WO2008075514A1 - 二次電池用負極活物質 - Google Patents
二次電池用負極活物質 Download PDFInfo
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- WO2008075514A1 WO2008075514A1 PCT/JP2007/071971 JP2007071971W WO2008075514A1 WO 2008075514 A1 WO2008075514 A1 WO 2008075514A1 JP 2007071971 W JP2007071971 W JP 2007071971W WO 2008075514 A1 WO2008075514 A1 WO 2008075514A1
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- active material
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- carbon
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- secondary battery
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- the present invention relates to a negative electrode active material for a secondary battery that has a high energy density and can be manufactured at low cost.
- a conventional lead storage battery has a manufacturing method in which dilute sulfuric acid is added to an active material raw material called lead powder obtained by oxidizing lead to form a paste, and this paste is filled in a grid-shaped current collector. It is common. Then, by forming this, the positive electrode contains an active material called lead dioxide and the negative electrode contains spongy lead. These active materials change to lead sulfate (discharge active material) when the battery is discharged. Since the volume increases with the change to the discharge active material, the pores of the porous structure in the active material become smaller, making it difficult to diffuse the electrolyte into the active material.
- lead acid batteries are preferable in that the raw material is inexpensive, the usage rate of lead is inevitably increased due to the low utilization rate of the active material, and as a result, the weight of lead with a high density is not enough. Furthermore, the energy density decreases and increases! The current energy density of lead-acid batteries is insufficient for hybrid and electric vehicles and cannot be used.
- Patent Documents 1 and 2 are conventional techniques for lead-acid batteries.
- Patent Document 1 discloses a method for producing a lead-acid battery anode plate having high conversion efficiency and high capacity and long life. Specifically, an outer active material paste layer in which tribasic lead sulfate, red lead and water (or sulfuric acid) are kneaded and filled is mixed with lead red and water on the inner active material paste layer. This is a manufacturing method in which an undried electrode plate is produced and dried to be formed.
- Patent Document 2 for the purpose of extending the life of the lead battery, lead powder, 13% by weight dilute sulfuric acid with respect to the lead powder, 12% by weight water with respect to the lead powder, 0 to; 0.3% by weight of DBP oil absorption of 100 to 300ml / 100g of amorphous carbon and / or 0.4 to 0.6% by weight of lignin sulfone for lead powder Disclosed is a negative electrode paste prepared by adding and kneading sodium acid.
- Patent Document 1 Japanese Patent Laid-Open No. 6-76815
- Patent Document 2 JP 2002-63905 A
- Patent Documents 1 and 2 are mainly aimed at extending the life of lead-acid batteries, and aiming to reduce the utilization rate of the active material as much as possible while realizing a longer life. Therefore, in the techniques of Patent Documents 1 and 2, the utilization factor of the active material is at most the current level, and the utilization factor of the active material exceeding 70%, which can obtain high energy density, is not realized.
- the main cause of the low energy density of lead-acid batteries is an increase in electrical resistance. Therefore, the utilization rate cannot be increased to 70% or more. In addition, the utilization rate is further reduced in the usage mode in which a large current is discharged. In addition, the utilization rate and life of active materials are said to have a trade-off. In other words, there is a fatal problem that the charge / discharge cycle life decreases when the utilization rate is increased.
- an object of the present invention is to provide a storage battery, that is, a secondary battery, capable of obtaining a high energy density using a raw material having a cost comparable to that of a lead storage battery. More specifically, an object of the present invention is to provide a negative electrode active material for a secondary battery in which the utilization factor of the active material is improved with a low-cost raw material for the negative electrode plate of the secondary battery.
- the present invention provides the following configuration.
- a negative electrode active material for a secondary battery according to claim 1 is an active material raw material containing a metal and an oxide of the metal, and a carbon having an amount of total oil absorption of 4.7 ml or more per mole of the active material raw material. containing the door, and that the kneaded product was 7 X 10_ 2 moles the amount of the sulfuric acid radical relative to active substance material 1 mol when containing or sulfate group containing no sulfate ion Features.
- a negative electrode active material for a secondary battery according to claim 2 is in an unformed state after the negative electrode active material for secondary battery is filled in a grid-shaped current collector and dried in claim 1.
- the bulk density is 2.2 X 1CT 1 ml / gram or more and 5 X 1CT 1 ml / gram or less.
- a negative electrode active material for a secondary battery according to claim 3 is characterized in that, in claim 1 or 2, the carbon is acetylene black.
- Negative-electrode active material for a secondary battery according to claim 4 in claim 3, in a weight ratio to said acetylene bra click with 5 X 10_ 2 or more, solubility in water at 20 ° C
- the negative electrode active material for a secondary battery according to claim 5 is the carbon of any one of claims 1 and 2. It is a kneaded material in which the carbon is furnace carbon and the carbon is contained at a ratio of 1.27 mol or less with respect to 1 mol of the active material raw material.
- the negative electrode active material for a secondary battery according to claim 6 is the kneaded material further containing silicic force according to any one of claims 1 to 5.
- a negative electrode active material for a secondary battery according to claim 7 is the first negative electrode active material produced in the first kneading step according to claim 1 or 2, wherein the carbon is kneaded with polybutyl alcohol and water or dilute sulfuric acid. It is a second kneaded product produced in a second kneading step in which the active material raw material is added to the kneaded product of 1 and further kneaded.
- the negative electrode active material for a secondary battery according to claim 8 is characterized in that in claim 7, silica is further added and kneaded in the first kneading step.
- the electrolytic solution dilute sulfuric acid
- the active material in order to improve the utilization rate of the negative electrode active material for secondary batteries, a configuration in which the electrolytic solution (dilute sulfuric acid) and the active material can be sufficiently in contact with each other and the electrical resistance is not increased is realized.
- a conductive network is formed in the negative electrode plate, and the network has innumerable holes for supporting the electrolyte, thereby increasing the bulk density of the negative electrode plate.
- the porosity the amount of the electrolyte present in the negative electrode plate is increased, and by allowing the electrolyte to permeate and diffuse from the outside of the negative electrode plate, the electrolyte is more effective against the active material. It was configured so that it could be supplied sufficiently.
