JP2011119201A - Electrochemical device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve a problem wherein, in a liquid injection sealing structure of a conventional electrochemical device such as a battery or a capacitor, sealing component mounting and sealing are synonymous, a sealing component can not be mounted at the optimum time point, and sealing in a gas substitution state or a depression state is difficult, so that there has been a limit in the VA on this premise. <P>SOLUTION: In the liquid injection sealing structure, liquid injection, gas substitution, and decompression are carried out by making a sealing component with a simple and low-cost sealing tap and with the tap in a held state, and sealing is also carried out in a gas substitution state or a depression state. By the VA of the injection liquid sealing through the structure, cost reduction and performance improvement are achieved. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

 The present invention provides a manufacturing process in which an electrolytic solution is injected into a container containing a power generation / storage element such as an electrode plate / separator, and then sealed with a container lid or the like, or the power generation / storage element is embedded and sealed. The present invention relates to an electrochemical device such as a battery or a capacitor having a manufacturing process in which an electrolyte is injected from a liquid injection port provided in a sealed container, and then the liquid injection port is sealed with a sealing component.

  The conventional sealing structure of the electrochemical device is a structure in which the container body is sealed with the container lid after the liquid is injected, or the liquid injection port provided on the container lid or the container lid is provided. In addition, after the liquid is injected from the liquid injection port of the sealing part holding member, the sealing part is attached to the liquid injection port and sealed. As the sealing type, there are a sealed type and an open type capable of always releasing the internal gas depending on the type of the device, and the sealed type is provided with a non-returnable safety valve or a resettable pressure control valve that operates by internal pressure. In addition, there are a non-removable type and an attachable / detachable type for replenishing and replenishing the sealing parts. Of course, the material and structure of the sealing part also differ depending on the type of the electrochemical device. Thus, there are various types of conventional liquid injection port sealing methods depending on the type of the electrochemical device as shown in the section of “Effects of the Invention” and “Mode for Carrying Out the Invention” Various improvement methods as shown in Patent Documents 1 to 7 have been proposed for the injection port sealing structure of the electrochemical device, the injection method, the injection port sealing method, and the related manufacturing processes and apparatus maintenance methods.

Patent application title: Sealed battery and method for sealing liquid injection hole thereof Patent application title: Sealed lead-acid battery and method for manufacturing the same JP 2003-142148 lead acid battery JP2003-142151 IMMEDIATE TYPE LEAD BATTERY AND METHOD OF USING THE SAME Patent 4422762 Controlled valve storage battery JP2008-146895 Lead acid battery JP 2008-186690 Lead acid battery

  The electrochemical device having a liquid inlet sealing structure for injecting from the liquid inlet provided in a conventional container or the liquid inlet of the sealing part holding member is the manufacturing process after the liquid injection. It is a precondition that sealing is performed by attaching a sealing part to the liquid injection port. That is, the mounting and sealing of the sealing part are performed simultaneously with substantially the same meaning. Therefore, in a state where the sealing part is mounted, it has a structure in which liquid injection or gas replacement / decompression inside the apparatus cannot be performed, and the sealing part cannot be mounted in advance at the optimal time before sealing, It is difficult to perform sealing and decompression sealing in a gas replacement state effective for improving the performance of the gas. In addition, the VA (value analysis) of the sealing-related parts is premised on the same meaning for the mounting and sealing of the sealing parts, and the improvement effect is also limited to this range. Furthermore, it is necessary to install and manage the sealing component mounting device in the production line after the liquid injection, which causes a reduction in the operating rate of the entire manufacturing line due to the trouble of the sealing component mounting device.

The present invention was devised in view of the above-described problems to solve the problem, and the sealing component is mounted on the sealing component holding member for providing the electrolyte injection passage. Provides the above-mentioned electrochemical device with reduced cost and improved performance and safety by VA (value analysis) from a new viewpoint of the injection port sealing structure that can be used for liquid injection and internal gas replacement / decompression For the purpose. That is, it is an object of the present invention to provide the electrochemical device that is reduced in total cost by optimally allocating component costs, facility-related costs, and labor costs because the sealing components can be mounted at an optimal time. In addition, including the case of sealing with the container lid, it is possible to perform sealing and decompression sealing in a gas replacement state with simple equipment modifications in the existing production line, and provide the electrochemical device with improved performance and safety The purpose is to do. To reduce the total cost, the sealing part holding member with the sealing part mounted may be purchased, or the sealing part may be mounted on the sealing part holding member offline or in a sub-production line, or the sealing may be press-fitted / inserted. This includes eliminating the decrease in the operating rate of the entire production line due to troubles in the sealing part mounting device by simplifying the mounting, screwing and contact.

In order to solve these problems, a first aspect of the present invention is directed to any one of the electrolyte injection passage, the electrolyte injection passage also serving as an external ventilation path, or the external ventilation path. And a sealing part for sealing the path, the sealing part can be mounted on the sealing part holding member for holding the sealing part and before sealing the sealing part holding member for holding the sealing part A first mounting state in which the path is constituted by the sealing part holding member and the sealing part and a second mounting state in which the path is sealed by the sealing part can be selectively maintained. The electrochemical device is characterized in that it is configured as follows.

  According to a second aspect of the present invention, a sealing part holding rib is provided on either the sealing part holding member or the sealing part, and the sealing part holding member is provided with a sealing passage portion of the path, and the sealing part is The first mounting state held by the sealing component holding rib and the second mounting state in which the sealing component is mounted and sealed in the sealing passage portion can be selectively maintained. An electrochemical device according to a first invention characterized by the above.

According to a third aspect of the present invention, the first mounting state and the second mounting state can be selectively maintained by rotation of the sealing component mounted on the sealing component holding member. An electrochemical device according to a first aspect of the invention.

According to a fourth aspect of the present invention, in a lead-acid battery having a plurality of battery cells, a sealing part mounting portion common to the plurality of adjacent battery cells is provided for the plurality of adjacent battery cells, and each battery cell is provided in the sealing part mounting part. An electrolyte solution injection path and an external air passage common to each of the battery cells or the plurality of adjacent battery cells, and the sealing parts common to the plurality of adjacent battery cells mounted on the sealing component mounting portion are rotated. The first mounting state in which the electrolyte injection passage is constituted by the sealing component mounting portion and the sealing component, and the second passage in which the electrolyte injection passage is sealed by the sealing component. The lead storage battery according to the third aspect of the present invention is characterized in that the mounting state of is configured to be selectively maintainable. The sealing component mounting method includes various methods such as press-fitting and abutting according to the shape of the sealing component and the sealing component mounting portion, but the cap-shaped sealing component is used as the sealing component mounting portion. The method of external fitting is the simplest and can provide a safety valve function. The external air passage is used for exhaust or intake or both, and an explosion-proof filter is provided if necessary.

According to a fifth aspect of the present invention, the sealing component mounting portion further includes an exhaust chamber for each battery cell that condenses and condenses moisture in the gas generated in the battery cell and is connected to the external air passage. The lead storage battery according to the fourth invention. The exhaust chamber passes through small chambers divided as much as possible in order to improve the condensation / condensation capability, and is provided with a step / gradient on the bottom so that the condensed and condensed water flows back into the battery cell. Further, the exhaust chamber is provided in the sealing part mounting portion that is integrally formed with the battery case lid, so that the upper surface is formed in an open state, but the upper surface is preferably sealed with the sealing part. .

A sixth invention is characterized in that a pressure control valve for controlling the pressure in the battery cell by opening and closing the external air passage is additionally provided in the sealing part mounting portion. It is the lead acid battery concerning invention. The pressure control valve includes a pressurization control valve for controlling the rising pressure in the battery and a pressure reduction control valve for controlling the pressure reduction in the battery. Either one or both are used.

A seventh invention according to the sixth invention is characterized in that, in the configuration of the sixth invention, when only the pressurization control valve is provided, a micro-ventilation passage that can be constantly ventilated opens to the outside. Lead acid battery. The micro air passage is provided in order to converge the internal pressure in the battery cell to the atmospheric pressure by a slight air amount that hardly affects the water loss of the electrolyte solution. Finally, all the battery cells converge to the same pressure (atmospheric pressure), and plastic deformation due to the pressure difference between the outer wall of the battery case and the partition walls between the battery cells is prevented.

In an eighth aspect of the invention, in order to optimize the thickness of the partition walls between the battery cells, the pressure control valve makes the partition wall thickness between the common battery cells thinner than the thickness of the partition walls between the other battery cells. A lead-acid battery according to a sixth aspect of the present invention. The partition wall between the battery cells of the battery case where the pressure control valve is not common is subjected to a differential pressure generated due to variation in the opening / closing operation pressure between the pressure control valves, so the thickness is increased in consideration of the differential pressure. Although it is necessary, since the differential pressure does not occur in the partition wall where the pressure control valve is common, the wall thickness can be reduced. The partition walls between battery cells of the battery case lid that do not share the pressure control valve need not necessarily be thick because the pressure receiving area is small and reinforced with the battery case cover.

According to a ninth aspect of the present invention, there is provided a partition wall between battery cells not sharing the pressure control valve in order to suppress partition wall deformation between the battery cells not sharing the pressure control valve, which is generated due to a variation in opening / closing operation pressure between the pressure control valves. A lead storage battery according to the sixth or eighth aspect of the present invention, characterized in that a micro vent is provided in the battery. The minute ventilation hole is provided with a minute hole in the partition wall of the battery case lid, or a portion that is not thermally fused by providing a notch such as a small triangle in a heat fusion part between the battery case and the battery case. The shape of the cut is not particularly limited to a triangle as long as a minute vent can be formed.

