JP5477643B2 - Electrode film composed of carbon nanotube, alkali metal salt and / or alkaline earth metal salt, ionic liquid and polymer, solid electrolyte film, actuator element - Google Patents

Description

  The present invention relates to an electrode film having conductivity and a high capacitor, a solid electrolyte film having high conductivity, an actuator element, and a manufacturing method thereof. Here, the actuator element is an actuator element whose driving force is an electrochemical process such as electrochemical reaction or charge / discharge of an electric double layer.

As an actuator element operable in air or in vacuum, an actuator using a carbon nanotube and ionic liquid gel as a conductive and stretchable active layer has been proposed (Patent Document 1).
However, there is a problem in the high-speed response and expansion / contraction rate of the actuator, and a technique for producing a high capacitance electrode film and a high conductivity solid electrolyte film is required.

JP-A-2005-176428

  It is an object of the present invention to provide an actuator with further improved performance.

  The present invention solves the above-mentioned problems, and by using an alkali metal salt and / or alkaline earth metal salt, a carbon nanotube, an alkali metal salt and / or an alkaline earth metal can be obtained by a simple method called a casting method. It was discovered that a high capacitance electrode film composed of a metal salt, an ionic liquid and a polymer can be obtained, and an alkali metal salt and / or alkaline earth metal salt, ionic liquid and It has been found that a solid electrolyte membrane composed of a polymer can be obtained, and further, it has been found that the expansion / contraction ratio of the actuator is dramatically increased and the high-speed response is improved.

The present invention provides the following electrode membrane, solid electrolyte membrane, actuator element, or manufacturing method thereof.
Item 1. An electrode film composed of carbon nanotubes, alkali metal salts and / or alkaline earth metal salts, ionic liquids and polymers.
Item 2. A solid electrolyte membrane comprising an alkali metal salt and / or an alkaline earth metal salt, an ionic liquid and a polymer.
Item 3. Item 3. The electrode membrane according to Item 1 or the solid electrolyte membrane according to Item 2, wherein the alkali metal salt is a lithium salt and the alkaline earth metal salt is a calcium salt and / or a magnesium salt.
Item 4. A laminate having the electrode film layer according to Item 1 and the solid electrolyte membrane layer according to Item 2.
Item 5. Item 5. An actuator element including the laminate according to Item 4.
Item 6. Item wherein at least two electrode film layers according to Item 1 are formed in an insulated state on the surface of the solid electrolyte membrane layer according to Item 2, and are configured to be deformable by applying a potential difference to the electrode film layer. 6. Actuator element according to item 7 An actuator element manufacturing method comprising the following steps:
Step 1: preparing a dispersion containing carbon nanotubes, alkali metal salt and / or alkaline earth metal salt, ionic liquid, polymer and solvent;
Step 2: preparing a solution containing a polymer and a solvent, an alkali metal salt and / or an alkaline earth metal salt, and if necessary, an ionic liquid;
Step 3: A step of forming a laminated body of an electrode membrane and a solid electrolyte membrane by simultaneously or sequentially forming an electrode membrane using the dispersion liquid of Step 1 and a solid electrolyte membrane using the solution of Step 2.
Item 8. An actuator element manufacturing method comprising the following steps:
Step 1: preparing a dispersion containing carbon nanotubes, alkali metal salt and / or alkaline earth metal salt, ionic liquid, polymer and solvent;
Step 2: preparing a solution containing a polymer and a solvent, an alkali metal salt and / or an alkaline earth metal salt, and if necessary, an ionic liquid;
Process 3: A process of forming an electrode film by casting, printing, coating, extrusion, or injection using the dispersion liquid of Process 1, and then increasing the density by thermally densifying the produced electrode film as necessary. Alternatively, several electrode films are thermocompression-bonded and simultaneously densified to increase the density. Step 4: Step of forming a solid electrolyte membrane by casting, printing, coating, extruding, or injection using the dispersion liquid of Step 2;
Step 5: A step of laminating the electrode film formed in Step 3 and the solid electrolyte membrane formed in Step 4 by pressure bonding to form a laminate.
Item 9. An actuator element manufacturing method comprising the following steps:
Step 1: preparing a dispersion containing carbon nanotubes, alkali metal salt and / or alkaline earth metal salt, ionic liquid, polymer and solvent;
Step 2: preparing a solution containing a polymer and a solvent, an alkali metal salt and / or an alkaline earth metal salt, and if necessary, an ionic liquid;
Step 3: Step of forming an electrode film by heating after casting using the dispersion of Step 1 Step 4: Step of forming a solid electrolyte membrane by heating after casting using the dispersion of Step 2;
Step 5: A step of laminating the electrode film formed in Step 3 and the solid electrolyte membrane formed in Step 4 by pressure bonding to form a laminate.

  According to the present invention, by using an alkali metal salt and / or an alkaline earth metal salt, an electrode film having a higher capacitance and a solid electrolyte film having a higher conductivity can be obtained. As a result, the response becomes quicker, the element can be reduced in weight or the element can be more easily deformed, and an actuator element with an efficient deformation response can be provided.

The laser displacement meter used for the actuator element displacement evaluation method in the Example of this invention is shown. FIG. 1A is a diagram showing an outline of the configuration of an example of the actuator element (three-layer structure) of the present invention, and FIG. 1B is the configuration of an example of the actuator element (five-layer structure) of the present invention. FIG. It is a figure which shows the operating principle of the actuator element of this invention. It is a figure which shows the outline of the other example of the actuator element of this invention.

