WO2022234746A1 - 無機粉体シート及びその製造方法 - Google Patents
無機粉体シート及びその製造方法 Download PDFInfo
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- WO2022234746A1 WO2022234746A1 PCT/JP2022/015041 JP2022015041W WO2022234746A1 WO 2022234746 A1 WO2022234746 A1 WO 2022234746A1 JP 2022015041 W JP2022015041 W JP 2022015041W WO 2022234746 A1 WO2022234746 A1 WO 2022234746A1
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- powder sheet
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- 239000000843 powder Substances 0.000 title claims abstract description 131
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000000835 fiber Substances 0.000 claims abstract description 46
- 238000009413 insulation Methods 0.000 claims abstract description 23
- 229910052902 vermiculite Inorganic materials 0.000 claims abstract description 20
- 239000010455 vermiculite Substances 0.000 claims abstract description 20
- 235000019354 vermiculite Nutrition 0.000 claims abstract description 20
- 230000006835 compression Effects 0.000 claims description 25
- 238000007906 compression Methods 0.000 claims description 25
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 16
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Images
Classifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/26—Polyamides; Polyimides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/30—Multi-ply
-
- 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
- H01M10/62—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
- H01M10/658—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
- H01M50/289—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by spacing elements or positioning means within frames, racks or packs
- H01M50/293—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by spacing elements or positioning means within frames, racks or packs characterised by the material
-
- 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 inorganic powder sheet and a manufacturing method thereof.
- Insulation sheets for insulating heating elements are used for various purposes.
- a vehicle or stationary power supply device in which a plurality of secondary battery cells are stacked, high output and high capacity are required, so a large number of high-capacity secondary battery cells are sometimes used.
- a power supply device there is concern that for some reason one secondary battery cell may become hot and thermally runaway, adversely affecting other adjacent secondary battery cells. Therefore, it is required to thermally insulate the adjacent secondary battery cells when thermal runaway occurs.
- high heat resistance and flame resistance are required. Under these circumstances, attempts have been made to interpose an inorganic powder sheet between secondary battery cells for heat insulation.
- a secondary battery cell such as a lithium-ion secondary battery has a structure in which a current collector is inserted into a rigid outer can made of aluminum, it is known that the outer can expands due to rapid charging and discharging. there is for this reason, when the heat diffusion sheet interposed between the outer cans expanded during the thermal runaway becomes thin due to being pressed with a high pressure, there is a problem that the heat insulating performance deteriorates. Therefore, there has been a demand for a heat diffusion sheet with little volume change.
- One of the objects of the present invention is to provide an inorganic powder sheet with small compression deformation while maintaining high heat insulation and heat resistance, and a method for producing the same.
- the inorganic powder sheet according to the first embodiment of the present invention is a heat-insulating inorganic powder sheet in which the inorganic powder contains 80% by weight or more of expanded vermiculite and 20% by weight or less of organic fiber. and With the above configuration, an inorganic powder sheet with small compressive deformation is realized while maintaining high heat insulation and heat resistance.
- the vermiculite has a median diameter of 20 ⁇ m to 70 ⁇ m.
- the organic fiber is para-aramid fiber, para-aramid pulp, meta-aramid pulp, polyphenylene sulfide fiber, PET fiber, flame retardant It contains at least one of PET fiber, flame-retardant rayon fiber, and natural cellulose fiber.
- the inorganic powder sheet according to the fourth embodiment of the present invention has a film thickness of 0.1 mm to 1.0 mm.
- the inorganic powder sheet according to the fifth aspect of the present invention in any one of the above aspects, has a bending resistance of 15 mN or more and 50 mN or less, and a density of 1.00 g/cm 3 or more and 1 .90 g/cm 3 or less.
- the inorganic powder sheet according to the sixth embodiment of the present invention has a thermal conductivity of 0.3 W / m K or less before compression, and a thermal conductivity of 0.3 W / m K or less when compressed at 4 MPa. Compression rate is 10% or less.
- an inorganic powder sheet according to a seventh aspect of the present invention is an inorganic powder sheet having heat insulation properties, and has a thermal conductivity of 0.3 W/m ⁇ K or less before compression and 4 MPa.
