WO2024082911A1 - 一种电池用阻燃隔热防火材料 - Google Patents

一种电池用阻燃隔热防火材料 Download PDF

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WO2024082911A1
WO2024082911A1 PCT/CN2023/120328 CN2023120328W WO2024082911A1 WO 2024082911 A1 WO2024082911 A1 WO 2024082911A1 CN 2023120328 W CN2023120328 W CN 2023120328W WO 2024082911 A1 WO2024082911 A1 WO 2024082911A1
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glass powder
parts
flame retardant
flame
oxide
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PCT/CN2023/120328
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English (en)
French (fr)
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丁凯
施晓丽
庞佩燕
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浙江葆润应用材料有限公司
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Priority to EP23844158.8A priority Critical patent/EP4379128A1/en
Publication of WO2024082911A1 publication Critical patent/WO2024082911A1/zh

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    • D—TEXTILES; PAPER
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    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D—TEXTILES; PAPER
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
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    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/45—Oxides or hydroxides of elements of Groups 3 or 13 of the Periodic Table; Aluminates
    • D—TEXTILES; PAPER
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/47—Oxides or hydroxides of elements of Groups 5 or 15 of the Periodic Table; Vanadates; Niobates; Tantalates; Arsenates; Antimonates; Bismuthates
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/76—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon oxides or carbonates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/61—Types of temperature control
    • H01M10/613—Cooling or keeping cold
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/658—Means for temperature control structurally associated with the cells by thermal insulation or shielding
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/30—Flame or heat resistance, fire retardancy properties
    • 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 invention relates to a silicone rubber flame retardant, heat insulating and fireproof material, in particular to a flame retardant, heat insulating and fireproof material for a new energy vehicle battery pack.
  • the probability of thermal runaway of a battery is one in ten million.
  • the probability of thermal runaway of the battery pack rises to one in ten thousand.
  • thermal runaway of one battery may cause thermal runaway of the entire battery pack.
  • the combustion temperature can reach 1500°C, and it also has a strong impact, which is a great challenge to the safety of electric vehicles.
  • ceramic silicone rubber is currently the most suitable material solution for new energy vehicle battery packs to prevent continuous thermal runaway of the battery cells and avoid ignition of adjacent modules.
  • Ceramic silicone rubber is a kind of ceramic polymer composite material. This material has the excellent properties of ordinary polymers at room temperature, and can form a dense ceramic structure at high temperature, thus having ceramic properties. Due to the high bond energy of Si-O bonds in silicone rubber, silicone rubber itself has good thermal stability. In addition, when burning under high-temperature flames, Si-O bonds will be transformed into continuous, anti-oxidation, insulating network-like SiO 2 ash covering the surface of the battery core, thereby effectively preventing further flame erosion. In addition, the smoke generated by the silicone rubber matrix during the combustion process is mainly CO 2 and H 2 O produced by the combustion of side chain groups, without the generation of toxic gases, and will not pollute the environment. The use of organosilicon polymers to prepare ceramic silicone rubber has unique advantages in terms of process and raw material selection, as well as in the high temperature resistance and mechanical properties of the ceramic products.
  • the main principle of ceramic silicone rubber flame retardant, heat insulation and fireproof is to improve the thermal stability of silicone rubber by adding catalysts, heat stabilizers, refractory fillers, glass powder, etc., and promote the formation and stability of the ceramic layer.
  • the specific process of ceramicization of ceramic silicone rubber after combustion is as follows: when encountering ablation or high temperature, the silicone rubber matrix first decomposes into amorphous SiO 2 and produces pores of varying sizes.
  • the low-melting-point glass powder also known as porcelain powder, porcelain flux
  • the low-melting-point glass powder first gradually melts, and liquid phase substances appear in the silicone rubber system, connecting the amorphous SiO 2 produced by the matrix and the temperature-resistant porcelain filler (such as mica, kaolin, wollastonite, etc.), forming a "low eutectic mixture" at the boundary of the filler, which is called eutectic reaction.
  • the low eutectic mixture acts as a bridge between amorphous SiO 2 and the filler, so that it remains in its original state at the ignition temperature.
  • Chinese patent CN110845850A discloses a ceramic halogen-free flame-retardant silicone rubber and its preparation method.
  • Chinese patent CN107286636A discloses a low-smoke flame-retardant ceramic thermoplastic polyurethane elastomer composite material and its preparation method and application.
  • Chinese patent CN202111191443.X discloses a ceramic flame-retardant heat-insulating fireproof material and its preparation method and application. The above patents all disclose ceramic silicone rubber and its application method, but they still have defects in the protection of battery packs.
  • the reaction temperatures of various components of ceramic silicone rubber vary greatly when they are burned at high temperatures.
  • silicone rubber begins to decompose to form amorphous SiO 2 at 350°C, and many pores of different sizes are generated on its surface; muscovite (a common ceramic filler) begins to decompose after 700°C; ordinary glass powder with different components has a melting point between 300°C and 700°C.
  • the combustion temperature will gradually reach 1500°C and be accompanied by thermal shock, which causes several problems.
  • the melting point of the glass powder is high (greater than 700°C), silicone rubber cannot form a continuous, complete, and dense ceramic structure with ceramic fillers and glass powder in the low temperature range (350°C-700°C), and the amorphous SiO 2 with pores is easily destroyed by the impact force and burned through. If the melting point of the glass powder is low (less than 700°C), in the high temperature range (above 1200°C), the glass powder will volatilize in the gas phase, and holes will be generated in the ceramic skeleton structure, which will reduce the density of the ceramic structure and easily be burned through by thermal shock.
  • the existing ceramic silicone rubber disclosed herein only adds one type of glass powder with an initial melting temperature, that is, the glass powder in the existing material cannot completely cover the melting temperature range of 300°C-1500°C, and the above-mentioned problems always occur.
  • the present invention aims at the deficiencies in the prior art and provides a flame-retardant, heat-insulating and fireproof material for batteries.
  • the present invention adds a variety of glass powders with different melting temperature ranges, so that the fireproof material always has molten glass powder inside when burning at 300°C to 1500°C.
  • These molten glass powders can timely fill the holes and cracks in the ceramic layer formed by the eutectic of SiO2 ash and refractory filler at different temperatures, and ensure the continuity, integrity and density of the ceramic layer as much as possible, so that the fireproof material has the characteristics of rapid ceramic formation at low temperature and high temperature resistance above 1500°C.
  • the existing materials have a single melting temperature range of glass powder, the high melting point glass powder cannot be melted in time to fill the gaps in the ceramic layer at low temperature, and the low melting point glass powder is easily gasified at high temperature to cause holes in the ceramic phase, the structural density is reduced, and it is easy to be burned through is solved.
  • a flame retardant, heat-insulating and fireproof material for a battery comprising a flame retardant, heat-insulating layer and an impact-resistant layer, wherein the flame retardant, heat-insulating layer is coated on the surface of the impact-resistant layer, and the thickness ratio of the flame retardant, heat-insulating layer to the impact-resistant layer is (2 ⁇ 10):1, and the flame retardant, heat-insulating layer comprises silicone rubber, a ceramic filler, a flame retardant and an additive, and also comprises a plurality of glass powders with different initial melting temperatures, and the melting temperature range of the plurality of glass powders covers 300°C to 1500°C.
  • the impact-resistant layer is glass fiber cloth.
  • the impact-resistant layer is composited by multiple layers of glass fiber cloth.
  • the glass powder may include glass powder A having a molten temperature range of 300° C. to 700° C. and glass powder B having a molten temperature range of 700° C. to 1500° C.
  • the ratio of glass powder A to glass powder B is 1-2:1-3 by mass.
  • the glass powder may include glass powder C with a molten temperature range of 300° C. to 550° C., glass powder D with a molten temperature range of 550° C. to 900° C., and glass powder E with a molten temperature range of 900° C. to 1500° C.
  • the ratio of glass powder C, glass powder D and glass powder E is 1 ⁇ 2:1 ⁇ 2:2 ⁇ 3.
  • the glass powder may include glass powder F with a molten temperature range of 300°C-800°C, glass powder G with a molten temperature range of 600°C-1000°C, glass powder H with a molten temperature range of 700°C-1250°C, and glass powder I with a molten temperature range of 1000°C to 1500°C.
  • the ratio of glass powder F, glass powder G, glass powder H to glass powder I is 1 ⁇ 3:1 ⁇ 3:1 ⁇ 3:1 ⁇ 3.
  • the glass powder raw material may include one or more of silicon oxide, boron oxide and metal oxides.
  • the metal oxides include one or more of lead oxide, aluminum oxide, lithium oxide, zinc oxide, titanium oxide, magnesium oxide, vanadium oxide, barium oxide, sodium oxide, calcium oxide, strontium oxide, tin oxide, bismuth oxide and antimony oxide.
  • the glass powder raw material also includes stannous fluoride.
  • optional ingredients include 40 to 60 parts of silicone rubber, 20 to 30 parts of porcelain-forming filler, 15 to 25 parts of flame retardant, 2 to 10 parts of glass powder, and 2 to 5 parts of additives.
  • the flame retardant, heat insulating and fireproof material will not burn through for at least 30 minutes under the impact of a flame at 1500°C.
  • Glass powder is generally made by mixing SiO 2 , B 2 O 3 , Al 2 O 3 , PbO and some metal oxides in a certain proportion, melting, water quenching and crushing. Adjusting the proportion of different components and adding different metal oxides will make the initial melting temperature and melting temperature range of glass powder slightly different.
  • the initial melting temperature of the glass powder in the existing materials is mostly selected between 300°C and 700°C, so that it melts after the silicone rubber begins to decompose and fills the pores as soon as possible.
  • the melting temperature of the glass powder between 300°C and 700°C basically does not exceed 1000°C, that is, when the burning temperature is higher than the melting temperature zone of the glass powder, the glass powder volatilizes in the gas phase, which will not only produce holes in the formed ceramic layer, but also reduce the density of the overall structure of the ceramic layer.
  • the existing fireproof materials are likely to be burned through by flames of 1000°C to 1500°C, causing the fireproof materials to fail.
  • thermal shock will occur during the entire combustion process, which can easily cause cracks in the ceramic layer. If the cracks are not remedied after they appear, the entire fireproof material will fail. That is, during the entire process of the fireproof material being burned, molten glass powder is needed to fill the holes and cracks at any time until the ceramic layer is continuous, complete and dense at 1500°C.
  • the present application adopts a mixture of glass powders with various initial melting temperatures to have a variety of melting temperature ranges, covering 300°C-1500°C. No matter how high the temperature at which the fireproof material is burned, there is always glass powder in a molten state to fill the holes and cracks in the ceramic layer, ensuring the continuity, integrity and density of the ceramic layer as much as possible, so that the ceramic layer can play the greatest role in heat insulation and flame retardancy.
