JP2010086885A - Storage container for used battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a structure of a storage container for solidifying and keeping cold an electrolyte solution (inflammable organic solvent solution). <P>SOLUTION: The inside of the container surrounded by a multiple insulating material wall is kept at cooled solidification temperature of an electrolyte by using a liquefied noninflammable gas, a low-temperature noninflammable gas, and a solidified noninflammable gas as a cooling medium. A battery is stored inside the container by passing through an outer cover inlet (opening with the minimum gap of an elastic body) contacting with the open air and a multiple inner cover inlet (self-closing type opening/closing door) prepared inside the container. Leakage of the chill is prevented by the structure of the inlets, and a refrigerating structure can be established by a structure wherein the cooling medium is poured into a gap of the insulating material. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a battery storage container including a waste lithium ion battery.

  Modern mankind has made it possible to use many electronic and electrical devices without a power cord by means of a battery, a relatively small device that can extract the chemical energy of a substance as an electric current. In recent years, there has been a remarkable development of a secondary battery that can recharge a used battery and return it to a full state of energy, that is, can be repeatedly discharged and charged. Among them, a lithium ion secondary battery requires a variety of portable devices such as a mobile phone, a notebook personal computer, and a digital camera due to its large electromotive force and a large amount of charge / discharge per volume or weight of the battery. Used in electronic and electrical equipment, its production volume reached 1 billion in 2006 alone (according to METI statistics). In the future, this type of battery will continue to increase in size, and is also widely used as a power source for electric vehicles, hybrid cars, and other large devices.

  On the other hand, this characteristic of the lithium ion battery is due to an element called lithium, which has a high oxidation-reduction potential and a large amount of charge transfer accompanying movement of ions of its unit weight, which is rich in reactivity, radical, It is difficult to control. In a lithium ion secondary battery, lithium ions move from the positive electrode to the negative electrode during charging and from the negative electrode to the positive electrode during discharging, but the potential difference is larger than the electrolysis potential difference of water, so that the electrolyte serving as the medium An aqueous solution cannot be used as the solution, and instead, a kind of organic solvent solution in which lithium ions can be dissolved is used.

  Known organic solvents that can be used in the electrolyte of lithium ion secondary batteries are γ-butyrolactone (boiling point 206 ° C., freezing point −42 ° C.), ethylene carbonate (boiling point 238 ° C., freezing point 36 ° C.), propylene carbonate ( Boiling point 90 ° C, freezing point -49 ° C), dimethyl carbonate (boiling point 90 ° C, freezing point 0.5 ° C), diethyl carbonate (boiling point 127 ° C, freezing point -43 ° C), 1.2-dimethoxymethane (boiling point 82 ° C, freezing point- 58 ° C), tetrahydrofuran (boiling point 65 ° C, freezing point -108 ° C), 12 dioxolane (boiling point 78 ° C, freezing point -95 ° C), diethyl ether (boiling point 34.5 ° C, freezing point -116 ° C) and the like. .

  Actually, among these solvents, the solvent having an ether bond has a boiling point that does not reach 80 ° C. and is relatively low. Therefore, the battery internal pressure rises due to the vapor pressure of the solvent in a high-temperature battery use environment, and the flash point is low. Because of its low heat resistance, it is rarely used. A mixed solution in which a plurality of carbonate solvents having a high boiling point are mixed and adjusted so as to have a low freezing point and a high boiling point, and a balance between heat resistance and cold resistance is used as an electrolytic solution. However, since all these solvents are flammable, this battery has a great weakness that it is easy to burn.

  Furthermore, when this lithium ion secondary battery is exposed to high temperature or repeatedly overcharged or overdischarged, the crystal structure of the positive electrode active material (mainly lithium cobaltate, lithium nickelate, etc.) Becomes unstable, collapses or decomposes, oxygen is liberated therefrom, heat is generated, and oxidation and combustion of the electrolyte solution easily occur. In addition, since the amount of energy contained in the battery is large, if a short circuit occurs due to contact between the positive electrode and the negative electrode, the short circuit current generated thereby is large. A plastic porous film called a separator that physically prevents contact between the positive electrode and negative electrode inside the battery is damaged due to deformation, destruction, etc. of the battery, and both electrodes come into contact through the damage, or both positive and negative electrodes outside the battery If an external short circuit occurs in which the terminal of the battery contacts via a conductive material, a large current flows suddenly and heat is generated in the battery, decomposition of the positive electrode active material (such as lithium cobalt oxide), liberation of oxygen, and heat generation. Runaway, which causes the electrolyte to boil, ignite, and explode. It has been reported for mobile phones and personal computers that smoke and combustion accidents actually occurred even without an explosion.