  In the present invention, carbon nanotubes, alkali metal salts and / or alkaline earth metal salts, ionic liquids and polymers are used for the electrode films used for the electrode film layers of the actuator elements.

The carbon nanotube used in the present invention is a carbon-based material having a shape in which a graphene sheet is wound into a cylindrical shape, and is roughly classified into single-walled nanotubes (SWNT) and multi-walled nanotubes (MWNT) based on the number of peripheral walls. Also, various types are known, such as being divided into a chiral type, a zigzag type, and an armchair type due to the difference in the structure of the graphene sheet. Any type of carbon nanotube can be used in the present invention as long as it is referred to as such a so-called carbon nanotube.

The aspect ratio of carbon nanotubes used in the present invention is preferably 10 ⁴ or more. The larger the aspect ratio, the better. However, the upper limit is, for example, about 10 ^6, about 10 ^7, or about 10 ⁸ . The length of the carbon nanotube is usually 1 μm or more, preferably 50 μm or more, more preferably 200 μm or more, and particularly 500 μm or more. The upper limit of the length of the carbon nanotube is not particularly limited, but is about 3 mm, for example.

  A suitable example of carbon nanotubes for practical use is HiPco (manufactured by Carbon Nanotechnology Inc.), which can be relatively mass-produced using carbon monoxide as a raw material. Of course, it is limited to this. is not.

  The electrode film of the present invention is basically composed of carbon nanotubes, alkali metal salts and / or alkaline earth metal salts, ionic liquids, and polymers, but has characteristics such as activated carbon fibers and reinforcing materials that are less conductive. It can also be added as long as it is not impaired.

Examples of the alkali metal salt used in the present invention include a salt of an alkali metal and an anion, and examples of the alkaline earth metal salt include a salt of an alkaline earth metal and an anion. Examples of the alkali metal include lithium, sodium, potassium, rubidium, cesium and the like, and lithium is particularly preferable. Alkali metal salts may be used alone or in admixture of two or more. Examples of the alkaline earth metal include calcium, magnesium, strontium, and barium, and calcium and magnesium are preferable. Alkaline earth metal salts may be used alone or in admixture of two or more. Further, only one of the alkali metal and the alkaline earth metal may be used, or two or more kinds of alkali metal / alkaline earth metal having different cations and / or anions may be used in combination. The anion component of the alkali metal salt and the alkaline earth metal salt is preferably the same as the ionic liquid or an anion capable of forming the ionic liquid. The anionic component of the alkali metal salt and alkaline earth metal salts, tetrafluoroborate ion ^{_{(BF 4 -), BF 3}} CF 3 -, BF 3 C 2 F 5 -, BF 3 C 3 F 7 -, BF 3 C ₄ F ₉ ^-, hexafluorophosphate ion (PF ₆ ^-),
Bis (trifluoromethanesulfonyl) imide ion ((CF ₃ SO ₂ ) ₂ N ⁻ ), bis (fluoromethanesulfonyl) imide ion ((FSO ₂ ) ₂ N ⁻ ), bis (pentafluoroethanesulfonyl) imide ion ((CF ₃ CF ₂ SO ₂ ) ₂ N ⁻ ), perchlorate ion (ClO ₄ ⁻ ), tris (trifluoromethanesulfonyl) carbonic acid ion (CF ₃ SO ₂ ) ₃ C ⁻ ), trifluoromethanesulfonic acid ion (CF ₃ SO ₃ ⁻ ) , dicyanamide ion ^{_{((CN) 2 N -)}} , trifluoroacetate ion (CF ₃ COO ^-)
And organic carboxylate ions and halogen ions.

  The ionic liquid used in the present invention is also called a room temperature molten salt or simply a molten salt, and is a salt that exhibits a molten state in a wide temperature range including room temperature (room temperature). It is a salt that exhibits a molten state at ℃, preferably -20 ℃, more preferably -40 ℃. The ionic liquid used in the present invention preferably has a high ionic conductivity.

In the present invention, various known ionic liquids can be used, but a stable one that exhibits a liquid state at normal temperature (room temperature) or a temperature close to normal temperature is preferable. A suitable ionic liquid used in the present invention comprises a cation (preferably an imidazolium ion or a quaternary ammonium ion) represented by the following general formulas (I) to (IV) and an anion (X ⁻ ). Things.

[NR _x H _4-x ] ⁺ (III)
[PR _x H _4-x ] ⁺ (IV)

In the above formulas (I) to (IV), R is a linear or branched alkyl group having 1 to 12 carbon atoms or a branched alkyl group or an ether bond, and the total number of carbon and oxygen is 3 to 12 In formula (I), R ¹ represents a linear or branched alkyl group having 1 to 4 carbon atoms or a hydrogen atom. In the formula (I), R and R ¹ are preferably not the same. In formulas (III) and (IV), x is an integer of 1 to 4, respectively. In formulas (III) and (IV), the two R groups may be taken together to form a 3- to 8-membered, preferably 5- or 6-membered aliphatic saturated cyclic group.

  Examples of the linear or branched alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, Examples include nonyl, decyl, undecyl, dodecyl and the like. Preferably carbon number is 1-8, More preferably, it is 1-6.

  Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and t-butyl.

Examples of the alkyl group having an ether bond and having a straight chain or a branched chain having a total number of carbon and oxygen of 3 to 12 include CH ₂ OCH ₃ , CH ₂ CH ₂ OCH ₃ , CH ₂ OCH ₂ CH ₃ and CH ₂ CH _2. OCH ₂ CH ₃ , (CH ₂ ) _p (OCH ₂ CH ₂ ) _q OR ² (
Here, p is an integer of 1 to 4, q is an integer of 1 to 4, and R ² represents CH ₃ or C ₂ H ₅ .