- the compression rate when compressed with is 10% or less.
- the inorganic powder sheet according to the eighth aspect of the present invention has a bending resistance of 15 mN or more and 50 mN or less in any one of the above aspects.
- the inorganic powder sheet according to the ninth aspect of the present invention is, in any one of the above aspects, the inorganic powder sheet when the surface temperature of the inorganic powder sheet is set to 250 ° C. and the inorganic powder sheet is compressed at 3 MPa. 10 minutes after, the back surface temperature is 240° C. or less.
- the above configuration it is possible to suppress deterioration of the heat insulating properties of the inorganic powder sheet due to compression.
- the inorganic powder sheet according to the tenth aspect of the present invention has a median diameter of 20 ⁇ m to 70 ⁇ m in the integrated distribution of the vermiculite particle size distribution measurement in any one of the above aspects.
- an inorganic powder sheet laminate according to an eleventh embodiment of the present invention is obtained by laminating one or more layers of the inorganic powder sheet according to any one of the above embodiments and a flame-retardant or flame-retardant additional layer.
- an inorganic powder sheet laminate according to a twelfth aspect of the present invention includes a sheet material as a base material, and the inorganic powder according to any one of the above aspects, which is laminated on at least one surface of the sheet material. a body sheet;
- a method for producing an inorganic powder sheet according to a thirteenth aspect of the present invention is a method for producing an inorganic powder sheet having heat insulating properties, wherein 80% by weight or more of expanded vermiculite is used as the inorganic powder.
- an inorganic powder sheet with small compressive deformation is realized while maintaining high heat insulation and heat resistance.
- the median diameter in the cumulative distribution of the vermiculite particle size distribution measurement is 20 ⁇ m to 70 ⁇ m.
- the organic fiber is para-aramid fiber, para-aramid pulp, meta-aramid pulp, polyphenylene sulfide fiber, PET fiber, flame It contains at least one of flame-retardant PET fiber, flame-retardant rayon fiber, and natural cellulose fiber.
- FIG. 1 is an exploded perspective view showing a power supply device according to Embodiment 1 of the present invention
- FIG. It is a schematic cross section showing the state of the test which measures the time change of the back surface temperature with respect to the surface temperature of 250 degreeC, when compressed by 3 MPa.
- It is a schematic diagram which shows the state of the test before compression.
- It is a graph which shows the time change of the back surface temperature with respect to the surface temperature of 250 degreeC when compressing by 3 MPa.
- 4 is a graph showing the change in rear surface temperature over time without compression.
- 1 is a schematic cross-sectional view showing an example of an inorganic powder sheet laminate;
- each of the elements constituting the present invention may be configured with the same member so that a single member may serve as a plurality of elements, or conversely, the function of one member may be performed by a plurality of members. It can also be realized by sharing.
- the inorganic powder sheet according to the embodiment of the present invention is required to have heat insulation properties and can be used as appropriate for applications for avoiding the spread of fire.
- it is suitable for applications such as lithium ion secondary batteries that require prevention of spread of fire from the viewpoint of safety when the temperature reaches a high temperature, such as during thermal runaway.
- an inorganic powder sheet as a spacer interposed between adjacent secondary battery cells in a power supply device in which a large number of rectangular secondary battery cells are stacked and connected in series or parallel will be described. .
- Such 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.
- electric vehicles such as electric vehicles, hybrid vehicles, electric buses, trains, and electric carts
- backup power source for factories and base stations
- storage battery for home use.
- it can be used as an inorganic powder sheet sandwiched between objects that expand and contract repeatedly.
- a power supply device 100 shown in this figure includes a plurality of secondary battery cells 20 and an inorganic powder sheet 10 interposed between the secondary battery cells 20 .
- the exterior can 21 has a bottomed cylindrical prismatic shape, and a plurality of the cans are stacked such that the main surfaces face each other.
- both end surfaces of a battery stack 25 in which secondary battery cells 20 are laminated are covered with end plates 30, and the end plates 30 are fastened together with a fastening member.
