JP2010108682A - Lead-acid battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lead-acid battery combining the effect suppressing decrease of an electrolyte with high vibration resistant property and enhancing reliability especially in a liquid type lead-acid battery. <P>SOLUTION: In the liquid type lead-acid battery having constitution sticking a sheet covering an exhaust hole of a vent plug to a battery lid with an adhesive and exhausting the exhaust gas from the exhaust hole to the outside of the battery through a gap between the sheet and the battery lid by arranging no adhesive in a portion corresponding to the exhaust hole, poles and/or connectors formed in a positive strap and a negative strap and the positive strap are made of a lead alloy containing antimony and the negative strap is made of a lead alloy such as a lead-tin alloy containing no antimony, and thereby, the lead-acid battery enhancing vibration resistant property without damaging the electrolyte decrease suppressing performance is obtained. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a lead-acid battery.

  Lead-acid batteries are used for various purposes such as vehicle engine starting and backup power supply. Among them, the start lead-acid battery supplies power to various electric and electronic devices mounted on the vehicle as well as power to the engine start cell motor. After the engine is started, the lead storage battery is charged by an alternator. Here, the output voltage and output current of the alternator are set so that charging and discharging are balanced and the SOC of the lead-acid battery is maintained in a fully charged state or a charged state close to full charge of approximately 90 to 100%.

  In most cases, the starting lead-acid battery is installed in the engine room. Therefore, since charging is performed in a high temperature atmosphere of 40 ° C. to 80 ° C., the lead storage battery is easily overcharged. As a result, the water in the electrolytic solution is decomposed into oxygen and hydrogen gas by electrolysis. It is discharged to the outside and the electrolyte level is lowered. Further, even when charging is not performed, the electrolytic solution level also decreases due to evaporation of moisture from the electrolytic solution and the electrolytic solution mist filled in the battery being dissipated outside the battery.

  The decrease in the electrolyte level in the lead-acid battery results in a decrease in battery capacity due to corrosion of the negative electrode strap and oxidation of the negative electrode active material. Therefore, a minimum liquid level line is set so that the entire surface of the negative electrode strap and the negative electrode plate is immersed in the electrolytic solution, and water replenishment work is necessary as appropriate so that the electrolytic solution level does not fall below the minimum liquid level line.

  In order to save the labor of such water replenishment work, technical development for suppressing the liquid reduction of the liquid lead-acid battery has been continued. For example, the use of an alloy that does not contain antimony that lowers the hydrogen overvoltage, such as a lead-calcium alloy or a lead-tin alloy, as a lead alloy for a lead-acid battery lattice, widely reduces the liquid loss due to electrolysis. Generally known.

  On the other hand, various studies have been made mainly from the viewpoint of improving the exhaust structure of lead-acid batteries, in order to suppress liquid evaporation due to water evaporation from the electrolyte and dissipation of electrolyte mist filled in the battery. Has been done.

  For example, a configuration has been proposed in which a sheet covering a liquid spout attached to a liquid spout is attached to a lid with an adhesive, and a gas exhaust port provided in the liquid spout is covered with a sheet. By covering the exhaust hole with such a sheet, the water vapor partial pressure difference inside and outside the battery, and the inside of the exhaust hole becomes a negative pressure due to the air flow outside the battery, so that the water vapor and electrolyte mist inside the battery go out of the battery. Can be suppressed.

  However, in a liquid lead-acid battery, oxygen / hydrogen gas is inevitably generated, and oxygen / hydrogen gas is always generated when the lead-acid battery is left or charged. Therefore, although the decrease of the electrolytic solution due to the evaporation of the electrolytic solution or the discharge of the electrolytic solution mist can be suppressed, the amount of liquid reduction due to the self-discharge of the lead storage battery or the water electrolysis when the lead storage battery is charged cannot be suppressed.

  Furthermore, when the strap is exposed to the gas phase from the electrolytic solution due to the progress of liquid reduction due to the long-term use of the lead storage battery and the electrolytic solution level being lowered, the joint between the negative electrode strap and the negative electrode ear is disconnected. was there.

  In order to solve these problems, in Patent Document 1, a sheet that covers the exhaust hole of the liquid spigot is bonded to a lid, lead-calcium alloy is used for the positive and negative grids, and the positive and negative electrodes have the same polarity. It has been proposed to use a lead alloy such as a lead-tin alloy that does not contain antimony as a lead alloy for a strap that joins the electrodes together.

  By adopting the configuration shown in Patent Document 1, not only the reduction of liquid due to the evaporation of the electrolytic solution and the dissipation of the electrolytic solution mist, but also the reduction due to the self-discharge of the lead storage battery or the electrolysis of water that proceeds during charging. The liquid can be remarkably suppressed.

