JP2007109618A - Lead-acid battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lead-acid battery having a long service life and excellent high rate discharge. <P>SOLUTION: The lead-acid battery uses an electrolyte containing dilute sulfuric acid as the main component, lead peroxide as a positive electrode, metallic lead as a negative electrode, and contains organic polymer having function increasing hydrogen overvoltage of the negative electrode in charging, and at least one selected from the group comprising gold and silver is contained in the electrolyte and/or the electrode. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a lead battery that can withstand long-term use and is superior in large current discharge characteristics as compared to conventional lead batteries.

Conventionally, as a method for recovering the characteristics of a lead-acid battery that has deteriorated due to long-term use, the present inventors have incorporated specific organic polymers, such as polyvinyl alcohol and polyacrylic, in the electrolyte, which have the effect of increasing the hydrogen overvoltage of the negative electrode. The inventors have invented a method for recovering the capacity and internal resistance of lead-acid batteries by adding acid esters, lignin, and the like (see Patent Document 1). Furthermore, the present inventors added indium to this to counteract the hydrogen overvoltage reduction effect of antimony used as an alloy component for increasing the strength of the electrode lattice, thereby reducing the lead sulfate of the negative electrode and the negative electrode. The inventors have invented a method in which crystal refinement proceeds in parallel and the characteristics of the electrode are recovered in a very short time (see Patent Document 2). However, in these lead batteries, the organic polymer is adsorbed on the active sites on the surface of the electrode active material, so there is a tendency that the large current discharge characteristics during discharge tend to be low. There was a drawback that the ranking current (CCA) was insufficient.
JP 2001-313064 A JP 2003-151618 A

  The present invention improves the high-current discharge characteristics during discharge by adding specific metal ions or colloids in addition to the effect of restoring electrode characteristics due to the organic polymer or the like, and an engine when used as an automobile battery. A lead battery with improved starting characteristics is provided.

  The present invention relates to a lead battery using an electrolyte containing dilute sulfuric acid as a main component, using lead peroxide as a positive electrode and metal lead as a negative electrode, and an organic polymer having a function capable of increasing the hydrogen overvoltage of the negative electrode during charging. In addition, a lead battery containing at least one member selected from the group consisting of gold and silver in the electrolytic solution and / or the electrode, and an electrolytic solution containing dilute sulfuric acid as a main component, In a lead battery using a positive electrode, metallic lead as a negative electrode, and containing the electrolyte and / or indium in the electrolyte and an organic polymer having a function capable of increasing the hydrogen overvoltage of the negative electrode during charging, further in the electrolyte and And / or a lead battery containing at least one member selected from the group consisting of gold and silver in the electrode. In these lead batteries, the organic polymer preferably contains at least one of polyvinyl alcohol, polyacrylic acid, and polyacrylic ester, and the amount thereof is 0.01 to 0.2% by weight. It is a lead battery in which the amount of indium is 1 to 1000 ppm and the total amount of gold and silver is 0.01 to 100 ppm.

  An organic polymer (hereinafter referred to as “organic polymer”) that can increase the hydrogen overvoltage of the negative electrode during charging used in the present invention is an active material for the negative electrode acting on the negative electrode surface during charge / discharge in a lead storage battery using dilute sulfuric acid as an electrolyte. It has the effect | action which makes the lead particle which is a remarkably fine. As the organic polymer, at least one selected from the group consisting of polyvinyl alcohol, polyacrylic acid, and polyacrylic acid ester can be used. The lead particles produced by the electrochemical reaction in the presence of this organic polymer are extremely active compared to the conventional lead particles produced by mechanical methods such as the Shimadzu ball mill method and the molten lead method. In addition, fine lead particles as a new substance are synthesized. The organic polymer used in the present invention is desirably present in an amount of 0.001 to 0.5% by weight, more preferably 0.01 to 0.2% by weight, in the electrolytic solution.

  Indium used in the present invention is usually added to the electrolyte in the form of indium ions, and antimony is eluted from the lead antimony alloy generally used for the purpose of increasing the mechanical strength of the electrode lattice, and is deposited on the negative electrode. It has the effect of canceling the action of lowering the hydrogen overvoltage, and it is desirable to contain 1 to 1000 ppm in the electrolyte and / or electrode active material.

