JP5888863B2 - High relative permittivity solid material, dielectric, and capacitor type storage battery - Google Patents

Description

  The present invention relates to a solid material having a high relative dielectric constant used for a capacitor-type storage battery, a dielectric, and a capacitor-type storage battery using the same.

  In recent years, in order to prevent global warming, it is necessary 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 use, for example, an electrolyte using a rare metal such as lithium (for example, Patent Document 1).

  When an electrolyte is used for a storage battery, charging takes time. Further, since the electrolyte is deteriorated, the life of the storage battery is short. Moreover, in order to implement | achieve a high output voltage, it was necessary to connect a some storage battery in series. On the other hand, when a capacitor is used as a storage battery, the charging time is short, the life is long, and a high output voltage can be realized. However, when a capacitor is used as a storage battery, it is necessary to increase the capacity per unit volume. For this purpose, a material having a high relative dielectric constant is required.

Japanese Patent No. 4428830

  An object of the present invention has been made in consideration of the above-described circumstances, and has a high relative dielectric constant, a high relative dielectric constant solid material and a dielectric material in which the occurrence of leakage current is suppressed, and use thereof Another object of the present invention is to provide a capacitor-type storage battery having a large capacity per unit volume and excellent pressure resistance.

The above problem is solved by the following means. That is,
The high relative permittivity solid material of the present invention is at least one silicon compound of silicic acid, siloxane, and siliconate, and has a covalent bond as well as an ionic bond with respect to at least a part of the hydroxyl group of the silicon compound. It is a solid material having a high dielectric constant made of a silicon compound in which metal ions are modified by bonding.
However, when at least part of the hydroxyl group of silicic acid is a bond that has both an ionic bond and a covalent bond, the metal ion is composed of a silicon compound, and when the metal ion is a magnesium ion, the molecular structure of the silicon compound Has a ≡Si—O—Si≡ bond as a skeleton, and has silicon atoms in the range of 20 to 10,000. The silicon compound is a bonded product obtained by bonding other siloxanes by dehydration condensation.

In the high relative dielectric constant solid material of the present invention, the silicon compound preferably has a leak current value of 1 × 10 ⁻⁹ A / cm ² or less at an electric field strength of 6 kV / cm or less in absolute value.

  In the high relative dielectric constant solid material of the present invention, the metal ion may be modified to at least a part of the hydroxyl group of the silicon compound by substituting a hydrogen atom of the hydroxyl group of the silicon compound. Good.

  In the high relative dielectric constant solid material of the present invention, the molecular structure of the silicon compound preferably has a ≡Si—O—Si≡ bond as a skeleton and has silicon atoms in the range of 20 or more and 10,000 or less.

In the high relative permittivity solid material of the present invention, the metal ion is selected from metal ions belonging to Group 2 of the periodic table, metal ions belonging to Group 13 of the periodic table, and phosphorus (P) ions 1 It should be a seed.
In the high relative dielectric constant solid material of the present invention, the silicon compound is preferably a bonded product in which another siloxane is bonded.

The dielectric of the present invention is
A dielectric comprising at least the high relative dielectric constant solid material of the present invention.

  The dielectric of the present invention may further include at least one selected from perovskite-based oxides and oxides having a crystal structure with a nonstoichiometric oxygen content of 0.01 to 0.2. .

The capacitor-type storage battery of the present invention is
A pair of electrodes;
A dielectric disposed between the pair of electrodes, the dielectric of the present invention;
It is a capacitor type storage battery having

  In the capacitor-type storage battery of the present invention, a reaction product between the pair of electrodes and the dielectric may be formed on a contact surface between the pair of electrodes and the dielectric.

  According to the present invention, a high relative permittivity solid material and a dielectric material having a high relative permittivity and a suppressed leakage current, and a large capacity per unit volume and excellent pressure resistance using the same. A capacitor-type storage battery can be provided.

It is a schematic diagram which shows the polymer structure (polymer structure) of dimethylsiloxane. It is a schematic diagram which shows the state by which the electric field is not provided to the silicon compound which is a high dielectric constant solid material of this invention. It is a schematic diagram which shows the state by which the electric field was provided to the silicon compound which is a high dielectric constant solid material of this invention. It is a graph which shows the relationship between a dielectric constant and the frequency of an electrical potential change. It is a graph which shows the relationship between the kind of polariser, polarizability, and frequency. It is a reaction formula which shows an example of the manufacturing method of the silicon compound which is a high dielectric constant solid material of this invention. It is a reaction formula which shows an example of the manufacturing method of the silicon compound which is a high dielectric constant solid material of this invention. It is a schematic block diagram which shows an example of the capacitor type storage battery of this invention.

  The present invention will be described in detail.