  Conventionally, battery manufacturers have improved the structure, material composition, manufacturing method, and the like of lithium ion secondary batteries to enhance the safety of the batteries themselves. For example, even when the operating environment temperature is high, the cathode material is less likely to be degraded and decomposed. When a large-current heat generation occurs due to a short circuit, the separator film melts to close the pores through which lithium ions pass, increasing the internal resistance of the battery. For example, a safety valve is built in to prevent the electrolyte vapor pressure from rising due to heat generation, and the pressure is released when the pressure exceeds the set pressure. In addition, battery manufacturers do not allow ordinary users to use lithium ion secondary batteries as they are (referred to as single cells), and always set control boards to prevent overcharge and overdischarge in single cells (pack batteries). Called).

  The battery pack differs depending on the electronic / electrical device in which the battery is incorporated, but in general, a case in which one or more control boards and single cells are connected to a plastic case, and a positive electrode and a negative electrode terminal are provided on the outer surface of the case. Some of them are connector terminals. Although battery packs have dramatically increased safety compared to single cells, there are still smoke and combustion accidents in lithium ion secondary batteries. Some battery users may disassemble the battery pack made by the manufacturer, take out the single cell, and use it independently according to the design specifications of their electronic equipment. In this case, the safety of the battery is guaranteed. Not.

  Lithium ion secondary batteries are packaged as products after production, and are stored and distributed in a state in which safety that does not cause deformation, destruction, short circuit, etc. is ensured. After these batteries are put to practical use, they are discharged as used batteries and disposed of when they are deteriorated due to long-term use or when the built-in equipment is renewed or discarded. Waste batteries are enlightened to be stored separately, but in practice, separation is not thorough, various batteries, and those with a lot of residual electricity, those with a small amount of electricity, primary batteries, secondary batteries, packs in plastic cases Batteries, exposed terminals, and terminals protected in the form of connectors are mixed and collected in the waste storage area. The environment of the storage container and storage location of the waste battery is incomparably inferior to that when it was stored as a product before use. In particular, there are few cases where the safety considerations required for lithium ion secondary batteries are not taken into consideration. Absent.

  A waste battery in which an electromotive force remains is often randomly inserted into a battery storage container of a waste storage area with an electrode terminal exposed. If the battery storage container contains a clip, a metal can, or other waste with exposed metal surfaces, the electrode terminal of the electromotive force remaining battery comes into contact with the battery, and an external short circuit occurs. Impact at the time of battery insertion, deformation destruction due to the load of a large amount of battery, high / low temperature and high humidity environment of storage place and corrosion due to leaked electrolyte, they are synergistically involved, leading to short circuit heat generation, electrolyte leakage, ignition, combustion, etc. In addition, it may affect neighboring batteries and cause chaining, resulting in a fire / explosion accident involving many batteries. Even if there is no abnormality when the waste battery storage container is left standing, when it is transported on a vehicle, the direction of the battery changes due to vibration, and a short circuit is promoted. There may be a case where energy such as a drop impact acts on the battery in the storage container to cause destruction of the battery. Especially in the case of a large lithium ion secondary battery used as a vehicle power source, the amount of built-in energy is large, so the possibility that a traffic accident on a transport vehicle during transportation could lead to a major accident involving combustion, explosion, etc. of a discarded battery is denied. It is not possible.

  However, with regard to the storage and transportation of lithium ion secondary batteries, the main focus is to ensure the safety by encouraging users to be aware of the danger or by restricting the carry-on of aircraft. .

  In order to ensure safe transportation as a product, battery manufacturers are reducing the charge amount of lithium ion secondary batteries to 50% of the maximum charge amount before shipping. Regarding product packaging to ensure safety, a patent for a packaging container for transportation having a breaking strength of 13.0 Kgf / cm2 or more according to the method specified by JIS, with a total weight of 25 Kg or less from the battery manufacturer. Is disclosed (see Patent Document 1). The method using this packing container is to be able to separate and store each battery individually by dividing the inside of the container with a partition plate so as not to damage the battery having a variety and history as a product. It is a thing. In the case of a waste battery, since it is natural to randomly put used products into a storage container, it is impossible to perform thorough placement into a partitioned space. It is difficult to put the used container into practical use as a storage container for a discarded battery. In other words, it is difficult for a large number of battery users to thoroughly arrange and accumulate individual waste batteries, and if the waste manager does not take measures to make the collection location of the waste batteries safe, the waste batteries It is considered that storage safety cannot be ensured.

  For the purpose of recovering raw materials from waste lithium ion secondary batteries, it is known to cool the inside of the tank where the battery exists to the temperature at which the electrolyte solution solidifies as a safety measure for short-circuit current when crushing the battery. (See Patent Document 2). In this case, it is necessary to cool the space only within the time required for crushing and a series of processing conveyances that follow it, and in the case of storage of the waste battery accumulation place and / or transportation from the accumulation place to the waste treatment factory. In comparison, it can be said that the cooling time is much shorter. Even if the cooling and cooling for the purpose of crushing is applied to storage and / or transportation, safety cannot be ensured.

