JP2011049073A - Power generation element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a power generation element which is suitable for a power source of portable electronic equipment, capable of further downsizing and weight reduction with high safety, and capable of using for a part requiring flexibility, and furthermore, has a charging function with high charging efficiency. <P>SOLUTION: The power generation element consists of a dielectric elastomeric layer 1 and a pair of conductive elastomeric layers (electrode layers) 2. The dielectric elastomeric layer 1 is constructed of rubber containing ionic liquid. The conductive elastomeric layer 2 is constructed of rubber containing a conductive filler. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a power generation element that can be used as a battery or a power source, and includes a pair of electrode layers and an intermediate layer disposed between the electrode layers, and the intermediate layer includes a dielectric elastomer layer.

  In recent years, demand for mobile electronic devices such as mobile phones and mobile computers has rapidly increased and has become one of the fields where further growth is expected. In addition, portable information terminals such as mobile phones and mobile computers are one of the fields where further growth is expected in the future. As a power supply source of such portable information terminals, lithium ion batteries have become the mainstream, and research and development related to lithium ion batteries are being actively pursued as the terminals become smaller and lighter.

For example, Patent Document 1 below discloses a lithium ion secondary battery using a polymer having a structure in which electrodes having catalyst layers are connected to both surfaces of an electrolyte layer. Patent Document 2 below discloses a charging mechanism for a mobile device that uses a piezoelectric element to generate power from an antenna member or movement during opening and closing.
On the other hand, there are various transducers for converting electrical energy and mechanical energy, such as power supplies (generators) for mobile devices, engines, artificial muscles, actuators for pumps, speakers, etc. Application to the field is being studied. In addition, application of dielectric rubber compositions constituting transducers to antennas and capacitors has been studied.

  Such a transducer (transducer) is composed of a dielectric elastomer laminate having a structure in which a polymer (dielectric rubber) is an intermediate layer and both ends thereof are sandwiched between a pair of electrode layers. For example, Patent Document 3 below discloses a dielectric elastomer laminate having a structure in which a material serving as an electrode is disposed on both sides of a dielectric elastomer based on silicon or acrylic rubber that functions as a transducer. .

  Further, as a material of this dielectric elastomer, the following Patent Document 4 discloses a ceramic material having a high dielectric constant dispersed in a base elastomer. Patent Document 5 below discloses an elastomer that exhibits a high dielectric loss factor (dielectric constant × dielectric loss tangent) by adding an active component that increases the dipole moment to the base elastomer.

JP 2006-294457 A JP 2002-190627 A Special table 2003-505865 gazette JP 2007-063337 A JP 2002-285013 A

Conventional lithium batteries have the following problems.
(1) Since the difference between the normal area and the dangerous area is very close and a protection mechanism is necessary to ensure safety, there are limits to weight reduction and miniaturization. (2) Since the constituent material is mainly metal or hard plastic, it is easily damaged when external force, bending stress, or vibration is applied, the stored electrolyte leaks, or a short circuit occurs inside the battery, causing the temperature to rise rapidly. The organic solvent in the electrolyte may volatilize and ignite. (3) Since the constituent material is metal or hard plastic, it cannot be used for parts that require flexibility.

On the other hand, the charging mechanism for mobile devices disclosed in Patent Document 2 has the following disadvantages.
(1) Regarding mobile phones, energy cannot be obtained frequently from the movement of opening and closing of antenna members and mobile phones. (2) Since a piezoelectric element is used, a certain level of impact force is required for power generation.

Further, the dielectric elastomer disclosed in Patent Documents 3 to 5 has the following problems.
(1) In order to achieve a high dielectric constant, a large amount of an active ingredient that increases the amount of dipole moment is added, so the flexibility inherent in the elastomer is impaired, and the performance as a transducer is sufficient. It is assumed that it will not be demonstrated. (2) Since a large amount of dielectric ceramics is added, not only the flexibility is impaired, but cracks and breaks may occur when it is repeatedly expanded and contracted. (3) There is a description that an additive may be added to improve the dielectric constant of the material, but the specific dielectric constant and elastic modulus are suitable as a transducer. Numbers are not shown. (4) Power generation depends on mechanical energy.

  Accordingly, the problem of the present invention is that it is suitable for a power source for portable electronic devices, can be further reduced in size and weight, has high safety, and can be used for a portion requiring flexibility. It is to provide a power generation element that also has a function and high charging efficiency.

  In order to solve the above-described problem, a power generation element of the present invention is a power generation element including a pair of electrode layers and an intermediate layer disposed between the electrode layers, and the intermediate layer is made of an elastomer containing an ionic liquid. It is characterized by being a dielectric elastomer layer. This power generation element has excellent power generation performance (charge performance and discharge performance) by having a dielectric elastomer layer made of an elastomer containing an ionic liquid as an intermediate layer. The ionic liquid is also referred to as an ionic liquid, an ionic fluid, an ionic fluid, or a room temperature molten salt.

  The power generating element of the present invention can recover the electromotive force without applying a deforming force from the outside or supplying power after discharging. In other words, the power generating element of the present invention is a battery having a natural charging action. Although the mechanism has not been elucidated, it is thought that an electric potential is generated by an electrode reaction involving an ionic liquid. For example, whether an electric potential is generated by an oxidation-reduction reaction with oxygen or moisture in the atmosphere involving an ionic liquid, or an electric double layer is formed by the involvement of an ionic liquid, and an electric potential is generated by diffusion from there. It is considered that a potential is generated by absorbing static electricity present in the space near the power generation element due to the ionic liquid.

When the electrode layer of the power generation element of the present invention is a conductive elastomer layer made of an elastomer containing a conductive filler, excellent flexibility as a whole element can be obtained.
When the conductive elastomer layer of the power generation element of the present invention contains an ionic liquid (that is, the electrode layer contains an ionic liquid as a conductive filler), more stable power generation performance (charging performance and discharging performance) can be obtained. .

When the elastomer constituting the dielectric elastomer layer and / or the conductive elastomer layer of the power generation element of the present invention is rubber, it is compared with a case where the elastomer (thermoplastic elastomer) other than rubber (thermosetting elastomer) is used. Better flexibility.
When the rubber having a molecular structure containing an oxygen atom is used, the power generation performance (charging performance and discharging performance) of the power generation element of the present invention is further improved. This effect is presumed to be due to the polarity of the molecule to which the oxygen atom is bonded.

  It is preferable to use acrylic rubber or silicon rubber as the rubber. These rubbers have a molecular structure containing oxygen atoms and are excellent in durability and flexibility. Therefore, the power generation element using acrylic rubber or silicon rubber as the rubber constituting the dielectric elastomer layer and the conductive elastomer layer has excellent power generation performance (charging performance and discharging performance), durability and flexibility. It becomes.

In the power generating element of the present invention, it is preferable that the rubber constituting the elastomer constituting the dielectric elastomer layer and the rubber constituting the elastomer constituting the conductive elastomer layer are the same. Thereby, since the adhesiveness between the intermediate layer and the electrode layer is improved, the power generating element of the present invention has high durability against repeated bending while maintaining flexibility.
The thickness of the dielectric elastomer layer of the power generation element of the present invention is preferably 10 μm to 2 mm. If the thickness of the dielectric elastomer layer is less than 10 μm, the mechanical strength during bending may be insufficient. If the thickness of the dielectric elastomer layer exceeds 2 mm, the power generation capacity / charge capacity of the power generation element increases, but the internal resistance and the like increase, so the balance with the degree of improvement in power generation capacity / charge capacity, that is, energy Inefficiency.

  The thickness of the conductive elastomer layer (electrode layer) of the power generation element of the present invention is preferably 5 μm to 1 mm. If the thickness of the conductive elastomer layer is less than 5 μm, holes and cracks are likely to occur during deformation, and film formation becomes difficult. If the thickness of the conductive elastomer layer exceeds 1 mm, it will be difficult to follow the deformation, and the internal resistance will increase and the conductivity will decrease, resulting in power generation performance and power generation efficiency (especially discharge efficiency). May decrease. In addition, when the electrode layer of the electric power generation element of this invention is a metal plate or a metal thin film, the thickness can be 0.05 micrometer-1 mm.

  As the ionic liquid contained in the dielectric elastomer layer and the conductive elastomer layer constituting the power generating element of the present invention, it is preferable to use a pyridinium ionic liquid or an imidazolium ionic liquid. As a result, a power generating element that is particularly excellent in charging performance and discharging performance can be obtained. In particular, the dielectric elastomer layer and the conductive elastomer layer are made of rubber having a molecular structure containing oxygen atoms (particularly acrylic rubber or silicon rubber), and contain pyridinium ionic liquid or imidazolium ionic liquid as the ionic liquid. Since the compatibility between the rubber and the ionic liquid is good, the charge / discharge efficiency of the power generating element of the present invention is particularly good.

When both the dielectric elastomer layer and the conductive elastomer layer constituting the power generation element of the present invention contain an ionic liquid, the power generation element of the present invention can obtain a high electromotive force and improve physical elongation. The durability against repeated bending and the like is improved, the flexibility at a low temperature is ensured, and the heat resistance at a high temperature is improved.
In the power generation element according to the present invention, it is preferable that the opposite side of the electrode layer to the dielectric elastomer layer is covered with an insulator. Thereby, the charging / discharging effect | action of the electric power generating element of this invention becomes a more excellent thing. The insulator is a dielectric that induces electric polarization when an electric field is applied, and it is preferable to use an insulator that becomes a charged body by electrostatic induction. When such an insulator is coated on the opposite side of the electrode layer from the dielectric elastomer layer, polarization inside the dielectric elastomer layer is promoted, so that an excellent charge / discharge action can be obtained. It is guessed. As this insulator, it is preferable to use a fluororesin such as PTFE (polytetrafluoroethylene) or fluororubber having excellent dielectric properties, insulation properties, and durability.

  The power generation element according to the present invention can be suitably used even in a portion where flexibility is required because the intermediate layer is made of a dielectric elastomer layer containing an ionic liquid and has excellent power generation performance and high deformability. . In addition, since no so-called electrolytic solution is used, there is no fear of ignition due to leakage of the electrolytic solution or volatilization of the solvent, and a minimum safety mechanism is sufficient, and miniaturization and weight reduction are possible.

