WO2013051385A1

WO2013051385A1 - Emergency molten salt assembly cell and method for using same, and emergency power supply device

Info

Publication number: WO2013051385A1
Application number: PCT/JP2012/073599
Authority: WO
Inventors: 新田　耕司; 稲澤　信二; 将一郎酒井; 篤史福永
Original assignee: 住友電気工業株式会社
Priority date: 2011-10-05
Filing date: 2012-09-14
Publication date: 2013-04-11
Also published as: JP2013080663A; KR20140073460A

Abstract

An emergency molten salt assembly cell comprising a grouping of a plurality of molten salt cells containing molten salt as the electrolyte, the electrolyte being stored in a solidified state after charging; wherein the emergency molten salt assembly cell is provided with: a plurality of molten salt cells for main operation; a heating device (first heating device) for heating the molten salt cells for main operation; at least one starting molten salt cell capable of actuating the heating device; and a starting heating device (second heating device). The starting heating device is provided so as to accompany the cell container of the starting molten salt cell. The starting heating device is, when not in operation, a regular-temperature body for maintaining the electrolyte of the starting molten salt cell at a temperature less than the melting point of the electrolyte, but when in operation, a heating body for heating the cell container.

Description

Emergency molten salt assembled battery, method of use thereof, and emergency power supply device

The present invention relates to a molten salt battery, that is, a battery using molten salt as an electrolyte.

When a power outage lasts for a long time due to a disaster, for example, if there is a large-capacity emergency power supply device in each home, it is possible to collect information and ensure nighttime lighting, which is very useful. Conventionally, in such an emergency power supply device, a type using a battery mainly uses a lead storage battery or a lithium ion battery (see, for example, Patent Document 1).

JP 2007-159379 A

However, since lead-acid batteries are self-discharged even if they are not used, it is necessary to charge them constantly or at least regularly. The same applies to lithium ion batteries. In other words, it is necessary to be careful not to neglect charging in case of emergency. Of course, electric energy is consumed for charging. That is, there has not yet been proposed a convenient and wasteful emergency power supply device that can be used in a case where it is completely maintenance-free and can be used at any time.

In view of such problems, an object of the present invention is to provide a battery and an emergency power supply that can be stored maintenance-free and can be used in an emergency such as a power failure.

(1) The present invention is an emergency molten salt assembled battery which is configured by collecting a plurality of molten salt batteries containing a molten salt as an electrolyte, and is stored in a state where the electrolyte is solidified after charging, Molten salt battery, a first heating device for heating the plurality of operational molten salt batteries, at least one starting molten salt battery capable of operating the first heating device, and the starting It is provided at the battery container of the molten salt battery for use, and is a room temperature body that maintains the electrolyte of the molten salt battery for starting at a temperature lower than the melting point when not in operation. And a second heating device for starting.

In the emergency molten salt assembled battery configured as described above, the electrolyte is maintained at a temperature lower than the melting point by not operating the first and second heating devices except for emergency use. Does not progress. When the battery needs to be started, the second heating device becomes a heating body, and the temperature of the molten salt battery for starting is set to a temperature equal to or higher than the melting point. Become. If the molten salt battery for start-up becomes usable, the first heating device is operated by the electric energy to heat the molten salt battery for actual operation, so that the entire assembled battery can be used. it can. Therefore, it is possible to provide an emergency molten salt assembled battery that can normally store each battery without discharging it and output a desired voltage / current in an emergency.

(2) Further, in the emergency molten salt assembled battery of (1), the second heating device may be an outer container for the battery container and capable of introducing a heat medium.
(3) Also, as a method of using the emergency molten salt assembled battery of the above (2), the second heating device is maintained at room temperature in the absence of a heat medium, and the second heat device is introduced by introducing the heat medium. The heating device can be changed to a heating body.
That is, the starting molten salt battery can be easily used, for example, by injecting hot water, injecting water and then heating, or passing hot air as the heat medium. Since introduction of such a heat medium is possible even at the time of a power failure, it is suitable for starting a molten salt battery in an emergency.