In a tenth aspect of the invention, at least one of the external ventilation path, the external ventilation path opened and closed by the pressure control valve, or the external ventilation path provided with the minute ventilation path and opened and closed by the pressurization control valve. The lead storage battery according to any one of the fourth to ninth inventions, wherein the battery is not provided in the sealing part mounting portion but is provided in the sealing part. This structure in which a part of the function of the sealing part mounting part is transferred to the sealing part is a structure for simplifying the shape of the sealing part mounting part and securing a larger area of the exhaust chamber.

  According to the present invention, the electrochemical device having improved performance and safety as described below can be provided at a lower cost. The effect includes an effect common to each type of the electrochemical device and an individual effect different for each type. The individual effect different for each type is described below for a typical type of the electrochemical device. In addition, the electrochemical device having a similar structure has the same effect as the following typical types of electrochemical devices. (For the individual effects on typical types of the electrochemical devices, see the description in the section “Description of Embodiments”)

1) Effects common to each type of apparatus The following describes common effects when the first invention is applied to the electrochemical apparatus.
a) Functional system of the sealing structure from a new point of view, that is, a liquid inlet sealing structure in which liquid injection and gas replacement / decompression of the inside of the electrochemical device can be performed with the sealing part mounted on the sealing part holding member This review makes it possible to improve the performance and safety of the electrochemical device and reduce the cost.
b) In addition to the electrochemical device sealed with the container lid, it is possible to easily inject and seal liquids in a reduced pressure state or gas replacement state with simple equipment modifications in the existing production line. Safety can be improved.
c) Since the sealing parts can be installed at the optimal time, parts costs (parts costs / management costs), equipment-related costs (depreciation costs, maintenance costs), direct / indirect labor costs, and the entire production line It is possible to reduce the total cost by optimizing the cost distribution including the operation rate of the system.
In addition to the above effects, the common effects for each type of the lead storage battery having a plurality of battery cells are as follows.
a) For each type of lead-acid battery, when the number of sealing parts and sealing part mounting parts is reduced to less than half compared to the individual exhaust system in which the liquid injection port and the liquid stopper are provided for each battery cell. In both cases, it becomes possible to standardize and standardize the sealing structure and sealing-related parts, reducing the total cost.
b) At any stage during product inventory / distribution / storage / use, deformation of the outer wall of the battery case and the battery cell partition wall is suppressed, and various problems due to plastic deformation of the battery case and electrolyte leakage due to battery case cracking Is prevented. This relaxes the design conditions for the material and thickness of the battery and enables weight reduction and cost reduction.
c) If the cap-shaped sealing part is detachably fitted to the sealing part mounting part, it can be used as an emergency gas release valve that releases internal gas when the battery internal pressure rises abnormally. There is no need to provide a separate valve, improving safety.

2) Individual effect on sealed battery Lithium ion that injects a non-aqueous electrolyte (organic solvent-based electrolyte) and then seals the electrolyte injection passage and is provided with a non-returnable safety valve The effect in Example 1 which employ | adopted said 2nd invention with respect to sealed batteries, such as a battery, is described below.
a) Nitrogen gas replacement or reduced pressure can be easily injected, so air and bubbles in the voids of power generation / storage elements such as electrode plates and separators in the battery can be easily and reliably discharged or nitrogen gas replacement The electrical performance is improved. Injection under reduced pressure facilitates injection even with high-viscosity electrolytes and promotes uniform penetration and internal diffusion, not only improving productivity but also eliminating variations in electrode plate formation and improving battery performance. Stable and improved lifespan.
b) When sealing under reduced pressure at an appropriate pressure, pressure is applied to the electrode plate and separator via the container due to atmospheric pressure, reducing the dropout of the electrode active material during use, improving mechanical strength and electrical performance, There is an effect such as lowering of the locally raised temperature due to increased heat dissipation of the generated heat to the battery surface. Even in an existing production line that is sealed with the container lid or the like, if the external terminal is also used as a sealing part holding member, sealing in a nitrogen gas replacement state or a reduced pressure state is facilitated by a simple equipment modification.
c) If the external terminal of the container lid is also used as the sealing part holding member, and the resistance of the sealing part to the outer side of the container is set to be less than the bursting strength of the container, the cost due to the need for a safety valve is eliminated. Safety can be improved by providing a function as a down or second safety valve. In this case, since the sealing component can be used as an internal pressure detecting component that operates when the internal pressure of the battery is abnormally increased, a current interrupt circuit when the internal pressure is abnormally increased can be easily attached.

3) Individual effects on starting lead-acid batteries with control valves.
A liquid lead-acid battery for starting an automobile is a lead-acid battery that has a sufficient amount of electrolyte and has a gas discharge port for an internally generated gas (water electrolysis gas, water vapor, electrolyte mist) always open. However, water replenishment is necessary due to the loss of water in the electrolyte during the period of use. On the other hand, the pressure control valve that operates only when the internal pressure rises is attached to the external vent passage to suppress the loss of moisture, and the control valve type start lead storage battery and control valve with no need for rehydration Lead acid batteries for starting have been proposed. On the other hand, the effect in the second embodiment adopting the fourth to seventh inventions and the third and fourth embodiments adopting the fourth, fifth, sixth, eighth and ninth inventions. Is described below.
a) Split exhaust type lead-acid battery that can reduce the height of the upper part of the electrode plate without using the above-mentioned conventional liquid stopper, so that the gas generated by two adjacent battery cells can be exhausted together. Can be provided. In addition, compared to a package exhaust type lead-acid battery that exhausts all gas generated from all battery cells, which is also used for miniaturization, the battery case top cover required for the package exhaust method and the battery case top cover There is no need for heat fusion to the battery case lid, and there is no need to provide the liquid injection port and the liquid stopper separately for each battery cell for replenishing water. Is reduced.
b) The amount of water lost in the electrolyte solution is equal to or less than that of conventional control valve type lead acid batteries, and it is possible to provide a long-lasting lead acid battery for start-up that does not require rehydration at low cost. Especially in Example 3 and Example 4, the service life is significantly extended. Also, if rehydration is necessary, it can be done on-board at any time.
c) Maintenance work such as supplementary charging to prevent battery case deformation is not required during the storage period, and compared with the current situation where this is necessary, the equipment burden and storage cost on the receiving side in product inventory, distribution and storage, especially in import and export. The reduction effect is great.

4) Individual effects on ready-to-use lead-acid batteries with control valves.
Ready-to-use lead-acid batteries are used for starting automobiles, etc., but if the electrolyte is discharged and sealed after the battery is formed, the product is stocked, distributed and stored, and if the electrolyte is injected before use It is a lead-acid battery that can be used. On the other hand, the effect in Example 5 which employ | adopted the structure substantially the same as Example 5 and Example 4 which employ | adopted the structure substantially the same as Example 3 is described below.
a) The same effect as the item a) of the individual effect on the starting lead-acid battery with the control valve is obtained.
b) The same effect as the item b) of the individual effect on the starting lead-acid battery with the control valve is obtained.
c) It has the same effect as the item c) of the individual effect on the starting lead-acid storage battery with the control valve. Furthermore, it is not necessary to separately attach or remove the liquid stopper for immediate use, and the liquid injection work is greatly simplified.

5) Individual effects on control valve type lead acid batteries.
The negative electrode absorption control valve type lead acid battery is used for starting automobiles, etc., but the negative electrode plate absorbs oxygen gas generated from the positive electrode plate during charging by suppressing the amount of electrolyte and partially exposing the electrode plate. Thus, in the sealed lead-acid battery in which the disappearance of moisture is suppressed, the pressurization control valve for releasing the internal gas when the internal gas pressure increases is provided in the liquid injection port. On the other hand, the effect in Example 7 which employ | adopted the structure substantially the same as Example 3 or Example 4 is described below.
a) Since the height above the electrode plate can be lowered without using the liquid stopper, the split exhaust lead-acid battery capable of being miniaturized can be provided. Installation steps such as heat-sealing the control valve pressing lid and the pressing lid to the battery case lid, which have been necessary in the past, become unnecessary, and the cost is reduced. In addition, since the water can be replenished at any time due to the presser lid, the life can be further extended.
b) The same effect as the item b) of the individual effect on the starting lead-acid battery with the control valve is obtained.
c) It has the same effect as the item c) of the individual effect on the starting lead-acid storage battery with the control valve.
d) The reduced pressure injection method has the effect of stabilizing the discharge capacity and improving the life of the lead-acid battery by reducing the variation in formation within the positive and negative electrode plates and between the battery cells.

6) Individual effects on 24V or 36V lead acid batteries.
In 24V and 36V lead acid batteries, the battery cells are arranged in a grid. On the other hand, the effect in Example 8 which employ | adopted the said 4th-9th invention is described below.
a) Compared to the individual exhaust type 24V or 36V lead acid battery, the number of the sealing parts and the sealing part mounting part is greatly reduced, and the part cost (part cost / management cost) and the mounting cost are reduced. The 24V series from 12 sets to 3 sets, 36V series from 18 sets to 5 sets (4 sets common to 4 battery cells and 1 set common to 2 battery cells) or 6 sets (3 sets common to 4 battery cells and 3 sets common to 2 battery cells) ).
b) It has the same effect as various 12V lead acid batteries.

