WO2020241885A1 - Batterie de stockage au plomb - Google Patents

Batterie de stockage au plomb Download PDF

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Publication number
WO2020241885A1
WO2020241885A1 PCT/JP2020/021482 JP2020021482W WO2020241885A1 WO 2020241885 A1 WO2020241885 A1 WO 2020241885A1 JP 2020021482 W JP2020021482 W JP 2020021482W WO 2020241885 A1 WO2020241885 A1 WO 2020241885A1
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negative electrode
polymer compound
electrode plate
ppm
regions
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PCT/JP2020/021482
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English (en)
Japanese (ja)
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雄輔 熊谷
宏樹 籠橋
泰如 ▲浜▼野
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株式会社Ｇｓユアサ
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Priority to JP2021521916A priority Critical patent/JPWO2020241885A1/ja
Publication of WO2020241885A1 publication Critical patent/WO2020241885A1/fr

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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
    • 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
    • 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 lead storage battery.
  • Lead-acid batteries are used for various purposes such as in-vehicle use and industrial use.
  • Lead-acid batteries include a negative electrode plate, a positive electrode plate, a separator (or mat), an electrolytic solution, and the like.
  • Additives may be added to the constituent members of the lead-acid battery from the viewpoint of imparting various functions.
  • Patent Document 1 proposes a lead-acid battery characterized in that a copolymer of propylene oxide and ethylene oxide is added to a negative electrode plate active material in combination with lignin sulfonate.
  • Patent Document 2 is characterized in that an activator containing an organic polymer is sealed in a small airtight container having a dehiscence mechanism into an electric tank, and the small airtight container is attached to the electric tank or a lid. Storage batteries have been proposed.
  • Patent Document 3 includes a plurality of fibers coated with a size composition, a binder composition, and one or more kinds of additives, and the additives include rubber additives, rubber derivatives, aldehydes, and metal salts.
  • the additive comprises one or more of ethylene-propylene oxide block copolymer, sulfuric acid ester, sulfonic acid ester, phosphoric acid ester, polyacrylic acid, polyvinyl alcohol, lignin, phenol aldehyde resin, cellulose, wood flour and the like. Fiber-attached mats that can function to reduce water loss in lead storage batteries have been proposed.
  • the specific gravity of the electrolytic solution at the bottom of the battery becomes higher than that at the top of the battery as the discharge progresses.
  • the difference in specific gravity of the electrolytic solution is further expanded during charging.
  • stratification The phenomenon in which the specific gravity difference of the electrolytic solution occurs in the vertical direction is called stratification. It is believed that repeated charging and discharging in a stratified state shortens not only the charging and discharging characteristics but also the battery life.
  • the stratification of the electrolytic solution can be eliminated by agitating the electrolytic solution by overcharging the lead-acid battery and generating gas on the electrode plate, but the decrease (reduction) of the electrolytic solution due to the gas generation becomes a problem. ..
  • One aspect of the present invention is a negative electrode plate for a lead storage battery including a negative electrode current collector and a negative electrode material, wherein the negative electrode material contains a polymer compound from an upper end portion to a lower end portion of the negative electrode plate.
  • the negative electrode plate is divided into 32 equal parts in an 8-row, 4-column matrix in which the direction of the electrode is the X direction, the direction intersecting the X direction is the Y direction, the Y direction is the row direction, and the X direction is the column direction.
  • the average value of the content of the polymer compound in the negative electrode material in all 32 regions is C0
  • the content of the polymer compound is the content of the polymer compound among the 16 regions in the first to fourth rows from the upper end side.
  • the number N (1-4) of the regions smaller than C0 and the number N (5-8) of the regions in which the content of the polymer compound is smaller than C0 among the 16 regions in the 5th to 8th rows are N.
  • the present invention relates to a negative electrode plate satisfying ⁇ N (5-8).
  • Another aspect of the present invention is a negative electrode plate for a lead storage battery comprising a negative electrode current collector and a negative electrode material, wherein the negative electrode material contains a polymer compound and the upper end to the lower end of the negative electrode plate.
  • the negative electrode plate is divided into 32 equal parts in an 8-row, 4-column matrix in which the direction toward the X direction is the X direction, the direction intersecting the X direction is the Y direction, the Y direction is the row direction, and the X direction is the column direction.
  • the content of the polymer compound among the eight regions in the first to second rows from the upper end side is The number N (1-2) of the regions where is smaller than C0 and the number N (3-4) of the regions where the content of the polymer compound is smaller than C0 among the eight regions in the third to fourth rows are The number of regions N (5-6) that satisfy N (1-2) ⁇ N (3-4) and have a content of the polymer compound smaller than C0 among the eight regions in rows 5 to 6.
  • the number N (7-8) of the regions in which the content of the polymer compound is smaller than C0 among the eight regions in the 7th to 8th rows is N (5-6) ⁇ N (7-8).
  • the lead storage battery according to the embodiment of the present invention includes a positive electrode plate, a negative electrode plate, and an electrolytic solution, the positive electrode plate includes a positive electrode current collector and a positive electrode electrode material, and the negative electrode plate is a negative electrode current collector. It comprises a body and a negative electrode material, and the negative electrode material contains a polymer compound. The polymer compound has an action of increasing the overvoltage of the negative electrode material.
  • the negative electrode plate in which the negative electrode material contains a polymer compound hydrogen is less likely to be generated during overcharging, and the higher the content of the polymer compound in the negative electrode material, the greater the tendency to suppress hydrogen generation. In this portion, the reduction of the electrolytic solution is suppressed.
  • the polymer compound has an effect of suppressing the amount of overcharged electricity. It is considered that the above effects can be obtained by covering the surface of lead in the negative electrode material with the polymer compound.
  • polymer compounds particularly polymer compounds that easily have a linear structure
  • a small amount of polymer compound is expected to be present in the negative electrode material. It was found that a remarkable effect of increasing the hydrogen overvoltage can be obtained even when the above is included.
  • hydrogen is relatively likely to be generated in a portion where the negative electrode material does not contain a polymer compound or a portion where the content of the polymer compound in the negative electrode material is low.
  • the electrolytic solution can be efficiently agitated by hydrogen generation. That is, the stratification of the electrolytic solution is less likely to proceed.
  • the direction from the upper end portion (the side having the ear portion (tab)) of the negative electrode plate to the lower end portion is the X direction
  • the direction intersecting the X direction is the Y direction
  • the Y direction is the row direction
  • the negative electrode plate When the negative electrode plate is divided into 32 equal parts in a matrix of 8 rows and 4 columns with the X direction as the column direction and the average value of the content of the polymer compound in the negative electrode electrode material in all 32 regions is C0, the upper end side Of the 16 regions in rows 1 to 4, the number of regions N (1-4) in which the content of the polymer compound is smaller than C0, and among the 16 regions in rows 5 to 8, the polymer compound The number N (5-8) of the region whose content is smaller than C0 satisfies N (1-4) ⁇ N (5-8).
  • the number of regions N (5-6) in which the content of the polymer compound is smaller than C0, and the number N of the eight regions in rows 7 to 8 in which the content of the polymer compound is smaller than C0. (7-8) satisfies N (5-6) ⁇ N (7-8).
  • the X direction corresponds to the vertical direction, that is, the vertical direction in the normal usage state of the lead storage battery.
  • the Y direction corresponds to the horizontal direction.
  • FIG. 2 is a schematic view showing a negative electrode plate divided into 32 regions in a matrix.
  • the content of the polymer compound in the negative electrode material in R (x, y) is defined as C (x, y). That is, in the region R (x, y) where the content of the polymer compound is smaller than C0, C (x, y) ⁇ C0 is satisfied.
  • the ratio of the measured value of C0 to the measured value of C (x, y): C0 / C (x, y) is 0.95.
  • the region R (x, y) where C0 / C (x, y) is larger than 1.05 is defined as the region where C (x, y) ⁇ C0 is satisfied.
  • the target negative electrode plate When measuring the content of the negative electrode material contained in each region, the target negative electrode plate may be divided into 32 in a matrix of 8 rows and 4 columns as described above, and a sample of each region may be prepared. A plurality of the same negative electrode plates may be prepared, divided into 32 in the same manner, and samples having the same (x, y) value may be mixed to adjust the amount of the sample.
  • the negative electrode plate may further satisfy at least one of the following conditions. (1) In at least one column, the average value of C (1, y) to C (4, y) is larger than the average value of C (5, y) to C (8, y). (2) In at least one column, the average value of C (1, y) to C (4, y) is larger than the average value of C (6, y) to C (8, y). (3) In at least one column, the average value of C (1, y) to C (4, y) is larger than the average value of C (7, y) to C (8, y). (4) In at least one column, the average value of C (1, y) to C (4, y) is larger than C (8, y).
  • any of C (5, y) to C (8, y) is smaller than any of the rest.
  • C (8, y) is smaller than any of the rest.
  • C (8, y) is smaller than any of C (5, y) to C (7, y).
  • the average value C0 of the content of the polymer compound may be, for example, 3 ppm or more and 400 ppm or less. Further, the maximum value of the content of the polymer compound in the 16 regions of the first to fourth rows from the upper end side may be, for example, 400 ppm or less.
  • the lead-acid battery can be obtained by a manufacturing method including a step of assembling the lead-acid battery by accommodating the positive electrode plate, the negative electrode plate and the electrolytic solution in the battery case.
  • the separator is usually arranged so as to be interposed between the positive electrode plate and the negative electrode plate.
  • the step of assembling the lead storage battery may include a step of accommodating the positive electrode plate, the negative electrode plate and the electrolytic solution in the battery case, and then, if necessary, a step of forming the positive electrode plate and / or the negative electrode plate.
  • the positive electrode plate, the negative electrode plate, the electrolytic solution, and the separator are each prepared before being housed in the battery case.
