JPS62100952A - Charging method for zinc-chlorine cell for high output in short time - Google Patents

Abstract

PURPOSE:To stabilize the cell capacity and prevent a damage of the cell owing to an abnormal rise or drop of the inner pressure of a battery jar, by preparing a device to measure the inner pressure of the jar, and controlling the charging current density depending on the inner pressure. CONSTITUTION:In this cell are furnished a positive electrode of a chlorine electrode 5, a negative electrode of a zinc electrode 6, and an electrolyte of a water solution consisting of mainly zinc chloride. Between the electrodes 5 and 6, plural bipolar electrodes 7 combining a chlorine electrode 5a and a zinc electrode 6a are arranged parallel. At the upper part of a battery jar 1, a linking hole to link cell chambers 8a to 8d which are separated by the electrodes 7, and at one of the cell chambers are furnished a pressure detecting protector 11 and a sensor 12. By this sensor 12, the inner pressure of the jar 1 is measured, and when the pressure is low, the charging current density is increased, and when the pressure exceeds a specific value, the current density is decreased or the charging is halted to maintain the cell capacity constant. Therefore, a damage of the cell from an abnormal rise or drop of the inner pressure depending on an inadequate charging current density can be prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention provides zinc-
The present invention relates to a method of charging a chlorine battery.

Conventional Technology In general, when electric power companies experience an accident on power transmission lines or equipment due to lightning or other causes, they detect the accident at high speed and disconnect the equipment in order to minimize damage to the power equipment. However, even with the most advanced protective relay system, the voltage will drop significantly for 0.07 to 2 seconds before the fault is isolated. By the way, a typical computer has a voltage drop of 10 to 20% or more of 0.003 to 0.0.
If this continues for 2 seconds, a calculation error will occur, so normally the calculation is automatically stopped. Therefore, for extremely important items such as online real-time systems using computers, a constant voltage, constant frequency power supply equipped with a secondary battery is required so that power can be supplied uninterrupted even if the commercial power supply is interrupted. Device C (hereinafter simply abbreviated as CVCF) is used.

As a CVCF, for example, as shown in Figure 4, a rectifier (0, DC filter,
Connect the inverter [F] and AC filter [F] in series, and connect the charger between the commercial power supply and the DC filter.
, secondary whistle, pond U, and thyristor switch (I) are connected in parallel.1 Furthermore, between the inverter (■) and the AC output (03), a frequency oscillator (J) e is connected, and a phase/phase control circuit with a frequency control circuit (J) and voltage control (2) are connected. This circuit connects circuits in parallel and constantly exchanges commercial power to direct current, which is reconverted to alternating current at the desired voltage and frequency through waveform shaping. In this way, the secondary battery is constantly charged with a small amount of power from the commercial power supply, and when the voltage drops instantaneously, the DC current from the secondary battery is applied instead of the DC generated by converting the commercial power supply by activation of the SIRISK switch. , it becomes AC output by waveform shaping. When the commercial power supply returns to normal, the thyristor switch is activated, the secondary battery is turned off, and the battery is charged again using the commercial power supply at a constant low power level. In the figure, the solid line shows the current flow when the AC input is healthy, and the dotted line shows the current flow when the AC output is stopped.

If a CVCF allows continuous uninterrupted power even during a long-term power outage (more than 5 minutes), it is sufficient to attach an engine generator, etc. to the CVCF, and for momentary power outages (0.07 to 2 seconds) Batteries are sufficient. Such a secondary battery only needs to have a large output and be able to stably extract power for 5 seconds at the longest, and does not need to have a large battery capacity. Conventionally, lead storage batteries and alkaline storage batteries have been used to store and release power of about IW to 1000 KW. All of these have a large capacity (hours) compared to output (watts), and can extract a large amount of integrated electric power (watt hours) during discharge, but they can also generate large amounts of power for short periods of time, such as 1 hour. Not suitable for discharging within minutes.

That is, with the development of CVCF technology, there is a trend toward smaller size and lighter weight, but due to the structure of the secondary battery, it has not been possible to make it smaller and lighter.

