JPH10294128A - High temperature sodium secondary battery module and battery system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high temperature sodium secondary battery module and a battery system wherein handling such as assembling and battery replacement is easy, damage spreading over an adjacent battery hardly occurs even when an active material is leaked, and it is highly safe even for water infiltration. SOLUTION: This secondary battery module contains high temperature sodium secondary batteries 2 such as a sodium-sulfur battery in a heat insulated container 1 in plural quantity. In this case, the high temperature sodium secondary batteries 2 and a power or fiber state insulating material 4 is contained in a bottomed metallic container 3, and a plurality of the bottomed metallic containers 3 are installed inside the heat insulated container 1. A battery system is composed by using a high temperature sodium secondary battery module having the above mentioned structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-temperature sodium secondary battery module which is easy to handle and excellent in safety, and a battery system such as an electric power storage device and an electric vehicle using the same.

[0002]

2. Description of the Related Art High-temperature sodium secondary batteries using sodium for the negative electrode and sulfur, selenium, tellurium, metal halide, etc. for the positive electrode have attracted attention because of their high efficiency and energy density. The use for is expected. These batteries are operated as a module in which a plurality of batteries are housed in an insulated container to maintain the temperature. In these modules, it is extremely important in practice that even if one battery in the heat insulating container is damaged and the active material leaks out, the damage does not spread to other batteries in the heat insulating container.

As an example of this, as disclosed in JP-A-3-283272 and JP-A-5-266925, a plurality of high-temperature sodium secondary batteries are housed in a heat-insulating container and an insulating material such as dry sand is interposed between the batteries. Modules filled with material have been proposed. According to this method, even if the active material leaks from the battery, the active material is blocked by the filled insulating material, so that damage is not easily spread to an adjacent battery, and there is an advantage that safety in an emergency is high, but the weight of the module is high. Is heavy due to the dry sand, which makes it difficult to handle.When replacing batteries after filling with dry sand, it is necessary to remove a large amount of dry sand in the module, and it takes time to replace the batteries. There was a problem. In particular, if it is necessary to replace the battery with leaked active material after installing the module on the site, or to move the entire module for the purpose of battery replacement, the removal of dry sand and the weight of the module will be significant. It was a problem. In addition, these modules have the drawback that if water enters from the entrance of the electrical input / output terminal provided in the heat insulating container in the event of water discharge or flooding in the event of a fire, the battery is likely to be damaged due to the splashing of water on the battery, In addition, since the entire surface of the module is covered with water, the entire dry sand in the module gets wet, and it takes a long time to dry when the module is restarted.

On the other hand, in JP-A-3-283270, a storage container for an inert agent such as dry sand is provided outside, and a valve of a pipe connecting the storage container and the heat insulating container is opened when the active material leaks.
A method of discharging the inert agent into the insulated container is described, but this method requires a complicated and large-scale apparatus,
Since the release of the deactivator occurs after the active material leaks from the battery, it is effective in preventing fires, but is not effective in preventing damage to adjacent batteries due to the leaked active material or preventing damage to the battery due to flooding. There was a safety problem. As described above, it is difficult for the conventional high-temperature sodium secondary battery module to simultaneously satisfy the safety at the time of battery breakage and the ease of handling.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the drawbacks of the prior art described above, and to facilitate handling such as assembly and battery replacement, and to prevent damage from spreading to other batteries even when an active material leaks. An object of the present invention is to provide a high-temperature sodium secondary battery module that is highly safe against inundation. Another object of the present invention is to provide a power storage device, an electric vehicle, an emergency power source, an uninterruptible power source, a power system peak shift device, and a power handling device using the high-temperature sodium secondary battery module, which has high handleability and safety. An object of the present invention is to provide a battery system such as a frequency / voltage stabilizing device.

[0006]

To achieve the above object, a high temperature sodium secondary battery module according to the present invention comprises a bottomed metal container containing a plurality of high temperature sodium secondary batteries such as sodium sulfur batteries. It is characterized in that a plurality of bottomed metal containers are installed in a heat insulating container. In addition,
It is preferable that a powdered or fibrous insulating material is accommodated in the bottomed metal container together with the high-temperature sodium secondary battery. Also, a plurality of high temperature sodium secondary batteries can be arranged in a square or staggered arrangement in the bottomed metal container, and the side wall shape of the bottomed metal container can be formed according to the arrangement. Further, an insulating plate is provided in the bottomed metal container,
It is desirable to electrically insulate the high-temperature sodium secondary batteries from each other and / or between the high-temperature sodium secondary battery and the bottomed metal container. Here, as the insulating material, ceramic powder such as alumina and silica, dry sand, glass, zeolite, expanded olivine, expanded pearlite, and other granular or powdery materials, and fibrous materials such as glass fibers and ceramic fibers And hollow lightweight particles such as Shirasu or a mixture thereof.

