JP7410635B2 - Heat-expandable fire-resistant resin composition, heat-expandable fire-resistant sheet, and battery cell equipped with the heat-expandable fire-resistant sheet - Google Patents
Heat-expandable fire-resistant resin composition, heat-expandable fire-resistant sheet, and battery cell equipped with the heat-expandable fire-resistant sheet Download PDFInfo
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- JP7410635B2 JP7410635B2 JP2018013276A JP2018013276A JP7410635B2 JP 7410635 B2 JP7410635 B2 JP 7410635B2 JP 2018013276 A JP2018013276 A JP 2018013276A JP 2018013276 A JP2018013276 A JP 2018013276A JP 7410635 B2 JP7410635 B2 JP 7410635B2
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- heat
- fire
- resistant
- thermally expandable
- battery
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- BFPBWJGVRNQWEK-UHFFFAOYSA-N bis(4-methoxyphenyl)phosphinic acid Chemical compound C1=CC(OC)=CC=C1P(O)(=O)C1=CC=C(OC)C=C1 BFPBWJGVRNQWEK-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- UOKRBSXOBUKDGE-UHFFFAOYSA-N butylphosphonic acid Chemical compound CCCCP(O)(O)=O UOKRBSXOBUKDGE-UHFFFAOYSA-N 0.000 description 1
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- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
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- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
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- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
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- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
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- BYYQOWAAZOHHFN-UHFFFAOYSA-N dioctylphosphane Chemical compound CCCCCCCCPCCCCCCCC BYYQOWAAZOHHFN-UHFFFAOYSA-N 0.000 description 1
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- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
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- NXHKQBCTZHECQF-UHFFFAOYSA-N ethyl(methyl)phosphinic acid Chemical compound CCP(C)(O)=O NXHKQBCTZHECQF-UHFFFAOYSA-N 0.000 description 1
- GATNOFPXSDHULC-UHFFFAOYSA-N ethylphosphonic acid Chemical compound CCP(O)(O)=O GATNOFPXSDHULC-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
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- 229920001973 fluoroelastomer Polymers 0.000 description 1
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- 238000010097 foam moulding Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
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- 230000001771 impaired effect Effects 0.000 description 1
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- 238000009830 intercalation Methods 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
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- 239000011133 lead Substances 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- SZTJCIYEOQYVED-UHFFFAOYSA-N methyl(propyl)phosphinic acid Chemical compound CCCP(C)(O)=O SZTJCIYEOQYVED-UHFFFAOYSA-N 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- NJGCRMAPOWGWMW-UHFFFAOYSA-N octylphosphonic acid Chemical compound CCCCCCCCP(O)(O)=O NJGCRMAPOWGWMW-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- MLCHBQKMVKNBOV-UHFFFAOYSA-N phenylphosphinic acid Chemical compound OP(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000011495 polyisocyanurate Substances 0.000 description 1
- 229920000582 polyisocyanurate Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- NSETWVJZUWGCKE-UHFFFAOYSA-N propylphosphonic acid Chemical compound CCCP(O)(O)=O NSETWVJZUWGCKE-UHFFFAOYSA-N 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- 235000011835 quiches Nutrition 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 239000002470 thermal conductor Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- 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
Description
本発明は、熱膨張性耐火樹脂組成物、熱膨張性耐火シート及び該熱膨張性耐火シートを備えたバッテリーセルに関する。 The present invention relates to a heat-expandable fire-resistant resin composition, a heat-expandable fire-resistant sheet, and a battery cell equipped with the heat-expandable fire-resistant sheet.
リチウム電池に代表される各種バッテリーでは、内部短絡などが原因でバッテリーが熱暴走し、発火、発煙等の災害が生じることがある。こうした災害を最小限に抑えるために、異常高温になったバッテリーの熱を周囲のバッテリー及びバッテリーを収容した筐体に伝え難くする対策が重要である。 BACKGROUND ART In various types of batteries, such as lithium batteries, internal short circuits can cause the batteries to overheat, resulting in fire, smoke, and other disasters. In order to minimize such disasters, it is important to take measures to make it difficult for the heat of an abnormally high-temperature battery to be transmitted to the surrounding batteries and the casing that houses the battery.
バッテリーセルを火災から保護する為に、バッテリーセルの周辺に熱膨張性耐火材を用いる場合がある。例えば特許文献１は、その外側の少なくとも一部が耐火性コーティングで覆われている電池セルについて開示している。耐火性コーティングはアブレーティブコーティング、膨張性コーティング又は吸熱性コーティングであり、市販のポリウレタン系コーティングが例示として挙げられている。 In order to protect battery cells from fire, a thermally expandable fireproof material is sometimes used around the battery cells. For example, U.S. Pat. No. 5,001,301 discloses a battery cell whose outside is at least partially covered with a fire-resistant coating. The fire-resistant coating can be an ablative coating, an intumescent coating or an endothermic coating, commercially available polyurethane-based coatings being mentioned by way of example.
バッテリーの熱暴走時のバッテリーセルから隣接するバッテリーセルへの熱連鎖を防止又は抑制できる熱膨張性耐火材が求められている。 There is a need for a thermally expandable refractory material that can prevent or suppress heat chain from one battery cell to an adjacent battery cell during battery thermal runaway.
本発明の目的は、バッテリーセルの熱暴走時のセルの急速な温度上昇時に、膨張してバッテリーセル間の空間を確保あるいはバッテリーセル間を離間させる断熱層を形成することができる熱膨張性耐火樹脂組成物、該熱膨張性耐火樹脂組成物からなる熱膨張性耐火シート、並びに及該熱膨張性耐火シートを備えたバッテリーセルを提供することにある。 The object of the present invention is to provide a thermally expandable fireproofing material that can expand to secure space between battery cells or form a heat insulating layer that separates battery cells when the temperature of the battery cells rapidly increases due to thermal runaway. The present invention provides a resin composition, a heat-expandable fire-resistant sheet made of the heat-expandable fire-resistant resin composition, and a battery cell equipped with the heat-expandable fire-resistant sheet.
上記課題を解決するために、本発明の以下の態様が提供される。
項１．樹脂成分及び熱膨張性黒鉛を含有し、膨張圧力が０．０５ＭＰａ以上である熱膨張性耐火樹脂組成物。
項２．樹脂成分１００質量部に対して、熱膨張性黒鉛を１０質量部以上含有する項１に記載の熱膨張性耐火樹脂組成物。
項３．前記樹脂成分が、熱可塑性樹脂、及びエラストマー樹脂からなる群から選択される少なくとも一種である項１又は２に記載の熱膨張性耐火樹脂組成物。
項４．バッテリーセル保護用熱膨張性耐火樹脂組成物である項１～３に記載の熱膨張性耐火樹脂組成物。
項５．項１～４のいずれか一項に記載の熱膨張性耐火樹脂組成物からなる熱膨張性耐火シート。
項６．項５に記載の熱膨張性耐火シートを備えたバッテリーセル。
項７．複数個のバッテリーセルを備え、隣接するバッテリーセルの間に項５に記載の熱膨張性耐火シートが配置されているバッテリーモジュール。
項８．項１～４のいずれか一項に記載の熱膨張性耐火樹脂組成物からなる熱膨張性耐火コーティング。
In order to solve the above problems, the following aspects of the present invention are provided.
Item 1. A heat-expandable fire-resistant resin composition containing a resin component and heat-expandable graphite and having an expansion pressure of 0.05 MPa or more.
Item 2. Item 2. The heat-expandable fire-resistant resin composition according to item 1, which contains 10 parts by mass or more of heat-expandable graphite based on 100 parts by mass of the resin component.
Item 3. Item 3. The thermally expandable fire-resistant resin composition according to item 1 or 2, wherein the resin component is at least one selected from the group consisting of thermoplastic resins and elastomer resins.
Item 4. Item 4. The thermally expandable fireproof resin composition according to Items 1 to 3, which is a thermally expandable fireproof resin composition for protecting battery cells.
Item 5. Item 5. A heat-expandable fire-resistant sheet comprising the heat-expandable fire-resistant resin composition according to any one of items 1 to 4.
Item 6. Item 5. A battery cell comprising the thermally expandable fireproof sheet according to item 5.
Section 7. A battery module comprising a plurality of battery cells, wherein the thermally expandable fireproof sheet according to item 5 is disposed between adjacent battery cells.
Section 8. Item 5. A thermally expandable fire-resistant coating comprising the thermally expandable fire-resistant resin composition according to any one of items 1 to 4.
本発明によれば、バッテリーの熱暴走時に、膨張して隣接するバッテリーセル間の空間を確保しつつ、隣接するセル間に断熱層を形成することができるため、そのようなバッテリーを使用する電子機器又は自動車等に優れた耐火性能を付与することができる。 According to the present invention, when a battery experiences thermal runaway, it expands to ensure space between adjacent battery cells while forming a heat insulating layer between adjacent cells. Excellent fire resistance can be imparted to equipment, automobiles, etc.
以下、本発明を熱膨張性耐火シートに具体化した一実施形態について説明する。 Hereinafter, an embodiment in which the present invention is embodied in a thermally expandable fireproof sheet will be described.
本実施形態の熱膨張性耐火シートを構成する熱膨張性耐火樹脂組成物は、樹脂成分及び熱膨張性黒鉛を含有し、膨張圧力が０．０５ＭＰａ以上である。 The heat-expandable fire-resistant resin composition constituting the heat-expandable fire-resistant sheet of this embodiment contains a resin component and heat-expandable graphite, and has an expansion pressure of 0.05 MPa or more.
本発明者らは、バッテリーの発火時の熱暴走及び熱連鎖を抑制するために、熱膨張性黒鉛を含有する熱膨張性耐火樹脂組成物又は熱膨張性耐火シートを用いた場合に、熱膨張性黒鉛の膨張により生じる膨張圧力が重要であることを見出した。熱膨張性耐火樹脂組成物又は熱膨張性耐火シートの膨張圧力が０．０５ＭＰａ以上となるよう熱膨張性黒鉛を含有することで、膨張時に十分な断熱性を有する断熱層を形成することができ、バッテリーの発火時の熱暴走及び熱連鎖を効果的に抑制することができる。 In order to suppress thermal runaway and thermal chain when a battery fires, the present inventors have discovered that when using a thermally expandable fireproof resin composition or a thermally expandable fireproof sheet containing thermally expandable graphite, thermal expansion It was discovered that the expansion pressure caused by the expansion of graphite is important. By containing thermally expandable graphite so that the expansion pressure of the thermally expandable fireproof resin composition or the thermally expandable fireproof sheet is 0.05 MPa or more, a heat insulating layer having sufficient heat insulation properties can be formed during expansion. , thermal runaway and thermal chain reaction when the battery ignites can be effectively suppressed.
