JP2528798B2 - Laminate containing furan-based polymer complex film and its manufacturing method - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a laminate of a furan-based polymer complex film useful as an ion filter or a separator and a conductive material layer.

[0002]

2. Description of the Related Art It has been known that a furan-based monomer is polymerized to produce a polymer. However, in the conventional production method, the polymer is obtained in the form of a powder.
It has been difficult to form the following thin films and laminates with other materials. Therefore, the fact is that little research has been conducted on the properties of furan-based polymer thin films.

[0003]

[Object] An object of the present invention is to provide a novel laminate comprising a furan-based polymer complex thin film and a conductive material layer.

[0004]

[Structure] The present invention relates to a laminate comprising a furan-based polymer complex film and a conductive material layer. The membrane of the furan polymer complex is
The thickness is preferably about 5 to 150 μm. Especially 5 μm
If it is less than the above, pinholes may appear in the film. The laminate has the general formula

Embedded image (Wherein R ₁ and R ₂ are independently selected from the group consisting of hydrogen, an alkyl or alkoxy group having 1 to 2 carbon atoms, and halogen, and n is an integer of 1 to 3) It is obtained by electrolytically polymerizing a solution containing a furan-based monomer and an electrolyte salt to form a furan-based polymerized complex film on an anode made of a conductive material. The laminate can also be obtained by laminating a furan-based polymer complex film obtained by an electrolytic polymerization method and an organic polymer active material layer. In this case, the organic polymer active material layer may be a thin film formed by an electrolytic polymerization method.

The furan polymer complex in the present invention is a polymer complex formed of a furan-based monomer and an anion. Examples of the furan-based monomer include those represented by the following general formula.

Embedded image In the formula, R ₁ and R ₂ are hydrogen, C _{1 to} C ₂ alkyl, alkoxy or halogens, and n is an integer of 1 to 3. On the other hand, the anion is an anion of an electrolyte salt that is used as a raw material in the electrolytic polymerization described later. The electrolytic polymerization can be carried out by applying electricity in an organic solvent containing a furan-based monomer and an electrolyte salt.

Examples of the electrolyte salt include those containing a cation and an anion as exemplified below. Cation; alkali metal such as Li (+), Na (+), K (+), ammonium, H (+), etc. anion: PF ₆ (−), SbF ₆ (−), AsF
₆ (−), SbCl ₆ (−) and other Va group element halide anions, BF ₄ (−) and other IIIa group element halide anions, ClO ₄ (−) and other perchlorate anions, etc. [The above (+) and (-) represent a positive ion and a negative ion, respectively. The same applies hereinafter. ] As electrolyte salts composed of these, LiPF ₆ , Li
SbF ₆ , LiAsF ₆ , LiClO ₄ , LiAlCl ₄ ,
LiBF ₄ , NaClO ₄ , KI, KPF ₆ , KSbF ₆ ,
KAsF ₆ , KClO ₄ , NaBF ₄ , NaAsF ₆ , Na
PF ₆ , AgBF, AgClO ₄ [(n-Bu) ₄ N]
_{(+) · (AsF 6)} (-), [(n-Et) ₄ N]
(+) · ClO ₄ (−), (n-Bu) ₄ N] (+) · C
Examples include 10 ₄ (−). Among these, LiCl
O ₄ , AgClO ₄ , KClO ₄ , [(n-Et) ₄ N]
(+) ・ ClO ₄ (−), [(n-Bu) ₄ N] (+) ・
ClO ₄ (−) and the like are preferable, and especially LiClO ₄ ,
AgClO ₄ and KClO ₄ easily form a good film. The content of the furan-based monomer in the electrolytic solution is about 0.02 to
1.00 mol is preferable, and about 0.10 to 0.30 mol is particularly effective. If it is less than 0.02 mol, the film-forming efficiency will be poor, while if it exceeds 1.00 mol, it tends to be difficult to obtain a uniform film. On the other hand, the content of the salt in the electrolytic solution is preferably about 1.0 mol or less. If it exceeds 1.0 mol, the homogeneity of the film is lost, and the film forming property tends to deteriorate.

