Patent Application
20250183418
The present invention relates to a heat transfer suppression sheet, a production method therefor, and a battery pack including the heat transfer suppression sheet.
In recent years, from the viewpoint of environmental protection, an electric vehicle or a hybrid vehicle driven by an electric motor has been actively developed. The electric vehicle or the hybrid vehicle is equipped with a battery pack in which a plurality of battery cells are connected in series or in parallel to serve as a power source for a driving electric motor.
In addition, a lithium ion secondary battery, which has higher capacity and is capable of higher output than a lead-acid battery, a nickel-metal hydride battery, or the like, is mainly used for the battery cells. When a certain battery cell suddenly rises in temperature due to an internal short circuit or overcharging of the battery, and then causes thermal runaway that continues to generate heat, the heat from the battery cell that has experienced thermal runaway may propagate to other adjacent battery cells, thereby causing thermal runaway in other battery cells.
As a method of suppressing the propagation of heat from the battery cell that has experienced thermal runaway as described above, a method of interposing a heat insulation sheet between battery cells is commonly used.
For example, Patent Literature 1 discloses a heat insulation sheet for a battery pack, which contains a first particle constituted of a silica nanoparticle and a second particle constituted of a metal oxide, in which the content of the first particle is limited. In addition, Patent Literature 1 discloses that the heat insulation sheet may contain a binding material made of at least one kind selected from a fiber, a binder, and a heat-resistant resin.
In recent battery packs, the capacity of the battery cells has been further improved, so that an expansion rate during charging and discharging has been increased. Therefore, in the case where a heat insulation sheet is disposed between the battery cells of a battery pack, when strength of the entire heat insulation sheet is low; the heat insulation sheet is compressed by the expansion of the battery cells during charging and discharging of the battery cells, and powder falling occurs, resulting in a decrease in heat insulation performance. As a result, when the battery cell experiences thermal runaway and reaches a high temperature, the heat insulation sheet may not be able to exhibit an effect and a thermal chain reaction may occur. Therefore, there is a need for a heat insulation sheet that has high strength to retain a shape, can suppress powder falling, and can maintain an excellent heat insulation property, and a production method therefor.
Although the heat insulation sheet disclosed in the above Patent Literature 1 maintains an excellent heat insulation property even when a compressive stress increases, further improvements in heat insulation property, strength, and performance to suppress powder falling are required.
The present invention has been made in view of the above problems, and an object thereof is to provide a method for producing a heat transfer suppression sheet that can provide strength to retain a shape of a heat transfer suppression sheet even applied with a compressive stress and that can provide a high inorganic particle retention performance, thereby maintaining an excellent heat insulation performance, a heat transfer suppression sheet, and a battery pack including the heat transfer suppression sheet.
The above object of the present invention is achieved by the following configuration [1] relating to a method for producing a heat transfer suppression sheet.
[1] A method for producing a heat transfer suppression sheet including:
Preferred embodiments of the present invention relating to the method for producing a heat transfer suppression sheet relate to the following [2] to [9].
[2] The method for producing a heat transfer suppression sheet according to [1], in which the melting point of the third organic material is equal to or lower than the melting point of the second organic material.
[3] The method for producing a heat transfer suppression sheet according to [1], in which the melting point of the third organic material is higher than the melting point of the second organic material.
[4] The method for producing a heat transfer suppression sheet according to any one of [1] to [3], in which the melting point of the first organic material is 60° C. or more higher than a higher melting point of the melting points of the second organic material the third organic material.
[5] The method for producing a heat transfer suppression sheet according to any one of [1] to [4], in which the processing step includes a step of pressurizing the mixture and a step of heating the mixture.
[6] The method for producing a heat transfer suppression sheet according to [5], in which a heating temperature in the step of heating the mixture is a temperature which is higher than a higher melting point of the melting points of the second organic material and the third organic material, and is lower than the melting point of the first organic material.
[7] The method for producing a heat transfer suppression sheet according to any one of [1] to [6], in which in the processing step, the mixture is processed into a sheet by a dry method.
[8] The method for producing a heat transfer suppression sheet according to any one of [1] to [7], in which the inorganic particle includes at least one kind of particle selected from a dry silica particle and silica aerogel.
[9] The method for producing a heat transfer suppression sheet according to [8], in which the inorganic particle further includes at least one kind of particle selected from titania, zircon, zirconia, silicon carbide, zinc oxide, and alumina.
The above object of the present invention is achieved by the following configuration [10] relating to a heat transfer suppression sheet.
[10] A heat transfer suppression sheet including:
Preferred embodiments of the present invention relating to the heat transfer suppression sheet relate to the following [11] to [19].
[11] The heat transfer suppression sheet according to [10], in which
[12] The heat transfer suppression sheet according to [10] or [11], in which the melting point of the third organic material is equal to or lower than the melting point of the second organic material.
[13] The heat transfer suppression sheet according to [10] or [11], in which the melting point of the third organic material is higher than the melting point of the second organic material.
[14] The heat transfer suppression sheet according to any one of [10] to [13], in which both the melting point of the second organic material and the melting point of the third organic material are 60° C. or more lower than the melting point of the first organic material.
[15] The heat transfer suppression sheet according to any one of [10] to [14], in which
[16] The heat transfer suppression sheet according to any one of [10] to [15], in which the third organic material is at least one kind selected from a polyethylene, a polyester, a polyamide, and ethylene vinyl acetate.
[17] The heat transfer suppression sheet according to any one of [10] to [16], in which the inorganic particle is a particle composed of at least one kind of inorganic material selected from an oxide particle, a carbide particle, a nitride particle, and an inorganic hydrate particle.
[18] The heat transfer suppression sheet according to [17], in which the inorganic particle includes at least one kind of particle selected from a dry silica particle and silica aerogel.
[19] The heat transfer suppression sheet according to [18], in which the inorganic particle further includes at least one kind of particle selected from titania, zircon, zirconia, silicon carbide, zinc oxide, and alumina.
The above object of the present invention is also achieved by the following configuration [20] relating to a battery pack.