(High dielectric constant solid material)
The high dielectric constant solid material of the present invention comprises at least one silicon compound of silicic acid, siloxane, and siliconate.
In the silicon compound, at least a part of the hydroxyl group of the silicon compound is modified with a metal ion by a bond that has both an ionic bond and a covalent bond.
However, when at least part of the hydroxyl group of silicic acid is a bond that has both an ionic bond and a covalent bond, the metal ion is composed of a silicon compound, and when the metal ion is a magnesium ion, the molecular structure of the silicon compound Has a ≡Si—O—Si≡ bond as a skeleton, and has silicon atoms in the range of 20 to 10,000. The silicon compound is a bonded product obtained by bonding other siloxanes by dehydration condensation.

As a result of diligent research, the inventors of the present invention have a high relative dielectric constant in which the generation of leakage current is suppressed by a space charge distribution type dielectric solid material whose molecular structure moves (changes) by an electric field. It has been found that a solid material can be obtained.
Specifically, it is as follows.
First, the inventors have found that carbon-based compounds having carbon as a main skeleton element (for example, polymers such as acrylic resins and epoxy resins) generally have a molecular structure due to steric hindrance and hydrogen bonding due to the influence of electric fields. It is difficult to think about the movement (change) of the material, and it was considered that this would not be a space charge distribution type dielectric solid material.
Therefore, the present inventors applied at least one silicon compound of silicic acid, siloxane, and siliconate having a silicon skeleton as a dielectric solid material instead of carbon to form a loose three-dimensional structure, The perovskite structure that occurs due to the displacement of the atomic structure due to the electric field (molecules, atomic polarization) by modifying the metal ion with a bond that has both an ionic bond and a covalent bond for at least a portion of the hydroxyl group possessed. In contrast, it has been found that the movement and rotation of molecules due to the electric field, that is, the movement of polarization due to space charge distribution, can be realized, and a high dielectric constant can be realized.

Here, basic properties regarding silicon (Si) and its compounds will be described.
Silicon (Si) belongs to group 14 of the periodic table, and is located directly below carbon (C). Its outer electron configuration is 3s ² 3p ^2, which is an isoelectronic structure with 2s ² 2p ^{2 of} carbon. For this reason, silicon has a property similar to that of carbon, and easily forms a stable four-coordinate compound (for example, SiH ₄ , SiCl ₄ , SiMe ₄ , SiO ₂ (tetrahedral), etc.).
Silicon also forms a polymer linked by bonds such as -Si-O-, -Si-Si-, -Si-C-, and -Si-N-. FIG. 1 shows a polymer structure (polymer structure) of siloxane (dimethylsiloxane) linearly linked by a typical “—Si—O—” bond.

  These tetracoordinate compounds and polymers linked by the above bond exhibit remarkable properties unique to silicon.

Specifically, the silicon molecular orbital has an empty d-orbital, and the silicon shared radius is 1.17 mm, which is larger than 0.77 cm for carbon. For this reason, the carbon-silicon and silicon-oxygen bonds are about 25% and 50% longer than the carbon-carbon bonds, respectively.
As a result, the silicon-carbon bond and silicon-oxygen bond have a small rotation barrier (high degree of freedom of rotation), and it is difficult to form multiple bonds. In particular, a skeleton of a silicon-oxygen bond (specifically, for example, a skeleton of “≡Si—O—Si≡” bond) has a large degree of freedom in displacement of the angle of the oxygen (O) bond branch.
For example, a siloxane linearly linked by a “—Si—O—” bond having this structure becomes a soft gel or rubber. This is because, as shown in FIG. 1, the helical structure of siloxane linearly linked by a “—Si—O—” bond extends and rotates with a weak force.
Moreover, since the empty d-orbital spread is larger than that of hydrogen ions (protons), the reactivity is also high, and a reactant may be produced at the contact portion with a metal (for example, an electrode of a storage battery). For example, “≡Si-H + M → ≡Si-M ⁽⁺⁾ + H ⁽⁺⁾ ” (where M represents a metal) to generate a reactant, and H ⁽⁺⁾ binds to the peripheral reactive edge. To do. The most common reaction probably reacts with metal oxides to become “—OH”.

In addition, since the electronegativity of silicon is 1.9, which is much smaller than 3.44 for oxygen, unlike carbon-carbon bonds, silicon-oxygen bonds are polarized to Si ⁽⁺⁾ -O ^(-) . To do.
That is, the hydroxyl group bonded to silicon is polarized and functions as a polarizer.
In addition, since the polarization of the silicon-oxygen bond is large, for example, the silanol group of water-soluble silicon oil is easily dehydrated and condensed by natural standing or heating. In addition, silicon easily forms highly coordinated compounds such as pentacoordinate and hexacoordinate.

Then, when metal ions are modified with a bond having both an ionic bond and a covalent bond with respect to at least a part of hydroxyl groups of silicon compounds of silicic acid, siloxane, and siliconate having properties peculiar to silicon (specifically, When the hydrogen atom of the hydroxyl group of the silicon compound is replaced with a metal ion), the hydroxyl group modified with the metal ion becomes a group having a greater polarization.
That is, when an electric field is applied to a silicon compound, a hydroxyl group modified with a metal ion can move greatly with respect to silicon (Si) and has a large polarization. Therefore, “Si ⁽⁺⁾ -O ^(-) -M ⁽⁺⁾ "can be created (where M represents a metal ion).

