or an alkaline earth metal.
Alkaline metals and alkaline earth metals have a high ionization tendency. That is, the redox potential is low. Therefore, when the active material occludes an alkali metal and an alkaline earth metal, a large amount of energy can be stored. In addition, alkaline earth metals become divalent ions, so a large amount of energy can be stored.

(4) In the electrode for a power storage device of the present invention, the metal ion is preferably lithium ion.
Lithium ion is a metal ion that has a high ionization tendency and is suitable for storing a large amount of energy.

(5) In the electrode for the power storage device of the present invention, the binder is preferably a polyimide resin.
Polyimide resin is a compound having heat resistance and strength. Therefore, when the active material is bound by a binder made of a polyimide resin, it is possible to make it difficult for the electrode layer to be peeled off from the current collector plate even if the volume of the active material changes due to the occlusion and release of metal ions.

(6) In the electrode for a power storage device of the present invention, the binder preferably contains a conductive auxiliary agent.
When the binder contains a conductive auxiliary agent, the conductivity of the electrode for the power storage device can be increased. Therefore, it is possible to efficiently collect current.

(7) In the electrode for a power storage device of the present invention, the conductive auxiliary agent is preferably carbon black.
Carbon black can ensure conductivity with a small amount. Therefore, when carbon black is a conductive auxiliary agent, the conductivity of the electrode for the power storage device can be improved.

(8) In the electrode for a power storage device of the present invention, it is preferable that the electrode layer is provided on the first main surface and the second main surface.
When the electrode layers are provided on the first and second main surfaces of the current collector plate, even if the volume of the active material changes due to the occlusion and release of metal ions, the first main surface and the first main surface of the current collector plate The rate of change in the volume of the electrode layer on the two main surfaces is the same. Therefore, it is possible to prevent the current collector plate from being warped.

(9) In the electrode for a power storage device of the present invention, the current collector plate has a plurality of through holes penetrating from the first main surface to the second main surface, and the electrode is inside the through holes. It is preferable that a layer is provided.
When the electrode layer is provided inside the through hole, the electrode layer on the first main surface side and the electrode layer on the second main surface side are connected through the through hole of the current collector plate.
Therefore, the electrode layer on the first main surface side and the electrode layer on the second main surface side are less likely to peel off, and the electrode layers on both main surfaces exert the same force on each other, so that the current collector plate is warped. Difficult to do.

(10) In the electrode for a power storage device of the present invention, the current collector plate is preferably made of austenitic stainless steel.
Austenitic stainless steel has high corrosion resistance and high elastic modulus.
Therefore, when the current collector plate is made of austenitic stainless steel, the current collector plate is resistant to corrosion and is less likely to warp or wrinkle.

(11) The electrode for a power storage device of the present invention is preferably a metal ion supply electrode for doping the positive electrode and / or the negative electrode with metal ions.
The electrode for a power storage device of the present invention can occlude a large amount of metal ions. Furthermore, since it is occluded by binding to metal ions, it is chemically stable and can safely occlude metal ions. Therefore, it can be suitably used as a metal ion supply electrode for doping the positive electrode and / or negative electrode of a power storage device such as a lithium ion secondary battery or a lithium ion capacitor with metal ions.

(12) The electrode for a power storage device of the present invention may be used as a negative electrode for an air battery.
Since the active material of the positive electrode for an air battery is air, the positive electrode is a power storage device having a compact configuration. The electrode for a power storage device of the present invention has a large amount of metal ions that can be occluded and has a large electric capacity. Therefore, the electrode for the power storage device of the present invention can be suitably used as a negative electrode for an air battery in combination with a compact positive electrode.

(13) The power storage device of the present invention is enclosed in the power storage package, a separator that separates the positive electrode, the negative electrode, the positive electrode and the negative electrode, a power storage package that houses the positive electrode, the negative electrode, and the separator. The storage device further comprises a metal ion supply electrode for doping the positive electrode and / or the negative electrode with metal ions, and the metal ion supply electrode contains metal ions. It is characterized by being a doped electrode for the power storage device of the present invention.

As described above, the electrode for a power storage device of the present invention has a large amount of metal ions that can be occluded per unit volume. Therefore, the electrode for the power storage device of the present invention can be miniaturized, and the metal ion supply source that first supplies the electrolyte necessary for the operation of the power storage device, the metal ion is consumed in the power storage device and the metal ion concentration is increased. It can be suitably used as a metal ion supply source for adjusting the concentration of the electrolytic solution when the concentration is lowered.
Further, the power storage device using the electrode for the power storage device of the present invention can also be miniaturized.

(14) The air battery of the present invention includes a positive electrode made of a conductive porous body, a negative electrode made of the electrode for a power storage device of the present invention doped with metal ions, a separator separating the positive electrode and the negative electrode, and the above. It is composed of a storage package containing a positive electrode, the negative electrode and the separator, and an organic electrolytic solution contained in the storage package, and a part of the positive electrode is exposed from the storage package.

Since an air battery uses air as an active material for a positive electrode, it is characterized by a large electric capacity. Therefore, the effect on the electric capacity is dominated by the amount of metal ions occluded at the negative electrode.
Since the electrode for the power storage device of the present invention uses silicon as an active material, the electric capacity of the battery can be efficiently increased, and the capacity of the air battery of the present invention can be increased.

(15) The air cell of the present invention is an air battery composed of an anode tank having a positive electrode made of a conductive porous body and a storage package having a cathode tank having a negative electrode, and a part of the positive electrode is made of a storage package. It is exposed, and the anode tank and the cathode tank are separated by a solid electrolyte. The anode tank contains an aqueous electrolytic solution, and the cathode tank contains an organic electrolytic solution. The negative electrode is a negative electrode made of the electrode for the power storage device of the present invention, which is doped with metal ions.

Since an air battery uses air as an active material for a positive electrode, it is characterized by a large electric capacity. Therefore, the effect on the electric capacity is dominated by the amount of metal ions occluded at the negative electrode.
Since the electrode for a power storage device of the present invention uses silicon having a large occlusion of metal ions as an active material, the electric capacity of the battery can be efficiently increased.

Further, in an air battery using an aqueous electrolytic solution and an organic electrolytic solution, metal ions of the negative electrode move to the positive electrode side with discharge, and the concentration of metal hydroxide in the aqueous electrolytic solution increases.
Therefore, such an air battery can be easily "mechanically charged" by exchanging the negative electrode or the water-based electrolytic solution.
When a metal is used for the negative electrode of the air battery, the metal generally used for the negative electrode of the air battery is a highly reactive metal, so that there is a high risk of ignition when the negative electrode is replaced.
However, when the electrode for the power storage device of the present invention is used for the negative electrode, the metal is bonded to silicon and is occluded in the electrode for the power storage device of the present invention, so that the risk of ignition can be reduced.

(16) The all-solid-state battery of the present invention includes a positive electrode, a negative electrode composed of the electrode for the power storage device of the present invention doped with metal ions, a solid electrolyte that separates the positive electrode and the negative electrode, and the positive electrode and the above. It is characterized by comprising a negative electrode and a storage package containing the solid electrolyte.