- the battery stack 25 is fixed onto the base plate 40 as necessary.
- the base plate 40 can function as a cooling plate by circulating a coolant inside, for example.
- Each secondary battery cell 20 accommodates an electrode body inside an outer can 21 and seals the open end with a sealing plate 22 .
- a pair of electrodes 23 and an explosion-proof valve 24 are provided on the sealing plate 22 located on the upper surface of the outer can 21 in FIG.
- the plurality of secondary battery cells 20 are electrically connected in series and/or in parallel with each other by connecting the electrodes 23 with bus bars.
- the explosion-proof valve 24 is a member for discharging high-pressure gas inside the armored can 21 by detecting that the internal pressure of the armored can 21 has increased and opening the valve.
- Each explosion-proof valve 24 is connected with a gas duct for guiding high-pressure gas to the outside as required.
- An inorganic powder sheet 10 is interposed between adjacent secondary battery cells 20 .
- the inorganic powder sheet 10 is called a spacer, a separator, or the like, and insulates the outer can 21 between the adjacent secondary battery cells 20 so that a short circuit does not occur. (Inorganic powder sheet 10)
- the inorganic powder sheet has heat insulating properties and insulating properties.
- This inorganic powder sheet contains inorganic powder and organic fibers. It preferably contains 80% by weight or more of inorganic powder and 20% by weight or less of organic fiber.
- Expanded vermiculite can be used as the inorganic powder. Here, 80% to 82.5% by weight of expanded vermiculite and 20% to 17.5% by weight of organic fiber were blended. Such a configuration realizes an inorganic powder sheet with small compressive deformation while maintaining high heat insulation and heat resistance.
- Vermiculite preferably has a volume average particle size of 1 ⁇ m to 500 ⁇ m, more preferably 1 to 200 ⁇ m.
- the median diameter in the integrated distribution is preferably 20 ⁇ m to 70 ⁇ m.
- the volume average particle diameter and median diameter can be measured using a known device such as a laser diffraction particle size distribution analyzer.
- Organic fibers include organic synthetic fibers such as para-aramid fiber, para-aramid pulp, meta-aramid pulp, polyphenylene sulfide fiber, PET fiber, flame-retardant PET fiber, and flame-retardant rayon fiber, or wood (softwood, hardwood) pulp, cotton, hemp, etc. any one or more of the natural cellulose fibers of The form of the fiber is not limited, and may be fibrillated. JIS P 8121 (2012) Canadian Standard Freeness Method can be suitably used for determining the degree of fibrillation of fibers.
- the blending ratio of organic fibers is preferably 0 to 20% by weight, more preferably 5 to 20% by weight. If it is equal to or less than the upper limit of the above range, the amount of deformation during compression can be suppressed, and the decrease in heat resistance tends to be suppressed.
- the film thickness of the inorganic powder sheet is preferably 0.1 mm to 2.0 mm, more preferably 0.2 mm to 1.5 mm, even more preferably 0.3 mm to 1.0 mm. .
- the bending resistance of the inorganic powder sheet is preferably 50 mN or less. Preferably, it is 27mN to 49mN. Within the above range, the inorganic powder sheet tends to maintain its compression resistance and flexibility, and is excellent in handleability.
- the density of the inorganic powder sheet is preferably 1.00 g/cm 3 or more, more preferably 1.30 g/cm 3 or more. By making it equal to or higher than the lower limit value described above, a characteristic of small compressive deformation can be obtained.
- the upper limit is not particularly limited, it is usually 1.90 g/cm 3 or less.
- heat and pressure processing may be performed using a hot calender roll or the like. This makes it possible to adjust the denseness of the interior and improve the compression resistance performance.
- the thermal conductivity of the inorganic powder sheet before compression is preferably 0.300 W/m ⁇ K or less, more preferably 0.200 W/m ⁇ K or less. It is preferably 0.145 W/m ⁇ K to 0.149 W/m ⁇ K.
- an improved unsteady planar heat source method can be suitably used for measuring a thin film and low thermal conductivity material as in the present invention.
- the compression ratio when the inorganic powder sheet is compressed at 4 MPa is preferably 10% or less, more preferably 9% or less.
