Process of manufacturing an electrically conductive material and a secondary battery using the electrically conductive material

Abstract: An electrically conductive material containing no sub­ antial amount of water and prepared by polymerizing, in the presence of an oxidizing agent, a compound having conjugat­ ed double bonds on a base material in a gas phase. The base material has spaces capable of retaining the oxidizing agent. The elecrically conductive material is used for at least one electrode of a secondary battery.

Description: It is known that polymers having conjugated double bonds in the main chain, such as polyacetylene, poly-p-phenylene, polythienylene, polypyrrole, polyaniline, and poly-p-phenylene-vinylene, are remarkably improved in electric conductivity when they are treated with a P- or N-type doping agent such as arsenic pentafluoride, antimony pentafluoride, iodine, bromine, sulfur trioxide, n-butyllithium, or sodium naphthalene, whereby they are changed from an insulator to a semiconductor or a conductor. These electrically conductive materials (so-called "electrically conductive polymers") are obtained in the form of powder, grain, bulk, or film, which is used either as such or after molding thereof in accordance with the purpose of use thereof. They are now under investigations on application thereof to a wide variety of fields involving not only functional elements such as an antistatic material, an electromagnetic wave shielding material, a photoelectric conversion element, an optical memory (holographic memory), and various sensors but also a display element (electrochromism), a switch, various hybrid materials (transparent conductive film, and the like), various terminal equipment, and a secondary battery. However, this type of electrically conductive polymers are generally poor in moldability and processability. Particularly in order to obtain a film form of an electrically conductive polymer, a special process must be adopted. Today, known films of such electrically conductive polymers include a polyacetylene film which is generally prepared by blowing an acetylene gas against a glass wall coated with a polymerization catalyst to form a film and peeling the film from the glass wall, and polypyrrole and polythienylene films which are prepared by forming a film on an electrolysis electrode according to an electrochemical oxidation reaction (electrolytic oxidation polymerization) and peeling the film from the electrode. Among the above-mentioned conventional electrically conductive polymer films, the polyacetylene film disadvantageously is so unstable in air as to undergo the progress of oxidation deterioration, and has a low mechanical strength, while the polypyrrole and polythienylene films and the like obtained by the above-mentioned electrolytic oxidation polymerization disadvantageously have their film size restricted by the size of the electrolysis electrode, and involve complicated steps and a high cost. In Japanese Journal of Applied Physics, Vol. 23, No. 12, 1984, pp. L899 - L900, the preparation of an electrically conductive material by pre-deposition of an oxidative polymerisation catalyst on a glass substrate and thereafter polymerising thereon a monomer like thiophene or pyrrole from the gas phase is disclosed. DE-A-33 26 193 discloses the preparation of an electrode consisting of a porous metal and an electrically conductive polymer film like a polypyrrole film polymerised on said porous metal. Further, the preparation of electrically conductive polymer films on various substrates has been known from EP-A-152 632 and EP-A-144 127 and also from EP-A-206 133. Further, Journal of Electronic Materials, Vol. 13, No. 1, pp. 211 - 230 (1984) revealed an electrically conductive material prepared by immersing a filter paper in 0.01 M aqueous HC1 containing FeCl₃·6H₂O, bringing the filter paper into contact with pyrrole vapor or immersing the filter paper in a pyrrole solution to effect gas-phase or solution polymerization of the pyrrole on the filter paper. It further revealed an electrically conductive material prepared by bringing a pyrrole vapor into contact with a filter paper after immersion thereof in a solution of FeCl₃·6H₂O-C₂H₅OH to effect gas-phase polymerization of the pyrrole into polypyrrole on the filter paper. However, the former, namely the electrically conductive material prepared by the method involving immersion of a filter paper in 0.01 M aqueous HC1 containing FeCl₃·6H₂O, contains water and disadvantageously undergoes drastic reduction in electric conductivity when dried. Thus, this electrically conductive material can be used only in a wet state (hydrous state). This presents such a problem that this material cannot be used, for example, as the electrode material of a secondary battery of the non-aqueous electrolytic solution system in reality. Further, in this electrically conductive material, iron compounds used for the polypyrrole formation remains as an impurity without being removed. The presence of this impurity presents problems of providing low performance and limited use and application of the electrically conductive material when it remains as it is due to its low electrical conductivity. On the other hand, the latter, namely the electrically conductive material prepared by the method involving immersion in a solution of FeCl₃·6H₂O-C₂H₅OH has an electric conductivity as low as 1/1000 of that of the above-mentioned material prepared by the method involving immersion in 0.01 M aqueous HC1 containing FeCl₃·6H₂O, thus presenting a problem of being notably poor in performance as the electrically conductive material. On the other hand, there has recently been proposed a secondary battery prepared by using an electrically conductive polymer as mentioned above as the electrode material. Although such an electrically conductive polymer usually has a slight electric conductivity as described above, the electric conductivity thereof can be dramatically increased by doping since it can be doped with a dopant such as any one of various anions and cations, or can be undoped. In constituting a secondary battery with such an electrically conductive polymer as the electrode material, an electrically conductive polymer capable of being doped with anions is used as the anode material, and/or an electrically conductive material