  • the present invention adds a variety of glass powders with different melting temperature ranges, so that there is always molten glass powder in the temperature range of 300°C to 1500°C, so that the molten glass powder can timely fill the holes and cracks on the ceramic layer at different temperatures, and ensure the continuity, integrity and density of the ceramic layer as much as possible, so that the flame-retardant, heat-insulating and fire-proof materials for batteries have the characteristics of rapid ceramic formation at low temperature and high temperature resistance of about 1500°C.
  • Figure 1 is a physical picture of the flame retardant, heat insulating and fireproof material for batteries prepared by Example 17 of the present invention, which presents a complete ceramic form after being subjected to a 15-minute, 1500°C flame impact, and 5 standard atmospheres deflagration test.
  • Figure 2 is a physical picture of the flame retardant, heat insulating and fireproof material for batteries prepared by Example 17 of the present invention, which shows a ceramic crack morphology after being subjected to a 15-minute, 1500°C flame impact and 7 standard atmospheres deflagration test.
  • Example 3 is a physical picture of the flame retardant, heat insulating and fireproof material for batteries prepared in Example 17 of the present invention, which shows a ceramic breakdown morphology after being subjected to a 15-minute, 1500° C. flame impact and 10 standard atmospheres deflagration test.
  • the organic silicone rubber is any one of liquid silicone rubber, methyl vinyl silicone rubber or methyl phenyl vinyl silicone rubber, or a combination of at least two thereof.
  • the organic silicone rubber is methyl vinyl silicone rubber: 1103, sourced from Guangzhou Siyou New Material Technology Co., Ltd. In practical applications, it is not limited to methyl vinyl silicone rubber.
  • the ceramic filler is any one of muscovite, phlogopite, kaolin, brucite and talc, or a combination of at least two thereof.
  • the ceramic filler is muscovite, which is sourced from Guangdong Yongfeng Chemical Co., Ltd. In practical applications, it is not limited to muscovite.
  • the incremental filler is any one of diatomite, wollastonite, calcium carbonate and fumed silica or a combination of at least two thereof.
  • the incremental filler includes diatomite, sourced from Guangzhou Haozhao Chemical Co., Ltd.; calcium carbonate, 325-6250 (mesh), sourced from Dongguan Xinke New Materials Co., Ltd.; nano-silicon dioxide, KS-8200, sourced from Jinan Kasong Chemical Co., Ltd.
  • the mass ratio of diatomite, calcium carbonate and nano-silicon dioxide is 0.8:1:3, and is not limited to the mixture of the above materials in practical applications.
  • the flame retardant is any one of antimony trioxide, aluminum hydroxide, magnesium hydroxide, phosphorus-containing inorganic flame retardant, boron-containing inorganic flame retardant and phosphorus-containing organic flame retardant or a combination of at least two.
  • the flame retardant includes aluminum hydroxide, Hefei Zhongke Flame Retardant New Material Co., Ltd.; phosphorus-containing inorganic flame retardant, Shijiazhuang Xinsheng Chemical Co., Ltd.; phosphorus-containing organic flame retardant, Zhengzhou Hanshuo Chemical Raw Materials Co., Ltd.
  • the mass ratio of aluminum hydroxide, phosphorus-containing inorganic flame retardant and phosphorus-containing organic flame retardant is 3:0.9:1.3, and is not limited to the mixture of the above materials in practical applications.
  • the auxiliary agent includes a silane coupling agent, silicone oil and a vulcanizing agent.
  • the vulcanizing agent is one of benzoyl peroxide, tert-butyl perbenzoate, di-tert-butyl peroxide, diisopropylbenzene peroxide, 2,5-dimethyl-2,5-di-tert-butyl peroxide hexane, and platinum vulcanizing agent.
  • the auxiliary agents are silane coupling agents and silicone oil, Jiangsu Quanli Chemical Co., Ltd.; the vulcanizing agent is benzoyl peroxide.
  • the mass ratio of silane coupling agent, silicone oil and benzoyl peroxide is 0.5:5:1.8, which is not limited to the mixture of the above materials in practical applications.
  • the glass powder is any one of silicon oxide, boron oxide and metal oxides or a combination of at least two thereof.
  • the metal oxide is any one of lead oxide, aluminum oxide, lithium oxide, zinc oxide, titanium oxide, magnesium oxide, vanadium oxide, barium oxide, sodium oxide, calcium oxide, strontium oxide, tin oxide, bismuth oxide and antimony oxide or a combination of at least two thereof.
  • Some glass powders also include stannous fluoride.
  • Glass powder has a variety of initial melting temperatures and molten temperature coverage ranges depending on the composition and ratio. In the present application, the molten temperature coverage range only means that the glass powder is molten within this range. The two end point temperatures are not melting points and boiling points. The glass powder can also be molten outside the temperature coverage range.
  • the glass powder is provided by Guangzhou Yifeng Chemical Technology Co., Ltd. according to the applicant's requirements, or is prepared by the applicant himself.
  • the glass powder A comprises SnF 2 , P 2 O 5 , SiO 2 , Sb 2 O 3 , and Bi 2 O 3 , and comprises, by mass, 40 to 50 parts of SnF 2 , 35 to 45 parts of P 2 O 5 , 1 to 7 parts of SiO 2 , 1 to 7 parts of Sb 2 O 3 , and 1 to 7 parts of Bi 2 O 3 .
  • the glass powder A comprises 45 parts of SnF 2 , 40 parts of P 2 O 5 , 5 parts of SiO 2 , 5 parts of Sb 2 O 3 , and 5 parts of Bi 2 O 3 .
  • the melting temperature range of the glass powder A covers 300° C. to 700° C. In practical applications, regardless of the composition of the glass powder A, it is only necessary that the melting temperature range of the glass powder A covers 300° C. to 700° C. The above is only an example of the composition of the glass powder A.
  • the components of glass powder B include SiO 2 , B 2 O 3 , and PbO. In parts by mass, the components include 25 to 35 parts of SiO 2 , 10 to 15 parts of B 2 O 3 , and 15 to 25 parts of PbO.
  • glass powder B includes 30 parts of SiO 2 , 11 parts of B 2 O 3 , and 22 parts of PbO.
  • the melting temperature range of glass powder B covers 700°C to 1500°C. In practical applications, regardless of the components of glass powder B, it is only necessary that the melting temperature range of glass powder B covers 700°C to 1500°C. The above is only an example of the components of glass powder B.
  • the glass powder C comprises SnF 2 , P 2 O 5 , V 2 O 5 , Sb 2 O 3 , and Bi 2 O 3 , and comprises 45 to 55 parts of SnF 2 , 30 to 40 parts of P 2 O 5 , 1 to 7 parts of V 2 O 5 , 1 to 7 parts of Sb 2 O 3 , and 1 to 7 parts of Bi 2 O 3 , by mass.
  • the glass powder C comprises 50 parts of SnF 2 , 35 parts of P 2 O 5 , 5 parts of V 2 O 5 , 5 parts of Sb 2 O 3 , and 5 parts of Bi 2 O 3 .
  • the melting temperature range of the glass powder C covers 300° C. to 550° C. In practical applications, regardless of the composition of the glass powder C, it is only necessary that the melting temperature range of the glass powder C covers 300° C. to 550° C. The above is only an example of the composition of the glass powder C.
  • the glass powder D comprises SiO 2 , TiO 2 , B 2 O 3 , and PbO, and in parts by mass, 10 to 15 parts of SiO 2 , 1 to 5 parts of TiO 2 , 10 to 15 parts of B 2 O 3 , and 15 to 20 parts of PbO.
  • the glass powder D comprises 14 parts of SiO 2 , 2 parts of TiO 2 , 12 parts of B 2 O 3 , and 17 parts of PbO.
  • the melting temperature range of the glass powder D covers 550° C. to 900° C. In practical applications, regardless of the composition of the glass powder D, it is only necessary that the melting temperature range of the glass powder D covers 550° C. to 900° C. The above is only an example of the composition of the glass powder D.
  • the glass powder E comprises SiO 2 and PbO, and comprises 30 to 40 parts of SiO 2 and 20 to 25 parts of PbO by weight. Optionally, the glass powder E comprises 35 parts of SiO 2 and 20 parts of PbO.
  • the melting temperature range of the glass powder E covers 900°C to 1500°C. In practical applications, regardless of the composition of the glass powder E, it is only necessary that the melting temperature range of the glass powder E covers 900°C to 1500°C. The above is only an example of the composition of the glass powder E.
  • the glass powder F comprises SnF2 , P2O5 , SiO2 , Bi2O3 and V2O5 . In parts by mass, it comprises 35 to 45 parts of SnF2, 35 to 45 parts of P2O5 , 1 to 7 parts of V2O5 , 5 to 15 parts of SiO2 and 1 to 7 parts of Bi2O3 .
  • the glass powder F comprises 40 parts of SnF2 , 40 parts of P2O5 , 5 parts of V2O5 , 10 parts of SiO2 and 5 parts of Bi2O3 .
  • the melting temperature range of the glass powder F covers 300°C to 800°C. In practical applications, no matter what the composition of the glass powder F is, it is only necessary that the melting temperature range of the glass powder F covers 300°C to 800°C. The above is only an example of the composition of the glass powder F.
  • the glass powder G comprises SiO 2 , TiO 2 , B 2 O 3 , and PbO, and in parts by mass, 10 to 20 parts of SiO 2 , 7 to 13 parts of TiO 2 , 10 to 15 parts of B 2 O 3 , and 10 to 15 parts of PbO.
  • the glass powder G comprises 15 parts of SiO 2 , 10 parts of TiO 2 , 13 parts of B 2 O 3 , and 12 parts of PbO.
  • the melting temperature range of the glass powder G covers 600°C-1000°C. In practical applications, regardless of the composition of the glass powder G, it is only necessary that the melting temperature range of the glass powder G covers 600°C-1000°C. The above is only an example of the composition of the glass powder G.
  • the components of glass powder H include SiO 2 , B 2 O 3 , TiO 2 , and PbO. In parts by mass, it includes 15 to 20 parts of SiO 2 , 10 to 15 parts of TiO 2 , 10 to 20 parts of B 2 O 3 , and 15 to 25 parts of PbO.
  • glass powder H includes 17 parts of SiO 2 , 12 parts of TiO 2 , 15 parts of B 2 O 3 , and 20 parts of PbO.
  • the melting temperature range of glass powder H covers 700°C-1250°C. In practical applications, regardless of the components of glass powder H, it is only necessary that the melting temperature range of glass powder H covers 700°C-1250°C. The above is only an example of the components of glass powder H.
  • the glass powder I comprises SiO 2 and PbO. In parts by mass, it comprises 25 to 35 parts of SiO 2 and 10 to 15 parts of PbO. Optionally, the glass powder I comprises 30 parts of SiO 2 and 13 parts of PbO.
  • the melting temperature range of the glass powder I covers 1000°C to 1500°C. In practical applications, regardless of the composition of the glass powder I, it is only necessary that the melting temperature range of the glass powder I covers 1000°C to 1500°C. The above is only an example of the composition of the glass powder I.
