JP2008192469A - Electrochemical cell and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel electrochemical cell and its manufacturing method. <P>SOLUTION: The manufacturing method of the electrochemical cell comprises the following processes. Two frame-like adhesive layers are formed in crimping on a counter-electrode film. A sol-like gel precursor or gel solution is formed inside the adhesive layer. A gel electrolyte film is formed inside the adhesive layer. A work electrode film is attached to the adhesive layer in opposition to the counter-electrode film. Light-hardened resin is introduced between the two adhesive layers. The light-hardened resin existing between the two adhesive layers is hardened. A part of the gel electrolyte film is fused. A single electrochemical cell is made by cutting the work electrode film and the counter-electrode film. The electrochemical cell can be applied for electronic paper, an electric double-layer capacitor, a dye-sensitized solar cell, a lithium-ion cell, or light-controlling glass. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an electrochemical cell. The present invention also relates to a method for producing an electrochemical cell.

  In recent years, electrochemical cells such as electronic paper, electric double layer capacitors, dye-sensitized solar cells, lithium ion batteries, or light control glass have attracted attention. In an electrochemical cell, there is a method of producing a cell by sandwiching a polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP) gel electrolyte membrane between electrode films.

  FIG. 7 shows a configuration of a dye-sensitized solar cell as an example of a conventional electrochemical cell. As the working electrode film 5, for example, a film in which a titanium oxide electrode is formed on glass is used. As the counter electrode film 1, for example, a film in which a platinum electrode is formed on glass is used. A gel electrolyte membrane 4 made of, for example, PVdF-HFP gel is sandwiched between the working electrode film 5 and the counter electrode film 1. A sealing portion 2 is disposed around the gel electrolyte membrane 4.

PVdF-HFP gel has an excellent property that ionic conductivity is not significantly impaired even at a solid content of 50%. At the laboratory level using PVdF-HFP gel, an electrochemical cell using a hard working electrode film and a hard counter electrode film has been reported (for example, see Patent Document 1 and Non-Patent Document 1).
JP 2003-16833 A Supervised by Noboru Oyama “Latest Polymer Battery Technology” CMC

  However, the above-described conventional electrochemical cell ensures the adhesion between the gel electrolyte membrane and the electrode formed on the working electrode film, and the adhesion between the gel electrolyte membrane and the electrode formed on the counter electrode film. There is a problem that can not be. This is because the gel electrolyte membrane has no tack, and the adhesion between the gel electrolyte membrane and the electrode cannot be ensured.

Further, the conventional electrochemical cell described above has air bubbles between the gel electrolyte membrane and the electrode provided on the working electrode film, and between the gel electrolyte membrane and the electrode provided on the counter electrode film. There is a problem that it is difficult to prevent the occurrence.
These two problems are very serious when a display application such as electronic paper is assumed, and should be solved by all means.

  On the other hand, the conventional electrochemical cell described above uses a hard working electrode film and a hard counter electrode film. Therefore, it is unsuitable for production by a roll-to-roll method, and there is a problem that mass production is not possible.

  In order to solve this, a method of producing by a roll-to-roll method using a flexible working electrode film and a flexible counter electrode film can be considered.

However, the production of the roll-to-roll method has the following problems. The gel cannot be made in a defined shape and placed in a defined position on the roll. When a gel electrochemical cell is produced by a roll-to-roll method, a method generally used for an adhesive sheet cannot be applied as it is. Since the gel has no mechanical strength, the gel cannot be punched or processed in the cell production. This is because if the gel is cut, it will collapse and cannot be processed.
On the other hand, in order to improve the performance of the electrochemical cell device, the gel electrolyte membrane is required to have a uniform thickness.

The present invention has been made in view of such problems, and an object thereof is to provide a novel electrochemical cell.
Another object of the present invention is to provide a novel method for producing an electrochemical cell.

  In order to solve the above problems and achieve the object of the present invention, an electrochemical cell of the present invention comprises a working electrode film, a counter electrode film facing the working electrode film, and a gel sandwiched between the working electrode film and the counter electrode film. An electrochemical cell having an electrolyte membrane and a sealing portion that seals the periphery of the gel electrolyte membrane has two adhesive layers around the gel electrolyte membrane, and the working electrode film and the counter electrode film have flexibility. It is characterized by that.

  The electrochemical cell of the present invention includes a working electrode film, a counter electrode film facing the working electrode film, a gel electrolyte membrane sandwiched between the working electrode film and the counter electrode film, and a seal that seals the periphery of the gel electrolyte membrane The electrochemical cell having a portion has a pressure-sensitive adhesive layer around the gel electrolyte membrane, and the working electrode film and the counter electrode film have flexibility.

  The method for producing an electrochemical cell of the present invention comprises a step of forming two frame-like pressure-sensitive adhesive layers on a counter electrode film, a step of forming a gel electrolyte membrane inside the pressure-sensitive adhesive layer, and a working electrode film. , Having a step of attaching to the pressure-sensitive adhesive layer facing the counter electrode film, a step of introducing and curing a photocurable resin between the two pressure-sensitive adhesive layers, and a step of melting a part of the gel electrolyte membrane It is characterized by.

  In the method for producing an electrochemical cell of the present invention, a step of forming a frame-like pressure-sensitive adhesive layer and a frame-like photocurable resin layer on a counter electrode film, and a gel electrolyte membrane inside the pressure-sensitive adhesive layer are formed. Characterized in that it includes a step, a step of attaching the working electrode film to the counter electrode film and attaching to the pressure-sensitive adhesive layer, a step of curing the photocurable resin layer, and a step of melting a part of the gel electrolyte membrane. To do.

The present invention has the following effects.
The present invention provides a working electrode film, a counter electrode film facing the working electrode film, a gel electrolyte membrane sandwiched between the working electrode film and the counter electrode film, and an electric part having a sealing portion for sealing the periphery of the gel electrolyte membrane. Since the chemical cell has two adhesive layers around the gel electrolyte membrane, and the working electrode film and the counter electrode film have flexibility, a novel electrochemical cell can be provided.