capable of being doped with cations is used as the cathode material, while a solution containing a dopant as mentioned above is used as the electrolytic solution. Thus, there can be produced a secondary battery capable of charging and discharging via electrochemically reversible doping and undoping. Known electrically conductive polymers of the kind as described above include the aforementioned polymers having conjugated double bonds in the main chain, such as polyacetylene, poly-p-phenylene, polypyrrole, polythienylene, polyaniline, and poly-p-phenylene-vinylene. In an instance of polyacetylene, it is used as the electrode material for at least one of the anode and the cathode, while anions such as BF₄⁻, ClO₄⁻, SbF₆⁻ or PF₆⁻, or cations such as Li⁺, Na⁺ or R₄N⁺ (wherein R represents an alkyl group) are employed to constitute an electrochemically reversible system capable of doping and undoping. These electrically conductive polymers are obtained in the form of powder, grain, bulk, or film. In the case of using a powdery, grainy, or bulky form of an electrically conductive polymer as the electrode material in constituting a secondary battery with a non-aqueous electrolytic solution or a solid electrolyte, there is needed a step of press-molding the polymer into an electrode either as such or after addition of an adequate electrically conductive material for improving the electric conductivity and/or a thermoplastic resin for improving the mechanical strength of the resulting electrode. In this respect, the use of a film form of an electrically conductive polymer provides, for example, such a characteristic feature that the film can be only punched with a predetermined size into an electrode to considerably facilitate the electrode production. Known examples of such an electrically conductive polymer film include not only polyacetylene, polypyrrole, and polythienylene films as described before, but also composite electrically conductive films obtained by coating a base material such as a PET film with a solution containing an oxidizing agent and a polymer binder and bringing the resulting base material into contact with a vapor of pyrrole, aniline, or the like to form a layer of an electrically conductive polymer film on the base material. However, in the case of using a conventional electrically conductive polymer film as mentioned above as a battery electrode material in constituting a secondary battery, a polyacetylene film quite disadvantageously undergoes polymer deterioration due to slight amounts of oxygen and water present in the battery, leading to a poor performance of the electrode, and causes, for example, a rapid increase in charging voltage and a decrease in charging and discharging efficiency during cycles, leading to a shortened cycling life span. Further, there have arisen such problems that the film is liable to be oxidized with oxygen contained in a working atmosphere, leading to a difficult and complicated work in production of electrodes, and that the preservability of electrodes is poor due to grave deterioration of the material by oxidation. In the case of using a polythienylene or polypyrrole film prepared by the electrochemical oxidation polymerization reaction, not only is the size of the film restricted by the size of the electrolysis electrode, but also a complicated production process and a need for a special production apparatus are involved, thus leading to a high battery production cost. Further, since a difficulty is encountered in obtaining a thick and uniform film, combined use of this film as a battery electrode with a collector involves such problems that the contact of the film with the collector may become poor during charging and discharging cycles, and that the battery reaction may occur concentratedly in a portion of the electrode, thus causing deterioration in battery performance. In the case of using a composite electrically conductive film as mentioned above, since the polymer binder is used in order to keep the oxidizing agent on the base material, an electrically conductive polymer obtained by the polymerization reaction is in the form of a composite electric conductor made of a mixture of a polymer of pyrrole or aniline with the polymer binder. This decreases the concentration of the polymer of pyrrole or aniline having an electric conductivity in the electrically conductive polymer. Thus, when it is used as an electrode material, a problem of poor performance arises due to the disadvantageous reduction in the effective polymer concentration since the same performance as that in the case of using, for example, a conventional electrically conductive polymer film as mentioned above cannot be attained even if desired. SUMMARY OF THE INVENTION An object of the present invention is to provide a process for preparing an electrically conductive material comprising a specific base material and, polymerized thereon, a specific compound having conjugated double bonds, which does not involve the above-mentioned problems, which is stable in air and has a high electric conductivity, and which can be rendered electrically conductive, for example, in an arbitrary direction in an arbitrary portion or in one surface thereof. A still another object of the present invention is to provide a process for preparing a secondary battery prepared by using an electrically conductive material of the kind as described above, which greatly facilitates the control of an electrode preparation atmosphere since the control must not be so severe as compared with that in the case where a polyacetylene film is used as the electrode material, and which uses an electrode not only improved in itself in preservability but also causing neither denaturing nor decomposition even when exposed to oxygen and water present inside the battery or excessive charging to avoid a rapid increase in voltage in the course of charging, leading to improvements in charging efficiency and cycling life span. A further object of the present invention is to provide a process for preparing a secondary battery of the kind as described above, the cycling life span of which is improved by providing better contact of an electrode with a collector. A still further object of the present invention is to provide a process for preparing a secondary battery of the kind as described above, the