WO2021256093A1 - Feuille isolante et dispositif d'alimentation électrique la comprenant - Google Patents

Feuille isolante et dispositif d'alimentation électrique la comprenant Download PDF

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Publication number
WO2021256093A1
WO2021256093A1 PCT/JP2021/016675 JP2021016675W WO2021256093A1 WO 2021256093 A1 WO2021256093 A1 WO 2021256093A1 JP 2021016675 W JP2021016675 W JP 2021016675W WO 2021256093 A1 WO2021256093 A1 WO 2021256093A1
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WIPO (PCT)
Prior art keywords
heat insulating
insulating sheet
intermediate layer
surface layer
layer
Prior art date
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PCT/JP2021/016675
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English (en)
Japanese (ja)
Inventor
裕也 西尾
洋史 千葉
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阿波製紙株式会社
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Priority to JP2022532357A priority Critical patent/JPWO2021256093A1/ja
Publication of WO2021256093A1 publication Critical patent/WO2021256093A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00—Thermal insulation in general
    • F16L59/02—Shape or form of insulating materials, with or without coverings integral with the insulating materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/61—Types of temperature control
    • H01M10/613—Cooling or keeping cold
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/658—Means for temperature control structurally associated with the cells by thermal insulation or shielding
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a heat insulating sheet and a power supply device including the heat insulating sheet.
  • Sheet materials with heat insulating properties are used in various applications such as spacers for heat insulation and insulation of secondary battery cells, explosion-proof sheets, and sheet materials for covering members with different temperatures such as refrigerators.
  • a spacer for heat insulation of a secondary battery cell will be described.
  • a power supply device in which multiple secondary battery cells are stacked is used as a power source for driving electric vehicles such as electric vehicles, hybrid vehicles, electric buses, and trains, as a backup power source for factories and base stations, and as a storage battery for home use. (For example, Patent Documents 1 and 2).
  • Patent Documents 1 and 2 In recent years, there has been a demand for weight reduction and high capacity of power supply devices, and high capacity types such as lithium ion secondary batteries are used for secondary battery cells.
  • the thermal conductivity is low. Therefore, as shown in the schematic cross-sectional view of FIG. 4, even if hot spot HS occurs in any of the secondary battery cells 1. This high heat cannot be thermally conducted and dissipated by the heat insulating sheet 10X, and as a result, the generation of high temperature cannot be suppressed and thermal runaway occurs. However, if the thermal conductivity is increased, the heat insulating performance cannot be exhibited and the high temperature propagates to the adjacent secondary battery cells, and the occurrence of burning cannot be suppressed. As described above, the suppression of the generation of hot spots and the prevention of burning are contradictory characteristics, and it is difficult to achieve both.
  • Patent Document 2 a configuration has been proposed in which a composite sheet including a heat insulating layer and heat conductive sheets arranged on both sides thereof is formed between the secondary battery cells. According to this, it is said that the heat dissipation from the battery cell to the housing is excellent and the heat insulation between adjacent battery cells is excellent.
  • PET polyethylene terephthalate
  • silica xerogel a PET non-woven fabric impregnated with silica xerogel
  • the present invention has been made in view of such a background, and one of the purposes thereof is to provide a heat insulating sheet having reduced processing costs while maintaining heat insulating performance and a power supply device provided with the heat insulating sheet.
  • the heat insulating sheet includes an intermediate layer and a surface layer laminated on the surface of the intermediate layer, and the thermal conductivity of the surface layer in the thickness direction is 0.
  • the thermal conductivity of the intermediate layer in the thickness direction is 1.00 W / m ⁇ K or more, and the pore diameter of the surface layer can be 50 ⁇ m or less.
  • an intermediate layer and a surface layer laminated on the surface of the intermediate layer are provided, and the surface layer is provided with the intermediate layer.
  • the thermal conductivity in the thickness direction is 0.50 W / m ⁇ K or less
  • the thermal conductivity in the thickness direction of the intermediate layer is 1.00 W / m ⁇ K or more
  • the surface layer is The air permeation resistance can be set to 3 to 5000 sec / 100 mL with a Garley standard type densometer conforming to the JIS P 8117 (2009) test.
  • the surface layer can be laminated on both sides of the intermediate layer.
  • the thermal conductivity of the intermediate layer in the plane direction may be 1000 W / m ⁇ K or less. can.
  • the thermal conductivity of the intermediate layer in the thickness direction is set to 3.00 W / m ⁇ K or less. can do.
  • the thermal conductivity in the plane direction of the intermediate layer is five times the thermal conductivity in the thickness direction. The above can be done. With the above configuration, even if a hot spot is partially generated in the surface direction, heat is conducted in the surface direction to suppress the generation of hot spots, and thus the generation of burning can be suppressed.
  • the intermediate layer can be composed of a papermaking sheet.
  • the intermediate layer can contain fibers or a heat conductive filler.
  • the intermediate layer can contain any of graphite, boron nitride, and aluminum.
  • the ash on the back surface when heated for 10 minutes according to the JIS L 1091 A-1 method (1999) test can be 500 mm 2 or less.
  • the volume resistivity of the surface layer can be set to 10 10 or more in addition to any of the above configurations. With the above configuration, the insulation after combustion can be maintained.
  • the surface layer can contain at least one of fibers, a filler, and a binder. With the above configuration, it is possible to prevent powder from falling from the surface layer.
  • the adhesive layer for adhering the intermediate layer and the surface layer is an acrylic adhesive or a vinyl chloride adhesive. , Vinyl acetate-based adhesive, or at least one of hot melt.