  • Example 1 In parts by mass, it includes 40 parts of silicone rubber, 20 parts of ceramic filler, 10 parts of bulk filler, 15 parts of flame retardant, 2 parts of glass powder and 2 parts of additives.
  • the glass powder includes glass powder A and glass powder B.
  • the mass ratio of glass powder A to glass powder B is 1:1.
  • the impact-resistant layer is a single layer of glass fiber cloth, the flame-retardant heat-insulating layer is composited with the impact-resistant layer, the thickness ratio of the flame-retardant heat-insulating layer to the impact-resistant layer is 10:1, and the total thickness of the material is 2 mm.
  • Example 2 In parts by mass, it includes 60 parts of silicone rubber, 30 parts of ceramic filler, 17 parts of bulk filler, 25 parts of flame retardant, 10 parts of glass powder and 5 parts of additives.
  • the glass powder includes glass powder C, glass powder D and glass powder E.
  • the mass ratio of glass powder C, glass powder D and glass powder E is 1:1:2.
  • the impact-resistant layer is three layers of glass fiber cloth, the flame-retardant heat-insulating layer is composited with the impact-resistant layer, the thickness ratio of the flame-retardant heat-insulating layer to the impact-resistant layer is 2:1, and the total thickness of the material is 1 mm.
  • Example 3 In parts by mass, it includes 50 parts of silicone rubber, 25 parts of ceramic filler, 15 parts of bulk filler, 20 parts of flame retardant, 6 parts of glass powder and 3 parts of additives.
  • the glass powder includes glass powder F, glass powder G, glass powder H and glass powder I.
  • the mass ratio of glass powder F, glass powder G, glass powder H and glass powder I is 1:1:1:1.
  • the impact-resistant layer is two layers of glass fiber cloth, the flame-retardant heat-insulating layer is composited with the impact-resistant layer, the thickness ratio of the flame-retardant heat-insulating layer to the impact-resistant layer is 6:1, and the total thickness of the material is 2.5 mm.
  • Example 4 In parts by mass, it includes 45 parts of silicone rubber, 27 parts of ceramic filler, 14 parts of bulk filler, 22 parts of flame retardant, 8 parts of glass powder and 2 parts of additives.
  • the glass powder includes glass powder A and glass powder B, and the mass ratio of glass powder A to glass powder B is 1:1.
  • the impact-resistant layer is a single layer of glass fiber cloth, and the flame retardant and heat-insulating layer is composited with the impact-resistant layer, the thickness ratio of the flame retardant and heat-insulating layer to the impact-resistant layer is 4:1, and the total thickness of the material is 1 mm.
  • Example 5 In parts by mass, it includes 45 parts of silicone rubber, 27 parts of ceramic filler, 14 parts of bulk filler, 22 parts of flame retardant, 8 parts of glass powder and 2 parts of additives.
  • the glass powder includes glass powder A and glass powder B, and the mass ratio of glass powder A to glass powder B is 1:2.
  • the impact-resistant layer is a single layer of glass fiber cloth, the flame-retardant heat-insulating layer is composited with the impact-resistant layer, the thickness ratio of the flame-retardant heat-insulating layer to the impact-resistant layer is 4:1, and the total thickness of the material is 1 mm.
  • Example 6 In parts by mass, it includes 45 parts of silicone rubber, 27 parts of ceramic filler, 14 parts of bulk filler, 22 parts of flame retardant, 8 parts of glass powder and 2 parts of additives.
  • the glass powder includes glass powder A and glass powder B, and the mass ratio of glass powder A to glass powder B is 2:3.
  • the impact-resistant layer is a single layer of glass fiber cloth, the flame-retardant heat-insulating layer is composited with the impact-resistant layer, the thickness ratio of the flame-retardant heat-insulating layer to the impact-resistant layer is 4:1, and the total thickness of the material is 1 mm.
  • Example 7 In parts by mass, it includes 45 parts of silicone rubber, 27 parts of ceramic filler, 14 parts of bulk filler, 22 parts of flame retardant, 8 parts of glass powder and 2 parts of additives.
  • the glass powder includes glass powder C, glass powder D and glass powder E.
  • the mass ratio of glass powder C, glass powder D and glass powder E is 1:1:2.
  • the impact-resistant layer is a single layer of glass fiber cloth, the flame-retardant heat-insulating layer is composited with the impact-resistant layer, the thickness ratio of the flame-retardant heat-insulating layer to the impact-resistant layer is 4:1, and the total thickness of the material is 1 mm.
  • Example 8 In parts by mass, it includes 45 parts of silicone rubber, 27 parts of ceramic filler, 14 parts of bulk filler, 22 parts of flame retardant, 8 parts of glass powder and 2 parts of additives.
  • the glass powder includes glass powder C, glass powder D and glass powder E.
  • the mass ratio of glass powder C, glass powder D and glass powder E is 1:2:3.
  • the impact-resistant layer is a single layer of glass fiber cloth, the flame-retardant heat-insulating layer is composited with the impact-resistant layer, the thickness ratio of the flame-retardant heat-insulating layer to the impact-resistant layer is 4:1, and the total thickness of the material is 1 mm.
  • Example 9 In parts by mass, it includes 45 parts of silicone rubber, 27 parts of ceramic filler, 14 parts of bulk filler, 22 parts of flame retardant, 8 parts of glass powder and 2 parts of additives.
  • the glass powder includes glass powder C, glass powder D and glass powder E.
  • the mass ratio of glass powder C, glass powder D and glass powder E is 2:2:3.
  • the impact-resistant layer is a single layer of glass fiber cloth, the flame-retardant heat-insulating layer is composited with the impact-resistant layer, the thickness ratio of the flame-retardant heat-insulating layer to the impact-resistant layer is 4:1, and the total thickness of the material is 1 mm.
  • Example 10 In parts by mass, it includes 45 parts of silicone rubber, 27 parts of ceramic filler, 14 parts of bulk filler, 22 parts of flame retardant, 8 parts of glass powder and 2 parts of additives.
  • the glass powder includes glass powder F, glass powder G, glass powder H and glass powder I.
  • the mass ratio of glass powder F, glass powder G, glass powder H and glass powder I is 1:1:1:1.
  • the impact-resistant layer is a single layer of glass fiber cloth, the flame-retardant heat-insulating layer is composited with the impact-resistant layer, the thickness ratio of the flame-retardant heat-insulating layer to the impact-resistant layer is 4:1, and the total thickness of the material is 1 mm.
  • Example 11 In parts by mass, it includes 45 parts of silicone rubber, 27 parts of ceramic filler, 14 parts of bulk filler, 22 parts of flame retardant, 8 parts of glass powder and 2 parts of additives.
  • the glass powder includes glass powder F, glass powder G, glass powder H and glass powder I.
  • the mass ratio of glass powder F, glass powder G, glass powder H and glass powder I is 1:1:2:2.
  • the impact-resistant layer is a single layer of glass fiber cloth, the flame-retardant heat-insulating layer is composited with the impact-resistant layer, the thickness ratio of the flame-retardant heat-insulating layer to the impact-resistant layer is 4:1, and the total thickness of the material is 1 mm.
  • Example 12 In parts by mass, it includes 45 parts of silicone rubber, 27 parts of ceramic filler, 14 parts of bulk filler, 22 parts of flame retardant, 8 parts of glass powder and 2 parts of additives.
  • the glass powder includes glass powder F, glass powder G, glass powder H and glass powder I.
  • the mass ratio of glass powder F, glass powder G, glass powder H and glass powder I is 1:2:2:3.
  • the impact-resistant layer is a single layer of glass fiber cloth, the flame-retardant heat-insulating layer is composited with the impact-resistant layer, the thickness ratio of the flame-retardant heat-insulating layer to the impact-resistant layer is 4:1, and the total thickness of the material is 1 mm.
  • Example 13 In parts by mass, it includes 45 parts of silicone rubber, 27 parts of ceramic filler, 14 parts of bulk filler, 22 parts of flame retardant, 8 parts of glass powder and 2 parts of additives.
  • the glass powder includes glass powder F, glass powder G, glass powder H and glass powder I.
  • the mass ratio of glass powder F, glass powder G, glass powder H and glass powder I is 1:1:1:2.
  • the impact-resistant layer is a single layer of glass fiber cloth, the flame-retardant heat-insulating layer is composited with the impact-resistant layer, the thickness ratio of the flame-retardant heat-insulating layer to the impact-resistant layer is 4:1, and the total thickness of the material is 1 mm.
  • Example 14 In parts by mass, it includes 52 parts of organic silicone rubber, 27 parts of ceramic filler, 17 parts of bulk filler, 23 parts of flame retardant, 5 parts of glass powder and 2 parts of auxiliary agent. The rest of the contents are the same as those of Example 12.
  • Example 15 In parts by mass, it includes 47 parts of organic silicone rubber, 25 parts of ceramic filler, 15 parts of bulk filler, 20 parts of flame retardant, 4 parts of glass powder and 2 parts of auxiliary agent. The rest of the contents are the same as those of Example 12.
  • the number of glass powders with different initial melting temperatures is not limited to the content disclosed in this application, as long as the molten temperature of the glass powder covers 300°C to 1500°C. That is, the mixing of glass powders is not limited to the mixing of glass powder A and glass powder B, glass powder C, glass powder D and glass powder E, glass powder F, glass powder G, glass powder H and glass powder I. As long as the requirements are met, they can be mixed together, and it is not limited to the glass powder A, glass powder B, glass powder C, glass powder D, glass powder E, glass powder F, glass powder G, glass powder H and glass powder I disclosed in this application. As long as the molten temperature range requirements are met, the glass powders can be mixed together.
  • Example 16 In parts by mass, it includes 47 parts of silicone rubber, 25 parts of ceramic filler, 15 parts of bulk filler, 20 parts of flame retardant, 4 parts of glass powder and 2 parts of additives.
  • the glass powder includes glass powder A, glass powder G, glass powder H and glass powder I.
  • the mass ratio of glass powder A, glass powder G, glass powder H and glass powder I is 1:1:2:2.
  • the impact-resistant layer is a single layer of glass fiber cloth, the flame-retardant heat-insulating layer is composited with the impact-resistant layer, the thickness ratio of the flame-retardant heat-insulating layer to the impact-resistant layer is 4:1, and the total thickness of the material is 1 mm.
  • Example 17 In parts by mass, it includes 47 parts of silicone rubber, 25 parts of ceramic filler, 15 parts of bulk filler, 20 parts of flame retardant, 4 parts of glass powder and 2 parts of additives.
  • the glass powder includes glass powder A, glass powder G, glass powder H and glass powder E.
  • the mass ratio of glass powder A, glass powder G, glass powder H and glass powder E is 1:1:1:2.
  • the impact-resistant layer is a single layer of glass fiber cloth, the flame-retardant heat-insulating layer is composited with the impact-resistant layer, the thickness ratio of the flame-retardant heat-insulating layer to the impact-resistant layer is 4:1, and the total thickness of the material is 1 mm.
