JP2016115396A - Lead power storage battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lead storage battery that is applicable to an idling stop vehicle used in a "bit riding" mode and has both of sufficient charging acceptability and charge recoverability after overdischarge.SOLUTION: A lead power storage battery has an electrode plate group in which plural positive electrode plates and negative electrode plates are stacked through separators, and which is mounted in a cell chamber together with electrolytic liquid. The negative electrode plate has an electrode grid formed of lead or lead alloy which contains no antimony, a surface layer formed of lead alloy containing antimony which is formed on the surface of the negative electrode grid, and a negative electrode active material filled in the negative electrode grid. The electrolytic liquid contains aluminum ions ranging from 0.03 to 0.27 mol/L, and sodium ions ranging from 0.03 to 0.28 mol/L.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a lead storage battery used in an idling stop vehicle.

  The idling stop vehicle can improve fuel consumption by stopping the engine while the vehicle is stopped. However, since the lead storage battery supplies all electric power such as an air conditioner and a fan during idling stop, the lead storage battery tends to be insufficiently charged. Therefore, the lead storage battery is required to have a high charge acceptability that can be charged more in a short time in order to solve the shortage of charging. In addition, since idling stop vehicles frequently turn the engine on and off repeatedly, the lead discharge produced immediately after the lead sulfate generated by discharge is restored to lead dioxide and lead by charging. Life is likely to decrease. Therefore, the lead storage battery is also required to have high durability in order to eliminate the decrease in life.

  In order to improve the charge acceptability of the lead storage battery, Patent Document 1 describes a lead storage battery in which aluminum ions are contained in an electrolytic solution. Aluminum ions have the effect of suppressing the coarsening of the lead sulfate crystals produced at the positive and negative electrodes during discharge, thereby improving the charge acceptance performance of the lead storage battery.

  Further, in order to improve the durability of the lead storage battery, Patent Document 2 describes a lead storage battery in which a lead alloy layer containing antimony is provided on the surface of a negative electrode lattice not containing antimony. The lead alloy layer containing antimony has an effect of efficiently charging and recovering the negative electrode plate, and thereby the durability of the lead storage battery can be improved.

Patent Document 3 discloses that by adding an alkali metal sulfate such as Na ₂ SO ₄ to the electrolytic solution, generation of lead ions accompanying a decrease in sulfuric acid concentration during overdischarge is suppressed, and on the negative electrode during charging. A technique for preventing a short circuit from occurring between the positive electrode and the negative electrode due to the growth of PbSO ₄ is described. In addition, Na ₂ SO ₄ added to the electrolytic solution has an effect of suppressing a decrease in conductivity of the electrolytic solution accompanying a decrease in sulfuric acid concentration during overdischarge and improving charge recovery after overdischarge.

JP 2006-4636 A JP 2006-156371 A JP-A-1-267965

  Lead-acid batteries used in idling stop vehicles tend to be undercharged. Therefore, for the purpose of preventing overdischarge of the lead storage battery, the idling stop vehicle may be provided with a fail-safe mechanism that does not discharge the lead storage battery when the state of charge (SOC) becomes a predetermined value (for example, 60%) or less. is there.

  FIG. 1 is a graph schematically showing a state of charge (SOC) when a lead-acid battery is repeatedly discharged and charged in an idling stop vehicle. The line graph shown in FIG. 1 shows a pattern in which the lead storage battery is discharged while the vehicle is stopped, the SOC decreases, the vehicle travels again, the lead storage battery is charged, the SOC is recovered, and this is repeated. It is shown.

  If the lead-acid battery has a high charge acceptance, the lead-acid battery recovers to about 100% while the car is running. Therefore, even if the idling stop car is run for a long time as shown in the line graph A in FIG. The charge / discharge of the lead storage battery can be repeated.

  However, if the rechargeability of the lead storage battery is not high, as shown in the line graph B in FIG. 1, when the car stops in a state where the charging cannot be sufficiently performed during traveling and the SOC does not recover to 100%, Decrease in SOC due to discharge increases. When such charging / discharging is repeated, the SOC gradually decreases. In this case, when the fail-safe mechanism is provided in the idling stop vehicle, the fail-safe mechanism is activated and the discharge is stopped when the SOC becomes a predetermined value (for example, 60%) or less.

  In particular, when driving a car with a short mileage (hereinafter referred to as “choy ride”), the fail-safe mechanism is frequently used because the SOC cannot be fully charged and the SOC does not recover to 100%. Invite the situation to operate. Furthermore, when “choy ride” is performed only on weekends, the state of operation of the fail-safe mechanism becomes more conspicuous because the SOC is further lowered due to self-discharge and dark current while the vehicle is stopped.

