Patent Publication Number: US-2004058239-A1

Title: Electrode structure, battery and electrical double-layer capacitor and method of manufacturing same

Description:
BACKGROUND OF THE INVENTION  
       [0001] 1. Field of the Invention  
       [0002] The present invention relates to a novel method of manufacturing an electrode structure, and to a manufacturing method for producing a battery and an electrical double-layer capacitor utilizing the electrode structure.  
       [0003] 2. Description of Related Art  
       [0004] A typical electrode structure of the prior art is manufactured by coating a current-collecting member surface with a compound mixture containing an electrode material, a powdered electrically-conducting substance, binder and solvent, vaporizing the solvent by applying heated air to the coating in a hot air heating oven, and drying the coating to attach an electrode film to the surface of the current-collecting member. Unfortunately, the electrode film is prone to peel away from the current-collecting member and as a consequence the electrical resistance of the electrode film does not decrease. This prior art process is constituted as shown for example in FIG. 11. As shown, the electrode structure consisting of an electrode film h coated on a current-collecting member g, is transported on a conveyor d into a cabinet c inside a heated air oven. Heated air f is blown towards the electrode film h from the hot air blow outlet b, and the solvent contained in the electrode film h is made to vaporize. The heated air moves the solvent outwards by way of the cabinet outlet e.  
       SUMMARY OF THE INVENTION  
       [0005] This invention is directed to a method of manufacturing an electrode structure by coating a compound mixture comprising an electrode material and binder and solvent onto a current-collecting member, directing infrared radiation onto the coating to vaporize the solvent and form an electrode film on the current-collecting member.  
       [0006] This invention is further directed to a method of manufacturing an electrode structure by coating a compound mixture comprising an electrode material covered with an ion-conducting polymer and a solvent, onto a current-collecting member, directing infrared radiation onto the coating mixture to vaporize the solvent and form an electrode film on the current-collecting member.  
       [0007] This invention is still further directed to an electrode structure manufacturing method as described above, wherein the compound mixture also contains a powdered electrically-conducting substance.  
       [0008] This invention still further is directed to a method of manufacturing a battery with the electrode structures as described above as the battery electrodes, wherein a compound mixture comprising a powdered electrode active substance, powdered electrically-conducting substance, binder and solvent is coated onto a current-collecting member, infrared radiation is directed onto the coating of mixed material to vaporize the solvent and to form an electrode film on the current-collecting member to constitute the electrode structure.  
       [0009] This invention is also directed to a method of manufacturing a battery with the electrode structures as described above as battery electrodes, wherein a compound mixture comprising a powdered electrode active substance coated with ion-conducting polymer, powdered electrically-conducting substance, and solvent is coated onto a current-collecting member, infrared radiation is directed onto the coating of mixed material to vaporize the solvent and to form an electrode film on the current-collecting member to constitute the electrode structure.  
       [0010] This invention still further is directed to a method of manufacturing an electrical double-layer capacitor with the electrode structures as described above used as the capacitor electrodes, wherein a compound mixture comprising a large surface area material, binder and solvent is coated onto a current-collecting member, infrared radiation is directed onto the coating of mixed material to vaporize the solvent and to form an electrode film on the current-collecting member to constitute the electrode structure.  
       [0011] This invention yet further is directed to a method of manufacturing an electrical double-layer capacitor with the electrode structures as above described used as the capacitor electrodes, wherein a compound mixture comprising a large surface area material coated with an ion-conducting polymer and a powdered electrically-conducting substance and solvent is coated onto a current-collecting member, infrared radiation is directed onto the coating of mixed material to vaporize the solvent and to form an electrode film on the current-collecting member to constitute the electrode structure.  
       [0012] In view of the above problems with the prior art methods of forming electrode structure, this invention has the object of providing an electrode structure comprised of an electrode film which strongly adheres to the current-collecting member.  
       [0013] This invention has the further object of providing an electrode structure comprised of an electrode film with low electrical resistance.  
       [0014] This invention has the yet further object of providing a method of manufacturing a battery and an electrical double-layer capacitor comprised of an electrode structure with an electrode film of low electrical resistance. 
