JP2669672B2 - Joint - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a joined body of aluminum and a conductive polymer material, which is useful for electrochromic devices, switching devices, batteries and the like, a method for producing the same, and a reduction treatment method for the same. About.

[Prior art] Polymer materials such as polypyrrole, polythiophene, polyphenylene, and polyaniline are [polypyrrole: AFDinz.
J. Chem. Soc., Chem. Commun., 1975, 635, polythiophene: JP-A-56-47421), polyphenylene: Electroche
m., Acta, 27 , 61 (1982), polyaniline: F. Diaz, J Elect
roanal.Chem. 111. 1524 (1980)] It is known that doping with impurities makes an insulator or semiconductor have electric conductivity similar to that of metal, and that this doping is reversible, Because of changes, application to display devices, secondary batteries, electromagnetic shield materials, various sensors, etc. is being actively researched.

When such a polymer material is used, it is generally used as an element by being compounded with another conductor (mainly metal), but the characteristics (light weight, thin film, etc.) of the polymer material are impaired. Aluminum is preferable as the conductor that can be used without any modification. Aluminum is another metal (Fe, Ni, Cu, etc.)
Compared with, it is a material that is relatively light and rich in extensibility, so that it is actively applied to elements, composite materials, and the like aiming at lightening and thinning. In addition to the characteristics of light weight and spreadability, in addition to these characteristics, characteristics such as ease of forming an oxide film and ease of etching are used for electrolytic capacitors, and vapor deposition on substances with various materials due to low melting point. It is also widely used for forming conductive layers and reflective layers.

Although a composite of aluminum and a polymer material has various expectations as a functional electrode, the inventors of the present invention have prepared a series of composite electrodes of aluminum and a polymer material, in which the adhesion between the aluminum and the polymer material, the polymer, It has been described that it is preferable to perform electrolytic etching on aluminum in terms of improvement of current collection efficiency from the viewpoint of, and ease of removal of an aluminum oxide film. However, although the adhesion with a polymer material is improved by subjecting ordinary aluminum to electrolytic etching to increase the surface area, it is still not sufficiently satisfactory.

[PROBLEMS TO BE SOLVED BY THE INVENTION] Therefore, an object of the present invention is to improve the adhesion of a bonded body of aluminum and a polymer material, improve the interface impedance characteristics, a bonded body electrode, a method for producing the same, and a reduction treatment thereof. To provide the law.

[Means for Solving the Problems] In view of the above problems, the present inventors have made various studies to realize even higher adhesion in a joined body of aluminum and a polymer material, and as a result, have a crystal of the aluminum surface. It has been found that the object can be achieved by using aluminum having a (HOO) plane (H = 1, 2, 4) as a main crystal plane.

That is, the present invention relates to a joined body of aluminum and a conductive polymer material, characterized in that the crystallinity of the surface of aluminum is (HOO) plane (H = 1,2,4) as a main crystal plane. The body and its production method and its reduction treatment method.

The polymer material used for the conjugate of the present invention is, for example, a hetero five-membered ring compound polymer having pyrrole, thiophene, etc. as a monomer, and an aromatic hydrocarbon compound polymer having benzene, azulene, etc. as a monomer. It is possible to use an amine-based compound polymer having coalesce, aniline, diphenylbenzidine and the like as monomers. As the method for polymerizing the monomer, a chemical polymerization method using an oxidizing agent or an electrolytic polymerization method utilizing electric energy can be used.

The chemical polymerization is carried out by adding an oxidizing agent to a solution containing a monomer and oxidizing the monomer. Oxidizing agents include halogens such as iodine, arsenic and iodide; metal halides such as arsenic pentafluoride, antimony pentafluoride, silicon fluoride and phosphorus pentachloride; sulfuric acid, nitric acid,
Protonic acids such as fluorosulfuric acid and chlorosulfuric acid; oxygen-containing compounds such as sulfur trioxide, nitrogen dioxide, potassium permanganate and potassium dichromate; persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate; peroxidation An oxidizing agent such as a peroxide such as hydrogen, peracetic acid, or difluorosulfonyl peroxide is used. In the chemical polymerization method, when a polymer having a high degree of polymerization is synthesized, the polymer is insoluble and synthesized in a powder form. Therefore, in order to carry out the bonded body of the present invention, it is necessary to mechanically adhere aluminum and the polymer mechanically, but this method has a drawback that the aluminum and the polymeric material are poorly adhered and the interface impedance becomes high. ing. On the other hand, in the electrolytic polymerization method using electric energy, aluminum is used as a reaction electrode, so that an aluminum-polymer material joined body can be manufactured in substantially one step and the interface impedance can be reduced. It is preferably used rather than legal. However, direct electrolytic polymerization of the monomer on aluminum is difficult, and it is generally difficult to uniformly form a polymer. The present inventors have already disclosed in Japanese Patent Application No.
No. 2134, Japanese Patent Application No. 62-248093, Japanese Patent Application No. 63-53829, etc., the aluminum electrode surface is mechanically polished with emery paper or electrolytically etched to remove the thick oxide film on the surface to some extent. It was described that direct electrolytic polymerization of the monomer was possible on an aluminum base material. As a result of further research by the present inventor, when aluminum having a crystallinity of the surface mainly having a (HOO) plane (H = 1,2,4) is used, the etching of the aluminum surface as described above is performed. It was discovered that the polymer polymerized uniformly on the aluminum surface without manipulation.

