WO2011108175A1 - 鉛蓄電池 - Google Patents
鉛蓄電池 Download PDFInfo
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- WO2011108175A1 WO2011108175A1 PCT/JP2011/000058 JP2011000058W WO2011108175A1 WO 2011108175 A1 WO2011108175 A1 WO 2011108175A1 JP 2011000058 W JP2011000058 W JP 2011000058W WO 2011108175 A1 WO2011108175 A1 WO 2011108175A1
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
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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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/627—Expanders for lead-acid accumulators
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M2010/4292—Aspects relating to capacity ratio of electrodes/electrolyte or anode/cathode
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a liquid lead-acid battery having an electrolytic solution released from an electrode plate group / separator in a battery case.
- Lead-acid batteries are inexpensive and highly reliable. Therefore, they are widely used as power sources for starting automobiles, power sources for electric vehicles such as golf carts, and power supplies for industrial equipment such as uninterruptible power supplies. in use.
- ISS vehicles idling stop vehicles
- a micro-hybrid vehicle such as a power generation control vehicle that controls the alternator so as to reduce the load as much as possible and uses the rotation of the engine for power without waste is being studied.
- the number of engine starts increases, and the lead-acid battery is repeatedly discharged with a large current each time. Further, in an ISS vehicle or a power generation control vehicle, the amount of power generated by the alternator is reduced, and the lead storage battery is charged intermittently, so charging is often insufficient. Therefore, it is necessary for the lead storage battery used in the ISS car to have a performance capable of charging as much as possible in a short time, that is, to improve the charge acceptance.
- PSOC Partial State Of Charge
- Lead acid batteries tend to have a shorter life when used under PSOC than when used in a fully charged state.
- the reason for the shortening of the life when used under PSOC is that if charging / discharging is repeated in a state where charging is insufficient, lead sulfate produced on the negative electrode plate becomes coarse during discharge, and lead sulfate is generated by charging. It is thought that it is difficult to return to the metallic lead that is a thing. Therefore, lead-acid batteries used under PSOC have an excessive charge shortage by improving the charge acceptance (allowing as many charges as possible in a short time) to extend their life. It is necessary to prevent repeated charging / discharging in a state in which the lead sulfate is charged, and to prevent lead sulfate from becoming coarse due to repeated charging / discharging.
- Patent Document 1 and Patent Document 2 propose to improve the charge acceptability by increasing the amount of carbonaceous conductive material added to the negative electrode active material and to improve the life of the lead-acid battery under PSOC.
- the amount of carbonaceous conductive material added to the negative electrode active material has to be limited, and by adding the carbonaceous conductive material to the negative electrode active material, the charge acceptability of the lead acid battery as a whole is increased. There are limits to improving
- Sealed lead-acid batteries not only have a low battery capacity due to the limited amount of electrolyte, but also cause a phenomenon called thermal escape when the operating temperature is high. Use is inevitable. Therefore, when a sealed lead-acid battery is used in an automobile, it is necessary to mount the battery in a luggage room or the like. However, mounting a battery in a luggage room or the like is not preferable because it increases the number of wire harnesses. As a lead acid battery for automobiles, it is preferable to use a liquid type lead acid battery without such restrictions. Therefore, there is an urgent need to improve the charge acceptability of the liquid lead-acid battery.
- the negative electrode active material produced in association with charging / discharging is inhibited from becoming coarse, the surface area of the negative electrode is suppressed from decreasing, and the reactivity of the charge / discharge reaction is maintained at a high level.
- An organic compound that acts to suppress the coarsening of the substance is added to the negative electrode active material.
- lignin which is a main component of wood, has been used as an organic compound that suppresses the coarsening of the negative electrode active material.
- lignin has a wide variety of structures in which a plurality of unit structures are combined in a complex manner, and usually has a portion that is easily oxidized or reduced, such as a carbonyl group.
- the moiety is oxidized or reduced and decomposed. For this reason, even when lignin is added to the negative electrode active material, the effect of suppressing deterioration in performance due to repeated charge and discharge cannot be maintained for a long period of time.
- lignin adsorbs to lead ions that dissolve from lead sulfate during charging and reduces the reactivity of lead ions, thus inhibiting the charging reaction of the negative electrode active material and suppressing the improvement of charge acceptance. There are side effects. Therefore, the lignin added to the negative electrode active material has a problem in that although the discharge characteristics are improved, the improvement in charge acceptability is hindered.
- Patent Document 3 and Patent Document 4 disclose adding a bisphenol, aminobenzenesulfonic acid, formaldehyde condensate, and a carbonaceous conductive material to the negative electrode active material.
- Patent Document 4 shows the effect of suppressing the coarsening of lead sulfate by selecting bisphenols, aminobenzenesulfonic acid, and formaldehyde condensates as organic compounds that suppress the coarsening of lead sulfate associated with charge and discharge.
- Sustaining and adding a carbonaceous conductive material to improve charge acceptance are disclosed.
- Patent Document 5 discloses that conductive carbon and activated carbon are added to the negative electrode active material to improve the discharge characteristics under PSOC.
- JP 2003-36882 A Japanese Patent Application Laid-Open No. 07-201331 JP-A-11-250913 JP 2006-196191 A JP 2003-051306 A
- the purpose is to improve the life performance in use.
- the present invention provides an electrode plate group in which a negative electrode plate in which a negative electrode active material is filled in a negative electrode current collector and a positive electrode plate in which a positive electrode active material is filled in a positive electrode current collector are stacked via a separator. It is intended for a liquid lead-acid battery that has a configuration that is housed in a battery case together with a liquid, in which charging is performed intermittently and high-rate discharge to a load is performed in a partially charged state.
- At least a carbonaceous conductive material and an organic compound that suppresses the coarsening of the negative electrode active material due to repeated charge / discharge (hereinafter referred to as “an organic compound that suppresses the coarsening of the negative electrode active material”). Is added to the negative electrode active material.
- the positive electrode plate a plate in which the utilization rate of the positive electrode active material related to the discharge reaction is set in a range of 50% to 65% is used.
- the present inventor improves the utilization rate of the positive electrode active material with respect to the discharge reaction, the reaction overvoltage in the charge reaction of the positive electrode active material is reduced to facilitate the progress of the charge reaction, and the charge acceptance of the positive electrode active material is improved. And the positive electrode plate thus improved in charge acceptability is charged by adding to the negative electrode active material at least a carbonaceous conductive material and an organic compound that suppresses the coarsening of the negative electrode active material.
- a negative electrode plate with improved performance hereinafter referred to as “a negative electrode plate with improved performance”
- the charge acceptability of the lead acid battery as a whole is further improved compared to the conventional lead acid battery, It has been found that the lifetime performance when used under PSOC can be further improved.
- the utilization rate regarding the discharge reaction of the positive electrode active material is less than 50%, the effect of improving the charge acceptance of the entire lead storage battery cannot be remarkably obtained, but the utilization rate of the positive electrode active material is 50% or more. If it carries out, the effect which improves the charge acceptance of the whole lead acid battery can be acquired notably. If the charge acceptance of the entire lead-acid battery can be improved, high-rate discharge to the load under PSOC (partial charge state) can be performed without hindrance, and charge and discharge are repeated in a state of insufficient charge Therefore, it is possible to suppress the lead sulfate, which is a discharge product, from being coarsened, so that the life performance of the battery when used under PSOC can be improved.