  In addition, the power generating element of the present invention is not only composed of a dielectric elastomer layer as an intermediate layer, but also composed of a conductive elastomer layer as an electrode layer, so that even if stress such as strain is repeatedly applied, cracks and cracks, Breakage and the like are prevented in advance, and stable charge / discharge performance can be exhibited.

It is sectional drawing which shows the electric power generating element corresponded to 1st Embodiment of this invention. It is sectional drawing which shows the electric power generating element corresponded to 2nd Embodiment of this invention. It is sectional drawing which shows the electric power generating element corresponded to 3rd Embodiment of this invention. It is sectional drawing which shows the electric power generating element corresponded to 4th Embodiment of this invention. It is sectional drawing which shows the power generation element laminated body on which the power generation element of this invention was laminated | stacked. It is sectional drawing which shows the power generation element laminated body on which the power generation element of this invention was laminated | stacked. It is sectional drawing which shows the power generation element laminated body on which the power generation element of this invention was laminated | stacked. It is sectional drawing which shows the power generation element laminated body on which the power generation element of this invention was laminated | stacked. It is a top view which shows the electric power generating apparatus which used the electric power generating element of this invention as a power generation source. It is a side view of the electric power generating apparatus shown in FIG. It is the perspective view (a) of the electric power generating apparatus which provided the electric power generating element of this invention on the cylindrical core material, and its top view (b). They are the perspective view (a) of the power generator which provided the power generating element of this invention on the cylindrical core material, and its top view (b). They are a perspective view (a) and a plan view (b) of a power generator in which a plurality of power generating elements of the present invention are provided in the axial direction on a cylindrical core material. They are a perspective view (a) and a plan view (b) of a power generation device in which a plurality of power generation elements of the present invention are provided in a circumferential direction on a cylindrical core material. It is the expanded sectional view which showed the structure of the operation key of the portable information terminal which incorporates the electric power generating element of this invention. It is the expanded sectional view which showed the structure of the operation key of the portable information terminal which incorporates the electric power generating element of this invention. FIG. 16 is a cross-sectional view illustrating the movement of the operation key in FIG. 15. FIG. 16 is a cross-sectional view illustrating the movement of the operation key in FIG. 15. It is a figure which shows the electric power generation element which impregnated the ionic liquid to a part of electroconductive elastomer member. It is a figure which shows the electric power generation element which impregnated the ionic liquid to the whole conductive elastomer member. It is a figure which shows the electroconductive elastomer member used as the basis of the electric power generating element of FIG. 19 and FIG. It is sectional drawing which shows the power generation element laminated body on which the power generation element of this invention was laminated | stacked. It is sectional drawing which shows the power generation element laminated body on which the power generation element of this invention was laminated | stacked. It is a figure which shows the circuit which measures the performance of the electric power generating element of this invention. It is the graph which measured the time change of the voltage waveform of the electric power generation element of Example 1-1. It is the graph which showed the time-dependent change of the electric potential difference (voltage V) of the electric power generation element of Example 5-1 and 5-2. It is the graph which showed the voltage waveform of the electric power generation element of Example 6-1. It is the graph which showed the voltage waveform of the electric power generation element of Example 7-1.

Embodiments of the present invention will be described below.
[First Embodiment]
As shown in FIG. 1, the power generating element of this embodiment includes a dielectric elastomer layer 1 and a pair of conductive elastomer layers (electrode layers) 2. The dielectric elastomer layer 1 is made of rubber (elastomer) containing an ionic liquid. The conductive elastomer layer 2 is made of rubber (elastomer) containing a conductive filler.
<About rubber>
As the rubber constituting the dielectric elastomer layer 1 and the conductive elastomer layer 2, those shown in Table 1 below are preferably used.

  These rubbers have a dielectric constant of 3 or more, a hardness as a molded body of 30 to 50 durometer A, and a maximum elongation of more than 500%. It has good compatibility and compatibility with the conductive filler, is excellent in stability and elongation after molding, and is excellent in terms of dielectric performance, power generation performance, flexibility, moldability, price, and availability.

  Moreover, it is preferable that the rubber constituting the dielectric elastomer layer 1 and the conductive elastomer layer 2 is crosslinked by adding a crosslinking agent. The kind and addition amount of the crosslinking agent are appropriately selected according to the kind of rubber used.

<About ionic liquid>
In the power generation element of the present invention, it is essential that the dielectric elastomer layer constituting the intermediate layer contains an ionic liquid. Moreover, when the electric power generating element of this invention is equipped with the electrode layer which consists of a conductive elastomer layer, it is preferable to contain an ionic liquid as a conductive ferrule.
Examples of the ionic liquid that can be used in the power generation element of the present invention include pyridinium-based ionic liquid, imidazolium-based ionic liquid, alicyclic amine-based ionic liquid, and aliphatic amine-based ionic liquid shown in the following chemical formulas 1 to 4. And aliphatic phosphonium-based ionic liquids. These may be used alone or in combination of two or more.

R, R ′, R ″ and R ′ ″ in the formula are hydrogen or a hydrocarbon-containing group or an alkyl group, and may be the same or different. X ⁻ represents (CF ₃ SO ₂ ) ₂ N ⁻ ; TFSI, B (C ₂ O ₄ ) ₂ ⁻ , BF ₄ ⁻ , Br ⁻ , Cl ⁻ , I ⁻ , PF ₆ ⁻ , CF ₃ SO ₃ ^−. , CF ₃ COO ⁻ , CH ₃ SO ₄ ⁻ , C ₆ H ₄ CH ₃ SO ₃ ⁻ , SCN ⁻ , [P (C ₂ F ₅ ) ₃ F ₃ ] ⁻ ; FAP, [B (CN) ₄ ] ⁻ ; TCB, (NC) ₂ N ⁻ , FeCl ₄ ⁻ , CH ₃ SO ₃ ⁻ , HSO ₄ ⁻ , CH ₃ CH ₂ OSO ₃ ⁻ , CH ₃ (OCH ₂ CH ₂ ) ₂ OSO ₃ ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , AlCl ₄ ⁻ , Tf ₂ N ⁻ , C (CN) ₃ ^{− and the} like.

Preferably, a pyridinium-based ionic liquid or an imidazolium-based ionic liquid can be used. It is also preferable to use a mixture of a pyridinium ionic liquid and an imidazolium ionic liquid. Among these, a pyridinium-based ionic liquid or an imidazolium-based ionic liquid, in which the anion is (NC) ₂ N ⁻ or (CF ₃ SO ₂ ) ₂ N ⁻ , is particularly preferable. Specifically, as shown in the following chemical formulas 5 and 6, 1-ethyl-3-methylimidazolium is used as a cation, and (NC) ₂ N ⁻ or (CF ₃ SO ₂ ) ₂ N ⁻ is used as an anion. An ionic liquid is mentioned.

Moreover, it is preferable that the viscosity of the ionic liquid to be used is 1-1500 cP (0.1-150 Pa * s) in 25 degreeC.
The content of the ionic liquid in the dielectric elastomer layer and the conductive elastomer layer is appropriately set according to the target power generation performance and the type of the base rubber and the ionic liquid. What was mixed in the ratio of 70 mass parts is preferable, More preferably, it is 1-50 mass parts, More preferably, it is 5-20 mass parts. If the content of the ionic liquid is less than 5 parts by mass, sufficient power generation performance cannot be obtained, and if it exceeds 70 parts by mass, the upper limit of compatibility with the base rubber is exceeded, and the flexibility of the dielectric elastomer layer and the conductive elastomer layer is increased. The properties may be greatly impaired.

<Dielectric filler>
The dielectric elastomer layer constituting the power generating element of the present invention may contain a dielectric filler other than the ionic liquid as long as the performance such as flexibility is not impaired.
Examples of the dielectric filler include a high dielectric ceramic powder and an organic compound having a thiocarbonyl group.
High dielectric ceramic powders include barium titanate (BaTiO ₃ ), lead zirconate titanate (PZT), lanthanum doped lead zirconate titanate (PLZT), strontium titanate (SrTiO ₃ ), lead titanate (PbTiO ₃ ). , Bismuth titanate, barium titanate and the like are suitable. Of these, lead zirconate titanate (PZT) is most suitable because it has both a Curie point of 200 ° C. or higher and a high dielectric constant. In addition, as long as it has a fixed dielectric constant and a Curie point, compounds other than these may be used.

  The dielectric filler made of high dielectric ceramic powder can be added at a ratio of 1 to 100 parts by weight with respect to 100 parts by weight of the base rubber. If the amount is less than 1 part by weight, the effect of improving the dielectric property is small, and if it exceeds 100 parts by weight, flexibility and the like may be impaired. The amount is preferably 5 to 60 parts by weight with respect to 100 parts by weight of the base rubber, and more preferably 5 to 40 parts by weight with respect to 100 parts by weight of the base rubber.

  As the organic compound having a thiocarbonyl group, thiourea derivatives, thioamide derivatives, thioketone derivatives, dithiocarbamic acid ester derivatives and the like shown in the following chemical formulas 7 to 10 are preferable. These organic compounds are appropriately selected in consideration of processing temperature, use temperature, target dielectric constant, and compatibility with the base rubber to be used. Among them, thiourea derivatives are used in air and water. It is the most suitable organic compound because it is very stable, has excellent compatibility with the base rubber and exhibits a low melting point.

In formula, R1-R3 shows hydrogen or a hydrocarbon containing group, and may be same or different, respectively.
When an organic compound having a thiocarbonyl group is used as the conductive filler, the content is appropriately selected depending on the target dielectric constant, the type of base rubber, etc., but is approximately 5 with respect to the total amount of the base rubber composition. -40% by weight, more preferably 10-30% by weight. If the content is less than 5% by weight, the relative amount is not so much improved because the absolute amount present in the base rubber is too small. Moreover, when adding exceeding 40 weight%, the limit of compatibility with a base rubber will be exceeded, and there exists a possibility that flexibility may be impaired significantly.

<About thickness and hardness of dielectric elastomer layer>
The thickness of the dielectric elastomer layer is appropriately set depending on the application or depending on the type of base rubber to be used, but preferably 10 μm to 2 mm, more preferably 100 to 500 μm, which can maintain durability and deformability. Most preferably, it is 150-300 micrometers. If the thickness is less than 10 μm, holes or cracks may occur during deformation. If the thickness exceeds 2 mm, the distance between the electrode layers 10 and 10 will increase, resulting in a decrease in power generation performance and a decrease in deformability due to an increase in internal resistance. It becomes easy.