FIG. 3 is an explanatory view showing a first mounting state of the sealed battery of Example 1. The electrolyte is injected through the arrowed path. FIG. 1-3 shows an example when the sealing plug is a metal sheet press product. FIG. 6 is an explanatory view showing a sealing plug holding member caulked to the container lid of Example 1 and a first mounting state of the sealing plug. Gas replacement and liquid injection methods are also described. An imaginary seal plug indicates the second wearing state. It is explanatory drawing which shows the 1st mounting state in the case of providing the sealing stopper holding rib of Example 1 in a sealing stopper. FIGS. 3-3 and 3-4 are explanatory views showing the sealing plug when the double D cut is performed. The electrolytic solution is injected through the path indicated by the arrow. It is explanatory drawing which shows an example of the electric current interruption circuit at the time of abnormal rise of internal pressure at the time of using the sealing stopper of Example 1 also as internal pressure detection components. External appearance explanatory drawing of the 2nd mounting state of the lead acid battery of Example 2, 3, 5, 7. It is explanatory drawing which shows the 1st, 2nd mounting state of the lead livestock battery of Example 2, 3, 5 and 7, It demonstrates also about a liquid injection path | route and a gas discharge | release path | route. 6-1 and 3 are explanatory views (plan view, cross-sectional view) showing the first mounting state, and FIGS. 6-5 and 6 are explanatory views (plan view) showing the second mounting state in which the sealing part is rotated 180 degrees. FIGS. 6-2 and 4 are explanatory views (plan view, cross-sectional view) of the sealing part mounting portion excluding the sealing part, the pressurization control valve, and the explosion-proof filter. External appearance explanatory drawing of the 2nd mounting state of the lead acid battery of Example 4, 6, 7. FIG. It is explanatory drawing which shows the 1st, 2nd mounting state of the lead livestock battery of Example 4, 6, and 7, and demonstrates a liquid injection path | route and a gas discharge | release path | route. FIGS. 8-1 and 3 are explanatory diagrams showing the first mounting state (plan view, cross-sectional view), and FIGS. 8-5 and 6 are explanatory diagrams showing the second mounting state in which the sealing part is rotated 180 degrees (plan view). FIGS. 8-2 and 4 are explanatory views (a plan view and a sectional view) of the sealing part mounting part excluding the sealing part. Exhaust paths and intake paths will also be described with reference to the control valve mounting portions of Examples 2-7. FIGS. 9-1 and 2 are explanatory views of the pressurizing control valve mounting portion, and FIGS. 9-3 are explanatory views of the pressure-reducing control valve mounting portion. The gas discharge path will also be described with reference to the first and second mounting states of the lead-acid battery when the pressurization control valve mounting portion 8j of the second and third embodiments is provided for each battery cell. FIG. 10-1 is an explanatory view showing a first mounting state, FIG. 10-3 is an explanatory view showing a second mounting state in which the sealing part is rotated 180 degrees, and FIG. 10-2 is a sealing part excluding the sealing part. It is explanatory drawing of a mounting part. FIG. 6 is an explanatory diagram showing first and second mounting states of a lead-acid battery when the pressurization control valve mounting portion 8j and the pressure reducing valve mounting portion 8t of Example 4 are provided for each battery cell. Also explained. Fig. 11-1 is an explanatory diagram showing the first mounting state, Fig. 11-3 is an explanatory diagram showing the second mounting state in which the sealing part is rotated 180 degrees, and Fig. 11-2 is the sealing member excluding the sealing parts. It is explanatory drawing of a component mounting part. FIG. 5 is an explanatory diagram when the pressurizing control valve and the micro-groove for continuous ventilation are not provided in the sealing part mounting portion but are provided in the sealing part. It is explanatory drawing at the time of not providing a pressure-reduction control valve in a sealing component mounting part, but providing in a sealing component. FIG. 9 is an external explanatory diagram of first and second mounting states of a 24V lead-acid battery of Example 8.

  Since the specific sealing structure varies depending on the type of electrochemical device, the sealing structure of the present invention will be described below for typical types of electrochemical devices. However, the following description items show typical examples, and are also applied to electrochemical devices such as batteries and capacitors having similar structures, and are not limited to the description examples. In addition, the same reference numerals are used for those having the same function as much as possible.

1) Sealed battery An embodiment for a sealed battery in which the sealing part holding rib adopting the second invention is provided on the sealing part holding member will be described below. The lithium ion battery of a typical electrochemical device whose usage is rapidly expanding has a structure in which the container lid is sealed with the container lid after being injected into the container body, but is provided on the sealing component holding member. An example of a liquid inlet sealing structure in which liquid is injected from the liquid inlet is first described, and then a method of sealing in a gas replacement or reduced pressure state when sealing with the container lid is described. The configuration and operation of each component are as follows. (See Figures 1-4)

a) The lid for a container having a positive and negative electrode plate and a separator built in a metal container body which also serves as an electrode, and the other electrode, except for a conventional liquid-injection sealing structure of a lithium ion battery It is sealed with. The positive / negative electrode plate and the positive / negative electrode are electrically connected before sealing. The electrolyte is injected from a liquid inlet provided in the sealing part holding member of the container lid, and the liquid inlet is then sealed. In this example, only the liquid inlet sealing structure related to the container lid will be described in detail.
b) The injection passage 21 is provided in either the sealing plug (sealing part) holding member caulked to the container lid 1 for sealing the aluminum container or the external terminal, but the external terminal is held by the sealing plug. It is of course more advantageous in terms of cost to use it as a structural component. The container lid 1 may be molded as necessary to be used as a sealing plug holding member. The sealing plug holding member 2 also serving as an external terminal is between the sealing plug (sealing part) holding rib 2f and the sealing plug holding rib 2f that hold the sealing plug 3 in the head 2a and the central shaft hole 2e serving as the external terminals. Sealing plug (sealing part) holding part 2b with passage 2g on the inside of the container of sealing plug holding part 2b is continuously provided on the same axis, and sealed by press-fitting sealing plug (sealing part) 3 after pouring A sealing passage portion 2c having a sealing hole 2h and a thin portion 2j for caulking. A recess 2d for preventing overflow at the time of liquid injection is provided at the inlet of the liquid inlet of the sealing plug holder 2b. The portion inside the container of the sealing hole 2h of the sealing passage portion 2c is a conical hole 2i having a large diameter on the inner side of the container, and the sealing plug is pulled out to the outer side of the container with a smaller pressure input than in the case of the straight hole. Increases resistance to If the sealing plug 3 is provided with a large-diameter head, the sealing passage portion 2c can be provided in the overflow preventing recess 2d.
c) The sealing plug 3 is a columnar body made of an elastic body such as a synthetic rubber, a thermoplastic elastomer or a synthetic resin, or a soft metal such as aluminum, or a metal thin plate press, and having a recess 3a opened only on the inner side of the container. The sealing plug holding member 2 is put into the production line while being held by the sealing plug holding rib 2f. You may purchase in this unitized state. The surface may be coated with anticorrosion or lubrication.
d) The sealing plug holding member 2 holding the sealing plug 3 is caulked and attached to the aluminum sealing lid 1 together with the insulating materials 4 a and 4 b and the inner terminal 5. Further, the container lid 1 to which the power generation elements and the like are connected is laser welded to the aluminum container. Next, through the electrolyte pouring described below, the sealing plug 3 is press-fitted from the sealing plug holding portion 2b into the sealing passage portion 2c. When the internal pressure of the battery rises, the sealing plug 3 is retained even by frictional force and deformation resistance, but by the frictional force due to the pressure on the sealing hole 2h and / or the conical hole 2i due to the pressure acting on the inner surface of the recess 3a. Is also retained.
e) As for the injection, the gas replacement nozzle 6 equipped with the elastic tip 6a made of synthetic rubber is pressed and sealed against the container lid 1, and after the pressure inside the battery is reduced, the liquid is injected from the injection nozzle 7 and then injected. The liquid injection nozzle 7 is replaced with nitrogen gas or opened to atmospheric pressure. This improves the electrical performance by easily and reliably discharging air and air bubbles in the voids of the power generation / storage element such as the electrode plate and separator in the battery and replacing it with nitrogen gas. In addition, even high-viscosity electrolytes can be easily injected, and internal osmotic diffusion is also uniformly promoted, which not only improves productivity but also eliminates variations in electrode plate formation, stabilizes battery performance, and provides a long service life. Improved.
f) The sealing is performed by pressing the sealing plug 3 into the sealing passage 2c after the pressure is reduced to a predetermined pressure in the next stage. The vacuum sealing may be continuously performed after the injection. When the decompression seal is performed at an appropriate pressure, pressure is applied to the electrode plate and the separator via the container due to atmospheric pressure, so that the electrode active material during use is reduced and mechanical strength and electrical performance are improved. In addition, there is an effect such as lowering of locally raised temperature due to increased heat dissipation of internally generated heat to the battery surface. In addition, after performing the charging process in the open state after the injection, the sealing may be performed in the same manner as described above with nitrogen gas replacement, nitrogen gas replacement state or reduced pressure state. As a result, the gas and bubbles generated by the charging process are discharged and the performance becomes more stable. The gas replacement nozzle 6 may be pressed and sealed not on the container lid 1 but on the battery mounting surface of the production facility, so that the inside and outside of the battery are replaced with gas simultaneously. In order to secure the sealing, an elastic material for sealing such as an O-ring or packing is attached or coated on the sealing portion of the sealing plug holding member 2 or the sealing plug 3. When the sealing plug 3 is completely fixed, an adhesive or the like may be injected onto the sealing plug 3 after press-fitting.
g) The above is a method in the case of pouring from the liquid filling port, but when the container is sealed with the container lid 1 after pouring into the container, the container is provided with an external terminal also serving as a sealing plug holding member 2 After sealing with the lid 1, the sealing is performed in a gas-replaced or depressurized state as described above. Thus, even in an existing production line that seals with a container lid or the like, if the external terminal is also used as a member for holding a sealing plug, sealing in a nitrogen gas replacement state or a reduced pressure state is facilitated by a simple facility modification.
h) When the sealing plug holding rib 3f is provided on the sealing plug 3 side, the structure shown in FIG. Further, as shown in FIGS. 3-3 and 3-4, the sealing plug holding rib 3f is not provided, and a double D-cut shape may be used.
If the sealing plug 3 is provided with a head having a diameter larger than that of the sealing plug holding rib 3f, the sealing passage 2c can be provided in the overflow preventing recess 2d.
i) If the external terminal of the container lid 1 is also used as a member for holding the sealing plug, and the resistance of the sealing plug 3 to the outside of the container is set to be less than the bursting strength of the container, the gas release against the abnormal increase in internal pressure Can be used as a safety valve.
j) If the sealing plug 3 is used as an internal pressure detecting component that operates when the internal pressure of the battery rises abnormally, it is possible to easily attach a current interruption circuit during abnormal rise. An example shown in FIG. 4 will be described below. The connecting pin 55 fixed to the movable contact spring plate 52 provided with the movable contact 52a is pressed by the sealing plug 3, and the movable contact 52a and the fixed contact 53a are brought into contact to constitute an energization circuit. If the internal pressure rises abnormally and the sealing plug 3 moves to the outside of the battery, the contact portion is opened and the current is cut off.