Preferably, the height of the upper surface of the bottomed metal container is higher than the vertical height of the entrance of the electric input / output terminal provided on the heat insulating container. If the height is lower than or the same as the height of the entrance of the terminal, it is desirable to provide a water-proof lid on the upper surface of the bottomed metal container. A heater for heating the battery may be attached to the lid. Further, if necessary, a hole for passing water can be provided in a lower portion of the bottomed metal container.

Further, the battery system of the present invention includes a power storage device using the above-described high-temperature sodium secondary battery module, an electric vehicle, an emergency power source, an uninterruptible power source, a power system peak shift device, and a frequency / voltage stabilizing device. And the like.

In the high-temperature sodium secondary battery module of the present invention, a plurality of bottomed metal containers are installed in the heat-insulating container, and the high-temperature sodium secondary battery is housed therein. Inspection, transfer, replacement, etc. can be easily performed in a unit with a light bottomed metal container. Further, by storing the insulating material in the bottomed metal container, the safety of the high-temperature sodium secondary battery module is improved. Here, if hollow particles such as shirasu are used as the insulating material, the weight of the bottomed metal container containing the battery is reduced, and handling is easy. The filling amount of the dry sand or the like in the heat-insulating container is determined by laws, ordinances, ordinances related to dangerous substances as a fire extinguisher for an active material contained in all the high-temperature sodium secondary batteries in the heat-insulating container. It is desirable that the amount be more than the required amount. Specifically, Article 30 of the Regulations on the Regulation of Dangerous Goods (Government Ordinance No. 55), Appendix 2 of the Regulations (Related to Article 31), and Cabinet Order on the Regulation of Dangerous Goods (Government Decree No. 306) Specified in Schedule 3 (related to Article 1-11), 50 kg of sodium or 5 sulfur
It is sufficient if the dry sand is 50 liters or more per 00 kg.

When the battery is replaced after the module is installed on site, the corresponding bottomed metal container is taken out of the module in units of the corresponding bottomed metal container, and when the insulating material is stored, only the insulating material in the corresponding bottomed metal container is removed. Since it is sufficient to remove the battery, the battery can be easily replaced. Furthermore, even if water is flooded into the insulated container due to water discharge in the event of fire, etc., it is difficult for water to enter the bottomed metal container at a position away from the water inlet into the insulated container, so the number of batteries that come into contact with water Is reduced, the probability of battery breakage is reduced, and safety against flooding is improved. In addition, there is no need to dry the high-temperature sodium secondary battery or the insulating material stored in the bottomed metal container in which water has not entered, and the module can be easily restarted.

Further, even if the battery is damaged and the active material leaks from the battery container, the battery can be prevented from spreading outward by the bottomed metal container, so that the batteries in the adjacent bottomed metal container are kept healthy. The safety of the high-temperature sodium secondary battery module is improved. In particular, if the inside of the bottomed metal container is filled with powdered or fibrous insulating material, the leaked active material is retained and fixed in the gaps between the insulating material particles and fibers, and the adjacent battery is damaged. There is no risk of emergency and the safety in an emergency is extremely high. If an insulating plate such as mica is provided as a partition in the bottomed metal container, electrical insulation between adjacent batteries or with the bottomed metal container can be performed, and the degree of freedom in battery arrangement and connection is advantageously increased. In addition, even in the event of a battery break, the leaked active material is blocked by the insulating plate to protect the adjacent battery, thereby further improving the safety of the module.

When a plurality of high-temperature sodium secondary batteries are arranged in a square or staggered arrangement in the bottomed metal container, the side wall shape of the bottomed metal container is formed in accordance with the arrangement, so that the bottomed metal container is formed. The storage in the heat-insulating container is easy, and the useless space for storing the battery in the bottomed metal container can be reduced, and the energy density of the high-temperature sodium secondary battery module can be increased.