In all-solid-state batteries, metal ions move through the solid electrolyte. Since there are few substances in the solid electrolyte that inhibit the movement of metal ions, the all-solid-state battery can exhibit high performance.
When the electrode for the power storage device of the present invention is used as the negative electrode, the active material of the electrode for the power storage device of the present invention is silicon and contains metal ions at a high concentration, so that the metal ions in the electrode for the power storage device are the positive electrode. Even if it moves to the side, the silicon concentration on the surface of the electrode for the power storage device does not easily increase. In addition, all-solid-state batteries will typically be used at 30-200 ° C. That is, it will be used at a high temperature. Therefore, diffusion of metal ions is likely to occur. For these reasons, the all-solid-state battery of the present invention is unlikely to deteriorate in performance even when discharged.

In the electrode for a power storage device of the present invention, since the active material is only silicon, the amount of occlusion per weight of the active material can be increased. Therefore, the electrode for the power storage device can be miniaturized.

FIG. 1 is a perspective view schematically showing an example of an electrode for a power storage device of the present invention. FIG. 2 is an enlarged schematic view schematically showing an example of the electrode layer of the electrode for a power storage device of the present invention in an enlarged manner. FIG. 3 is a cutting diagram schematically showing an example of a cross section for cutting the current collector plate of the electrode for a power storage device along the thickness direction. FIG. 4 is a partially enlarged view showing an example of the electrode for a power storage device of the present invention with the electrode layer transparent. FIG. 5 is a cross-sectional view taken along the line AA of FIG. 6 (a) to 6 (e) are process diagrams schematically showing an example of a process of manufacturing a power storage device using the electrode for a power storage device of the present invention containing metal ions in order. FIG. 7 is a schematic view schematically showing an example of the air battery of the present invention. FIG. 8 is a schematic view schematically showing another example of the air battery of the present invention. FIG. 9 is a schematic view schematically showing an example of the all-solid-state battery of the present invention.

(Detailed description of the invention)
Hereinafter, the electrode for the power storage device of the present invention will be described with reference to the drawings, but the electrode for the power storage device of the present invention is not limited to the following description.

FIG. 1 is a perspective view schematically showing an example of an electrode for a power storage device of the present invention.
FIG. 2 is an enlarged schematic view schematically showing an example of the electrode layer of the electrode for a power storage device of the present invention in an enlarged manner.
As shown in FIG. 1, the electrode 10 for a power storage device includes a current collector plate 20 made of metal having a first main surface 21 and a second main surface 22 opposite to the first main surface 21, and a first main surface 21. It is composed of an electrode layer 30 provided on the second main surface 22 and an electrode layer 30.
Further, as shown in FIG. 2, in the electrode 10 for a power storage device, the electrode layer 30 is composed of an active material 31 made of only silicon, a binder 32 for binding the active material 31, and a conductive auxiliary agent 33.

In the electrode 10 for a power storage device, since the active material 31 is composed only of silicon, the amount of metal ions occluded per weight of the active material can be increased. Therefore, the electrode 10 for the power storage device can be miniaturized.
Further, since the active material 31 is bound by the binder 32, even if the volume of the active material changes due to the occlusion and release of metal ions, the electrode layer 30 can be made difficult to peel off from the current collector plate 20.

The average particle size of the active material 31 is not particularly limited, but is preferably 1 to 10 μm. When the average particle size of the active material 31 is 1 μm or more, the average particle size of the active material can be easily adjusted. When the average particle size of the active material 31 is 10 μm or less, the specific surface area is sufficiently large, so that the time required for doping can be shortened.

In the electrode 10 for a power storage device, the active material 31 preferably occludes metal ions by chemically bonding with metal ions.
Silicon forming the active material 31 can occlude metal ions by chemically bonding with metal ions.
Therefore, for example, more metal ions can be occluded than a substance such as carbon that occludes metal ions by intercalation.
The electrode 10 for a power storage device that occludes metal ions in this way can be suitably used as an electrode for a power storage device.

The metal ion is not particularly limited, but is preferably an ion of an alkali metal and / or an alkaline earth metal, and more preferably a lithium ion.
Alkaline metals and alkaline earth metals have a high ionization tendency. That is, the redox potential is low. Therefore, when the active material occludes alkali metal and alkaline earth metal, a large amount of energy can be stored. In addition, alkaline earth metals become divalent ions, so a large amount of energy can be stored.
In particular, lithium ion is a metal ion that has a high ionization tendency and is suitable for storing a large amount of energy.

The material of the binder 32 is not particularly limited, and examples thereof include a polyimide resin and a polyamide-imide resin. Among these, a polyimide resin is preferable.
Polyimide resin is a compound having heat resistance and strength. Therefore, when the active material 31 is bonded by the binder 32 made of the polyimide resin, even if the volume of the active material changes due to the occlusion and release of metal ions, it is difficult to peel the electrode layer 30 from the current collector plate 20. it can.

The weight ratio of the active material 31 and the binder 32 in the electrode layer 30 is preferably active material: binder = 70:30 to 90:10.

The material of the conductive auxiliary agent 33 contained in the binder 32 is not particularly limited, and examples thereof include carbon black, carbon fibers, and carbon nanotubes. Of these, it is preferably made of carbon black.
When the binder 32 contains the conductive auxiliary agent 33, the conductivity of the electrode 10 for the power storage device can be increased. Therefore, it is possible to efficiently collect current.
In particular, carbon black can ensure conductivity with a small amount. Therefore, when the carbon black is the conductive auxiliary agent 33, the conductivity of the electrode 10 for the power storage device can be further improved.

When the conductive auxiliary agent 33 is made of carbon black, its average particle size is preferably 3 to 500 nm.

In the electrode layer 30, the weight ratio of the conductive auxiliary agent 33 to the binder 32 is preferably 20 to 50%.

In the electrode 10 for a power storage device, the electrode layer 30 is provided on the first main surface 21 and the second main surface 22.
When the electrode layer 30 is provided on the first main surface 21 and the second main surface 22 of the current collector plate 20, even if the volume of the active material 31 changes due to the occlusion and release of metal ions, the current collector plate 20 The rate of change in the volume of the electrode layer 30 on the first main surface 21 and the second main surface 22 is the same. Therefore, it is possible to prevent the current collector plate 20 from being warped.
It is preferable that the weight ratio of the electrode layer 30 provided on the first main surface 21 and the electrode layer 30 provided on the second main surface 22 is the same.

The thickness of the electrode layer 30 is not particularly limited, but is preferably 5 to 50 μm.
If the thickness of the electrode layer is less than 5 μm, the amount of the active material is smaller than that of the current collector plate, so that the electric capacity is likely to decrease.
When the thickness of the electrode layer exceeds 50 μm, the size of the power storage device manufactured by using the electrode for the power storage device becomes large. In addition, the distance that the metal ions move in the electrode layer becomes long, and it takes time to charge and discharge.

The surface density of the electrode layer 30 on one side is not particularly limited, but is preferably 0.1 to 10 mg / cm ² .

In the electrode 10 for a power storage device, the thickness of the current collector plate 20 is not particularly limited, but is preferably 5 to 30 μm.
If the thickness of the current collector plate is less than 5 μm, the current collector plate is easily torn because it is too thin.
If the thickness of the current collector plate exceeds 30 μm, it is too thick, so that the size of the current collector device using the electrode for the current collector device including the current collector plate having such a thickness tends to increase.

The tensile strength of the current collector plate 20 is not particularly limited, but is preferably 300 to 1500 MPa.

