JP4704376B2 - POLYMER ELECTROLYTE MEMBRANE ACTUATOR AND METHOD FOR PRODUCING THE SAME - Google Patents

Description

  The present invention relates to a polymer electrolyte membrane actuator that is driven (curved or deformed) by applying a voltage, and a manufacturing method thereof.

  A touch panel display is used as an input device from a user in a small electronic device such as a mobile phone, a digital camera, or a car navigation system display. The touch panel display is a display including an input device that can input a signal to an apparatus by pressing a predetermined portion with a finger or the like. However, in this touch panel type display, the operator can only know the confirmation of the input from the sound that is emitted simultaneously with the input or the color change in the display screen.

In recent years, drivers, drivers who are unable to see the touch panel display during driving, and operators including visually handicapped people can feel the reaction force as if they were pressing an analog switch, even if they were unable to see the display. Various devices have been proposed in order to receive or reach (achievement).
An actuator that can be used as one of such devices has been proposed (Patent Document 1). The polymer actuator described in Patent Document 1 has a configuration in which an ion exchange resin molded product and a metal electrode are provided in an insulating state on the surface of the ion exchange resin molded product, and a potential difference is applied between the metal electrodes in a water-containing state. Thus, the ion-exchange resin molded product is bent and deformed.
This polymer actuator is made to adsorb in an ion exchange resin molded product in a metal complex aqueous solution, and the adsorbed metal complex is reduced to deposit metal to form a dendritic metal electrode inside the ion exchange resin molded product. By doing so, an ion exchange resin molded product provided with a metal electrode can be constituted. Since the metal electrode is a dendritic electrode, the electrode area increases, and it is said that practical displacement and stress can be obtained.

Japanese Patent No. 2961125

  However, the dendritic electrode provided in the ion-exchange resin molded article of the polymer actuator adsorbs the metal complex by immersing it in an aqueous solution containing the metal complex, and then uses a reducing agent to form the metal into a dendritic shape. Since it is deposited (plated), it is difficult to control the various conditions such as the concentration of the metal complex and the temperature of the plating solution to form the metal electrode layer with a constant thickness. If the thickness of the metal electrode layer is not uniform, the electric field concentrates on the part where the distance between the dendritic electrodes is short, and the dendritic electrodes facing each other come into contact with each other due to bending deformation of the ion-exchange resin molded product. As a result, there is a problem that short-circuiting occurs, overheating, and there is a risk of ignition due to these, resulting in loss of safety. Such a problem becomes more prominent as the dendritic electrodes are denser and the metal electrode layer is larger.

  Accordingly, in order to solve the above problems, the present invention provides a highly safe polymer electrolyte membrane actuator that is less likely to be ignited by a short circuit or overheating in a polymer electrolyte membrane actuator that is driven by applying a voltage. It is another object of the present invention to provide a method for manufacturing an actuator that does not require adjustment of a plating process for forming electrodes.

In order to achieve the above object, the present invention provides an actuator driven by applying a voltage, wherein the actuator layer is formed of a polymer electrolyte membrane impregnated with an electrolyte solution, and the actuator layer includes the actuator layer. A pair of electrodes provided so as to be opposed to each other along different surfaces of the actuator layer, and provided between the pair of electrodes, and by dividing the region of the actuator layer into two regions. There is provided a polymer electrolyte membrane actuator comprising an electrode and a separate layer including at least a porous membrane as a layer .

At that time, before Symbol separation layer is more preferably in the porous membrane is a structure coated with the polymer electrolyte membrane. Moreover, it is preferable that the said porous membrane is comprised with the material whose softening point is 100 degrees C or less.
The separate layer preferably includes a polymer electrolyte membrane as a layer.

Furthermore, the present invention is a method for producing a polymer electrolyte membrane actuator driven by applying a voltage, the adsorption step of adsorbing metal ions on the polymer electrolyte membrane, and the reduction step of reducing the adsorbed metal ions In order to separate the pair of polymer electrolyte membranes between the pair of polymer electrolyte membranes, a pair of polymer electrolyte membranes in which metal ions have been reduced are prepared by the adsorption step and the reduction step. It provides a method of making a polymer electrolyte membrane actuator and having a bonding step of bonding across the film material comprising a quality film.