[20] A battery pack including:
The method for producing a heat transfer suppression sheet according to the present invention includes the processing step of processing a mixture containing an inorganic particle, a binder fiber having a core-sheath structure, and a hot melt powder into a sheet, and in the binder fiber, the melting point of the first organic material constituting the core portion is higher than the melting point of the second organic material constituting the sheath portion and the melting point of the third organic material constituting the hot melt powder. Therefore, during production, the core portion can remain to form a framework, the sheath portion can be melted to fuse the surrounding inorganic particle, and even in a region where the sheath portion is not present, the hot melt powder can be melted to form the hardened portion including the surrounding inorganic particle. Therefore, the inorganic particle can be suppressed from falling off from the heat transfer suppression sheet, and a heat transfer suppression sheet that achieves both excellent strength and heat transfer suppression effect can be obtained. In addition, with the method for producing a heat transfer suppression sheet according to the present invention, the melting point of the core portion of the binder fiber is higher than the melting points of the sheath portion and the hot melt powder, so that it is easy to control the temperature for melting the sheath portion and the hot melt powder with only the core portion remaining.
The heat transfer suppression sheet according to the present invention contains an inorganic particle having an excellent heat transfer suppression effect, and can thus provide an excellent heat insulation property. In addition, since the heat transfer suppression sheet according to the present invention includes an organic fiber and a fusion portion covering an outer peripheral surface of the organic fiber, and the fusion portion increases an apparent fiber diameter of the organic fiber, the strength of the framework constituted of the organic fiber can be improved.
Further, with the heat transfer suppression sheet according to the present invention, even in a region excluding the framework made of the organic fiber and the fusion portion, there is a hardened portion obtained by hardening the hot melt powder and the inorganic particle. Therefore, excellent strength can be obtained, thereby making it possible to prevent powder falling and maintain an excellent heat insulation performance.
With the battery pack according to the present invention, since the heat transfer suppression sheet has high strength and an excellent heat insulation performance as described above, thermal runaway of the battery cells in the battery pack and spread of flame to the outside of the battery case can be suppressed.
The inventors of the present invention have conducted intensive studies on a heat transfer suppression sheet that can solve the above problems.
As a result, it is found that when a heat transfer suppression sheet is produced using a hot melt powder and a binder fiber having a core-sheath structure including a core portion having a high melting point and a sheath portion having a low melting point, high strength is obtained with the core portion as a framework, the hot melt powder hardens even in a region other than the framework to improve the strength, and further, the sheath portion and the hot melt powder can be melted to retain an inorganic particle, thereby suppressing powder falling.
Specifically, in the production of the heat transfer suppression sheet, when heating a sheet material, if a heating temperature is set so as not to melt the core portion, only the sheath portion and the hot melt powder which have a melting point lower than that of the core portion can be melted. Thereafter, by cooling, the sheath portion is fused to the core portion again while incorporating the surrounding inorganic particle. In addition, the hot melt powder hardens while incorporating the surrounding inorganic particle. Therefore, after cooling, the core portion and a fusion portion containing the inorganic particle serve as a framework, and a hardened portion containing the hot melt powder and the inorganic particle between frameworks supports the frameworks, so that the strength of the heat transfer suppression sheet can be improved. In addition, when the sheath portion is melted and is, together with the inorganic particle, fused to the core portion, and the hot melt powder hardens on a surface of the heat transfer suppression sheet to form a plurality of hardened layers, the inorganic particle on the surface of the heat transfer suppression sheet is retained on the sheet surface, so that powder falling can be suppressed. As a result, even when a pressure or impact is applied to the heat transfer suppression sheet, a high heat insulation performance can be maintained.
Hereinafter, a method for producing a heat transfer suppression sheet, a heat transfer suppression sheet, and a battery pack according to an embodiment of the present invention will be described in detail. Note that the present invention is not limited to the embodiment described below; and can be freely changed and implemented without departing from the gist of the present invention.
As shown in
Note that, the binder fiber 3 includes a core portion 1 extending in a longitudinal direction of the fiber, and a sheath portion 2 formed to cover an outer peripheral surface of the core portion 1, the core portion 1 is constituted of a first organic material, and the sheath portion 2 is constituted of a second organic material. In addition, a melting point of the first organic material is higher than a melting point of the second organic material.
The hot melt powder 14 is obtained by shaping a third organic material, for example, ethylene vinyl acetate (EVA) into a powder form. The melting point of the first organic material constituting the core portion 1 is higher than a melting point of the third organic material constituting the hot melt powder 14. The hot melt powder 14 will be described later.
Thereafter, the obtained mixture 9 is charged into a predetermined mold, pressurized with a pressing machine or the like, and heated, to melt the sheath portion 2 of the binder fiber 3, and to form a molten portion (not shown) containing the inorganic particle 4 present around the core portion 1. At the same time, the hot melt powder is also melted, and a molten portion (not shown) is formed in a region other than being around the core portion 1. Thereafter, as shown in
In the present embodiment, the material of the heat transfer suppression sheet 13 includes the hot melt powder 14, and the hot melt powder 14 melted by heating is likely to segregate on a surface of a molded body. Therefore, as shown in
With the production method according to the present embodiment, the melting point of the first organic material constituting the core portion 1 is higher than the melting point of the second organic material constituting the sheath portion 2 and the melting point of the third organic material constituting the hot melt powder 14, so that when heating the mixture 9, the sheath portion 2 and the hot melt powder 14 can be melted while the core portion 1 remains. Therefore, strength of the heat transfer suppression sheet 13 can be ensured by the core portion 1.
By cooling, the sheath portion 2 is fused to the core portion 1 again while incorporating the surrounding inorganic particle 4 so that the fusion portion 5 is formed, and the hot melt powder 14 hardens while incorporating the surrounding inorganic particle 4 so that the hardened portion 16 is formed. Therefore, the outer peripheral surface of the core portion 1 can be covered with the fusion portion 5 and the inorganic particle 4 can be retained. In addition, the inorganic particle 4 can be retained by the hardened portion 16 even in a region excluding the fusion portion 5. In particular, as described above, the hot melt powder 14 melted by heating is likely to segregate on the surface of the molded body, and the thin hardened layers 17 are formed on the surface of the heat transfer suppression sheet 13, so that a high powder falling suppression effect can be obtained.