  In addition, even if the liquid reduction progresses due to long-term use and the strap is exposed to the gas phase from the electrolyte, it does not contain antimony in the negative strap and the negative electrode plate ear, so it is highly corrosive consisting of antimony and calcium. A compound is not produced | generated, the corrosion disconnection in the junction part of a negative electrode strap and a negative electrode plate ear | edge part can be suppressed, and a lead storage battery with high reliability can be provided.

  However, the lead storage battery having the configuration shown in Patent Document 1 includes a lead alloy that forms a positive electrode and a negative electrode strap, and a lead alloy that does not contain antimony as a lead alloy for internal connection such as a pole column and a connection body connected to the lead alloy. Therefore, the mechanical strength of the internal connection member such as the strap, the pole column, and the connection body is reduced as compared with the conventional lead alloy containing antimony.

Such a decrease in the mechanical strength of the internal connection member causes a disconnection when vibration is applied to the lead storage battery. As a result, the lead storage battery suddenly becomes unusable or an electric spark generated at the disconnection site is generated. In some cases, the hydrogen gas inside the battery is ignited, and the battery exterior such as the battery case or the lid is deformed or damaged by the impact at the time of ignition.
JP 2008-41473 A

  An object of the present invention is to obtain both the effect of suppressing the amount of liquid reduction of the lead storage battery as described above and the effect of improving vibration resistance. Furthermore, even if the negative electrode strap is exposed from the electrolyte due to long-term use of the lead storage battery, the corrosion disconnection at the joint between the strap and the electrode plate ear is suppressed, and a lead storage battery having excellent reliability is provided. With the goal.

  In order to solve the above-described problem, the invention according to claim 1 of the present invention uses a lead-calcium alloy for each of the positive electrode grid body and the negative electrode grid body, and each of the positive electrode grid body and the negative electrode grid body has electrode plate ears. Are integrally provided, a positive electrode plate and a negative electrode plate are arranged via a separator, and the electrode plate ears having the same polarity are collectively welded to a strap corresponding to the polarity, and the strap is connected to a terminal. An electrode plate group provided with a connecting body for connecting pole poles and / or cells is housed in a battery case together with an electrolytic solution, and the electrolytic solution has an amount for immersing at least the strap, and the opening of the battery case A liquid port plug provided with an exhaust hole for discharging the gas in the battery to the outside of the battery is attached to the liquid port provided on the lid joined to the part, and an adhesive or an adhesive is provided so as to cover the exhaust hole. Is attached to the lid by A sheet, and a non-joining portion that does not have the adhesive or the adhesive on a bonding surface of the sheet and the lid, through a gap between the lid and the sheet formed by the non-joining portion, The exhaust gas from the exhaust hole is disposed so as to be discharged out of the battery at a position spaced from the exhaust hole, and the pole column and the connection body provided on the straps of both poles, and the strap on the positive electrode side are provided with antimony. The lead-acid battery is made of a lead alloy containing the lead-acid battery, and the strap on the negative electrode side is made of a lead alloy containing no antimony.

  In addition, it is preferable to use a lead-tin alloy containing tin as the strap on the negative electrode side.

  Furthermore, it is preferable to form a lead-tin alloy layer on the surface of the negative electrode side of the negative electrode.

  The lead-tin alloy layer can be formed by pressure bonding to the surface of the electrode plate ear. For example, when an expanded lattice is used as the lattice body on the negative electrode side, a lead-tin alloy layer may be pressure-bonded to a portion corresponding to the electrode plate ear portion of a rolled lead alloy sheet used as the expanded lattice material. When such a rolled lead alloy sheet is rolled into a rolled lead alloy sheet by rolling a lead-calcium alloy cast slab, lead is placed at a predetermined position of the cast slab, that is, a position corresponding to the electrode plate ear after rolling. -It can be formed by stacking and rolling a sheet of tin alloy.

  Since the lead-tin alloy layer formed by such a method has a uniform thickness and a smooth surface, variation in the thickness of the negative electrode tab is remarkably suppressed, and the negative strap Since the wettability with the negative electrode strap alloy is also good when forming the electrode, it is preferable that the gap between the negative electrode strap after the completion of welding and the negative electrode plate ear portion can be remarkably suppressed, which can be a starting point of corrosion. .

  According to the configuration of the present invention described above, it is possible to achieve both the effect of suppressing the amount of liquid reduction of a lead storage battery and the effect of improving vibration resistance, which has been difficult in the past. Even if it becomes an exposed state, the corrosion disconnection of the junction part of a strap and an electrode plate ear | edge part is suppressed, and there exists a remarkable effect that the lead storage battery excellent in reliability can be obtained.