  • glass powders with different initial melting temperatures are mixed with silicone rubber, ceramic fillers, incremental fillers or flame retardants separately, and glass powders with different initial melting temperatures must not be mixed together and then mixed with silicone rubber, ceramic fillers, incremental fillers or flame retardants.
  • Comparative Example 1 by mass, including 45 parts of silicone rubber, 27 parts of ceramic filler, 14 parts of bulk filler, 22 parts of flame retardant, 8 parts of glass powder and 2 parts of additives.
  • the glass powder is glass powder A.
  • the impact-resistant layer is a single layer of glass fiber cloth, the flame-retardant heat-insulating layer is composited with the impact-resistant layer, the thickness ratio of the flame-retardant heat-insulating layer to the impact-resistant layer is 4:1, and the total thickness of the material is 1 mm.
  • Comparative Example 2 by mass, including 45 parts of silicone rubber, 27 parts of ceramic filler, 14 parts of bulk filler, 22 parts of flame retardant, 8 parts of glass powder and 2 parts of additives.
  • the glass powder is glass powder B.
  • the impact-resistant layer is a single layer of glass fiber cloth, the flame-retardant heat-insulating layer is composited with the impact-resistant layer, the thickness ratio of the flame-retardant heat-insulating layer to the impact-resistant layer is 4:1, and the total thickness of the material is 1 mm.
  • Comparative Example 3 In parts by mass, it includes 45 parts of silicone rubber, 27 parts of ceramic filler, 14 parts of bulk filler, 22 parts of flame retardant, 8 parts of glass powder and 2 parts of additives.
  • the glass powder is glass powder C.
  • the impact-resistant layer is a single layer of glass fiber cloth, the flame-retardant heat-insulating layer is composited with the impact-resistant layer, the thickness ratio of the flame-retardant heat-insulating layer to the impact-resistant layer is 4:1, and the total thickness of the material is 1 mm.
  • Comparative Example 4 by mass, including 45 parts of silicone rubber, 27 parts of ceramic filler, 14 parts of bulk filler, 22 parts of flame retardant, 8 parts of glass powder and 2 parts of additives.
  • the glass powder is glass powder D.
  • the impact-resistant layer is a single layer of glass fiber cloth, the flame-retardant heat-insulating layer is composited with the impact-resistant layer, the thickness ratio of the flame-retardant heat-insulating layer to the impact-resistant layer is 4:1, and the total thickness of the material is 1 mm.
  • Comparative Example 5 by mass, including 45 parts of silicone rubber, 27 parts of ceramic filler, 14 parts of bulk filler, 22 parts of flame retardant, 8 parts of glass powder and 2 parts of additives.
  • the glass powder is glass powder E.
  • the impact-resistant layer is a single layer of glass fiber cloth, the flame-retardant heat-insulating layer is composited with the impact-resistant layer, the thickness ratio of the flame-retardant heat-insulating layer to the impact-resistant layer is 4:1, and the total thickness of the material is 1 mm.
  • Comparative Example 6 In parts by mass, it includes 45 parts of silicone rubber, 27 parts of ceramic filler, 14 parts of bulk filler, 22 parts of flame retardant, 8 parts of glass powder and 2 parts of additives.
  • the glass powder is glass powder F.
  • the impact-resistant layer is a single layer of glass fiber cloth, the flame-retardant heat-insulating layer is composited with the impact-resistant layer, the thickness ratio of the flame-retardant heat-insulating layer to the impact-resistant layer is 4:1, and the total thickness of the material is 1 mm.
  • Comparative Example 7 In parts by mass, it includes 45 parts of silicone rubber, 27 parts of ceramic filler, 14 parts of bulk filler, 22 parts of flame retardant, 8 parts of glass powder and 2 parts of additives.
  • the glass powder is glass powder G.
  • the impact-resistant layer is a single layer of glass fiber cloth, the flame-retardant heat-insulating layer is composited with the impact-resistant layer, the thickness ratio of the flame-retardant heat-insulating layer to the impact-resistant layer is 4:1, and the total thickness of the material is 1 mm.
  • Comparative Example 8 In parts by mass, it includes 45 parts of silicone rubber, 27 parts of ceramic filler, 14 parts of bulk filler, 22 parts of flame retardant, 8 parts of glass powder and 2 parts of additives.
  • the glass powder is glass powder H.
  • the impact-resistant layer is a single layer of glass fiber cloth, the flame-retardant heat-insulating layer is composited with the impact-resistant layer, the thickness ratio of the flame-retardant heat-insulating layer to the impact-resistant layer is 4:1, and the total thickness of the material is 1 mm.
  • Comparative Example 9 In parts by mass, it includes 45 parts of silicone rubber, 27 parts of ceramic filler, 14 parts of bulk filler, 22 parts of flame retardant, 8 parts of glass powder and 2 parts of additives.
  • the glass powder is glass powder I.
  • the impact-resistant layer is a single layer of glass fiber cloth, the flame-retardant heat-insulating layer is composited with the impact-resistant layer, the thickness ratio of the flame-retardant heat-insulating layer to the impact-resistant layer is 4:1, and the total thickness of the material is 1 mm.
  • the flame retardant heat-insulating layer and the impact-resistant layer are composited, that is, obtained by the following preparation method:
  • S1 glass powders with different initial melting temperatures are mixed separately with silicone rubber, ceramic filler, bulk filler, flame retardant, and other additives except vulcanizer in batches through an internal mixer, and then kneaded to obtain a mixed rubber;
  • Density ASTM D792-2013; densitometer.
  • the density of Examples 4 to 17 is 1.6 ⁇ 0.1 g/cm 3 .
  • Tensile strength ASTM D412; tensile testing machine. The tensile strength of Examples 4 to 17 is greater than 15 MPa.
  • Flame retardancy UL94; horizontal and vertical burning tester. Flame retardancy of Examples 4 to 17: V0.
  • Thermal conductivity ASTM D5470; thermal conductivity tester.
  • the thermal conductivity of Examples 4 to 17 is less than or equal to 0.3 W/(m ⁇ k).
  • Withstand voltage voltage adjusted to 2700V DC, time 60s, leakage current; withstand voltage tester.
  • the leakage current of Examples 4 to 17 is less than 1mA.
  • Insulation voltage adjusted to 1000V DC, time 60s, resistance; insulation tester.
  • the resistance of Examples 4 to 17 is greater than 1G ⁇ .
  • Voltage breakdown ASTM D149; voltage breakdown tester.
  • the breakdown voltage of Examples 4 to 17 is greater than 20 kV.
  • Hardness ASTM D2240; Durometer. Hardness of Examples 4 to 17: 65 ⁇ 7 Shore A.
  • Water absorption 24h water absorption mass ratio: Examples 4 to 17 are less than or equal to 3%.
  • Ozone aging resistance ASTM D1171, ozone concentration 2ppm, temperature 23°C, humidity 65%, stretch 15%, moisturizing 46h. Examples 4 to 17 have no cracks.
  • Complete ceramicization means that the flame retardant, heat insulating and fireproof material for batteries prepared in the examples has a relatively complete surface without obvious defects after the deflagration test.
  • Ceramic cracks refer to obvious cracks on the surface of the flame-retardant, heat-insulating and fire-proof material for batteries prepared in the examples after the deflagration test.
  • Ceramic breakdown refers to the appearance of obvious holes and cracks on the surface of the flame-retardant, heat-insulating and fire-proof material for batteries prepared in the examples after the deflagration test.
  • each embodiment and comparative example has slightly different morphologies after the deflagration test. As shown in Table 1, after 30 minutes, 1500°C flame impact, and 3 standard atmospheres, Examples 4 to 17 can ensure the integrity of the main body, while the thermal insulation and fireproof functions of Comparative Examples 1 to 9 have partially failed.
  • Example 4 to 17 As can be seen from Table 1, the performance of Examples 4 to 17 is completely better than that of Comparative Examples 1 to 9, indicating that the performance of the thermal insulation and fireproofing material with full coverage in the molten state is better than that of the thermal insulation and fireproofing material with partial coverage. From the states under different temperatures and atmospheric pressures in Examples 4 to 17, it can be seen that when the content of high-melting-point glass powder is higher than that of low-melting-point glass powder, the performance of the thermal insulation and fireproofing material is better, such as Examples 12 to 17. When the content of high-melting-point glass powder is equal to that of low-melting-point glass powder, the performance decreases. It is speculated that due to the rapid temperature rise of deflagration, the temperature quickly reaches 1500°C, and the glass powder needs to be in a molten state at 1500°C for a long time when burning at 1500°C for a long time.
  • Examples 4 to 17 and Comparative Examples 1 to 9 cannot pass the deflagration test under the conditions of 15 minutes, 1500°C flame impact, and 2 standard atmospheres, that is, the flame retardant and heat-insulating layer is not composited with the impact-resistant layer, and its heat insulation and fireproof performance is insufficient.
  • the main structure of most flame retardant and heat-insulating layers in Comparative Examples 1 to 9 is incomplete and cannot be used normally.
  • Examples 4 to 17 will only show ceramic phase cracks and breakdown during the deflagration test under the conditions of 15 minutes, 1500°C flame impact, and 1.5 standard atmospheres.
  • Examples 4 to 17 can guarantee basic thermal insulation and fireproof performance.
  • Comparative Examples 1 to 9 have different states according to the different glass powders added.
  • the comparative examples adding low-melting-point glass powder can still guarantee basic thermal insulation and fireproof performance, while the comparative examples adding high-melting-point glass powder cannot form a complete ceramic layer under long-term low-temperature combustion. Only when the temperature can be quickly raised to 1500°C, the addition of high-melting-point glass powder alone will have an effect.
  • the flame retardant insulation material with a glass powder molten state temperature range covering 300°C to 1500°C in this application is superior to the flame retardant insulation material with only a single melting temperature glass powder. It can withstand a high temperature of 1500°C for a long time under high pressure.
  • the principle is that when it is above 350°C, part of the glass powder can always be kept in a molten state, allowing the silica matrix and the glass powder to be continuously compounded, and the ceramic layer can be kept as continuous, complete and dense as possible. If only a single melting temperature glass powder is added, it can either only withstand low-temperature combustion, or the ceramic layer will break down and rupture during low-temperature combustion.
  • the thicker the total thickness of the material the better the material's impact resistance and flame retardant and heat insulation performance.
  • the total thickness of the material tested is about 1 mm.
  • the thickness of the material of this application is not limited to the thickness disclosed in the specific implementation. In different application scenarios, the thickness of the impact resistance layer, the thickness of the flame retardant and heat insulation layer, and the total thickness of the material can be set according to actual needs.

