Composite materials

Abstract

This specification discloses composite materials and fire extinguishing devices that are applied to products or elements that are in or potentially in an abnormal state and that can effectively respond to said abnormal state. For example, the composite materials, etc., are applied to articles containing multiple such products or elements and can respond to abnormal heat generation, explosions, and ignition occurring in any one of the elements or products, and can prevent or minimize the propagation of such heat generation, explosions, and ignition to adjacent elements or products. The composite materials, etc., also exhibit excellent handling and storage stability. This specification can also provide applications for the composite materials, etc.

Description

[Technical Field]

[0001] This application claims priority rights based on Korean Patent Application No. 10-2024-0043318 dated March 29, 2024, and Korean Patent Application No. 10-2024-0174266 dated November 28, 2024, and all content disclosed in the documents of said Korean Patent Applications is included herein as part of this specification.

[0002] This specification discloses composite materials, fire extinguishing systems including the composite materials, and applications of the composite materials and fire extinguishing systems. [Background technology]

[0003] While the importance of technologies for handling heat generated from products is increasing, processing, managing, and controlling heat in products composed of multiple heat-generating elements remains a challenging problem.

[0004] For example, preventing so-called TR (Thermal Runaway) or TP (Thermal Propagation) phenomena that occur in battery modules or battery packs is extremely important. A battery module or battery pack contains multiple battery cells or multiple battery modules, which are located relatively adjacent to each other.

[0005] In such a structure, the phenomenon in which abnormal heat generation, ignition, and / or explosion occurring in one battery cell and / or battery module propagates in a chain reaction to other adjacent battery cells, etc., is called the TR or TP phenomenon. Such chain ignitions and chain explosions caused by the TR or TP phenomenon must be controlled from a stability standpoint. [Overview of the project] [Problems that the invention aims to solve]

[0006] This specification discloses composite materials, fire extinguishing devices, and their uses. This specification aims to disclose composite materials and fire extinguishing devices that are applicable to products or elements in which an abnormal state occurs or there is a possibility of the occurrence of the abnormal state, and that can effectively respond to the abnormal state.

[0007] For example, the composite materials and fire extinguishing devices disclosed in this specification are applicable to articles containing a plurality of the products or elements, and can prevent or minimize the propagation of an abnormal state occurring in any one of the products or elements to other products or elements.

[0008] This specification also aims to disclose the composite materials and fire extinguishing devices having excellent handleability and storage stability. This specification also aims to disclose the uses of the composite materials and fire extinguishing devices.

Means for Solving the Problems

[0009] Among the physical properties referred to in this specification, for physical properties affected by temperature, unless otherwise specified, they are physical properties measured at normal temperature.

[0010] The term normal temperature refers to the natural temperature without artificial heating and cooling, for example, any temperature within the range of about 10°C to 30°C, for example, a temperature of about 23°C or about 25°C.

[0011] Unless otherwise specified, the unit of temperature referred to in this specification is °C.

[0012] Among the physical properties referred to in this specification, when pressure affects the result, unless otherwise specified, the physical property is the physical property measured at normal pressure.

[0013] The term normal pressure refers to the natural pressure without artificial pressurization and depressurization, and the pressure within the range of usually about 700 mmHg to 800 mmHg is generally referred to as normal pressure.

[0014] In this specification, if humidity affects the results of any physical property mentioned herein, unless otherwise specified, such physical property is measured at ambient temperature and pressure with unadjusted humidity.

[0015] In this specification, the term "abnormal" refers to a condition in which a product or component experiences abnormal heat generation, ignition, and / or explosion, or a condition in which there is a risk of such abnormal heat generation, ignition, and / or explosion.

[0016] In this specification, the term "normal state" refers to the state of a product or component that is not in the abnormal state described above.

[0017] This specification discloses composite materials.

[0018] This specification also discloses a fire extinguishing device comprising the composite material.

[0019] The fire extinguishing device includes a case having a sealed space inside, and a composite material present in the sealed space inside.

[0020] For example, the fire extinguishing device may include a case, and the composite material may be located inside the case. The case may have a sealed space inside, and the composite material may be located inside such a sealed space.

[0021] The case is a container for holding the composite material. The case has a sealed space inside. The fact that the case has a sealed space inside means that the sealed space is formed inside the case, or that there is a certain space inside the case, and although that space is not sealed, the case exists in such a way that a sealed space can be formed by sealing the open portion. The sealed space means a space that is formed so that the components of the composite material, etc., do not substantially leak out to the outside under normal conditions.

[0022] In one example, the case may include a portion having a predetermined range of WVTR (Water Vapor Transmission Rate) as described later. For example, at least the sealed space in which the composite material exists may be substantially surrounded by a portion having a predetermined range of WVTR (Water Vapor Transmission Rate) as described later.

[0023] The case has a vent region. The term "vent region" can mean a region that is sealed in a first state and exists to maintain that sealed state, but is opened in a second state so that all or part of the substance inside the space can be discharged. The second state can mean, for example, an abnormal state as described later, and the first state can mean a normal state as described later. Such a vent region can be formed in the manner described later.

[0024] In one example, the case may include portions having a predetermined range of WVTR (Water Vapor Transmission Rate). For example, a sealed space inside the case may, in a sealed state, be surrounded by a material having a WVTR within the range described below. In the above, the fact that a sealed space is surrounded by a material having a specific WVTR in a sealed state means that the space is substantially surrounded by the material, for example, that 80% to 100%, 85% to 100%, 90% to 100%, 95% to 100%, or substantially 100% of the area of ​​the case forming the sealed space has the specific WVTR. The upper limit of such WVTR (Water Vapor Transmission Rate) may be around 10, 9.5, 9, 8.5, 8, 7.5, 7, 6.5, 6, 5.5, 5, 4.5, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.5, 0.45, 0.4, 0.35, 0.3, 0.25, 0.2, 0.15, 0.1, 0.05, 0.01, 0.005, or 0.001, and its lower limit may be around 0, 0.1, 0.2, 0.3, 0.4, or 0.5. The WVTR may be within a range where it is less than or equal to any one upper limit arbitrarily selected from the listed upper limits; or it may be greater than or equal to or greater than any one lower limit arbitrarily selected from the listed lower limits, while being less than or equal to any one upper limit arbitrarily selected from the listed upper limits. Having such a WVTR ensures storage stability for the composite material present inside the sealed space, and allows the fire extinguishing system to perform its intended fire extinguishing action more efficiently.

[0025] The unit of the aforementioned WVTR (Water Vapor Transmission Rate) is g / m³. 2 It is a day and can be evaluated using the method described in "6. WVTR (Water Vapor Transmission Rate) Evaluation" of the Examples section of this specification.

[0026] The fire extinguishing device is configured to maintain a composite material in a sealed space under normal conditions, and to effectively release the vaporized substance inside to the outside under abnormal conditions.

[0027] This effect will be explained assuming that the fire extinguishing device is applied to a battery module.