- the total oil absorption amount of carbon with respect to 1 mol of the active material raw material should be 4.7 ml (milliliter) or more.
- a particle chain structure substance is a substance in which a plurality of particulate substances are fused together and extend in a chain as a whole.
- Such carbon is dispersed in water or dilute sulfuric acid, and lead powder as an active material raw material is added thereto and kneaded to prepare a negative electrode active material as a paste-like kneaded material.
- the bulk density is 2.2 X 10— Top, SX
- an active material source is formed on a conductive network formed of carbon.
- the lead powder which is a material, is distributed almost uniformly and placed in the network.
- Carbon which is a particle chain structure material, is entangled vertically and horizontally to form a network, and at the same time forms numerous pores to form a porous structure. These holes can hold a sufficient amount of electrolyte. In addition, good conductivity can be maintained with carbon.
- the dilute sulfuric acid retained in these holes is continuously supplied to the dispersed active material raw material. As a result, the conductive network can prevent a sudden increase in electrical resistance immediately before the end of discharge.
- silica is not electrically conductive, silica can also form a porous structure having an oil absorption equivalent to that of carbon. Therefore, even if a part of carbon is replaced with silica, absorption and diffusion of the electrolytic solution are not required. The same effect can be obtained.
- the silica content was increased by increasing the silica content with the same silica and carbon oil absorption amount, and the carbon content was decreased by the same amount, but the contribution to the utilization rate was measured. It is only necessary to obtain a desired amount of oil absorption and secure a porous structure.
- the active material composed of a small particle diameter / active material raw material facilitates discharge and improves the active material utilization rate during discharge. If containing sulfate group, a 7 X 10_ 2 moles or less relative to the raw active material 1 mole the amount of the sulfate group.
- the sulfate radical is generally used as a kneading medium in producing a kneaded product of the negative electrode active material! /, Derived from dilute sulfuric acid.
- the particle size of the lead oxide-containing particles of the active material raw material contained in the produced negative electrode active material can be reduced as compared with the conventional case, so that the diffusion of the electrolytic solution into the active material is prevented. It is stable and discharge proceeds smoothly. As a result, it was possible to achieve a significant improvement in the active material utilization during discharge.
- particles of lead powder particles that 75% to 80% of one particle is oxidized and the portion near the center remains in an unoxidized state when viewed microscopically
- a particle size of about l ⁇ m it is a very weak force.
- lead oxide partial force changes to basic lead sulfate (3PbO'PbSO ⁇ ⁇ ⁇ ).
- the particle size is further increased by adding an aging step. Sulfuric acid in the kneaded product By restricting the roots, the amount of tribasic lead sulfate formed is reduced or eliminated, so the lead oxide-containing particles of the active material are kept small overall.
- the inclusion of the particle chain structure material improves the porosity of the negative electrode active material to promote the supply of the electrolyte solution, and limits the sulfate radical in the paste kneaded product.
- the utilization rate of the negative electrode active material can exceed 70%, which has been the theoretical limit. If the conventional low-rate discharge utilization rate is 40%, the utilization rate is nearly doubled. Similarly, even in high rate discharge, an improvement of about 2 times was observed.
- acetylene black is preferable because it has a higher utilization rate than furnace carbon.
- polybulual alcohol exhibits an effect as a dispersant for the kneaded material while ensuring the conductivity of carbon, and can also improve the adhesion of the negative electrode paste to the electrode plate.
- acetylene black was used as carbon, 5 X 10- 2 or more solubility 20 ° C with 4 X 10- 1 that benefit less contain a polyvinyl alcohol kneaded with water in Weight ratio of acetylene black Is preferred. Since such polybulal alcohol is relatively inexpensive, a higher active material utilization rate can be obtained than before without increasing the material cost.
- carbon (sometimes partly silica) is added to the negative electrode active material, and polybutyl alcohol is preferably dispersed as a dispersant, and the paste in a state where the sulfate radical is restricted.
- the utilization rate of the active material could be greatly improved by using a kneaded material in the form of a kneaded product.
- the lead powder which is an active material raw material required to exhibit the desired battery capacity, is about 1/2 of the conventional amount. Is possible.
- the negative electrode active material for secondary batteries according to the present invention (abbreviated as “negative electrode active material” or “active material”) is substantially intended for lead-acid batteries.
- the negative electrode active material is a paste-like kneaded product in which the active material raw material is the main component and other necessary components are added.
- the kneaded product is filled into a negative electrode plate, which is a grid-like current collector, and dried (unformed state). Thereafter, the negative electrode plate is incorporated into a storage battery, and a conversion process is performed to complete a lead storage battery.
- the kneaded material which is the negative electrode active material, contains an active material raw material containing a metal and an oxide of the metal, and a strong bond.
- the active material material is lead powder.
- Carbon shall be in such an amount that the total oil absorption is 4.7 ml or more per mole of active material raw material.
- Total oil absorption amount is the total oil absorption amount of carbon in the carbon content per mole of active material raw material in relation to the relative content of carbon contained in the active material and active material raw material ( The details are shown in the calculation formula described later), which is different from the DBP oil absorption, which is an indicator of carbon characteristics.
- water alone ie, no dilute sulfuric acid is used
- dilute sulfuric acid is used.
- the bulk density is 2.2 X 10-nl / g or more in an unformed state after being filled in a grid-like current collector and dried. 5 X 10—iml / g or less.
- acetylene black or furnace carbon can be used, and these may be used in combination.
- the acetylene black yielded a higher active material utilization than the furnace carbon.
- the active material utilization rate was higher than before by adding 1.27 mol or less to 1 mol of the active material raw material.
- polykal alcohol PVA
- Polybutal alcohol is added for the purpose of improving the dispersibility of carbon or the like, but also contributes to increasing the adhesion strength when the kneaded product is filled in a grid-like current collector.
- the negative electrode active material according to the present invention is produced by the following production process (specifically, a kneaded material production process).
- a kneaded material production process carbon is kneaded with polybutyl alcohol and water or dilute sulfuric acid to produce a first kneaded product.
- an active material raw material is added to the first kneaded material and further kneaded to produce a second kneaded material.
- the obtained second kneaded material is the negative electrode active material.
- Conventional negative electrode active materials have not been kneaded in such two steps.