  It is preferable that the hardness of the dielectric elastomer layer 1 is 20 to 60, more preferably 30 to 50 on the dirometer A scale. When the hardness is less than 20, the deformability increases, but the mechanical strength becomes insufficient, and the practicality is lowered. On the other hand, when the hardness exceeds 60, the deformability is insufficient and the practicality is lowered.

<Conductive filler>
As an electrode layer constituting the power generating element of the present invention, a metal or a metal thin film having a relatively high conductivity such as platinum, gold, silver, copper, etc., or a single carbon powder or a mixture of carbon powder and metal powder A so-called carbon electrode that is solidified may be used, but a conductive elastomer layer is preferable from the viewpoint of deformability.

A conductive elastomer layer is a layer obtained by making an elastomer contain a conductive filler. The elastomer described above is preferably used as the elastomer, and the conductive filler preferably has a volume resistivity of 10 Ω · cm or less, more preferably 1 × 10 ⁻¹ Ω · cm. When the volume resistivity exceeds 10 Ω · cm, sufficient conductivity as an electrode layer cannot be obtained.

  Inorganic conductive fillers are classified into carbon-based conductive fillers and metal-based conductive fillers. Examples of the carbon-based conductive filler include conductive carbon black, graphite, carbon nanofiber, carbon nanotube, and fullerene. Examples of the metallic conductive filler include fine particles such as platinum, gold, silver, and copper, and fine fibers. These can be used alone or in admixture of two or more. Preferably, carbon nanofibers and carbon nanotubes are used.

  As the organic conductive filler, a conductive material obtained by adding an appropriate dopant such as anion or cation to polythiophine, polyacetylene, polyaniline, polypyrrole, polyparaphenylene, polyparaphenylenevinylene, or a derivative thereof shown in Chemical formulas 11 to 15. Can be used.

  These conductive fillers are preferably mixed at a ratio of 5 to 70 parts by mass, more preferably 10 to 50 parts by mass, with respect to 100 parts by mass of the base rubber. Most preferably, it is 20-40 weight part. When the content of the conductive filler is less than 5 parts by mass, sufficient conductivity as the electrode layer cannot be obtained.

  When the content of the conductive filler exceeds 70 parts by mass, the flexibility of the conductive elastomer is lowered in the case of a particulate or powder-based conductive filler, and in the case of a liquid conductive filler, The shape may not be retained, and may be softened, or may not be mixed because the compatibility limit is exceeded.

<About other additives>
The dielectric elastomer layer and the conductive elastomer may contain various coupling agents and surface treatment agents. As the coupling agent, aluminum-based, silane-based, titanium-based and the like are preferable. In addition, when the dielectric elastomer layer contains a particulate or powdery dielectric filler, it is preferable to use what has been subjected to so-called electret treatment (charging treatment).

<Thickness and hardness of conductive elastomer layer>
The thickness of the conductive elastomer layer is 5 μm to 1 mm. Preferably it is 10-300 micrometers, More preferably, it is 10-200 micrometers, Most preferably, it is 10-80 micrometers. If the conductive elastomer layer is thinner than 5 μm, holes and cracks are likely to occur during deformation, and film formation becomes difficult. On the other hand, when the conductive elastomer layer exceeds 1 mm, it becomes difficult to follow the deformation, and the internal resistance increases, so that sufficient conductivity as an electrode cannot be obtained.

In addition, it is preferable that the thickness and hardness of the conductive elastomer layer be equal to those of the dielectric elastomer layer, and the behavior of the conductive elastomer layer with respect to bending or the like be the same as that of the dielectric elastomer layer. In particular, when repeated bending or the like is given, the hardness is in the range of 20-60 on the durometer A scale, and more preferably in the range of 30-50.
It is preferable that the composition of the base elastomer forming the dielectric elastomer layer and the composition of the base elastomer forming the electrode layer 10 are the same or the same. For example, one electrode layer 10 may be an electrode layer 10 containing a conductive filler other than an ionic liquid, and the other electrode layer 10 may be an electrode layer 10 containing an ionic liquid as a conductive filler.
Moreover, you may arrange | position the conductive elastomer layer of different hardness on both sides of a dielectric elastomer layer.

<Example of power generation element manufacturing method>
As a material for the dielectric elastomer layer, a base rubber, an ionic liquid, a crosslinking agent, a dielectric filler other than the ionic liquid, and the like are prepared, and these are mixed to obtain a liquid mixture. A dielectric elastomer layer is obtained by forming this into a semi-cured film having a predetermined thickness using a roll coater or the like.

As a material for the conductive elastomer layer, a base rubber, a conductive filler, a crosslinking agent, an ionic liquid, and the like are prepared, and these are mixed to obtain a liquid mixture. A conductive elastomer layer is obtained by forming this into a semi-cured film having a predetermined thickness using a roll coater or the like.
A laminate is obtained by sandwiching the semi-cured dielectric elastomer layer between the two semi-cured conductive elastomer layers thus obtained, and this laminate is pressure-heat-molded. At the time of this pressure heating molding, cross-linking and interlayer bonding are performed. Here, if the base rubber of the dielectric elastomer layer and the conductive elastomer layer is the same type or a compatible combination, these layers can be bonded at a relatively low temperature and pressure.

  Alternatively, the dielectric elastomer layer may be cured, and electrode layers (such as a cured conductive elastomer layer) may be attached to both surfaces with an adhesive or the like. Alternatively, the dielectric elastomer layer may be cured first, and a semi-cured conductive elastomer layer may be disposed on both surfaces thereof, followed by pressure heating molding.

[Second Embodiment]
As shown in FIG. 2, the power generating element of this embodiment includes a dielectric elastomer layer 1, a pair of conductive elastomer layers (electrode layers) 2, and an insulator layer (covering layer made of an insulator) 3. Become. The dielectric elastomer layer 1 is made of rubber (elastomer) containing an ionic liquid. The conductive elastomer layer 2 is made of rubber (elastomer) containing a conductive filler.
The dielectric elastomer layer 1 and the conductive elastomer layer (electrode layer) 2 are described in detail in the first embodiment.
The material constituting the insulator layer 3 is preferably a material having a higher dielectric constant and charge rate and higher insulation resistance, and the following can be exemplified.

<Example of material constituting insulator layer 3>
Heat represented by phenol resin (PF), urea resin (UF), melamine resin (MF), unsaturated polyester resin (UP), epoxy resin (EP), direal phthalate resin (PDAP), polyurethane (PU), etc. Curable resin.

  Polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (CTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), perfluoroalkoxy fluororesin (PFA), ethylene tetrafluoride and propylene hexafluoride Fluororesin represented by coalescence (FEP), ethylene / tetrafluoroethylene copolymer (ETFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE) and the like.

  Polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), polyvinyl acetate (PCAc), polycarbonate (PC), acrylic resin (PMMA), ABS resin, AS resin, polyamide (PA) , Polyacetal (POM), polyethylene terephthalate (PET), polymethylpentene (TPX), polyphenylsulfide (PPS), polyetheretherketone (PEEK), liquid crystal polymer (LCP), polyetherimide (PEI), polyarylate ( Thermoplastic resins represented by PAR), polysulfone (PSF), polyethersulfone (PES), polyamideimide (PAI), silicon resin and the like.

Various rubber compositions such as synthetic rubber and natural rubber, substances containing cellulose such as calcium carbide, carbide, ebonite, glass, paper, rayon and cellophane.
Natural fibers such as cotton, hemp, linen, silk, wool and cashmere.
Of these materials, it is preferable to use a fluorine resin, a polyamide resin, or a rubber composition, and polytetrafluoroethylene (PTFE) or polyamide (PE) is particularly preferable.

A material obtained by forming these materials into a film or sheet is joined to the conductive elastomer layer (electrode layer) 2. In the case of resin, it may be made into a solution with a predetermined solvent or melted, applied to the conductive elastomer layer (electrode layer) 2 and dried.
By covering the conductive elastomer layer (electrode layer) 2 with the insulator layer 3, an effect of suppressing current leakage from the power generating element main body A can be obtained. The insulator layer 3 also has a function as an outer packaging material of the power generation element main body A. It also has an action of suppressing oozing of the ionic liquid from the dielectric elastomer layer 1 containing the ionic liquid and the conductive elastomer layer 2 containing the ionic liquid. Further, it is considered that a part of the electric charge charged in the insulating layer 3 plays a part of the natural charging action of the power generation element.

The insulator layer 3 preferably covers a wider area of the conductive elastomer layer (electrode layer) 2 and is usually covered except for a connection portion between the conductive elastomer layer (electrode layer) 2 and a lead wire or the like. It is desirable to do.
Furthermore, when using resin as the material of the insulator layer 3, it is preferable to contain a dielectric filler to such an extent that the insulating property is not impaired. Thereby, the dielectric property and charging property of the insulator layer 3 are improved. Since the dielectric property and charging property of the insulator layer 3 are improved, a larger amount of charged electricity is taken into the power generation element, so that the natural charging action is improved.

  Specifically, when the insulator layer 3 is charged, the polarization and orientation of the conductive filler in the conductive elastomer layer (electrode layer) 2 that is in contact are naturally promoted. In addition, the charge of the insulator layer 3 moves to the dielectric elastomer layer 1 through the conductive elastomer layer (electrode layer) 2, and the polarization and orientation of the dielectric filler inside the dielectric elastomer layer 1 are naturally promoted. . Thereby, it is thought that the charging efficiency of a power generation element improves.

[Third Embodiment]
As shown in FIG. 3, the power generating element of this embodiment includes a dielectric elastomer layer 1, a pair of conductive elastomer layers (electrode layers) 2, an insulator layer (covering layer made of an insulator) 3, leads 4 and. The dielectric elastomer layer 1 is made of rubber (elastomer) containing an ionic liquid. The conductive elastomer layer 2 is made of rubber (elastomer) containing a conductive filler.

The dielectric elastomer layer 1 and the conductive elastomer layer (electrode layer) 2 are described in detail in the first embodiment.
In this embodiment, three sides of the power generation element main body A composed of the dielectric elastomer layer 1 and the conductive elastomer layer (electrode layer) 2 are covered with the insulator layer 3, and the uncovered portion is discharged with electric power. Lead 4 for fixing is fixed. The power generating element of this embodiment is manufactured by forming the insulator layer 3 after bonding the leads 4 to the conductive elastomer layer (electrode layer) 2 of the power generating element main body A.