  • FIG. 1 shows the appearance of an example of a lead storage battery according to an embodiment of the present invention.
  • the lead-acid battery 1 includes an electric tank 12 that houses a electrode plate group 11 and an electrolytic solution (not shown).
  • the inside of the electric tank 12 is partitioned into a plurality of cell chambers 14 by a partition wall 13.
  • One electrode plate group 11 is housed in each cell chamber 14.
  • the opening of the battery case 12 is closed by a lid 15 including a negative electrode terminal 16 and a positive electrode terminal 17.
  • the lid 15 is provided with a liquid spout 18 for each cell chamber. At the time of rehydration, the liquid spout 18 is removed and the rehydration liquid is replenished.
  • the liquid spout 18 may have a function of discharging the gas generated in the cell chamber 14 to the outside of the battery.
  • the electrode plate group 11 is formed by laminating a plurality of negative electrode plates 2 and positive electrode plates 3 with a separator 4 interposed therebetween.
  • the bag-shaped separator 4 that accommodates the negative electrode plate 2 is shown, but the form of the separator is not particularly limited.
  • the negative electrode shelf portion 6 for connecting the plurality of negative electrode plates 2 in parallel is connected to the through connecting body 8, and the positive electrode shelf portion for connecting the plurality of positive electrode plates 3 in parallel. 5 is connected to the positive electrode column 7.
  • the positive electrode column 7 is connected to the positive electrode terminal 17 outside the lid 15.
  • the negative electrode column 9 is connected to the negative electrode shelf 6, and the through connector 8 is connected to the positive electrode shelf 5.
  • the negative electrode column 9 is connected to the negative electrode terminal 16 outside the lid 15.
  • Each through-connecting body 8 passes through a through-hole provided in the partition wall 13 and connects the electrode plates 11 of the adjacent cell chambers 14 in series.
  • the positive electrode shelf 5 is formed by welding the ears provided on the upper part of each positive electrode plate 3 by a cast-on strap method or a burning method.
  • the negative electrode shelf portion 6 is also formed by welding the ear portions provided on the upper portions of the negative electrode plates 2 as in the case of the positive electrode shelf portion 5.
  • the lid 15 of the lead storage battery has a single structure (single lid), but is not limited to the case shown in the illustrated example.
  • the lid 15 may have, for example, a double structure including an inner lid and an outer lid (or upper lid).
  • the lid having a double structure is provided with a reflux structure between the inner lid and the outer lid for returning the electrolytic solution to the inside of the battery (inside the inner lid) from the reflux port provided on the inner lid. May be good.
  • FIG. 3 is a diagram showing the distribution of the polymer compound in the negative electrode plate according to the first aspect of the present embodiment. “C ⁇ C0” is displayed in the area satisfying C (x, y) ⁇ C0, and “ ⁇ ” is displayed in the other areas.
  • the negative electrode material in the region (R (8, y)) in the eighth row at the lowermost end does not contain a polymer compound, or the content of the polymer compound is low. In this case, hydrogen is more likely to be generated in the lowermost region of the negative electrode plate than in other regions, so that the electrolytic solution can be efficiently agitated.
  • C (8, y) ⁇ C0 may be satisfied in at least one column.
  • the following is satisfied in at least one row.
  • the average value of C (1, y) to C (4, y) is larger than the average value of C (5, y) to C (8, y).
  • the average value of C (1, y) to C (4, y) is larger than the average value of C (6, y) to C (8, y).
  • the average value of C (1, y) to C (4, y) is larger than the average value of C (7, y) to C (8, y).
  • the average value of C (1, y) to C (4, y) is larger than that of C (8, y).
  • Any one of C (5, y) to C (8, y) is smaller than any of the rest.
  • C (8, y) is smaller than any of the rest.
  • C (8, y) is smaller than any of C (8, y) is smaller than any of C (5, y) to C (7, y).
  • the negative electrode material in the region (R (7, y)) in the seventh row does not contain the polymer compound, or the content of the polymer compound is low. Also in this case, hydrogen is more likely to be generated in the region near the lowermost end of the negative electrode plate than in other regions, so that the electrolytic solution can be efficiently agitated.
  • C (7, y) ⁇ C0 may be satisfied in at least one column.
  • the following is satisfied in at least one row.
  • the average value of C (1, y) to C (4, y) is larger than the average value of C (5, y) to C (8, y).
  • the average value of C (1, y) to C (4, y) is larger than the average value of C (6, y) to C (8, y).
  • An example in which the average value of C (1, y) to C (4, y) is larger than the average value of C (7, y) to C (8, y).
  • Any one of C (5, y) to C (8, y) is smaller than any of the rest.
  • FIG. 5 is a diagram showing the distribution of polymer compounds in the negative electrode plate according to the third aspect of the present embodiment.
  • the negative electrode material in the region (R (5, y)) in the fifth row does not contain the polymer compound, or the content of the polymer compound is low. Also in this case, hydrogen is more likely to be generated in the region near the lower end of the negative electrode plate than in the region near the upper end, so that the electrolytic solution can be agitated relatively efficiently.
  • C (5, y) ⁇ C0 may be satisfied in at least one column.
  • the following is satisfied in at least one row.
  • the average value of C (1, y) to C (4, y) is larger than the average value of C (5, y) to C (8, y).
  • Any one of C (5, y) to C (8, y) is smaller than any of the rest.
  • FIG. 6 is a diagram showing the distribution of the polymer compound in the negative electrode plate according to the fourth aspect of the present embodiment.
  • the negative electrode material of the 4th row region (R (4, y)) and the 7th and 8th row regions (R (7, y), R (8, y)) is polymer. Contains no compounds or has a low content of polymer compounds. Also in this case, hydrogen is more likely to be generated in a wider region including the lowermost end portion of the negative electrode plate than in other regions, so that the electrolytic solution can be agitated relatively efficiently. Further, since the negative electrode material in the region of the fourth row near the center does not contain the polymer compound or the content of the polymer compound is low, the stirring efficiency of the electrolytic solution can be further improved.
  • C (4, y) ⁇ C0, C (7, y) ⁇ C0 and C (8, y) ⁇ C0 may be satisfied in at least one column.
  • the following is satisfied in at least one row.
  • the average value of C (1, y) to C (4, y) is larger than the average value of C (5, y) to C (8, y).
  • the average value of C (1, y) to C (4, y) is larger than the average value of C (6, y) to C (8, y).
  • the average value of C (1, y) to C (4, y) is larger than the average value of C (7, y) to C (8, y).
  • the average value of C (1, y) to C (4, y) is larger than that of C (8, y).
  • FIG. 7 is a diagram showing the distribution of the polymer compound in the negative electrode plate according to the first aspect of the present embodiment.
  • the negative electrode material of the region (R (4, y)) in the fourth row and the negative electrode material in the region (R (8, y)) in the eighth row does not contain a polymer compound, or the negative electrode material is made of a polymer compound.
  • the content is low. In this case, hydrogen is more likely to be generated in the lowermost region of the negative electrode plate than in other regions, so that the electrolytic solution can be agitated relatively efficiently. Further, since the negative electrode material in the region of the fourth row near the center does not contain the polymer compound or the content of the polymer compound is low, the stirring efficiency of the electrolytic solution can be further improved.
  • C (4, y) ⁇ C0 and C (8, y) ⁇ C0 may be satisfied in at least one column.
  • FIG. 8 is a diagram showing the distribution of the polymer compound in the negative electrode plate according to the second aspect of the present embodiment.
  • the negative electrode material of the regions of the third and fourth rows (R (3, y), R (4, y)) and the region of the eighth row (R (8, y)) is polymer. It contains no compounds or has a low content of polymer compounds. In this case, hydrogen is more likely to be generated in the lowermost region of the negative electrode plate than in other regions, so that the electrolytic solution can be agitated relatively efficiently. Further, since the negative electrode material in the regions of the third and fourth rows near the center does not contain the polymer compound or the content of the polymer compound is low, the stirring efficiency of the electrolytic solution can be further improved.
  • C (3, y) ⁇ C0, C (4, y) ⁇ C0 and C (8, y) ⁇ C0 may be satisfied in at least one column.
  • the first embodiment and the second embodiment are merely examples, and may be any form in which more hydrogen gas is generated near the lower end portion.
  • the polymer compound contained in the negative electrode material may have an effect of increasing the overvoltage of the negative electrode material.
  • such a polymer compound may also have an action of suppressing the amount of overcharged electricity.
  • a polymer compound having a peak in the range of 3.2 ppm or more and 3.8 ppm or less in a chemical shift of 1 H-NMR spectrum which is a preferable polymer compound, or a polymer containing a repeating structure of an oxyC 2-4 alkylene unit.
  • the compounds will be described in detail.
  • the peak appearing in the range of 3.2 ppm or more and 3.8 ppm or less in the 1 H-NMR spectrum is derived from the oxyC 2-4 alkylene unit.
  • the 1 H-NMR spectrum is measured using deuterated chloroform as a solvent.
  • the negative electrode material contains the above-mentioned polymer compound. It is important that the negative electrode material contains the polymer compound, regardless of whether or not the components of the lead-acid battery other than the negative electrode material contain the polymer compound.
  • the reaction during overcharging is greatly affected by the reduction reaction of hydrogen ions at the interface between lead and the electrolytic solution. Therefore, in the lead-acid battery according to the present invention, the surface of lead, which is the negative electrode active material, is covered with the polymer compound, so that the hydrogen overvoltage rises and a side reaction in which hydrogen is generated from protons during overcharging occurs. It is considered to be hindered. Since the polymer compound has an oxyC 2-4 alkylene unit, it is easy to form a linear structure, so that it is difficult to stay in the negative electrode material and it is expected that the polymer compound is easily diffused into the electrolytic solution.