[0028] Figure 1 is a schematic diagram showing the case where the fire extinguishing device (S) is applied to a battery module. As shown in Figure 1, the battery module can be configured by arranging a plurality of battery cells (11, 12, 13, 14, 15, 16) adjacent to each other, and the fire extinguishing device (S) can be placed between the battery cells (for example, between 12 and 13 and / or between 14 and 15 in Figure 1).

[0029] The fire extinguishing device (S) maintains vaporized material inside under normal conditions. In abnormal conditions, the internal material is ejected from the fire extinguishing device (S) through the vent area (dotted arrow in Figure 1), and the ejected internal material can respond to the heat generation, flames, and / or explosions in the abnormal conditions. Figure 1 shows a case where the internal material is ejected from both the upper and lower ends of the fire extinguishing device (S), but the ejection direction is not limited to Figure 1. The ejection direction may be one direction of the fire extinguishing device (S), or it may be two or more directions.

[0030] For a fire extinguishing system to effectively perform its functions in an abnormal state, it is required that vaporized substances and the like that present inside the case in a normal state be stably maintained, that the internal substances be able to be quickly discharged to the outside when an abnormal state occurs, and that the vaporized substances present inside the case in an abnormal state be able to be discharged to the outside in a state where they have been vaporized as much as possible.

[0031] For the fire extinguishing system to perform its function effectively even in an abnormal state, the vaporization rate of the vaporizable substance must be appropriately maintained. When the vaporizable substance vaporizes at an appropriate rate, it is possible to prevent the collapse of the internal pores due to changes in surface tension, etc., after the consumption of latent heat.

[0032] The fire extinguishing devices disclosed herein can satisfy the above requirements.

[0033] The principle by which the fire extinguishing device performs the above-mentioned function will be explained.

[0034] Figure 2 is a diagram showing only the fire extinguishing device (S) in Figure 1. In a configuration similar to that in Figure 1, if abnormal heat generation, abnormal ignition, and / or abnormal explosion occurs in at least one of the battery cells adjacent to the fire extinguishing device (S), a certain level of heat or higher will be instantaneously applied to the fire extinguishing device, as indicated by the solid arrows in Figure 2. In Figure 2, in the sealed internal space of the fire extinguishing device case (1001), vaporized material propagates randomly in all directions within the space, as indicated by the dotted arrows. At this time, if the WVTR of the portion forming the sealed space of the case (1001) is within the aforementioned range, the vaporized gas cannot be released to the outside, and the inside of the case (1001) becomes extremely high-pressure. At this time, if the vent region (1002) of the case is configured to be opened instantaneously at a certain level of high pressure, the vent region (1002) is opened instantaneously in the high-pressure state, and the gas inside is rapidly discharged to the outside through the opened vent region (1002).

[0035] If the WVTR of the case is high, the pressure inside the case (1001) does not increase effectively in an abnormal state. As a result, the vent area (1002) may not open effectively, or even if the vent area (1002) is opened, the internal pressure may be insufficient, preventing all of the internal gas from being discharged to the outside, or the discharge rate may not be adequately ensured.

[0036] By keeping the WVTR of the case low, the storage stability of the internal materials can also be effectively ensured under normal conditions.

[0037] The method for forming the vent region (1002) is not particularly limited. The vent region can be formed by designing a certain area of ​​the case forming the sealed space so that it can be opened when a certain level of pressure and / or heat is applied. For example, if a part of the case forming the sealed space is configured to have lower strength than other areas, the increased internal pressure can open the part with lower strength. Alternatively, a method can be used in which the sealed space is formed by sealing using a hot melt material, so that opening occurs due to melting at a predetermined temperature. Another method is to make only a certain part of the case forming the sealed space thinner than other areas, thereby forming the vent region. Such methods for forming a vent region can be easily adopted by those skilled in the art.

[0038] For example, when the fire extinguishing device is applied to a battery module or pack, for convenience of application, the case may be a rectangular case, a pouch-type case, and / or a cylindrical case, such as a battery cell. In such cases, a vent area can also be formed by controlling the bonding strength of the lid that forms a sealed space in the rectangular or cylindrical case.

[0039] The aforementioned case can be constructed using known materials, provided that they can satisfy the aforementioned WVTR requirements, and the materials may have a single layer or a laminated structure of two or more layers.

[0040] For example, the case can be formed using a suitable organic and / or inorganic layer made of a material capable of exhibiting the WVTR within the specified range.

[0041] As the organic layer, for example, a known polymer film or sheet can be used. Examples of organic films include cellulose polymer films; COP (Cyclo Olefin Polymer) films; acrylic polymer films; polyolefin films; PVA (polyvinyl alcohol) films; PVC (poly(vinyl chloride)) films, PES (poly ether sulfone) films; PEEK (polyetheretherketon) films; PPS (polyphenylsulfone) films; PEI (polyetherimide) films; PEN (polyethylene naphthalate) films; polyester films such as PET (poly(ethylene terephthalate)) films; PI (polyimide) films; PSF (polysulfone) films and / or PAR (polyarylate) films.

[0042] For example, the inorganic layer can be a metal layer, a metal oxide layer, a metal nitride layer, or a metal oxynitride layer. For example, the inorganic layer may be a metal layer, a metal oxide layer, a metal nitride layer, or a metal oxynitride layer containing one or more elements selected from the group consisting of In, Sn, Pb, Au, Cu, Ag, Zr, Hf, Zn, Al, Si, La, Ti, and Ni. For example, a foil, sheet, or film of the material can be applied, or a layer formed by vapor deposition or the like on a suitable substrate using the metal layer, metal oxide layer, metal nitride layer, or metal oxynitride layer can be used.

[0043] The material forming the case may be a single layer selected from the inorganic layer and the organic layer, or a multilayer structure in which two or more of the aforementioned layers are laminated.

[0044] The thickness of the inorganic layer and / or organic layer is selected considering the desired physical properties such as WVTR, and is not particularly limited. For example, the lower limit of the thickness may be around 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, or 30 μm, and the upper limit may be around 5,000 μm, 4,000 μm, 3,000 μm, 2,000 μm, 1,000 μm, 500 μm, 200 μm, 150 μm, 100 μm, 90 μm, 80 μm, 70 μm, 60 μm, 50 μm, 40 μm, or 30 μm. The thickness may be within a range where it is less than or equal to any one upper limit arbitrarily selected from the listed upper limits; or within a range where it is greater than or equal to any one lower limit arbitrarily selected from the listed lower limits; or within a range where it is greater than or equal to any one lower limit arbitrarily selected from the listed lower limits, and less than or equal to any one upper limit arbitrarily selected from the listed upper limits.

[0045] The fire extinguishing device may include additional configurations to ensure that the above action is performed more effectively.

[0046] For example, the fire extinguishing device may further include a heat conductive layer. Such a heat conductive layer may be located in an appropriate position within the fire extinguishing device, for example, in the fire extinguishing device, the heat conductive layer may be located between the case and the composite material described later.

[0047] Figure 3 is an example of the fire extinguishing device in Figure 2 in which the heat conductive layer (2001) is added. The heat conductive layer can be located between the case (1001) and the composite material, as shown in Figure 3, but its position is not limited thereto. The heat conductive layer may be located in other positions, such as inside the case, and there may be one or more layers.