  As shown in FIG. 1, the lead storage battery 1 according to the embodiment of the present invention includes a positive electrode plate 2 having a positive electrode lattice of lead-calcium alloy and a negative electrode plate 3 having a negative electrode lattice of lead-calcium alloy. , And a configuration in which the separators 4 are stacked. In addition, since the negative electrode plate 3, the separator 4, and the positive electrode plate 2 are laminated, the positive electrode plate 2 does not appear in FIG. 1, but the positive electrode plate 2 is located under the separator 4 for the sake of understanding. The positive electrode plate 2 is indicated by a broken line.

  The positive electrode tabs 2 a of the positive electrode plate 2 are connected to each other by a positive electrode strap 9, and the negative electrode plate ears 3 a of the negative electrode plate 3 are connected to each other by a negative electrode strap 10. In addition, the positive pole strap 9 and the negative pole strap 10 are connected to the pole column 12 for connection with the external terminal 11 and / or the connection body 13 for connecting the adjacent electrode plate groups 8. An electrode plate group 8 is configured.

  1 shows the first electrode plate group 8 of the lead-acid battery 1 from the external terminal 11 on the positive electrode side. Therefore, the positive pole column 12 is connected to the positive electrode strap 9, and the negative electrode strap 10 is connected to the negative electrode strap 10. Although an example in which the connection body 13 is connected is shown, in the electrode plate group 8 connected in series, the electrode plate group 8 positioned in the middle and not located at both ends is connected to the positive electrode strap 9 and the negative electrode strap 10. Of course, in the electrode plate group 8 both connected to the negative electrode end and positioned at the negative electrode end, the positive electrode strap 9 is connected to the negative electrode strap 12 and the negative electrode strap 10 is connected to the negative electrode strap 10. .

  In the present invention, a lead-antimony alloy containing antimony is used for the positive electrode strap 9, the connection body 13, and the pole columns 12 on both the positive electrode side and the negative electrode side. The amount of antimony added is approximately 2.0 to 3.5% by mass, but is not limited thereto.

  Further, in the above lead-antimony alloy, in order to improve the alloy strength and the corrosion resistance, about 0.05 mass% to 0.50 mass% arsenic, about 0.001 mass% to 0.01 mass% selenium. It is also possible to add a nucleating agent such as In addition, components such as copper, nickel, sulfur, silver, bismuth, and tin, which are included as inevitable impurities in the lead-antimony alloy, also adversely affect the strength and corrosion resistance of the positive electrode strap 9, the pole column 12, and the connection body 13. It does not matter if it is contained in a range that does not give any odor.

  On the other hand, in the present invention, the negative electrode strap 10 uses a lead alloy containing no antimony. This is because when the negative electrode strap 10 contains antimony, the hydrogen overvoltage decreases, the water in the electrolyte is electrolyzed, the generation of hydrogen gas is promoted, and the amount of liquid reduction increases. . In addition, a lead-tin alloy can be used as a lead alloy not containing antimony. In this case, the tin content is preferably about 1.6 to 3.5% by mass from the viewpoint of the strength and corrosion resistance of the negative electrode strap 10.

  In general, antimony is included as an inevitable impurity in lead and lead alloys, but in the present invention, the lead-tin alloy used for the negative electrode strap 10 is also in a trace amount that does not increase the amount of liquid reduction. Therefore, it can be treated as a lead alloy substantially free of antimony. The content of antimony in the lead alloy at a level that does not increase the amount of liquid reduction is preferably 50 ppm or less.

  For the purpose of suppressing the amount of liquid reduction, it is preferable to use a lead alloy containing no antimony for not only the negative electrode strap 10 but also the positive electrode strap 9 and the pole columns of the positive electrode and the negative electrode for all lead parts. Although considered, the inventors of the present invention show that the degree of influence of antimony in these lead parts excluding the negative electrode strap 10 on the increase in the amount of liquid reduction is extremely low compared to the antimony contained in the negative electrode strap 10. It is what I found.

  On the other hand, lead parts such as straps, connectors, and poles made of lead alloys that do not contain antimony are more weldable and mechanical than lead parts made of lead-antimony alloys that have been used in starting lead-acid batteries. Strength decreases. As a result of detailed investigations by the inventors, a lead alloy such as a lead-tin alloy that does not contain antimony is used only for the negative electrode strap 10, and a lead-antimony alloy is used for the other positive electrode strap 9, the pole column 12, and the connection body 13. By using a sheet 23 that covers the exhaust hole 22 to be described later, a highly reliable lead storage battery that achieves both the effect of significantly reducing the amount of liquid reduction and the vibration resistance of the lead storage battery 1 can be obtained. .