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Abstract

本发明公开了一种电池用阻燃隔热防火材料，涉及一种硅橡胶阻燃隔热材料，包括阻燃隔热层和抗冲击层，阻燃隔热层包括有机硅橡胶、成瓷填料、阻燃剂、助剂和具有不同始熔温度的玻璃粉，玻璃粉的熔融态温度区间覆盖300℃至1500℃。本材料通过添加多种具有不同熔融态温度区间玻璃粉，使得防火材料在300℃至1500℃温度区间内被灼烧形成陶瓷层时，其内始终具有熔融态的玻璃粉，熔融态的玻璃粉可以及时填充不同温度下陶瓷层内出现的孔洞和裂缝，尽可能保证陶瓷层的连续、完整、致密，使得该防火材料同时具有低温快速成瓷和耐1500℃左右高温的特点。解决现有玻璃粉熔融态温度区间单一，高温时玻璃粉气化造成陶瓷层产生孔洞，结构密实度降低，容易被烧穿的问题。

Description

一种电池用阻燃隔热防火材料 相关申请的交叉引用
本申请主张在2022年10月18日在中国提交的中国专利申请号202211274999.X的优先权，其全部内容通过引用包含于此。
技术领域
本发明涉及一种硅橡胶阻燃隔热防火材料，尤其涉及一种新能源汽车电池组用阻燃隔热防火材料。
 背景技术
一般电池热失控概率是千万分之一，但是在电动汽车中，集成上千个电池形成电池组后，电池组的热失控概率就上升至万分之一，且一个电池热失控可能会引起整个电池组热失控，电池组热失控后燃烧温度可达1500℃，并且还具有很强的冲击，这对电动汽车的安全是一个极大的挑战。研究表明陶瓷化硅橡胶是目前最适合用于新能源汽车电池组防止电芯连续热失控、避免引燃相邻模组的材料方案。
陶瓷化硅橡胶是一种可瓷化的高分子复合材料，这种材料在常温下有着普通聚合物的优良性能，并且在高温下能形成致密的陶瓷结构从而具有陶瓷特性。硅橡胶中由于Si—O键的键能较高，使得硅橡胶本身就拥有良好的热稳定性，此外在高温火焰下燃烧时，Si—O键会转变成连续、抗氧化、绝缘的网络状SiO2灰烬覆盖在电芯表面，从而有效的阻止火焰进一步的烧蚀。此外，硅橡胶基体在燃烧过程中产生的烟气主要是侧链基团燃烧所产生的CO2和H2O，无有毒气体产生，不会对环境产生污染。用有机硅类聚合物来制备陶瓷化硅橡胶，无论是在工艺及原材料的选取，还是在瓷化产物的耐高温和力学性能等方面都具有独特的优势。
陶瓷化硅橡胶阻燃隔热防火的主要原理是通过添加催化剂、热稳定剂、耐火填料、玻璃粉等提高硅橡胶的热稳定性，促进陶瓷层的生成和稳定。通常陶瓷化硅橡胶燃烧后陶瓷化的具体过程为：在遇到烧蚀或者高温时，硅橡胶基体首先分解为无定型SiO2，并产生大小不一的气孔。然后，随着温度的升高，低熔点玻璃粉（也称瓷化粉、成瓷助熔剂）首先逐渐熔融，在硅橡胶体系中出现液相物质，将基体产生的无定形SiO2和耐温成瓷填料（如云母、高岭土、硅灰石等）进行连接，在填料的边界处形成“低共熔混合物”，称为共晶反应。低共熔混合物在无定型SiO2和填料之间起桥接作用，从而使其在着火温度下保持原状。最后，随着时间的推移，温度进一步升高，成瓷填料和无定型 SiO2与低共熔混合物之间相互渗透更加充分，填料边界消失，新的无机相生成，形成连续、完整、致密的陶瓷体结构。
中国专利CN110845850A公开了一种可瓷化无卤阻燃硅橡胶及其制备方法。中国专利CN107286636A公开了一种低烟阻燃可陶瓷化热塑性聚氨酯弹性体复合材料及其制备方法和应用。中国专利CN202111191443.X 公开了一种陶瓷化阻燃隔热防火材料及其制备方法和应用。上述专利都公开了陶瓷化硅橡胶以及其应用方法，但在电池组的防护中仍具有缺陷。
通常陶瓷化硅橡胶经历高温灼烧时其各个组分的反应温度差异较大，如硅橡胶在350℃的时候开始分解生成无定型SiO2，其表面产生很多大小不一的气孔；白云母（常见成瓷填料）在700℃后才开始分解；成分不同的普通玻璃粉其始熔温度在300℃-700℃之间。电池热失控时燃烧温度会逐渐达到1500℃并且伴随热冲击，这就造成了几个问题，如果玻璃粉始熔温度较高（大于700℃），在低温区间内（350℃-700℃）硅橡胶无法和成瓷填料、玻璃粉形成连续、完整、致密的陶瓷体结构，具有气孔的无定型SiO2容易被冲击力破坏从而被烧穿。如果玻璃粉始熔温度较低（小于700℃），在高温区间内（1200℃以上），玻璃粉会气相挥发，陶瓷体骨架结构上产生孔洞，使得陶瓷体结构的密实度降低，容易受热冲击而被烧穿。
现有公开的陶瓷化硅橡胶都只添加一种始熔温度的玻璃粉，即现有材料中的玻璃粉无法完全覆盖300℃-1500℃熔融态温度区间，总会发生上述问题。
 发明内容
本发明针对现有技术中的不足，提供了一种电池用阻燃隔热防火材料，本发明通过添加多种具有不同熔融态温度区间的玻璃粉，使得防火材料在300℃至1500℃灼烧时其内部始终具有熔融态玻璃粉，这些熔融态玻璃粉可以及时填充由SiO2灰烬和耐火填料共晶形成的陶瓷层在不同温度下出现的孔洞和裂缝，尽可能保证陶瓷层的连续、完整、致密，使得防火材料同时具有低温快速成瓷和耐1500℃以上高温的特点。解决现有材料因为玻璃粉熔融态温度区间单一，高熔点玻璃粉在低温时无法及时熔融填充陶瓷层的缝隙，以及低熔点玻璃粉在高温时易被气化造成陶瓷相产生孔洞，结构密实度降低，容易被烧穿的问题。
为了解决上述技术问题，本发明通过下述技术方案得以解决：一种电池用阻燃隔热防火材料，包括阻燃隔热层和抗冲击层，所述阻燃隔热层涂覆在所述抗冲击层表面，所述阻燃隔热层与所述抗冲击层的厚度比为（2~10）:1，所述的阻燃隔热层包括有机硅橡胶、成瓷填料、阻燃剂和助剂，还包括若干具有不同始熔温度的玻璃粉，若干玻璃粉的熔融态温度区间覆盖300℃至1500℃。
上述技术方案中，可选择的，所述的抗冲击层为玻璃纤维布。
上述技术方案中，可选择的，所述抗冲击层由多层玻璃纤维布复合而成。
上述技术方案中，可选择的，玻璃粉包括熔融态温度区间覆盖300℃至700℃之间的玻璃粉A和熔融态温度区间覆盖700℃至1500℃之间的玻璃粉B。以质量比计，玻璃粉A与玻璃粉B的比值为1~2:1~3。
上述技术方案中，可选择的，玻璃粉包括熔融态温度区间覆盖300℃至550℃之间的玻璃粉C、熔融态温度区间覆盖550℃至900℃之间的玻璃粉D和熔融态温度区间覆盖900℃至1500℃的玻璃粉E。以质量比计，玻璃粉C、玻璃粉D与玻璃粉E的比值为1~2:1~2: 2~3。
上述技术方案中，可选择的，玻璃粉包括熔融态温度区间覆盖300℃-800℃之间的玻璃粉F、熔融态温度区间覆盖600℃-1000℃之间的玻璃粉G、熔融态温度区间覆盖700℃-1250℃之间的玻璃粉H和熔融态温度区间覆盖1000℃至1500℃的玻璃粉I。以质量比计，玻璃粉F、玻璃粉G、玻璃粉H与玻璃粉I的比值为1~3:1~3:1~3:1~3。
上述技术方案中，可选择的，玻璃粉原料包括氧化硅、氧化硼以及金属氧化物的一种或多种。金属氧化物包括氧化铅、氧化铝、氧化锂、氧化锌、氧化钛、氧化镁、氧化钒、氧化钡、氧化钠、氧化钙、氧化锶、氧化锡、氧化铋和氧化锑的一种或多种。
上述技术方案中，可选择的，玻璃粉原料还包括氟化亚锡。
上述技术方案中，可选择的，包括40份至60份有机硅橡胶、20份至30份成瓷填料、15份至25份阻燃剂，2份至10份玻璃粉，2份至5份助剂。
上述技术方案中，可选择的，还包括10份至17份增量填料。
上述技术方案中，可选择的，阻燃隔热防火材料在1500℃火焰冲击下至少30分钟不烧穿。
玻璃粉一般是由SiO2、B2O3、Al2O3、PbO与一些金属氧化物按一定的比例充分混合后，经熔融、水淬、粉碎而制成。调整不同组分比例以及添加不同的金属氧化物，会使玻璃粉的始熔温度以及熔融态温度区间略不相同。
锂电池热失控时，会出现爆燃现象，即高温燃烧伴随冲击。硅橡胶在350℃的时候，开始分解生成无定型SiO2，产生很多大小不一的气孔。这时就需要玻璃粉熔融，开始形成液相，填充到气孔中，将无定型SiO2和成瓷填料连接在一起，使其在燃烧和冲击下保持稳定。由此现有材料中的玻璃粉始熔温度大多选择在300℃-700℃之间，让其在硅橡胶开始分解后就熔融，尽早填充气孔，但是始熔温度在300℃-700℃之间玻璃粉熔融态温度区间基本不超过1000℃，即当灼烧温度高于玻璃粉的熔融态温度区时，玻璃粉气相挥发，既会在已形成的陶瓷层中产生孔洞，使得陶瓷层整体结构的密实度降低，在热冲击和燃烧的双重作用下现有防火材料很可能被1000℃至1500℃火焰烧穿，造成防火材料失效。不仅如此，在整个燃烧过程中都会出现热冲击，这种冲击极易造成陶瓷层出现裂纹，裂纹出现后不进行补救也会造成整个防火材料失效，即在防火材料被灼烧的整个过程中都需要具有熔融态的玻璃粉随时填充孔洞和裂纹，直到1500℃时陶瓷层仍连续、完整、致密。
为此本申请采用混合多种始熔温度的玻璃粉，使其具有多种熔融态温度区间，覆盖300℃-1500℃，无论防火材料被灼烧的温度达到多高，始终有玻璃粉处于熔融态填充陶瓷层的孔洞和裂纹，尽可能的保证陶瓷层的连续、完整、致密，让陶瓷层发挥最大的隔热阻燃作用。