- the utilization rate of the positive electrode active material is excessively high, the porosity of the positive electrode active material becomes too high, and the structure of the active material collapses due to repeated charge and discharge, and a so-called muddy state occurs.
- the life of the plate is shortened, and a lead-acid battery that can withstand practical use cannot be obtained. Therefore, the utilization rate of the positive electrode active material relating to the discharge reaction is not necessarily increased.
- the utilization factor of the positive electrode active material is in the range of 50% to 65%, it is clear that the charge acceptability and life performance of the battery are improved, but the utilization factor of the positive electrode active material is 65%.
- the upper limit of the utilization rate of the positive electrode active material relating to the discharge reaction is preferably set to 65%.
- a negative electrode plate improved in performance by adding at least a carbonaceous conductive material and an organic compound that suppresses coarsening of the negative electrode active material accompanying charge / discharge to the negative electrode active material, and a positive electrode related to a discharge reaction
- a lead-acid battery is assembled using a positive electrode plate in which the utilization factor of the active material is set in the range of 50% or more and 65% or less
- conventional lead that has improved charge acceptability by improving the performance of the negative electrode exclusively.
- the charge acceptability is further improved than the storage battery, enabling high rate discharge to the load under PSOC, and lead sulfate as a discharge product is coarser by repeated charging and discharging in a state where charging is insufficient. Therefore, it is possible to obtain a lead-acid battery with improved life performance when used under PSOC.
- the carbonaceous conductive material added to the negative electrode active material in order to improve the charge acceptability of the negative electrode active material is a carbon-based conductive material, and conventionally known graphite, carbon black, activated carbon And at least one selected from the group of carbonaceous conductive materials composed of carbon fibers and carbon nanotubes.
- the carbonaceous conductive material is preferably graphite, and more preferably flaky graphite.
- the particle size of the flaky graphite is preferably 100 ⁇ m or more.
- scale-like graphite Since the electrical resistivity of scale-like graphite is an order of magnitude smaller than that of carbon blacks such as acetylene black, the use of scale-like graphite as the carbonaceous conductive material to be added to the negative electrode active material results in the electrical resistance of the negative electrode active material. Can be reduced to improve the charge acceptance performance.
- the charging reaction of the negative electrode active material depends on the concentration of lead ions dissolved from lead sulfate, which is a discharge product, and the charge acceptance increases as the amount of lead ions increases.
- the carbonaceous conductive material added to the negative electrode active material has a function of finely dispersing lead sulfate generated in the negative electrode active material during discharge. If the charge / discharge cycle is repeated in a state of insufficient charge, lead sulfate, which is a discharge product, is coarsened, and the concentration of lead ions dissolved from lead sulfate decreases, resulting in a decrease in charge acceptability.
- carbonaceous conductive material If carbonaceous conductive material is added, it is possible to keep lead sulfate in a fine state by suppressing the coarsening of lead sulfate, and to maintain a high concentration of lead ions dissolved from lead sulfate.
- the charge acceptability of the negative electrode can be maintained in a high state over a long period.
- an organic compound to be added to the negative electrode active material in order to suppress the coarsening of the negative electrode active material due to charge / discharge it is preferable to use a compound mainly composed of bisphenols, aminobenzenesulfonic acid and formaldehyde condensate.
- the condensate has a smaller amount of adsorption to lead ions than lignin, the side effect of inhibiting the charging reaction is small. Therefore, adding bisphenols, aminobenzenesulfonic acid and formaldehyde condensate together with the carbonaceous conductive material to the negative electrode active material maintains the improved charge acceptance of the negative electrode active material, and the charge / discharge reaction by repeated charge / discharge. It is possible to improve the charge acceptability and the life performance of the negative electrode plate by suppressing the deterioration of the properties.
- the surface opposite to the surface of the negative electrode plate of both surfaces in the thickness direction of the separator is made of a group of materials consisting of glass, pulp and polyolefin. It is preferable to comprise the nonwoven fabric which consists of the fiber of the at least 1 material selected from the inside.
- the present invention charges a lead-acid battery by using a positive electrode plate in which the utilization rate of the positive electrode active material for the discharge reaction is set in an appropriate range in combination with a negative electrode plate with improved performance (charge acceptance and life performance).
- the effect of improving the acceptability and life performance when used under PSOC can be remarkably obtained.
- As the negative electrode plate it is preferable to use one having as high charge acceptability and life performance as possible.
- the amount of carbonaceous conductive material added to the negative electrode active material in order to improve the charge acceptance of the negative electrode plate and the organic added to the negative electrode active material to suppress the coarsening of the negative electrode active material due to charge / discharge is not particularly defined, it is natural to set the addition amount of the additive so as to improve the performance of the negative electrode plate as much as possible in carrying out the present invention.
- the positive electrode plate having improved utilization of the positive electrode active material with respect to the discharge reaction of 50% or more and 65% or less, and the coarseness of the carbonaceous conductive material and the negative electrode active material in the negative electrode active material.
- the present invention as an organic compound added to the negative electrode active material in order to suppress the coarsening of the negative electrode active material due to charge / discharge, bisphenols, aminobenzenesulfonic acid, formaldehyde with reduced side effects that inhibit the charging reaction When the main component is a condensate, the charge acceptability and life performance of the lead storage battery can be greatly improved.
- the lead storage battery according to the present invention is a liquid lead storage battery in which charging is performed intermittently and high rate discharge to a load is performed under PSOC, and is used in a micro hybrid vehicle such as an ISS vehicle or a power generation control vehicle. Is preferred.
- a lead storage battery according to the present invention is configured by laminating a negative electrode plate formed by filling a negative electrode current collector with a negative electrode active material and a positive electrode plate formed by filling a positive electrode current collector with a positive electrode current collector through a separator.
- the electrode plate group is housed in the battery case together with the electrolytic solution.
- the present inventor reduced the reaction overvoltage and improved the charge acceptance.
- improving the charge acceptability of the positive electrode plate significantly improves the charge acceptability of the lead acid battery as a whole, compared to the conventional lead acid battery that only improved the charge acceptability of the negative electrode plate. I found out that I could make it. If the charge acceptability can be improved, not only can high-rate discharge to the load under PSOC be performed without trouble, but lead sulfate is coarsened by repeated charge and discharge in a state of insufficient charge. The life performance can be improved.
- FIG. 1 shows the relationship between the charging current and the potentials of the negative electrode plate and the positive electrode plate when charging an automotive lead-acid battery having an open circuit voltage of 12 V with a charging voltage of 14 V (constant).
- the vertical axis represents the charging current
- the horizontal axis represents the potential (vs. SHE) of the positive electrode plate and the negative electrode plate measured with reference to the standard hydrogen electrode.
- N1 and N2 indicate the charging current versus potential curve of the negative electrode plate
- P1 and P2 indicate the charging current versus potential curve of the positive electrode plate.
- the charging current vs. potential curve of the negative electrode plate should be shown in the third quadrant of the orthogonal coordinate system, but in FIG. In the first quadrant, the polarity of the potential and current is reversed and the charging current vs. potential curve of the positive electrode plate is shown.