- the lower limit is not particularly limited, it is usually 0.1% or more. Preferably, it is 2.8-8.7%.
- the inorganic powder sheet according to the present embodiment has a small amount of displacement during compression, and therefore has the advantage of being able to maintain heat insulation in a compressed state.
- the conditions for compression are as follows: using a universal material testing machine (manufactured by Instron), press with a flat circular compressor with a diameter of 50 mm at a rate of 0.1 mm/min until reaching 4 MPa.
- the inorganic powder sheet was compressed at 3 MPa by a hot press and held at 250 ° C. with the press plate on one side as the high temperature side and at 40 ° C. with the press plate on the opposite side as the low temperature side for 10 minutes.
- the surface temperature of the body sheet on the low temperature side is preferably 240° C. or less.
- the temperature after 5 minutes is 192.4°C to 196.8°C and the temperature after 10 minutes is 233.8°C to 235.7°C.
- the powder sheet according to the present embodiment has an excellent feature that heat transmission during compression can be suppressed to a low level even though it has a higher thermal conductivity than the mica sheet.
- the inorganic powder sheet may be composed of a single layer, or may have a laminated structure of multiple layers. This allows different properties to be added. Additional layers may be added, for example with flame-retardant or flame-retardant properties. By adding a material with excellent flame resistance in this way, it is possible to suppress the spread of fire at high temperatures.
- the additional layer is composed of inorganic fillers such as silicate minerals, metal oxides and graphite, inorganic fibers such as glass fibers, organic fibers with excellent flame retardancy such as aramid, and organic fibers containing flame retardants.
- an additional sheet containing mica and organic fibers is used as the additional layer.
- the inorganic powder sheet laminate may be configured by laminating an inorganic powder sheet on at least one surface of a sheet material.
- a sheet material 1 such an example is shown in the schematic cross-sectional view of FIG.
- the inorganic powder sheet laminate shown in this figure has a two-layer structure in which an inorganic powder sheet 10 is laminated on the upper surface of a sheet material 1 .
- the inorganic powder sheet 10 is not limited to one layer, and two or more layers may be laminated. Moreover, it may be laminated on both sides of the sheet material 1 .
- a flexible material or a highly rigid material can be used for the sheet material 1 serving as the base material.
- an elastic body such as rubber or a sheet material made of urethane sponge or the like can be used.
- a hard resin plate or the like can be used as the material with high rigidity.
- wet papermaking can be used as a method for manufacturing such inorganic powder sheets.
- inorganic powder 80% by weight or more of expanded vermiculite and 20% by weight or less of organic fiber are dispersed in water to form a papermaking slurry, which is dewatered on a wire mesh and dried to form a wet papermaking sheet. is obtained.
- a known machine can be used as the papermaking machine. For example, a fourdrinier paper machine, a cylinder paper machine, an inclined short-mesh paper machine, a twin-wire paper machine and the like can be mentioned. Also, if necessary, the density of the sheet can be adjusted by equipment such as a wet press and a touch press.
- Further calendering may be performed for the purpose of increasing the density of the wet-made sheet.
- the calendering process may be continuous with or independent of the wet papermaking process.
- Known calenders can be used, and examples thereof include metal rolls, resin rolls, rubber rolls, double belt presses, and the like.
- the calender may be heated to increase density and processing efficiency. Preferably, it is carried out by heating in a temperature range below the melting point of the organic fibers to be blended. As a result, an inorganic powder sheet with small compressive deformation is realized while maintaining high heat insulation and heat resistance.
- Example 1 80% by weight of expanded vermiculite having a median diameter of 25 ⁇ m, 10% by weight of para-aramid pulp, and 10% by weight of softwood pulp were dispersed in water to prepare a papermaking slurry.
- the resulting papermaking slurry was subjected to wet papermaking using a fourdrinier machine to obtain an inorganic powder precursor sheet having a basis weight of 170 g/m 2 .
- the obtained inorganic powder precursor sheets were laminated in three layers, and subjected to thermal calendering by passing between a pair of metal rolls with a roll temperature of 190° C. and a nip pressure of 200 KPa/cm. got a sheet.
