WO2005101550A1 - 蓄電池用被覆集電体、該被覆集電体の製造方法、および被覆集電体を有する蓄電池 - Google Patents
蓄電池用被覆集電体、該被覆集電体の製造方法、および被覆集電体を有する蓄電池 Download PDFInfo
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- WO2005101550A1 WO2005101550A1 PCT/JP2004/006782 JP2004006782W WO2005101550A1 WO 2005101550 A1 WO2005101550 A1 WO 2005101550A1 JP 2004006782 W JP2004006782 W JP 2004006782W WO 2005101550 A1 WO2005101550 A1 WO 2005101550A1
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- current collector
- storage battery
- conductive
- coating
- conductive material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/68—Selection of materials for use in lead-acid accumulators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- Coated current collector for storage battery for producing the coated current collector, and storage battery having the coated current collector
- the present invention improves the conductivity of the electrodes of a storage battery, reduces the thickness of the electrodes, and improves the lightness.
- An electrode current collector that can extend the life, a method of manufacturing the current collector, and the current collector
- It relates to a storage battery.
- lead-acid batteries are relatively inexpensive and have stable performance, so they are used in all fields, including automotive and industrial applications.
- a lead storage battery uses lead as a negative electrode active material, uses lead dioxide as a positive electrode active material, and uses a sulfuric acid aqueous solution as an electrolyte.
- the electrode of the storage battery is formed by supporting the active material on an electrode terminal called a current collector.
- Lead-acid batteries use a lead alloy as the current collector, while other secondary batteries generally use nickel, iron, stainless steel, titanium, aluminum, etc. as the current collector for the positive electrode.
- zinc and force domes are used.
- the conventional 10 storage batteries have the above-mentioned structure and charging / discharging mechanism, and are low-cost and long-life batteries.However, since lead is used as an active material, the actual use People are often complained about being heavy or big. One of the factors is that the density of lead, which is the main raw material, is high. One of the factors is power factor. One of the design factors is that, for example, to extend the life of the float divided by the life of the charge / discharge cycle, it is necessary to design the current collector thicker in order to ensure that the corrosion of the positive electrode current collector, which is a lead alloy, proceeds reliably. At one point. As the electrode plate becomes thicker, the surface area of the electrode per unit volume of the storage battery (that is, the surface area of the active material layer) decreases, and the utilization rate of the active material decreases. To compensate for this, storage batteries are becoming larger and heavier.
- a copolymer or two or more resins are used as a synthetic resin which is a main component of a paint for forming a coating covering a current collector.
- the coatings in this technology are: (1) Acrylic polymer / polysiloxane mono blend, chlorosulfonated poly Ethylene Z epoxy resin-blend, chlorosulfonated biethylene acetate biel polymer zepoxy resin, blend of vinylidene fluoride / hexaphnoleo propylene copolymer, polytetrafluoroethylene, tetrafluoroethylene z perfluoro Copolymer of oral alkoxy vinyl ether, copolymer with tetrafluoroethylene and hexafluoropropylene, polyvinylidene fluoride, fluorinated dioxole polymer, fluorinated dioxole / tetrafluoroethylene monocopolymer, A film-forming binder selected from the group consisting of fluorinated dioxole, vinylidene fluoride mono-copolymer, fluorinated di
- the coating material for example, in the epoxy resin blend composition, black sulfonated polyethylene or black crosslinked sulfonated butyl acetate polymer is used as a main component. Resin is added.
- a resin coating with a powerful structure a high molecular weight ethylene-based resin, which is the main component, is used as a crosslinking agent by an epoxy resin to form a high molecular weight coating.
- a feature of the resin paint with a strong structure is that the ethylene resin easily forms a film, but on the other hand, a relatively large amount of solvent is required because the ethylene resin forming the film has a high molecular weight. This is a disadvantage.
- the resins disclosed in the above prior art such as the above (chlorosulfonated polyethylene + epoxy resin) and ataryl-based / polysiloxane-polymer blends are resins referred to as synthetic rubbers in a broad sense. Adhesion to current collector is not high. Therefore, according to the technique 1 disclosed in Japanese Patent Application Laid-Open No.
