WO2012043667A1

WO2012043667A1 - Capacitive storage cell and storage layer for capacitive storage cell

Info

Publication number: WO2012043667A1
Application number: PCT/JP2011/072258
Authority: WO
Inventors: 匠浅沼
Original assignee: 古河電気工業株式会社
Priority date: 2010-09-28
Filing date: 2011-09-28
Publication date: 2012-04-05
Also published as: JP5901181B2; JP2012094827A

Abstract

Provided is a thin film capacitive storage cell, which has a high capacitance and excellent strength. A capacitive storage cell of the first embodiment is provided with a first laminated base material (11) having laminated therein a first composite layer (12) wherein conductive or semiconductive first particles (12A) are embedded in an organic polymer, and a first base material (13) composed of a first conductive film or a first semiconductor film. On the first base material (13) of the first laminated base material (11), a first insulating layer (21) is provided, and on the first composite layer (12) of the first laminated base material, a second insulating layer (22) is provided. On the first insulating layer (21), a first conductive path (31), which extends in the lengthwise direction of the first laminated base material (11) (the direction toward the further side from the front of the sheet in fig. 1) is provided, and on the second insulating layer (22), a second conductive path (32) is provided such that the path extends in the lengthwise direction of the first laminated base material, and that the path is in parallel to the first conductive path (31).

Description

Capacitor-type storage battery, storage layer for capacitor-type storage battery

The present invention relates to a capacitor-type storage battery, and more particularly to a thin-film capacitor-type storage battery having a high electrostatic capacity and excellent retention characteristics, and a storage layer for a capacitor-type storage battery.

Recently, in order to prevent global warming, there is an urgent need to efficiently store and store the generated energy. As such power storage systems, applications such as secondary batteries such as nickel metal hydride batteries and lithium ion batteries, electric double layer capacitors, lithium ion capacitors, etc. that have made significant progress until reaching the theoretical energy density as storage batteries for portable devices have been attempted. ing. These power storage systems have drawbacks in that they use rare metals such as lithium and do not have high energy density and power density at the same time.

On the other hand, a capacitor (hereinafter referred to as a “thin film capacitor type storage battery”) that far exceeds the energy capacity per unit withstand voltage of the secondary battery has been invented (see, for example, International Publication No. 09/116668 pamphlet).
The thin film capacitor type storage battery described in the pamphlet of International Publication No. 09/116668 includes a first laminated substrate on which a first conductive film or a first semiconductor film and a first insulating layer are laminated, and a first laminated layer on the first insulating layer. A first conductive path extending in the longitudinal direction of the substrate, and a second conductive path extending in the longitudinal direction of the first laminated substrate on the first insulating layer and provided in parallel with the first conductive path; And a second insulating layer provided on the outer surface of each of the first conductive path and the second conductive path.

In this thin film capacitor type storage battery, power is stored according to the following principle.
When a predetermined potential difference is applied to the ends of the first conductive path and the second conductive path, a photon − is generated between the conductive film or semiconductor film disposed via the insulating layer and the electromagnetic field spread between the conductive paths, that is, photons. Phonon energy exchange takes place. For this reason, the speed of the electromagnetic energy flowing on the first conductive path and the second conductive path is slowed, and the equivalent action of increasing the electrical length, that is, the capacity of the storage battery is increased, and charges are received. The energy is excited in a band in the conductive film.

Based on this principle, the development of a transmission line capacitor type storage battery having a large capacity per unit volume is expected, and the withstand voltage of the storage battery alone is 100 V or more, and in the state where voltage or current is applied, 100 V or more is obtained. It is possible to store electricity with a large capacity up to the potential of.

• Phonons that have exchanged energy with photons lose energy due to inactivation due to thermal relaxation, so they are not suitable for long-term energy retention. As a method for preventing this, it is useful to hold the substrate in a state where the heat is not relaxed. Examples of the state in which the thermal relaxation does not occur include that the particles are in the range of 30 nm to 3000 nm, and interband excitation energy using a quantum dot structure.

When the maximum width of the particle or particle aggregate is less than 100 nm, an intrinsic electronic state is formed, and the energy of the electrons is not a continuous band structure of a bulk scale, but generates a plurality of discrete energy levels. be able to. That is, it becomes a quantum dot and a quantum effect appears.

The dense state obtained by the electromagnetic wave and surface plasmon interference is a transition from the base energy level to the high energy level in the discrete energy level obtained by the quantum effect of the quantum dots, that is, interlevel excitation. Can be. In the continuous band structure of the bulk scale, energy is relaxed in the band and it is difficult to maintain it. On the other hand, excitation between discrete energy levels can exhibit an energy holding action. In other words, even in the continuous energy order of metals, the quantum dot-like structure results in a discrete energy order, and an energy holding action can be exhibited.

In order to disperse the quantum dot-shaped particles in the conductive film or semiconductor film, it is necessary to prevent the particles from fusing together. A specific method is disclosed, for example, in JP-A-2006-89786. In these methods, in order to prevent the nanoparticles from coming into contact with each other and becoming coarse, organic polymers are combined around the nanoparticles to avoid contact with each other.

On the other hand, since surface plasmons accumulate energy due to the density of charge on the particle surface, it is important that the charge is sufficiently injected into the particle surface in order to accumulate energy at a high level. Conductivity as a film is required.

As a result of intensive studies by the present inventors based on the above situation, a quantum dot structure is formed in order to achieve both high capacity and storage performance in the thin film capacitor type storage battery, and the conductivity as the film It was found that it was necessary to be high.

In order to form a quantum dot structure due to the development of high retention characteristics, it is necessary to devise measures for preventing the particles from contacting each other, the conductivity as a film is lowered, and the capacitance is lowered. Also, if the distance between the particles is reduced for the purpose of imparting conductivity in order to improve the capacitance, the particles are fused together, resulting in particles that lose their properties as quantum dots. I understood it.

Therefore, an object of the present invention is to provide a capacitor-type storage battery having a high capacitance and high charge retention performance, and a capacitor-type storage battery storage layer.

As a result of intensive studies in view of the above problems, the present inventors have provided conductive films or semiconductor particles, or aggregates of these particles by providing a film in which conductive particles or semiconductor particles are embedded in a polymer resin. It has been found that the quantum dot structure can be maintained without being in direct contact with each other, and the capacitance can be maintained high by the presence of a high-conductivity thin film composed of a conductive film or a semiconductor film on the conductive path side of the film.

That is, the means for solving the above problems are as follows.
The capacitor-type storage battery according to the first aspect of the present invention is:
A first composite layer in which first conductive particles or first semiconductor particles are embedded in an organic polymer, and a first base material that is provided on the first composite layer and includes the first conductive film or the first semiconductor film And a first insulating layer provided on the first substrate of the first laminated substrate,
A second insulating layer provided on the first composite layer of the first laminated substrate;
A first conductive path extending in the longitudinal direction on the first insulating layer;
A second conductive path extending in a longitudinal direction on the second insulating layer and provided in parallel to the first conductive path;
It is a capacitor type storage battery having

The capacitor-type storage battery of the second aspect of the present invention is
A first base material comprising a first composite layer in which first conductive particles or first semiconductor particles are embedded in an organic polymer, and a first conductive film or a first semiconductor film provided on the first composite layer. And a first laminated base material laminated,
A first insulating layer provided on the first substrate of the first laminated substrate;
A first conductive path provided on the first insulating layer so as to extend in the longitudinal direction of the first laminated substrate;
A second conductive path extending in the longitudinal direction of the first laminated base material on the first insulating layer and provided in parallel to the first conductive path;
It is a capacitor type storage battery having

In the capacitor type storage battery of the second aspect of the present invention,
A second insulating layer continuously provided on outer surfaces of the first conductive path and the second conductive path;
A second base material composed of a second conductive film or a second semiconductor film provided on the second insulating layer, and a second conductive particle or second semiconductor particle provided on the second base material are in an organic polymer. The second composite layer embedded in this order, a second laminated base material laminated in this order,
You may have.

In the capacitor-type storage battery according to the first to second aspects of the present invention, the distance between the first conductive particles or the first semiconductor particles contained in the first composite layer is preferably 30 nm or more and 3000 nm or less.
On the other hand, in the capacitor type storage battery according to the second aspect of the present invention, the distance between the second conductive particles or the second semiconductor particles contained in the second composite layer is preferably 30 nm or more and 3000 nm or less.

In the capacitor-type storage battery according to the first to second aspects of the present invention, the surface of the first base material in contact with the first insulating layer has irregularities, and the width of the irregularities of the irregularities is not less than 30 nm and not more than 3000 nm. Is preferred.
On the other hand, in the capacitor-type storage battery according to the second aspect of the present invention, the surface of the second base material in contact with the second insulating layer has irregularities, and the width of the concave and convex portions of the irregularities is not less than 30 nm and not more than 3000 nm. preferable.

In the capacitor-type storage battery according to the first to second aspects of the present invention, when the surface of the first base material in contact with the first insulating layer has irregularities, the first insulating layer is adjacent to the first base material. It is preferable that the first adhesive layer and the second adhesive layer provided on the side farther from the surface of the first base material than the first adhesive layer are two or more layers.
On the other hand, in the capacitor-type storage battery according to the second aspect of the present invention, when the surface of the second base material in contact with the second insulating layer has irregularities, the second insulating layer is adjacent to the second base material. And a third adhesive layer provided on the side farther from the surface of the second base material than the third adhesive layer.

Here, the first adhesive layer and the third adhesive layer are preferably organic polymer layers having a storage elastic modulus in the range of 1 × 10 ⁴ Pa or more and less than 1 × 10 ⁵ Pa, The second adhesive layer and the fourth adhesive layer are preferably organic polymer layers having a storage elastic modulus of 1 × 10 ⁵ Pa or more.

The first adhesive layer and the third adhesive layer are preferably organic polymer layers having a dielectric loss tangent (tan δ) in the range of 0.1 to 1, and the second adhesive layer and the third adhesive layer The fourth adhesive layer is preferably an organic polymer layer having a tan δ of 0.5 or less.

It is preferable that the second adhesive layer is a layer formed by dispersing inorganic compound powder in a resin, or a layer formed by impregnating a porous material using a polymer resin with a resin.

Furthermore, between the 1st adhesive layer and the 2nd adhesive layer, 1st strength ensuring which prevents the unevenness | corrugation of the surface of the 1st base material from contacting the 1st conductive path and the 2nd conductive path It is preferable to have a layer, and prevent unevenness on the surface of the second base material from contacting the first conductive path and the second conductive path between the third adhesive layer and the fourth adhesive layer. It is preferable to have a second strength securing layer.

The first conductive film and the second conductive film are independently composed of Fe, Al, Co, Cr, Ni, Ag, Mg, Cu, Sn, Au, Pt, Pd, In, Ti, Ta, and C. Including at least one element selected from the group, an alloy or eutectoid composed of at least two elements selected from the group, or at least one element selected from the group, and 3 in the periodic table It is preferable to contain an alloy or a eutectoid containing at least one element selected from the group consisting of Group 14 to Group 14. In the case of Fe, Al, Co, Cr, Ni, Ag, Mg, Cu, Sn, Au, Pt, Pd, and In having conductivity alone, there is no problem even if they are formed of a single element.