- N1 represents a charging current versus potential curve when the overvoltage of the charging reaction performed on the negative electrode plate is higher than that of N2.
- the charging current vs. potential curve of the negative electrode plate is greatly swelled outward as shown in the figure, but when the overvoltage is low, it stands up from N1 as in N2. Become a curved line.
- P1 shows a charging current versus potential curve when the overvoltage of the charging reaction performed on the positive electrode plate is higher than that of P2.
- the charging current vs. potential curve P1 swells outward from the charging current vs. potential curve P2 when the reaction overvoltage is low, and when the reaction overvoltage is low, the curve rises more than P1.
- the overvoltage ⁇ of the charging reaction is a change in potential generated at each electrode when the charging voltage is applied in an open circuit state.
- the charging current vs. potential curve of the negative electrode plate that is not particularly devised to improve the charge acceptability of the negative electrode active material takes a shape bulging outward as shown by N1 in FIG. 1, but the negative electrode active material is a carbonaceous conductive material.
- the charge current vs. potential curve of the negative electrode plate improved in charge acceptance by adding an appropriate amount of an organic compound that suppresses the coarsening of the negative electrode active material caused by charging and discharging takes an upright shape like N2. .
- the charge current vs. potential curve of the positive electrode plate that is not particularly devised to improve the charge acceptability of the positive electrode active material takes the form of P1 in FIG.
- P1 is a charge current vs. potential curve of the positive electrode plate used in the conventional lead-acid battery, and is a curve that stands up compared to N1. This means that in a lead-acid battery, the charge acceptability of the negative electrode plate is originally low and the charge acceptability of the positive electrode plate is high. When the overvoltage of the charge reaction of the positive electrode active material is reduced to improve the charge acceptance of the positive electrode plate, the charge current vs. potential curve of the positive electrode plate takes a more upright shape than P1 as P2 in FIG. .
- a lead-acid battery is formed by combining a negative electrode plate with improved charge acceptance by reducing the overvoltage of the charge reaction so that the charge current vs. potential characteristic curve is N2, and a positive electrode plate where the charge current vs. potential curve is P1.
- the charging current that flows when a charging voltage of 14 V is applied is I21 (> I11). From this, it can be seen that the charging current can be greatly increased even if the charging current vs. potential curve of the positive electrode plate remains P1 (without particularly improving the performance of the positive electrode plate). That is, if the charge acceptability of the negative electrode active material is improved so that the charge current vs. potential characteristic curve is N2, the charge acceptability of the lead acid battery as a whole can be greatly increased without particularly improving the charge acceptability of the positive electrode plate. Can be improved.
- a lead-acid battery is assembled by combining a positive electrode plate having a reduced reaction overvoltage so that the charge current vs. potential curve is P2, and a negative electrode plate having a charge current vs. potential curve of N1, a charge voltage of 14V is obtained.
- the charging current that flows when applied is I12 (> I11), and the charge acceptance is improved as compared with the case where the positive electrode plate having a charging current vs. potential curve of P1 and the negative electrode plate having a charging current vs. potential curve of N1 is used. Can do. However, the charge acceptability cannot be improved as much as the combination of the positive electrode plate having the charge current vs. potential curve P1 and the negative electrode plate having the charge current vs. potential curve N2.
- the positive electrode plate is used in combination with the negative electrode plate having improved charge acceptability, thereby charging the lead acid battery as a whole. Attention was paid to the fact that the acceptability can be significantly improved over conventional lead-acid batteries that have only improved the charge acceptability of the negative electrode plate.
- the charge current vs. potential curve is P2 in FIG. It has been found that the charge acceptability of the positive electrode plate can be improved so as to obtain an upright curve.
- a lead-acid battery in combination with a positive electrode plate with improved charge acceptance by setting the active material utilization rate in the range of 50 to 65% the entire battery can be improved by improving only the charge acceptability of the negative electrode plate. It has been found that the charge acceptability of the lead acid battery as a whole can be greatly improved and the life performance during use under PSOC can be further improved as compared with the conventional lead acid battery which has improved the charge acceptability of the battery.
- the utilization rate of the positive electrode active material related to the discharge reaction is defined as follows. That is, using a positive electrode plate to determine the active material utilization rate, a liquid lead storage battery having a theoretical capacity of the negative electrode active material sufficiently larger than the theoretical capacity of the positive electrode active material is assembled, and this lead storage battery is fully charged. After that, the battery was discharged at a rated capacity of 0.2 C current, and before the negative electrode active material was consumed, the discharge reaction was impossible due to the consumption of the positive electrode active material. In this discharge test, the ratio of the amount of discharge electricity until the end of discharge and the theoretical discharge capacity of the positive electrode active material of the positive electrode plate is defined as the positive electrode active material utilization rate.
- a negative electrode plate disposed on both sides of one positive electrode plate with a separator interposed between the electrode plate group of one positive electrode plate and two negative electrode plates in a battery case the theoretical capacity of the positive electrode active material
- a lead acid battery for testing was prepared by pouring electrolyte (diluted sulfuric acid with a specific gravity of 1.28) into the battery case with a liquid volume of 1.5 times the theoretical capacity of the battery.
- a discharge test was performed in which discharge was performed at a current of 0.2C.
- a negative electrode plate having a negative electrode active material having a theoretical capacity 1.5 times or more larger than the theoretical capacity of the positive electrode active material was used. The reason why the electrolytic solution capacity and the theoretical capacity of the negative electrode active material are set to 1.5 times or more of the theoretical capacity of the positive electrode active material is to ensure that the discharge reaction is terminated with positive electrode control.
- the high utilization rate of the positive electrode active material for the discharge reaction means that the state in which the diffusion and transfer of hydrogen ions (H + ) and sulfate ions (SO 4 2 ⁇ ), which are the reaction species of the discharge reaction, are performed quickly is maintained for a long time. This means that the discharge reaction can be continued for a long time.
- the fact that the diffusion of the reactive species is maintained for a long time means that there are many diffusion paths of the reactive species.
- At least a carbonaceous conductive material and an organic compound that suppresses coarsening of the negative electrode active material due to charge / discharge are added to the negative electrode active material.
- the carbonaceous conductive material is preferably selected from a material group consisting of graphite, carbon black, activated carbon, carbon fiber, and carbon nanotube.
- the addition amount of the carbonaceous conductive material is preferably in the range of 0.1 to 3 parts by mass with respect to 100 parts by mass of the fully charged negative electrode active material (spongy metal lead).
- graphite is selected, and more preferably, scaly graphite is selected.
- the average primary particle size of the flaky graphite is preferably 100 ⁇ m or more.
- the scaly graphite refers to that described in JIS M-8601 (2005).
- the electrical resistivity of the scaly graphite is 0.02 ⁇ ⁇ cm or less, which is an order of magnitude less than about 0.1 ⁇ ⁇ cm of carbon blacks such as acetylene black. Therefore, by using scale-like graphite in place of the carbon blacks used in conventional lead-acid batteries, the electrical resistance of the negative electrode active material can be lowered and the charge acceptance performance can be improved.
- the average primary particle diameter of the scaly graphite is obtained according to the laser diffraction / scattering method described in JISM8511 (2005).