As anions (X ⁻ ), tetrafluoroborate ion (BF ₄ ⁻ ), BF ₃ CF ₃ ⁻ , BF ₃ C ₂ F ₅ ⁻ , BF ₃ C ₃ F ₇ ⁻ , BF ₃ C ₄ F ₉ ⁻ , hexa Fluorophosphate ion (PF ₆ ⁻ ), bis (trifluoromethanesulfonyl) imide ion ((CF ₃ SO ₂ ) ₂ N ⁻ ), bis (fluoromethanesulfonyl) imide ion ((FSO ₂ ) ₂ N ⁻ ), bis (pentafluoro Ethanesulfonyl) imide ion ((CF ₃ CF ₂ SO ₂ ) ₂ N ⁻ ), perchlorate ion (ClO ₄ ⁻ ), tris (trifluoromethanesulfonyl) carbonic acid ion (CF ₃ SO ₂ ) ₃ C ⁻ ), trifluoromethane Examples include sulfonate ions (CF ₃ SO ₃ ⁻ ), dicyanamide ions ((CN) ₂ N ⁻ ), trifluoroacetate ions (CF ₃ COO ⁻ ), organic carboxylate ions, and halogen ions.

Among these, as the ionic liquid, for example, the cation is 1-ethyl-3-methylimidazolium ion, [N (CH ₃ ) (CH ₃ ) (C ₂ H ₅ ) (C ₂ H ₄ OC ₂ H ₄ OCH ₃ )] ⁺ , [N (CH ₃ ) (C ₂ H ₅ ) (C ₂ H ₅ ) (C ₂ H ₄ OCH ₃ )] ⁺ , anion is halogen ion, tetrafluoroborate ion, bis (trifluoromethanesulfonyl ) Imide ion ((CF ₃ SO ₂ ) ₂ N ⁻ ) can be specifically exemplified, and 1-ethyl-3-methylimidazolium ion and bis (trifluoromethanesulfonyl) imide ion ((CF ₃ SO ₂ ) ₂ N ^- ) Is particularly preferred. In addition, it is possible to use two or more kinds of cations and / or anions to further lower the melting point.

However, the present invention is not limited to these combinations, and any ionic liquid that has a conductivity of 0.1 Sm ⁻¹ or more can be used.

  The electrode film of the present invention is prepared by preparing a solution containing carbon nanotubes, alkali metal salt and / or alkaline earth metal salt, ionic liquid, polymer and solvent, and casting, printing, applying, extruding or injecting the resulting solution. It can be carried out. If necessary, the produced electrode film may be thermally densified to increase the density, or several electrode films may be thermocompression bonded and simultaneously densified to increase the density.

  Formation of the solid electrolyte membrane can be performed by casting, printing, coating, extrusion, or injection using a dispersion containing a polymer and a solvent, an alkali metal salt and / or an alkaline earth metal salt, and if necessary, an ionic liquid. .

  Here, the solvent used for forming the electrode membrane and the solid electrolyte membrane may be a mixed solvent of a hydrophilic solvent and a hydrophobic solvent.

  Examples of the hydrophilic solvent include carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propylene carbonate, and butylene carbonate, ethers such as tetrahydrofuran, carbon numbers of 1 to 3 such as acetone, methanol, and ethanol. And lower alcohols, acetonitrile and the like. Examples of the hydrophobic solvent include ketones having 5 to 10 carbon atoms such as 4-methylpentan-2-one, halogenated hydrocarbons such as chloroform and methylene chloride, aromatic hydrocarbons such as toluene, benzene and xylene, Aliphatic or alicyclic hydrocarbons such as hexane and cyclohexane are exemplified.

In the present invention, the polymer used for the electrode membrane and the solid electrolyte membrane is a copolymer of a fluorinated olefin having a hydrogen atom and a perfluorinated olefin such as polyvinylidene fluoride-hexafluoropropylene copolymer [PVDF (HFP)]. Copolymers, homopolymers of fluorinated olefins having hydrogen atoms such as polyvinylidene fluoride (PVDF), perfluorosulfonic acid (Nafion), poly-2-hydroxyethyl methacrylate (poly-HEMA), polymethyl methacrylate (PMMA) And poly (meth) acrylates such as polyethylene oxide (PEO) and polyacrylonitrile (PAN).

The electrode film used for the electrode film layer of the actuator element is composed of carbon nanotubes, alkali metal salts and / or alkaline earth metal salts, ionic liquid polymers, and the like. The preferred blending ratio of these components in the electrode membrane layer is:
carbon nanotube:
1 to 98 parts by weight, preferably 33 to 66 parts by weight, more preferably 17 to 50 parts by weight;
Ionic liquid:
1 to 98 parts by weight, preferably 17 to 50 parts by weight, more preferably 17 to 50 parts by weight;
Alkali metal salts and / or alkaline earth metal salts:
1 to 98 parts by weight, preferably 33 to 66 parts by weight, more preferably 5 to 30 parts by weight;
Polymer: 1 to 98 parts by weight, preferably 33 to 66 parts by weight, more preferably 17 to 50 parts by weight;
It is.

The electrode film can be prepared by mixing carbon nanotubes (CNT), alkali metal salt and / or alkaline earth metal salt, ionic liquid, and polymer in an arbitrary ratio. From the problem of the strength of the obtained electrode film, it is preferable that CNT is contained in a certain amount or more.