In this embodiment, a material having a volume resistivity of 10 ⁷ Ω · cm or more is used as a material constituting the insulator layer 3. When the volume resistivity is less than 10 ⁷ Ω · cm, the insulation is insufficient and the electric energy is likely to leak to the outside. Preferably, those with 10 ⁹ Ω · cm or more are used.
The covering area of the power generating element main body A by the insulator layer 3 is preferably 80% or more of the total surface area of at least one of the conductive elastomer layers (electrode layers) 2. If it is 80% or more, the possibility of electrical energy leaking to the outside due to contact with an external atmosphere such as humidity or an external material is further reduced. Preferably, both are 80% or more, more preferably 90% or more.

The relative dielectric constant of the insulating layer 3 is 1 or more and 50 or less, more preferably 1 or more and 30 or less. Most preferably, it is 1 or more and 10 or less. When the relative dielectric constant exceeds 50, the charge generated by its own dielectric polarization interacts with the charge in the electrode, which may reduce power generation or charging efficiency as a power generation element.
The insulator layer 3 can be bonded to the power generating element body A using a known adhesive or the like. When the insulating layer 3 is an insulating elastomer layer having the same base rubber as that of the conductive elastomer layer (electrode layer) 2, cross-linking adhesion by pressure heating and the like is also possible.
The power generation element of this embodiment can prevent electrical energy input to and output from the power generation element from leaking to the outside, and thus can more reliably prevent a decrease in power generation efficiency.

[Fourth Embodiment]
As shown in FIG. 4, the power generating element of this embodiment includes a dielectric elastomer layer 10 made of rubber (elastomer) containing an ionic liquid, and a pair of surfaces formed by impregnating a conductive filler on the surface layers of both sides. The conductive elastomer layer (electrode layer) 20a and the lead 4 are included.

In the power generation element of this embodiment, a clear interface is not formed between the conductive elastomer layer 20a and the dielectric elastomer layer 10. Therefore, the conductive elastomer layer 20a is extremely difficult to peel from the dielectric elastomer layer 10. Therefore, the power generating element of this embodiment is particularly excellent in durability during long-term use.
The conductive elastomer layer 20 a is formed, for example, by impregnating the surface layer of the dielectric elastomer layer 10 with an organic conductive filler having a volume resistivity of 10 ³ Ω · cm or less. Since the dielectric elastomer layer 10 contains an ionic liquid, the conductive elastomer layer 20a also has an ionic liquid.

Examples of the organic conductive filler include a conductive polymer material obtained by adding a suitable dopant such as anion or cation to polythiophine, polyacetylene, polyaniline, polypyrrole, polyparaphenylene, polyparaphenylenevinylene, or a derivative thereof. .
Organic conductive fillers have a higher affinity with elastomers, especially rubber compositions, compared to conductive fillers such as metal materials and carbon materials, and therefore inhibit the intrinsic properties of elastomers such as stretchability and hardness. Less is. For this reason, when used as an elastomer transducer which is a so-called piezoelectric element, an elastomer transducer having excellent durability can be obtained.

As a method for impregnating an organic conductive filler, a dielectric elastomer layer 10 and a conductive filler are introduced into a carbon dioxide atmosphere in a subcritical state or a supercritical state, and the conductive filler is used as a surface layer of the dielectric elastomer layer 10. The method of impregnating is used.
Here, the “subcritical carbon dioxide” means carbon dioxide in a liquid state whose pressure is equal to or higher than the critical pressure of carbon dioxide (7.38 MPa) and whose temperature is lower than the critical temperature (31.1 ° C.), Alternatively, the carbon dioxide is in a liquid state in which the pressure is less than the critical pressure of carbon dioxide and the temperature is equal to or higher than the critical temperature, or the temperature and pressure are both less than the critical point but close to this. In addition, “supercritical carbon dioxide” refers to carbon dioxide in a state where the pressure is equal to or higher than the critical pressure of carbon dioxide and the temperature is equal to or higher than the critical temperature.

  As a method for introducing the dielectric elastomer layer 10 and the conductive filler into the carbon dioxide atmosphere in the subcritical state or the supercritical state, the dielectric elastomer and the conductive filler are separately used, or the conductive filler is used as the dielectric elastomer. You may introduce it by making it adhere. The conductive filler may be introduced as a single substance or in a state dispersed in an aqueous solvent or an organic solvent.

Examples of such organic solvents include alcohol solvents such as methanol, ethanol, and propanol, ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as dibutyl ether and tetrahydrofuran, and aromatic solvents such as benzene and toluene. be able to.
The treatment conditions in the subcritical state or the supercritical state can be appropriately determined within a range in which the dielectric elastomer layer 10 does not undergo performance deterioration in the specific permittivity or elastic state due to modification such as dissolution.

  The dielectric elastomer layer 10 may be subjected to electret treatment (charging treatment) or the like in order to increase energy conversion efficiency. In that case, the timing of forming the conductive elastomer layer (electrode layer) 20a by impregnating the conductive filler may be before or after the electret treatment or the like.

[Fifth Embodiment]
The power generating element of the present invention can be used by being stacked in order to increase efficiency. In this case, for example, the power generating element of the fourth embodiment is preferably stacked. In the power generation element of the fourth embodiment, since the conductive elastomer layer 20a is formed by impregnating the surface of the dielectric elastomer layer 10 with a conductive filler, power generation in which the conductive elastomer layer (electrode layer) is separately formed. Compared with the case of stacking elements, the overall thickness can be reduced.

In this embodiment, as shown in FIGS. 5 to 8, a power generation element stack in which power generation elements are stacked will be described.
In the power generating element laminate 300 of FIG. 5, the two power generating elements 200 are overlapped so that the electrode layers 20 </ b> A serving as the positive electrodes are in contact with each other, and the electrode layers 20 </ b> B serving as the negative electrodes are electrically connected to each other by the conductive wires 90. In addition, the electrode layer 20B serving as a negative electrode and the electrode layer 20A serving as a positive electrode are respectively connected to terminals 80 for electrical extraction. The insulator layer 3 is fixed to the electrode layer 20B.

  The dielectric elastomer layer 10 and the electrode layers 20A and 20B have the same material and configuration as the dielectric elastomer layer 10 and the conductive elastomer layer 20a of the fourth embodiment. As with the insulator layer 3 of the second embodiment, the insulator layer 3 has a wide operating temperature range, chemical resistance, electrical insulation, low friction, non-adhesiveness, and weather resistance as well as chargeability (insulation). It is made of a material that satisfies flame retardancy. Specifically, it is desirable to use, for example, a fluororesin such as PTFE (polytetrafluoroethylene), a thermosetting resin such as a phenol resin, a hydrocarbon resin such as polyethylene, a thermoplastic resin such as polyamide.

According to the power generation element laminate 300 of FIG. 5, the power generation performance that is twice that of the power generation element 200 alone can be exhibited. Since the power generating element 200 is configured so that the positive electrodes are in contact with each other, the size of the power generating element 200 can be minimized. Thus, the present invention can be easily applied to electronic devices such as mobile phones that require small size and light weight.
As shown in FIGS. 6 and 7, if more power generation elements 200 are stacked, power generation performance (output power, output voltage) proportional to the number of power generation elements 200 can be exhibited. In addition, it is possible to exert even more excellent power generation performance by covering and compressing and expanding the entire or part of the stacked power generation elements with the insulator layer 3.

  The power generating element laminate 300 in FIG. 6 is obtained by superimposing five power generating elements 200, and the power generating element laminated body 300 in FIG. 7 is obtained by further superposing N power generating elements 200. And as shown in the drawing, the negative electrodes and the positive electrodes of the adjacent power generation elements 200 are connected in parallel by the conductive wires 90, respectively, and each electrode layer 20A, 20B of the power generation element 200 located at the uppermost position is used for electrical extraction. The terminal 80 is connected. Moreover, it can also be set as the structure shown in FIG.

[Sixth Embodiment]
9 to 13 illustrate a power generation device 400 using the power generation element 100 of the present invention as a power generation source.
First, the power generating device 400 of FIG. 9 is obtained by integrally bonding the power generating element 100 of the first embodiment on an insulating flat core member 60. Since the power generation device 400 is a flat and small-sized and light-weight device, it can be used as a power source for electronic devices with many space restrictions such as a mobile phone. In this case, if at least the surface of the core member 60 that is in contact with the power generation element 100 is formed of the material constituting the insulator layer 3 described in the second embodiment, a part of the charged electric charge contributes to the improvement of the power generation performance. Is obtained.

  Next, in the power generation device 400 of FIGS. 10 and 11, a plurality of power generation elements 100 of the first embodiment are arranged on a sheet-like core material 60, and each of the power generation elements 100 is electrically connected by a conductive wire 70. They are connected in series. With such a configuration, not only a large amount of electricity to which a voltage corresponding to the number of the power generating elements 100 is added can be taken out, but also the sheet-like core material 60 itself exhibits appropriate flexibility. it can. Therefore, for example, since it can be installed so as to be affixed to the inner surface of the casing of the electronic device, it can be used as a more convenient power source with less restrictions on its installation shape and location.

When the plurality of power generating elements 100 are connected in series as described above, for example, if the lower electrode is a negative electrode and the upper electrode is a positive electrode, the conductive line 70 is adjacent to the upper and lower electrodes as shown in the figure. Connect each other directly. Further, when a plurality of power generating elements 100 are arranged in this way, the power generating elements 100 can be electrically connected in parallel.
Further, the power generation device 400 of FIG. 11 is obtained by integrally bonding the power generation element 100 of the first embodiment to the surface of a cylindrical core member 60. And if it is such a structure, it can install efficiently in a narrow space etc., without sacrificing the magnitude | size (area) of the electric power generation element 100. FIG. Also in this case, when the core member 60 is formed of the material constituting the insulator layer 3 described in the second embodiment, an effect that a part of the charged charges contributes to the improvement of the power generation performance can be obtained.

The shape of the core material is not limited to a cylindrical shape. Moreover, the joining method of the electric power generation element 100 and the core material 60 is not restricted to adhesion, and various joining methods such as joining by pressure and heating crosslinking, mechanical joining by a resin screw or a resin rivet can be employed.
Furthermore, if a cylindrical core member 60 as shown in FIG. 12 is used as this modification, the power generating element 100 can be integrally bonded or attached not only to the surface (outer surface) but also to the inside thereof. As a result, it is possible to exhibit even more excellent power generation capacity without changing the overall size.