At that time, prior to the adsorption step, there is a step of providing a protective film on one surface of the polymer electrolyte membrane to block the penetration of the treatment liquid used in the adsorption step and the reduction step, and the reduction A step of removing the protective film from the polymer electrolyte membrane between the step and the bonding step, wherein in the bonding step, each of the surfaces of the pair of polymer electrolyte membranes from which the protective film has been removed As a bonding surface, it is preferable to bond with the film material interposed therebetween.
Alternatively, prior to the adsorption step, a step of providing a protective film on one surface of the polymer electrolyte membrane to block the penetration of the treatment liquid used in the adsorption step and the reduction step, and the reduction step A pair of polymer electrolyte membranes reduced by metal ions produced by the adsorption step and the reduction step, including a removal step of removing the protective film from the polymer electrolyte membrane between the bonding step and A pair of polymer electrolyte membranes, which are previously integrated with a protective film sandwiched from both sides, are treated by the adsorption step and the reduction step, and then the metal ions are reduced by the removal step. The protective film is obtained by separating the protective film from the molecular electrolyte film, and in the bonding step, each of the surfaces of the polymer electrolyte film from which the protective film has been removed is used as a bonding surface. Preferably bonded across the.
Further, the pair of polymer electrolyte membranes reduced by the metal ions are preferably treated by using the surfaces on both sides of each polymer electrolyte membrane as the treatment surfaces of the adsorption step and the reduction step. .
Alternatively, in the adsorption step and the reduction step, one polymer electrolyte membrane is treated, and the pair of polymer electrolyte membranes reduced in the metal ions used in the joining step are the adsorption step and the reduction step. It is also preferable to produce the polymer electrolyte membrane treated in step 1 by cutting it into two parts in the thickness direction.

  The membrane material is preferably a porous membrane coated with a polymer electrolyte membrane of the same type as the pair of polymer electrolyte membranes reduced by the metal ions.

In the polymer electrolyte membrane actuator of the present invention, a separate layer including at least a porous membrane as a layer is provided between a pair of electrodes provided along different surfaces on both sides of the actuator layer. Since the electrodes are separated, a constant distance between the electrodes is ensured. For this reason, the electric field does not concentrate on a portion where the distance between the electrodes is short, and even if the actuator layer is deformed, the opposing electrodes come into contact with each other and short-circuit, and the short-circuit does not cause overheating. As a result, a highly safe polymer electrolyte membrane actuator that is less likely to ignite due to short-circuiting or overheating due to electric field concentration can be realized.
Furthermore, when a material having a softening point of 100 ° C. or lower is used for the porous film of the separate layer, the porous film melts and closes the pores of the porous film when the temperature exceeds 100 ° C. The function as an actuator is stopped. Therefore, the actuator is not heated to a high temperature state of 100 ° C., and a highly safe polymer electrolyte membrane actuator that is unlikely to ignite due to overheating can be realized.

Furthermore, in the manufacturing method of the present invention, when an electrode is provided on the actuator layer, an electrode is provided on the pair of polymer electrolyte membranes, and then a membrane material including a porous membrane is sandwiched between the pair of polymer electrolyte membranes. Join. Therefore, compared to the conventional case where electrodes are provided by plating treatment from both sides of one polymer electrolyte membrane, the distance between the electrodes is closer than necessary, and the electrodes on both sides are connected to each other. No need to worry. Therefore, it is less necessary to control the degree of deposition of the metal formed in the polymer electrolyte membrane as an electrode compared with the conventional case.

FIG. 1A is a schematic cross-sectional view showing an embodiment of a polymer electrolyte membrane actuator (hereinafter referred to as actuator) of the present invention.
An actuator 10 shown in FIG. 1A includes an actuator layer 12 formed of a polymer electrolyte membrane, and electrodes 15 that are provided along different surfaces on both sides of the actuator layer 12 and apply a voltage from both sides of the actuator layer 12. 17 and the actuator layer 12 are divided into two regions on both sides (upper side and lower side in FIG. 1A) along the electrodes 15 and 17, and voltages are applied to the electrodes 15 and 17, respectively. A power source 20 to be applied and a controller 22 for controlling the application of voltage are included.