  The electrode plate group 8 is housed in a cell chamber 6 a that is compartment-molded in the battery case 6 together with the electrolyte 5 that immerses the entire surface of the electrode plates of the positive electrode plate 2 and the negative electrode plate 3, and a lid 7 is joined to the upper part of the battery case 6. Has been. The positive strap 9 and the negative strap 10 are also immersed in the electrolyte 5. In general, the lowest liquid level line (not shown) of the electrolytic solution 5 is generally set at a position corresponding to the lower surface or the upper surface of the positive electrode strap 9 and the negative electrode strap 10. 5 can be set at a position where at least the positive electrode strap 9 and the negative electrode strap 10 are immersed, and the lower part of the pole column 12 and the connection body 13 are immersed.

  The lid 7 is provided with a liquid port 7a corresponding to the cell chamber 6a, and a liquid port plug 21 is attached to the liquid port 7a. An exhaust hole 22 is provided in the head of the liquid spout 21. In order to prevent the electrolytic solution 5 swayed by vibration from directly reaching the exhaust hole 22 and leaking out of the battery, a splash-proof body 21 a may be provided inside the liquid spout 21. Further, an explosion-proof filter 21b as conventionally known may be provided between the splash-proof body 21a and the exhaust hole 22.

  In the present invention, as described above, the sheet 23 covering the upper portion of the exhaust hole 22 is bonded to the lid 7 by the adhesive 23b. In addition, since the adhesive 23b is used for the purpose of fixing the sheet 23 on the lid 7, an adhesive may be used instead of the adhesive 23b. In addition, as an adhesive, the thing of aqueous emulsion type, such as an acrylic resin, is especially preferable at the point which reduces environmental impact.

  In addition, the aqueous emulsion type pressure-sensitive adhesive reduces the generation of static electricity at the time of peeling compared to other solvent-based pressure-sensitive adhesives. As a result, even if the user of the lead storage battery accidentally peels off the sheet 23 from the lid 7, the generation of static electricity in the lid 7 and the resulting discharge spark are suppressed. The probability of igniting the hydrogen gas staying inside can be significantly reduced.

  The sheet 23 is not bonded to the lid 7 with the adhesive 23b on the entire surface, but is provided with a non-joining portion 23a where the adhesive 23b does not exist at least at a portion corresponding to the exhaust hole 22. In the non-joining portion 23a, the lid 7 and the sheet 23 are not bonded to each other and have a minute gap 25, and oxygen / hydrogen gas discharged from the exhaust hole 22 through the gap 25 is discharged out of the battery. In order to function as a gas discharge path, as shown in FIG. 2, for example, a non-joining portion 23a is provided to the end of the sheet 23 so that gas is discharged from all the exhaust holes 22 to the outside of the battery. At the end of the sheet 23, the gas can finally be discharged from the lead storage battery 1 to the atmosphere.

  In addition, in the bonding surface of the sheet | seat 23 and the lid | cover 7, the part except the non-joining part 23a, ie, the part bonded with the adhesive 23b, was shown as the shaded part A in FIG.

  By disposing the sheet 23 so as to face the exhaust hole 22, the exhaust hole 22 is not exposed to the air flow around the battery, and the phenomenon that water vapor or electrolyte mist inside the battery is sucked out from the exhaust hole 22 is suppressed. Therefore, liquid reduction due to evaporation of moisture in the electrolytic solution or dissipation of the electrolytic solution mist to the outside of the battery is suppressed.

  Further, the gas discharge path from the exhaust hole 22 to the outside of the battery exists as a narrow gap 25 between the lid 7 and the sheet 23 or exists in a state where the lid 7 and the sheet 23 are in contact with each other. As long as the pressure does not increase above the atmospheric pressure, the gas, water vapor, and electrolyte mist in the battery are hardly discharged out of the battery. As a result, the decrease of the electrolyte is remarkably suppressed. In addition, as this sheet | seat 23, what has the thickness of about 0.05 mm-0.5 mm, such as an acid-resistant polypropylene resin, should just be used.

  The present invention pays attention to the fact that the antimony contained in the negative electrode strap in the prior art significantly increases the amount of liquid reduction compared to the antimony contained in the positive electrode strap, the connecting body, and the pole column. By having the structure covered with 23, the liquid reduction amount of the lead storage battery is remarkably reduced synergistically, and excellent vibration resistance can be secured.

  Unlike a control valve type lead acid battery, a lead acid battery, particularly a liquid type lead acid battery such as the present invention, does not have a structure for absorbing oxygen gas generated during charging at the negative electrode, so during charging or standing A reduction (decrease) of water in the electrolytic solution inevitably occurs. This also applies to the lead-acid battery of the present invention, and although the liquid reduction is remarkably suppressed as compared with the conventional lead-acid battery, the lead-acid battery of the present invention can be charged, left in a high-temperature atmosphere, or specified. When charging is performed at a voltage exceeding the charged voltage, it is assumed that liquid reduction proceeds and the joint between the negative electrode strap 10 and the negative electrode tab 3a is exposed from the electrolytic solution 5. .