Further, as shown in FIG. 13 and FIG. 14, a plurality of power generating elements 100 are integrally bonded to the cylindrical core member 60 in the circumferential direction or the axial direction, If the power generating elements 100 are electrically connected in series or in parallel by a conductive wire (not shown), more excellent power generation capability can be exhibited.
9-14, the core material 60 has a wide operating temperature range, chemical resistance, electrical insulation, low friction, non-adhesiveness, weather resistance, flame resistance, and mechanical strength. It is desirable to use a satisfactory material, and among the materials constituting the insulator layer 3 mentioned in the second embodiment, it is preferable to use a fluororesin such as PTFE (polytetrafluoroethylene).

[Seventh Embodiment]
The power generating element of the present invention is incorporated in an operation key 500 of a portable information terminal as shown in FIGS. 15 and 16, for example, and used as a power source for the portable information terminal.
First, the operation key 500 shown in FIG. 15 has a dielectric elastomer layer interposed between the operation key body 50 of the portable information terminal directly touched by a human finger and the switch 51 positioned below the operation key body 50. 1 and a lead 4 for power extraction, which is also an electrode, is connected to one end of the dielectric elastomer layer 1.

  As shown in FIG. 17A, the operation key 500 shown in FIG. 15 is clicked on when the operation key body 50 is clicked and a load F is applied to the operation key body 50. After 1 is bent downward, the operation key body 50 is returned by the repulsive force of the switch 51 to return the dielectric elastomer layer 1 to its original state, as shown in FIG. The dielectric elastomer layer 1 can follow such a series of movements, and can supply power through the leads 4. That is, the space in the small device can be used effectively as a battery. Moreover, since the dielectric elastomer layer 1 is flexible, the space of the operating part can be used as a battery as described above.

Further, as shown in FIGS. 18A and 18B, the entire operation key body 50 or its lower end and the movable support member 52 are made of a conductive material such as copper, and a lead 4 for power extraction is provided on these. Even if it is the structure which connects, the same effect | action and effect can be exhibited.
On the other hand, the operation key 500 in FIG. 16 has an upper electrode 61 and a lower electrode 62 installed in a flexible embossed sheet 60 protruding on the dome, and the upper surface of the embossed sheet 60 is covered with the dielectric elastomer layer 1. In addition to covering, the upper surface thereof is covered with an insulating sheet 63, and a power extraction lead 4, which is also an electrode, is connected to one end of the dielectric elastomer layer 1.

  In the case of the operation key 500 having such a configuration, the dome portion of the embossed sheet 60 is pushed down and deformed downward, so that the dielectric elastomer layer 1 bends downward, and then the upper electrode 61 is deformed. And the lower electrode 62 come into contact with each other and the switch is turned on, and then the dielectric elastomer layer 1 returns to the original state by the repulsive force of the embossed sheet 60. Thus, it becomes possible to use the space of a small apparatus efficiently as a battery. Moreover, since the dielectric elastomer layer 1 is flexible, the space of the operating part can be used as a battery as described above.

In this embodiment, flexible electrodes 61 and 62 that can follow the deformation may be provided on the surface layer of the dielectric elastomer layer 1 serving as a so-called dielectric elastomer type generator. In addition to metal, carbon, the above-described conductive elastomer layer can be preferably used, and it is also preferable to use conductive grease or the like in combination.
The material of the movable support member 52 is not particularly limited, and examples thereof include metal and plastic. In order to transmit a stress from an external force to the dielectric elastomer layer, it is preferably flexible.

[Eighth Embodiment]
A power generation element 600 of FIG. 19 is obtained by impregnating a part of a strip-shaped conductive elastomer member 20 shown in FIG. 21 with an ionic liquid.
A power generation element 600 in FIG. 20 is obtained by impregnating the entire strip-shaped conductive elastomer member 20 shown in FIG. 21 with an ionic liquid.

The conductive elastomer member 20 is made of the same material (base rubber + conductive filler) as that used for the conductive elastomer layer (electrode layer) 2 of the first embodiment.
The ratio of the conductive filler is appropriately set depending on the type of the conductive filler. In particular, the carbon material which is preferable for the conductive filler, particularly CNF, is preferably 5 parts by mass or more. When the amount is less than 5 parts by mass, the conductivity of the conductive elastomer member 20 is lowered, and it is difficult to develop a power generation function. In order to make it more difficult for such problems to occur, at least 5 parts by mass, more preferably 10 parts by mass or more are required. As the conductive filler, CNF is particularly preferable.

As the ionic liquid impregnated in the conductive elastomer member 20, a pyridinium ionic liquid, an imidazolium ionic liquid, an alicyclic amine ionic liquid, an aliphatic amine ionic liquid, an aliphatic phosphonium ionic liquid, or the like may be used. it can. Among these, a pyridinium-based ionic liquid or an imidazolium-based ionic liquid, in which the anion is (NC) ₂ N ⁻ or (CF ₃ SO ₂ ) ₂ N ⁻ , is particularly preferable. Examples thereof include ionic liquids having ethyl-3-methylimidazolium as a cation and (NC) ₂ N ⁻ or (CF ₃ SO ₂ ) ₂ N ⁻ as an anion.

  Further, the content of the ionic liquid is preferably 5 parts by mass or more, more preferably 10% by mass or more with respect to the base rubber, at least in a part of the strip-shaped conductive elastomer member 20. Electricity can be taken out by impregnating the strip-shaped conductive elastomer member 20 with the ionic liquid. Alternatively, the conductive elastomer member 20 impregnated with the ionic liquid and the conductive elastomer member 20 not impregnated can be laminated and used.

  Since this conductive elastomer member 20 generates electricity due to a potential difference between the high concentration side and the low concentration side of the ionic liquid, electrodes (or lead wires corresponding to the electrodes) are attached to the low concentration side and the high concentration side. Therefore, it can be used as a power source. The power generation element 600 of this embodiment shows an example in which the electrodes 40 are attached to both ends of the conductive elastomer member 20.

[Ninth Embodiment]
In this embodiment, a power generation element laminate in which the power generation elements of the present invention are laminated via an insulator layer will be described.
The power generating element 100 constituting the power generating element laminate 300 shown in FIG. 22 includes a pair of conductive elastomer layers 2 and a dielectric elastomer layer 1 disposed therebetween. In the power generation element 100, as in the first embodiment, the dielectric elastomer layer 1 is made of rubber containing an ionic liquid, and the conductive elastomer layer 2 is made of rubber containing a conductive filler.

  Three layers of this power generation element 100 are laminated, and between each power generation element 100, an insulator layer 31 made of a material that easily charges negatively and an insulator layer 32 made of a material that easily charges positively are arranged. Further, an insulator layer 31 made of a material that is easily negatively charged is disposed on the upper surface of the power generating element 100 disposed on the uppermost side, and the lower surface of the power generating element 100 disposed on the lowermost side is charged positively. An insulator layer 32 made of a material that is easy to do is disposed.

As a material constituting the insulator layers 31 and 32, a material having a different charging performance from the material constituting the insulator layer 3 described in the second embodiment, preferably a substance at a position distant from the charge train. Use in combination. Thereby, the electrode reaction involving the ionic liquid can be made stable.
As a combination of the insulator layer 31 and the insulator layer 32, in consideration of insulation performance, mechanical strength and the like, polytetrafluoroethylene (PTFE) and polyamide (PA), polyethylene and polyamide (PA), polychlorinated A combination of vinyl (PVC) and polyamide (PA) is preferred.

In addition, silicon-containing resins such as silicon resins are preferably used in combination with polytetrafluoroethylene (PTFE), polyamide (PA), and polyvinyl chloride (PVC) having a positive charge column and a negative charge column. Can do.
The power generating element 100 constituting the power generating element laminate 300 shown in FIG. 23 includes a pair of conductive elastomer layers 2 and a dielectric elastomer layer 1 disposed therebetween. In the power generation element 100, as in the first embodiment, the dielectric elastomer layer 1 is made of rubber containing an ionic liquid, and the conductive elastomer layer 2 is made of rubber containing a conductive filler.

Three layers of the power generation element 100 are laminated, and the positive electrode insulator layer 33 is disposed on the upper surface of the power generation element 100 disposed on the uppermost side, and the negative electrode insulator layer is disposed between the power generation element 100 and the lower power generation element 100. 34 is disposed, and the positive electrode insulator layer 33 is disposed between the power generation element 100 and the lower power generation element 100, and the negative electrode insulator layer 34 is disposed on the lower surface of the lowermost power generation element 100. Yes.
The material constituting the positive electrode insulator layer 33 and the negative electrode insulator layer 34 is the same as that of the insulator layers 31 and 32 described above, from the material constituting the insulator layer 3 described in the second embodiment. Those having different charging performance, preferably, a combination of substances located at different positions in the charging train are used. Thereby, the electrode reaction involving the ionic liquid can be made stable.

  In the power generating element laminate 300 of FIG. 23, two conductive elastomer layers (electrode layers) 2 in contact with the positive electrode insulator layer 33 act as positive electrodes, and two conductive elastomers in contact with the negative electrode insulator layer 34. The layer (electrode layer) 2 functions as a negative electrode. The negative electrodes and the positive electrodes of the adjacent power generation elements 100 are connected in series by conductive wires 90, respectively. In addition, an electrical extraction terminal 80 is connected to the positive electrode of the power generating element 100 disposed on the uppermost side and the negative electrode of the power generating element 100 disposed on the lowermost side, respectively. As a connection method, series connection or parallel connection can be selected as appropriate.

  By adopting such a structure, the force of the electric field formed between the insulator layers 33 and 34 increases, so that the amount of charge accumulated in the conductive elastomer layer (electrode layer) 2 of each power generating element 100 increases. Can be achieved.

[Examples 1-1, 1-2, Reference Examples 1-1, 1-2, Comparative Example 1-1]
(Examples 1-1 and 1-2 and Reference Examples 1-1 and 1-2)
A power generation element having the structure shown in FIG. 1 was produced by the following method.
As shown in Table 2, in Examples 1-1 and 1-2, 100 parts by mass of a reactive acrylic rubber (indicated as ACM) (“Toacron SA-310” manufactured by Towpe Co., Ltd.) is added to a crosslinking agent for acrylic rubber. 8 parts by mass (“Polynate 70” manufactured by Toyo Polymer Co., Ltd.) and 40 parts by mass of pyridinium ionic liquid (“IL-P14” manufactured by Guangei Chemical Industry Co., Ltd.) were added and mixed. Using a control coater (manufactured by Matsuo Seisakusho), a thin film having a thickness of 250 μm was obtained to obtain a semi-cured rubber thin film. After the rubber thin film was crosslinked, the hardness was measured with a durometer and found to be 30 on the durometer A scale. This was used as the dielectric elastomer layer 1.