  The present invention provides a working electrode film, a counter electrode film facing the working electrode film, a gel electrolyte membrane sandwiched between the working electrode film and the counter electrode film, and an electric part having a sealing portion for sealing the periphery of the gel electrolyte membrane. Since the chemical cell has an adhesive layer around the gel electrolyte membrane, and the working electrode film and the counter electrode film have flexibility, a novel electrochemical cell can be provided.

  The present invention includes a step of forming two frame-shaped pressure-sensitive adhesive layers on a counter electrode film, a step of forming a gel electrolyte membrane inside the pressure-sensitive adhesive layer, and a working electrode film facing the counter electrode film. Since it has a step of attaching to the pressure-sensitive adhesive layer, a step of introducing and curing a photocurable resin between the two pressure-sensitive adhesive layers, and a step of melting a part of the gel electrolyte membrane, A manufacturing method can be provided.

  The present invention includes a step of forming a frame-shaped pressure-sensitive adhesive layer and a frame-shaped photocurable resin layer on a counter electrode film, a step of forming a gel electrolyte membrane inside the pressure-sensitive adhesive layer, and a working electrode film. A process for attaching the adhesive layer facing the counter electrode film, a step for curing the photocurable resin layer, and a step for melting a part of the gel electrolyte membrane. Can be provided.

Hereinafter, the best mode for carrying out the present invention will be described.
First, the best mode for carrying out the first invention according to the electrochemical cell and the manufacturing method thereof will be described.

  A method for producing an electrochemical cell will be described. 1-3 show the manufacturing process of the cell of an electronic paper as an example of the manufacturing process of an electrochemical cell. In each of A to I in FIGS. 1 to 3, what is described above is a cross-sectional view, and what is described below is a plan view.

  The set electrolyte film thickness and the set pressure-sensitive adhesive layer film thickness are defined. The set electrolyte film thickness refers to the thickness of the gel electrolyte film 4 in step I (described later). The set pressure-sensitive adhesive layer thickness refers to the thickness of the pressure-sensitive adhesive layers 12 and 13 in step I.

  Step A will be described. In step A, as shown in FIG. 1A, two frame-like pressure-sensitive adhesive layers 12 and 13 are formed on the counter electrode film 1 by pressure bonding.

The counter electrode film 1 will be described.
As the counter electrode film 1, a transparent film with an electrode (Zeonor, manufactured by Nippon Zeon Co., Ltd.) was used. The counter electrode film 1 functions as a display electrode.

  The counter electrode film 1 has a thickness of 100 μm. The thickness of the counter electrode film 1 is not limited to this thickness. In addition, the thickness is preferably in the range of 50 to 5000 μm. There exists an advantage that mechanical strength can be given that thickness is 50 micrometers or more. When the thickness is 5000 μm or less, there is an advantage that it is possible to ensure the ease of bending corresponding to an application that requires bending.

  The material of the base film of the counter electrode film 1 is norbornene resin. Of course, the material of the base film of the counter electrode film 1 is not limited to this.

  The electrode of the counter electrode film 1 is a silver-plated electrode. The electrode is not limited to this silver-plated electrode. In addition, an electrode made of a silver compound, platinum, gold, or the like can be used.

The pressure-sensitive adhesive layers 12 and 13 will be described.
As the adhesive layers 12 and 13, an adhesive (G9000, manufactured by Sony Chemical Corporation) was used. This pressure-sensitive adhesive is a solventless acrylic double-sided pressure-sensitive adhesive.

  The pressure-sensitive adhesive layers 12 and 13 have a frame shape. The pressure-sensitive adhesive layers 12 and 13 are produced as follows. A film made of the above-mentioned pressure-sensitive adhesive is formed on the cover film. A frame-shaped cut is made in the adhesive film, and unnecessary portions are peeled off. Of the adhesive film surface, the surface opposite to the cover film is pressure-bonded to the counter electrode film 1. Remove the cover film. Frame-shaped pressure-sensitive adhesive layers 12 and 13 are formed on the counter electrode film 1.

  Of course, the production method of the pressure-sensitive adhesive layers 12 and 13 is not limited to the above-described method, and other methods can be adopted.

  The thicknesses of the pressure-sensitive adhesive layers 12 and 13 are determined so as to reach the set pressure-sensitive adhesive layer thickness through the process up to Step I.

  The width of the frame of the pressure-sensitive adhesive layers 12 and 13 is 1 mm. The width of the frame of the pressure-sensitive adhesive layers 12 and 13 is not limited to this value. The width of the frame is preferably in the range of 0.2 to 3 mm. There exists an advantage that sufficient adhesion | attachment can be performed in the process E as the width | variety of a frame is 0.2 mm or more. When the width of the frame is 3 mm or less, there is an advantage that the sealing portion is not bulky and space can be saved.

  The size of the inner part of the frame of the pressure-sensitive adhesive layer 12 is the size of the sol-like gel precursor 3 (gel solution 7) in step B (described later) and the size of the sol-like gel precursor 3 (gel solution 7). It is determined by the width of the gap formed around.

  A space 11 having a width of 1 mm is provided between the outside of the frame of the pressure-sensitive adhesive layer 12 and the inside of the frame of the pressure-sensitive adhesive layer 13. The width of the space 11 is not limited to this value. The width of the space portion 11 is preferably in the range of 0.5 to 5 mm. When the width of the space portion 11 is 0.5 mm or more, there is an advantage that an adhesive can be easily placed and an error in positioning accuracy can be sufficiently absorbed. There exists an advantage that it can prevent that a sealing part becomes large too much that the width | variety of the space part 11 is 5 mm or less.

  The material of the adhesive layers 12 and 13 is not limited to the above-mentioned adhesive (G9000, manufactured by Sony Chemical Corporation). In addition, in order to maintain the stability as a product, those having resistance to electrolytic solution can be used.