     
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS  
     [0015] FIGS.  1 (A)- 1 (F) are views showing different types of electrode structures.  
     [0016]FIG. 2 is a schematic view of the fabrication of an electrode structure.  
     [0017]FIG. 3 is a schematic view of drying an electrode structure by an infrared lamp device.  
     [0018] FIGS.  4 (A) and  4 (B) are views illustrating the drying of the coated compound mixture by heated air and by infrared radiation.  
     [0019] FIGS.  5 (A) and  5 (B) are views showing alternative battery structures.  
     [0020] FIGS.  6 (A) and  6 (B) are views showing alternative electric double-layer capacitors.  
     [0021] FIGS.  7 (A)- 7 (C) show various levels of peeling strength as tested.  
     [0022]FIG. 8 is a schematic view illustrating the covering of ion-conducting polymer.  
     [0023] FIGS.  9 (A)- 9 (D) illustrates the press-sliding mixer.  
     [0024]FIG. 10 is a view showing the sealing and pressing device.  
     [0025]FIG. 11 is a schematic view of a heated air oven. 
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS  
     [0026] The embodiments of the invention are next described while referring to the accompanying drawings.  
     [0027] Electrode Structure  
     [0028] The electrode structure of this invention can be used in the electrode(s) of electronic components wherein typically an electrolyte is provided between the electrodes. When the electrical component is a battery, the electrode structure exchanges electricity by way of electrolyte ions. When the electrical component is a double-layer capacitor, the electrode structure forms an electrical double-layer between a material with a large surface area and electrolyte.  
     [0029] FIGS.  1 (A)- 1 (F) illustrate examples of typical electrode structures. The electrode structure of FIG. 1(A) is used as the positive electrode of a battery. In this figure, the electrode structure  1  is an electrode film  18  consisting of a powdered electrode active substance as an electrode material  11 , a powdered conductor material  14  and binder  17 , attached to the surface of the current-collecting member  13 . Here, LiCoO 2 , for example, is used as the powdered electrode active substance  11 . In FIG. 1(B), an ion-conducting polymer  12  is attached to the electrode material  11  of FIG. 1(A), and the ion-conducting polymer  12  also functions as a binder. FIG. 1 (C) shows an electrode structure used in the negative electrode of a battery. In this figure, the electrode structure  1  is an electrode film  18  consisting of a powdered electrode active substance as an electrode material  11  and a binder  17 , attached to the surface of the current-collecting member  13 . Here, graphite powder is, for example, used as the powdered electrode active substance  11 . In FIG. 1 (D), the electrode material  11  of FIG. 1 (C) is covered with an ion-conducting polymer  12 . This ion-conducting polymer  12  also functions as a binder. In FIG. 1(E), the electrode structure is used as an electrode for the double-layer capacitor. In this figure, the electrode structure  1  is an electrode film  18  consisting of a large surface area material as an electrode material  11  and a binder  17 , attached to the surface of the current-collecting member  13 . Here, active carbon material is used, for example, as the large surface area material. In FIG. 1(F), the powdered active carbon material of FIG. 1(E) is covered by the ion-conducting polymer  12 . This ion-conducting polymer also functions as a binder. When the electrode material  11  is covered with the ion-conducting polymer  12 , this ion-conducting polymer functions as a binder. The electrode material covered with the ion-conducting polymer is described in detail later on.  
     [0030] Manufacturing Method for the Electrode Structure  
     [0031] An example of the manufacturing method of this invention to produce an electrode structure is shown in FIG. 2. The electrode material  11 , powdered conductor material  14 , binder  17  and solvent  19  are mixed together in a mixer  3  to obtain the mixed material  31 . The mixed material  31  is lightly coated onto the surface of the current-collecting member  13 . The method for coating the mixed material is by surgical knife applicator, etc. The mixed material coating is vaporized, dried and attached to the current-collecting member  13  as the electrode film  18 . Here, vaporizing and drying the solvent  19  and coating the mixed material  31  onto the current-collecting member  13  is not performed by applying heated air, but instead by directing infrared radiation  52  from an infrared lamp device (not shown).  