In addition, if the metal ion that modifies the hydroxyl group of the silicon compound is modified with an ionic bond and a bond that also has a covalent bond, an electric field is applied to the silicon compound, and charge arrangement occurs at the hydroxyl group of the silicon compound. However, since the bond of the metal ions modified to these groups is not cleaved, for example, the metal ions are not induced and reacted on the electrode surface.
In the case of silicic acid or siloxane having a large number of silicon (Si atoms) (for example, a molecular structure having a “≡Si—O—Si≡” bond as a skeleton and having silicon atoms in the range of 20 to 10,000. Since these silicon compounds are easy to maintain flexibility and rotation, the silicon compound itself has a large degree of freedom of rotation and deformation, and the hydroxyl group modified with a metal ion that functions as a polarizer is silicon ( That is, since it moves more while being bonded (while being connected) to the “≡Si—O—Si≡” bond skeleton), it is stronger than “Si ⁽⁺⁾ −O ⁽⁻⁾ −M ⁽⁺⁾ ”. A polarization state can be created (where M represents a metal ion).

This state is schematically shown in FIGS. 2 and 3 using one silicon compound molecule as a model. 2 and 3, when a silicon compound is placed between a pair of electrodes (see FIG. 2) and a voltage is applied between the pair of electrodes (see FIG. 3; in FIG. 3, the upper electrode has a minus and the lower electrode has a plus The voltage is applied), and the polarizer moves to the lower electrode side with the rotation and deformation of the molecule.
2 and 3, a hydroxyl group in which a hydrogen atom is substituted with an aluminum ion (Al ³⁺ ) is shown as a hydroxyl group modified with a metal ion that functions as a polarizer of a silicon compound.

Here, FIG. 2 shows a state where no electric field is applied to the silicon compound (that is, a state where no voltage is applied between the pair of electrodes). In FIG. 2, the polarizer is shown surrounded by an elliptical line.
On the other hand, FIG. 3 shows a state where an electric field is applied to the silicon compound (that is, a state where a voltage is applied between a pair of electrodes). In FIG. 3, the polarizer after movement by the electric field is surrounded by an elliptical line, and the region where the polarizer before the movement by the electric field (that is, before application of the electric field) exists is surrounded by an elliptical dotted line.
2 and 3, 11 indicates an upper electrode, and 12 indicates a lower electrode.

From the above, the high relative permittivity solid material made of the above silicon compound exhibits many polarizers even at the same potential difference, and therefore the ratio of the number of charges Q appearing on the electrode surface corresponding to the voltage V applied between the electrodes is high. Since the electrostatic capacity C = Q / V, the electrostatic capacity is large, that is, the relative dielectric constant is increased.
In addition, the high relative permittivity solid material made of the above silicon compound has an electric field applied to the silicon compound, and even when charge arrangement occurs in the hydroxyl group of the silicon compound, the bond of the metal ion modified to these groups does not occur. Since it is not cut, leakage current is unlikely to occur, that is, withstand voltage is increased.

  Here, the orientation of the polarizer is generally referred to as molecular polarization. In this state, the molecules are deformed and rotated, and when the moving distance is increased, the space charge distribution polarization is also used.

The displacement rate due to the molecular polarization potential of the hydroxyl group (—OH) is in the 1 GHz region, but the spatial charge distribution displacement accompanied by molecular structure deformation and rotation is as slow as about 0.001 Hz to 10 Hz (see FIGS. 4 and 5). . However, since the potential change in the storage battery has a slower frequency than this, the high relative permittivity solid material made of the silicon compound sufficiently takes this polarization effect into consideration.
4 and 5 are relationship diagrams showing the general concept of the type of polarization and the frequency response of potential change. Specifically, FIG. 4 shows the relationship between the relative permittivity and the frequency of potential change. FIG. 5 is a graph showing the relationship between the type of polariser, the polarizability, and the frequency.

Hereinafter, the high relative dielectric constant solid material of the present invention will be described in more detail.
The silicon compound, which is a solid material having a high relative dielectric constant of the present invention, is a silicic acid or siloxane in which a metal ion is modified with a bond having both an ionic bond and a covalent bond with respect to at least a part of the hydroxyl group of the silicon compound , And at least one of siliconate.
Specific embodiments of the silicon compound that is the solid material having a high relative dielectric constant of the present invention are as follows.
1) A metal ion modified to at least a part of a plurality of hydroxyl groups of silicic acid (specifically, a hydrogen atom of the hydroxyl group is substituted with a metal ion)
2) A metal ion is modified to at least a part of a plurality of hydroxyl groups of siloxane (specifically, a hydrogen atom of the hydroxyl group is substituted with a metal ion)
3) A metal ion is modified to at least a part of a plurality of hydroxyl groups of the siliconate (specifically, a hydrogen atom of the hydroxyl group is substituted with a metal ion)
4) Mixtures of these

The silicic acid will be described.
Examples of silicic acid (silicic acid before being modified with a metal ion: hereinafter the same) include a chain compound or a cyclic compound represented by a chemical formula of [SiO _x (OH) _4-2x ] _n . However, in these chemical formulas, x and n represent a natural number of 1 or more.
The silicic acid may be a metal salt such as sodium (for example, sodium silicate: at least some of a plurality of hydroxyl groups of silicic acid are modified with sodium ions).