For Reference Examples 1-1 and 1-2, rubber thin films were obtained in the same manner except that no pyridinium ionic liquid was mixed. After the rubber thin film was crosslinked, the hardness was measured with a durometer and found to be 33 on the durometer A scale. This was used as the dielectric elastomer layer 1.
Further, 100 parts by mass of a reactive acrylic rubber (indicated as ACM) (“Toaaclon SA-310” manufactured by Toupe Co., Ltd.), 8 parts by mass of a crosslinking agent for acrylic rubber (“Polynate 70” manufactured by Toyo Polymer Co., Ltd.), carbon Add nanofiber (indicated as CNF) (“VGCF” manufactured by Showa Denko KK) and / or pyridinium-based ionic liquid (indicated as IL) (“IL-P14” manufactured by Guangei Chemical Industry Co., Ltd.) and add and mix Then, the obtained mixed solution was made into a thin film having a thickness of 50 μm using a K control coater (manufactured by Matsuo Seisakusho) and subjected to crosslinking treatment to obtain a rubber thin film. This was used as the conductive elastomer layer 2 for the upper electrode layer and the lower electrode layer. In addition, each hardness of the rubber thin film for upper electrode layers and the rubber thin film for lower electrode layers is as described.

Using the dielectric elastomer layer 1 and the conductive elastomer layer 2 obtained in this way, the dielectric elastomer layer 1 is disposed between a pair of the conductive elastomer layers 2, and pressurizing and heat-molding is shown in FIG. A power generating element having a structure was obtained.
(Comparative Example 1-1)
As shown in Table 2, to 100 parts by mass of reactive acrylic rubber (indicated as ACM) (“Toacron SA-310” manufactured by Toupe Co., Ltd.), a crosslinking agent for acrylic rubber (“Polynate 70” manufactured by Toyo Polymer Co., Ltd.) was added. 8 parts by mass was added and mixed, and the resulting mixed solution was made into a thin film having a thickness of 250 μm using a K control coater (manufactured by Matsuo Seisakusho) to obtain a semi-cured rubber thin film. When the hardness of the power generation rubber thin film was measured with a durometer, it was 33 on the durometer A scale. This was used as the dielectric elastomer layer 1.

  Further, 100 parts by mass of a reactive acrylic rubber (indicated as ACM) (“Toaaclon SA-310” manufactured by Toupe Co., Ltd.), 8 parts by mass of a crosslinking agent for acrylic rubber (“Polynate 70” manufactured by Toyo Polymer Co., Ltd.), carbon 35 parts by mass of nanofiber (denoted as CNF) (“VGCF” manufactured by Showa Denko KK) was added and mixed, and the resulting mixture was made into a thin film having a thickness of 50 μm using a K control coater (manufactured by Matsuo Seisakusho) Rubber thin films for the upper electrode layer and the lower electrode layer were obtained. This was used as the conductive elastomer layer 2 for the upper electrode layer and the lower electrode layer. Each hardness of the rubber thin film for upper electrode layers and the rubber thin film for lower electrode layers was 40.

Using the dielectric elastomer layer 1 and the conductive elastomer layer 2 obtained in this way, the dielectric elastomer layer 1 is disposed between a pair of the conductive elastomer layers 2, and pressurizing and heat-molding is shown in FIG. A structure was obtained.
(Power generation test as a power generation element)
Each power generating element (Example, Reference Example) and structure (Comparative Example) produced above were measured for electromotive force and generated current using the measurement circuit shown in FIG. The results are also shown in Table 2.

  The difference between Examples 1-1 and 1-2 and Reference Examples 1-1 and 1-2 is whether or not the dielectric elastomer layer 1 contains an ionic liquid, but contains an ionic liquid. It can be seen that the higher electromotive force can be obtained in Examples 1-1 and 1-2. The difference between Example 1-1 and Example 1-2 is whether or not the conductive elastomer layer 2 contains an ionic liquid, but the example 1-2 containing the ionic liquid is different. It can be seen that higher electromotive force can be obtained. In Comparative Example 1-1 in which neither the dielectric elastomer layer 1 nor the conductive elastomer layer 2 contains an ionic liquid, no electromotive force was obtained.

FIG. 25 shows a chart in which the time change of the voltage waveform of the power generation element of Example 1-1 is measured. It can be seen that stable power generation is performed.
[Examples 2-1 to 2-4, Comparative Example 2-1]
(Examples 2-1 to 2-4)
A power generation element having the structure shown in FIG. 1 was produced by the following method.

  As shown in Table 3, 100 parts by mass of a reactive acrylic rubber (indicated as ACM) (“Toaaclon SA-310” manufactured by Toupe Co., Ltd.) and a crosslinking agent for acrylic rubber (“Polynate 70” manufactured by Toyo Polymer Co., Ltd.) 5 parts by mass of the following imidazolium-based ionic liquid is added to and mixed with a base rubber containing 8 parts by mass, and the resulting mixture is made into a thin film with a thickness of 250 μm using a K control coater (Matsuo Seisakusho). A cured rubber thin film was obtained. When the hardness of the rubber thin film after the crosslinking treatment was measured with a durometer, it was 33 on the durometer A scale. This was used as the dielectric elastomer layer 1.

<Imidazolium-based ionic liquid used>
In Example 2-1, “1-ethyl-3-methylimidazolium tetrafluoroborate (EMI-BF ₄ ⁻ )” manufactured by Guangei Chemical Industry Co., Ltd. was used.
In Example 2-2, 1-ethyl-3-methylimidazolium dicyanamide (EMI- (CN) ₂ N ⁻ ) manufactured by Tokyo Chemical Industry Co., Ltd. was used.
In Example 2-3, “1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (EMI-IFSI ⁻ )” manufactured by Tokyo Chemical Industry Co., Ltd. was used.
In Example 2-4, “1-ethyl-3-methylimidazolium methanesulfonate (EMI-CH ₃ SO ₃ ⁻ )” manufactured by Tokyo Chemical Industry Co., Ltd. was used.

Further, 100 parts by mass of a reactive acrylic rubber (indicated as ACM) (“Toaaclon SA-310” manufactured by Toupe Co., Ltd.), 8 parts by mass of a crosslinking agent for acrylic rubber (“Polynate 70” manufactured by Toyo Polymer Co., Ltd.), carbon 35 parts by mass of nanofiber (denoted as CNF) (“VGCF” manufactured by Showa Denko KK) was added and mixed, and the resulting mixture was made into a thin film having a thickness of 50 μm using a K control coater (manufactured by Matsuo Seisakusho) Crosslinking was performed to obtain a rubber thin film. When the hardness of the electrode rubber thin film after the crosslinking treatment was measured with a durometer, it was 40 on the durometer A scale. Further, the volume resistivity was measured and found to be 6.0 × 10 ⁻¹ Ω · cm. This was used as the conductive elastomer layer 2 for the upper electrode layer and the lower electrode layer.

Using the dielectric elastomer layer 1 and the conductive elastomer layer 2 obtained in this way, the dielectric elastomer layer 1 is disposed between a pair of the conductive elastomer layers 2, and pressurizing and heat-molding is shown in FIG. A power generating element having a structure was obtained.
(Comparative Example 2-1)
The structure shown in FIG. 1 was produced in the same manner as in Examples 2-1 to 2-4 except that the ionic liquid was not contained in the base rubber.

(Evaluation of power generation function as a power generation element)
Each power generation element (Example) and structure (comparative example) produced above were evaluated for their function as a power generation material using the measurement circuit shown in FIG. The generated voltage and power generation time were observed by observing with a voltage waveform measuring device. The results are also shown in Table 3.

As shown in Table 3, the power generation elements of Examples 2-1 to 2-4 generated power because the dielectric elastomer layer 1 contained an imidazolium-based ionic liquid, but the structure of Comparative Example 2-1 Since the dielectric elastomer layer 1 did not contain an ionic liquid, no power generation occurred. In the power generation elements of Examples 2-2 and 2-3, the dielectric elastomer layer 1 contains an imidazolium-based ionic liquid having (NC) ₂ N ⁻ and (CF ₃ SO ₂ ) ₂ N ⁻ as anions. Therefore, a particularly excellent power generation capability was obtained with a small addition amount of 5 parts by mass.

[Examples 3-1 to 3-3, Comparative example 3-1]
A power generation element having the structure shown in FIG. 2 was produced by the following method.
As shown in Table 4, to 100 parts by mass of reactive acrylic rubber (indicated as ACM) (“Toacron SA-310” manufactured by Toupe Co., Ltd.), a crosslinking agent for acrylic rubber (“Polynate 70” manufactured by Toyo Polymer Co., Ltd.) 8 parts by mass, 10 parts by mass of pyridinium-based ionic liquid (“IL-P14” manufactured by Guangei Chemical Industry Co., Ltd.) was added and mixed, and the resulting mixture was thickened using a K control coater (Matsuo Seisakusho). A thin rubber film having a thickness of 250 μm was obtained. After the crosslinking treatment, the hardness of the rubber thin film was measured with a durometer and found to be 33 on the durometer A scale. This was used as the dielectric elastomer layer 1.

Further, 100 parts by mass of a reactive acrylic rubber (indicated as ACM) (“Toaaclon SA-310” manufactured by Toupe Co., Ltd.), 8 parts by mass of a crosslinking agent for acrylic rubber (“Polynate 70” manufactured by Toyo Polymer Co., Ltd.), carbon 35 parts by mass of nanofiber (denoted as CNF) (“VGCF” manufactured by Showa Denko KK) was added and mixed, and the resulting mixture was made into a thin film having a thickness of 50 μm using a K control coater (manufactured by Matsuo Seisakusho) Crosslinking was performed to obtain a rubber thin film. When the hardness of this rubber thin film was measured with a durometer, it was 40 on the durometer A scale. Further, the volume resistivity was measured and found to be 6.0 × 10 ⁻¹ Ω · cm. This was used as the conductive elastomer layer 2 for the upper electrode layer and the lower electrode layer.