与现有技术相比，本发明通过添加多种具有不同熔融态温度区间的玻璃粉，使得在300℃至1500℃温度区间内始终具有熔融态玻璃粉，让熔融态玻璃粉可以及时填充不同温度下陶瓷层上出现的孔洞和裂缝，尽可能保证陶瓷层的连续、完整、致密，使得电池用阻燃隔热防火材料同时具有低温快速成瓷和耐1500℃左右高温的特点。解决现有材料因为玻璃粉熔融态温度区间单一，高熔点玻璃粉在低温时无法及时熔融填充陶瓷层的缝隙，以及低熔点玻璃粉在高温时易被气化造成陶瓷层产生孔洞，结构密实度降低，容易被烧穿的问题。
 附图说明
图1是通过本发明实施例17制备得到的电池用阻燃隔热防火材料经15min、1500℃火焰冲击、5标准大气压爆燃测试后呈现出陶瓷化完整形态的实物图。
图2是通过本发明实施例17制备得到的电池用阻燃隔热防火材料经15min、1500℃火焰冲击、7标准大气压爆燃测试后呈现出陶瓷化裂纹形态的实物图。
图3是本发明实施例17制备得到的电池用阻燃隔热防火材料经15min、1500℃火焰冲击、10标准大气压爆燃测试后呈现出陶瓷化击穿形态的实物图。
 实施方式
为便于理解本发明，本发明列举实施例如下。本领域技术人员应该明了，所述实施例仅是帮助理解本发明，不应视为对本发明的具体限制。
在本申请的实施例中，有机硅橡胶为液态硅橡胶、甲基乙烯基硅橡胶或甲基苯基乙烯基硅橡胶中的任意一种或至少两种的组合。在下述实施例以及对比例中，有机硅橡胶为甲基乙烯基硅橡胶：1103，来源广州市矽友新材料科技有限公司。在实际应用中并不限于甲基乙烯基硅橡胶。
成瓷填料为白云母、金云母、高岭土、水镁石和滑石粉中的任意一种或至少两种的组合。在下述实施例以及对比例中，成瓷填料为白云母，来源广东永丰化工有限公司。在实际应用中并不限于白云母。
增量填料为硅藻土、硅灰石、碳酸钙和气相二氧化硅的任意一种或至少两种的组合。在下述实施例以及对比例中，增量填料包括硅藻土，来源广州市昊兆化工有限公司；碳酸钙，325-6250（目），来源东莞市昕科新材料有限公司；纳米二氧化硅，KS-8200，来源济南卡松化工有限公司。硅藻土、碳酸钙和纳米二氧化硅的质量比为0.8：1：3，在实际应用中并不限于上述材料的混合物。
阻燃剂为三氧化二锑、氢氧化铝、氢氧化镁、含磷无机阻燃剂、含硼无机阻燃剂和含磷有机阻燃剂中的任意一种或至少两种的组合。在下述实施例以及对比例中，阻燃剂包括为氢氧化铝，合肥中科阻燃新材料有限公司；含磷无机阻燃剂，石家庄市鑫盛化工有限公司；含磷有机阻燃剂，郑州翰硕化工原料有限公司。氢氧化铝、含磷无机阻燃剂、含磷有机阻燃剂的质量比为3：0.9：1.3，在实际应用中并不限于上述材料的混合物。
助剂包括硅烷偶联剂、硅油和硫化剂。其中硫化剂为过氧化苯甲酰、过苯甲酸叔丁酯、过氧化二叔丁基、过氧化二异丙苯、2,5-二甲基-2,5-二叔丁基过氧化己烷、铂金硫化剂中的一种。在下述实施例以及对比例中，助剂为硅烷偶联剂和硅油，江苏全力化学有限公司；硫化剂为过氧化苯甲酰。硅烷偶联剂、硅油、过氧化苯甲酰的质量比为0.5：5：1.8，在实际应用中并不限于上述材料的混合物。
玻璃粉为氧化硅、氧化硼以及金属氧化物的任意一种或至少两种的组合。其中金属氧化物为氧化铅、氧化铝、氧化锂、氧化锌、氧化钛、氧化镁、氧化钒、氧化钡、氧化钠、氧化钙、氧化锶、氧化锡、氧化铋和氧化锑的任意一种或至少两种的组合。部分玻璃粉还包括氟化亚锡。玻璃粉根据成分和配比的不同具有多种始熔温度以及熔融态温度覆盖区间，在本申请中熔融态温度覆盖区间仅表示玻璃粉在此区间内是熔融态，两端点温度并不是熔点和沸点，在超出温度覆盖区间外玻璃粉亦可以是熔融状态。
在下述实施例以及对比例中，玻璃粉由广州亿峰化工科技有限公司根据申请人要求提供，或由申请人自行配置。
在本申请的实施例中，玻璃粉A的成分包括SnF2、P2O5、SiO2、Sb2O3、Bi2O3，以质量份计，包括40份~50份SnF2、35份~45份P2O5、1份~7份SiO2、1份~7份Sb2O3和1份~7份Bi2O3。可选择的，玻璃粉A的包括45份SnF2、40份P2O5、5份SiO2、5份Sb2O3 和5份Bi2O3。玻璃粉A熔融态温度区间覆盖300℃至700℃，在实际应用中无论玻璃粉A的成分，仅需玻璃粉A熔融态温度区间覆盖300℃至700℃即可，上述仅为玻璃粉A的一个成分示例。
玻璃粉B的成分包括SiO2、B2O3、PbO，以质量份计，包括25份~35份SiO2、10份~15份B2O3、15份~25份PbO。可选择的，玻璃粉B包括30份SiO2、11份B2O3、22份PbO。玻璃粉B熔融态温度区间覆盖700℃至1500℃，在实际应用中无论玻璃粉B的成分，仅需玻璃粉B熔融态温度区间覆盖700℃至1500℃即可，上述仅为玻璃粉B的一个成分示例。
玻璃粉C的成分包括SnF2、P2O5、V2O5、Sb2O3、Bi2O3，以质量份计，包括45份~55份SnF2、30份~40份P2O5、1份~7份V2O5、1份~7份Sb2O3和1份~7份Bi2O3。可选择的，玻璃粉C包括50份SnF2、35份P2O5、5份V2O5、5份Sb2O3和5份Bi2O3。玻璃粉C熔融态温度区间覆盖300℃至550℃，在实际应用中无论玻璃粉C的成分，仅需玻璃粉C熔融态温度区间覆盖300℃至550℃即可，上述仅为玻璃粉C的一个成分示例。
玻璃粉D的成分包括SiO2、TiO2、B2O3、PbO，以质量份计，10份~15份SiO2、1份~5份TiO2、10份~15份B2O3、15份~20份PbO。可选择的，玻璃粉D包括14份SiO2、2份TiO2、12份B2O3、17份PbO。玻璃粉D熔融态温度区间覆盖550℃至900℃，在实际应用中无论玻璃粉D的成分，仅需玻璃粉D熔融态温度区间覆盖550℃至900℃即可，上述仅为玻璃粉D的一个成分示例。
玻璃粉E的成分包括SiO2、PbO，以质量份计，包括30份~40份SiO2、20份~25份PbO。可选择的，玻璃粉E包括35份SiO2、20份PbO。玻璃粉E熔融态温度区间覆盖900℃至1500℃，在实际应用中无论玻璃粉E的成分，仅需玻璃粉E熔融态温度区间覆盖900℃至1500℃即可，上述仅为玻璃粉E的一个成分示例。
玻璃粉F的成分包括SnF2、P2O5、SiO2、Bi2O3、V2O5。以质量份计，包括35份~45份SnF2、35份~45份P2O5、1份~7份V2O5、5份~15份SiO2、1份~7份Bi2O3。可选择的，玻璃粉F的包括40份SnF2、40份P2O5、5份V2O5、10份SiO2和5份Bi2O3。玻璃粉F熔融态温度区间覆盖300℃至800℃，在实际应用中无论玻璃粉F的成分，仅需玻璃粉F熔融态温度区间覆盖300℃至800℃即可，上述仅为玻璃粉F的一个成分示例。
玻璃粉G的成分包括SiO2、TiO2、B2O3、PbO，以质量份计，10份~20份SiO2、7份~13份TiO2、10份~15份B2O3、10份~15份PbO。可选择的，玻璃粉G包括15份SiO2、10份TiO2、13份B2O3、12份PbO。玻璃粉G熔融态温度区间覆盖600℃-1000℃，在实际应用中无论玻璃粉G的成分，仅需玻璃粉G熔融态温度区间覆盖600℃-1000℃即可，上述仅为玻璃粉G的一个成分示例。
玻璃粉H的成分包括SiO2、B2O3、TiO2、PbO。以质量份计，包括15份~20份SiO2、10份~15份TiO2、10份~20份B2O3、15份~25份PbO。可选择的，玻璃粉H包括17份SiO2、12份TiO2、15份B2O3、20份PbO。玻璃粉H熔融态温度区间覆盖700℃-1250℃，在实际应用中无论玻璃粉H的成分，仅需玻璃粉H熔融态温度区间覆盖700℃-1250℃即可，上述仅为玻璃粉H的一个成分示例。
玻璃粉I的成分包括SiO2、PbO。以质量份计，包括25份~35份SiO2、10份~15份PbO。可选择的，玻璃粉I包括30份SiO2、13份PbO。玻璃粉I熔融态温度区间覆盖1000℃至1500℃，在实际应用中无论玻璃粉I的成分，仅需玻璃粉I熔融态温度区间覆盖1000℃至1500℃即可，上述仅为玻璃粉I的一个成分示例。
实施例1：以质量份计，包括40份有机硅橡胶、20份成瓷填料、10份增量填料、15份阻燃剂、2份玻璃粉和2份助剂。玻璃粉包括玻璃粉A和玻璃粉B。玻璃粉A和玻璃粉B的质量比为1:1。抗冲击层为单层玻璃纤维布，阻燃隔热层与抗冲击层复合，阻燃隔热层与抗冲击层的厚度比为10:1，材料总厚度2mm。
实施例2：以质量份计，包括60份有机硅橡胶、30份成瓷填料、17份增量填料、25份阻燃剂，10份玻璃粉和5份助剂。玻璃粉包括玻璃粉C、玻璃粉D和玻璃粉E。玻璃粉C、玻璃粉D和玻璃粉E的质量比为1:1:2。抗冲击层为三层玻璃纤维布，阻燃隔热层与抗冲击层复合，阻燃隔热层与抗冲击层的厚度比为2:1，材料总厚度1mm。
实施例3：以质量份计，包括50份有机硅橡胶、25份成瓷填料、15份增量填料、20份阻燃剂，6份玻璃粉和3份助剂。玻璃粉包括玻璃粉F、玻璃粉G、玻璃粉H和玻璃粉I。玻璃粉F、玻璃粉G、玻璃粉H和玻璃粉I的质量比为1:1:1:1。抗冲击层为两层玻璃纤维布，阻燃隔热层与抗冲击层复合，阻燃隔热层与抗冲击层的厚度比为6:1，材料总厚度2.5mm。