Siloxane will be described.
Examples of siloxane (siloxane before being modified with metal ions: the same applies hereinafter) include, for example, dimethylpolysiloxane (dimethylsilicone) whose terminal group is a hydroxyl group (silicate group), dihydroxypolysiloxane, and hydroxyl group (silicate group) whose terminal group is a hydroxyl group. And hexamethyldisiloxane.

The siliconate will be described.
Examples of the siliconate (siliconate before being modified with a metal ion: the same applies hereinafter) include methyl siliconate, phenylene siliconate, xylene siliconate and the like.
The siliconate may be a metal salt such as sodium (for example, sodium methylsiliconate: a product in which at least some of the hydroxyl groups of the siliconate are modified with sodium ions).

The metal ion will be described.
A metal ion modifies a hydroxyl group of a silicon compound with a bond having both an ionic bond and a covalent bond.
Specifically, the metal ion is modified with respect to at least a part of the hydroxyl group of the silicon compound by substituting the hydrogen atom of the hydroxyl group of the silicon compound. That is, a metal salt structure is formed by substituting a metal ion for a hydrogen atom of a hydroxyl group of a silicon compound.

  Note that the metal ion modification of at least a part of the hydroxyl groups of the silicon compound means that the metal ions may be modified for all of the hydroxyl groups of the silicon compound or may be partially modified. It means that a metal ion may be modified with respect to a hydroxyl group so that a hydroxyl group not to be present is present.

  Examples of a metal ion that realizes modification with a bond having a covalent bond as well as an ionic bond with respect to a hydroxyl group of a silicon compound include, for example, metal ions belonging to Group 2 of the periodic table and metals belonging to Group 13 of the periodic table. One type selected from ions and phosphorus (P) ions is preferred.

Typical examples of metals belonging to Group 2 of the periodic table include magnesium (Mg) and calcium (Ca).
Typical examples of the metals belonging to Group 13 of the periodic table include boron (B) and aluminum (Al).

  Among these metal ions, aluminum ions and boron ions are particularly preferable from the viewpoint of reaction yield and chemical stability.

Here, it can be verified by examining the leakage current value of the silicon compound that the hydroxyl group of the silicon compound is modified with a bond having both a ionic bond and a covalent bond.
In the case where the metal ion is modified with a bond having only an ionic bond with respect to the hydroxyl group of the silicon compound, a leak current is likely to be generated by cutting the bond of the metal ion by applying an electric field.
On the other hand, when the metal ion is modified with a bond having a covalent bond as well as an ionic bond with respect to a hydroxyl group of the silicon compound, the bond of the metal ion is difficult to be cut by applying an electric field, and a leak current is hardly generated.
Therefore, by examining the leakage current value of the silicon compound, it is possible to verify that the metal ion is modified with a bond having a covalent bond as well as an ionic bond with respect to the hydroxyl group of the silicon compound.
Specifically, when the leakage current value of the silicon compound (leakage current value at an electric field intensity of 6 kV / cm or less in absolute value: details will be described later) is 1 × 10 ⁻⁹ A / cm ² or less, the metal ion It can be said that it is modified with a bond having both an ionic bond and a covalent bond.

Next, the morphological form and characteristics of the silicon compound which is the high relative dielectric constant solid material of the present invention will be described.
The silicon compound has a “≡Si—O—Si≡” bond as a skeleton, and has a silicon atom in the range of 20 or more and 10,000 or less (preferably 50 or more and 8,000 or less, more preferably 100 or more and 8,000 or less). It is preferable that the silicon compound has a molecular structure.
Specifically, the silicon compound is, for example, silicic acid having 20 to 10,000 silicon atoms, or siloxane.
Since this silicon compound easily maintains flexibility and rotation, the silicon compound itself has a high degree of freedom of rotation and deformation, and the hydroxyl group modified with a metal ion that functions as a polarizer is silicon (that is, “≡Si The bond moves (is still connected) to the —O—Si≡ ”skeleton), and moves more and the relative permittivity is improved.