  The actuator layer 12 is composed of polymer electrolyte membranes 14 and 16 provided to be bonded to both sides of the separate layer 18 so as to sandwich the separate layer 18 therebetween. The polymer electrolyte membranes 14 and 16 are not limited as long as they are ionic conductive materials, but ion exchange resin membranes can be preferably used particularly from the viewpoint of ionic conductivity and durability. The ion exchange resin membrane is not particularly limited. For example, a cation exchange resin membrane, an anion exchange resin membrane, or a both ion exchange resin membrane is used. Among them, a cation exchange resin film is preferably used from the viewpoint of operation as an actuator. In the case of a cation exchange resin membrane, a material obtained by introducing a substituent such as a sulfonic acid group or a carboxyl group into polyethylene, polystyrene, polyamide, polyimide, fluorine resin, or the like is used. As the cation exchange resin membrane, “Nafion” (registered trademark, product name manufactured by Du Pont) or “Flemion” (registered trademark, product manufactured by Asahi Glass Co., Ltd.) is used. Also, ion exchange resin membranes having a benzimidazole skeleton, or sulfonated polyethersulfone ion exchange resin membranes, polyaryl ether ion exchange resin membranes or sulfonated polyether ether ketone ion exchange resin membranes, and polyimide An ion exchange resin membrane and the like are also exemplified.

  The electrodes 15 and 17 are provided so as to face each other along different surfaces of the actuator layer 12, and are provided in a dendritic shape in the polymer electrolyte membrane of the actuator layer 12 from the surfaces on both sides of the actuator layer 12 to the inside. The electrode is composed of a metal and a plating film 19 formed on the surface of the actuator layer 12. The dendritic metal is provided with a substantially uniform thickness along both sides of the actuator layer 12 (dot region in FIG. 1A). For this reason, the electrodes 15 and 17 have a large electrode area in the polymer electrolyte membrane of the actuator layer 12. The electrodes 15 and 17 are obtained by so-called plating treatment in which metal ions are adsorbed using ion adsorption and then metal ions are reduced to deposit metal. The electrodes 15 and 17 are made of, for example, gold, platinum, or palladium. In particular, it is preferable to use gold from the viewpoint of flexibility. A method for manufacturing the electrodes 15 and 17 will be described later.

  The separate layer 18 is a layer that is provided between the electrodes 15 and 17 and physically separates the electrodes 15 and 17 by dividing the region of the actuator layer 12 into two regions. The thickness is 1 to 50 μm. In the actuator 10, the cation in the electrolyte solution impregnated in the actuator layer 12 moves toward the cathode of the polymer electrolyte membrane 17, and the solvent molecules move along with this movement, so that the solvent is unevenly distributed on the cathode side. To do. Due to the unevenly distributed solvent, the actuator layer 12 is bent or deformed as shown in FIG. In order to make such an action, only the cation and the solvent can move in the separate layer 18, and it is preferable to limit the movement of the anion. It is also necessary to have flexibility and flexibility to follow the bending deformation of the actuator layer 12. At this time, in order to increase the operating speed of the actuator 10, the separate layer 18 preferably does not suppress the conductivity of the cation activated by the polymer electrolyte. Further, the thickness of the entire actuator 10 is preferably thin in order to efficiently perform bending deformation, and therefore the separate layer 18 is also preferably thin.

Such a separate layer 18 has the following three forms.
(I) a form composed of a porous membrane (or membrane membrane),
(II) A form in which polymer electrolyte membranes 18b and 18c are coated on both sides of a porous membrane (or membrane membrane) 18a (see FIG. 1 (b)),
(III) A configuration composed of a polymer electrolyte membrane.

(I) Form comprised of porous membrane (or membrane membrane) A material that is electrochemically stable and has a large potential window is suitably used for the porous membrane (or membrane membrane) of this form. Examples of the porous film include organic resin materials such as polyolefin resin films such as polyethylene and polypropylene, and fluorine resin films such as PTFE (polytetrafluoroethylene) and PVDF (polyvinylidene fluoride). Examples of the inorganic material include glass and aluminum oxide. Furthermore, the surface of the separate layer 18 may be subjected to a hydrophilic treatment or a hydrophobic treatment. In the case of a porous membrane, the shape of the pore is not particularly limited, but it is preferable that the porosity is high from the viewpoint of cation conductivity. The form of the porous film may be a film having a large number of holes, or a film having a structure of a nonwoven fabric or a woven fabric. The film material preferably has flexibility so as not to limit the bending deformation of the actuator layer 12.