charging and discharging characteristics of which are improved by improving the liquid containing capacity of an electrode itself. The above-mentioned objects have been attained according to the present invention by a process for preparing an electrically conductive material containing no substantial amount of water and oxidizing agent by polymerizing in a gas phase in the presence of an oxidizing agent a pyrrole or thiophene compound on a specific base material having spaces capable of retaining the oxidizing agent in a gas phase to form a polymer of the above-mentioned compound on the base material and thereafter washing the resulting product with an organic solvent. As said base material a metallic foam is used having a pore volume of 70 to 98% and spaces capable of retaining the oxidizing agent in the form of molecules or aggregates. The above-mentioned oxidizing agent is a compound having an activity of polymerizing a monomer compound having conjugated double bonds. The oxidizing agent may be used in the form of a single compound as described above or in combination of two or more kinds of such compounds. Usually used is a metallic salt containing a residue group of a strong acid, a halogen or a cyano group, a peroxide, a nitrogen oxide, or the like. Specific examples of such compounds include Fe(ClO₄)₃, Fe(BF₄)₃, Fe₂(SiF₆)₃, Cu(ClO₄)₂, Cu(BF₄)₂, CuSiF₆, FeCl₃, CuCl₂, K₃[Fe(CN)₆], RuCl₃, MoCl₅, WCl₆. Those compounds can also be used as they have water of crystallization or as they are obtained in the form of a solution. In addition, other compounds such as (NH₄)₂S₂O₈, K₂S₂O₈, Na₂S₂O₈, NaBO₃, H₂O₂, NOBF₄, NO₂BF₄, NO₂PF₆, NOClO₄, NOAsF₆, and NOPF₆ can be used. In the base material used according to the present invention the spaces are satisfactory if only their size is enough to retain the oxidizing agent at least in the form of molecules or aggregates. It is not preferred that the spaces be too small to retain the oxidizing agent in the form of molecules or too large to retain the oxidizing agent in the form of aggregates. These spaces are distributed in the form of micropores or voids having any of various shapes on or inside the base material. In the case of micropores, the average size thereof is specifically 0.001 to 100 µm, preferably 0.005 to 50 µm. It has been known that the depth of the micropores is 0.001 µm or deeper, preferably 0.005 µm or deeper. The base material to be used includes materials of metal, alloy and their mixture types. Specific examples of such materials include chromium, titanium, nickel, gold, platinum, tantalum, copper, silver, iron and stainless steel. Pyrrole and thiophene compounds are used as the compound having conjugated double bonds to be used in the present invention. They may be used alone or in mixture. Preferred examples are pyrrole and thiophene compounds having no substituents in the 2- and 5-positions of the skeletal structure of the pyrrole or thiphene ring. Specific examples of pyrrole compounds include pyrrole, N-methylpyrrole, N-ethylpyrrole, N-n-propylpyrrole, N-n-butylpyrrole, N-phenylpyrrole, N-tolylpyrrole, N-naphthylpyrrole, 3-methylpyrrole, 3,5-dimethylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-n-butylpyrrole, 3-phenylpyrrole, 3-tolylpyrrole, 3-naphthylpyrrole, 3-methoxypyrrole, 3,5-dimethoxypyrrole, 3-ethoxypyrrole, 3-n-propoxypyrrole, 3-phenoxypyrrole, 3-methyl-N-methylpyrrole, 3-methoxy-N-methylpyrrole, 3-chloropyrrole, 3-bromopyrrole, 3-methylthiopyrrole, and 3-methylthio-N-methylpyrrole. Specific examples of thiophene compounds include 2,2'-bithiophene, 3-methyl-2,2'-bithiophene, 3,3'-dimethyl-2,2'-bithiophene, 3,4-dimethyl-2 , 2'-bithiophene, 3,4-dimethyl-3', 4'-dimethyl-2,2'-bithiophene, 3-methoxy-2,2'-bithiophene, 3,3'-dimethoxy-2,2'-bithiophene, 2,2', 5',2''-terthiophene, 3-methyl-2,2', 5', 2''-terthiophene, and 3,3'-dimethyl-2,2', 5', 2''-terthiophene. The method of retaining the oxidizing agent on the base material may comprise the step of contacting the base material with the oxidizing agent itself or a dispersion or solution of the oxidizing agent in an adequate solvent to make the base material retain the oxidizing agent thereon. In order to facilitate retention of the oxidizing agent on the base material, the base material may be preliminarily subjected to an arbitrary treatment such as washing, degassing, rendering hydrophilic, or rendering hydrophobic. The oxidizing agent may be retained on all or a predetermined portion of the base material according to the need. For example, when the oxidizing agent is retained only on one surface of the base material, the polymer of the compound having conjugated double bonds is formed only on one surface portion to obtain an electrically conductive material having only one surface thereof made electrically conductive. As another example, when the oxidizing agent is retained in the form of a continuous line in a given direction on the base material, the polymer of the compound having conjugated double bonds is formed in the form of a continuous line only on that portion of the base material to obtain an anisotropic electrically conductive material having an electric conductivity only in a given direction. In such a way, an electric conductivity can be imparted to the base material only on an arbitrary portion only in an arbitrary direction. Thus, the electrically conductive material of the present invention can also be utilized as a material for forming an electrically conductive circuit. Although the molar ratio of the oxidizing agent to the compound having conjugated double bonds is associated with the amount of the polymer to be formed, it is usually 0.001 to 10,000/1, preferably 0.005 to 5,000/1. The polymer of the compound having conjugated double bonds on the base material is formed in a gas phase. Specifically, gas phase polymer formation is effected in the sole presence of a vapor of the compound having conjugated double bonds or in the conjoint presence of such a vapor with nitrogen, argon, air, other gas, or a mixture thereof. Although the whole system may be under high, ordinary, or reduced pressure, the ordinary pressure is preferred from the viewpoint of process control or the like. The reaction temperature is not particularly limited, provided that the compound having conjugated double bonds can be polymerized at that temperature. It