  • the thickness can be 0.2 mm to 6.0 mm in addition to any of the above configurations.
  • the compression rate when the surface layer is compressed at 100 kPa can be set to 10% or more.
  • the heat resistant temperature can be set to 300 to 600 ° C. in addition to any of the above configurations.
  • a heat insulating sheet used for a power supply device in which a plurality of secondary battery cells are laminated the heat insulating sheet and the intermediate layer.
  • a surface layer laminated on the surface of the intermediate layer is provided, and the thermal conductivity of the surface layer in the thickness direction is 0.50 W / m ⁇ K or less, and the heat conductivity of the surface layer is 0.50 W / m ⁇ K or less in the thickness direction.
  • the thermal conductivity of the surface layer is 1.00 W / m ⁇ K or more, and the pore diameter of the surface layer can be 50 ⁇ m or less.
  • any one of the above heat insulating sheets and a plurality of secondary battery cells laminated with the heat insulating sheet interposed therebetween can be provided.
  • FIG. 3 is a vertical sectional view taken along line II-II of the power supply device of FIG.
  • FIG. 3 is an enlarged schematic cross-sectional view showing a heat insulating sheet according to the first embodiment. It is a schematic cross-sectional view which shows the state which the hot spot occurred in the structure which insulated between the secondary battery cells with the conventional heat insulating sheet. It is a schematic cross-sectional view which shows the state which hot spot occurred in the structure which insulated between pouch type secondary battery cells by the heat insulating sheet which concerns on Embodiment 1.
  • FIG. 6A is a side view showing the mounting position of the ceramic heater and the thermocouple in the front and back temperature evaluation test
  • FIG. 6B is a plan view showing the mounting position of the thermocouple on the upper surface of the heater
  • FIG. 6C shows the mounting position of the thermocouple on the back side of the sample. It is a bottom view which shows.
  • FIG. 7A is a photograph of the sample of Example 1 taken from the heater surface
  • FIG. 7B is a photograph taken from the back surface side with a thermography camera
  • FIG. 8A is a photograph of the sample of Example 2 taken from the heater surface
  • FIG. 8B is a photograph taken from the back surface side with a thermography camera.
  • FIG. 9A is a photograph of the heater surface of the sample of Example 3, and FIG.
  • FIG. 9B is a photograph of the back surface side of the sample, respectively, taken by a thermography camera.
  • FIG. 10A is a photograph of the heater surface of the sample of Example 4, and FIG. 10B is a photograph of the back surface side of the sample, respectively, taken by a thermography camera.
  • FIG. 11A is a photograph of the heater surface of the sample of Comparative Example 1 and FIG. 11B is a photograph of the back surface side of the sample taken by a thermography camera. It is a schematic diagram which shows the combustion test of a sample.
  • FIG. 13A is a photograph showing how the incinerated area is measured by the image processing software
  • FIG. 13B is a photograph showing how the carbonized area is measured.
  • FIG. 13A is a photograph showing how the incinerated area is measured by the image processing software
  • FIG. 13B is a photograph showing how the carbonized area is measured.
  • FIG. 14A is a photograph of the combustion surface of the sample of Example 1 after the combustion test
  • FIG. 14B is a photograph of the back surface of the sample.
  • FIG. 15A is a photograph of the combustion surface of the sample of Example 2 after the combustion test
  • FIG. 15B is a photograph of the back surface of the sample.
  • FIG. 16A is a photograph of the combustion surface of the sample of Example 3 after the combustion test
  • FIG. 16B is a photograph of the back surface of the sample.
  • FIG. 17A is a photograph of the combustion surface of the sample of Example 4 after the combustion test
  • FIG. 17B is a photograph of the back surface of the sample.
  • FIG. 18A is a photograph of the combustion surface of the sample of Comparative Example 1 after the combustion test
  • FIG. 18B is a photograph of the back surface of the sample. It is a schematic cross-sectional view which shows the conventional composite sheet.
  • each element constituting the present invention may be configured such that a plurality of elements are composed of the same member and the plurality of elements are combined with one member, or conversely, the function of one member is performed by the plurality of members. It can also be shared and realized.
  • the heat insulating sheet according to the embodiment of the present invention can be appropriately used for applications requiring heat insulating properties.
  • it can be used as a heat insulating material for insulating refrigerators, freezers, etc., a heat insulating sheet for building materials, and the like.
  • a heat insulating sheet is used as a spacer interposed between adjacent secondary battery cells in a power supply device in which a large number of secondary battery cells are stacked and connected in series or in parallel will be described.
  • a power supply device is used as a power source for driving electric vehicles such as electric vehicles, hybrid vehicles, electric buses, trains, and electric carts, as a backup power source for factories and base stations, and as a storage battery for home use. ..
  • a power supply device using the heat insulating sheet according to the first embodiment is shown in a perspective view of FIG. 1 and a vertical sectional view of FIG.
  • the power supply device 100 shown in these figures includes a plurality of secondary battery cells 1 and a heat insulating sheet 10 interposed between the secondary battery cells 1. In this way, the secondary battery cell 1 and the heat insulating sheet 10 are alternately laminated to form a battery laminate. Further, a side plate 2 is arranged on the side surface of the battery laminate as needed. The side plate 2 is thermally coupled to the side surface of the secondary battery cell 1 and functions as a heat radiating plate that dissipates heat by heat conduction. (Insulation sheet 10)
  • a heat insulating sheet 10 is interposed between the adjacent secondary battery cells 1.
  • the heat insulating sheet 10 is called a spacer, a separator, or the like, and is a member for insulating between adjacent secondary battery cells 1 to prevent or suppress burning.