The first semiconductor film and the second semiconductor film are each independently formed of nickel nitride, anatase structure titanium oxide, tin oxide mixed indium oxide, tin oxide, zirconium oxide, gallium nitride, aluminum nitride, It is preferable to contain at least one compound selected from the group consisting of silicon and carbon.
Furthermore, it is preferable to dope these compounds with an n-type or p-type transition metal, rare earth metal or nonmagnetic metal from the viewpoint of generating 50% or more excited electrons from the impurity level at room temperature.

A mode in which a plurality of rows of the first conductive paths and the second conductive paths are provided on the same surface of the first insulating layer is also preferable. The first terminal connected to the plurality of rows of first conductive paths, and the second terminal connected to the plurality of rows of second conductive paths, wherein the first terminal and the second terminal are the first terminals. The first conductive path and the second conductive path have a portion whose width becomes narrower. In this part, two sides extending in the same direction as the first conductive path have an angle of 30 ° or less. Preferably there is.

In addition, a composite layer in which conductive particles or semiconductor particles are embedded in an organic polymer, and a base material that is provided on the composite layer and includes a conductive film or a semiconductor film, What has the insulating layer provided on the base material of the laminated base material is useful as a power storage layer for capacitor-type storage batteries.

According to the present invention, a capacitor-type storage battery and a capacitor-type storage battery storage layer having high capacitance and high strength can be obtained.

It is sectional drawing in the elongate direction (width direction) which shows an example of the capacitor type storage battery which concerns on 1st Embodiment in this invention. It is sectional drawing in the elongate direction (width direction) which shows an example of the capacitor type storage battery which concerns on 2nd Embodiment in this invention. It is sectional drawing in the elongate direction (width direction) which shows an example of the capacitor type storage battery which concerns on 3rd Embodiment in this invention. It is sectional drawing in the elongate direction (width direction) which shows an example of the capacitor type storage battery which concerns on 4th Embodiment in this invention. It is sectional drawing in the elongate direction (width direction) which shows an example of the capacitor type storage battery which concerns on 5th Embodiment in this invention. It is sectional drawing in the elongate direction (width direction) which shows an example of the capacitor type storage battery which concerns on 6th Embodiment in this invention. It is a graph which shows the evaluation result in an Example.

The capacitor-type storage battery according to the first aspect of the present invention is:
A first composite layer in which first conductive particles or first semiconductor particles are embedded in an organic polymer, and a first base material that is provided on the first composite layer and includes the first conductive film or the first semiconductor film And a first insulating layer provided on the first substrate of the first laminated substrate,
A second insulating layer provided on the first composite layer of the first laminated substrate;
A first conductive path extending in the longitudinal direction on the first insulating layer;
A second conductive path extending in a longitudinal direction on the second insulating layer and provided in parallel to the first conductive path;
Have

The capacitor-type storage battery of the second aspect of the present invention is
A first base material comprising a first composite layer in which first conductive particles or first semiconductor particles are embedded in an organic polymer, and a first conductive film or a first semiconductor film provided on the first composite layer. And a first laminated base material laminated,
A first insulating layer provided on the first substrate of the first laminated substrate;
A first conductive path provided on the first insulating layer so as to extend in the longitudinal direction of the first laminated substrate;
A second conductive path extending in the longitudinal direction of the first laminated base material on the first insulating layer and provided in parallel to the first conductive path;
Have

Here, the electromagnetic wave traveling in the length direction of the conductive path generated by the current flowing through the pair of the first conductive path and the second conductive path is reduced in speed by the insulating layer in contact with the first conductive path and the second conductive path. Occurs and has a TE component and a TM component. These components are likely to interfere with electron dense waves, that is, surface plasmons in the conductive film or semiconductor film, or in the conductive particles or semiconductor particles.

In particular, when the constituent elements of the conductive film or semiconductor film are particles, the TM component and the surface plasmon are likely to interfere with the surface plasmon because the wavefront matching probability between the TM component and the surface plasmon increases. By this interference, the density wave (surface plasmon) gains energy, but due to the influence of the electric field, an electron density state is generated in the conductive film or the semiconductor film. As a result, electrons are collected in a portion where electrons are densely present. In a continuous metal / semiconductor, this collection of electrons is thermally relaxed by thermal vibration of the atomic lattice during propagation, and energy is lost.

However, metal particles / semiconductors (conductive particles / semiconductor particles; hereinafter, these particles may be collectively referred to as “particles”) are arranged at the locations where the dense waves are generated, and the particles or aggregates of the particles. By reducing the maximum width of (for example, 10 μm or less), energy is propagated at a distance that does not relax heat. Furthermore, the particles or particle aggregates having the maximum width do not come into contact with each other, and an insulating material is present between the particles, so that the waves can be returned from electromagnetic waves to electromagnetic waves. Again, energy is converted from electromagnetic waves to dense waves. By repeating this, thermal relaxation can be suppressed and charge retention performance can be improved.

On the other hand, in the present invention (capacitor-type storage battery of the first and second embodiments), as described above, the first composite layer in which the first conductive particles or the first semiconductor particles are embedded in the organic polymer, and the first composite A first laminated base material laminated with a first base material made of a first conductive film or a first semiconductor film provided on the layer; Here, in the composite layer, the conductive particles or the semiconductor particles are embedded in the organic polymer means that the conductive particles, the semiconductor particles, or the particle aggregates do not contact each other in the organic polymer. , Means included in a distributed state.

In the first composite layer, the first conductive particles or the first semiconductor particles are embedded in an insulator that is an organic polymer, and the surface (the first base material made of the first conductive film or the first semiconductor film and the first base material) TM surface and surface plasmon can be converted into energy on the contact surface), and the first substrate made of the first conductive film or the first semiconductor film has low conductivity and can inject electrons. ing.

In the present invention, “particle” means a finite unit composed of a uniform solid phase, and the solid phase is separated by a boundary in contact with another phase. For example, when an insulator (other phase) is filled around conductive particles or semiconductor particles (solid phase), a metal phase or semiconductor phase having another crystal orientation is surrounded around a metal phase having a specific crystal orientation. When it is filled, a case where an ultrathin oxide film (another layer) is formed can be mentioned. That is, the solid phase may be a single crystal, a polycrystal of the above size, or an amorphous.

In general, the boundary between the solid phase and the other phase is subject to some restrictions on the movement of electrons, unlike the bulk body, but the particles in the composite layer are in contact with the substrate made of a conductive film or a semiconductor film. Some electric charges can pass through the contact surface when the particles are in contact with the substrate.
On the other hand, propagation of coarse waves is hindered by the boundary that forms the periphery of the particles in the composite layer.

Therefore, by continuously forming the composite layer and the base material made of a conductive film or a semiconductor film, a state in which TM waves and surface plasmons are likely to occur and charge injection as the basis of the surface plasmons are simultaneously achieved.

Here, the distance between the particles of the first conductive particles or the first semiconductor particles included in the first composite layer (or between the particle aggregates) is preferably 30 nm or more and 3000 nm or less. By setting the mutual distance to 30 nm or more, energy is converted from the dense wave to the electromagnetic wave, and from the electromagnetic wave to the dense wave, and as a result, the capacity of the storage battery is increased. Moreover, in order to obtain a large capacity, it is necessary not to reduce the number of particles below a certain level. From this viewpoint, the distance between each other is preferably 3000 nm or less.

Furthermore, when the maximum width of the first conductive particles or the particles of the first semiconductor particles (or the particle aggregate thereof) included in the first composite layer is less than 100 nm, the quantum effect described below appears. .

When the maximum width is less than 100 nm, an intrinsic electronic state is formed, and the energy of electrons can generate a plurality of discrete energy levels instead of a continuous band structure of a bulk scale. That is, it becomes a quantum dot and a quantum effect appears.

In the discrete excitation state, electrons are excited in the conductor to create holes in the shell of electrons, and energy is retained in the electron hole pair state. In this state, it is electrically neutral when viewed from the outside. That is, the energy is converted from the electromagnetic energy to the electron hole pair excitation energy, and the energy holding state is different from the state where electrons are held on one side of the counter electrode and holes are held on the other side by so-called electrostatic electric field strength. .

Also, since electrons are gathered on one electrode side, positive charges (holes) are polarized and located on the other side in the range where the coupling exists. Since the probability of existence of positive heat-relaxing charges is small, neutralization is unlikely to occur, and this is effective for maintaining a strong and dense state of electrons.

In the capacitor-type storage battery according to the second aspect of the present invention, the stabilization function of power storage by the above mechanism can be utilized not only on one surface of the pair wire of the first conductive path and the second conductive path but also on the other surface. A continuous second insulating layer is provided on the outer surfaces of the first conductive path and the second conductive path, and a second base material made of the second conductive film or the second semiconductor film is formed on the second insulating layer; A second composite layer in which two conductive particles or second semiconductor particles are embedded in an organic polymer may be laminated in this order.
That is, the capacitor-type storage battery according to the second aspect of the present invention is provided on the second insulating layer and the second insulating layer that are continuously provided on the outer surfaces of the first conductive path and the second conductive path. , A second base material made of the second conductive film or the second semiconductor film, and a second composite layer provided on the second base material, wherein the second conductive particles or the second semiconductor particles are embedded in the organic polymer May have a second laminated substrate laminated in this order,

From the above, it is considered that the capacitor-type storage battery according to the first and second embodiments of the present invention is a capacitor-type storage battery having a high electrostatic capacity and high charge retention performance.

In the capacitor-type storage batteries according to the first and second aspects of the present invention, the surface of the first base material with which the first insulating layer is in contact has irregularities, and the width of the irregularities is preferably 30 nm or more and 3000 nm or less.
Moreover, in the capacitor type storage battery according to the second aspect of the present invention, when the second insulating layer and the second laminated base material are provided, the surface of the second base material in contact with the second insulating layer has unevenness, The width of the recess is preferably 30 nm or more and 3000 nm or less.

Here, in a base material made of a conductive film or a semiconductor film in contact with the insulating layer, when the surface of the base material in contact with the insulating layer has irregularities, like the particles contained in the composite layer, TM The energy of wave and surface plasmon can be converted, that is, energy is converted from dense waves to electromagnetic waves, and from electromagnetic waves to dense waves, at the concave and convex portions of the substrate made of conductive film or semiconductor film, and the capacity of the storage battery Becomes larger.

The width of the concave and convex portions corresponds to the distance between the particles contained in the composite layer, and the energy is converted from dense waves to electromagnetic waves and from electromagnetic waves to electromagnetic waves by setting the width of the concave and convex portions to 30 nm or more. As a result, the capacity of the storage battery increases. In order to obtain a large capacity, the width of the concave and convex portions is preferably 3000 nm or less.
In addition, as for the unevenness | corrugation, it is good for the convex part to be provided with the space | interval, and the width | variety of the recessed part which is the said space | interval is good in the said range.
In addition, the maximum height of the concave and convex portions is preferably 10 μm or less (30 nm or more is desirable, 10 μm or less from the viewpoint of ease of formation), the maximum width of the convex portion is 10 μm or less, and the maximum width of the concave portion is 3 μm or less. Good.