is usually -20 to 100°c, preferably 0 to 80°c. Although the reaction time is dependent on the reaction temeprature, the amount of the oxidizing agent, the amount of the compound having conjugated double bonds, etc., it is usually 0.01 to 200 hours, preferably 0.02 to 100 hours. After polymerization, a homogeneous, dark brown to black polymer appears on a portion of the base material where the oxidizing agent is retained. An oxidizing agent may be further retained on the formed polymer as mentioned above, and the polymerization reaction may be continued while contacting the oxidizing agent with the same or another kind of compound having conjugated double bonds, whereby an increase in the amount of the polymer formed, or formation of two or more kinds of polymers can be attained. After completion of the polymerization reaction, the compound having conjugated double bonds and the oxidizing agent which remains on the base material are removed. They can be usually removed by immersing the base material in an alcohol or other organic solvent to effect washing. The washing in the present invention which is important for completely removing the oxidizing agent to improve the electrical conductivity is carried out, depending upon the kinds of the oxidizing agent, as set forth below: when a metallic salt containing residual group of strong acids or halogen or cyano group is used as an oxidizing agent, washing is carried out with organic solvent, and then with alcohol repeatedly; and when a peroxide or a nitrogen oxide is used as an oxidizing agent, washing is carried out with water at first to resolve the oxidizing agent and then with organic solvent and alcohol, repeatedly. By washing, a remaining amount of the oxidizing agent relative to the amount of the formed polymer must be held 1% or less, and preferably less than 0.5%, otherwise an electrically conductive material having high electrical conductivity for a practical application is not obtained. Thereafter, the base material may be dried by a conventional drying method to obtain an electrically conductive material. In the present invention, a water content of the obtained electrically conductive material is less than 1.0% and, preferably, less than 0.5%. As the above-mentioned base material having spaces capable of retaining the oxidizing agent in the above-mentioned way there may be used a metallic foam showing hydrophobicity at least on one surface thereof. When the oxidizing agent is to be retained, for example, only on one surface of a base material having no such hydrophobicity for forming an electrically conductive polymer layer only on one surface of the base material, the oxidizing agent may permeate up to the other surface of the base material because the above-mentioned base material is liable to allow the oxidizing agent to permeate into all the spaces and be retained there. Thus, an electrically conductive polymer may be formed in every portion of the base material by the gas-phase polymerization. In view of this, great care must be taken in forming an electrically conductive polymer only on one surface of the base material. This may entail a very complicated procedure in manufacturing. When the above-mentioned hydrophobic base material is used, an electrically conductive polymer layer can be easily provided on either one of the surfaces of an electrically conductive polymer film. This provides an advantage in industrial manufacturing, whereby the industrial application of the electrically conductive polymer film can be expected to further spread in the fields of a planar heating element, a laminated functional material for photoelectric conversion, a collector, a separator-integrated electrode material, a collector-integrated electrode material, and the like. The above-mentioned hydrophobicity is 90° or more in terms of contact angle with water. In this case, the oxidizing agent is used in the form of an aqueous solution, so that retention of the oxidizing agent on either one of the surfaces of the base material can be readily materialized. This can be easily understood from the fact that, when a solvent capable of permeating into the base material, such as methanol, ethanol, acetonitrile, or tetrahydrofuran, is used as the solvent of the oxidizing agent, a difficulty is encountered in retaining the oxidizing agent only on either one of the surfaces of the base material because the oxidizing agent readily permeates into or up to the hydrophobic surface even if one surface of the base material is hydrophobic. Where the sheet base material has, for example, one hydrophobic surface and the other hydrophilic surface, the oxidizing agent can be easily retained on the hydrophilic surface by immersing the base material in an aqueous solution of the oxidizing agent, or coating the hydrophilic surface with an aqueous solution of the oxidizing agent. Where the sheet base material is hydrophobic on both of the surfaces, retention of the oxidizing agent on one surface of the base material can be materialized by repeatedly coating the one surface with an aqueous solution of the oxidizing agent, or by treating the one surface with a hydrophilicity-imparting agent such as polyethylene oxide or polyvinyl alcohol and subsequently immersing the base material in an aqueous solution of the oxidizing agent or coating the hydrophilicity-imparted surface with the oxidizing agent. Where the sheet base material is hydrophilic on both of the surfaces, one surface is treated with, for example, a silicone or fluorocarbon water repellant to make the surface hydrophobic, followed by immersion in an aqueous solution of the oxidizing agent or coating of the hydrophilic surface with an aqueous solution of the oxidizing agent, whereby retention of the oxidizing agent on the hydrophilic surface can be materialized. The secondary battery to be prepared according to the present invention, which can attain the aforementioned objects, is obtained by using as at least one electrode of the anode and cathode thereof a film of an electrically conductive material of the kind as discussed above, which is prepared by polymerizing in the presence of an oxidizing agent the compound having conjugated double bonds on the base material having spaces capable of retaining the oxidizing agent in a gas phase to form a polymer of the compound having conjugated double