2) Lead-acid storage battery with control valve (1)
Examples of the lead-acid battery for starting with the control valve adopting the fourth to seventh inventions will be described below. In the conventional lead-acid battery for control valve type starting, the amount of electrolyte is suppressed, and the injection port is provided in each battery cell, and each is sealed with a pressure control valve or a liquid stopper with a pressure control valve. In the example, a liquid type lead storage battery having a sufficient amount of electrolytic solution is used except for the liquid inlet sealing structure, and the sealing part mounting portion common to the two adjacent battery cells is used for two adjacent battery cells. An electrolyte solution injection passage (injection port) for each battery cell, an exhaust chamber for each battery cell for condensing and condensing moisture in the gas generated in the battery cell, and The common external vent hole having the micro-ventilation passage for continuous ventilation and having the pressurization control valve attached thereto is provided. The common sealing part has a cap shape and is provided with a liquid injection port for each battery cell and the common gas discharge port.
The configuration and operation of each component are as follows. (See FIGS. 5, 6, and 9)

a) Except for the injection hole sealing structure of this example, the conventional liquid type lead storage battery for start-up was used, and the positive / negative electrode plate and separator were built in the monoblock battery case of 6 battery cells. The battery case lid is heat-sealed to form external terminals. The positive and negative electrode plates and the positive and negative external terminals are electrically connected before heat-sealing the battery case lid. In this example, only the liquid inlet sealing structure related to the battery case lid will be described in detail.
b) The sealing part mounting portion 8a is integrally formed with the battery case lid 8 made of synthetic resin. The sealing part mounting portion 8a has a slightly conical disk shape having a center on the battery cell partition wall 8b, and has a pilot hole 8c for the tapping screw 11 at the center of the upper surface. Inside is a continuous exhaust chamber 8d divided by a liquid injection port 8h and an exhaust chamber partition wall 8e for each battery cell, and a columnar portion 8g for sealing the liquid injection port 10h of the sealing part 10 in the second mounted state, and on the bottom surface. The gas inlet 8f is provided on the battery cell partition wall 8b with a pressure control valve mounting portion 8j common to the battery cells. The shape of the gas inlet 8f is preferably a rectangle of 1 to 3 mm × 2 to 4 mm. The upper end surface of the exhaust chamber partition wall 8e that comes into contact with the inner surface of the sealing part 10 has a U-shaped shape with a minimal contact area in order to avoid sticking. A narrow vertical groove 8i for exhaust throttling is provided between the exhaust chamber 8d of each battery cell and the pressure control valve mounting portion 8j. Moisture / electrolyte mist in the generated gas is mostly condensed and condensed in the exhaust chamber 8d until it reaches the narrow vertical groove 8i for exhaust throttling, and then recirculates into the battery cell. However, the gas generated in each battery cell is prevented from flowing directly into the adjacent battery cell as much as possible by the narrow vertical groove 8i for exhaust throttling. The pressurizing control valve mounting portion 8j is provided with a columnar projection 8k having a conical sealing surface 8m at the center and a vertical groove 8p for ventilation at the periphery. Two to three micro-grooves 8n for ventilation are always provided on the sealing surface 8m. The dimensions of the constant ventilation micro-groove 8n are about 1 mm in height and about 0.4 mm in width. The bottom surface of the exhaust chamber 8d is formed so that the bottom surface of the exhaust chamber having the gas inlet 8f is sequentially raised to the lowest position so that the condensed moisture and electrolyte are recirculated into the battery cell from the gas inlet 8f. A lower cylindrical portion 8q is provided below the gas inlet 8f to make it difficult for electrolyte or droplets to flow directly into the gas inlet 8f. Is provided with a narrow ventilation slit 8s. The discharge path 8r changes the cross section of the path to make it difficult for the electrolyte to flow directly into the exhaust chamber 8d. Instead of the discharge path 8r, a splash-proof body that is mounted inside the conventional liquid stopper may be mounted inside the lower cylindrical portion 8q.
c) Pressurize and pressurize the pressurization control valve 13 that opens at 5 to 15 kPa into the pressurization control valve mounting portion 8j and the explosion-proof filter 12 into the cylindrical portion 13a of the pressurization control valve 13. The pressurization control valve 13 is made of an elastic body such as synthetic rubber, thermoplastic elastomer, or synthetic resin, and includes a cylindrical portion 13a and a thin valve 13b, and has a gas discharge port 13c at the center of the thin valve 13b. The pressurization control valve 13 and the explosion-proof filter 12 are not only held by press-fitting, but also pressed by the head portion 10a of the sealing part 10 so as not to fall off. In addition, either the pressurization control valve 13 or the explosion-proof filter 12 is pressed against the inner surface of the head 10a in an airtight manner. If there is a concern about sticking of the sealing surface of the thin valve 13b, it is better to apply a sealing agent such as silicone oil or grease to the sealing surface. Alternatively, a coating such as a fluorine resin may be applied.
d) The cap-shaped sealing part 10 that also serves as the emergency gas release valve is made of an elastic body such as synthetic rubber, thermoplastic elastomer, or synthetic resin, and includes a head 10a and thin ribs 10b on the outer periphery. The head 10a is provided with a hexagonal head 10d for rotation and a mounting hole 10c for the tapping screw 11 at the center, and two liquid injection ports 10h and the common gas discharge port 10j at the outer periphery. The valve opening pressure of the sealing component 10 is set to a pressure that does not crack the battery case, for example, 25 to 35 kPa. The sealing part 10 is airtightly detachably fitted to the sealing part mounting part 8a of the battery case lid 8 on which the pressurization control valve 13 and the explosion-proof filter 12 are mounted, and can be rotated by a tapping screw 11. Fix it. Instead of using the tapping screw 11, a press-fitting pin with a flange may be press-fitted. In order to improve the sealing performance and reduce the rotational resistance during sealing, a lubricating sealant such as silicon oil or grease is applied at least to the inner surface of the thin rib 10b. Or you may coat fluororesin etc.
e) The battery case lid 8 fitted with the sealing part 10 is heat-sealed to the battery case in which the positive and negative electrode plates and the separator are incorporated, and can be injected from the injection port 10h. It is better to purchase and store the battery case lid 8 with the sealing part 10 in the first mounted state and put it into the production line. In this case, if the gas outlets 10j3 are sealed with a continuous adhesive tape, they will be easily peeled off during the sealing process, and dust will not accumulate on the explosion-proof filter 12 during storage. It is not polluted by electrolytes in chemical conversion processes. If the sealing part 10 is not installed in the production line, the pressurization control valve 13 and the explosion-proof filter 12 can be purchased and stored in the battery case cover, or before the sealing part 10 is installed. It is better to purchase and store the battery while it is attached to the battery case lid. If it is purchased without mounting the sealing part 10, there is an advantage that the sealing part 10 is not contaminated with the electrolytic solution in the process of injecting electrolyte or forming a battery case. There is a disadvantage that installation and management of the equipment is necessary and the supply work of the sealing parts 10 and the like is also necessary.
f) The generated gas during the formation of the battery case is directly discharged to the outside from the liquid injection port 10h for each battery cell. Next, if necessary, after adjusting the concentration and amount of the electrolytic solution, the sealing component 10 is half-turned and sealed. The sealing part 10 is held by the friction force between the thin rib 10b and the outer peripheral wall of the sealing part mounting part 8a and the tapping screw 11, the liquid injection port 10h is sealed by the columnar part 8g, and the gas discharge port 10j is an explosion-proof filter. -Located above 12
g) The internally generated gas (water electrolysis gas / water vapor / electrolyte mist) flows from the stepped discharge path 8r of the lower cylindrical portion 8q through the gas inlet 8f to the exhaust chamber 8d. Moisture / electrolyte condensed / condensed in the exhaust chamber 8d flows back into each battery cell from the gas inlet 8f, and the others are pressurized from the gas exhaust vertical groove 8p via the narrow exhaust vertical groove 8i. Pour into the valve mounting part 8j. If the amount of gas is small, such as during self-discharge, it passes through the gas vent 13c of the pressurization control valve 13 and the explosion-proof filter 12 through the micro-groove 8n for continuous ventilation on the sealing surface 8m, and from the gas outlet 10j to the outside of the battery. To be released.