It is preferable to perform sonication by mixing CNT and alkali metal salt and / or alkaline earth metal salt, ionic liquid and polymer at an arbitrary ratio by stirring. The sonication time is about 30 minutes to 15 hours, preferably about 1 to 7 hours.

As an actuator element manufactured by the method of the present invention, for example, the solid electrolyte membrane layer 1,
From both sides, there is a three-layer structure sandwiched between electrode membrane layers (electrode membranes) 2 and 2 containing carbon nanotubes, ionic liquid, polymer, alkali metal salt and / or alkaline earth metal salt (Fig. 2A). . Further, in order to increase the surface conductivity of the electrode, it may be a five-layer actuator element in which solid electrolyte membrane layers 3 and 3 are further formed outside the electrode membrane layers 2 and 2 (FIG. 2B).

In order to obtain an actuator element by forming an electrode film layer on the surface of the solid electrolyte membrane layer, the electrode film may be thermocompression bonded to the surface of the solid electrolyte membrane layer.
The thickness of the solid electrolyte membrane layer is preferably 5 to 200 μm, and more preferably 10 to 100 μm. The thickness of the electrode film layer is preferably 10 to 500 μm, and more preferably 50 to 300 μm. Moreover, spin coating, printing, spraying, etc. can also be used for film formation of each layer. Furthermore, an extrusion method, an injection method, or the like can also be used.

The thickness of the electrode film layer is preferably 10 to 50 nm. The electrode film layer can be formed by laminating a plurality of thin films composed of CNT, alkali metal salt and / or alkaline earth metal salt, ionic liquid, polymer, etc. by thermocompression bonding. Good.

  The actuator element thus obtained has an element length of 0.5 to 1 within a few seconds when a DC voltage of 0.5 to 4 V is applied between the electrodes (the electrodes are connected to the conductive thin film layer). Double displacement can be obtained. The actuator element can be flexibly operated in air or in vacuum.

As shown in FIG. 3, the operating principle of such an actuator element is that when a potential difference is applied to the electrode film layers 2 and 2 formed on the surface of the solid electrolyte membrane layer 1 in an insulated state, the electrode film layer 2 and This is because an electric double layer is formed at the interface between the carbon nanotube phase and the ionic liquid phase in 2, and the electrode film layers 2 and 2 expand and contract due to the interfacial stress. As shown in FIG. 3, the bending to the positive electrode side is due to the fact that the carbon nanotube has a larger effect on the negative electrode side due to the quantum chemical effect. This is considered to be because the minus pole side extends more greatly due to the three-dimensional effect. In FIG. 3, 4 indicates a cation of the ionic liquid, and 5 indicates an anion of the ionic liquid.

According to the actuator element that can be obtained by the above method, since the effective area of the interface between the gel of the carbon nanotube and the ionic liquid is extremely large, the impedance in the interfacial electric double layer is reduced, and the electrical stretching effect of the carbon nanotube is reduced. Contributes to effective use. Also, mechanically, the adhesion at the interface is good, and the durability of the device is increased. As a result, it is possible to obtain a durable element having a high responsiveness and a large amount of displacement in air or vacuum. Moreover, the structure is simple, the size can be easily reduced, and the apparatus can be operated with low power.

  The actuator element of the present invention operates with durability in air and vacuum, and operates flexibly at a low voltage. Therefore, an actuator of a robot that contacts a person who needs safety (for example, a home robot, a pet robot, Actuators for personal robots such as amusement robots), robots that work in special environments such as space environments, in vacuum chambers and rescue, medical and welfare robots such as surgical devices and muscle suits, and micro Ideal as an actuator for machines.

  In particular, in order to obtain high-purity products, in the production of materials in a vacuum environment and in an ultra-clean environment, there is an increasing demand for actuators for sample transportation and positioning in order to obtain high-purity products. In addition, the actuator element of the present invention using an ionic liquid that does not evaporate at all can be effectively used as an actuator for a process in a vacuum environment as an actuator that does not cause contamination.

Note that at least two conductive thin film layers are required on the surface of the ion conductive layer.
As shown in FIG. 2, it is possible to make a complicated movement by arranging a large number of electrode film layers 2 on the surface of the planar solid electrolyte membrane layer 1. By such an element, conveyance by a peristaltic motion, a micromanipulator, and the like can be realized. In addition, the shape of the actuator element of the present invention is not limited to a planar shape, and an element having an arbitrary shape can be easily manufactured. For example, what is shown in FIG. 4 is one in which four electrode film layers 2 are formed around a rod of the solid electrolyte membrane layer 1 having a diameter of about 1 mm. With this element, an actuator that can be inserted into a narrow tube can be realized.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, it cannot be overemphasized that this invention is not limited to these Examples.