The pressure bonding between the counter electrode film 1 and the pressure-sensitive adhesive layers 12 and 13 will be described.
The pressure for pressure bonding was 5000 N / cm ² . The pressure for pressure bonding is not limited to this value. When various thicknesses and materials are applied to the counter electrode film 1 and the pressure-sensitive adhesive layers 12 and 13, the pressure for pressure bonding is preferably in the range of 1000 to 15000 N / cm ² .

  The temperature for pressure bonding is normal temperature. The temperature of pressure bonding is not limited to this. When various thicknesses and materials are applied to the counter electrode film 1 and the pressure-sensitive adhesive layers 12 and 13, it is preferable that the temperature for pressure bonding be in the range of 5 to 80 ° C.

  The peel strength of the pressure bonding was 15 N / 2 cm. The peel strength of pressure bonding is not limited to this value. When various thicknesses and materials are applied to the counter electrode film 1 and the pressure-sensitive adhesive layers 12 and 13, it is preferable that the peel strength of the pressure bonding is 15/2 cm or more.

When the pressure, temperature, and peel strength of the pressure bonding are within the above-mentioned ranges, there is an advantage that sufficient adhesion can be achieved.
The peel strength was measured using a tensile tester (Tensilon, manufactured by ORIENTEC).

  Step B will be described. In step B, as shown in FIG. 1B, a sol-like gel precursor 3 or a gel solution 7 is formed inside the pressure-sensitive adhesive layer 12. In the case of the sol-like gel precursor 3, the sol-like gel precursor 3 is heated and screen-printed inside the pressure-sensitive adhesive layer 12. In the case of the gel solution 7, the gel solution 7 is heated and screen-printed inside the pressure-sensitive adhesive layer 12.

  The process B in the case of the sol gel precursor 3 will be described.

The sol gel precursor 3 will be described.
The conditions required for the gel electrolyte membrane are as follows. That is, the ion conductivity is 1 × 10 ⁻⁵ S / cm or more, it is a reversible gel that becomes liquid at high temperature and gels at room temperature, holds the electrolyte, and some external pressure is applied to the gel electrolyte membrane. However, the electrolyte does not flow out.

The sol-form gel precursor 3 was produced by heating and mixing the following components.
Polyvinylidene fluoride-hexafluoropropylene copolymer 20 parts (PVdF-HFP) (Kynar 2801, manufactured by Atofin Japan)
Electrolytic solution (γ-BL) 120 parts Titanium oxide 20 parts Here, the composition of the electrolytic solution (γ-BL) is as follows.
Silver iodide 250 mmol / L
Sodium iodide 350 mmol / L
Triethanolamine 10 g / L
Coumarin 5 g / L
2-mercaptobenzimidazole 5 g / L

  The composition of the gelling agent PVdF-HFP is preferably in the range of 5 to 50% by mass. There exists an advantage that gelatinization can be made easy as a composition is 5 mass% or more. When the composition is 50% by mass or less, there is an advantage that the ionic conductivity can be maintained high.

  The gelling agent is not limited to the PVdF-HFP described above. In addition, polyvinylidene fluoride (PVdF), polyvinylidene fluoride-tetrafluoroethylene copolymer, polyvinylidene fluoride-trifluoroethylene copolymer, polyvinylidene fluoride-acrylonitrile copolymer, polyacrylonitrile, and the like can be used.

  In the production of the sol-form gel precursor, what is blended in addition to the gelling agent and the electrolytic solution is not limited to titanium oxide. In addition, aluminum oxide, zinc oxide, and the like can be blended.

  A screen printer will be described. A screen printer (LS-150, manufactured by Neurong Seimitsu Kogyo Co., Ltd.) makes it possible to heat the sol-like gel precursor. In screen printing, the sol-shaped gel precursor is sufficiently heated in advance, and the metal mask plate is further heated by a hot stage. Install a heater and sensor on the hot stage so that the temperature can be controlled. This can prevent gelation of the sol-like gel precursor on the metal mask plate.

  The heating temperature of the sol-form gel precursor and the heating temperature of the metal mask plate in the screen printing machine are set so that the viscosity of the sol-form gel precursor immediately after being formed on the counter electrode film becomes the set sol-form gel precursor viscosity. To decide. The set sol-like gel precursor viscosity is defined later.

  By screen printing, the adhesion between the electrode of the counter electrode film 1 and the sol-form gel precursor 3 can be secured. This is because the sol precursor is in a molten state, so that the sol precursor can flow corresponding to the uneven shape of the electrode formed on the counter electrode film 1.

  Of course, the method of forming the sol-like gel precursor 3 on the counter electrode film 1 is not limited to the above-described screen printing method.

  The thickness of the sol-like gel precursor 3 is determined so as to reach the set electrolyte film thickness through the process up to Step I.

  The size of the sol-like gel precursor 3 is 25 mm in vertical length and 40 mm in horizontal length in the plan view of FIG. 1B. The size of the sol-like gel precursor 3 is not limited to this value. The vertical and horizontal lengths of the sol-like gel precursor 3 are preferably in the range of 5 to 500 mm. When the length and width are 5 mm or more, there is an advantage that the sol-like gel precursor 3 can be easily screen-printed in the sealing portion 2. When the vertical and horizontal lengths are 500 mm or less, there is an advantage that the thickness of the sol-like gel precursor 3 can be kept uniform.

  It is preferable to provide a gap having a width of 0.5 to 5 mm between the sol-like gel precursor 3 and the pressure-sensitive adhesive layer 12. There exists an advantage that the contact with electrolyte solution and the adhesive layer 12 can be prevented as the width | variety of a clearance gap is 0.5 mm or more. When the width of the gap is 5 mm or less, there is an advantage that the sol-like gel precursor 3 is sufficiently sandwiched between the electrode films and adhesion is maintained.

  In FIG. 1B, the longitudinal direction of the sol-like gel precursor 3 is the left-right direction. The longitudinal direction of the sol-like gel precursor 3 is not limited to this direction. Of course, the vertical direction, the vertical direction, the diagonal direction, and the like can be adopted.

