JP2018113131A - Activation charging method for lead acid storage battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To achieve an activation charging method for a stopping or used lead acid storage battery.SOLUTION: The lead acid storage battery is configured to: irradiate a positive electrode 1 positioned therein with gamma rays of an intensity of 2 msV or more and 100 msV or less; oxidative-decompose lead sulfate on the positive electrode for charging by an oxidation reaction; remove a non-conductor film consisted of lead sulfate of the positive electrode 1 of a used storage battery with an electromotive force thereof of 10 V or less to recover it until 12 V is obtained; and add a reaction accelerator to electrolyte to accelerate removal of the non-conductive film of the positive electrode 1.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for activating and charging lead-acid batteries in use or used.

  Lead storage batteries are widely used in transportation equipment such as automobiles and forklifts, electric vehicles such as golf carts, and various emergency power supplies.

  The major problem that limits the life of lead-acid batteries is that lead sulfate, which is a high-resistance substance, adheres and accumulates on the electrode surface during use of lead-acid batteries, and the internal electrode area that has a substantial effect is reduced. As a result, the resistance increases, causing deterioration of characteristics such as a voltage drop. As a result, sufficient battery characteristics cannot be exhibited, and the life period in which normal characteristics can be exhibited is shortened. Such a phenomenon is called a sulfation phenomenon, and since the phenomenon gradually proceeds immediately after the start of use of the lead storage battery, it is one of the main causes of deterioration of the characteristics of the lead storage battery.

  In this way, the lead storage battery that has caused the deterioration of characteristics due to the sulfation phenomenon, the electrode surface that should function normally is covered with an insulating material, so even if the electrolyte is changed or the charging operation is repeated, It is considered difficult to improve the characteristics.

  Conventionally, lead-acid batteries that have such internal resistances that increase their lifetime or shorten their lifetime, or have cells that have already expired, are disassembled into cell units, and are subjected to electrode regeneration processes, cleaning, electrode replacement, etc. However, the cost of disassembling and cleaning / replacement is almost the same as the replacement of batteries. Actually, they are often replaced with new ones, and there is a keen desire for cheap and effective characteristics improvement technology for used lead-acid batteries. Has been. There are various states of lead-acid batteries that actually prolong life or regenerate, but in most cases, they are left unless they can be reused by passing current. Therefore, it is desired to establish an appropriate electrochemical treatment for realizing life extension or regeneration as reliably as possible even in the regeneration treatment of a normal lead-acid battery. Therefore, a method has been proposed in which a reaction accelerator is added to the electrolytic solution and a high current is applied to peel off and dissolve the high-resistance substance generated on the electrode surface of the lead-acid battery (Patent Document 1).

JP 2005-174888 A

  However, when compared to other storage batteries, lead storage batteries are not significantly affected by the increase in charge / discharge cycles, but due to the structure of using lead dioxide for the positive electrode, lead for the negative electrode, and sulfuric acid for the electrolyte, In the case of lead sulfate hard crystals (sulfation) occur in the metal of the negative electrode, and it is difficult to regenerate if it deteriorates significantly. To suppress this sulfation as much as possible, "charge immediately after use" "overdischarge" It is important to consider proper use such as “do not do”. In particular, since a lead storage battery does not have a memory function, it can be said that it is particularly effective to perform charging at a shallow depth of discharge.

  In order to solve these problems of lead-acid batteries, the present inventors, as a result of diligent research, can ignore the influence on the human body on the basis of radiology if it is 100 mSV / year or less, and 2 mSV / year, preferably It has been found that when a gamma ray of 10 to 20 mSV / year or more is irradiated to the positive electrode of a lead storage battery, Joule heat is generated due to an oxidation reaction at the positive electrode, peeling of the high resistance material occurs, and a regenerative charging reaction occurs. Further, the inventors have found a synergistic phenomenon that when polyvinyl alcohol is added as a reaction accelerator to the electrolyte, polyvinyl alcohol is ionized by irradiation with gamma rays and the high resistance substance is easily dissolved.

  That is, the present invention is an activation charging method for a lead storage battery, characterized in that the positive electrode of the lead storage battery is irradiated with gamma rays having an intensity of 2 mSV or more and 100 mSV or less and the lead sulfate of the positive electrode is charged and reacted while being oxidized. .

  According to the present invention, a used storage battery, which is normally unrecyclable, is reduced to 10 V or less by oxidatively decomposing lead sulfate that is deconducting the positive electrode by irradiating gamma rays with an intensity of 2 mSV to 100 mSV. It is to be able to improve and regenerate to normal 12V without flowing current. In addition, since the charging reaction can be performed by irradiating gamma rays when the engine is stopped at night, charging can be performed at a stage where the depth of discharge is shallow, which is particularly effective for extending the life.