- a negative electrode active material having a suitable bulk density could be obtained through two kneading steps.
- the first kneading step can be replaced by means such as stirring and mixing.
- the utilization rate of the negative electrode active material according to the present invention is such that when a grid-like current collector is used, a 40-hour rate release Electricity (low rate discharge) was about 70%, and 10 minute rate discharge (high rate discharge) was about 40%. In all discharge rates at low rate discharge and high rate discharge, the utilization rate was significantly improved compared to conventional lead-acid batteries.
- As the current collector a conventional lattice can be used, or an active material can be applied to a sheet-like material such as a lead sheet. When filling the grid-like current collector, a certain degree of viscosity is required. Therefore, the amount of water as the kneading medium is set to be smaller than the other components to obtain a paste-like kneaded product.
- the amount of water is increased to lower the viscosity to obtain a slurry-like kneaded product.
- the kneaded product before application to the electrode plate is a paste or a slurry, the effects of the present invention can be obtained similarly.
- An electrode plate in which a grid current collector is filled with paste can basically be used for all uses of a conventional lead-acid battery, and can be made lighter in weight with the same battery capacity. it can.
- a lead-acid battery using a sheet electrode can form a cylindrical battery. In that case, the electrode plate is spirally wound to provide a battery with excellent high-rate discharge and strong vibration resistance. This is particularly suitable for hybrid vehicles and electric vehicles.
- nickel-metal hydride batteries and lithium-ion batteries are being used or studied in hybrid vehicles, but they all have the problem of high costs.
- the lead-acid battery according to the present invention is suitable for practical use because it is much cheaper than those.
- the lead-acid battery using the negative electrode active material according to the present invention is capable of discharging with a large current, has a long life, has a high active material utilization rate, and is low in cost.
- charge / discharge management is simpler than lithium ion batteries and nickel hydrogen batteries. Its optimal use is the hybrid use of engine and storage battery in automotive applications. In this application, the consumption of gasoline is reduced by charging regenerative power to the storage battery when the vehicle is braked and taking out the power from the storage battery when starting. In automobile companies, energy conservation is environmentally favorable due to the reduction of exhaust gas. Therefore, it is focusing on hybrid cars now and in the future, and the industrial applicability of the present invention can be said to be extremely high.
- a general storage battery is often used for float charging. This is a system that supplies power to a storage battery power load in the event of a power outage and is generally discharged at a rate of about 10 minutes. If such a storage battery is used with a conventional lead storage battery, it is released for a short time. Since it becomes electricity, that is, large current discharge, the active material utilization rate which is not originally high further decreases. Therefore, a lead-acid battery with a large rated capacity must be prepared, which is large and heavy.
- the lead-acid battery using the negative electrode active material of the present invention has an active material utilization rate that is about twice or more that of a conventional lead-acid battery, can be discharged with a large current, and can be lightweight.
- each example of the present invention when applied to a negative electrode plate using a grid-like current collector will be described.
- Example 1 a kneaded mixture of negative electrode active materials having different bulk densities (hereinafter referred to as "negative electrode paste”) was prepared, and the negative electrode plate filled with the negative electrode paste in a grid current collector was used. A test was conducted.
- Table 1 is a list showing the component composition of the negative electrode paste used in the test.
- component 10 of strike 10 indicates the weight of dilute sulfuric acid with a specific gravity of 1.15
- Lead powder is a main component of the active material, and the oxidation degree of lead is about 75 to 80%.
- As the carbon acetylene black having a DBP oil absorption of 175 ml / 100 g was used.
- Polybulu alcohol made by Kuraray Co., Ltd. having a polymerization degree of 2400 was used.
- DBP oil absorption indicates the amount of dibutyl phthalate absorbed per lOOg of the substance, and is one index indicating the liquid absorbency of the substance.
- the nature of the electrode plate using the negative electrode active material It is used as a bulk density parameter.
- the characteristics of the negative electrode active material according to the present invention are clearly related to the DBP oil absorption amount or the total oil absorption amount calculated based on the DBP oil absorption amount and the active material utilization rate and the battery capacity. The relationship between the utilization rate and battery capacity was clarified.
- the bulk density was controlled by the amount of carbon, graphite and water.
- a negative electrode paste prepared as a comparative example To 3 and 10 are force S that is simply kneaded lead powder, lignin, and barium sulfate in the amounts shown in Table 1, and the negative electrode paste 10 is not water. The generally used dilute sulfuric acid was used. Negative electrode paste 10 is a conventional negative electrode active material.
- the negative electrode pastes 4 to 9 thus prepared were filled into a 2 mm-thick grid-shaped current collector, then aged for 24 hours at a humidity of 98% and a temperature of 45 ° C, and then 24 hours at 60 ° C. After drying for a time, a negative electrode plate having a thickness of 2.2 mm was formed.
- the water adhering to the lower part of the unformed electrode plate is gently wiped, and the weight is measured.
- Bulk density of unformed active material volume of unformed active material / weight of unformed active material
- Fig. 1 is a graph showing the results for 0.0A discharge at a low rate
- Fig. 2 is for 6A discharge at a high rate. It is a graph which shows the result of.
- the value of the utilization rate tends to increase as the bulk density increases.
- Figure 1 and Figure 2 The increase rate of utilization due to the increase in bulk density tended to decrease.
- the negative electrode pastes 4 to 9 of the present invention all have a bulk density of 2.5 X 10-iml / g or more, and the utilization rate is 60% to 78% for low rate discharge and 32% for high rate discharge. ⁇ 47% was obtained.
- the bulk density is about 2 ⁇ 10-il / g, and the utilization rate is about 50% for low rate discharge and about 20% for high rate discharge. This is about the same as the upper limit value of the utilization rate known in the past.
- negative electrode paste that does not contain carbon and graphite without using dilute sulfuric acid;! ⁇ 3 has a higher utilization than those of negative electrode paste 10, but it uses carbon and graphite.
- the utilization rate is inferior to the negative electrode pastes 4 to 9 of the invention.
- the bulk density is small! /
- the electrolytic solution dilute sulfuric acid
- the electrolyte can be supplied from the vicinity of the active material, so that discharge becomes easier. Therefore, the results shown in FIGS. 1 and 2 were obtained. Utilization is an absolutely necessary item for improving battery energy density. Moreover, since the battery active material can be reduced if the utilization rate is high, the significance of cost reduction is also great.