In the electrode 10 for a power storage device, the material of the current collector plate 20 is not particularly limited, and examples thereof include copper, stainless steel, and precious metals.
Among these, copper or austenitic stainless steel is preferable.

Copper is easily available and has sufficient conductivity. Therefore, when the current collector plate 20 is made of copper, sufficient conductivity can be ensured.

Austenitic stainless steel is easily available, has high corrosion resistance, and has a high elastic modulus.
Therefore, when the current collector plate 20 is made of austenitic stainless steel, the current collector plate 20 is resistant to corrosion and is less likely to warp or wrinkle.
Austenitic stainless steel has a high electrical resistivity. Therefore, the electrical resistivity of the current collector plate is also high. However, when the electrode 10 for the power storage device is used to dope the positive electrode and / or the negative electrode of the power storage device with metal ions, or to adjust the concentration of the electrolytic solution in the power storage device, a large current is applied to the current collector plate 20. There is no need to shed. Therefore, even if the electrical resistivity of the current collector plate is slightly high, it is possible to sufficiently dope or adjust the concentration of the electrolytic solution.

When the current collector plate 20 is made of austenitic stainless steel, the current collector plate 20 preferably contains martensitic stainless steel.
Martensitic stainless steel has high hardness. Therefore, if the current collector plate 20 contains martensitic stainless steel, the current collector plate 20 can be made hard and have high strength.
Therefore, it becomes easy to prevent the current collector plate 20 from being warped or wrinkled.

FIG. 3 is a cutting diagram schematically showing an example of a cross section for cutting the current collector plate of the electrode for a power storage device along the thickness direction.

When the current collector plate 20 is made of austenitic stainless steel and contains martensitic stainless steel, as shown in FIG. 3, the power storage device electrode 10 cuts the current collector plate 20 along the thickness direction. The martensitic stainless steel 51 is preferably interspersed in the austenitic stainless steel 52 in an island shape.
Martensitic stainless steel has high hardness but low toughness. Therefore, in the current collector plate, when the martensitic stainless steel is unevenly distributed in a part of the austenitic stainless steel, the place where the martensitic stainless steel is unevenly distributed is likely to break.
However, in the current collector plate 20, if the martensitic stainless steel 51 is scattered in the austenitic stainless steel 52 in an island shape, the current collector plate 20 is less likely to break.

The presence of martensitic stainless steel and austenitic stainless steel can be analyzed by the electron backscatter diffraction pattern measurement method (EBSD method) under the following conditions.

(Conditions of EBSD method)
<Analyzer>
EF-SEM: JSM-7000F / EBSDD: TSL Solution manufactured by JEOL Ltd.
<Analysis conditions>
Range: 14 x 36 μm
Step: 0.05 μm / step
Measurement point: 233376
Magnification: 5000 times phase: γ-iron, α-iron

When the current collector plate 20 is made of austenitic stainless steel and contains martensitic stainless steel, the martensitic stainless steel occupies the cross section of cutting the current collector plate 20 in the direction perpendicular to the thickness direction. The area is preferably 5 to 20% of the entire cross section.
When the area occupied by the martensitic stainless steel is within the above range, the current collector plate 20 is less likely to corrode and has high strength.
If the area occupied by the martensitic stainless steel is less than 5%, it becomes difficult to obtain the effect of improving the strength of the current collector plate by containing the martensitic stainless steel.
When the area occupied by martensitic stainless steel exceeds 20%, the martensitic stainless steel is easily exposed to the surface, and the martensitic stainless steel existing inside is continuously connected to the entire current collector plate. It becomes easy to corrode. In addition, since the proportion of martensitic stainless steel is large, the current collector plate is easily broken.

In the electrode 10 for a power storage device, the current collector plate 20 has a plurality of through holes penetrating from the first main surface 21 to the second main surface 22, and the electrode layer 30 is provided inside the through holes. Is preferable.
When the electrode layer 30 is provided inside the through hole, the electrode layer 30 on the first main surface 21 side and the electrode layer 30 on the second main surface 22 side are connected through the through hole of the current collector plate 20. become.
Therefore, the electrode layer 30 on the first main surface 21 side and the electrode layer 30 on the second main surface 22 side are less likely to be peeled off, and the electrode layers 30 on both main surfaces exert the same force on each other to collect current. The plate 20 is less likely to warp. The through hole may or may not be completely filled with the electrode layer, and the electrode layer may be formed so as not to completely block the through hole of the current collector plate.

The shape of the through hole is not particularly limited, but may be cylindrical, or may be tapered with a large opening and a small opening.

The case where the through hole is tapered will be described with reference to the drawings.
FIG. 4 is a partially enlarged view showing an example of the electrode for a power storage device of the present invention with the electrode layer transparent.
FIG. 5 is a cross-sectional view taken along the line AA of FIG.

As shown in FIGS. 4 and 5, in the power storage device electrode 10, the current collector plate 20 may have a plurality of through holes 40, and the through holes 40 are widened toward the first main surface 21 side. It may be composed of one tapered hole 41 and a second tapered hole 42 extending toward the second main surface 22 side. In this case, the first tapered hole 41 and the second tapered hole 42 are filled with the electrode layer 30.
If the shape of the through hole is tapered so as to spread in only one direction of the first main surface or the second main surface, when the volume of the active material changes as the metal ions are occluded and released, one of the main surfaces is used. The force associated with the volume change becomes stronger, the current collector plate tends to be distorted, and the current collector plate tends to warp.
However, as shown in FIG. 5, when the through hole 40 includes a first tapered hole 41 widened on the first main surface 21 side and a second tapered hole 42 widened on the second main surface 22 side, the active material is formed. Even if the volume changes as the metal ions are occluded and released, the force due to the volume change is dispersed. As a result, it is possible to prevent the current collector plate 20 from being distorted, and the current collector plate 20 is less likely to warp.

In the electrode 10 for a power storage device, the aperture ratio of the through hole is not particularly limited, but is preferably 1 to 20%. The opening ratio of the through hole is defined as the area of the smaller hole in both the first tapered hole and the second tapered hole as the area ratio of the opening.
If the opening ratio of the through hole is less than 1%, the bonding force between the front and back electrode layers is weakened and the electrode layer is easily peeled off.
When the opening ratio of the through hole exceeds 20%, the resistance of the current collector plate becomes high and the emission of metal ions tends to be biased.
The density of the through holes is not particularly limited, but is preferably 300 to 7,000 pieces / cm ² .

When the through hole is cylindrical, its diameter is preferably 10 to 200 μm.
When the through hole is tapered, the diameter of the large opening is preferably 20 to 200 μm, and the diameter of the small opening is preferably 10 to 100 μm.

The power storage device electrode 10 may be used as an electrode for a positive electrode or a negative electrode, or may be a metal ion supply electrode for doping the positive electrode and / or the negative electrode with metal ions.
The electrode 10 for a power storage device has a large amount of metal ions that can be occluded. Furthermore, since it is occluded by binding to metal ions, it is chemically stable and can safely occlude metal ions. Therefore, it can be suitably used as a positive electrode or a negative electrode for a power storage device such as a lithium ion secondary battery or a lithium ion capacitor, and is preferably used as a metal ion supply electrode for doping the positive electrode and / or the negative electrode with metal ions. Can be used.