- Example 2 80% by weight of expanded vermiculite having a median diameter of 25 ⁇ m, 10% by weight of para-aramid pulp, and 10% by weight of softwood pulp were dispersed in water to prepare a papermaking slurry.
- the resulting papermaking slurry was subjected to wet papermaking
- Example 3 82.5% by weight of expanded vermiculite having a median diameter of 58 ⁇ m, 8.75% by weight of para-aramid pulp, and 8.75% by weight of softwood pulp were dispersed in water to prepare a papermaking slurry.
- the obtained papermaking slurry was subjected to wet papermaking with a fourdrinier machine to obtain an inorganic powder precursor sheet having a basis weight of 520 g/m 2 .
- the obtained inorganic powder precursor sheet was heat calendered in the same manner as in Example 1, except that it was made into a single layer, to obtain an inorganic powder sheet according to Example 2. (Example 3)
- the thickness and density of the inorganic powder sheets according to Examples 1 to 3 and Comparative Example 1 were measured according to JIS P 8118 (2014). (bending resistance)
- the bending resistance of the inorganic powder sheets according to Examples 1 to 3 and Comparative Example 1 was measured according to JIS L 1085 (1998) bending resistance test (Gurley method). The measurement was performed using a Gurley flexibility tester manufactured by Toyo Tester Kogyo Co., Ltd., with a fulcrum distance of 50 mm and a sample piece having a length of 89 mm and a width of 25 mm. (Thermal conductivity)
- the thermal conductivity of the inorganic powder sheets according to Examples 1 to 3 and Comparative Example 1 was measured according to ASTM D7984-16 by an improved unsteady planar heat source method.
- a thermal conductivity measuring device TCi (Max-k) manufactured by C-Therm was used.
- the inorganic powder sheet was cut out into a circle with a diameter of 30 mm as a sample, the sample sheet was placed on a sensor unit containing a heater, and a weight of 500 g was placed on the sample. In this state, heating was started with a steady output, the time change of the sensor temperature was measured, and the thermal effusivity and the thermal conductivity were measured from the following formula (1).
- volume change was measured when the inorganic powder sheets according to each example and comparative example were pressed with a high pressure. Specifically, an inorganic powder sheet is cut to 100 mm ⁇ 100 mm as a sample sheet, and a universal material testing machine (manufactured by Instron) is used with a flat circular compressor with a diameter of 50 mm at 0.1 mm / min. 4 MPa compression rate was calculated by calculating the percentage of the sheet thickness before the test. (250°C heating compression test)
- the time change of the back surface temperature with respect to the surface temperature of 250° C. was measured.
- the inorganic powder sheet is cut to 180 mm ⁇ 120 mm to obtain a sample sheet SS, and as shown in the schematic cross-sectional view of FIG. 2, two stainless steel plates 12 having a thickness of 10 mm and dimensions of 180 mm ⁇ 120 mm and a sample sheet SS were placed therebetween.
- Ten sheets of kraft paper 13 are laminated on the lower surface of the stainless steel plate 12 for the purpose of heat insulation and pressure homogenization.
- a thermocouple 15 is attached to the surface of the stainless plate 12 in contact with the kraft paper 13 with an aluminum tape.
- the temperature of the first hot-press plate 11 is set at 250° C.
- the temperature of the second hot-press plate 16 is set at 40° C.
- the entire apparatus is covered with a glass fiber heat insulating material.
- the pressure applied to the sample sheet was divided into cases of 760 Pa and cases of 3 MPa, and measurement was performed using new sample sheets in each case.
- the evaluation of the heat insulating performance was confirmed by the temperatures measured 5 minutes and 10 minutes after starting compression heating with a hot press device. In addition, as a blank measurement, the measurement was performed under each pressure condition without sandwiching the sample sheet between the stainless steel plates. (350°C heating compression test)
- the time change of the backside temperature with respect to the surface temperature of 350°C was measured for the inorganic powder sheets according to Example 2 and Comparative Example 1.
- the test equipment shown in FIG. 3 was used.