- FIG. 3 is a graph showing the result in the case of a 0.06 A discharge having a low rate with respect to the relationship between the bulk density of the unformed active material and the capacity.
- Figure 4 is a graph showing the results for a high rate 6A discharge.
- the low-rate discharge capacity in Fig. 3 decreased monotonically as the bulk density increased. The larger the bulk density, the less the active material, and the smaller the capacity that can be taken out.
- the high rate discharge shown in Fig. 4 when the bulk density increases, the capacity tends to decrease. In the presence of carbon and graphite, the capacity is higher than in the absence of these carbons. It became quantity. This is thought to be due to the increase in the capacity of high-rate discharge due to the conductivity or high liquid retention characteristics of carbon and graphite.
- the bulk density of the conventional unformed active material is 2 X From the results of Fig. 1 and Fig. 2, it is preferable that the bulk density of the unformed active material is 2.2 10_ 1/8 or more from the viewpoint of increasing the utilization rate, but from the results of Fig. 3 and Fig. 4, the absolute capacity is determined. In order to keep it to some extent, it is realistic to set it below 5 X 10 — il / g. This is because, in Figs. 1 and 2, the bulk density shows the highest utilization rate in the vicinity of 5 X l CTVil / g, which is a sufficiently practical area in the AND condition of utilization rate and bulk density. It is.
- lead powder as an active material raw material is mainly lead oxide, but also includes unoxidized metallic lead.
- Lead oxide reacts with the sulfuric acid in the electrolyte and changes to lead, the active material, by chemical conversion.
- lead thus produced is regarded as an active material.
- metallic lead As an active material, there is a debate about whether or not it was originally included, the power to regard metallic lead as an active material.
- the level of metallic lead that contributes as an active material is considerably lower than that of lead oxide, it is assumed here that the metallic lead originally contained in the active material raw material functions as an active material as well as lead oxide.
- the utilization factor of the active material in the discharge was calculated.
- the utilization ratio of the active material of the present invention is higher than that shown in this example. The same applies to other embodiments.
- Example 2 a negative electrode paste in which the DBP oil absorption amount of carbon was changed was prepared, and a test was performed on a negative electrode plate in which the negative electrode paste was filled in a grid-like current collector.
- Table 3 lists the component composition of the negative electrode paste used in the test.
- Component 7 of negative electrode '-strike 10 indicates the weight of dilute sulfuric acid with a specific gravity of 1,15
- Lead powder is a major component of the active material and has an oxidation degree of about 75 to 80%.
- Table 3 four types of acetylene black with oil absorption of 80, 140, 175 and 220ml / 100g were used.
- Graphite having an average particle size of about 13 m was used.
- Polybulu alcohol made by Kuraray Co., Ltd.
- the column of component 4 in Table 3 shows the DBP oil supply amount of each carbon, and the carbon amount was 8.6 g for all.
- Example 1 the bulk density was controlled by the amount of carbon, graphite, and water.
- Example 2 the bulk density of the kneaded product was controlled by changing the DBP oil absorption of carbon.
- carbon and graphite negative electrode pastes 7, 11 to 13
- lead powder and lignin are mixed into the kneaded product.
- barium sulfate were added and further kneading was carried out for 30 minutes.
- the negative electrode paste 10 produced as a comparative example used dilute sulfuric acid that is generally used instead of force water, which is simply kneaded of lead powder, lignin, and barium sulfate in the amounts shown in Table 1. .
- the negative electrode pastes 7, 11 to 13 prepared in this way were filled into a 2 mm thick grid-shaped current collector, and then aged for 24 hours at a humidity of 98% and a temperature of 45 ° C, and then at 60 ° C. After drying for 24 hours, a negative electrode plate having a thickness of 2.2 mm was formed. Similarly, the negative electrode paste 10 as a comparative example was filled in a grid-like current collector.
- the theoretical capacity of the active material is such that the positive electrode has a large excess, so that the utilization factor of the target negative electrode (that is, the active material) can be evaluated.
- These electrode plates were inserted into the battery case, and an ABS resin spacer was loaded in the gap between the battery case and the electrode plate group.
- a dilute sulfuric acid with a specific gravity of 1.223 was injected into the battery case, and 300% of the theoretical capacity of the positive electrode was passed through for chemical conversion.
- the specific gravity of the electrolyte after chemical conversion was 1.320.
- a capacity test was performed on the electrode plate group inserted into the battery case. Two types of capacity tests were performed: 0.06A and 6A. 0.06A is a low rate discharge with a rate of about 40 hours, and 6A is a high rate discharge with a rate of about 10 minutes. The end-of-discharge voltages were 1.7V and 1.2V per cell. The temperature is 25 ° C.
- Fig. 5 is a graph showing the results of 0.0A discharge, which is a low rate, regarding the relationship between carbon DBP oil absorption and utilization rate.
- Figure 6 is a graph showing the results for a 6A discharge with the same high rate.
- “practical paste” means the negative electrode paste of the present invention;!;! To 13
- “comparative paste” means the negative electrode paste 10 of the comparative example.
- the conventional general usage rate of 40% is about 10% higher than the conventional general usage rate of 50%, which is equivalent to the usage rate of 50% of the conventional paste used for testing, and the oil absorption is 80ml / 100g.
- the utilization rates of the low rate discharge and the high rate discharge were further larger than the conventional paste.
- Example 1 it was found that carbon increased the bulk density of the negative electrode paste. From the results of Example 2, the DBP oil absorption of carbon also increased the bulk density of the negative electrode paste. As a result, it has been found that the same effects as improving the utilization factor of the negative electrode are obtained.
- the lower limit value of DBP oil absorption at high rate discharge is about 5% higher than the utilization rate of the conventional paste at around 50ml / 100g.
- the total oil absorption of 8.6 g of carbon contained will be 4.3 ml based on 50 (ml / 100 g) X 8.6 (g).
- this value is converted into the amount of oil absorption relative to the molar amount of lead powder used as the active material, it is as follows.