  The current practice for ensuring safety when storing and transporting waste batteries is to apply an electrically insulating adhesive tape to the electrode terminals in order to prevent external shorting of the lithium ion battery. . However, in this method, it takes time and effort to ensure thorough execution of all individual batteries. Further, there is a risk of tape peeling, and internal short circuit due to factors such as deformation and destruction cannot be prevented, and the risk of combustion due to liquid leakage cannot be excluded.

  At the time of transportation, the storage state of the lithium ion secondary battery changes abruptly, and the risk factors are increased compared to those at the time of stationary storage. If the battery is transported in a state where the battery is randomly inserted in a general transport vehicle, even if the container is fixed to the loading platform, it may be suddenly stopped, shocked by sudden start-up, vibration, slope inclination change, etc. However, there are risk factors such as collision, overload due to acceleration, contact with mixed conductive materials, and in some cases, an increase in the temperature inside the vehicle, which makes the battery extremely unsafe. The risk of these risk factors due to traffic accidents is great, and it cannot be said that there is no possibility of a major accident.

JP 2002-75308 A JP-A-10-241748

  As described above, various primary batteries and secondary batteries are integrated as waste batteries in a waste storage area. Among them, safety necessary for waste batteries including lithium ion secondary batteries, which are particularly dangerous. A secure storage container has not been established. Although a container for storing lithium ion secondary batteries that are individually aligned and separated in a box partitioned as a product is known, it cannot be used as a storage container for randomly inserted waste batteries. One of the biggest causes of danger in lithium ion secondary batteries is the use of flammable organic solvents in the electrolyte. It is known that when a lithium ion secondary battery is pulverized, it is temporarily placed in a cooling bath and the solvent is solidified to prevent short circuit heat generation. In this case, the cooling time is short, so the cooling time is long. It is difficult to apply this cooling tank when storing waste batteries over time and transporting them from a storage location to a waste disposal or recycling factory.

The inventors should be able to avoid the danger of combustion and explosion by controlling this electrolyte for a long time in the storage container at the waste collection site. I thought it was necessary to make a technical solution.
a. In the storage container of the waste battery, the electrolyte ions, which are the current carriers in the battery, cannot be moved.
b. Leakage and vaporization of the organic solvent electrolyte, which is a combustion product in the battery, is made impossible in the storage container of the waste battery.
By technically solving the above two items, we established a storage container that can prevent heat generation and combustion accidents during storage and / or transportation of waste lithium ion secondary batteries, and has been placed in a dangerous state. It is an object of the present invention to ensure the safety of the discarded lithium ion secondary battery.

In order to achieve the above object, the present invention comprises the following means in a cooled storage container of a lithium ion battery.
A cooling storage container that cools and stores an externally charged lithium ion battery and absorbs impact during movement, and injects a cooling medium into the cooling storage container to cool and solidify the electrolyte of the lithium ion battery. Means, a means for maintaining the solidified state of the cooled and solidified electrolyte, and leakage of the low temperature gas in the cooling storage container to the outside when the cooling medium is injected into the cooling storage container and the lithium ion battery is inserted. And a means for opening and closing the opening to prevent.

  The means for cooling and solidifying the electrolyte is characterized by injecting a liquefied incombustible gas and / or injecting a solidified incombustible gas at a temperature at which the electrolyte is cooled and solidified.

  The means for maintaining the solidified state of the electrolyte comprises a multi-wall construction in which the bottom, top lid, and side walls of the cooling storage container are made of at least double insulation, and the outer wall of the cooling storage container and at least one inner wall The liquefied incombustible gas and / or incombustible gas is filled in the gap between the two or the gap between the inner walls.

  The cooling storage container is characterized in that at least one detachable inner container for storing the lithium ion battery is provided.

  By putting dry ice into the inner container, the cooling storage container and the inner container are filled with carbon dioxide heavier than air, and the cooling and solidification of the electrolyte is maintained.

  The first input port provided in the outer lid of the outer wall of the cooling storage container, the second input port provided in the inner cover of the at least one inner wall, and the upper side of the inner container are vertically connected vertically. The first insertion port provided in the outer lid is a lid that is opened by deformation of the elastic body, and the second insertion port provided in the inner lid is characterized by being an open / close lid.

  The inlet opening / closing means for preventing leakage of low-temperature gas to the outside is elastic when the liquefied incombustible gas injection funnel, dry ice, and lithium ion battery are pushed into the first inlet provided in the outer lid. The lid of the body deforms and opens its mouth, and when it is dropped into the second insertion port provided on the inner lid, the open / close door opens and passes by the weight and / or pushing force of dry ice and lithium ion battery After that, each door is closed by elasticity.

  The open / close door, which is the lid of the second inlet port provided in the inner lid, does not open only by the weight of the liquefied incombustible gas, and the liquefied incombustible gas flows between the outer wall and the inner wall and between the inner walls. There are features.