In the zinc-chlorine secondary battery, the electrolyte storage tank is omitted [7. The battery tank is sealed 2. Chlorine generated at the positive electrode during charging is charged into the tank 1. They discovered that high output could be supplied to an external load for a short period of time by dissolving it in an electrolytic solution and consuming it at the positive electrode during discharge. are placed opposite each other, a porous or large positive electrode with chlorine as an active material is provided on the positive electrode terminal surface, and a negative electrode with zinc as an active material is provided on the negative electrode terminal surface,
Multiple bipolar electrodes, which are a combination of a porous or large-specific-surface positive electrode that uses chlorine as an active material and a negative electrode that uses zinc as an active material, are arranged side by side with a gap between them so that the positive and negative electrodes face each other. The inside of the tank is divided into battery compartments, and an aqueous solution containing zinc chloride as the main component is charged into each compartment as an electrolyte.1-
A patent application was filed in 1973 for a small secondary battery for short-term, high-output use, which is characterized by sealing the battery compartment with a battery chamber and dissolving chlorine generated at the positive electrode during charging into an electrolytic solution, which is then consumed at the positive electrode during discharging.
Proposal 1 was made by No. 9-30043. According to this battery, it is possible to achieve a reduction in size and weight.

Problems to be Solved by the Invention When the above-mentioned short-term, high-output small-sized secondary battery is used by being attached to a CVCF or the like, it is necessary to charge it by constantly flowing a current equivalent to self-corrosion from a commercial power source. However, self-corrosion changes depending on the chlorine concentration in the electrolyte, the temperature of the electrolyte, and the state of zinc electrodeposition, so if the battery is charged with a constant current, the internal pressure of the battery cannot be kept constant, and the battery will be damaged due to an abnormal increase in internal pressure. There is a risk that Also, discharge the battery.

Electrical connection requires rapid recovery of battery capacity, but the disadvantage is that it takes too long to recover battery capacity with a constant current that prevents self-corrosion.

Means for Solving the Problems In view of this, and as a result of various studies, the present invention has developed a charging method for short-time, high-output zinc-chlorine batteries that can suppress the battery internal pressure below a certain value and restore battery capacity in a short time. The chlorine electrode is the positive electrode, the zinc electrode is the negative electrode, and the electrolyte is an aqueous solution containing zinc chloride as the main component. Detects all pressure,
The charging current density is controlled by the pressure.

That is, as shown in FIG. 1, the present invention includes a positive electrode terminal (2) made of platinum-plated titanium that protrudes from the nuclide (1) and a negative electrode terminal (3) in a polyvinyl chloride battery cell (1). The terminals for the positive electrode (2) are equipped with a current collector plate (4) made of graphite, and the chlorine electrodes (5) are attached to all the valves I2, and the terminals for the negative electrode (3) are equipped with the zinc electrodes (6). Between the chlorine electrode (5) and the zinc electrode (6), there is a chlorine electrode (5a) and a zinc electrode (6a).
) are combined (the figure shows a case of three) bipolar electrodes (7) are arranged side by side with a full gap so that the chlorine electrode (5a) and the zinc electrode (6a) face each other. (1) The interior is partitioned into battery compartments (8a), (8b), (8c), (8d) and each cell is electrically connected in series. Battery tank (1)
At the top of each battery compartment (8a) (8b) (8c) (8d)
The quartz glass vibrator (9) is fully attached, and the ultraviolet lamp (10) is placed inside the pipe (9).

In this way, an electrolytic solution consisting of an aqueous solution containing zinc chloride as a main component is charged and sealed in each battery chamber, and during charging, chlorine gas is generated at the chlorine electrode and metallic zinc is deposited at the zinc electrode. Hydrogen gas generated as a side reaction is reacted with chlorine gas and ultraviolet light to form hydrogen chloride, which is returned to the electrolyte.

In this short-term high-output zinc-chlorine battery, as shown in the figure, one of the battery compartments (battery compartment 3d in the diagram) is located in the battery compartment (battery compartment 3d).
1) Pressure detection protector (11) and sensor (
12) The current density during charging is controlled by the pressure inside the battery tank, and the protector protects the sensor from corrosion caused by chlorine. The pressure detection sensor should be one that can withstand corrosive atmospheres such as chlorine gas, hydrochloric acid, and electrolytes, or it should be equipped with a protector as shown in the figure.For example, a sensor using a strain gauge with a small Install it in the hole. In this way, the sensor converts the pressure inside the battery tank into an electrical signal, such as a voltage, and a charging current corresponding to the voltage is caused to flow.

[The electrode reaction during charging of the above-mentioned sealed zinc-chlorine battery is as described above. At the chlorine electrode, chlorine ions are oxidized to become chlorine molecules, and at the zinc electrode, zinc ions are reduced to metallic zinc. As a reaction, hydrogen ions are reduced to hydrogen. When the zinc is deposited, it reacts with the hydrochloric acid in the solution, generating all hydrogen.