In the capacitor-type storage battery according to the first and second aspects of the present invention, when the surface of the first base that is in contact with the first insulating layer has irregularities, the first insulating layer is provided adjacent to the first base. It is good to consist of two or more layers including the 1st adhesive layer and the 2nd adhesive layer provided in the side farther from the surface of the 1st substrate than the 1st adhesive layer.
The 1st adhesive layer provided adjacent to the 1st substrate is an adhesive layer closely_contact | adhered between the unevenness | corrugations of the surface of a 1st base material, and is the surface of a 1st base material rather than a 1st adhesive layer. The second adhesive layer provided on the side far from the unevenness is such that the unevenness on the surface of the first substrate is a conductive path (in the case of the first form, the first conductive path, in the case of the second form, the first conductive path and It functions as an adhesive layer that prevents contact with the second conductive path).
As a result, it is possible to prevent the uneven portion of the first base material from coming into contact with the conductive path, and the presence of an insulator without generating a void in the concave portion of the uneven portion of the first base material (that is, the uneven portion of the uneven portion). An insulator can be interposed between them. As a result, the surface plasmon generation is stable in the unevenness of the first base material made of the first conductive film or the first semiconductor film, and energy is converted from the dense wave to the electromagnetic wave, and from the electromagnetic wave to the dense wave, The capacity of the storage battery increases.

Further, in the capacitor type storage battery of the second aspect of the present invention, when the second insulating layer and the second laminated substrate are provided, and the surface of the second substrate in contact with the second insulating layer has irregularities, The two insulating layers include a third adhesive layer provided adjacent to the second base material, and two layers including a fourth adhesive layer provided on a side farther from the surface of the second base material than the third adhesive layer. It is good to consist of the above.
The third adhesive layer provided adjacent to the second base material is an adhesive layer that is in close contact between the irregularities of the second base material, and the first conductive path and the second conductive layer are more than the third adhesive layer. The fourth adhesive layer provided on the conductive path side functions as an adhesive layer that prevents the unevenness of the second base material from coming into contact with the first conductive path and the second conductive path.
As a result, the concave and convex portions of the second base material are prevented from coming into contact with the conductive path, and an insulator is present in the concave and convex portions of the concave and convex portions of the second base material (that is, an insulator between the convex and concave portions of the concave and convex portions). Can be interposed). As a result, the surface plasmon generation is stable in the convex and concave portions of the second base material made of the second conductive film or the second semiconductor film, and energy is converted from dense waves to electromagnetic waves, and from electromagnetic waves to dense waves, The capacity of the storage battery increases.

Here, an adhesive layer (first adhesive layer, third adhesive) provided adjacent to the base material in order not to generate voids by following the unevenness of the surface of the base material made of a conductive film or a semiconductor film. Layer) and the storage elastic modulus of the adhesive layer (second adhesive layer, fourth adhesive layer) provided closer to the conductive path than the adhesive layer (first adhesive layer, third adhesive layer). It is preferable to do. Specifically, each adhesive layer (first to fourth adhesive layers) is an organic polymer layer, and the storage elastic modulus of the first adhesive layer and the third adhesive layer is 1 × 10 ⁴ Pa or more and 1 × It is preferable that the range is less than 10 ⁵ Pa, and the storage elastic modulus of the second adhesive layer and the fourth adhesive layer is 1 × 10 ⁵ Pa or more.

It is also preferable to adjust the dielectric loss tangent (tan δ) of the first adhesive layer and the third adhesive layer, and the second adhesive layer and the fourth adhesive layer. Specifically, each adhesive layer (first to fourth adhesive layers) is an organic polymer layer, and the tan δ of the first adhesive layer and the third adhesive layer is in the range of 0.1 to 1, The tan δ of the second adhesive layer and the fourth adhesive layer is preferably 0.5 or less.

Furthermore, the inorganic compound powder is dispersed in the resin so as to increase the strength of the second adhesive layer and the fourth adhesive layer and effectively prevent the unevenness of the base material (its convex part) from contacting the conductive path. It is preferable to form a layer formed by impregnating a porous material using a polymer resin with a resin.

Further, a first strength securing layer is provided between the first adhesive layer and the second adhesive layer so as to more effectively prevent the unevenness of the base material (its convex part) from contacting the conductive path. A mode in which the second strength securing layer is provided between the third adhesive layer and the fourth adhesive layer is also suitable. The first and second strength securing layers may not have adhesiveness.

Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings.

<Capacitor type storage battery>
[First Embodiment]
FIG. 1 is a cross-sectional view in the short direction (width direction) showing an example of the capacitor-type storage battery according to the first embodiment.

As shown in FIG. 1, the capacitor-type storage battery according to the first embodiment includes a first composite layer 12 in which conductive or semiconductive first particles 12A are embedded in an organic polymer, and a first conductive film. Or it has the 1st base material 13 which laminated | stacked the 1st base material 13 which consists of a 1st semiconductor film.
A first insulating layer 21 is provided on the first base material 13 of the first laminated base material 11, and a second insulating layer is provided on the first composite layer 12 of the first composite layer 12 of the first laminated base material 11. 22 is provided.
On the first insulating layer 21, there is provided a first conductive path 31 extending in the longitudinal direction of the first laminated base material 11 (in FIG. 1, the direction from the front to the back of the page), and the second insulating layer 22. On the top, a second conductive path 32 is provided so as to extend in the longitudinal direction of the first laminated substrate and to be parallel to the first conductive path 31.

Hereinafter, each member will be described.

(First composite layer)
The first composite layer 12 is composed of an organic polymer film in which conductive or semiconductive first particles 12A (first conductive particles or first semiconductor particles) are embedded in an organic polymer.
Here, “the conductive or semiconductive first particles 12A (first conductive particles or first semiconductor particles) are embedded in the organic polymer” means that the first particles 12A are covered with the organic polymer. Means that The first particles 12A may be at least partially covered with the organic polymer, but are preferably completely covered with the organic polymer.

The conductive or semiconductive first particles 12A are embedded in a state of being dispersed in the organic polymer, and are embedded as an aggregate (aggregated) particle aggregate (first particle aggregate). It may be. The first particles 12A or the first particle aggregates are present in the first composite layer 12 with an insulator that is an organic polymer interposed therebetween.

In addition, the first particles 12A (including the first particle aggregate; the same applies hereinafter) are electrically conductive from the viewpoint of easily achieving a state in which TM waves and surface plasmons are likely to occur and charge injection as a basis for the surface plasmons. It is preferably present in the first composite layer 12 so as to be unevenly distributed on the first base material 13 side made of a film or a semiconductor film, specifically on the first base material 13 surface.
The first particle 12A may be a single type of particle or a combination of two or more types.

As the composition of the conductive first particles 12A, those described in the first conductive film to be described later can be applied, and the same applies to materials that are preferably used.
As the composition of the semiconductive first particles 12A, those described in the first semiconductor film described later can be applied, and the same applies to the materials that are preferably used.

Particularly in the semiconductive first particles 12A, n-type or p-type transition metals, rare earth metals, or non-type compounds are selected from the group so that 50% or more of excited electrons are generated from the impurity level at room temperature. It is effective to dope magnetic metal.
The first particles 12A are preferably made of a material having a high carrier density, easily generating surface plasmons, and easily forming particles.

The maximum width of the first particle 12A is, for example, 10 μm or less, and as described above, from the viewpoint of exerting the quantum effect, it is more preferably 5 nm or more and 100 nm or less, and further preferably 5 nm or more and 80 nm or less. .

Here, the maximum width of the first particle 12A is an extension image of the first conductive path 31 and the second conductive path 32, that is, a cross section including the first particle 12A along the surface plasmon traveling method is imaged by AFM. This is a value obtained by observing and measuring the maximum width of 100 or more arbitrary first particles 12A included in the cross-sectional image.

The distance between the first particles 12A is preferably 30 nm or more and 3000 nm or less, more preferably 30 nm or more and 1500 nm or less, and further preferably 50 nm or more and 1000 nm or less.
The distance between the first particles 12A can be adjusted by the amount (content) embedded in the organic polymer.

Here, the distance between the first particles 12A is a cross section observed by the same method as the measurement of the particle diameter of the first particles 12A, and the shortest distance between the adjacent first particles 12A is measured at this time. This is the value when

The organic polymer is an insulator, and specifically, for example, polyolefin resin, polyamide resin, polyester resin, polyether resin, polyketone resin, polyimide resin, polyurethane resin, polysiloxane resin. , Phenolic resin, epoxy resin, acrylic resin, natural rubber, diene rubber (eg, isoprene rubber, butadiene rubber, styrene butadiene rubber, etc.), non-diene rubber (eg, butyl rubber, ethylene propylene rubber, urethane rubber, Silicone rubber, etc.). These may be thermoplastic, may be thermosetting, or may be an uncured product thereof.
The organic polymer may be a modified product such as resin or rubber, a mixture, or a copolymer.
Among these, the organic polymer is preferably a polyimide resin from the viewpoint of excellent heat resistance.
The organic polymer is preferably made of a material different from the insulator constituting the first insulating layer 21 and the second insulating layer 22.

The organic polymer is coated with a coating liquid (a mixture of the organic polymer and the first particles 12A) for forming the first composite layer 12, and is formed in advance when the first composite layer 12 is formed. From the viewpoint of dispersibility when the first particles 12A are embedded in the film, the shear elastic modulus at room temperature is preferably 1 × 10 ³ Pa or more and 1 × 10 ⁷ Pa or less, more preferably 1 × 10 6. ^{It is 3} Pa or more and 1 × 10 ⁶ Pa or less, more preferably 1 × 10 ³ Pa or more and 5 × 10 ⁶ Pa or less.
The shear modulus is a value obtained by a method defined by JIS K 6254.

The thickness of the first composite layer 12 is preferably 10 μm to 1 mm, more preferably 10 μm to 200 μm, and still more preferably 10 μm to 100 μm.

(First base material)
The 1st base material 13 consists of a 1st electrically conductive film or a 1st semiconductor film, and may be comprised with any of the electrically conductive substance and the semiconductor substance. Further, the first base material 13 is composed of a conductive material or a semiconductor material, but may be made of a film aggregated in a state where particles of the conductive material or the semiconductor material (conductive particles or semiconductor particles) are in contact with each other, It may consist of a bulk film of a conductive material or a semiconductor material.
Here, the first base material 13 (first conductive film or first semiconductor film) is integrally formed with the first particles 12A (first conductive particles or first semiconductor particles) constituting the first composite layer 12. It is good. Specifically, for example, at the interface between the first base material 13 and the first composite layer 12, the first particles 12A (the conductive material or the semiconductor material forming the first base material 13 and the first particles 12A ( The first base material 13 and the first particles 12A may be integrally formed in a state where the first conductive particles or the first semiconductor particles are bonded to each other. Thereby, an extra layer (for example, oxide layer) does not intervene between the 1st base material 13 and the 1st particle 12A of the 1st compound layer, and internal resistance falls easily.

