JPS58212061A - Lead storage battery - Google Patents

Abstract

PURPOSE:To improve the over-discharge characteristic of a lead storage battery by providing a conductive water-proof layer near a current-collecting member, and providing a conductive liquid-holding layer between the conductive water-proof layer and a positive active material layer. CONSTITUTION:The positive plate 10 of a battery (A) is composed of a positive active material layer 11, a current-collecting member 12 made of a lead-calcium alloy, a conductive water-proof layer 13 provided near the member 12, and a conductive liquid- holding layer 14 provided between the conductive layer 13 and the positive active material layer 11. The negative plate 15 of the battery (A) is composed of a negative active material layer 16, a current-collecting member 17 made of a lead-calcium alloy, a conductive water-proof layer 18 and a conductive liquid-holding layer 19. When electric discharge characteristics achieved by subjecting the battery (A) and a reference battery (B) which contains a positive and a negative plate having no conductive liquid- holding layers to electric discharge at a current of 0.2c are compared, it will be observed that the battery (A) has an increased capacity and an enhanced battery performance. In addition, since the contact of electrolyte with an oxide corrosion layer existing on the surface of the current-collecting member can be suppressed, the over- discharge shelf characteristic can be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a lead-acid battery, particularly a so-called dithena type lead-acid battery (in which the amount of electrolyte is limited so that no free electrolyte is present), and the use of an electrolyte. improve the rate and
This is to improve the overdischarge characteristics and measure the same battery performance.

Discharge reaction behavior of this type of battery C: To explain, in the early stage of discharge, the amount of electrolyte on the electrode plate surface (2! However, when discharge starts, the reaction proceeds from the electrode plate surface, so the concentration of the electrolyte decreases at the electrode plate surface (-), creating a concentration gradient. C: In other words, the amount of electrolyte consumed by the electrode plate is diffused from the separator ζ
It is replenished by 2.

As is well known, the discharge reaction in a lead-acid battery (2) occurs when the active material on the anode plate changes from Pb02 (lead dioxide) to PBSO2.
a (lead sulfate), and in the cathode plate from p'b (lead) to pb
Compared to the case of PbO2 or Pb active material noodles, the pore diameter of the EO4 active material is smaller, so the electrolyte cannot be smoothly supplied to the deep part of the electrode plate. (There was an inconvenience that it was not possible to obtain a commensurate level of lucidity.

- 10,000, this kind of battery C: If you leave it over discharged,
Anode (at the second step, the interface C between the active material W- and the current collector made of lead bonding): irreversible PbS04 (lead sulfate) is generated, and the anode active material - The low resistance between the battery and the collector becomes high.If charging in such a state, normally (in double-lead acid hawk batteries, layer pressure charging is used due to problems such as overcharging (= corrosion of the current collector). However, during constant magnetic charging, the 14ai4. field rose to the set pressure of C2, and the battery was not fully charged (2), causing the battery to deteriorate.

Now, the generation mechanism of Pb3O4 in the irreversible state of the -1 anode active proboscis and the aggregate after over-discharge (-1) is due to the passage in Figure 41 tlLl~j (11). Conceivable.

First, from the state shown in the 11th momme (al), it becomes positive by charging!
47 tongue proboscis rfa: t+ is a statue? +YP r)02
i = changing temperature 4VfC1 The surface of the assembly +21 made of lead or lead alloy changes P-D O2C, P b
O2@(31 is formed.

(Shizu 1 cause b).

Next, the anode active material 1 (1) is either charged or discharged in the usual way (from the second step), or the anode active material 1 (1) is charged with P formed on the surface of the current collector (21).
I) 02@131 has a ph value even after repeated charging and discharging C2
It remains in the state of 0241 (Yuu 1 figure (c+)
(:, as shown, the assembly (surface number of 21 = p'
bO2 layer (31 is irreversible PI) changes to SO4 and p
'bSO4@+4) is formed, and this P'bSCz@
+4+ becomes inactive state 1, leading to a decrease in charging characteristics.C2.