  Define the set sol-gel precursor viscosity. The set sol-form gel precursor viscosity is the viscosity of the sol-form gel precursor immediately after being formed when the sol-form gel precursor is formed on the counter electrode film by a screen printer or the like. The set sol gel precursor viscosity is preferably 20 mPas or more. There exists an advantage that the shape of a sol-form gel precursor does not collapse that the setting sol-form gel precursor viscosity is 20 mPas or more.

  The process B in the case of the gel solution 7 is demonstrated.

The gel solution will be described.
The gel solution is produced by heating and mixing the following gel electrolyte membrane components and a solvent.
Gel electrolyte membrane component Polyvinylidene fluoride-hexafluoropropylene copolymer 20 parts (PVdF-HFP) (Kynar 2801, manufactured by Atofin Japan)
Electrolyte (γ-BL) 120 parts Titanium oxide 20 parts
Here, the electrolytic solution is the same as in the case of the sol-gel precursor.
Solvent Dimethyl carbonate (DMC) 60 parts

  The preferred range of the gelling agent PVdF-HFP composition in the gel electrolyte membrane component is the same as in the case of the sol-form gel precursor.

  The ratio of the solvent to the gel electrolyte membrane component is determined so that the viscosity of the gel solution immediately after being formed on the counter electrode film becomes the set gel solution viscosity. The set gel solution viscosity is defined later.

  The gelling agent and other components are the same as in the case of the sol gel precursor.

The solvent is not limited to dimethyl carbonate. In addition, diethyl carbonate, methyl ethyl carbonate, acetone and the like can be used. The solvent is an organic solvent other than the electrolytic solution, and preferably has a relatively low boiling point and is volatilized by heating and not mixed into the final product.

  A screen printer will be described. A screen printer (LS-150, manufactured by Neurong Seimitsu Kogyo Co., Ltd.) makes it possible to heat the gel solution. In the screen printing, the gel solution is sufficiently heated in advance, and further the metal mask plate is heated by a hot stage. Install a heater and sensor on the hot stage so that the temperature can be controlled. This can prevent the gel solution from gelling on the metal mask plate.

  The heating temperature of the gel solution and the heating temperature of the metal mask plate in the screen printer are determined so that the viscosity of the gel solution immediately after being formed on the counter electrode film becomes the set gel solution viscosity. The set gel solution viscosity is defined later.

  Other methods for forming the gel solution 7 on the counter electrode film 1 are the same as in the case of the sol gel precursor. The thickness of the gel solution 7 is determined in consideration of the evaporation of the solvent so that the thickness of the gel electrolyte 7 reaches the set electrolyte film thickness through the process up to the process I. The magnitude | size of the gel solution 7, the width | variety of the clearance gap between the gel solution 7 and the adhesive layer 12, and the direction of the gel solution 7 are the same as that of the case of a sol-form gel precursor.

  Define the set gel solution viscosity. The set gel solution viscosity is the viscosity of the gel solution immediately after the gel solution is formed on the counter electrode film by a screen printer or the like. The set gel solution viscosity is preferably 20 mPas or more. When the set gel solution viscosity is 20 mPas or more, there is an advantage that the shape of the gel solution does not collapse.

  Step C will be described. In step C, the gel electrolyte membrane 4 is formed inside the pressure-sensitive adhesive layer 12 as shown in FIG. 1C. In the case of the sol gel precursor, the gel electrolyte 4 is formed by cooling the sol gel precursor. In the case of a gel solution, the gel electrolyte membrane 4 is formed by heating the gel solution.

The cooling in the case of a sol gel precursor will be described.
As a cooling method, a method of spraying cold air on the sol-shaped gel precursor can be employed. Note that step C may be omitted. For example, when the process C is omitted, when the distance between the process B before the process C and the process E (described later) after the process C is sufficiently long, the sol-like gel precursor is naturally Can be cooled.

  The heating in the case of a gel solution will be described. As a heating method, a method of blowing hot air, a method of applying infrared rays, or the like can be used.

  Step D will be described. In step D, a working electrode film 5 is prepared as shown in FIG. 2D.

The working electrode film 5 will be described.
The working electrode film 5 is positioned to face the counter electrode film 1. As the working electrode film 5, an ITO film (OTEC, manufactured by Oji Toby) was used. This working electrode film 5 functions as a display electrode.

  The thickness of the working electrode film 5 is 100 μm. The thickness of the working electrode film 5 is not limited to this thickness. In addition, the thickness is preferably in the range of 50 to 5000 μm. There exists an advantage that mechanical strength can be given that thickness is 50 micrometers or more. When the thickness is 5000 μm or less, there is an advantage that it is possible to ensure the ease of bending corresponding to an application that requires bending.

  The material of the base film of the working electrode film 5 is polyethylene terephthalate (PET). The material of the base film of the working electrode film 5 is not limited to this. In addition, polybutylene phthalate, polyimide, polycarbonate, or the like can be used.

  The electrode of the working electrode film 5 is an ITO electrode. The electrode is not limited to this ITO electrode. In addition, a transparent conductive film IZO, ATO, or the like can be used.

  Step E will be described. In step E, as shown in FIG. 2E, the working electrode film 5 is attached to the pressure-sensitive adhesive layers 12 and 13 so as to face the counter electrode film 1. The working electrode film 5 and the adhesive layers 12 and 13 are pressure-bonded by a roller. The gel electrolyte membrane 4 is sandwiched between the working electrode film 5 and the counter electrode film 1.

The pressure bonding apparatus has a roller 6 installed on the upper side. Thus, since the roller 6 is installed on the upper side, it is possible to prevent bubbles from being formed between the gel electrolyte membrane 4 and the working electrode film 5. Generation of bubbles can be prevented by laminating while extruding air by laminating.
The lower side of the crimping apparatus may be a roller or a flat member.

The pressure for pressure bonding was 5000 N / cm ² . The pressure for pressure bonding is not limited to this value. When various thicknesses and materials are applied to the working electrode film 5, the pressure-sensitive adhesive layers 12 and 13, and the counter electrode film 1, the pressure for pressure bonding is preferably in the range of 1000 to 15000 N / cm ² .