Electropolymerization methods are generally described, for example, in J. Electrochem.
c., Vol. 130, No. 7, 1506-1509 (1983), Electrochem. Act
a., Vol.27, No.1,61-65 (1982), J.Chem.Soc., Chem.Co
mmun., 1199- (1984), etc., a solution prepared by dissolving a monomer and an electrolyte in a solvent is placed in a predetermined electrolytic cell, the electrode is immersed, and an electrolytic polymerization reaction by anodic oxidation or cathodic reduction is performed. Can be carried out.

As the electrolyte, for example, as anions, BF ₄ ⁻ , AsF _{6
^{-, SbF 6 -, PF 6}} -, ClO 4 -, HSO 4 -, SO 4 2- and aromatic sulfonate anion may also, H ^+, exemplified quaternary ammonium cations, such as lithium, sodium or potassium as the cation However, the present invention is not limited to these.

As the solvent, for example, water, acetonitrile,
Examples thereof include, but are not limited to, benzonitrile, propylene carbonate, γ-butyrolactone, dichloromethane, dioxane, dimethylformamide, and nitro solvents such as nitromethane, nitroethane, nitropropane, and nitrobenzene. The electrolytic polymerization can be any of low voltage electrolysis, constant current electrolysis and constant potential electrolysis.

Examples of the conductive polymer of the present invention include polymers of the above-mentioned monomers, which can be repeatedly doped and undoped, and more specifically, polypyrrole, polythiophene,
Examples thereof include poly-3-methylthiophene, polyphenylene, polyaniline, diphenylbenzidine polymers and derivatives thereof, and those having an electric conductivity in the doped state of 10 ⁻³ s / cm or more are preferable.

As the conductive polymer material used in the present invention, the above-mentioned materials are used, but in recent years, polyaniline, which has excellent chemical stability, has been attracting attention. The aniline and substituted polyaniline used in the present invention are polymers of a monomer represented by the following general formula.

(In the formula, R _{1 to} R ₅ are hydrogen, alkyl, alkoxy, silyl, but R ₂ , R ₃ , and R ₄ are not alkoxy) Specifically, aniline, 4-aminodiphenylamine,
N-methylaniline, N-ethylaniline, 4- (N-
Methylamino) diphenylamine, diphenylamine,
0-methylaniline, 0-ethylaniline, m-methylaniline, m-ethylaniline, 4- (N-ethylamino) diphenylamine, N, N'-diphenyl-p-phenylenediamine, N-trimethylsilylaniline, 0-
Trimethylsilylaniline, m-trimethylsilylaniline, 0-methoxyaniline, 0-ethoxyaniline,
m-methoxyaniline, m-ethoxyaniline, 2,5-
Examples thereof include dimethylaniline, 2,6-dimethylaniline, 2,5-dimethoxyaniline and 2,6-dimethoxyaniline.

Among them, aniline has a preferable characteristic especially with respect to the electrode characteristics for a battery.

In electrosynthesis of this polyaniline, unlike most other conductive polymers, it is not a non-aqueous synthesis, but a protonic acid such as H ₂ SO ₄ , HCl, HClO ₄ , and HBF ₄ containing aniline was used as the electrolyte. It is synthesized in an acidic aqueous solution.
62-96525, J. Electroanal Chem. 161,419 (1984)].
In the direct electrolytic synthesis of polyaniline on aluminum, the effect of the present invention is remarkable, for example, in the polymerization of aniline on aluminum in an aqueous solution of sulfuric acid, (HO
When aluminum is used as an electrode, the main crystal plane of which is the (O) plane (H = 1,2,4), and a thin film of polyaniline grows uniformly on the aluminum surface when an electric field is applied, whereas the (HOO) plane (H = 1 ,
It was observed that when an electric field is applied to aluminum that does not have 2,4) as the main crystal plane, polymerization hardly occurs, or even if it occurs, the polymer grows like islands on the aluminum surface and does not polymerize uniformly. You. This phenomenon is the same in the synthesis of other conductive polymers on aluminum, and is not limited to the polymerization of aniline, but is a remarkable phenomenon particularly in the synthesis of polyaniline. Also (HOO)
The growth of the polymer is extremely unfavorable when the surface of aluminum whose main crystal plane is the plane (H = 1,2,4) is roughened with emery paper and the orientation of the (HOO) plane (H = 1,2,4) is found. It becomes uniform.

In addition, as another embodiment of the method for producing a joined body of the present invention (HO
A method of forming a bonded body with the conductive polymer by etching aluminum having the O) plane (H = 1, 2, 4) as a main crystal plane may be considered. Also in this method, the direction of the crystal plane of aluminum is a very big problem.
That is, it is preferable that the crystallinity of the surface of aluminum to be electrolytically etched is the (HOO) plane (H = 1,2,4) as the main crystal plane.

The crystal structure of aluminum is a face-centered cubic structure, and the crystal planes formed by the arrangement of atoms have different atomic densities. Therefore, for reactions such as oxidation or etching, the rough surface (100) is more dense than the other dense surfaces (110), (111).
It is known to proceed faster than.

The (100) crystal plane of aluminum has the feature that microscopic irregularities on the aluminum surface due to electrolytic etching are uniformly formed in a direction perpendicular to aluminum (FIG. 1). In addition, this unevenness is particularly deep in the (100) crystal plane, or through holes can be obtained, and aluminum is removed due to the micro holes communicating with each other, resulting in a decrease in strength, a decrease in specific surface area, etc. Less likely to cause problems. On the other hand, aluminum with low crystallinity or aluminum with a lot of (110) and (111) crystallinity on the surface has uniform micro holes in the aluminum surface due to electrolytic etching in the direction perpendicular to the aluminum. Each hole is formed in a unique direction (FIG. 2). For this reason, there is a drawback that when the holes communicate with each other in a complicated manner, the aluminum falls off, the strength is reduced, and the specific surface area is reduced.