(4) Further, in the emergency molten salt assembled battery of (1), the second heating device is a seal in which a substance capable of generating heat due to a chemical reaction prevents a chemical reaction from starting in a case covering the battery container. And may be enclosed.
(5) In addition, as a method of using the emergency molten salt assembled battery of (4) above, the second heating device is maintained at room temperature in a state where the seal is provided, and the second heating is performed by removing the seal. The device can be changed to a heating element.
In the second heating device in this case, the chemical reaction is started and heat is generated by removing the seal, so that the starting molten salt battery can be easily used. Since the second heating device used in this manner can generate heat without depending on external energy, it is suitable for starting a molten salt battery in an emergency.

(6) Moreover, in the emergency molten salt assembled battery of the above (1), the second heating device may be provided on the outer surface of the battery container and heated by a general-purpose battery.
In this case, the second heating device generates heat by connecting a general-purpose battery such as a dry battery that is widely used and easy to use, and thus the molten salt battery for starting can be easily used. Such a second heating device can generate heat even during a power failure, and is therefore suitable for starting a molten salt battery in an emergency.

(7) In the emergency molten salt assembled battery of (1), the second heating device includes a device that condenses and heats sunlight directly or indirectly on the outer surface of the battery container. May be.
In this case, the second heating device heats the battery container simply by applying sunlight, and can easily use the starting molten salt battery. Since such a second heating device uses natural energy, it is suitable for starting a molten salt battery in an emergency.

(8) The emergency molten salt assembled battery of any one of (1), (2), (4), (6), (7) and the voltage output from the emergency molten salt assembled battery are: It is possible to provide an emergency power supply device including an inverter device for converting into commercial AC voltage.
Such an emergency power supply device can supply power with the same AC voltage as the commercial AC voltage in the event of a power failure due to a disaster or the like.

According to the present invention, it is possible to provide an emergency molten salt assembled battery that can be stored in a maintenance-free manner and can be used in an emergency such as a power failure, and an emergency power supply device using the same.

1 is a schematic diagram showing in principle the basic structure of a power generation element in a molten salt battery. It is a perspective view which shows simply the lamination structure of a molten salt battery main body (main-body part as a battery). It is a cross-sectional view about the structure similar to FIG. It is a perspective view which shows the outline of the external appearance of the molten salt battery of the state accommodated in the battery container. It is a perspective view which shows schematic structure of the emergency molten salt assembled battery which concerns on one Embodiment of this invention. FIG. 6 is a wiring diagram for starting the emergency molten salt assembled battery shown in FIG. 5. It is sectional drawing of the outer container (1st example of the heating apparatus for starting) of the molten salt battery for starting. It is sectional drawing which shows the outer container as a 2nd example of the heating apparatus for starting. It is sectional drawing which shows the 3rd example of the heating apparatus for starting. It is sectional drawing which shows the 4th example of the heating apparatus for starting. It is the schematic which shows the 5th example of the heating apparatus for starting. It is a block diagram which shows the emergency power supply device mainly for home use.

Hereinafter, an emergency molten salt assembled battery (including a method of use) according to an embodiment of the present invention and an emergency power supply device using the same will be described with reference to the drawings.
As secondary batteries with excellent energy density, for example, lithium ion batteries, sodium sulfur batteries, and nickel metal hydride batteries are known, but in recent years, secondary batteries have a strong advantage of nonflammability in addition to high energy density. As a result, a molten salt battery using a molten salt as an electrolyte has been developed.

The operating temperature range of the molten salt battery is 57 ° C. to 190 ° C., which is a wider temperature range than the other batteries described above. Therefore, there is no need for equipment such as exhaust heat space or fire prevention, and there is an advantage that even if individual unit cells are gathered at a high density to form an assembled battery, it is relatively compact as a whole. Such a molten salt assembled battery is suitable for power storage use at home. Further, the molten salt battery is solidified because it does not reach 57 ° C., which is the melting point of the electrolyte, at room temperature. When solidified, it does not function as a battery and does not self-discharge.