  • the heat insulating sheet 10 can be made to function as a heat radiating member by thermally coupling the upper end, the lower end, the side surface and the like with a heat radiating plate or the like.
  • heat dissipation fins can be arranged above and below the battery laminate, and the upper and lower ends of the heat insulating sheet can be thermally coupled to the heat dissipation fins, respectively. (Secondary battery cell 1)
  • a lithium ion secondary battery can be preferably used as the secondary battery cell 1.
  • the exterior material of the secondary battery cell 1 is made of a conductive member.
  • insulation is required in addition to heat insulation.
  • the heat insulating sheet 10 according to the present embodiment is suitably used for a power supply device using a secondary battery cell using such a conductive outer can by forming the surface layer 12 with a sheet having insulating properties. can.
  • the present invention can also be used for a secondary battery cell having an insulating outer material, for example, a pouch type or a laminated type having a plate-shaped outer shape. (Insulation sheet 10)
  • FIG. 1 An enlarged cross-sectional view of the heat insulating sheet 10 is shown in FIG.
  • the heat insulating sheet 10 shown in this figure is composed of an intermediate layer 11 and a surface layer 12 laminated on both sides so as to sandwich the intermediate layer 11.
  • the thermal conductivity is different between the intermediate layer 11 and the surface layer 12.
  • the thermal conductivity in the thickness direction of the surface layer 12 is 0.50 W / m ⁇ K or less
  • the thermal conductivity in the thickness direction of the intermediate layer 11 is 1.00 W / m ⁇ K or more. ..
  • the insulating sheet has a multi-layered structure in which each surface layer 12 is a heat insulating layer having suppressed thermal conductivity, and the intermediate layer 11 interposed between them is a heat radiating layer having improved thermal conductivity. Even if the layer 12 is thin, the heat insulating sheet 10 having excellent heat insulating performance can be realized.
  • the thermal conductivity of the intermediate layer 11 in the plane direction is 5 times or more in the thickness direction. As a result, it is possible to prevent burning while effectively eliminating the generation of hot spots while demonstrating the heat insulating performance of the heat insulating sheet 10 combined with the surface layer 12 having high heat insulating performance.
  • the conventional heat insulating sheet was made of a material with high heat insulating performance, in other words, low thermal conductivity, from the viewpoint of preventing burning.
  • this high heat is thermally conducted by the heat insulating sheet 10X to dissipate heat.
  • the hot spot HS which has no heat escape, becomes hotter and hot, and there is a possibility that it will eventually burn and run away from heat.
  • the surface layer 12 is opposed to the secondary battery cell 1 as a heat insulating layer having suppressed thermal conductivity.
  • the heat insulating sheet 10 interposed between the adjacent secondary battery cells 1 can insulate the left and right secondary battery cells with high heat insulating properties.
  • the surface layer 12 as an insulating layer, it is possible to avoid an unintended short circuit between the secondary battery cells.
  • a secondary battery cell whose outer can is made of metal it is possible to improve the insulation between the secondary battery cells and contribute to the improvement of safety and reliability.
  • the surface layer facing the secondary battery cell. 12 (on the right side in FIG. 5) exhibits heat insulating properties, but the heat that has reached the intermediate layer 11 is positively conducted in the plane direction, so that the heat is propagated and diffused over the entire surface of the surface layer 12.
  • the expansion of the hot spot can be suppressed by removing heat from the place where the high temperature is generated.
  • the thermal conductivity of the intermediate layer 11 in the surface direction is promoted, the heat conduction to the back surface side is suppressed, and the heat conduction to the back surface side is suppressed.
  • the end face of the heat insulating sheet 10 is thermally coupled to the side plate 2 or thermally coupled to the heat radiating member to further improve the heat radiating property, and heat is absorbed from the secondary battery cell to cause thermal runaway. Can be suppressed.
  • the heat insulating effect of the surface layer 12 on the back surface side can prevent or suppress the propagation of high heat to other secondary battery cells, and can reduce the risk of burning.
  • the heat insulating sheet 10 has a multi-layer structure, and a heat diffusion function is added to the intermediate layer 11 to suppress hot spot HS, while a heat insulating function is added to the surface layer 12 to the other secondary battery cells. By preventing burning, it enhances safety by achieving both the contradictory functions of heat dissipation performance and heat insulation performance, which were difficult to achieve in the past. (Surface layer 12)
  • the surface layer 12 has a thermal conductivity of 0.50 W / m ⁇ K or less in the thickness direction, more preferably 0.01 W / m ⁇ K to 0.30 W / m ⁇ K, still more preferably 0.02 W / m ⁇ K. It is set to K to 0.20 W / m ⁇ K.
  • Such a surface layer 12 preferably contains any of fibers, fillers, and binders in order to exhibit sufficient heat insulating performance.
  • the pore diameter of the surface layer 12 is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, and even more preferably 20 ⁇ m or less. As a result, it is possible to suppress the powder falling of the heat insulating sheet and eliminate the need for a treatment for preventing the powder falling such as sealing the surface layer.
  • the air permeability resistance of the surface layer 12 is preferably 3 to 5000 sec / 100 ml, more preferably 5 to 1000 sec / 100 ml, using a Garley standard densometer conforming to the JIS P 8117 (2009) test. If the air permeation resistance is smaller than this range, when the fiber or powder falls off from the intermediate layer described later, its scattering cannot be prevented and a short circuit may occur. Further, when the air permeation resistance is larger than this range, the adhesive strength with the adhesive layer described later tends to decrease.