In addition, in the atmosphere of the cooling solidification temperature of the electrolyte solution of the lithium ion battery, a buffer material is filled between and / or in the space around the inner container installed in the cooling storage container. .
The cushioning material has the role of absorbing impact from the outside, so it is made of foamed material, fiber cotton, non-woven fabric, etc., and packing, hail, string, etc. are intertwined or polyethylene bags It is preferable that it does not scatter, for example.

The insertion port has a shape that matches the shape of the lithium ion battery to be dropped, and is characterized by being a part that can be detached from the outer lid and the inner lid.
The outer lid and the inner lid are detachable from the cooling container.

  The storage container according to the present invention has a high ability to keep cold, and can safely store a lithium ion secondary battery for a long time. The freezing point of the electrolyte solution in the battery is lower than the freezing point of the physicochemically pure solvent due to the freezing point depressing action of the dissolved electrolyte, but it is sufficiently cooled and kept cool and kept below the freezing point. By doing so, the electrolyte solution in the battery loses its fluidity and ion migration becomes impossible, so that there is an effect that the short-circuit current does not flow even during a short circuit. When the electrolyte solution is solidified, the electrolyte solution does not flow out even if the battery is destroyed, and the vapor pressure of the combustible solvent can be ignored because the vapor pressure of the solidified product is low. That is, this storage container provides the effect of making it impossible to leak and vaporize the organic solvent electrolyte.

  The lithium ion battery containing the organic solvent electrolytic chamber solution can be solidified by cooling to −50 ° C. or lower, more certainly −60 ° C. or lower. Below this temperature, the electrolyte in the battery (lithium hexafluorophosphate, lithium hexafluoroborate, etc.) is present in the solidified crystal mixture of the electrolyte solution, but the lithium ion from the negative electrode to the positive electrode Even when the movement is blocked and a potential difference is generated, there is an effect that it is difficult for electricity to flow between the electrodes.

  Cooling is performed using a nonflammable low-temperature gas, liquid, or solid, which further increases the combustion inhibition effect. Due to the structure of the lid of the storage container and the lid of the inlet port provided in the lid, a part of the cooling medium enters the gap between the heat insulating material multiple walls constituting the storage container, so that it can also be cooled from between the walls. It has the effect of ensuring cold insulation. The structure in which the lid of the inlet is opened in a form matching the lithium ion battery has the effect of reducing the leakage of the cooling incombustible gas and keeping the cold for a long time.

  When transporting the storage container, it can be securely transported for an extended period of time by loading it in a cold storage vehicle equipped with a refrigerator and cooling the storage container. By cooling, there are almost no risk factors during transportation, and there is an effect of avoiding battery heat generation accidents.

  FIG. 1 is a top view 101 (partially a cross-sectional view), front view 102 (partially a cross-sectional view), and FIG. 2 is a front view showing a state where a part of an inlet is opened. This is illustrated by the section 104 (cross-sectional view). The external shape of the storage container is a rectangular parallelepiped, but various shapes such as a cylinder, an elliptic cylinder, other polygonal cylinders, and a cylinder having a complicated curved surface are possible. Although the shape having a small outer surface area has a high cooling effect as compared with the internal volume, the actual shape is preferably a rectangular parallelepiped or a cylinder that is easy to handle. In the storage container, an inner container 5 having an opening upward is installed, and a battery is accommodated therein.

  The surface material 4 of the outer wall 3 of the storage container needs to have a strength as a structural material and a surface scratching strength that protects the appearance. As such a material, a light material having a low thermal conductivity and no problem in practical use as compared with metals such as painted wood, plastic and fiber reinforced plastic is suitable. The outer wall surface material 4 is fixed with foamed polystyrene, foamed polyurethane, a molded heat insulating material of organic or inorganic fiber cotton, etc. as a heat insulating material of the outer wall 3 on the inner side.

The surface material 13 of the inner wall 1 of the storage container is preferably made of a material that does not easily damage the surface because there are many opportunities to come into contact with the inner container 5, and does not soak in moisture generated by condensation. 4 is made of the same material, and the same heat insulating material as that of the outer wall 3 is fixed.
The storage container has a multiple inner wall structure in which gaps are provided between the outer wall 3 and the inner wall 1 and partitioned by multiple heat insulating materials (1, 2 and 3 in FIG. 1, in this figure, the outer wall heat insulating material and the double wall). The triple wall structure of the inner wall insulation material). The heat insulating material can be used as long as it is not only a foam material but also has a low thermal conductivity and has the same strength as the foam material.