     [0032] As shown for example in FIG. 3, the electrode film  18  coated onto the current-collecting member  13  is moved by the conveyor  58  into the cabinet  54  and infrared radiation  52  generated by an infrared radiation generator  51  of the infrared lamp device  5  is directed onto the electrode film  18  coated onto the current-collecting member  13 . An infrared permeable wall  53  is installed to let the infrared radiation pass between the cabinet  54  and the infrared radiation generator  51 . This infrared permeable wall  53  may not be needed if no problem exists with the infrared radiation generator  51  and the type and concentration of vaporized solvent gas. The vaporized solvent  19  from the electrode film  18  is blocked off from the infrared radiation generator  51  by the infrared permeable wall  53 . The cabinet  54  filled inside by the solvent  19  reaches an equalized concentration when the concentration attains a high level, such that the vaporization is limited by recovery of the solvent by suctioning it into the solvent recovery unit  55  inside the cabinet  54  with the fan  56 . In that time, external air  57  is supplied into the cabinet  54  so the external pressure will match the gas pressure inside the cabinet  54 . However, this external air  57  is not for vaporizing the solvent  19  by air blow. A level of external air  57  to well agitate the uniform concentration of the solvent is sufficient and though dependent on the size of the cabinet  54 , a flow speed of for example 0.5 meters per minute is sufficient. When the electrode film  18  is coated on both surfaces of the current-collecting member  13 , the infrared radiation may be directed onto both sides of the electrode structure  1 .  
     [0033] Infrared radiation ranging from the near-infrared close to the visible light level to mid-infrared, to far-infrared close to the electromagnetic spectrum can be used rather than propagation of heat to the mixed material through the air. If the mixed material can be heated remotely with hardly any transmission through air, then any type of infrared radiation may be utilized. Near-infrared radiation has a high transmittance (permeance) rate into the interior of the mixed material so that the interior of the mixed material can be heated.  
     [0034] When infrared radiation is used as a means to vaporize the solvent  19  and dry the mixed material  31 , the electrode film  18  adheres (or bonds) well to the current-collecting member  11 , and the electrical resistance of the electrode film  18  is also low. The reason for the improved properties can be explained by referring to FIG. 4. FIG. 4 shows an enhanced view of the internal state of the mixed material  31  when the solvent  19  of the mixed material coated on the current-collecting member  12  is vaporized. FIG. 4(A) shows the conventional method of applying heated air f onto the mixed material  31  to vaporize the solvent  32  mixed with a binder. FIG. 4(B) shows the method of this invention wherein infrared radiation  52  is directed onto the mixed material  31  to vaporize the solvent  32  mixed with a binder.  
     [0035] The solvent vaporization process works as follows in the case of the conventional method of FIG. 4(A). When heated air f is applied to the surface of the mixed material, the area around the surface of the mixed material  31  suddenly warms up in the heated air, and the solvent on the surface is vaporized and blown away by the heated air f. The solvent near the surface therefore quickly vaporizes, and to compensate, the solvent at the interior of the mixed material and near the collector electrode moves to the vicinity of the surface. The binder contained in the solvent and the powdered conducting material are at this time carried to the surface of the mixed material  31  along with the solvent. As a result, the concentrations of binder on the current-collecting member side of the mixed material and powdered conducting material become weak (or thin). The electrode film therefore tends to easily peel away from the current-collecting member  13 , and the relative electrical resistance in the vicinity of the current-collecting member becomes high, and the resistance of the electrode overall becomes high.  
     [0036] In contrast, in the method of this invention shown in FIG. 4(B), the solvent vaporization process works as follows. When the infrared radiation  52  is directed onto the mixed material surface, the infrared radiation  52  permeates through into the interior of the mixed material, and heats up the entire mixed material. No heated air is blown at this time so that the solvent gradually evaporates (vaporizes) from the surface of the mixed material. The concentrations of binder and powdered conducting material  14  therefore remain uniform overall. As a result, the binder concentration in the vicinity of the current-collecting member does not become weak (or thin) in the electrode material of dried mixed material  31 . Accordingly, the electrode film adheres well to the current-collecting member  13 . Further, the concentration of the powdered conducting material in the vicinity of the current-collecting member does not become weak either, so that the electrical resistance of the overall electrode film is low.  