  • the smoothness of the surface layer 12 is a smoothness tester based on JIS P 8119 (1998), and the time until the pressure in the vacuum vessel changes from 50.7 kPa to 29.3 kPa is 15 to 150 sec. Is preferable.
  • the surface layer 12 has a compression rate of 10% or more when compressed at 100 kPa.
  • the surface layer 12 of the heat insulating sheet 10 includes a fiber base material, a filler, and a binder.
  • a fiber base material Preferably, natural pulp and inorganic fibers can be used as the fiber base material, silicate minerals can be used as the filler, and rubber compositions can be used as the binder.
  • the surface layer 12 according to the first embodiment contains hemp pulp and microglass as a fiber base material, talc and sepiolite as a filler, and NBR as a binder.
  • the fiber base material also called base fiber
  • inorganic fibers such as glass fibers, carbon fibers and ceramic fibers, or organic fibers such as aromatic polyamide fibers and polyethylene fibers
  • natural pulp of organic fiber is used as the fiber base material.
  • Hemp pulp can be preferably used as natural pulp.
  • the blending ratio of hemp pulp is, for example, 5% by weight to 20% by weight, preferably 10% by weight.
  • Inorganic fibers may also be included as the fiber base material.
  • the blending ratio of the inorganic fibers is 5% by weight to 20% by weight, preferably 8% by weight to 15% by weight.
  • 12% by weight of microglass is added as an inorganic fiber.
  • Inorganic filler can be used as the filler.
  • Inorganic fillers include silicate minerals such as sepiolite, talc, kaolin, mica, and sericite, magnesium carbonate, calcium carbonate, hard clay, calcined clay, barium sulfate, calcium silicate, wollastonite, sodium bicarbonate, and white carbon.
  • -Synthetic silica such as molten silica, natural silica such as silicate soil, aluminum hydroxide, magnesium hydroxide, glass beads and the like can be mentioned, and these may be used alone or in combination of two or more.
  • the addition of these inorganic fillers has the effects of maintaining the shape and improving the heat insulating property in a high temperature atmosphere.
  • talc having high flexibility was used.
  • the blending amount of the filler is preferably 5% by weight to 65% by weight in the heat insulating sheet.
  • magnesium silicate is used as a filler, and 58% by weight of talc and 14% by weight of sepiolite are added.
  • the binder includes vinyl chloride resin, vinylidene chloride resin, acrylic acid resin, urethane resin, vinyl acetate resin, polyethylene resin, polystyrene resin, acrylobutadiene styrene resin, acrylonitrile styrene resin, fluororesin, silicone resin, epoxy resin, and phenol.
  • acrylic nitrile butadiene rubber hydride acrylic nitrile butadiene rubber, acrylic rubber, acrylic nitrile rubber, ethylene propylene rubber, styrene butadiene rubber, chloroplane rubber, butadiene rubber, butyl rubber, fluororubber, silicone rubber , Fluorosilicone rubber, chlorosulphonized rubber, ethylene vinegar rubber, polyethylene chloride, butyl chloride rubber, epichlorohydrin rubber, nitrile isoprene rubber, natural rubber, isoprene rubber and the like can be used.
  • acrylic nitrile butadiene rubber NBR
  • NBR acrylic nitrile butadiene rubber
  • rubbers can be used alone or in combination of two or more. Further, for the purpose of higher water resistance and oil resistance, a sizing agent such as an alkyl ketene dimer and a fluorine-based or silicone-based water repellent can be used in combination.
  • a rubber composition is used as the binder, the amount of rubber to be blended is preferably 5.0 to 40% by weight in the heat insulating sheet. Here, 6.0% by weight of NBR Nipol 1562 is added.
  • chemicals such as paper strength agents, fixing agents, and antifoaming agents are added.
  • 0.5% by weight of WS4030 was added as a paper strength agent
  • 0.3% by weight of cogham 15H was added as a paper strength agent
  • 1.9% by weight of a sulfate band was added as a fixing agent
  • an appropriate amount of KM-70 was added as an antifoaming agent. ing.
  • the surface layer 12 has a thickness of 1 mm to 5.5 mm, preferably 0.15 mm to 2 mm, and more preferably 0.2 mm to 1 mm.
  • the surface layer 12 may be composed of a plurality of layers of inorganic fiber layers such as a layered glass fiber layer and a ceramic fiber layer.
  • the inorganic fiber a fiber having a fiber length of 13 mm or more can be preferably used from the viewpoint of compressive stability. It is more preferably 40 mm or more, and even more preferably uncut long fiber. (Middle layer 11)
  • the intermediate layer 11 has a thermal conductivity of 1.00 W / m ⁇ K or more in the thickness direction, preferably 2.00 W / m ⁇ K to 20.00 W / m ⁇ K, and more preferably 2.50 W / m ⁇ K. It is set to ⁇ 15.00 W / m ⁇ K.
  • the thermal conductivity of the intermediate layer 11 in the thickness direction may be 3.00 W / m ⁇ K or less.
  • the thermal conductivity of the intermediate layer 11 in the plane direction is preferably 1000 W / m ⁇ K or less.
  • such an intermediate layer 11 contains an organic fiber or a heat conductive filler in order to exhibit sufficient heat conductivity.
  • the organic fiber any one or more of para-aramid fiber, para-aramid pulp, meta-aramid pulp, polyphenylene sulfide fiber, PET fiber, flame-retardant PET fiber, and flame-retardant rayon fiber can be used.
  • the heat conductive filler magnesium oxide, aluminum oxide, boron nitride, aluminum nitride, aluminum, copper, graphite, carbon nanotubes and the like can be used.