<Basic structure of molten salt battery>
FIG. 1 is a schematic diagram showing in principle the basic structure of a power generation element in a molten salt battery. In the figure, the power generation element includes a positive electrode 1, a negative electrode 2, and a separator 3 interposed therebetween. The positive electrode 1 is composed of a positive electrode current collector 1a and a positive electrode material 1b. The negative electrode 2 includes a negative electrode current collector 2a and a negative electrode material 2b.

The material of the positive electrode current collector 1a is, for example, an aluminum nonwoven fabric (wire diameter: 100 μm, porosity: 80%). The positive electrode material 1b is a mixture of, for example, NaCrO ₂ as a positive electrode active material, acetylene black, PVDF (polyvinylidene fluoride), and N-methyl-2-pyrrolidone in a mass ratio of 85: 10: 5: 50. It is a thing. And what was kneaded in this way is filled in the positive electrode collector 1a of an aluminum nonwoven fabric, and after drying, it presses at 1000 kgf / cm < ² >, and it forms so that the thickness of the positive electrode 1 may be set to about 1 mm.
On the other hand, in the negative electrode 2, an Sn—Na alloy containing, for example, tin as a negative electrode active material is formed on the negative electrode current collector 2a made of aluminum by plating.

The separator 3 interposed between the positive electrode 1 and the negative electrode 2 is obtained by impregnating a glass non-woven fabric (thickness: 200 μm) with a molten salt as an electrolyte. This molten salt is, for example, a mixture of NaFSA (sodium bisfluorosulfonylamide) 0.45 mol% and KFSA (potassium bisfluorosulfonylamide) 0.55 mol%, and the melting point is 57 ° C. At a temperature equal to or higher than the melting point, the molten salt melts and becomes an electrolytic solution in which high-concentration ions are dissolved, and touches the positive electrode 1 and the negative electrode 2. Moreover, this molten salt is nonflammable. The operating temperature range of this molten salt battery is 57 ° C. to 190 ° C., and is normally used while maintaining the temperature at 85 ° C. to 95 ° C.

In addition, although the material, component, and numerical value of each part mentioned above are suitable examples, it is not limited to these.
For example, in addition to the above, a mixture of LiFSA-KFSA-CsFSA is also suitable as the molten salt. In addition, other salts may be mixed (such as organic cations). Generally, (a) a mixture containing NaFSA or LiFSA or (b) a mixture containing NaTFSA or LiTFSA is suitable as the molten salt. . In these cases, since the molten salt of each mixture has a relatively low melting point, the molten salt battery can be operated with a small amount of heating.

Next, a more specific configuration of the power generation element of the molten salt battery will be described. FIG. 2 is a perspective view schematically showing a laminated structure of a molten salt battery main body (main body portion as a battery) 10, and FIG. 3 is a cross-sectional view of the same structure.
2 and 3, a plurality (six are shown) of rectangular flat plate-like negative electrodes 2 and a plurality (five are shown) of rectangles accommodated in a bag-like separator 3 respectively. The flat positive electrodes 1 are opposed to each other and are stacked in the vertical direction in FIG. 3, that is, in the stacking direction, to form a stacked structure.

The separator 3 is interposed between the positive electrode 1 and the negative electrode 2 adjacent to each other. In other words, the positive electrode 1 and the negative electrode 2 are alternately stacked via the separator 3. For example, 20

positive electrodes

1 and 21

negative electrodes

2 and 20 separators 3 as “bags”, but 40 intervening between

positive electrodes

1 and 2 are actually stacked. is there. The separator 3 is not limited to a bag shape, and may be 40 separated.

In FIG. 3, the separator 3 and the negative electrode 2 are drawn so as to be separated from each other, but they are in close contact with each other when the molten salt battery is completed. Naturally, the positive electrode 1 is also in close contact with the separator 3. In addition, the vertical and horizontal dimensions of the positive electrode 1 are smaller than the vertical and horizontal dimensions of the negative electrode 2 in order to prevent the generation of dendrites, and the outer edge of the positive electrode 1 passes through the separator 3. Thus, it faces the peripheral edge of the negative electrode 2.