  Although the nonconductive film deposited on the surface of the positive electrode by gamma ray irradiation can be removed or peeled off, the removal of the nonconductive film can be promoted by adding polyvinyl alcohol as a reaction accelerator.

It is a perspective view which shows the internal structure of the lead storage battery which arrange | positioned the positive electrode and the negative electrode facing right and left. It is a perspective view which shows the internal structure of the lead storage battery which arrange | positioned the positive electrode and the negative electrode facing up and down.

As shown in FIG. 1, the lead storage battery includes a lead storage battery in which a positive electrode plate 1 and a negative electrode plate 2 are arranged opposite to each other with a separator 3 interposed therebetween, and a positive electrode plate 11 and a negative electrode plate 12 as shown in FIG. There is a lead storage battery in which the separators 13 are arranged to face each other with a separator 13 therebetween. A radiation ore powder layer capable of irradiating gamma rays with an intensity of 10 mSV to 20 mSV or less on the positive electrode inside the lead storage battery is molded into a box shape, and this box (may be a box without a bottom) 20, 20 ′ It is placed outside the position of the positive electrode plates 1 and 11 of the lead storage battery, filled with a predetermined sulfuric acid or lead sulfate aqueous solution, approximately 10 hours or less for about 12 hours when in use, and left for about a week when used ( Recovery will be faster if charging current is applied). Lead sulfate adhering to the positive electrode side by gamma ray irradiation is oxidized and decomposed and charged to return to the initial voltage of 12 volts.
Gamma rays (irradiation) → (positive electrode) PbSO ₄ (charge) → Pb ⁺ + SO ₄ ²⁻ + 2e−
At the anode, lead sulfate changes to lead peroxide, and the sulfate group returns to the battery fluid.
(Negative electrode) PbSO ₄ + 2e- (Charge) → Pb + SO ₄ ^2-
At the cathode, lead sulfate changes to spongy lead, and the sulfate group returns from the extreme plate to the battery fluid.

  When polyvinyl alcohol is added as a reaction accelerator to the electrolytic solution, the removal of the nonconductive film of the positive electrode is promoted. Polyvinyl alcohol has a great cleaning effect on the electrode surface and plays a significant role as a reaction accelerator for decomposing and removing lead sulfate adhering to the electrode surface. Polyvinyl alcohol also has the effect of protecting the electrode surface from which lead sulfate has been peeled off by a film effect, and a high-resistance substance such as lead sulfate adheres again to the electrode surface part where the new surface is exposed, causing the characteristics to deteriorate. There is an effect to prevent. Moreover, it is preferable to use this kind of reaction accelerator after ionization. Thus, by adding an aqueous solution containing polyvinyl alcohol and combining appropriate gamma ray irradiation condition operations, a 12 V electromotive force can be recovered and regenerated even in a lead storage battery that cannot be regenerated by charging.

  Also, in the case of lead-acid batteries in use, the lead sulfate battery characteristics can be improved by slightly removing the lead sulfate adhering to the electrode surface, and the discharge depth is shallow even when the engine at night is at rest. Charging can be performed in stages, and life extension processing is possible.

  In the present invention, activation can be achieved by irradiating the positive electrode with gamma rays and charging can be achieved. However, a reaction accelerator may be used to accelerate the charging reaction. Further, it is possible to charge the lead storage battery while adding electric energy.

The aqueous polyvinyl alcohol solution that is a reaction accelerator can be prepared as follows.
Stir 50 liters of water (soft water) for 30 minutes, raise the temperature to 40 ° C., add 2 kg of raw polyvinyl alcohol, and warm to 90 ° C. Continue stirring for another 10 minutes and homogenize.

  The addition amount of the reaction accelerator should be adjusted according to the intensity of irradiation gamma rays. If the intensity of the gamma ray is strong, use a slightly diluted one, and if it is weak, use it as it is.

  The intensity of gamma rays can be increased up to 100 mSV / year. Although there is a relationship with the recovery time, it is usually preferably 10 mSV to 20 mSV / year.

1, 11 ... positive electrode, 2, 12 ... negative electrode, 3, 13 ... separator,
20, 20 ... Gamma irradiation box

Claims (3)

  In a lead-acid battery, the positive charge inside the lead-acid battery is irradiated with gamma rays having an intensity of 2 mSV to 100 mSV, the lead sulfate on the positive electrode side is oxidatively decomposed, and charged by an oxidation reaction. .   2. The activated charging method for a lead storage battery according to claim 1, wherein an electromotive force of the lead storage battery is 10V or less, and the used storage battery is recovered to 12V by removing the non-conductive film made of lead sulfate of the positive electrode. 3. The lead-acid battery activation charging method according to claim 1 or 2, wherein a reaction accelerator is added to the electrolytic solution to promote removal of the non-conductive film of the positive electrode.

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