  The number of walls is determined by the relationship with the thickness of the heat insulating material, the thickness of one heat insulating material is 1 to 10 cm, the total thickness of the heat insulating materials is 10 to 30 cm, and the number of walls is 2 or more, preferably 3 or more. . If the heat insulating material is made thicker and the number thereof is increased, naturally the cold insulation capacity is increased, but the volume of the entire storage container is increased and becomes unsuitable for practical use. The gap between the heat insulating materials (14 and 15 in FIG. 1) is preferably 0.5 to 3 cm. If the gap is too wide, the volume of the entire storage container increases, and at the same time, warm air from the outside flows from the inlet and stays. The space becomes larger and the cold insulation gets worse. These gaps serve to increase the cooling effect by being filled with the cooling medium or the cold air overflowing from the inside of the storage container, and the warm air from the outside should not easily stay.

In the same way, it is desirable to provide a gap on the bottom surface for cooling. However, in order to do so, a bottom plate of heat insulating material having a strength capable of maintaining the gap and a column and a beam supporting it are provided between the gaps, and the weight of the battery to be accommodated is reduced. Therefore, it is necessary to prevent deformation such as indentation deflection, and this strength cannot be obtained only with a low thermal conductivity material such as a foam material. Therefore, in order to secure the storage capacity of the object to be stored and maintain the cold insulation capacity, a multi-layered structure in which the entire bottom surface is brought into contact with the entire surface of the heat insulating material in the lower layer without providing a gap (see FIG. 1). In the example, the inner bottom heat insulating material 17 + the inner bottom heat insulating material 18 + the outer bottom heat insulating material 19) are used so as to support the weight of stored items over the entire bottom surface. In this case, even if the battery is fully accommodated in the inner container 5, the load applied to the bottom surface is 0.03 to 0.2 Kg / square centimeter, and the insulation material such as the hard foam material such as the expanded polystyrene described above is used. Strength is sufficient.
Note that the heat transfer from the floor can be reduced by placing the storage container on a wooden or plastic pallet instead of directly placing it on the floor where it is installed. It is desirable to move the storage container with the forklift together with the pallet.

  It is possible to configure the storage container with multiple vacuum insulation walls, but in this case, the material must be a metal that can withstand vacuum and does not deform, and if it is large in shape, its thickness increases and its weight increases. Is not easy to handle. Therefore, the heat insulating material of the large-sized cold box is preferably a heat insulating material such as a lightweight foamed material or a molded material obtained by solidifying fiber cotton, or a low thermal conductive material equivalent thereto.

  In the storage container, an inner container with an opening upward is installed (in FIG. 1, the storage container is sized so that nine inner containers 5 can be installed, but is not limited to nine in particular. And a plurality of lids (6, 9, 10, 11 in FIG. 1) made of a heat insulating material. The lid is fitted on the edge of the wall so as to be detachable by covering the upper side surrounded by each side wall corresponding to the multiple side walls. Each lid is provided with a slot. Since the influence of the outside air is often due to warm air entering from the inlet, the top lid 6 is attached on the outer lid 9 so as to cover the inlet further in order to reduce the influence of the inlet. The top cover 6 may be removed during the charging operation in order to perform the battery charging operation quickly and efficiently, and may be covered when the charging is finished and storage for a long time starts.

  The outer lid 9, the inner lid 10, and the inner lid 11 are provided with inlets so as to be positioned on the inner container 5. The charging port is provided with a charging port lid (12, 7, 8), which is opened to drop the battery downward, and push the lower charging port lid one after another to pass through to reach the inner container. If the inlet lid is closed, the inner container is surrounded by multiple heat insulating walls, and the influence of the outside temperature can be cut off and kept cool. If the inlet and the inlet lid are not provided, the top lid 6, the outer lid 9, the inner lid 10, and the inner lid 11 must be removed in order, and the battery must be inserted into the inner container 5. In addition, the storage container does not play its role, and since the number of lids is large, it is very inconvenient because there are many operations to remove it.

  In FIG. 2, the state (6b) in which the top lid charging port lid 6 is lifted and removed, the state (12b) in which the outer lid charging port 12 is opened, the inner lid charging port lid 7 is pushed from above, the hinge 16 is folded down, It shows a state (7b) in which the double-open door is open (this hinge has a spring, and when the pushing force from the top disappears, the hinge is extended by the force of the spring and the door returns) )

  Even when the top lid 6 is removed, it is effective to block off the outside air by using multiple lids below the outer lid below it, so the thrower can be removed all at once so that all the inlets are in view. During normal storage, the lid 6 is fitted, and the entire cooling storage container has a structure that is effective for keeping cold without opening.