The molten salt battery main body 10 configured as described above is accommodated in a rectangular parallelepiped battery container made of, for example, an aluminum alloy, and forms a unit cell, that is, a physical individual as a battery.
FIG. 4 is a perspective view showing an outline of the appearance of the molten salt battery B in a state of being housed in such a battery container 11. 2 and 3,

terminals

1p and 1n are drawn out of the battery case 11 from the positive electrode 1 and the negative electrode 2, respectively, while being insulated from the battery case 11. Further, a safety valve 12 for releasing the pressure when the internal atmospheric pressure rises excessively is provided at the upper part of the battery container 11. In addition, the inner surface of the battery container 11 is subjected to insulation treatment, and the battery container 11 is electrically insulated from the internal electrolyte.

The individual shape of the molten salt battery B shown in FIG. 4 is merely an example, and the shape and dimensions can be arbitrarily configured.
The molten salt battery B as described above can be used in a state where a plurality of batteries are gathered together and connected in series or in series and parallel to form a battery pack in order to obtain a voltage and current capacity necessary for the application.

<Emergency Molten Salt Battery>
<< First Example of Heating Device for Starting >>
FIG. 5 is a perspective view showing a schematic structure of an emergency molten salt assembled battery according to an embodiment of the present invention. In the figure, the molten salt battery is composed of a plurality of actual operational molten salt batteries B1 and at least one starting molten salt battery B2. A heating device 14 (first heating device) is interposed between adjacent molten salt batteries B1 for actual operation. The starting molten salt battery B <b> 2 is accommodated in the outer container 13. 5 may be accommodated in a case (not shown).

FIG. 6 is a wiring diagram for starting the emergency molten salt assembled battery shown in FIG. 5 (not shown in FIG. 5). Note that the output wiring of the molten salt battery B1 for actual operation is not shown. For example, the terminal 1p of the starting molten salt battery B2 is connected to one terminal via a switch 15 to a plurality of heating devices 14 connected in parallel to each other. The terminal 1n of the starting molten salt battery B2 is connected to the other terminal of the plurality of heating devices 14 connected in parallel to each other.

FIG. 7 is a cross-sectional view of the outer container 13 of the starting molten salt battery B2. In the figure, support portions 13 s are provided on the bottom surface, front surface / rear surface, and both side surfaces of the inner surface of the outer container 13. The support portion 13s supports the starting molten salt battery B2, and does not hinder the flow of water between the outer container 13 and the starting molten salt battery B2. In a state where water (hot water) is not contained, the outer container 13 is not particularly meaningful, and the battery container 11 is at room temperature (room temperature). Therefore, the starting molten salt battery B2 is in a sleep state as a battery and does not self-discharge.

Here, when it is necessary to operate the emergency molten salt assembled battery due to a power failure, hot water is injected into the space between the outer container 13 and the starting molten salt battery B2 to start the molten salt battery for starting. The battery container 11 of B2 is immersed in high-temperature hot water to be heated. As a result, the electrolyte of the starting molten salt battery B2 is melted and can be used as a battery. In this state, the switch 15 in FIG. 6 is closed, whereby electric power is supplied from the starting molten salt battery B2 to each heating device 14.

When each heating device 14 generates heat, the electrolyte of the molten salt battery B1 for actual operation is melted and can be used as a battery. Note that when power is started to be supplied from the molten salt battery B1 for actual operation to a load (not shown), normally, a temperature equal to or higher than the melting point can be maintained due to heat generated by discharge, and therefore the molten salt battery B1 for actual operation. May start, the switch 15 may be opened. Note that the switch 15 is not necessarily required, and may be directly connected without a switch.