Further, in the present embodiment, when the crack 12 is formed between the thin hardened layers 17 dispersed in a plurality of regions, in the case where the heat transfer suppression sheet 13 is disposed between a plurality of battery cells, the heat transfer suppression sheet 13 is likely to deform as the battery cells expand and contract during charging and discharging. Therefore, damages to the heat transfer suppression sheet 13 can be suppressed, and the load on adjacent battery cells can also be reduced.
The fiber portion 6 including the core portion 1 and the fusion portion 5 has a large fiber diameter, and therefore has strength higher than the strength of the core portion 1 alone. In the mixture 9, the binder fibers 3 are present in irregular directions, and the binder fibers 3 may be in contact with each other in some parts. Then, as shown in a contact portion 11 in
Note that, even when an organic fiber without a core-sheath structure is used as the binder fiber, depending on temperature setting, it is possible that only the surface of the binder fiber is melted while the core portion thereof remains, and the inorganic particle is deposited on the surface. However, during the production of the heat transfer suppression sheet, it is common to perform heating from one side or both sides perpendicular to a thickness direction, and since a material having a high heat insulation performance is used, it is difficult to raise the temperature to the same degree on a surface side and on a center side of the sheet in the thickness direction. That is, when the temperature is set to melt only the surface of the organic fiber on the surface side of the sheet, the surface of the organic fiber is not melted on the center side of the sheet, and an ability to retain the inorganic particle 4 decreases. In addition, when the temperature is set to melt the surface of the organic fiber on the center side of the sheet, the organic fiber on the surface side of the sheet melts up to a radial center portion, making it difficult to ensure the strength of the sheet.
In contrast, in the present embodiment, since the melting point of the first organic material constituting the core portion 1 is higher than the melting point of the second organic material constituting the sheath portion 2, the temperature can be set extremely easily to make the core portion 1 remain and to melt the sheath portion 2. Then, the obtained heat transfer suppression sheet has an ideal structure in which the core portion 1 serves as a framework that retains the strength of the sheet on both the surface side and the center side, and the fusion portion 5 containing the inorganic particle 4 is formed on the surface of the core portion 1.
As a result, the heat transfer suppression sheet 13 produced by the production method according to the present embodiment has a strong framework, and even when a pressing force or impact is applied to the heat transfer suppression sheet, the shape can be maintained, the powder falling can be suppressed, and an excellent heat insulation performance can be maintained.
Note that, in order to further suppress the powder falling, the surface of the heat transfer suppression sheet 13 may be covered with a film or the like. Examples of a polymer film include a film made of a polyimide, a polycarbonate, PET, p-phenylene sulfide, a polyetherimide, a cross-linked polyethylene, a flame-retardant chloroprene rubber, polyvinylidene fluoride, rigid vinyl chloride, polybutylene terephthalate, PTFE, PFA, FEP, ETFE, rigid PCV, flame-retardant PET, a polystyrene, a polyethersulfone, a polyamide-imide, a polyacrylonitrile, a polyethylene, a polypropylene, and a polyamide. Note that, the method of covering the surface of the heat transfer suppression sheet 13 with a film is not particularly limited, and examples thereof include a method of pasting it with an adhesive or the like, a method of wrapping the heat transfer suppression sheet 13 in a film, and a method of housing the heat transfer suppression sheet 13 in a bag-shaped film.
Next, the binder fiber and heating conditions used in the method for producing a heat transfer suppression sheet according to the present embodiment will be described.
The binder fiber 3 that can be used in the present embodiment is not particularly limited as long as it has a core-sheath structure and the melting point of the first organic material constituting the core portion 1 is higher than the melting point of the second organic material constituting the sheath portion 2. As the first organic material constituting the core portion 1, at least one kind selected from polyethylene terephthalate, a polypropylene, and nylon can be selected. In addition, as the second organic material constituting the sheath portion 2, at least one kind selected from polyethylene terephthalate, a polyethylene, a polypropylene, and nylon can be selected.
When the melting point of the first organic material constituting the core portion 1 is sufficiently higher than the melting point of the second organic material constituting the sheath portion 2, a setting tolerance of the heating temperature in the heating step can be expanded, and the temperature setting for obtaining a desired structure can be made easier. For example, the melting point of the first organic material is preferably 60° C. or more higher, more preferably 70° C. or more higher, and still more preferably 80° C. or more higher than the melting point of the second organic material.
Note that, the binder fiber having a core-sheath structure as described above is generally commercially available, and the materials constituting the core portion and the sheath portion may be the same as or different from each other. Examples of the binder fiber in which the core portion 1 and the sheath portion 2 are constituted of the same material having different melting points include one in which the core portion 1 and the sheath portion 2 are constituted of polyethylene terephthalate, one in which the core portion 1 and the sheath portion 2 are constituted of a polypropylene, and one in which the core portion 1 and the sheath portion 2 are constituted of nylon. Examples of the binder fiber in which the core portion 1 and the sheath portion 2 are constituted of different materials include one in which the core portion 1 is constituted of polyethylene terephthalate and the sheath portion 2 is constituted of a polyethylene, and one in which the core portion 1 is constituted of a polypropylene and the sheath portion 2 is constituted of a polyethylene.
In the present embodiment, the melting point of the second organic material constituting the sheath portion of the binder fiber refers to a melting temperature at which the second organic material begins to undergo melting deformation, and softening accompanied by a change in shape is also considered to be a kind of melting deformation. The melting point of the sheath portion of the binder fiber can be measured, for example, by the following method.
A binder fiber to be measured is disposed in contact with a glass fiber having a higher melting point, heated from room temperature to, for example, 200° C. at a heating rate of 5° C./min, and thereafter cooled to room temperature.
At this time, when the surface of the binder fiber undergoes melting deformation and is fused at a portion in contact with the glass fiber, or a cross-sectional shape of the binder fiber changes, it can be determined that the melting point of the second organic material constituting the sheath portion is 200° C. or lower. In the present embodiment, when the heating temperature is changed variously, and the fusion state of the binder fiber and the glass fiber after cooling by the above method or the cross-sectional shape of the binder fiber is observed, the melting point of the second organic material constituting the sheath portion can be determined.
In the present embodiment, when a content of the binder fiber 3 in the mixture 9 is appropriately controlled, a sufficient framework reinforcement effect can be obtained in the obtained heat transfer suppression sheet 13.