实施例4：以质量份计，包括45份有机硅橡胶、27份成瓷填料、14份增量填料、22份阻燃剂、8份玻璃粉和2份助剂。玻璃粉包括玻璃粉A和玻璃粉B，玻璃粉A和玻璃粉B的质量比为1:1。抗冲击层为单层玻璃纤维布，阻燃隔热层与抗冲击层复合，阻燃隔热层与抗冲击层的厚度比为4:1，材料总厚度1mm。
实施例5：以质量份计，包括45份有机硅橡胶、27份成瓷填料、14份增量填料、22份阻燃剂、8份玻璃粉和2份助剂。玻璃粉包括玻璃粉A和玻璃粉B，玻璃粉A和玻璃粉B的质量比为1:2。抗冲击层为单层玻璃纤维布，阻燃隔热层与抗冲击层复合，阻燃隔热层与抗冲击层的厚度比为4:1，材料总厚度1mm。
实施例6：以质量份计，包括45份有机硅橡胶、27份成瓷填料、14份增量填料、22份阻燃剂、8份玻璃粉和2份助剂。玻璃粉包括玻璃粉A和玻璃粉B，玻璃粉A和玻璃粉B的质量比为2:3。抗冲击层为单层玻璃纤维布，阻燃隔热层与抗冲击层复合，阻燃隔热层与抗冲击层的厚度比为4:1，材料总厚度1mm。
实施例7：以质量份计，包括45份有机硅橡胶、27份成瓷填料、14份增量填料、22份阻燃剂、8份玻璃粉和2份助剂。玻璃粉包括玻璃粉C、玻璃粉D和玻璃粉E。玻璃粉C、玻璃粉D和玻璃粉E的质量比为1:1: 2。抗冲击层为单层玻璃纤维布，阻燃隔热层与抗冲击层复合，阻燃隔热层与抗冲击层的厚度比为4:1，材料总厚度1mm。
实施例8：以质量份计，包括45份有机硅橡胶、27份成瓷填料、14份增量填料、22份阻燃剂、8份玻璃粉和2份助剂。玻璃粉包括玻璃粉C、玻璃粉D和玻璃粉E。玻璃粉C、玻璃粉D和玻璃粉E的质量比为1:2: 3。抗冲击层为单层玻璃纤维布，阻燃隔热层与抗冲击层复合，阻燃隔热层与抗冲击层的厚度比为4:1，材料总厚度1mm。
实施例9：以质量份计，包括45份有机硅橡胶、27份成瓷填料、14份增量填料、22份阻燃剂、8份玻璃粉和2份助剂。玻璃粉包括玻璃粉C、玻璃粉D和玻璃粉E。玻璃粉C、玻璃粉D和玻璃粉E的质量比为2:2:3。抗冲击层为单层玻璃纤维布，阻燃隔热层与抗冲击层复合，阻燃隔热层与抗冲击层的厚度比为4:1，材料总厚度1mm。
实施例10：以质量份计，包括45份有机硅橡胶、27份成瓷填料、14份增量填料、22份阻燃剂、8份玻璃粉和2份助剂。玻璃粉包括玻璃粉F、玻璃粉G、玻璃粉H和玻璃粉I。玻璃粉F、玻璃粉G、玻璃粉H和玻璃粉I的质量比为1:1:1:1。抗冲击层为单层玻璃纤维布，阻燃隔热层与抗冲击层复合，阻燃隔热层与抗冲击层的厚度比为4:1，材料总厚度1mm。
实施例11：以质量份计，包括45份有机硅橡胶、27份成瓷填料、14份增量填料、22份阻燃剂、8份玻璃粉和2份助剂。玻璃粉包括玻璃粉F、玻璃粉G、玻璃粉H和玻璃粉I。玻璃粉F、玻璃粉G、玻璃粉H和玻璃粉I的质量比为1:1:2:2。抗冲击层为单层玻璃纤维布，阻燃隔热层与抗冲击层复合，阻燃隔热层与抗冲击层的厚度比为4:1，材料总厚度1mm。
实施例12：以质量份计，包括45份有机硅橡胶、27份成瓷填料、14份增量填料、22份阻燃剂、8份玻璃粉和2份助剂。玻璃粉包括玻璃粉F、玻璃粉G、玻璃粉H和玻璃粉I。玻璃粉F、玻璃粉G、玻璃粉H和玻璃粉I的质量比为1:2:2:3。抗冲击层为单层玻璃纤维布，阻燃隔热层与抗冲击层复合，阻燃隔热层与抗冲击层的厚度比为4:1，材料总厚度1mm。
实施例13：以质量份计，包括45份有机硅橡胶、27份成瓷填料、14份增量填料、22份阻燃剂、8份玻璃粉和2份助剂。玻璃粉包括玻璃粉F、玻璃粉G、玻璃粉H和玻璃粉I。玻璃粉F、玻璃粉G、玻璃粉H和玻璃粉I的质量比为1:1:1:2。抗冲击层为单层玻璃纤维布，阻燃隔热层与抗冲击层复合，阻燃隔热层与抗冲击层的厚度比为4:1，材料总厚度1mm。
实施例14：以质量份计，包括52份有机硅橡胶、27份成瓷填料、17份增量填料、23份阻燃剂，5份玻璃粉和2份助剂。其余内容与实施例12相同。
实施例15：以质量份计，包括47份有机硅橡胶、25份成瓷填料、15份增量填料、20份阻燃剂，4份玻璃粉和2份助剂。其余内容与实施例12相同。
在上述实施例中，不同始熔温度玻璃粉的数量并不局限于本申请公开的内容，只要玻璃粉熔融态温度覆盖300℃至1500℃即可。既玻璃粉的混合并不局限于玻璃粉A和玻璃粉B混合，玻璃粉C、玻璃粉D和玻璃粉E混合，玻璃粉F、玻璃粉G、玻璃粉H和玻璃粉I混合，只要符合要求，可以互混，并且也不局限本申请公开的玻璃粉A、玻璃粉B、玻璃粉C、玻璃粉D、玻璃粉E、玻璃粉F、玻璃粉G、玻璃粉H和玻璃粉I，只要符合熔融态温度区间要求，玻璃粉可以互混。
实施例16：以质量份计，包括47份有机硅橡胶、25份成瓷填料、15份增量填料、20份阻燃剂，4份玻璃粉和2份助剂。玻璃粉包括玻璃粉A、玻璃粉G、玻璃粉H和玻璃粉I。玻璃粉A、玻璃粉G、玻璃粉H和玻璃粉I的质量比为1:1:2:2。抗冲击层为单层玻璃纤维布，阻燃隔热层与抗冲击层复合，阻燃隔热层与抗冲击层的厚度比为4:1，材料总厚度1mm。
实施例17：以质量份计，包括47份有机硅橡胶、25份成瓷填料、15份增量填料、20份阻燃剂，4份玻璃粉和2份助剂。玻璃粉包括玻璃粉A、玻璃粉G、玻璃粉H和玻璃粉E。玻璃粉A、玻璃粉G、玻璃粉H和玻璃粉E的质量比为1:1:1:2。抗冲击层为单层玻璃纤维布，阻燃隔热层与抗冲击层复合，阻燃隔热层与抗冲击层的厚度比为4:1，材料总厚度1mm。
在上述实施例中，具有不同始熔温度的玻璃粉单独与有机硅橡胶、成瓷填料、增量填料或阻燃剂进行混合，不得将具有不同始熔温度的玻璃粉混杂在一起后再与有机硅橡胶、成瓷填料、增量填料或阻燃剂混合。
对比例1：以质量份计，包括45份有机硅橡胶、27份成瓷填料、14份增量填料、22份阻燃剂、8份玻璃粉和2份助剂。玻璃粉为玻璃粉A。抗冲击层为单层玻璃纤维布，阻燃隔热层与抗冲击层复合，阻燃隔热层与抗冲击层的厚度比为4:1，材料总厚度1mm。
对比例2：以质量份计，包括45份有机硅橡胶、27份成瓷填料、14份增量填料、22份阻燃剂、8份玻璃粉和2份助剂。玻璃粉为玻璃粉B。抗冲击层为单层玻璃纤维布，阻燃隔热层与抗冲击层复合，阻燃隔热层与抗冲击层的厚度比为4:1，材料总厚度1mm。
对比例3：以质量份计，包括45份有机硅橡胶、27份成瓷填料、14份增量填料、22份阻燃剂、8份玻璃粉和2份助剂。玻璃粉为玻璃粉C。抗冲击层为单层玻璃纤维布，阻燃隔热层与抗冲击层复合，阻燃隔热层与抗冲击层的厚度比为4:1，材料总厚度1mm。
对比例4：以质量份计，包括45份有机硅橡胶、27份成瓷填料、14份增量填料、22份阻燃剂、8份玻璃粉和2份助剂。玻璃粉为玻璃粉D。抗冲击层为单层玻璃纤维布，阻燃隔热层与抗冲击层复合，阻燃隔热层与抗冲击层的厚度比为4:1，材料总厚度1mm。
对比例5：以质量份计，包括45份有机硅橡胶、27份成瓷填料、14份增量填料、22份阻燃剂、8份玻璃粉和2份助剂。玻璃粉为玻璃粉E。抗冲击层为单层玻璃纤维布，阻燃隔热层与抗冲击层复合，阻燃隔热层与抗冲击层的厚度比为4:1，材料总厚度1mm。
对比例6：以质量份计，包括45份有机硅橡胶、27份成瓷填料、14份增量填料、22份阻燃剂、8份玻璃粉和2份助剂。玻璃粉为玻璃粉F。抗冲击层为单层玻璃纤维布，阻燃隔热层与抗冲击层复合，阻燃隔热层与抗冲击层的厚度比为4:1，材料总厚度1mm。
对比例7：以质量份计，包括45份有机硅橡胶、27份成瓷填料、14份增量填料、22份阻燃剂、8份玻璃粉和2份助剂。玻璃粉为玻璃粉G。抗冲击层为单层玻璃纤维布，阻燃隔热层与抗冲击层复合，阻燃隔热层与抗冲击层的厚度比为4:1，材料总厚度1mm。
对比例8：以质量份计，包括45份有机硅橡胶、27份成瓷填料、14份增量填料、22份阻燃剂、8份玻璃粉和2份助剂。玻璃粉为玻璃粉H。抗冲击层为单层玻璃纤维布，阻燃隔热层与抗冲击层复合，阻燃隔热层与抗冲击层的厚度比为4:1，材料总厚度1mm。
对比例9：以质量份计，包括45份有机硅橡胶、27份成瓷填料、14份增量填料、22份阻燃剂、8份玻璃粉和2份助剂。玻璃粉为玻璃粉I。抗冲击层为单层玻璃纤维布，阻燃隔热层与抗冲击层复合，阻燃隔热层与抗冲击层的厚度比为4:1，材料总厚度1mm。
所有实施例和对比例中阻燃隔热层和抗冲击层复合，即通过下述制备方法得到：
S1：将具有不同始熔温度的玻璃粉单独与有机硅橡胶、成瓷填料、增量填料、阻燃剂、除硫化剂以外的其它助剂分批经密炼机进行混合，再混炼，得到混炼胶；
S2：将混炼胶放入硫化机加入硫化剂，得到阻燃隔热防火硅胶；
S3：将阻燃隔热防火硅胶涂布在抗冲击层（即玻璃纤维布）上，压延，硫化温度控制在130-160℃。
最后得到电池用阻燃隔热防火材料。
对实施例4至实施例17进行性能测试，测试标准与结果如下：
密度：ASTM D792-2013；密度计。实施例4至实施例17密度在1.6±0.1g/cm 3 。
拉伸强度：ASTM D412；拉力机。实施例4至实施例17拉伸强度大于15MPa。
阻燃性：UL94；水平、垂直燃烧测试仪。实施例4至实施例17阻燃性V0。