The outer lid charging opening lid 12 is in direct contact with the outside air when the battery is inserted, and it is necessary to open the minimum necessary passage of the battery while preventing the intrusion of warm air and the leakage of cold air to the minimum. The outer lid charging port lid 12 is a polyurethane sponge elastic body that is reinforced with springs and reinforced with a wire and is reinforced with a water-repellent cloth. When closing the mouth, the opening joint is tightened from both sides. When the battery is inserted, the battery is pushed into the joint so that the mouth can be opened and passed. Since this outer lid insertion port lid becomes severely damaged when it is inserted frequently, only this portion can be detached and easily replaced with a new one. When the top lid is removed, the outer lid is in direct contact with the outside air, so that it is easy to condense with moisture in the air in a humid place. Therefore, in this case, the top lid is fitted after wiping off the water droplets appearing on the surface of the water-repellent outer lid.
In addition, the structure of the outer lid charging opening lid is not limited to the above-described structure when allowing a clearance when opened, but various structures, for example, a structure similar to the inner lid charging opening lid using a hinge, a manual fitting lid Etc. are also applicable.

  The inner lid charging port lid 7 and the inner lid charging port lid 8 are below and below the outer lid charging port 12, respectively, and the battery passes through the upper charging port and the upper charging port lid is located above the charging port. It opens after closing or just before closing. The inner lid charging port lid 7 and the inner lid charging port lid 8 are opened by the weight and / or pushing force when the battery and the dry ice lump are charged, and when liquid nitrogen is injected, the liquid flows sideways and stays. The weight of the liquid to be opened does not open. The liquid nitrogen and the low-temperature nitrogen gas that flow into the gap between the side heat insulating walls contribute to cooling the entire storage container in a short time in addition to cooling from the gap and cooling. When the gap between the walls is filled with liquid nitrogen and the liquid level rises above the inlet lid, the inlet lid is pushed downward to open, and the liquid flows into the space under the lid, and the lid The lid closes again when the top liquid is depleted.

  Changing the size of the inlet and the opening / closing method of the lid means that the outer lid 9, the inner lid 10 and the inner lid 11 are compatible fitting structures having different sizes and / or different opening / closing mechanisms. Or it can replace with the lid | cover of another structure, or it makes it possible to attach or detach the insertion opening lid | cover for every insertion opening, and can replace with a different insertion opening cover. In a collection place where waste batteries are accumulated little by little and the accumulated batteries must be stored for a long period of time, the inlet is made as small as possible to shorten the opening time, and a large amount of waste batteries are accumulated in a short period of time. By the way, each lid provided with a large opening that can be loaded with a large amount of discarded batteries in a short time without any trouble is selected and used.

  The size and internal volume of the storage container are determined by the storage amount and the cold storage capacity (corresponding to the amount of heat insulating material and the amount of gap) of the waste battery. After storage, waste batteries are transported together with storage containers (including inner containers) to the factory of the waste disposal company or recycling company, so the outer dimensions and size of the storage containers that are convenient for carrying vehicles and forklifts are required. Is done. It is necessary to take as large a storage container as possible and to ensure sufficient cooling capacity, but since the portion occupied by multiple thermal insulation layers is large, the ratio of the internal volume to the outer shell volume (referred to as the internal volume ratio) Becomes 20 to 60%. An internal volume ratio of 25 to 50% is a balanced range between the cold storage capacity and the internal volume. The storage container shown in FIG. 1 has a volume of 1100 liters, an internal volume of 350 liters, and an internal volume ratio of about 32%.

  Cooling is performed by putting granular or small pieces of dry ice (−78 ° C.) between the inner wall surface material 13 and the inner container 5, that is, in the inner container inner wall space 20 and the inner container 5, and closing all the lids. Sufficiently precool. Instead of dry ice, it is also possible to perform pre-cooling by connecting a cryogenic refrigerator and sending cold air. After the dry ice is charged, the first vaporized carbon dioxide pushes up the air that has existed before cooling and removes it from the closed door gap of each of the multiple charging ports to the upper space. Cool the vessel to near dry ice temperature.

  Next, liquid nitrogen is poured from the charging port, paying attention to vigorous boiling, solidifying the carbon dioxide gas, and at the same time, the low-temperature nitrogen gas that has just been vaporized rises from the gap between the inner lid 11 and the charging port lid 8 of the storage container. (Even if the peristaltic part (edge) where the lid is fitted is precisely finished without unevenness, the gas leaks from a slight gap in the joint because the internal pressure of the generated nitrogen gas is slightly high) The air reaches the gap 14 between the outer surface of the inner wall 1 and the inner surface of the inner wall 2, cools the space while replacing the gas present therein, and lowers the surface temperature of the inner surface of the inner wall 2. Similarly, the low-temperature nitrogen gas reaches the gap 15 between the outer surface of the inner wall 2 and the inner surface of the outer wall 3 and enhances the cooling effect of the inner wall 2. That is, low temperature gas is present in each gap between multiple heat insulating material walls, the discontinuity of the temperature gradient is increased by the gap, and the temperature gradient in each heat insulating material is made gentle to enhance the heat insulating effect. I can do it. The inside of the storage container can be effectively kept at a low temperature by a mechanism that blocks heat transfer from the outside air by a multi-layer partition including a gap. The cooling effect by this gap is obtained on the side surface and the upper surface.