  • the intermediate layer 11 may contain inorganic fibers.
  • the inorganic fiber carbon fiber, glass fiber, ceramic fiber and the like can be used.
  • the intermediate sheet composed of the papermaking sheet may be pressure-processed by a thermal calender roll or the like. As a result, the inside can be densified and the thermal conductivity can be increased.
  • a film-like metal such as iron, aluminum, copper, silver, and gold can be used as the intermediate layer 11.
  • the thickness of the intermediate layer 11 is 0.02 mm to 0.5 mm, preferably 0.03 mm to 0.4 mm, and more preferably 0.03 mm to 0.3 mm.
  • the air permeability resistance of the intermediate layer 11 is 3000 sec / ml or more with a Garley standard type densometer conforming to the JIS P 8117 (2009) test.
  • the intermediate layer 11 having heat diffusivity with less powder falling is realized, and there is an advantage that the production can be easily and inexpensively performed without the need for sealing the layer having heat diffusivity.
  • the intermediate layer 11 and the surface layer 12 are adhered with an adhesive.
  • An adhesive layer obtained by curing the adhesive is interposed between the intermediate layer 11 and the surface layer 12.
  • the adhesive material is preferably a material having excellent heat resistance.
  • an acrylic adhesive, a vinyl chloride adhesive, a vinyl acetate adhesive, a hot melt, or the like can be used.
  • the form of the adhesive can be liquid, slurry, or a heat-sealed sheet obtained by molding a hot melt adhesive into a non-woven fabric or a net.
  • the overall thickness of the heat insulating sheet 10 is 0.2 mm to 6.0 mm, preferably 0.2 mm to 4.0 mm, and more preferably 0.3 mm to 2.0 mm.
  • the heat insulating sheet 10 has flexibility and flexibility. As a result, when the secondary battery cell 1 expands as shown in the cross-sectional view of FIG. 5, it follows the deformation of the secondary battery cell 1 and maintains a close contact state, and is thermally conductive due to the formation of voids. Can be avoided.
  • many of the conventional heat insulating sheets are hard and have low followability to deformation. Therefore, voids are formed on the contact surface and the heat insulating effect of the air layer may reduce the thermal conductivity.
  • a hard heat insulating sheet is rather convenient because the heat insulating performance is further improved by the air layer.
  • the surface layer 12 should be a heat insulating sheet 10 having flexibility and flexibility rather than such a hard material in order to exhibit heat dissipation performance. Therefore, it is possible to maintain a high thermal conductivity and exhibit heat dissipation performance.
  • the heat insulating sheet 10 flexibility and flexibility, it becomes possible to wind it on a winding material such as a roll material, it becomes possible to store and transport it in a roll shape, and the handling property is improved.
  • a winding material such as a roll material
  • the handling property is improved.
  • in order to exhibit flexibility for example, when a cylinder having an outer diameter of 110 mm is applied to one side of the heat insulating sheet 10 and bent by 90 °, wrinkles or cracks can be prevented.
  • the heat insulating sheet 10 has heat resistance and flame retardancy. Even if the secondary battery cell 1 becomes hot, the heat insulating performance can be maintained by using a material that is not easily deformed or melted.
  • the heat resistant temperature of the heat insulating sheet 10 is 300 to 600 ° C.
  • the heat insulating sheet according to the present embodiment by forming the surface layer with fibers, a filler, and a binder, a high heat resistant temperature can be exhibited, and the insulating property can be maintained even in a high temperature environment. Further, it is preferable to suppress the ashed area on the back surface to 500 mm 2 or less when heated for 10 minutes according to the JIS L 1091 A-1 method (1999) test.
  • the smoothness of the entire heat insulating sheet is 15 to 150 sec. This has the advantage that the heat insulating sheet does not need to be sealed and can be manufactured easily and inexpensively.
  • the heat insulating sheet according to the present embodiment can be provided with deformable flexibility.
  • it has a flexibility that does not break even when wound around a paper tube having a radius of curvature of 55 mm.
  • the object with which the heat insulating sheet is in contact is deformed, such as by expanding, it is possible to maintain the close contact state by following the deformation, and it is possible to avoid the situation where voids are formed and the thermal conductivity is lowered.
  • the heat insulating sheet 10 is a roll-to-roll by sandwiching a heat-sealing sheet between, for example, a roll-shaped intermediate layer 11 and a surface layer 12, passing between two thermocompression bonding rolls, and adhering them. It can be manufactured. Further, a liquid adhesive may be applied to one or both sides of the intermediate layer 11 to the surface layer 12 and bonded to each other.
  • a polyethylene heat-sealing sheet is sandwiched between the intermediate layer 11 and the surface layer 12, and is pressed and bonded at 50 kPa for 20 seconds with a hot press at 150 ° C. rice field.
  • the present invention is not limited to such a three-layer structure, and may be a multi-layer structure having four or more layers, for example, a surface layer having a plurality of layers or an intermediate layer having a plurality of layers.
  • a two-layer structure in which a surface layer is provided on only one side of the intermediate layer may be used.
  • the secondary battery cell 1 is placed in a vertical position, but it goes without saying that the heat insulating sheet can be similarly applied to a power supply device in which the secondary battery cell is placed in a horizontal position.
  • the heat insulating sheet 10 can be used not only for heat insulation between secondary battery cells but also for heat insulation between battery modules composed of a plurality of secondary battery cells. [Examples 1 to 4; Comparative Example 1]
  • Example 1 the same sheet made of natural pulp, microglass, silicate mineral powder and a rubber-based resin as a binder was used as the surface layer.