Note that the conductivity (conductive film) means that the volume resistivity is 10 ⁻³ Ω · cm or less. Semiconductive (semiconductor film) means that the volume resistivity is more than 10 ⁻³ Ω · cm and not more than 10 ⁶ Ω · cm.

The first conductive film or the first semiconductor film is preferably a material having high carrier density and high charge mobility. Specifically, the following materials can be exemplified.
The first conductive film is not particularly limited as long as it exhibits conductivity. For example, Fe, Al, Co, Cr, Ni, Ag, Mg, Cu, Sn, Au, Pt, Pd, In, Ti, Ta And at least one element selected from the group consisting of C, and may be composed of a single element or two or more elements. When two or more elements are contained, an alloy or a eutectoid may be used. Further, there may be an alloy or a eutectoid containing at least one element selected from the above group and further containing at least one element selected from the group consisting of groups 3 to 14 of the periodic table. The alloy includes a solid solution having a solid solution limit or less. In addition, Fe, Al, Co, Cr, Ni, Ag, Mg, Cu, Sn, Au, Pt, Pd, In, Ti, Ta, and C which are electrically conductive are formed of a single element. There is no problem.
When Si-containing material is used as the first conductive film, at least one element selected from the group consisting of groups 3 to 15 of the periodic table, represented by B, Al, P, etc., is dissolved in Si. What was made into solid solution below the limit and provided electroconductivity can be used.

The first semiconductor film is not particularly limited as long as it exhibits semiconductivity, but nickel nitride, anatase structure titanium oxide, tin oxide mixed indium oxide, tin oxide, zirconium oxide, gallium nitride, aluminum It contains at least one compound selected from the group consisting of nitride, silicon, and carbon, and two or more compounds may be used in combination.

In particular, in a semiconductor, a compound selected from the above group may be doped with an n-type or p-type transition metal, rare earth metal or nonmagnetic metal so that 50% or more of excited electrons are generated from the impurity level at room temperature. It is valid.

Even if the first base material 13 is a single layer composed of either one of the first conductive film or the first semiconductor film, a multilayer in which two or more first conductive films composed of different materials are stacked. Even in the case of a multilayer in which two or more first semiconductor films made of different materials are stacked, two or more layers selected from the first conductive film and the first semiconductor film are stacked. Also good.

The thickness of the first base material 13 is preferably 20 nm or more and 30000 nm or less, and preferably 1 μm or more and 20 μm or less from the viewpoint of securing a charge amount for improving electric capacity when modularized.

The surface roughness Rz (μm) of the first substrate 13 is preferably 1 μm or more and 10 μm or less, and more preferably 2 μm or more and 5 μm or less.

The method for measuring the surface roughness Rz is as follows.
The uneven state of the surface of the first substrate 13 is measured using an atomic force microscope (AFM). From this roughness curve, according to JIS B0601-1994, a reference length is extracted in the direction of the average line, and the distance between the peak line and the valley line of the extracted part is measured in the direction of the vertical magnification of the roughness curve.

(First insulating layer, second insulating layer)
The first insulating layer 21 and the second insulating layer 22 may be formed of any of an organic insulator, an inorganic insulator, or a composite of an organic insulator and an inorganic insulator.
Examples of the organic insulator include polyester, PET (polyethylene terephthalate), PPC (polyester polycarbonate), vinylidene, polyimide, polystyrene, rubber, acrylic, and epoxy.
Examples of the inorganic insulator include metal oxides such as borosilicate glass, soda lime glass, barium titanate and strontium titanate.

In particular, it is advantageous to use a material having an effectively high dielectric constant for the first insulating layer 21 and the second insulating layer 22 in order to generate a TE component and a TM component and to add a capacitance component due to space charge distribution. Therefore, it is preferable.
The first insulating layer 21 and the second insulating layer 22 are preferably formed of an acrylic adhesive. The acrylic adhesive has high tackiness, and prevents the presence of air or the like between the conductive path and the conductive film, thereby improving the manufacturability of the capacitor.
The first insulating layer 21 and the second insulating layer 22 are preferably formed of a material different from the organic polymer constituting the first composite layer 12.

The first insulating layer 21 and the second insulating layer 22 may each be a single layer or a multilayer of two or more layers.

The thickness of the first insulating layer 21 and the second insulating layer 22 (the total thickness when two or more layers are used in an overlapping manner) is 20 nm or more and 10,000 nm or less, respectively, from the viewpoint of efficient energy exchange between electromagnetic waves and surface plasmons. preferable. With regard to the film thickness, consideration is given to withstand voltage, and it is preferable to secure the minimum thickness that can withstand the voltage suitable for the application.

(First conductive path, second conductive path)
As a composition of the 1st conductive path 31 and the 2nd conductive path 32, what was demonstrated by the 1st conductive film can be applied, and it is the same also about the material used suitably. The first conductive path 31 and the second conductive path 32 may be formed of the same material, or may be formed of different materials.

The length (width) w in the short direction of the first conductive path 31 and the second conductive path 32 is, for example, not less than 1 μm and not more than 100 mm, respectively, and the distance d between the first conductive path 31 and the second conductive path 32 (first The layer thickness of each film interposed between the conductive path 31 and the second conductive path 32 is, for example, not less than 1 μm and not more than 100 mm. The thickness (height) t of the first conductive path 31 and the second conductive path 32 is, for example, not less than 0.5 μm and not more than 10 μm, respectively. The relationship between the width w and the distance d is preferably w / d ≧ 1.5. The relationship between the width w and the height t is preferably t / w ≦ 1, and more preferably t / w ≦ 0.5.

(Production method)
The manufacturing method of the capacitor type storage battery according to the first embodiment is not particularly limited as long as it is a method capable of forming the capacitor type storage battery having the above configuration. An example of the manufacturing method will be described below.

First, an organic polymer film is formed on a base material sheet by a method such as coating, bonding, vapor deposition, plating, ion plating, CVD, thermal spraying, etc., such as a bar coating method. The first particles 12A (first conductive particles or first semiconductor particles) are physically deposited with high energy on the surface of the molecular film.
As a result, the first particles 12A deposited first are broken so that the bonds of the organic polymer are broken and embedded in the organic polymer film, so that the first composite layer 12 is formed. On the other hand, after being dispersed inside the organic polymer film, the first particles 12A exiting the organic polymer film are bonded to each other on the surface of the organic polymer film (first composite layer 12) and deposited in a film shape. As a result, the first base material 13 made of a conductive film or a semiconductor film is formed.
Here, specific examples of the method for depositing the first particles 12A with high energy include magnetron sputtering, DC sputtering, RF sputtering, and ion beam sputtering. The energy for vapor deposition is determined by, for example, the particle acceleration energy and the binding energy of the organic polymer.

In addition, the formation method of the 1st composite layer 12 and the 1st base material 13 is not restricted to this, For example, the mixture of organic polymer and 1st particle | grains 12A (1st electroconductive particle or 1st semiconductor particle) is used previously. For example, after the first composite layer 12 is formed by a technique such as coating, bonding, or thermal spraying, the first composite layer 12 is formed on the first composite layer 12 by a technique such as sputtering, vapor deposition, plating, ion plating, CVD, or thermal spraying. A method of forming the first base material 13 made of the first conductive film or the first semiconductor film may be employed.

Next, the first insulating layer 21 is formed by a technique such as coating, bonding, vapor deposition, plating, ion plating, CVD, thermal spraying or the like such as a bar coating method. Further, the first conductive path 31 is formed on the first insulating layer 21.

On the other hand, the base material sheet is peeled off from the laminate in which these films are laminated, and on the peeled surface, that is, on the surface of the first composite layer 12 (the surface opposite to the surface in contact with the first base material 13). In addition, the second insulating layer 22 is formed by a method similar to the method of forming the first insulating layer 21. Further, a second conductive path 32 is formed on the second insulating layer 22.

Through the above steps, the capacitor-type storage battery according to the first embodiment can be manufactured.

(use)
Although not shown, in the capacitor-type storage battery according to the first embodiment, the first conductive path 31 and the second conductive path 32 are exposed at one end in the longitudinal direction of the storage battery. A first terminal and a second terminal for applying a voltage to the first conductive path 31 and the second conductive path 32 are connected to the exposed portions, respectively. When a predetermined potential difference is applied to the first terminal and the second terminal, a photon − is generated between the first base material 13 and the electromagnetic field spread between the first conductive path 31 and the second conductive path 32, that is, photons. Surface plasmon is exchanged for energy storage with a large capacity. The same applies to the following embodiments.

[Second Embodiment]
FIG. 2 is a cross-sectional view in the short direction (width direction) showing an example of the capacitor-type storage battery according to the second embodiment.

As shown in FIG. 2, the capacitor-type storage battery according to the second embodiment is the surface of the first base material 13 made of the first conductive film or the first semiconductor film in the capacitor-type storage battery according to the first embodiment ( On the surface in contact with the first insulating layer 21, there are irregularities formed by the convex portions 13 A and the concave portions 13 B.

(First base material)
The unevenness on the surface of the first base material 13 is constituted by, for example, a plurality of conductive particles, semiconductor particles, or aggregated particles scattered on the surface of the first base material 13. That is, for example, the convex portions 13A constituting the irregularities are constituted by conductive particles or semiconductor particles, or aggregate particles thereof, and are constituted by particles or aggregate particles interspersed with the concave portions 13B constituting the irregularities.
Here, the conductive particles or semiconductor particles constituting the irregularities on the surface of the first base material 13 are:
What was demonstrated with the electroconductive or semiconductive 1st particle | grains 12A can be applied, and it is the same also about the material used suitably.

In addition, the unevenness | corrugation which has on the surface of the 1st base material 13 is not restricted to the said structure, You may comprise the dent provided in the surface of the 1st base material 13. FIG.

The maximum width and the maximum height of the concavo-convex convex portions 13A on the surface of the first base material 13 (in this embodiment (in this embodiment, the maximum width of conductive particles or semiconductor particles, or aggregate particles thereof) are: It is preferably 10 μm or less, more preferably 100 nm or less, and particularly preferably 80 nm or less.

Here, the maximum width and the maximum height of the convex portion 13A are an extension image of the first conductive path 31 and the second conductive path 32, that is, a cross section including the convex portion 13A along the surface plasmon traveling method is imaged by AFM. And the maximum width and the maximum height of 100 or more arbitrary convex portions 13A included in the cross-sectional image are measured.

The width of the concave-convex concave portion 13B on the surface of the first base material 13 (in this embodiment, the distance between conductive particles or semiconductor particles, or aggregate particles thereof) is 30 nm or more and 3000 nm or less, more preferably They are 30 nm or more and 1500 nm or less, More preferably, they are 50 nm or more and 1000 nm or less.

Here, the width of the concave portion 13B is a value obtained by observing the cross section by the same method as the measurement of the maximum width of the convex portion 13A and measuring the shortest distance between the adjacent convex portions 13A. Say.

