WO2019188626A1 - Feuille d'absorption de chaleur de bloc-batterie et bloc-batterie - Google Patents

Feuille d'absorption de chaleur de bloc-batterie et bloc-batterie Download PDF

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Publication number
WO2019188626A1
WO2019188626A1 PCT/JP2019/011613 JP2019011613W WO2019188626A1 WO 2019188626 A1 WO2019188626 A1 WO 2019188626A1 JP 2019011613 W JP2019011613 W JP 2019011613W WO 2019188626 A1 WO2019188626 A1 WO 2019188626A1
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Prior art keywords
endothermic
hydrate
sheet
endothermic sheet
battery
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PCT/JP2019/011613
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English (en)
Japanese (ja)
Inventor
直己 高橋
清成 畑中
寿 安藤
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イビデン株式会社
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Publication of WO2019188626A1 publication Critical patent/WO2019188626A1/fr

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    • 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
    • H01M50/249—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders specially adapted for aircraft or vehicles, e.g. cars or trains
    • 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
    • H01M10/62—Heating or cooling; Temperature control specially adapted for specific applications
    • H01M10/625—Vehicles
    • 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
    • H01M10/64—Heating or cooling; Temperature control characterised by the shape of the cells
    • H01M10/647—Prismatic or flat cells, e.g. pouch cells
    • 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
    • H01M10/651—Means for temperature control structurally associated with the cells characterised by parameters specified by a numeric value or mathematical formula, e.g. ratios, sizes or concentrations
    • 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
    • H01M10/653—Means for temperature control structurally associated with the cells characterised by electrically insulating or thermally conductive 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
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/655—Solid structures for heat exchange or heat conduction
    • H01M10/6554—Rods or plates
    • H01M10/6555—Rods or plates arranged between the cells
    • 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
    • H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
    • 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
    • H01M50/233—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions
    • H01M50/24—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions adapted for protecting batteries from their environment, e.g. from corrosion
    • 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 an endothermic sheet for an assembled battery that is preferably used for an assembled battery serving as a power source for an electric motor that drives an electric vehicle or a hybrid vehicle, for example.
  • this battery cell Compared to lead-acid batteries and nickel-metal hydride batteries, this battery cell mainly uses lithium-ion secondary batteries capable of high capacity and high output, but due to internal short circuit or overcharge of the batteries.
  • a thermal runaway occurs in one battery cell (that is, in an abnormal state)
  • heat may propagate to other adjacent battery cells, which may cause thermal runaway of other battery cells.
  • Patent Document 1 discloses a power storage device including one or more power storage elements, which is one of the one or more power storage elements.
  • a first plate member and a second plate member disposed on the side of the power storage element, the first plate member and the second plate member disposed so that their surfaces face each other, the first plate member and the second plate member
  • a low thermal conductive layer for example, an air layer
  • Radiant heat or radiant heat toward the first power storage element is blocked by the two plate materials, and heat transfer from one of the two plate materials to the other is suppressed by the low heat conductive layer.
  • Patent Document 2 discloses a battery casing containing an electrolyte and a thermal runaway suppressing substance provided in the battery casing.
  • various materials such as aluminum hydroxide hydrate are disclosed as examples of the thermal runaway suppressing substance.
  • the temperature of the battery cell surface is a predetermined value or less (for example, it is necessary to maintain at 150 ° C. or lower.
  • a heat insulating layer is provided between the plurality of battery cells in order to suppress heat propagation during thermal runaway, the battery cells that generate heat during the charge / discharge cycle can be effectively cooled. It was not a thing.
  • Patent Document 2 is only intended to quickly bring a lithium ion secondary battery to a safe state when an abnormal situation occurs, as a solution thereof, aluminum hydroxide hydrate It is only assumed that a thermal runaway suppression substance that discharges moisture and cools the surroundings under such a high temperature (for example, 200 ° C. or higher) condition is contained in the battery. Therefore, it cannot be said that it is necessarily sufficient to effectively cool the battery cells that generate heat during the charge / discharge cycle.
  • an object of the present invention is to provide an endothermic sheet for assembled batteries that can cool each battery cell during normal use.
  • the summary of the heat-absorbing sheet for assembled battery according to one aspect of the present invention is a set in which a plurality of battery cells are arranged via the heat-absorbing sheet, and the plurality of battery cells are connected in series or in parallel.