[0048] The term "thermal conduction layer" refers to a layer whose thermal conductivity (based on 20°C) is within the range described below. The lower limit of the thermal conductivity (based on 20°C) of the thermal conduction layer may be approximately 15, 18, 20, 50, 100, 150, 200, 250, 300, 350, or 400, and the upper limit may be approximately 2,000, 1,500, 1,000, 900, 800, 700, 600, 500, 400, 300, 200, 100, or 50. The thermal conductivity may be within a range that is greater than or greater than any one lower limit arbitrarily selected from the listed lower limits; or within a range that is greater than or greater than any one lower limit arbitrarily selected from the listed lower limits, and less than or equal to any one upper limit arbitrarily selected from the listed upper limits. The unit of the thermal conductivity is W / m·K.

[0049] The type of thermal conductive layer is not particularly limited as long as it has the aforementioned thermal conductivity. Generally, metal materials can be used as thermal conductive layers because they have excellent thermal conductivity. For example, a layer made of a metal material such as aluminum, gold, pure silver, tungsten, copper, nickel, or platinum can be applied.

[0050] There are no particular restrictions on the thickness of the heat conductive layer, and an appropriate thickness can be set considering the specifications of the fire extinguishing system, etc. For example, the lower limit of the thickness of the heat conductive layer may be around 1 μm, 5 μm, 10 μm, 15 μm, 50 μm, 75 μm, or 90 μm, and the upper limit may be around 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, 50 μm, 40 μm, or 30 μm. The thickness may be within a range that is less than or equal to any one upper limit arbitrarily selected from the listed upper limits; or within a range that is greater than or equal to any one lower limit arbitrarily selected from the listed lower limits; or within a range that is greater than or equal to any one lower limit arbitrarily selected from the listed lower limits, and less than or equal to any one upper limit arbitrarily selected from the listed upper limits.

[0051] As shown in Figure 3, in some cases, the heat generated in an abnormal state may not be uniformly applied to the fire extinguishing system, but rather locally applied to only certain areas. However, in order for the vaporizable substances inside the fire extinguishing system to vaporize rapidly and achieve a high-pressure state, the heat generated in the abnormal state must be uniformly applied to the fire extinguishing system. If a heat conduction layer is present, even if the heat generated in the abnormal state is applied locally, this heat can be quickly and evenly transferred to the fire extinguishing system, thereby enabling the fire extinguishing action of the fire extinguishing system to occur quickly and efficiently.

[0052] This specification discloses composite materials that can be present in the sealed space of the fire extinguishing system.

[0053] The term "composite material" refers to a material containing two or more components. Such a material may contain additional components, as long as it contains at least two components.

[0054] The composite material can exhibit a certain level of compressive strength, and such compressive strength can show a certain level of increase after exposure to a harsh environment.

[0055] For example, the composite material can maintain a constant level of compressive strength before and after the convection test. The convection test is conducted using the method described in "1. Convection Test" of the Examples section of this specification. The compressive strength is a physical quantity evaluated using the method described in "8. Compressive Strength Evaluation" of the Examples section of this specification, and is the compressive stress at which the compressive strain of the composite material reaches 60%.

[0056] For example, the lower limit of the ratio of the compressive strength of the composite material at 60% compression before and after the convection test may be approximately 1.2, 1.3, 1.4, 1.5, 1.7, 1.9, 2.1, or 2.3, and the upper limit may be approximately 20, 18, 16, 14, 12, 10, 8, 6, 4, 3, or 2.5. The ratio may be within the range of being greater than or exceeding any one of the lower limits arbitrarily selected from the listed lower limits; or it may be within the range of being greater than or exceeding any one of the lower limits arbitrarily selected from the listed lower limits, while being less than or equal to any one of the upper limits arbitrarily selected from the listed upper limits.

[0057] The ratio is determined by the compressive strength of the composite material before the convection test, C f1 The compressive strength of the composite material after the convection test is C f2 Therefore, C f2 / C f1 This is the value calculated as follows. The fact that the ratio falls within the aforementioned range means that even when the composite material is subjected to high temperature and strong pressure under abnormal conditions, it can stably maintain its components and form and effectively perform its intended fire extinguishing function.

[0058] The compressive strength of the composite material, for example, the compressive strength C at 60% compression before the convection test. f1 The lower limit may be around 0.1, 0.3, 0.5, 0.7, 0.9, 1.1, or 1.2, and the upper limit may be around 5, 4.5, 4.3, 4.1, 3.9, 3.7, 3.5, 3.3, 3.1, 2.9, 2.7, 2.5, 2.3, 2.1, 1.9, 1.7, 1.5, or 1.3. The compressive strength may be greater than or greater than any one lower limit arbitrarily selected from the listed lower limits, and less than or equal to any one upper limit arbitrarily selected from the listed upper limits.

[0059] Through the compressive strength characteristics described above, the composite material can stably maintain its composition and form even when subjected to high temperature and strong pressure, and can effectively exhibit its intended fire extinguishing function.

[0060] The aforementioned composite material can exhibit a low thickness shrinkage rate.

[0061] For example, the upper limit of the absolute value of the thickness shrinkage rate of the composite material may be around 10%, 9%, 8%, 7%, or 6%, and the lower limit may be around 0%, 1%, 2%, 3%, 4%, or 5%. The absolute value is the absolute value of formula A confirmed by the method described in "9. Thickness Shrinkage Rate" of the Examples section of this specification. The ratio may be within a range that is greater than or greater than any one lower limit arbitrarily selected from the listed lower limits; or within a range that is greater than or greater than any one lower limit arbitrarily selected from the listed lower limits, and less than or equal to any one upper limit arbitrarily selected from the listed upper limits.

[0062] To maintain compressive strength, thickness shrinkage rate, etc., at the aforementioned levels, the components and ratios applied to the composite material can be controlled.

[0063] The composite material may contain a vaporizable substance. Such a vaporizable substance may, in some cases, be supported inside an inorganic gel and / or inorganic fiber, as described later. The term "vaporizable substance" refers to a substance that vaporizes at a predetermined temperature. Such a vaporizable substance can exist in liquid form at room temperature (25°C). Such a vaporizable substance can be used to reduce heat by heat exchange or the like in abnormal conditions of an object adjacent to the fire extinguishing device, or to remove flames generated by ignition and / or explosion. Such a vaporizable substance can rapidly vaporize in abnormal conditions to increase the pressure in a sealed space, open the vent area, and discharge to the outside through the opened vent area.

[0064] The vaporizable substance can be any substance that can be vaporized and is non-flammable, without any particular limitations. For example, the vaporizable substance can be a solvent having a predetermined range of freezing point and / or boiling point.