The porous membrane (or membrane membrane) may be composed of a single layer or a multilayer porous membrane (or membrane membrane) so as to have different characteristics. For example, by laminating a porous film having flexibility on both sides or one side of a porous film having high mechanical strength, the mechanical separation of the electrodes 15 and 17 and the conductivity of ions as an actuator can be ensured. Strength can also be secured.
Further, the porous membrane (or membrane membrane) can be provided with a function of interrupting conduction between the electrodes 15 and 17 when the actuator 10 abnormally generates heat due to a short circuit or the like and becomes a high temperature state. For example, by using a porous film that melts or softens when the temperature reaches a predetermined temperature, for example, 100 ° C., the pores of the porous film are closed at a predetermined temperature and the conduction between the electrodes 15 and 17 is interrupted. Therefore, safety can be ensured when abnormal heat generation or high temperature occurs. For example, those having a softening point of 100 degrees or less, such as polyethylene, are preferably used.
Such a separate layer 18 is bonded with good adhesion at the bonding surface with the polymer electrolyte membranes 14 and 16.

(II) A form in which polymer electrolyte membranes 18b and 18c are coated on both sides of a porous membrane (or membrane membrane) 18a (see FIG. 1B)
In the case of the separate layer 18 in this form, the polymer electrolyte membranes 18b and 18c shown in FIG. 1B are made of the same material as the polymer electrolyte membranes 14 and 16 of the actuator layer 12 in terms of adhesion. Preferably used. The separate layer 18 of this form can improve the adhesiveness with the actuator layer 12 compared with the separate layer 18 of the form comprised by the said porous membrane (or membrane film), and is the actuator of the actuator which repeats a bending deformation. Durability is improved.
Furthermore, when the porous membrane is covered with a polymer electrolyte membrane made of the same material as the polymer electrolyte membrane, a part of the material of the polymer electrolyte membrane penetrates into the pores of the porous membrane. The hole is closed and the metal powder deposited by the plating process is prevented from entering the porous film 18a. Therefore, even if the actuator layer 12 is bent and deformed, it is not short-circuited by the metal powder, and separation between the electrodes 15 and 17 can be ensured. For this reason, the safety of the actuator 10 can be ensured. On the other hand, since the polymer electrolyte membranes 18b and 18c that block the pores of the porous membrane 18a transmit cations and anions in the electrolyte solution, the materials of the polymer electrolyte membranes 18b and 18c are placed inside the pores of the porous membrane 18a. Even if it enters, there is no inconvenience in the operation of the actuator.

(III) Form Consists of Polymer Electrolyte Membrane The polymer electrolyte membrane of this embodiment uses the same material as the polymer electrolyte membranes 14 and 16 of the actuator layer 12. In this case, as described later, electrodes 15 and 17 are provided on the polymer electrolyte membranes 14 and 16 of the actuator layer 12 by plating so that the electrodes are not formed on the polymer electrolyte membrane used for the separate layer 18. Thereafter, it is manufactured by a method of bonding with the separate layer 18 interposed therebetween. In this embodiment, not only a single layer structure but also a multilayer polymer electrolyte membrane may be stacked.

The power source 20 applies a voltage to give a predetermined potential difference between the electrodes 15 and 17, and a DC power source is used. For example, a voltage of −2 to +2 V is applied between the electrodes 15 and 17 via the controller 22. Is done.
The controller 22 is a part that adjusts the application of voltage in accordance with a control signal from an external device (not shown).

In such an actuator 10, the actuator layer 12 is activated as an actuator by impregnating the electrolyte solution with an electrolyte solution and causing the actuator layer 12 to swell. Any electrolyte solution may be used as long as the electrolyte salt dissolves and has conductivity. For example, lithium ions can be suitably used as the cation. In addition, a cation selected from the group consisting of a dialkylimidazolium ion, a tetraalkylammonium ion, a trialkylimidazolium ion, a piperidinium ion, a pyrazolium ion, a pyrrolium ion, and a pyrrolidinium ion can also be used. As anions, AlCl ₄ ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , Cl ⁻ , sulfoniumimide anion, (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) Those selected from the group consisting of ₂ N ⁻ can be used. As the solvent, water or a low-volatile non-aqueous solvent, for example, an organic solvent such as propylene carbonate, ethylene carbonate, diethylene glycol, glycerin, sulfolane, and butyrolactone can be used. In particular, a low-volatile organic solvent is preferable from the viewpoint of air operation and long-term use. As the electrolyte solution, an ionic liquid or gel electrolyte which is a salt existing as a liquid even at room temperature can be used.
The actuator 10 is preferably provided with a cover layer (not shown) in order to prevent solvent volatilization.