h) The gas discharge path shown in FIG. 6 is an example and is not limited to this. However, if it is necessary to invert the lead battery and discharge the electrolyte from the injection port 8h, the injection port It is necessary to arrange 8h and gas inlet 8f as far apart as possible in the width direction of the lead-acid battery so that the electrolyte does not flow into gas inlet 8f. In addition, the external terminals are also arranged so that they are at the top when they are reversed so that they are not contaminated by the electrolyte. Similarly, the gas discharge port 10j is arranged so as to be on the upper side or sealed with a continuous tape as described above.
i) When a large amount of gas is generated due to large current charging, etc., and the internal pressure rises above the opening pressure of the pressurization control valve 13, the thin valve 10b is deformed outward and a gap is formed between the sealing surface 8m. Internal gas is also released from the section. This gas discharge method can provide a split exhaust type lead-acid battery that can be downsized because the height above the electrode plate can be made lower than the conventional liquid stopper mounting method. In addition, it is not necessary to heat seal the top cover or top cover to the battery case cover, which is necessary for the package exhaust type lead-acid battery adopted for miniaturization, and it is necessary to provide a liquid injection port and a sealing plug for each battery cell. In addition, the necessary part cost, mold cost, and mounting cost are reduced.
j) As described in the above-mentioned “Patent Document 6 Japanese Unexamined Patent Application Publication No. 2008-146895 Lead Acid Battery”, the lead-acid battery is always slightly opened to the outside by the micro-groove 8n for constant ventilation, and the internal pressure of which battery cell Since it converges to atmospheric pressure, no differential pressure is generated between the battery cells. For this reason, pressure that causes plastic deformation is not constantly applied to the outer wall of the battery case or the battery cell partition wall. Therefore, at any stage during product inventory, distribution, storage, or use, pressurization / decompression of the outer wall of the battery case and the battery cell partition is suppressed, and various problems due to plastic deformation of the battery case and electrolyte leakage due to cracks Is prevented. As a result, the battery case can be made of an inexpensive material and the thickness can be reduced, which is effective in reducing the weight and cost of the lead-acid battery.
k) When the internal pressure abnormally rises above the valve opening pressure of the sealing component 10 during use of the battery due to an internal short circuit or the like, the head 10a of the sealing component 10 and the thin rib 10b on the outer peripheral portion are deformed. As a result, the gas flows into the sealing part mounting part 8a on the adjacent battery cell side, and the internal gas is released from the gap formed between the sealing part mounting part 8a and the outer peripheral wall of the sealing part mounting part 8a and the liquid injection port 10h. In this case, it is not necessary to consider the continued use of lead-acid batteries, and it is only necessary to prevent leakage and scattering of the electrolyte due to cracking or rupture of the battery case. However, unlike conventional cap-shaped small explosion-proof valves, Therefore, even if there is some sticking of the sealing valve, it operates reliably and there is little change in the valve opening pressure. The thin rib 10b may be provided with a partial thin wall portion or a small notch so that the thin rib 10b is reliably expanded or broken. Since the sealing component 10 is held by the tapping screw 11 and the positional relationship with the sealing component mounting portion 8a does not change, it does not drop off after the operation and returns to the original mounting state.
l) Although there is very slight ventilation due to the always fine ventilation groove 8n, the loss of water in the electrolyte due to the attachment of the pressurization control valve 13 is described in the above-mentioned “Patent Document 6 Japanese Patent Application Laid-Open No. 2008-146895 Lead Acid Battery”. As a result, the lead-acid battery usually has a long service life.However, if the sealing part 10 is rotated halfway, it can be refilled without removing the sealing part 10 at any time. Water can be replenished with the lead-acid battery mounted on the vehicle body.
m) If the continuous sheet 15 common to the gas outlet 10j is attached as shown in FIG. 5, the influence of the air current around the lead storage battery is eliminated, the amount of water loss is reduced, and the dust inside the gas outlet 10i is reduced. There is no sinking. In order to secure a gas discharge route, the adhesive on the continuous sheet is limited to the shaded area.
n) The above is the case where the pressure adjusting valve 13 is shared, but as shown in FIG. 10, the inside of the sealing part mounting portion 8a is separated for each battery cell, and the pressure adjusting valve mounting portion 8j is connected to the battery cell. May be provided for each. In this case, the gas discharge port 10i of the sealing part 10 is also used as the liquid injection port 10h. The lead storage battery for start-up is often installed in the engine room where the temperature is high, and the temperature of the battery cells at both ends becomes higher, and the moisture evaporation of the electrolyte solution tends to increase more than the inner battery cells. Therefore, when the pressurization regulating valve 13 common to the battery cell at the end and the battery cell at the inside is used, depending on the use conditions, even if there is a narrow vertical groove 8i for exhaust throttle, There is a possibility that gas containing moisture will flow into the battery cell unilaterally, and the electrolyte in the inner battery cell will increase and overflow due to long-term use. For this, use this structure that separates the inside of the sealing part mounting part 8a for each battery cell, and the opening pressure of the pressure regulating valve 13 is made higher than the inner battery cell. Is preferable, and the thickness of the battery cell partition is also increased.
o) According to the tenth aspect of the present invention, the pressure adjusting valve 13 and the constant ventilation micro groove 8n may be provided in the sealing component 10 without being provided in the sealing component mounting portion 8a. In order to provide the functions of the pressurization regulating valve 13 and the constant ventilation micro groove 8n inside the sealing part head 10a, the following structure is adopted. Sealing part A pressure adjusting valve shaft mounting portion 10k for mounting the pressure adjusting valve shaft 16 on the head 10a is provided. The pressure adjusting valve shaft mounting portion 10k includes a disk-shaped recess 10l on both upper and lower end surfaces of the sealing part head 10a, and a thin valve 10n integrally formed with the sealing part 10 between the recesses 10l. A through hole 10m having a diameter larger than that of the central shaft 16b is provided at the center of 10n. The thin valve 10n is pressed against the sealing surface of the flange portion 16a. The thin-walled valve 10n may be a ring-shaped thin-walled valve that is not integrally molded with the sealing part 10, and may be airtightly attached to the pressure regulating valve shaft attaching portion 10k. The pressure regulating valve shaft 16 is composed of a flange portion 16a and a central shaft 16b. The ring-shaped explosion-proof filter 12 is fixed to the center shaft 16b so that the flange portion 16a is airtightly attached to the pressure adjusting valve shaft attachment portion 10k. Also, a ring-shaped groove 16d is formed on the outer periphery of the sealing surface of the flange portion 16a with the thin valve 10n, a plurality of constant ventilation microgrooves 16n are formed on a part of the sealing surface, and the ring-shaped groove 16d and the exhaust chamber 8d. Make a ventilation hole 16e to connect the. The ventilation hole 16e is arranged so that gas flows through the exhaust throttle narrow vertical groove 8i. The material of the pressure regulating valve shaft 16 is a non-conductive material such as a synthetic resin in order to prevent ignition and explosion of the sealing valve mounting portion 8a due to external spark. The thin valve 10n is hermetically pressed against the flange portion 16a when the pressure of the sealing part mounting portion 8a is reduced, and is deformed outward when pressurized. As a result, the internally generated gas exceeding the on-off valve pressure is externally passed through the ventilation hole 16e through the ring groove 16d, the gap between the thin valve 10n and the flange 16a, the through hole 10m, and the ring explosion-proof filter 12. Is discharged. This structure simplifies the shape of the sealing part mounting part 8a, reduces the cost of the molding die, and secures a larger area of the exhaust chamber 8d, thereby improving the condensation / condensation capacity and eliminating water in the electrolyte. The amount is reduced. (See Figure 12)
p) If the liquid injection port 10h is not provided in the sealing component 10 in the configuration of the fourth invention, the first mounting state and the second mounting state cannot be selectively maintained, and the sealing component 10 is mounted. Sealing is synonymous, and there is no common effect of reducing the total cost by optimizing the cost allocation mentioned above, and there is no individual effect of water replenishment without removing the sealing part 10, but all other effects are possible. In this case, the columnar portion 8g for sealing the liquid injection port 10h is naturally unnecessary. In addition, since the shape of the sealing part mounting portion 8a can be a rectangle that does not consider the rotation of the sealing part 10, it is possible to improve the condensation / condensation capability by expanding the area of the exhaust chamber 8d.