  On the other hand, the lead storage battery used in the “choi riding” mode as shown in FIG. Even if the lead-acid battery is recovered after overdischarge, if it is used again in the “choi riding” mode, overdischarge due to a decrease in SOC occurs. It is preferable that the number of repetitions of “choi riding” and overdischarge is as small as possible, but sufficient charge acceptance and overdischarge that can be applied to idling stop vehicles used in such “choi riding” mode in the past. There was no lead-acid battery that had both later charge recovery properties.

  The present invention has been made in view of such problems, and its main purpose is to provide sufficient charge acceptance and charge recovery after overdischarge that can be applied to an idling stop vehicle used in the “choi ride” mode. The purpose is to provide a lead-acid storage battery.

  A lead storage battery according to the present invention is a lead storage battery in which a group of electrode plates in which a plurality of positive and negative electrode plates are laminated via a separator is housed in a cell chamber together with an electrolyte, and the positive electrode plate contains antimony A negative electrode plate made of lead or a lead alloy not containing antimony, and a positive electrode lattice made of lead or a lead alloy, and a positive electrode active material filled in the positive electrode lattice; A surface layer made of a lead alloy containing antimony and a negative electrode active material filled in a negative electrode lattice, and an electrolytic solution containing aluminum ions in a range of 0.03 to 0.27 mol / L, 0.03 to 0 It is characterized by containing sodium ions in a range of .28 mol / L.

  In a preferred embodiment, negative electrode plates accommodated in the bag-shaped separator are arranged on both sides of the electrode plate group.

  ADVANTAGE OF THE INVENTION According to this invention, the lead storage battery which has sufficient charge acceptance property and charge recovery property after overdischarge which can be applied to the idling stop vehicle used in "choi riding" mode can be provided.

A graph schematically showing the state of charge (SOC) when the lead-acid battery is repeatedly discharged and charged in an idling stop vehicle. 1 is an overview diagram schematically showing the configuration of a lead storage battery according to an embodiment of the present invention.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In addition, this invention is not limited to the following embodiment. Moreover, it can change suitably in the range which does not deviate from the range which has the effect of this invention. Furthermore, combinations with other embodiments are possible.

  FIG. 2 is an overview diagram schematically showing the configuration of the lead storage battery 1 in one embodiment of the present invention.

  As shown in FIG. 2, in the lead storage battery 1, an electrode plate group 5 in which a plurality of positive electrode plates 2 and a negative electrode plate 3 are stacked via a separator 4 is accommodated in a cell chamber 6 together with an electrolytic solution.

  Here, the positive electrode plate 2 includes a positive electrode lattice and a positive electrode active material filled in the positive electrode lattice, and the negative electrode plate 3 includes a negative electrode lattice and a negative electrode active material filled in the negative electrode lattice. Note that the positive electrode lattice and the negative electrode lattice in this embodiment are both made of lead or a lead alloy containing no antimony (Sb), for example, a Pb—Ca alloy, a Pb—Sn alloy, or a Pb—Sn—Ca alloy.

  The plurality of positive electrode plates 2 are connected in parallel with each other by the positive electrode straps 7 between the positive electrode lattice ears 9, and the plurality of negative electrode plates 3 are connected in parallel with each other through the negative electrode lattice ears 10 between the negative electrode straps 8. Has been. Further, the plurality of electrode plate groups 5 accommodated in each cell chamber 6 are connected in series by a connection body 11. Polar columns (not shown) are welded to the positive strap 7 and the negative strap 8 in the cell chambers 6 at both ends, respectively, and the respective polar columns are connected to the positive terminal 12 and the negative terminal 13 disposed on the lid 14. Each is welded.

  In the present embodiment, a surface layer (not shown) made of a lead alloy containing antimony is formed on the surface of the negative electrode lattice. The lead alloy containing antimony has an effect of lowering the hydrogen overvoltage, whereby the charge acceptability of the lead storage battery 1 can be improved. In addition, it is preferable that a surface layer consists of a Pb-Sb type | system | group alloy whose content of antimony is 1.0-5.0 mass%.

  Moreover, in this embodiment, electrolyte solution contains the aluminum ion of the range of 0.03-0.27 mol / L, and the sodium ion of the range of 0.03-0.28 mol / L. The aluminum ions in the electrolytic solution have an effect of improving charge acceptance so as to be able to cope with a short charging time in the “choi riding” mode. On the other hand, sodium ions in the electrolyte have an effect of improving charge recovery after overdischarge. As a result, it is easy to push up the SOC during a short charging time in the “choi riding” mode, and even if the lead storage battery recovered after overdischarge is used again in the “choi riding” mode and is repeatedly charged and discharged, Since the decrease in SOC can be suppressed, the operation of the fail-safe mechanism can be suppressed. If an excessive amount of aluminum ions is added, the effect of sodium ions is offset, and if an excessive amount of sodium ions is added, the effect of aluminum ions is canceled. Therefore, the aluminum ions contained in the electrolytic solution are in the range of 0.03 to 0.27 mol / L, and the sodium ions are in the range of 0.03 to 0.28 mol / L.