  • An endothermic sheet for use in a battery comprising two or more substances having different dehydration temperatures, and at least one of the substances can be dehydrated during normal use of the battery cell.
  • One type is characterized in that dehydration is possible when the battery cell is abnormal.
  • the substance that can be dehydrated during normal use is a dehydrating agent that can be dehydrated at a temperature of 150 ° C. or less, and the substance that can be dehydrated at the time of abnormality is the start of thermal decomposition. It is an inorganic hydrate having a temperature of 200 ° C. or higher.
  • the dehydrating agent is silica gel, activated alumina, activated carbon, zeolite, ion exchange resin, sulfate hydrate, sulfite hydrate, phosphate hydrate, nitrate hydrate. , Acetate hydrate, and metal hydrate.
  • the dehydrating agent is zeolite.
  • the inorganic hydrate includes aluminum hydroxide, magnesium hydroxide, calcium hydroxide, zinc hydroxide, iron hydroxide, manganese hydroxide, zirconium hydroxide, and gallium hydroxide. At least one of the group consisting of: In a preferred embodiment of the assembled battery endothermic sheet, the inorganic hydrate is aluminum hydroxide.
  • the content of the substance that can be dehydrated in the normal use increases as it goes from the central part in the thickness direction of the endothermic sheet to both ends, and the thickness direction in the endothermic sheet
  • the content of the substance that can be dehydrated at the time of the abnormality increases as it goes from both ends to the center.
  • the heat absorbing sheet is formed on both surfaces of the first endothermic layer mainly composed of a substance that can be dehydrated at the time of abnormality, and dehydrated during the normal use. It has a second endothermic layer mainly composed of a possible substance.
  • the gist of the assembled battery according to one embodiment of the present invention is characterized in that a plurality of battery cells are arranged via the above-described assembled battery heat absorbing sheet, and the plurality of battery cells are connected in series or in parallel.
  • the endothermic sheet for an assembled battery in configuring an assembled battery in which a plurality of battery cells are connected in series or in parallel, normal use is performed while suppressing the propagation of heat between the battery cells at the time of abnormality. It is possible to provide an endothermic sheet for assembled battery that can cool each battery cell at the time.
  • FIG. 1 is a cross-sectional view schematically showing a configuration example of an endothermic sheet for assembled battery according to the first embodiment of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing another configuration example of the assembled battery endothermic sheet according to the first embodiment of the present invention.
  • FIG. 3 is a cross-sectional view schematically showing a configuration example of the endothermic sheet for assembled battery according to the second embodiment of the present invention.
  • FIG. 4 is a cross-sectional view schematically showing another configuration example of the assembled battery endothermic sheet according to the second embodiment of the present invention.
  • FIG. 5 is a cross-sectional view schematically showing a configuration example of an assembled battery to which the assembled battery endothermic sheet according to the first embodiment of the present invention is applied.
  • FIG. 1 is a cross-sectional view schematically showing a configuration example of an endothermic sheet for assembled battery according to the first embodiment of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing another configuration example of
  • FIG. 6 is a graph plotting changes in the temperature of the battery cell surface serving as a heat source with respect to the elapsed time when the endothermic sheets of Example 1, Comparative Example 1, and Comparative Example 2 were heated with a heater (heater temperature: 150 ° C.). is there.
  • FIG. 7 plots the temperature change of the adjacent battery cell surface with respect to elapsed time when the endothermic sheets of Example 1, Comparative Example 1, Comparative Example 2, and Reference Example 1 were heated with a heater (heater temperature: 700 ° C.). It is a graph.
  • the present inventors can cool each battery cell at the time of normal use where heat at a relatively low temperature is generated while suppressing the propagation of heat between the battery cells at the time of abnormality where high-temperature heat is generated.
  • intensive studies have been conducted.
  • the battery cell temperature rises at a relatively low temperature by containing a substance that can be dehydrated during normal use where the battery cell temperature is relatively low, the substance releases water when the battery cell temperature rises at a relatively low temperature.
  • the battery cell can be effectively cooled.
  • the temperature range of the battery cell during normal use is generally from room temperature (about 20 ° C.) to a maximum of about 150 ° C.
  • dehydration is possible at a temperature of 150 ° C. or less as a substance that can be dehydrated during normal use. It has also been found that it is preferable to use possible dehydrating agents.