[0065] For example, the lower limit of the freezing point of the vaporized substance may be around -5°C, -4°C, -3°C, -2°C, -1°C, or 0°C, and the upper limit may be around 10°C, 9°C, 8°C, 7°C, 6°C, 5°C, 4°C, 3°C, or 2°C. The freezing point may be within a range that is less than or equal to any one upper limit arbitrarily selected from the listed upper limits; or within a range that is greater than or equal to any one lower limit arbitrarily selected from the listed lower limits; or within a range that is greater than or equal to any one lower limit arbitrarily selected from the listed lower limits, while being less than or equal to any one upper limit arbitrarily selected from the listed upper limits. The freezing point is the freezing point at 1 atmosphere.

[0066] For the vaporized substance to efficiently respond to abnormal conditions, it may be advantageous that it can be vaporized by the heat generated in the abnormal conditions, and for this purpose, the boiling point of the vaporized substance can be controlled.

[0067] The lower limit of the boiling point of the vaporized substance may be around 80°C, 85°C, 90°C, or 95°C, and the upper limit may be around 120°C, 115°C, 110°C, or 105°C. The boiling point may be within a range of less than or equal to any one upper limit arbitrarily selected from the listed upper limits; or within a range of greater than or equal to any one lower limit arbitrarily selected from the listed lower limits; or within a range of greater than or equal to any one lower limit arbitrarily selected from the listed lower limits, while being less than or equal to any one upper limit arbitrarily selected from the listed upper limits. The boiling point is the boiling point at 1 atmosphere.

[0068] As for the vaporizing substance, any suitable type can be selected and used without particular limitation, as long as it has a freezing point and / or boiling point within the aforementioned range and is non-flammable. A typical example of such a vaporizing substance is water, and accordingly, water can be used as the vaporizing substance, but the types of vaporizing substances that can be applied are not limited to those mentioned above.

[0069] The lower limit of the ratio of the volatile substance in the composite material may be, for example, around 40% by weight, 45% by weight, 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, or 80% by weight, and the upper limit may be around 95% by weight, 90% by weight, 85% by weight, 80% by weight, 75% by weight, 70% by weight, 65% by weight, 60% by weight, 55% by weight, 50% by weight, 45% by weight, or 40% by weight. The ratio may be within a range where it is greater than or greater than any one lower limit arbitrarily selected from the listed lower limits; or within a range where it is greater than or greater than any one lower limit arbitrarily selected from the listed lower limits, and less than or equal to any one upper limit arbitrarily selected from the listed upper limits. By adjusting the content of the volatile substance, the desired properties such as the amount of heat absorbed can be achieved.

[0070] The aforementioned ratio is calculated assuming that the total weight of all substances present in the composite material is 100% by weight.

[0071] The composite material may contain additional components to ensure appropriate fire extinguishing function and compressive strength, etc.

[0072] The composite material may further include an inorganic gel and / or inorganic fibers. Such inorganic gel and / or inorganic fibers can cause the composite material to exhibit the aforementioned compressive strength properties and, if necessary, can play a role in supporting some or all of the aforementioned volatile substances and other components.

[0073] The inorganic gel may be, for example, an oxide network formed by a so-called sol-gel process. Such an oxide network may include a network in which inorganic elements are linked by oxygen atoms. Examples of the inorganic elements include one or more selected from the group consisting of silicon, titanium, zirconium, niobium, tantalum, molybdenum, and tungsten. For example, if the inorganic element is silicon, the inorganic gel may be silica gel.

[0074] By controlling the density of the inorganic gel network, the functional groups, and their content, it is possible to achieve the desired compressive strength characteristics.

[0075] The lower limit of the ratio of the inorganic gel in the composite material may be, for example, around 0.1% by weight, 0.5% by weight, 1% by weight, 1.5% by weight, 2% by weight, or 2.5% by weight, and the upper limit may be around 13% by weight, 12% by weight, 11% by weight, 10% by weight, 9% by weight, 8% by weight, 7% by weight, 6% by weight, 5% by weight, 4% by weight, 3% by weight, or 2% by weight. The ratio may be greater than or greater than any one lower limit arbitrarily selected from the listed lower limits, and less than or less than any one upper limit arbitrarily selected from the listed upper limits. The ratio is calculated with the total weight of all substances present in the composite material set to 100% by weight.

[0076] In other examples, the lower limit of the content of the inorganic gel per 100 parts by weight of the vaporizable substance may be approximately 0.001 parts by weight, 0.005 parts by weight, 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.15 parts by weight, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, or 20 parts by weight, and the upper limit may be approximately 30 parts by weight, 25 parts by weight, 20 parts by weight, 15 parts by weight, 10 parts by weight, 5 parts by weight, 4 parts by weight, 3 parts by weight, 2 parts by weight, 1 part by weight, or 0.5 parts by weight. The ratio may be within a range where it is less than or equal to any one upper limit arbitrarily selected from the listed upper limits; or it may be greater than or equal to any one lower limit arbitrarily selected from the listed lower limits, while being less than or equal to any one upper limit arbitrarily selected from the listed upper limits.

[0077] By including inorganic gels with appropriate networks and functional groups within the aforementioned range, it may be possible to achieve the desired compressive strength characteristics and other properties.

[0078] As the inorganic fiber, for example, inorganic fibers commonly used to form thermal insulation materials can be used, and examples of such are so-called glass fiber and / or ceramic fiber. Such inorganic fibers may exist, for example, in the form of woven fabric or nonwoven fabric. The category of woven fabric or nonwoven fabric may also include materials referred to as so-called paper, wool, or blanket.

[0079] For example, the inorganic fibers can include ceramic paper, ceramic paper with / with an inorganic binder, binder-free fibers, ceramic fiber, glass fiber, glass felt, basalt fiber, basalt felt, aramid fabric, silica felt, oxpan carbon felt, carbon fiber felt, and / or melamine fiber, and an organic binder can be used. When the inorganic fibers are used, they have excellent heat insulation properties and the sol absorbs moisture easily, so substances such as gels and heat absorbers can be uniformly positioned within the substrate, thereby increasing stability.

[0080] The properties of the inorganic fibers can be adjusted according to the purpose.

[0081] For example, the inorganic fiber may have a moisture absorption within a predetermined range based on the ASTM-C 1511 standard. For example, the lower limit of the moisture absorption may be around 55%, 57%, 59%, or 61%, and the upper limit may be around 100%, 95%, 90%, 85%, 80%, 75%, 70%, or 65%. The moisture absorption can be evaluated according to the ASTM-C 1511 standard. The moisture absorption may be within a range that is greater than or greater than any one lower limit arbitrarily selected from the listed lower limits; or within a range that is greater than or greater than any one lower limit arbitrarily selected from the listed lower limits, while being less than or equal to any one upper limit arbitrarily selected from the listed upper limits.

[0082] The inorganic fibers can exhibit the aforementioned range of moisture absorption while contained within the composite material. Therefore, for example, if the inorganic fibers are contained within the composite material in the form of a woven or nonwoven fabric, the woven or nonwoven fabric can exhibit the aforementioned moisture absorption.