Next, production of the electrodes 15 and 17 will be described.
The electrodes 15 and 17 made of dendritic metal formed on the actuator layer 12 are produced by subjecting the polymer electrolyte membrane of the actuator layer 12 to metal ion adsorption treatment and reduction treatment. That is, a plating process is performed. Specifically, it is produced by repeating the five steps (a) to (e) once or more, for example, 3 to 5 times.
(A) Cleaning step (b) Swelling step (c) Metal ion adsorption step (d) Metal ion reduction step (e) Cleaning step An example of each step is as follows. The polymer electrolyte membrane is cleaned by heating in boiling pure water for 1 hour. (B) In the swelling step, the polymer electrolyte membrane is swollen by immersing in methanol for 1 hour. (C) In the metal ion adsorption step, gold ions are adsorbed on the polymer electrolyte membrane by immersing in a gold phenanthroline complex solution as a plating solution for 12 hours. (D) In the metal ion reduction step, a sodium sulfite aqueous solution is permeated into the polymer electrolyte membrane adsorbed with gold ions to reduce the gold ions and deposit gold. (E) In the washing step, washing is performed by immersing in pure water at 70 ° C. for 30 minutes.

  In the actuator 10 having such a configuration, when a potential difference is applied between the electrodes 15 and 17 in a state where the electrolyte solution is impregnated and swollen and activated, a large number of protons contained in the electrolyte solution are exchanged with the solvent molecules by ion exchange. Large volume change is caused by moving to the side. Thereby, bending deformation occurs as shown in FIG. At this time, since the electrodes 15 and 17 are physically separated by the separate layer 18, even if bending deformation occurs, the dendritic electrodes do not come into contact with each other, and the distance between the electrodes is also small. Since it does not approach below a certain level, there is no danger of ignition due to short-circuiting due to uneven thickness of the electrodes 15 and 17 and overheating due to short-circuiting. Therefore, in order to make the thickness of the electrode uniform, it is not necessary to accurately control the conditions of the conventional plating process.

Next, a method for manufacturing the actuator 10 will be described.
The manufacturing method of the actuator 10 according to the present invention is a method in which the electrodes 15 and 17 are provided on each polymer electrolyte membrane of the actuator layer 12 (plating treatment) and then integrated with the separation layer 18. In addition, the actuator 10 can also be produced by a method in which the electrodes 15 and 17 are provided by plating after the separation layer 18 is integrated with the actuator layer 12 interposed therebetween. Hereinafter, a method of integrating the separation layers 18 after electrodes 15 and 17 are provided on each polymer electrolyte membrane of the actuator layer 12 (plating treatment) will be described.

FIGS. 2A to 2C are diagrams for explaining a method of manufacturing the actuator 10, and three methods, that is, a method 1, a method 2, and a method 3 are listed. In any method, after the actuator layer is plated, the separate layer is joined (integrated).
In Method 1, as shown in FIG. 2A, polymer electrolyte membranes 14 ′ and 16 ′ without electrodes are prepared. The pair of polymer electrolyte membranes 14 ′ and 16 ′ are provided with electrodes 15 and 17, respectively, by the electrode manufacturing method (plating process) described above.
Thereafter, the polymer electrolyte membranes 14 and 16 provided with the electrodes 15 and 17 are joined from both sides of the membrane material to be the separation layer 18 by hot pressing or adhesion, and the membrane to be the polymer electrolyte membrane 14 and the separation layer 18. The material and the polymer electrolyte membrane 16 are integrated.

  In the plating process, in addition to the method of performing the plating process from both sides of the polymer electrolyte membranes 14 'and 16', as shown in FIG. 3, the plating solution is applied to one side of the polymer electrolyte membranes 14 'and 16'. Plating can be performed from one surface with the protective film 30 blocking penetration, ie, one-side plating can be performed. The protective film 30 is peeled off after the plating process, and then the peeled surface is joined and integrated with a film material that becomes the separate layer 18 as a joint surface with the separate layer 18. The protective film 30 is not particularly limited, but is preferably resistant to a plating solution, a reducing agent, and a solution used in the swelling process, and is preferably easily peelable from the polymer electrolyte membranes 14 and 16. For example, a Teflon (registered trademark) film is suitably used as the protective film 30. By performing the plating process using the protective film 30, the plating process proceeds from one side where the protective film 30 is not provided, so that the density of the dendritic metal gradually decreases from this one side toward the other side. Electrode to be formed can be formed. For this reason, it is possible to prevent the formation of electrodes in which metal is unevenly distributed on both sides of the polymer electrolyte membranes 14 'and 16'.