  In a conventional lead storage battery in which lead-calcium alloy negative electrode plate ears are collectively welded with a lead-antimony alloy negative electrode strap, when the negative electrode strap and negative electrode plate ears are exposed from the electrolyte, this negative electrode strap and negative electrode There is a case where the joint portion of the plate ear portion is corroded and disconnected. Lead-antimony alloys are used for straps of conventional lead-acid batteries, particularly liquid-type start-up lead-acid batteries, in order to improve weldability and mechanical strength in manufacturing. The corrosion phenomenon occurs in the case where the negative electrode lattice uses a lead-calcium alloy and the negative electrode strap uses a lead-antimony alloy.

  This is because when the negative electrode plate ear is welded with the negative electrode strap, antimony is highly corrosive due to calcium contained in the negative electrode plate ear and antimony contained in the lead-antimony alloy for forming the negative electrode strap. This is because an intermetallic compound of calcium is generated.

  In the present invention, when the negative electrode strap 10 is formed, a lead alloy not containing antimony is used, so that the antimony having high corrosive properties as described above is formed at the joint between the negative electrode strap 10 and the negative electrode plate ear 3a during welding. Since no intermetallic compound of calcium and calcium is produced, the corrosion resistance of the joint portion between the negative electrode tab 3a and the negative strap 10 is improved, and the reliability of the negative strap 10 is improved.

  As a more preferable form, it is preferable to form the lead-tin alloy layer 24 on the surface of at least the portion of the negative electrode tab 3a that is in contact with the negative strap 10. FIG. 3A is a view showing a cross section of the negative electrode plate ear portion 3a, and FIG. 3B is a view showing a cross section of a joint portion between the negative electrode strap 10 and the negative electrode plate ear portion 3a. By forming the lead-tin alloy layer 24 on the surface of the negative electrode plate ear portion 3a, the negative electrode plate ear portion 3a made of lead-calcium alloy whose surface is easily oxidized is protected from oxidation. The weldability with the strap 10 is improved.

  Furthermore, as the lead-tin alloy layer 24, a so-called solder alloy having a lower melting point than the negative electrode strap 10 and the negative electrode plate ear portion 3a (for example, 40 mass% lead-60 mass% tin, 50 mass% lead-50 mass%). The lead-tin alloy layer 24 melted by heat at the time of melting the lead (not shown) of the lead-tin alloy used to form the negative electrode strap 10 is used to form the negative electrode tab 3a. In order to fill a gap generated between the lead-calcium alloy which is a base material of the negative electrode strap 10 and the negative electrode strap 10, the joining of the negative electrode plate ear 3 a and the negative electrode strap 10 due to crevice corrosion, which has conventionally occurred with such a gap as a base point. The corrosion of the part can be more effectively suppressed.

  As a method for forming the lead-tin alloy layer 24 on the negative electrode tab 3a, (1) the negative electrode tab 3a is immersed in a molten lead alloy having the composition of the lead-tin alloy layer 24. (2) lead -There is a method of applying a solder paste in which minute solder balls made of tin alloy are dispersed in a flux to the negative electrode plate ear portion 3a, and the most suitable method is (3) a grid used for the negative electrode plate 3 A method of forming an expanded lattice body obtained by expanding a lead-calcium alloy rolled sheet and forming a lead-tin alloy layer 24 at the position corresponding to the negative electrode tab 3a of the rolled lead-calcium alloy sheet by simultaneous rolling It is.

  In the method (3), when rolling a cast slab of lead-calcium alloy, the cast slab is superposed on a lead-tin alloy sheet having the same composition as the lead-tin alloy layer 24, and both are rolled simultaneously. Can be realized.

  According to the present invention, in particular, the liquid reduction amount can be remarkably suppressed while ensuring the vibration resistance of the liquid lead-acid battery.

Example 1
Hereinafter, the effects of the present invention will be described with reference to examples. The lead storage battery according to the present invention and the comparative example was 80D26 shown in JIS D5301: 2006 (starting lead storage battery), and the amount of liquid reduction during charging was evaluated while applying vibration.

  The positive electrode plate was obtained by expanding a rolled sheet of a lead alloy of lead-0.07% by mass calcium-1.6% by mass tin, and ball mill type lead powder (oxidation degree 70%) with water. A paste kneaded with sulfuric acid was filled and then aged and dried.

