JPS5916279A - Lead storage battery - Google Patents

Abstract

PURPOSE:To improve discharge continuing characteristic of battery by adjusting battery capacity, theoretical capacity of anode and theoretical capacity of electrolyte. CONSTITUTION:In case a battery capacity is considered as A, theoretical capacity of anode as B and theoretical capacity of electrolyte as C, the theoretical capacity of anode and theoretical capacity of electrolyte are restricted for battery capacity so that the relation indicated by the equations can be obtained. It becomes difficult for the electrolyte to diffuse at the center of electrode plate while discharging is continued by precipitating discharge products emphatically at the surface of electrode plate, and if the electrolyte diffuses, a little amount of SO4<--> ion remains in the electrode plate, a lot of remaining PbO2 is partly changed to PbSO4', the SO4<--> ion is consumed and the belt-shaped layer of PbO2 remains at the center of the active layer in the thickness direction. Moreover, when the So4<--> ion is consumed, change to PbSO4 of the corrosion layer at the surface of collector can also be suppressed, resulting in maintaining the battery characteristic.

Description

DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD The present invention relates to lead-acid batteries, and more particularly to so-called retained lead-acid batteries in which electrolyte sales are restricted so that no free electrolyte is present.

Background Art This type of electrolyte limits the electrolyte volume and makes the cathode capacity 10-30% larger than the anode capacity, so that the anode is fully charged first during charging, and overcharging. The cathode absorbs and consumes the oxygen generated from the first offering of the sun.

If this battery is left for a long period of time after discharging, a corroded layer on the surface of the anode current collector, which is cooler than the lead or lead alloy supporting the anode active material η layer at the anode, becomes inert Pb5o4 (lead sulfate).
As a result, the resistance between the anode active material η and the anode current collector becomes high, resulting in poor charging efficiency and insufficient recovery of the container, resulting in deterioration of electric current and characteristics. It turns out.

Now, according to the investigation conducted by the inventors, as mentioned above, γ
Pbs with an inactive corrosion layer on the anode current collector surface after being left to wander;
The generation mechanism for conversion into the o4 layer is thought to be due to the following final velocity. That is, during repeated charging and discharging after battery assembly, a corrosive layer of PbO2 (lead dioxide) is often formed on the surface of the battery due to anodization. During repeated discharges, there is no problem as it exists as a PbO2 layer even in the discharge state, but if it is left in this state for a long time, the current collector metal PB will ionize and become PB++ ions, and the layer will corrode. Similarly, pb of Pboz layer is -pb++
ion, and this Pb ion combines with the 804-- ion remaining in the electrolyte to form an inactive Pb ion.
A b5o4 layer is generated.

On the other hand, in this type of battery, the VC electrolyte is involved in the battery reaction as shown in the above equation.

(Anode) (Saliva) (Anode) - (Anode) ([Monovalent) From this, it can be seen that the capacity of this type of battery is controlled by the negative electrode, the negative electrode, and the electrolyte.

DISCLOSURE OF THE INVENTION The present invention prevents the PbO2 layer on the surface of the current collector from converting into an inactive PbSO41 layer during discharging, and also prevents the active material layer r [remaining PbO2 from converting to PbSO41].
An effective method is to suppress the conversion to Pb0z and to leave highly conductive Pb0z in the active material layer in contact with the current collector. It has been found that the above-mentioned problems can be solved by adjusting the theoretical capacity of the liquid.

The present invention was made based on this fact, and in a so-called lead-acid battery with a retainer, when the Miike capacity is A, the theoretical field of the anode is C, and the theoretical capacity of the electrolyte is C, It is characterized by defining the theoretical ambiguity of positive and polar and the theoretical capacity of the electrolyte with respect to the capacity of the brewing pond so that it becomes the first line.

Therefore, the present invention regulates the theoretical capacity of the anode electrolyte in relation to the required battery capacity IK, thereby separating pbSO4 as a discharge product generated during air blowing from the vicinity of the electric body. In other words, PbO is generated in an adult state on the surface of the electrode plate, causing the live ducts near the current collector to become PbO.
2, and by making the middle part in the thickness direction of the electrode plate a band-like layer of Pbo 2, the acceptability of the current from the current collector to the active material layer is maintained in a good state. This is intended to improve charging efficiency after long periods of storage.