以下、熱膨張性耐火樹脂組成物中の各成分について説明する。
［樹脂成分］
樹脂成分としては、例えば、熱可塑性樹脂、熱硬化性樹脂、エラストマー樹脂、及びそれらの組み合わせが挙げられる。
Each component in the thermally expandable fire-resistant resin composition will be explained below.
[Resin component]
Examples of the resin component include thermoplastic resins, thermosetting resins, elastomer resins, and combinations thereof.
熱可塑性樹脂としては、例えば、ポリプロピレン樹脂、ポリエチレン樹脂、ポリ（１－）ブテン樹脂、ポリペンテン樹脂等のポリオレフィン樹脂、ポリエチレンテレフタレート等のポリエステル樹脂、ポリスチレン樹脂、アクリロニトリル－ブタジエン－スチレン（ＡＢＳ）樹脂、エチレン酢酸ビニル共重合体（ＥＶＡ）、ポリカーボネート樹脂、ポリフェニレンエーテル樹脂、（メタ）アクリル系樹脂、ポリアミド樹脂、ポリ塩化ビニル樹脂（ＰＶＣ）、塩素化ポリ塩化ビニル樹脂（ＣＰＶＣ）、ノボラック樹脂、ポリウレタン樹脂、ポリイソブチレン等の合成樹脂が挙げられる。 Examples of thermoplastic resins include polyolefin resins such as polypropylene resins, polyethylene resins, poly(1-)butene resins, and polypentene resins, polyester resins such as polyethylene terephthalate, polystyrene resins, acrylonitrile-butadiene-styrene (ABS) resins, and ethylene. Vinyl acetate copolymer (EVA), polycarbonate resin, polyphenylene ether resin, (meth)acrylic resin, polyamide resin, polyvinyl chloride resin (PVC), chlorinated polyvinyl chloride resin (CPVC), novolak resin, polyurethane resin, Examples include synthetic resins such as polyisobutylene.
熱硬化性樹脂としては、例えば、ポリウレタン樹脂、ポリイソシアネート樹脂、ポリイソシアヌレート樹脂、フェノール樹脂、エポキシ樹脂、尿素樹脂、メラミン樹脂、不飽和ポリエステル樹脂、シリコーン樹脂、ポリイミド等の合成樹脂が挙げられる。エポキシ樹脂は、エポキシ基をもつエポキシ化合物と硬化剤とを反応させることにより得られる。 Examples of the thermosetting resin include synthetic resins such as polyurethane resin, polyisocyanate resin, polyisocyanurate resin, phenol resin, epoxy resin, urea resin, melamine resin, unsaturated polyester resin, silicone resin, and polyimide. Epoxy resins are obtained by reacting an epoxy compound having an epoxy group with a curing agent.
エラストマー樹脂としては、アクリロニトリルブタジエンゴム、液状アクリロニトリルブタジエンゴム、エチレン－プロピレン－ジエンゴム（ＥＰＤＭ）、液状エチレン－プロピレン－ジエンゴム（液状ＥＰＤＭ）、エチレン－プロピレンゴム、液状エチレン－プロピレンゴム、天然ゴム、液状天然ゴム、ポリブタジエンゴム、液状ポリブタジエンゴム、ポリイソプレンゴム、液状ポリイソプレンゴム、スチレン－ブタジエンブロック共重合体、液状スチレン－ブタジエンブロック共重合体、水素添加スチレン－ブタジエンブロック共重合体、液状水素添加スチレン－ブタジエンブロック共重合体、水素添加スチレン－ブタジエン－スチレンブロック共重合体、液状水素添加スチレン－ブタジエン－スチレンブロック共重合体、水素添加スチレン－イソプレンブロック共重合体、液状水素添加スチレン－イソプレンブロック共重合体、水素添加スチレン－イソプレン－スチレンブロック共重合体、液状水素添加スチレン－イソプレン－スチレンブロック共重合体等が挙げられる。これらの中では、アクリロニトリルブタジエンゴム、液状アクリロニトリルブタジエンゴム及びエチレン－プロピレン－ジエンゴム、液状エチレン－プロピレン－ジエンゴム、及びブチルゴム（イソブチレン－イソプレンゴム）が好ましい。 Examples of elastomer resins include acrylonitrile butadiene rubber, liquid acrylonitrile butadiene rubber, ethylene-propylene-diene rubber (EPDM), liquid ethylene-propylene-diene rubber (liquid EPDM), ethylene-propylene rubber, liquid ethylene-propylene rubber, natural rubber, and liquid natural rubber. Rubber, polybutadiene rubber, liquid polybutadiene rubber, polyisoprene rubber, liquid polyisoprene rubber, styrene-butadiene block copolymer, liquid styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, liquid hydrogenated styrene- Butadiene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer, liquid hydrogenated styrene-butadiene-styrene block copolymer, hydrogenated styrene-isoprene block copolymer, liquid hydrogenated styrene-isoprene block copolymer Examples include hydrogenated styrene-isoprene-styrene block copolymers, liquid hydrogenated styrene-isoprene-styrene block copolymers, and the like. Among these, acrylonitrile butadiene rubber, liquid acrylonitrile butadiene rubber, ethylene-propylene-diene rubber, liquid ethylene-propylene-diene rubber, and butyl rubber (isobutylene-isoprene rubber) are preferred.
これらの熱可塑性樹脂、熱硬化性樹脂、及び／又はエラストマー樹脂は、一種もしくは二種以上を使用することができる。 These thermoplastic resins, thermosetting resins, and/or elastomer resins may be used alone or in combination of two or more.
これらの熱可塑性樹脂、熱硬化性樹脂、及び／又はエラストマー樹脂の中でも、成形加工性の点では、ＰＶＣ、ＥＶＡが好ましい。耐火性の点では、ＰＶＣが好ましい。樹脂自体の難燃性を上げて防火性能を向上させるという観点からは、エポキシ樹脂が好ましい。柔軟でゴム的性質を有しているもの又は低粘度であるものは、熱膨張性黒鉛、吸熱剤等を樹脂成分中に高充填できるため好ましい。柔軟でゴム的性質を得るためには、ブチルゴム等の非加硫ゴム及びポリオレフィン樹脂が好ましい。ゴムは自己粘着性を有するため、バッテリーセルと熱伝導性熱膨張性シートとの間に接着剤又は接着シート等の接着手段を用いなくとも、熱伝導性熱膨張性シートをバッテリーセルに取り付けることができる。 Among these thermoplastic resins, thermosetting resins, and/or elastomer resins, PVC and EVA are preferred in terms of moldability. PVC is preferred in terms of fire resistance. Epoxy resins are preferred from the viewpoint of increasing the flame retardance of the resin itself and improving fire protection performance. Those that are flexible and have rubber-like properties or those that have low viscosity are preferable because thermally expandable graphite, heat absorbing agents, etc. can be highly filled in the resin component. In order to obtain soft and rubbery properties, non-vulcanized rubber such as butyl rubber and polyolefin resin are preferred. Since rubber has self-adhesive properties, it is possible to attach the thermally conductive thermally expandable sheet to the battery cell without using adhesive means such as an adhesive or an adhesive sheet between the battery cell and the thermally conductive thermally expandable sheet. I can do it.
［熱膨張性黒鉛］
熱膨張性黒鉛は、加熱時に膨張する従来公知の物質であり、天然鱗状グラファイト、熱分解グラファイト、キッシュグラファイト等の粉末を無機酸と強酸化剤とで処理してグラファイト層間化合物を生成させたもので、炭素の層状構造を維持したままの結晶化合物である。無機酸としては濃硫酸、硝酸、セレン酸等が挙げられる。強酸化剤としては濃硝酸、過塩素酸、過塩素酸塩、過マンガン酸塩、重クロム酸塩、過酸化水素等が挙げられる。
[Thermally expandable graphite]
Thermally expandable graphite is a conventionally known substance that expands when heated, and is produced by treating powders such as natural scale graphite, pyrolytic graphite, and quiche graphite with an inorganic acid and a strong oxidizing agent to generate graphite intercalation compounds. It is a crystalline compound that maintains a carbon layered structure. Examples of inorganic acids include concentrated sulfuric acid, nitric acid, and selenic acid. Examples of strong oxidizing agents include concentrated nitric acid, perchloric acid, perchlorates, permanganates, dichromates, and hydrogen peroxide.
熱膨張性黒鉛は任意選択で中和処理されてもよい。つまり、上記のように酸処理して得られた熱膨張性黒鉛を、更にアンモニア、脂肪族低級アミン、アルカリ金属化合物、アルカリ土類金属化合物等で中和する。 The thermally expandable graphite may optionally be neutralized. That is, the thermally expandable graphite obtained by the acid treatment as described above is further neutralized with ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound, or the like.
上記のように酸処理して得られた熱膨張性黒鉛は、更にアンモニア、脂肪族低級アミン、アルカリ金属化合物、アルカリ土類金属化合物等でさらに中和してもよい。 The thermally expandable graphite obtained by acid treatment as described above may be further neutralized with ammonia, aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound, or the like.
熱膨張性耐火樹脂組成物及び熱膨張性耐火シートにおける熱膨張性黒鉛の含有量は、熱膨張性耐火樹脂組成物及び熱膨張性耐火シートが０．０５ＭＰａ以上の膨張圧力を発現できるように調整される限り、限定されない。樹脂成分１００質量部に対して、好ましくは１０質量部以上であり、より好ましくは３０質量部以上である。１０質量部より高いと、十分な耐火性能を得る点で好ましい。熱膨張性黒鉛の含有量の上限値は、断熱性能を有すると共に一定の強度を有する燃焼残渣を形成する点で、３５０質量部以下であることが好ましい。 The content of heat-expandable graphite in the heat-expandable fire-resistant resin composition and heat-expandable fire-resistant sheet is adjusted so that the heat-expandable fire-resistant resin composition and heat-expandable fire-resistant sheet can express an expansion pressure of 0.05 MPa or more. There are no limitations as long as it is done. The amount is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, based on 100 parts by mass of the resin component. A content higher than 10 parts by mass is preferred in terms of obtaining sufficient fire resistance. The upper limit of the content of thermally expandable graphite is preferably 350 parts by mass or less in terms of forming a combustion residue that has heat insulating performance and has a certain strength.