  The negative electrode plate is obtained by expanding a negative electrode grid obtained by expanding a rolled sheet of lead-0.07 mass% calcium-0.25 mass% lead alloy with ball mill type lead powder (oxidation degree 70%) and water. The paste was prepared by adding sulfuric acid and additives (lignin, barium sulfate and carbon) and kneading. In addition, about the negative electrode plate, the electrode plate which formed the 50 mass% lead -50 mass% tin alloy layer by thickness 10 micrometers on the both surfaces of the negative electrode plate ear | edge part (henceforth, negative electrode plate ear part process is provided), and such an alloy layer Was formed on both surfaces of the negative electrode plate ears, and the base material lead-0.07% by mass calcium-0.25% by mass was exposed (hereinafter, no negative electrode plate ears were treated).

  The separator was formed by processing a polyethylene resin microporous film into a bag shape and wrapping the positive electrode plate. Lead-2.5 mass% tin alloy (hereinafter referred to as Pb-Sb alloy in this example) is used as a lead alloy for the positive and negative straps, connectors and poles of the lead storage batteries of the present invention and comparative examples. A lead-2.5 mass% antimony alloy (hereinafter, Pb-Sb in this example) was prepared.

  As a sheet (corresponding to the sheet 23 used in the lead storage battery of the present invention in FIG. 1) used for the lead storage batteries of the present invention example and the comparative example, a 0.2 mm thick polypropylene resin film having a width of 40 mm, As shown in FIG. 2, a belt-like portion having a width of 20 mm is formed as a non-joining portion 23a at the center in the width direction of the sheet 23, and the portion other than the non-joining portion 23a is made of acrylic resin. The sheet | seat 23 was bonded together to the lid | cover 7 using the aqueous | water-based emulsion adhesive (shaded part A of FIG. 2).

  In addition, the sheet | seat 23 was bonded together to the lid | cover 7 so that the non-joining part 23a might correspond to the liquid stopper 21 arrange | positioned in line. Therefore, the exhaust gas from the exhaust hole 22 is exhausted from both ends of the sheet 23 through the gap 25 between the lid 7 and the sheet 23 corresponding to the non-joining portion 23a.

  A combination of these positive electrode strap alloy, negative electrode strap alloy, type of alloy used for connecting body and pole, presence / absence of treatment of negative electrode plate ear, and presence / absence of sheet covering the exhaust hole of the liquid spigot will be described later. Batteries A to P of the invention examples and comparative examples shown in Table 1 were produced.

  While these batteries were charged at a constant voltage of 2000 hours at a charging voltage of 14.5 V (maximum current of 25 A) in a temperature atmosphere of 60 ° C., vibration was applied in the vertical direction at an acceleration of 1 G (15 Hz), and the mass of the battery The decrease was measured as the liquid reduction amount.

  Next, for each of the batteries A to P described above, the electrolytic solution surface was set at a position 5 mm below the lower surface of the negative electrode strap so that the negative electrode strap was exposed from the electrolytic solution. After performing constant voltage charging for 2000 hours at a charging voltage of 14.5 V under a temperature atmosphere of 0 ° C. and with vibration, each battery was disassembled to confirm the state of the negative strap.

  Table 1 shows the configurations of the batteries of the present invention and comparative examples, and the amount of liquid reduction and the state of the negative electrode strap in the tests described above. In Table 1, the liquid reduction amount of each battery is shown as a percentage when the battery A is used as a reference, with no sheet attached to the lid. In addition, in the item of the state of the negative electrode strap, “◎” indicates that there is no gap at the junction between the negative electrode strap and the negative electrode tab and the corrosion does not progress, and “◯” indicates that the negative electrode strap and the negative electrode Although there is a gap in the joint part of the plate ear part, the corrosion has not progressed, `` △ '' is the one where corrosion has progressed in the joint part of the negative electrode strap and the negative electrode plate ear part, and `` × '' It was shown that the corrosion of the joint between the negative electrode strap and the negative electrode plate ear progressed and a disconnection occurred between the negative electrode strap and the negative electrode plate ear.

  From the results shown in Table 1, the batteries I to T using the Pb—Sn alloy as the negative electrode strap alloy are less liquid than the batteries A to H using the Pb—Sb alloy as the negative electrode strap alloy of the comparative example. Results with smaller amounts were obtained. Further, from the results in Table 1, the difference in whether the positive electrode strap alloy, the connecting body, and the pole column alloy are Pb—Sb alloy or Pb—Sn alloy greatly affects the amount of liquid reduction of the battery. However, the amount of liquid reduction of the battery was almost determined by the strap alloy of the negative electrode.

  Battery K to Battery L, Battery O to Battery P, and Battery S to Battery T using Pb-Sn alloy for the negative electrode strap alloy and a cover for covering the exhaust hole of the liquid spigot on the lid are made of Pb The amount of liquid reduction was about ½ compared to batteries A to G using the —Sb alloy.