(Production method)
The manufacturing method of the capacitor type storage battery according to the second embodiment is not particularly limited as long as it is a method capable of forming the capacitor type storage battery having the above configuration. An example of the manufacturing method will be described below.

First, the first composite layer 12 and the first base material 13 are formed in this order on the base material sheet in the same manner as in the first embodiment.
Next, magnetron sputtering, vapor deposition, plating, ion plating, CVD, thermal spraying are used to form irregularities of conductive particles or conductive particles on the surface of the first base material 13 (first conductive film or first semiconductor film). The conductive particles or the conductive particles are applied on the first base material 13 so as to have the unevenness of the above size by a method such as the above. Alternatively, the conductive particles or the conductive particles are deposited on the first base material 13 so as to have the unevenness of the above size by a technique such as electroplating, ion plating, CVD, or thermal spraying.
Here, the size of the unevenness by the conductive particles or conductive particles to be formed can be adjusted by optimizing the film forming conditions in the case of sputtering, or by optimizing the applied current conditions in the electrolytic plating method. .

In the case where the first substrate 13 (the first conductive film or the first semiconductor film) and the unevenness formed by the conductive particles or conductive particles formed on the surface thereof are integrally formed, the first process is performed by a series of processes using the same technique. This can be realized by changing the film forming condition of the base material 13 and the film forming condition of the unevenness by the conductive particles or the conductive particles. Of course, these may be formed by different conditions and different methods.

Next, the first insulating layer 21 is formed on the first base material 13 provided with irregularities on the surface in the same manner as in the first embodiment. However, at this time, it is beneficial to control the fluidity of the insulator to be used so that the first insulating layer 21 is interposed in the concave and convex recesses 13 B provided on the surface of the first base material 13.

Thereafter, the first conductive path 31, the second insulating layer 22, and the second conductive path 32 are sequentially formed in the same manner as in the first embodiment.

Through the above steps, the capacitor-type storage battery according to the second embodiment can be manufactured.

In addition, since it is the same as that of 1st Embodiment except having demonstrated above, description is abbreviate | omitted.

[Third Embodiment]
FIG. 3 is a cross-sectional view in the short direction (width direction) showing an example of the capacitor-type storage battery according to the third embodiment.

As shown in FIG. 3, the capacitor type storage battery according to the third embodiment is the same as the capacitor type storage battery according to the second embodiment. From the (semiconductor film) side, a first insulating layer 21 composed of three layers in which a first adhesive layer 211, a first strength securing layer 213, and a second adhesive layer 212 are laminated in this order is provided.
Although the first strength securing layer 213 is arbitrarily provided, it is ensured that the unevenness (the convex portion 13A) provided on the first base material 13 is in contact with the first conductive path 31 by increasing the strength of the insulating layer. It is preferable to provide from a viewpoint of preventing.

(First insulation layer)
The first insulating layer 21 includes at least a first adhesive layer 211 provided adjacent to the first base material 13, and a second adhesive layer 212 provided closer to the first conductive path 31 than the first adhesive layer 211. Further, a first strength securing layer 213 is provided between the first adhesive layer 211 and the second adhesive layer 212, and the first adhesive layer 211, the first strength securing layer 213, and The second adhesive layer 212 has a three-layer structure.
The first adhesive layer 211, the first strength securing layer 213, and the second adhesive layer 212 may each be composed of two or more layers.

The total thickness of the first insulating layer 21 is preferably 1000 nm or more and 30000 nm or less, and more preferably 5000 nm or more and 20000 nm or less from the viewpoint of increasing the efficiency of energy exchange between electromagnetic waves and surface plasmons and increasing the capacitance.

The first adhesive layer 211 is preferably a layer that is soft enough to follow the unevenness of the surface of the first base material 13 during pressure bonding. The second adhesive layer 212 is located between the first adhesive layer 211 and the first conductive path 31, and the first adhesive path 31 has a corner (end) and irregularities on the surface of the first base material 13. The first conductive path 31 and the first base material 13 may be harder than the first adhesive layer 211 so that the first conductive path 31 and the first base material 13 are adhered to each other while maintaining a certain distance without damaging each other. preferable. Specifically, it is preferable to adjust the storage elastic modulus, and specific physical property values thereof will be described later.

In addition, the dielectric loss tangent (tan δ) is preferably adjusted so that the first adhesive layer 211 and the second adhesive layer 212 effectively function as an insulating layer. The specific numerical value will be described later.
Hereinafter, the first adhesive layer 211, the second adhesive layer 212, and the first strength ensuring layer 213 will be described.

-First adhesive layer-
The first adhesive layer 211 is an adhesive layer that adheres following the unevenness of the surface of the first base material 13. The first adhesive layer 211 is preferably a layer that is soft enough to follow the unevenness on the surface of the first base material 13 during pressure bonding.
Specifically, when the first adhesive layer 211 is an organic polymer layer, the storage elastic modulus is preferably in the range of 1 × 10 ⁴ Pa to less than 1 × 10 ⁵ Pa, preferably 2 × 10 ⁴ Pa. The range is more preferably 9 × 10 ⁴ Pa or less, and still more preferably 3 × 10 ⁴ Pa or more and 6 × 10 ⁴ Pa or less.

In addition, the dielectric loss tangent (tan δ) of the first adhesive layer 211 is preferably in the range of 0.1 or more and 1 or less from the viewpoint of improving the adhesion with the first particle layer, and is 0.2 or more and 0.00. A range of 8 or less is more preferable, and a range of 0.3 to 0.6 is even more preferable.

For the first adhesive layer 211, for example, an acrylic adhesive, an epoxy adhesive, a silicon adhesive, a low molecular rubber adhesive, or the like can be applied.

The first adhesive layer 211 may be a single layer or a multilayer of two or more layers. The thickness of the first adhesive layer 211 (the total thickness when two or more layers are used in an overlapping manner) is preferably 500 nm or more and 20000 nm or less, respectively, from the viewpoint of closely following the unevenness of the surface of the first base material 13. 2,000 to 15000 nm is more preferable.

-Second adhesive layer-
The second adhesive layer 212 is provided closer to the first conductive path 31 than the first adhesive layer 211, and the unevenness (the convex portion 13 A) on the surface of the first base material 13 is in contact with the first conductive path 31. It is an adhesive layer that prevents Even when the first adhesive layer 211 is pressure-bonded, the first adhesive is used to reliably prevent the unevenness on the surface of the first base material 13 (the convex portion 13A) from coming into contact with the first conductive path 31. A layer having higher strength than the layer 211 is preferable.

Specifically, when the second adhesive layer 212 is an organic polymer layer, the storage elastic modulus is preferably 1 × 10 ⁵ Pa or more, and preferably 2 × 10 ⁵ Pa or more and 1 × 10 ⁷ Pa or less. The range is more preferable, and the range of 5 × 10 ⁵ Pa to 1 × 10 ⁶ Pa is more preferable.

Further, the dielectric loss tangent (tan δ) of the second adhesive layer 212 is set to 0.5 or less from the viewpoint of increasing the strength of the second adhesive layer 212 and preventing the second adhesive layer 212 from being broken by the end surface of the first conductive path 31. The range is preferably 0.05 to 0.5, and more preferably 0.1 to 0.2.

For the second adhesive layer 212, for example, a rubber adhesive such as butyl rubber, CR rubber, or CSM rubber, a polymer acrylic adhesive, or a polymer silicone adhesive can be applied. .

The second adhesive layer 212 is a layer formed by dispersing inorganic compound powder in the resin so that the first conductive path 31 and the first base material 13 can be held at a constant interval even during pressure bonding. It is preferable to form a layer formed by impregnating a porous material using a polymer resin with the resin.

As the inorganic compound powder _can be exemplified by SiO 2, MgO, ZrO ₂ and TiO ₂ or the like.
Moreover, as resin which disperse | distributes inorganic compound powder, as long as inorganic compound powder can be disperse | distributed, any, such as a thermoplastic resin, a thermosetting resin, and UV curable resin, may be sufficient. For example, acrylic resin, polycarbonate resin, polyester resin (for example, PET), alloy resin containing polycarbonate and polyester, ABS resin, AS resin, polystyrene resin, polyolefin resin, vinyl chloride resin, and fluorine resin Resin etc. can be illustrated.

The content of the inorganic compound powder in the resin is preferably 20% by mass to 85% by mass, more preferably 30% by mass to 80% by mass, and 40% by mass to 80% by mass. More preferably.

Examples of the porous material using a polymer resin include polymer resins represented by polytetrafluoroethylene (PTFE) or polyethylene (PE). In order to obtain a porous material, a foaming agent may be added.
Moreover, what was illustrated as resin which disperse | distributes inorganic compound powder | flour etc. can be suitably applied as resin impregnated to a porous material.

The second adhesive layer 212 may be a single layer or a multilayer of two or more layers. From the viewpoint of reliable insulation between the first base material 13 and the first conductive path 31, the thickness of the second adhesive layer 212 (total thickness when two or more layers are used in an overlapping manner) is 500 nm or more and 10,000 nm or less, respectively. Preferably, 1000 nm or more and 5000 nm or less are more preferable.

-Combination example of the first adhesive layer and the second adhesive layer-
A combination example of the first adhesive layer 211 and the second adhesive layer 212 is shown below.
(1) The first adhesive layer 211 is an organic polymer layer having a storage elastic modulus in the range of 1 × 10 ⁴ Pa or more and less than 1 × 10 ⁵ Pa, and the second adhesive layer 212 has a storage elastic modulus of 1 × 10. Organic polymer layer of ⁵ Pa or higher.
(2) The first adhesive layer 211 is an organic polymer layer having a dielectric loss tangent (tan δ) in the range of 0.1 to 1, and the second adhesive layer 212 has a dielectric loss tangent (tan δ) of 0.5 or less. Organic polymer layer.
(3) The first adhesive layer 211 is an organic polymer layer having a storage modulus of 1 × 10 ⁴ Pa or more and less than 1 × 10 ⁵ Pa, and the second adhesive layer 212 disperses the inorganic compound powder. Formed layer.
(4) A layer in which the first adhesive layer 211 is an organic polymer layer having a dielectric loss tangent (tan δ) in the range of 0.1 to 1, and the second adhesive layer 212 is formed by dispersing inorganic compound powder.
(5) The first adhesive layer 211 is an organic polymer layer having a storage modulus of 1 × 10 ⁴ Pa or more and less than 1 × 10 ⁵ Pa, and the second adhesive layer 212 uses a polymer resin. A layer formed by impregnating a porous material with resin.
(6) The first adhesive layer 211 is an organic polymer layer having a dielectric loss tangent (tan δ) in the range of 0.1 to 1, and the second adhesive layer 212 is a porous material using a polymer resin. Layer formed by impregnating resin.
(7) The organic polymer layer in which the first adhesive layer 211 is in the range of the storage elastic modulus 1 × 10 ⁴ Pa or more and less than 1 × 10 ⁵ Pa and the dielectric loss tangent (tan δ) is 0.1 or more and 1 or less. And the second adhesive layer 212 is an organic polymer layer having a storage modulus of 1 × 10 ⁵ Pa or more and a dielectric loss tangent (tan δ) of 0.5 or less.
(8) The organic polymer layer in which the first adhesive layer 211 is in the range of the storage elastic modulus 1 × 10 ⁴ Pa or more and less than 1 × 10 ⁵ Pa and the dielectric loss tangent (tan δ) is 0.1 or more and 1 or less. The second adhesive layer 212 is a layer formed by dispersing inorganic compound powder.
(9) The organic polymer layer in which the first adhesive layer 211 is in the range of the storage elastic modulus 1 × 10 ⁴ Pa or more and less than 1 × 10 ⁵ Pa and the dielectric loss tangent (tan δ) is 0.1 or more and 1 or less. The second adhesive layer 212 is formed by impregnating a porous material using a polymer resin with a resin.