  In the present invention, at least one of the group consisting of a water-soluble gold compound, silver compound, colloidal gold, and silver is added to the electrode surface or the grid surface in the electrolyte solution, thereby increasing the internal resistance of the battery, particularly the large resistance. It has been found that the internal resistance at the time of current discharge is reduced and large current discharge is possible, and for example, the engine starting characteristics of automobiles are remarkably improved. Although the mechanism affecting the cell reaction of gold and silver in the present invention is not clear, the presence of these noble metals or their alloys between the grid and the electrode active material or between the electrode active materials causes the interface at these interfaces. Electron conduction is facilitated, electrode reactions occur across the entire electrode, and the electrical resistance of the electrode itself is also reduced. As a result, it is considered that the internal resistance of the battery is significantly reduced.

  The gold and silver used in the present invention may be prepared by adding a dispersion of these colloids or a solution of those compounds to the electrolyte, or adding a dispersion of these colloids or a solution of these compounds to the electrode grid or electrode active material. It is preferably used by spraying or coating on the surface of the material or mixing them with an electrode active material.

  Hereinafter, the effect of the additive of the present invention will be described with specific examples.

即ち、試験番号１に示す添加物を含まない従来の鉛電池では、ＣＣＡは３８５アンペアであったが、これを長寿命とする目的で充電時に負極の水素過電圧を上昇せしめ得る有機ポリマーとしてポリビニルアルコール０．１％を電解液中に添加した試験番号２の試験体では、かえってＣＣＡが３６０アンペアと低下しており、自動車エンジンの始動特性の低下が懸念される。これに対し、本発明の一実施例である試験番号３の試験体では、ＣＣＡが４８０アンペアと著しく増加しており、有機ポリマーの添加と金および銀の複合添加により、長寿命化とエンジン始動特性の向上とが両立している。With respect to a commercially available 40B19 type lead battery, each of the five lead batteries was in a fully charged state, and cold cranking current (CCA) was indirectly measured by a conductance method using a Midtronics tester. Table 1 shows the average values for five lead batteries under each condition.

That is, in the conventional lead battery not containing the additive shown in Test No. 1, CCA was 385 amperes, but for the purpose of extending its life, polyvinyl alcohol is used as an organic polymer that can increase the hydrogen overvoltage of the negative electrode during charging. In the test body of test number 2 in which 0.1% is added to the electrolyte, the CCA is rather lowered to 360 amperes, and there is a concern that the starting characteristics of the automobile engine may be lowered. On the other hand, in the test body of test number 3 which is an embodiment of the present invention, the CCA is remarkably increased to 480 amperes. By adding an organic polymer and a composite addition of gold and silver, the service life is extended and the engine is started. The improvement of characteristics is compatible.

Claims (5)

  In a lead battery using an electrolyte containing dilute sulfuric acid as a main component, using lead peroxide as a positive electrode and metal lead as a negative electrode, and further comprising an organic polymer having a function of increasing the hydrogen overvoltage of the negative electrode during charging, A lead battery comprising at least one member selected from the group consisting of gold and silver in the electrolyte and / or the electrode.   Function using an electrolyte containing dilute sulfuric acid as a main component, using lead peroxide as a positive electrode and metal lead as a negative electrode, and increasing the hydrogen overvoltage of the negative electrode during charging with indium in the electrolyte and / or the electrode A lead battery comprising an organic polymer comprising: at least one member selected from the group consisting of gold and silver in the electrolyte and / or the electrode.   3. The lead battery according to claim 1, wherein the organic polymer contains at least one of polyvinyl alcohol, polyacrylic acid, and polyacrylic acid ester, and the amount thereof is 0.01 to 0.2% by weight. .   4. The lead battery according to claim 2, wherein the amount of indium is 1 to 1000 ppm.   5. The lead battery according to claim 1, wherein the total amount of gold and silver is 0.01 to 100 ppm.