<Common explanation of experimental methods>
1. Chemicals and materials used Ethylmethylimidazolium bis (trifluoromethanesulfonyl) imide (EMITFSI) Ethylmethylimidazolium tetrafluoroborate (EMIBF ₄ )

Carbon nanotubes used:
As the carbon nanotubes used in Examples and Comparative Examples, HiPco (manufactured by Carbon Nanotechnology Inc.) capable of relatively mass production using carbon monoxide as a raw material was also used.
Base polymer for ionic conductor used: Polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF (HFP)) (III)

Solvent used
N, N'-dimethylacetamide (DMAc)
Propylene carbonate (PC)
Methyl pentanone (MP)
Alkali metal salts and / or alkaline earth metal salts:
Li [BF4], Li [TFSI], Mg [TFSI], Ca [TFSI]

2． Displacement measuring method of actuator element having three-layer structure of electrode membrane / solid electrolyte membrane / electrode membrane

As shown in FIG. 1, a laser displacement meter was used to cut the element into 1 mm × 10 mm strips, and the displacement at a position of 5 mm when a voltage was applied was measured. The expansion / contraction rate (ε) is

L: Element length when no voltage is applied
D: Element thickness δ: Displacement

3. Solid Electrolyte Conductivity Measurement Method The prepared solid electrolyte membrane was cut into a diameter of 7 mm and sandwiched between stainless steel electrodes, and impedance measurement was performed.
4). Capacitance measurement

The prepared electrode film was cut to a diameter of 7 mm, sandwiched between stainless steel electrodes, and measured by the cyclic voltammetry method under the conditions of ± 0.5 V and 0.001 V / s. The measured value was expressed as a capacitance value per gram of carbon nanotubes in the electrode film (Fg ⁻¹ ).

5. Electrode, Solid Electrolyte, Actuator Element Film Thickness Measurement The thickness of the prepared electrode film, solid electrolyte membrane, and actuator element film composed of a laminate thereof was measured using a micrometer.

Example 1
Preparation of electrode film 50 mg of CNT, 80 mg of PVdF (HFP) EMIBF ₄ 120 mg LiBF ₄ 5.68 mg is put in a sample bottle, and 4 ml of solvent DMAc is put in it and stirred with a magnetic stirrer for 3 days. Further, the sample bottle was subjected to ultrasonic dispersion (20 KHz) for 1 hour, and then 5 ml of the solvent DMAc was added and stirred with a magnetic stirrer for 1 day, followed by ultrasonic dispersion (20 KHz) for 4 hours to obtain a cast solution. Thereafter, the sample bottle was solidified so as not to flow even if it was turned upside down. It seems that CNTs are dispersed and formed into a gel and solidified by forming a network. 2.4 ml of the cast solution was cast into 25 mm square Teflon (registered trademark) molds, and dried at a temperature of 55 ° C. for a whole day and night. Thereafter, the temperature was set to 80 ° C., and drying under reduced pressure was performed all day and night to obtain an electrode film.
Production of solid electrolyte membrane
PVdF (HFP) 200 mg EMIBF ₄ 200 mg, LiBF ₄ 9.47 mg was placed in a sample bottle, solvent PC 500 mg and MP 6 ml were added, and stirring was performed at 80 ° C. for 3 hours to obtain a casting solution. 25mm square Teflon (
0.5 ml of the cast solution was cast into a registered trademark mold and dried at room temperature for a whole day and night. Thereafter, the temperature was set to 80 ° C., and drying under reduced pressure was performed all day and night to obtain an electrolyte membrane. Measurements were made according to common experimental methods. The properties of this film are shown in Table 1. It can be seen that the conductivity of the solid electrolyte membrane is dramatically increased as compared with Comparative Example 1.

Also, by using two electrode membranes and one solid electrolyte membrane, sandwiching the gel electrolyte membrane prepared by the method of the common experimental method 2 and pressing at 70 ° C. and 60 N pressure for 1 minute, the electrode / solid electrolyte / An electrode composite element was prepared. Table 2 shows the displacement observed when a triangular wave voltage of ± 2.0 V having a different frequency was applied between the electrodes. Table 1 shows the results of the capacitance of the element. It can be seen that the capacitance and response performance (high-speed response) of the device are dramatically increased as compared with Comparative Example 1.

Example 2
Production of electrode film In Example 1, LiBF4 5.68 mg was changed to 28.4 mg.
Production of solid electrolyte membrane
In Example 1, 9.47 mg of LiBF4 was changed to 47.4 mg. Table 3 shows the characteristics of this film. It can be seen that the conductivity of the solid electrolyte membrane is dramatically increased as compared with Comparative Example 1.
Table 4 shows the displacement observed when a triangular wave voltage of ± 2.0 V having a different frequency was applied between the electrodes. Table 3 shows the result of the capacitance of the element. It can be seen that the capacitance and response performance (high-speed response) of the element are dramatically increased as compared with Comparative Example 1.

Example 3
Production of electrode film In Example 1, LiBF4 5.68 mg was changed to 56.8 mg.
Production of solid electrolyte membrane
In Example 1, 9.47 mg of LiBF4 was changed to 94.7 mg.
Table 6 shows the displacement observed when a triangular wave voltage of ± 2.0 V having a different frequency was applied between the electrodes. Table 5 shows the result of the capacitance of the element. It can be seen that the capacitance and response performance of the device are dramatically increased as compared with Comparative Example 1.

Comparative Example 1
Production of electrode film In Example 1, LiBF4 5.68 mg was changed to 0 mg.
Production of solid electrolyte membrane
In Example 1, 9.47 mg of LiBF4 was changed to 0 mg. The properties of this film are shown in Table 7. From the results of Example 1-2, it can be seen that the conductivity is dramatically increased as compared with Comparative Example 1.
Table 8 shows the displacement observed when a triangular wave voltage of ± 2.0 V having a different frequency was applied between the electrodes. Table 7 shows the result of the capacitance of the element. From the results of Example 1-2, it can be seen that the capacitance of the element and the response performance (high-speed response) are dramatically increased. From the results of Example 3, it can be seen that the capacitance and response performance of the device are dramatically increased as compared with Comparative Example 1.