     [0037] Current-Collecting Member  
     [0038] The current-collecting member  13  may be any material capable of conducting electricity, and the material and shape can be selected according to the electronic component. As one example, the electrolyte may be aluminum or copper and formed in a plate, leaf or mesh shape. When the current-collecting member is a plate or leaf shape, one or both sides are used according to the structure of the electronic component.  
     [0039] The electrode film  18  for adhering to the current-collecting member  13  may be pressed into the current-collecting member to make it further adhere. The bonding (adhering) may for instance be performed with a sealing and pressing device  4  such as shown in FIG. 10. An electrode structure  1  made from current-collecting member coated with mixed material is enclosed by the pressure rollers  41 , and the electrode film can be bonded to the current-collecting member by applying a rotating pressure with the pressure device  43  by means of the backroller  42 .  
     [0040] Battery  
     [0041] The electrode structure of FIG. 1(A) or FIG. 1(B) can be used as the positive electrode, and an electrode structure useful as a negative electrode is shown in FIG. 1(C) or FIG. 1(D). An electrolyte is positioned between these electrodes. FIGS.  5 (A) and  5 (B) show an example of a battery with an electrode structure the same as the positive electrode in FIG. 1 (B) and a battery with an electrode structure the same as the negative electrode in FIG. 1(D). Here, FIG. 5(A) shows the case when the electrolyte is a liquid electrolyte  16 , and a separator  15  is placed between the electrodes. FIG. 5(B) shows the case when the electrolyte is an ion-conducting polymer  12  in solid. The separator  15  is installed to isolate one pair of electrode structures  1 , and the electrolyte can be used in solid when required according to circumstances.  
     [0042] Double-Layer Capacitor  
     [0043] The double-layer capacitor has a structure with electrolyte placed between one pair of electrodes of the electrode structure of FIG. 1(E) or one pair of electrodes of the electrode structure of FIG. 1(F). A double-layer capacitor utilizing the electrode structure of FIG. 1(E) is shown in FIG. 6(A), and a double-layer capacitor utilizing the electrode structure of FIG. 1(F) is shown in FIG. 6(B). In FIG. 6(A), a separator  15  is placed between the electrodes when the electrolyte is the liquid electrolyte  16 . FIG. 6(B) shows the case when the electrolyte is an ion-conducting polymer  12  in solid. The separator  15  is installed to isolate one pair of electrode structures  1 , and the electrolyte can be used in solid when required according to circumstances.  
     [0044] Examples of the electrode structure are described next.  
     [0045] Making the Electrode Structure Sample Pieces  
     [0046] Eleven electrode structure sample pieces 1-11 were dried using two types of heating methods; one method was infrared heating and the other was the heated air method of the prior art. The peeling strength and impedance (Ω/ohm) of these sample pieces were measured. The ratio (proportions) of electrode material, powdered conducting material, binder, and solvent material used in the preparation of the sample pieces are shown in Table 1. The results of peeling strength and impedance (Ω/ohm) are shown in Table 2.  
                       TABLE 1                                      ACTUAL ELECTRODE COMPOSITION (per weight)                                     Active carbon;   Powder                   electrically   conducting   Binders                                                         conducting   material                   Thermo-   Thickness   Solvent           carbon or   (carbon   Polymer   Polymer           plastic   of   (per       Sample   LiCoO 2     black)   A1   A2   Teflon   PVDF   resin   electrode   weight)                                                             1   20   0   0.8       0.24           350   NMP (30)       2   20   0   1                   75   NMP (30)       3   20   0       1               50   NMP (30)       4   20   0           1           75   NMP (30)       5   18   2   1                   350   NMP (30)       6   18   2           1           350   NMP (30)           (LiCoO2)       7   18                       1   75   NMP (30)       8   18                       1   350   NMP (30)       9   91   6                   3   85   NEK (20) +                                           NMP (10)       10   91   9       11               92   NMP (20)       11                           3   85   NMP (30)           (LiCoO 2 )                  
 
     [0047]                                   TABLE 2                                      INFRARED HEATING       HOT AIR HEATIN                                           Peeling   Impedance   Peeling           Sample   Strength   (Ω/ohm)   Strength                                               1   a   1.9   c             2   a   0.39   b             3   a   0.59   b             4   b   0.34   c             5   a   0.17   b             6   a   0.19   c             7   a   0.15   b             8   a   0.17   b             9   b   2   c             10   a   1   b             11   a   1.4   b                          
     [0048] The samples 1 through 8 are electrodes useful for capacitors. The electrode material was made from phenol resin (made by Kansai Chemical Corp.) which was dry mixed with carbon black as the powdered conductive material, utilizing a mixer. The samples 9 through 11 are positive electrodes for batteries. Carbon black as the powdered conductive material was added to LiCoO 2  which served as the electrode material by dry type mixing performed utilizing a mixer. The binder was then added to all the samples 1 through 11 and mixing performed. A specified amount of solvent was further added and mixing performed. After mixing, the material was coated onto the collector element with a surgical knife applicator. The samples were then heated by infrared radiation or by heated air.  