  Liquid nitrogen is injected by inserting a funnel into the outer lid inlet 12, and the position of the funnel tip outlet is adjusted and injected directly into the space where the inner container is installed, or the space above the inner lid inlet 8, Whether to enter the space above the inner lid inlet 7 can be determined. By positioning the outlet of the funnel in the target space and slowly injecting liquid nitrogen, the inner lid charging port lid is not opened, but liquid nitrogen is allowed to flow laterally from the edge of the inner lid to the side insulation wall. The storage container can be efficiently cooled over the gap.

  By using solidified incombustible gas such as dry ice and liquid nitrogen and / or liquefied incombustible gas as a cooling medium, oxygen is excluded from the generated incombustible gas, so that no combustion occurs in the storage container. And safety is further enhanced.

  The size of the inner container 5 is a volume that can accommodate a waste battery and can be carried by a human. There is no essential limitation as long as it can fit in a storage container, but it is preferably 10 liters. Thus, 30 liters or less is suitable. The inner container 5 must be filled with a waste battery and have a strength that does not break, but it is necessary that the strength does not decrease greatly even when wet. That is, in an industrial waste treatment or recycling factory, in order to treat a waste battery, only the inner container with the battery is taken out and the empty storage container is returned to the waste battery discharge source as a returnable container. To do. Condensation occurs when the inner container is exposed to a normal temperature of the outside air from a low temperature state, and the strength that can withstand it is necessary.

  In industrial waste processing or recycling processing plants, waste batteries are often put into incinerators together with their inner containers, so the inner containers can be incinerated in incinerators, and when they are used as storage containers, battery heat is generated in an emergency. It is desirable that it does not burn immediately. Practical materials that satisfy this requirement include high-density polyethylene, polypropylene, acrylonitrile butadiene styrene resin, phenol resin, urea resin, vinyl chloride resin, fiber reinforced unsaturated polyester resin, fiber reinforced epoxy resin, etc. Water resistant and high strength cardboard is preferred.

With the lid of the storage container (6, 9, 10, 11 in FIG. 1) removed, the inner container is installed in the storage container, and the inner wall space 20 of the inner container is filled with dry ice and / or cushioning material. Close the multiple lids and attach the fasteners so that the lids do not come off.
The inner container inner wall space 20 between the inner container 5 and the inner wall surface material 13 is necessary for smooth installation and removal of the inner container 5. Further, by allowing dry ice and / or a substance having a large heat capacity, a cold storage material, and the like to exist in this space, the cold insulation can be effectively continued for a longer period of time. When there is no dry ice or the like and the space is wide, the inner container 5 may collide with the inner wall surface material 13 especially when transported by a vehicle, and if the space is wide, the inner container 5 may fall down. In order to prevent an impact caused by a sudden movement of the inner container in the storage container, a buffer material is filled between the inner container inner wall space 20 and / or the inner container. As this cushioning material, foamed plastic molded products, plastic sheets containing a large amount of air, organic inorganic fiber cotton, non-woven fabric, and the like are generally suitable. If these cushioning materials are easy to handle, such as gravel moldings, irregular shaped pieces, fiber cotton, etc., put them in a polyethylene bag so that they do not scatter in the storage container. It is desirable to fill the inner wall 20 of the inner container by wrapping or entwining it gently if it is a string or belt.

If the temperature sensor inside the storage container is set at the bottom of the storage container, the temperature sensor of the thermometer, for example, a platinum resistance thermometer, can be pulled out of the individual container and recorded continuously. It is. As a simple measurement method, attach a thermometer (for example, an alcohol thermometer) capable of low temperature measurement to the tip of a stick or tube, open the inlet to the minimum, insert it into a cold box, and leave it for 1-2 minutes. This can be done by immediately reading the thermometer's instructions.
There is no particular lower limit to the cooling temperature up to absolute zero, and even if liquid helium or liquid argon is used instead of liquid nitrogen, there is no problem in cooling. The cooling holding temperature range is preferably from zero to -60 ° C, and even in the range from more than -60 ° C to -50 ° C, it can be carried out in a solvent used as a normal electrolytic solution.
The storage container according to the present invention can hold -50 ° C. or less for a long time, but the change in the internal temperature differs depending on the input amount, the input frequency, the outside air temperature, etc., so the temperature can be continuously recorded and monitored. It is preferable to use a self-recording thermometer. If it exceeds -50 ° C due to long-term storage, add dry ice or liquid nitrogen. The internal temperature is lowered to -50 ° C or lower.

  When transporting this storage container containing waste batteries from a waste battery collection site to a waste disposal or recycling plant, it is most desirable to transport them in a refrigerated container vehicle, but even ordinary container vehicles and flat body vehicles are discarded. Safe transport of lithium ion secondary batteries is possible.