In addition, as an embodiment of the present invention when etching aluminum, it is considered to electrochemically etch aluminum in an etching solution and then directly bond a conductive polymer onto aluminum in a polymerization solution. However, in the case of a polyaniline-aluminum conjugate, the aniline monomer is added to this solution while electrochemically etching aluminum in an etching solution using an acid capable of direct electropolymerization of aniline onto aluminum, which will be described later. By adding, it is also possible to form an aluminum-polyaniline conjugate in almost one step. In the case of this method, the polymerization of aniline proceeds immediately on the etched surface, so that it is possible to bond aluminum and polyaniline while suppressing the oxidation of the etched surface to some extent.

From the above, the aluminum used in the present invention is an aluminum whose surface crystallinity is mainly (HOO) (H = 1,2,4). The (HOO) plane referred to in the present invention means (100) plane, (200) plane, (400) plane crystallographically.
The crystallinity is determined by an X-ray diffraction method on the aluminum surface. The X-ray diffraction pattern of the aluminum surface used in the present invention is
The diffraction line by the (200) plane is mainly, and quantitatively, the integrated intensity of the diffraction line by the (200) plane is 0.4 or more, preferably 0.6 or more with respect to the integrated intensity of all the diffraction lines.

Further, as an embodiment of the present invention, whether electrolytic polymerization is directly performed on aluminum having a (HOO) plane as a main crystal plane, or after electrolytic etching or while electrolytic etching is performed is selected depending on the application of the bonded body. , It is not uniquely determined.

However, in general, it is possible to uniformly synthesize a conductive polymer on aluminum by using such aluminum, and when applied to an electrochromic electrode, for example, it is possible to reduce the change in the electric field. Uniform color change is possible. In addition, when applied to secondary battery electrodes, the film grows uniformly, so it is possible to use electrodes with lower internal resistance than electrodes grown in an island shape, and the voltage drop that accompanies this is also possible. It is possible to improve a decrease in energy capacity and the like due to the above.

Electropolymerization of aniline is carried out in an acidic aqueous solution, but it is essential to use a specific acid when synthesizing polyaniline on aluminum.
Acids having a pka value in the range of -2.5 to +2.5 give favorable results.

Examples of such an acid include sulfonic acids such as sulfuric acid, paratoluenesulfonic acid, benzenesulfonic acid, and naphthalenesulfonic acid, and trifluoroacetic acid. When perchloric acid (PKa about -3.1), tetrafluoroboric acid (PKa about -4.9), and hydrochloric acid (PKa about -4) are used, the electrolytic current of aluminum is observed at the polymerization potential of aniline and the polymerization does not proceed. When nitric acid (PKa about -3) is used, no current flows at the polymerization potential of aniline and aluminum does not dissolve, but polyaniline does not form. A similar phenomenon is observed when hydrofluoric acid (PKa about 3.2) is used, and the polymerization of aniline does not proceed. It is considered that these phenomena are affected by elution and oxidation of aluminum, and as a result of examination, it was found that good results can be obtained by using an acid in the range of PKa-2.5 to +2.5 described above. .

When electrolytic polymerization is performed using an acid that cannot directly polymerize aniline onto aluminum, for example, hydrochloric acid, borofluoric acid, or the like, as shown in the prior art, H ₂
By forming a polyaniline thin film once using an acid capable of direct polymerization such as SO ₄ and then forming a thin film such as polypyrrole on aluminum by a method of performing polymerization in HCl or HBF ₄ or a chemical polymerization method. , HCl, HBF ₄ can be electropolymerized.

Further, as another production mode of the joined body of the present invention, an acid capable of direct polymerization such as H ₂ SO ₄ is used on aluminum to form a polyaniline thin film or other conductive polymer thin film once, and then the polyaniline thin film is formed on the polyaniline thin film. It is possible to further compound a conductive polymer such as polyaniline using a chemical polymerization method. As a composite method using a chemical polymerization method of polyaniline, the polymer thin film and an aluminum conjugate are allowed to coexist in a polymerization system containing a protonic acid, an oxidizing agent, water, and aniline, or as a reaction electrode in the chemical polymerization system. The polymer thin film-
By applying an electric field using the aluminum junction electrode, the polymerization of aniline can proceed on aluminum with the polymer thin film synthesized previously as a nucleus. In the latter method, compared with the electrolysis required to carry out electrolytic polymerization in a system containing no oxidizing agent, it is possible to produce a bonded body even in a small electric field in which aniline does not polymerize in a system containing no oxidizing agent. At the same time, more polyaniline can be deposited on the aluminum.

(NH ₄ ) ₂ S ₂ O ₈ , Fe as the oxidizing agent used in the chemical polymerization method
_{Cl 3, NaClO 3, MnO 2} , H 2 O 2, PbO 2, KMnO 4, K 2 Cr 2 O 7 or the like can be used, as the protonic acid have a similar acid and when an electric field polymerization of aniline it can.

In the electrolytic synthesis of polyaniline, the electric potential applied to the electrode is preferably an electric potential in the range of +0.75 to +0.95 V with respect to the saturated sweet koh electrode.

When the voltage is + 0.95V or more, the solubility in the electrolyte solution using PC or the like for doping and dedoping deteriorates, and the life as an electrode decreases. When it is + 0.75V or less, the solubility does not deteriorate so much, but the development of fibrils of polyaniline is poor, and particularly when it is + 0.7V or less, the current value flowing during polymerization is small and the production efficiency is poor.

This polymerization method is a potentiostatic electrolysis method, but if the potential difference between the reaction electrode and the reference electrode (SCE) falls within the range of + 0.75V to + 0.95V, constant current electrolysis may be performed.