Next, an example of the method for manufacturing the electrode for the power storage device of the present invention will be described.

(1) Process of manufacturing a current collector plate First, a current collector plate made of metal having a thickness of 5 to 30 μm is prepared.
The material of the current collector plate is not particularly limited, and copper, austenitic stainless steel, ferritic stainless steel, and the like can be used, and it is preferable to select the material according to the application of the electrode for the power storage device to be manufactured.

Next, a through hole is formed in the current collector plate as needed. The method for forming the through hole is not particularly limited, and the through hole may be formed by an etching method, a punching method, or a laser processing method.
Among these, the etching method is preferable. By forming through holes by an etching method, many through holes can be formed at the same time to form tapered through holes.

Since the shape, size, density, etc. of the through hole are as described above, the description thereof is omitted here.

(2) Preparation Step of Active Material Slurry A binder made of silicon and a thermosetting resin is mixed to prepare an active material slurry.

The weight ratio of the active material to the binder is not particularly limited, but it is preferable to prepare the active material: binder = 70:30 to 90:10.

The binder is not particularly limited, and examples thereof include a polyimide resin precursor and a polyamide-imide resin precursor. Among these, a polyimide resin precursor is preferable.

From the viewpoint of coatability, the viscosity of the active material slurry is preferably 1 to 10 Pa · s. The viscosity of the slurry is measured using a B-type viscometer under the condition of 1 to 10 rpm.
The viscosity of the active material slurry can be adjusted by adjusting the ratio of the active material and the binder. Further, the viscosity may be adjusted with a thickener or the like, if necessary.

(3) Coating process of active material slurry The active material slurry is applied to both main surfaces of the current collector plate.
The amount of the active material slurry to be coated is not particularly limited, but is preferably 0.1 to 10 mg / cm ² after heating and drying.

(4) Pressing process Next, the current collector plate coated with the active material slurry is pressed.
The pressing pressure is not particularly limited, but it is sufficient if the active material can be suppressed so as to be flat.

(5) Heating Step Next, the current collector plate in which the active material slurry is processed is heated to cure the binder made of the thermosetting resin contained in the active material slurry.
The heating conditions are preferably determined according to the type of binder used.
When the binder contains a polyimide resin precursor, the heating temperature is preferably 250 to 350 ° C. Further, the atmosphere at the time of heating is preferably an inert atmosphere such as a nitrogen gas atmosphere.

Through the above steps, the electrode for the power storage device of the present invention can be manufactured.

Next, a method of doping metal ions in order to use the electrode for a power storage device of the present invention as a metal ion supply electrode will be described.

(1) Organic Electrolyte Coating Step First, the organic electrolytic solution is applied to the electrode layer on one main surface side of the current collector plate of the electrode for the power storage device of the present invention.
The organic electrolytic solution is not particularly limited, but a solution in which a metal salt is dissolved as an electrolyte in an organic solvent can be used.
Examples of the organic solvent include cyclic carbonates such as propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), vinylene carbonate (VC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate ( EMC), chain carbonates such as dipropyl carbonate (DPC), aliphatic carboxylic acid esters such as methyl formate, methyl acetate, ethyl propionate, γ-lactones such as γ-butyrolactone, 1,2-diethoxy Chain ethers such as ethane (DEE) and ethoxymethoxyethane (EME), cyclic ethers such as tetrahydrofuran and 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, acetamide, dimethylformamide, acetonitrile, propylnitrile , Nitromethane, ethyl monoglyme, phosphate triester, trimethoxymethane, dioxolane derivative, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, propylene carbonate derivative, tetrahydrofuran derivative , Ethyl ether, 1,3-propanesulton, anisole, N-methylpyrrolidone, fluorinated carboxylic acid ester and other aproton organic solvents and the like.
One of these may be used alone, or two or more thereof may be mixed and used.
When lithium is used as the metal ion source as described later, the organic electrolytic solution preferably has lithium ion conductivity.
(2) Heating Step Next, the electrode layer coated with the organic electrolytic solution and the metal ion source are brought into contact with each other and heated to dope the metal ions.
The metal ion source is not particularly limited, and examples thereof include lithium, sodium, magnesium, and calcium. Of these, lithium is preferred.
The heating conditions are not particularly limited, but it is preferable to heat at 250 to 300 ° C. for 10 to 120 minutes.

(3) Drying step Doping is completed by washing the electrode for the power storage device after doping with a solvent and allowing it to dry naturally. As the solvent, DMC (dimethyl carbonate) or the like can be preferably used.

The doping method is not limited to the method of contacting with such a metal ion source, and other methods can also be used. For example, the metal ion source and the electrode for the power storage device can be connected to an external circuit and electrically doped.

Next, a method of manufacturing a power storage device using the electrode for the power storage device of the present invention containing the metal ions thus obtained will be described.
6 (a) to 6 (e) are process diagrams schematically showing an example of a process of manufacturing a power storage device using the electrode for a power storage device of the present invention containing metal ions in order.

(1) Assembling Step of Power Storage Device First, as shown in FIG. 6A, the power storage device electrode 10, the positive electrode 161 and the negative electrode 162, and the separator 163 are housed in the power storage package 164.
At this time, the separator 163 is arranged so that the electrode 10 for the power storage device, the positive electrode 161 and the negative electrode 162 are separated from each other.

The positive electrode 161 is composed of a positive electrode current collector and a positive electrode active material provided in the positive electrode current collector.
The positive electrode current collector is not particularly limited, but is preferably made of aluminum, nickel, copper, silver or an alloy thereof.
The positive electrode active material is not particularly limited, but Li MnO ₂ , Li _x Mn ₂ O ₄ (0 <x <2), Li ₂ MnO ₃ , Li _x Mn _1.5 Ni _0.5 O ₄ (0 <x <2). ) Etc. or lithium manganate having a layered structure such as); LiCoO ₂ , LiNiO ₂ or a part of these transition metals replaced with another metal; LiNi _1/3 Co _1/3 Mn Lithium transition metal oxides in which specific transition metals such as _1/3 O ₂ do not exceed half; Lithium transition metal oxides in excess of Li than the chemical composition; olivine structures such as LiFePO ₄ Examples include those that have.
In addition, some of these metal oxides are made of aluminum, iron, phosphorus, titanium, silicon, lead, tin, indium, bismuth, silver, barium, calcium, mercury, palladium, platinum, tellurium, zirconium, zinc, lantern, etc. Substituted materials can also be used. In particular, Li _α Ni _β Co _γ Al _δ O ₂ (1 ≦ α ≦ 2, β + γ + δ = 1, β ≧ 0.7, γ ≦ 0.2) or Li _α Ni _β Co _γ Mn _δ O ₂ (1 ≦ α) ≤1.2, β + γ + δ = 1, β ≥ 0.6, γ ≤ 0.2) are preferable.
As the positive electrode active material, one type may be used alone, or two or more types may be used in combination.

Activated carbon may be used for the positive electrode instead of the positive electrode active material. Activated carbon has a very large surface area, and the electrolyte forms an electric double layer on the surface and acts as a capacitor. When the electrolyte is a lithium salt, it becomes a lithium ion capacitor.