     [0049] A far-infrared ceramic panel heater PH-100, iPH100C (made by SAKAGUCHI E.H VOC CORP.) was utilized as the infrared lamp device. The infrared radiation drying conditions for all the samples were 30 volts for one hour.  
     [0050] A device as shown in FIG. 11 was utilized as the heated air oven to apply heated air onto the surface of the mixed material from the hot air blow outlet. The heated air was regulated to a temperature of approximately 80 to 200 degrees centigrade and a flow speed of 15 to 25 meters per minute.  
     [0051] The samples 1 to 8 utilized active carbon material as the electrode material. Sample 9 utilized LiCoO 2  as the electrode material and PVDF as the binder. Sample 10 utilized LiCoO 2  as the electrode material and polymer A2 as the binder, and was covered with ion-conducting polymer. Sample 11 uses LiCoL 2  as the electrolyte and thermoplastic resin as a binder. Samples 1 through 4 contained no carbon black powdered electrically-conducting substance, and samples 5 through 11 contained carbon black though there were differences in the concentrations used in the samples. Polymer A1, polymer A2, Teflon powder, PVDF (polyvinylidene fluoride), and thermoplastic resin were used as the binders. Polymer A1, and polymer A2 were ion-conducting polymers. The raw materials used to form polymers A1 and A2 are shown in Table 3 and Table 4, respectively. NMP (N methyl-2-pyrrolidone) was mainly used as the solvent, and MEK (methyl ethyl ketone) was used only in preparing sample 7.  
               TABLE 3                          Ion-conducting polymer raw material (A1)                         Mixing ratio           (weight       Substance   parts)                             Difunctional (propylene glycol/ethylene glycol) random   8.36       copolymer, SANNIX FA-103 (PO/EO = 2/8,       Mw = 3,282, Sanyo Chemical Industries, Ltd.)       Difunctional 1,4-butanediol   0.34       Ethylene cyanohydrin   1.27       Reaction catalyst NC-IM (Sankyo Air Products K.K.)   0.03       Total   10                  
 
     [0052] Thermoplastic resin is composed as follows: A preheat-dehydrated polycaprolactonediol (Placcel 220N, DAICEL CHEMICAL INDUSTRIES, LTD) of 4.34 by weight, 4,4′-diphenylmethane diisocyanate of 28.57 by weight are to be prepared in a reactor having an agitation device, a thermometer, and a cooling pipe and are agitated and mixed 2 hours at  120° C. under nitrogen current;  1,4-butanediol of 7.09 by weight is added and similarly reacted at 120° C. under nitrogen current. As the reaction proceeds and stops when the reactant becomes a rubber like substance. Then, the reactant is removed from the reactor and heated for 12 hours at 100° C. The heating is stopped after verifying an extinction of the absorption peak of isocyanate base due to the infrared absorption spectrum, thereby obtaining a solid thermoplastic resin. The weight average molecular of thermoplastic resin as a result (Mw) was 1.71×10 5 .  