3) Lead-acid storage battery with control valve (2)
Embodiments for a liquid-type lead-acid storage battery with a control valve adopting the above fourth, fifth, sixth, eighth, and ninth inventions that do not have a micro-ventilation passage that can be continuously ventilated are described below. . Since the present embodiment is the sealing structure of the second embodiment except that there is no micro-groove 8n for constant ventilation and the battery cell partition wall 8b is partially different, the description of the same configuration part is omitted, and the different configuration part. Only listed. (See FIGS. 5, 6, and 9)

In the present embodiment, since there is no always fine ventilation groove 8n, the battery cell is sealed for each pressurization control valve 13. For this reason, as described below, there are advantages in that the lead-acid battery has a longer life and disadvantages that the battery case is easily deformed, and the measures described below are taken in the disadvantages.
a) The advantage is that the battery cell is sealed with a pressurization control valve, so that not only the electrolyte can be reduced, but the life can be extended. It will operate as a lead storage battery, and as shown in the above-mentioned “Patent Document 3, Japanese Patent Application Laid-Open No. 2003-142148, lead storage battery”, the life is significantly extended. The lead storage battery of this embodiment having an exhaust chamber for condensation / condensation of the electrolyte has a longer life because the electrolyte is reduced more than the lead storage battery of Patent Document 3 that does not have the exhaust chamber.
b) The first disadvantage is that it cannot cope with the internal decompression that occurs during the storage period, and the battery case is deformed or cracked as described in “Patent Document 5 Patent 4224762 Controlled lead-acid battery”. There is a risk of leakage of electrolyte and performance (discharge capacity / lifetime). In the lead-acid battery after the formation of the battery case, if the partial pressure of water vapor, electrolyte mist, and oxygen gas / hydrogen gas generated in the positive and negative electrode plates is high, sealing (sealing) in this state will result in oxygen gas being stored during the storage period. Absorbed by the negative electrode, hydrogen gas passes through the battery case and is released to the outside, and water vapor and electrolyte mist are condensed. Therefore, the pressure inside the lead-acid battery is reduced during the storage period, which may cause cracking and electrolyte leakage due to creep deformation of the battery case, and performance deterioration due to irreversible deformation of the separator due to battery cell partition deformation. As a countermeasure, the space inside the lead-acid battery is replaced with nitrogen gas before sealing (sealing) to prevent decompression during storage. In the case of the present embodiment, the injection port 10h having a sufficient diameter, which is not equipped with a control valve, is open to each battery cell, so that a sufficient level of nitrogen gas can be obtained by inserting a nitrogen gas nozzle here. Replacement is easy. Thereafter, the sealing part 10 is sealed by half-turning. The nozzle opens to the side of the tip and blows nitrogen gas to the side and does not spray it directly onto the electrolyte.
c) The second disadvantage is that the internal pressure does not converge to the atmospheric pressure, and the differential pressure due to the variation in the switching pressure between the pressure control valves 13 is generated between the battery cells where the sealing parts 10 are not common, and continues. . Although this differential pressure is small, the pressure receiving area is large, so if the group pressure is not applied to the electrode plate group and the battery case case partition wall is not supported by the electrode plate group, the partition wall may be greatly deformed to one side. If the partition wall is deformed greatly, the electrolyte cell level will be higher and the other will be lower due to the volume change of the battery cell, and there is a risk of electrolyte overflow or strap corrosion. For this, the measures according to the eighth and / or the ninth invention are implemented.
d) According to the eighth invention, cost reduction and weight reduction are achieved while preventing the above problems. In addition, a plurality of narrow thin vertical grooves are provided on both surfaces of the partition between battery cells where the pressurization regulating valve 13 is not common, so that an electrolyte passage can be secured even if the partition and the electrode plate are in close contact with each other. It is better to
e) As with the eighth aspect of the invention, the ninth aspect of the invention is intended to reduce costs and reduce weight while preventing the above-described problems. The measures according to the eighth and ninth inventions may be implemented in parallel. The area of the micro vent is preferably 10% or less of the area of the gas inlet 8f. The minute vent is for converging the pressure of adjacent battery cells to the same pressure, and most of the gas generated in the high-pressure battery cell flows into its own exhaust chamber 8d to condense and condense it with moisture. Reflux the electrolyte. Since all the battery cells communicate with each other through the sealing valve 10 and the minute vent, they finally converge to the same pressure. When the area of the micro vent is increased, a large amount of generated gas flows directly from the battery cell on the high-pressure side to the low-pressure side. An imbalance occurs and must be avoided. This method has the advantage that there is no need to change the specifications of the battery case, only the specifications of the battery case cover are changed, and there is no need for new mold costs.
f) As described above, at any stage of product inventory, distribution, storage, or use, the lead-acid storage battery with a control valve that suppresses the deformation of the outer wall of the battery case and the battery cell partition wall becomes a plastic deformation of the battery case. Electrolytic leakage due to various defects and cracks is prevented. As a result, the battery case can be made of an inexpensive material and the wall thickness can be reduced, which is effective in reducing the weight and cost of lead-acid batteries. In addition, the maintenance work required during storage, which was previously required for a start-up lead-acid battery with a control valve type or control valve, is no longer necessary, and the equipment burden and storage cost on the receiving side in inventory / distribution / storage of products, especially import / export. Greatly effective in reducing In addition, the starting lead-acid battery of this example is a starting lead-acid battery with a control valve whose life is significantly extended from that of Example 2 at substantially the same cost as that of Example 2. Moreover, this structure is applicable also to lead acid batteries other than the starting lead acid battery.
g) The above is the case where the pressure adjusting valve 13 is the same as the above, but as in the second embodiment, the inside of the sealing valve mounting portion 8a is separated for each battery cell, and the pressure adjusting valve mounting portion 8j is set for each battery cell. May be provided. In this case, since each battery cell is hermetically sealed, it is better to provide the micro vent in the battery cell partition wall. (See Figure 10)
h) In the configuration of the fourth aspect of the invention, the case where the sealing member 10 is not provided with the liquid injection port 10h is the same as that of the second embodiment.

4) Lead-acid storage battery with control valve (3)
Embodiments for liquid start lead-acid storage batteries with control valves adopting the fourth, fifth, sixth, eighth and ninth inventions will be described below. The present embodiment is almost the same as the sealing structure of the third embodiment, but there are two control valve mounting portions common to the battery cells, and the pressurization control valve and the pressure reduction control valve are mounted. Further, in the second mounting state, the liquid injection port 10h is located above the control valve mounting portion and also serves as a gas discharge port, so that the common gas discharge port 10j is not provided. Moreover, nitrogen gas substitution after battery case formation is not performed. (See Figures 7-9)
The configuration and operation of each component are as follows. In the same manner as in the third embodiment, the description is simplified or omitted.