The negative electrode 162 is composed of a negative electrode current collector and a negative electrode active material provided in the negative electrode current collector.
The negative electrode current collector is not particularly limited, but is preferably made of aluminum, nickel, copper, silver, an alloy thereof, or the like.
The negative electrode active material is not particularly limited, but is preferably made of silicon, silicon monoxide, silicon dioxide, carbon or the like.

The separator 163 is not particularly limited, but a porous film such as polypropylene or polyethylene or a non-woven fabric can be used. Further, as the separator, one in which they are laminated can also be used. Further, polyimide, polyamide-imide, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), cellulose, and glass fiber having high heat resistance can also be used. It is also possible to use a woven fabric separator in which these fibers are bundled into a thread to form a woven fabric.

(2) Electrolyte Solution Injection Step Next, as shown in FIG. 6B, the electrolytic solution 165 is injected into the power storage package 164.
The electrolytic solution 165 is not particularly limited, but a solution in which a metal salt is dissolved as an electrolyte in a solvent can be used.
As the solvent, cyclic carbonates such as propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), vinylene carbonate (VC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC). ), Chain carbonates such as dipropyl carbonate (DPC), aliphatic carboxylic acid esters such as methyl formate, methyl acetate, ethyl propionate, γ-lactones such as γ-butyrolactone, 1,2-diethoxyethane (DEE), chain ethers such as ethoxymethoxyethane (EME), cyclic ethers such as tetrahydrofuran and 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, acetamide, dimethylformamide, acetonitrile, propylnitrile, Nitromethane, ethyl monoglyme, phosphate triester, trimethoxymethane, dioxolane derivative, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, propylene carbonate derivative, tetrahydrofuran derivative, Examples thereof include aprotonic organic solvents such as ethyl ether, 1,3-propanesulton, anisole, N-methylpyrrolidone, and fluorinated carboxylic acid esters.
One of these may be used alone, or two or more thereof may be mixed and used.

The metal salt is not particularly limited, but a lithium salt, a sodium salt, a calcium salt, a magnesium salt and the like can be used.
When a lithium salt is used as the metal salt, the lithium salts include LiPF ₆ , LiAsF ₆ , LiAlCl ₄ , LiClO ₄ , LiBF ₄ , LiSbF ₆ , LiCF ₃ SO ₃ , LiC ₄ F ₉ CO ₃ , LiC (CF ₃ SO). ₂ ) ₂ , LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiB ₁₀ Cl ₁₀ , lower aliphatic lithium carboxylate, lithium chloroborane, lithium tetraphenylborate, LiBr, LiI, LiSCN , LiCl, imides and the like.
One of these may be used alone, or two or more thereof may be mixed and used.

The electrolyte concentration of the electrolytic solution 165 is not particularly limited, but is preferably 0.5 to 1.5 mol / L.
If the electrolyte concentration is less than 0.5 mol / L, it becomes difficult to make the electric conductivity of the electrolytic solution sufficient.
When the electrolyte concentration exceeds 1.5 mol / L, the density and viscosity of the electrolytic solution tend to increase.

(3) Step of Dope of Metal Ion to Negative Electrode Active Material Next, as shown in FIG. 6C, the negative electrode 162 and the electrode 10 for the power storage device are electrochemically connected and occluded in the electrode 10 for the power storage device. The metal ion is transferred to the negative electrode 162.
In this step, the negative electrode 162 functions as a positive electrode, and the electrode 10 for a power storage device functions as a negative electrode.
By performing this step, metal ions are doped into the negative electrode active material of the negative electrode 162.
When the power storage device originally contains metal ions in the positive electrode or the negative electrode, the doping step is not essential, but the doping step may be performed so as to make up for the shortage of metal ions as an electrolyte. Further, the doping may be performed not only before the power storage device is completed but also at the stage when the metal ions are insufficient.
When the power storage device is a lithium ion capacitor, the positive electrode and the negative electrode do not contain metal ions, so metal ions are supplied to the inside of the power storage device so that the power storage device can operate by doping the positive electrode or the negative electrode. Will be done.

After performing the metal ion doping step on the negative electrode active material, as shown in FIG. 6D, the storage device 100 is formed by disconnecting the electrochemical connection between the negative electrode 162 and the storage device electrode 10. Can be manufactured.
The power storage device 100 manufactured in this way is also an example of the power storage device of the present invention.
That is, the power storage device 100 is enclosed in a positive electrode 161, a negative electrode 162, a separator 163 that separates the positive electrode 161 and the negative electrode 162, a power storage package 164 that houses the positive electrode 161, the negative electrode 162, and the separator 163, and a power storage package 164. The power storage device is composed of the electrolytic solution 165, and the power storage device 100 further includes an electrode 10 for the power storage device for doping the negative electrode 162 with metal ions.

The electrode 10 for a power storage device of the present invention has a large amount of metal ions that can be occluded per unit volume. Therefore, the electrode 10 for the power storage device can be miniaturized, and the metal ion supply source, which first supplies the electrolyte necessary for the operation of the power storage device, and the metal ions are consumed in the power storage device, and the metal ion concentration is lowered. It can be suitably used as a metal ion supply source for adjusting the concentration of an electrolytic solution such as when.
Further, the power storage device 100 using such a power storage device electrode 10 can also be miniaturized.

Further, as shown in FIG. 6 (e), a current can be passed by connecting the positive electrode 161 and the negative electrode 162 of the power storage device 100.

The electrode 10 for a power storage device remains inside the power storage device 100 while containing metal ions, but it is highly safe because an active metal such as lithium does not remain inside the power storage device alone.

Next, an air battery using the electrode for the power storage device of the present invention doped with metal ions as a negative electrode will be described.
In addition, such an air battery is also the air battery of the present invention.

FIG. 7 is a schematic view schematically showing an example of the air battery of the present invention.
As shown in FIG. 7, the air battery 200 includes a positive electrode 261 made of a conductive porous body, a negative electrode made of an electrode 10 for a power storage device, a separator 263 that separates the positive electrode 261 and an electrode 10 for a power storage device, and a positive electrode 261. It is composed of a power storage package 264 containing an electrode 10 for a power storage device and a separator 263 and an organic electrolytic solution 265 housed in the power storage package 264, and a part of the positive electrode 261 is exposed from the power storage package 264.

The electrode 10 for the power storage device in the air battery 200 is doped with metal ions.
Since the constituent materials and the like of the electrode 10 for the power storage device, which is the negative electrode, are as described above, the description thereof is omitted here.

The positive electrode 261 is composed of a catalyst and a porous material that supports the catalyst.
The catalyst is not particularly limited, but is preferably composed of manganese oxide, cobalt oxide, nickel oxide, iron oxide, copper oxide and the like.
The porous material is not particularly limited, but is preferably made of carbon.

The separator 263 is not particularly limited, but a porous film such as polypropylene or polyethylene or a non-woven fabric can be used. Further, as the separator, one in which they are laminated can also be used. Further, polyimide, polyamide-imide, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), cellulose, and glass fiber having high heat resistance can also be used. It is also possible to use a woven fabric separator in which these fibers are bundled into a thread to form a woven fabric.

