JP2012089292A - Method of regenerating lead storage battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To regenerate a deteriorated lead storage battery by removing the cause of deterioration.SOLUTION: As a means for removing the insulator of PbSOprecipitated mainly on a negative electrode plate from a lead storage battery structure, a regeneration method of causing micro bubbling in an electrolytic solution with a diameter of 50 μm or less, passing the bubbles between electrode plates of each cell, ionizing PbSO(SO) by a physical mechanism of "reduction of bubbles→increase of internal pressure of bubbles→high pressure burst and disappearance" and reducing into the electrolytic solution (HSO+HO) is provided.

Description

  The present invention relates to a method for regenerating a lead storage battery.

  Lead-acid battery deterioration is a phenomenon that continues to be used through charging / discharging, and the internal resistance increases due to long-term or intermittent use, resulting in a lower specific gravity of the electrolyte (dilute sulfuric acid). It is a state change that does not recover to voltage. In general, the time when the capacity is reduced to 80% of the rated value is used as a standard of life, and these events are also clarified in the literature of secondary batteries.

The cause of this deterioration phenomenon is the electrode in the storage battery, especially as PbSO ₄ (white crystalline insulator called lead sulfate) precipitates on the surface of the negative electrode and grows as a large crystal is grown on the electrode surface. The reason for the high resistance has been clarified.

Therefore, it has been found that the regeneration method of the storage battery may be reduced by reducing the size of the PbSO ₄ crystal and reducing SO ₄ ²⁻ (sulfate ion) to the electrolyte H ₂ SO ₄ . Patent Document 1 proposes a method for regenerating by refining PbSO ₄ by electric pulse impact.

Further, in Patent Document 2, a method of performing a regeneration treatment by putting a special additive (for example, polyvinyl alcohol) into an electrolytic solution (H ₂ SO ₄ and H ₂ O) and performing a discharge test and an electrical charging operation. Presents.

Japanese Patent No. 3723895 JP 2009-016329 A

  The regenerative storage battery by application of the technology described in the above-mentioned patent document is sold, and it is also posted on the mail order list, and the price of the regenerative storage battery is about 1/2 to 1/3 than the new storage battery. However, the regeneration life is about a half of the record, and the customer satisfaction is low because the effect is small depending on the use of the storage battery.

Here, the cause of the recovery rate with a lifetime of about ½ is that PbSO ₄ crystals remain at the time of regeneration, and SO ₄ ^-2 ions are not sufficiently reduced in the electrolytic solution. Accordingly, an object of the present invention is to provide a method for performing a regeneration process that further reduces the PbSO ₄ crystal on the electrode surface and prolongs the regeneration life.

The positive electrode material of the lead storage battery is PbO ₂ , the negative electrode material is Pb, the electrolyte is 2H ₂ SO ₄ , the specific gravity is 1.28 (sulfuric acid concentration 37.4%), and the separator is porous between the positive and negative electrodes Overlaying with a plastic material or the like, an output of (2 V / cell) × (6 cells) = 12 V / set is obtained. Details are described in JIS D5301 (lead battery for automobiles) and the like.

  The electrochemical reaction equation has also been clarified and is as follows.

Positive electrode side: PbO ₂ + 4H ⁺ + SO ₄ ^{2 −} + 2e ⁻ → PbSO ₄ + 2H ₂ O −−−−−− (1)
Negative electrode side: Pb + SO ₄ ²⁻ → PbSO ₄ + 2e ^— ------------------------- (2)
Overall reaction: Pb + PbO ₂ + 2H ₂ SO ₄ → PbSO ₄ + 2H ₂ O ---------- (3)
Gas generation: (+) side H ₂ O → 1 / 2O ₂ + 2H ⁺ + 2e ⁻ ---------------- (4)
: (−) Side 2H ⁺ + 2e ⁻ → H ₂ ----------------------------- (5)

That is, the liquid mixture of H ₂ SO ₄ and H _{2 O} in the electrolyte H ₂ gas O ₂ gas is generated for each of charge and discharge, requires rehydration operations H _{2 O} in the open type storage battery, the seal The type storage battery has a structure that suppresses the generation of H ₂ gas unless it is overcharged by a cathode absorption seal.