- the silane is used to secure the adhesiveness to the current collector, which is an inorganic material. Since the coating step of the coupling agent is further required, the number of manufacturing steps has to be further increased, and since the resin has a relatively high molecular weight, it is compared with a case where a uniform coating is used. It is necessary to use a very large amount of solvent, which must be removed during film formation so as not to pollute the environment, which requires more man-hours.
- JP-A-2003-155313 discloses a resin composition for forming a film having good adhesion to a metal, and discloses a secondary battery (a current collector thereof) as one application example. Have been.
- a resin component for forming a film a copolymer of vinylidene fluoride and an acrylic vinyl monomer having a small amount of an epoxy group is used.
- the vinylidene fluoride is a so-called fluoro rubber, and becomes a synthetic rubber in a broad sense by being cross-linked with acrylyl vinyl monomer as a copolymerization partner.
- the epoxy group contained in the acrylic vinyl monomer plays a role as a so-called crosslinking point monomer (crosslinking agent) when producing (crosslinking) synthetic rubber.
- Japanese Patent Application Laid-Open No. 2003-155313 also has the same problems as the technology disclosed in Japanese Patent Application Laid-Open No. 61-165958, and achieves both cost reduction and performance maintenance. It has become difficult to let.
- the present invention has been made in view of the above-mentioned conventional circumstances, and its purpose is to provide a strong and highly adhesive coating on the surface of a current collector for a storage battery such as a lead storage battery without a lot of man-hours.
- the purpose of the present invention is to prevent the current collector from corroding and to reduce the thickness of the current collector, thereby realizing an improved output per unit volume and a longer life at a low cost. Disclosure of the invention
- a paint is prepared by using a simple epoxy resin or a single phenol resin as the resin component, and a conductive material such as a carbon material is uniformly mixed with the paint and applied to the surface of the current collector to form a coating.
- a conductive material such as a carbon material
- the coating layer is made into two layers, the first layer is made by uniformly mixing a carbon material such as carbon or black bell as the conductive material, and the second layer is made by uniformly mixing tin dioxide as the conductive material. It was also confirmed that the overcharge life could be further improved.
- the current collector for a storage battery according to the present invention comprises at least a current collector body made of an inorganic conductive material and a conductive film formed on the surface of the current collector body, wherein the conductive film is It is characterized in that the conductive material is composed of an epoxy resin dispersed uniformly.
- Another configuration of the current collector for a storage battery according to the present invention includes at least a current collector body made of an inorganic conductive material and a conductive film formed on a surface of the current collector body. The coating is made of a phenolic resin in which a conductive material is uniformly dispersed.
- a carbon material such as graphite or carbon as the conductive material.
- the conductive film may have a two-layer structure, a carbon material may be used as a conductive material for the first layer directly in contact with the current collector, and tin dioxide may be used as the conductive material for the second layer.
- the method for producing a skin-covered current collector for a storage battery according to the present invention comprises the steps of: adding a conductive material to an epoxy-based resin coating; stirring uniformly to prepare a uniform conductive coating;
- the present invention is characterized in that a coated current collector is obtained by coating the surface of a current collector body made of an inorganic conductive material and curing the obtained coating film.
- Another method of manufacturing a coated current collector for a storage battery according to the present invention is to add a conductive material to a phenolic resin coating and uniformly stir to prepare a uniform conductive coating.
- the present invention is characterized in that a coated current collector is obtained by coating the surface of a current collector body made of a conductive material and hardening the obtained coating film.
- the second conductive coating film is further dispersed in the same coating material with another conductive material uniformly dispersed in the second conductive film.
- the second coating film may be formed by applying a coating material and curing the second coating film.
- a carbon material such as graphite or carbon
- the conductive film has a two-layer structure, it is preferable to use a carbon material as the conductive material of the first layer and to use tin dioxide as the conductive material of the second layer.
- a storage battery according to the present invention is characterized by having the above-mentioned coated current collector as a current collector.
- a strong and highly adhesive coating is formed on the surface of the current collector without much man-hours, thereby preventing corrosion of the current collector and collecting the current.