熱膨張性黒鉛の粒度は、２０～２００メッシュが好ましい。粒度が２００メッシュかそれより大きい（粗い）と、黒鉛の膨張度が膨張断熱層を得るのに十分であり、また粒度が２０メッシュかそれより小さい（細かい）と、樹脂に配合する際の分散性が良い。粒度は、市販のレーザ回折／散乱式粒度測定装置を用いて測定することができる。 The particle size of the thermally expandable graphite is preferably 20 to 200 mesh. When the particle size is 200 mesh or larger (coarse), the degree of expansion of graphite is sufficient to obtain an intumescent insulation layer, and when the particle size is 20 mesh or smaller (fine), it is difficult to disperse the graphite when compounded into the resin. Good sex. Particle size can be measured using a commercially available laser diffraction/scattering particle size measuring device.
熱膨張性黒鉛の平均アスペクト比は、特に限定されないが、２以上であることが好ましく、５以上であることがより好ましく、１０以上であることが更に好ましい。熱膨張性黒鉛の平均アスペクト比の上限は特に限定されないが、熱膨張性黒鉛の割れ防止の観点から、１０００以下であることが好ましい。熱膨張性黒鉛の平均アスペクト比が２以上であることにより、熱膨張性耐火樹脂組成物の高い膨張性と燃焼後の高い残渣硬さに寄与する。 The average aspect ratio of thermally expandable graphite is not particularly limited, but is preferably 2 or more, more preferably 5 or more, and even more preferably 10 or more. The upper limit of the average aspect ratio of thermally expandable graphite is not particularly limited, but from the viewpoint of preventing cracking of thermally expandable graphite, it is preferably 1000 or less. When the average aspect ratio of the thermally expandable graphite is 2 or more, it contributes to high expandability of the thermally expandable fireproof resin composition and high residual hardness after combustion.
熱膨張性黒鉛片の最大寸法（長径）を最小寸法（短径）で除した値をアスペクト比とする。そして、１０個以上の膨張黒鉛片につきアスペクト比を測定し、その平均値を平均アスペクト比とする。熱膨張性黒鉛の長径及び短径は、例えば、電界放出型走査電子顕微鏡（ＦＥ－ＳＥＭ）を用いて測定することができる。 The aspect ratio is the value obtained by dividing the maximum dimension (major axis) of the thermally expandable graphite piece by the minimum dimension (minor axis). Then, the aspect ratio of 10 or more pieces of expanded graphite is measured, and the average value thereof is defined as the average aspect ratio. The long axis and short axis of thermally expandable graphite can be measured using, for example, a field emission scanning electron microscope (FE-SEM).
［無機充填剤］
本発明の実施形態の熱膨張性耐火樹脂組成物及び熱膨張性耐火シートは、無機充填剤をさらに含むことができる。無機充填剤は、膨張断熱層が形成される際、熱容量を増大させ伝熱を抑制するとともに、骨材的に働いて膨張断熱層の強度を向上させる。無機充填剤としては特に限定されず、例えば、アルミナ、酸化亜鉛、酸化チタン、酸化カルシウム、酸化マグネシウム、酸化鉄、酸化錫、酸化アンチモン、フェライト等の金属酸化物；水酸化カルシウム、水酸化マグネシウム、水酸化アルミニウム、ハイドロタルサイト等の金属水酸化物；塩基性炭酸マグネシウム、炭酸カルシウム、炭酸マグネシウム、炭酸亜鉛、炭酸ストロンチウム、炭酸バリウム等の金属炭酸塩；難燃剤としての無機リン酸塩；硫酸カルシウム、石膏繊維、ケイ酸カルシウム等のカルシウム塩；シリカ、珪藻土、ドーソナイト、硫酸バリウム、タルク、クレー、マイカ、モンモリロナイト、ベントナイト、活性白土、セピオライト、イモゴライト、セリサイト、ガラス繊維、ガラスビーズ、シリカ系バルーン、窒化アルミニウム、窒化ホウ素、窒化ケイ素、カーボンブラック、グラファイト、炭素繊維、炭素バルーン、木炭粉末、各種金属粉、チタン酸カリウム、硫酸マグネシウム、チタン酸ジルコン酸鉛、ステアリン酸亜鉛、ステアリン酸カルシウム、アルミニウムボレート、硫化モリブデン、炭化ケイ素、ステンレス繊維、ホウ酸亜鉛、各種磁性粉、スラグ繊維、フライアッシュ、脱水汚泥等が挙げられる。これらの無機充填剤は一種もしくは二種以上を使用することができる。
[Inorganic filler]
The heat-expandable fire-resistant resin composition and heat-expandable fire-resistant sheet of the embodiments of the present invention may further contain an inorganic filler. When the expanding heat insulating layer is formed, the inorganic filler increases the heat capacity and suppresses heat transfer, and acts as an aggregate to improve the strength of the expandable heat insulating layer. Inorganic fillers are not particularly limited, and include metal oxides such as alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrite; calcium hydroxide, magnesium hydroxide, Metal hydroxides such as aluminum hydroxide and hydrotalcite; metal carbonates such as basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, barium carbonate; inorganic phosphates as flame retardants; calcium sulfate , gypsum fiber, calcium salts such as calcium silicate; silica, diatomaceous earth, dawsonite, barium sulfate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica balloon , aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balloon, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, zinc stearate, calcium stearate, aluminum borate , molybdenum sulfide, silicon carbide, stainless steel fiber, zinc borate, various magnetic powders, slag fibers, fly ash, dehydrated sludge, etc. These inorganic fillers can be used alone or in combination of two or more.
無機充填剤の平均粒径としては、０．５～１００μｍが好ましく、より好ましくは１～５０μｍである。無機充填剤は、含有量が少ないときは、分散性が性能を大きく左右するため、平均粒径の小さいものが好ましいが、０．５μｍ未満では二次凝集が起こり分散性が悪くなるため、０．５μｍ以上であることが好ましい。含有量が多いときは、高充填が進むにつれて、熱膨張性耐火樹脂組成物の粘度が高くなり成形性が低下するが、平均粒径を大きくすることで熱膨張性耐火樹脂組成物の粘度を低下させることができる。このため、平均粒径の大きいものが好ましいが、平均粒径が１００μｍを超えると、成形体の表面性や熱膨張性耐火樹脂組成物の力学的性能が低下するため、１００μｍ以下であることが望ましい。無機充填剤の粒径は、市販のレーザ回折／散乱式粒度測定装置を用いて測定することができる。 The average particle size of the inorganic filler is preferably 0.5 to 100 μm, more preferably 1 to 50 μm. When the content of inorganic fillers is small, the dispersibility greatly affects the performance, so those with a small average particle size are preferable, but if the content is less than 0.5 μm, secondary agglomeration will occur and the dispersibility will deteriorate. It is preferable that it is .5 μm or more. When the content is high, the viscosity of the heat-expandable fire-resistant resin composition increases and the moldability decreases as the filling progresses; however, by increasing the average particle size, the viscosity of the heat-expandable fire-resistant resin composition can be reduced. can be lowered. For this reason, particles with a large average particle size are preferable, but if the average particle size exceeds 100 μm, the surface properties of the molded product and the mechanical performance of the thermally expandable fire-resistant resin composition will deteriorate, so it is preferable that the average particle size is 100 μm or less. desirable. The particle size of the inorganic filler can be measured using a commercially available laser diffraction/scattering particle size measuring device.
上記無機充填剤の市販品では、例えば、炭酸カルシウムとして、平均粒径１．８μｍの「ホワイトンＳＢ赤」（白石カルシウム社製）、平均粒径８μｍの「ＢＦ３００」（白石カルシウム社製）等が挙げられる。また、粒径の大きい無機充填剤と粒径の小さいものを組み合わせて使用することがより好ましく、組み合わせることによって、さらに高充填化が可能となる。 Examples of commercially available inorganic fillers include calcium carbonate such as "Whiten SB Red" (manufactured by Shiroishi Calcium Co., Ltd.) with an average particle size of 1.8 μm and "BF300" (manufactured by Shiroishi Calcium Co., Ltd.) with an average particle size of 8 μm. can be mentioned. Further, it is more preferable to use a combination of an inorganic filler with a large particle size and one with a small particle size, and by combining them, even higher filling becomes possible.
熱膨張性耐火樹脂組成物及び熱膨張性耐火シートにおける無機充填剤の含有量は特に限定されないが、樹脂成分１００質量部に対して、１０～１０００質量部であり、好ましくは１０～５００質量部である。１０質量部より低いと、十分な温度上昇の緩和効果を得ることができない。１０００質量部より高いと、機械的物性を維持する点で好ましくない。 The content of the inorganic filler in the heat-expandable fire-resistant resin composition and the heat-expandable fire-resistant sheet is not particularly limited, but is 10 to 1000 parts by mass, preferably 10 to 500 parts by mass, based on 100 parts by mass of the resin component. It is. If it is less than 10 parts by mass, a sufficient temperature rise mitigation effect cannot be obtained. If it is higher than 1000 parts by mass, it is not preferable in terms of maintaining mechanical properties.
［リン化合物］
さらに、本発明の実施形態の熱膨張性耐火樹脂組成物及び熱膨張性耐火シートは、膨張断熱層の強度を増加させ防火性能を向上させるために、前記の各成分に加えて、さらにリン化合物を含むことができる。リン化合物としては、特に限定されず、例えば、赤リン；トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェート、キシレニルジフェニルホスフェート等の各種リン酸エステル；リン酸ナトリウム、リン酸カリウム、リン酸マグネシウム等のリン酸金属塩；ポリリン酸アンモニウム；下記化学式（１）で表される化合物等が挙げられる。これらのうち、防火性能の観点から、赤リン、ポリリン酸アンモニウム、及び、下記化学式（１）で表される化合物が好ましく、性能、安全性、コスト等の点においてポリリン酸アンモニウムがより好ましい。
[Phosphorus compound]
Furthermore, the thermally expandable fireproof resin composition and the thermally expandable fireproof sheet of the embodiments of the present invention further contain a phosphorus compound in addition to the above-mentioned components in order to increase the strength of the expandable heat insulating layer and improve fire protection performance. can include. Phosphorus compounds are not particularly limited, and include, for example, red phosphorus; various phosphoric acid esters such as triphenyl phosphate, tricresyl phosphate, tricylenyl phosphate, cresyl diphenyl phosphate, and xylenyl diphenyl phosphate; sodium phosphate; Examples include metal phosphate salts such as potassium phosphate and magnesium phosphate; ammonium polyphosphate; and a compound represented by the following chemical formula (1). Among these, red phosphorus, ammonium polyphosphate, and the compound represented by the following chemical formula (1) are preferred from the viewpoint of fire protection performance, and ammonium polyphosphate is more preferred from the viewpoint of performance, safety, cost, etc.