In the high-temperature sodium secondary battery module of the present invention, if the height of the upper surface of the bottomed metal container is higher than the height of the entrance of the electric input / output terminal provided on the heat-insulating container, the high-temperature sodium Since the secondary battery and insulating material are not exposed to water, there is no risk of battery damage due to rapid water cooling, and there is no need to dry the high-temperature sodium secondary battery and insulating material at the time of restarting. The ease of handling is greatly improved. A similar effect is obtained when the upper surface of the bottomed metal container is almost the same as or lower than the height of the inlet / outlet of the electric input / output terminal provided on the insulated container. Is realized by providing
Also in this case, a module excellent in safety and handleability can be obtained. A heater for heating the battery is attached to this lid, and can be used for heating and keeping the heat inside the heat insulating container.

When the entire module is completely submerged for a long period of time, for example, in a flood, the volume of gas such as air in the heat insulating container is reduced during cooling, and water infiltrates into the module. Although it is difficult to completely prevent flooding of the next battery, in this case, too, water is prevented from directly spraying on the upper part of the battery, and the lower part of the battery is first immersed in water to lower the temperature of the battery. Has a metal / ceramic seal, which reduces the cooling rate of the upper part of the battery, which is easily damaged by direct water cooling from high temperatures, to prevent battery damage during flooding. can do. For this purpose,
By providing a hole for water through the bottom of the bottomed metal container and letting water in from this part, the lower part of the battery can be cooled first to lower the battery temperature, and damage due to rapid cooling of the upper part of the battery can be prevented. . If the active material leaks due to breakage of the battery during flooding in a high-temperature sodium secondary battery, sodium and water react with each other, possibly causing a hydrogen explosion. It is extremely important to ensure that the module is safe, especially to prevent water from splashing on the upper part of the battery and prevent the battery from being damaged.

Further, by using the battery system using the high-temperature battery module of the present invention, the power storage device,
The safety and handling of battery systems such as electric vehicles, emergency power supplies, uninterruptible power supplies, power system peak shifters, frequency and voltage stabilizers, etc. are significantly improved.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to embodiments.

FIG. 1 shows an example of the structure of a high-temperature sodium secondary battery module according to the present invention. In FIG. 1, reference numeral 1 denotes a heat insulating container containing a high-temperature sodium secondary battery, and a vacuum heat insulating container is usually used because of its excellent heat insulating performance.
Although not shown, a heater for heating is attached to a side surface of the heat insulating container. Reference numeral 2 denotes a high-temperature sodium secondary battery such as a sodium-sulfur battery, which is housed in a bottomed metal container 3 made of SUS or carbon steel. Reference numeral 4 denotes an insulating material such as dry sand filled in a bottomed metal container, and reference numeral 5 denotes an insulating plate such as mica. On the other hand, 6 and 7 are a positive electrode terminal and a negative electrode terminal provided in the high-temperature sodium secondary battery, respectively.
It is connected to an external circuit not shown. Also, 9
Are entrances and exits of electric terminals (bus bars) provided on the heat insulating container.

In this structure, the high-temperature sodium secondary battery 2 is housed in the bottomed metal container 3 via the insulating plate 5 together with the insulating material 4.
It is installed in. For this reason, when the battery is damaged, the effect of the bottomed metal container and the insulating material does not spread to other batteries in the heat insulating container. In addition, the initial performance test of the battery, installation in the heat insulating container, replacement of the defective battery Since it is possible to perform such operations in units of bottomed metal containers, there is an advantage that it is easy to handle and suitable for automation of assembly. Further, at the time of battery replacement, only the insulating material in the corresponding bottomed metal container needs to be removed, so that battery replacement is also easy. Furthermore, even if water penetrates through the gap between the lids of the heat insulating container due to water discharge and soaks into a nearby bottomed metal container, only the high-temperature sodium secondary battery and the insulating material filled in the corresponding bottomed metal container are removed. Since the drying is sufficient, the module can be easily restarted. Further, in the structure of FIG. 1, since the upper surface of the bottomed metal container 3 is located at a position higher than the entrance / exit 9 of the input / output terminal provided in the heat insulating container, even if water enters through the entrance / exit 9 of the input / output terminal due to water discharge or the like, There is no danger of water splashing on batteries and insulation,
Module safety is high.

FIG. 2 shows another example of the structure of the high-temperature sodium secondary battery module of the present invention. Components indicated by the same reference numerals as those in FIG. 1 have the same contents. In the figure, reference numeral 10 denotes a water-covering lid provided on the upper surface of the bottomed metal container 3. In this example, a heater 11 for heating is provided on the upper surface of the lid.
The bus bar 8 is insulated from the bus bar 8 by an insulating plate 12. Reference numeral 13 denotes a hole for passing the bus bar 8 provided on the lid,
An insulator (not shown) is packed to prevent water from entering there. In the figure, the end of the lid 10 is bent to increase the waterproof effect, but a flat lid may be used. Further, in this example, a hole 14 for passing water is provided in a lower portion of the bottomed metal container 3.