- FIG. 1 is a plan view of a conventional current collector
- FIG. 2 is an explanatory view of a method for measuring a specific resistance value of a coating of a coated current collector according to the present invention
- FIG. 4 is a graph showing the relationship between the amount of carbon added to the coating of the coated current collector according to the present invention and the specific resistance of the coating
- FIG. 6 is an explanatory view of a method for measuring the adhesive strength of the coating of the coated current collector according to the present invention.
- FIG. 7 is a graph showing the relationship, FIG.
- FIG. 7 is a diagram showing a laminated configuration of a coated current collector according to the present invention having a two-layer structure film
- FIG. FIG. 3 is a graph showing the overcharge life of the storage battery of FIG. BEST MODE FOR CARRYING OUT THE INVENTION
- the coated current collector for a storage battery of the present invention includes at least a current collector body made of an inorganic conductive material and a conductive film formed on the surface of the current collector body, wherein the conductive film is made of a conductive material. It is characterized by being composed of epoxy resin dispersed uniformly.
- another configuration of the current collector for a storage battery according to the present invention includes at least a current collector body made of an inorganic conductive material and a conductive film formed on a surface of the current collector body.
- the conductive film is made of a phenolic resin in which conductive materials are uniformly dispersed.
- epoxy resin examples include the following.
- glycidyl ether type Z bifunctional phenol type epoxy resins include bisphenol type epoxy resin, stilbene type epoxy resin, biphenyl type epoxy resin, monocyclic aromatic epoxy resin, condensed polycyclic aromatic resin
- Glycidyl ether type z Polyfunctional phenol type epoxy resin such as epoxy resin, polyphenol type epoxy resin, phenol nopolak type epoxy resin, methylene group »phenol novolak type epoxy resin, alkylene modified phenol nopolak type epoxy resin
- Aliphatic epoxy resins, such as aralkyl-modified phenol novolak type epoxy resins can be used for alicyclic epoxy resins by direct oxidation, and for glycidyl etherification of functional groups.
- modified epoxy resins such as alicyclic epoxy resins, dichloropentadiene-type epoxy resins, on-chain aliphatic epoxy resins, silicone-modified epoxy resins, urethane-modified epoxy resins, polyimide and polyamide-modified epoxy resins, and optical Other than the curable epoxy resin and the like, a phosphorus-containing epoxy resin, a sulfur-containing epoxy resin, a nitrogen-containing epoxy resin, and the like can be given.
- the hydrogenated epoxy resin include a hydrogenated bisphenol A type epoxy resin, a hydrogenated bisphenol F type epoxy resin, and the like, preferably a bisphenol type, and more preferably a bisphenol A type.
- the bisphenol-type epoxy resin has an ether bond in the main chain and has a hydroxyl group as a side chain. Ether bonds contribute to the improvement of acid resistance, and hydroxyl groups improve the adhesion to inorganic materials.
- phenolic resin examples include a phenol-formaldehyde resin, a phenol.furfural resin, a resorcin-formaldehyde resin, and the like, and a phenol-formaldehyde resin is preferable. This is due to good adhesion.
- the carbon material that is uniformly dispersed in the coating and used as the conductive material for ensuring the conductivity of the coating may be any carbon material as long as it is a carbon material.
- Specific examples include carbon particles, graphite particles, and the like, and preferred are carbon particles and graphite particles. This is because these are optimal in consideration of ensuring the conductivity of the current collector film.
- carbon particles carbon black is preferable. This is because the particle size is small and easy to obtain. If the particle size is small, it is possible to incorporate a larger amount into the resin paint. These may be used alone or in combination of carbon particles and graphite particles, but the combination is more preferable.
- the particle size of the carbon particles and graphite particles is not particularly limited, but the smaller the particle size, the more preferable the surface area of the carbon particles as a whole, thereby improving the conductive properties between the particles.
- Solvents in this case include, for example, acetone and methyl.
- examples include rutile ketone, methyl isobutyl ketone, ethyl alcohol, and the like, and preferred are ketone solvents such as methinoleethynoleketone and methylisobutinoleketone, and more preferably methinoleethyl ketone.
- the amount of the solvent can be appropriately adjusted so as to be suitably used as a paint. ,
- the conductive paint for film formation in the present invention may further contain a dispersant.