The organic electrolytic solution 265 is not particularly limited, but a solution in which a metal salt is dissolved as an electrolyte in an organic solvent can be used.
Examples of the organic solvent include cyclic carbonates such as propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), vinylene carbonate (VC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate ( EMC), chain carbonates such as dipropyl carbonate (DPC), aliphatic carboxylic acid esters such as methyl formate, methyl acetate, ethyl propionate, γ-lactones such as γ-butyrolactone, 1,2-diethoxy Chain ethers such as ethane (DEE) and ethoxymethoxyethane (EME), cyclic ethers such as tetrahydrofuran and 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, acetamide, dimethylformamide, acetonitrile, propylnitrile , Nitromethane, ethyl monoglyme, phosphate triester, trimethoxymethane, dioxolane derivative, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, propylene carbonate derivative, tetrahydrofuran derivative , Ethyl ether, 1,3-propanesulton, anisole, N-methylpyrrolidone, fluorinated carboxylic acid ester and other aproton organic solvents and the like.
One of these may be used alone, or two or more thereof may be mixed and used.

The metal salt is not particularly limited, but a lithium salt, a sodium salt, a calcium salt, a magnesium salt and the like can be used.
When a lithium salt is used as the metal salt, the lithium salts include LiPF ₆ , LiAsF ₆ , LiAlCl ₄ , LiClO ₄ , LiBF ₄ , LiSbF ₆ , LiCF ₃ SO ₃ , LiC ₄ F ₉ CO ₃ , LiC (CF ₃ SO). ₂ ) ₂ , LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiB ₁₀ Cl ₁₀ , lower aliphatic lithium carboxylate, lithium chloroborane, lithium tetraphenylborate, LiBr, LiI, LiSCN , LiCl, imides and the like.
One of these may be used alone, or two or more thereof may be mixed and used.

The electrolyte concentration of the organic electrolyte 265 is not particularly limited, but is preferably 0.5 to 1.5 mol / L.
If the electrolyte concentration is less than 0.5 mol / L, it becomes difficult to make the electric conductivity of the electrolytic solution sufficient.
When the electrolyte concentration exceeds 1.5 mol / L, the density and viscosity of the electrolytic solution tend to increase.

Since an air battery uses air as an active material for a positive electrode, it is characterized by a large electric capacity. Therefore, the effect on the electric capacity is dominated by the amount of metal ions occluded at the negative electrode.
Since the electrode 10 for the power storage device uses silicon as the active material, the electric capacity of the air battery 200 can be efficiently increased.

Further, the air battery using the electrode 10 for the power storage device may have the following configuration.
FIG. 8 is a schematic view schematically showing another example of the air battery of the present invention.

As shown in FIG. 8, the air battery 300 is an air battery composed of a power storage package 364 having an anode tank 371 having a positive electrode 361 made of a conductive porous body and a cathode tank 372 having an electrode 10 for a power storage device which is a negative electrode. A part of the positive electrode 361 is exposed from the storage package 364, the anode tank 371 and the cathode tank 372 are separated by a solid electrolyte 363, and the anode tank 371 contains the aqueous electrolyte 365a. In the cathode tank 372, the organic electrolytic solution 365b is housed.

The electrode 10 (negative electrode) for the power storage device in the air battery 200 is doped with metal ions.
Since the constituent materials and the like of the electrode 10 for the power storage device are as described above, the description thereof is omitted here.

The structure of the positive electrode 361 made of the conductive porous body is preferably the same as that of the positive electrode 261.

The solid electrolyte 363 is not particularly limited if there is metal ion conductivity, for _example, Li 3 _N, Garnet-Type type lithium ion conductor, NASICON type lithium ion _{conductor, β-Fe 2 (SO 4} ) lithium-ion A conductor, a perovskite type lithium ion conductor, a thioLISION type lithium ion conductor, a polymer type lithium ion conductor and the like can be used.

The aqueous electrolytic solution 365a is not particularly limited, but is preferably an aqueous alkaline electrolytic solution, more preferably one in which lithium hydroxide is dissolved in water or an aqueous solvent, and further preferably an aqueous solution of lithium hydroxide. Further, the aqueous alkaline electrolytic solution may contain lithium halide, and preferred examples of lithium halide are lithium fluoride (LiF), lithium chloride (LiCl), lithium bromide (LiBr), and iodide. Examples thereof include lithium (LiI).

The organic electrolytic solution 365b is not particularly limited, but a solution in which a metal salt is dissolved as an electrolyte in an organic solvent can be used.
Examples of the organic solvent include cyclic carbonates such as propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), vinylene carbonate (VC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate ( EMC), chain carbonates such as dipropyl carbonate (DPC), aliphatic carboxylic acid esters such as methyl formate, methyl acetate, ethyl propionate, γ-lactones such as γ-butyrolactone, 1,2-diethoxy Chain ethers such as ethane (DEE) and ethoxymethoxyethane (EME), cyclic ethers such as tetrahydrofuran and 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, acetamide, dimethylformamide, acetonitrile, propylnitrile , Nitromethane, ethyl monoglyme, phosphate triester, trimethoxymethane, dioxolane derivative, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, propylene carbonate derivative, tetrahydrofuran derivative , Ethyl ether, 1,3-propanesulton, anisole, N-methylpyrrolidone, fluorinated carboxylic acid ester and other aproton organic solvents and the like.
One of these may be used alone, or two or more thereof may be mixed and used.

The metal salt is not particularly limited, but a lithium salt, a sodium salt, a calcium salt, a magnesium salt and the like can be used.
When a lithium salt is used as the metal salt, the lithium salts include LiPF ₆ , LiAsF ₆ , LiAlCl ₄ , LiClO ₄ , LiBF ₄ , LiSbF ₆ , LiCF ₃ SO ₃ , LiC ₄ F ₉ CO ₃ , LiC (CF ₃ SO). ₂ ) ₂ , LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiB ₁₀ Cl ₁₀ , lower aliphatic lithium carboxylate, lithium chloroborane, lithium tetraphenylborate, LiBr, LiI, LiSCN , LiCl, imides and the like.
One of these may be used alone, or two or more thereof may be mixed and used.

The electrolyte concentration of the organic electrolyte 365b is not particularly limited, but is preferably 0.5 to 1.5 mol / L.
If the electrolyte concentration is less than 0.5 mol / L, it becomes difficult to make the electric conductivity of the electrolytic solution sufficient.
When the electrolyte concentration exceeds 1.5 mol / L, the density and viscosity of the electrolytic solution tend to increase.

In the air battery 300 using the aqueous electrolytic solution 365a and the organic electrolytic solution 365b, the metal ions of the electrode 10 for the power storage device, which is the negative electrode, move to the positive side with the discharge, and the metal hydroxide in the aqueous electrolytic solution 365a Concentration increases.
Therefore, the air battery 300 can be easily "mechanically charged" by exchanging the electrode 10 for the power storage device or exchanging the water-based electrolytic solution 365a.
When a metal is used for the negative electrode of the air battery, the metal generally used for the negative electrode of the air battery is a highly reactive metal, so that there is a high risk of ignition when the negative electrode is replaced.
However, when the power storage device electrode 10 is used for the negative electrode, the metal is bonded to silicon and is occluded in the power storage device electrode 10, so that the risk of ignition can be reduced.

Next, an all-solid-state battery using the electrode for the power storage device of the present invention doped with metal ions as a negative electrode will be described.
In addition, such an all-solid-state battery is also an all-solid-state battery of the present invention.