From the above-mentioned irreversible Pt)804% generation mechanism, when left unattended C; the pb02 at the surface of the current collector is
If it is possible to prevent the change to pt) 804, the overdischarge characteristics will be improved.

The present invention is based on the point that the force λ is small, and the gist of the filter is that at least 44 plates are provided with a conductive waterproof layer near the current collector made of lead or a lead alloy. , with a conductive waterproof layer! q! Between active material and Sa
The point of disposing a liquid retaining layer (= yes, or λ: Yes) is to measure the utilization rate of the dissolving liquid and the dispersion and leaving characteristics.

Hereinafter, one embodiment of the present invention will be described in detail based on flash surface C.

(101 is an anode plate which is the gist of the present invention, and includes anode active material layers 111 and 2, an assembly 121 made of lead-calcium alloy, and a current collector C2 arranged near the current collector I21. It is composed of a conductive waterproof 111Q31, and a conductive liquid retaining liquid 114 arranged between the conductive waterproof 113 and the active material chamber IB.

Reference numeral 115 denotes a cathode plate, which includes an anode plate (same as IQI, cathode active material 1161, lead-calcicum base assembly 11η, conductive waterproof 〇8, and conductive infusion retaining layer 119).
It is composed of 1 and (2).

In addition, in the example, both sides of the electrode plate B1, C2, and conductive waterproof I! Although we were able to carry out the case where a conductive liquid retaining layer was installed,
The anode plate (even if only the second one is applied, it will not look elegant.

Next (2, 1 E, I will explain a specific example of making two Lucid plates C.

First, let's talk about the cathode plate (1111 + two): casting, punching &ffl
The Calciwaum gobon has dimensions of 50 x 50 x 2 m (; the politically determined one is 1121. This current collector 1
A conductive waterproof film 13 is viewed across from 3.

The method for creating this conductive waterproof layer will be explained in detail according to the process diagram C2 shown in Figure 2. For example, apply a conductive powder such as carbon black powder to a hot water layer of 10 cm. Cool the $1 waterproofing treatment by soaking it in a tetrafluoroethylene (LA, referred to as FTFB) dispersion. This waterproofed conductive powder was placed in a dryer at approximately 60°C.
Dry the moisture with a @crystal. After pulverizing with a pulverizer, the powder was pulverized in a magnetic furnace containing nitrogen (N2) gas at a rate of 1:35.
Heat treated at D°C 1. After the conductive powder (PTFE was secretly observed) was concentrated in two places, the PTFE powder was mixed at ℃, and shearing force was applied using a crusher. The reason why the PTFF powder was blended (fiberized) and the conductive powder was made to wait in the process room was by adding a thickener such as a polyethylene oxide bath solution and kneading it in a kneading machine. d - The straight C is rolled by roller C2 to approximately 0
．． The conductive waterproof layer pressed to a length of 5 m was cut into the specified size (2 pieces) using a Wr machine C2, and the current collector 12
Both sides C of 1 are crimped and both sides of the current collector Q21 are opened (-conductive waterproof-131 is arranged).

In this way, both sides of the current collector +13 (2.
After arranging the IK layer +31, the conductive powder, e.g. carbon black, was yeasted with a thickener 1/2% oxide solution. Burn things from Laura C2 o, s m
ζ Two rolled magnetically conductive retaining liquid @14; are respectively crimped.

Sara C:, this protection! II on (diP'bO(-lead oxide)
and water. Press the tongue @ guest yeast with a roller (thickness tOm + 2, FE rolled size 50) and press it with a roller brace (2), and press it to the positive j4 with a thickness of 2.4 m.・Obtain 01.

嘗! l! For temporary '1!5ic, the anode plate 1 is connected
Same as 101 C:, 50 x 50 x 1 mm (= cut current collector 'I' 71C1 conductive waterproof layer 118I and conductive liquid retaining layer r191 are crimped, then the specified dimensions of 50 x 50 m (
; A pair of the cut living material sheets were treated with conductive liquid-0
Both sides C of 1: Roller press (press from the second side, thickness 1.2
m cathode plates 1151 are obtained.