- the dispersant include a vinyl resin—a polyamino acid amidoamine resin and a polypyrrolidone.
- a resin having a higher molecular weight is preferable. This is because the high molecular weight resin has better dispersibility and the durability of the resin is better.
- the mixing amount of the dispersant is preferably 0.1 to 20% by mass based on the total mass of the carbon to be mixed. If the amount is less than 0.1% by mass, no effect is observed, and if the amount exceeds 20% by mass, the effect corresponding to the compounding amount cannot be observed.
- the conductive paint for forming a film in the present invention may further contain barium sulfate, lignin, and more preferably ligninsulfonic acid. By containing these, metal aggregation is suppressed.
- the combination amount of barium sulfate, lignin, and ligninsulfonic acid is preferably 0.1 to 5% by mass based on the total mass of the metal to be mixed. If the content is less than 0.1% by mass, no effect is observed, and if it exceeds 5%, the effect corresponding to the composition cannot be obtained.
- the amount of the conductive material to be added is preferably 20 to 60% by mass of the total solid content of the paint. When the amount is less than 20% by mass, no effect is recognized, and when the amount exceeds 60% by mass, the effect corresponding to the composition cannot be recognized.
- the current collector body is preferably in a sheet shape or a film shape.
- the current collector body is made of a lead alloy, and its thickness is preferably adjusted to 0.05 mm to 1 mm.
- the conductive film may have a two-layer structure, a carbon material may be used as a conductive material for the first layer directly in contact with the current collector, and tin dioxide may be used as the conductive material for the second layer. Yes.
- the method of manufacturing a coated current collector for a storage battery comprises the steps of: adding a conductive material to an epoxy resin coating; stirring uniformly to prepare a uniform conductive coating; and converting the conductive coating to an inorganic conductive coating.
- the present invention is characterized in that a coated current collector is obtained by applying it to the surface of a current collector body made of a material and curing the obtained coating film.
- a phenolic resin paint is used as a paint
- a conductive material is similarly added to the phenolic resin paint and uniformly stirred to prepare a uniform conductive paint, and the conductive paint is made of an inorganic conductive material.
- a coated current collector can be obtained by applying the composition on the surface of the current collector body and curing the obtained coating film.
- the conductive film of the second layer is further coated with the same coating material as another conductive material. Is formed by applying a second conductive coating material in which is dispersed uniformly and curing the second coating film. If the conductive film has a two-layer structure, use carbon material for the conductive material of the first layer and tin dioxide for the conductive material of the second layer! / Puru.
- the method for producing a coated current collector according to the present invention is characterized in that a conductive paint having the above-mentioned composition is applied to the current collector, and dried and cured. The drying is preferably performed at a temperature 20 ° C.
- a second heat treatment is preferably performed in order to further completely remove the solvent.
- the thickness of the coating is preferably from 0.01 to 1 mm, more preferably from 0.05 to 0.5 mm. If it is less than 0.01 mm, it will not be possible to disperse a sufficient amount of conductive material to ensure conductivity.If it exceeds 1 mm, the current collector protection function will be sufficient, This is because the effect of thinning is lost.
- a storage battery according to the present invention is characterized in that the coated current collector is used as a current collector.
- an aqueous solution of sulfuric acid is used as an electrolyte.
- the specific gravity of the aqueous sulfuric acid solution is preferably from 1.2 to 1.4. It is for capacity maintenance and life balance.
- the lead-acid battery obtained by using the coated current collector for a storage battery of the present invention as a lead-acid battery can be applied to all the uses of lead-acid batteries so far.
- the basic deterioration when using float charging is corrosion of the positive electrode current collector, and the storage battery according to the present invention has a form in which countermeasures are taken from the front against the conventional deterioration when using float.
- a thin electrode is used, it is desirable to lower the float charging voltage a little, because a large float charging current is likely to flow during constant voltage charging with float charging.
- the typical deterioration when the storage battery was used in the charge / discharge cycle was due to the corrosion of the positive electrode current collector and the breakage of the electrical connection between the positive electrode active materials.
- the corrosion of the current collector can be solved by using the coated current collector of the present invention.
- the inferior dwelling caused by the rupture of the electrical connection between the active materials due to repeated charging and discharging of the other one can actually be greatly improved by using the coated current collector of the present invention. I have.