               TABLE 4                          Ion-conducting polymer raw material (A2)                         Mixing ratio           (weight       Substance   parts)                             Cyanoethylated/dihydroxypropylated polyvinyl alcohol   0.625       Methoxypolyethyleneglycol methacrylate (mol. wt. 468)   3.125       Trimethylolpropanetrimethacrylate (mol. wt. 536)   6.25       Total   10                  
 
     [0053] Electrode Structure Measurement Results  
     [0054] To measure the peeling strength, cellophane tape (KOKUYO TSS18N width 18 mm, thickness 50 μm) was attached to the electrode film fabricated on the surface of the current-collecting member, and the cellophane tape then pulled away to make the electrode film stuck to the cellophane tape separate from the current-collecting member. A peeling strength ranking could then be established according to the amount of electrode film peeled from the surface of the current-collecting member. FIG. 7 taken from photographs shows the electrode film stuck to the cellophane tape. In FIG. 7(A), a mere fraction of the upper layer of the electrode film has thinly peeled away (The black portion is the portion where the electrode film has peeled.) and is rank a. In FIG. 7(B), a middle layer of the electrode film has thinly peeled off (The black portion is the portion where the electrode film has peeled.) and is rank b. In FIG. 7(C), a the electrode film has completely peeled off from the current-collecting member (The black portion is the portion where the electrode film has peeled.) and is rank c.  
     [0055] To measure the impedance (Ω/ohm), the electrodes formed on the collector element were enclosed by copper plates of 2 centimeters in diameter and 5 millimeters thick. A pressure of 4.5 kilograms per centimeter was applied from above and below, and the resistance at 10 kilohertz AC was measured with an impedance analyzer.  
     [0056] On comparing infrared heated samples and hot air heated samples having the same sample numbers, in all cases, the peeling strength for the infrared heated samples was found to be one or two ranks higher than the heated air samples. In the impedance test results also, the infrared heated samples had an impedance (Ω/ohm) which was small, indicating low resistance.  
     [0057] The electrode material coated with ion-conducting polymer is described next.  
     [0058] Electrode Structure Coated with Ion-Conducting Polymer  
     [0059] In FIG. 1, the powdered electrode active substance  11  has the shape of particles consisting of bonded particles like LiCoO 2 , and the process for depositing the ion-conducting polymer  12  is shown. The term “coating” refers to a state where ions can migrate sufficiently between the ion-conducting polymer  12  and the powdered electrode active substance  11  over their entire surfaces. The ion-conducting polymer  12  is deposited on the surface of the powdered electrode active substance  11  as a coating of ion-conducting polymer  12 . The finer the particles, the more active the powdered electrode active substance  11  becomes. However, this increased activity is suppressed by depositing a coating of ion-conducting polymer  12  on the electrode active substance  11 , so the powdered electrode active substance  11  can become stable. When the deposit of ion-conducting polymer  12  is thick, the electrical conduction decreases, and the current (charge) collection is poor. Accordingly, forming a thin coating of ion-conducting polymer is preferable. Inventions relating to electrode structures coated with ion-conducting polymer have already been proposed by the applicants of this invention (Japanese Patent Application 11-262501, and Japanese Patent Application 11-262502).  
     [0060] The powder shape such as for the powdered electrode active substance  11  and powdered conducting material  14  is a fine particle substance. Further such a powder is a collection of many substances. In certain cases, this fine particle substance refers to a state wherein a large number of substances in a fine particle state constitute an agglomeration.  
     [0061] Powdered Electrode Active Substance  
     [0062] The powdered electrode active substance uses ion insertable-separable materials and π-conjugated conductive macromolecular materials. There are no particular restrictions on the electrode active substance used as the positive electrode for non-aqueous electrolyte batteries. However, in the case of chargeable batteries, chalcogen compounds allowing ion insertion/separation or composite chalcogen compounds containing lithium are recommended.  
