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JP-7857103-B2 - Negative electrode plate for lead-acid batteries and lead-acid batteries

JP7857103B2JP 7857103 B2JP7857103 B2JP 7857103B2JP-7857103-B2

Inventors

  • ▲浜▼野 泰如
  • 辻中 彬人

Assignees

  • 株式会社ＧＳユアサ

Dates

Publication Date
20260512
Application Date
20200924
Priority Date
20190927

Claims (18)

  1. It includes a negative electrode current collector and a negative electrode material, The negative electrode current collector comprises a frame portion having ears, and a grid portion provided continuously with the frame portion. It has, The aforementioned grid section has multiple square cells, The square grid has a pair of first vertices whose diagonals are in a first direction from the frame to the grid, and a pair of second vertices whose diagonals are in a second direction intersecting the first direction. The angle θ between the two sides forming the second vertex is 55° or more and 100° or less. In a cross-section perpendicular to the length direction of any one of the four grid bones surrounding the square grid, when the length of each of the two sides corresponding to the thickness of the negative electrode current collector is x, and the length of each of the remaining two sides is y, the ratio of y to x: y/x is 0.8 or greater and 1.4 or less. The negative electrode material includes an organic condensate, The aforementioned organic condensate includes units of aromatic compounds, The aforementioned aromatic compound has a sulfur-containing group, The aforementioned aromatic compound comprises both a bisarene compound and a monocyclic compound, and is used as a negative electrode plate for a lead-acid battery.
  2. The negative electrode plate for a lead-acid battery according to claim 1, wherein the width of the inner dimensions of the square grid in the second direction is 11 mm or more and 22.5 mm or less.
  3. The negative electrode plate for a lead-acid battery according to claim 1 or 2, wherein the negative electrode current collector is an expanded grid body with the first direction as the grid unfolding direction.
  4. The negative electrode plate for a lead-acid battery according to any one of claims 1 to 3, wherein the ratio of y to x: y/x is 0.85 or greater.
  5. The negative electrode plate for a lead-acid battery according to any one of claims 1 to 4, wherein the ratio of y to x: y/x is 1.1 or less.
  6. The negative electrode plate for a lead-acid battery according to any one of claims 1 to 5, wherein the bisarene compound comprises a bisphenol compound.
  7. The negative electrode plate for a lead-acid battery according to claim 6, wherein the bisphenol compound comprises at least one selected from the group consisting of bisphenol A and bisphenol S.
  8. The anode plate for a lead-acid battery according to any one of claims 1 to 7, wherein the monocyclic compound comprises a hydroxyarene compound.
  9. The negative electrode plate for a lead-acid battery according to claim 8, wherein the hydroxyarene compound comprises a phenol sulfonic acid compound.
  10. A negative electrode plate for a lead-acid battery according to any one of claims 1 to 9, wherein the sulfur element content of the organic condensate is 2000 μmol/g or more.
  11. A negative electrode plate for a lead-acid battery according to any one of claims 1 to 10, wherein the sulfur element content of the organic condensate is 3000 μmol/g or more.
  12. A negative electrode plate for a lead-acid battery according to any one of claims 1 to 11, wherein the sulfur element content of the organic condensate is 9000 μmol/g or less.
  13. The negative electrode plate for a lead-acid battery according to claim 1, wherein the aromatic compound that forms the basis of the aromatic compound unit includes both a bisarene compound and a monocyclic compound, and the molar ratio of the bisarene compound to the monocyclic compound is in the range of 1:9 to 9:1.
  14. The negative electrode plate for a lead-acid battery according to claim 1, wherein the aromatic compound that forms the basis of the aromatic compound unit includes both a bisarene compound and a monocyclic compound, and the molar ratio of the bisarene compound to the monocyclic compound is in the range of 2:8 to 8:2.
  15. The negative electrode plate for a lead-acid battery according to any one of claims 1 to 14, wherein the content of nitrogen atom-containing groups in the organic condensate is 1% by mass or less.
  16. The negative electrode plate for a lead-acid battery according to any one of claims 1 to 15, wherein the weight-average molecular weight (Mw) of the organic condensate is 7,000 or more and 100,000 or less.
  17. The negative electrode plate for a lead-acid battery according to any one of claims 1 to 16, wherein the content of the organic condensate contained in the negative electrode material is 0.01% by mass or more and 1.0% by mass or less.
  18. A negative electrode plate for a lead-acid battery according to any one of claims 1 to 17, A lead-acid battery comprising a positive electrode plate and an electrolyte containing sulfuric acid.