The content of the binder fiber 3 is preferably 5 mass % or more, and more preferably mass % or more, with respect to a total mass of the mixture 9. When the content of the binder fiber 3 is too large, the content of the inorganic particle 4 decreases relatively. Therefore, in order to obtain a desired heat insulation performance, the content of the binder fiber 3 is preferably 25 mass % or less, and more preferably 20 mass % or less, with respect to the total mass of the mixture 9.
The kind of the inorganic particle 4 that can be used in the present embodiment will be described later.
In the present embodiment, when a content of the inorganic particle 4 in the mixture 9 is appropriately controlled, a sufficient heat insulation property can be ensured in the obtained heat transfer suppression sheet 13.
The content of all inorganic particles 4 contained in the mixture 9 is preferably 60 mass % or more, and more preferably 70 mass % or more, with respect to the total mass of the mixture 9. When the content of the inorganic particle 4 is too large, the content of the binder fiber 3 decreases relatively. Therefore, in order to obtain a sufficient framework reinforcement effect, the content of the inorganic particle 4 is preferably 95 mass % or less, and more preferably 90 mass % or less, with respect to the total mass of the mixture 9.
The hot melt powder is a powder that contains, for example, a third organic material different from the first organic material and the second organic material, and has a property of being melted by heating. By adding the hot melt powder into the mixture 9 and heating it, the hot melt powder melts. After that by cooling, the hot melt powder hardens while incorporating the surrounding inorganic particle 4 so that the hardened portion 16 is formed. As described above, the hardened portion 16 includes the thin hardened layers 17 dispersed in a plurality of regions on the surface of the heat transfer suppression sheet 13, and the surface of the heat transfer suppression sheet 13 is covered with the thin hardened layers, so that falling off of the inorganic particle 4 from the heat transfer suppression sheet 13 can be further suppressed.
Examples of the hot melt powder include those having various melting points, and it is sufficient to select a hot melt powder having an appropriate melting point in consideration of the melting points of the core portion 1 and the sheath portion 2 of the binder fiber 3 used. In the present embodiment, the melting point of the first organic material constituting the core portion 1 is higher than the melting point of the second organic material constituting the sheath portion 2 and the melting point of the third organic material constituting the hot melt powder 14, so that the heating temperature can be set to melt the sheath portion 2 and the hot melt powder 14 while the core portion 1 remains. Further, when the melting point of the hot melt powder 14 is equal to or lower than the melting point of the sheath portion 2, it is sufficient to set the heating temperature during the production between the melting point of the core portion 1 and the melting point of the sheath portion 2, so that the heating temperature can be set much more easily.
On the other hand, the kind of the hot melt powder 14 to be used can also be selected such that the melting point of the hot melt powder 14 is between the melting point of the core portion 1 and the melting point of the sheath portion 2. In the case of using the hot melt powder 14 having such a melting point, when both the sheath portion 2 and the hot melt powder 14 are cooled and harden after melting, the hot melt powder 14 present in the various regions excluding the organic fiber (core portion 1) and the surrounding molten sheath portion 2 firstly hardens.
As a result, the position of the organic fiber can be fixed, and thereafter the molten sheath portion 2 is fused to the organic fiber, making it easier to form a three-dimensional framework. Therefore, the strength of the entire sheet can be further improved.
When the melting point of the third organic material constituting the hot melt powder 14 is sufficiently lower than the melting point of the first organic material constituting the core portion 1, the setting tolerance of the heating temperature in the heating step can be expanded, and the temperature setting for obtaining a desired structure can be made easier. For example, the melting point of the first organic material is preferably 60° C. or more higher, more preferably 70° C. or more higher, and still more preferably 80° C. or more higher than the melting point of the third organic material.
Note that, examples of the component constituting the hot melt powder 14 include a polyethylene, a polyester, a polyamide, and ethylene vinyl acetate.
Even when a content of the hot melt powder 14 is very small, the powder falling suppression effect can be obtained.
Therefore, the content of the hot melt powder 14 is preferably 0.5 mass % or more, and more preferably 1 mass % or more, with respect to the total mass of the mixture 9.
On the other hand, when the content of the hot melt powder 14 is increased, the content of the inorganic particle 4 decreases relatively. Therefore, in order to obtain a desired heat insulation performance, the content of the hot melt powder 14 is preferably 5 mass % or less, and more preferably 4 mass % or less, with respect to the total mass of the mixture 9.
The step of processing the mixture 9 into a sheet includes a step of pressurizing the mixture 9 and a step of heating the mixture 9. The heating temperature in the heating step is preferably a temperature higher than the higher one of the melting point of the second organic material constituting the sheath portion 2 and the melting point of the third organic material constituting the hot melt powder 14, and lower than the melting point of the first organic material constituting the core portion 1. By setting the heating temperature like this, as described above, the strength of the sheet can be further improved by the framework constituted by the fiber portion 6 and the hardened portion 16, and the inorganic particle 4 can be prevented from falling off by the fusion portion 5 and the hardened layers 17.
Note that, when the melting point of the first organic material constituting the core portion 1 is sufficiently higher than the melting point of the second organic material constituting the sheath portion 2, the setting tolerance of the heating temperature in the heating step can be expanded, and the temperature setting for obtaining a desired structure can be made easier. For example, the melting point of the first organic material is preferably 60° C. or more higher, more preferably 70° C. or more higher, and still more preferably 80° C. or more higher than the melting point of the second organic material. That is, in order to sufficiently expand the setting tolerance of the heating temperature, the melting point of the first organic material is preferably 60° C. or more higher, more preferably 70° C. or more higher, and still more preferably 80° C. or more higher than the higher melting point of the melting point of the second organic material and the melting point of the third organic material.
In addition, the heating temperature in the heating step is preferably set higher, more preferably 10° C. or more higher, and still more preferably 20° C. or more higher than the higher one of the melting point of the second organic material constituting the sheath portion 2 and the melting point of the third organic material constituting the hot melt powder 14. On the other hand, the heating temperature is preferably set lower, more preferably 10° C. or more lower, and still more preferably 20° C. or more lower than the melting point of the first organic fiber constituting the core portion 1.
A heating time is not particularly limited, and it is preferable to set a heating time that allows the sheath portion 2 and the hot melt powder 14 to be sufficiently melted. For example, it can be set to 3 minutes or longer and 15 minutes or shorter.