The chlorine and hydrogen thus generated are reacted with ultraviolet rays (17) to become hydrogen chloride, and by keeping the pressure inside the battery tank constant, the same amounts of chlorine and zinc are retained and stabilized at n1 battery capacity. Therefore, the total internal pressure of the battery tank is measured 1~, and the internal pressure is a constant pressure! : When V becomes low, charging starts at a current density near the self-corrosion current density range17, and when the internal pressure exceeds a certain pressure, charging is stopped or the current density is completely lowered to maintain the battery capacity at a constant level. In addition, due to discharge, the internal pressure of the battery cell drops significantly below a constant pressure, and in a state where the current density is several times the self-corrosion current density, the battery capacity is increased by starting charging at a current density corresponding to the internal pressure. Either the battery recovers in a short time and the charging current density is reduced to near the self-corrosion current density as the internal pressure of the battery tank increases, and charging is stopped when the internal pressure exceeds a certain level. , Maintaining the internal pressure of the battery tank at a constant pressure [, Battery capacity can be kept constant in a short time.

Example (1) A sealed zinc-chlorine battery having a laminated structure shown in FIG. 1 was used, and according to the present invention, as shown in FIG. 2,
The pressure inside the battery tank [? Charging at a current density of 7 mA/crA tn until s 0.08/Crl, renal pressure P++ (0,08 amount -/c!) to P2 (0,
12 to 9/ca) at a current density of 1 mA/crI. When the pressure is 22 or higher, the charging current is zero. In addition, Fig. 2 shows the self-corrosion current density f0.5 to 1.5 of Honfueike.
mA/crl was assumed.

By controlling the charging current density in accordance with the battery internal pressure in this way, the total internal pressure P+ can be reduced.

It can be controlled between P2, and the battery capacity can also be controlled within a certain range, although there is some variation.

Also, during discharging, the pressure decreases as chlorine molecules are reduced to chlorine ions at the chlorine electrode, but when the internal pressure drops below P, the pressure recovers because charging is performed at a relatively large current density of 7 mA/cA. .

As mentioned above, the internal pressure of the battery is kept constant during charging and discharging,
Control to maintain battery capacity becomes possible.

Example 2 In Example 1, as shown in Figure 3, the current density is constant at pressures below P3, and from P3 to P4 is inversely proportional to the internal pressure 1-
A current density of 1 was applied during charging.

As a result, in response to the self-corrosion current during charging, the battery capacity cannot be maintained at the pressure below, and after discharging, the current density gradually increases as the internal pressure decreases until pressure P3, and below P3, the current density rapidly increases due to the large current density. As the internal pressure was restored, it was again able to reach an equilibrium state at a pressure equivalent to self-corrosion, and was able to maintain its capacity.

Effects of the Invention As described above, according to the present invention, the current density during charging of a short-term, high-output zinc-chlorine battery is controlled by the pressure inside the battery tank, thereby stabilizing the battery capacity and preventing inappropriate charging current density. This has significant industrial effects, such as being able to prevent damage to batteries due to abnormal rise or fall in internal pressure of the battery tank.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram showing an example of the method of the present invention, FIGS. 2 and 3 are explanatory diagrams each showing the relationship between battery tank internal pressure and charging current density in an embodiment of the method of the present invention, and FIG. 4 is an explanatory diagram showing an example of the method of the present invention.
It is an explanatory view showing an example of F. A Commercial power supply B AC output C rectifier
D DC filter E Inverter
F AC filter G Photoelectric equipment
H battery I thyristor switch J frequency oscillator K phase control L! Pressure control 1i1F, pond tank
2 Terminal for positive electrode 3 Terminal for negative electrode 4
Collection/discharge plate 5.5a Salt electrode 6,6a Zinc electrode 7 Bipolar electrode 8a, 8b, 8c, 8d Battery chamber 9 Quartz glass pipe 1o Ultraviolet lamp 5060 in Fig. 2 t j (! C * ff (kg) /cm21 Figure 3 Internal pressure (kg/cm21

Claims (2)

[Claims] (1) Detecting the pressure inside the battery tank when charging a short-time, high-output battery with a sealed structure using a chlorine electrode as a positive electrode and a zinc electrode as a negative electrode, and using an aqueous solution containing zinc chloride as the main component as an electrolyte,
A method for charging a short-time, high-output zinc-chlorine battery, characterized in that the charging current density is controlled by the pressure. (2) Set the charging current density higher than the self-corrosion current density band when the tank pressure is low, set it near the self-corrosion current density band when the tank pressure is high, and stop charging when the tank pressure is even higher. A method for charging a short-time, high-output zinc-chlorine battery according to claim 1.