In this way, if discharge products are generated at specific points on the surface of the electrode plate, it will be difficult for the electrolyte to diffuse into the center of the electrode plate when it is left to discharge, and even if it does diffuse, However, only a small amount of 504-ion remains in the electrode plate, and a part of Pboz, which remains in abundance, is converted to Pb8o4, and 804 (on is consumed by rF, and the central part in the thickness direction of the active material is Pbo 2 band-like layer remains P
C becomes. By consuming S Oa- ions through the above-mentioned mechanism, it is possible to suppress the corrosion layer on the surface of the aggregate from becoming PbSO4, thereby making it possible to maintain battery characteristics.

As described above, according to the present invention, the discharge characteristics of this type of battery can be modified.

Embodiments of the Invention Preparation of a battery: A lead-calcium alloy obtained by casting, punching, or expanding processing is used as the negative and anode current collectors, and a prescribed active material paste is applied to each current collector and dried. Use as negative and anode.

Next, after inserting the electrode body with a glass fiber separator interposed between these electrodes into the battery container, a sulfuric acid electrolyte with a specific gravity of 1.60 was poured into B, 5ea (corresponding to the theoretical field of electrolyte 1i1t2AH). Then, the electrodes and separators are impregnated and retained.

After that, a battery case lid is attached to obtain a lead-acid battery with a capacity of 1 AH, which is chemically converted and made usable.

In producing the above batteries, trial batteries were produced by varying the theoretical boundaries of the anode as shown in Table 1rc.

In addition, each cathode company set the capacity of each battery to be larger than the anode capacity.

Table 1 In Table I, A is the battery capacity, B is the theoretical manufacturer of the anode, and C is the theoretical capacity of the electrolyte.

Figure 1 compares the discharge characteristics of these batteries.First, the battery after chemical formation was subjected to constant voltage (2.5V).
) After charging for 16 hours [L, 0.201 FtJa], the discharge capacity until reaching the final discharge voltage (1.7 V) was 1
00, left it in a discharged state for 3 months, 6 months, and 12 months, then charged it at a constant voltage (2.5V) for 16 hours, and 0.20
A method was used in which the discharge capacity was measured by discharging with a current and setting the voltage to 1.7V.

From Figure 1, the theoretical capacity ji (B) of the anode is expressed as the battery capacity (A).
According to the batteries of the present invention (No. 11 and No. 2), in which the battery capacity was 40 times or more, the discharge capacity was 9096 or more compared to the initial capacity even after being left for a long period of 12 months, and charging was performed efficiently. It can be seen that

In addition, the study of various theoretical companies of electrolyte, that is, theoretical sulfuric acid and battery capacity, was carried out by varying the amount of electrolyte (varying the amount of sulfuric acid electrolyte injected) as shown in Table 2. ] A prototype battery was created.

On the other hand, Yin Nai Yong Kai also had a great singing performance on 6-den N1J and Tomo Anode Yong Kai.

Table 2 (Blood, A, B, c in Table 21/c) tyl *, B.

Shows the same thing as C. ] Figure 2 compares the discharge characteristics of these prototype batteries, and the measurement conditions were the same as those in Figure 1 above.
Ta.

@2 As shown in Figure 2, the theoretical capacity of the electrolyte is 1.4 times or less than the battery capacity (A). It can be seen that charging is performed efficiently even if the battery is left unused for a long period of time.

As explained above, according to the battery of the present invention, the discharge characteristics are improved, and its industrial value is extremely large.

[Brief explanation of the drawing]

The drawings show the discharge characteristics of the battery of the present invention. Figure 1 shows the characteristics when the anode logical container is used. Figure 2 shows the characteristics when the theoretical volume of the electrolyte is changed. It is.

Claims (1)

[Scope of Claims] fl) Negative and anode plates, a separator interposed between these plates, and impregnated and retained electrolyte in the electrode plates and separator so that substantially no free electrolyte is present. In a lead-acid battery equipped with a solid electrolyte, when the battery capacity is human, the theoretical capacity 1 of the anode is B, and the theoretical capacity of the electrolyte is C, the electric capacity is In contrast, a lead-acid battery is characterized in that the theoretical capacity of the anode and the theoretical capacity of the electrolyte are regulated.