The dielectric elastomer layer 1 and the conductive elastomer layer 2 thus obtained are used, the dielectric elastomer layer 1 is disposed between a pair of the conductive elastomer layers 2, and pressure-heat molding is performed to generate the power generation shown in FIG. A power generating element body A having a structure in which the insulator layer 3 was removed from the element was obtained.
The power generation element body A was measured for the power generation voltage and the power generation time with a voltage waveform measuring device using the measurement circuit shown in FIG.

  Next, the insulator layer 3 was joined to the conductive elastomer layer 2 on the lower side of the power generation element main body A, and the power generation element shown in FIG. 2 was produced. The insulator layer 3 was made of a different material in each example. In Example 3-1, PTFE film (“Nitoflon No. 900UL” manufactured by Nitto Denko Corporation), MC nylon plate (“MC Nylon” manufactured by Nippon Polypenco Co., Ltd.) in Example 3-2, and high quality in Example 3-3 Paper was used.

  After the insulator layer 3 was bonded and left for one week, the power generation voltage and power generation time of this power generation element were measured with a voltage waveform measurement device using the measurement circuit shown in FIG. Then, the ratio between the generated voltage in the state of the power generating element main body A and the generated voltage as the power generating element having the structure of FIG. For Comparative Example 3-1, the generated voltage was measured after leaving the power generation element body A as it was. The results are also shown in Table 4.

As shown in FIG. 2, it can be seen that the decrease in the power generation function is suppressed or improved by bonding the insulator layer 3 to the power generation element body A as shown in FIG.
Further, from this, a general elastomer power generation element (here, the power generation element main body A) not provided with the insulator layer 3 is wrapped with a film or sheet made of an insulator (dielectric material) during storage, thereby generating power. It can also be seen that can be maintained.

[Example 4-1 and Comparative example 4-1]
A power generation element having the structure shown in FIG. 1 was produced by the following method.
As shown in Table 5, except that 95% by mass of a reactive liquid acrylic rubber containing 8% by mass of a crosslinking agent was used as a base rubber and 5% by mass of a pyridinium-based ionic liquid was used as a high dielectric filler. A rubber thin film having a film thickness of 250 μm, a relative dielectric constant of 10, and a maximum tensile elongation of 250% was produced by the same method as 1-1. This was used as the dielectric elastomer layer 1.
In addition, a reactive liquid acrylic rubber containing 8% by mass of a crosslinking agent was used as the base rubber, and 70% by mass of CNF was used as the conductive filler. A rubber thin film having physical properties of 100 mm × width 50 mm × thickness 50 μm, volume resistance 1 × 10 Ω · cm, and maximum tensile elongation 50% was prepared. This was used as a conductive elastomer layer (electrode layer) 2.

These were joined by the same method as in Example 1-1 to obtain a power generation element having the structure shown in FIG.
(Comparative Example 4-1)
As shown in Table 5 below, Example 1 was used except that 100 parts by mass of a reactive liquid acrylic rubber containing 8% by mass of a crosslinking agent as a base rubber and 50 parts by mass of PZT as a high dielectric filler were used. A rubber thin film having a film thickness of 250 μm, a relative dielectric constant of 6, and a maximum tensile elongation of 200% was prepared by the same method as in No. 1. This was used as the dielectric elastomer layer 1.

This dielectric elastomer layer 1 and the same conductive elastomer layer 2 as in Example 4-1 were joined by the same method as in Example 1-1 to obtain a power generation element having the structure shown in FIG.
Thereafter, a microammeter was connected to the upper and lower surfaces of the power generation elements of Example 4-1 and Comparative Example 4-1 obtained in this manner via flaky copper electrodes, respectively. Next, one end of the power generation element was fixed, the other end was mechanically extended by 50%, the force was removed, and the current value was measured in this state. From this measured value, the relative value with Comparative Example 4-1 as “1” was calculated as “specific power generation amount”. The results are also shown in Table 5.

As a result, as shown in the lower column of Table 5, the power generation element of Example 4-1 has a power generation amount superior to that of the power generation element of Comparative Example 4-1, even when there is a mechanical action such as elongation. I was able to demonstrate it.
[Examples 5-1 to 5-2, Comparative Example 5-1]
(Examples 5-1 and 5-2)
A power generation element having the structure shown in FIG. 1 was produced by the following method.
As shown in Table 6 below, 8 parts by mass of a crosslinking agent as a base rubber, 100 parts by mass of a reactive liquid acrylic rubber, and a pyridinium-based ionic liquid as a high dielectric filler (manufactured by Koei Chemical Industry Co., Ltd. (IL-P14)) ) A rubber thin film having a thickness of 250 μm, hardness, and durometer A33 was prepared in the same manner as in Example 1-1 except that 10 parts by mass was used. This was used as the dielectric elastomer layer 1.

  Further, the same method as in Example 1 except that 8.0 parts by mass of the crosslinking agent as the base rubber, 100 parts by mass of the reactive liquid acrylic rubber, and 35 parts by mass of carbon nanofiber (CNF) as the conductive filler were used. Thus, a rubber thin film having a volume resistivity of 6 × 10 −1 Ω · cm, hardness, and durometer A40 physical properties was produced. This was used as a conductive elastomer layer (electrode layer) 2.

These were joined by the same method as in Example 1-1 to obtain a power generation element having the structure shown in FIG.
Thereafter, the power generation element of Example 5-1 was subjected to a process of applying an external voltage (150 V) between the two conductive elastomer layers (electrode layers) 2 for 30 minutes. In Example 5-2, such an external voltage application process was not performed.

(Comparative Example 5-1)
As shown in Table 6 below, the dielectric elastomer layer 1 was made of a reactive liquid acrylic rubber containing 8 parts by mass of a cross-linking agent, by the same method as in Examples 5-1 and 5-2. The structure shown in (1) was obtained. In addition, the application process of the external voltage is not performed in Comparative Example 5-1.

The power generation elements of Examples 5-1 and 5-2 and the structure of Comparative Example 5-1 obtained in this manner were evaluated using the measurement circuit shown in FIG.
Specifically, when the potential difference between the conductive elastomer layers 2 of the test specimen was measured, the discharge recovery treatment consisting of the following (1) to (3) was repeated.

<Discharge recovery process>
(1) Short-circuit both electrodes (conductive elastomer layer) 2 to make the potential difference 0V.
(2) Then, it preserve | saves in air | atmosphere for the predetermined time in the state which eliminated the short circuit between both electrodes (conductive elastomer layer) 2.
(3) Investigate the change over time of the potential difference between the two electrodes (conductive elastomer layer) 2.

  As a result, as shown in the lower column of Table 6, in the structure of Comparative Example 5-1, a potential difference could not be obtained between the two conductive elastomer layers 2. In contrast, the power generation elements of Examples 5-1 and 5-2 were found to have a potential difference between the two conductive elastomer layers 2 by being stored in the atmosphere after discharge.

FIG. 26 is a graph showing the change over time of the potential difference (voltage V) of the power generation elements of Examples 5-1 and 5-2. The potential difference may gradually increase with time. I understand.
In addition, the power generation element of Example 5-1 to which an external voltage was applied at the time of production significantly increased the generated voltage value at the time of discharge recovery compared to the power generation element of Example 5-2 to which no external voltage was applied. I also understood that

[Examples 6-1 to 6-5, Comparative Example 6-1]
(Examples 6-1 to 6-5)
The power generation element having the structure shown in FIG.
First, as shown in the upper part of Table 7 below, reactive bulk acrylic rubber (ACM) to which 8 parts by mass of an acrylic rubber cross-linking agent (Polynate 70 manufactured by Toyo Polymer Co., Ltd.) was added (Toacron SA-310 manufactured by Toupe Co., Ltd.) As a base rubber, and as an organic additive, Noxeller TMU (trimethylthiourea manufactured by Ouchi Shinsei Chemical Co., Ltd.) (Examples 6-7 to 6-3) or Noxeller EUR (Ouchi Shinsei Chemical Industry Co., Ltd.) 1,3-diethylthiourea (Example 6-4) or Noxeller TMTU (Tetramethyldiethylthiourea manufactured by Tokyo Chemical Industry Co., Ltd.) (Example 6-5) was added, and a K control coater (Matsuo Seisakusho) was added. A semi-cured elastomer layer was prepared. This was used as the dielectric elastomer layer 1. The measurement results of the film thickness, hardness, and elongation at break are shown in the same table.

Next, as shown in the lower part of the same table, reactive bulk acrylic rubber (ACM) (Toacron SA-310 manufactured by Toupe Co., Ltd.) is used as a base rubber, and CNF (carbon nad fiber: 30 parts by mass of Showa Denko VGCF) and 10 parts by mass of ionic liquid (pyridinium-based ionic liquid, IL-P14 made by Koei Chemical Co., Ltd.) were added and a K control coater (Matsuo Seisakusho) was used. A semi-cured elastomer layer was prepared. This was used as a conductive elastomer layer (electrode layer) 2. The measurement results of the film thickness, hardness, and elongation at break are shown in the same table.

  Using the dielectric elastomer layer 1 and the conductive elastomer layer 2 obtained in this manner, the dielectric elastomer layer 1 is disposed between a pair of the conductive elastomer layers 2, and pressurization and heating molding is performed to obtain FIG. 1. A power generation element having the structure shown was obtained. In addition, the crosslinking process of the dielectric elastomer layer 1 and the conductive elastomer layer 2 was performed at the time of this pressure heating.

(Comparative Example 6-1)
A dielectric elastomer layer 1 was produced in the same manner as in Example 6-1 except that no organic additive was added. Moreover, the conductive elastomer layer 2 was produced by the same method as Example 6-1 except that no ionic liquid was added. Using these, the dielectric elastomer layer 1 was disposed between the pair of conductive elastomer layers 2 and subjected to pressure heating molding to obtain the structure shown in FIG. In addition, the crosslinking process of the dielectric elastomer layer 1 and the conductive elastomer layer 2 was performed at the time of this pressure heating.

  The power generation elements of Examples 6-1 to 6-5 and the structure of Comparative Example 6-1 obtained in this way were evaluated for functions as power generation elements using the measurement circuit shown in FIG. In this evaluation, an electrode was bonded to both conductive elastomer layers 2 with a conductive adhesive (Dotite XA-819A manufactured by Fujikura Kasei Co., Ltd.), and a voltage waveform measuring device (manufactured by Yokogawa Electric Co., Ltd.) was connected to this electrode. went. The results are shown in the bottom column (power generation voltage) and FIG. 27 (voltage waveform) of Table 7.