The silicon compound is preferably a bonded product in which other siloxanes (for example, dimethylpolysiloxane having a terminal hydroxyl group, dihydroxypolysiloxane, etc.) are bonded from the viewpoint of increasing the molecular weight and imparting plasticity.
Specifically, for example, the combined product obtained by combining dehydration condensation of a hydroxyl group of silicic acid and another siloxane (hydroxyl group of silicic acid and a hydroxyl group which is a terminal group of another siloxane), and siloxane Condensates in which other siloxanes and each other's hydroxyl groups (hydroxyl groups that are terminal groups of siloxanes and hydroxyl groups that are terminal groups of other siloxanes) are bonded by dehydration condensation, siliconate and other siloxanes are mutually hydroxylated (hydroxyl group of siliconate) And other hydroxyl groups, which are terminal groups of other siloxanes, are combined by dehydration condensation.
The other siloxane may be modified with a bond in which the metal ion has a covalent bond as well as an ionic bond with respect to the hydroxyl group of the siloxane, or is not modified with the metal ion. May be.

  The silicon compound may be in a gel state or a crystalline state as long as it is solid.

The leakage current value (leakage current value at an electric field strength of 6 kV / cm or less) of the silicon compound is preferably 1 × 10 ⁻⁹ A / cm ² or less, more preferably 1 × 10 ⁻¹⁰ A / cm. ² or less, more preferably 1 × 10 ⁻¹¹ A / cm ² or less.
In addition, the measuring method of a leakage current value is based on the description in the Example mentioned later.

Next, the manufacturing method of the silicon compound which is the high dielectric constant solid material of the present invention will be described.
When a silicon compound is modified with a metal ion at its hydroxyl group (that is, when a hydrogen atom of the hydroxyl group is substituted), for example, as a raw material, silicic acid, siloxane, and siliconate are prepared, and a metal hydroxide for this purpose is prepared. Or by mixing with nitrate.
Further, when a sodium salt such as sodium silicate or sodium methylsiliconate is used as a raw material, it can be obtained by mixing it with a metal hydroxide or nitrate.
Here, examples of the target metal hydroxide include magnesium hydroxide, aluminum hydroxide, and boron hydride.
Examples of the target metal nitrate include magnesium nitrate and aluminum nitrate.

Hereinafter, an example using sodium silicate as a raw material will be shown as a specific example.
First, as shown in the reaction formula shown in FIG. 6, when sodium polysilicate and aluminum hydroxide are prepared and mixed, sodium ions having high ion binding properties are replaced with aluminum ions. Polyaluminum silicate (polysilicate in which the hydrogen atom of the hydroxyl group is replaced with an aluminum ion) is obtained.
Here, sodium polysilicate as a raw material is generally easily available as a silicon compound mainly composed of silicon (Si) containing a large amount of a cationic metal.
Hydroxides such as aluminum hydroxide contain a lot of metal ions (cations) (more than 50% ratio), and the polarization of silicon compounds increases as the number of metal ions (cations) increases. Therefore, it is preferable as a raw material.

In addition, when the obtained polysilicate aluminum is polymerized to impart plasticity, the resulting polysilicate aluminum is used as a starting material, and other siloxanes (hydroxyl groups (silanols as end groups) are added to an aqueous solution containing the polysilicate aluminum. Water-soluble dimethylsiloxane having a group): oil-like or gel-like substance) is mixed at a ratio of, for example, 5% by mass or more and 20% by mass, and this is applied to an object to be coated (for example, an electrode). As shown in the formula, dehydration condensation of a hydroxyl group of sodium polysilicate and a hydroxyl group (silanol group) as a terminal group of another siloxane proceeds.
At this time, drying may be performed to remove excess moisture.
The dehydration condensation reaction and drying are carried out at a temperature of 150 ° C. or less, at which an appropriate heating temperature exists from room temperature, but is preferably less likely to cause deterioration of an object to be coated (for example, an electrode).

  Here, it is preferable to remove moisture after synthesizing these silicon compounds such as polyaluminum silicate and a polymer obtained by bonding other siloxane to this polymer. As a result, there is no free water (free water) in the obtained silicon compound, and there is no action like a metal ion dissolved in the free water (free water), that is, no electrolyte behavior, so that a leak current is less likely to occur. That is, the pressure resistance becomes higher.

(Dielectric)
The dielectric of the present invention includes at least the high relative dielectric constant solid material of the present invention.
The dielectric of the present invention may be a single material of the high relative dielectric constant solid material of the present invention or a mixture containing the high relative dielectric constant solid material of the present invention and other additives. Good.

Examples of other additives include perovskite oxides and non-stoichiometric oxygen amounts of 0.01 or more and 0.2 or less (preferably 0.05 or more and 0.18 or less, more preferably 0.08 or more and 0.15. Suitable examples include at least one selected from oxides having the following crystal structure.
Examples of the oxide having a crystal structure with a nonstoichiometric oxygen amount of 0.01 or more and 0.2 or less include a rutile oxide and an anatase oxide.
In addition, the amount of nonstoichiometric oxygen is calculated | required by the heating weight measurement by a differential thermal balance (TG-DTA).