-First strength securing layer-
The first strength securing layer 213 is disposed between the first adhesive layer 211 and the second adhesive layer 212, and the unevenness (the convex portion 13 A) on the surface of the first base material 13 is in contact with the first conductive path 31. It is a layer which prevents the above more effectively.

From the viewpoint of surely preventing the unevenness on the surface of the first base material 13 (the convex portion 13A) from coming into contact with the first conductive path 31 during the pressure bonding, the physical property values required for the first strength securing layer 213 Is the same as that required for the second adhesive layer 212. Therefore, the suitable storage elastic modulus and dielectric loss tangent (tan δ) described in the second adhesive layer 212 are also applied to the first strength securing layer 213. Applicable.

In the first strength securing layer 213, a more preferable storage elastic modulus is in the range of 2 × 10 ⁵ Pa to 1 × 10 ⁸ Pa, and more preferably 1 × 10 ⁶ Pa to 1 × 10 ⁷ Pa. It is a range. A more preferable dielectric loss tangent (tan δ) is in the range of 0.05 to 0.2, and more preferably in the range of 0.05 to 0.1.

Since the first adhesive layer 211 and the second adhesive layer 212 have adhesiveness, the first strength securing layer 213 provided between these layers is not necessarily required to have adhesiveness and has adhesiveness. It does not have to be.

As the first strength securing layer 213, a commercially available thermoplastic resin sheet can be used and is not particularly limited. For example, acrylic resin, polycarbonate resin, polyester resin (for example, PET), alloy resin containing polycarbonate and polyester, ABS resin, AS resin, polystyrene resin, polyolefin resin, vinyl chloride resin, and fluorine resin Examples of the resin sheet include resins. Even if it is obtained in the form of a sheet, it may be a non-solid material such as a thermosetting resin or a UV curable resin and cured after being applied on the insulating layer.

The first strength securing layer 213 is a layer formed by dispersing inorganic compound powder in the resin so that the first conductive path 31 and the first base material 13 can be held at a constant interval even during pressure bonding. It is preferable to form a layer formed by impregnating a porous material using a polymer resin with the resin. The layer formed by dispersing the inorganic compound powder and the layer formed by impregnating the porous material using the polymer resin with the resin are the same as those described in the second adhesive layer 212, and thus description thereof is omitted. .

The first strength ensuring layer 213 may be provided with various well-known additives and stabilizers such as an antistatic agent, an ultraviolet ray preventing agent, a plasticizer, and a lubricant on the surface. Further, in order to improve the adhesion between the first adhesive layer 211 and the second adhesive layer 212, a corona discharge treatment, a low temperature plasma treatment, an ion bombardment treatment, a chemical treatment, a solvent treatment, etc. may be performed as a pretreatment. Good.

The first strength securing layer 213 may be a single layer or a multilayer of two or more layers. From the viewpoint of thinning of the storage battery, the thickness of the first strength securing layer 213 (total thickness when two or more layers are used) is preferably 200 nm or more and 5000 nm or less, and more preferably 500 nm or more and 2000 nm or less.

(Production method)
The manufacturing method of the capacitor type storage battery according to the third embodiment of the present invention is not particularly limited as long as it is a method capable of forming the capacitor type storage battery having the above-described configuration. An example of the manufacturing method will be described below.

First, in the same manner as in the second embodiment, the first composite layer 12 and the first base material 13 provided with irregularities on the surface are formed in this order on the base material sheet.
Next, a first insulating layer 21 (a first adhesive layer 211, a first strength securing layer 213, and a second adhesive layer 212, which are separately prepared) are formed in this order on the first base material 13 having an uneven surface. A laminate composed of three layers to be laminated) is placed and pressed. At this time, it is beneficial to laminate by heating so that the first adhesive layer 211 of the first insulating layer 21 is embedded in the concave and convex recesses 13 B provided on the surface of the first base material 13.

Thereafter, the first conductive path 31, the second insulating layer 22, and the second conductive path 32 are sequentially formed in the same manner as in the second embodiment.

Through the above steps, the capacitor-type storage battery according to the third embodiment can be manufactured.

In addition, since it is the same as that of 2nd Embodiment except having demonstrated above, description is abbreviate | omitted.

[Fourth Embodiment]
FIG. 4 is a cross-sectional view in the short direction (width direction) showing an example of the capacitor-type storage battery according to the fourth embodiment.
As shown in FIG. 4, the capacitor-type storage battery according to the fourth embodiment includes a first composite layer in which conductive or semiconductive first particles 12A are embedded in an organic polymer on a base sheet 41. 12 and the 1st base material 13 which consists of a 1st electrically conductive film or a 1st semiconductor film have the 1st laminated substrate 11 laminated | stacked in this order.
A first insulating layer 21 is provided on the first substrate 13 of the first laminated substrate 11.
On the 1st insulating layer 21, the 1st conductive path 31 extended in the elongate direction (The direction which goes to the back from the near side of a paper surface in FIG. 4) of the 1st lamination | stacking base material 11 is parallel to the 1st conductive path 31. The second conductive path 32 is provided.

(Substrate sheet)
As long as the base material sheet 41 can laminate the first base material 13 made of the first conductive film or the first semiconductor film, the base material sheet 41 has any property of conductivity, semiconductivity, and insulation. Also good. If it is insulative, when the capacitor-type storage battery is wound and used, the base sheet is conductive or semiconductive between the first base 13 and the first conductive path 31 and the second conductive path 32. Can play a role in insulating.

Among the base sheet 41, the conductive sheet can be applied to the first base 13 as described in the first conductive film, and the semiconductive sheet is the first base 13 first. It can be applied as described for the semiconductor film, and as the insulating sheet, the one described for the first insulating layer 21 can be applied. The same applies to materials that are preferably used.

The thickness of the base sheet 41 is preferably 1 μm or more and 25 μm or less.
The application of the base sheet 41 is arbitrary, and the base sheet 41 may not be provided.

(Production method)
The manufacturing method of the capacitor type storage battery according to the fourth embodiment of the present invention is not particularly limited as long as it is a method capable of forming the capacitor type storage battery having the above configuration. An example of the manufacturing method will be described below.

First, the first composite layer 12, the first base material 13, and the first insulating layer 21 are formed on the base material sheet 41 in the same manner as in the first embodiment.
Next, the first conductive path 31 and the second conductive path 32 are formed on the first insulating layer 21 so as to be parallel to each other.

Through the above steps, the capacitor-type storage battery according to the fourth embodiment can be manufactured.

Except for what has been described above, the second embodiment is the same as the first embodiment, and a description thereof will be omitted.
However, in this embodiment, the thickness of the first base material 13 made of a conductive film or a semiconductor film is not particularly limited, but is preferably 20 nm or more and 30000 nm or less, and the charge amount for improving the electric capacity when modularized. From the viewpoint of ensuring the thickness, it is preferably 1 μm or more and 20 μm or less.
The thickness of the first insulating layer 21 is preferably 20 nm or more and 10000 nm or less from the viewpoint of efficiency of energy exchange between electromagnetic waves and surface plasmons. With regard to the film thickness, consideration is given to withstand voltage, and it is preferable to secure the minimum thickness that can withstand the voltage suitable for the application.

Here, the capacitor-type storage battery according to the fourth embodiment is similar to the first base material 13 described in the second embodiment, and the surface of the first base material 13 made of the first conductive film or the first semiconductor film. The surface having the projections 13A and the depressions 13B on the (surface in contact with the first insulating layer 21), the projections and depressions on the surface in the same manner as the first insulation layer 21 described in the third embodiment Three layers in which the first adhesive layer 211, the first strength securing layer 213, and the second adhesive layer 212 are laminated in this order from the first base material 13 (first conductive film or first semiconductor film) side provided with The form which provided the 1st insulating layer 21 which consists of may be sufficient.

[Fifth Embodiment]
FIG. 5 is a cross-sectional view in the short direction (width direction) showing an example of the capacitor-type storage battery according to the fifth embodiment.
As shown in FIG. 5, the capacitor-type storage battery according to the fifth embodiment is the same as that of the capacitor-type storage battery according to the fourth embodiment, on the outer surfaces of the first conductive path 31 and the second conductive path 32. 2 insulating layers 23 are provided continuously, and on the outer surface of the second insulating layer 23, a second base material 16 made of a second conductive film or a second semiconductor film, and conductive or semiconductive second particles 15A. Is provided with a second laminated substrate 14 in which the second composite layer 15 embedded in an organic polymer is laminated in this order. A substrate sheet 42 is further provided on the second composite layer 15 of the second laminated substrate 14.

Here, the second insulating layer 23 is the second insulating layer 22 described in the first embodiment, the second base material 16 is the first base material 13 described in the first embodiment, and the second composite layer 15. Can be applied to the first composite layer 12 described in the first embodiment, and the base sheet 42 can be the same as the base sheet 41 described in the fourth embodiment. It is.
However, in this embodiment, although the 2nd insulating layer 23 and the 2nd base material 16 are shown as a flat thing, it is not limited to such a shape, By the 1st conductive path 31 and the 2nd conductive path 32 It may be provided along the unevenness.

(Production method)
The manufacturing method of the capacitor type storage battery according to the fifth embodiment of the present invention is not particularly limited as long as it is a method capable of forming the capacitor type storage battery having the above-described configuration. An example of the manufacturing method will be described below.

First, after forming the first composite layer 12, the first base material 13, and the first insulating layer 21 on the base material sheet 41 in the same manner as in the fourth embodiment, on the first insulating layer 21. The first conductive path 31 and the second conductive path 32 are formed so as to be parallel to each other. This is the first laminate.

Next, on the other hand, the second composite layer 15, the second composite layer 12, the second base material 42, and the first composite layer 12, the first base material, and the first insulating layer 21 described in the first embodiment are formed. The base material 16 and the second insulating layer 23 are sequentially formed. This is the second laminate.

Next, the first stacked body and the second stacked body thus obtained are arranged so that the first insulating layer 21 of the first stacked body and the second insulating layer 23 of the second stacked body face each other. Between the 1 insulating layer 21 and the 2nd insulating layer 23, it arrange | positions so that the 1st conductive path 31 and the 2nd conductive path 32 may be parallel, and may be bonded together.

Through the above steps, the capacitor-type storage battery according to the fifth embodiment can be manufactured.

In addition, since it is the same as that of 4th Embodiment except having demonstrated above, description is abbreviate | omitted.