  In addition, in a lead storage battery in which a sheet covering the exhaust hole of the liquid spigot is attached to the lid, a battery K to a battery L using a Pb—Sb alloy for the positive strap alloy and a Pb—Sn alloy only for the negative strap alloy Compared to batteries O to P using Pb-Sn alloy for positive and negative strap alloys, batteries S to battery T using Pb-Sn alloy for positive and negative straps and connectors and poles There was no difference.

  Further, the state of the negative electrode strap is that the batteries I to T using the Pb—Sn alloy for the negative strap have no abnormality in the strap, and the batteries A to G using the Pb—Sb alloy for the negative strap are Corrosion is observed at the joint with the negative electrode plate ear, and in particular, the battery A to the battery C, the battery E, and the battery G are more prominently corroded, so that there is a gap between the negative electrode strap and the negative electrode plate ear. It was disconnected.

  Further, in the batteries A to H, the batteries B, B, D, F, and H in which the negative electrode plate ear is provided with a 50 mass% lead-50 mass% tin alloy layer are joined to the negative electrode strap and the negative electrode plate ear. There are no gaps, and the bonding state is good even when compared with Battery A, Battery C, Battery E, and Battery G, and even if the amount of liquid reduction is large and the negative strap is exposed to the gas phase, Battery A and Battery C It is considered that the degree of corrosion was smaller than that of batteries E and G.

  Further, in the batteries I to T, the battery J, the battery L, the battery N, the battery P, the battery R, and the battery T, each of which has a 50 mass% lead-50 mass% tin alloy layer applied to the negative electrode plate ear, There is no gap in the joint portion of the negative electrode plate ear, and the welded state is better than that of the battery I, the battery K, the battery M, the battery O, the battery Q, and the battery S, which is a more preferable configuration.

(Example 2)
A vibration resistance test was performed on each of the batteries A to P shown in Example 1 described above. The vibration resistance test conditions were based on vibration resistance test conditions defined in JIS D5301: 2006 (lead storage battery for starting).

That is, after each of the batteries A to P is fully charged, the battery A is fixed to a vibration testing machine, the vibration direction is a single vertical vibration, and the double amplitude (distance from the upper end to the lower end of the vibration) is 2. The vibration was continuously vibrated for 2 hours at 3 to 2.5 mm and a vibration acceleration of 29.4 m / s ² (3G). In the vibration resistance test in the JIS standard, the capacity was confirmed at a discharge rate of 5 hours. In this test, the open circuit voltage of each battery was measured in an atmosphere at 25 ° C. after the vibration test for 2 hours. Thereafter, discharging was performed at a constant current of 300 A for 5 seconds, and the voltage at the 5th discharge was measured. In addition, about the open circuit voltage value, 12.65V or more was considered normal and less than 12.65 was abnormal. Further, regarding the voltage at the fifth discharge, 9.5 V or higher was regarded as normal and less than 9.5 V was regarded as abnormal. Moreover, the external appearance of the battery after discharge was observed.

Also, if there is no abnormality in the above measured open circuit voltage value, discharge 5 second voltage and battery appearance, the battery is fully charged to a fully charged state and the vibration acceleration is increased by 9.8 m / s ² (1 G). 39.2 m / s ² (4G), the vibration resistance test described above was performed, and the vibration acceleration was increased by 9.8 m / s ² (1 G) for each test.

Then, when an abnormality occurs in the open circuit voltage after the vibration test, the voltage at the discharge 5 seconds, and the battery appearance, the vibration test is terminated, and 9.8 m / s ² (1G) from the vibration acceleration in the vibration test in which the abnormality occurred. The vibration acceleration obtained by subtracting is used as the limit vibration acceleration, and the vibration resistance parameter. These results are shown in Table 2. The higher the limit vibration acceleration, the better the vibration resistance.

Batteries A to D, in which the positive strap and the negative strap are both Pb—Sb alloys, the positive straps are Pb—Sn alloys, the negative batteries are Eb to H, and the positive straps are Pb—Sb. Batteries I to L, which are alloys and the negative electrode strap is a Pb—Sn alloy, have a limit vibration acceleration of 78.4 m / s ² (8G) or more, whereas the positive electrode strap and the negative electrode strap are both Pb—Sn alloys. The limit vibration acceleration of M to battery P was 39.2 m / s ² (4G) to 49.0 m / s ² (5G).