  • the present inventors have found that, in fact, the effect of increasing the hydrogen overvoltage can be obtained even when the negative electrode material contains a very small amount of polymer compound. From this, it is considered that by incorporating the polymer compound in the negative electrode material, it can be present in the vicinity of lead, whereby the high adsorption action of the oxyC 2-4 alkylene unit on lead is exhibited. Be done. In addition, even a very small amount of polymer compound has the effect of increasing the hydrogen overvoltage, so that the polymer compound spreads thinly on the surface of lead, and the reduction reaction of hydrogen ions is suppressed in a wide range of the lead surface. it is conceivable that. This is consistent with the fact that polymer compounds tend to have a linear structure. In addition, since hydrogen generation during overcharging is suppressed, liquid reduction can be reduced, which is advantageous for extending the life of the lead storage battery.
  • an aqueous sulfuric acid solution is used as the electrolytic solution. Therefore, when an organic additive (oil, polymer, organic shrink-proofing agent, etc.) is contained in the negative electrode material, it elutes into the electrolytic solution and becomes lead. It becomes difficult to balance with adsorption. For example, when an organic additive having low adsorptivity to lead is used, it becomes easy to elute into the electrolytic solution, and it becomes difficult to raise the hydrogen overvoltage. On the other hand, when an organic additive having high adsorptivity to lead is used, it becomes difficult to attach the organic additive thinly to the surface of lead, and the organic additive tends to be unevenly distributed in the pores of lead.
  • an organic additive oil, polymer, organic shrink-proofing agent, etc.
  • the organic additive When the organic additive is unevenly distributed in the pores of lead, the movement of ions (lead ion, sulfate ion, etc.) is hindered by the steric hindrance of the unevenly distributed organic additive. Therefore, the low temperature high rate (HR) performance is also lowered. If the content of the organic additive is increased in order to secure a sufficient effect of reducing the amount of overcharged electricity, the movement of ions in the pores is further inhibited, and the low temperature HR discharge performance is also lowered.
  • HR low temperature high rate
  • the lead surface is covered with the polymer compound in a thinly spread state as described above. Will be told. Therefore, as compared with the case of using other organic additives, even if the content in the negative electrode electrode material is small, the effect of increasing the hydrogen overvoltage and the effect of reducing the amount of overcharged electricity can be ensured. Further, since the polymer compound thinly covers the lead surface, the elution of lead sulfate generated during discharge during charging is less likely to be inhibited, and thus a decrease in charge acceptability can be suppressed.
  • the polymer compound may contain an oxygen atom bonded to a terminal group and an -CH 2 -group and / or -CH ⁇ group bonded to an oxygen atom.
  • the integrated value of the peaks of 3.2 ppm ⁇ 3.8 ppm, and the integral value of the peak, -CH 2 bonded to an oxygen atom - and the integral value of the peak of the hydrogen atoms of the group, an oxygen atom The ratio of the peak of the hydrogen atom of the -CH ⁇ group bonded to the group to the integrated value is preferably 85% or more.
  • Such polymer compounds contain a large amount of oxyC 2-4 alkylene unit in the molecule.
  • the lead surface is easily covered thinly by easily adsorbing to lead and easily forming a linear structure. Therefore, it is possible to more effectively increase the hydrogen overvoltage and reduce the amount of overcharged electricity. In addition, the charge acceptability and / or the effect of suppressing a decrease in low temperature HR discharge performance can be further enhanced.
  • the polymer compound having a peak in the chemical shift range of 3.2 ppm to 3.8 ppm preferably contains a repeating structure of an oxyC 2-4 alkylene unit.
  • a polymer compound containing a repeating structure of an oxyC 2-4 alkylene unit it is considered that it becomes easier to adsorb to lead and it becomes easier to thinly cover the lead surface by easily taking a linear structure. Therefore, it is possible to more effectively increase the hydrogen overvoltage and reduce the amount of overcharged electricity.
  • a polymer compound is defined to have a repeating unit of oxyC 2-4 alkylene unit and / or have a number average molecular weight (Mn) of 500 or more.
  • the oxyC 2-4 alkylene unit is a unit represented by —OR 1 ⁇ (R 1 represents a C 2-4 alkylene group).
  • Polymeric compounds include at least one selected from the group consisting of esters of hydroxy compounds having a repeating structure of ethers of hydroxy compounds, and oxy C 2-4 alkylene unit having a repeating structure oxy C 2-4 alkylene unit It may be.
  • the hydroxy compound is at least one selected from the group consisting of a poly C 2-4 alkylene glycol, a copolymer containing a repeating structure of oxy C 2-4 alkylene, and a C 2-4 alkylene oxide adduct of a polyol.
  • the repeating structure of the oxyC 2-4 alkylene unit may include at least the repeating structure of the oxypropylene unit (-O-CH (-CH 3 ) -CH 2- ). It is considered that such a polymer compound has a high adsorptivity to lead, yet easily spreads thinly on the lead surface, and has an excellent balance between them.
  • the polymer compound has a high adsorptivity to lead and can cover the lead surface thinly. Therefore, even if the content of the polymer compound in the negative electrode material is small (for example, less than 400 ppm). It is possible to increase the hydrogen overvoltage and reduce the amount of overcharged electricity. Further, even if the content is small, a sufficient effect of reducing the amount of overcharged electricity can be ensured, so that a decrease in charge acceptability can be suppressed. Since the steric hindrance of the polymer compound in the lead pores can be reduced and the structural change of the negative electrode active material due to the collision of hydrogen gas can be suppressed, the low temperature HR discharge performance is deteriorated even after the high temperature and light load test. It can also be suppressed. From the viewpoint of ensuring a higher effect, the content of the polymer compound in the negative electrode material is preferably more than 8 ppm.
  • the polymer compound preferably contains a compound having an Mn of at least 1000 or more.
  • the adsorptivity to lead is enhanced, so that the effect of increasing the hydrogen overvoltage and the effect of reducing the amount of overcharged electricity are further enhanced.
  • structural changes in the negative electrode active material due to collision of hydrogen gas with the negative electrode material can also be suppressed. Therefore, even after the high-temperature light load test in which the structural change of the negative electrode active material is likely to occur, the effect of suppressing the deterioration of the low-temperature HR discharge performance can be enhanced.
  • the origin of the polymer compound contained in the negative electrode material is not particularly limited as long as the polymer compound can be contained more or less in the negative electrode material at a predetermined position on the negative electrode plate.
  • the polymer compound may be contained in any of the components of the lead-acid battery (for example, a negative electrode plate, a positive electrode plate, an electrolytic solution, and / or a separator) when the lead-acid battery is manufactured.
  • the polymer compound may be contained in one component or in two or more components (for example, a negative electrode plate and an electrolytic solution).
  • the negative electrode material may further contain an organic shrinkage proofing agent (first organic shrinkage proofing agent) having a sulfur element content of 2000 ⁇ mol / g or more.
  • first organic shrinkage proofing agent organic shrinkage proofing agent
  • Charge acceptability is governed by the dissolution rate of lead sulfate during charging in the negative electrode plate.
  • the particle size of lead sulfate generated during discharge has a small sulfur element content (for example, less than 2000 ⁇ mol / g, preferably 1000 ⁇ mol / g or less) when the first organic shrink-proofing agent is used.
  • the negative electrode material may contain a second organic shrinkage proofing agent.
  • the particle size of the colloid can be reduced, so that the effect of suppressing the deterioration of the low temperature HR discharge performance can be further enhanced.
  • the negative electrode material may contain a second organic shrinkage proofing agent in addition to the first organic shrinkage proofing agent.
  • a second organic shrinkage proofing agent in addition to the first organic shrinkage proofing agent.
  • the first organic shrinkage proofing agent contains a condensate containing a unit of an aromatic compound having a sulfur-containing group, and the condensate is a unit of an aromatic compound from a unit of a bisarene compound and a unit of a monocyclic aromatic compound. It may contain at least one selected from the group. Further, the condensate may contain a unit of a bisarene compound and a unit of a monocyclic aromatic compound. The unit of the monocyclic aromatic compound may include a unit of a hydroxyarene compound. Such a condensate is more advantageous in suppressing the deterioration of the low temperature HR discharge performance after the high temperature light load test because the low temperature HR discharge performance is not impaired even if the environment is higher than the normal temperature.
  • the content of sulfur element in the organic shrinkage proofing agent is X ⁇ mol / g means that the content of sulfur element contained in 1 g of the organic shrinkage proofing agent is X ⁇ mol / g.
  • the content of the polymer compound in the negative electrode material and the concentration of the polymer compound in the electrolytic solution shall be obtained for the fully charged lead-acid battery.
  • the lead-acid battery may be either a control valve type (sealed type) lead-acid battery or a liquid type (vent type) lead-acid battery.
  • the fully charged state of the liquid lead-acid battery is defined by the definition of JIS D 5301: 2006. More specifically, electrolysis of a lead-acid battery with a current (A) 0.2 times the value described as the rated capacity (Ah), which is measured every 15 minutes and converted to the terminal voltage during charging or 20 ° C.
  • a fully charged state is defined as a state in which the liquid density is charged three times in a row until it shows a constant value with three significant figures.
  • the fully charged state of the control valve type lead-acid battery is 2.23 V at a current (A) 0.2 times the value described in the rated capacity (Ah) in an air tank at 25 ° C ⁇ 2 ° C.
  • the cell is charged with a constant current and a constant voltage, and the charging is completed when the charging current at the time of constant voltage charging becomes 0.005 times the value described as the rated capacity (Ah).
  • the numerical value described as the rated capacity is a numerical value in which the unit is Ah.
  • the unit of current set based on the numerical value described as the rated capacity is A.
  • a fully charged lead-acid battery is a fully charged lead-acid battery.