As described above, the outer container 13 provided in association with the battery container 11 of the starting molten salt battery B2 is a starting heating device (second heating device) 100, and is in a normal state without hot water ( In other words, when the heating is not in operation, it is a room temperature body that maintains the electrolyte of the starting molten salt battery B2 at a temperature below the melting point, and becomes a heating body of the battery container 11 by pouring hot water (that is, during the heating operation). ). In the above-mentioned emergency molten salt assembled battery, since the electrolyte is maintained at a temperature lower than the melting point in normal cases (without hot water) other than in an emergency, the discharge of the battery does not proceed. Therefore, if the electrolyte is solidified after the molten salt batteries B1 and B2 are fully charged in advance, there is no need to charge them again unless they are used.

And when starting as a battery is needed, the molten salt battery B2 for starting will be in a usable state by making the electrolyte of the molten salt battery B2 for starting into temperature more than melting | fusing point by operation which puts in hot water. . If the starting molten salt battery B2 is ready for use, the electric energy may be used to heat the operating molten salt battery B1 using the heating device 14 so that the entire assembled battery can be used. it can. Therefore, it is possible to provide an emergency molten salt assembled battery that can normally store each battery without discharging it and output a desired voltage / current in an emergency. That is, such an emergency molten salt assembled battery can be stored maintenance-free and can be used in an emergency such as a power failure.

Further, by injecting hot water as a heat medium, the starting molten salt battery B2 can be easily used. Since introduction of such a heat medium is possible even at the time of a power failure, it is suitable for starting a molten salt battery in an emergency. In addition to hot water, the metal outer container 13 filled with water may be heated by burning fuel to make the water hot water.

«Second example of starting heating device»
FIG. 8 is a cross-sectional view showing an outer container 15 as a second example of the starting heating device 100. A support portion 15s is provided on the inner surface of the outer container 15 as in the first example (FIG. 7). On the other hand, unlike the first example, an opening 15a is provided and a hose 16 for sending hot air is connected. That is, the molten salt battery for start-up B2 can be similarly used by sending hot air instead of hot water. If hot air is not supplied, the battery container 11 is at room temperature (room temperature), and the starting molten salt battery B2 does not function as a battery and does not self-discharge.

<< Third example of starting heating apparatus >>
FIG. 9 is a cross-sectional view showing a third example of the starting heating device 100. In the figure, the starting molten salt battery B2 is covered with a case 17 except for the upper surface. In the case 17, for example, a powdery material 18 in which iron powder, salt, activated carbon, water, and vermiculite are mixed is enclosed in a state where oxygen is removed. The case 17 is provided with a large number of small holes, and a seal 19 is attached so as to close the holes. Normally, the powdery body 18 stored and sealed in this state does not come into contact with air. When the operation of peeling off the seal 19 is performed, the powdery body 18 comes into contact with air through the hole, and heat is generated by oxidation of iron (the principle of disposable body warmers). Thereby, the molten salt battery B2 for starting can be heated and used more than melting | fusing point.
In addition, a substance that reacts with water such as magnesium oxide or calcium oxide to generate heat is sealed in a state separated from water by a seal, and reacted with water by removing or breaking the seal. It can also generate heat.

In the starting heating device 100 in this case, the chemical reaction is started and heat is generated by removing the seal 19, so that the starting molten salt battery B2 can be easily used. Since the starting heating device 100 can generate heat without depending on external energy, it is suitable for starting a molten salt battery in an emergency.
In this case, since the starting heating device 100 cannot be reused, it is necessary to replace the entire or part of the starting heating device 100 once used.

<< Fourth example of heating device for starting >>
FIG. 10 is a cross-sectional view showing a fourth example of the starting heating device 100. In the figure, a sheet-like heater 20 is wound around the outer surface of the starting molten salt battery B2. A power supply line to the heater 20 is connected to a battery holder 21 to which a predetermined number of dry batteries 22 can be mounted, for example. Normally, the dry battery 22 is not attached. However, if the heater 20 is energized by attachment, the starting molten salt battery B2 can be heated to the melting point or higher to be usable. Instead of the dry battery, a lithium ion battery or other general-purpose battery used for a mobile phone or a digital camera may be used.