Furthermore, the critical vibration acceleration of the battery Q to the battery T using the Pb—Sn alloy for the positive electrode strap, the negative electrode strap, the connection body, and the pole column is also 39.2 m / s ² (4G) to 49.0 m / s ² (5G Battery M to battery P (39.2 m / s ² (4G) to 49.0 m) in which the positive strap, the negative strap are Pb—Sn alloy, and the connecting body and the pole column are Pb—Sb alloys. / S ² (5G)). It should be noted that no abnormal appearance of the battery occurred in the vibration acceleration (corresponding to the acceleration obtained by adding 29.4 m / s ² to the limit vibration acceleration) in all the batteries A to T, and the content of the abnormality is It was limited to open circuit voltage abnormality or discharge 5 second voltage abnormality. That is, the internal connection breakage in the battery was a cause of abnormality in the vibration resistance test.

  From the above results, if either one of the positive electrode strap or the negative electrode strap is a Pb—Sb alloy having excellent mechanical strength, the conventional positive electrode can be used even if the other is a Pb—Sn alloy having inferior mechanical strength. It can be seen that both the strap and the negative strap have vibration resistance equivalent to that of a battery made of a Pb—Sb alloy.

  On the other hand, if both the positive strap and the negative strap are made of lead-tin alloy, the mechanical strength of the strap will have a significant effect on the reduction of vibration resistance, regardless of the lead alloy composition of the connecting body and pole. It is done.

  And from the result of Example 1 and Example 2, while the battery K and battery L of this invention have the very favorable liquid reduction performance of a lead storage battery, the corrosion disconnection of the junction part of a negative electrode strap and a negative electrode plate ear | edge part As can be seen from the graph, the vibration resistance is remarkably suppressed and the vibration resistance is excellent.

  Therefore, according to the present invention, liquid reduction due to evaporation of the electrolyte of the lead storage battery and dissipation of sulfuric acid mist is remarkably suppressed. It can be seen that even when exposed to the gas phase, corrosion of the negative strap can be suppressed, and a lead storage battery having excellent vibration resistance can be obtained.

  The present invention can remarkably suppress the liquid reduction in the lead storage battery, and further can provide a lead storage battery with improved vibration resistance and improved reliability against corrosion at the joint between the negative electrode strap and the negative electrode plate ear. Therefore, it is suitable for many liquid type lead acid batteries including a lead acid battery for starting, and its utility value is extremely high.

Sectional drawing which shows the lead acid battery of this invention The top view of the lead storage battery of the present invention (A) The figure which shows the cross section of a negative electrode plate ear | edge part (b) The figure which shows the cross section of the junction part of a negative electrode strap and a negative electrode plate ear | edge part

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Lead acid battery 2 Positive electrode plate 2a Positive electrode plate ear | edge part 3 Negative electrode plate 3a Negative electrode plate ear | edge part 4 Separator 5 Electrolytic solution 6 Battery case 6a Cell chamber 7 Lid 7a Liquid port 8 Electrode plate group 9 Positive electrode strap 10 Negative electrode strap 11 External terminal 12 Electrode Column 13 Connector 21 Liquid spout 21a Splash-proof body 21b Filter 22 Exhaust hole 23 Sheet 23a Non-joining part 23b Adhesive 24 Lead-tin alloy layer 25 Crevice

Claims (4)

Using a lead-calcium alloy for each of the positive and negative grids,
Each of the positive electrode grid body and the negative electrode grid body is provided with electrode plate ears integrally,
The positive electrode plate and the negative electrode plate are arranged via a separator,
While the electrode plate ears of the same polarity are collectively welded to the strap according to the polarity,
In the strap, an electrode plate group in which a pole column for terminal connection and / or a connection body for inter-cell connection is provided is housed in a battery case together with an electrolyte, and the electrolyte has at least an amount for immersing the strap. Have
The liquid port provided in the lid joined to the opening of the battery case is equipped with a liquid port plug provided with an exhaust hole for discharging the gas in the battery to the outside of the battery,
And,
A sheet adhered to the lid with an adhesive or an adhesive so as to cover the exhaust hole,
A non-joining portion that does not have the pressure-sensitive adhesive or the adhesive is bonded to the bonding surface between the sheet and the lid through the gap between the lid and the sheet formed by the non-joining portion. The exhaust gas is arranged to be discharged out of the battery at a position spaced from the exhaust hole,
The pole column and the connection body provided on the straps of both poles, and the strap on the positive electrode side is made of a lead alloy containing antimony,
And the said strap by the side of a negative electrode is a lead acid battery which consists of a lead alloy which does not contain antimony. The lead acid battery according to claim 1, wherein the strap on the negative electrode side is made of a lead alloy containing tin. The lead-acid battery according to claim 2, wherein a lead-tin alloy layer is formed on the surface of the electrode plate ear on the negative electrode side. The lead-acid battery according to claim 3, wherein the lead-tin alloy layer is pressure-bonded to the surface of the electrode tab portion.

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