  • the lead-acid battery may be fully charged after the chemical conversion, immediately after the chemical conversion, or after a lapse of time from the chemical conversion (for example, after the chemical conversion, the lead-acid battery in use (preferably at the initial stage of use) is fully charged. May be).
  • An initial use battery is a battery that has not been used for a long time and has hardly deteriorated.
  • the number average molecular weight Mn is determined by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the standard substance used to determine Mn is polyethylene glycol.
  • the negative electrode plate usually includes a negative electrode current collector in addition to the negative electrode material.
  • the negative electrode electrode material is a negative electrode plate obtained by removing the negative electrode current collector.
  • Members such as mats and pacing papers may be attached to the negative electrode plate. Since such a member (pasting member) is used integrally with the negative electrode plate, it is included in the negative electrode plate.
  • the negative electrode material is the one excluding the negative electrode current collector and the sticking member.
  • the thickness of the sticking member is included in the thickness of the separator.
  • the negative electrode current collector may be formed by casting lead (Pb) or a lead alloy, or may be formed by processing a lead sheet or a lead alloy sheet. Examples of the processing method include expanding processing and punching processing. It is preferable to use a negative electrode lattice as the negative electrode current collector because it is easy to support the negative electrode material.
  • the lead alloy used for the negative electrode current collector may be any of Pb-Sb-based alloy, Pb-Ca-based alloy, and Pb-Ca-Sn-based alloy. These leads or lead alloys may further contain at least one selected from the group consisting of Ba, Ag, Al, Bi, As, Se, Cu and the like as an additive element.
  • the negative electrode current collector may include a surface layer. The composition of the surface layer and the inner layer of the negative electrode current collector may be different. The surface layer may be formed on the selvage portion of the negative electrode current collector. The surface layer of the selvage portion may contain Sn or a Sn alloy.
  • the negative electrode material contains the above polymer compound.
  • the negative electrode material further contains a negative electrode active material (lead or lead sulfate) that develops a capacity by a redox reaction.
  • the negative electrode material may contain shrink-proofing agents, carbonaceous materials, and / or other additives. Examples of the additive include, but are not limited to, barium sulfate, fibers (resin fibers, etc.) and the like.
  • the negative electrode active material in the charged state is spongy lead, but the unchemicald negative electrode plate is usually produced by using lead powder.
  • the polymer compound has a peak in the range of 3.2 ppm or more and 3.8 ppm or less in the chemical shift of 1 H-NMR spectrum.
  • Such polymer compounds have an oxyC 2-4 alkylene unit.
  • the oxyC 2-4 alkylene unit includes an oxyethylene unit, an oxypropylene unit, an oxytrimethylene unit, an oxy2-methyl-1,3-propylene unit, an oxy1,4-butylene unit, and an oxy1,3-butylene unit. And so on.
  • the polymer compound may have one kind of such oxyC 2-4 alkylene unit, or may have two or more kinds.
  • the polymer compound preferably contains a repeating structure of oxyC 2-4 alkylene units.
  • the repeating structure may contain one type of oxyC 2-4 alkylene unit, or may contain two or more types of oxy C 2-4 alkylene unit.
  • the polymer compound may contain one kind of the above-mentioned repeating structure, or may contain two or more kinds of repeating structures.
  • polymer compound examples include a hydroxy compound having a repeating structure of an oxy C 2-4 alkylene unit (poly C 2-4 alkylene glycol, a copolymer containing a repeating structure of oxy C 2-4 alkylene, and C 2- of a polyol. (4 alkylene oxide adduct, etc.), etherified products or esterified products of these hydroxy compounds, and the like.
  • copolymer examples include a copolymer containing different oxyC 2-4 alkylene units, a poly C 2-4 alkylene glycol alkyl ether, a poly C 2-4 alkylene glycol ester of a carboxylic acid, and the like.
  • the copolymer may be a block copolymer.
  • the polyol may be any of an aliphatic polyol, an alicyclic polyol, an aromatic polyol, a heterocyclic polyol and the like. From the viewpoint that the polymer compound is thin and easily spreads on the lead surface, an aliphatic polyol, an alicyclic polyol (for example, polyhydroxycyclohexane, polyhydroxynorbornane, etc.) and the like are preferable, and an aliphatic polyol is particularly preferable.
  • the aliphatic polyol include an aliphatic diol and a polyol above triol (for example, glycerin, trimethylolpropane, pentaerythritol, sugar alcohol, etc.).
  • Examples of the aliphatic diol include alkylene glycol having 5 or more carbon atoms.
  • Alkylene glycol for example, be a C 5 ⁇ 14 alkylene glycol or C 5-10 alkylene glycol.
  • sugar alcohols include erythritol, xylitol, mannitol, sorbitol and the like.
  • the alkylene oxide adduct of the polyol the alkylene oxide corresponds to the oxyC 2-4 alkylene unit of the polymer compound and comprises at least C 2-4 alkylene oxide. From the viewpoint that the polymer compound easily has a linear structure, the polyol is preferably a diol.
  • the etherified product is composed of at least a part of the terminal -OH group (hydrogen atom of the terminal group and the oxygen atom bonded to the hydrogen atom) of the hydroxy compound having the repeating structure of the above oxyC 2-4 alkylene unit. -OH group) having etherified -OR 2 group (wherein, R 2 is an organic group.).
  • R 2 is an organic group.
  • ends of the polymer compound some ends may be etherified, or all ends may be etherified. For example, in one end of the main chain is -OH groups of a linear polymer compound, the other end may be an -OR 2 group.
  • the esterified product is composed of at least a part of a terminal-OH group (a hydrogen atom of the terminal group and an oxygen atom bonded to the hydrogen atom) of the hydroxy compound having a repeating structure of the oxyC 2-4 alkylene unit.
  • R 3 is an organic group.
  • some ends may be esterified, or all ends may be esterified.
  • Examples of the organic groups R 2 and R 3 include hydrocarbon groups.
  • the hydrocarbon group may have a substituent (eg, a hydroxy group, an alkoxy group, and / or a carboxy group).
  • the hydrocarbon group may be any of an aliphatic, alicyclic, and aromatic group.
  • the aromatic hydrocarbon group and the alicyclic hydrocarbon group may have an aliphatic hydrocarbon group (for example, an alkyl group, an alkenyl group, an alkynyl group, etc.) as a substituent.
  • the number of carbon atoms of the aliphatic hydrocarbon group as a substituent may be, for example, 1 to 20, 1 to 10, or 1 to 6 or 1 to 4.
  • Examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group having 24 or less carbon atoms (for example, 6 to 24). The number of carbon atoms of the aromatic hydrocarbon group may be 20 or less (for example, 6 to 20), 14 or less (for example, 6 to 14) or 12 or less (for example, 6 to 12).
  • Examples of the aromatic hydrocarbon group include an aryl group and a bisaryl group. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the bisaryl group include a monovalent group corresponding to bisarene. Examples of the bisarene include biphenyl and bisaryl alkane (for example, bis C 6-10 aryl C 1-4 alkane (2,2-bisphenylpropane, etc.)).
  • Examples of the alicyclic hydrocarbon group include an alicyclic hydrocarbon group having 16 or less carbon atoms.
  • the alicyclic hydrocarbon group may be a crosslinked cyclic hydrocarbon group.
  • the number of carbon atoms of the alicyclic hydrocarbon group may be 10 or less or 8 or less.
  • the number of carbon atoms of the alicyclic hydrocarbon group is, for example, 5 or more, and may be 6 or more.
  • the number of carbon atoms of the alicyclic hydrocarbon group may be 5 (or 6) or more and 16 or less, 5 (or 6) or more and 10 or less, or 5 (or 6) or more and 8 or less.
  • Examples of the alicyclic hydrocarbon group include a cycloalkyl group (cyclopentyl group, cyclohexyl group, cyclooctyl group, etc.), a cycloalkenyl group (cyclohexenyl group, cyclooctenyl group, etc.) and the like.
  • the alicyclic hydrocarbon group also includes the hydrogenated additive of the above aromatic hydrocarbon group.
  • an aliphatic hydrocarbon group is preferable from the viewpoint that the polymer compound is thin and easily adheres to the lead surface.
  • the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, and a dienyl group.
  • the aliphatic hydrocarbon group may be linear or branched chain.
  • the number of carbon atoms of the aliphatic hydrocarbon group may be, for example, 30 or less, 26 or less or 22 or less, 20 or less or 16 or less, 14 or less or 10 or less. It may be 8 or less or 6 or less.
  • the lower limit of the number of carbon atoms is 1 or more for an alkyl group, 2 or more for an alkenyl group and an alkynyl group, and 3 or more for a dienyl group, depending on the type of aliphatic hydrocarbon group.
  • Alkyl groups and alkenyl groups are particularly preferable from the viewpoint that the polymer compound is thin and easily adheres to the lead surface.
  • alkyl group examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, neopentyl, i-pentyl, s-pentyl, Examples thereof include 3-pentyl, t-pentyl, n-hexyl, 2-ethylhexyl, n-octyl, n-decyl, i-decyl, lauryl, myristyl, cetyl, stearyl and behenyl.
  • alkenyl group examples include vinyl, 1-propenyl, allyl, palmitrail, oleyl and the like.
  • the alkenyl group may be, for example, a C 2-30 alkenyl group or a C 2-26 alkenyl group, a C 2-22 alkenyl group or a C 2-20 alkenyl group, and a C 10-20 alkenyl group. It may be.
  • esters of hydroxy compounds having a repeating structure of ethers of hydroxy compounds, and / or oxy-C 2-4 alkylene unit having a repeating structure oxy C 2-4 alkylene unit, of charge acceptance This is preferable because the effect of suppressing the decrease can be further enhanced. Further, even when these polymer compounds are used, a high liquid reduction suppressing effect can be ensured.
  • the negative electrode material may contain one kind of polymer compound or two or more kinds.
  • the repeating structure includes at least the repeating structure of the oxypropylene unit.