Here, the capacitor-type storage battery according to the fifth embodiment is similar to the first base material 13 described in the second embodiment, and the surface of the first base material 13 made of the first conductive film or the first semiconductor film. The surface having the projections 13A and the depressions 13B on the (surface in contact with the first insulating layer 21), the projections and depressions on the surface in the same manner as the first insulation layer 21 described in the third embodiment Three layers in which the first adhesive layer 211, the first strength securing layer 213, and the second adhesive layer 212 are laminated in this order from the first base material 13 (first conductive film or first semiconductor film) side provided with The form which provided the 1st insulating layer 21 which consists of may be sufficient.
In addition, the capacitor-type storage battery according to the fifth embodiment is similar to the first substrate 13 described in the second embodiment, and the surface of the second substrate 16 made of the second conductive film or the second semiconductor film. The surface having the projections and recesses 13A and the recesses 13B on the surface in contact with the second insulation layer 23, the projections and depressions on the surface, similar to the first insulation layer 21 described in the third embodiment. Three layers in which the first adhesive layer 211, the first strength securing layer 213, and the second adhesive layer 212 are laminated in this order from the second base material 16 (second conductive film or second semiconductor film) side provided with The form which provided the 2nd insulating layer 23 which consists of may be sufficient.

[Sixth Embodiment]
FIG. 6 is a cross-sectional view in the short direction (width direction) showing an example of the capacitor-type storage battery according to the sixth embodiment.
As shown in FIG. 6, the capacitor-type storage battery according to the sixth embodiment is the same as the capacitor-type storage battery according to the fifth embodiment, on the same surface of the first insulating layer 21, as shown in FIG. 6. A plurality of conductive paths 32 are alternately provided, and although not shown, a plurality of first conductive paths 31 are connected to the same first terminal, and a plurality of second conductive paths 32 are connected to the same second terminal. .

It is desirable that the width w of the first conductive path 31 and the second conductive path 32 forming a pair and the distance d therebetween satisfy the relationship of w / d ≧ 1.5. When the distance between the first conductive path 31 and the second conductive path 32 not forming a pair is s, it is desirable to satisfy s / d ≧ 1.

The first terminal and the second terminal have a portion whose width becomes narrower as they are separated from the first conductive path 31 and the second conductive path 32, and in this part, the first conductive path 31 and the second conductive path 32. Is an angle θ formed by two sides extending by 30 ° or less. Thereby, the resistance loss of the electric power in a 1st terminal and a 2nd terminal can be decreased.

The first terminal is directly connected to the first conductive path 31, but the second terminal is connected to the second conductive path 32 through a through electrode (not shown). The through electrode passes through the insulating layer provided on the first terminal and on the first conductive path 31 and the second conductive path 32. The second terminal is located on the insulating layer.

Even with the capacitor-type storage battery according to the sixth embodiment, the same effects as those of the capacitor-type storage batteries according to the first to fifth embodiments can be obtained. In particular, in the capacitor-type storage battery according to the sixth embodiment, since the number of the first conductive paths 31 and the second conductive paths 32 is increased, the capacity of the storage battery is further increased.
In the capacitor type storage battery according to the sixth embodiment, the capacitor type storage battery according to the fifth embodiment has a configuration in which a plurality of first conductive paths 31 and a plurality of second conductive paths 32 are alternately provided. In the configuration of the capacitor-type storage battery according to the first to fourth embodiments, a plurality of the first conductive paths 31 and the second conductive paths 32 may be alternately provided.

[Other Embodiments]
The capacitor-type storage battery according to the first to sixth embodiments has been described as having a sheet shape, but the sheet may be wound in a roll shape in the longitudinal direction.

<Capacitor type storage battery storage layer>
A composite layer in which conductive particles or semiconductor particles are embedded in an organic polymer, and a base material formed on the composite layer and made of a conductive film or a semiconductor film; What has the insulating layer provided on the base material is useful as a power storage layer for capacitor-type storage batteries.
In the capacitor-type storage battery storage layer, the composite layer, the base material made of a conductive film or a semiconductor film, and the insulating layer are the first composite layer 12, the first base material 13, and the first insulating layer 21 described in the first embodiment. And the same applies to the preferred range.

The disclosures of Japanese application 2010-217128 and Japanese application 2011-189599 are incorporated herein by reference in their entirety.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference, Incorporated herein by reference.

Hereinafter, examples of the present invention will be described together with comparative examples. The present invention is not limited to the following examples, and various modifications can be made without departing from the spirit of the present invention.

Example 1
On a polyethylene terephthalate film having a thickness of 12 μm as a support sheet, silicone rubber (shear elastic modulus at normal temperature: 1 × 10 ⁷ Pa) and Cu nanoparticle dispersion (Cu nanoparticle diameter: 10 nm, volume fraction: 10 wt%) as a composite layer The coating liquid was dried so that the thickness after drying was 20 μm. On this composite layer (the distance between the conductive particles embedded in the organic polymer (Cu nanoparticles) or the particle aggregate is 50 nm), the above Cu nanoparticle dispersion is applied alone to a thickness of 10 μm. Then, heating was performed at 140 ° C. or higher to form a uniform metal plate, which was used as a base material made of a conductive film, to obtain a power storage substrate 1.

Next, methyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxyethyl acrylate were mixed, and an appropriate amount of a curing agent was added to synthesize resin 1 as an organic polymer. When the viscoelasticity of the above resin was measured by a method in accordance with JIS-K7244, the storage elastic modulus was 1.2 × 10 ⁵ Pa and tan δ was 0.4 under the conditions of 25 ° C. and 1 Hz.

Next, the resin 1 is coated on the base material made of the conductive film of the electricity storage substrate 1 that is not on the polyethylene terephthalate film side by a bar coating method so that the thickness after drying becomes 10 μm, and dried to form the insulating layer 1. While forming, a 2 cm wide copper foil was further bonded onto the insulating layer 1 to form a conductive path.
Thereafter, the support sheet of the electricity storage substrate 1 is peeled off, and the resin 1 is applied to the opposite surface (composite layer) so that the thickness after drying is 10 μm, and the insulating layer 2 is further formed by drying. A copper foil having a width of 2 cm was bonded onto the insulating layer 2 to form a conductive path, and a capacitor type storage battery for test was produced.

(Example 2)
The insulating layer 1 was formed by applying and drying the resin 1 produced in Example 1 on the electricity storage board 1 produced in Example 1 by a bar coating method so that the thickness after drying was 10 μm. Two conductive paths were formed on the insulating layer 1 by arranging copper foils having a width of 2 cm in parallel at intervals of 1 mm, and a test capacitor type storage battery was produced.

(Example 3)
On a 12 μm-thick polyethylene terephthalate film (shear elastic modulus at normal temperature 3.8 × 10 ⁹ Pa) as a support sheet, 20 μm-thick silicone rubber (shear elastic modulus at normal temperature: 1 × 10 ⁷ Pa) as an organic polymer On this substrate, Al is sputtered by applying a voltage so that the substrate temperature is kept at room temperature and having a particle energy of 7 eV by facing target type magnetron sputtering, and a composite layer (embedded in an organic polymer) And a 100 nm thick Al layer is formed on the composite layer, and this is used as a base material made of a conductive film. Got.

Next, a capacitor type storage battery for testing was manufactured by the same manufacturing method as in Example 2 except that the power storage substrate 2 was used instead of the power storage substrate 1.

Example 4
On the surface of the electricity storage substrate 1 produced in Example 1 that is not on the polyethylene terephthalate film side, that is, on the base material made of a conductive film (Cu layer), Cu nanoparticles are applied and dried at 120 ° C. or lower, and the surface of the base material is Concavities and convexities (the maximum width and maximum height of the protrusions and the width of the recesses of 100 nm) made of Cu nanoparticles or particle aggregates thereof were formed, and the electricity storage substrate 3 was produced.

Next, a test type capacitor type storage battery was manufactured by the same manufacturing method as in Example 2 except that the power storage substrate 3 was used instead of the power storage substrate 1.

(Example 5)
On a 12 μm thick polyethylene terephthalate film (shear elastic modulus at normal temperature 3.8 × 10 ⁹ Pa) as a support sheet, 20 μm thick silicone rubber (shear elastic modulus at normal temperature: 3 × 10 ⁷ Pa) as an organic polymer On the substrate, Al is applied by a facing target type magnetron sputtering method, the substrate temperature is kept at room temperature, a voltage is applied so as to have a particle energy of 8 eV, sputtering is performed, and a composite layer (embedded in an organic polymer) is formed. The electrically conductive particles (Al particles) or the distance between the particle aggregates were 51 nm), and a 100 nm-thick Al layer was formed.

Next, a test capacitor type storage battery was manufactured by the same manufacturing method as in Example 2 except that the power storage substrate 4 was used instead of the power storage substrate 1.

(Example 6)
On the base material made of the conductive film (Al layer) of the electricity storage substrate 4, Sn is sputtered by applying a voltage so as to have a particle energy of 8 eV while keeping the substrate temperature at room temperature by the opposed target type magnetron sputtering method. Concavities and convexities (the maximum width and the maximum height of the protrusions and the width of the recesses of 50 nm) made of Sn particles or particle aggregates were formed on the surface of the material, and the electricity storage substrate 5 was manufactured.

Next, a test capacitor-type storage battery was manufactured by the same manufacturing method as in Example 2 except that the power storage substrate 5 was used instead of the power storage substrate 1.

(Example 7)
First, 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate were used as monomers, and these were mixed, and an appropriate amount of a curing agent was added to synthesize resin 2 as an organic polymer.
In addition, methyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxyethyl acrylate were used as monomers, mixed, and an appropriate amount of a curing agent was added to synthesize resin 3 as an organic polymer.

Here, when the viscoelasticity of the above resin was measured by a method in accordance with JIS-K7244, the storage elastic modulus was 5.1 × 10 ⁴ Pa and the dielectric loss tangent tan δ was 0 under the conditions of 25 ° C. and 1 Hz. 4. Resin 3 had a storage elastic modulus of 1.2 × 10 ⁵ Pa and a dielectric loss tangent tan δ of 0.4.

After a resin 3 is applied to a 25 μm thick polyethylene terephthalate film as a support sheet by a bar coating method so that the thickness after drying is 10 μm and dried, the thickness after drying the resin 2 further becomes 10 μm thick. Thus, the insulating layer 3 which consists of two adhesive layers was obtained.

The power storage substrate 1 is bonded to the surface of the adhesive layer made of the resin 2 of the insulating layer 3 (the base material made of the conductive film (Cu layer) formed on the surface of the power storage substrate 1 is bonded oppositely), A test-capacitor type storage battery was prepared by forming two conductive paths by arranging and bonding 2 cm-wide copper foils in parallel at 1 mm intervals on the surface of the adhesive layer made of the resin 2 of the insulating layer. .