  The temperature for pressure bonding is normal temperature. The temperature for pressure bonding is not limited to this value. When various thicknesses and materials are applied to the working electrode film 5, the pressure-sensitive adhesive layers 12 and 13, and the counter electrode film 1, it is preferable that the temperature for pressure bonding be in the range of 5 to 80 ° C.

The peel strength between the working electrode film 5 and the counter electrode film 1 through the pressure-sensitive adhesive layers 12 and 13 was 15 N / 2 cm. The peel strength of pressure bonding is not limited to this value. When various thicknesses and materials are applied to the working electrode film 5, the pressure-sensitive adhesive layers 12 and 13, and the counter electrode film 1, it is preferable that the pressure-release peel strength is in a range of 15 N / 2 cm or more.
When the pressure, temperature, and peel strength of the pressure bonding are within the above-mentioned ranges, there is an advantage that sufficient adhesion can be achieved.

  Step F will be described. In Step F, as shown in FIG. 2F, the photocurable resin 10 is introduced between the pressure-sensitive adhesive layer 12 and the pressure-sensitive adhesive layer 13.

  As the photocurable resin, 2-ethylhexyl or the like was used. The photocurable resin is not limited to this. In addition, an acrylic monomer or the like can be selected according to the sealing application.

  A method for injecting the photocurable resin will be described. As shown in FIG. 2F, the photocurable resin 10 is introduced into the space 11 from the injection tube 8 that has penetrated the pressure-sensitive adhesive layer 13. On the other hand, the air in the space 11 is discharged from the exhaust pipe 9 that has penetrated the adhesive layer 13. When the space 11 is filled with the photocurable resin 10, the injection pipe 8 and the exhaust pipe 9 are pulled out from the adhesive layer 13. As a result, the space 11 is filled with the photocurable resin 10.

  The method of injecting the photocurable resin is not limited to the method using the injection pipe 8 and the exhaust pipe 9 described above. In addition, a method such as vacuum injection can be employed.

  Step G will be described. In the process G, as shown to FIG. 3G, the photocurable resin 10 which exists between the adhesive layer 12 and the adhesive layer 13 is hardened.

  The photocurable resin 10 is cured by irradiating the photocurable resin 10 with ultraviolet rays. Curing of the photocurable resin 10 is not limited to this ultraviolet irradiation, and can be performed by irradiating light such as radiation polymerization such as γ rays.

  Irradiation with ultraviolet rays is not limited to irradiation from above as shown in FIG. 3G. Irradiation from the lower direction may be used, and irradiation from both the upper and lower directions may be used.

  The curing method of the photocurable resin 10 is not limited to the above-described method by light irradiation, and other methods such as irradiation with a spotlight can be employed.

  Step H will be described. In Step H, as shown in FIG. 3H, a part of the gel electrolyte membrane 4 is melted.

  As shown in FIG. 3H, the heating region of the heater 15 coincides with the region of the gel electrolyte membrane 4. By matching in this way, the gel electrolyte membrane 4 can be heated uniformly. As a result, the gel electrolyte membrane 4 can have a uniform film thickness, and the performance as a device of an electrochemical cell can be improved.

The pressure was 5000 N / cm ² . The pressure is not limited to this value. When various thicknesses and materials are applied to the working electrode film 5, the gel electrolyte membrane 4, and the counter electrode film 1, the pressure is preferably in the range of 1000 to 15000 N / cm ² .

  The heating temperature was 140 ° C. The heating temperature is not limited to this value. When various thicknesses and materials are applied to the working electrode film 5, the gel electrolyte membrane 4, and the counter electrode film 1, the heating temperature is preferably in the range of 120 to 180 ° C.

  As shown in FIG. 3H, the heater 15 is pressed from above. Thereby, a part of the upper side of the gel electrolyte membrane 4 is melted. Adhesion between the electrode of the working electrode film 5 and the gel electrolyte membrane 4 can be ensured. Since the working electrode film 5 has flexibility, the electrode of the working electrode film 5 can be pressed against the gel electrolyte membrane by applying pressure from the outside.

  Step I will be described. In Step I, as shown in FIG. 3I, a single electrochemical cell is produced by cutting the working electrode film 5 and the counter electrode film 1.

  As shown on the left side of FIG. 3I, the counter electrode film 1 is exposed to the electrodes of the working electrode film 5 and the sealing portion 2 by cutting the counter electrode film 1 longer. Moreover, the electrode of the working electrode film 5 is exposed by making the working electrode film 5 longer and cut with respect to the counter electrode film 1 and the sealing portion 2 as shown on the right side of FIG. 3I.

  In this way, the reason for exposing the electrode is that the electrode of the counter electrode film 1 and the flexible substrate and the electrode of the working electrode film 5 and the flexible substrate are bonded by an anisotropic conductive film (ACF) in a later step. This is for electrical connection.

  The set electrolyte film thickness is 100 μm. The set electrolyte film thickness is not limited to this value. The set electrolyte film thickness is preferably in the range of 30 to 500 μm. When the set electrolyte film thickness is 30 μm or more, there is an advantage that it functions as a display element such as electronic paper. When the set electrolyte film thickness is 500 μm or less, there is an advantage that an increase in internal resistance, which is an electrochemical characteristic of the electrolyte film, can be prevented.

  The set adhesive layer thickness was the same as the set electrolyte thickness. The reason is that the change in thickness of the gel electrolyte membrane containing no solvent is small.

  In a step different from the steps A to I, a driver IC COF (chip on flexible substrate) for mounting an IC chip on a flexible substrate is connected.

  In a step after step I, an anisotropic conductive film (ACF Anisotropic Conductor Film) is connected. Since the anisotropic conductive film contains conductive particles, the circuit of the flexible substrate and the electrode of the film can be electrically connected by heating and pressing with a bonder.

  The steps A to I and the subsequent steps have been described above. In these steps, an electrochemical cell is produced by a roll-to-roll method. The production of the electrochemical cell of the present invention is not limited to this roll-to-roll method. In addition, a single electrochemical cell can be produced by a so-called batch method.