In the aluminum-conductive polymer conjugate produced in the present invention, a polymer is deposited on aluminum while doping of ions occurs during electrolytic polymerization. Therefore, the aluminum-conductive polymer conjugate produced by electrolytic polymerization is produced while keeping the doped state. In order to remove the dopant from the aluminum-conductive polymer junction electrode, electrochemical dedoping reaction is performed electrochemically by applying a base potential sufficient to release ions from the polymer ion complex in the electrolytic solution. A method of carrying out or chemically dedoping with a reducing medium can be considered.

In the electrochemical method, the electrolyte is preferably a non-aqueous electrolyte. When the dedoping operation is performed from the aluminum-conductive polymer composite electrode of the present invention in an aqueous electrolyte, the composite of the present invention shows a mixed potential of aluminum and the conductive polymer, and the conductive polymer is sufficiently formed. There is a possibility that it cannot be reduced. Particularly in the aluminum-polyaniline conjugate, since the aniline is electropolymerized in an acidic aqueous solution, when the dedoping operation is similarly performed in the acidic aqueous solution, the junction electrode shows a potential considered to be a mixed potential of aluminum and polyaniline, and No doping operation can be performed.

Therefore, the operation of dedoping from the conjugate of the present invention is preferably performed in a non-aqueous solution. However, polyaniline is synthesized in an acidic aqueous solution and has an unpaired electron pair on nitrogen, which causes a large difference in the chemical structure between the synthetic state (doped state) and the undoped state. When polyaniline functions as an electrochromic device, for example, it is possible to bring about a color change by potential sweeping even if the aluminum-polyaniline conjugate at the time of synthesis in the present invention is directly brought into a non-aqueous solution, but the electrode of a non-aqueous battery is produced. When applied as a battery, the polyaniline synthesized by electrolytic polymerization was not undoped, and the battery performance was evaluated directly in a non-aqueous electrolyte solution. Compared with the one subjected to the dedoping operation, the battery characteristics were slightly reduced and unstable. It is. This is thought to be due to the difference in the structure between the polyaniline in the synthetic state (doped state) and the polyaniline in the reduced state, and when polyaniline is expected to have stable battery performance, it was bonded onto aluminum by direct electrolytic polymerization. It is necessary to carry out the dedoping operation on the polyaniline at the time of synthesis and then bring it into the non-aqueous electrolyte. However, as described above, the aluminum-polyaniline composite electrode exhibits a mixed potential of polyaniline and aluminum in an acidic aqueous solution, and polyaniline cannot be subjected to a dedoping operation.

In order to solve such a problem, the present invention investigates various reduction methods in an aluminum-polyaniline joined body, and brings the polyaniline-aluminum joined body at the time of synthesis (doped state) into contact with a reducing medium other than metal to chemically react. To be reduced to

And / or by bringing the polyaniline into contact with a reducing metal, a bonded body of the reduced polyaniline and aluminum was successfully obtained. The reduction method of the present invention is effective for other conductive polymer-aluminum joined bodies, but the effect is particularly remarkable in the polyaniline-aluminum joined body. Specifically, a reducing agent such as H ₂ , hydrazine, phenylhydrazine, or titanium (III) chloride is used as the reducing medium, but it is not preferable to use ammonia. With ammonia it is possible to remove the dopant from polyaniline,
The polyaniline does not enter a completely reduced state, but remains in an oxidized state. The reduced state and the oxidized state are specifically a benzeneoid structure and a quinoid structure,
In the reduction treatment, the goal is to have a benzenoid structure. Therefore, the reducing agent is not limited to the above-described reducing agent as long as it can reduce the doped polyaniline-Al junction to a reduced state. As a specific reduction method, the reduction agent may be brought into direct contact with the above-mentioned reducing agent, or the joined body may be immersed in a solution dissolved in another solvent. The concentration of the solution is preferably 10% to 70%, and among them, a method of immersing the aluminum-polyaniline conjugate in a hydrazine 20% to 60% solution can be suitably adopted. Regarding the reduction treatment of polyaniline, it is clarified in JP-A-62-149724 that reduction treatment of polyaniline is performed with hydrazine or the like. However, in the present invention, polyaniline at the time of synthesis (doped state) is subjected to electrolysis in an acidic aqueous solution. It is said that a chemical dedoping operation, a reduction treatment with hydrazine, and an alcohol treatment are preferably adopted as the most preferable treatment method. However, the aluminum-polyaniline bonding in the present invention is performed. It was mentioned earlier that the body could not be dedoped in an acidic aqueous solution. Since the aluminum-polyaniline conjugate is intentionally subjected to a dedoping operation in an acidic aqueous solution, if a more base potential is applied, the solubility of polyaniline in a non-aqueous solution will increase and the aluminum-polyaniline junction surface will deteriorate. The problem occurs. Therefore, it is not suitable, or even inappropriate, to apply an electrochemical dedoping operation to the aluminum-polyaniline electrode of the present invention in combination with a chemical reduction treatment as part of the reduction treatment of polyaniline. In this regard, the idea of the present invention is different from the prior invention. Another method for reducing the aluminum-polyaniline conjugate may be a reduction method by contact with a reducing metal. Specifically, the reducing metal is L
It is an alkali metal such as i, Na, K, Mg, Ca and the like. In this method, the dedoping operation of polyaniline can be achieved by a simple operation of directly contacting polyaniline and a reducing metal in a non-aqueous solvent or solution.
Regarding the method of dedoping a conductive polymer with a metal, JP-A-62-246926 discloses a method of contacting a conductive polymer compound with a metal whose standard redox potential is −0.1 V or less based on the standard hydrogen electrode standard. A undoping method of removing impurity ions in a molecule is disclosed. According to the results, aluminum (standard redox potential E _O = -1.66
2V) or nickel (E _O = -0.250) can be dedoped from the conductive polymer by contact with the conductive polymer compound. Polyaniline, polypyrrole,
N, N'-diphenylbenzidine polymer does not undergo dedoping when contacted with nickel. Further, in the junction element of the present invention, the phenomenon that undoping occurs even when aluminum is brought into contact is not observed. Further, in the reduction method of the present invention, Li
(E _O = −3.045), Na (E _O = −2.714), K (E _O = −2.92)
5), Mg (E _O = -2.363), Ca (E _O = -2.866), etc. are contacted with an alkali metal to carry out the reduction treatment. In the prior invention, acetonitrile is used as the organic solvent for the reduction treatment. And nitromethane, nitrobenzene, benzonitrile, and dimethyl sulfate, and further discloses that it is preferable to use the same solvent as that used in the electrolytic polymerization.
A common solvent for polyaniline is water, polypyrrole,
A common solvent for N, N'-diphenylbenzidine polymers is acetonitrile. In addition, nitro solvents are often used for polyparaphenylene. As the solvent for the contact between the alkali metal and the conductive polymer, which is the reduction method of the present invention, water which reacts with the alkali metal is not preferable, and acetonitrile is also not preferable because it reacts with Li, Na, K and the like. Also, benzonitrile is not preferable because it reacts with Na, K and the like. Nitromethane and nitrobenzene are not necessarily preferable because they are not strong solvents for reduction. As described above, there are many technical questions in the prior invention, and it is a fact that there is no disclosure about the operation of dedoping the conductive polymer by contact with these alkali metals.