[0083] For example, the lower limit of the tensile strength of the inorganic fiber may be around 0.5, 1, 5, 10, 50, 70, 90, 95, or 100, and the upper limit may be around 500, 450, 400, 350, 300, 250, 200, 150, 100, 80, 60, 40, 20, 15, or 10. The tensile strength may be greater than or exceeding any one of the lower limits arbitrarily selected from the listed lower limits, and less than or equal to any one of the upper limits arbitrarily selected from the listed upper limits. The unit of the tensile strength is kPa.

[0084] For example, the lower limit of the compressive strength of the inorganic fiber may be around 1, 5, 8, 10, 50, 100, 110, 120, 130, 140, 145, or 150, and the upper limit may be around 500, 450, 400, 350, 300, 250, 200, 150, 100, 50, 40, 30, 20, 15, or 10. The compressive strength may be greater than or greater than any one lower limit arbitrarily selected from the listed lower limits, and less than or equal to any one upper limit arbitrarily selected from the listed upper limits. The unit of the compressive strength is kPa.

[0085] For example, the lower limit of the Young's modulus of the inorganic fiber may be around 0.1, 0.5, 1, 1.5, 2, 2.5, or 3, and its upper limit may be around 20, 18, 16, 14, 12, 10, 8, 6, or 4. The Young's modulus may be within a range where it is less than or equal to any one upper limit arbitrarily selected from the listed upper limits; or within a range where it is greater than or equal to any one lower limit arbitrarily selected from the listed lower limits; or within a range where it is greater than or equal to any one lower limit arbitrarily selected from the listed lower limits, and less than or equal to any one upper limit arbitrarily selected from the listed upper limits. The unit of the Young's modulus is MPa.

[0086] The inorganic fibers, when contained in the composite material, can exhibit one or more of the tensile strength, compressive strength, and Young's modulus within the specified range. Therefore, for example, if the inorganic fibers are contained in the composite material in the form of a woven or nonwoven fabric, the woven or nonwoven fabric can exhibit one or more of the tensile strength, compressive strength, and Young's modulus within the specified range. The tensile strength, compressive strength, and Young's modulus can be measured according to the KS K ISO 9073-3 standard.

[0087] By applying inorganic fibers exhibiting tensile strength, compressive strength, and / or Young's modulus within the aforementioned ranges, it is possible to form composite materials with the desired properties.

[0088] The lower limit of the density of the inorganic fiber may be approximately 0.01, 0.05, or 0.1, and the upper limit may be approximately 10, 8, 6, 4, 2, 1, 0.5, or 0.3. The density may be within a range where it is less than or equal to any one upper limit arbitrarily selected from the listed upper limits; or within a range where it is greater than or equal to any one lower limit arbitrarily selected from the listed lower limits; or within a range where it is greater than or equal to any one lower limit arbitrarily selected from the listed lower limits, and less than or equal to any one upper limit arbitrarily selected from the listed upper limits. The unit of density is g / cm³ 3 That is the case.

[0089] The inorganic fibers can exhibit the density within the specified range while contained within the composite material. Therefore, for example, if the inorganic fibers are contained within the composite material in the form of a woven or nonwoven fabric, the woven or nonwoven fabric can exhibit the density within the specified range.

[0090] If the inorganic fibers are included in the form of a woven or nonwoven fabric, the thickness of the woven or nonwoven fabric can be selected within a range that allows it to exhibit the aforementioned properties. For example, the lower limit of the thickness may be approximately 0.01 mm, 0.05 mm, 0.1 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, or 3 mm, and the upper limit may be approximately 100 mm, 50 mm, 30 mm, 10 mm, 8 mm, 6 mm, or 4 mm. The thickness may be within a range that is less than or equal to any one upper limit arbitrarily selected from the listed upper limits; or within a range that is greater than or equal to any one lower limit arbitrarily selected from the listed lower limits; or within a range that is greater than or equal to any one lower limit arbitrarily selected from the listed lower limits, while being less than or equal to any one upper limit arbitrarily selected from the listed upper limits.

[0091] The lower limit of the ratio of inorganic fibers in the composite material may be, for example, around 0.5% by weight, 1% by weight, 5% by weight, 10% by weight, 15% by weight, or 20% by weight, and the upper limit may be around 60% by weight, 40% by weight, 30% by weight, 25% by weight, 20% by weight, 15% by weight, or 10% by weight. The ratio may be greater than or greater than any one lower limit arbitrarily selected from the listed lower limits, and less than or less than any one upper limit arbitrarily selected from the listed upper limits. The ratio is calculated with the total weight of all substances present in the composite material set to 100% by weight.

[0092] In other examples, the lower limit of the weight ratio of the inorganic fiber to 100 parts by weight of the vaporizing substance may be approximately 0.5 parts by weight, 1 part by weight, 5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, or 75 parts by weight, and the upper limit may be approximately 150 parts by weight, 100 parts by weight, 95 parts by weight, 90 parts by weight, 85 parts by weight, 80 parts by weight, 75 parts by weight, 70 parts by weight, 65 parts by weight, 60 parts by weight, 55 parts by weight, 50 parts by weight, 45 parts by weight, 40 parts by weight, 35 parts by weight, 30 parts by weight, 25 parts by weight, or 20 parts by weight. The ratio may be within a range where it is greater than or greater than any one lower limit arbitrarily selected from the listed lower limits, and less than or equal to any one upper limit arbitrarily selected from the listed upper limits.

[0093] When the inorganic fibers and inorganic gel are present simultaneously, the inorganic gel may be attached to the inorganic fibers, or the inorganic gel and inorganic fibers may be intertwined with each other. For example, by performing the gelation process in the presence of the inorganic fibers, as described later, the above-described structure can be realized, thereby enabling the composite material to more effectively perform the desired properties and functions, such as compressive strength.

[0094] The composite material may further contain ionic compounds. Ionic compounds are compounds that can dissociate to form ions; examples include acids, bases, and salts.

[0095] The ionic compound may be a catalyst applied to form the inorganic gel, a freezing point modifier described later, or a carbonization catalyst. The ionic compound may be included in the composite material in an undissociated state, i.e., in a state without forming ions, or in a state in which it has dissociated and formed ions.

[0096] The ionic compound plays an important role in forming an inorganic gel having a target network structure and functional groups, and in enabling the composite material to exhibit the target effect over a wide temperature range.

[0097] As described later, the inorganic gel can be formed by polymerizing a metal alkoxide (sol-gel process) in the vaporizable substance. The metal alkoxide has a condensable functional group, and such a condensable functional group usually exhibits polarity. Therefore, the density or polarity of the network structure of the inorganic gel formed by the polymerization of the alkoxide can be determined by the remaining amount of the condensable functional group. On the other hand, when present, the ionic compound can induce the so-called freezing point depression phenomenon with respect to the vaporizable substance or the like. The freezing point of the medium in which the polymerization proceeds is related to the attractive force between the constituent molecules of the medium and the energy of the molecules. Therefore, the ionic compound affects the polymerization efficiency in cooperation with the polymerization temperature, and the result is one of the factors that determine the density and crosslinking degree of the network of the inorganic gel and the remaining amount of the condensable functional group.