- P B_ ⁇ 2 reaction odor Te as a cathode active material is varied between P b 0 2 and P b S_ ⁇ 4.
- the active material dissolves in the form of lead ions and then precipitates again. It is said to go through. Therefore, the electrical connection between the active materials is broken as the number of times of charge / discharge increases. As a result, the resistance between the active materials increases, and the capacity of the storage battery is hardly increased.
- FIG. 1 shows the shape of a conventional grid-like current collector.
- the rectangular grid of the grid-like current collector is carried by being filled with an active material.
- This active material is a reactant, but the active material layer also serves as a conduction path for the discharged electrons.
- the electrical resistance in the active material layer increases due to disconnection of the active material in the active material layer due to repeated charging and discharging, the voltage drop increases, and the electric capacity that can be taken out of the storage battery decreases.
- the current collector body is formed in a sheet shape, and as described above, a conductive dense film is formed on the surface thereof.
- the active material can be thinly applied to this film.
- the active material is in contact with the conductive particles of the coating and is collected through the coating. Electrons can be conducted to electric conductors.
- the active material only functions as a pure discharge material, and does not need to have an electronic conduction function. It is possible to maintain the specified capacity.
- That lead alloy having a composition A 1 mm-thick rolled sheet was degreased and washed, then immersed in a mixed solution of acetic acid and hydrogen peroxide to wash the surface, and then dried.
- a bisphenol-type epoxy resin was used as a resin component of the coating material for coating the surface of the thin sheet-shaped current collector body.
- Nagase ChemteX Co., Ltd. uses a bisphenol-type epoxy resin (product number: XNR3114) manufactured by Nagase ChemteX Corporation.
- the curing agent is an epoxy curing agent manufactured by Nagase ChemteX Corporation (product number: XNH314). Was used.
- a curing agent for resin methyl ethyl ketone was used as a solvent, and a vinyl dispersant was added to form a paint.
- Graphite having a particle size of about 2 to 10 ⁇ m was used as a conductive material to be added to this paint.
- the graphite particles were mixed with an epoxy resin diluted with methyl ethyl ketone, and then a curing agent was added, followed by uniform mixing using a mill. After applying the uniformly dispersed paint to the current collector body, the temperature was raised to 70 ° C. to vaporize methyl ethyl ketone and cure the epoxy resin. The curing time was one hour. The thickness of the coating was 20 ⁇ m.
- Fig. 2 shows the method of measuring the electrical resistance at this time.
- a copper plate 3, 3 is pressed from the outside of each of the graphite-added epoxy resin coatings 2, 2 on both sides of a current collector body 1 made of a lead alloy sheet, and a resistance (not shown) is applied to these copper plates 3, 3.
- the positive and negative terminals of the meter were applied, and the and resistance (resistivity) were measured.
- the obtained measured value is compared with the previously measured surface electric resistance value (specific resistance value) of the current collector body 1 before coating, and the resistance of the graphite-added epoxy resin film is determined from the difference between the two. Values were calculated.
- Table 1 below. Further, the data in Table 1 was graphed as shown in FIG.
- a conductive film was formed on the current collector main body in the same manner as in Example 1, except that carbon powder was used as the conductive material instead of the graphite particles.
- carbon powder a product having a surface area of 80 O m 2 Z g was used.
- the electrical resistance of the coating in each of the samples thus obtained was measured in the same manner as in Example 1.
- the obtained measured value is compared with the previously measured surface electric resistance value (specific resistance value) of the current collector body 1 before coating, and the resistance value of the graphite-added epoxy resin coating is determined from the difference in resistance between the two. Was calculated.
- the results are shown in Table 2 below. Further, the data in Table 2 was graphed as shown in FIG.
- the specific resistance of the epoxy resin coating decreases as the proportion of carbon powder added increases.
- a sharp decrease was observed while the addition ratio of the graphite particles shifted from 20% by mass to 30% by mass. 20 mass% In the case of 0.5% OQ cm, it decreased to 0.20 Q cm at 30% by mass.