The solvent used in the reduction method of the present invention is not particularly limited as long as it is stable to the alkali metal used, and specifically, propylene carbonate, ethylene carbonate, butylene carbonate, γ-butyrolactone, sulfolane,
One or a mixture of two or more carbonates such as 3-methylsulfolane, tetrahydrofuran and 2-methyltetrahydrofuran, esters, sulfolanes and ethers can be used. The reduction method of the present invention can be carried out even in a state where an electrolyte is added to these solvents. There is an appropriate value for the contact time between the alkali metal and the conductive polymer depending on the contact area, the type of polymer, the thickness, and the type of alkali metal, but 2 seconds or less for a conductive polymer thin film of 20 μm or less 20 When it is ˜100 μm, it is preferably 15 seconds or less, and contact for a long time of 1 minute or more is not preferable because it may cause decomposition or deterioration of the conductive polymer.

Considering this operation electrochemically, it seems that the same thing as applying a standard electrode potential of alkali metal to polyaniline at the time of synthesis (doped state) is performed. However, the performance as a battery electrode of polyaniline which has been dedoped by the triode method using the aluminum-polyaniline conjugate of the present invention as the working electrode in a non-aqueous solution is better than that of polyaniline which has been dedoped by the contact operation with aluminum metal. Therefore, the polyaniline reduction method of the present invention may have some factor other than the potential, but the exact reason for this is not known.

Various devices are conceivable as the method of using the bonded body of the present invention, but if it is one utilizing the behavior of doping and dedoping of a conductive polymer, it must be used in a non-aqueous solution or using a solid electrolyte. This is because, as described above, the undoping behavior of the joined body of the present invention from the conductive polymer is not performed smoothly in an aqueous solution.

Next, a battery using a joined body of aluminum and a conductive polymer material as an electrode will be described.

The battery of the present invention is basically composed of a positive electrode, a negative electrode and an electrolytic solution, and a separator can be provided between the electrodes. The electrolyte is composed of a solvent and an electrolyte,
It is also possible to use a solid electrolyte.

The battery of the present invention stores energy by being doped with anions or cations, and releases energy through an external circuit by undoping. Further, in the battery of the present invention, since the doping and undoping are performed reversibly, the battery can be used as a secondary battery.

In the present invention, at least the joined body of aluminum and the conductive polymer material of the present invention is used for the positive electrode.

Examples of the dopant for the polymer electrode include the following anions or cations. The cation-doped conductive polymer complex is an n-type material, and the anion-doped conductive polymer complex is This gives a p-type material. p
The mold material can be used for the positive electrode and the n-type material can be used for the negative electrode. However, polyaniline is also suitable for the positive electrode because it becomes a stable p-type material by anion doping.

(1) _{^{anion: PF 6 -, SbF 6 -}} , AsF 6 -, SbCl 6 - V , such as
halide anion of a Group elements; BF ₄ ^- like III a
Halide anions of group III elements; perchlorate anions such as ClO _{4 and} the like.

(2) Cations: alkali metal ions such as Li ⁺ , Na ⁺ K ⁺ , (R ₄ N) ⁺ [R: hydrocarbon group having 1 to 20 carbon atoms] and the like.

Specific examples of the compound that gives the above dopant,
_{LiPF 6, LiSbF 6, LiAsF 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] ⁺ · ClO ₄ ⁻ , LiAlCl ₄ , LiBF _4, etc. are exemplified, and these are used as the electrolyte of the battery.

Among them, preferred as the battery of the present invention are LiBF ₄ , L
iSbF ₆

As a solvent for the electrolyte solution of the battery, a non-pront solvent having a large relative dielectric constant and a so-called polar non-pron solvent is preferable. Specifically, for example, ketones, nitriles,
Esters (lactones), ethers, carbonates, nitro compounds, sulfolane compounds and the like, or a mixed solvent thereof can be used, and among these, nitriles, carbonates, sulfolane compounds and lactones are preferable. . Typical examples of this are acetonitrile, propionitrile, butyronitrile, valeronitrile, benzonitrile, ethylene carbonate, propylene carbonate, γ-butyrolactone, sulfolane, 3-methylsulfolane, tetrahydrofuran, 2-
Methyl tetrahydrofuran etc. can be mentioned. More specifically, DME based on propylene carbonate,
Those prepared by adding derivatives of sulfolane and THF are excellent in performance, and a polymer may be added to these to form a paste to improve processability.