  • the papermaking slurry obtained by adding a rubber-based resin to this was made by a wet papermaking method to obtain a surface layer base material sheet having a thickness of about 0.70 mm.
  • the thermal conductivity (thickness direction) of this surface layer base material sheet is 0.18 W / m ⁇ K
  • the thermal conductivity (plane direction) is 0.18 W / m ⁇ K
  • the smoothness is 46.8 sec
  • the air permeability resistance The degree was 30 sec / 100 ml.
  • a papermaking sheet containing 90% graphite powder was used as the intermediate layer of Example 1. Specifically, a papermaking slurry in which graphite powder and organic fibers are dispersed in water so as to have a weight ratio of 90:10 is prepared, and the sheet obtained by the wet papermaking method is subjected to thermal pressure processing to obtain an intermediate layer base material. I got a sheet. Its thickness was 0.23 mm.
  • Example 2 A surface layer is laminated on both sides of the obtained intermediate layer base material sheet, a polyethylene heat-sealing sheet is sandwiched between the surface layer and the intermediate layer, and a pressure is applied at 50 kPa for 20 seconds by a hot press at 150 ° C.
  • the heat insulating sheet according to Example 1 was obtained. (Example 2)
  • Example 3 As the intermediate layer of Example 2, a papermaking slurry in which graphite powder and organic fibers were dispersed in water so as to have a weight ratio of 75:25 was prepared, and the sheet obtained by the wet papermaking method was subjected to thermal pressure processing. A surface layer base material sheet 2 was obtained. Its thickness was 0.07 mm. A surface layer was laminated on both sides of the obtained intermediate layer base material sheet in the same manner as in Example 1 to obtain a heat insulating sheet according to Example 2. (Example 3)
  • the intermediate layer of Example 3 was an aluminum film.
  • a shim plate aluminum TA200-300-02 manufactured by Iwata Seisakusho with a thickness of 0.2 mm was used as an intermediate layer base material sheet.
  • the surface layer of this intermediate layer base material sheet was bonded to each surface in the same manner as in Example 1 and the like to obtain a heat insulating sheet according to Example 3. (Example 4)
  • Example 4 A thin aluminum film was used as the intermediate layer of Example 4.
  • a shim plate aluminum TA200-300-01 manufactured by Iwata Seisakusho with a thickness of 0.1 mm was used as an intermediate layer base material sheet.
  • the surface layer of this intermediate layer base material sheet was bonded to each surface in the same manner as in Example 1 and the like to obtain a heat insulating sheet according to Example 4. (Comparative Example 1)
  • a heat-insulating papermaking sheet was used as in the surface layer.
  • the papermaking slurry obtained by mixing the raw materials in the same weight ratio as in Example 1 was made by a wet papermaking method to obtain an intermediate layer base material sheet having a thickness of about 0.3 mm.
  • the obtained intermediate layer base material sheet was laminated with surface layers on both sides in the same manner as in Example 1 and the like to obtain a heat insulating sheet according to Comparative Example 1.
  • Table 1 shows the thickness of the intermediate layer, the thickness of the entire heat insulating sheet, and the thermal conductivity (thickness direction and surface direction) of the heat insulating sheets according to Examples 1 to 4 and Comparative Example 1.
  • the front and back temperature evaluation test of the samples was first performed. Specifically, as shown in the side view of FIG. 6A, a ceramic heater HT (MS-1000 manufactured by Sakaguchi Electric Heat Co., Ltd.) is fixed to one side of the sample of the heat insulating sheet 10 with aluminum tape, and the upper surface of the heater HT and the heater HT are fixed. Thermocouples T0, T1, T2, and T3 were attached to the opposite surface of the heat insulating sheet 10 in contact with the heat as shown in FIGS. 6B and 6C. In this state, the temperature difference between the front and back of the heat insulating sheet was measured from the difference between the heater temperature and the back surface temperature of the sheet when the heater HT was raised to 200 ° C. with an output of 9.5 W to 20 W. (Flexibility test)
  • the heat insulating sheets according to Examples 1 to 4 and Comparative Example 1 were tested for flexibility. Specifically, a heat insulating sheet cut into 120 mm ⁇ 65 mm was pressed against the outer periphery of a paper tube having an outer diameter of 110 mm, and it was confirmed whether damage such as wrinkles or cracks occurred and evaluated. The evaluation was described in three stages as follows. ⁇ : Does not occur, ⁇ : Minor damage, ⁇ : Serious damage that makes it unusable. These results are shown in Table 2.
  • Example 3 in which aluminum is used for the intermediate layer has a larger temperature difference between the front and back surfaces than Examples 1 and 2 in which graphite powder is used, in other words, the heat insulating effect is higher.
  • Example 4 also exhibits a high heat insulating effect, although it is inferior to Example 3.
  • the aluminum of Examples 3 and 4 has the same thermal conductivity in the thickness direction and the surface direction and has no anisotropy, while the heat diffusion layer using the graphite powder of Examples 1 and 2 is shown in Table 1. As such, the thermal conductivity in the plane direction is 40 to 60 times higher than that in the thickness direction.
  • FIGS. 7A to 11B The photographs taken by the thermography camera are shown in FIGS. 7A to 11B.
  • FIG. 7A is a photograph of the sample of Example 1 taken from the heater surface
  • FIG. 7B is a photograph taken from the back surface side by a thermography camera.
  • FIG. 8A is a photograph of the sample of Example 2 taken from the heater surface
  • FIG. 8A is a photograph of the sample of Example 2 taken from the heater surface
  • FIG. 8B is a photograph taken from the back surface side with a thermography camera.