- a laser diffraction / scattering type particle size distribution measuring device for example, Nikkiso Co., Ltd .: Microtrac 9220FRA
- a commercially available surfactant polyoxyethylene octyl is used as a dispersant.
- aqueous solution containing 0.5 vol% of phenyl ether for example, Roton Diagnostics Co., Ltd .: Triton X-100
- phenyl ether for example, Roton Diagnostics Co., Ltd .: Triton X-100
- an appropriate amount of a flaky graphite sample was added to this aqueous solution, and a 40 W ultrasonic wave was stirred. Is measured for 180 seconds, and then the average particle size is measured.
- the obtained average particle diameter (median diameter: D50) is defined as the average primary particle diameter.
- Lead-acid batteries mounted on micro hybrid vehicles such as ISS cars and power generation control cars are used in a partially charged state called PSOC.
- PSOC partially charged state
- a phenomenon called sulfation in which lead sulfate, which is an insulator generated in the negative electrode active material during discharge, becomes coarse with repeated charging and discharging, is an early phenomenon. To occur. When sulfation occurs, the charge acceptability and discharge performance of the negative electrode active material are significantly reduced.
- the carbonaceous conductive material added to the negative electrode active material suppresses the coarsening of lead sulfate, maintains the lead sulfate in a fine state, suppresses the decrease in the concentration of lead ions dissolved from the lead sulfate, It acts to maintain a state with high charge acceptability.
- the organic compound that suppresses the coarsening of the negative electrode active material it is preferable to use bisphenols, aminobenzenesulfonic acid, and formaldehyde condensates.
- the bisphenols include bisphenol A, bisphenol F, and bisphenol S.
- the bisphenol A / aminobenzenesulfonic acid / formaldehyde condensate represented by the chemical structural formula of [Chemical Formula 1] below is particularly preferable.
- the charging reaction of the negative electrode active material depends on the concentration of lead ions dissolved from lead sulfate, which is a discharge product, and the charge acceptability increases as the amount of lead ions increases.
- Lignin which is widely used as an organic compound added to the negative electrode active material in order to suppress the coarsening of the negative electrode active material due to charge / discharge, decreases the reactivity of lead ions by adsorbing to lead ions, There is a side effect of inhibiting the charging reaction of the negative electrode active material and suppressing the improvement of charge acceptability.
- bisphenols, aminobenzenesulfonic acid and formaldehyde condensates having the chemical structural formula of [Chemical Formula 1] have weak adsorptive power to lead ions and have a small amount of adsorption.
- the condensate is used, the charge acceptability is less likely to be hindered, and the maintenance of the charge acceptability due to the addition of the carbonaceous conductive material is less likely to be hindered.
- the present invention prevents selection of sodium lignin sulfonate or the like represented by the chemical structural formula (partial structure) of [Chemical Formula 2] below as an organic compound that suppresses the coarsening of the negative electrode active material associated with charge and discharge. is not.
- sodium lignin sulfonate is frequently used as an organic compound that suppresses the coarsening of the negative electrode active material, it has a drawback that it has a strong adsorption power to lead ions and has a strong side effect of suppressing a charging reaction.
- bisphenols, aminobenzene sulfonic acid, and formaldehyde condensates have a weak adsorption capacity to lead ions and are less likely to be adsorbed by lead ions. Will not be disturbed.
- a normal polyethylene separator made of a polyethylene microporous sheet can be used as the separator.
- a polyethylene separator can be used alone, but from a non-woven fabric made of fibers of materials such as glass fiber, polyolefin (polyethylene, polypropylene, etc.) fiber, pulp, etc., rather than using a polyethylene separator alone. It is preferable to use a separator made of polyethylene (hereinafter simply referred to as “separator made of nonwoven fabric”) and a polyethylene separator.
- a separator made of nonwoven fabric and a polyethylene separator are used in combination, a polyethylene separator and a separator made of nonwoven fabric are overlapped so that the surface facing the negative electrode plate of the separator is made of a separator made of nonwoven fabric.
- the separator made of a nonwoven fabric can appropriately contain inorganic powder such as silica. Since the nonwoven fabric can be produced by dispersing the fibers in water and paper making them, the inorganic powder can be easily contained in the nonwoven fabric by dispersing the inorganic powder together with the fibers during paper making.
- nonwoven fabric composed of such a mixture of a plurality of fibers, for example, a glass fiber alone, such as a nonwoven fabric constituting a thin separator applied to a control valve type lead storage battery disclosed in Japanese Patent Application Laid-Open No. 2002-260714. It is not made by the non-woven fabric made by a mixture of glass fibers and acid-resistant organic resin fibers, or by a mixture of glass fibers and acid-resistant organic resin fibers with silica added as necessary. A nonwoven fabric can be suitably used.
- an unformed positive electrode plate was prepared.
- water is added to a mixture of lead oxide, red lead and cut fiber (polyethylene terephthalate short fiber, the same shall apply hereinafter) and kneaded, and then this mixture is added little by little with dilute sulfuric acid.
- the positive electrode active material paste was manufactured by kneading. This active material paste is filled into an expanded current collector produced by subjecting a rolled sheet made of a lead alloy to an expanding process, and aged for 24 hours in an atmosphere of 40 ° C. and 95% humidity, and then the current collector. The positive electrode active material filled in was dried to produce an unchemically formed positive electrode plate.
- positive electrode plates having positive electrode active materials with different utilization rates for the discharge reaction were prepared as follows. That is, as the amount of dilute sulfuric acid added at the time of preparing the positive electrode active material paste increases, the porosity of the active material increases and the utilization rate of the positive electrode active material related to the discharge reaction is improved. Thus, positive electrode plates having different active material utilization rates related to the discharge reaction were obtained.
- an unformed negative electrode plate was produced.
- water is added to a mixture of lead oxide, cut fiber, barium sulfate, carbonaceous conductive material, and an organic compound that functions to suppress coarsening of the negative electrode active material, and kneaded.
- this mixture was kneaded while dilute sulfuric acid was added little by little to prepare a negative electrode active material paste.
- This active material paste is filled into an expanded current collector produced by subjecting a rolled sheet made of a lead alloy to an expanding process, aged in an atmosphere of 40 ° C. and 95% humidity for 24 hours, and then dried.
- An unformed negative electrode plate was produced.
- the following negative electrode plates A, B, C, and B ′ were prepared by using different organic compounds and carbonaceous conductive materials that suppress the coarsening of the negative electrode active material.
- Negative electrode plate A In the negative electrode plate A, an organic compound that suppresses the coarsening of the negative electrode active material is selected as a main component of sodium lignin sulfonate represented by the chemical structural formula of [Chemical Formula 2] as a carbonaceous conductive material. Carbon black (specific surface area 260 m 2 / g) using heavy oil as a raw material was used, and the amount of carbon black added to the negative electrode active material was 0.2 parts by mass with respect to 100 parts by mass of the active material.
- Negative electrode plate B In the negative electrode plate B, as an organic compound that suppresses the coarsening of the negative electrode active material, a bisphenol A / aminobenzenesulfonic acid / formaldehyde condensate represented by the chemical structural formula of [Chemical Formula 1] (molecular weight: 17,000-2. (100,000, sulfur content in the compound is 6 to 11% by mass), and the carbon black is used as the carbonaceous conductive material, and the amount of carbon black added to the negative electrode active material is selected. And 0.2 part by mass with respect to 100 parts by mass of the active material.