Hereinafter, an embodiment of a heat transfer suppression sheet produced by the method for producing a heat transfer suppression sheet according to the present invention will be described.
As shown in
Note that, in the present embodiment, a material mixture contains the hot melt powder 14, and since this hot melt powder 14 is present in the various regions of a molded body; when cooling is performed after heating in the production process, the fusion portion 5 may contain the third organic material that is a component constituting the hot melt powder 14. Similarly, in the vicinity of the organic fiber (core portion 1), the hardened portion 16 may contain the second organic material that is a component of the sheath portion 2. In either case, the effects of the present invention are not influenced.
In the heat transfer suppression sheet 13 according to the present embodiment configured in this manner, as described in the above [1. Method for producing a heat transfer suppression sheet], the fiber portion 6 including the organic fiber (core portion 1) and the fusion portion 5 serves as a framework, and the hardened portion 16 containing the hot melt powder 14 and the inorganic particle 4 between frameworks supports the frameworks, so that the shape of the entire heat transfer suppression sheet can be retained with even higher strength. In addition, since the outer peripheral surface of the organic fiber is covered with the fusion portion 5, and the hardened portion 16 is formed even in the region excluding the fusion portion 5, the inorganic particle 4 can be retained. Further, since the thin hardened layers 17 are formed on the surface of the heat transfer suppression sheet 13, a high powder falling suppression effect can be obtained. Further, when the crack 12 is formed, the heat transfer suppression sheet 13 easily follows deformation as the battery cells expand and contract during charging and discharging. Therefore, for example, even when the heat transfer suppression sheet 13 according to the present embodiment is disposed between a plurality of battery cells to be described later, and the battery cells expand to apply a compressive stress or impact to the heat transfer suppression sheet 13, an excellent heat insulation performance can be maintained.
In the present embodiment, as a mechanism with which falling off of the inorganic particle 4 from the surface of the sheet (powder falling) can be suppressed, it is thought that the organic fiber (core portion 1) and the fusion portion 5 form a three-dimensional and strong framework, and the shape of the heat transfer suppression sheet 13 is retained, so that deformation or compression of the heat transfer suppression sheet 13 is suppressed. In addition, the reason why the inorganic particle 4 is retained is also thought to be that the fiber portion 6, which includes the fusion portion 5 and the organic fiber (core portion 1) exposed on the fiber portion 6 and the thin hardened layers 17 formed on the sheet surface, can cover the surface of the heat transfer suppression sheet 13 and can absorb an impact applied to the heat transfer suppression sheet 13.
Note that, as shown in
Hereinafter, the materials constituting the heat transfer suppression sheet according to the present embodiment will be described in detail.
In the heat transfer suppression sheet 13, the core portion 1 constituted of the first organic material serves as an organic fiber that retains the strength and the shape of the sheet. The organic fiber is not particularly limited as long as the melting point of the first organic material constituting the organic fiber is higher than the melting point of the second organic material present on the outer peripheral surface of the organic fiber and the melting point of the third organic material contained in the hardened portion 16. Examples of the first organic material include at least one kind selected from polyethylene terephthalate, a polypropylene, and nylon.
In the present embodiment, when a content of the organic fiber in the heat transfer suppression sheet 13 is appropriately controlled, a sufficient framework reinforcement effect can be obtained.
The content of the organic fiber is preferably 2 mass % or more, and more preferably 4 mass % or more, with respect to a total mass of the heat transfer suppression sheet 13. When the content of the organic fiber is too large, the content of the inorganic particle 4 decreases relatively. Therefore, in order to obtain a desired heat insulation performance, the content of the organic fiber is preferably 10 mass % or less, and more preferably 8 mass % or less, with respect to the total mass of the heat transfer suppression sheet 13.
A fiber length of the organic fiber is not particularly limited, and from the viewpoint of ensuring moldability and processability, an average fiber length of the organic fiber is preferably 10 mm or less.
On the other hand, from the viewpoint of making the organic fiber function as a framework and ensuring compressive strength of the heat transfer suppression sheet, the average fiber length of the organic fiber is preferably 0.5 mm or more.
The fusion portion 5 is formed by once melting the sheath portion 2 of the binder fiber 3 having a core-sheath structure by heating and then performing cooling, and contains the second organic material and the inorganic particle 4.
The second organic material is not particularly limited as long as it has a melting point lower than the first organic material constituting the organic fiber. Examples of the second organic material include at least one kind selected from polyethylene terephthalate, a polyethylene, a polypropylene, and nylon.
Note that, the melting point of the second organic material is preferably 90° C. or higher, and more preferably 100° C. or higher. In addition, the melting point of the second organic material is preferably 150° C. or lower, and more preferably 130° C. or lower.
The hardened portion 16 is formed by once melting the hot melt powder by heating and then performing cooling, and contains the third organic material constituting the hot melt powder and the inorganic particle 4.
As described above, the third organic material, which is a component constituting the hot melt powder, is not particularly limited as long as it has a melting point lower than the first organic material constituting the organic fiber. In order to easily control the heating temperature during the production, the melting point of the hot melt powder (third organic material) is preferably equal to or lower than the melting point of the second organic material constituting the sheath portion. However, in order to form a more three-dimensional framework and improve the strength of the heat transfer suppression sheet, the melting point of the third organic material may be higher than the melting point of the second organic material, that is, between the melting point of the first organic material and the melting point of the second organic material.
As described above, in order to sufficiently expand the setting tolerance of the heating temperature, both the melting point of the second organic material and the melting point of the third organic material are preferably 60° C. or more lower, more preferably 70° C. or more lower, and still more preferably 80° C. or more lower than the melting point of the first organic material.
Note that, the melting point of the hot melt powder (third organic material) is preferably 80° C. or higher, and more preferably 90° C. or higher. In addition, the melting point of the hot melt powder (third organic material) is preferably 180° C. or lower, and more preferably 150° C. or lower. In addition, it is preferable that the third organic material constituting the hot melt powder is at least one kind selected from a polyethylene, a polyester, a polyamide, and ethylene vinyl acetate.