In the negative electrode of the battery of the present invention, in addition to the above-mentioned polymer substance, Li, Zn, Cu, Ag, Al, Al-Li binary alloy, Li-Al
Metals and alloys such as -Mg, Li-Al-Mn ternary alloys and wood alloys can also be used. Among these, the negative electrode preferable for the battery of the present invention is a Li-Al alloy, and a ternary alloy of Li-Al-Mg and Li-Al-Mn based on Li-Al is preferably used.

In this case, when the metal itself has a current collecting function with the active material, when the current collecting materials Ni, Al, etc. are used in close contact, or when the current collector is used, the active material is formed by the precipitation of cations in the electrolytic solution. There are cases such as supply.

As the separator, a separator having low resistance to ion movement of the electrolyte solution and excellent in solution retention is used. For example, glass fiber filters; polyester,
Polymer pore filters such as Teflon, polyflon, and polypropylene, and nonwoven fabrics; and nonwoven fabrics composed of glass fibers and these polymers can be used.

In addition, a solid electrolyte can be used as a component replacing the electrolytic solution and the separator. For example, in the inorganic system, AgCl, AgBr, AgI, metal halides such as LiI,
Examples include RbAg ₄ I ₅ and RbAg ₄ I ₄ CN. In the organic system, polyethylene oxide, polypropylene oxide, polyvinylidene fluoride, polyacrylonitrile, etc. are used as the polymer matrix, and the above-mentioned electrolyte salt is dissolved in the polymer matrix to form a composite, or a cross-linked product or low molecular weight polyethylene oxide thereof. And a polymer electrolyte in which an ion-dissociating group such as polyethyleneimine and crown ether is grafted to the polymer main chain.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 [Integrated intensity of diffraction line by (200) plane / thickness 60 μm /
Integral intensity of all diffraction lines = 0.9] 0.5M aniline, 5.0N using aluminum as electrode for electrolysis
Electrolytic polymerization was performed in a sulfuric acid aqueous solution at 0.8 V vs SCE to obtain an aluminum-polyaniline electrode. At this time, polyaniline was uniformly polymerized on the aluminum.

As shown in FIG. 3, this aluminum-polyaniline electrode was electrochemically repetitively active in a non-aqueous electrolyte (propylene carbonate: dimethoxyethane = 7: 3, 3.0M LiBF ₄ solution), and was subjected to a potential sweep. Electrochromism was observed. Next, this aluminum-polyaniline electrode was immersed in a 50% hydrazine aqueous solution and dried, and this was used as a positive electrode and as a negative electrode in an electrolyte solution dissolved in a mixed solvent (3: 3) of 3M LiBF ₄ propylene carbonate and dimethoxyethane. A battery test was conducted by repeating charging and discharging at mA / cm ² .

Example 2 The same procedure as in Example 1 was repeated except that lithium was contacted in the electrolytic solution instead of being immersed in the hydrazine solution.
A polyaniline conjugate was synthesized and a battery test was performed.

Example 3 After contacting with lithium in Example 2, an additional 50
% Hydrazine aqueous solution, and the aluminum-polyaniline conjugate was synthesized and battery tested in the same manner as in Example 1 except that the reduction treatment was performed.

Comparative Example 1 An aluminum-polyaniline electrode was manufactured in the same manner as in Example 1 except that aluminum having [integrated intensity of diffraction lines by (200) plane / integrated intensity of all diffraction lines = 0.05] was polished with Cw1000 emery paper. I got At this time, the film thickness of polyaniline was not uniform, and electrochromism accompanying potential sweep did not cause uniform color change. Example 1 using this aluminum-polyaniline electrode as a positive electrode
A battery test was conducted in the same manner as in.

Comparative Example 2 An aluminum-polyaniline conjugate was synthesized in the same manner as in Example 1, and a battery test was performed without treating this with hydrazine.

Comparative Example 3 Example 1 except that aluminum of [integrated intensity of diffraction line by (200) plane / integrated intensity of all diffraction lines = 0.05] was used.
In the same manner as above, polymerization of aniline was attempted. As a result, the formation of the polymer was extremely uneven.

Comparative Example 4 Polymerization of aniline was carried out in the same manner as in Example 1 except that aluminum of [integrated intensity of diffraction line by plane of (200) plane / integrated intensity of total diffraction line = 0.94] was used after polishing with Cw1000 emery paper. Tried. As a result, the formation of the polymer was extremely uneven.

Example 4 Pyrrole 0.1 mol / in a glass reaction vessel under Ar atmosphere,
Paratoluene sulfonate tetraethylammonium 0.1m
An acetonitrile solution containing ol / was prepared. Aluminum [(200)] plane integrated intensity / total diffraction line integrated intensity = 0.94 (thickness 50 μm) as an anode] Nickel was used as a cathode, and a constant voltage of 5 V was applied between both electrodes for electrolytic oxidation. Polymerization was performed. At this time, black polypyrrole was uniformly deposited on aluminum. The dry weight of this electrode is 5
It was 6.4 mg. Next, using this electrode as a working electrode and platinum as a counter electrode and SCE as a reference electrode, a potential of 0.75 V vs. SCE was applied in a 3N HBF ₄ 0.5 M aniline aqueous solution to flow a charge amount of 5 c / cm ² .
The dry weight was 74.3 mg, and aniline could be polymerized without elution of aluminum.