化学式（１）中、Ｒ1及びＲ3は、同一又は異なって、水素、炭素数１～１６の直鎖状もしくは分岐状のアルキル基、又は、炭素数６～１６のアリール基を示す。Ｒ2は、水酸基、炭素数１～１６の直鎖状もしくは分岐状のアルキル基、炭素数１～１６の直鎖状あるいは分岐状のアルコキシル基、炭素数６～１６のアリール基、又は、炭素数６～１６のアリールオキシ基を示す。 In the chemical formula (1), R 1 and R 3 are the same or different and represent hydrogen, a linear or branched alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms. R 2 is a hydroxyl group, a linear or branched alkyl group having 1 to 16 carbon atoms, a linear or branched alkoxyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, or a carbon Indicates an aryloxy group having numbers 6 to 16.
赤リンとしては、市販の赤リンを用いることができるが、耐湿性、混練時に自然発火しない等の安全性の点から、赤リン粒子の表面を樹脂でコーティングしたもの等が好適に用いられる。ポリリン酸アンモニウムとしては特に限定されず、例えば、ポリリン酸アンモニウム、メラミン変性ポリリン酸アンモニウム等が挙げられるが、取り扱い性等の点からポリリン酸アンモニウムが好適に用いられる。市販品としては、例えば、クラリアント社製「ＡＰ４２２」、「ＡＰ４６２」、Ｂｕｄｅｎｈｅｉｍ Ｉｂｅｒｉｃａ社製「ＦＲ ＣＲＯＳ ４８４」、「ＦＲ ＣＲＯＳ ４８７」等が挙げられる。 As the red phosphorus, commercially available red phosphorus can be used, but red phosphorus particles whose surfaces are coated with a resin are preferably used from the viewpoint of safety such as moisture resistance and not spontaneously igniting during kneading. Ammonium polyphosphate is not particularly limited, and examples thereof include ammonium polyphosphate, melamine-modified ammonium polyphosphate, etc., but ammonium polyphosphate is preferably used from the viewpoint of ease of handling. Examples of commercially available products include "AP422" and "AP462" manufactured by Clariant, and "FR CROS 484" and "FR CROS 487" manufactured by Budenheim Iberica.
化学式（１）で表される化合物としては特に限定されず、例えば、メチルホスホン酸、メチルホスホン酸ジメチル、メチルホスホン酸ジエチル、エチルホスホン酸、ｎ－プロピルホスホン酸、ｎ－ブチルホスホン酸、２－メチルプロピルホスホン酸、ｔ－ブチルホスホン酸、２，３－ジメチル－ブチルホスホン酸、オクチルホスホン酸、フェニルホスホン酸、ジオクチルフェニルホスホネート、ジメチルホスフィン酸、メチルエチルホスフィン酸、メチルプロピルホスフィン酸、ジエチルホスフィン酸、ジオクチルホスフィン酸、フェニルホスフィン酸、ジエチルフェニルホスフィン酸、ジフェニルホスフィン酸、ビス（４－メトキシフェニル）ホスフィン酸等が挙げられる。中でも、ｔ－ブチルホスホン酸は、高価ではあるが、高難燃性の点において好ましい。前記のリン化合物は、一種もしくは二種以上を使用することができる。 The compound represented by the chemical formula (1) is not particularly limited, and examples thereof include methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, n-propylphosphonic acid, n-butylphosphonic acid, and 2-methylpropylphosphonic acid. Acid, t-butylphosphonic acid, 2,3-dimethyl-butylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, dioctyl phenylphosphonate, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphine acid, phenylphosphinic acid, diethylphenylphosphinic acid, diphenylphosphinic acid, bis(4-methoxyphenyl)phosphinic acid, and the like. Among these, t-butylphosphonic acid is preferable in terms of high flame retardancy, although it is expensive. The above-mentioned phosphorus compounds can be used alone or in combination of two or more.
熱膨張性耐火樹脂組成物及び熱膨張性耐火シートにおけるリン化合物の含有量は、特に限定されないが、樹脂成分１００質量部に対して、１０～１０００質量部であることが好ましく、好ましくは１０～５００質量部であることが好ましい。１０質量部より高いと、十分な温度上昇の緩和効果を得ることができる。１０質量部より低いと、機械的物性を維持する点で好ましい。 The content of the phosphorus compound in the heat-expandable fire-resistant resin composition and the heat-expandable fire-resistant sheet is not particularly limited, but is preferably 10 to 1000 parts by mass, preferably 10 to 1000 parts by mass, based on 100 parts by mass of the resin component. Preferably, it is 500 parts by mass. When the content is higher than 10 parts by mass, a sufficient temperature rise mitigation effect can be obtained. A content of less than 10 parts by mass is preferable in terms of maintaining mechanical properties.
［可塑剤］
さらに、本実施形態の熱膨張性耐火シートを構成する熱膨張性耐火樹脂組成物は、可塑剤をさらに含有することができる。特に樹脂成分がポリ塩化ビニル樹脂又は塩素化ポリ塩化ビニルである場合、熱膨張性耐火樹脂組成物は可塑剤を含むことが好ましい。
[Plasticizer]
Furthermore, the heat-expandable fire-resistant resin composition constituting the heat-expandable fire-resistant sheet of this embodiment can further contain a plasticizer. In particular, when the resin component is a polyvinyl chloride resin or chlorinated polyvinyl chloride, the thermally expandable fire-resistant resin composition preferably contains a plasticizer.
可塑剤は、一般にポリ塩化ビニル樹脂成形体を製造する際に使用されている可塑剤であれば、特に限定されない。具体的には、例えば、ジ－２－エチルヘキシルフタレート（ＤＯＰ）、ジブチルフタレート（ＤＢＰ）、ジヘプチルフタレート（ＤＨＰ）、ジイソデシルフタレート（ＤＩＤＰ）等のフタル酸エステル可塑剤、ジ－２－エチルヘキシルアジペート（ＤＯＡ）、ジイソブチルアジペート（ＤＩＢＡ）、ジブチルアジペート（ＤＢＡ）等の脂肪酸エステル可塑剤；エポキシ化大豆油等のエポキシ化エステル可塑剤；アジピン酸エステル、アジピン酸ポリエステル等のポリエステル可塑剤；トリー２－エチルヘキシルトリメリテート（ＴＯＴＭ）、トリイソノニルトリメリテート（ＴＩＮＴＭ）等のトリメリット酸エステル可塑剤；鉱油等のプロセスオイルなどが挙げられる。可塑剤は一種もしくは二種以上を使用することができる。 The plasticizer is not particularly limited as long as it is a plasticizer that is generally used in manufacturing polyvinyl chloride resin molded articles. Specifically, for example, phthalate ester plasticizers such as di-2-ethylhexyl phthalate (DOP), dibutyl phthalate (DBP), diheptyl phthalate (DHP), and diisodecyl phthalate (DIDP), di-2-ethylhexyl adipate ( Fatty acid ester plasticizers such as DOA), diisobutyl adipate (DIBA), and dibutyl adipate (DBA); Epoxidized ester plasticizers such as epoxidized soybean oil; Polyester plasticizers such as adipic acid ester and adipic acid polyester; tri-2-ethylhexyl Examples include trimellitate ester plasticizers such as trimellitate (TOTM) and triisononyl trimellitate (TINTM); process oils such as mineral oil; and the like. One kind or two or more kinds of plasticizers can be used.
可塑剤の含有量は、少ないと押出成形性が低下する傾向があり、多くなると得られた成形体が柔らかくなり過ぎる傾向がある。このため可塑剤の含有量は限定されないが、樹脂成分がポリ塩化ビニル又は塩素化ポリ塩化ビニルを含む場合、２０～２００重量部であることが好ましい。 If the content of the plasticizer is small, extrusion moldability tends to decrease, and if the content is too large, the resulting molded product tends to become too soft. Therefore, the content of the plasticizer is not limited, but when the resin component contains polyvinyl chloride or chlorinated polyvinyl chloride, it is preferably 20 to 200 parts by weight.
［その他成分］
本実施形態の熱膨張性耐火樹脂組成物及び熱膨張性耐火シートには、本発明の目的が損なわれない範囲で、必要に応じて各種の添加成分を含有させることができる。
[Other ingredients]
The heat-expandable fire-resistant resin composition and heat-expandable fire-resistant sheet of the present embodiment may contain various additive components as necessary, as long as the object of the present invention is not impaired.
この添加成分の種類は特に限定されず、発泡成形に通常使用される各種添加剤を用いることができる。このような添加剤として、例えば、滑剤、収縮防止剤、気泡核剤、結晶核剤、可塑剤、着色剤（顔料、染料等）、紫外線吸収剤、酸化防止剤、老化防止剤、上記熱伝導体を除いた充填剤、補強剤、難燃剤、難燃助剤、帯電防止剤、界面活性剤、加硫剤、及び表面処理剤等が挙げられる。添加剤の添加量は、気泡の形成等を損なわない範囲で適宜選択でき、通常の樹脂の発泡及び成形に用いられる添加量を採用できる。かかる添加剤は、単独で又は二種以上組み合わせて用いることができる。 The type of this additive component is not particularly limited, and various additives commonly used in foam molding can be used. Such additives include, for example, lubricants, anti-shrinkage agents, bubble nucleating agents, crystal nucleating agents, plasticizers, colorants (pigments, dyes, etc.), ultraviolet absorbers, antioxidants, anti-aging agents, and the above thermal conductors. Examples include fillers excluding fillers, reinforcing agents, flame retardants, flame retardant aids, antistatic agents, surfactants, vulcanizing agents, and surface treatment agents. The amount of the additive to be added can be appropriately selected within a range that does not impair the formation of bubbles, etc., and the amount to be added that is commonly used for foaming and molding of resins can be adopted. Such additives can be used alone or in combination of two or more.