  • the temperature range of the battery cell at the time of abnormality is generally 200 ° C. or higher, it is preferable to use an inorganic hydrate having a thermal decomposition starting temperature of 200 ° C. or higher as a substance that can be dehydrated at the time of abnormality. I also found.
  • a space for releasing the generated heat to the outside is provided between the battery cells, or the propagation of heat between the battery cells at the time of abnormality is suppressed.
  • This space is not provided between the battery cells, so that it is not necessary to make the distance between the battery cells extremely large. For this reason, it is also possible to reduce the thickness of the entire endothermic sheet (for example, 5 mm or less). As a result, the volume energy of the assembled battery is ensured while ensuring the safety of the assembled battery and sufficient charge / discharge performance of the battery cell. It is also possible to improve the density.
  • FIG. 1 is a cross-sectional view schematically showing a configuration example of an endothermic sheet 10 for an assembled battery according to the first embodiment.
  • the assembled battery endothermic sheet 10 according to the present embodiment includes a dehydrating agent 22 that can be dehydrated at a temperature of 150 ° C. or lower, and an inorganic hydrate 24 having a thermal decomposition start temperature of 200 ° C. or higher.
  • the assembled battery endothermic sheet according to the present embodiment has a dehydrating agent 22 that can be dehydrated within a temperature range from room temperature (about 20 ° C.) to a maximum of about 150 ° C., which is the temperature range of the battery cell 20 during normal use. .
  • room temperature about 20 ° C.
  • maximum of about 150 ° C. which is the temperature range of the battery cell 20 during normal use.
  • the assembled battery endothermic sheet according to the present embodiment has the inorganic hydrate 24 having a thermal decomposition start temperature within a temperature range of 200 ° C. or more which is the temperature range of the battery cell 20 at the time of abnormality. And when the thermal runaway that is an abnormal time as the battery cell 20 occurs and the temperature of the battery cell 20 rises abnormally, an endothermic reaction occurs due to the decomposition of the inorganic hydrate 24, and thus each battery cell 20 at the abnormal time. The propagation of heat between them can be effectively suppressed.
  • the assembled battery 100 is configured by being stored in the battery case 30 in a state of being connected in parallel (the connected state is not shown).
  • the lithium ion secondary battery is used suitably, for example, the battery cell 20 is not limited to this, It can apply also to another secondary battery.
  • the dehydrating agent 22 constituting the assembled battery endothermic sheet 10 will be described.
  • the dehydrating agent 22 can be dehydrated at a temperature of 150 ° C. or lower.
  • Examples of the dehydrating agent 22 include water adsorbents such as silica gel, activated alumina, activated carbon, zeolite, ion exchange resin, sulfate hydrate, sulfite hydrate, phosphate hydrate, and nitrate hydration. Products, acetate hydrates, metal hydrates and the like. These dehydrating agents 22 may be used alone or in combination of two or more.
  • sulfate hydrate for example, ammonium aluminum sulfate 12 hydrate, sodium aluminum sulfate 12 hydrate, aluminum sulfate 27 hydrate, aluminum sulfate 18 hydrate, aluminum sulfate 16 hydrate, sulfuric acid Aluminum 10 hydrate, Aluminum sulfate 6 hydrate, Potassium aluminum sulfate 12 hydrate, Iron sulfate 7 hydrate, Iron sulfate 9 hydrate, Potassium sulfate 12 hydrate, Magnesium sulfate 7 hydrate, Examples thereof include sodium sulfate decahydrate, nickel sulfate hexahydrate, zinc sulfate heptahydrate, beryllium sulfate tetrahydrate, and zirconium sulfate tetrahydrate.
  • Examples of the sulfite hydrate include zinc sulfite dihydrate and sodium sulfite heptahydrate.
  • Examples of the phosphate hydrate include, for example, aluminum phosphate dihydrate, cobalt phosphate octahydrate, magnesium phosphate octahydrate, magnesium ammonium phosphate hexahydrate, magnesium hydrogen phosphate 3 water. Japanese hydrate, magnesium hydrogen phosphate heptahydrate, zinc phosphate tetrahydrate, zinc dihydrogen phosphate dihydrate, and the like.