Comparative Example 5 Pyrrole was electrolytically oxidized in the same manner except that [integrated intensity of diffraction line by (200) plane / integral intensity of all diffraction lines = 0.05 (thickness: 50 μm)] was used. At this time, the deposition of pyrrole was extremely non-uniform, and its dry weight was 54.4 mg. Next, polymerization of aniline was attempted in the same manner as in Example 1 using this electrode as a working electrode. Since the dry weight of the electrode was 52.0 mg and the pyrrole was non-uniform, it is considered that the elution of aluminum took precedence.

Example 5 Gold was vapor-deposited on polyaniline of the aluminum-polyaniline electrode produced in Example 1 to take out a terminal, an element having a three-layer structure of aluminum / polyaniline / gold was produced, and its current-voltage characteristics were examined. The switching characteristics as shown in FIG. 4 appeared.

Example 6 N, N'-diphenylbenzidine 0.0
4 mol /, tetrabutyl ammonium perchlorate 0.1 mol /
Acetonitrile solution containing 0.05 mol / of 2,6-lutidine was prepared. The polymerization was carried out using a three-electrode method, in which aluminum used for the anode of Example 1 was used as a working electrode, platinum was used as a counter electrode,
Saturated can sweet electrode (SCE) is inserted as a reference electrode and 1.2VvsS
Polymerization was performed by applying a potential of CE. At this time, a black oxide polymer was uniformly deposited on aluminum.

Comparative Example 6 The same procedure as in Example 6 was carried out except that the aluminum having [integrated intensity of diffraction lines by (200) plane / integrated intensity of all diffraction lines = 0.05] was used, and the precipitation of the polymer on the aluminum was uneven. Met.

Comparative Example 7 Aluminum having a ratio of [integrated intensity of diffraction line by (200) plane / integral intensity of all diffraction lines = 0.94] was used as Cw1000.
Example 6 except that the one polished with the emery paper of
The same operation was performed. Precipitation of the polymer on aluminum was very non-uniform.

Example 7 A solution was prepared by adding 5 ml of benzene, 70 ml of nitrobenzene, a saturated amount of LiAsF _{6 and a} saturated amount of cadmium sulfate in a glass reaction vessel under an Ar atmosphere. Aluminum [integral intensity of diffraction line by (200) plane / integral intensity of total diffraction line = 0.65] (thickness 50 μm) as anode, nickel as cathode, and electrolytic oxidation polymerization by applying constant voltage of 15 V between both ends Was performed. At this time, black polyphenylene was uniformly deposited on the aluminum electrode.

Comparative Example 8 Aluminum which was operated in the same manner as in Example 7 except that the aluminum used was [integrated intensity of diffraction line by (200) plane / integrated intensity of all diffraction lines = 0.28] (thickness 50 μm). Precipitation of the polymer on top was heterogeneous.

In the battery test of the polyaniline-aluminum conjugate according to Example 8 and thereafter, the conjugate was subjected to a reduction treatment with a 20% hydrazine aqueous solution, and then the test was performed.

Example 8 Pyrrole 0.1 mol / in a glass reaction vessel under Ar atmosphere,
An acetonitrile solution containing 0.1 mol / of tetrabutylammonium perchlorate was prepared. Electrolytically etched aluminum as the anode [integrated intensity of diffraction lines from (200) plane / integrated intensity of all diffraction lines = 0.94] (thickness 50 μm)]
(Immersion area 16 × 32 mm) Nickel was used as a cathode, and a constant voltage of 5 V was applied between both electrodes, and an electric quantity of 1.0 c / cm ² was applied to carry out electrolytic oxidation polymerization. At this time, black polypyrrole was uniformly deposited on aluminum. After taking out the composite electrode and washing it, a square flaw of 4 mm × 4 mm was applied to one side of the composite electrode as shown in FIG. Adhesive tape is attached to this surface, the tape is peeled off at a speed of 60 mm / sec in the direction parallel to the composite electrode surface, and the adhesion between aluminum and polymer is tested by how many 4 × 4 mm grids are peeled off. Was. As a result, there was no portion to be peeled off.

Comparative Example 9 The same operation as in Example 8 was carried out except that aluminum which was [integrated intensity of diffraction line by (200) plane / integrated intensity of all diffraction lines = 0.35] (thickness = 50 μm) was used. Peeling occurred at two places.

Example 9 A solution was prepared by adding 5 ml of benzene, 70 ml of nitrobenzene, a saturated amount of LiAsF _{6 and a} saturated amount of cadmium sulfate to a glass reaction vessel under an Ar atmosphere. Aluminum which has been subjected to electrolytic etching as an anode [integrated intensity of diffraction lines by (200) plane / integrated intensity of all diffraction lines = 0.65] (thickness: 50 μm),
Nickel was used as a cathode, a constant voltage of 15 V was applied between both electrodes, and an electric quantity of 1.0 c / cm ² was applied to carry out electrolytic oxidation polymerization.
At this time, black polyphenylene was deposited on the aluminum electrode. When a peeling test was conducted in the same manner as in Example 8, there was no portion to peel off.

Comparative Example 10 The same operation as in Example 9 was carried out except that aluminum having an intensity of [integral intensity of diffraction line of (200) plane / integral intensity of total diffraction line = 0.28] (thickness of 50 μm) was used. Peeling occurred at three places.

Example 10 N, N'-diphenylbenzidine 0.0 in a glass reaction vessel
4 mol /, tetrabutyl ammonium perchlorate 0.1 mol /
Acetonitrile solution containing 0.05 mol / of 2,6-lutidine was prepared. The polymerization was carried out using a three-electrode method, using aluminum used for the anode of Example 8 as the working electrode, platinum as the counter electrode,
Saturated can sweet electrode (SCE) is inserted as a reference electrode and 1.2VvsS
Polymerization was carried out by applying a potential of CE and passing an electric quantity of 1.0 c / cm ² . At this time, a black oxide polymer was uniformly deposited on aluminum. When a peeling test was conducted in the same manner as in Example 8, 1
Peeling occurred at some places.