本実施形態の熱膨張性耐火シートの厚みは特に限定されないが、３０００μｍ以下であることが好ましく、６０～２０００μｍがより好ましい。なお、本明細書でいう熱膨張性耐火シートの「厚み」とは、熱膨張性耐火シートの幅方向３点の平均厚みを指す。 The thickness of the thermally expandable fireproof sheet of this embodiment is not particularly limited, but is preferably 3000 μm or less, more preferably 60 to 2000 μm. Note that the "thickness" of the thermally expandable fireproof sheet as used herein refers to the average thickness of three points in the width direction of the thermally expandable fireproof sheet.
本実施形態の熱膨張性耐火シートの膨張倍率は、熱膨張性耐火シートの試験片の（加熱後の試験片の厚さ）／（加熱前の試験片の厚さ）として算出される。 The expansion ratio of the thermally expandable fireproof sheet of this embodiment is calculated as (thickness of the test piece after heating)/(thickness of the test piece before heating) of the test piece of the thermally expandable fireproof sheet.
膨張性耐火シートの膨張倍率は、セルが熱暴走した際に、瞬時に膨張層により断熱し、かつその膨張層の強度があれば特に限定されない。５００℃のホットプレートで１分間加熱した後の膨張倍率が３倍以上であればよい。 The expansion ratio of the expansible fireproof sheet is not particularly limited as long as the expansion layer provides instant insulation when the cell undergoes thermal runaway and the expansion layer has strength. It is sufficient if the expansion ratio after heating on a 500° C. hot plate for 1 minute is 3 times or more.
本実施形態の熱膨張性耐火樹脂組成物及び熱膨張性耐火シートの膨張圧力は、熱膨張性耐火樹脂組成物及び熱膨張性耐火シートを５００℃で１分間加熱したときに生じる膨張圧力である。熱膨張性耐火樹脂組成物及び熱膨張性耐火シートの膨張圧力は、ホットプレート上に耐火材シートを配置すると共に、ホットプレートを固定した台に取り付けられたデジタルフォースゲージを耐火材シートに接触させておき、耐火材シートを５００℃のホットプレートの上で加熱し、加熱開始１分経過後の最大荷重をデジタルフォースゲージにより読み取り、該最大荷重をアタッチメントの断面積で除することにより算出することができる。 The expansion pressure of the heat-expandable fire-resistant resin composition and heat-expandable fire-resistant sheet of this embodiment is the expansion pressure that occurs when the heat-expandable fire-resistant resin composition and heat-expandable fire-resistant sheet are heated at 500°C for 1 minute. . The expansion pressure of the heat-expandable fire-resistant resin composition and the heat-expandable fire-resistant sheet can be determined by placing the fire-resistant sheet on a hot plate and contacting the digital force gauge attached to the stand on which the hot plate is fixed. Heat the refractory material sheet on a hot plate at 500°C, read the maximum load after 1 minute from the start of heating with a digital force gauge, and calculate by dividing the maximum load by the cross-sectional area of the attachment. I can do it.
熱膨張性耐火樹脂組成物及び熱膨張性耐火シートの膨張圧力は、バッテリーセル間の空間を確保する点で、０．１ＭＰａ以上であることが好ましく、０．３ＭＰａ以上であることがより好ましい。 The expansion pressure of the heat-expandable fire-resistant resin composition and the heat-expandable fire-resistant sheet is preferably 0.1 MPa or more, more preferably 0.3 MPa or more, from the viewpoint of ensuring space between battery cells.
本実施形態の熱膨張性耐火樹脂組成物及び熱膨張性耐火シートは、バッテリーセル用の断熱材として機能し、バッテリーの熱暴走時に、膨張して隣接するバッテリーセル間の空間を確保し、隣接するセル間に断熱層を形成することができる。このため、バッテリーセルを火災等の熱から保護し、そのようなバッテリーを使用する電子機器又は自動車等に優れた耐火性能を付与することができる。 The heat-expandable fire-resistant resin composition and heat-expandable fire-resistant sheet of the present embodiment function as a heat insulating material for battery cells, and when the battery goes into thermal runaway, expand to secure a space between adjacent battery cells. A heat insulating layer can be formed between the cells. Therefore, battery cells can be protected from heat such as fire, and excellent fire resistance can be imparted to electronic devices, automobiles, etc. that use such batteries.
熱膨張性耐火シートは、上記のマトリックス成分、熱膨張性黒鉛、及び任意選択のその他の成分を単軸押出機、二軸押出機、射出成型機、バンバリーミキサー、ニーダーミキサー、混練ロール、ライカイ機、遊星式撹拌機等の公知の装置を用いて混合した耐火性熱膨張性耐火樹脂組成物を、塗工又は成形することにより製造することができる。成形にはプレス成形、押出し成形、射出成形が含まれる。塗工又は成形は当該技術分野において周知である。 The heat-expandable fireproof sheet is produced by processing the above matrix components, heat-expandable graphite, and optional other ingredients in a single-screw extruder, twin-screw extruder, injection molding machine, Banbury mixer, kneader mixer, kneading roll, or Raikai machine. It can be produced by coating or molding a fire-resistant and thermally expandable fire-resistant resin composition mixed using a known device such as a planetary stirrer. Molding includes press molding, extrusion molding, and injection molding. Coating or molding is well known in the art.
図１は、本発明の一実施形態の熱膨張性耐火シート２と基材３とが積層された耐火多層シート１の略断面図である。 FIG. 1 is a schematic cross-sectional view of a fireproof multilayer sheet 1 in which a thermally expandable fireproof sheet 2 and a base material 3 are laminated together according to an embodiment of the present invention.
基材３は、可燃層であっても、準不燃層又は不燃層であってもよい。基材の厚みは特に限定されないが、例えば５μｍ～１ｍｍである。 The base material 3 may be a combustible layer, a semi-noncombustible layer, or a noncombustible layer. The thickness of the base material is not particularly limited, but is, for example, 5 μm to 1 mm.
可燃層に使用される素材としては、例えば、布材、紙材、木材、天然樹脂、合成樹脂等の一種もしくは二種以上を挙げることができる。 Examples of the material used for the combustible layer include one or more of cloth materials, paper materials, wood, natural resins, synthetic resins, and the like.
準不燃層又は不燃層に使用される素材としては、例えば、金属、無機材等の一種もしくは二種以上を挙げることができる。 Examples of the material used for the quasi-noncombustible layer or the noncombustible layer include one or more of metals, inorganic materials, and the like.
布材としては、例えば、木綿、絹、ナイロン、ポリエステル、ポリプロピレン等の織布、不織布からなるもの等を挙げることができる。 Examples of the cloth material include woven fabrics and nonwoven fabrics such as cotton, silk, nylon, polyester, and polypropylene.
紙材としては、例えば、木材等の植物から取り出した繊維状物質、化学繊維を水等の分散媒中に分散させ、これを濾過して均一層を形成してから乾燥させた紙等が挙げられる。 Examples of paper materials include paper made by dispersing fibrous substances extracted from plants such as wood or chemical fibers in a dispersion medium such as water, filtering this to form a uniform layer, and then drying it. It will be done.
紙に対して、塗料、撥水剤等を塗布して得られる加工紙、波状の紙をライナーと呼ばれる平面の紙により挟んで接着した段ボール等が挙げられる。 Examples include processed paper obtained by coating paper with paint, water repellent, etc., and corrugated paper made by sandwiching and bonding corrugated paper between flat sheets of paper called liners.
木材としては、例えば、天然木材から得られる木素材に限られず、木素材を含む集成木材、積層木材、積層木板等が挙げられる。 Examples of the wood include, for example, not only wood materials obtained from natural wood, but also laminated wood, laminated wood, laminated wood boards, etc. containing wood materials.
天然樹脂としては、例えば、セルロース誘導体、ゼラチン、アルギン酸塩、キトサン、プルラン、ペクチン、カラゲナン、タンパク質、タンニン、リグニン、ロジン酸等を主成分とする高分子、天然ゴム等が挙げられる。 Examples of natural resins include cellulose derivatives, gelatin, alginates, chitosan, pullulan, pectin, carrageenan, proteins, tannins, lignins, polymers whose main components are rosin acid, and natural rubber.
合成樹脂としては、例えば、イソプレンゴム、ブタジエンゴム、１，２－ポリブタジエンゴム、スチレン－ブタジエンゴム、クロロプレンゴム、ニトリルゴム、ブチルゴム、エチレン－プロピレンゴム、クロロスルホン化ポリエチレン、アクリルゴム、エピクロルヒドリンゴム、シリコーンゴム、フッ素ゴム、ウレタンゴム、ポリイソブチレンゴム、塩化ブチルゴム等の合成ゴム、
ポリプロピレン樹脂、ポリエチレン樹脂、ポリ（１－）ブテン樹脂、ポリペンテン樹脂等のポリオレフィン樹脂、
ポリスチレン樹脂、アクリロニトリル－ブタジエン－スチレン樹脂、ポリカーボネート樹脂、アクリル樹脂、ポリアミド樹脂、ポリ塩化ビニル樹脂、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、ポリフェニレンエーテル樹脂、全芳香族ポリエステル樹脂、ポリエーテルスルホン樹脂、フェノール樹脂、ポリウレタン樹脂、エポキシ樹脂等が挙げられる。
Examples of synthetic resins include isoprene rubber, butadiene rubber, 1,2-polybutadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, ethylene-propylene rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, and silicone. Synthetic rubber such as rubber, fluororubber, urethane rubber, polyisobutylene rubber, butyl chloride rubber,
Polyolefin resins such as polypropylene resin, polyethylene resin, poly(1-)butene resin, polypentene resin,
Polystyrene resin, acrylonitrile-butadiene-styrene resin, polycarbonate resin, acrylic resin, polyamide resin, polyvinyl chloride resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyphenylene ether resin, wholly aromatic polyester resin, polyether sulfone resin, phenolic resin , polyurethane resin, epoxy resin, etc.
金属としては、例えば、アルミニウム、鉄、ステンレス、錫、鉛、錫鉛合金、銅等が挙げられる。 Examples of the metal include aluminum, iron, stainless steel, tin, lead, tin-lead alloy, and copper.
また金属として金属箔を使用することが好ましく、前記金属箔としては、例えば、アルミニウム箔、鉄箔、ステンレス箔、錫箔、鉛箔、錫鉛合金箔、銅箔等が挙げられる。 Further, it is preferable to use a metal foil as the metal, and examples of the metal foil include aluminum foil, iron foil, stainless steel foil, tin foil, lead foil, tin-lead alloy foil, and copper foil.