In this structure, the effect of preventing damage to adjacent batteries and the ease of handling are the same as in FIG.
In addition, since the lid 10 for draining water is provided on the upper surface of the bottomed metal container 3, even if water enters from the gap of the lid of the heat insulating container 1 or the entrance 9 of the input / output terminal due to water discharge or the like, the battery Also, there is no possibility that water is directly applied to the insulating material. Further, a hole 14 through which water is provided is provided at a lower portion of the bottomed metal container. Even if a large amount of water enters the module, such as a flood, the lower portion of the battery is first filled with water. The battery can be prevented from being damaged by lowering the temperature of the battery by contacting the battery. Further, a heater 11 is provided on the upper surface of the lid 10, and by combining with a heater on the side of the heat insulating container (not shown), the temperature distribution in the heat insulating container can be made uniform, and the reliability of the module can be improved. Safety is improved.

FIG. 3 shows a structural example of the high-temperature sodium secondary battery of the present invention. Reference numeral 21 denotes a sodium ion conductive solid electrolyte tube which is usually made of β ″ alumina sintered body. Reference numeral 22 denotes sodium as a negative electrode active material, reference numeral 23 denotes a positive electrode active material. As a material, sulfur or sodium polysulfide is used by impregnating a carbon mat, and the battery is usually operated at a temperature of about 300 to about 400 ° C. As a positive electrode active material, a sodium-sulfur battery uses sulfur or polysulfide. Although sodium sulfide is used, selenium, tellurium, and halides of metal elements may be used in other high-temperature sodium secondary batteries, 24 is a sodium container having a bottom hole, 25 is a negative electrode container, and 26 is a negative electrode container. Is a positive electrode container, which is made of aluminum, iron, SUS, or a corrosion-resistant layer mainly composed of chromium, molybdenum, titanium, etc. .27 the one provided is used is an insulating ring made of ceramics such as α- alumina solid electrolyte tube 21
And the negative electrode container 25 and the positive electrode container 26 are bonded using an aluminum alloy or the like. An inert gas such as argon and nitrogen is sealed in the sodium container 24 together with sodium, and sodium is supplied to a gap between the solid electrolyte tube 21 and the sodium container 24 by this gas pressure. Reference numerals 6 and 7 denote a positive terminal and a negative terminal, respectively. As in this structure, it is common to provide a seal portion in which a metal (25, 26) and a ceramic (27) are joined on the upper part of the high-temperature sodium secondary battery. In such a case, the ceramic may be cracked, and the active material may leak. Therefore, it is important to take safety measures so that water does not splash on the upper part of the battery at high temperatures.

FIG. 4 shows a side wall 3 of the bottomed metal container 3 when a plurality of high temperature sodium secondary batteries are housed in a square array.
FIG. 5 shows a side wall 31 of the bottomed metal container 3 when a plurality of high-temperature sodium secondary batteries are stored in a staggered arrangement.
3 shows an example of the shape. By forming the side wall shape of the bottomed metal container according to the arrangement of the high-temperature sodium secondary batteries in this manner, the storage of the battery in the bottomed metal container and the storage of the bottomed metal container in the insulated container are easy. And especially in FIG.
In the structure (1), the filling density of the high-temperature sodium secondary battery can be increased, and the energy density of the high-temperature sodium secondary battery module can be improved. As a specific example, the capacity per one piece is about 56
Using a sodium-sulfur battery of 0 Wh, a rated output of about 70 W, and a height of about 40 cm, each of the 36 batteries is 45 × 45 × 45.
It was placed in a bottomed metal container made of carbon steel having a size of ³ cm3, the cells and the cell / bottomed metal container were insulated with mica, and dry sand was filled between the cells. Next, six such bottomed metal containers were placed in a vacuum insulated container having a length of about 1 m, a width of about 1.5 m and a height of about 0.55 m to obtain a module having a capacity of 120 kWh similar to that shown in FIG. In this module, even if one battery is forcibly destroyed, the spread of the leaked active material is prevented by the bottomed metal container and the dry sand, so that there is no possibility that the adjacent battery is damaged. Also, handling such as assembly and battery replacement is easy. Furthermore, even if water is discharged from the outside of the module assuming a fire, water does not splash on the batteries and dry sand, and the safety against water discharge is high.