     [0063] Useful chalcogen compounds may be FeS 2 , TiS 2 , MoS 2 , V 2 O 5 , V 6 O 13 , MnO 2 , etc. Typical chalcogen compounds containing lithium are LiCoO 2 , Li x Ni y M 1-y O 2 , (where M expresses one or more metallic elements selected from transitional metals and aluminum, and preferably one or more metallic elements selected from among cobalt, manganese, titanium, chromium, vanadium, aluminum, and 0.05≦x≦1.10, 0.5≦y≦1.0) and composite lithium oxides, LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , etc. These compounds may be obtained by using lithium, cobalt, nickel, manganese oxides, salts or hydroxides as starting materials, mixing these starting materials together according to the composition desired and baking the mixture in an oxygen atmosphere at a temperature of 600 to 1,000 degrees centigrade.  
     [0064] There are no particular restrictions on the electrode active substance used as the negative electrode for non-aqueous electrolyte batteries. However, a material allowing lithium ion insertion/separation may be used, and lithium metal, lithium alloys (alloys such as lithium and aluminum, lead, indium) and carbon quality materials may be utilized.  
     [0065] Polyacetylene types, polyaniline types, polypyrrole types, polythiophene types, poly ρ(para)-phenylene types, polycarbazole types, polyacene types and sulfur polymer types are among the useful π-conjugated conductive macromolecular materials.  
     [0066] Using lithium metals in the negative electrode achieves a large battery capacity particularly in primary non-aqueous electrolyte batteries.  
     [0067] Also in non-aqueous electrolyte batteries, using carbon materials in the negative electrodes, that are capable of lithium ion insertion/separation yields a longer battery cycle life span. There are no particular restrictions on the carbon material used but materials such as pyrolytic carbon types, coke types (pitch coke, needle coke and petroleum coke, etc.) graphite types, glass carbon types, organic macromolecular compound fired products (carbonized pieces baked to a suitable temperature such as phenol resin, furan resin) carbon fibers and active carbon may be utilized.  
     [0068] Powdered Electrically-Conducting Substance  
     [0069] The powdered electrically-conducting substance raises the conductivity of the electrode structure and though there are no particular restrictions, materials such as metal powder and carbon powder may be used. Particularly preferred carbon powders are pyrolytic carbons such as carbon black, and their graphite products, artificial and natural scaly graphite powder, carbon fibers and their graphite products, etc. Product mixtures of these carbon powders are also utilized.  
     [0070] Ion-Conducting Polymer  
     [0071] The ion-conducting polymer is a polymer which can dissolve at least the lithium salts described hereafter at a concentration of at least 0.1M (moles/l), the polymer containing the lithium salt at a concentration of at least 0.1M having an electrical conductivity of 10 −8  S (siemens)/cm at room temperature. It is to be particularly preferred that the ion-conducting polymer dissolves at least lithium salts to a concentration of 0.8M-1.5M, the resulting polymer having an electrical conductivity of 10 −2  S/cm-10 −5  S/cm at room temperature.  
     [0072] The lithium salt is at least one type of lithium salt having ClO 4   − , CF 3 SO 3   − , BF 4   − , PF 6   − , AsF 6   − , SbF 6   − , CF 3 CO 2   −  or (CF 3 SO 2 ) 2 N −  as anion.  
     [0073] The ion-conducting polymer raw material is a substance which produces the ion-conducting polymer by cross-linking, etc., when energy is supplied externally. The energy may be heat, ultraviolet light, light or electron radiation.  
     [0074] The method of manufacturing these electrode structures will now be described.  
     [0075] (a) Manufacture of Electrode Structure  
     [0076] The method of coating the powdered conductive material with the ion-conducting polymer as is shown in FIG. 8 is to press-slide the ion-conducting polymer and the powdered electrode active substance against each other.  
     [0077] In this process, by using only a minute amount of the ion-conducting polymer, the particle surfaces of the powdered electrode active substance are coated with the ion-conducting polymer, no voids are formed, and gaps in the powdered substance are reduced.  
     [0078] (b) Press-Sliding  
     [0079] Press-sliding is the action of sliding while pressing mixtures  10  of the ion-conducting polymer  12  or the raw material of the ion-conducting polymer  12  and the powdered substance  11  together. An external force is applied to the mixtures so that they cohere to each other and the particles rotate, and this process is performed repeatedly to obtain a press-sliding product.  