As the inorganic particle, a single kind of inorganic particle may be used, or two or more kinds of inorganic particles may be used in combination. From the viewpoint of the heat transfer suppression effect, as the kind of the inorganic particle, it is preferable to use a particle composed of at least one kind of inorganic material selected from an oxide particle, a carbide particle, a nitride particle, and an inorganic hydrate particle, and it is more preferable to use an oxide particle. The form thereof is not particularly limited. It is preferable to contain at least one kind selected from a nanoparticle, a hollow particle, and a porous particle. Specifically, a silica nanoparticle, a metal oxide particle, an inorganic balloon such as a microporous particle or a hollow silica particle, a particle composed of a thermally expandable inorganic material, a particle composed of a hydrous porous material, or the like can also be used.
When an average secondary particle diameter of the inorganic particle is 0.01 μm or more, the inorganic particle is easily available and an increase in production cost can be suppressed. When the average secondary particle diameter is 200 μm or less, a desired heat insulation effect can be obtained. Therefore, the average secondary particle diameter of the inorganic particle is preferably 0.01 μm or more and 200 μm or less, and more preferably 0.05 μm or more and 100 μm or less.
Note that, when two or more kinds of inorganic particles having different heat transfer suppression effects are combined, a heating element can be cooled in multiple stages and a heat absorption effect can be exhibited over a wider temperature range. Specifically, it is preferable to use a large-diameter particle and a small-diameter particle in combination. For example, in the case of using a nanoparticle as one of the inorganic particles, it is preferable to contain an inorganic particle composed of a metal oxide as the other inorganic particle. Hereinafter, the inorganic particle will be described in more detail, with a small-diameter inorganic particle as a first inorganic particle and a large-diameter inorganic particle as a second inorganic particle.
An oxide particle has a high refractive index and has a high effect of diffusely reflecting light, so that when the oxide particle is used as the first inorganic particle, radiant heat transfer can be suppressed, particularly in a high temperature range with abnormal heat generation or the like. As the oxide particle, at least one kind of particle selected from silica, titania, zirconia, zircon, barium titanate, zinc oxide, and alumina can be used. That is, among the above oxide particle that can be used as the inorganic particle, only one kind or two or more kinds of oxide particles may be used. Particularly, silica is a component having a high heat insulation property, and titania is a component having a high refractive index compared to other metal oxides, and has a high effect of diffusely reflecting light and blocking radiant heat in a high temperature range of 500° C. or higher. Therefore, silica and titania are most preferably used as the oxide particle.
Since the particle diameter of the oxide particle may influence an effect of reflecting radiant heat, when an average primary particle diameter thereof is limited to a predetermined range, an even higher heat insulation property can be obtained.
That is, when the average primary particle diameter of the oxide particle is 0.001 μm or more, a wavelength thereof is sufficiently larger than a wavelength of light that contributes to heating, and it diffusely reflects the light efficiently. Therefore, in a high temperature range of 500° C. or higher, the radiant heat transfer of heat within the heat transfer suppression sheet can be suppressed, and the heat insulation property can be further improved.
On the other hand, when the average primary particle diameter of the oxide particle is 50 μm or less, even with compression, the number of contact points between the particles does not increase, and it is difficult to form a conductive heat transfer path. Therefore, the influence on the heat insulation property particularly in a normal temperature range where the conductive heat transfer is dominant can be reduced.
Note that, in the present invention, the average primary particle diameter can be determined by observing particles with a microscope, comparing the particles with a standard scale, and taking an average of any 10 particles.
In the present invention, the nanoparticle refers to a nanometer-order particle having a spherical or nearly spherical shape and having an average primary particle diameter of less than 1 μm. The nanoparticle has a low density and thus suppresses the conductive heat transfer, and when the nanoparticle is used as the first inorganic particle, voids are further finely dispersed, so that an excellent heat insulation property of suppressing convective heat transfer can be obtained. Therefore, it is preferable to use a nanoparticle since it can suppress the conduction of heat between adjacent nanoparticles during normal use of a battery in a normal temperature range.
Further, when the nanoparticle having a small average primary particle diameter is used as the oxide particle, even when the heat transfer suppression sheet is compressed by expansion due to thermal runaway of the battery cell and the internal density increases, an increase in conductive heat transfer of the heat transfer suppression sheet can be suppressed. This is thought to be because the nanoparticle tends to form fine voids between particles due to a repulsive force caused by static electricity, and the bulk density thereof is low, so that it is filled with the particle so as to provide a cushioning property.
Note that, in the present invention, when the nanoparticle is used as the first inorganic particle, the kind thereof is not particularly limited as long as the above definition of nanoparticle is met. For example, since a silica nanoparticle is a material having a high heat insulation property and has a few contact points between particles, the amount of heat conducted by the silica nanoparticle is smaller than that in a case of using a silica particle having a large particle diameter. In addition, since a generally available silica nanoparticle has a bulk density of about 0.1 (g/cm3), for example, even when battery cells disposed on both sides of the heat insulation sheet thermally expand and a large compressive stress is applied to the heat insulation sheet, the size (area) or the number of contact points between the silica nanoparticles does not increase remarkably, and the heat insulation property can be maintained. Therefore, it is preferable to use a silica nanoparticle as the nanoparticle. Examples of the silica nanoparticle include wet silica, dry silica, and aerogel. A silica nanoparticle that is particularly suitable for the present embodiment will be described below:
Note that, as described above, in order to further improve the heat insulation performance, in the case of using dry silica or silica aerogel, which has a low thermal conductivity; as the inorganic particle, it is preferable to process a mixture containing the materials into a sheet by a dry method.
When the average primary particle diameter of the nanoparticle is limited to a predetermined range, an even higher heat insulation property can be obtained.
That is, when the average primary particle diameter of the nanoparticle is 1 nm or more and 100 nm or less, the convective heat transfer and the conductive heat transfer of the heat within the heat transfer suppression sheet can be suppressed particularly in a temperature range of lower than 500° C., and the heat insulation property can be further improved. In addition, even when a compressive stress is applied, voids remaining between the nanoparticles and contact points between many particles can suppress the conductive heat transfer, and the heat insulation property of the heat transfer suppression sheet can be maintained.
Note that the average primary particle diameter of the nanoparticle is more preferably 2 nm or more, and still more preferably 3 nm or more. On the other hand, the average primary particle diameter of the nanoparticle is more preferably 50 nm or less, and still more preferably 10 nm or less.