bonds in the above-mentioned spaces. Such an electrically conductive film material preferably contains no substantial water just like the above-mentioned electrically conductive material. Where such an electrically conductive film material is used as an electrode of a secondary battery, an electrode which can be easily produced at a relatively low cost and which has a uniform thickness even when the thickness thereof is large can be materialized. When a highly conductive metallic foam material (in the form of plate, gauze, or the like) made of a metal such as gold, platinum, stainless steel or steel is used as the base material which is designed also to serve as the collector, the contact of the polymer of the compound having conjugated double bonds as the electrode material with the base material as the collector can be remarkably increased. This leads to an improvement in the cycling life span of the battery. The use of the base material also as the separator or the collector as described above allows the battery assembling process to be greatly simplified, since the steps of battery assembling including those of separately preparing a separator or a collector in the battery assembling, and disposing it between two electrodes in close contact therebetween or between an electrode and a battery case in close contact therebetween can be dispensed with. In the secondary battery prepared according to the present invention, there are an embodiment wherein electrodes made of the above-mentioned electrically conductive material are used as the anode and cathode, and an embodiment wherein an electrode made of the above-mentioned electrically conductive material is used as one of the two electrodes while the other electrode uses an electrode material selected from among metals, metallic oxides, other inorganic compounds, known electrically conductive polymers and organic compounds other than the reaction product used in the present invention, and organometallic compounds. As an example, in the embodiment wherein the above-mentioned electrically conductive material is used only in the anode while a metal is used as the electrode material of the cathode, the metal constituting the cathode has preferably an electronegativity of 1.6 or less. Examples of metals having such an electronegativity include Li, Na, K, Mg, Al, and alloys thereof. Particularly preferred are Li and its alloys. Where electrically conductive material obtained by the present invention is applied in a secondary battery of a non-aqueous electrolyte type, a solution of an electrolyte in an organic solvent is used as the electrolytic solution. Examples of such an electrolyte include cations of metals having an electronegativity of 1.6 or less, organic cations, and salts thereof with anions. Examples of onium ions include quaternary ammonium ions, carbonium ions, and oxonium ions. Examples of anions include BF₄⁻' ClO₄⁻, PF₆⁻, AsF₆⁻, CF₃SO₃⁻, I⁻, Br⁻, Cl⁻, and F⁻. Specific examples of the electrolyte include lithium tetrafluoroborate (LiBF₄), lithium perchlorate (LiClO₄), lithium hexafluorophosphate (LiPF₆), lithium tetrachloroaluminate (LiAlCl₄), tetraethylammonium tetrafluoroborate [(C₂H₅)₄NBF₄], tetraethylammonium perchlorate[(C₂H₅)₄NClO₄], lithium trifluoromethanesulfonate (LiCF₃SO₃), lithium iodide (LiI), and lithium bromide (LiBr), to which the electrolyte is, however, not limited. When, for example, a battery, wherein the electrically conductive material obtained according to the present invention is used in the anode and the cathode while an electrolytic solution of LiBF₄ as the electrolyte disolved therein is used, is in the process of being charged, the electrically conductive material in the anode is doped with BF₄⁻ in the electrolytic solution, while that in the cathode is doped with Li⁺ in the electrolytic solution. In contrast, when the battery is in the process of being discharged, BF₄⁻ and Li⁺ doped in the anode and the cathode, respectively, are released into the electrolytic solution. An organic aprotic solvent having a high dielectric constant is preferably used as the solvent for dissolving therein the electrolyte. Such an organic solvent includes nitriles, carbonates, ethers, nitro compounds, amides, sulfurcontaining compounds, chlorinated hydrocarbons, ketones, esters, and so on. They may be used alone or in mixture. Representative examples of such an organic solvent include acetonitrile, propionitrile, butyronitrile, benzonitrile, propylene carbonate, ethylene carbonate, tetrahydrofuran, dioxolane, 1,4-dioxane, nitromethane, N-N-dimethylformamide, dimethyl sulfoxide, sulfolane, 1,2-dichloroethane, γ-butylolactone, 1,2-dimethoxyethane, methyl phosphate, and ethyl phosphate, to which the solvent is, however, not limited. The concentration of the electrolytic solution used in the present invention is usually 0.001 to 10 mol/ℓ, preferably 0.1 to 3 mol/ℓ. The electrolytic solution may be used either by pouring it or by incorporating it into an electrode using the electrically conductive material obtained according to the present invention. In the present invention, a solid electrolyte may be used instead of the above-mentioned electrolytic solution of the electrolyte. Examples of such a solid electrolyte include electrically conductive solid electrolytes based on lithium, such as LiI, LiI-Al₂O₃, Li₃N, and LiSICON; glasses of a lithium ion conduction type, such as Li₂S-P₂S₅-LiI; electric conductors of a lithium ion conduction type having a structure of a γ II -Li₃PO₄ type, such as Li₄SiO₄-Li₃PO₄; polyelectrolytes of a lithium ion conduction type, such as polyethylene oxide-LiClO₄, and their mixtures with an additive. Although the foregoing description has been given to the method of forming an electrode without any doping treatment of an electrically conductive material, the electrically conductive material may be preliminarily doped with a dopant before use thereof as an electrode. In the present invention, electrodes may be covered with drainboard-like or porous glass, Teflon, polyethylene, plate, or the like in order to fix the electrodes in an electrolyte. In the battery prepared according to the present invention, a filter paper of a glass fiber, or a porous film of Teflon, polyethylene, polypropylene, or nylon may be used as the separator. Further, as at least one of the anode and the