  • nitrate hydrate examples include, for example, aluminum nitrate nonahydrate, zinc nitrate hexahydrate, calcium nitrate tetrahydrate, cobalt nitrate hexahydrate, bismuth nitrate pentahydrate, zirconium nitrate pentahydrate. Products, cerium nitrate hexahydrate, iron nitrate hexahydrate, iron nitrate nonahydrate, nickel nitrate hexahydrate, magnesium nitrate hexahydrate and the like.
  • acetate hydrate examples include zinc acetate dihydrate and cobalt acetate tetrahydrate.
  • metal hydrate salt examples include chloride salts such as cobalt chloride hexahydrate and iron chloride tetrahydrate, borax (sodium tetraborate pentahydrate, sodium tetraborate decahydrate). And borate salts such as disodium octaborate tetrahydrate and zinc borate 3.5 hydrate.
  • zeolite is not particularly limited, and examples thereof include ⁇ -type zeolite, Y-type zeolite, ferrierite, ZSM-5-type zeolite, mordenite, forgesite, zeolite A, and zeolite L.
  • Zeolite is an aluminosilicate having a three-dimensional network structure. Since zeolite that adsorbs moisture is stably present, moisture and the like are usually adsorbed in the gaps of the three-dimensional network structure under normal temperature conditions. However, when heat above a certain temperature is applied, the moisture adsorbed on the zeolite is desorbed from the zeolite. However, since the zeolite that does not adsorb moisture is unstable, the dehydrated zeolite has a high adsorption action, and therefore adsorbs moisture again after the temperature decreases.
  • the dehydrating agent 22 that can be dehydrated at a temperature of 150 ° C. or lower, such as zeolite, has a large overlap between the temperature rise and the temperature range on the surface of the battery cell 20 when performing a charge / discharge cycle. As the temperature of the cell 20 rises, the battery cell 20 can be effectively cooled by releasing moisture.
  • a preferable upper limit is 90 mass% with respect to the total mass of the material which comprises the endothermic sheet 10 for assembled batteries, and a more preferable upper limit is 65 mass%.
  • the preferable minimum of the compounding quantity of the said dehydrating agent 22 is 10 mass%, and a more preferable minimum is 35 mass%. If the amount is less than 10% by mass, sufficient dehydration effect may not be obtained. Moreover, when this compounding quantity exceeds 90 mass%, there exists a possibility that sufficient intensity
  • the inorganic hydrate 24 has a thermal decomposition start temperature of 200 ° C. or higher.
  • Examples of the inorganic hydrate 24 include aluminum hydroxide (Al (OH) 3 ), magnesium hydroxide (Mg (OH) 2 ), calcium hydroxide (Ca (OH) 2 ), and zinc hydroxide (Zn (OH) 2 ), iron hydroxide (Fe (OH) 2 ), manganese hydroxide (Mn (OH) 2 ), zirconium hydroxide (Zr (OH) 2 ), gallium hydroxide (Ga (OH) 3 ) and the like. It is done.
  • These inorganic hydrates 24 may be used alone or in combination of two or more.
  • the thermal decomposition start temperature of aluminum hydroxide is about 200 ° C.
  • the thermal decomposition start temperature of magnesium hydroxide is about 330 ° C.
  • the thermal decomposition start temperature of calcium hydroxide is about 580 ° C.
  • zinc hydroxide The thermal decomposition start temperature of iron hydroxide is about 200 ° C.
  • the thermal decomposition start temperature of iron hydroxide is about 350 ° C.
  • the thermal decomposition start temperature of manganese hydroxide is about 300 ° C.
  • the thermal decomposition start temperature of zirconium hydroxide is about 300 ° C.
  • the battery cell 20 whose temperature has increased can be cooled in a wide temperature range, and the heat between the battery cells during thermal runaway Is preferable because it is possible to effectively suppress the propagation of.
  • the aluminum hydroxide has about 35% water of crystallization.
  • the water of crystallization is released at the time of thermal decomposition, thereby providing a flame extinguishing function (endothermic reaction). It can be demonstrated. 2Al (OH) 3 ⁇ Al 2 O 3 + 3H 2 O With this function, high-temperature heat generated in the battery cell 20 can be absorbed, and the amount of heat generated by the battery cell 20 can be reduced.