- lead powder has an oxidation degree of about 75 to 80%. Therefore, an example will be described in which the lead oxide component is 75% and the lead component is 25%.
- Figure 5 shows the utilization rate of low rate discharge
- Fig. 6 which shows the utilization rate of high-rate discharge
- the total oil absorption amount of a single bon is not less than 4.7ml / mol with respect to the molar amount of the active material raw material (that is, 4. If the amount of carbon is 7 ml or more, the utilization rate is higher than that of the conventional paste.
- Example 3 negative electrode pastes with different amounts of sulfate radicals were prepared, and tests were performed on negative electrode plates in which the negative electrode paste was filled in a grid-like current collector. ⁇ Preparation of sample>
- Table 4 is a list of component composition of the negative electrode paste was subjected to the test c
- Component 7 of negative electrode ⁇ -S ⁇ 0 indicates the weight of dilute sulfuric acid with a specific gravity of 1.15
- Lead powder is a main component of the active material, and the degree of oxidation of lead is about 75 to 80%.
- As the carbon acetylene black having a DBP oil absorption of 220 ml / 100 g was used. Graphite with an average particle size of about 13 mm was used. Polybulu alcohol (made by Kuraray Co., Ltd.) having a polymerization degree of 2400 was used.
- the negative electrode paste 14 does not contain a sulfate group.
- Negative electrode pastes 15 and 16 contain the sulfate radical of component 8 shown in Table 4.
- the negative electrode paste 10 of the comparative example is an example of a conventionally used negative electrode paste, and 32 ml (about 37 g) of dilute sulfuric acid having a specific gravity of 1.15 was used as the component 7. This is equivalent to 7.8 g of sulfate radical (shown as component 8 in Table 4), and is contained in the above 37 g of dilute sulfuric acid.
- negative electrode paste 10 produced as a comparative example dilute sulfuric acid was used as described above, not force water, which was simply kneaded lead powder, lignin, and barium sulfate in the amounts shown in Table 4.
- the negative electrode pastes 14 to 16 prepared in this way were filled into a 2 mm thick grid-shaped current collector, then aged at 98% humidity and 45 ° C for 24 hours, and then at 60 ° C for 24 hours. After drying, a negative electrode plate having a thickness of 2.2 mm was formed. Similarly, the negative electrode paste 10 as a comparative example was filled in a grid-like current collector. [0083] Next, a fine glass fiber separator was brought into contact with both sides of the single negative electrode plate, and further, one positive electrode plate was brought into contact with the outside. With such a configuration, the theoretical capacity of the active material is such that the positive electrode has a large excess, so that the utilization factor of the target negative electrode (that is, the active material) can be evaluated.
- Electrode plates were inserted into the battery case, and an ABS resin spacer was loaded in the gap between the battery case and the electrode plate group.
- a dilute sulfuric acid with a specific gravity of 1.223 was injected into the battery case, and 300% of the theoretical capacity of the positive electrode was passed through for chemical conversion.
- the specific gravity of the electrolyte after chemical conversion was 1.320.
- a capacity test was performed on the electrode plate group inserted into the battery case. Two types of capacity tests were performed: 0.06A and 6A. 0.06A is a low rate discharge with a rate of about 40 hours, and 6A is a high rate discharge with a rate of about 10 minutes. The end-of-discharge voltages were 1.7V and 1.2V per cell. The temperature is 25 ° C.
- Fig. 7 is a graph showing the results of 0.0A discharge with a low rate of the relationship between the amount of sulfate radicals and the utilization rate.
- Figure 8 is a graph showing the results for a 6A discharge with the same high rate.
- the upper limit of the amount of sulfate radical is about 6 g for low rate discharge and about 4 g for high rate discharge, assuming that the utilization rate is higher than that of the conventional paste. Therefore, the upper limit of the sulfate radical derived from dilute sulfuric acid is 6 g in the case of low rate discharge.
- Example 3 Although dilute sulfuric acid was used in Example 3, for example, an aqueous solution of sodium sulfate or sulfuric acid It was confirmed that even when a similar kneaded material was prepared using an aqueous solution of sodium chloride, the utilization factor of the negative electrode active material similarly decreased if the sulfate radical increased.
- Negative electrode pastes with different amounts of silica were prepared, and tests were performed on negative electrode plates in which the negative electrode paste was filled in a grid-like current collector.
- Table 5 lists the component composition of the negative electrode paste used in the test.
- Lead powder is a main component of the active material, and the oxidation degree of lead is about 75 to 80%.
- As the carbon acetylene black having a DBP oil absorption of 170 ml / 100 g was used. Graphite with an average particle size of about 13 mm was used. Polybulle alcohol (manufactured by Kuraray Co., Ltd.) having a polymerization degree of 2400 was used.
- the paste shown in Table 5 was prepared with the same amount of oil absorption for carbon and silica, with part of the carbon replaced by silica force.
- As a comparative example the conventional negative electrode paste 10 shown in Table 1 was also tested.
- negative electrode pastes 17--19 carbon, graphite, and silica (if included) were kneaded with water and polybutyl alcohol for 30 minutes, and then lead powder, lignin, and barium sulfate were added to the kneaded product. Then, further kneading was performed for 30 minutes.
- the negative electrode paste 10 of the comparative example was also kneaded in the same manner as in the previous examples.
- the negative electrode pastes 17 to 19 prepared in this way were filled into a 2 mm thick grid-shaped current collector, then aged at 98% humidity and 45 ° C for 24 hours, and then at 60 ° C for 24 hours. After drying, a negative electrode plate having a thickness of 2.2 mm was formed. Similarly, the negative electrode paste 10 as a comparative example was filled in a grid-like current collector.
- a fine glass fiber separator is brought into contact with both sides of the negative electrode plate, and the outside is further removed.
- One positive electrode was in contact with each side.
- the theoretical capacity of the active material is such that the positive electrode has a large excess, so that the utilization factor of the target negative electrode (that is, the active material) can be evaluated.
- These electrode plates were inserted into the battery case, and an ABS resin spacer was loaded in the gap between the battery case and the electrode plate group.
- a dilute sulfuric acid with a specific gravity of 1.223 was injected into the battery case, and 300% of the theoretical capacity of the positive electrode was passed through for chemical conversion.