cathode, there may be used an electrically conductive material having an electric conductivity on one surface thereof obtained according to the present invention, which is prepared by treating with an oxidizing agent the base material having spaces capable of retaining the oxidizing agent and having only one hydrophobic surface to allow the oxidizing agent to be retained only on the one surface, and polymerizing the compound having conjugated double bonds on the base material in a gas phase to form a polymer of the above-mentioned compound only on the one surface of the base material. Where the base material also serves as the collector, said metallic foam having a porosity of 70 to 98% and containing the electrically conductive polymer formed in the cell spaces of the foam is used as the base material. The use of an electrode made of the metallic foam containing the electrically conductive polymer formed in the cell spaces of the foam by gas-phase polymerization as metnioned above is advantageous in that the electrode has a uniform thickness easily attained due to large polymer retentivity in cell spaces of the foam even when the amount of the formed polymer is increased in order to increase the capacity. Furthermore, since the polymer is formed and retained up to the inside of the micropores of the foam, the polymer in the electrode never peels or scales off from the metallic foam as the base material by mechanical shock or the like. Thus, the mechanical strength of the electrode is remarkably improved as compared with that of an electrode prepared by press-bonding to a collector a polymer film formed by the conventional electrolytic polymerization and peeled off from an electrolytic electrode. Usable materials of the above-mentioned metallic foam include gold, platinum, silver, copper, nickel, stainless steel, nickel-aluminum alloys, nickel-chromium alloys, copper-nickel alloys, and nickel-chromium-alminum alloys. When the above-mentioned electrically conductive material comprising the metallic foam with a porosity of 70 to 90% as the base material is used as a collector-integrated type electrode, the bond of the electrically conductive polymer to the collector is improved, leading to a prolonged cycling life span of the resulting battery. Moreover, since the metallic foam as the base material of the electrode is porous, the liquid containing capacity of the electrode itself is improved, contributing to betterment in the charging and discharging efficiency of the electrode. The reasons why the porosity of the metallic foam is set within a range of 70 to 98% as mentioned above are as follows. When the porosity is less than 70%, the specific area of the metallic foam (the ratio of the surface area to the volume in the metallic foam) is too small, with the result that the area of the metallic foam in contact with the electrically conductive polymer is small while the liquid-containing capacity is also low, thus decreasing the utilization of the electrically conductive polymer. On the other hand, when the porosity exceeds 98%, the necessary strength of the electrode cannot be secured. In contrast, when the porosity of the metallic foam is in the range of 70 to 98%, a secondary battery having good properties can be obtained without involving the above-mentioned problems. Furthermore, when the porosity of the metallic foam is in the range of 70 to 98%, the ratio of the area to the volume in the metallic foam as the base material (specific surface area) is large, with the result that the amount of the polymer in the electrode in direct contact with the electrolytic solution is not decreased so much even when the amount of the formed polymer is increased in order to increase the capacity of the electrode. Therefore, even under severe charging and discharging conditions, the utilization of the electrically conductive polymer does not decrease so much. Thus, even under such conditions, high charging and discharging efficiency can be secured while a prolonged cycling life span can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a crosssectional view of the structure of a secondary battery formed in an example according to the present invention; Fig. 2 is a crossectional view of comparative batteries; Fig. 3 is a graph showing variations in voltage of batteries according to the present invention and comparative batteries with time during the course of charging in their 20th cycle; Fig. 4 is a graph showing the cycling characteristics of the batteries according to the present invention and the comparative batteries; Fig. 5 is a graph showing variations in voltage of batteries according to the present invention and comparative batteries with time during the course of charging and discharging in their 140th cycle; DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS Example 1 An aqueous solution containing polytetrafluoroethylene dispersed therein was sprayed over the upper surface of a foamed nickel plate having a thickness of 1.0 mm, a length of 10 cm, and a width of 20 cm by means of a spray, followed by drying at a temperature of 60°C under reduced pressure for several hours. Thereafter, the polytetrafluoroethylene was fusion-bonded to the plate by a heat treatment in an argon atmosphere at a temperature of 375 °C for 30 min. The lower surface of the foamed nickel plate was coated with an aqueous saturated solution of Fe(ClO₄)₃·8H₂O three times. Thus, the Fe(ClO₄)₃·8H₂O component was uniformely retained on said surface of the plate. Subsequently, 4 ml of pyrrole was placed in the bottom of a glass container (length: 10 cm, width: 25 cm, height: 15 cm), and the porous plate treated as described above was suspended from the upper portion of the glass container, followed by tightly covering the upper portion of the container with a glass plate, whereby the porous plate was contacted with a pyrrole vapor. Upon contact with the pyrrole vapor a black portion of polypyrrole on the lower surface of the foamed nickel plate was formed, the electric conductivity of which portion was 1.0 x 10⁻¹ Scm⁻¹. Example 2 Substantially the same procedure as in Example 1 was repeated except that use was made of a foamed nickel plate (length: 10 cm, width: 20 cm) having a thickness of 1.0 mm, over the upper surface of which an aqueous solution of polyethylene oxide dispersed therein was sprayed by means