(Comparative Example 1)
On a polyethylene terephthalate film having a thickness of 12 μm as a support sheet, silicone rubber (shear elastic modulus at normal temperature: 1 × 10 ⁷ Pa) and Cu nanoparticle dispersion (Cu nanoparticle diameter: 10 nm, volume fraction: 10 wt%) as a composite layer Was dispersed and coated so that the thickness after drying was 20 μm, whereby an electricity storage substrate 6 was obtained.
The distance between the conductive particles (Cu nanoparticles) embedded in the organic polymer in the composite layer or the particle aggregates was 50 nm.

Next, a test capacitor type storage battery was manufactured by the same manufacturing method as in Example 1 except that the power storage substrate 6 was used instead of the power storage substrate 1.

(Comparative Example 2)
A capacitor type storage battery for test was manufactured by the same manufacturing method as in Example 2 except that the power storage substrate 6 was used instead of the power storage substrate 1.

(Comparative Example 3)
On a 12 μm thick polyethylene terephthalate film as a support sheet, a Cu nanoparticle dispersion (Cu nanoparticle diameter: 10 nm, volume fraction: 10 wt%) was applied alone to a thickness of 10 μm, and heated at 140 ° C. or higher uniformly. A metal plate was formed, and this was used as a base material made of a conductive film to obtain a power storage substrate 7.

A capacitor-type storage battery for test was manufactured by the same manufacturing method as in Example 2 except that the power storage substrate 7 was used instead of the power storage substrate 1.

(Evaluation)
About the capacitor type storage battery type battery for test produced in each example, the electric capacity was evaluated using a constant current charging device. The evaluation method is shown below. The results are shown in Table 1.

(1) The object to be measured was charged at a rate of 10 C and left for 10 to 720 hours in a state disconnected from the power source.
(2) After the above (1), discharging was performed at a rate of 1C.
(3) The amount of electricity discharged was measured, and the elapsed days when the amount of electricity was 60 mAh or less was taken as the holding time and compared.
The acceptable line as a product was based on a retention day of 20 days or more.

As shown in Table 1, the test capacitor type storage battery of the comparative example does not have a standing period of 10 days, but in the case of the test capacitor type storage battery of the example, the retention days are significantly improved. Recognize.

In the test capacitor type storage batteries of Comparative Examples 1 and 2, the electrical capacity that requires a large voltage drop at the start of discharge is not satisfactory when the standing time is short due to insufficient contact between the metal particles. On the other hand, in the test capacitor type storage battery of Comparative Example 3, the voltage drop is small and the electric capacity at the start of standing is large, but the retention characteristics are poor and the standard is not satisfied because there is energy release due to thermal relaxation.

On the other hand, the test capacitor type storage batteries of Examples 1 and 3 satisfied the standard because they maintained conductivity and retention characteristics.
Further, in the test capacitor type storage battery of Example 4, the conductive particles contained in the composite layer or a particle aggregate thereof are present on one side of the base material made of the conductive film, and the conductive particles or It is considered that plasmons are likely to be generated due to the presence of the irregularities formed by the particle aggregate, and that the surface plasmon density is improved and the capacity is improved because the surface area is increased.
Further, in the test capacitor type storage battery of Example 5, since the base material made of the conductive film is formed of conductive particles, high capacity and retention characteristics are satisfied at the same time.
Further, in the test capacitor-type storage battery of Example 6, the base material made of the conductive film is formed of conductive particles, and the conductive particles contained in the composite layer on one surface side of the base material made of the conductive film or its In addition to the presence of particle aggregates, the other surface has irregularities made of conductive particles or particle aggregates, so that plasmons are likely to be generated, and the surface area is large, resulting in surface plasmon density. It is considered that the capacity has been greatly improved.

From the above results, it can be seen that the capacitor type storage battery for testing of the example can provide a storage battery that can achieve both high capacitance and high retention characteristics.

Claims

A first composite layer in which first conductive particles or first semiconductor particles are embedded in an organic polymer, and a first base material that is provided on the first composite layer and includes the first conductive film or the first semiconductor film And a first insulating layer provided on the first substrate of the first laminated substrate,
A second insulating layer provided on the first composite layer of the first laminated substrate;
A first conductive path extending in the longitudinal direction on the first insulating layer;
A second conductive path extending in a longitudinal direction on the second insulating layer and provided in parallel to the first conductive path;
A capacitor-type storage battery.
A first base material comprising a first composite layer in which first conductive particles or first semiconductor particles are embedded in an organic polymer, and a first conductive film or a first semiconductor film provided on the first composite layer. And a first laminated base material laminated,
A first insulating layer provided on the first substrate of the first laminated substrate;
A first conductive path provided on the first insulating layer so as to extend in the longitudinal direction of the first laminated substrate;
A second conductive path extending in the longitudinal direction of the first laminated base material on the first insulating layer and provided in parallel to the first conductive path;
A capacitor-type storage battery.
A second insulating layer continuously provided on outer surfaces of the first conductive path and the second conductive path;
A second base material composed of a second conductive film or a second semiconductor film provided on the second insulating layer, and a second conductive particle or second semiconductor particle provided on the second base material are in an organic polymer. The second composite layer embedded in this order, a second laminated base material laminated in this order,
The capacitor-type storage battery according to claim 2, comprising:
The capacitor-type storage battery according to any one of claims 1 to 3, wherein a distance between the first conductive particles or the first semiconductor particles contained in the first composite layer is 30 nm or more and 3000 nm or less.
The capacitor type storage battery according to claim 3 or 4, wherein a distance between the particles of the second conductive particles or the second semiconductor particles contained in the second composite layer is 30 nm or more and 3000 nm or less.
The capacitor type according to any one of claims 1 to 5, wherein a surface of the first base material in contact with the first insulating layer has unevenness, and a width of the concave portion of the unevenness is 30 nm or more and 3000 nm or less. Storage battery.
The capacitor type according to any one of claims 3 to 6, wherein a surface of the second base material in contact with the second insulating layer has irregularities, and a width of the concave portion of the irregularities is not less than 30 nm and not more than 3000 nm. Storage battery.
The first insulating layer includes a first adhesive layer provided adjacent to the first base material, and a second adhesive provided on a side farther from the surface of the first base material than the first adhesive layer. The capacitor type storage battery according to claim 6 or 7, comprising two or more layers including layers.
The second insulating layer includes a third adhesive layer provided adjacent to the second base material, and a fourth adhesive provided on a side farther from the surface of the second base material than the third adhesive layer. The capacitor-type storage battery according to claim 7 or 8, comprising two or more layers including layers.
The first adhesive layer is an organic polymer layer having a storage elastic modulus in a range of 1 × 10 4 Pa or more and less than 1 × 10 5 Pa, and the second adhesive layer has a storage elastic modulus of 1 ×. The capacitor-type storage battery according to claim 8 or 9, which is an organic polymer layer of 10 5 Pa or more.
The first adhesive layer is an organic polymer layer having a dielectric loss tangent (tan δ) in the range of 0.1 to 1, and the second adhesive layer has a dielectric loss tangent (tan δ) of 0.5 or less. The capacitor-type storage battery according to any one of claims 8 to 10, which is an organic polymer layer.
The capacitor-type storage battery according to any one of claims 8 to 11, wherein the second adhesive layer is a layer formed by dispersing inorganic compound powder in a resin.
The capacitor-type storage battery according to any one of claims 8 to 12, wherein the second adhesive layer is a layer formed by impregnating a porous material using a polymer resin with a resin.
14. The capacitor-type storage battery according to claim 8, further comprising a first strength securing layer between the first adhesive layer and the second adhesive layer.
The third adhesive layer has a storage elastic modulus in a range of 1 × 10 4 Pa or more and less than 1 × 10 5 Pa, and the fourth adhesive layer has an organic storage elastic modulus of 1 × 10 5 Pa or more. The capacitor-type storage battery according to any one of claims 9 to 14, which is an organic polymer layer which is a polymer layer.
The third adhesive layer is an organic polymer layer having a dielectric loss tangent (tan δ) in the range of 0.1 to 1, and the fourth adhesive layer has a dielectric loss tangent (tan δ) of 0.5 or less. The capacitor-type storage battery according to any one of claims 9 to 15, which is an organic polymer layer.
The capacitor-type storage battery according to any one of claims 9 to 16, wherein the fourth adhesive layer is a layer formed by dispersing inorganic compound powder in a resin.
The capacitor-type storage battery according to any one of claims 9 to 17, wherein the fourth adhesive layer is a layer formed by impregnating a porous material using a polymer resin with a resin.
The capacitor-type storage battery according to any one of claims 9 to 18, further comprising a second strength securing layer between the third adhesive layer and the fourth adhesive layer.
The first conductive film is at least one element selected from the group consisting of Fe, Al, Co, Cr, Ni, Ag, Mg, Cu, Sn, Au, Pt, Pd, In, Ti, Ta, and C; An alloy or eutectoid composed of at least two elements selected from the above group, or at least one element selected from the above group, and further selected from the group consisting of groups 3 to 14 of the periodic table The capacitor type storage battery according to any one of claims 1 to 19, comprising an alloy or a eutectoid containing at least one element.
The second conductive film is at least one element selected from the group consisting of Fe, Al, Co, Cr, Ni, Ag, Mg, Cu, Sn, Au, Pt, Pd, In, Ti, Ta, and C; An alloy or eutectoid composed of at least two elements selected from the above group, or at least one element selected from the above group, and further selected from the group consisting of groups 3 to 14 of the periodic table The capacitor type storage battery according to any one of claims 3 to 20, comprising an alloy or a eutectoid containing at least one element.
The first semiconductor film is selected from the group consisting of nickel nitride, anatase structure titanium oxide, tin oxide mixed indium oxide, tin oxide, zirconium oxide, gallium nitride, aluminum nitride, silicon and carbon. The capacitor-type storage battery according to any one of claims 1 to 21, comprising at least one compound.
The second semiconductor film is selected from the group consisting of nickel nitride, anatase structure titanium oxide, tin oxide mixed indium oxide, tin oxide, zirconium oxide, gallium nitride, aluminum nitride, silicon and carbon. The capacitor-type storage battery according to any one of claims 3 to 22, comprising at least one compound.
24. The compound according to claim 22 or 23, wherein the compound is doped with an n-type or p-type transition metal, rare earth metal or nonmagnetic metal so that 50% or more of excited electrons are generated from an impurity level at room temperature. Capacitor type storage battery.
The capacitor-type storage battery according to any one of claims 2 to 24, comprising a plurality of rows of the first conductive paths and the second conductive paths on the same surface of the first insulating layer.
A first terminal connected to the plurality of rows of first conductive paths;
A second terminal connected to the plurality of rows of second conductive paths;
With
The first terminal and the second terminal have a portion whose width becomes narrower as the distance from the first conductive path and the second conductive path increases. In this part, the first terminal and the second terminal extend in the same direction as the first conductive path. 26. The capacitor-type storage battery according to claim 25, wherein an angle formed between the two sides is 30 ° or less.
A laminated base material in which conductive layers or semiconductor particles are embedded in an organic polymer, and a base material formed on the composite layer and made of a conductive film or a semiconductor film, and the laminated base material An insulating layer provided on the base material of
An electricity storage layer for a capacitor-type storage battery.