The inorganic hydrate particle exhibits a so-called “heat absorption effect” that the inorganic hydrate particle receives heat from the heating element, thermally decomposes when reaching a thermal decomposition start temperature or higher, releases crystal water thereof, and lowers the temperature of the heating element and surroundings. The inorganic hydrate particle forms a porous material after releasing the crystal water, and exhibits a heat insulation effect due to countless air pores thereof.
Specific examples of the inorganic hydrate include aluminum hydroxide (Al(OH)3), magnesium hydroxide (Mg(OH)2), calcium hydroxide (Ca(OH)2), zinc hydroxide (Zn(OH)2), iron hydroxide (Fe(OH)2), manganese hydroxide (Mn(OH)2), zirconium hydroxide (Zr(OH)2), and gallium hydroxide (Ga(OH)3).
For example, aluminum hydroxide has about 35% crystal water, and as shown in the following formula, thermally decomposes to release the crystal water and exhibits a heat absorption effect. Then, after releasing the crystal water, aluminum hydroxide forms alumina (Al2O3), which is a porous material, and functions as a heat insulation material.
2Al(OH)3→Al2O3+3H2O
Note that, as will be described later, the heat transfer suppression sheet 13 according to the present embodiment is preferably interposed between, for example, battery cells, but in a battery cell that has experienced thermal runaway, the temperature rapidly rises to over 200° C. and continues to rise to about 700° C. Therefore, it is preferable that the inorganic particle is composed of an inorganic hydrate whose thermal decomposition start temperature is 200° C. or higher.
The thermal decomposition start temperature of the above inorganic hydrates is about 200° C. for aluminum hydroxide, is about 330° C. for magnesium hydroxide, is about 580° C. for calcium hydroxide, is about 200° C. for zinc hydroxide, is about 350° C. for iron hydroxide, is about 300° C. for manganese hydroxide, is about 300° C. for zirconium hydroxide, and is about 300° C. for gallium hydroxide. All of these almost overlap the temperature range of the rapid temperature rise of a battery cell that has experienced thermal runaway, and can effectively prevent the temperature rise. Therefore, these are preferred inorganic hydrates.
In the case where the inorganic hydrate particle is used as the first inorganic particle, when the average particle diameter thereof is too large, it takes a certain amount of time for the first inorganic particle (inorganic hydrate) near the center of the heat transfer suppression sheet 13 to reach the thermal decomposition temperature thereof, so that the first inorganic particle near the center of the sheet may not be completely thermally decomposed. Therefore, the average secondary particle diameter of the inorganic hydrate particle is preferably 0.01 μm or more and 200 μm or less, and more preferably 0.05 μm or more and 100 μm or less.
Examples of the thermally expandable inorganic material include vermiculite, bentonite, mica, and perlite.
Specific examples of the hydrous porous material include zeolite, kaolinite, montmorillonite, acid clay, diatomaceous earth, wet silica, dry silica, aerogel, mica, and vermiculite.
The heat insulation material used in the present invention may contain an inorganic balloon as the first inorganic particle.
When the inorganic balloon is contained, the convective heat transfer or the conductive heat transfer of the heat within the heat insulation material can be suppressed in a temperature range of lower than 500° C., and the heat insulation property of the heat insulation material can be further improved.
As the inorganic balloon, at least one kind selected from a whitebait balloon, a silica balloon, a fly ash balloon, a perlite balloon, and a glass balloon can be used.
(Content of Inorganic Balloon: 60 Mass % or Less with Respect to Total Mass of Heat Insulation Material)
The content of the inorganic balloon is preferably 60 mass % or less with respect to the total mass of the heat insulation material.
The average particle diameter of the inorganic balloon is preferably 1 μm or more and 100 μm or less.
When the heat transfer suppression sheet contains two kinds of inorganic particles, the second inorganic particle is not particularly limited as long as it is different from the first inorganic particle in material, particle diameter, or the like. As the second inorganic particle, an oxide particle, a carbide particle, a nitride particle, an inorganic hydrate particle, a silica nanoparticle, a metal oxide particle, an inorganic balloon such as a microporous particle or a hollow silica particle, a particle composed of a thermally expandable inorganic material, a particle composed of a hydrous porous material, or the like can be used. Details of these are as described above.
Note that the nanoparticle has extremely low conductive heat transfer, and can maintain an excellent heat insulation property even when a compressive stress is applied to the heat transfer suppression sheet. In addition, a metal oxide particle such as titania has a high effect of blocking radiant heat. Further, when a large-diameter inorganic particle and a small-diameter inorganic particle are used, the small-diameter inorganic particle enters gaps between the large-diameter inorganic particles, leading to a more dense structure, and the heat transfer suppression effect can be improved. Therefore, for example, when the nanoparticle is used as the first inorganic particle, it is preferable that the heat transfer suppression sheet further contains a particle composed of a metal oxide having a diameter larger than that of the first inorganic particle as the second inorganic particle.
Examples of the metal oxide include silicon oxide, titanium oxide, aluminum oxide, barium titanate, zinc oxide, zircon, and zirconium oxide. Particularly; titanium oxide (titania) is a component having a high refractive index compared to other metal oxides, and has a high effect of diffusely reflecting light and blocking radiant heat in a high temperature range of 500° C. or higher. Therefore, titania is most preferably used.
For example, when at least one kind of particle selected from a dry silica particle and silica aerogel is used as the first inorganic particle, and at least one kind of particle selected from titania, zircon, zirconia, silicon carbide, zinc oxide, and alumina is used as the second inorganic particle, in order to obtain an excellent heat insulation performance within a temperature range of 300° C. or lower, the content of the first inorganic particle is preferably 50 mass % or more, more preferably 60 mass % or more, and still more preferably 70 mass % or more, with respect to a total mass of the inorganic particles. In addition, the content of the first inorganic particle is preferably 95 mass % or less, more preferably 90 mass % or less, and still more preferably 80 mass % or less, with respect to the total mass of the inorganic particles.
On the other hand, in order to obtain an excellent heat insulation performance within a temperature range of higher than 300° C., the content of the second inorganic particle is preferably 5 mass % or more, more preferably 10 mass % or more, and still more preferably 20 mass % or more, with respect to the total mass of the inorganic particles. In addition, the content of the second inorganic particle is preferably 50 mass % or less, more preferably 40 mass % or less, and still more preferably 30 mass % or less, with respect to the total mass of the inorganic particles.