Example 4
Preparation of electrode film CNT 50mg, PVdF (HFP) 80mg EMITFSI 237.2mg LiTFSI 17.4mg in a sample bottle,
The solvent DMAc (4 ml) was added and stirring was performed with a magnetic stirrer for 3 days. Furthermore, the sample bottle was ultrasonically dispersed (20 KHz) for 1 hour, and then 5 ml of solvent DMAc was added and stirred with a magnetic stirrer.
The casting liquid was obtained by performing ultrasonic dispersion (20 KHz) for 4 hours. Thereafter, the sample bottle was solidified so as not to flow even if it was turned upside down. It seems that CNTs are dispersed and formed into a gel and solidified by forming a network. 2.4 ml of the cast solution was cast into 25 mm square Teflon (registered trademark) molds, and dried at a temperature of 55 ° C. for a whole day and night. Thereafter, the temperature was set to 80 ° C., and drying under reduced pressure was performed all day and night to obtain an electrode film.
Production of solid electrolyte membrane
PVdF (HFP) 200 mg EMITFSI 395.3 mg LiTFSI 29.0 mg was placed in a sample bottle, the solvent PC 500 mg and MP 6 ml were added, and the mixture was stirred at 80 ° C. for 3 hours to obtain a casting solution. 0.5 ml of the above cast solution was cast into a 25 mm square Teflon (registered trademark) mold and dried at room temperature all day and night. Thereafter, the temperature was set to 80 ° C., and drying under reduced pressure was performed all day and night to obtain an electrolyte membrane. Table 9 shows the characteristics of this film measured according to the common experimental method. It can be seen that the conductivity of the solid electrolyte membrane is significantly higher than that of Comparative Example 2.

Also, by using two electrode membranes and one solid electrolyte membrane, sandwiching the solid electrolyte membrane prepared by the method of the common experimental method 2 and pressing at 70 ° C. and 60 N pressure for 1 minute, the electrode / solid electrolyte / An electrode composite element was prepared. Table 10 shows the displacement observed when a triangular wave voltage of ± 2.0 V having a different frequency was applied between the electrodes. Table 9 shows the result of the capacitance of the element. Further, it can be seen that the capacitance and response performance (high-speed response) of the element are dramatically increased as compared with Comparative Example 2.

Example 5
Production of electrode film In Example 4, LiTFSI 17.4 mg was changed to 52.2 mg.
Production of solid electrolyte membrane
In Example 4, LiTFSI 29.0 mg was changed to 87.0 mg. The properties of this film are shown in Table 11. It can be seen that the conductivity of the electrolyte membrane is dramatically higher than that of Comparative Example 2. Table 12 shows the displacement observed when a triangular wave voltage of ± 2.0 V having a different frequency was applied between the electrodes. Table 11 shows the result of the capacitance of the element. It can be seen that the capacitance of the element and the response performance (high-speed response) are dramatically increased.

Example 6
Production of electrode film In Example 4, LiTFSI 17.4 mg was changed to 87.0 mg.
Production of solid electrolyte membrane
In Example 4, LiTFSI 29.0 mg was changed to 145.0 mg.
Table 14 shows the displacement observed when a triangular wave voltage of ± 2.0 V having a different frequency was applied between the electrodes. Table 13 shows the result of the capacitance of the element. It can be seen that the capacitance and response performance of the device are dramatically increased as compared with Comparative Example 2.

Example 7
Preparation of electrode film In Example 4, LiTFSI 17.4 mg was changed to 174.0 mg.
Production of solid electrolyte membrane
In Example 4, LiTFSI 29.0 mg was changed to 290.0 mg.
Table 16 shows the displacement observed when a triangular wave voltage of ± 2.0 V having a different frequency was applied between the electrodes. Table 15 shows the result of the capacitance of the element. It can be seen that the capacitance and response performance of the device are dramatically increased as compared with Comparative Example 2.

Comparative Example 2
Production of electrode film In Example 2, LiTFSI 17.4 mg was changed to 0 mg.
Production of solid electrolyte membrane
In Example 2, LiTFSI 29.0 mg was changed to 0 mg.
The properties of this film are shown in Table 17. From the results of Example 4-5, it can be seen that the solid electrolyte conductivity is dramatically increased.

Table 18 shows the displacement observed when a triangular wave voltage of ± 2.0 V having a different frequency was applied between the electrodes. Table 17 shows the result of the capacitance of the element.
From the results of Example 5, it can be seen that the capacitance and response performance (high-speed response) of the device are dramatically increased. In addition, it can be seen from the results of Examples 6-7 that the capacitance and the response performance of the device are dramatically increased.

Example 8
Preparation of electrode film CNT 50mg, PVdF (HFP) 80mg EMITFSI 237.2mg MgTFSI 35.4mg in a sample bottle,
The solvent DMAc (4 ml) was added and stirring was performed with a magnetic stirrer for 3 days. Furthermore, the sample bottle was ultrasonically dispersed (20 KHz) for 1 hour, and then 5 ml of solvent DMAc was added and stirred with a magnetic stirrer.
The casting liquid was obtained by performing ultrasonic dispersion (20 KHz) for 4 hours. Thereafter, the sample bottle was solidified so as not to flow even if it was turned upside down. It seems that CNTs are dispersed and formed into a gel and solidified by forming a network. 2.4 ml of the cast solution was cast into 25 mm square Teflon (registered trademark) molds, and dried at a temperature of 55 ° C. for a whole day and night. Thereafter, the temperature was set to 80 ° C., and drying under reduced pressure was performed all day and night to obtain an electrode film.
Production of solid electrolyte membrane
PVdF (HFP) 200 mg EMITFSI 395.3 mg MgTFSI 59.1 mg was placed in a sample bottle, the solvent PC 500 mg and MP 6 ml were added, and the mixture was stirred at 80 ° C. for 3 hours to obtain a casting solution. 0.5 ml of the above cast solution was cast into a 25 mm square Teflon (registered trademark) mold and dried at room temperature all day and night. Thereafter, the temperature was set to 80 ° C., and drying under reduced pressure was performed all day and night to obtain a solid electrolyte membrane. The properties of this membrane, measured according to common experimental methods, are summarized in Table 19. It can be seen that the conductivity of the solid electrolyte membrane is dramatically higher than that of Comparative Example 2.