[0098] In addition, due to the freezing point determined by the addition of the ionic compound, the composite material can stably exhibit the target effect even at a relatively low temperature, and the carbonization layer formation efficiency of the carbonizable organic substance described later can also be determined.

[0099] For example, the ionic compound can be present in an amount such that △T of the following formula 1 f is within a predetermined range. [Formula 1] △T f = K f × M × I

[0100] In formula 1, K f is the freezing point depression constant of the vaporizable substance, M is the molar concentration of the ionic compound with respect to the vaporizable substance, and I is the number of moles of ions generated when 1 mole of the ionic compound dissociates.

[0101] K in formula 1 fis the freezing point depression constant of a vaporized substance, and its unit is K / m or °C / m. For example, if the vaporized substance is water, then the K f It is 1.86.

[0102] In Equation 1, M is the molar concentration of the freezing point modifier, which is the molar concentration relative to the vaporized substance. Therefore, M is the number of moles of the ionic compound present per 1 kg of the vaporized substance in the composite material.

[0103] In Equation 1, I is the number of ions (moles) that form 1 mole of the ionic compound when the ionic compound dissociates, and in this case, dissociation means that the freezing point modifier has completely dissociated.

[0104] If two or more ionic compounds are present in the composite material, then the ΔT for each compound f Calculate the value and sum it up to obtain the ΔT for the composite material. f Set this as the value.

[0105] △T in Equation 1 f The lower limit may be, for example, around 5, 10, 15, 20, or 25, and the upper limit may be around 50, 45, 40, 35, 30, 25, 20, or 15. f This range is greater than or greater than any one lower limit arbitrarily selected from the listed lower limits; or less than or equal to any one upper limit arbitrarily selected from the listed upper limits; or greater than or greater than any one lower limit arbitrarily selected from the listed lower limits, while simultaneously being less than or equal to any one upper limit arbitrarily selected from the listed upper limits. ΔT in Equation 1 f The unit is °C. By adjusting the content of the ionic compound within the aforementioned range, the aforementioned objective can be achieved.

[0106] In order for the ionic compound contained in the aforementioned content to exert its appropriate effect, the solubility of the ionic compound in the volatile substance (e.g., water) can be adjusted.

[0107] For example, the lower limit of solubility of the ionic compound in 100g of water at 25°C is 10g, 15g, 20g, 25g, 30g, 35g, 40g, 45g, 50g, 55g, 60g, 65g, 70g, 75g, 80g, 85g, 90g, 95g, 100g, 110g, 115g, 120g, 125g, 130g, 135g, 140g, 145g, 150g, 155g, 160g It may be approximately 165g, 170g, 175g, 180g, 185g, 190g, 195g, 200g, 205g, 210g, 215g, 225g, 230g, 235g, 240g, 255g, 260g, 265g, 270g, 275g, 280g, 285g, 290g, 295g, 300g, 305g, 310g, 315g, or 320g, with an upper limit of 1.00 0g, 900g, 800g, 700g, 600g, 500g, 400g, 350g, 345g, 340g, 335g, 330g, 325g, 320g, 315g, 310g, 305g, 3 00g, 295g, 290g, 280g, 275g, 270g, 265g, 260g, 255g, 250g, 245g, 240g, 235g, 230g, 225g, 220g, 215g, The solubility may be approximately 210g, 205g, 200g, 195g, 190g, 185g, 180g, 175g, 170g, 165g, 160g, 155g, 150g, 145g, 140g, 135g, 130g, 125g, 120g, 115g, 110g, 105g, 100g, 95g, 90g, 85g, 80g, 75g, 70g, 65g, 60g, 55g, 50g, 45g, 40g, 35g, or 30g. The solubility is within the range of being greater than or exceeding any one of the lower limits arbitrarily selected from the listed lower limits; it may also be within the range of being greater than or exceeding any one of the lower limits arbitrarily selected from the listed lower limits, while being less than or equal to any one of the upper limits arbitrarily selected from the listed upper limits. The solubility is the weight (g) of the ionic compound that can be dissolved in 100g of water at 25°C. The solubility can be evaluated using the method described in "7. Solubility Evaluation" of the Examples section of this specification.

[0108] The lower limit of the solubility of the ionic compound in 100g of water at 0°C may be approximately 10g, 15g, 20g, 25g, 30g, 35g, 40g, 45g, 50g, 55g, 60g, 65g, 70g, 75g, 80g, 85g, 90g, 95g, 100g, 110g, 115g, 120g, 125g, 130g, 135g, 140g, 145g, 150g, 155g, 160g, 165g, 170g, 175g, 180g, 185g, 190g, 195g, 200g, 205g, 210g, or 215g, and the upper limit may be approximately 1,000g, 900g, 8 00g, 700g, 600g, 500g, 400g, 300g, 250g, 245g, 240g, 235g, 230g, 225g, 220g, 215g, 210g, 205g, 200g, 195g, 190g, 185g, 180g, 175g, 170g, 165g, 160g, 155g, 150g, 145g, 140g, 135g, 130g, 125g, 120g, 115g, 110g, 105g, 100g, 95g, 90g, 85g, 80g, 75g, 70g, 65g, 60g, 55g, 50g, 45g, 40g, or even around 35g or 30g. The solubility is within a range that is greater than or greater than any one lower limit arbitrarily selected from the listed lower limits; or it may be within a range that is greater than or greater than any one lower limit arbitrarily selected from the listed lower limits, and less than or less than any one upper limit arbitrarily selected from the listed upper limits. The solubility is the weight (g) of the ionic compound that can be dissolved in 100g of water at 0°C. The solubility can be evaluated by the method described in "7. Solubility Evaluation" of the Examples section of this specification.

[0109] The type of ionic compound is determined according to the purpose and is not particularly limited. For example, examples of ionic compounds having a freezing point depression effect include one or more selected from the group consisting of formate salts, acetate salts, carbonates, and sulfates. Specifically, for example, one or more substances consisting of sodium acetate (CH3COONa), sodium formate (HCOONa), potassium acetate (CH3COOK), potassium formate (HCOOK), calcium formate ((HCOO)2Ca), magnesium formate ((HCOO)2Mg), potassium carbonate (K2CO3), and ammonium sulfate ((NH4)2SO4) can be used as the ionic compound.

[0110] For example, the lower limit of the amount of an ionic compound applied to adjust the freezing point relative to 100 parts by weight of the vaporized substance may be approximately 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, or 55 parts by weight, and the upper limit may be approximately 200, 150, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, or 30 parts by weight. The ratio may be greater than or greater than any one of the lower limits arbitrarily selected from the listed lower limits, and less than or equal to any one of the upper limits arbitrarily selected from the listed upper limits.

[0111] If other ionic compounds (for example, ionic compounds used as carbonization catalysts, as described later, or acids and bases added for the formation of inorganic gels) are added to the composite material in addition to the freezing point modifier, then all ionic compounds present in the composite material will be ΔT of Equation 1. f It can be present in an amount that falls within the predetermined range.