a) Except for the injection hole sealing structure of this example, the conventional lead-acid storage battery for start-up described above is used, and a positive / negative electrode plate and a separator are built into a 6-cell monoblock synthetic resin battery case. The tank lid is heat-sealed to form external terminals. Also in this example, only the injection port sealing structure related to the battery case lid will be described in detail.
b) As shown in FIG. 8, the sealing component mounting portion 8a has two control valve mounting portions, a pressurization control valve mounting portion 8j and a pressure reduction control valve mounting portion 8t, and a liquid injection port 8h and a control valve mounting portion 8j. , 8t is substantially the same as the third embodiment except that the positional relationship with the rotation is a position corresponding to the rotation. However, there is no columnar portion 8g for sealing, and the pressure control valve mounting portion 8j is not always provided with the ventilation groove 8n.
c) The pressurization control valve 13 in which the explosion-proof filter 12 is press-fitted in an airtight manner is press-fitted in the pressurization control valve mounting portion 8j, and the pressure-reduction control valve 14 is press-fitted in the pressure-reduction control valve mounting portion 8t in an airtight manner. The on-off valve pressure is 5-15 kPa from atmospheric pressure. The decompression control valve 14 is also made of an elastic body such as synthetic rubber, thermoplastic elastomer, or synthetic resin, and includes a cylindrical portion 14a and a cylindrical valve 14b. A gas discharge port 14c is formed at the center of the cylindrical valve 14b. Have. If there is a concern about sticking of the sealing surface of the cylindrical valve 14b, it is better to apply a sealing agent such as silicone oil or grease to the sealing surface. Or you may coat with fluororesin.
d) The cap-shaped sealing part 10 is the same as that of Example 3 except that the liquid injection port 10h also serves as a ventilation port and therefore there is no gas discharge port 10j.
e) The liquid injection method, the formation of the battery case, the adjustment of the concentration and the amount of the electrolyte when necessary, and the sealing method are the same as in Example 3 except that the nitrogen gas replacement after the formation of the battery case is not performed. However, in the second mounting state, the liquid injection port 10h is located above the pressurizing control valve mounting portion 8j and the pressure reducing control valve mounting portion 8t.
f) As described above, the internally generated gas is discharged to the outside from the injection port 10h of the pressurization control valve mounting portion 8j, and the cylindrical valve 14b of the pressure reduction control valve 14 expands from the injection port 10h for internal decompression. Since the external air is sucked through the intake port 14c, the battery case is not plastically deformed by pressurization / decompression.
g) For the differential pressure due to the variation in the opening / closing pressure of the pressure regulating valve, the measures according to the eighth and / or ninth invention are implemented as in the third embodiment.
h) As described above, the effect of the present embodiment is the same as that of the third embodiment.
i) If a common continuous sheet 15 is affixed to the injection port 10h as shown in FIG. 7, the effect of the air current around the battery is eliminated, the amount of water lost is reduced, and the amount of dust in the injection port 10h is reduced. There will be no sedimentation. In order to secure the ventilation path, the adhesive to the continuous sheet is only the hatched portion.
j) The above is the case where the pressure adjusting valve 13 and the pressure reducing valve 14 are the same, but the inside of the sealing part mounting portion 8a as in the third embodiment is separated for each battery cell to adjust the pressure. A valve mounting portion 8j and a pressure reducing valve mounting portion 8t may be provided for each battery cell. In this case, since each battery cell is hermetically sealed, it is better to provide the micro vent in the battery cell partition wall. (See Figure 11)
k) By adopting the tenth aspect of the present invention, the pressurizing regulating valve 13 and the pressure reducing regulating valve 14 can be provided in the sealing component 10 without being provided in the sealing component mounting portion 8a. In order to provide the function of the pressure reducing control valve 14 inside the sealing part head 10a, the following structure is adopted. The pressurizing adjustment valve 13 is the same as that in the first embodiment. A pressure adjusting valve shaft mounting portion 10k for mounting the pressure adjusting valve shaft 16 is provided on the sealing component head portion 10a. The pressure adjusting valve shaft mounting portion 10k includes a disk-shaped recess 10l on both upper and lower end surfaces of the sealing component head 10a, and a thin valve 10n integrally formed with the sealing component 10 between the recesses 101. A through hole 10m having a diameter larger than that of the pressure adjusting valve center shaft 16b is provided at the center of 10n. The thin valve 10n is pressed against the sealing surface of the flange portion 16a. The thin-walled valve 10n may be a ring-shaped thin-walled valve that is not integrally molded with the sealing part 10, and may be mounted airtight on the pressure adjusting valve shaft mounting portion 10k. The pressure regulating valve shaft 16 is composed of a flange portion 16a, a central shaft 16b, and a ring portion 16c. The ring portion 16c has a central shaft 16b so that the pressure regulating valve shaft 16 is airtightly mounted on the pressure regulating valve shaft mounting portion 10k. It is fixed to. The flange portion 16a is provided with a ventilation notch portion 16f, and the central shaft 16b is provided with a ventilation vertical groove 16g. A ventilation hole 16e may be provided in the ring portion 16c instead of the ventilation vertical groove 16g. The ventilation vertical groove 16g or the ventilation hole 16e is arranged so that external air flows into the exhaust chamber 8d through the exhaust throttle narrow vertical groove 8i. When the ring part 16c is the explosion-proof filter 12, neither the ventilation vertical groove 16g nor the ventilation hole 16e is provided. The material of the pressure regulating valve shaft 16 is a non-conductive material such as a synthetic resin in order to prevent ignition and explosion of the sealing valve mounting portion 8a due to external spark. The thin valve 10n is hermetically pressed by the flange 16a when the pressure of the sealing part mounting portion 8a is higher than the atmospheric pressure, and is deformed inward when the pressure is reduced, so that the gap between the thin valve 10n and the flange 16a is less than the ventilation notch 16f. The air is sucked in from the outside through the through hole 10m and the vertical groove 16g for ventilation. Similar to the case where the pressurizing regulating valve 13 is provided in the sealing part 10, this structure simplifies the shape of the sealing part mounting portion 8a, reduces the molding die cost, and increases the area of the exhaust chamber 8d. Since it can be secured, the condensation / condensation capacity is improved, and the amount of water lost in the electrolyte is reduced. (See Figure 13)
l) The case where the sealing part 10 is not provided with the liquid injection port 10h in the configuration of the fourth invention is the same as in Example 3. However, a gas discharge port is provided at a position corresponding to the pressurization control valve mounting portion 8j of the sealing component 10, and an air suction port is provided at a position corresponding to the pressure reduction control valve mounting portion 8t.
In addition, the structure of a present Example is applicable not only to the start lead acid battery with a control valve but to other control valve type lead acid batteries, and has the same effect.

5) Ready-to-use lead acid battery with control valve (1)
An example of a liquid type lead acid storage battery with a control valve that employs the sealing structure of Example 3 will be described below. The present embodiment has a sealing structure similar to that of the third embodiment, but the manufacturing process, distribution, and storage method are partially different. In the case similar to the third embodiment, the description is simplified or omitted. (See FIGS. 5, 6, and 9)

a) The production process up to the formation of the battery case is the same as in Example 3. After the formation of the battery case, the electrolytic solution is discharged from the injection port, and after the replacement with nitrogen gas, the sealing part 10 is sealed by half rotation. Product inventory, distribution, and storage are performed in this state, and the sealing part 10 is opened by half-turning before use, and a predetermined electrolytic solution is injected and then half-turned again to make a finished product. This eliminates the need for maintenance work during storage to prevent battery case deformation, which was necessary in the past, and also eliminates the need to attach or remove a liquid stopper separately, which greatly simplifies the liquid injection work before use. The
b) Responding to changes in internal pressure during product inventory, distribution, storage, and use, including the effect of extending the life of lead-acid batteries, and the effect are the same as in Example 3.
c) The same applies to the continuous sheet 15 common to the gas discharge port 10j.
d) As in Example 3, the inside of the sealing component mounting portion 8a may be separated for each battery cell. (See Fig. 10)
e) When the pressurizing regulating valve 13 and the like are provided in the sealing part 10, the same as in the third embodiment.
f) The case where the sealing part 10 is not provided with the liquid injection port 10h in the configuration of the fourth invention is the same as in Example 3.

5) Ready-to-use lead acid battery with control valve (2)
An example of a liquid type lead acid storage battery with a control valve that employs the sealing structure of Example 4 will be described below. The present embodiment has a sealing structure similar to that of the fourth embodiment, but the manufacturing process, distribution, and storage method are partially different. In the case similar to the fourth embodiment, the description is simplified or omitted. (See Figures 7-9)

a) The manufacturing process up to the formation of the battery case is the same as in Example 4. Example 4 is the same as Example 4 except that the nitrogen gas replacement is not performed after the formation of the battery case.
b) Responding to changes in internal pressure during product inventory, distribution, storage, and use, including the effect of extending the life of lead-acid batteries, and the effect are the same as in Example 4.
c) The continuous sheet 15 common to the liquid injection port 10h is the same as in Example 4.
d) The case where the pressurizing regulating valve 13 and the like are provided in the sealing part 10 is the same as in the fourth embodiment.
e) The case where the sealing part 10 is not provided with the liquid injection port 10h in the configuration of the fourth invention is the same as in Example 4.

7) Control valve type lead acid battery The conventional negative electrode absorption type control valve type lead acid battery has a liquid injection port provided in each battery cell, and each pressure cell is sealed (sealed) with a pressure control valve holding lid. Since it is fixed to the battery case lid or sealed with a liquid stopper with a pressure control valve, the maintenance work during storage is necessary. In some cases, the maintenance work during storage is not required by the pressurization / decompression control valve of the “Patent Document 5 Patent 4224762 Control Valve Lead Acid Battery”. These disadvantages are that when sealing with the liquid stopper, the height above the electrode plate cannot be lowered, and there is a limit to downsizing the lead-acid battery. It is in fact impossible. On the other hand, the Example with respect to the control valve type lead acid battery which employ | adopted the sealing structure substantially the same as Example 3 or Example 4 is described below. In the case similar to the third embodiment or the fourth embodiment, the description is simplified or omitted. (See Figures 5-9)

a) Other than the sealed structure of the control valve type lead-acid battery, it is a conventional one, and a 6-cell monoblock synthetic resin battery case has a positive and negative electrode plate and a separator built in, and the battery case lid is heat-sealed to external terminals. Is formed. Also in this example, only the sealing structure related to the battery case lid will be described in detail.
b) The sealing part mounting part 8a is substantially the same as in Example 3 or Example 4, but the lower cylindrical part 8q is unnecessary because the amount of the electrolyte is suppressed. Further, since the water vapor flowing into the exhaust chamber 8d is condensed and condensed and then returned to each battery cell, the pressurization to the pressurization control valve due to the partial pressure of water vapor is reduced, and the valve opening probability is lowered. The amount of water loss is suppressed and the life is extended compared to the control valve type lead storage battery without 8d.
c) The sealing part 10 is the same as in Example 3 or Example 4. Since the sealing part 10 is fixed by the tapping screw 11 and does not fall off, the pressing cover, which has been necessary in the past, is unnecessary, and it is not necessary to fix the pressing cover to the battery case cover by heat fusion or the like. It becomes. This not only reduces the cost, but also makes it possible to replenish water at any time because of the presser cover, which can extend the life of the lead-acid battery.
d) A pressure reducing nozzle covering the entire battery is pressed and sealed on the battery mounting table, the inside and outside of the battery are evacuated, and then the electrolyte is injected so that the positive and negative electrode plates are completely buried. Open. According to this injection method, the air in the battery, including the air in the positive / negative electrode plate and separator, is almost completely discharged before injection, and then the electrolyte is pushed into the positive / negative electrode plate / separator at atmospheric pressure. Be turned. As a result, the penetration and diffusion speed of the electrolyte in the positive and negative electrode plates and the separator is improved, homogenization is achieved by eliminating bubbles, and the amount of liquid that can be injected is increased by reducing the apparent volume of the positive and negative plates and separator. In addition, it has the effect of stabilizing discharge capacity and improving the life of lead-acid batteries by reducing the variation in chemical formation between battery cells.
e) Battery formation after electrolyte injection is performed in a manner that suppresses the gas generated from the positive and negative electrode plates during battery formation by repeated charging and discharging while suppressing the charging current. Adjust the concentration and volume of the electrolyte after forming the battery case. The gas generated during the formation of the battery case is discharged to the outside through the injection port 10h.
f) The control valve type lead-acid battery has a part of the electrode plate exposed and must be kept sealed to prevent oxidation. The measures against pressure and pressure reduction generated in the sealed lead-acid battery and the effects thereof are the same as those in the third or fourth embodiment. However, in the control valve type lead-acid battery in which a predetermined group pressure is applied to the electrode plate group, the battery cell partition wall is repelled and supported by the electrode plate group, and the amount of the electrolyte is suppressed. No countermeasure is required.
g) By the above, maintenance work during storage is unnecessary, and it is possible to reduce the size, weight, and cost, and the negative electrode absorption has a longer life with less electrolyte reduction than any conventional control valve type lead-acid battery. Type control valve type lead acid battery can be provided. In addition, as shown in the above-mentioned “Patent Document 3 Japanese Patent Application Laid-Open No. 2003-142148 lead acid battery”, if the amount of the electrolyte is not suppressed from the beginning and the amount of the electrolyte is sufficient, the amount of the electrolyte is reduced in the liquid lead acid battery at the beginning. If this is done, it will become a control valve type lead-acid battery, and the life will be further extended.
h) The above configuration includes an exhaust chamber 8d for each battery cell that condenses and condenses moisture. However, the control valve type lead-acid battery is not an essential component and may not have the exhaust chamber 8d. . However, the amount of water lost in the electrolyte is about the same as that of a conventional control valve type lead storage battery, and there is no life extension effect.
i) When the sealing structure of Example 3 is adopted, the inside of the sealing component mounting portion 8a may be separated for each battery cell. (See Figure 10)
j) When the pressure adjusting valve 13 or the like is provided in the sealing part 10, it is the same as in the third or fourth embodiment.
k) In the configuration of the fourth aspect of the invention, the case where the sealing part 10 is not provided with the liquid injection port 10h is the same as in Example 3 or Example 4.