- Negative electrode plate C In the negative electrode plate C, as an organic compound that suppresses the coarsening of the negative electrode active material, a bisphenol A / aminobenzenesulfone / formaldehyde condensate (molecular weight: 17,000 to 2.0) represented by the chemical structural formula of [Chemical Formula 1] If the sulfur content in the compound is 6 to 11% by mass), the carbonaceous conductive material is flaky graphite (particle size 180 ⁇ m) and added to the negative electrode active material. The amount was 2 parts by mass with respect to 100 parts by mass of the active material.
- Negative electrode plate B ′ In the negative electrode plate B ′, a bisphenol A / aminobenzenesulfonic acid / formaldehyde condensate represented by the chemical structural formula of [Chemical Formula 1] (molecular weight: 17,000 to 2) is used as an organic compound for suppressing the coarsening of the negative electrode active material. (100,000, sulfur content in the compound was 6 to 11% by mass), and a carbonaceous conductive material was not added to the negative electrode active material.
- a lead storage battery was assembled by combining the negative plates A, B, C, and B ', a positive plate with various utilization rates of the positive electrode active material related to the discharge reaction, and two types of separators.
- the battery is assembled by alternately laminating positive and negative plates through separators to form a group of six positive plates and seven negative plates, and using the cast-on-strap (COS) method, Electrode groups were prepared by welding the ears of the plates.
- the assembled lead storage battery is a D23 size lead storage battery defined in JIS standards.
- separator two types of separators were prepared: a separator P composed of only a polyethylene separator and a separator Q composed of a nonwoven fabric at least on the surface facing the surface of the negative electrode plate.
- the separator Q used in this example has a structure in which a nonwoven fabric made of glass fibers is placed on one surface of a polyethylene separator, and the nonwoven fabric is opposed to the surface of the negative electrode plate when forming the electrode plate group. Be placed.
- a glass fiber nonwoven fabric was used as the nonwoven fabric constituting the separator Q.
- the nonwoven fabric constituting the separator Q is not limited to a glass fiber nonwoven fabric, but instead of a glass fiber nonwoven fabric, a polyolefin-based nonwoven fabric is used.
- a nonwoven fabric made of fibers of materials such as materials and pulp may be used, and a nonwoven fabric made of a mixture of fibers of these materials may be used.
- the separator Q was formed by overlapping a polyethylene separator and a nonwoven fabric made of glass fiber.
- the separator Q had a surface facing the negative electrode plate made of a material such as glass, polyolefin, or pulp.
- the separator Q may be constituted only by a nonwoven fabric made of glass fiber or the like.
- a dilute sulfuric acid having a specific gravity of 1.24 was injected into the battery case, and charged with an amount of electricity of 200% of the theoretical capacity based on the amount of active material charged to complete the lead acid battery.
- NMR nuclear magnetic resonance
- the lead storage battery of Example 1 after the chemical conversion was disassembled the negative electrode plate was taken out, and the taken out negative electrode plate was washed with water to wash away the sulfuric acid content.
- the negative electrode active material after chemical conversion is porous metallic lead.
- the negative electrode plate was dried in an inert gas such as nitrogen.
- the negative electrode active material is separated from the dried negative electrode plate, pulverized, the pulverized product is put into a 10% sodium hydroxide solution, and the extracted liquid from which the generated precipitate (lead hydroxide) is removed is analyzed with the spectroscopic device. ⁇ It was measured.
- the measurement conditions are as shown in Table 1 below.
- FIG. 2 shows a spectrum measured by NMR spectroscopy.
- the horizontal axis in FIG. 2 indicates chemical shift (ppm), and the vertical axis indicates peak intensity.
- P-aminobenzene a formaldehyde condensate of bisphenol A aminobenzene sulfonic acid sodium salt represented by the chemical structural formula of [Chemical Formula 1] as indicated by the chemical shift of 6.7 ppm and 7.5 ppm with double circles A peak derived from a sulfonic acid group was observed.
- the electrode plate group produced in this example has the following seven types.
- Type 1 Positive electrode plate: A positive electrode plate was prepared in which the active material utilization rate for the discharge reaction was changed in six steps from 48% to 68%.
- Negative electrode plate As an organic compound that suppresses the coarsening of the negative electrode active material by adding 0.2 parts by mass of carbon black using heavy oil having a specific surface area of 260 m 2 / g as a raw material to 100 parts by mass of the active material [ The negative electrode plate B using the condensate of Chemical formula 1] was used.
- 100 mass parts of active material means 100 mass parts of active material (spongy metal lead) in a fully charged state.
- Separator A polyethylene separator P was used.
- Positive electrode plate A positive electrode plate was prepared in which the active material utilization rate for the discharge reaction was changed in six steps from 48% to 68%.
- Negative electrode plate the negative electrode plate B using the condensate of [Chemical Formula 1] as an organic compound that suppresses the coarsening of the negative electrode active material by adding 0.2 parts by mass of the carbon black to 100 parts by mass of the active material.
- Separator A separator Q in which a polyethylene separator and a nonwoven fabric made of glass fiber are overlapped is used.
- Positive electrode plate A positive electrode plate was prepared in which the active material utilization rate for the discharge reaction was changed in six steps from 48% to 68%.
- Negative electrode plate The amount of carbon black added is 0.2 parts by mass with respect to 100 parts by mass of the active material, and the main component is sodium lignin sulfonate of [Chemical Formula 2] as an organic compound that suppresses the coarsening of the negative electrode active material.
- the selected negative electrode plate A was used.
- Separator A separator P made of polyethylene was used.
- [Type 4] Positive electrode plate A positive electrode plate was prepared in which the active material utilization rate for the discharge reaction was changed in six steps from 48% to 68%.
- Negative electrode plate The amount of carbon black added is 0.2 parts by mass with respect to 100 parts by mass of the active material, and sodium lignin sulfonate having a chemical structural formula of [Chemical Formula 2] is used as an organic compound that suppresses the coarsening of the negative electrode active material.
- the negative electrode plate A selected as the main component was used.
- Separator A separator Q made of a polyethylene separator and a nonwoven fabric made of glass fiber was used.
- Positive electrode plate A positive electrode plate was prepared in which the active material utilization rate for the discharge reaction was changed in six steps from 48% to 68%.
- Negative electrode plate The amount of natural flake graphite added is 2 parts by mass with respect to 100 parts by mass of the active material, and the negative electrode plate C using the condensate of [Chemical Formula 1] as an organic compound that suppresses the coarsening of the negative electrode active material is used. It was. Separator: A polyethylene separator P was used. [Type 6] Positive electrode plate: A positive electrode plate was prepared in which the active material utilization rate for the discharge reaction was changed in six steps from 48% to 68%.