of a spray, followed by drying at a temperature of 60° C under reduced pressure for several hours. Thus a black portion of polypyrrole was formed on the upper surface of the foamed nickel plate and the electric conductivity of this portion was 1.1 x 10⁻¹ Scm⁻¹. Description will now be given to Examples of secondary batteries using any of the foregoing electrically conductive materials as an electrode thereof. Example 3 One surface of a stainless steel foam having a porosity of 70% was immersed in a saturated solution of FeCl₃·6H₂O - methanol at room temperature for 30 min, dried in air, and rid of droplets of the solution of FeCl₃·6H₂O - methanol partially remaining on the surface of the foam by making them absorbed with a filter paper. Thus, the FeCl₃ component was uniformly retained on the one surface of the foam. Subsequently, 4 ml of pyrrole was placed in the bottom of a glass container (length: 10 cm, width: 25 cm, height: 15 cm), and the foam treated as described above was suspended from the upper portion of the glass container, followed by tightly covering the upper portion of the container with a glass plate, whereby the foam was contacted with a pyrrole vapor. Upon such contact, the one surface of the foam rapidly discolored through dark green to black, and polypyrrole was foamed on the one surface of the foam. The foam was picked up after contact with the pyrrole vapor for 40 hours, and then immersed in methanol for 30 min to remove unreacted pyrrole and the FeCl₃ component by extraction. This procedure was repeated three times, followed by drying in air. With an anode having a predetermined size punched from the resulting foam and a cathode having a predetermined size punched from lithium, a secondary battery as shown in Fig. 1 according to the present invention (battery G of the present invention) was produced. In this figure, the metallic foam 13 was bonded to the inner bottom surface of an anode case, and was also to serve as an anode collector. In this Example, propylene carbonate was used as the solvent for an electrolyte, while lithium tetrafluoroborate (LiBF₄) was used as the electrolyte. A separator made of a non-woven polypropylene fabric was used. In addition to propylene carbonate, usable solvents for the electrolyte include ethylene carbonate, acetonitrile, propionitrile, butylonitrile, benzonitrile, dioxolane, 1,4-dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-dichloroethane, nitromethane, N,N-dimethylformamide, dimethyl sulfoxide, sulfolane, methyl phosphate, ethyl phosphate, and γ-butyrolactone. These solvents may be used alone or in mixture. In addition to lithium tetrafluoroborate (LiBF₄), usable electrolytes include lithium perchlorate (LiClO₄), lithium hexafluorophosphate (LiPF₆), lithium tetrachloroaluminate (LiAlCl₄), tetraethylammonium tetrafluoroborate (LiAlCl₄), tetraethylammonium tetrafluoroborate [(C₂H₅)₄NBF₄] , tetraethylammonium perchlorate [(C₂H₅)₄NClO₄], lithium trifluoromethanesulfonate (LiCF₃SO₃), lithium bromide (LiBr), and lithium iodide (LiI). Batteries (batteries H and I of the present invention) having substantially the same structure as that of the battery G of the present invention except for the use of a stainless steel foam having a porosity of 80% or 98%, respectively, were produced. For comparison, secondary batteries (comparative batteries J and K) having the structure as shown in Fig. 2 were produced using a stainless steel foam having a porosity of 60% or 40%, respectively. To this effect the electrically conductive material was punched into a predetermined size of an anode, while lithum was punched into a predetermined size of a cathode. The separator was made of a non-woven polypropylene fabric, and the electrolytic solution contained lithium tetrafluoroborate LiBF₄ (electrolyte) dissolved in propylene carbonate (solvent). In this figure, the numeral 3 refers to the anode, 4 to the cathode, 5 to the separator, 6 to an insulating gasket, 7 to an anode case, 8 to a cathode case and 9 to a cathode collector. Further, a comparative battery L having the same structure as that of the battery G of the present invention except that a conventional polypyrrole film prepared by the electrolytic polymerization method was press-bonded through a collector to an anode case and was used as the anode, was produced. The above-mentioned six batteries were charged with an electric current of 0.5 mA for one hour, and subjected to a series of repeated charging and discharging cycles wherein discharging was made up to a battery voltage of 2.5 V with an electric current of 0.5 mA. Fig. 3 shows variations in voltage of the batteries G to I of the present invention and the comparative batteries J to L with time in charging and discharging of the 20th cycle. In this figure, solid lines refer to voltage variations in charging, while dotted lines refer to those in discharging. It will be understood from Fig. 3 that the batteries G to I of the present invention has a low charging voltage and a high discharging voltage as compared with the comparative batteries J to L, and has a good charging and discharging efficiency. The charging and discharging efficiencies of the batteries G to I of the present invention were 92%, 93%, and 93%, respectively, while those of the comparative batteries were 89%, 87%, and 81%, respectively. The reason for such an impprovement in charging and discharging efficiencies of the batteries G to I of the present invention is believed to be that, in the batteries G to I of the present invention, a stainless steel foam having a high porosity of 70 to 98% and hence a very good liquid containing capacity was used as the electrode base material, so that the area of the stainless steel foam in contact with the electrically conductive material was large, thus increasing the area of the direct contact between the electrically conductive polymer and the electrolytic solution to improve the utilization of the polymer. On the other hand, since the comparative batteries J and K used a stainless steel foam as the electrode base material, they had a good liquid containing capacity as compared with the comparative battery L and hence a high utilization of the electrically conductive polymer, whereby the charging and discharging efficiencies thereof were increased. Since, however, the porosities of the steinless steel foams