8) 24V or 36V lead acid battery The 24V or 36V lead acid battery adopting the above fourth to ninth inventions is a sealing part 10 that is arranged in a grid and is common to four adjacent battery cells. And the place which becomes sealing part mounting part 8a differs from 12V type lead acid battery. The external vent is either the external vent for each battery cell, the external vent common to two adjacent battery cells, or the external vent common to four adjacent battery cells. However, depending on the arrangement of the battery cells, the sealing component 10 and the sealing component mounting portion 8a common to two adjacent battery cells are also used. The internal structures of the sealing component 10 and the sealing component mounting portion 8a are substantially the same as those in Examples 2 to 7 depending on the type of the lead storage battery, but the area of the sealing component mounting portion 8a per battery cell is the same. Therefore, it is preferable that the pressure control valve is provided not in the sealing part mounting portion 8a but in the sealing part 10 to secure the area of the exhaust chamber 8d. FIG. 14 shows an external view of an embodiment in which a pressurizing control valve 13 for a 24V lead acid battery is provided in the sealing part 10.

9) Example Comparison Table The comparison of Examples 1 to 8 is shown in the table below.

1 Container lid 2 (also used as external terminal) Sealing plug retaining member
21 Injection channel
2a Head of the member for holding the sealing plug
2b Seal plug holding part of the seal plug holding member (2d ~ 2g)
2c Sealing passage part (2h to 2i)
2d Overflow-preventing recess in the sealing plug holder of the sealing plug holder
2e Center shaft hole of the sealing plug holding part of the sealing plug holding member
2f Seal plug holding rib of the seal plug holding part of the seal plug holding member
2g Passage of the sealing plug holding part of the sealing plug holding member
2h Sealing hole in the sealing part of the sealing plug retaining member
2i Conical hole in the sealing part of the sealing plug retaining member
2j Thin part of the sealing plug retaining member 3 Sealing plug
3a Concave part opened only on the inner side of the container of the sealing plug
3f Seal plug retention rib of the seal plug
3g Seal plug passage
3m conical contact surface of sealing plug
4a, 4b Insulation material
5 Inner terminal
51 Electrical lead plate
52 Spring plate for movable contacts
52a Movable contact
53 Terminal board
53a Fixed contact
54 Insulation block
55 Connecting pin
6 Gas replacement nozzle
6a Synthetic rubber tip of the gas replacement nozzle
7 Injection nozzle
8 Battery case lid
8a Sealing part mounting part of battery case lid
8b Battery cell partition of battery case lid
8c Tapping screw pilot hole in sealing part mounting part
8d Exhaust chamber of sealing part mounting part
8e Exhaust chamber partition wall for sealing parts
8f Gas inlet for sealing part mounting part
8g Sealing column part of sealing part mounting part
8h Injection port for sealing parts
8i Narrow vertical groove for exhaust throttling at sealing part mounting part
8j Pressure control valve mounting part of sealing part mounting part
8k Columnar projection of control valve mounting part
8m Conical sealing surface of columnar protrusion of control valve mounting part
8n Micro-grooves for continuous ventilation in the columnar protrusions of the control valve mounting part
8p Vertical groove for ventilation of control valve mounting part
8q Lower cylindrical part of sealing part mounting part
8r Stepped discharge path of lower cylindrical part
8s Ventilation slit in the lower cylindrical part
8t Pressure reducing valve mounting part of sealing part mounting part
10 Sealing parts
10a Sealing part head
10b Thin ribs on the outer periphery of the sealing part
10c Tapping screw mounting hole for sealing parts
10d Hexagon head of sealing part head
10h Injection port for sealing parts
10j Gas outlet for sealing parts
10k Sealing parts decompression adjustment valve shaft mounting part
10 l Disc-shaped recess on the pressure reducing valve shaft mounting part of the sealing part
10m Through hole in the pressure reducing valve shaft mounting part of the sealing part
10n Thin valve on the pressure reducing adjustment valve shaft mounting part of the sealing part
11 Tapping screw
12 Explosion-proof filter
13 Pressure control valve
13a Cylindrical part of pressurizing control valve
13b Thin valve of pressurization control valve
13c Gas outlet of pressurization control valve
14 Depressurization control valve
14a Cylindrical part of pressure reducing control valve
14b Cylindrical valve of pressure reducing control valve
14c Inlet of pressure reducing control valve
15 Continuous seal for gas outlet
16 Depressurization adjusting valve stem
16a Flange part of pressure reducing adjustment valve shaft
16b Center axis of pressure reducing adjustment valve shaft
16c Ring part of pressure reducing valve shaft
16d Ventilation notch in the flange of the pressure reducing valve shaft
16e Ventilation longitudinal groove on the central axis of the pressure reducing valve shaft

Claims (10)

Electrochemical apparatus provided with a path for electrolyte injection, a path for electrolyte injection also serving as an external ventilation path, or a path of the external ventilation path and a sealing part for sealing the path The sealing part is provided with a sealing structure in which the sealing part can be attached to the sealing part holding member for holding the sealing part before sealing, and the path is defined by the sealing part holding member and the sealing part. An electrochemical device characterized in that a first mounting state to be configured and a second mounting state in which the path is sealed by the sealing component can be selectively maintained. A sealing part holding rib is provided on either the sealing part holding member or the sealing part, and the sealing part holding member is provided with a sealing passage portion of the path, and the sealing part is provided with the sealing part holding rib. The first mounting state to be held and the second mounting state in which the sealing component is mounted and sealed in the sealing passage portion are configured to be selectively maintainable. The electrochemical device according to claim 1. The first mounting state and the second mounting state can be selectively maintained by rotating the sealing component mounted on the sealing component holding member. The electrochemical device according to claim 1. In a lead-acid battery having a plurality of battery cells, a sealing component mounting portion common to the plurality of adjacent battery cells is provided for a plurality of adjacent battery cells, and the electrolytic solution injection for each battery cell is provided in the sealing component mounting portion. The liquid passage and the external vent passage common to the plurality of adjacent battery cells or each battery cell are provided, and the sealing parts common to the plurality of adjacent battery cells mounted on the sealing part mounting portion are rotated. Accordingly, the first mounting state in which the electrolyte injection passage is constituted by the sealing component mounting portion and the sealing component, and the second mounting state in which the electrolyte injection passage is sealed by the sealing component. The lead acid battery according to claim 3, which is configured to be selectively maintainable. 5. The sealing part mounting portion further includes an exhaust chamber for each battery cell that condenses and condenses moisture in the gas generated in the battery cell and is connected to the external air passage. Lead acid battery. The lead storage battery according to claim 4 or 5, further comprising a pressure control valve for controlling a pressure in the battery cell by opening and closing the external air passage in the sealing part mounting portion. 7. The configuration according to claim 6, wherein when only the pressurization control valve for controlling the rising pressure in the battery cell is provided, a micro-ventilation passage that can be continuously vented is opened to the outside. Lead acid battery. 7. The lead-acid battery according to claim 6, wherein the pressure control valve has a wall thickness between the battery cells that is common to the pressure control valve thinner than a wall thickness between the other battery cells. The lead storage battery according to claim 6 or 8, wherein a minute vent is provided in a partition wall between battery cells not sharing the pressure control valve. At least one of the external ventilation path, the external ventilation path that is opened and closed by the pressure control valve, or the external ventilation path that is provided with the minute ventilation path and is opened and closed by the pressurization control valve is used as the sealing component. The lead storage battery according to claim 4, wherein the lead storage battery is provided in the sealing part without being provided in the mounting portion.

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