As the solvent used for the electrolytic solution, acetonitrile, benzonitrile, propylene carbonate, γ
There may be mentioned polar solvents such as butyrolactone, nitrobenzene, nitromethane, nitroethane, dichloromethane, dioxane and dimethylformamide. From the viewpoint of reactivity, acetonitrile, benzonitrile and propylene carbonate are preferable, nitriles are more preferable, and benzonitrile is particularly preferable. Further, it is preferable that the solvent does not contain water or oxygen because a more homogeneous polymer complex is formed.

The furan polymer complex film used in the present invention is produced by placing a solution of the above-mentioned furan-based monomer and salt in a solvent in a predetermined electrolytic cell, followed by an electrolytic polymerization reaction by anodic oxidation. To be done. If necessary, additives such as a catalyst may be added. The electrolysis may be constant voltage electrolysis, constant current electrolysis, or constant potential electrolysis,
Electrolysis with constant current and constant potential is suitable.

The material constituting the electrode during electrolytic polymerization, that is, the conductive substance, is, for example, a metal such as Au, Pt, or Ni, a metal oxide such as SnO ₂ , In ₂ O ₃ , or a composite electrode or coating of these. An electrode can be mentioned, and it is particularly preferable to use a metal oxide for the anode because a film having a strong polymer complex can be obtained. As another example of the conductive substance, an organic polymer substance having a conjugated system in its main chain on at least one side is used, and specific examples thereof include polyacetylene, polyparaphenylene, poly (3-methyl-2,
5-thienylene), polypyrrole, polyphenylacetylene, and other polymers, or thermal decomposition products of polyimide, polyacrylonitrile, poly-α-cyanoacryl, and the like,
Examples thereof include polyacene. Since these polymer substances generally have high conductivity in a doped state or in a state as they are, they can be used as electrodes for electrolytic polymerization. In particular, since polypyrrole and polythienylene can be produced by an electrolytic polymerization method, it is also possible to form these polymers by electrolytic polymerization directly on the furan polymerization complex film as an electrode. It is also possible to form a polypyrrole or polythienylene film on an electrode by electrolytic polymerization of polypyrrole or polythienylene, and electrolytically polymerize it with a furan-based monomer using this as an anode to form the laminate of the present invention. The furan polymer complex electrochemically synthesized in this manner has an extremely low electronic conductivity and an electric conductivity of 10 in a dry state.
^-5 S / cm or less, but the ion conductivity is extremely high, but the anion is released with the passage of time or by laminating with a metal such as Li as shown in FIG. become. This furan polymer film can be made into a polymerized complex film again by doping with anions.

Next, an embodiment in which a laminate of an electrode active material and a furan polymer complex is formed by an electrochemical method is illustrated by the drawings. In FIG. 1, a film of the active material A (5) is previously formed on the surface of the anode (1) and the active material A (5) is formed.
The membrane surface of (5) is used as an electrode surface, and this and the cathode (2) are arranged to prepare an electrolytic cell (4) containing an electrolytic solution (3), and the furan polymerization complex (6) is electrochemically formed into a membrane. After being formed into a sheet shape, the anode (1) is peeled off to obtain a laminate. However, in this case, the active material A (5) does not necessarily have to be formed electrochemically.
In FIG. 2, after the furan polymer complex is formed into a film in the example of FIG. 1, the active material B (7) is further electrochemically formed into a film on the film. In FIG. 3, the furan polymer complex is obtained by forming a film on the electrode (1) and then electrochemically forming the active material C (8). The laminate thus obtained can exchange ions with the surface of the active material without containing an electrolytic solution. Therefore, it is more effective if it is moistened with about 1/5 or less of the electrolytic solution as compared with the conventional battery.

Therefore, the laminate of the present invention has a use as an organic secondary battery as shown in FIG. That is, L
It can be used as a battery consisting of i electrode / furan polymer complex film / pyrrole polymer film electrode, and if the furan polymer complex film holds a small amount of electrolyte solution or semi-solid electrolyte solution component, it will be an extremely excellent secondary battery. . The supporting electrolyte for the electrolytic solution of the battery in such a case includes (1) PF ₆ (−), SbF ₆ (−), AsF ₆ (−),
Anion dopants such as halide anions of Group Va elements such as SbCl ₆ (−), halide anions of Group IIIa elements such as BF ₄ (−), perchlorate anions such as ClO ₄ (−) (2 ) Alkali metal ions such as Li and K, R ₄ N
Examples of the cation dopant include (+) (R: hydrocarbon group having 1 to 20 carbon atoms). The cation dopant gives an n-type conductive conjugated polymer, and the anion dopant gives a p-type. Specific examples of the compound that gives the above dopant include LiPF ₆ , LiSbF ₆ , and LiA.
sF ₆ , LiClO ₄ , NaClO ₄ , KI, KPF ₆ , K
SbF ₆ , KAsF ₆ , KClO ₄ [(n-Bu) ₄ N]
(+) - AsF ₆ (-), [(n-Bu) ₄ N] (+) -
Examples thereof include ClO ₄ (−), LiAlCl ₄ , LiBF ₄ (Bu: butyl group).