  • Polymeric compounds containing oxypropylene units, at chemical shift of 1 H-NMR spectrum, in the range of 3.2 ppm ⁇ 3.8 ppm, -CH oxypropylene units ⁇ and -CH 2 - has a peak derived from. Since the electron densities around the nuclei of hydrogen atoms in these groups are different, the peaks are split.
  • Such a polymer compound has peaks in the chemical shift of 1 H-NMR spectrum, for example, in the range of 3.2 ppm or more and 3.42 ppm or less and in the range of 3.42 ppm or more and 3.8 ppm or less. Peaks in the range of 3.2 ppm or more and 3.42 ppm or less are derived from -CH 2- , and peaks in the range of more than 3.42 ppm and 3.8 ppm or less are derived from -CH ⁇ and -CH 2- .
  • Examples of such a polymer compound include polypropylene glycol, a copolymer containing a repeating structure of oxypropylene, a propylene oxide adduct of the above-mentioned polyol, and an etherified product or an esterified product thereof.
  • Examples of the copolymer include an oxypropylene-oxyalkylene copolymer (where oxyalkylene is C 2-4 alkylene other than oxypropylene), polypropylene glycol alkyl ether, polypropylene glycol ester of carboxylic acid and the like.
  • Examples of the oxypropylene-oxyalkylene copolymer include an oxypropylene-oxyethylene copolymer and an oxypropylene-oxytrimethylene copolymer.
  • the oxypropylene-oxyalkylene copolymer may be a block copolymer.
  • the proportion of the oxypropylene unit is, for example, 5 mol% or more, and may be 10 mol% or more or 20 mol% or more.
  • the polymer compound preferably contains a large amount of oxyC 2-4 alkylene unit from the viewpoint of increasing the adsorptivity to lead and facilitating the formation of a linear structure.
  • Such polymer compounds include, for example, an oxygen atom attached to a terminal group and an -CH 2 -group and / or -CH ⁇ group attached to an oxygen atom.
  • the ratio of the peak of hydrogen atom to the integral value of the peak becomes large.
  • This ratio is, for example, 50% or more, and may be 80% or more. From the viewpoint of further enhancing the effect of reducing the amount of overcharged electricity and further enhancing the effect of suppressing the decrease in charge acceptability and / or low temperature HR discharge performance, the above ratio is preferably 85% or more, preferably 90% or more. Is more preferable.
  • the polymer compound having an -OH group at the terminal, -CH 2 bonded to an oxygen atom of the -OH group - if having a group or -CH ⁇ group the 1 H-NMR spectrum, -CH 2 - group The peak of the hydrogen atom of the -CH ⁇ group has a chemical shift in the range of more than 3.8 ppm and 4.0 ppm or less.
  • the polymer compound may contain a compound having a Mn of 500 or more, a compound having a Mn of 600 or more, or a compound having a Mn of 1000 or more.
  • the Mn of such a compound is, for example, 20000 or less, and may be 15000 or less or 10000 or less. From the viewpoint that the compound is easily retained in the negative electrode material and spreads thinner on the lead surface, the Mn of the compound is preferably 5000 or less, and may be 4000 or less or 3000 or less.
  • the Mn of the above compounds is 500 or more (or 600 or more) 20000 or less, 500 or more (or 600 or more) 15000 or less, 500 or more (or 600 or more) 10000 or less, 500 or more (or 600 or more) 5000 or less, 500 or more ( Or 600 or more and 4000 or less, 500 or more (or 600 or more) 3000 or less, 1000 or more and 20000 or less (or 15000 or less), 1000 or more and 10000 or less (or 5000 or less), or 1000 or more and 4000 or less (or 3000 or less). May be good.
  • the polymer compound preferably contains a compound having at least Mn of 1000 or more.
  • the Mn of such a compound may be 1000 or more and 20000 or less, 1000 or more and 15000 or less, or 1000 or more and 10000 or less.
  • the Mn of the compound is preferably 1000 or more and 5000 or less, may be 1000 or more and 4000 or less, and is 1000 or more and 3000 or less. You may.
  • the hydrogen overvoltage can be increased more easily and the amount of overcharged electricity can be reduced.
  • structural changes in the negative electrode active material due to collision of hydrogen gas with the negative electrode active material can also be suppressed.
  • the polymer compound two or more compounds having different Mns may be used. That is, the polymer compound may have a plurality of Mn peaks in the distribution of molecular weight.
  • the average value C0 of the polymer compound contents is based on the mass. For example, it is more than 8 ppm, preferably 13 ppm or more, and more preferably 15 ppm or more or 16 ppm or more.
  • the average value C0 is in such a range, the hydrogen generation voltage can be easily increased, and the effect of reducing the amount of overcharged electricity can be further enhanced.
  • the average value C0 may be 50 ppm or more or 80 ppm or more.
  • the average value C0 is, for example, 400 ppm or less, preferably 360 ppm or less, and more preferably 350 ppm or less.
  • the average value C0 is 400 ppm or less, the surface of lead is suppressed from being excessively covered with the polymer compound, so that the decrease in low temperature HR discharge performance can be effectively suppressed.
  • the average value C0 is preferably 240 ppm or less, more preferably 200 ppm or less, and may be 165 ppm or less or 164 ppm or less. These lower limit value and upper limit value can be arbitrarily combined.
  • the maximum value of the content of the polymer compound in the 16 regions in the first to fourth rows from the upper end side of the negative electrode plate is, for example, 400 ppm from the viewpoint of suppressing the surface of lead from being excessively covered with the polymer compound. It may be less than or equal to, preferably 190 ppm or less, and more preferably 180 ppm or less.
  • Mean value C0 is 3ppm or more (or 13ppm or more) 400ppm or less, 3ppm or more (or 13ppm or more) 360ppm or less, 3ppm or more (or 13ppm or more) 350ppm or less, 3ppm or more (or 13ppm or more) 240ppm or less, 3ppm or more (or 13ppm) 200ppm or less, 3ppm or more (or 13ppm or more) 165ppm or less, 3ppm or more (or 13ppm or more) 164ppm or less, 15ppm or more (or 16ppm or more) 400ppm or less, 15ppm or more (or 16ppm or more) 360ppm or less, 15ppm or more (or 16ppm) 350 ppm or less, 15 ppm or more (or 16 ppm or more) 240 ppm or less, 15 ppm or more (or 16 ppm or more) 200 ppm or less, 15 ppm or more (or 16 ppm or more
  • the negative electrode material can include a shrink-proofing agent.
  • an organic shrink proofing agent is preferable.
  • the organic shrinkage proofing agent lignins and / or synthetic organic shrinkage proofing agents may be used.
  • lignins include lignin and lignin derivatives.
  • the lignin derivative include lignin sulfonic acid or a salt thereof (alkali metal salt (sodium salt, etc.), etc.).
  • Organic shrink proofing agents are usually roughly classified into lignins and synthetic organic shrink proofing agents. It can be said that the synthetic organic shrinkage proofing agent is an organic shrinkage proofing agent other than lignins.
  • the synthetic organic shrinkage proofing agent is an organic polymer containing a sulfur element, and generally contains a plurality of aromatic rings in the molecule and also contains a sulfur element as a sulfur-containing group.
  • a sulfur element as a sulfur-containing group.
  • the sulfur-containing groups a sulfonic acid group or a sulfonyl group in a stable form is preferable.
  • the sulfonic acid group may be present in the acid form or in the salt form such as the Na salt.
  • the negative electrode material may contain one type of shrink-proofing agent, or may contain two or more types.
  • the organic shrinkage proofing agent it is preferable to use a condensate containing at least a unit of an aromatic compound.
  • a condensate include a condensate of an aromatic compound made of an aldehyde compound (such as an aldehyde (for example, formaldehyde) and / or a condensate thereof).
  • the organic shrink proofing agent may contain a unit of one kind of aromatic compound, or may contain a unit of two or more kinds of aromatic compounds.
  • the unit of the aromatic compound means a unit derived from the aromatic compound incorporated in the condensate.
  • the organic shrinkage proofing agent one synthesized by a known method may be used, or a commercially available product may be used.
  • a condensate containing a unit of an aromatic compound can be obtained, for example, by reacting an aromatic compound with an aldehyde compound.
  • an aromatic compound containing a sulfur element for example, bisphenol S
  • an organic shrinkage proofing agent containing a sulfur element can be obtained.
  • the sulfur element content in the organic shrink-proofing agent can be adjusted by adjusting the amount of sulfites and / or the amount of aromatic compounds containing sulfur elements. When other raw materials are used, it can be obtained according to this method.
  • Examples of the aromatic ring contained in the aromatic compound include a benzene ring and a naphthalene ring.
  • the plurality of aromatic rings may be directly bonded or linked by a linking group (for example, an alkylene group (including an alkylidene group), a sulfone group, etc.).
  • Examples of such a structure include a bisarene structure (biphenyl, bisphenylalkane, bisphenylsulfone, etc.).
  • Examples of the aromatic compound include the above-mentioned compounds having an aromatic ring and a hydroxy group and / or an amino group.
  • the hydroxy group or amino group may be directly bonded to the aromatic ring, or may be bonded as an alkyl chain having a hydroxy group or amino group.
  • the hydroxy group also includes a salt of the hydroxy group (-OMe).
  • the amino group also includes a salt of the amino group (salt with an anion). Examples of Me include alkali metals (Li, K, Na, etc.) and Group 2 metals of the periodic table (Ca, Mg, etc.).
  • aromatic compound examples include bisarene compounds (bisphenol compounds, hydroxybiphenyl compounds, bisarene compounds having an amino group (bisarylalkane compounds having an amino group, bisarylsulfone compounds having an amino group, biphenyl compounds having an amino group, etc.), Hydroxyarene compounds (hydroxynaphthalene compounds, phenol compounds, etc.), aminoarene compounds (aminonaphthalene compounds, aniline compounds (aminobenzenesulfonic acid, alkylaminobenzenesulfonic acid, etc.), etc.) are preferable.