  The storage container according to the present invention can be used for storing and transporting a waste lithium ion secondary battery. In addition, it can be used for a similar object requiring storage at a low temperature of −50 ° C. or lower for a long time. It can be used against. As those objects, peroxides, organometallic compounds, and other reactive compounds that are highly reactive or decomposable in a normal living environment can be stored and transported safely at low temperatures. Furthermore, it can be used for a longer time as a storage container under a condition where the cold temperature is high.

The triple wall cooling storage container is a cross-sectional view of a top view and a front view thereof. FIG. 5 is a partial cross-sectional view of the triple-wall cooled storage container front view, showing a state where the outer lid inlet and the intermediate inner lid inlet are opened and the inner lid of the innermost wall is closed.

Explanation of symbols

101 Top view of triple wall cooling storage container 102 Front view of triple wall cooling storage container 103 Slope view of inner container 104 Example of opening and closing of inlet at part of front view of triple wall cooling storage container 1 Inner wall 2 Inner wall 3 Outer wall 4 Outer wall surface material 5 Inner container 6 Top lid 6b Removed top lid 7 Inner lid inlet lid 7b Opened inner lid inlet 8 Inner lid inlet lid 9 Outer lid 10 Inner lid 11 Inner lid 12 Outer lid inlet lid 12b Opened outer lid inlet 13 Inner wall 14 Gap between inner walls 15 Gap between inner wall and outer wall 16 Hinge 17 Inner bottom heat insulating material 18 Inner bottom heat insulating material 19 Outer bottom heat insulating material 20 Inner container inner wall space 50 Center line 51 Cross section 52 cross section 53 cross section

Claims (11)

  A cooling storage container that cools and stores an externally charged lithium ion battery and absorbs impact during movement, and injects a cooling medium into the cooling storage container to cool and solidify the electrolyte of the lithium ion battery. Means, a means for maintaining the solidified state of the cooled and solidified electrolyte, and the introduction of the cooling medium into the cooling storage container and the introduction of the lithium ion battery to the outside of the low-temperature gas in the cooling storage container A cooling storage container for a lithium ion battery, comprising: an opening opening / closing means for preventing leakage of the lithium ion battery.   2. The lithium according to claim 1, wherein the means for cooling and solidifying the electrolytic solution injects a liquefied incombustible gas having a temperature for cooling and solidifying the electrolytic solution from the charging port and / or inputs a solidified incombustible gas. Ion battery cooling storage container.   The means for maintaining the solidified state of the electrolytic solution includes a multi-wall structure in which the bottom, top cover, and side walls of the cooling storage container are formed of at least a double heat insulating material, and at least one of the outer wall of the cooling storage container. 3. The cooling storage container for a lithium ion battery according to claim 1, wherein the liquefied incombustible gas and / or the incombustible gas is filled in a gap between two inner walls or a gap between the inner walls.   4. The lithium ion according to claim 1, further comprising at least one detachable inner container in which the lithium ion battery is accommodated inside the cold storage container. 5. Battery storage container.   The dry storage container and the inner container are filled with carbon dioxide heavier than air by charging dry ice into the inner container, and cooling and solidification of the electrolyte solution is maintained. The cooling storage container for the lithium ion battery according to any one of 4.   The first input port provided in the outer lid of the outer wall of the cooling storage container, the second input port provided in the inner cover of the at least one inner wall, and the upper side of the inner container are vertically connected to each other The first inlet provided in the outer lid is a lid opened by deformation of the elastic body, and the second inlet provided in the inner lid is an opening / closing lid. The cooled storage container for a lithium ion battery according to any one of claims 1 to 5.   The inlet opening / closing means for preventing leakage of the low temperature gas to the outside includes the liquefied incombustible gas injection funnel, the dry ice, and the lithium ion battery in the first inlet provided in the outer lid. When pushed, the mouth opens due to deformation of the elastic lid, and when dropped into the second slot provided in the inner lid, the weight of the dry ice and the lithium ion battery and / or the pushing force The lithium ion battery cooling storage container according to any one of claims 1 to 6, wherein the opening / closing lid is opened and closed by an elastic body after passing.   The opening / closing lid of the second inlet provided in the inner lid does not open at the start of the injection of the liquefied incombustible gas, and flows into the gap between the outer lid and the inner lid and between the inner walls. The lithium ion battery cooled storage container according to any one of claims 1 to 7.   In the atmosphere of the cooling and solidification temperature of the electrolyte solution of the lithium ion battery, a buffer material is filled between and / or in the space around the inner container installed in the cold storage container. The cooling storage container for a lithium ion battery according to any one of claims 1 to 8.   The said insertion port has a form according to the shape of the said lithium ion battery to drop, and is a component which can be attached or detached from the said outer lid | cover and the said inner lid | cover. A cooling storage container for the lithium ion battery according to 1.   11. The cold storage container for a lithium ion battery according to claim 1, wherein the outer cover and the inner cover are detachable from the cold storage container. 11.

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