- a laminate obtained by sandwiching both sides of a sample sheet SS of 145 mm ⁇ 90 mm between aluminum plates 17 of 10 mm thickness and size of 180 mm ⁇ 120 mm was placed on a hot plate 18 of 250 mm ⁇ 150 mm. placed on top of the Hot plate 18 is heated to 350°C.
- a thermocouple 15 was placed on the upper surface of the laminate, a glass needle mat 19 was placed thereon for heat insulation, and a weight WT of 1.3 kg was placed on the upper surface.
- the pressure applied to the sample sheet was calculated to be 1.5 KPa.
- the inorganic powder sheets according to Examples 1 to 3 had a lower 4 MPa compressibility than Comparative Example 1, although the bending resistance was lower than that of Comparative Example 1.
- the present invention has the advantage that it can be easily wound or attached to a curved surface, and that compression deformation is small, as compared with the comparative example.
- Fig. 4 shows the time change of the back surface temperature with respect to the surface temperature of 250°C when compressed at 3 MPa.
- a comparison of Examples 1 and 3 shows that vermiculite has a faster initial rise in back surface temperature than mica, but the temperature reverses after about 4 minutes, and it was confirmed that vermiculite has higher heat insulation performance.
- Fig. 5 shows the results of measuring the back surface temperature in the 350°C heat insulation test.
- the inorganic powder sheet of the present invention can be used as a heat insulating sheet sandwiched between objects that expand and contract repeatedly.
- a heat insulating spacer interposed between secondary battery cells or between secondary battery cell modules, a buffer sheet interposed between an explosion-proof valve and a gas duct, or a heat insulating material that protects a drive circuit such as an ECU. etc. can be suitably used.
- it can also be used as building materials such as heat insulating materials and heat-resistant materials that prevent the spread of fire.
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Abstract
Description
[実施形態1]
(無機粉体シート10)
(有機繊維)
[無機粉体シートの製造方法]
[実施例]
(実施例1)
メジアン径が25μmである膨張バーミキュライト80重量%と、パラアラミドパルプ10重量%と、針葉樹パルプ10重量%とを水に分散し、抄紙スラリーとした。得られた抄紙スラリーを長網抄紙機にて湿式抄紙して、坪量が170g/m2である無機粉体前駆体シートを得た。得られた無機粉体前駆体シートを3層に積層し、ロール温度190℃、ニップ圧を200KPa/cmとした1対の金属ロール間を通して熱カレンダー加工を行い、実施例1に係る無機粉体シートを得た。
(実施例2)
(実施例3)
(比較例1)
(坪量)
(厚さ、密度)
(剛軟度)
(熱伝導率)
(4MPa圧縮試験)
(250℃加熱圧縮試験)
(350℃加熱圧縮試験)
10…無機粉体シート
11…第一熱プレス板
12…ステンレス板
13…クラフト紙
15…熱電対
16…第二熱プレス板
17…アルミ板
18…ホットプレート
19…ガラスニードルマット
20…二次電池セル
21…外装缶
22…封口板
23…電極
24…防爆弁
25…電池積層体
30…端面板
40…基礎板