  • the inorganic hydrate 24 having a thermal decomposition temperature of 200 ° C. or higher such as aluminum hydroxide, has a large overlap between the temperature rise and temperature range of the battery cell 20 when the battery cell 20 is thermally runaway. Therefore, with the temperature rise of the battery cell 20 at the time of abnormality, the dehydration reaction (endothermic reaction) is caused by thermal decomposition, so that the propagation of heat between the battery cells can be effectively suppressed.
  • the thermal decomposition start temperature is lower (thermal decomposition start temperature: about 200 ° C.) in the inorganic hydrate 24, so that the initial stage (relatively lower) when the battery cell is abnormal.
  • the temperature of the battery cell 20 is preferable because the battery cell 20 can be cooled.
  • a preferable upper limit is 90 mass% with respect to the total mass of the material which comprises the endothermic sheet 10 for assembled batteries, and a more preferable upper limit is 65 mass%.
  • the preferable minimum of the compounding quantity of the said dehydrating agent 22 is 10 mass%, and a more preferable minimum is 35 mass%. If the amount is less than 10% by mass, sufficient dehydration effect may not be obtained. Moreover, when this compounding quantity exceeds 90 mass%, there exists a possibility that sufficient intensity
  • the endothermic sheet for assembled battery 10 may contain inorganic fibers and pulp fibers for the purpose of improving the strength during molding.
  • the inorganic fiber examples include silica-alumina fiber, alumina fiber, silica fiber, rock wool, alkaline earth silicate fiber, glass fiber, zirconia fiber, and potassium titanate whisker fiber. These inorganic fibers are preferable in terms of heat resistance, strength, availability, and the like.
  • the said inorganic fiber may be used independently and may be used in combination of 2 or more types.
  • silica-alumina fiber, alumina fiber, silica fiber, rock wool, alkali earth silicate fiber, and glass fiber are particularly preferable from the viewpoint of handleability.
  • the cross-sectional shape of the inorganic fiber is not particularly limited, and examples thereof include a circular cross section, a flat cross section, a hollow cross section, a polygon cross section, and a core-sheath cross section.
  • a modified cross-section fiber having a hollow cross section, a flat cross section or a polygonal cross section can be preferably used because the heat insulation is slightly improved.
  • the preferable lower limit of the average fiber length of the inorganic fibers is 0.1 mm, and the more preferable lower limit is 0.5 mm.
  • the preferable upper limit of the average fiber length of the inorganic fibers is 50 mm, and the more preferable upper limit is 10 mm. If the average fiber length of the inorganic fibers is less than 0.1 mm, the entanglement between the inorganic fibers is difficult to occur, and the mechanical strength of the obtained heat-absorbing sheet 10 may be reduced.
  • the thickness exceeds 50 mm although the reinforcing effect is obtained, the inorganic fibers cannot be intertwined closely or rounded with only a single inorganic fiber. There is a risk of lowering.
  • the preferable lower limit of the average fiber diameter of the inorganic fibers is 1 ⁇ m, the more preferable lower limit is 2 ⁇ m, and the still more preferable lower limit is 3 ⁇ m.
  • the preferable upper limit of the average fiber diameter of the inorganic fibers is 10 ⁇ m, and the more preferable upper limit is 7 ⁇ m. If the average fiber diameter of the inorganic fiber is less than 1 ⁇ m, the mechanical strength of the inorganic fiber itself may be lowered. Further, from the viewpoint of the influence on human health, the average fiber diameter of the inorganic fibers is preferably 3 ⁇ m or more.
  • the average fiber diameter of the inorganic fiber is larger than 10 ⁇ m, solid heat transfer using the inorganic fiber as a medium may increase, resulting in a decrease in heat insulating property, and the moldability of the heat absorbing sheet 10 may be deteriorated. There is.
  • These inorganic fibers and pulp fibers can be used as necessary in the range of 10 to 70% by mass with respect to the total weight of the materials constituting the endothermic sheet 10.
  • An organic binder may be used as necessary as a material constituting the endothermic sheet 10. This organic binder is useful for the purpose of improving the strength at the time of molding. For example, a polymer flocculant or an acrylic emulsion can be suitably used. The blending amount of the organic binder can be used as necessary in the range of 0.5 to 5.0 mass% with respect to the total weight of the materials constituting the endothermic sheet 10.