In this case, the starting heating device 100 generates heat by connecting a general-purpose battery that is widespread and easy to use. Therefore, the starting molten salt battery can be easily used. Since such a starting heating device can generate heat even during a power failure, it is suitable for starting a molten salt battery in an emergency.

<< Fifth example of starting heating apparatus >>
FIG. 11 is a schematic diagram showing a fifth example of the starting heating device 100. This starting heating device 100 condenses sunlight by the condensing device 23 provided with the condensing lens 23L, and attempts to heat the starting molten salt battery B2 via the heat absorbing plate 24 excellent in heat ray absorption. It is the structure to do.
In this case, the starting heating device 100 heats the battery container 11 only by being exposed to sunlight, and can easily use the starting molten salt battery B2. Such a starting heating device 100 uses natural energy and is suitable for starting a molten salt battery in an emergency.

<Emergency power supply>
FIG. 12 is a block diagram showing an emergency power supply apparatus 400 mainly for home use. In the figure, the DC voltage output from the emergency molten salt assembled battery 200 including the starting molten salt battery B2 provided with any of the above-described starting heating devices 100 is converted into AC 100V by the inverter device 300. . A control power supply voltage for driving the inverter device 300 can also be provided from the emergency molten salt assembled battery 200. Such an emergency power supply apparatus 400 can supply power with the same AC voltage as the commercial AC voltage in the event of a power failure due to a disaster or the like.

The embodiment disclosed this time should be considered as illustrative in all points and not restrictive. The scope of the present invention is defined by the terms of the claims, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

11: Battery container 13: Outer container 14: Heating device (first heating device)
15: Outer container 17: Case 18: Powdered body (substance)
19: Seal 22: Dry battery (general-purpose battery)
23: Condensing device 100: Heating device for starting (second heating device)
200: Emergency molten salt assembled battery 300: Inverter device 400: Emergency power supply device B: Molten salt battery B1: Molten salt battery for actual operation B2: Molten salt battery for starting

Claims

It is an emergency molten salt battery that is composed of a plurality of molten salt batteries containing molten salt as an electrolyte, and is stored in a state where the electrolyte is solidified after being charged,
A plurality of production molten salt batteries;
A first heating device for heating the plurality of production-use molten salt batteries;
At least one starting molten salt battery capable of operating the first heating device;
It is provided at the battery container of the starting molten salt battery, and is a room temperature body that maintains the electrolyte of the starting molten salt battery at a temperature below the melting point when not in operation, but heating the battery container during operation An emergency molten salt assembled battery comprising: a starting second heating device as a body.
The emergency molten salt assembled battery according to claim 1, wherein the second heating device is an outer container for the battery container, and is capable of introducing a heat medium.
3. The method of using an emergency molten salt battery according to claim 2, wherein the second heating device is maintained at room temperature in the absence of the heating medium, and the second heating is performed by introducing the heating medium. A method of using an emergency molten salt assembled battery in which the apparatus is changed to a heating element.
2. The emergency molten salt according to claim 1, wherein the second heating device encloses a substance capable of generating heat due to a chemical reaction in a case covering the battery container with a seal for preventing the start of the chemical reaction. Assembled battery.
5. The method for using an emergency molten salt assembled battery according to claim 4, wherein the second heating device is maintained by maintaining the second heating device at a normal temperature in a state where the seal is provided, and removing the seal. To use the molten salt assembled battery for emergency which changes the heat to a heating element.
The emergency molten salt assembled battery according to claim 1, wherein the second heating device is provided on an outer surface of the battery container and can be heated by a general-purpose battery.
2. The emergency molten salt assembled battery according to claim 1, wherein the second heating device includes a device that condenses and heats sunlight directly or indirectly on an outer surface of the battery container.
The emergency molten salt assembled battery according to any one of claims 1, 2, 4, 6, and 7, and an inverter device that converts a voltage output from the emergency molten salt assembled battery into a commercial AC voltage. Emergency power supply equipped.