  Since this oxide is a dielectric material that can store electricity by changing the potential at a high frequency (for example, about 1 MHz), the potential change from a low frequency to a high frequency can be achieved by adding this compound to a solid material with a high relative dielectric constant. Can be stored.

Examples of perovskite-based oxides include barium titanate, strontium titanate, and barium strontium titanate.
Examples of the rutile oxide include titanium oxide and tin oxide.
Examples of the anatase oxide include titanium oxide.
The addition amount of the oxide is preferably 20% by mass or more and 80% by mass or less, and more preferably 40% by mass or more and 60% by mass or less with respect to the high relative dielectric constant solid material.

(Storage battery)
FIG. 8 is a schematic configuration diagram showing an example of the storage battery of the present invention.
As shown in FIG. 8, the storage battery according to the present invention includes a pair of electrodes composed of an upper electrode 11 and a lower electrode 12 disposed to face each other, and a dielectric 10 disposed between the upper electrode 11 and the lower electrode 12. And is composed of.
The dielectric 10 of the present invention (the high relative dielectric constant solid material of the present invention) is applied as the dielectric 10.
Thereby, it becomes a capacitor type storage battery with a large capacity per unit volume. In addition, a capacitor-type storage battery having excellent pressure resistance is obtained.

In the storage battery of the present invention, the pair of electrodes (upper electrode 11 and lower electrode 12) are made of metal (eg, gold, silver, copper, nickel), metal oxide (eg, SnO ₂ (tin oxide), In ₂ O). ₃ (indium oxide), ITO (indium tin oxide), IZO (zinc indium oxide)), or an organic material (for example, polypyrrole, polythiophene, etc.).
In addition, a pair of electrodes (upper electrode 11 and lower electrode 12) in which a conductive film made of the conductive material is formed over a resin substrate can be applied.

In the storage battery of the present invention, a reaction product of the pair of electrodes and the dielectric may be formed on a contact surface between the pair of electrodes (the upper electrode 11 and the lower electrode 12) and the dielectric.
As described above, the silicon compound (high relative dielectric constant solid material) that constitutes the dielectric has a larger d-orbital spread than hydrogen ions (protons), and thus has high reactivity, and an electrode (for example, metal oxide) In some cases, a reaction product (reaction layer) is formed on the contact surface with the electrode.
In this way, a reaction product of a pair of electrodes and a dielectric is formed on the contact surfaces of each other, so that the charge introduced into the electrode and the reaction product cause a redox reaction, thereby forming a kind of redox capacitor. Further, the dielectric constant increases.

The storage battery of the present invention may be a unit obtained by connecting a plurality of units each having a dielectric disposed between a pair of electrodes (upper electrode 11 and lower electrode 12) in series or in parallel.
The storage battery of this invention can be comprised by shapes, such as a sheet form and the roll shape which wound this, for example.

  The storage battery of the present invention forms, for example, a coating film by applying a coating solution containing the dielectric of the present invention (the high dielectric constant solid material of the present invention) to one of the pair of electrodes (lower electrode 12). Then, the other of the pair of electrodes (the upper electrode 11) is overlaid, and after sandwiching the coating film, the dielectric film 10 can be formed and manufactured by performing a treatment such as drying the coating film. .

Hereinafter, the present invention will be described more specifically with reference to examples. However, these examples do not limit the present invention. In addition, Examples 1-2 correspond to a reference example.

(Comparative Example 1)
An oily dimethylsiloxane was uniformly applied to a thickness of 40 μm on a 0.2 mm thick copper plate as a lower electrode by a spin coating method, and a 0.2 mm thick copper plate as an upper electrode was formed on the formed coating film. A capacitor type storage battery (capacitor) in which a dielectric was sandwiched between a pair of electrodes was fabricated by pasting and air drying.

(Comparative Example 2)
35: 65 = 10% weight ratio of water-soluble dimethyl, dihydroxysilicone oil (dimethylsiloxane having hydroxyl group (silanol group) as terminal group: dmS, the same shall apply hereinafter) to sodium silicate having Na: Si component Mixed.
The obtained mixture was uniformly applied to a thickness of 40 μm by spin coating on a 0.2 mm thick copper plate as the lower electrode.
Thereafter, a copper plate having a thickness of 0.2 mm as an upper electrode was pasted on the formed coating film and air-dried to produce a capacitor-type storage battery (capacitor) in which a dielectric was sandwiched between a pair of electrodes.

Example 1
35: 65 = While stirring at room temperature so that an aqueous solution of Al (OH) ₃ (40% by weight) is 1: 1 with respect to an aqueous solution of sodium silicate having a Na: Si component (40% by weight) Slowly dropwise, Compound A was obtained.
Compound A was uniformly applied to a thickness of 40 μm by spin coating on a 0.2 mm thick copper plate as the lower electrode.
Thereafter, a copper plate having a thickness of 0.2 mm as an upper electrode was pasted on the formed coating film and air-dried to produce a capacitor-type storage battery (capacitor) in which a dielectric was sandwiched between a pair of electrodes.