  • the thickness of the endothermic sheet 10 is not particularly limited, but is preferably in the range of 0.05 to 5 mm. If the thickness of the endothermic sheet 10 is less than 0.05 mm, sufficient mechanical strength cannot be imparted to the endothermic sheet 10. On the other hand, if the thickness of the endothermic sheet 10 exceeds 5 mm, it may be difficult to form the endothermic sheet 10 itself.
  • the moisture adsorption amount is increased even at a relatively high temperature (about 100 ° C. to 150 ° C.).
  • a combination of the above zeolite and aluminum hydroxide having a lower thermal decomposition start temperature in the inorganic hydrate 24 (thermal decomposition start temperature: about 200 ° C.) is preferable. This is because the battery cell 20 can be effectively cooled even in the boundary temperature range (about 150 ° C. to 200 ° C.) between the temperature range during normal use and the temperature range at the time of abnormality in the battery cell 20. preferable.
  • FIG. 1 shows an example in which the dehydrating agent 22 and the inorganic hydrate 24 are uniformly dispersed, but as shown in FIG. 2, the thickness direction in the endothermic sheet 10 (vertical direction in the figure). )
  • the content of the dehydrating material 22 that can be dehydrated during normal use is, the more from the center to the both ends, the more the dehydrating agent 22 is contained. It is preferred that the content of possible substances, ie the inorganic hydrate 24, is large.
  • FIG. 5 since both end portions of the heat absorbing sheet 10 are close to the battery cell 20, it is necessary to cool the battery cell 20 efficiently during normal use of the battery cell 20. For this reason, it is preferable that more dehydrating agents 22 that can sufficiently exhibit the effect during normal use are present on both end portions in the endothermic sheet 10.
  • the second embodiment is a case where the endothermic sheet is a multilayer (laminated body).
  • FIG. 3 is a cross-sectional view schematically showing a configuration example of the assembled battery endothermic sheet 10 according to the second embodiment.
  • the assembled battery endothermic sheet 10 according to the present embodiment is formed on both surfaces of the first endothermic layer 14 whose main component is a substance that can be dehydrated at the time of abnormality, that is, an inorganic hydrate 24, as an intermediate layer. It is composed of three layers having a substance that can be dehydrated during normal use, that is, the second endothermic layer 12 mainly composed of the dehydrating agent 22.
  • the main component means the most abundant component, and the content is usually more than 50% by mass, preferably more than 70% by mass, and more preferably more than 90% by mass.
  • the content of the dehydrating agent 22 increases as it goes from the central portion in the thickness direction of the endothermic sheet 10 to both ends, and from the both end portions in the thickness direction of the endothermic sheet 10 to the central portion. Since the structure which the content of the inorganic hydrate 24 becomes large can be easily implement
  • FIG. 3 shows an example in which the first endothermic layer 14 is made of only the inorganic hydrate 24 and the second endothermic layer 12 is made of only the dehydrating agent 22.
  • FIG. 3 shows an example in which the first endothermic layer 14 is made of only the inorganic hydrate 24 and the second endothermic layer 12 is made of only the dehydrating agent 22.
  • the first endothermic layer 14 and the second endothermic layer 12 include the dehydrating agent 22 and the inorganic hydrate 24
  • the first endothermic layer 14 contains the inorganic hydrate 24. It may be included as a main component
  • the second endothermic layer 12 may include a dehydrating agent 22 as a main component.
  • the endothermic sheet 10 according to this embodiment is manufactured by molding a material composed of at least the dehydrating agent 22 and the inorganic hydrate 24 by a dry molding method or a wet molding method. Below, the manufacturing method in the case of obtaining the endothermic sheet 10 by each shaping
  • the dehydrating agent 22 and the inorganic hydrate 24, and further, if necessary, inorganic fibers, pulp fibers, or organic binders are charged into a mixer such as a V-type mixer in a predetermined ratio. After thoroughly mixing the materials put into the mixer, the mixture is put into a predetermined mold and pressed to obtain the endothermic sheet 10. You may heat as needed at the time of a press.
  • the press pressure is preferably in the range of 0.98 to 9.80 MPa. If the press pressure is less than 0.98 MPa, the endothermic sheet 10 to be obtained may not be able to maintain strength and may collapse. On the other hand, when the press pressure exceeds 9.80 MPa, workability may be reduced due to excessive compression, and further, the bulk density may be increased, so that solid heat transfer may increase and heat insulation may be deteriorated.