  On the other hand, when plating is performed from both sides of the polymer electrolyte membranes 14 ′ and 16 ′ without using the protective film 30, that is, in the case of both-side plating, a film material that becomes the separate layer 18 is joined after plating. It is not necessary to control the plating speed or the like as in the prior art, and it is sufficient to perform the plating process easily, so that the production is easy. In addition, since the plating process is performed from both sides of the polymer electrolyte membranes 14 'and 16', the electrodes are formed with a high density and a wide area up to the side (lower electrode side) joined to the membrane material to be the separation layer 18. can do. Thereby, a high-speed response and large deformation of the actuator are possible. In the conventional method, the polymer electrolyte membrane is plated from both sides, and since there is no separate layer, from the point of preventing a short circuit between the electrodes, from the bottom of the electrode, that is, to the inside of the polymer electrolyte membrane It is impossible to form electrodes with high density. For this reason, a wide electrode area cannot be provided.

  In Method 2, as shown in FIG. 2 (b), both sides of the polymer electrolyte membrane having the total thickness of the polymer electrolyte membranes 14 and 16 are sufficiently plated. A pair of polymer electrolyte membranes 14 and 16 are produced by cutting into two in the thickness direction so as to be halved. Thereafter, the polymer electrolyte membranes 14 and 16 provided with the electrodes 15 and 17 are joined from both sides of the membrane material to be the separation layer 18 by hot pressing or adhesion, and the membrane to be the polymer electrolyte membrane 14 and the separation layer 18. The material and the polymer electrolyte membrane 16 are integrated. In the plating process, a dense dendritic electrode can be obtained up to the lower side of the electrode on one side when the polymer electrolyte membrane is divided into two by densely plating the central part inside the polymer electrolyte membrane. it can. Since a thin metal layer is not partially formed inside the polymer electrolyte membranes 14 and 16, resistance during energization does not increase. For this reason, an increase in the applied voltage of the actuator can be suppressed.

  In Method 3, as shown in FIG. 2 (c), the peelable protective film 22 is sandwiched between the polymer electrolyte membranes 14 ′ and 16 ′ and attached, and then integrated. Electrodes 15 and 17 are provided from the outer surfaces of the electrolyte membranes 14 'and 16' by one-side plating. The protective film 22 is peeled off to obtain a pair of polymer electrolyte membranes 14 and 16. Thereafter, the polymer electrolyte membranes 14 and 16 provided with the electrodes 15 and 17 are hot-pressed or bonded so as to sandwich both sides of the film material to be the separation layer 18 with the peeled surface of the protective film 30 as a bonding surface. Etc. are joined and integrated. This one-side plating process is effective in terms of production efficiency because a polymer electrolyte membrane provided with a pair of electrodes can be produced at the same time.

  As described above, in any of the methods 1 to 3, since the separate layer is joined (integrated) after the actuator layer is plated, the necessity of controlling the plating process is reduced. Therefore, an actuator provided with a large-area electrode can be easily manufactured. Further, since the distance between the electrodes is kept constant by the separate layer, the concentration of the electric field is eliminated, and the operation variation is reduced when a large-area actuator is manufactured.

〔Example〕
Hereinafter, the actuator 10 was produced using the various methods described above, and it was confirmed whether or not it would function as an actuator.
The manufacturing method of the actuator 10 is shown in Table 1 below.
“Nafion” (registered trademark) in Table 1 is a trade name, a fluorinated cation exchange resin membrane manufactured by Du Pont, and a membrane of perfluorosulfonic acid / PTFE copolymer.
In Table 1, PVDF means polyvinylidene fluoride and PE means polyethylene.
Furthermore, “cast Nafion” (registered trademark) in Table 1 means that a 20% ethanol solution of “Nafion” (registered trademark) was used as a slurry to form a film using a casting method. The adhesion of “Nafion” (registered trademark) with an ethanol solution in Table 1 means that an ethanol solution of “Nafion” (registered trademark) was used as an adhesive. “Hot press” in Table 1 is joining under conditions of 150 ° C. and 250 MPa.