(Example 2)
An aqueous solution of Al (OH) ₃ (40% weight ratio) with respect to water-soluble dimethyl and dihydroxyl silicone oil was slowly added dropwise at room temperature with stirring to obtain a ratio of 1: 1 to obtain Compound B.
The compound B was uniformly applied to a thickness of 40 μm by spin coating on a 0.2 mm thick copper plate as the lower electrode.
Thereafter, a copper plate having a thickness of 0.2 mm as an upper electrode was pasted on the formed coating film and air-dried to produce a capacitor-type storage battery (capacitor) in which a dielectric was sandwiched between a pair of electrodes.

(Example 3)
The compound A produced in Example 1 was mixed with water-soluble dimethyl and dihydroxy silicone oil at a 10% weight ratio to obtain a compound C.
The compound C was uniformly applied to a thickness of 40 μm by spin coating on a 0.2 mm thick copper plate as the lower electrode.
Thereafter, a copper plate having a thickness of 0.2 mm as an upper electrode was pasted on the formed coating film and air-dried to produce a capacitor-type storage battery (capacitor) in which a dielectric was sandwiched between a pair of electrodes.

Example 4
35: 65 = Compound D was obtained by mixing 10% by weight of water-soluble dimethyl and dihydroxyl silicone oil with magnesium silicate having Mg: Si component.
The obtained compound D was uniformly applied to a thickness of 40 μm by spin coating on a 0.2 mm thick copper plate as the lower electrode.
Thereafter, a copper plate having a thickness of 0.2 mm as an upper electrode was pasted on the formed coating film and air-dried to produce a capacitor-type storage battery (capacitor) in which a dielectric was sandwiched between a pair of electrodes.

(Example 5)
A sodium methyl siliconate solution (Na ₂ O: 10.7%, CH ₃ SiO _1.5 : 20%, water: 69.3%) and an aqueous aluminum hydroxide solution are stirred at room temperature to a ratio of 1: 1. While slowly dropping, Compound E was obtained. Compound E2 was mixed with water-soluble dimethyl and dihydroxysilicone oils at a 10% weight ratio to obtain compound E2.
The obtained compound E2 was uniformly applied to a thickness of 40 μm by spin coating on a 0.2 mm thick copper plate as the lower electrode.
Thereafter, a copper plate having a thickness of 0.2 mm as an upper electrode was pasted on the formed coating film and air-dried to produce a capacitor-type storage battery (capacitor) in which a dielectric was sandwiched between a pair of electrodes.

(Example 6)
35: 65 = While stirring at room temperature with a Sr (OH) ₂ aqueous solution (40% weight ratio) at a ratio of 1: 1 to a sodium silicate aqueous solution (40% weight ratio) having a Na: Si component Slowly dropwise, Compound F was obtained. Compound F2 was mixed with water-soluble dimethyl and dihydroxysilicone oils at a 10% weight ratio.
The obtained compound F2 was uniformly applied to a thickness of 40 μm by spin coating on a 0.2 mm thick copper plate as the lower electrode.
Thereafter, a copper plate having a thickness of 0.2 mm as an upper electrode was pasted on the formed coating film and air-dried to produce a capacitor-type storage battery (capacitor) in which a dielectric was sandwiched between a pair of electrodes.

(Example 7)
35: 65 = Phosphoric acid aqueous solution (40% weight ratio) is slowly added dropwise with stirring at room temperature to a ratio of 1: 1 to sodium silicate aqueous solution (40% weight ratio) having a Na: Si component. Compound G was obtained. This compound G and water-soluble dimethyl and dihydroxy silicone oil were mixed at a 10% weight ratio to obtain a compound G2.
The obtained compound G2 was uniformly applied to a thickness of 40 μm by spin coating on a 0.2 mm thick copper plate as the lower electrode.
Thereafter, a copper plate having a thickness of 0.2 mm as an upper electrode was pasted on the formed coating film and air-dried to produce a capacitor-type storage battery (capacitor) in which a dielectric was sandwiched between a pair of electrodes.

(Example 8)
40% by weight of strontium titanate (perovskite oxide) was mixed with Compound C obtained in Example 3.
The obtained mixture was uniformly applied to a thickness of 40 μm by spin coating on a 0.2 mm thick copper plate as the lower electrode.
Thereafter, a copper plate having a thickness of 0.2 mm as an upper electrode was pasted on the formed coating film and air-dried to produce a capacitor-type storage battery (capacitor) in which a dielectric was sandwiched between a pair of electrodes.