  By the method of steps A to I, an electrochemical cell can be produced in a roll-to-roll manner. By producing gel electrochemical cells in a roll-to-roll manner, they can be produced in large quantities at low cost. Moreover, the gel to be used does not require initiators, such as a peroxide, for a physical gel, and can be manufactured safely.

  The electronic paper produced by the steps A to I and the subsequent steps was evaluated. Evaluation items were (1) adhesion between the working electrode film and the gel electrolyte membrane and the counter electrode film and the gel electrolyte membrane, (2) air bubbles at the interface between the working electrode film and the gel electrolyte membrane, and the interface between the counter electrode film and the gel electrolyte membrane. (3) The performance of electronic paper as a device.

An electronic paper evaluation method will be described.
Evaluation of the adhesion between the working electrode film and the gel electrolyte membrane and the adhesion between the counter electrode film and the gel electrolyte membrane were performed as follows. After leaving the device at 60 ° C. for 7 days, the device was visually inspected for peeling and judged to be white.

  Evaluation of bubble generation at the interface between the working electrode film and the gel electrolyte membrane and at the interface between the counter electrode film and the gel electrolyte membrane was performed as follows. In the dot matrix cell, the entire surface was displayed, and it was examined with an optical microscope whether black was displayed on the entire surface.

The performance of electronic paper as a device, specifically, the ionic conductivity (S / cm) of the gel electrolyte membrane was evaluated as follows. The ionic conductivity (S / cm) was measured by the alternating current impedance method (Solatron 1260). The ionic conductivity is calculated from the following equation.
σ = 1 / (S × R)
Where l: cell length, S: electrode area

The evaluation result will be described.
As for the adhesion between the working electrode film and the gel electrolyte membrane, and the adhesion between the counter electrode film and the gel electrolyte membrane, no white portions were found as a result of visual inspection.

  Regarding the generation of bubbles at the interface between the working electrode film and the gel electrolyte membrane and the interface between the counter electrode film and the gel electrolyte membrane, black dots were confirmed on the entire surface as a result of inspection with an optical microscope.

The ion conductivity σ (S / cm) of the gel electrolyte membrane of the PVdF-HFP gel was σ = 8.8 × 10 ⁻⁵ (S / cm).

  An electrochemical cell using a gel electrolyte membrane of PVdF-HFP gel has good adhesion of the gel electrolyte membrane and can prevent the generation of bubbles. Further, the gel electrolyte membrane has high ionic conductivity and excellent film thickness uniformity. Due to the flexibility of the electrochemical cell, there is a possibility of finding a completely new use that has not been considered in the past. Furthermore, by sealing with a photo-curable resin, it is possible to add a gas barrier function, which was a problem with conventional thermoplastic sealants, and the composition in the cell remains the same, extending the life of the device. Connected. Further, the gel electrolyte membrane has chemical stability.

  From the above, according to the best mode for carrying out the present invention, a working electrode film, a counter electrode film facing the working electrode film, a gel electrolyte membrane sandwiched between the working electrode film and the counter electrode film, In an electrochemical cell having a sealing portion for sealing the periphery of the gel electrolyte membrane, the adhesive layer has two adhesive layers around the gel electrolyte membrane, and the working electrode film and the counter electrode film have flexibility. An electrochemical cell can be provided.

  According to the best mode for carrying out the present invention, a step of forming two frame-like pressure-sensitive adhesive layers on a counter electrode film, a step of forming a gel electrolyte membrane inside the pressure-sensitive adhesive layer, and an action The step of attaching the electrode film to the counter electrode film and attaching it to the pressure-sensitive adhesive layer, the step of introducing a photocurable resin between the two pressure-sensitive adhesive layers and curing it, and the step of melting a part of the gel electrolyte membrane Therefore, a novel method for producing an electrochemical cell can be provided.

  The present invention is not limited to the best mode for carrying out the above-described invention, and various other configurations can be adopted without departing from the gist of the present invention.

  Next, the best mode for carrying out the second invention according to the electrochemical cell and the method for producing the same will be described.

  A method for producing an electrochemical cell will be described. 4-6 shows the manufacturing process of the cell of an electronic paper as another example of the manufacturing process of an electrochemical cell. In each of A to H in FIGS. 4 to 6, what is described above is a cross-sectional view, and what is described below is a plan view.

  The electrochemical cell manufacturing method is the same as the best mode for carrying out the first invention except for the matters described below.

  The setting electrolyte film thickness, the setting sealing part film thickness, and the setting adhesive layer film thickness are defined. The set electrolyte film thickness refers to the thickness of the gel electrolyte film 4 in step H (described later). The set sealing portion film thickness refers to the thickness of the sealing portion 2 in the process H. The set pressure-sensitive adhesive layer thickness refers to the thickness of the pressure-sensitive adhesive layer 12 in the process H.

  Step A will be described. In step A, as shown in FIG. 4A, a frame-shaped pressure-sensitive adhesive layer 12 and a frame-shaped photocurable resin layer 16 are formed on the counter electrode film 1.

  The photocurable resin layer 16 will be described. As shown to FIG. 4A, the photocurable resin layer 16 is formed in the outer side of the adhesive layer 12 by screen printing.

  A screen printer will be described. A screen printer (LS-150, manufactured by Neurong Seimitsu Kogyo Co., Ltd.) was used to form the photocurable resin layer 16.

  Of course, the method of forming the photocurable resin layer 16 is not limited to the screen printing method.

  The photocurable resin which comprises the composition of the photocurable resin layer 16 is demonstrated. Light acrylate IB-XA (manufactured by Kyoeisha Chemical Co., Ltd.) was used as the photocurable resin. Of course, the photocurable resin is not limited to this.

  The photocurable resin was supplied to a screen printer by increasing its viscosity by various methods. The reason is that when the photocurable resin is printed on the counter electrode film 1 using a screen printer, the shape of the photocurable resin is lost because the viscosity of the photocurable resin is low. By increasing the viscosity of the photocurable resin, it is possible to prevent the shape from collapsing.