  • Aromatic compounds are further substituents.
  • the organic shrinkage proofing agent may contain one or more residues of these compounds.
  • bisphenol compound bisphenol A, bisphenol S, bisphenol F and the like are preferable.
  • the condensate preferably contains at least a unit of an aromatic compound having a sulfur-containing group.
  • a condensate containing at least a unit of a bisphenol compound having a sulfur-containing group when used, the effect of suppressing a decrease in low-temperature HR discharge performance after a high-temperature light load test can be enhanced.
  • the sulfur-containing group may be directly bonded to the aromatic ring contained in the compound, or may be bonded to the aromatic ring as an alkyl chain having a sulfur-containing group, for example.
  • the sulfur-containing group is not particularly limited, and examples thereof include a sulfonyl group, a sulfonic acid group, or a salt thereof.
  • the organic shrinkage proofing agent for example, a condensation containing at least one selected from the group consisting of the above-mentioned unit of a bisalene compound and a unit of a monocyclic aromatic compound (such as a hydroxyarene compound and / or an aminoarene compound). At least one may be used.
  • the organic shrink-proofing agent may contain at least a condensate containing a unit of a bisalene compound and a unit of a monocyclic aromatic compound (particularly, a hydroxyarene compound). Examples of such a condensate include a condensate of a bisarene compound and a monocyclic aromatic compound with an aldehyde compound.
  • hydroxyarene compound a phenol sulfonic acid compound (phenol sulfonic acid or a substitute thereof, etc.) is preferable.
  • aminoarene compound aminobenzenesulfonic acid, alkylaminobenzenesulfonic acid and the like are preferable.
  • monocyclic aromatic compound a hydroxyarene compound is preferable. Such a condensate is more advantageous in suppressing the deterioration of the low temperature HR discharge performance after the high temperature light load test because the low temperature HR discharge performance is not impaired even if the environment is higher than the normal temperature.
  • the content of the organic shrink-proofing agent contained in the negative electrode electrode material is, for example, 0.01% by mass or more, and may be 0.05% by mass or more.
  • the content of the organic shrink proofing agent is, for example, 1.0% by mass or less, and may be 0.5% by mass or less.
  • the content of the organic shrink-proofing agent contained in the negative electrode electrode material is 0.01 to 1.0% by mass, 0.05 to 1.0% by mass, 0.01 to 0.5% by mass, or 0.05 to 0.05. It may be 0.5% by mass.
  • Carbonaceous material As the carbonaceous material contained in the negative electrode material, carbon black, graphite, hard carbon, soft carbon and the like can be used. Examples of carbon black include acetylene black, ketjen black, furnace black, and lamp black.
  • the graphite may be any carbonaceous material containing a graphite-type crystal structure, and may be either artificial graphite or natural graphite. As the carbonaceous material, one kind may be used alone, or two or more kinds may be combined.
  • the content of the carbonaceous material in the negative electrode material is, for example, 0.05% by mass or more, and may be 0.10% by mass or more.
  • the content of the carbonaceous material is, for example, 5% by mass or less, and may be 3% by mass or less.
  • the content of the carbonaceous material in the negative electrode material may be 0.05 to 5% by mass, 0.05 to 3% by mass, 0.10 to 5% by mass, or 0.10 to 3% by mass. ..
  • barium sulfate The content of barium sulfate in the negative electrode electrode material is, for example, 0.05% by mass or more, and may be 0.10% by mass or more. The content of barium sulfate in the negative electrode electrode material is 3% by mass or less, and may be 2% by mass or less. These lower limit values and upper limit values can be arbitrarily combined.
  • the content of barium sulfate in the negative electrode electrode material may be 0.05 to 3% by mass, 0.05 to 2% by mass, 0.10 to 3% by mass, or 0.10 to 2% by mass.
  • the lead-acid battery after chemical conversion is fully charged and then disassembled to obtain a negative electrode plate to be analyzed.
  • the obtained negative electrode plate is washed with water to remove sulfuric acid from the negative electrode plate.
  • the washing with water is carried out by pressing the pH test paper against the surface of the negative electrode plate washed with water until it is confirmed that the color of the test paper does not change. However, the time for washing with water shall be within 2 hours.
  • the negative electrode plate washed with water is dried at 60 ⁇ 5 ° C. for about 6 hours in a reduced pressure environment. If the attached member is included after drying, the attached member is removed from the negative electrode plate by peeling.
  • the direction from the upper end to the lower end of the negative electrode plate is the X direction
  • the direction intersecting the X direction is the Y direction
  • the Y direction is the row direction
  • the X direction is the column direction, forming a matrix of 8 rows and 4 columns.
  • the negative electrode plate is divided into 32 equal parts, and the negative electrode material in all 32 regions is collected to obtain a sample in 32 regions (hereinafter, also referred to as sample A).
  • Sample A is pulverized as needed and subjected to analysis.
  • (1-1) Qualitative Analysis of Polymer Compound 150.0 ⁇ 0.1 mL of chloroform is added to 100.0 ⁇ 0.1 g of pulverized sample A, and the mixture is stirred at 20 ⁇ 5 ° C.
  • Chloroform-soluble components are recovered by distilling off chloroform under reduced pressure from the chloroform solution in which the polymer compound obtained by extraction is dissolved.
  • the chloroform-soluble component is dissolved in deuterated chloroform, and the 1 H-NMR spectrum is measured under the following conditions. From this 1 1 H-NMR spectrum, a peak with a chemical shift in the range of 3.2 ppm or more and 3.8 ppm or less is confirmed.
  • the type of oxyC 2-4 alkylene unit is specified from the peak in this range.
  • V 1 From the 1 H-NMR spectrum, the integral value (V 1 ) of the peaks in which the chemical shift exists in the range of 3.2 ppm or more and 3.8 ppm or less is obtained.
  • V 2 the sum of the integrated values of the peaks in the 1 H-NMR spectrum (V 2 ).
  • the straight line connecting the intervals is used as the baseline.
  • the straight line connecting the two points of 3.2 ppm and 3.8 ppm in the spectrum is used as the baseline.
  • the straight line connecting the two points of 3.8 ppm and 4.0 ppm in the spectrum is used as the baseline.
  • N a is a value obtained by averaging using a molar ratio of each monomer unit contained in the structure repeated N a value of each monomer unit (mol%), M a is the monomer It is determined according to the type of unit.
  • the integrated value of the peak in the 1 H-NMR spectrum is obtained by using the data processing software "ALICE” manufactured by JEOL Ltd.
  • the negative electrode plate can be formed by applying or filling a negative electrode paste to a negative electrode current collector, aging and drying to produce an unchemicald negative electrode plate, and then forming an unchemicald negative electrode plate.
  • the negative electrode paste is prepared by adding water and sulfuric acid to lead powder, an organic shrink-proofing agent, and various additives as necessary, and kneading them. At the time of aging, it is preferable to ripen the unchemicald negative electrode plate at a temperature higher than room temperature and high humidity.
  • Chemical formation can be performed by charging the electrode plate group in a state where the electrode plate group including the unchemical negative electrode plate is immersed in the electrolytic solution containing sulfuric acid in the electric tank of the lead storage battery. However, the chemical conversion may be carried out before assembling the lead-acid battery or the electrode plate group. The chemical formation produces spongy lead.
  • the positive electrode plate of a lead storage battery can be classified into a paste type, a clad type and the like.
  • the paste-type positive electrode plate includes a positive electrode current collector and a positive electrode material.
  • the positive electrode material is held in the positive electrode current collector.
  • the positive electrode electrode material is the positive electrode plate from which the positive electrode current collector is removed.
  • the positive electrode current collector may be formed by casting lead (Pb) or a lead alloy, or may be formed by processing a lead sheet or a lead alloy sheet. Examples of the processing method include expanding processing and punching processing. It is preferable to use a grid-shaped current collector as the positive electrode current collector because it is easy to support the positive electrode material.
  • the clad type positive electrode plate is a positive electrode filled in a plurality of porous tubes, a core metal inserted in each tube, a current collector connecting the plurality of core metals, and a tube in which the core metal is inserted. It comprises an electrode material and a coupling that connects a plurality of tubes.
  • the positive electrode material is the one excluding the tube, the core metal, the current collector, and the collective punishment.
  • the core metal and the current collector may be collectively referred to as a positive electrode current collector.
  • the positive electrode plate may be attached to the positive electrode plate. Since such a member (pasting member) is used integrally with the positive electrode plate, it is included in the positive electrode plate. Further, when the positive electrode plate includes such a member, the positive electrode electrode material is a paste type positive electrode plate obtained by removing the positive electrode current collector and the sticking member from the positive electrode plate.
  • the positive electrode current collector may include a surface layer.
  • the composition of the surface layer and the inner layer of the positive electrode current collector may be different.
  • the surface layer may be formed on a part of the positive electrode current collector.
  • the surface layer may be formed only on the lattice portion of the positive electrode current collector, only the ear portion, or only the frame bone portion.
  • the positive electrode material contained in the positive electrode plate contains a positive electrode active material (lead dioxide or lead sulfate) whose capacity is developed by a redox reaction.
  • the positive electrode material may contain other additives, if necessary.
  • the unchemical paste type positive electrode plate is obtained by filling the positive electrode current collector with the positive electrode paste, aging and drying.
  • the positive electrode paste is prepared by kneading lead powder, additives, water, and sulfuric acid.
  • the unchemical clad type positive electrode plate is formed by filling a porous tube into which a core metal connected by a current collector is inserted with lead powder or slurry-like lead powder, and connecting a plurality of tubes in a collective punishment. Will be done. Then, a positive electrode plate is obtained by forming these unchemical positive electrode plates.