- the specific gravity of the electrolyte after chemical conversion was 1.320.
- a capacity test was performed on the electrode plate group inserted into the battery case. Two types of capacity tests were performed: 0.06A and 6A. 0.06A is a low rate discharge with a rate of about 40 hours, and 6A is a high rate discharge with a rate of about 10 minutes. The end-of-discharge voltages were 1.7V and 1.2V per cell. The temperature is 25 ° C.
- FIG. 9 is a graph showing the result of a 0.06 A discharge with a low rate regarding the relationship between the amount of silica and the utilization rate.
- Figure 10 is a graph showing the results for a 6A discharge with the same high rate.
- the negative electrode pastes 17 to 19 had a low utilization rate discharge of 0.06 A, and the utilization rates were 72% to 74%, which was higher than the 48% of the negative electrode paste 10 of the comparative example.
- the utilization rate of the same level could be obtained.
- the negative electrode pastes 17 to 19 exhibited a utilization rate of 42 to 44% even at 6A, which was high rate discharge, which was higher than the 19% of the negative electrode paste 10 of the comparative example. Moreover, even if a part of carbon was changed to sili- cal power, almost the same utilization rate could be obtained.
- Silica has a high DBP oil absorption like carbon. Therefore, even if a part of carbon having the same DBP oil absorption is replaced with silica, the utilization rate of the active material can be high. .
- silica amount and / or silica oil absorption amount adjust the silica amount and / or silica oil absorption amount so that the total oil absorption amount per mole of active material raw material is the same as that of carbon alone. Almost the same oil absorption can be obtained.
- Negative electrode pastes were prepared with varying amounts of polybulal alcohol, and tests were performed on negative electrode plates filled with the negative electrode paste in a grid-like current collector. Polybulal alcohol is added as a dispersant for carbon and graphite.
- Table 6 lists the composition of the negative electrode paste used in the test.
- Lead powder is the main component of the active material.
- the degree of oxidation of lead is about 75-80%.
- As the carbon acetylene black having a DBP oil absorption of 220 ml / 100 g was used.
- polybulal alcohol polybulal alcohol with relatively low solubility in water (Exeval RS-4105 manufactured by Kuraray Co., Ltd.) and ordinary polybulal alcohol (manufactured by Kuraray Co., Ltd.) with relatively high solubility in water are used. It was. The former is “polybulal alcohol-1” and the latter is “polybulal alcohol-2”.
- the negative electrode paste 20 to 26 produced in this way was filled into a 2 mm thick grid-shaped current collector, and then aged for 24 hours at a humidity of 98% and a temperature of 45 ° C, and then at 60 ° C. After drying for 24 hours, a negative electrode plate having a thickness of 2.2 mm was formed.
- the solubility of polybulal alcohol-1 at 20 ° C was 12 percent, and the solubility of polybulal alcohol-2 at 20 ° C was 38 percent.
- the solubility refers to a limit value at which a certain solute can be dissolved in a certain amount of solvent.
- Electrode plates were inserted into the battery case, and an ABS resin spacer was loaded in the gap between the battery case and the electrode plate group.
- a dilute sulfuric acid with a specific gravity of 1.223 was injected into the battery case, and 300% of the theoretical capacity of the positive electrode was passed through for chemical conversion.
- the specific gravity of the electrolyte after chemical conversion was 1.320.
- FIG. 11 is a graph showing the relationship between the addition amount of polybutyl alcohol and the utilization rate, in the case of high rate discharge (6A) and in the case of low rate discharge (0.06A).
- Polybulal Alcohol-2 which has a high solubility
- the utilization rate of the active material decreased both in the low rate discharge and the high rate discharge as the amount of added Polybulal alcohol increased.
- polybulal alcohol-1 having low solubility was added, the utilization rate of the active material did not decrease even when the amount added was increased.
- the upper limit of the addition amount of polybulualcohol-2 is that an active material utilization rate of approximately 55% or more with low rate discharge and approximately 35% or more with high rate discharge can be obtained (negative electrode paste).
- the solubility of polybulal alcohol-2 is 38% at 20 ° C
- the solubility of polybulal alcohol in general is 40% or less. (i.e., 4 X 10- 1 or less in the solubility 20 ° C for water) is appropriate.
- the original purpose of polybulu alcohol is carbon while ensuring the conductivity of carbon.
- it also has the effect of increasing the adhesion strength of the negative electrode paste to the grid current collector when it is filled into the grid current collector. In that case, if you want to increase the adhesion strength, you need to increase the added amount of polybulualcohol. Low solubility, if polybuturol-1 is used, even if the added amount increases, the utilization rate does not decrease Therefore, it is preferable.
- a negative electrode paste in which the type of carbon was changed was prepared, and a test was performed on a negative electrode plate in which the negative electrode paste was filled in a grid-like current collector. In addition, tests were also conducted on negative electrode pastes with different amounts of polybum alcohol added to carbon.
- Table 7 lists the component composition of the negative electrode paste used in the test.
- Lead powder is a main component of the active material, and the oxidation degree of lead is about 75 to 80%.
- acetylene black having a DBP oil absorption of 170 ml / 100 g
- furnace carbon having a DBP oil absorption of 185 ml / 100 g
- Graphite with an average particle size of about 13 m was used.
- Polybulle alcohol (Kuraray Co., Ltd.) having a polymerization degree of 2400 was used.
- the case in a weight ratio of poly Bulle alcohols force carbon 5 X 10_ 2 Comparative tests have been carried out even for the case of 1 X 10- 1.
- the negative electrode paste 27 to 34 thus prepared was filled into a 2 mm thick grid-like current collector, and then aged for 24 hours at a humidity of 98% and a temperature of 45 ° C, and then at 60 ° C. After drying for 24 hours, a negative electrode plate having a thickness of 2.2 mm was formed.
- the polybulal alcohol used in this example is polybulal alcohol-2 in Example 5, and its solubility is as described in Example 5.
- Fig. 12 is a graph showing the utilization rate by 0.06 A low rate discharge with respect to the relationship between the amount of carbon and the utilization rate.
- FIG. 13 is a graph showing the utilization factor by 6A high rate discharge.