  • FIG. 9A is the heater surface of the sample of Example 3
  • FIG. 9B is the back surface side
  • FIG. 10A is the heater surface of the sample of Example 4
  • FIG. 10B is the back surface side
  • FIG. 11A is the heater surface of the sample of Comparative Example 1.
  • 11B is a photograph of the back surface side, respectively. From these figures, in Comparative Example 1 composed of only the heat insulating layer, the back surface side is hot as shown in FIG. 11B, whereas in Examples 1 to 4 in which both sides of the heat diffusion layer are covered with the heat insulating layer. It was confirmed that the temperature rise on the back surface side was suppressed in both cases.
  • Example 1 in which the thickness is relatively large, as compared with Example 2 in which the thickness is relatively large, the temperature rise is suppressed, the local temperature change is also suppressed, and uniform heat dissipation in the surface direction is achieved. It was confirmed that. (600 ° C combustion test)
  • each sample is attached to the jig at an angle of 45 ° as shown in Fig. 12, and the thermocouple is attached to the flame contact part of the gas burner GB and its back surface.
  • TC1 and TC2 were attached respectively, the flame of the gas burner GB was applied, the temperature of the thermocouple TC2 on the back surface at the time when the thermocouple TC1 of the flame contact portion reached 600 ° C. was measured, and the temperature difference was calculated.
  • each sample attached to the jig without a thermocouple was exposed to the flame of the gas burner GB for 10 minutes, the presence or absence of combustion was observed, the state of both sides of the sample after the test was photographed, and the organic component was burned.
  • the area was measured using the image processing software "leafareacounter_plus3_3".
  • the image processing software as for the ashed area, as shown by the red line in FIG. 13A, the area where the organic component disappeared by combustion and only the inorganic component was ashed white was measured.
  • the area burnt black including the ashed area was measured so as to be surrounded by the red line in FIG. 13B.
  • FIGS. 14A to 18B The photographs of the samples of Examples 1 to 4 and Comparative Example 1 after the combustion test are shown in FIGS. 14A to 18B, respectively.
  • FIG. 14A is a photograph of the combustion surface of the sample of Example 1
  • FIG. 14B is a photograph of the back surface
  • FIG. 15A is a photograph of the combustion surface of the sample of Example 2
  • FIG. 15B is a photograph of the back surface
  • FIG. 16A is a photograph of Example 3.
  • the combustion surface of the sample FIG. 16B is a photograph of the back surface
  • FIG. 17A is a photograph of the combustion surface of the sample of Example 4
  • FIG. 17B is a photograph of the back surface
  • FIG. 18A is a photograph of the combustion surface of the sample of Comparative Example 1
  • FIG. 18B is a photograph of the back surface.
  • Comparative Example 1 composed of only the heat insulating layer, as shown in FIG. 18A, it is confirmed that the portion of the combustion surface that seems to have been exposed to the flame is ashed white. It is presumed that this is because the organic component burned and only the inorganic component remained in the spot shape. Also on the back surface side, as shown in FIG. 18B, a similarly whitish ashed state was confirmed at the corresponding portion. Similarly, it is considered that the organic component is burned and only the inorganic component remains in the spot shape.
  • Example 1 and 2 coated with the heat diffusion layer of graphite powder the state of combustion was not confirmed on the combustion surface, and black soot like slightly burnt was confirmed as shown in FIGS. 14A and 15A. rice field. Further, on the back surface side as well, in Example 1, only the occurrence of some wrinkles is confirmed as shown in FIG. 14B. It is considered that this is because the resin of the adhesive material was softened by heat and wrinkles were generated.
  • Example 2 as shown in FIG. 15B, although the occurrence of wrinkles was confirmed, the state of combustion was not confirmed. As described above, in Examples 1 and 2, it was confirmed that the heat conduction to the back surface side was suppressed even if the front surface side was exposed to the flame.
  • Table 4 shows a summary of these test results. As described above, it was confirmed that Examples 1 to 4 are superior in flame retardancy as compared with Comparative Example 1.
  • Example 5 papermaking was carried out in the same manner as in Example 1 except that the thickness was 0.30 mm, and a surface layer base material sheet was obtained. Using the obtained surface layer base material sheet, it was laminated on both sides of the intermediate layer base material sheet similar to that of Example 1 and bonded in the same manner as in Example 1 to obtain a heat insulating sheet according to Example 5. (Example 6)
  • Example 6 In order to prepare the surface layer of Example 6, first, the dissociated natural pulp was prepared, and microglass, chopped glass, synthetic silica and diatomaceous earth were uniformly dispersed. A rubber-based resin was added thereto, and paper was made by a wet papermaking method to obtain a surface layer base material sheet having a thickness of about 0.80 mm. The thermal conductivity (thickness direction) of this sheet was 0.08 W / m ⁇ K, and the thermal conductivity (plane direction) was 0.08 W / m ⁇ K. Using the obtained surface layer base material sheet, it was laminated on both sides of the intermediate layer base material sheet similar to that of Example 1 and bonded in the same manner as in Example 1 to obtain a heat insulating sheet according to Example 6. (Comparative Example 2)
  • the smoothness was measured for each sample of Examples 1, 5, 6 and Comparative Example 2.
  • a decibel smoothness tester (DB-2 type manufactured by Toyo Seiki Seisakusho) conforming to JIS P 8119 (1998) was used.
  • the volume of the vacuum container is 380 mL, which is the JIS standard 8.
  • the test start pressure was 50.7 KPa and the test end pressure was 29.3 KPa.