Example 9
The compound C obtained in Example 3 was mixed with 40% by weight of rutile-type titanium oxide (oxide having a crystal structure with a predetermined non-stoichiometric oxygen amount). The non-stoichiometric amount of oxygen of the titanium oxide particles was 0.08 when measured by heating weight measurement with a differential thermal balance (TG-DTA).
The obtained mixture was uniformly applied to a thickness of 40 μm by spin coating on a 0.2 mm thick copper plate as the lower electrode.
Thereafter, a copper plate having a thickness of 0.2 mm as an upper electrode was pasted on the formed coating film and air-dried to produce a capacitor-type storage battery (capacitor) in which a dielectric was sandwiched between a pair of electrodes.

(Evaluation)
−Leakage current value−
With respect to the capacitor-type storage battery (capacitor) produced in each example, the change in the leakage current value when the value of the electric field strength (applied voltage) was changed was measured. The measurement area was 0.25 cm ² .
Then, in the capacitor type storage battery (capacitor), the maximum value of the leakage current value measured in the range of electric field strength of 0 to −6 kV / cm was examined. The maximum value of the leakage current value is an average value of nine capacitor type storage batteries (capacitors).

-Relative permittivity-
For the capacitor-type storage battery (capacitor) produced in each example, the capacitance was measured under the conditions of a frequency of 10 Hz and 10 V using an LCR meter, and the relative dielectric constant was determined.

  The details of the dielectric of the capacitor-type storage battery (capacitor) produced in each example are shown in Table 1, and the evaluation results are shown in Table 2.

In Comparative Example 1, dimethylsiloxane constituting the dielectric did not have a metal ion (cationic metal) that causes space charge distribution polarization, so a large charge arrangement did not occur and the dielectric constant was low.
Further, in Comparative Example 2, the silicic acid (the hydroxyl group) constituting the dielectric is modified with a metal having a very high ion binding property such as sodium (Na), so that the current leakage is large and cannot be measured. Met.

  On the other hand, in Examples 1-9, a larger dielectric constant was realized than in the comparative example. This is because the metal ion is modified with a bond having both an ionic bond and a covalent bond with respect to the hydroxyl group of the silicon compound (silicic acid, siloxane, and siliconate), so that the hydroxyl group modified with the metal ion is a space charge. It can be said that this is because the distribution polarization is caused.

  In particular, in Examples 3 to 9, since dimethyl and dihydroxysilicone oils were dehydrated and condensed into silicic acid whose hydroxyl group was modified with a metal ion, the hydroxyl group modified with the metal ion was more efficient. It is considered that the space charge distribution polarization was caused, and the relative dielectric constant was increased as compared with Example 1.

  From the above results, in this example, compared to the comparative example, a capacitor type storage battery (capacitor) having a high relative dielectric constant, a small leak current value, a large capacity per unit volume, and excellent pressure resistance is obtained. You can see that

10 Dielectric 11 Upper electrode 12 Lower electrode

Claims (10)

Siloxane, and at least one silicon compound of the siliconate for less part of the hydroxyl groups possessed by the silicon compound, a bond having both a covalent bond with an ionic bond, Ri Do from silicon compounds metal ions is modified ,
In addition, the silicon compound is a solid material having a high relative dielectric constant , which is a bonded product in which other siloxane is bonded by dehydration condensation . It consists of a silicon compound in which a metal ion is modified with a bond having a covalent bond as well as an ionic bond for at least part of the hydroxyl group of silicic acid,
When the metal ion is a magnesium ion, the molecular structure of the silicon compound has a ≡Si—O—Si≡ bond as a skeleton, and has silicon atoms in the range of 20 to 10,000.
In addition, the silicon compound is a solid material having a high relative dielectric constant , which is a bonded product in which other siloxane is bonded by dehydration condensation . The high relative dielectric constant solid material according to claim 1, wherein the silicon compound has a leak current value of 1 × 10 ⁻⁹ A / cm ² or less at an electric field intensity of an absolute value of 6 kV / cm or less.   The said metal ion is modified with respect to at least one part of the hydroxyl group which the said silicon compound has by replacing with the hydrogen atom of the hydroxyl group which the said silicon compound has. High relative dielectric constant solid material.   5. The high dielectric constant solid according to claim 1, wherein the molecular structure of the silicon compound has a ≡Si—O—Si≡ bond as a skeleton, and has silicon atoms in the range of 20 to 10,000. material.   6. The metal ion according to claim 1, wherein the metal ion is one selected from a metal ion belonging to Group 2 of the periodic table, a metal ion belonging to Group 13 of the periodic table, and a phosphorus (P) ion. The high dielectric constant solid material according to Item 1. A dielectric comprising at least the high relative permittivity solid material according to any one of claims 1 to 6 . The dielectric according to claim 7 , further comprising at least one selected from perovskite-based oxides and oxides having a crystal structure with a nonstoichiometric oxygen amount of 0.01 to 0.2. A pair of electrodes;
A dielectric disposed between the pair of electrodes, wherein the dielectric according to claim 7 or 8,
A capacitor-type storage battery. The capacitor-type storage battery according to claim 9, wherein a reaction product of the pair of electrodes and the dielectric is formed on a contact surface between the pair of electrodes and the dielectric.