- acetylene black can maintain the same utilization rate regardless of the amount of carbon in both low rate discharge and high rate discharge. If the amount is small, the utilization rate is about the same as that of acetylene black, but the utilization rate with a large amount of carbon decreases.
- the polybulal alcohol used in this example is the polybulal alcohol used in Example 5. From Fig. 12 and Fig. 13, the lower limit of the amount of polybutyl alcohol-2 added when acetylene black is used is shown from the force S, which is le-2.
- poly Bulle alcohol to the content of ⁇ Se Ji Ren Black - in any amount of 2 at a weight ratio of 5 X 1 0_ 2 or 1 X 10- 1 also nearly low rate discharge 50
- An active material utilization rate of about 20% or more can be obtained with a high rate discharge. Therefore, when using acetylene black, poly Bulle alcohol - amount of 2 can be more than connexion lower limit 5 X 10_ 2 by weight relative to the acetylene black.
- polybulual alcohol-1 As shown in Fig. 11 of Example 5, for polybulual alcohol-1, the use rate of polybulal alcohol-1 was higher than that of polybulal alcohol-2. since, poly Bulle alcohol - a 1 5 X 10_ 2 in a weight ratio of acetylene black also may be more than connexion lower limit.
- Furnace carbon has a lower cost than acetylene black, and is advantageous in terms of cost.
- the utilization rate higher than the conventional paste shown in Fig. 1 and Fig. 2 (negative electrode paste 10 in Table 1) is obtained. This is the case.
- the utilization factor at this time is about 50% for the low rate discharge in FIG. 12, and about 30% for the high rate discharge in FIG.
- the utilization rate of the conventional paste is about 48% for low rate discharge and about 20% for high rate discharge
- the polybutyl alcohol content is the weight ratio to acetylene black. Therefore, the superiority of the present invention can be confirmed by setting 5 ⁇ 10 2 as the lower limit.
- the negative electrode paste according to the present invention and the conventional negative electrode paste were subjected to a life test for charge / discharge cycles.
- Table 8 lists the component composition of the negative electrode paste used in the test.
- the negative electrode paste 14 according to the present invention was used in Example 4 described above.
- the amount of water in Component 7 was adjusted so that the bulk density of the conventional negative electrode paste 35 without carbon was about the same as that of the negative electrode paste 14.
- the improvement in the utilization rate in the negative electrode paste according to the present invention is mainly due to the force S that is considered to be due to the bulk density, that is, the porosity is larger than that of the conventional paste. Increasing the value has been considered to decrease the life expectancy. Therefore, in this example, the lifetimes of both were compared at the same bulk density as that of the negative electrode paste of the present invention. Therefore, the negative electrode paste 35 has a larger bulk density than the negative electrode paste that has been generally used in the past.
- the negative electrode pastes 14 and 35 thus prepared were filled into a 2 mm thick grid-shaped current collector, then aged at 98% humidity and a temperature of 45 ° C for 24 hours, and then dried at 60 ° C for 24 hours. Thus, a negative electrode plate having a thickness of 2.2 mm was formed.
- a fine glass fiber separator was brought into contact with both sides of the single negative electrode plate, and one positive electrode plate was brought into contact with the outside.
- three positive plates and four negative plates were used.
- the electrode plate group was inserted into the battery case, and an ABS resin spacer was loaded in the gap between the battery case and the electrode plate group.
- Chemical conversion was performed by injecting dilute sulfuric acid with a specific gravity of 1.223 into the battery case, and flowing 300% of the electric capacity of the theoretical capacity of the positive electrode.
- the specific gravity of the electrolyte after chemical conversion was 1.320. In this way, a storage battery having a capacity of 7 A-h (ampere hour) was produced.
- the amount of charge was approximately 105% of the amount of discharge.
- the temperature is 25 ° C.
- FIG. 14 is a graph showing the results of the life test.
- the vertical axis in Fig. 14 is the ratio to the initial capacity of the battery.
- the life of the negative electrode paste 35 of the comparative example was about 100 cycles.
- the life of the negative electrode paste 14 according to the present invention is 500 cycles or more. Therefore, when compared at the same bulk density, it was confirmed that the negative electrode paste 14 of the present invention has a significantly superior life performance compared to the negative electrode paste 35 having the same components as the conventional paste.
- the lifetime is longer than that of the negative electrode paste 35 because the bulk density is smaller than that of the negative electrode paste 35, but it is still about 300 cycles at most.
- the negative electrode paste of the present invention does not have a reduced life even when the bulk density is large, and that the strength is greatly improved.
- the negative electrode paste 35 of the comparative example has more voids in the active material because the bulk density is higher than that of a general conventional paste. It is thought.
- the negative electrode paste according to the present invention has a large bulk density of the active material, but since the carbon network supports porous active material particles, the active material does not collapse even after repeated charge and discharge. Suppressed and improved life performance can be realized.
- the cycle life performance of the storage battery can be significantly improved as compared with the conventional storage battery.
- improvement in utilization rate and cycle life performance are in a trade-off relationship, and it has been considered as an unavoidable phenomenon that cycle life performance decreases if utilization rate is increased. Both can be stretched.
- FIG. 1 is a graph showing the result of 0.0A discharge at a low rate, regarding the relationship between the bulk density and the utilization factor of the negative electrode active material of the present invention.
- FIG. 2 is a graph showing the result of high-rate 6A discharge regarding the relationship between the bulk density and the utilization factor of the negative electrode active material of the present invention.
- FIG. 3 is a graph showing the result of 0.0A discharge at a low rate regarding the relationship between the bulk density and capacity of the negative electrode active material of the present invention.
- FIG. 4 is a graph showing the results of high-rate 6A discharge regarding the relationship between the bulk density and capacity of the negative electrode active material of the present invention.
- FIG. 5 is a graph showing the result of 0.06 A discharge, which is a low rate, regarding the relationship between the amount of carbon absorbed and the utilization rate of the negative electrode active material of the present invention.
- FIG. 6 is a graph showing the result of a high rate 6A discharge regarding the relationship between the carbon oil absorption amount and the utilization rate of the negative electrode active material of the present invention.
- FIG. 7 is a graph showing the result in the case of a low rate 0.06 A discharge regarding the relationship between the amount of sulfate radicals and the utilization rate of the negative electrode active material of the present invention.