  As a method for increasing the viscosity of the photocurable resin, there are a method of irradiating the photocurable resin with light such as ultraviolet rays, a method of blending a filler or the like with the photocurable resin, and the like.

  As the filler, VEMA (manufactured by Daicel Chemical Industries) was used. The filler is not limited to this. It can be used in accordance with the sealing application.

  The viscosity of the photocurable resin is preferably 20 mPas or more. If the viscosity is 20 mPas or more, there is an advantage that the shape does not collapse after printing.

  The photocurable resin layer 16 has a frame shape. The thickness of the photocurable resin layer 16 is determined so as to be the set sealing portion film thickness through the process up to the process H.

The width of the frame of the photocurable resin layer 16 is preferably in the range of 0.5 to 5 mm.
The size of the inner portion of the frame of the photocurable resin layer 16 is determined by the size of the pressure-sensitive adhesive layer 12 and the width of the gap formed around the pressure-sensitive adhesive layer 12.

  Step B will be described. In Step B, as shown in FIG. 4B, the sol-shaped gel precursor 3 or the gel solution 7 is formed inside the pressure-sensitive adhesive layer 12. In the case of the sol-like gel precursor 3, the sol-like gel precursor 3 is heated and screen-printed inside the pressure-sensitive adhesive layer 12. In the case of the gel solution 7, the gel solution 7 is heated and screen-printed inside the pressure-sensitive adhesive layer 12.

  Step E will be described. In step E, as shown in FIG. 5E, the working electrode film 5 is attached to the pressure-sensitive adhesive layer 12 so as to face the counter electrode film 1. The working electrode film 5 and the adhesive layer 12 are pressure-bonded by a roller.

  Step F will be described. In step F, as shown in FIG. 5F, the photocurable resin layer 16 is cured. About others, it is the same as that of the process G of the best form for implementing 1st invention.

  Process G is the same as Process H of the best mode for carrying out the first invention.

  Step H will be described. In step H, as shown in FIG. 6H, a single electrochemical cell is produced by cutting the working electrode film 5 and the counter electrode film 1. An adhesive layer 12 is present around the gel electrolyte membrane 4.

  The set sealing portion film thickness was the same as the set electrolyte film thickness. This is because, unlike a thermoplastic resin, it does not collapse due to heat melting. The rest of the process H is the same as the process I of the best mode for carrying out the first invention.

  The production of the electrochemical cell of the present invention is not limited to the roll-to-roll method, and the fact that a single electrochemical cell can be produced by a so-called batch method is the best mode for carrying out the first invention. It is the same.

  The electronic paper produced by the steps A to H and the subsequent steps was evaluated. The evaluation items and the evaluation method of the electronic paper are the same as the evaluation items and the evaluation method described in the best mode for carrying out the first invention.

The evaluation result will be described.
As for the adhesion between the working electrode film and the gel electrolyte membrane, and the adhesion between the counter electrode film and the gel electrolyte membrane, no white portions were found as a result of visual inspection.

  Regarding the generation of bubbles at the interface between the working electrode film and the gel electrolyte membrane and the interface between the counter electrode film and the gel electrolyte membrane, black dots were confirmed on the entire surface as a result of inspection with an optical microscope.

The ion conductivity σ (S / cm) of the gel electrolyte membrane of the PVdF-HFP gel was σ = 8.9 × 10 ⁻⁵ (S / cm).

  An electrochemical cell using a gel electrolyte membrane of PVdF-HFP gel has good adhesion of the gel electrolyte membrane and can prevent the generation of bubbles. Further, the gel electrolyte membrane has high ionic conductivity and excellent film thickness uniformity. Due to the flexibility of the electrochemical cell, there is a possibility of finding a completely new use that has not been considered in the past.

  From the above, according to the best mode for carrying out the present invention, a working electrode film, a counter electrode film facing the working electrode film, a gel electrolyte membrane sandwiched between the working electrode film and the counter electrode film, In an electrochemical cell having a sealing portion that seals the periphery of the gel electrolyte membrane, the adhesive layer is provided around the gel electrolyte membrane, and the working electrode film and the counter electrode film have flexibility. A cell can be provided.

  According to the best mode for carrying out the present invention, a step of forming a frame-like pressure-sensitive adhesive layer and a frame-like photocurable resin layer on a counter electrode film, and a gel electrolyte membrane inside the pressure-sensitive adhesive layer The step of forming the working electrode film, the step of attaching the adhesive film to the pressure-sensitive adhesive layer, the step of curing the photocurable resin layer, and the step of melting a part of the gel electrolyte membrane. A novel method for producing an electrochemical cell can be provided.

  The present invention is not limited to the best mode for carrying out the above-described invention, and various other configurations can be adopted without departing from the gist of the present invention.

  Next, a comparative example according to the electrochemical cell and the manufacturing method thereof will be described.

[Comparative Example 1]
An electronic paper using a gel electrolyte membrane made of PVdF-HFP gel and a rigid electrode plate was prepared. A square-shaped sealing film was affixed to the rigid electrode plate, and the sol-like gel precursor heated and melted therein was dropped with a dispenser, and further sealed with another rigid electrode plate.

  The produced electronic paper was evaluated. The evaluation items and the evaluation method are the same as in the best mode for carrying out the first invention.

The evaluation result will be described.
The adhesion between the working electrode film and the gel electrolyte membrane, and the adhesion between the counter electrode film and the gel electrolyte membrane was visually inspected, and as a result, a white portion was found on a part of the entire surface.

  As to the generation of bubbles at the interface between the working electrode film and the gel electrolyte membrane and the interface between the counter electrode film and the gel electrolyte membrane, only 50% of the black dots were confirmed on the entire surface.

The ion conductivity σ (S / cm) of the gel electrolyte membrane of the PVdF-HFP gel was 1.0 × 10 ⁻⁶ (S / cm).

The application of the electrochemical cell produced by the present invention will be described.
The application of the electrochemical cell produced by the present invention is not limited to electronic paper. In addition, the present invention can be applied to an electric double layer capacitor, a dye-sensitized solar cell, a lithium ion battery, or a light control glass (hereinafter referred to as “application example of an electric double layer capacitor”).