  No. 1-No. 7 is an example in which the actuator 10 was manufactured by the method described above, that is, the method in which the electrodes 15 and 17 were provided on each polymer electrolyte membrane of the actuator layer 12 and then integrated with the separate layer 18. No. Reference numeral 8 is a conventional example manufactured with a conventional actuator, that is, a configuration without the separate layer 18.

No. 1-4 are configurations of “Nafion” (registered trademark) / “Nafion” (registered trademark) / PVDF / “Nafion” (registered trademark) / “Nafion” (registered trademark). It is a layer structure of “Nafion” (registered trademark) / PVDF / “Nafion” (registered trademark). No. No. 5 is a configuration of “Nafion” (registered trademark) / PVDF / “Nafion” (registered trademark). Reference numeral 6 denotes a configuration of “Nafion” (registered trademark) / PE / “Nafion” (registered trademark). No. Reference numeral 7 denotes a configuration of “Nafion” (registered trademark) / “Nafion” (registered trademark) / “Nafion” (registered trademark).
No. In No. 2, both-side plating treatment was performed, and in order to confirm the formation of the electrode at this time, when a cross section was observed with a microscope, it was confirmed that the dendritic metal grown from both sides was extended and connected. At this time, the resistance between both sides of the 1 cm × 1 cm square film was about 1 ohm.

No. In the plating process of the actuators 1 to 8, the above-described (a) cleaning process to (e) cleaning process were repeated five times to form electrodes. At this time, in the (a) washing step, the polymer electrolyte membrane of the actuator layer 12 was washed by heating in boiling pure water for 1 hour. (B) In the swelling step, the polymer electrolyte membrane was swollen by immersing in methanol for 1 hour. (C) In the metal ion adsorption step, gold ions were adsorbed on the polymer electrolyte membrane by immersing in a gold phenanthroline complex solution as a plating solution for 12 hours. (D) In the metal ion reduction step, the sodium sulfite aqueous solution was permeated into the polymer electrolyte membrane adsorbed with gold ions to reduce the gold ions to deposit gold. (E) In the cleaning process, the substrate was cleaned by being immersed in pure water at 70 ° C. for 30 minutes.
The actuator layer of the actuator thus manufactured was infiltrated with a lithium perchlorate solution to perform ion exchange to activate the actuator. The actuator was operated by applying a potential of −2 to +2 V to the electrode and sweeping.

No. No. 1 actuator (Example) is No. 1. It was confirmed that the actuator did not short-circuit and operated smoothly and stably as compared with the actuator of No. 8 (conventional example).
No. No. 2 actuator (Example) operates smoothly and stably without short-circuiting. Compared to the actuator No. 1, it was confirmed that large deformation and bending occurred.
No. No. 3 actuator (Example) operates smoothly and stably without short-circuiting. As compared with the actuator of No. 2, it was confirmed that even greater deformation and bending occurred.
No. No. 4 actuator (Example) is No. 4. It was confirmed that the actuator operated smoothly without short-circuiting as with the actuator No. 1.
No. No. 5 actuator (example) is also No. It was confirmed that the actuator operated smoothly without short-circuiting as with the actuator No. 1.
No. The separate layer 18 of the actuator (Example 6) is a porous film made of PE and has a softening temperature of 100 ° C. or lower. Therefore, when left at 100 ° C. for 5 minutes, The resistance was infinite and it was confirmed that the electrodes were interrupted. Furthermore, no. It was confirmed that the actuator operated smoothly without short-circuiting as with the actuator No. 1.
No. No. 7 actuator (Example) is No. 7. It was confirmed that the actuator operated smoothly without short-circuiting as with the actuator No. 1.
From the above, no. 1 to 7 all operate smoothly without short-circuiting, and it has been found that a highly safe polymer electrolyte membrane actuator can be realized that is less likely to ignite due to short-circuit and overheat caused by short-circuit. .
No. In No. 6, since the electrodes of the actuator were cut off in a temperature atmosphere of 100 ° C., it was found that a highly safe polymer electrolyte membrane actuator that is unlikely to ignite due to overheating can be realized.

  As described above, the polymer electrolyte membrane actuator and the manufacturing method thereof according to the present invention have been described in detail. However, the present invention is not limited to the above-described embodiment, and various improvements and modifications can be made without departing from the gist of the present invention. Of course.