In the present invention, as a means for removing the PbSO ₄ insulator mainly deposited on the negative electrode plate from the lead-acid battery structure, micro publishing with a diameter of 50 μm or less is generated in the electrolyte solution, and the electrode plate between each cell PbSO ₄ is ionized (SO ₄ ²⁻ ) and separated in the electrolyte (H ₂ SO ₄ + H ₂ O) by the physical mechanism of [reduction of bubbles → increase in bubble internal pressure → high pressure burst extinction]. ) Is provided. Furthermore, the present invention provides a regeneration method that uses microbubbles charged with H ⁺ and OH ⁻ ions at the bubble interface.

  According to the present invention, the following effects can be obtained.

PbSO ₄ can be ionized and separated and reduced into the electrolytic solution by the physical mechanism of bubble reduction → increase in bubble internal pressure → high pressure fracture extinction.

Since the microbubble generator is provided in the electrolyte in the storage battery and microbubbles of 50 μm or less are released into the electrolyte, H ⁺ and OH ⁻ ions are bubbled at the bubble interface (gas-liquid interface) in the electrolyte. Since PbSO ₄ on the electrode surface reacts as SO ₄ ²⁻ at the time of high-pressure rupture after shrinkage and can be reduced into the electrolyte (H ₂ SO ₄ ), the crystal of PbSO ₄ can be efficiently reduced as SO ₄ ^2−. . As a result, the PbSO ₄ crystal causing the deterioration is reduced, and the lead storage battery has an effect of being recovered by charging.

By setting the lead-acid storage battery upside down, a microbubble generating part is placed on the lower side of the electrolyte, and the microbubble rises along the electrode surface while rising, causing high-pressure rupture. Since the PbSO ₄ crystal on the electrode surface wider than that of the PbSO ₄ crystal is removed, the regeneration efficiency can be significantly increased.

By contrast recovering electrolyte solution in the electrolyte circulation device side by adding H ₂ gas mixed adjustment function to the mixer unit, to the storage battery electrodes of different various sizes can be decreased increase the number of bubbles microbubble generator, optimal cell count Therefore, the regeneration operation efficiency is improved.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. Explanatory drawing of a microbubble generation | occurrence | production part. The apparatus operation structure explanatory drawing of this invention Example. Structure explanatory drawing of the well-known automotive lead acid battery.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In FIG. 1, a lead storage battery 1 to be regenerated is an automobile open-type lead storage battery. The general structure is as shown in Fig. 4 (announced from No. 050330009, published on March 30, 2005). The outer shape is determined by the lid 1a and the battery case 1b, the electrical output terminal is a positive / negative terminal 1c, 6 internal cells structure can add missing moisture per liquid spout 1d (distilled water), the lower in superimposed structure of a negative electrode plate 1 g ₁ and separator 1 g ₂ and the positive electrode the positive electrode plate 1 g ₃ of each cell inside the negative electrode saddle The electrode is fixed to the battery case 1b by 1f. The liquid level line 1e of the electrolytic solution of the electrolytic solution (H ₂ SO ₄ + H ₂ O) becomes visible from the outside. 1 g ₄ indicates a strap, and 1 g ₅ indicates a glass mat.

  In FIG. 1, a lead battery 1 to be tested is fixed by a stopper 7 on a base portion 8 having a rotating shaft 9 as a fixing point. Note that the base portion 8 has a structure in which the O1 point can be rotated by the O2 point with a rotation angle θ of 180 ° with respect to the rotation shaft 9. In the lead plug 1b of the lead storage battery, the electrolyte suction connection pipe 4, the discharge connection pipe 5, and the inlet pipe of the liquid level gauge 6 (fixed to the stopper 7) are drawn out of the battery case 1b. Although not shown in FIG. 1, the DC12V storage battery has a configuration of 2V / cell × 6 cells = 12V as shown in FIG. There are 1-6.

The microbubble generator 3 is in contact with the electrolytic solution 1e. The internal configuration of the electrolytic solution circulation device 2 is composed of a suction pipe 2e via a filter 2f from a suction connection pipe 4 (No. 1 to 6) on the suction side centering on a pump 2a. The replenishment can be adjusted from the electrolyte tank (H ₂ SO ₄ + H ₂ O) 2c to the suction side by the control valve 2d.

  The discharge side of the circulation pump 2a is pressurized to the discharge pipe 2i via the mixer 2g via the check valve 2b, and the No. The microbubble generator 3 is reached from 1 to 6 discharge connecting pipes 5. In the mixer 2g, the amount of bubble gas mixed in the liquid is adjusted and supplied by the adjusting valve 2d having an adjusting function by the gas cylinder 2h. Thereby, the bubbling amount from the microbubble generator 3 is variable.