- Negative electrode plate The amount of natural flake graphite added is 2 parts by mass with respect to 100 parts by mass of the active material, and the negative electrode plate C using the condensate of [Chemical Formula 1] as an organic compound that suppresses the coarsening of the negative electrode active material is used. It was. Separator: A separator Q made of a polyethylene separator and a nonwoven fabric made of glass fiber was used. [Type 7] Positive electrode plate: A positive electrode plate was prepared in which the active material utilization rate for the discharge reaction was changed in six steps from 48% to 68%.
- Negative electrode plate A negative electrode plate B ′ using a condensate of [Chemical Formula 1] as an organic compound that suppresses the coarsening of the negative electrode active material without adding a carbonaceous conductive material was used.
- Separator A separator Q made of a polyethylene separator and a nonwoven fabric made of glass fiber was used.
- the utilization rate of the positive electrode active material related to the discharge reaction was measured by the method described above. That is, an electrode plate group of one positive electrode plate and two negative electrode plates, which is configured by arranging a negative electrode plate on both sides of one positive electrode plate (the theoretical capacity of the negative electrode active material is the theoretical capacity of the positive electrode active material). 1.5 times or more) is stored in the battery case, and an electrolytic solution (diluted sulfuric acid having a specific gravity of 1.28) is placed in the battery case with a liquid volume of 1.5 times or more the theoretical capacity of the positive electrode active material. After configuring the poured lead storage battery and making it fully charged, the lead storage battery is discharged at a rated capacity of 0.2 C current, before the negative electrode active material is consumed.
- a positive electrode-dominated discharge test was conducted in which the discharge reaction became impossible due to wear and the discharge ended.
- the ratio of the amount of discharge electricity until the end of discharge and the theoretical discharge capacity of the positive electrode active material of the positive electrode plate was defined as the positive electrode active material utilization rate.
- the charge acceptability was measured as follows. Adjust the SOC (charged state) to 90% of the fully charged state in a constant temperature bath at 25 ° C and apply 14V charging voltage (however, the current before reaching 14V is limited to 100A). ) A charging current value at 5 seconds from the start (5th charging current value) was measured as a charging current value indicating initial charge acceptance. The higher the 5th second charging current value, the higher the initial charge acceptability.
- the charging voltage is 14.8 V (however, the current before reaching 14.8 V is limited to 25 A), and after charging for 10 minutes, the discharging current is 25 A (constant) ),
- the charge test was performed under the same conditions as those for the initial charge acceptance measurement after 5000 cycles of a cycle test in which the charge / discharge cycle for performing the constant current discharge for 4 minutes was set to 1 cycle. A higher charge current value at 5 seconds after 5000 cycles means that the initial good charge acceptability is maintained thereafter.
- Cycle characteristic measurement (life test) was performed as follows. Charging / discharging with constant current / constant voltage charging for 100A-14V-60 seconds after adjusting the ambient temperature so that the battery temperature is 25 ° C, performing constant current discharging for 45A-59 seconds and 300A-1 seconds A life test was performed with one cycle. This test is a cycle test that simulates the use of lead-acid batteries in ISS cars. In this life test, since the amount of charge is small relative to the amount of discharge, the battery gradually becomes insufficient when charging is not performed completely. As a result, the voltage at the first second when the discharge current is 300 A for 1 second is obtained. Decrease gradually.
- Tables 2 to 8 show the measurement results of the 5 second charge current and the measurement results of the cycle characteristics, respectively, performed on the type 1 to 7 lead acid batteries having the type 1 to type 7 electrode plate group configuration.
- the case where the utilization rate of the positive electrode active material related to the discharge reaction is 48% is a conventional example
- the utilization rate of the positive electrode active material related to the discharge reaction is set to 48%.
- % Was set as a comparative example
- Tables 5 to 7 a case where the utilization rate of the positive electrode active material related to the discharge reaction was set to 68% was set as a reference example.
- Table 8 showing examples in which no carbonaceous conductive material was added to the negative electrode active material, all examples in which the utilization rate of the positive electrode active material was 48% to 68% were used as reference examples.
- the 5 second charging current and cycle characteristics shown in each table are evaluated based on the conventional example of Table 4 as 100 (the initial value is 100 for the 5 second charging current).
- the utilization rate of the positive electrode active material related to the discharge reaction is 48%. From the conventional example, it can be seen that the charging current at 5 seconds (charge acceptance) and the cycle characteristics (life performance under PSOC) can be greatly improved. Further, by setting the utilization factor of the positive electrode active material to 50% or more, the charging current and cycle characteristics at the 5th second can be clearly improved as compared with the case where the utilization factor is 48%.
- the charging current and cycle characteristics at the 5th second peaked as the utilization rate of the positive electrode active material increased, and when the utilization rate of the positive electrode active material reached 68%, the cycle rate was higher than when the utilization rate of the positive electrode active material was 65%. There is a tendency for the characteristics to deteriorate.
- the life performance tends to be lower than that in the case of%.
- the utilization factor of the positive electrode active material is set to 50% or more.
- the charging current at 5 seconds and the cycle characteristics are improved as compared with the case where the utilization factor is 48%. Also in this case, the charging current and the cycle characteristics at the fifth second tend to reach a peak as the utilization rate of the positive electrode active material is increased.
- Table 6 shows the results of adding 2 parts by weight of flake graphite under the condition that the organic compound that suppresses the coarsening of the negative electrode active material is the main component of the condensate of [Chemical Formula 1]. Shows the result of adding 0.2 parts by mass of carbon black under the condition that the organic compound that suppresses the coarsening of the negative electrode active material is the main component of the condensate of [Chemical Formula 1].
- flake graphite has the characteristic that the physical property of the active material paste does not change even if the amount added is increased (the paste does not become hard), the amount added to the negative electrode active material can be increased.
- the charging current and cycle characteristics at the 5th second can be clearly improved as compared with the case where the utilization rate is set to 48%.
- the eye charging current and the cycle characteristics reach a peak as the utilization rate of the positive electrode active material increases, and when the utilization rate of the positive electrode active material reaches 68%, the cycle characteristics are higher than when the utilization rate of the positive electrode active material is 65%. Tend to decrease.
- the cycle characteristics can be greatly improved when the separator Q using a nonwoven fabric is used as the separator facing the negative electrode plate, compared to the case where the polyethylene separator P is used.
- the Also in this case by setting the utilization rate of the positive electrode active material to 50% or more, the charging current and cycle characteristics at the 5th second can be clearly improved as compared with the case where the utilization rate is set to 48%.
- the eye charging current and the cycle characteristics reach a peak as the utilization rate of the positive electrode active material increases. When the utilization rate of the positive electrode active material reaches 68%, the life performance is higher than when the utilization rate of the positive electrode active material is 65%. Tend to decrease.
- Table 5 shows an example in which no carbonaceous conductive material is added as a reference example.
- the initial 5 second charging current value is not much different from the cases of Tables 3 and 7.
- the cycle characteristics are 3 Remarkably worse than in Table 7. That is, the initial charge acceptability is good, but the good state cannot be maintained over the charge / discharge cycle, and the charge acceptability is lowered with the progress of the charge / discharge cycle. Became worse. If the carbonaceous conductive material is not added, cycle characteristics cannot be improved even if the active material utilization of the positive electrode plate is adjusted appropriately.
- the utilization rate of the positive electrode active material is increased.