(A) is a schematic cross section which shows one Embodiment of the polymer electrolyte membrane actuator of this invention, (b) is a figure which shows one form of the membrane material used for the separate layer of the actuator shown to (a). (C) is a figure explaining an example of operation | movement of the actuator shown to (a). (A)-(c) is a figure explaining each method in the preparation methods of the polymer electrolyte membrane actuator of this invention. It is a figure explaining the protective film used with the preparation methods of the polymer electrolyte membrane actuator of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Polymer electrolyte membrane actuator 12 Actuator layer 14, 16 Polymer electrolyte membrane 15, 17 Electrode 18 Separate layer 18a Porous membrane 18b, 18c Polymer electrolyte membrane 19 Plating membrane 20 Power supply 22 Controller 30 Protective membrane

Claims (9)

An actuator driven by applying a voltage,
An actuator layer formed by a polymer electrolyte membrane impregnated with an electrolyte solution;
A pair of electrodes provided in the actuator layer so as to face each other along different surfaces of the actuator layer, to which a voltage is applied,
A separation layer that is provided between the pair of electrodes and separates the pair of electrodes by dividing the region of the actuator layer into two regions and includes at least a porous film as a layer. Molecular electrolyte membrane actuator. The polymer electrolyte membrane actuator according to claim 1 , wherein the separate layer has a configuration in which the porous membrane is covered with a polymer electrolyte membrane. The polymer electrolyte membrane actuator according to claim 1 , wherein the separate layer includes a polymer electrolyte membrane as a layer. A method for producing a polymer electrolyte membrane actuator that is driven by applying a voltage,
An adsorption process for adsorbing metal ions to the polymer electrolyte membrane;
A reduction step for reducing the adsorbed metal ions;
Wherein the adsorption step and the reduction step, to produce a pair of polymer electrolyte membrane the reduced metal ions, between the pair of the polymer electrolyte membrane, a porous membrane to separate the pair of the polymer electrolyte membrane A bonding step of bonding with a film material including
A method for producing a polymer electrolyte membrane actuator, comprising: Before the adsorption step, the method includes a step of providing a protective film on one surface of the polymer electrolyte membrane to block the penetration of the treatment liquid used in the adsorption step and the reduction step, and the reduction step and the During the bonding step, it has a removal step of removing the protective film from the polymer electrolyte membrane,
5. The method for producing a polymer electrolyte membrane actuator according to claim 4 , wherein in the joining step, the surfaces of the pair of polymer electrolyte membranes from which the protective film has been removed are used as joining surfaces and the membrane material is sandwiched therebetween. Before the adsorption step, the method includes a step of providing a protective film on one surface of the polymer electrolyte membrane to block the penetration of the treatment liquid used in the adsorption step and the reduction step, and the reduction step and the During the bonding step, it has a removal step of removing the protective film from the polymer electrolyte membrane,
The pair of polymer electrolyte membranes reduced by metal ions prepared by the adsorption step and the reduction step are integrated in advance by sandwiching a protective film from both sides by a pair of polymer electrolyte membranes. It was obtained by separating the protective membrane from a pair of integrated polymer electrolyte membranes treated with a reduction step and then reduced with metal ions by the removal step.
5. The method for producing a polymer electrolyte membrane actuator according to claim 4 , wherein in the joining step, each of the surfaces of the polymer electrolyte membrane from which the protective film has been removed is used as a joining surface and the membrane material is sandwiched therebetween. The pair of polymer electrolyte membrane reducing the said metal ions, high according to claim 4 in which the processed both surfaces of each of the polymer electrolyte membrane as the processing surface of the adsorption step and the reduction step A method for producing a molecular electrolyte membrane actuator. In the adsorption step and the reduction step, one polymer electrolyte membrane is treated,
The pair of polymer electrolyte membranes reduced in the metal ions used in the joining step is prepared by cutting the one polymer electrolyte membrane treated in the adsorption step and the reduction step into two parts in the thickness direction. The method for producing a polymer electrolyte membrane actuator according to claim 4 . The said membrane | film | coat material coat | covers the said porous membrane with the same kind of polymer electrolyte membrane as the said pair of polymer electrolyte membrane which the said metal ion reduced. Of manufacturing a polymer electrolyte membrane actuator.

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