  • the dehydrating agent 22 and the inorganic hydrate 24, and if necessary, inorganic fibers, pulp fibers, or organic binders are mixed and stirred in water to sufficiently disperse, and then the flocculant is added. Add to obtain primary aggregates.
  • an emulsion of an organic elastic substance or the like is added to the water within a predetermined range, and then a polymer flocculant is added to obtain a slurry containing aggregates.
  • a slurry containing the agglomerate is put into a predetermined mold to obtain a wet endothermic sheet 10.
  • the intended endothermic sheet 10 is obtained by drying the obtained endothermic sheet 10.
  • the endothermic sheet 10 can be obtained by either a dry molding method or a wet molding method, but it is preferable to use a wet molding method in terms of ease of integral molding and mechanical strength.
  • the content of the dehydrating agent 22 increases from the central portion in the thickness direction (vertical direction in the drawing) of the endothermic sheet 10 toward both ends, and both ends in the thickness direction of the endothermic sheet 10.
  • FIG. 3 for example, as shown in FIG. 3, the endothermic sheet 10 in which the content of the inorganic hydrate 24 increases toward the center from the first endothermic layer 14.
  • Each of the second endothermic layers 12 having the dehydrating agent 22 as a main component is produced, and the second endothermic layers 12 are laminated on both sides of the first endothermic layer 14.
  • a first endothermic layer 14 mainly composed of an inorganic hydrate 24 as an intermediate layer, and a second endothermic layer 14 which is formed on both surfaces and mainly includes a dehydrating agent 22.
  • An endothermic sheet 10 composed of three layers having an endothermic layer 12 is prepared by preparing the first endothermic layer 14 and the second endothermic layer 12 based on the above-described manufacturing method, and then these layers are in a wet state. It can be obtained by a pressure press or a method of adhering using an adhesive after drying these members.
  • Example 1 40% by mass of aluminum hydroxide (Al (OH) 3 ) powder (average particle size: 1 ⁇ m), 40% by mass of zeolite powder (average particle size: 7 ⁇ m), 10% by mass of rock wool as an inorganic fiber, and pulp fiber 9% by mass and 1% by mass of the polymer agglomerate were added, and the mixture was sufficiently stirred and mixed to prepare a slurry.
  • the slurry was made into a heat-absorbing sheet for assembled batteries having a thickness of 2 mm.
  • the thermal decomposition starting temperature of the used aluminum hydroxide was 200 ° C., and the zeolite could be dehydrated at a temperature of 150 ° C. or lower.
  • a sheet having a thickness of 2 m constituted by alkaline earth silicate (AES) fiber was prepared and used as an endothermic sheet for an assembled battery.
  • AES alkaline earth silicate
  • the slurry was made into a heat-absorbing sheet for assembled batteries having a thickness of 2 mm.
  • Al (OH) 3 aluminum hydroxide
  • a metal plate simulating a battery cell serving as a heat source is arranged so as to be in contact with one surface of the endothermic sheet for assembled battery obtained in Example 1, Comparative Example 1 and Comparative Example 2, and further adjacent to the metal plate.
  • the heater was arranged as follows.
  • a thermocouple was attached to the metal plate and heated so that the heater temperature became 150 ° C., and the temperature change of the surface of the battery cell (metal plate) serving as a heat source with respect to the elapsed time was measured.
  • the graph which plotted the temperature change of the battery cell surface used as the heat source with respect to elapsed time in Example 1, the comparative example 1, and the comparative example 2 is shown in FIG.
  • a heater is disposed so as to be adjacent to one surface of the endothermic sheet for assembled battery obtained in Example 1, Comparative Example 1, Comparative Example 2, and Reference Example 1, and a battery cell adjacent to the other surface is simulated.
  • a metal plate was placed.
  • a thermocouple was disposed on the metal plate, and the heater was heated to a temperature of 700 ° C., and the temperature change of the adjacent battery cell (metal plate) surface with respect to the elapsed time was measured.
  • FIG. 7 shows a graph in which the temperature change of the adjacent battery cell surface with respect to the elapsed time in Example 1, Comparative Example 1, Comparative Example 2, and Reference Example 1 is plotted.
  • the endothermic sheet for the assembled battery of Example 1 using both zeolite and aluminum hydroxide is as large as the endothermic sheet of Comparative Example 2 using only zeolite.