  • the chemical conversion can be carried out by charging the electrode plate group in a state where the electrode plate group including the unchemical positive electrode plate is immersed in the electrolytic solution containing sulfuric acid in the electric tank of the lead storage battery.
  • the chemical conversion may be carried out before assembling the lead-acid battery or the electrode plate group.
  • Chemical formation can be performed by charging the electrode plate group in a state where the electrode plate group including the unchemical positive electrode plate is immersed in the electrolytic solution containing sulfuric acid in the electric tank of the lead storage battery.
  • the chemical conversion may be carried out before assembling the lead-acid battery or the electrode plate group.
  • the separator may be in the shape of a sheet or in the shape of a bag.
  • a sheet-shaped separator may be sandwiched between the positive electrode plate and the negative electrode plate.
  • the electrode plate may be arranged so as to sandwich the electrode plate with one sheet-shaped separator in a bent state.
  • the positive electrode plate sandwiched between the bent sheet-shaped separators and the negative electrode plate sandwiched between the bent sheet-shaped separators may be overlapped, and one of the positive electrode plate and the negative electrode plate may be sandwiched between the bent sheet-shaped separators. , May be overlapped with the other electrode plate.
  • the sheet-shaped separator may be bent in a bellows shape, and the positive electrode plate and the negative electrode plate may be sandwiched between the bellows-shaped separators so that the separator is interposed between them.
  • the separator may be arranged so that the bent portion is along the horizontal direction of the lead storage battery (for example, the bent portion is parallel to the horizontal direction), and is along the vertical direction. (For example, the separator may be arranged so that the bent portion is parallel to the vertical direction).
  • recesses are alternately formed on both main surface sides of the separator.
  • the positive electrode plate is formed only in the recess on one main surface side of the separator.
  • a negative electrode plate is arranged (that is, a double separator is interposed between the adjacent positive electrode plate and the negative electrode plate).
  • a separator may be provided in a single layer between the adjacent positive electrode plate and the negative electrode plate.
  • the bag-shaped separator may accommodate a positive electrode plate or a negative electrode plate.
  • the vertical direction of the electrode plate means the vertical direction of the lead storage battery in the vertical direction.
  • the electrolytic solution is an aqueous solution containing sulfuric acid, and may be gelled if necessary.
  • the electrolytic solution may contain the above-mentioned polymer compound.
  • the concentration of the polymer compound in the electrolytic solution may be 1 ppm or more and 500 ppm or less, 1 ppm or more and 300 ppm or less, 1 ppm or more and 200 ppm or less, 5 ppm or more and 500 ppm or less, 5 ppm or more and 300 ppm or less, or 5 ppm or more and 200 ppm or less on a mass basis.
  • the concentration of the polymer compound in the electrolytic solution is determined by adding chloroform to a predetermined amount (m 1 (g)) of electrolytic solution taken out from a ready-made fully charged lead-acid battery, mixing the mixture, and allowing it to stand to separate into two layers. After that, only the chloroform layer is taken out. After repeating this operation several times, chloroform is distilled off under reduced pressure to obtain a chloroform-soluble component. An appropriate amount of chloroform-soluble matter is dissolved in deuterated chloroform together with TCE 0.0212 ⁇ 0.0001 g, and 1 1 H-NMR spectrum is measured.
  • the electrolyte may optionally include cations (eg, metal cations such as sodium ions, lithium ions, magnesium ions, and / or aluminum ions) and / or anions (eg, anions other than sulfate anions such as phosphate ions). ) May be included.
  • cations eg, metal cations such as sodium ions, lithium ions, magnesium ions, and / or aluminum ions
  • anions eg, anions other than sulfate anions such as phosphate ions.
  • the specific gravity of the electrolytic solution in a fully charged lead-acid battery at 20 ° C. is, for example, 1.20 or more, and may be 1.25 or more.
  • the specific gravity of the electrolytic solution at 20 ° C. is 1.35 or less, preferably 1.32 or less. These lower limit values and upper limit values can be arbitrarily combined.
  • the specific gravity of the electrolytic solution at 20 ° C. may be 1.20 or more and 1.35 or less, 1.20 or more and 1.32 or less, 1.25 or more and 1.35 or less, or 1.25 or more and 1.32 or less. .. (2) Evaluation A single-plate cell test battery with a rated capacity of 6.2 Ah is composed of one negative electrode plate and two positive electrode plates, and various performances are evaluated.
  • the fully charged test battery is discharged at a current (A) 0.2 times the rated capacity (Ah) for 1 hour, and then the rated capacity (Ah). It is charged with a constant current (A) 1.0 times the value described as Ah), and when the voltage reaches 2.5 V / cell, it is charged with a constant voltage for 2 hours.
  • the upper limit current during charging shall be a current value (A) that is 1.0 times the value described as the rated capacity (Ah).
  • the numerical value described as the rated capacity is a numerical value in which the unit is Ah.
  • the unit of current set based on the numerical value described as the rated capacity is A.
  • (B) Amount of electricity overcharged 1 minute discharge-10 minutes charge in a water tank at 60 ° C ⁇ 2 ° C to make the overcharge condition more than the normal 4-10 minute test specified in JIS D5301. 1 to 10 minutes test) is carried out (high temperature and light load test). In the high temperature light load test, charging and discharging are repeated for 450 cycles. The amount of overcharged electricity (Ah) per cycle is obtained by summing and averaging the amount of overcharged electricity (charged electricity amount-discharged electricity amount) in each cycle up to 450 cycles. Discharge: Constant current 3.57A, 1 minute Charging: Constant voltage 2.47V / cell, upper limit current is 1 times the rated capacity (Ah) value, 10 minutes
  • a negative electrode plate for a lead storage battery comprising a negative electrode current collector and a negative electrode material.
  • the negative electrode material contains a polymer compound and contains An 8-row, 4-column matrix in which the direction from the upper end to the lower end of the negative electrode plate is the X direction, the direction intersecting the X direction is the Y direction, the Y direction is the row direction, and the X direction is the column direction.
  • the negative electrode plate is divided into 32 equal parts and the average value of the content of the polymer compound in the negative electrode material in all 32 regions is C0.
  • N (1-4) of regions in which the content of the polymer compound is smaller than C0 the number of regions in which the content of the polymer compound is smaller than C0
  • a negative electrode plate in which the number N (5-8) in the region where the content of the polymer compound is smaller than C0 satisfies N (1-4) ⁇ N (5-8).
  • the polymer compound may have a peak in the range of 3.2 ppm or more and 3.8 ppm or less in the chemical shift of 1 H-NMR spectrum.
  • the polymer compound may contain a repeating structure of an oxyC 2-4 alkylene unit.
  • the 32 regions of the matrix are indicated by R (x, y), respectively (where x is an integer of 1 to 8 indicating the row position and y is the column position).
  • C (x, y) When the content of the polymer compound in the negative electrode material in R (x, y) is defined as C (x, y), the following: (A) In at least one column, the mean value of C (1, y) to C (4, y) is larger than the mean value of C (5, y) to C (8, y); (B) In at least one column, the mean of C (1, y) to C (4, y) is greater than the mean of C (6, y) to C (8, y); (C) In at least one column, the mean of C (1, y) to C (4, y) is greater than the mean of C (7, y) to C (8, y); (D) In at least one column, the mean value of C (1, y) to C (4, y) is greater than C (8, y); (
  • a negative electrode plate for a lead storage battery comprising a negative electrode current collector and a negative electrode material.
  • the negative electrode material contains a polymer compound and contains An 8-row, 4-column matrix in which the direction from the upper end to the lower end of the negative electrode plate is the X direction, the direction intersecting the X direction is the Y direction, the Y direction is the row direction, and the X direction is the column direction.
  • the negative electrode plate is divided into 32 equal parts and the average value of the content of the polymer compound in the negative electrode material in all 32 regions is C0. Of the eight regions in the first and second rows from the upper end side, the number N (1-2) of regions in which the content of the polymer compound is smaller than C0, and the eight regions in the third to fourth rows.
  • the number N (3-4) of the region in which the content of the polymer compound is smaller than C0 satisfies N (1-2) ⁇ N (3-4), and Of the eight regions in rows 5 to 6, the number N (5-6) of regions in which the content of the polymer compound is smaller than C0, and among the eight regions in rows 7 to 8, the polymer compound A negative electrode plate in which the number N (7-8) in the region where the content of is smaller than C0 satisfies N (5-6) ⁇ N (7-8).
  • a plurality of positive electrode plates, a plurality of negative electrode plates, and an electrolytic solution are provided.
  • the content of the polymer compound in the negative electrode material which is obtained by the above-mentioned procedure, is 0 ppm, 15 ppm, 66 ppm, 200 ppm or 370 ppm in terms of mass ratio, and the content of barium sulfate is 0.6 mass.
  • Each component is mixed so that the content of%, carbon black is 0.3% by mass, and the content of organic shrinkage-proofing agent is 0.1% by mass to obtain five types of negative electrode pastes.
  • a negative electrode paste was prepared so as to contain 15 ppm of the polymer compound in the negative electrode electrode material, which was obtained in the above procedure, and among the expanded lattices made of Pb—Ca—Sn alloy, the negative electrode plate Fill the mesh portion corresponding to the area of 1 to 2 rows.
  • a negative electrode paste was prepared so as to contain 66 ppm of the polymer compound in the negative electrode electrode material, which was obtained in the above procedure, and among the expanded lattices made of Pb—Ca—Sn alloy, the negative electrode plate Fill the mesh portion corresponding to the area of 1 to 2 rows.
  • a negative electrode paste was prepared so as to contain 200 ppm of the polymer compound in the negative electrode electrode material, which was obtained in the above procedure, and among the expanded lattices made of Pb—Ca—Sn alloy, the negative electrode plate Fill the mesh portion corresponding to the area of 1 to 2 rows.