Also, by using two electrode membranes and one solid electrolyte membrane, sandwiching the solid electrolyte membrane prepared by the method of the common experimental method 2 and pressing at 70 ° C. and 60 N pressure for 1 minute, the electrode / electrolyte / An electrode composite element was prepared. Table 20 summarizes the displacement observed when a triangular wave voltage of ± 2.0 V having a different frequency is applied between the electrodes. Further, it can be seen that the capacitance and response performance (including high-speed response) of the element are dramatically increased as compared with Comparative Example 2.

Example 9
Preparation of electrode film CNT 50mg, PVdF (HFP) 80mg EMITFSI 237.2mg CaTFSI 18.2mg was put in a sample bottle,
The solvent DMAc (4 ml) was added and stirring was performed with a magnetic stirrer for 3 days. Furthermore, the sample bottle was ultrasonically dispersed (20 KHz) for 1 hour, and then 5 ml of solvent DMAc was added and stirred with a magnetic stirrer.
The casting liquid was obtained by performing ultrasonic dispersion (20 KHz) for 4 hours. Thereafter, the sample bottle was solidified so as not to flow even if it was turned upside down. It seems that CNTs are dispersed and formed into a gel and solidified by forming a network. 2.4 ml of the cast solution was cast into 25 mm square Teflon (registered trademark) molds, and dried at a temperature of 55 ° C. for a whole day and night. Thereafter, the temperature was set to 80 ° C., and drying under reduced pressure was performed all day and night to obtain an electrode film.
Production of solid electrolyte membrane
PVdF (HFP) 200 mg EMITFSI 395.3 mg CaTFSI 30.3 mg was placed in a sample bottle, the solvent PC 500 mg and MP 6 ml were added, and the mixture was stirred at 80 ° C. for 3 hours to obtain a casting solution. 0.5 ml of the above cast solution was cast into a 25 mm square Teflon (registered trademark) mold and dried at room temperature all day and night. Thereafter, the temperature was set to 80 ° C., and drying under reduced pressure was performed all day and night to obtain a solid electrolyte membrane. Measurements were made according to common experimental methods. The properties of this film are summarized in Table 21. It can be seen that the conductivity of the solid electrolyte membrane is dramatically higher than that of Comparative Example 2.

In addition, an electrode / electrolyte / electrode composite element was prepared by sandwiching the gel electrolyte membrane prepared by the method according to the common experimental method 3 and pressing it at 70 ° C. and a pressure of 60 N for 1 minute using two electrode membranes. . Table 22 summarizes the displacements observed when square wave voltages of ± 2.0 V having different frequencies are applied between the electrodes. Table 21 shows the results of the capacitance of the element. It can be seen that the capacitance and response performance (including the high-speed response) of the device are dramatically increased as compared with Comparative Example 2.

Example 10
Preparation of electrode film In Example 9, CaTFSI was changed from 18.2 mg to 36.4 mg.
Preparation of electrolyte membrane
In Example 9, CaTFSI 30.3 mg was changed to 60.6 mg. The properties of this film are summarized in Table 23. It can be seen that the conductivity of the electrolyte membrane is dramatically higher than that of Comparative Example 2.
Table 24 summarizes the displacements observed when square wave voltages of ± 2.0 V with different frequencies were applied between the electrodes. Table 23 shows the result of the capacitance of the element. It can be seen that the capacitance and response performance (including the high-speed response) of the device are dramatically increased as compared with Comparative Example 2.

Claims (7)