导热系数：ASTM D5470；导热系数测试仪。实施例4至实施例17导热系数小于等于0.3W/（m·k）。
耐电压：电压调至2700V DC，时间60s，漏电流；耐压测试仪。实施例4至实施例17漏电流小于1mA。
绝缘：电压调至1000V DC，时间60s，电阻；绝缘测试仪。实施例4至实施例17电阻大于1GΩ。
电压击穿：ASTM D149；电压击穿测试仪。实施例4至实施例17击穿打压大于20kv。
硬度：ASTM D2240；硬度计。实施例4至实施例17硬度65±7Shore A。
吸水性：24h吸水质量比。实施例4至实施例17小于等于3%。
耐臭氧老化：ASTM D1171，臭氧浓度2ppm，温度23℃，湿度65%，拉伸15%，保湿46h。实施例4至实施例17无裂纹。
低温性能：-40℃/24小时，180°对折。实施例4至实施例17无裂纹。
长期耐候性：-40℃至85℃间，以不超过5℃/min的温度梯度完成500个循环，在每个循环中，在最高温度和最低温度处分别停留15min。85℃，85%湿度，1000小时。120℃老化1200h。实施例4至实施例17分别经过高低温循环、高温高湿和高温老化后，以上所有性能仍可以达到标椎要求。
实施例4至实施例17以及对比例1至对比例9进行不同压强下爆燃测试。如表1所示。
[根据细则26改正 18.10.2023]
表1：实施例4至实施例17，对比例1至对比例9复合玻纤状态下爆燃测试
[根据细则26改正 18.10.2023][已删除]
陶瓷化完整指由实施例制备得到的电池用阻燃隔热防火材料经爆燃测试后材料表面较为完整，无明显缺陷。
陶瓷化裂纹指由实施例制备得到的电池用阻燃隔热防火材料经爆燃测试后材料表面出现明显裂纹。
陶瓷化击穿指由实施例制备得到的电池用阻燃隔热防火材料经爆燃测试后材料表面出现明显孔洞及裂纹裂穿。
陶瓷化完整、陶瓷化裂纹以及陶瓷化击穿状态可参考图1至图3，实际上每个实施例以及对比例经爆燃测试后形态略有不同。由表1可见，经30min、1500℃火焰冲击、3标准大气压时实施例4至实施例17都能保证主体完整，此时对比例1至9部分隔热防火功能已经失效。
在30min、1500℃火焰冲击、5标准大气压下时实施例4至实施例17隔热防火功能性能下降，但仍具有一定的隔热防火功能。对比例1至9隔热防火功能都失效。
在15min、1500℃火焰冲击、5标准大气压下时实施例4至实施例17大部分实施例隔热防火功能依然存在，对比例1至9隔热防火功能都失效。
在15min、1500℃火焰冲击、7标准大气压下时实施例4至实施例17部分实施例隔热防火功能失效，对比例1至9隔热防火功能都失效。
在15min、1500℃火焰冲击、10标准大气压时实施例4至实施例17以及对比例1至9隔热防火功能都失效。
由表1可知，实施例4至实施例17性能完全优于对比例1至9，表明具有熔融态全覆盖的隔热防火材料性能优于部分覆盖的隔热防火材料。从实施例4至实施例17中不同温度大气压下状态可知，当高熔点玻璃粉含量高于低熔点玻璃粉时，隔热防火材料性能更好，如实施例12至实施例17。当高熔点玻璃粉与低熔点玻璃粉含量相等时，性能下降。推测由于爆燃升温快，温度很快达到1500℃，在1500℃长期燃烧时需要玻璃粉长时间在1500℃处于熔融态。
按实施例4至实施例17以及对比例1至对比例9中形成阻燃隔热层的原料配比单独制备阻燃隔热层，并进行不同压强下爆燃测试。具体如表2所示。
[根据细则26改正 18.10.2023]
表2：实施例4至实施例17，对比例1至对比例9无复合玻纤状态下爆燃测试
[根据细则26改正 18.10.2023][已删除]
由表2可见，如果不具有抗冲击层，则实施例4至实施例17以及对比例1至对比例9无法通过15min、1500℃火焰冲击、2标准大气压条件下的爆燃测试，即阻燃隔热层不与抗冲击层复合，其隔热防火性能不足。同时在15min、1500℃火焰冲击、1标准大气压条件下爆燃测试中对比例1至对比例9中大多数阻燃隔热层的主体结构已不完整，无法正常使用。与其相反实施例4至实施例17在15min、1500℃火焰冲击、1.5标准大气压条件下爆燃测试时才会出现陶瓷相裂纹和击穿。
对实施例4至实施例17进行不同温度下爆燃测试。如表3所示。
[根据细则26改正 18.10.2023]
表3：实施例4至实施例17，对比例1至对比例9复合玻纤后不同温度下爆燃测试
[根据细则26改正 18.10.2023][已删除]
由表3可见，在15min、700℃火焰冲击、5标准大气压和15min、1000℃火焰冲击、5标准大气压下，实施例4至实施例17能保证基本的隔热防火性能。则对比例1至对比例9根据添加的不同玻璃粉具有不同的状态，在700℃下，添加低熔点玻璃粉的对比例仍能保证基本的隔热防火性能，添加高熔点玻璃粉的对比例在长时间低温燃烧下不能形成完整的陶瓷层。只有当温度能快速升温到1500℃时，单独添加高熔点玻璃粉才具有效果。
通过上述实验，可见本申请中具有覆盖300℃至1500℃玻璃粉熔融态温度区间的阻燃隔热材料比仅具有单一始熔温度玻璃粉的阻燃隔热材料性能更为优越。可长时间在高压环境下耐受1500℃高温，其原理为在350℃以上时就能始终保持部分玻璃粉处于熔融态，让二氧化硅基体与玻璃粉的不间断复合，尽可能的保持陶瓷层的连续、完整、致密。如果只添加单一始熔温度玻璃粉，要么只能耐受低温燃烧，要么在低温燃烧时陶瓷层就击穿破裂。
一般情况下，材料总厚度越厚，则材料抗冲击性能和阻燃隔热性能越好，在本具体实施方式中，进行试验的材料总厚度在1mm左右。但本申请材料的厚度并不局限于具体实施方式中公开的厚度，在不同的应用场景，抗冲击层厚度、阻燃隔热层厚度、材料总厚度可根据实际需求设置。

Claims (12)

  1. 一种电池用阻燃隔热防火材料，其特征为，包括阻燃隔热层和抗冲击层，所述的阻燃隔热层涂覆在所述的抗冲击层表面，所述的阻燃隔热层与所述的抗冲击层的厚度比为（2~10）:1，所述的阻燃隔热层包括有机硅橡胶、成瓷填料、阻燃剂和助剂，还包括若干具有不同始熔温度的玻璃粉，若干玻璃粉的熔融态温度区间覆盖300℃至1500℃。
  2. 根据权利要求1所述的一种电池用阻燃隔热防火材料，其特征为，所述的抗冲击层为玻璃纤维布。
  3. 根据权利要求2所述的一种电池用阻燃隔热防火材料，其特征为，所述抗冲击层由多层玻璃纤维布复合而成。
  4. 根据权利要求1所述的一种电池用阻燃隔热防火材料，其特征为，玻璃粉包括熔融态温度区间覆盖300℃至700℃之间的玻璃粉A和熔融态温度区间覆盖700℃至1500℃之间的玻璃粉B；以质量比计，玻璃粉A与玻璃粉B的比值为1~2:1~3。
  5. 根据权利要求1所述的一种电池用阻燃隔热防火材料，其特征为，玻璃粉包括熔融态温度区间覆盖300℃至550℃之间的玻璃粉C、熔融态温度区间覆盖550℃至900℃之间的玻璃粉D和熔融态温度区间覆盖900℃至1500℃的玻璃粉E；以质量比计，玻璃粉C、玻璃粉D与玻璃粉E的比值为1~2:1~2: 2~3。
  6. 根据权利要求1所述的一种电池用阻燃隔热防火材料，其特征为，玻璃粉包括熔融态温度区间覆盖300℃-800℃之间的玻璃粉F、熔融态温度区间覆盖600℃-1000℃之间的玻璃粉G、熔融态温度区间覆盖700℃-1250℃之间的玻璃粉H和熔融态温度区间覆盖1000℃至1500℃的玻璃粉I；以质量比计，玻璃粉F、玻璃粉G、玻璃粉H与玻璃粉I的比值为1~3:1~3:1~3:1~3。
  7. 根据权利要求1至6任一所述的一种电池用阻燃隔热防火材料，其特征为，玻璃粉原料包括氧化硅、氧化硼以及金属氧化物的一种或多种。
  8. 根据权利要求6任一所述的一种电池用阻燃隔热防火材料，其特征为，金属氧化物包括氧化铅、氧化铝、氧化锂、氧化锌、氧化钛、氧化镁、氧化钒、氧化钡、氧化钠、氧化钙、氧化锶、氧化锡、氧化铋和氧化锑的一种或多种。
  9. 根据权利要求6任一所述的一种电池用阻燃隔热防火材料，其特征为，玻璃粉原料还包括氟化亚锡。
  10. 根据权利要求1至6任一所述的一种电池用阻燃隔热防火材料，其特征为，以质量份计，所述的阻燃隔热层包括40份至60份有机硅橡胶、20份至30份成瓷填料、15份至25份阻燃剂，2份至10份玻璃粉，2份至5份助剂。
  11. 根据权利要求10所述的一种电池用阻燃隔热防火材料，其特征为，所述的阻燃隔热层还包括10份至17份增量填料。
  12. 根据权利要求1所述的一种电池用阻燃隔热防火材料，其特征为，阻燃隔热防火材料在1500℃火焰冲击下至少30分钟不烧穿。
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CN115491037A (zh) * 2022-10-18 2022-12-20 浙江葆润应用材料有限公司 一种电池用阻燃隔热防火材料拼混生产方法
CN115538175A (zh) * 2022-10-18 2022-12-30 浙江葆润应用材料有限公司 一种电池用阻燃隔热防火材料

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