[0112] The composite material may include a carbonization catalyst and a carbonizable organic substance as additional components. The combination of components ensures that carbides of the carbonizable organic substance are formed at the required time (e.g., the abnormal state). These formed carbides can block heat transfer. The carbonization catalyst can promote the carbonization of the carbonizable organic substance. The carbonization catalyst forms acids or acidic salts or ions at high temperatures, and these components can promote the carbonization and gas generation processes. Depending on the type of carbonization catalyst, it may impart flame retardancy to the carbides or form components that exhibit flame retardancy on their own. For example, the carbonization catalyst may form phosphoric acid-based substances through decomposition at high temperatures, and these substances can polymerize to become flame retardant. This allows the carbonization catalyst to be included in the composite material, enabling the composite material to effectively respond to abnormal states.

[0113] The carbonization catalyst and the carbonizable organic matter must be applied together with the vaporizable substance, and in this case, the carbonization catalyst used must have a solubility of a certain level or higher in the vaporizable substance (e.g., water). That is, the components dispersed in the vaporizable substance can come into contact with each other more effectively at the necessary time and interact to efficiently form the desired carbides, etc. Furthermore, by adjusting the solubility of the carbonization catalyst in the vaporizable substance, aggregation and phase separation phenomena of the components cannot occur within the composite material, and the formation of the carbides and / or the flame retardant can be promoted more effectively. For example, the lower limit of the solubility of the carbonization catalyst in the vaporized substance or water may be around 5g, 10g, 15g, 20g, 25g, 30g, 35g, or 40g, and the upper limit may be around 1000g, 900g, 800g, 700g, 600g, 500g, 400g, 300g, 200g, 100g, 90g, 80g, 70g, 60g, 50g, 40g, or 30g. The solubility may be within a range that is greater than or greater than any one lower limit arbitrarily selected from the listed lower limits; or within a range that is greater than or greater than any one lower limit arbitrarily selected from the listed lower limits, and less than or equal to any one upper limit arbitrarily selected from the listed upper limits. The solubility is the weight (g) of the carbonization catalyst that can be dissolved in 100g of the solvent (e.g., water) at 25°C. The solubility is measured by the method described in "7. Solubility Evaluation" of the Examples section of this specification.

[0114] The carbonization catalyst can be used without particular limitations as long as it can be decomposed at high temperatures to form an acid or an acidic salt or ion, and has the aforementioned solubility. Examples of the carbonization catalyst include phosphoric acid, phosphate compounds such as phosphates, phosphonate compounds, or phosphate compounds. The carbonization catalyst may be, for example, primary or secondary ammonium phosphate, urea phosphate, guanylurea phosphate, or polyammonium phosphate, and one or more of these can be selected and used.

[0115] The carbonization catalyst can be present in an appropriate content considering the desired effect. For example, the lower limit of the weight ratio of the carbonization catalyst to 100 parts by weight of the vaporizable substance is 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, and 100 parts by weight. The amount may be approximately 1,000 parts, 900 parts, 800 parts, 700 parts, 600 parts, 500 parts, 100 parts, 50 parts, 400 parts, 10 parts, or 5 parts. The upper limit may be approximately 1,000 parts, 900 parts, 800 parts, 700 parts, 600 parts, 500 parts, 400 parts, 100 parts, 50 parts, 40 parts, 30 parts, 20 parts, 15 parts, 10 parts, or 5 parts. The ratio may be within a range that is less than or equal to any one upper limit arbitrarily selected from the listed upper limits; or within a range that is greater than or equal to any one lower limit arbitrarily selected from the listed lower limits; or within a range that is greater than or equal to any one lower limit arbitrarily selected from the listed lower limits, while being less than or equal to any one upper limit arbitrarily selected from the listed upper limits. If the content of the carbonization catalyst is excessively high, the content of the vaporizable substance that can be applied to the composite material will be limited, and the vaporization characteristics of the vaporizable substance will be affected by the carbonization catalyst, making it difficult to secure the desired properties. Therefore, the amount of the carbonization catalyst can be adjusted with this in mind.

[0116] The carbonizable organic matter is an organic substance that carbonizes and forms a carbide when exposed to a flame or heat at a predetermined temperature. The carbide formed by such an organic substance is often porous, and therefore can have an insulating function. Thus, when the composite material is exposed to abnormal heat generation, ignition, or explosion, the organic substance can form an appropriate carbide and exhibit an insulating function. As described above, by adding the specific carbonization catalyst and the carbonizable organic matter to a vaporized substance, it is possible to form a carbide that can effectively respond to abnormal heat generation, ignition, and / or explosion, even when a small amount of the carbonizable organic matter is applied.

[0117] The aforementioned organic material can be any suitable type without particular limitations, as long as it is a substance that forms char when exposed to heat or flame.

[0118] Examples of such organic substances include sugars such as sorbitol and mannitol, polysaccharides such as starch or dextrins (e.g., maleated cyclodextrin (MC) and metal salts of MC), polyhydric alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, or THEIC (tris(hydroxyethyl)isocyanurate), cellulose, BSPPO (bi(4-methoxy-1-phospha-2,6,7-trioxabicyclo[2.2.2]-octan-1-sulfide)phenylphosphate), lignin (alkali lignin and urea-modified liginin, etc.), and methylol melamine (methylol Examples include, but are not limited to, melamine compounds such as melamine, phenol-formaldehyde resins, and / or char-forming polymers such as PA6T (Poly-hexa methylene terephthalamide).

[0119] A typical example of a carbonizable organic substance is starch. Starch is relatively easy to obtain and can form suitable carbonized materials when exposed to heat or flame.

[0120] The type of starch can be adjusted in order to efficiently form the aforementioned char and to ensure that the formed char effectively exhibits the desired fire-extinguishing or heat-insulating effect.

[0121] For example, the starch can be a starch containing amylose and amylopectin, in which their ratio is adjusted to an appropriate level. As is well known, amylopectin and amylose are types of polysaccharides mainly found in plants, and starch, among polysaccharides, is composed of amylose and amylopectin. Amylose is composed of glucose molecules linked by α(1→4) glycosidic bonds and has a linear structure, while amylopectin has relatively short, highly branched chains. Amylose crystallizes relatively easily compared to amylopectin, and amylopectin has relatively higher solubility in water compared to amylose.

[0122] By using starch containing amylose and amylopectin having the aforementioned properties in an appropriate ratio, the desired composite material can be provided more efficiently.

[0123] For example, in the starch containing amylose and amylopectin, the lower limit of the weight ratio of amylopectin to 100 parts by weight of amylose may be around 150 parts by weight, 200 parts by weight, 250 parts by weight, or 300 parts by weight, and the upper limit may be around 900 parts by weight, 850 parts by weight, 800 parts by weight, 750 parts by weight, 700 parts by weight, 650 parts by weight, 600 parts by weight, 550 parts by weight, 500 parts by weight, 450 parts by weight, 400 parts by weight, 350 parts by weight, or 300 parts by weight. The ratio may be within a range where it is less than or equal to any one upper limit arbitrarily selected from the listed upper limits; or within a range where it is greater than or equal to any one lower limit arbitrarily selected from the listed lower limits; or within a range where it is greater than or equal to any one lower limit arbitrarily selected from the listed lower limits, and less than or equal to any one upper limit arbitrarily selected from the listed upper limits. The ratio of amylose to amylopectin can be measured according to the method described in "5. Measurement of Amylopectin and Amylose Content" in the Examples section of this specification.