  Further, in the present embodiment, the negative electrode plate 3 is preferably disposed on both sides of the electrode plate group 5, and the negative electrode plate 3 is accommodated in a bag-like separator 4. As a result, the electrolyte solution can also flow into the negative electrode plates 3 arranged on both sides of the electrode plate group 5, so that the charge acceptance of the lead storage battery 1 is further improved, and the idling stop used in the “choi riding” mode. Even when applied to a vehicle, the operation of the fail-safe mechanism can be more effectively suppressed.

Hereinafter, the structure and effect of the present invention will be further described with reference to examples of the present invention. The present invention is not limited to these examples.
(1) Production of lead acid battery The lead acid battery 1 produced in the present example is a liquid lead acid battery having a D23L type size defined in JIS D5301. Each cell chamber 6 accommodates seven positive electrode plates 2 and eight negative electrode plates 3, and the negative electrode plate 3 is accommodated in a bag-like polyethylene separator 4.

  The positive electrode plate 2 was prepared by kneading lead oxide powder with sulfuric acid and purified water to prepare a paste, and filling this into an expanded lattice made of a calcium-based lead alloy composition.

  The negative electrode plate 3 is prepared by adding an organic additive to lead oxide powder, kneading with sulfuric acid and purified water to prepare a paste, and filling this into an expanded lattice composed of a calcium-based lead alloy composition. Produced.

  After the produced positive electrode plate 2 and negative electrode plate 3 are aged and dried, the negative electrode plate 3 is accommodated in a polyethylene bag-like separator 4 and is alternately stacked with the positive electrode plates 2 to form seven positive electrode plates 2 and eight negative electrode plates. An electrode plate group 5 in which 3 and 3 were laminated via a separator 4 was produced. Each of the electrode plate groups 5 was accommodated in a cell chamber 6 partitioned into six, and a lead storage battery 1 in which six cells were directly connected was produced.

An electrolytic solution made of dilute sulfuric acid having a density of 1.28 g / cm ³ was put into the lead storage battery 1 and a battery case was formed to obtain a lead storage battery 1 of 12V48Ah.
(2) Evaluation of lead-acid battery (2-1) Characteristic evaluation of “cho-riding” mode The lead-acid battery 1 was repeatedly charged / discharged assuming the “cho-riding” mode, and the lead-acid battery “choy riding” The mode characteristics were evaluated. The ambient temperature was 25 ° C. ± 2 ° C.
(A) Discharge at 9.6 A for 2.5 hours and leave for 24 hours.
(B) Discharge at a discharge current of 20 A for 40 seconds.
(C) Charge for 60 seconds at a charge voltage of 14.2 V (limit current 50 A).
(D) Charge / discharge of (B) and (C) is repeated 18 times, and then discharged at a discharge current of 20 mA for 83.5 hours.
(E) Charging / discharging of (B) to (D) is set as one cycle, and 20 cycles are repeated.

The state of charge (SOC) of the lead-acid battery after the above 20 cycles was measured, and this value was taken as the “choy ride” mode characteristic.
(2-2) Charge recovery after overdischarge Assuming the case where the lead storage battery 1 recovered after overdischarge is used again in the “choi riding” mode with respect to the produced lead storage battery 1 The charge recovery property when repeated was evaluated by the following method.
(A) Discharge to 10.5 V with a 5-hour rate current (discharge current 9.8 A).
(B) Then, after applying a load corresponding to 10 W and discharging at a temperature of 40 ° C. ± 2 ° C. for 14 days, it is left in an open circuit state for 14 days.
(C) Thereafter, the battery is charged for 4 hours at a charging voltage of 15.0 V (limit current 25 A) at a temperature of 25 ° C. ± 3 ° C.
(D) Then, after leaving it in the atmosphere of −15 ° C. ± 1 ° C. for 16 hours or more, it is discharged to 6.0 V at 300 A.

  The duration until the lead-acid battery voltage reached 6.0 V was evaluated as the charge recovery after overdischarge.

Example 1
A surface layer made of a lead alloy containing antimony is formed on the surface of the negative electrode lattice, and 0.01 to 0.30 mol / L of aluminum ions and 0.01 to 0.45 mol / L of sodium ions contained in the electrolytic solution. Batteries 1 to 7 that were changed to the range of L were prepared, and the characteristics of the “choi riding” mode of each battery and the charge recovery after overdischarge were evaluated. The negative electrode plate was disposed on both sides of the electrode plate group and housed in a bag-shaped separator.