  • the standard test start pressure is 50.7 KPa and the test end pressure is 48.0 KPa, but since the measurement time was shorter than 15 seconds under this condition, the test end pressure was changed to a lower value. And are testing.
  • Table 4 Since Comparative Example 2 had extremely high smoothness, the measurement was stopped when the measured value was 3000 sec. (Bubble point test and pore diameter)
  • Example 1 the bubble point value of the surface layer base material sheet before being bonded to the intermediate layer was measured according to JIS K 3832 (1990), and the pore diameter was calculated. Specifically, a sample of the surface layer cut into 4 cm ⁇ 4 cm is immersed in a test solution made of Fluorinert FC-40 having a surface tension of 16 mN / m, and the sample completely filled with the test solution is a palm poromometer. The measurement was performed by attaching to CFP-1100AE (manufactured by Polouse Materials Inc.). From the obtained bubble point value, the pore diameter d [ ⁇ m] was calculated by the following formula. The results are shown in Table 4.
  • Example 1 a Garley standard type densometer compliant with the JIS P 8117 (2009) test was used to determine the air permeability resistance of the surface layer base material sheet before being bonded to the intermediate layer. was measured. The results are shown in Table 4.
  • Comparative Example 2 the air permeability resistance was extremely high, and the measurement was stopped when the measured value was 6000 sec / ml. (Compression / recovery rate)
  • the compressibility was measured when the pressure of the surface layer base material sheet before bonding with the intermediate layer was 100 kPa.
  • Instron's universal material testing machine type 5985 was used.
  • thermocouple TC1 was removed by allowing the sample to cool while attached to the jig, and the electrodes of the digital tester TST-KJ830 (manufactured by Ohm Electric) were applied to the flame contact part and the back surface to confirm whether the sample was conducting.
  • the results are shown in Table 5. ( ⁇ : no continuity, ⁇ : with continuity)
  • the heat insulating sheet of the present invention is used as a heat insulating spacer interposed between secondary battery cells, a cushioning sheet interposed between an explosion-proof valve and a gas duct, or a heat insulating material for protecting a drive circuit such as an ECU. It can be suitably used.
  • Power supply devices using heat insulating sheets include mobile electronic devices, power devices driven by battery-powered motors, electric vehicles such as electric vehicles and hybrid vehicles, electric two-wheeled vehicles such as assisted bicycles and electric scooters, electric golf carts and drones. , Can be suitably used for power storage systems and the like.

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Abstract

La présente invention concerne une feuille isolante qui permet de conserver la performance d'isolation tout en réduisant les coûts de fabrication. Une feuille isolante (10) comprend : une couche intermédiaire (11) et des couches de surface (12) stratifiées sur des surfaces de la couche intermédiaire (11). Les couches de surface (12) ont une conductivité thermique inférieure ou égale à 0,50 W/m ∙ K dans le sens de l'épaisseur, et la couche intermédiaire (11) a une conductivité thermique supérieure ou égale à 1,00 W/m ∙ K dans le sens de l'épaisseur. Le diamètre de pore des couches de surface (12) peut être inférieur ou égal à 50 µm. Cette configuration confère des propriétés isolantes aux couches de surface (12) et, par conséquent, empêche le feu de se propager et élimine la nécessité d'isoler les couches de surface (12), ce qui permet d'obtenir la caractéristique avantageuse d'une production facile et peu onéreuse.
PCT/JP2021/016675 2020-06-18 2021-04-26 Feuille isolante et dispositif d'alimentation électrique la comprenant WO2021256093A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023120435A1 (fr) * 2021-12-24 2023-06-29 パナソニックホールディングス株式会社 Bloc-batterie
WO2023120436A1 (fr) * 2021-12-24 2023-06-29 パナソニックホールディングス株式会社 Bloc-batterie

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Publication number Priority date Publication date Assignee Title
JP2011108617A (ja) * 2009-10-19 2011-06-02 Nitto Denko Corp 熱伝導部材、及びそれを用いた組電池装置
JP2015532778A (ja) * 2013-06-19 2015-11-12 アモグリーンテック カンパニー リミテッド ハイブリッド断熱シートおよびこれを備えた電子機器
WO2016017670A1 (fr) * 2014-07-29 2016-02-04 日東シンコー株式会社 Feuille d'isolation
US20170034959A1 (en) * 2013-12-31 2017-02-02 Amogreentech Co., Ltd. Composite sheet and portable terminal having same
JP2019147357A (ja) * 2018-02-28 2019-09-05 リンテック株式会社 難燃断熱シートおよび蓄電モジュール

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Publication number Priority date Publication date Assignee Title
JP2011108617A (ja) * 2009-10-19 2011-06-02 Nitto Denko Corp 熱伝導部材、及びそれを用いた組電池装置
JP2015532778A (ja) * 2013-06-19 2015-11-12 アモグリーンテック カンパニー リミテッド ハイブリッド断熱シートおよびこれを備えた電子機器
US20170034959A1 (en) * 2013-12-31 2017-02-02 Amogreentech Co., Ltd. Composite sheet and portable terminal having same
WO2016017670A1 (fr) * 2014-07-29 2016-02-04 日東シンコー株式会社 Feuille d'isolation
JP2019147357A (ja) * 2018-02-28 2019-09-05 リンテック株式会社 難燃断熱シートおよび蓄電モジュール

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023120435A1 (fr) * 2021-12-24 2023-06-29 パナソニックホールディングス株式会社 Bloc-batterie
WO2023120436A1 (fr) * 2021-12-24 2023-06-29 パナソニックホールディングス株式会社 Bloc-batterie

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