As the solvent of the electrolytic solution of the battery, an aprotic solvent, which is called a polar aprotic solvent having a large relative dielectric constant, is preferable. Specifically, for example, ketones,
Nitriles, esters, ethers, carbonates, nitro compounds, sulfolane compounds and the like or a mixed solvent thereof can be used, and among these, nitriles, carbonates and sulfolane compounds are preferable. Representative examples of these include acetonitrile, propionitrile, butyronitrile, valeronitrile, benzonitrile, ethylene carbonate, propylene carbonate, γ-butyrolactone, sulfolane, 3-methylsulfolane, and gels thereof. Alcohol and water are not preferable because the electrolyte in the furan polymer complex escapes and the ionic conductivity is lost. When the laminate is used as a power generation element, the conductive polymer can be a positive electrode or a negative electrode depending on its structure. In the examples, the case where the conductive polymer is used for the positive electrode and lithium is used for the negative electrode is shown. As a current collector that constitutes a battery, for example, Ni, Al, Au, P which is usually used in this technical field is used.
Examples thereof include t, stainless steel, or one of these placed on a plastic surface.

[0013]

EXAMPLES The present invention will be described in more detail with reference to the following examples and application examples. Example 1 A laminate using the polypyrrole of the embodiment shown in FIG. 1 as an active material was formed as follows. Pyrrole (0.1 mol)
A solution prepared by dissolving and NaAsF (0.2 mol) in acetonitrile was placed in an electrolytic cell using Nesa glass as an anode and Nickel as a cathode, and then constant current electrolysis was performed at ² mA / cm ^2. A pyrrole polymer film having a thickness of about 50 μm was obtained. Then, in this state, put a solution of furan (0.05 mol) and LiClO ₄ (0.2 mol) in benzonitrile into an electrolytic cell having the pyrrole polymer film as an anode and nickel as a cathode. After that, constant voltage electrolysis was performed at 6.5 V to give a thickness of about 35 μm on the pyrrole polymer film.
m furan polymer film was formed. After this, Nesa glass was peeled off to prepare a laminated body. Application Example 1 After stacking a Li film on the surface of the furan polymer of the above-mentioned laminated body, sandwiched by a nickel plate and integrally bonded by pressure (Fig. 4).
), Propylene carbonate / lM LiClO
_It was immersed in the electrolytic solution of ₄ . The nickel plate was removed by taking out after repeating charging and discharging about 6 times. Next, this was pressure-inserted into a nickel container (current collector) filled with an electrolytic solution of the same composition, and the mouth was sealed with an insulating adhesive to form a battery system as shown in FIG. Configured. The organic secondary battery had no liquid leakage and the current density was about 1.2 mA / cm ² .

Example 2 Furan (0.05 mol) and AgClO ₄ (0.2 mol)
The solution of and was dissolved in benzonitrile was placed in an electrolytic cell with Nesa glass as the anode and nickel as the cathode, and then 4.0 V.
Was subjected to constant voltage electrolysis to obtain a furan polymer film having a thickness of about 45 μm. On the other hand, a method generally known as the Shirakawa method [for example, Polymer Journal No.
2, 231 (1971)], an acetylene gas was blown onto the surface of the Ziegler-Natta catalyst solution in an argon gas atmosphere to obtain a film of an acetylene polymer having a thickness of about 200 μm. The furan polymer film and the polyacetylene film thus obtained were sequentially laminated on the Li film to form a laminate. Application Example 2 A battery system was constructed using the laminated body of Example 2 in the same manner as in Application Example 1. The organic secondary battery had no liquid leakage and the current density was about 3.5 mA / cm ² .