無機材としては、例えば、グラスウール、ロックウール、セラミックウール、石膏繊維、炭素繊維、ステンレス繊維、スラグ繊維、シリカアルミナ繊維、アルミナ繊維、シリカ繊維、ジルコニア繊維等が挙げられる。無機繊維層は、前記無機繊維を用いた無機繊維クロスを使用することが好ましい。また無機繊維層に使用する無機繊維は、金属箔をラミネートしたものを使用することが好ましい。 Examples of the inorganic material include glass wool, rock wool, ceramic wool, gypsum fiber, carbon fiber, stainless steel fiber, slag fiber, silica-alumina fiber, alumina fiber, silica fiber, and zirconia fiber. It is preferable that the inorganic fiber layer uses an inorganic fiber cloth using the above-mentioned inorganic fibers. Furthermore, it is preferable that the inorganic fiber used in the inorganic fiber layer be laminated with metal foil.
金属箔ラミネート無機繊維の具体例としては、例えば、アルミニウム箔ラミネートガラスクロス、銅箔ラミネートガラスクロス等がさらに好ましい。 As specific examples of the metal foil laminated inorganic fiber, aluminum foil laminated glass cloth, copper foil laminated glass cloth, etc. are more preferable.
一実施形態では、基材が不織布である。この場合、破断防止などの膨張材保護の点が優れている。 In one embodiment, the substrate is a nonwoven fabric. In this case, it is excellent in terms of protection of the expanding material, such as prevention of breakage.
図２は、図１の耐火性多層シート１を施工したバッテリーモジュール１０の例の略縦断面図である。 FIG. 2 is a schematic vertical cross-sectional view of an example of a battery module 10 in which the fire-resistant multilayer sheet 1 of FIG. 1 is constructed.
本明細書において、「バッテリー」とは、リチウムイオン電池、リチウムイオンポリマー電池、ニッケル・水素電池、リチウム・硫黄電池、ニッケル・カドミウム電池、ニッケル・鉄電池、ニッケル・亜鉛電池、ナトリウム・硫黄電池、鉛蓄電池、空気電池等の二次電池を意味する。 In this specification, "battery" refers to a lithium ion battery, a lithium ion polymer battery, a nickel-metal hydride battery, a lithium-sulfur battery, a nickel-cadmium battery, a nickel-iron battery, a nickel-zinc battery, a sodium-sulfur battery, Refers to secondary batteries such as lead-acid batteries and air batteries.
上記リチウムイオン電池は、セルの形状により、円筒型、角型、ラミネート型に分類される。 The lithium ion batteries are classified into cylindrical, prismatic, and laminate types depending on the shape of the cell.
本明細書において、「バッテリーセル」とは、正極材、負極材、セパレータ、正極端子、負極端子等が外装部材に収容されたバッテリーの構成単位を指す。 In this specification, a "battery cell" refers to a structural unit of a battery in which a positive electrode material, a negative electrode material, a separator, a positive electrode terminal, a negative electrode terminal, etc. are housed in an exterior member.
バッテリーセルが円筒型の場合、正極材、負極材、セパレータ、正極端子、負極端子、絶縁材、ガス排出弁、ガスケット、正極キャップ等が外装缶に収容されているバッテリーの構成単位を指す。 When the battery cell is cylindrical, it refers to the structural unit of the battery in which the positive electrode material, negative electrode material, separator, positive electrode terminal, negative electrode terminal, insulating material, gas discharge valve, gasket, positive electrode cap, etc. are housed in the outer can.
バッテリーセルが角型の場合、正極材、負極材、セパレータ、正極端子、負極端子、絶縁材、ガス排出弁等が外装缶に収容されているバッテリーの構成単位を指す。 When the battery cell is square, it refers to the structural unit of the battery in which the positive electrode material, negative electrode material, separator, positive electrode terminal, negative electrode terminal, insulating material, gas exhaust valve, etc. are housed in the outer can.
バッテリーセルがラミネート型の場合、正極材、負極材、セパレータ、正極端子、負極端子、等が外装フィルムに収容されているバッテリーの構成単位を指す。外装フィルムとしては例えば、ポリエチレンテレフタレートフィルムが積層されたアルミニウムフィルム等が挙げられる。 When the battery cell is a laminate type, it refers to a structural unit of the battery in which a positive electrode material, a negative electrode material, a separator, a positive electrode terminal, a negative electrode terminal, etc. are housed in an exterior film. Examples of the exterior film include an aluminum film laminated with a polyethylene terephthalate film.
本明細書において、「バッテリーモジュール」とは複数のバッテリーセルを筐体に収容したバッテリーの構成単位を指す。「バッテリーパック」とは複数のバッテリーモジュールを筐体に収容したものを指す。バッテリーモジュール及びバッテリーパックの内部には、バッテリーセルの他に、バッテリーセルと電気的に接続される電気接続ケーブル等必要な部材が必要に応じて使用される。 In this specification, the term "battery module" refers to a battery constituent unit in which a plurality of battery cells are housed in a housing. A “battery pack” refers to a case that houses multiple battery modules. Inside the battery module and battery pack, in addition to the battery cells, necessary members such as electrical connection cables that are electrically connected to the battery cells are used as necessary.
図２を参照すると、バッテリーモジュール１０の筐体１２内には複数のバッテリーセル５（図では３個を図示）が互いに離間して垂直方向に延在するように並べて収容されている。隣り合うバッテリーセル５の間には、耐火性多層シート１（及びその熱膨張性耐火シート２）が配置され、耐火性多層シート１（及びその熱膨張性耐火シート２）はバッテリーセル５の一面に取り付けられている。 Referring to FIG. 2, a plurality of battery cells 5 (three are shown in the figure) are housed in the housing 12 of the battery module 10 so as to be spaced apart from each other and arranged in a vertically extending manner. A fire-resistant multilayer sheet 1 (and its thermally expandable fire-resistant sheet 2) is arranged between adjacent battery cells 5, and the fire-resistant multilayer sheet 1 (and its thermally expandable fire-resistant sheet 2) covers one side of the battery cell 5. is attached to.
一つのバッテリーセル５の表面は、通常、ＰＥＴフィルムが積層されたアルミニウムシート又は円筒形状等の金属等で形成されている。バッテリーセル５の少なくとも一面（例えば片面又は対をなす両面）の一部又は全部に熱膨張性耐火シート２を設置する方法としては、例えば、熱膨張性耐火シート２を一つのバッテリーセル５の表面に粘着材を介して又は熱膨張性耐火シート２の自己粘着性により貼り付けて固定する方法や、バッテリーセル５と熱膨張性耐火シート２とを積層した後で枠を用いて固定する方法等が挙げられる。 The surface of one battery cell 5 is usually formed of an aluminum sheet on which a PET film is laminated or a cylindrical metal or the like. As a method for installing the thermally expandable fireproof sheet 2 on a part or all of at least one surface (for example, one side or a pair of both surfaces) of the battery cell 5, for example, the thermally expandable fireproof sheet 2 is installed on the surface of one battery cell 5. A method of fixing the battery cells 5 and the heat-expandable fire-resistant sheet 2 by pasting them through an adhesive or using the self-adhesive properties of the heat-expandable fire-resistant sheet 2, a method of laminating the battery cells 5 and the heat-expandable fire-resistant sheet 2, and then fixing them using a frame, etc. can be mentioned.
このため、熱膨張性耐火シート２はバッテリーの通常の使用時には放熱性に優れ、バッテリーセル５の作動により生じた熱を良好に放散することができる。また、熱膨張性耐火シート２は、異常発熱又は火災等により熱膨張性耐火シート２が加熱されると、比較的低温でも膨張を開始し、火や熱の流路となる空間を閉塞し、膨張圧により隣り合うバッテリーセル５の間を離間させて間隔を確保する。また、熱膨張性耐火シート２は隣り合うバッテリーセル５の間にバッテリー間を離間させる断熱層を形成する。このため、あるバッテリーセル５から隣りのバッテリーセル５への熱伝達又は引火を防止するか又は遅延させることができ、バッテリーの安全性が確保される。 Therefore, the thermally expandable fireproof sheet 2 has excellent heat dissipation properties during normal use of the battery, and can effectively dissipate heat generated by the operation of the battery cells 5. In addition, when the thermally expandable fireproof sheet 2 is heated due to abnormal heat generation or fire, the thermally expandable fireproof sheet 2 starts to expand even at a relatively low temperature, blocking the space that serves as a flow path for fire and heat. Adjacent battery cells 5 are spaced apart by expansion pressure to ensure an interval. Further, the thermally expandable fireproof sheet 2 forms a heat insulating layer between adjacent battery cells 5 to separate the batteries. Therefore, heat transfer or ignition from one battery cell 5 to an adjacent battery cell 5 can be prevented or delayed, and battery safety is ensured.
熱膨張性耐火シート２の寸法は特に限定されず、バッテリーセル５の大きさ及びバッテリーモジュール１０内の空間の大きさに応じて変更され得る。 The dimensions of the thermally expandable fireproof sheet 2 are not particularly limited, and may be changed depending on the size of the battery cell 5 and the size of the space within the battery module 10.
筐体１２は例えば金属製又は樹脂成型品の筐体であるが、これに限定されない。バッテリーセル５及び熱膨張性耐火シート２は図２では平板状の略直方体であり、互いに略平行に配置されている。筐体１２内のバッテリーセル５及び熱膨張性耐火シート２の周囲には空間６が設けられ、また、バッテリーセル５と該バッテリーセル５に隣り合う熱膨張性耐火シート２との間にも空間７が設けられている。これらの空間６，７はバッテリーセル５の放熱のための空気の通路として作用する。例えばバッテリーセル５は作動時に加熱される場合があるが、かかる空間６，７を確保することによりバッテリーセル５をより早く放熱することができる。 The housing 12 is, for example, a metal or resin molded housing, but is not limited thereto. In FIG. 2, the battery cell 5 and the thermally expandable fireproof sheet 2 have a flat plate-like substantially rectangular parallelepiped shape, and are arranged substantially parallel to each other. A space 6 is provided around the battery cell 5 and the thermally expandable fireproof sheet 2 in the housing 12, and a space is also provided between the battery cell 5 and the thermally expandable fireproof sheet 2 adjacent to the battery cell 5. 7 is provided. These spaces 6 and 7 act as air passages for heat radiation of the battery cells 5. For example, the battery cell 5 may be heated during operation, but by securing such spaces 6 and 7, the battery cell 5 can dissipate heat more quickly.