  • a negative electrode paste was prepared so as to contain 370 ppm of the polymer compound in the negative electrode electrode material, which was obtained in the above procedure, and among the expanded lattices made of Pb—Ca—Sn alloy, the negative electrode plate Fill the mesh portion corresponding to the area of 1 to 2 rows.
  • a negative electrode paste having a polymer content of 0 ppm containing no polymer compound is filled in the rest of the mesh portion of each expanded lattice, and then the entire negative electrode material is aged and dried to obtain an unmodified negative electrode plate.
  • (B) Preparation of Positive Electrode Plate The lead powder as a raw material is mixed with an appropriate amount of an aqueous sulfuric acid solution to obtain a positive electrode paste.
  • the positive electrode paste is filled in the mesh portion of the expanded lattice made of Pb—Ca—Sn alloy and aged and dried to obtain an unchemicald positive electrode plate.
  • the test battery has a rated voltage of 2 V / cell and a rated 5-hour rate capacity of 32 Ah.
  • the electrode plate group of the test battery is composed of one negative electrode and two positive electrodes sandwiching the negative electrode.
  • the negative electrode plate is housed in a bag-shaped separator and laminated with the positive electrode plate to form a group of electrode plates.
  • a group of electrode plates is housed in a polypropylene electric tank together with an electrolytic solution (sulfuric acid aqueous solution) and chemically formed in the electric tank to prepare a liquid lead-acid battery.
  • the specific gravity of the electrolytic solution after chemical conversion is 1.28 (20 ° C. conversion).
  • the integrated value of the peaks of 3.2 ppm ⁇ 3.8 ppm, and the integral value of the peak, -CH 2 bonded to an oxygen atom - and the integral value of the peak of the hydrogen atoms of the group is 98.1%.
  • FIG. 9 shows the distribution of polymer compounds in batteries A1 to A4.
  • Examples 5 to 8 Lead-acid batteries were produced in the same manner as in Examples 1 to 4 except that the following points were changed in the method for producing the negative electrode plate.
  • a negative electrode paste was prepared so as to contain 15 ppm of the polymer compound in the negative electrode electrode material, which was obtained in the above procedure, and among the expanded lattices made of Pb—Ca—Sn alloy, the negative electrode plate Fill the mesh portion corresponding to the area of 1 to 4 rows.
  • a negative electrode paste was prepared so as to contain 66 ppm of the polymer compound in the negative electrode electrode material, which was obtained in the above procedure, and among the expanded lattices made of Pb—Ca—Sn alloy, the negative electrode plate Fill the mesh portion corresponding to the area of 1 to 4 rows.
  • a negative electrode paste was prepared so as to contain 200 ppm of the polymer compound in the negative electrode electrode material, which was obtained in the above procedure, and among the expanded lattices made of Pb—Ca—Sn alloy, the negative electrode plate Fill the mesh portion corresponding to the area of 1 to 4 rows.
  • a negative electrode paste was prepared so as to contain 370 ppm of the polymer compound in the negative electrode electrode material, which was obtained in the above procedure, and among the expanded lattices made of Pb—Ca—Sn alloy, the negative electrode plate Fill the mesh portion corresponding to the area of 1 to 4 rows.
  • FIG. 10 shows the distribution of polymer compounds in batteries A5 to A8.
  • Examples 9 to 12 Lead-acid batteries are produced in the same manner as in Examples 1 to 4 except that the following points are changed in the method for producing the negative electrode plate.
  • a negative electrode paste was prepared so as to contain 15 ppm of the polymer compound in the negative electrode electrode material, which was obtained in the above procedure, and among the expanded lattices made of Pb—Ca—Sn alloy, the negative electrode plate The mesh portion corresponding to the area of lines 1 to 6 is filled.
  • a negative electrode paste was prepared so as to contain 66 ppm of the polymer compound in the negative electrode electrode material, which was obtained in the above procedure, and among the expanded lattices made of Pb—Ca—Sn alloy, the negative electrode plate The mesh portion corresponding to the area of lines 1 to 6 is filled.
  • a negative electrode paste was prepared so as to contain 200 ppm of the polymer compound in the negative electrode electrode material, which was obtained in the above procedure, and among the expanded lattices made of Pb—Ca—Sn alloy, the negative electrode plate The mesh portion corresponding to the area of lines 1 to 6 is filled.
  • a negative electrode paste was prepared so as to contain 370 ppm of the polymer compound in the negative electrode electrode material, which was obtained in the above procedure, and among the expanded lattices made of Pb—Ca—Sn alloy, the negative electrode plate The mesh portion corresponding to the area of lines 1 to 6 is filled.
  • FIG. 11 shows the distribution of polymer compounds in batteries A9 to A12.
  • a negative electrode paste was prepared so as to contain 15 ppm of the polymer compound in the negative electrode material, which was obtained in the above procedure, and the entire mesh portion of the expanded lattice made of Pb—Ca—Sn alloy was covered. Fill.
  • a negative electrode paste was prepared so as to contain 66 ppm of the polymer compound in the negative electrode material, which was obtained in the above procedure, and the entire mesh portion of the expanded lattice made of Pb—Ca—Sn alloy was covered. Fill.
  • a negative electrode paste was prepared so as to contain 200 ppm of the polymer compound in the negative electrode material, which was obtained in the above procedure, and the entire mesh portion of the expanded lattice made of Pb—Ca—Sn alloy was covered. Fill.
  • a negative electrode paste was prepared so as to contain 370 ppm of the polymer compound in the negative electrode material, which was obtained in the above procedure, and the entire mesh portion of the expanded lattice made of Pb—Ca—Sn alloy was covered. Fill.
  • FIG. 13 shows a bar graph showing the difference in specific gravity of the electrolytic solution
  • FIG. 14 shows the difference in specific gravity of the electrolytic solution when the horizontal line is the PPG filling ratio.
  • the PPG filling ratio is 25% when the polymer compound is contained in the region of 1 to 2 rows of the negative electrode plate, 50% when it is contained in the region of 1 to 4 rows, and 1 to 6 rows.
  • the case of being contained in the area of 1 to 8 is 100%, and the case of Comparative Example 5 is 0%.
  • the difference in specific gravity of the electrolytic solution is smaller in the batteries A1 to A12 than in the batteries B1 to B4, and stratification is difficult to proceed.
  • the battery B5 since a considerable amount of hydrogen is generated in the entire region of the negative electrode plate, the difference in specific gravity is as small as in the examples. However, the amount of overcharged electricity of the battery B5 is remarkably large.
  • FIG. 15 shows a bar graph showing the amount of overcharged electricity of the electrolytic solution
  • FIG. 16 shows a line graph showing the amount of overcharged electricity when the horizontal line is the PPG filling ratio.
  • the amount of overcharged electricity is reduced in the batteries A1 to 12 as compared with the battery B5. Further, as the average concentration C0 of the polymer compound is large as a whole and the number of regions satisfying C ⁇ C0 is small in the examples, the amount of overcharged electricity tends to be reduced. However, the amount of overcharged electricity of the batteries A4 to A12 in which the number of regions satisfying C ⁇ C0 is 50% or less is at the same level as the batteries B1 to B4.
  • the lead-acid battery according to the present invention can be suitably used as, for example, a power source for starting a vehicle (automobile, motorcycle, etc.) or an industrial power storage device for an electric vehicle (forklift, etc.). It should be noted that these uses are merely examples and are not limited to these uses.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne une plaque d'électrode négative pour une batterie de stockage au plomb, la plaque d'électrode négative comportant un collecteur d'électrode négative et un matériau d'électrode négative. Le matériau d'électrode négative contient un composé polymère. La plaque d'électrode négative est divisée en 32 parties égales dans une forme de matrice mesurant 8 rangées et 4 colonnes dans lesquelles la direction de rangée est une direction Y et la direction de colonne est une direction X, la direction X étant une direction allant de la partie d'extrémité supérieure vers la partie d'extrémité inférieure de la plaque d'électrode négative et la direction Y étant une direction croisant la direction X. Lorsque la valeur moyenne de la teneur en composé polymère du matériau d'électrode négative dans toutes les 32 régions est représentée par C0, le nombre N(1-4) de régions, parmi les 16 régions en 1-4, dans lesquelles la teneur en composé polymère est inférieur à C0, et le nombre N(5-8) de régions, parmi les 16 régions en 5-8, dans lesquelles la teneur en composé polymère est inférieur à C0, satisfont la relation N(1-4) < N(5-8).
PCT/JP2020/021482 2019-05-31 2020-05-29 Batterie de stockage au plomb WO2020241885A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113193176A (zh) * 2021-04-26 2021-07-30 江西京九电源（九江）有限公司 一种蓄电池极板固化室

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60182662A (ja) * 1984-02-28 1985-09-18 Japan Storage Battery Co Ltd 鉛蓄電池
JPH0234758Y2 (fr) * 1986-07-29 1990-09-19
JP2003331908A (ja) * 2002-05-16 2003-11-21 Takehara:Kk 鉛蓄電池用添加剤
JP2017016782A (ja) * 2015-06-29 2017-01-19 株式会社Ｇｓユアサ 鉛蓄電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60182662A (ja) * 1984-02-28 1985-09-18 Japan Storage Battery Co Ltd 鉛蓄電池
JPH0234758Y2 (fr) * 1986-07-29 1990-09-19
JP2003331908A (ja) * 2002-05-16 2003-11-21 Takehara:Kk 鉛蓄電池用添加剤
JP2017016782A (ja) * 2015-06-29 2017-01-19 株式会社Ｇｓユアサ 鉛蓄電池

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113193176A (zh) * 2021-04-26 2021-07-30 江西京九电源（九江）有限公司 一种蓄电池极板固化室

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