FIG. 9 is a schematic view schematically showing an example of the all-solid-state battery of the present invention.
As shown in FIG. 9, the all-solid-state battery 400 includes a positive electrode 461, an electrode 10 for a power storage device which is a negative electrode, a solid electrolyte 463 which separates a positive electrode 461 and an electrode 10 for a power storage device, and a positive electrode 461 and a power storage device. It is composed of an electrode 10 and a storage package 464 containing a solid electrolyte 463.

The electrode 10 for the power storage device in the all-solid-state battery 400 is doped with metal ions.
Since the constituent materials and the like of the electrode 10 for the power storage device are as described above, the description thereof is omitted here.

The positive electrode 461 is composed of a positive electrode current collector and a positive electrode active material provided in the positive electrode current collector.
The positive electrode current collector is not particularly limited, but is preferably made of aluminum, nickel, copper, silver or an alloy thereof.
The positive electrode active material is not particularly limited, but Li MnO ₂ , Li _x Mn ₂ O ₄ (0 <x <2), Li ₂ MnO ₃ , Li _x Mn _1.5 Ni _0.5 O ₄ (0 <x <2). ) Etc. or lithium manganate having a layered structure such as); LiCoO ₂ , LiNiO ₂ or a part of these transition metals replaced with another metal; LiNi _1/3 Co _1/3 Mn Lithium transition metal oxides in which specific transition metals such as _1/3 O ₂ do not exceed half; Lithium transition metal oxides in excess of Li than the chemical composition; olivine structures such as LiFePO ₄ Examples include those that have.
In addition, some of these metal oxides are made of aluminum, iron, phosphorus, titanium, silicon, lead, tin, indium, bismuth, silver, barium, calcium, mercury, palladium, platinum, tellurium, zirconium, zinc, lantern, etc. Substituted materials can also be used. In particular, Li _α Ni _β Co _γ Al _δ O ₂ (1 ≦ α ≦ 2, β + γ + δ = 1, β ≧ 0.7, γ ≦ 0.2) or Li _α Ni _β Co _γ Mn _δ O ₂ (1 ≦ α) ≤1.2, β + γ + δ = 1, β ≥ 0.6, γ ≤ 0.2) are preferable.
As the positive electrode active material, one type may be used alone, or two or more types may be used in combination.

The solid electrolyte 463 is not particularly limited, but is 8Li ₂ O / 67Li ₂ S / 25P ₂ S ₅ , Li ₂ S, P ₂ S ₅ , Li ₂ S-SiS ₂ , LiI-Li ₂ S-SiS ₂ , LiI. _{-Li 2 S-P 2 S 5} , LiI-Li 2 and _S-B sulfide such as 2 _{S 3} amorphous solid _{electrolyte, Li 2 O-B 2 O} 3 -P 2 O 5, Li 2 O- Oxide-based amorphous solid electrolytes such as SiO ₂ , Li _1.3 Al _0.3 Ti _0.7 (PO ₄ ) ₃ , Li _{1 + x + y} A _x Ti _2-x Si _y P _3-y O ₁₂ (A) Can use crystalline oxides such as Al or Ga, 0 ≦ x ≦ 0.4, 0 <y ≦ 0.6).

In the all-solid-state battery 400, metal ions move in the solid electrolyte 463. Since there are few substances in the solid electrolyte 463 that inhibit the movement of metal ions, the all-solid-state battery 400 can exhibit high performance.
When the power storage device electrode 10 is used as the negative electrode, the active material of the power storage device electrode 10 is silicon. Therefore, even if the metal ions in the power storage device electrode 10 move to the positive electrode side, the surface of the power storage device electrode 10 The silicon concentration does not increase easily. In addition, the all-solid-state battery 400 will typically be used at 30-200 ° C. That is, it will be used at a high temperature. Therefore, diffusion of metal ions is likely to occur, and deterioration of performance can be prevented even when discharged.

(Example)
Examples of the present invention will be described in more detail below, but the present invention is not limited to these examples.

(Example 1)
(1) Manufacturing process of current collector plate A copper plate having a thickness of 20 μm was prepared.
The prepared copper plate was etched with a 37% aqueous solution of cupric chloride at 40 ° C. for 20 minutes to form tapered through holes.
The density of the through holes was 2500 holes / cm ² .
The diameter of the large opening of the through hole was 120 μm, and the diameter of the small opening was 60 μm.
(2) Preparation Step of Active Material Slurry Next, 7 g of silicon, 2.5 g of a polyimide resin precursor, and 0.5 g of carbon black were mixed to prepare an active material slurry.
The viscosity of the active material slurry was 10 Pa · s.

(3) Coating process of active material slurry The active material slurry was applied to both main surfaces of the current collector plate so that the amount of the active material slurry became 3 mg / cm ² after heating and drying.

(4) Pressing process The current collector plate coated with the active material slurry was pressed so that the active material became flat.

(5) Heating Step The current collector plate after press working was heated at 250 ° C. for 1 hour in a nitrogen atmosphere to cure the polyimide resin precursor contained in the active material slurry to form an electrode layer.

Through the above steps, the electrode for the power storage device according to Example 1 was manufactured.

(Example 2)
In the above (1) manufacturing process of the current collector plate, a SUS304 plate having a thickness of 20 μm is prepared instead of a copper plate having a thickness of 20 μm, and etching treatment is performed at 40 ° C. for 1 hour with a 37% ferric chloride aqueous solution. Except for the above, the electrode for the power storage device according to the second embodiment was manufactured in the same manner as the method for manufacturing the electrode for the power storage device according to the first embodiment.

(Example 3)
The electrode for the power storage device according to the third embodiment can be manufactured by doping the electrode for the power storage device according to the first embodiment with lithium ions by the following method.

(1) Organic Electrolyte Coating Step The electrode for the power storage device according to Example 1 is cut into a length × width = 37.5 × 50 mm, and 1 is applied to the electrode layer on the first main surface side of the current collector plate of the electrode for the power storage device. Apply an organic electrolyte of 0.0 mol / L LiPF ₆ / propylene carbonate (PC).

(2) Doping Step After that, a lithium foil having a length of 52 mm and a width of 52 mm is attached to the first main surface of the electrode for the power storage device, sealed with a laminate, and the Li electrode and the electrode for the power storage device are short-circuited 45. It is left in a high temperature bath at ° C. for 2 hours to dope lithium ions.

(3) Drying step The electrode for the power storage device after doping is washed with dimethyl carbonate and naturally dried.

(Example 4)
Using the power storage device electrode according to the third embodiment, the power storage device can be manufactured as follows.

(1) Assembly process of power storage device A positive electrode is prepared in which the positive electrode current collector is aluminum and the positive electrode active material is LiMnO ₂ .
Prepare a negative electrode in which the negative electrode current collector is aluminum and the negative electrode active material is carbon.
Prepare a separator made of polypropylene.

Next, as shown in FIG. 6A, the storage device electrode, the positive electrode, the negative electrode, and the separator according to the first embodiment are housed in the power storage package.
At this time, the separator is arranged so that the electrode for the power storage device, the positive electrode, and the negative electrode according to the first embodiment are separated from each other.

(2) Electrolyte Solution Injection Step Next, an electrolytic solution in which the solvent is propylene carbonate (PC) and LiPF ₆ is dissolved is prepared.
Then, the electrolytic solution is injected into the electricity storage package.