熱膨張性耐火シート２は断熱層として機能し、あるバッテリーセル５から隣りのバッテリーセル５へ熱伝達又は引火するのを防止するか又は遅延させることができ、バッテリーモジュール１０の発火遅延性が向上し、安全性が確保される。 The thermally expandable fireproof sheet 2 functions as a heat insulating layer and can prevent or delay heat transfer or ignition from one battery cell 5 to an adjacent battery cell 5, improving the ignition retardancy of the battery module 10. and safety is ensured.
図３は、図２のバッテリーモジュール１０を備えたバッテリーパック２０の略縦断面図である。バッテリーパック２０の筐体２２内には複数のバッテリーモジュール１０（図では２個を図示）が収容されている。筐体２２は例えば金属製又は樹脂成型品の筐体であるが、これに限定されない。また、隣り合うバッテリーモジュール１０の間には熱膨張性耐火シート２が配置されている。複数のバッテリーモジュール１０が直列又は並列に配置され、円筒型バッテリーを構成する。 FIG. 3 is a schematic vertical cross-sectional view of a battery pack 20 including the battery module 10 of FIG. 2. As shown in FIG. A plurality of battery modules 10 (two are shown in the figure) are housed in the housing 22 of the battery pack 20. The housing 22 is, for example, a metal or resin molded housing, but is not limited thereto. Further, a thermally expandable fireproof sheet 2 is arranged between adjacent battery modules 10. A plurality of battery modules 10 are arranged in series or in parallel to constitute a cylindrical battery.
異常発熱又は火災等により、熱膨張性耐火シート２が加熱されると、熱膨張性耐火シート２は膨張する。これにより、火や熱の流路となる空間を閉塞する。 When the thermally expandable fireproof sheet 2 is heated due to abnormal heat generation, fire, etc., the thermally expandable fireproof sheet 2 expands. This blocks the space that serves as a flow path for fire and heat.
このような構成により、図３のバッテリーパック２０においても、バッテリーセル５の放熱用の空気の通路を確保しつつ、異常発熱又は火災等の高温時には熱膨張性耐火シート２が断熱材として作用することによりバッテリーモジュール１０及びバッテリーパック２０は発火遅延性を発揮できる。バッテリーパックは通常時の放熱性と、高温時の安全性とを兼ね備えることができる。なお、図２及び３において、バッテリーセル５と熱膨張性耐火シート２とは、接触していても良いし、空間を介して隔てられていても良い。また、空間６，７が存在しなくても良い。 With such a configuration, in the battery pack 20 of FIG. 3 as well, the thermally expandable fireproof sheet 2 acts as a heat insulating material during high temperatures such as abnormal heat generation or fire while ensuring an air passage for heat radiation of the battery cells 5. As a result, the battery module 10 and the battery pack 20 can exhibit ignition delay properties. A battery pack can have both heat dissipation properties under normal conditions and safety at high temperatures. In addition, in FIGS. 2 and 3, the battery cell 5 and the thermally expandable fireproof sheet 2 may be in contact with each other, or may be separated from each other with a space between them. Further, the spaces 6 and 7 may not exist.
本発明によれば、バッテリーの熱暴走を防止又は抑制することができるため、そのようなバッテリーを使用する携帯電話及びスマートフォン等の小型電子機器、ノートパソコン、並びに自動車等に優れた耐火性能を付与することができる。 According to the present invention, thermal runaway of batteries can be prevented or suppressed, thereby imparting excellent fire resistance to small electronic devices such as mobile phones and smartphones, notebook computers, automobiles, etc. that use such batteries. can do.
ここまで、本発明の実施形態の熱膨張性耐火シート、バッテリー、バッテリーモジュールを説明したが、本発明はこれに限られず、本発明の技術的思想に基づく以下のような種々の変形が可能である。 Up to this point, the thermally expandable fireproof sheet, battery, and battery module according to the embodiments of the present invention have been described, but the present invention is not limited thereto, and various modifications such as the following based on the technical idea of the present invention are possible. be.
図１において、熱膨張性耐火シート２の片面に基材３が積層されていたが、熱膨張性耐火シート２の両面に基材３が積層されてもよい。あるいは、基材３は省略されてもよい。 In FIG. 1, the base material 3 is laminated on one side of the thermally expandable fireproof sheet 2, but the base material 3 may be laminated on both sides of the thermally expandable fireproof sheet 2. Alternatively, the base material 3 may be omitted.
熱伝導性熱膨張性樹脂組成物は、第１実施形態の熱膨張性耐火シート２のシート以外の形状の成形体に成形してもよい。 The thermally conductive thermally expandable resin composition may be molded into a molded body having a shape other than the thermally expandable fireproof sheet 2 of the first embodiment.
熱伝導性熱膨張性樹脂組成物を、吹付け、噴霧又は塗布等によりバッテリーセル５上に直接施したり、離型紙等に吹付け、噴霧又は塗布等により成形、製造してもよい。 The thermally conductive thermally expandable resin composition may be applied directly onto the battery cell 5 by spraying, spraying, or coating, or may be molded and manufactured by spraying, spraying, coating, etc. onto release paper.
例えば、熱伝導性熱膨張性樹脂組成物は、上記の実施形態の熱膨張性耐火シート２の代わりに、図４に示すように、バッテリーセル５の周囲を被覆する熱膨張性耐火コーティングの形態で設けられてもよい。例えば、バッテリーセル５の周囲が熱伝導性熱膨張性樹脂組成物からなる熱膨張性耐火コーティング２'により被覆されてもよい。また、図４では熱膨張性耐火コーティング２'はバッテリーセル５の外表面の全体を被覆しているが、バッテリーセル５の一面を被覆してもよく、又は対をなす２面を被覆してもよい。バッテリーセル５から別のバッテリーセル５への伝熱又は引火を抑制又は防止する程度にバッテリーセル５の表面が熱膨張性耐火コーティング２'で被覆されていればよい。熱伝導性熱膨張性樹脂組成物を、吹付け、噴霧又は塗布等によりバッテリーセル５の表面に施して硬化させるか、金型、枠材等の容器へ液状の熱伝導性熱膨張性樹脂組成物を入れ、かかる容器中にバッテリーセル５を浸漬することにより、熱膨張性樹脂組成物からなる熱膨張性耐火コーティング２'を備えたバッテリーセル５を得ることができる。 For example, the thermally conductive thermally expandable resin composition is in the form of a thermally expandable fireproof coating that covers the periphery of the battery cell 5, as shown in FIG. 4, instead of the thermally expandable fireproof sheet 2 of the above embodiment. may be provided. For example, the periphery of the battery cell 5 may be covered with a thermally expandable fireproof coating 2' made of a thermally conductive thermally expandable resin composition. Further, in FIG. 4, the thermally expandable fireproof coating 2' covers the entire outer surface of the battery cell 5, but it may also cover one side of the battery cell 5, or it may cover two opposing sides. Good too. It is sufficient that the surface of the battery cell 5 is coated with the thermally expandable fire-resistant coating 2' to the extent that heat transfer from one battery cell 5 to another battery cell 5 or ignition is suppressed or prevented. The thermally conductive thermally expandable resin composition is applied to the surface of the battery cell 5 by spraying, spraying, coating, etc. and cured, or the liquid thermally conductive thermally expandable resin composition is applied to a container such as a mold or a frame material. By immersing the battery cell 5 in such a container, the battery cell 5 provided with the heat-expandable fire-resistant coating 2' made of the heat-expandable resin composition can be obtained.
このようなバッテリーセル５を備えたバッテリーモジュール１０を図５に示す。このような構成でも、通常時は熱膨張性耐火コーティング２'がバッテリーセル５からの放熱を促し、異常発熱又は火災等により、バッテリーセル５が加熱されると、熱膨張性耐火コーティング２'はバッテリーセル５の周囲で膨張して、バッテリーセル５の間の空間７を閉塞し、断熱材として作用する。このため、あるバッテリーセル５から隣りのバッテリーセル５への伝熱又は引火を防止するか又は遅延させることができ、バッテリーモジュール１０の安全性が確保される。 A battery module 10 including such a battery cell 5 is shown in FIG. Even with this configuration, the thermally expandable fireproof coating 2' normally promotes heat dissipation from the battery cell 5, and when the battery cell 5 is heated due to abnormal heat generation or fire, the thermally expandable fireproof coating 2' It expands around the battery cells 5, closes the spaces 7 between the battery cells 5, and acts as a heat insulator. Therefore, heat transfer or ignition from one battery cell 5 to an adjacent battery cell 5 can be prevented or delayed, and the safety of the battery module 10 is ensured.
熱膨張性耐火シート２は、図１に示すバッテリーセル５の一面に施された構成に限られず、図６に示すように各バッテリーセル５の２つの側面に設けられてもよい。また、各バッテリーセル５の４面、又は６面全部に設けられてもよい。 The thermally expandable fireproof sheet 2 is not limited to the configuration in which it is provided on one side of the battery cell 5 shown in FIG. 1, but may be provided on two sides of each battery cell 5 as shown in FIG. Further, it may be provided on all four or six sides of each battery cell 5.
図７に示すように、熱膨張性耐火シート２は、バッテリーモジュール１０の内側、特には筐体１２の内表面１３に設けられていてもよい。 As shown in FIG. 7, the thermally expandable fireproof sheet 2 may be provided inside the battery module 10, particularly on the inner surface 13 of the casing 12.
図８に示すように、熱膨張性耐火シート２は、バッテリーモジュール１０の外側、特には筐体１２の外表面１４に設けられていてもよい。 As shown in FIG. 8, the thermally expandable fireproof sheet 2 may be provided on the outside of the battery module 10, particularly on the outer surface 14 of the casing 12.
図３において、熱膨張性耐火シート２は、バッテリーパック２０を構成する筐体２２の内表面又は外表面、バッテリーモジュール１０とバッテリーパック２０との間の空間等に設けられてもよい。 In FIG. 3, the thermally expandable fireproof sheet 2 may be provided on the inner or outer surface of the casing 22 constituting the battery pack 20, the space between the battery module 10 and the battery pack 20, or the like.