  As a result, the structure of Comparative Example 6-1 did not generate any power, whereas the power generation elements of Examples 6-1 to 6-5 were all capable of exhibiting excellent power generation capability of 150 mV or more. I understood. FIG. 27 shows a voltage waveform in the power generating element of Example 6-1, and it was found that a stable electromotive force can be exhibited.

[Examples 7-1 to 7-2, Comparative example 7-1]
A power generating element 600 shown in FIGS. 19 and 20 was produced by the following method.
As shown in Table 8 below, reactive bulk acrylic rubber (ACM) (Toacron SA-310 manufactured by Tope Co., Ltd.) is used as a base rubber, this base rubber is dissolved in methyl ethyl ketone, and carbon nanofiber (Showa Showa) is used as a conductive filler. An electrical solution was prepared by adding and stirring VCGFR-H).
Using this solution, a thin film was produced by a K control coater (manufactured by Matsuo Seisakusho), and a conductive elastomer member 20 shown in FIG. 21 was produced. The conductivity of the conductive elastomer member 20 was 5.0 × 10 ⁻¹ Ω · cm, and the effect of improving the conductivity could be confirmed by adding carbon nanofibers.

  Next, as shown in FIGS. 19 and 20, an ionic liquid (Guangei Chemical Industry Co., Ltd.) is applied to one end (Example 7-1) and all (Example 7-2) of the conductive elastomer member 20 thus obtained. A power generation element 600 was produced by impregnating IL-P14). After this power generation element 600 was stored in the atmosphere for 1 hour, a voltage waveform measuring device (manufactured by Yokogawa Electric Co., Ltd.) was connected to both ends of the power generation element 600 through the copper electrode 40, and the voltage waveform was measured. In addition, as shown in FIG. 21, the voltage was measured in the same manner for the conductive elastomer member 20 (Comparative Example 7-1) that was not impregnated with any ionic liquid, and the results were shown in the lower column and FIG. 28.

  As a result, the electroconductive elastomer member 20 of Comparative Example 7-1 not impregnated with any ionic liquid did not obtain any electromotive force, whereas the electroconductive elastomer member 20 was impregnated with the ionic liquid. Electromotive forces were obtained from the power generating elements 600 of 7-1 and 7-2. In particular, in the power generation element 600 of Example 7-1 in which the ionic liquid was applied only to one end of the conductive elastomer member 20, an excellent electromotive force was obtained as shown in FIG. Thus, even in a continuous layer, the electromotive force can be improved by including an ionic liquid in at least a part thereof.

[Examples 8-1 to 8-2]
The power generation elements of Examples 8-1 to 8-2 have the structure shown in FIG. 2, and the dielectric elastomer layer 1 and the conductive elastomer layer (electrode layer) 2 having the structure shown in Table 9 and PTFE (polytetrafluoroethylene). And an insulator layer 3 made of a sheet.
After producing this power generation element by the same method as Example 3-1, the process which applies the voltage of 150V from the outside for 30 minutes was performed. The functions of the power generation elements of Examples 8-1 and 8-2 thus obtained were evaluated using the measurement circuit shown in FIG.
Specifically, when measuring the potential difference between the conductive elastomer layers 2 of the power generation element, the discharge recovery treatment consisting of the following (1) to (3) was repeated 5 cycles.

<Discharge recovery process>
(1) Short-circuit both electrodes (conductive elastomer layer) 2 to make the potential difference 0V.
(2) Thereafter, in a state where the short circuit between the two electrodes (conductive elastomer layer) 2 is eliminated, in a reduced pressure atmosphere (1 × 10 ⁻¹ Pa) (Example 8-1) or in the air (Example 8-2) ) For a predetermined time.
(3) Investigate the change over time of the potential difference between the two electrodes (conductive elastomer layer) 2.

  As a result, as shown in the lower column of Table 9, the power generation element of Example 8-1 stored under reduced pressure obtained the same generated voltage (400 mV) as the power generation element of Example 8-2 stored in the atmosphere. It was.

[Examples 9-1 to 9-3, Comparative Example 9-1]
A power generation element having the structure shown in FIG. 2 and a power generation element laminate having the structure shown in FIGS. 5, 6, and 8 were produced by the following method.
As shown in Table 10, 8 parts by mass of an acrylic rubber cross-linking agent (Polynate 70 manufactured by Toyo Polymer Co., Ltd.) as a base rubber, and 100 parts by mass of reactive bulk acrylic rubber (ACM) (Toacron SA-310 manufactured by Towpe Co., Ltd.) A mixed solution in which 10 parts by mass of pyridinium-based ionic liquid (IL-P14 manufactured by Guangei Chemical Industry Co., Ltd.) is added to this base rubber is prepared, and a semi-cured state is obtained using a K control coater (manufactured by Matsuo Seisakusho). A rubber thin film was created. This was used as dielectric elastomer layers 1 and 10. The film thickness and hardness measurement results are shown in Table 10.

  Next, as also shown in Table 10, 8 parts by mass of the acrylic rubber cross-linking agent (Polynate 70 manufactured by Toyo Polymer Co., Ltd.) and reactive bulk acrylic rubber (ACM) (Toacron SA-310 manufactured by Toupe Co., Ltd.) are used as the base rubber. ) Using 100 parts by mass, a mixture in which 35 parts by mass of conductive filler (CNF) was dispersed was prepared, and a semi-cured thin film was prepared using a K control coater (manufactured by Matsuo Seisakusho). This was used as conductive elastomer layers (electrode layers) 2 and 20. The measurement results of the film thickness and hardness are as shown in Table 10 below.

  Next, the dielectric elastomer layer 10, the conductive elastomer layer (electrode layer) 20, and the insulating layer (electrode placement material) 3 made of PTFE (polytetrafluoroethylene) thus obtained are shown in FIGS. 5 and 6. As shown in the figure, the power generating element laminate 300 was manufactured by overlapping and bonding (Examples 9-1 and 9-2). Further, the structure shown in FIG. 2 is obtained by sandwiching the dielectric elastomer layer 1 between a pair of electrode layers 2, disposing an insulating layer 3 made of PTFE (polytetrafluoroethylene) on the negative electrode side, and bonding them together. (Example 9-3) was produced.

Further, the dielectric elastomer layer 10, the conductive elastomer layer (electrode layer) 20, and the insulating layer 3 made of PTFE (polytetrafluoroethylene) are laminated and bonded as shown in FIG. It produced (Comparative Example 9-1).
For the power generation element laminate 300 of Example 9-1, as shown in FIG. 5, two power generation elements 200 are connected in parallel with the conductive wire 90, and the terminal 80 is connected to the electrode layers 20 </ b> A and 20 </ b> B, The generated voltage and generated current were measured. This measurement was performed after one week had elapsed since the power generation element laminate 300 was produced.

For the power generation element laminate 300 of Example 9-2, as shown in FIG. 6, five power generation elements 200 are connected in parallel with conductive wires 90, and terminals 80 are connected to the electrode layers 20 </ b> A and 20 </ b> B, The generated voltage and generated current were measured. This measurement was performed after one week had elapsed since the power generation element laminate 300 was produced.
For the power generation element of Example 9-3, the generated voltage and generated current between the two conductive elastomer layers (electrode layers) 2 were measured after one week had elapsed after the production.

For the power generation element laminate 300 of Comparative Example 9-1, as shown in FIG. 8, two power generation elements 200 are connected in parallel with the conductive wire 90, and the terminal 80 is connected to the electrode layers 20 </ b> A and 20 </ b> B, The generated voltage and generated current were measured. This measurement was performed after one week had elapsed since the power generation element laminate 300 was produced.
Next, generation of the power generating element laminate 300 of Examples 9-1 and 9-2 and Comparative Example 9-1 when the generated voltage and generated current of the power generating element of Example 9-3 are each “1”. The relative values of voltage and generated current were calculated as “specific generated voltage and specific generated current”. The results are also shown in the lower column of Table 10.

  As can be seen from the results in Table 10, the generated currents of the power generation element laminate of Example 9-1 having the structure shown in FIG. 5 and the power generation element laminate of Example 9-2 having the structure shown in FIG. -3, the current generated by the power generating element 200 was 2 times and 5 times (the same multiple as the number of laminated dielectric elastomer layers 10). On the other hand, in the power generation element laminated body 300 of Comparative Example 9-1 having the structure shown in FIG. 8, both the generated voltage and the generated voltage were as low as about 1/10 of the power generation element 200 of Example 9-3. .

1,10 Dielectric elastomer layer 2,20a Conductive elastomer layer (electrode layer)
DESCRIPTION OF SYMBOLS 20 Conductive elastomer member 3,31-34 Insulator layer 100 Power generation element 200 Power generation element 300 Power generation element laminated body 400 Power generation apparatus 500 Operation key 600 Power generation element

Claims (11)

A power generation element comprising a pair of electrode layers and an intermediate layer disposed therebetween,
The power generation element, wherein the intermediate layer is a dielectric elastomer layer made of an elastomer containing an ionic liquid.   The power generating element according to claim 1, wherein the electrode layer is a conductive elastomer layer made of an elastomer containing a conductive filler.   The power generating element according to claim 2, wherein the conductive elastomer layer contains an ionic liquid.   The power generation element according to claim 1, wherein the elastomer is rubber.   The power generation element according to claim 4, wherein the rubber has a molecular structure containing an oxygen atom.   The power generation element according to claim 4, wherein the rubber is acrylic rubber or silicon rubber.   The power generating element according to claim 4, wherein the rubber constituting the elastomer constituting the dielectric elastomer layer and the rubber constituting the elastomer constituting the conductive elastomer layer are the same.   The power generating element according to claim 1, wherein the dielectric elastomer layer has a thickness of 10 μm to 2 mm.   The power generating element according to claim 2, wherein the conductive elastomer layer has a thickness of 5 μm to 1 mm.   The power generating element according to claim 1, wherein the ionic liquid is a pyridinium-based ionic liquid or an imidazolium-based ionic liquid.   The power generating element according to any one of claims 1 to 10, wherein an opposite side of the electrode layer from the dielectric elastomer layer is covered with an insulator.

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