Example 3 Pyrrole (0.1 mol) and [(n-Bu) ₄ N] (+)
A solution obtained by dissolving ClO ₄ (−) (0.2 mol) in acetonitrile is placed in an electrolytic cell using Nesa glass as an anode and nickel as a cathode, and constant current electrolysis is performed at 4 mA / cm ² to obtain a thick film on the Nesa glass. A 70 μm thick pyrrole polymer film was obtained. A laminate was obtained in the same manner as in Example 2 using the pyrrole polymer film and the furan polymer film obtained in the same manner as in Example 2. Application Example 3 A battery system was constructed using the laminate obtained in Example 3 in the same manner as in Application Example 1. The organic secondary battery had no liquid leakage and the current density was about 1.7 mA / cm ² .

Comparative Example 1 A battery system was constructed in the same manner as in Example 1 and Application Example 1 except that a pyrrole polymer membrane was prepared in the same manner as in Example 1 and a glass fiber filter was used instead of the furan polymer membrane. did. The organic secondary battery had a large electrolyte content and a current density of about 0.6 mA / cm ² .

[0017]

[Effect] The novel laminate of the present invention is capable of exchanging ions between the furan-based polymer complex film and the active material layer, and thus is useful as a battery separator or an ion filter.
Since the organic secondary battery using the laminate of the present invention as a separator may contain almost no electrolyte, it has no liquid leakage and has high current efficiency.

[Brief description of drawings]

FIG. 1 is a diagram showing an embodiment in which, as shown in Example 1, after forming an active material by electrolytic polymerization, a furan-based polymer complex film is further formed thereon by electrolytic polymerization to produce a laminate.

FIG. 2 is an embodiment diagram in which an active material is further formed on the furan-based polymer complex by electrolytic polymerization following the method for producing the laminate as shown in FIG.

FIG. 3 is an embodiment diagram in which a furan-based polymer complex film is first formed on an electrode by an electrolytic polymerization method, and then an active material layer is formed on the electrode by an electrolytic polymerization method.

FIG. 4 is a cross-sectional view showing a specific structural example of an organic secondary battery using the laminate of the present invention.

[Explanation of symbols]

 1 Anode 2 Cathode 3 Electrolyte 4 Electrolyzer 4 Active Material A 6 Furan Polymerization Complex Film 7 Active Material B 8 Active Material C 9 Furan Polymerization Complex Film 10 Li 11 Pyrrole Polymer Film 12 Ni Container 13 Insulating Seal

Claims (8)

(57) [Claims] 1. A laminate comprising a furan polymer complex film and a conductive material layer. 2. The furan-based polymer complex film has a thickness of 5 to 150 μm.
The laminated body according to claim 1, which is a thin film of m. 3. The laminate according to claim 1, wherein the conductive substance layer is an anode forming material. 4. The laminate according to claim 1 or 2, wherein the conductive material is an organic polymer active material. 5. A general formula: (Wherein R ₁ and R ₂ are independently selected from the group consisting of hydrogen, an alkyl or alkoxy group having 1 to 2 carbon atoms, and halogen, and n is an integer of 1 to 3) A furan-based polymer complex film and a conductive material layer, characterized in that a furan-based polymer complex film is formed on an anode made of a conductive material by electrolytically polymerizing a solution containing a furan-based monomer and an electrolyte salt. A method of manufacturing a laminated body including and. 6. An electrode having an organic polymer active material layer on its surface is used as an anode, and a compound represented by the general formula: (Wherein R ₁ and R ₂ are independently selected from the group consisting of hydrogen, an alkyl or alkoxy group having 1 to 2 carbon atoms, and halogen, and n is an integer of 1 to 3) Furan-based polymer complex film and organic polymer active film characterized by forming a furan-based polymer complex film on an organic polymer active material layer by electropolymerizing a solution containing a furan-based monomer and an electrolyte salt A method for producing a laminate comprising a material layer. 7. A laminate comprising a furan-based polymer complex film and an organic polymer active material layer, characterized in that a furan-based polymer complex film obtained by an electropolymerization method is laminated with an organic polymer active material layer. Manufacturing method. 8. A laminate comprising a furan-based polymerized complex film and an organic polymer active material layer according to claim 7, wherein the organic polymer active material layer is a thin film formed by an electrolytic polymerization method. Manufacturing method.