上記のいずれかの場所に熱膨張性耐火シート２を設けることで熱膨張性耐火シート２が加熱されると、熱膨張性耐火シート２は断熱材として作用し、火及び熱の流路となる空間を閉塞する。火及び熱の流路となる空間としては、バッテリーセル５とバッテリーセル５との間の空間、バッテリーセル５とバッテリーモジュール１０の筐体１２との間の空間、バッテリーモジュール１０とバッテリーモジュール１との間の空間、バッテリーモジュール１０とバッテリーパック２０の筐体２２との間の空間等が挙げられる。 By providing the thermally expandable fireproof sheet 2 in any of the above locations, when the thermally expandable fireproof sheet 2 is heated, the thermally expandable fireproof sheet 2 acts as a heat insulating material and becomes a flow path for fire and heat. Block the space. The spaces that serve as flow paths for fire and heat include the space between the battery cells 5, the space between the battery cell 5 and the housing 12 of the battery module 10, and the space between the battery module 10 and the battery module 1. Examples include a space between the battery module 10 and the housing 22 of the battery pack 20, and the like.
以下に実施例を挙げて本発明をより具体的に説明するが、本発明はこれらに限定されない。 EXAMPLES The present invention will be described in more detail with reference to Examples below, but the present invention is not limited thereto.
１．熱膨張性耐火シートの製造
実施例１～５及び比較例１～２
表１（質量部で示す）に示した樹脂成分、熱膨張性黒鉛、無機充填剤、及びリン化合物を含有する熱膨張性耐火樹脂組成物を、一軸押出機に供給し、１５０℃で押出成形し、厚さ１．０ｍｍの実施例１～５及び比較例１～２の熱膨張性耐火シートを得た。各成分は以下のものを使用した。
1. Production of thermally expandable fireproof sheets Examples 1 to 5 and Comparative Examples 1 to 2
A thermally expandable fire-resistant resin composition containing the resin components shown in Table 1 (shown in parts by mass), thermally expandable graphite, an inorganic filler, and a phosphorus compound was fed to a single screw extruder and extruded at 150°C. Then, thermally expandable fireproof sheets of Examples 1 to 5 and Comparative Examples 1 to 2 having a thickness of 1.0 mm were obtained. The following components were used.
エチレン－酢酸ビニル（ＥＶＡ）樹脂 製品名 エバフレックスＥＶ４６０、三井デュポンポリケミカル株式会社
ブチルゴム 製品名 Ｂｕｔｙｌ０６５ ＪＳＲ社
熱膨張性黒鉛 製品名 ＡＤＴ５０１ ＡＤＴ社製
熱膨張性黒鉛 製品名 ＣＡ－６０ 日本化成社製
無機充填剤 炭酸カルシウム 製品名 ホワイトンＢＦ－３００ 備北粉化株式会社
リン化合物 製品名 ＡＰ４２２ ポリリン酸アンモニウム クラリアント社
Ethylene-vinyl acetate (EVA) resin Product name Evaflex EV460, Mitsui DuPont Polychemical Co., Ltd. Butyl rubber Product name Butyl065 JSR Co., Ltd. Thermal expandable graphite Product name ADT501 ADT Co., Ltd. Thermal expandable graphite Product name CA-60 Nippon Kasei Co., Ltd. Inorganic Filler Calcium carbonate Product name Whiten BF-300 Bihoku Funka Co., Ltd. Phosphorus compound Product name AP422 Ammonium polyphosphate Clariant
２．熱暴走防止の評価
（膨張圧力）
２５mm角にカットした耐火材シートをホットプレートの上に置き、ホットプレートを固定した台にデジタルフォースゲージ（株式会社イマダ ZTA-2500N）を取り付けた。デジタルフォースゲージの先端に取り付けられた圧縮用アタッチメントを耐火性シートに対しシートの上面で接触させた。次に、ホットプレートを５００℃に設定して加熱を開始し、加熱開始から１分経過後の最大荷重をデジタルフォースゲージにより読み取り、該最大荷重を圧縮用アタッチメントの断面積で除することにより膨張圧力を算出した。
（膨張倍率）
５００℃にホットプレートを設定し、２５mm角にカットした耐火材をホットプレートの上に置き、１分経過後、（加熱後の試験片の厚さ）／（加熱前の試験片の厚さ）から膨張倍率を算出した。
2. Evaluation of thermal runaway prevention (expansion pressure)
A refractory sheet cut into 25 mm squares was placed on a hot plate, and a digital force gauge (IMADA ZTA-2500N) was attached to the table to which the hot plate was fixed. A compression attachment attached to the tip of the digital force gauge was brought into contact with the fireproof sheet on the top surface of the sheet. Next, set the hot plate to 500℃, start heating, read the maximum load after 1 minute has passed from the start of heating, and expand by dividing the maximum load by the cross-sectional area of the compression attachment. The pressure was calculated.
(Expansion magnification)
Set the hot plate at 500℃, place the refractory material cut into 25 mm squares on the hot plate, and after 1 minute, (thickness of the test piece after heating) / (thickness of the test piece before heating) The expansion ratio was calculated from
（結果）
表１に示すように、実施例１～５の熱膨張性耐火シートは膨張圧力及び膨張倍率が高く、比較例１～２の熱膨張性耐火シートは膨張圧力及び膨張倍率が実施例１～５の熱膨張性耐火シートに比べて低かった。
(result)
As shown in Table 1, the thermally expandable fireproof sheets of Examples 1 to 5 have high expansion pressures and expansion ratios, and the thermally expandable fireproof sheets of Comparative Examples 1 to 2 have high expansion pressures and expansion ratios of Examples 1 to 5. It was lower than that of thermally expandable fireproof sheet.
実施例１～５の熱膨張性耐火シートは十分に断熱できる断熱層を形成することで、隣接するバッテリーセルの温度上昇を緩和可能であることが示された。 It was shown that the thermally expandable fireproof sheets of Examples 1 to 5 can alleviate the temperature rise of adjacent battery cells by forming a heat insulating layer that can sufficiently insulate.
以上、本発明の実施形態及び実施例について具体的に説明したが、本発明は、上述の実施形態に限定されるものではなく、本発明の技術的思想に基づく各種の変形が可能である。 Although the embodiments and examples of the present invention have been specifically described above, the present invention is not limited to the above-described embodiments, and various modifications can be made based on the technical idea of the present invention.
例えば、上述の実施形態及び実施例において挙げた構成、方法、工程、形状、材料及び数値などはあくまでも例に過ぎず、必要に応じてこれと異なる構成、方法、工程、形状、材料及び数値などを用いてもよい。 For example, the configurations, methods, processes, shapes, materials, numerical values, etc. mentioned in the above-mentioned embodiments and examples are merely examples, and different configurations, methods, processes, shapes, materials, numerical values, etc. may be used as necessary. may also be used.
また、上述の実施形態の構成、方法、工程、形状、材料及び数値などは、本発明の主旨を逸脱しない限り、互いに組み合わせることが可能である。 Moreover, the configurations, methods, processes, shapes, materials, numerical values, etc. of the above-described embodiments can be combined with each other without departing from the gist of the present invention.
２・・・熱膨張性耐火シート、２' …熱膨張性耐火コーティング、５…バッテリーセル、１０…バッテリーモジュール。 2... Heat-expandable fireproof sheet, 2'... Heat-expandable fireproof coating, 5... Battery cell, 10... Battery module.
Claims (4)
前記熱膨張性耐火樹脂組成物は、樹脂成分、熱膨張性黒鉛、無機充填剤及びリン化合物を、それぞれ、前記樹脂成分１００質量部に対して、前記熱膨張性黒鉛を１０～３５０質量部、前記無機充填剤を１０～１０００質量部、前記リン化合物を１０～１０００質量部、含有し、
前記基材の厚みが５μｍ～１ｍｍであり、
前記熱膨張性樹脂組成物の膨張圧力が０．０５ＭＰａ以上であることを特徴とする、バッテリーセル保護用耐火多層シート。 A fire-resistant multilayer sheet for protecting battery cells in which a heat-expandable fire-resistant sheet made of a heat-expandable fire-resistant resin composition and a base material are laminated,
The heat-expandable fire-resistant resin composition includes a resin component, heat-expandable graphite, an inorganic filler, and a phosphorus compound, each of which contains 10 to 350 parts by mass of the heat-expandable graphite, based on 100 parts by mass of the resin component. Containing 10 to 1000 parts by mass of the inorganic filler and 10 to 1000 parts by mass of the phosphorus compound,
The thickness of the base material is 5 μm to 1 mm,
A fire-resistant multilayer sheet for protecting battery cells, characterized in that the expansion pressure of the thermally expandable resin composition is 0.05 MPa or more.
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| CN114269832A (en) * | 2019-08-26 | 2022-04-01 | 积水化学工业株式会社 | Heat-expandable refractory |
| JP7032360B2 (en) * | 2019-08-27 | 2022-03-08 | イビデン株式会社 | Insulation sheet for assembled battery and assembled battery |
| KR20210109714A (en) * | 2020-02-27 | 2021-09-07 | 주식회사 엘지에너지솔루션 | Battery module having a structure capable of rapid cooling and the Energy Storage System comprising the same |
| JPWO2021171782A1 (en) | 2020-02-28 | 2021-09-02 | ||
| GB2598534A (en) * | 2020-03-18 | 2022-03-09 | Cummins Inc | Battery pack antipropagation techniques |
| KR20210120700A (en) | 2020-03-27 | 2021-10-07 | 주식회사 엘지에너지솔루션 | Battery pack and energy storage system comprising the battery pack |
| US20220393282A1 (en) * | 2020-04-24 | 2022-12-08 | Teijin Limited | Battery box component wherein fiber-reinforced plastic is provided with refractory layer, and method for producing battery box component |
| WO2022186289A1 (en) | 2021-03-03 | 2022-09-09 | 旭化成アドバンス株式会社 | Battery unit |
| KR102636482B1 (en) * | 2021-06-17 | 2024-02-14 | 주식회사 인지디스플레이 | Eco friendly fireproof coating composition and spray coating method, battery module coated with eco friendly fireproof coating composition |
| CN113488721A (en) * | 2021-07-06 | 2021-10-08 | 孚能科技(赣州)股份有限公司 | Battery system and vehicle |
| CN116423939B (en) * | 2023-04-28 | 2023-11-03 | 武汉长盈通热控技术有限公司 | Rapid heat absorption thermal runaway protection material and preparation method thereof |
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