- the resistivity decreases even after the addition ratio of the graphite particles exceeds 30% by mass. The rate of the decrease in the force becomes fairly moderate, and when it exceeds 50% by mass, the resistivity decreases little.
- the adhesiveness to the current collector body was examined by changing the addition ratio of graphite particles in the epoxy resin paint.
- the ends of the two current collector bodies 1 and 1 are bonded to each other by forming a coating 4 between the ends using an epoxy resin paint containing graphite.
- the bow I tension test was performed.
- the method of hardening the epoxy resin paint is the same as in the above embodiment.
- An adhesive sample was prepared by changing the graphite particle addition ratio of the coating 4 to 10, 30, 40, 50, 60, and 80% by mass.
- Table 3 shows the measurement results of the tensile test. Further, the data in Table 3 was graphed as shown in FIG.
- the adhesive strength of the epoxy resin coating to the lead alloy (current collector body) decreases. At 50% by mass, the adhesive strength (tensile strength) becomes 30 ON / cm 2 , and at 60% by mass, it further decreases to 150 N / cm 2 and at 80% by mass, 100 N / cm 2 cm 2 .
- the proportion of graphite to be added is preferably 30% by mass or more from the viewpoint of specific resistance, and is preferably 60% by mass or less from the viewpoint of adhesive strength. From the viewpoint of satisfying both, the graphite addition ratio is preferably from 30 to 60% by mass.
- the thickness of the current collector main body was set to lmm in order to evaluate the specific resistance of the coating and the adhesive force of the coating to the current collector main body.
- the current collector body (lead alloy sheet) of the positive electrode was made 0.3 mm thick.
- a graphite-added epoxy resin paint was prepared on the current collector body in the same manner as in each of the above-mentioned examples, and applied to the current collector.
- the graphite addition ratio was determined to be 50, 60 and 70% by mass based on the solid content of the paint after drying. This was applied on both sides of the current collector body to a thickness of 20 ⁇ , dried and cured after application to form a film.
- the paste obtained by plastering lead oxide and dilute sulfuric acid as active materials was applied to the thus-obtained coated current collector to form a positive electrode.
- the thickness of the applied paste was 0.3 mm on one side.
- the obtained positive electrode was immersed in dilute sulfuric acid having a specific gravity of 1.05 for 1 second.
- the current collector body of the negative electrode (98.34 mass 0/0 lead one 0.06 wt% calcium one 1.6% by weight of tin) a composition consisting of lead alloy 0. 2 mm thick
- the rolled sheet was immersed in a mixed solution of acetic acid and hydrogen peroxide to wash the surface, and then dried.
- a paste obtained by mixing a lead oxide as an active material and additives such as dilute sulfuric acid oxide expander was applied to the current collector body to form a negative electrode. The thickness of the applied paste was set to 0.2 mm. Thereafter, the obtained negative electrode was immersed in dilute sulfuric acid having a specific gravity of 1.05 for 1 second, and then dried naturally.
- a separator made of glass fiber having an average diameter of 0.1 ⁇ m was laminated between the positive electrode and the negative electrode while applying a pressure of 100 kg / cm 2 . Fifteen positive electrodes and sixteen negative electrodes were used. The electrode group was placed in a battery case, diluted sulfuric acid was injected, and the battery was charged for the first time to obtain a storage battery. The specific gravity of the electrolyte during injection was adjusted so that the specific gravity of the electrolyte after the completion of the first charge was 1.320.
- the storage battery obtained as described above was discharged at 0.1 ° and 2 ° at 25 ° C.
- C is a number indicating a 10-hour rate rated capacity value.
- 0-1 CA is equivalent to about 10 hour rate
- 2 CA is equivalent to 10 minute rate discharge.
- Table 4 shows the coating composition of the positive electrode of the storage battery and the results of the discharge test.
- Table 4 shows comparative examples (sample numbers). No. 4) shows the measured value of a conventional storage battery without a coated current collector for the positive electrode.
- the 0.1 CA discharge capacity did not differ greatly between the three types of storage batteries, but the 2 CA discharge capacity was 20 mass% of graphite particles added. /.
- the storage battery using the current collector having the above-mentioned coating was inferior. This is because the electrical resistance of the epoxy resin film was large. Nevertheless, the capacity was higher than that of the conventional battery.