Comparative Example 11 Example except that aluminum of [integrated intensity of diffraction line by (200) plane / integrated intensity of total diffraction line = 0.05] was used.
The same operation as in 10. Peeling occurred at six places.

Reference Example 1 [Integrated intensity of diffraction line by (200) plane / Integrated intensity of all diffraction lines = 0.82] Aluminum having a thickness of 50 μm was treated with 1.5N hydrochloric acid,
Electrolytic etching was performed in an aqueous solution containing 0.3 mol / of oxalic acid and 0.3 mol / of aluminum chloride. This etched aluminum was subjected to a tensile test using a test piece having a measurement area of 10 × 100 mm (the testing machine conformed to JIS 7721). The result was 1.4 kg / cm.

Reference Example 2 [Integrated intensity of diffraction line by (200) plane / Integrated intensity of all diffraction lines = 0.2] The same operation as in Reference Example 1 was performed except that aluminum having a thickness of 50 μm was used. The result was 1.1 kg / cm.

Example 11 Using the aluminum-polypyrrole electrode prepared in Example 8 as a reaction electrode, electrolytic polymerization was performed by 0.7 V vs. SCE potentiostatic electrolysis in an electrolytic solution in which 0.5 M aniline and 1.0 M HBF ₄ were dissolved.
Next, using this composite electrode as the positive electrode and Li as the negative electrode, 3M LiBF ₄ was dissolved and mixed in a mixed solvent (7: 3) of propylene carbonate and dimethoxyethane, and repeatedly charged and discharged at 0.2 mA / cm ² to evaluate the battery performance. did.

Comparative Example 12 The same operation as in Example 11 was performed except that the aluminum-polypyrrole electrode prepared in Comparative Example 9 was used.

Example 12 [Integrated intensity of diffraction line by (200) plane / 60 μm in thickness /
Sulfuric acid is converted to aluminum with integrated intensity of all diffraction lines = 0.94].
Electrolytic etching was performed in an aqueous solution containing 5.5 N and 0.15 M aluminum sulfate.

0.5M aniline using this aluminum as an electrode for electrolysis,
Electrolytic polymerization was performed at 0.8 V vs SCE in a 5.5 N aqueous sulfuric acid solution to obtain an aluminum-polyaniline electrode. At this time, the polyaniline was uniformly polymerized on the aluminum, and the adhesion was good. This aluminum-polyaniline electrode was electrochemically active in the electrolyte of the battery used in Example 11. Next, this aluminum-polyaniline electrode was used as a positive electrode and evaluated in the same manner as in Example 11.

Comparative Example 13 Example 12 except that aluminum of [integrated intensity of diffraction line by (200) plane / integrated intensity of total diffraction line = 0.05] was used.
An aluminum-polyaniline electrode was obtained in the same manner as described above.
At this time, the film thickness of the polyaniline was not uniform, the adhesion was poor, and a part of the film was observed.

 Next, the battery performance was evaluated in the same manner as in Example 11.

Example 13 A battery test was performed in the same manner as in Example 3 except that a Li-Al alloy was used for the negative electrode.

Example 14 In the battery test in Example 12, Li-Al alloy in the negative electrode,
The same test was performed except that LiSbF ₆ was used as the electrolyte.

[Effects] As described above, the bonded body of the present invention has improved adhesion between the aluminum and the conductive polymer interface, improved mechanical strength, and a uniform thickness of the conductive polymer. For this reason, it can be applied to electrodes of various elements, and the battery of the present invention using this bonded body as an electrode can withstand repeated use of charge and discharge and has excellent performance. Further, application to various electrodes such as switching elements is also possible.

[Brief description of the drawings]

FIG. 1 shows that the main crystal plane of the surface used in the present invention is (20
FIG. 2 schematically illustrates the surface state of aluminum which is electrolytically etched, FIG. 2 schematically illustrates the surface state of conventional aluminum electrolytically etched, and FIG. 3 illustrates the aluminum-polyaniline of the present invention. FIG. 4 is a graph showing the electrochemical characteristics of the electrode (Example 1), FIG. 4 is a graph showing the switching characteristics of the aluminum / polyaniline / gold triple-layer structure element (Example 7) of the present invention, and FIG. 5 is a peel test. The figure to explain.

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Claims (5)

(57) [Claims] 1. A joined body of aluminum and a conductive polymer material, characterized in that the crystallinity of the surface of aluminum has a (HOO) plane (H = 1,2,4) as a main crystal plane. body. 2. A conductive polymer is directly deposited on aluminum by electrolytic polymerization using aluminum having a (HOO) plane (H = 1, 2, 4) as a main crystal plane as a reaction electrode. The method for producing a joined body according to claim 1, wherein 3. An aluminum having a (HOO) plane (H = 1,2,4) as a main crystal plane as a crystallinity of the surface is subjected to an etching treatment, and then this is used as a reaction electrode on the aluminum by an electrolytic polymerization method. The method for producing a joined body according to claim 2, wherein the conductive polymer is directly deposited. 4. The method for reducing treatment of a joined body according to claim 1, wherein the conductive polymer in an oxidized state is subjected to reduction treatment with a reducing medium other than metal. 5. The reduction treatment method for a joined body according to claim 4, wherein the reduction treatment is carried out by bringing a conductive polymer in an oxidized state into contact with a reducing metal.