An electrode film composed of a carbon nanotube, an alkali metal salt and / or an alkaline earth metal salt, an ionic liquid and a polymer , wherein the alkali metal salt is a lithium salt, and the alkaline earth metal salt is a calcium salt and / or Alternatively, the anion component of the ionic liquid and the anion component of the alkali metal salt or alkaline earth metal salt are the same, and the anion component is BF ₄ ⁻ , BF ₃ CF ₃ ⁻ , BF ₃ C ₂ F _{5. ^{-, BF 3 C 3 F 7}} -, BF 3 C 4 F 9 -, PF 6 -, (CF 3 SO 2) 2 N -, (FSO 2) 2 N -, (CF 3 CF 2 SO 2) 2 N ^{_{-, ClO 4 -, CF 3}} SO 2) 3 C -, CF 3 SO 3 -, (CN) 2 N -, CF 3 COO - and is selected from the group consisting of halogen ions, the electrode film. A laminate comprising the electrode membrane layer according to claim 1 and a solid electrolyte membrane composed of an alkali metal salt and / or an alkaline earth metal salt, an ionic liquid and a polymer , wherein the alkaline earth metal salt is a calcium salt. And / or magnesium salt, and the anion component of the ionic liquid is the same as the anion component of the alkali metal salt or alkaline earth metal salt, and the anion component is BF ₄ ⁻ , BF ₃ CF ₃ ⁻ , or BF ₃ C _{2. ^{F 5 -, BF 3 C 3}} F 7 -, BF 3 C 4 F 9 -, PF 6 -, (CF 3 SO 2) 2 N -, (FSO 2) 2 N -, (CF 3 CF 2 SO 2) _A laminate selected from the group consisting of ₂ N ⁻ , ClO ₄ ⁻ , CF ₃ SO ₂ ) ₃ C ⁻ , CF ₃ SO ₃ ⁻ , (CN) ₂ N ⁻ , CF ₃ COO ⁻ and halogen ions . The actuator element containing the laminated body of Claim 2 . On the surface of the solid electrolyte membrane layer according to claim 2, at least two electrode membrane layers according to claim 1 are formed in an insulated state from each other, and are configured to be deformable by applying a potential difference to the electrode membrane layer. The actuator element according to claim 3 . The following steps:
Step 1: preparing a dispersion containing carbon nanotubes, alkali metal salt and / or alkaline earth metal salt, ionic liquid, polymer and solvent;
Step 2: preparing a solution containing a polymer and a solvent, an alkali metal salt and / or an alkaline earth metal salt, and if necessary, an ionic liquid;
Step 3: Forming an electrode film using the dispersion of Step 1 and forming a solid electrolyte membrane using the solution of Step 2 simultaneously or sequentially to form a laminate of the electrode film and the solid electrolyte membrane,
A method for producing an actuator element comprising: the alkali metal salt is a lithium salt; the alkaline earth metal salt is a calcium salt and / or a magnesium salt; Anion of metal salt, alkaline earth metal salt
The components are the same, and the anion component is BF ₄ ⁻ , BF ₃ CF ₃ ⁻ , BF ₃ C ₂ F ₅ ⁻ , BF ₃ C ₃ F ₇ ⁻ , BF ₃ C ₄ F ₉ ⁻ , PF ₆ ⁻ , ( ^{_{CF 3 SO 2) 2 N -}} , (FSO 2) 2 N -, (CF 3 CF 2 SO 2) 2 N -, ClO 4 -, CF 3 SO 2) 3 C -, CF 3 SO 3 -, (CN ) A method for manufacturing an actuator element selected from the group consisting of ₂ N ⁻ , CF ₃ COO ⁻ and halogen ions . The following steps:
Step 1: preparing a dispersion containing carbon nanotubes, alkali metal salt and / or alkaline earth metal salt, ionic liquid, polymer and solvent;
Step 2: preparing a solution containing a polymer and a solvent, an alkali metal salt and / or an alkaline earth metal salt, and if necessary, an ionic liquid;
Process 3: A process of forming an electrode film by casting, printing, coating, extrusion, or injection using the dispersion liquid of Process 1, and then increasing the density by thermally densifying the produced electrode film as necessary. Alternatively, several electrode films are thermocompression-bonded and simultaneously densified to increase the density. Step 4: Step of forming a solid electrolyte membrane by casting, printing, coating, extruding, or injection using the dispersion liquid of Step 2;
Step 5: A step of laminating the electrode film formed in Step 3 and the solid electrolyte membrane formed in Step 4 by pressure bonding to form a laminate,
A method for producing an actuator element comprising: the alkali metal salt is a lithium salt; the alkaline earth metal salt is a calcium salt and / or a magnesium salt; The anion component of the metal salt and the alkaline earth metal salt is the same, and the anion component is BF ₄ ⁻ , BF ₃ CF ₃ ⁻ , BF ₃ C ₂ F ₅ ⁻ , BF ₃ C ₃ F ₇ ⁻ , BF ₃ C ^{_{4 F 9 -, PF 6 -}} , (CF 3 SO 2) 2 N -, (FSO 2) 2 N -, (CF 3 CF 2 SO 2) 2 N -, ClO 4 -, CF 3 SO 2) 3 C ^{_{-, CF 3 SO 3 -,}} (CN) 2 N -, CF 3 COO - and is selected from the group consisting of halogen ion, a manufacturing method of the actuator element. The following steps:
Step 1: preparing a dispersion containing carbon nanotubes, alkali metal salt and / or alkaline earth metal salt, ionic liquid, polymer and solvent;
Step 2: preparing a solution containing a polymer and a solvent, an alkali metal salt and / or an alkaline earth metal salt, and if necessary, an ionic liquid;
Step 3: Step of forming an electrode film by heating after casting using the dispersion of Step 1 Step 4: Step of forming a solid electrolyte membrane by heating after casting using the dispersion of Step 2;
Step 5: A step of laminating the electrode film formed in Step 3 and the solid electrolyte membrane formed in Step 4 by pressure bonding to form a laminate,
A method for producing an actuator element comprising: the alkali metal salt is a lithium salt; the alkaline earth metal salt is a calcium salt and / or a magnesium salt; The anion component of the metal salt and the alkaline earth metal salt is the same, and the anion component is BF ₄ ⁻ , BF ₃ CF ₃ ⁻ , BF ₃ C ₂ F ₅ ⁻ , BF ₃ C ₃ F ₇ ⁻ , BF ₃ C ^{_{4 F 9 -, PF 6 -}} , (CF 3 SO 2) 2 N -, (FSO 2) 2 N -, (CF 3 CF 2 SO 2) 2 N -, ClO 4 -, CF 3 SO 2) 3 C ^{_{-, CF 3 SO 3 -,}} (CN) 2 N -, CF 3 COO - and is selected from the group consisting of halogen ion, a manufacturing method of the actuator element.

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