Description

This invention relates to a negative electrode plate for a lead-acid battery and a lead-acid battery. Lead-acid batteries are used in a variety of applications, including automotive and industrial use. A lead-acid battery consists of a negative electrode plate, a positive electrode plate, and an electrolyte. The negative electrode plate includes a current collector and a negative electrode material. Organic shrinkage inhibitors are added to the negative electrode material. These include naturally derived organic shrinkage inhibitors such as sodium ligninsulfonate, as well as synthetic organic shrinkage inhibitors. Cold cranking current (CCA) is a well-known important indicator of lead-acid battery performance. For example, the higher the terminal voltage at 30 seconds after the start of discharge, measured using a predetermined procedure, the higher the CCA performance. Generally, lead-acid batteries with high CCA performance have superior low-temperature high-rate performance. Patent Document 1 describes a negative electrode plate for a lead-acid battery in which a lignin sulfonate is dispersed in an active material layer, characterized in that the lignin sulfonate has an average molecular weight of 4,000 to 10,000 and a sulfonation rate of 90% or more. Furthermore, Patent Document 2 provides a lead-acid battery that offers excellent low-temperature high-rate discharge performance and low-rate discharge performance within a practical range. The negative electrode plate contains an organic shrinkage inhibitor with an S element content of 3900 μmol/g to 6000 μmol/g, the ratio of the electrolyte volume to the total volume of the positive and negative electrode plates is 1.8 to 3.0, and the concentration of the organic shrinkage inhibitor in the negative electrode material is 0.05 mass% to 0.3 mass%. On the other hand, Patent Document 3 proposes a valve-regulated lead-acid battery characterized in that the ratio of the volume V of the positive electrode plate excluding the current collector ears and the mass W of the positive electrode expanded grid excluding the current collector ears (W/V) to the volume V is 1.20 g/ cm³ or more, the ratio of the area S to the perimeter L of the grid area S of the positive electrode expanded grid excluding the current collector ears (S/L) is 2.3 mm or less, the angle θ between two sides of the expanded grid lattice is less than 90°, and the apparent density of the positive electrode active material filled in the positive electrode expanded grid lattice is 4.0 g/ cm³ or more. Japanese Patent Application Publication No. 10-144305Japanese Patent Publication No. 2019-53998Japanese Patent Publication No. 2007-157613 This is a plan view showing the structure of the negative electrode current collector.Figure 1 is an enlarged view of the grid portion of the negative electrode current collector.This is a partially cutaway exploded perspective view showing the external appearance and internal structure of a lead-acid battery.This graph shows the relationship between the angle θ formed by the two sides that make up the second vertex of the negative electrode current collector and the CCA performance.This graph shows the relationship between the width L of the inner dimensions in the second direction of the rectangular grid of the negative electrode current collector and the CCA performance, when the angle θ formed by the two sides that make up the second vertex of the negative electrode current collector is 50°.This graph shows the relationship between the width L of the inner dimensions in the second direction of the rectangular grid of the negative electrode current collector and the CCA performance, when the angle θ formed by the two sides that make up the second vertex of the negative electrode current collector is 80°. [Lead acid battery] An embodiment of the present invention comprises a negative electrode plate, a positive electrode plate, and an electrolyte containing sulfuric acid, which will be described later. The lead-acid battery may be either a valve-regulated (sealed) lead-acid battery or a liquid-type (vented) lead-acid battery. In this specification, the fully charged state of a liquid-type lead-acid battery is defined according to the definition in JIS D 5301:2006. More specifically, the fully charged state is defined as the state in which a lead-acid battery is charged in a water bath at 25°C ± 2°C with a current (A) equal to 0.2 times the Ah value stated as the rated capacity, until the terminal voltage during charging, measured every 15 minutes, or the electrolyte density converted to a temperature of 20°C, shows a constant value with three significant figures for three consecutive measurements. In the case of a valve-regulated lead-acid battery, the fully charged state is defined as the state in which the lead-acid battery is charged in an air bath at 25°C ± 2°C with a constant current and constant voltage of 2.23 V/cell at a current (A) equal to 0.2 times the Ah