- the negative electrode plate B and the negative electrode plate in which the organic compound that suppresses the coarsening of the negative electrode active material is selected as the main component of the condensate of [Chemical Formula 1] while the charge acceptability cannot be significantly improved.
- the charge acceptability is greatly improved by increasing the utilization rate of the positive electrode active material, and the charge acceptability is maximized, which is about twice that when the utilization rate of the positive electrode active material is 48%. It became clear to reach.
- This cycle test is a heavy load life test, not a life mode due to coarsening or sulfation of the negative electrode active material, but a cycle in a life mode where the discharge becomes impossible due to the active material muddying of the positive electrode plate. It is a life test. In this test, the lifetime was defined as the voltage at the first hour of discharge was below 10.2V. The results of this cycle life test are shown in Table 9. The cycle results in Table 9 are the number of cycles when the lifetime when a positive electrode plate with a utilization factor of 48% is used is 100. The test results were the same when any of the negative electrodes A, B, and C was used.
- the utilization rate of the positive electrode active material is preferably in the range of 50% to 65% from the viewpoint of heavy load use.
- the cycle characteristics shown in Tables 2 to 7 are in the life mode mainly due to coarsening and sulfation of the negative electrode active material on the side where the active material utilization rate is low, and as the active material utilization rate increases, The life mode is shifted due to the muddying of the positive electrode active material.
- the cycle number is about three times that of the conventional example due to the synergistic effect with the improvement in charge acceptability of the negative electrode plate.
- the charge acceptance and life performance of the battery can be improved by using the negative electrode plate with improved charge acceptance and increasing the utilization factor of the active material of the positive electrode plate for the discharge reaction.
- the separator is made of polyethylene both when the condensate of [Chemical Formula 1] is used and when the main component is sodium lignin sulfonate of [Chemical Formula 2]. It was revealed that the cycle characteristics were greatly improved by changing the separator P from the separator P to the separator Q made of nonwoven fabric.
- a condensate of a basic structural unit in which a p-aminobenzenesulfonic acid group is bonded to the benzene nucleus of a bisphenol has a particularly high effect.
- the same effect can be obtained by using a condensate bonded to the benzene nucleus.
- the average primary particle diameter of the flaky graphite is preferably in the range of 100 ⁇ m or more.
- the optimum value of the average primary particle diameter of the flaky graphite is 180 ⁇ m.
- the flaky graphite is generally produced by refining natural graphite, and the production of flaky graphite having a particle diameter exceeding 220 ⁇ m makes it difficult to obtain an industrially used amount because the yield is lowered.
- the charge acceptability of the lead storage battery was improved only by improving the characteristics of the negative electrode plate.
- the utilization rate of the positive electrode active material related to the discharge reaction is improved.
- the charge acceptability has been improved, thereby making it possible to further improve the charge acceptability of the whole battery as compared to the prior art, and to enable a higher rate discharge under PSOC.
- it is possible to improve the charge acceptability of the lead storage battery so that it is possible to prevent repeated charge and discharge in a state of insufficient charge, so that discharge is generated by repeated charge and discharge in a state of insufficient charge.
- the present invention makes it possible to provide a liquid lead-acid battery with improved charge acceptability and lifetime performance under PSOC, and is a micro hybrid vehicle such as an ISS vehicle or a power generation control vehicle. It contributes to the spread of such. Therefore, the present invention is useful for solving the global problem of reducing carbon dioxide emission by improving the fuel efficiency of automobiles and suppressing global warming, and has great industrial applicability. .
Abstract
Description
負極板Aにおいては、負極活物質の粗大化を抑制する有機化合物として、前記[化2]の化学構造式で示されるリグニンスルホン酸ナトリウムを主成分とするものを選択し、炭素質導電材として、重油を原料としたカーボンブラック(比表面積260m2/g)を用いて、カーボンブラックの負極活物質への添加量を、活物質100質量部に対し0.2質量部とした。
負極板Bにおいては、負極活物質の粗大化を抑制する有機化合物として、[化1]の化学構造式で示されるビスフェノールA・アミノベンゼンスルホン酸・ホルムアルデヒド縮合物(分子量1.7万~2.0万,化合物中のイオウ含有量は6~11質量%)を主成分とするものを選択し、炭素質導電材として、上記カーボンブラックを用いて、カーボンブラックの負極活物質への添加量を、活物質100質量部に対し0.2質量部とした。