- a coated current collector was prepared in the same manner as in Example 4 except that the graphite particles were added at 50, 60, and 80% by mass, and a storage battery using the coated current collector as a positive electrode current collector was prepared. It was created.
- an epoxy resin film 5 containing 50% by mass of graphite was formed on the surface of the current collector body 1, and a further 70% by mass of tin dioxide was coated on the outside of the film 5.
- the containing / dispersed epoxy resin film 6 was formed to form a current collector having a two-layer structure film, and a storage battery using this coated current collector as a current collector for the positive electrode was also prepared.
- a storage battery with a conventional structure was added to these, and the float life performance was evaluated.
- a paste-type electrode plate using a grid-like current collector, a control valve storage battery having a thickness of 3.3 mm, and having an electrolyte specific gravity of 1.320 was used.
- the life of the battery was determined to be less than 70% of the initial capacity, the life of the conventional battery reached about 50,000 hours. This corresponds to 100 CAh. In other words, it survived an overcharge of 100 times the rated capacity.
- the storage battery of the present invention was able to maintain a normal capacity from 700,000 to 1,300,000 hours or more. This corresponds to 140 to 260 C Ah or more.
- the service life is about twice that of the conventional battery.
- the storage battery with a high proportion of graphite in the epoxy coating has a low adhesion to the current collector, and the black bell particles are oxidized and consumed by oxygen due to overcharge. The service life was rather short.
- the initial capacity was slightly lower due to the high resistance, but the durability of the coating was good, so the capacity decreased during the life test. The proportion was small.
- the initial capacity of a storage battery using a current collector in which an epoxy resin film containing dioxin tin is further formed on the outside of an epoxy resin film containing black tin as the current collector of the positive electrode is also long.
- the change in capacity during the test was also excellent. This is because tin dioxide suppresses graphite consumption.
- the storage battery of the present invention was able to obtain overcharge life performance higher than that of the conventional battery, despite having extremely thin electrodes than the conventional battery. Furthermore, the storage battery using a current collector with a two-layered film has twice the life of the conventional product despite its electrode thickness being about 1/4 thinner than the conventional product. This is due to the improvement in the corrosion resistance of the current collector.
- a feature of the present invention is that the surface of the current collector used for the positive electrode is covered with an epoxy resin in which graphite is uniformly dispersed, or the outside of the epoxy resin film is further covered with an epoxy resin film in which tin dioxide is dispersed. This drastically reduces the current collector corrosion and ensures long-term stability of the battery life.
- the current collector body was made of a lead alloy sheet, and an epoxy resin coating material to which graphite was uniformly added was applied to the lead alloy sheet, followed by hardening to form a film.
- the suppression of corrosion is due to the effects of black bell and epoxy resin, and it is also possible to form a long-life battery by forming a similar coating on the surface of a conventional grid-like current collector.
- the current collector body is not limited to a sheet.
- the coating has a two-layer structure
- tin dioxide is used as the conductive material of the outer coating
- a conductive metal oxide other than tin dioxide can be used as a material for suppressing the oxidation of graphite.
- the epoxy resin is used as the resin component of the paint for forming the coating film.
- the same effect can be obtained by using a phenol resin instead of the epoxy resin. .
- the storage battery using the coated current collector according to the present invention since the storage battery using the coated current collector according to the present invention has a long service life, is inexpensive, and has a very high utilization rate, the hybrid use of the engine and the storage battery in an automotive application or the like is required. First, it is also effective in reducing the size and weight of conventional lead-acid batteries. In addition, it can be used as a power source for portable devices that use lithium-ion batteries, taking advantage of its cost advantages.