(3) Step of Dope of Metal Ion to Negative Electrode Active Material Next, the negative electrode and the electrode for the power storage device according to Example 1 were electrochemically connected and occluded in the electrode for power storage device according to Example 1. Transfer lithium ions.

The electrochemical connection between the negative electrode and the electrode for the power storage device according to the first embodiment is broken.
Through the above steps, the power storage device according to the fourth embodiment is manufactured.
Further, the electrode for the power storage device according to the first embodiment can supply lithium ions to the negative electrode active material again when the lithium ions in the power storage device are consumed and the lithium ion concentration decreases.
As a result, the concentration of the electrolytic solution can be adjusted and the concentration of lithium ions in the power storage device can be restored.

(Example 5)
The air battery can be manufactured as follows by using the electrode for the power storage device according to the third embodiment.

(1) Assembly step A positive electrode made of porous carbon carrying manganese oxide is prepared as a catalyst.
Prepare a separator made of polypropylene.
Next, as shown in FIG. 7, the positive electrode, the electrode for the power storage device according to the third embodiment, and the separator are housed in the power storage package so that a part of the positive electrode is exposed from the power storage package.

(2) Electrolyte Solution Injection Step Next, an electrolytic solution in which the solvent is propylene carbonate (PC) and LiPF ₆ is dissolved is prepared.
Then, the electrolytic solution is injected into the electricity storage package.

Through the above steps, the air battery according to the fifth embodiment is manufactured.

(Example 6)
The air battery can be manufactured as follows by using the electrode for the power storage device according to the third embodiment.

(1) Assembly step A positive electrode made of porous carbon carrying manganese oxide is prepared as a catalyst.
Preparing a solid electrolyte consisting of li ₃ N.
Next, as shown in FIG. 8, the positive electrode, the electrode for the power storage device according to the third embodiment, and the solid electrolyte are housed in the power storage package so that a part of the positive electrode is exposed from the power storage package.

(2) Electrolyte injection step A lithium hydroxide aqueous solution is prepared as an aqueous electrolytic solution.
As the organic electrolytic solution, an electrolytic solution in which the solvent is propylene carbonate (PC) and LiPF ₆ is dissolved is prepared.
Next, the aqueous electrolytic solution is injected into the positive electrode side, and the organic electrolytic solution is injected into the negative electrode side.

Through the above steps, the air battery according to the sixth embodiment is manufactured.

(Example 7)
An all-solid-state battery can be manufactured as follows by using the electrode for the power storage device according to the third embodiment.

Prepare a positive electrode in which the positive electrode current collector is aluminum and the positive electrode active material is LiMnO ₂ .
Prepare a solid electrolyte consisting of 8Li ₂ O ・ 67Li ₂ S ・ 25P ₂ S ₅ .
Next, as shown in FIG. 9, the solid electrolyte is housed in the power storage package so as to separate the positive electrode and the electrode for the power storage device according to Example 3, and the all-solid-state battery according to Example 7 is manufactured.

The electrode for the power storage device can be suitably used for doping the positive electrode and / or the negative electrode of the power storage device with metal ions.
Further, it can be suitably used as an electrode of a power storage device, an air battery and an all-solid-state battery.

10 Electrode for power storage device 20 Current collector plate 21 1st main surface 22 2nd main surface 30 Electrode layer 31 Active material 32 Binder 33 Conductive aid 40 Through hole 41 1st tapered hole 42 2nd tapered hole 51 Martensite-based stainless steel 52 Austenite-based stainless steel 100 Power storage device 161, 261, 361, 461 Positive electrode 162 Negative electrode 163, 263 Separator 164, 264, 364, 464 Power storage package 165 Electrode 200, 300 Air battery 265, 365b Organic electrolyte 363, 463 Solid electrolyte 365a Aqueous electrolyte 371 Anode tank 372 Cathode tank 400 All-solid-state battery

Claims (15)

It is composed of a current collector plate made of a metal having a first main surface and a second main surface opposite to the first main surface, and an electrode layer provided on the first main surface and / or the second main surface. ,
The electrode layer includes an active material composed of silicon alone, Ri Do and a binder for binding the active material,
The current collector plate is made of austenitic stainless steel and contains martensitic stainless steel.
In a cross section cut in the direction perpendicular to the thickness direction of the collector plate, the area occupied by the martensitic stainless steel is for an electricity storage device electrodes, wherein 5-20% der Rukoto the entire cross-section. The electrode for a power storage device according to claim 1, wherein the active material occludes the metal ions by chemically bonding with the metal ions. The electrode for a power storage device according to claim 2, wherein the metal ion is an ion of an alkali metal and / or an alkaline earth metal. The electrode for a power storage device according to claim 2 or 3, wherein the metal ion is a lithium ion. The electrode for a power storage device according to any one of claims 1 to 4, wherein the binder is a polyimide resin. The electrode for a power storage device according to any one of claims 1 to 5, wherein the binder contains a conductive auxiliary agent. The electrode for a power storage device according to claim 6, wherein the conductive auxiliary agent is carbon black. The electrode for a power storage device according to any one of claims 1 to 7, wherein the electrode layer is provided on the first main surface and the second main surface. The current collector plate has a plurality of through holes penetrating from the first main surface to the second main surface.
The electrode for a power storage device according to claim 8, wherein the electrode layer is provided inside the through hole. The electrode for a power storage device according to any one of claims 1 to 9 , wherein the electrode for the power storage device is a metal ion supply electrode for doping the positive electrode and / or the negative electrode with metal ions. The electrode for a power storage device according to any one of claims 1 to 9 , wherein the electrode for the power storage device is used as a negative electrode for an air battery. With the positive electrode
With the negative electrode
A separator that separates the positive electrode and the negative electrode,
A storage package containing the positive electrode, the negative electrode, and the separator,
A power storage device composed of an electrolytic solution enclosed in the power storage package.
The power storage device further comprises a metal ion supply electrode for doping the positive electrode and / or the negative electrode with metal ions.
The storage device according to claim 10 , wherein the metal ion supply electrode is a metal ion-doped electrode for a power storage device. A positive electrode made of a conductive porous body and
The negative electrode comprising the electrode for a power storage device according to claim 11 , which is doped with metal ions,
A separator that separates the positive electrode and the negative electrode,
A storage package containing the positive electrode, the negative electrode, and the separator,
It consists of an organic electrolyte contained in the power storage package.
An air battery characterized in that a part of the positive electrode is exposed from the power storage package. An air battery including an anode tank having a positive electrode made of a conductive porous body and a storage package having a cathode tank having a negative electrode.
A part of the positive electrode is exposed from the storage package.
The anode tank and the cathode tank are separated by a solid electrolyte.
The anode tank contains an aqueous electrolyte solution, and is contained in the anode tank.
The cathode tank contains an organic electrolytic solution and is contained.
An air battery characterized in that the negative electrode is a negative electrode composed of the electrode for a power storage device according to claim 11 , which is doped with metal ions. With the positive electrode
A negative electrode comprising the electrode for a power storage device according to any one of claims 1 to 9 doped with metal ions, and a negative electrode.
A solid electrolyte that separates the positive electrode and the negative electrode,
An all-solid-state battery comprising the positive electrode, the negative electrode, and a storage package containing the solid electrolyte.

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