     [0080] (c) Press-Sliding Mixer  
     [0081] The press-sliding mixer is shown, for example, in FIG. 9(A). The mixture  10  of the ion-conducting polymer  12  or its raw material with the powdered substance  11 , or the mixture  10  comprising this mixture and a solvent or the like, is introduced into a container  21  via container top  212 , and the main blade  22  is rotated such as by motor  222 . There is a gap between a base  211  of the container  21  and a bottom surface of the main blade  22 . When the main blade  22  is rotated, part of the mixture  10  enters the space between the base  211  of the container and the main blade  22 , is subjected to press-sliding, and is kneaded. This process is repeated so that the ion-conducting polymer  12  or its raw material coats the powdered substance  11 .  
     [0082] A press-sliding mixer  2  may if necessary be provided with a dispersion blade  23  in the container  21 . The dispersion blade  23  is rotated at high speed via motor  231  to disperse the press-slid mixture  10 .  
     [0083] (d) Container  
     [0084] The container  21  is provided for holding the mixture  10  which is press-slid and stirred. The bottom surface or base  211  of the container  21  slants upwards from the central bottom part  2111  towards the circumference of container  21 . The bottom  211  may be formed in the shape of, for example, a grinding mortar, and the angle of the slant of bottom part  211  may, for example, be 120 degrees. The bottom  211  of the container is wear-resistant, and can be formed by thermal spraying with tungsten or carbide using SUS. Plural bottom parts of this type may also be formed on the bottom surface  211 .  
     [0085] (e) Main Blade  
     [0086] The main blade  22  functions together with the bottom surface  211  of the container  21 , serving to press-slide and stir the mixture  10 .  
     [0087] The main blade  22 , is positioned via shaft  221  to the desired location relative to the bottom  211  of the container  21  as shown for example in FIGS.  9 (A) and  9 (B). Main blade  22  curves upwards corresponding to the slant of bottom  211  of the container  21 . The main blade  22  may comprise two blades attached from the center part as shown in FIG. 9(B), or it may comprise a larger number of blades, e.g. 10 or more, depending on the amount and type of mixture.  
     [0088] The number of rotations of a main motor  222  driving the main shaft  221  is set low for example to 120 rpm or less, when press-sliding is performed.  
     [0089] The gap between the bottom surface  211  of the container  21  and the base surface of the main blade  22  is set as narrow as is necessary for press-sliding the mixture, for example 15 mm or less. This distance depends on the capacity of the press-sliding mixer  2  and on the shape of the main blade, etc.  
     [0090] The surface in the motion direction (press-sliding direction) of the main blade  22  is formed so that a pressing angle θ relative to the bottom surface of the container  21  is an acute angle. For example, if the cross-section of the main blade  22  is a reverse trapezoid as shown in FIG. 9(C), the pressing angle is from 3 degrees to 70 degrees. The cross-section of the main blade  22  may also be circular or have a rounded corner as shown in FIG. 9(D).  
     [0091] The material of the main blade has wear-resistant properties, and is formed for example by thermal spraying with tungsten or carbide using SUS.  
     [0092] If a surface in a direction opposite to the motion direction (press-sliding direction) of the main blade  22  is formed for example effectively perpendicular to or at an obtuse angle to the bottom surface, the mixture  10  can be collected around the main shaft  221  by rotating the main shaft  221  in the reverse direction.  
     [0093] If there are plural bottom parts on the bottom surface  211 , the center parts of the main blade  22  are also disposed in positions of the bottom part corresponding to their number.  
     [0094] (f) Dispersing Blade  
     [0095] The dispersion blade  23  is intended to disperse the mixture  10  which has been press-slid by the main blade  22 . The dispersion blade  23  is disposed in a position at which the mixture  10  can be dispersed, and it rotates at a high speed such as 1000-4000 rpm. Due to this high speed rotation, the ion-conducting polymer  12  or its raw material coated on the particle surfaces of the powdered substance  11  uniformly disperses through the whole of the powdered substance.  
     [0096] This invention as described above, renders the following effects.  
     [0097] An electrode film that adheres well to the current-collecting member can be obtained.  
     [0098] An electrode film with low electrical resistance can be obtained.  
     [0099] A battery or double-layer capacitor with an electrode film having low electrical resistance and good bonding can be obtained.