  • the temperature could not be kept low, the maximum temperature of the cell surface serving as a heat source could be kept lower than the endothermic sheet of Comparative Example 1 using AES.
  • the endothermic sheet of Example 1 was able to suppress the maximum temperature of the adjacent cell surface significantly lower than the endothermic sheets of Comparative Example 1 and Comparative Example 2.
  • the maximum temperatures of the adjacent cell surfaces were substantially the same.
  • the endothermic sheet of Example 1 is effective in cooling the battery cells during normal use as battery cells, while also effectively transmitting heat between the battery cells during an abnormality as a battery cell. It was experimentally shown that it can be suppressed.

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  • General Chemical & Material Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Aviation & Aerospace Engineering (AREA)
  • Physics & Mathematics (AREA)
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  • Battery Mounting, Suspending (AREA)

Abstract

L'invention concerne une feuille d'absorption de chaleur de bloc-batterie. Lorsqu'elle est incorporée dans un bloc-batterie qui comprend une pluralité de cellules de batterie qui sont connectées en série ou en parallèle, la feuille d'absorption de chaleur peut supprimer la propagation de la chaleur entre les cellules de batterie lorsqu'une anomalie s'est produite et refroidir les cellules de batterie pendant une utilisation normale. Une feuille d'absorption de chaleur de bloc-batterie (10) qui est destinée à être utilisée dans un bloc-batterie (100) dans lequel une pluralité de cellules de batterie (20) sont agencées avec la feuille d'absorption de chaleur (10) entre celles-ci, la pluralité de cellules de batterie (20) étant connectées en série ou en parallèle. La feuille d'absorption de chaleur (10) est caractérisée en ce qu'elle contient, en tant que substance qui peut éliminer l'eau pendant une utilisation normale, un agent de déshydratation (22) qui peut éliminer l'eau à des températures allant jusqu'à 150 °C et, en tant que substance qui peut éliminer l'eau lorsqu'une anomalie s'est produite, un hydrate inorganique (24) qui a une température de décomposition thermique initiale d'au moins 200° C.
PCT/JP2019/011613 2018-03-29 2019-03-19 Feuille d'absorption de chaleur de bloc-batterie et bloc-batterie WO2019188626A1 (fr)

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JP2018065759A JP7092536B2 (ja) 2018-03-29 2018-03-29 組電池用吸熱シートおよび組電池
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JP6879981B2 (ja) 2018-08-30 2021-06-02 第一工業製薬株式会社 絶縁性シートおよび組電池
JP7203870B2 (ja) 2021-01-18 2023-01-13 イビデン株式会社 組電池用熱伝達抑制シート及び組電池
JP7488202B2 (ja) 2021-01-18 2024-05-21 イビデン株式会社 組電池用熱伝達抑制シート及び組電池
EP4280347A1 (fr) 2021-01-18 2023-11-22 IBIDEN Co., Ltd. Feuille de suppression de transfert de chaleur pour bloc-batterie, et bloc-batterie
US20230068367A1 (en) 2021-08-30 2023-03-02 Prologium Technology Co., Ltd. Thermal runaway suppression element and the related applications

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WO2010026732A1 (fr) * 2008-09-05 2010-03-11 パナソニック株式会社 Bloc-batterie
JP2010053196A (ja) * 2008-08-27 2010-03-11 Asahi Kasei E-Materials Corp 吸熱シート
JP2010165597A (ja) * 2009-01-16 2010-07-29 Toyota Motor Corp 蓄電装置
JP2017523584A (ja) * 2014-05-21 2017-08-17 サーマル・セラミック・インコーポレイテッドＴｈｅｒｍａｌ Ｃｅｒａｍｉｃｓ， Ｉｎｃ． 受動的断熱材

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010053196A (ja) * 2008-08-27 2010-03-11 Asahi Kasei E-Materials Corp 吸熱シート
WO2010026732A1 (fr) * 2008-09-05 2010-03-11 パナソニック株式会社 Bloc-batterie
JP2010165597A (ja) * 2009-01-16 2010-07-29 Toyota Motor Corp 蓄電装置
JP2017523584A (ja) * 2014-05-21 2017-08-17 サーマル・セラミック・インコーポレイテッドＴｈｅｒｍａｌ Ｃｅｒａｍｉｃｓ， Ｉｎｃ． 受動的断熱材

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