In the gas cylinder 2h, a bubble reaction of [H ₂ ⁺² + SO ₄ ⁻² ] is generated based on H ₂ gas. In a hermetically sealed battery, O ₂ gas is the main component, which causes a bubble reaction of [O ⁻ + H ₂ ²⁺ ].

The internal configuration of the microbubble generator 3 will be described with reference to FIG. The definition of microbubble is a bubble of 50 μm or less, and it is known that when dissolved in water, it stabilizes in water in a fine state of 100 nm or less. That is, when the diameter of the microbubbles in water is 50 μm or less, when the pressure rapidly becomes high due to the shrinkage of bubbles and ruptures and disappears into nanobubbles of 100 nm or less, the bubble interface of the microbubbles is charged with H ⁺ and OH ⁻ ions. It acts on the SO ₄ ²⁻ ions of PbSO ₄ at the time of the rupture and can easily separate Pb and SO ₄ .

The principle of making the microbubbles is that the high-pressure electrolyte 1e entering the discharge port 5 and the H ₂ gas mixed from the gas cylinder 2h flow in, but are converted into a spiral flow in a spiral flow path at the guide vane portion 3a. Then, the current cutter unit 3b is finely crushed by a mushroom-like collision body to form a microparticle group, and a bubble group such as a pure white cloud is swirled into the electrolytic solution 1e by the microbubble jet discharge 5c. The emitted microbubbles are diffused upward at about 1 mm / sec.

As shown in FIG. 3, the base 8 is rotated 180 degrees to reversely install the lead storage battery 1, and the microbubbles rise and diffuse upward from the lower electrolyte 1e, so that the PbSO ₄ efficiently travels along the electrode surface. Has the effect of separating. At this time, it is also possible to charge the lead storage battery 1 with an electric pulse by the switch 11 using a known electric regenerator 10 and further crush PbSO ₄ to increase the efficiency. The charge level is determined by monitor 12 using specific gravity ρ, voltage V, and current I. Further, the liquid level meter 6 determines whether or not the electrolytic solution 1e is in an appropriate amount by the electrolytic solution circulating device 2. Both liquid and gas can be operated by the control valve 2d.

  There are various modifications of the example of the open type storage battery shown in FIG. Since the sealed storage battery does not have the liquid spigot 1d shown in FIG. 4, when the present invention is carried out, the opening is processed every 6 cells and the liquid spigot 1d shown in FIG. 1 is attached. It can be applied in the same way.

  DESCRIPTION OF SYMBOLS 1 ... Lead storage battery, 2 ... Electrolyte circulation apparatus, 2a ... Pump, 2b ... Check valve, 2c ... Electrolyte tank, 2d ... Control valve, 2e ... Suction pipe, 2f ... Filter, 2g ... Mixer, 2h ... Gas cylinder, 2i ... discharge pipe, 3 ... micro bubble generating part, 4 ... suction connection pipe, 5 ... discharge connection pipe, 6 ... liquid level meter, 7 ... clasp, 8 ... base part, 9 ... rotating shaft, 10 ... electrical regeneration 11 ... switch, 12 ... monitor meter, θ ... rotation angle.

Claims (5)

  In a method for regenerating a lead-acid battery whose performance has deteriorated, an electrode surface of the lead-acid battery is cleaned by microbubbles from an electrolyte circulation device having a microbubble generator in the electrolyte in the battery. Playback method. The method for regenerating a lead battery according to claim 1, wherein microbubbles in which H ⁺ and OH ⁻ ions are charged at a bubble interface are used as microbubbles.   3. The method for regenerating a lead storage battery according to claim 1, wherein the lead storage battery to be regenerated is turned upside down and the electrode surface is cleaned by an electrolyte circulation device. According to claim 3, by performing charging by electrical pulses in electrical regenerator relative lead-acid battery, a lead storage battery reproducing method, wherein a P _b SO ₄ on the electrode surface to impact fracture.   The lead-acid battery according to any one of claims 1 to 4, wherein a bubbling amount can be varied by providing a mixer with a function of adjusting a mixing amount of a gas serving as a source of microbubbles on a discharge side of a circulation pump of the electrolytic solution circulation device. How to play.

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