  A manufacturing method of an application example such as an electric double layer capacitor will be described. In principle, the manufacturing method of the application example such as the electric double layer capacitor is the same as the manufacturing method of the electronic paper cell described above. In the following description, differences from the manufacturing method of the above-described electronic paper cell in the manufacturing method of the application example such as the electric double layer capacitor will be described.

  Each electrode of the counter electrode film 1 of an application example such as an electric double layer capacitor will be described. A carbon electrode etc. can be used for the electrode of the counter electrode film 1 of an electric double layer capacitor. A platinum electrode, a carbon electrode, etc. can be used for the electrode of the counter electrode film 1 of a dye-sensitized solar cell. A carbon electrode etc. can be used for the electrode of the counter electrode film 1 of a lithium ion battery. A carbon electrode, a metal oxide electrode, etc. can be used for the electrode of the counter electrode film 1 of light control glass.

The sol-form gel precursor electrolytes of application examples such as electric double layer capacitors will be described respectively. As the electrolytic solution of the sol-like gel precursor of the electric double layer capacitor, a nonaqueous solvent such as propylene carbonate and an electrolyte containing a quaternary ammonium salt, a quaternary sulfonium salt, or the like can be used. As the electrolyte solution for the sol-gel precursor of the dye-sensitized solar cell, a nonaqueous solvent containing iodine and iodide as main electrolytes can be used. The electrolyte solution of the sol-like gel precursor of the lithium ion battery may be a nonaqueous solvent such as propylene carbonate and an electrolyte containing lithium salt (LiPF ₆ ) or the like. As the electrolyte solution of the sol-like gel precursor of the light control glass, a nonaqueous solvent such as propylene carbonate and an electrochromic material such as viologen as an electrolyte can be used.

Each electrode of the working electrode film 7 of the application example such as an electric double layer capacitor will be described. As an electrode of the working electrode film 7 of the electric double layer capacitor, a carbon electrode or the like can be used. As the electrode of the working electrode film 7 of the dye-sensitized solar cell, an electrode in which a dye is held on a titanium oxide film can be used. LiCoO ₃ , LiNiO ₂ , LiMn ₂ O ₄ or the like can be used as the electrode of the working electrode film 7 of the lithium ion battery. A transparent conductive film (ITO) etc. can be used for the electrode of the working electrode film 7 of light control glass.

  The application of the electrochemical cell produced by the present invention is not limited to electronic paper, electric double layer capacitor, dye-sensitized solar cell, lithium ion battery, or light control glass. In addition, the electrochemical cell produced according to the present invention can be applied to other batteries, electrochemical sensors, and the like.

It is a figure which shows an example of the manufacturing process of an electrochemical cell (the 1). It is a figure which shows an example of the manufacturing process of an electrochemical cell (the 2). It is a figure which shows an example of the manufacturing process of an electrochemical cell (the 3). It is a figure which shows the other example of the manufacturing process of an electrochemical cell (the 1). It is a figure which shows the other example of the manufacturing process of an electrochemical cell (the 2). It is a figure which shows the other example of the manufacturing process of an electrochemical cell (the 3). It is a perspective view which shows the structure of the conventional electrochemical cell.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Counter electrode film, 2 ... Sealing part, 3 ... Sol-form gel precursor, 4 ... Gel electrolyte membrane, 5 ... Working electrode film, 6 ... Roller, 7 ... Gel solution, 8 ... Injection pipe, 9 ... Exhaust pipe, 10 ... Photocurable resin, 11 ... Space, 12, 13 ... Adhesive layer, 14 ... Ultraviolet light, 15 ... Heater, 16 ... Photocurable resin layer

Claims (8)

A working electrode film;
A counter electrode film facing the working electrode film;
A gel electrolyte membrane sandwiched between the working electrode film and the counter electrode film;
In an electrochemical cell having a sealing portion for sealing the periphery of the gel electrolyte membrane,
Having two adhesive layers around the gel electrolyte membrane,
The electrochemical cell, wherein the working electrode film and the counter electrode film have flexibility. 2. The electrochemical cell according to claim 1, wherein the electrochemical cell is an electronic paper, an electric double layer capacitor, a dye-sensitized solar cell, a lithium ion battery, or a light control glass. A working electrode film;
A counter electrode film facing the working electrode film;
A gel electrolyte membrane sandwiched between the working electrode film and the counter electrode film;
In an electrochemical cell having a sealing portion for sealing the periphery of the gel electrolyte membrane,
Having an adhesive layer around the gel electrolyte membrane,
The electrochemical cell, wherein the working electrode film and the counter electrode film have flexibility. 4. The electrochemical cell according to claim 3, wherein the electrochemical cell is an electronic paper, an electric double layer capacitor, a dye-sensitized solar cell, a lithium ion battery, or a light control glass. Forming two frame-shaped pressure-sensitive adhesive layers on the counter electrode film;
Forming a gel electrolyte membrane inside the pressure-sensitive adhesive layer;
The working electrode film is opposed to the counter electrode film and applied to the pressure-sensitive adhesive layer;
A step of introducing and curing a photocurable resin between the two pressure-sensitive adhesive layers;
A method for producing an electrochemical cell, comprising a step of melting a part of the gel electrolyte membrane. Forming a frame-like pressure-sensitive adhesive layer and a frame-like photocurable resin layer on the counter electrode film;
Forming a gel electrolyte membrane inside the pressure-sensitive adhesive layer;
The working electrode film is opposed to the counter electrode film and applied to the pressure-sensitive adhesive layer;
Curing the photocurable resin layer;
A method for producing an electrochemical cell, comprising a step of melting a part of the gel electrolyte membrane. The method for producing an electrochemical cell according to claim 6, wherein the photocurable resin layer is formed by increasing the viscosity of the photocurable resin. The method for producing an electrochemical cell according to claim 6, wherein the photocurable resin layer contains a filler.

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