1) Modified A'-electrode plate 01 obtained as above and two cathode plates 1151!151 are combined with a glass fiber separator 1) Q
Alternately through C: The stacked metal parts are placed in a resin battery case 121.
) C: Inserted, then injected with 1QCe of sulfuric acid solution with a ratio tE of 1.50 to impregnate the electrode plate and separator. The lid 124) was molded to obtain a lead-acid reservoir of volume @IAH.

This battery is then chemically converted to make it usable.

Figure 84 shows a comparison battery IBI, which is similar to the present invention except that the exposed anode plate does not have a conductive liquid retainer, at a current of 0.2 (!). FIG. 3 is a comparison diagram of discharge characteristics when discharged.

From FIG. 4, it can be seen that according to the magnetic battery C according to the present invention, the battery capacity increases by 1 and the battery performance is the same as above.

FIG. 5 shows a comparison of the overdischarge characteristics of the present invention's Saikei battery and the aforementioned comparative battery (Bl).

In the measurement, first, the battery after chemical formation was charged at a constant current ([110), and then discharged at a waterfall of 112 cg to bring the final discharge voltage to t7V.
The following cycle conditions are repeated 10 times, and the average discharge capacity at that time is defined as 1PO.

Then, after discharging the magnetoelectric IAI of the present invention and the comparative battery (Bl) as described above, the resistor C of 200 Ω was connected and allowed to rise for 7 days.
After leaving it for one month in an atmosphere of
Charge and discharge with 0.2ON current until the final discharge voltage is 1.7
A method was used to measure the discharge capacity each time as v.

It can be seen from FIG. S that the battery of the present invention has improved overdischarge characteristics.

As explained above, C:, according to the present invention Aike C2, when C: arranging the abrasive waterproofing near the assembly, C: between the 1 ryu waterproofing and the active material (: the conducting material). Since a magnetic liquid retaining layer is provided, electrolyte is supplied to the tentative center of the kite at the time of taking the kite, improving the utilization of the electrolyte and increasing the size of the pond. As it increases, it becomes possible to suppress the contact of (2) !f metal corrosion order CP+' on the surface of the material body, and it becomes possible to suppress the contact of 2. Corrosion @ (p b O2) is irreversible P 1) 804
It is possible to maintain the current state in a stable state without any change in C, and it is possible to improve the over-discharge characteristics.
Its industrial value is enormous.

[Brief explanation of the drawing]

Figure 1 is a mechanism to explain the mechanism by which lead sulfate is produced by the magnetic collector of the polar plate, and Figure 2 is a diagram showing the various possibilities of the waterproofing theory. Fig. 6 is a vertical cross-sectional diagram of the pond of the present invention 1, Fig. 4 and Fig. 5 are the longitudinal cross-sectional diagram of the pond of the present invention
This is a comparison of the special i-sei with the comparative Saya IBI, and the 4th
The figure is a comparison diagram of the discharge characteristics of the 1st section and the 51st section. 10... Anode plate, 11... Anode single pole active/Z screen-112
, 17... Chrysanthemum body, 16.1B... One-way magnetically conductive water -
214, 19... Conductive liquid retention theory, 15... Yin-tentative,
16...; I have a lot of active breasts, 20...-I have a hard time. Applicant: Sanyo Electric Company Representative Patent Attorney: Ten Sano - Figure 1 Figure 3 Figure 2

Claims (1)

[Claims] (1) - Between the end and hot plate and these I plates (: the intervening separator, the electrode plate and the separator C: impregnated and retained so that there is virtually no free electrolyte (two restricted leaves) At least the anode plate is provided with an electrolytic solution near the current collector made of lead or a lead alloy (double-conducting waterproof brass). A lead-acid battery characterized in that a magnetically permeable retaining liquid is disposed between the battery and the battery.