- FIG. 8 is a graph showing the results of a high rate 6A discharge regarding the relationship between the amount of sulfate radicals and the utilization rate of the negative electrode active material of the present invention.
- FIG. 10 is a graph showing the results of a high rate 6A discharge regarding the relationship between the amount of silica and the utilization rate of the negative electrode active material of the present invention.
- FIG. 11 is a graph showing the relationship between the amount of addition of polybulu alcohol and the utilization rate of the negative electrode active material of the present invention, in the case of low rate discharge (0.06A) and in the case of high rate discharge (6A), respectively.
- FIG. 12 is a graph showing the utilization rate by 0.06 A low rate discharge with respect to the relationship between the amount of carbon and the utilization rate of the negative electrode active material of the present invention.
- FIG. 13 is a graph showing the utilization rate by 6A high rate discharge with respect to the relationship between the amount of carbon and the utilization rate of the negative electrode active material of the present invention.
- FIG. 14 Results of life tests of the negative electrode active material of the present invention and the conventional negative electrode active material are shown.
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Abstract
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US12/519,629 US20100051857A1 (en) | 2006-12-19 | 2007-11-13 | Negative-electrode active material for secondary battery |
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JP2006341688A JP4523580B2 (ja) | 2006-12-19 | 2006-12-19 | 二次電池用負極活物質及びそれらを生成するための中間の混練物 |
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JP (1) | JP4523580B2 (ja) |
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CN101969120B (zh) * | 2010-09-15 | 2012-08-08 | 超威电源有限公司 | 铅酸蓄电池极板制造工艺 |
US9112231B2 (en) * | 2010-11-05 | 2015-08-18 | Cabot Corporation | Lead-acid batteries and pastes therefor |
AU2011323198B2 (en) | 2010-11-05 | 2015-06-18 | Thermochem Recovery International, Inc. | Solids circulation system and method for capture and conversion of reactive solids |
US9281520B2 (en) * | 2011-04-04 | 2016-03-08 | Cabot Corporation | Lead-acid batteries and pastes therefor |
JP5934352B2 (ja) * | 2011-06-21 | 2016-06-15 | カウンシル オブ サイエンティフィク アンド インダストリアル リサーチ | 改良超伝導ペーストを用いた(bi,pb)−2223酸化物高温超伝導体の管の接合方法 |
WO2013049368A1 (en) | 2011-09-27 | 2013-04-04 | Thermochem Recovery International, Inc. | System and method for syngas clean-up |
CN102496697A (zh) * | 2011-12-31 | 2012-06-13 | 河南三丽电源股份有限公司 | 一种碳铅蓄电池铅膏及其制备方法 |
WO2014052753A1 (en) * | 2012-09-28 | 2014-04-03 | Cabot Corporation | Active material compositions comprising high surface area carbonaceous materials |
JP6135143B2 (ja) * | 2013-01-21 | 2017-05-31 | 株式会社Gsユアサ | 鉛蓄電池 |
WO2015087749A1 (ja) * | 2013-12-11 | 2015-06-18 | 新神戸電機株式会社 | 制御弁式鉛蓄電池 |
US20160118668A1 (en) * | 2014-10-22 | 2016-04-28 | Cabot Corporation | Carbon additives for negative electrodes |
JP6870207B2 (ja) * | 2016-03-08 | 2021-05-12 | 昭和電工マテリアルズ株式会社 | 鉛蓄電池 |
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JPH05242887A (ja) * | 1992-02-27 | 1993-09-21 | Shin Kobe Electric Mach Co Ltd | 鉛蓄電池用極板の製造方法 |
JP2000149981A (ja) * | 1998-11-02 | 2000-05-30 | Jec Service Kk | 鉛蓄電池および鉛蓄電池用添加剤 |
JP3267075B2 (ja) * | 1994-11-14 | 2002-03-18 | 松下電器産業株式会社 | 鉛蓄電池用極板の製造法 |
JP2002367613A (ja) * | 2001-04-03 | 2002-12-20 | Hitachi Ltd | 鉛蓄電池 |
JP2003123760A (ja) * | 2001-10-12 | 2003-04-25 | Furukawa Battery Co Ltd:The | 鉛蓄電池用負極 |
JP2005222926A (ja) * | 2003-08-27 | 2005-08-18 | Shin Kobe Electric Mach Co Ltd | 負極用ペースト状活物質及び正極用ペースト状活物質の製造方法 |
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JP2006128056A (ja) * | 2004-11-01 | 2006-05-18 | Kazuo Tagawa | 鉛蓄電池および鉛蓄電池用添加剤 |
-
2006
- 2006-12-19 JP JP2006341688A patent/JP4523580B2/ja not_active Expired - Fee Related
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2007
- 2007-11-13 CN CNA2007800403617A patent/CN101529623A/zh active Pending
- 2007-11-13 WO PCT/JP2007/071971 patent/WO2008075514A1/ja active Application Filing
- 2007-11-13 US US12/519,629 patent/US20100051857A1/en not_active Abandoned
- 2007-11-16 TW TW096143396A patent/TW200836389A/zh unknown
Patent Citations (6)
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JPH05242887A (ja) * | 1992-02-27 | 1993-09-21 | Shin Kobe Electric Mach Co Ltd | 鉛蓄電池用極板の製造方法 |
JP3267075B2 (ja) * | 1994-11-14 | 2002-03-18 | 松下電器産業株式会社 | 鉛蓄電池用極板の製造法 |
JP2000149981A (ja) * | 1998-11-02 | 2000-05-30 | Jec Service Kk | 鉛蓄電池および鉛蓄電池用添加剤 |
JP2002367613A (ja) * | 2001-04-03 | 2002-12-20 | Hitachi Ltd | 鉛蓄電池 |
JP2003123760A (ja) * | 2001-10-12 | 2003-04-25 | Furukawa Battery Co Ltd:The | 鉛蓄電池用負極 |
JP2005222926A (ja) * | 2003-08-27 | 2005-08-18 | Shin Kobe Electric Mach Co Ltd | 負極用ペースト状活物質及び正極用ペースト状活物質の製造方法 |
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US20100051857A1 (en) | 2010-03-04 |
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