100…電源装置
SS…サンプルシート
WT…重り
Claims (15)
- 断熱性を有する無機粉体シートであって、
無機粉体として、膨張処理済バーミキュライトを80重量%以上と、
有機繊維を20重量%以下と
を含んでなる無機粉体シート。 - 請求項1に記載の無機粉体シートであって、
前記バーミキュライトのメジアン径が、20μm~70μmである無機粉体シート。 - 請求項1又は2に記載の無機粉体シートであって、
前記有機繊維が、パラアラミド繊維、パラアラミドパルプ、メタアラミドパルプ、ポリフェニレンサルファイド繊維、PET繊維、難燃PET繊維、難燃レーヨン繊維、天然セルロース繊維のいずれか一以上を含んでなる無機粉体シート。 - 請求項1~3のいずれか一項に記載の無機粉体シートであって、
前記無機粉体シートの膜厚が、0.1mm~1.0mmである無機粉体シート。 - 請求項1~4のいずれか一項に記載の無機粉体シートであって、
剛軟度が、15mN以上、50mN以下であり、
密度が、1.00g/cm3以上、1.90g/cm3以下である無機粉体シート。 - 請求項1~5のいずれか一項に記載の無機粉体シートであって、
圧縮前の熱伝導率が、0.3W/m・K以下であり、
4MPaで圧縮した場合の圧縮率が、10%以下である無機粉体シート。 - 断熱性を有する無機粉体シートであって、
圧縮前の熱伝導率が、0.3W/m・K以下であり、
4MPaで圧縮した場合の圧縮率が、10%以下である無機粉体シート。 - 請求項7に記載の無機粉体シートであって、
剛軟度が、15mN以上、50mN以下である無機粉体シート。 - 請求項1~8のいずれか一項に記載の無機粉体シートであって、
前記無機粉体シートの表面温度を250℃とし、3MPaで圧縮した時の、前記無機粉体シートの10分後の裏面温度が、240℃以下である無機粉体シート。 - 請求項1~9のいずれか一項に記載の無機粉体シートであって、
前記バーミキュライトの粒度分布測定の積算分布において、メジアン径が20μm~70μmである無機粉体シート。 - 請求項1~10のいずれか一項に記載の無機粉体シートを一層以上と、
難燃性又は防炎性の付加層を積層してなる無機粉体シート積層体。 - 基材となるシート材と、
前記シート材の少なくとも一方の面に積層された、請求項1~10のいずれか一項に記載の無機粉体シートとを備える無機粉体シート積層体。 - 断熱性を有する無機粉体シートの製造方法であって、
無機粉体として、膨張処理済バーミキュライトを80重量%以上に、有機繊維を20重量%以下配合して、水に分散させてスラリー化して湿式抄紙する工程と、
シート状に抄紙されたものを熱カレンダー加工する工程と、
を含む無機粉体シートの製造方法。 - 請求項13に記載の無機粉体シートの製造方法であって、
前記バーミキュライトの粒度分布測定の積算分布において、メジアン径が20μm~70μmである無機粉体シートの製造方法。 - 請求項13又は14に記載の無機粉体シートの製造方法であって、
前記有機繊維が、パラアラミド繊維、パラアラミドパルプ、メタアラミドパルプ、ポリフェニレンサルファイド繊維、PET繊維、難燃PET繊維、難燃レーヨン繊維、天然セルロース繊維のいずれか一以上を含んでなる無機粉体シートの製造方法。
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JPS60180802A (ja) * | 1984-02-28 | 1985-09-14 | Nippon Sekisoo Kogyo Kk | 繊維質成形層体の製造法 |
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CN102503299A (zh) * | 2011-10-27 | 2012-06-20 | 苏州晟保隆新材料科技有限公司 | 含膨胀蛭石的建筑内饰防火板材及其制造方法 |
JP2013155828A (ja) * | 2012-01-31 | 2013-08-15 | Imae Kogyo Kk | 筒状断熱材及びこれを装着した機器 |
CN104418557A (zh) * | 2013-09-05 | 2015-03-18 | 上海斯米克控股股份有限公司 | 一种轻质高强蛭石硅酸钙板及其制备方法 |
JP2020165065A (ja) * | 2019-03-29 | 2020-10-08 | 王子ホールディングス株式会社 | 耐熱断熱シートとその製造方法、及び組電池 |
JP2020193413A (ja) * | 2019-05-29 | 2020-12-03 | パナソニックIpマネジメント株式会社 | 断熱シートおよびその製造方法、ならびに電子機器および電池ユニット |
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JP7303017B2 (ja) | 2019-05-10 | 2023-07-04 | イビデン株式会社 | 電池セル及び組電池 |
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- 2022-03-28 WO PCT/JP2022/015041 patent/WO2022234746A1/ja active Application Filing
- 2022-03-28 CN CN202280031906.2A patent/CN117222839A/zh active Pending
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JPS60180802A (ja) * | 1984-02-28 | 1985-09-14 | Nippon Sekisoo Kogyo Kk | 繊維質成形層体の製造法 |
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