  Here, the negative electrode lattice is composed of an expanded lattice of Pb-1.2Sn-0.1Ca, and the surface layer is composed of Pb-3 mass% Sb foil. Moreover, the positive electrode lattice is an expanded lattice of Pb-1.6Sn-0.1Ca, and no surface layer is provided.

  (Table 1) is a table showing the evaluation results of each characteristic. As comparative examples, a battery 8 in which a surface layer was not provided on the surface of the negative electrode grid, and a battery 9 in which a positive electrode plate instead of the negative electrode plate was accommodated in a bag-shaped separator were produced.

  As shown in (Table 1), the electrolytic solution contains both aluminum ions in the range of 0.03 to 0.27 mol / L and sodium ions in the range of 0.03 to 0.28 mol / L. In the batteries 2 to 6, the SOC indicating “choy ride” mode characteristics is 78% or more, and the duration of 2.9 minutes or more indicating the overdischarge recoverability is excellent. When using an idling stop vehicle in the mode, it has suitable performance.

  On the other hand, in the battery 1 having a sodium ion content of 0.01 mol / L in the electrolytic solution, the duration of the overdischarge recoverability is as short as 2.5 minutes. This is thought to be due to the lack of sodium ions in the electrolyte. On the other hand, in the battery 5 having a sodium ion content of 0.45 mol / L in the electrolytic solution, the SOC showing the “choy ride” mode characteristic is slightly low at 75%. This is thought to be because sodium ions in the electrolytic solution inhibit the charging reaction.

  Further, in the battery 6 in which the content of aluminum ions in the electrolytic solution is 0.01 mol / L, the SOC showing the “choy ride” mode characteristic is slightly low as 75%. This is presumably because the aluminum ions in the electrolyte are insufficient. On the other hand, in the battery 9 in which the content of sodium ions in the electrolytic solution is 0.3 mol / L, the duration indicating the overdischarge recoverability is as short as 2.5 minutes. This is considered because the aluminum ion in electrolyte solution has inhibited the charge recovery property after overdischarge.

  On the other hand, in the battery 11 in which the surface layer is not provided on the negative electrode lattice, the SOC showing the “choy ride” mode characteristic is very low as 75%. This is presumably because the lead alloy foil containing Sb was not provided on the surface of the negative electrode lattice, so that the hydrogen overvoltage was not lowered and the charge acceptance was low.

  In addition, the battery 11 in which the positive electrode plate was housed in the bag-shaped separator also had a low SOC of 75%, which exhibited “choy ride” mode characteristics. This is because the negative electrode plates arranged on both sides of the electrode plate group are not accommodated in the bag-shaped separator, so the negative electrode plate is pressed against the inner wall of the cell chamber, and as a result, the electrolyte solution to the negative electrode plate on the cell chamber side This is thought to be due to a decrease in charge acceptance due to insufficient wraparound.

  From the above results, a surface layer made of a lead alloy containing antimony is formed on the surface of the negative electrode lattice containing no antimony, and negative electrode plates contained in a bag-like separator are arranged on both sides of the electrode plate group. Further, by allowing the electrolyte to contain both aluminum ions in the range of 0.03 to 0.27 mol / L and sodium ions in the range of 0.03 to 0.28 mol / L, the operation of the fail-safe mechanism can be improved. It is possible to provide a lead-acid battery suitable for an idling stop vehicle that is used in the “choi riding” mode, including suppressed charge recovery after overdischarge.

  As mentioned above, although this invention was demonstrated by suitable embodiment, such description is not a limitation matter and of course various modifications are possible.

  The present invention is useful for a lead storage battery used in an idling stop vehicle.

DESCRIPTION OF SYMBOLS 1 Lead acid battery 2 Positive electrode plate 3 Negative electrode plate 4 Separator 5 Electrode plate group 6 Cell chamber 7 Positive electrode strap 8 Negative electrode strap 9, 10 Ear part 11 Connection body 12 Positive electrode terminal 13 Negative electrode terminal 14 Cover

Claims (2)

An electrode plate group in which a plurality of positive electrode plates and negative electrode plates are laminated via a separator is a lead storage battery housed in a cell chamber together with an electrolyte solution,
The positive electrode plate includes a positive electrode lattice made of lead or a lead alloy containing no antimony, and a positive electrode active material filled in the positive electrode lattice,
The negative electrode plate includes a negative electrode lattice made of lead or a lead alloy not containing antimony, a surface layer made of a lead alloy containing antimony formed on the surface of the negative electrode lattice, and a negative electrode active material filled in the negative electrode lattice And
The said electrolyte solution is a lead acid battery containing the aluminum ion of the range of 0.03-0.27 mol / L, and the sodium ion of the range of 0.03-0.28 mol / L.   The lead acid battery according to claim 1, wherein negative electrode plates accommodated in the bag-shaped separator are disposed on both sides of the electrode plate group.

Images