used in the comparative batteries J and K were as low as 60% and 40%, respectively, the specific areas of the anodes were small to that extent, and hence the liquid containing capacities of the anodes were low. Thus, the areas of the stainless steel foam in contact with the polypyrrole were reduced with the amounts of the polymer in this experiment, and the amounts of polypyrrole in direct contact with the electrolyte were also reduced. As a result, the utilizations of polypyrrole in these batteries were believed to be lowered, leading to the lower charging and discharging efficiencies than those of the batteries G and I of the present invention. Fig. 4 shows variations in charging and discharging efficiency (%) of the batteries G to I of the present invention and the comparative batteries J to L with cycles. As is apparent from the figure, the charging and discharging efficiencies in the 140th cycle of the batteries G to I of the present invention were as high as 93%, 94%, and 93%, respectively, thus providing a good cycling life span. In contrast, the charging and discharging efficiency of the comparative battery L began to drastically aggravate when the number of cycles exceeded about 30. The reason for the poor cycling characteristics of the comparative battery L is believed to be that the polypyrrole film of the anode was scaled or peeled off from the collector in the course of charging and discharging cycles while gradually aggravating the bond therebetween, so that electric current might begin to concentratedly flow locally in the anode, leading to marked reduction in the utilization of polypyrrole in the anode and hence to large reduction in the charging and discharging efficiency of the battery. In the case of the comparative batteries J and K, relativley high charging and discharging efficiencies thereof could be maintained. This is because the use of the stainless steel foam as both the anode and the collector provided a good bond of the polypyrrole film polymer to the stainless steel foam and a good liquid containing capacity of the anode as compared with the comparative battery L. In comparison with the batteries G to I of the present invention, the porosities of the above-mentioned stainless steel foams were by far low in the cases of the comparative batteries J and K. This is believed to provide lower utilizations of polypyrrole than those of the batteries G to I of the present invention, thus causing the initiation around over the 100th cycle of concentration of the electric current in a localized portion of the anode. This may have caused degradation of the polypyrrole itself which may have given rise to a rapid rise of the charging voltage to cause decomposition of the electrolyte, decomposition and polymerization of the solvent, etc. On the other hand, the batteries G to I of the present invention used a stainless steel foam having a porosity ranging from 70% to 98% as both the anode base material and the collector, increasing the utilization of polypyrrole and hence providing the excellent cycling characteristics. Fig. 5 shows variations in battery voltage of the batteries G to I of the present invention and the comparative batteries J to L with time in charging and discharging of the 140th cycle. As is apparent from the figure, the batteries G to I of the present invention showed no rise of charging voltage even in 140th cycle, and a flatter charging voltage curve than those of the comparative batteries J and K. As a result, it can be understood that the batteries G to I of the present invention maintained good cycling characteristics in a large number of cycles. Although description has been made of the batteries using the electrically conductive material only in the anode, it will be apparent that an equivalent effect may also be attained where the electrically conductive material according to the present invention is used in the cathode or in both of the anode and cathode.

Claims: Process for preparing an electrically conductive material containing no substantial amount of water and oxidizing agent by polymerizing a pyrrole or thiophene compound on a base material in a gas phase in the presence of an oxidizing agent and thereafter washing the resulting product with an organic solvent, characterized in that as a base material a metallic foam is used having a pore volume of 70 to 98 % and spaces capable of retaining the oxidizing agent in the form of molecules or aggregates. Process according to claim 1, wherein a metallic foam is used having at least one hydrophobic surface. Process according to claim 2, wherein said metallic foam has said oxidizing agent retained on one surface thereof by immersing a metallic foam, wherein one surface is hydrophobic and the other hydrophilic, in an aqueous solution of said oxidizing agent, or by applying an aqueous solution of said oxidizing agent to said other surface to make said oxidizing agent retained on said other surface. Process according to claim 2, wherein said metallic foam has said oxidizing agent retained on one surface thereof by applying an aqueous solution of said oxidizing agent on one surface of a metallic foam which is hydrophobic on both of the surfaces thereof. Process according to claim 2 or 3, wherein said metallic foam is one treated with a hydrophilicity-imparting agent on one surface thereof. Process according to claim 2 or 3, wherein said metallic foam is a hydrophilic one treated with a water-repellant on one surface thereof. Process as claimed in claims 1 to 6, wherein said metallic foam is chromium, titanium, nickel, gold, platinum, tantalum, copper, silver, iron or stainless steel. Process of preparing a battery cell comprising a rechargeable anode, a rechargeable cathode and an electrolyte layer positioned between said anode and said cathode which process includes the step of preparing an electrode by the method of anyone of claims 1 to 7.

Inventors: FUJIMOTO MASAHISA, FURUKAWA NOBUHIRO, HASEGAWA KAZUMI, NISHIO KOJI, SUZUKI TETSUMI, YOSHINAGA NORIYUKI, FUJIMOTO, MASAHISA, FURUKAWA, NOBUHIRO, HASEGAWA, KAZUMI, NISHIO, KOJI, SUZUKI, TETSUMI, YOSHINAGA, NORIYUKI
Applicants: MITSUBISHI CHEM IND, SANYO ELECTRIC CO, MITSUBISHI KASEI CORPORATION, SANYO ELECTRIC CO., LTD.
Application year: 1986
Main classification: H01M4
IPC codes: H01M10, H01M4, C08L101, H01B1, C08L67, C08L69, C08G61