Further, the power storage device, the electric vehicle, the emergency power source, the uninterruptible power source, the peak shift device of the power system using the sodium-sulfur battery module having the above-described structure, which is easy to handle and has high safety. And a battery system such as a frequency / voltage stabilizer.

[0024]

According to the present invention, a high-temperature sodium secondary battery module which is easy to handle such as assembling and battery replacement and has high safety against battery breakage and flooding, and a battery system using the same are realized. Is done.

[Brief description of the drawings]

FIG. 1 is a diagram showing a structural example of a high-temperature sodium secondary battery module of the present invention.

FIG. 2 is a diagram showing a structural example of a high-temperature sodium secondary battery module of the present invention.

FIG. 3 is a diagram showing an example of the structure of a high-temperature sodium secondary battery.

FIG. 4 is a diagram showing an example of the relationship between the arrangement of high-temperature sodium secondary batteries and the shape of the side wall of a bottomed metal container.

FIG. 5 is a diagram showing an example of the relationship between the arrangement of a high-temperature sodium secondary battery and the side wall shape of a bottomed metal container.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Insulated container, 2 ... High temperature sodium secondary battery, 3 ... Bottomed metal container, 4 ... Insulating material, 5 ... Insulating plate, 9 ... Terminal entrance,
10 ... lid, 11 ... heater, 14 ... hole, 31 ... side wall.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Mitsuru Suzuki 3-2-2, Sachimachi, Hitachi-shi, Ibaraki Inside Hitachi New Clear Engineering Co., Ltd. (72) Kenzo Kikuchi 3-chome, Sachimachi, Hitachi-shi, Ibaraki No. 2 within Hitachi New Clear Engineering Co., Ltd. (72) Inventor Seiichi Tamura 3-2-2, Sachimachi, Hitachi City, Ibaraki Pref. Within Hitachi New Clear Engineering Co., Ltd. (72) Inventor Katsuo Abo Tokyo Hitachi Engineering Consulting Co., Ltd. 4-6, Kanda Surugadai, Chiyoda-ku, Tokyo

Claims (10)

[Claims] 1. A high-temperature sodium secondary battery module containing a plurality of high-temperature sodium secondary batteries such as a sodium-sulfur battery in a heat insulating container, wherein a plurality of the high-temperature sodium secondary batteries are stored in a bottomed metal container. A high temperature sodium secondary battery module, wherein a plurality of the bottomed metal containers are installed in the heat insulating container. 2. A high temperature sodium secondary battery module, wherein a powdered or fibrous insulating material is stored in the bottomed metal container according to claim 1. 3. The high-temperature sodium secondary battery according to claim 1, wherein a plurality of the high-temperature sodium secondary batteries according to claim 1 or 2 are arranged in a square or staggered pattern in the bottomed metal container. A high-temperature sodium secondary battery module, which is formed according to the arrangement of secondary batteries. 4. The high-temperature sodium secondary battery and / or the high-temperature sodium secondary battery and / or the bottomed metal by providing an insulating plate inside the bottomed metal container according to claim 1 or 2. A high-temperature sodium secondary battery module, wherein the containers are electrically insulated. 5. The insulating material according to claim 2, wherein said insulating material is a granular or powdered material such as ceramic powder such as alumina or silica, dry sand, glass, zeolite, expanded vermiculite, expanded pearlite, glass fiber or ceramic. A high temperature sodium secondary battery module characterized by being a fibrous material such as fiber, hollow particles such as shirasu, or a mixture thereof. 6. The high-temperature sodium nitrate according to claim 1, wherein an upper surface height of the bottomed metal container according to claim 1 or 2 is higher than a vertical height of an entrance of an electric input / output terminal provided in the heat insulating container. Next battery module. 7. The height of the upper surface of the bottomed metal container according to claim 1 or 2 is lower than or approximately the same as the vertical height of the entrance of the electric input / output terminal provided on the heat insulating container. A high-temperature sodium secondary battery module, wherein a water-proof lid is provided on the upper surface of the bottomed metal container. 8. A high-temperature sodium secondary battery module, wherein a heater for heating a battery is attached to the lid according to claim 7. 9. A high-temperature sodium secondary battery module, wherein a hole for passing water is provided in a lower part of the bottomed metal container according to any one of claims 1, 2, 6, and 7. 10. A battery system using the high-temperature sodium secondary battery module according to any one of claims 1 to 9.