In the case where the second inorganic particle composed of a metal oxide is contained in the heat transfer suppression sheet, when the average primary particle diameter of the second inorganic particle is 1 μm or more and 50 μm or less, the radiant heat transfer can be efficiently suppressed in a high temperature range of 500° C. or higher. The average primary particle diameter of the second inorganic particle is more preferably 5 μm or more and 30 μm or less, and most preferably 10 μm or less.
In the present embodiment, when a content of the inorganic particle 4 in the heat transfer suppression sheet 13 is appropriately controlled, a sufficient heat insulation property can be ensured in the heat transfer suppression sheet 13.
The content of the inorganic particle 4 is preferably 60 mass % or more, and more preferably 70 mass % or more, with respect to the total mass of the heat transfer suppression sheet 13. When the content of the inorganic particle 4 is too large, the contents of the organic fiber and the fusion portion decrease relatively. Therefore, in order to obtain a sufficient framework reinforcement effect and inorganic particle retention effect, the content of the inorganic particle 4 is preferably 95 mass % or less, and more preferably 90 mass % or less, with respect to the total mass of the heat transfer suppression sheet 13.
Note that, the content of the inorganic particle in the heat transfer suppression sheet 13 can be calculated, for example, by heating the heat transfer suppression sheet at 800° C., decomposing organic components, and then measuring the mass of the remaining portion.
In addition, the heat transfer suppression sheet 13 according to the present embodiment may contain an organic fiber constituted of an organic material different from the first organic material, or an inorganic fiber, in addition to the organic fiber (core portion 1), the inorganic particle 4, the fusion portion 5, and the hardened portion 16. Further, the heat transfer suppression sheet 13 may contain an organic material different from the first organic material to the third organic material, and the inorganic particle may be retained in this organic material.
A thickness of the heat transfer suppression sheet according to the present embodiment is not particularly limited, and is preferably 0.05 mm or more and 10 mm or less. When the thickness is 0.05 mm or more, sufficient compressive strength can be obtained. On the other hand, when the thickness is 10 mm or less, a good heat insulation property of the heat transfer suppression sheet can be obtained.
For example, as shown in
Note that, the heat transfer suppression sheet 13 is as described above.
In the battery pack 100 configured in this manner, even when a certain battery cell 20a has a high temperature, since the heat transfer suppression sheet 13 having a heat transfer suppression effect is present between the battery cell 20a and the battery cell 20b, it is possible to suppress the propagation of heat to the battery cell 20b.
In addition, since the heat transfer suppression sheet 13 according to the present embodiment has high compressive strength, thermal expansion of the battery cells 20a, 20b, and 20c can also be suppressed during charging and discharging of the battery cells. Therefore, a distance between the battery cells can be ensured, an excellent heat insulation performance can be maintained, and the thermal runaway of the battery cells can be prevented. In addition, since it has the effect of suppressing powder falling, it can be easily handled.
Note that the battery pack 100 according to the present embodiment is not limited to the battery pack shown in
In the battery pack 100 configured in this manner, when a certain battery cell ignites, it is possible to suppress the flame from spreading to the outside of the battery case 30.
For example, the battery pack 100 according to the present embodiment is used in an electric vehicle (EV) or the like, and is sometimes disposed under a passenger's floor. In this case, even when the battery cell ignites, the safety of the passenger can be ensured.
In addition, since the heat transfer suppression sheet 13 can be disposed not only between the battery cells but also between the battery cells 20a, 20b, and 20c and the battery case 30, it is not necessary to newly prepare a flame retardant material or the like, and a safe battery pack 100 can be easily formed at a low cost.
In the battery pack according to the present embodiment, the heat transfer suppression sheet 13 disposed between the battery cells 20a, 20b, and 20c and the battery case 30 may be in contact with the battery cell or may have a gap therebetween. However, in the case where there is a gap between the heat transfer suppression sheet 13 and the battery cells 20a, 20b, and 20c, even when the temperature of any one battery cell of the plurality of battery cells rises and the volume expands, the deformation of the battery cell is allowable.
Note that, the heat transfer suppression sheet 13 according to the present embodiment can be produced into various shapes depending on the production method. Therefore, it is not influenced by the shapes of the battery cells 20a, 20b, and 20c and the battery case 30, and can be adapted to any shape. Specifically, it can be applied to cylindrical batteries, flat batteries, and the like, in addition to prismatic batteries.
Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
Test materials for heat transfer suppression sheets in Examples and Comparative Examples were prepared, and surfaces of the test materials were observed and a powder falling suppression performance (scattering rate) was evaluated.
As the inorganic particle, dry silica and titania were prepared, and a hot melt powder and a binder fiber having a core-sheath structure were prepared. The specific content and name of each component are shown below.
The above materials were charged into a mixer to prepare a mixture. Thereafter, the obtained mixture was charged into a predetermined mold, pressurized with a pressing machine or the like, heated, and cooled. Then, a test material of Example No. 1 having a basis weight of 740 (g/m2) and a thickness of 2 mm was obtained. Note that, the heating conditions were 150° C. for 15 minutes.
The materials in Example No. 1 above excluding a hot melt powder were prepared. The specific content and name of each component are shown below.
Thereafter, a test material in Comparative Example No. 1 having a basis weight of 740 (g/m2) and a thickness of 2 mm was prepared by a dry method which is the same way as Example No. 1. Note that, the heating conditions were 150° C. for 15 minutes.
A photograph was taken of the surface of each test material using a scanning electron microscope (SEM), and the appearance of the surface was observed.
On the other hand, as shown in
For each test material, the scattering rate was measured and the powder falling suppression performance was evaluated.
Although various embodiments have been described above, it is needless to say that the present invention is not limited to such examples. It is apparent to those skilled in the art that various changes and modifications can be conceived within the scope of the claims, and it is understood that such changes and modifications are also encompassed within the technical scope of the present invention. In addition, the constituent elements in the above embodiments may be freely combined without departing from the gist of the present invention.
Note that the present application is based on a Japanese patent application (Japanese Patent Application No. 2022-038554) filed on Mar. 11, 2022, and the contents thereof are incorporated herein by reference.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2022-038554 | Mar 2022 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2023/009464 | 3/10/2023 | WO |