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- Cell Electrode Carriers And Collectors (AREA)
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JP2004-107186 | 2004-03-31 | ||
JP2004107186A JP2005294024A (ja) | 2004-03-31 | 2004-03-31 | 蓄電池用被覆集電体、該被覆集電体の製造方法、および該被覆集電体を有する蓄電池 |
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WO2005101550A1 true WO2005101550A1 (ja) | 2005-10-27 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9786919B2 (en) | 2012-05-15 | 2017-10-10 | Uacj Corporation | Current collector, electrode structure, nonaqueous electrolyte battery and electrical storage device, and method for producing current collector |
EP3422442A4 (en) * | 2016-02-24 | 2019-03-13 | Nissan Motor Co., Ltd. | ELECTRODE FOR A LITHIUM ION SECONDARY BATTERY AND METHOD OF MANUFACTURING THEREOF |
WO2022070791A1 (ja) * | 2020-09-30 | 2022-04-07 | 古河電気工業株式会社 | バイポーラ型鉛蓄電池 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2008114738A1 (ja) * | 2007-03-15 | 2010-07-01 | 株式会社ジーエス・ユアサコーポレーション | 鉛蓄電池および組電池 |
JP5386900B2 (ja) * | 2008-09-18 | 2014-01-15 | 日産自動車株式会社 | 有機構造体を含む双極型リチウムイオン二次電池用集電体 |
CN102324492B (zh) * | 2011-05-25 | 2013-11-27 | 深圳市金钒能源科技有限公司 | 复合导电电极及其制造方法 |
JP7098558B2 (ja) * | 2018-09-19 | 2022-07-11 | 株式会社東芝 | 電極、二次電池、電池パック、車両、及び、定置用電源 |
JP7085142B2 (ja) * | 2018-12-26 | 2022-06-16 | トヨタ自動車株式会社 | リチウムイオンキャパシタ |
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JPS5760663A (en) * | 1980-09-29 | 1982-04-12 | Shin Kobe Electric Mach Co Ltd | Manufacture of lead battery electrode plate |
JPH0528988A (ja) * | 1991-07-23 | 1993-02-05 | Shin Kobe Electric Mach Co Ltd | 鉛蓄電池用極板の製造方法 |
JPH06231750A (ja) * | 1992-09-07 | 1994-08-19 | Kiyoji Sawa | 密閉型電池 |
JPH08153499A (ja) * | 1994-02-07 | 1996-06-11 | Seiko Instr Inc | アルカリ電池 |
JPH0997625A (ja) * | 1995-09-29 | 1997-04-08 | Seiko Instr Inc | 非水電解質二次電池およびその製造方法 |
JP2002203562A (ja) * | 2000-12-28 | 2002-07-19 | Toshiba Corp | 非水電解質二次電池 |
Family Cites Families (1)
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JP2644470B2 (ja) * | 1996-07-19 | 1997-08-25 | ヤンマー農機株式会社 | 田植機の苗植装置 |
-
2004
- 2004-03-31 JP JP2004107186A patent/JP2005294024A/ja active Pending
- 2004-05-13 WO PCT/JP2004/006782 patent/WO2005101550A1/ja active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS5760663A (en) * | 1980-09-29 | 1982-04-12 | Shin Kobe Electric Mach Co Ltd | Manufacture of lead battery electrode plate |
JPH0528988A (ja) * | 1991-07-23 | 1993-02-05 | Shin Kobe Electric Mach Co Ltd | 鉛蓄電池用極板の製造方法 |
JPH06231750A (ja) * | 1992-09-07 | 1994-08-19 | Kiyoji Sawa | 密閉型電池 |
JPH08153499A (ja) * | 1994-02-07 | 1996-06-11 | Seiko Instr Inc | アルカリ電池 |
JPH0997625A (ja) * | 1995-09-29 | 1997-04-08 | Seiko Instr Inc | 非水電解質二次電池およびその製造方法 |
JP2002203562A (ja) * | 2000-12-28 | 2002-07-19 | Toshiba Corp | 非水電解質二次電池 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9786919B2 (en) | 2012-05-15 | 2017-10-10 | Uacj Corporation | Current collector, electrode structure, nonaqueous electrolyte battery and electrical storage device, and method for producing current collector |
EP3422442A4 (en) * | 2016-02-24 | 2019-03-13 | Nissan Motor Co., Ltd. | ELECTRODE FOR A LITHIUM ION SECONDARY BATTERY AND METHOD OF MANUFACTURING THEREOF |
WO2022070791A1 (ja) * | 2020-09-30 | 2022-04-07 | 古河電気工業株式会社 | バイポーラ型鉛蓄電池 |
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JP2005294024A (ja) | 2005-10-20 |
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