負極板Cにおいては、負極活物質の粗大化を抑制する有機化合物として、[化1]の化学構造式で示されるビスフェノールA・アミノベンゼンスルホン・ホルムアルデヒド縮合物(分子量1.7万~2.0万,化合物中のイオウ含有量は6~11質量%)を主成分とするものを選択し、炭素質導電材として、鱗片状黒鉛(粒径180μm)を用いて、その負極活物質への添加量を、活物質100質量部に対し2質量部とした。
負極板B’においては、負極活物質の粗大化を抑制する有機化合物として、[化1]の化学構造式で示されるビスフェノールA・アミノベンゼンスルホン酸・ホルムアルデヒド縮合物(分子量1.7万~2.0万,化合物中のイオウ含有量は6~11質量%)を主成分とするものを選択し、負極活物質には炭素質導電材を添加しなかった。
化学シフト6.7ppmと7.5ppmに二重丸を付して示したように、[化1]の化学構造式に示されるビスフェノールAアミノベンゼンスルホン酸ナトリウム塩のホルムアルデヒド縮合物のp-アミノベンゼンスルホン酸基に由来するピークが認められた。さらに、化学シフト0.5ppm~2.5ppmの領域に三角印を付して示したように、[化1]の化学構造式で示されるビスフェノールA・アミノベンゼンスルホン酸・ホルムアルデヒド縮合物のビスフェノールA骨格に由来するピークが認められた。
上記の結果から、負極活物質中に[化1]に示されたビスフェノールA・アミノベンゼンスルホン酸・ホルムアルデヒド縮合物が存在することを確認できた。
[タイプ1]
正極板:放電反応に関する活物質利用率を48%から68%まで6段階に変化させた正極板を用意した。
負極板:比表面積が260m2/gである重油を原料としたカーボンブラックの添加量を活物質100質量部に対し0.2質量部とし、負極活物質の粗大化を抑制する有機化合物として[化1]の縮合物を用いた負極板Bを用いた。ここで、活物質100質量部とは、満充電状態における活物質(海綿状金属鉛)100質量部を言う。以下同様である。
セパレータ:ポリエチレン製セパレータPを用いた。
[タイプ2]
正極板:放電反応に関する活物質利用率を48%から68%まで6段階に変化させた正極板を用意した。
負極板:上記カーボンブラックの添加量を活物質100質量部に対し0.2質量部とし、負極活物質の粗大化を抑制する有機化合物として[化1]の縮合物を用いた負極板Bを用いた。
セパレータ:ポリエチレン製セパレータとガラス繊維からなる不織布とを重ね合わせたセパレータQを用いた。
[タイプ3]
正極板:放電反応に関する活物質利用率を48%から68%まで6段階に変化させた正極板を用意した。
負極板:上記カーボンブラックの添加量を活物質100質量部に対し0.2質量部とし、負極活物質の粗大化を抑制する有機化合物として[化2]のリグニンスルホン酸ナトリウムを主成分とするものを選択した負極板Aを用いた。
セパレータ:ポリエチレン製のセパレータPを用いた。
[タイプ4]
正極板:放電反応に関する活物質利用率を48%から68%まで6段階に変化させた正極板を用意した。
負極板:上記カーボンブラックの添加量を活物質100質量部に対し0.2質量部とし、負極活物質の粗大化を抑制する有機化合物として[化2]の化学構造式のリグニンスルホン酸ナトリウムを主成分とするものを選択した負極板Aを用いた。
セパレータ:ポリエチレン製セパレータとガラス繊維からなる不織布とからなるセパレータQを用いた。
[タイプ5]
正極板:放電反応に関する活物質利用率を48%から68%まで6段階に変化させた正極板を用意した。
負極板:天然鱗片状黒鉛の添加量を活物質100質量部に対し2質量部とし、負極活物質の粗大化を抑制する有機化合物として[化1]の縮合物を用いた負極板Cを用いた。
セパレータ:ポリエチレン製セパレータPを用いた。
[タイプ6]
正極板:放電反応に関する活物質利用率を48%から68%まで6段階に変化させた正極板を用意した。
負極板:天然鱗片状黒鉛の添加量を活物質100質量部に対し2質量部とし、負極活物質の粗大化を抑制する有機化合物として[化1]の縮合物を用いた負極板Cを用いた。
セパレータ:ポリエチレン製セパレータとガラス繊維からなる不織布とからなるセパレータQを用いた。
[タイプ7]
正極板:放電反応に関する活物質利用率を48%から68%まで6段階に変化させた正極板を用意した。
負極板:炭素質導電材を添加せず、負極活物質の粗大化を抑制する有機化合物として[化1]の縮合物を用いた負極板B’を用いた。
セパレータ:ポリエチレン製セパレータとガラス繊維からなる不織布とからなるセパレータQを用いた。
上記の試験により、定電圧充電時の充電受入れ性と、PSOC下で使用されたときの耐久性とを評価できる。
即ち負極活物質の粗大化を抑制する有機化合物として、[化1]の縮合物を主成分とするものを選択した負極板B及び負極板Cを用いた場合、放電反応に関する正極活物質の利用率が48%であったとしても、従来例よりも充電受入れ性が大きく向上したことが分る。
また、負極活物質の粗大化を抑制する有機化合物として[化2]のリグニンスルホン酸ナトリウムを主成分とするものを選択した負極種別Aを用いた場合には、正極活物質の利用率を高くしても充電受入れ性を大幅には改善できないのに対し、負極活物質の粗大化を抑制する有機化合物として[化1]の縮合物を主成分とするものを選択した負極板B及び負極板Cを用いた場合には、正極活物質の利用率を高くすることにより充電受入れ性が大きく向上し、充電受入れ性が最大で正極活物質の利用率を48%とした場合の約2倍に達することが明らかになった。
Claims (8)
- 負極活物質を負極集電体に充填してなる負極板と、正極活物質を正極集電体に充填してなる正極板とをセパレータを介して積層した極板群を、電解液とともに電槽内に収容した構成を有して、充電が間欠的に行われ、部分充電状態で負荷への高率放電が行われる液式鉛蓄電池であって、
少なくとも、炭素質導電材と、充放電に伴う負極活物質の粗大化を抑制する有機化合物とが前記負極活物質に添加され、
前記正極板の放電反応に関する活物質利用率が50%以上65%以下の範囲に設定されていること、
を特徴とする鉛蓄電池。 - 前記充放電に伴う負極活物質の粗大化を抑制する有機化合物は、ビスフェノール類・アミノベンゼンスルホン酸・ホルムアルデヒド縮合物を主成分とする有機化合物である請求項1に記載の鉛蓄電池。
- 前記炭素質導電材は、黒鉛、カーボンブラック、活性炭、炭素繊維及びカーボンナノチューブからなる材料群から選択された少なくとも1つである請求項2または3に記載の鉛蓄電池。
- 前記炭素質導電材は、鱗片状黒鉛である請求項4に記載の鉛蓄電池。
- 鱗片状黒鉛の平均一次粒子径が100μm以上である請求項5に記載の鉛蓄電池。
- 前記セパレータは、前記負極板の表面に相対する表面が、ガラス、パルプ及びポリオレフィンからなる材料群から選択された少なくとも1つの材料の繊維で構成される不織布からなるように構成されている請求項2,3,4,5または6に記載の鉛蓄電池
- 前記正極板の活物質利用率は、55%以上65%以下の範囲に設定されている請求項7に記載の鉛蓄電池。
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EP11750291.4A EP2544292A4 (en) | 2010-03-02 | 2011-01-07 | LEAD ACCUMULATOR |
US13/581,664 US20130029210A1 (en) | 2010-03-02 | 2011-01-07 | Lead acid storage battery |
CN201180000081XA CN102265448A (zh) | 2010-03-02 | 2011-01-07 | 铅蓄电池 |
KR1020127022913A KR20130033349A (ko) | 2010-03-02 | 2011-01-07 | 납 축전지 |
JP2012502973A JP5598532B2 (ja) | 2010-03-02 | 2011-01-07 | 鉛蓄電池 |
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US (1) | US20130029210A1 (ja) |
EP (1) | EP2544292A4 (ja) |
JP (1) | JP5598532B2 (ja) |
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WO2013005733A1 (ja) * | 2011-07-05 | 2013-01-10 | 株式会社Gsユアサ | 液式鉛蓄電池 |
JP5618008B2 (ja) * | 2011-09-01 | 2014-11-05 | 新神戸電機株式会社 | 鉛蓄電池 |
WO2017110594A1 (ja) * | 2015-12-25 | 2017-06-29 | 株式会社Gsユアサ | 鉛蓄電池 |
JP2017162602A (ja) * | 2016-03-08 | 2017-09-14 | 日立化成株式会社 | 鉛蓄電池 |
JP2018018747A (ja) * | 2016-07-29 | 2018-02-01 | 株式会社Gsユアサ | 鉛蓄電池 |
JP2018018744A (ja) * | 2016-07-29 | 2018-02-01 | 株式会社Gsユアサ | 鉛蓄電池 |
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US9553335B2 (en) | 2010-12-21 | 2017-01-24 | Hitachi Chemical Company, Ltd. | Lead-acid battery |
JP6222239B2 (ja) * | 2013-10-28 | 2017-11-01 | 日立化成株式会社 | 樹脂組成物、電極、鉛蓄電池及びこれらの製造方法 |
WO2015145800A1 (ja) * | 2014-03-28 | 2015-10-01 | 新神戸電機株式会社 | 鉛蓄電池及び鉛蓄電池用の電極集電体 |
JP6202477B1 (ja) * | 2016-04-21 | 2017-09-27 | 株式会社Gsユアサ | 鉛蓄電池 |
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EP2544292A4 (en) | 2014-11-19 |
KR20130033349A (ko) | 2013-04-03 |
JPWO2011108175A1 (ja) | 2013-06-20 |
EP2544292A1 (en) | 2013-01-09 |
CN102265448A (zh) | 2011-11-30 |
US20130029210A1 (en) | 2013-01-31 |
JP5598532B2 (ja) | 2014-10-01 |
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