[0124] As the starch, a starch having a molecular weight, for example, a weight-average molecular weight (Mw), within a predetermined range can be used. For example, the lower limit of the weight-average molecular weight of the starch is 200,000, 250,000, 300,000, 350,000, 400,000, 450,000, 500,000, 550,000, 600,000, 650,000, 700,000, 750,000, 800,000, 850,000, 900,000, 950,000. 00, 1,000,000, 1,500,000, 2,000,000, 2,500,000, 3,000,000, 3,500,000, 4,000,000, 4,500,000, 5,000,000, 5,500,000, 6,000,000, 6,500,000, 7,000,000, 7,500,000, 8,000 It may be around 1,000, 8,500,000, 9,000,000, 9,500,000, 10,000,000, 20,000,000, 30,000,000, 40,000,000 or 50,000,000, with the upper limit being 1,000,000,000, 900,000,000, 800,000,000, and 700 The molecular weight may be approximately ,000,000, 600,000,000, 500,000,000, 400,000,000, 300,000,000, 200,000,000, 150,000,000, 100,000,000, 90,000,000, 80,000,000, 70,000,000, or 60,000,000. The molecular weight may be within a range where it is less than or equal to any one upper limit arbitrarily selected from the listed upper limits; or within a range where it is greater than or equal to any one lower limit arbitrarily selected from the listed lower limits; or within a range where it is greater than or equal to any one lower limit arbitrarily selected from the listed lower limits, and less than or equal to any one upper limit arbitrarily selected from the listed upper limits. Starch having the aforementioned molecular weight (Mw) can more effectively form carbides that have the desired function (e.g., heat insulation) when exposed to heat or flame. The molecular weight can be measured by the method described in "4. Molecular Weight Measurement" of the Examples section of this specification. The unit of the molecular weight is g / mol.

[0125] The carbonizable organic material (for example, the starch) can be one having a gelatinization viscosity within a certain range. This gelatinization viscosity is related to the properties of the carbonizable organic material when it is present in a vaporized substance, and by controlling the gelatinization viscosity, carbides can be formed more effectively. The lower limit of the gelatinization viscosity of the carbonizable organic matter (e.g., starch) may be around 150, 200, 250, 300, 350, 400, 450, 500, 550, 650, 700, 750, 800, 850, 900, 950, or 1,000, and the upper limit may be around 5,000, 4,500, 4,000, 3,500, 3,000, 2,500, 2,000, 1,500, 1,000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, or 300. The gelatinization viscosity may be within a range where it is less than or equal to any one upper limit arbitrarily selected from the listed upper limits; or within a range where it is greater than or equal to any one lower limit arbitrarily selected from the listed lower limits; or within a range where it is greater than or equal to any one lower limit arbitrarily selected from the listed lower limits, and less than or equal to any one upper limit arbitrarily selected from the listed upper limits. The unit of the gelatinization viscosity is BU (Brabender unit).

[0126] The lower limit of the weight ratio of the carbonizable organic matter to 100 parts by weight of the vaporizable substance may be approximately 0.001 parts by weight, 0.005 parts by weight, 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, or 6 parts by weight, and the upper limit may be approximately 50 parts by weight, 45 parts by weight, 40 parts by weight, 35 parts by weight, 30 parts by weight, 25 parts by weight, 20 parts by weight, 15 parts by weight, 10 parts by weight, 5 parts by weight, 4 parts by weight, 3 parts by weight, 2 parts by weight, or 1 part by weight. The ratio may be within a range where it is less than or equal to any one upper limit arbitrarily selected from the listed upper limits; or within a range where it is greater than or equal to any one lower limit arbitrarily selected from the listed lower limits; or within a range where it is greater than or equal to any one lower limit arbitrarily selected from the listed lower limits, while being less than or equal to any one upper limit arbitrarily selected from the listed upper limits. Carbonizable organic matter included in such a ratio allows the composite material to effectively form carbides when needed, and can have excellent overall handling and storage stability.

[0127] The composite material may include an absorbent polymer as an optional additional component. The absorbent polymer is a polymer that has the property of absorbing water.

[0128] In one example, the superabsorbent polymer may be a so-called hydrogel polymer or hydrogel, generally defined as a crosslinked hydrophilic polymer. Such polymers are also known as SAPs (Super Absorbent Polymers).

[0129] The aforementioned superabsorbent polymer is a material capable of absorbing tens to thousands of times its own weight in water. Such a material can serve to ensure that the composite material exists in a gel state as a whole, thereby ensuring handling and storage stability.

[0130] There are no particular restrictions on the type of superabsorbent polymer; generally, any polymer that can be applied as a SAP can be used without limitation.

[0131] Typically, the material used is a polyacrylate-based vinyl polymer. The polyacrylate-based polymer is a polymer made from acrylate monomers, and if necessary, other copolymers can be added to form the polymer.

[0132] The superabsorbent polymer may, in one example, be a particulate polymer. By applying the superabsorbent polymer, the weight-based size distribution of the particulate superabsorbent polymer can be controlled in order to ensure the desired viscosity characteristics and digestive function. In this specification, the term "weight-based size distribution of superabsorbent polymer" refers to a size distribution measured according to the EDANA WSP 220.3 standard, where the sample of particulate superabsorbent polymer is divided into fractions with a size of less than 150 μm (hereinafter referred to as "fraction A"), fractions in the range of 150 μm to 300 μm (hereinafter referred to as "fraction B"), fractions in the range of 300 μm to 600 μm (hereinafter referred to as "fraction C"), fractions in the range of 600 μm to 850 μm (hereinafter referred to as "fraction D"), and fractions exceeding 850 μm (hereinafter referred to as "fraction E"), and the weight of each fraction is expressed as a percentage (weight ratio of each fraction) of the total weight of the particulate superabsorbent polymer sample.

[0133] The particulate superabsorbent polymer may have a maximum weight size in the weight-based size distribution that falls within the range of 150 μm to 850 μm. In the above, the maximum weight size is the size of the fraction that shows the highest weight ratio among the weight ratios of fraction A, fraction B, fraction C, fraction D, and fraction E. That is, the fact that the maximum weight size is within the range of 150 μm to 850 μm means that the weight ratio of the particulate superabsorbent polymer belonging to one or more of fractions B, C, and D is the largest. The weight ratios of two fractions may be the same, and that weight ratio may be the highest among the weight ratios of all fractions, so there may be one or more fractions with the maximum weight size. In one example, the fraction with the maximum weight size may be fraction C among fractions B, C, and D. Therefore, the maximum weight size in the weight-based size distribution may fall within the range of 300 μm to 600 μm.

[0134] In the weight-based size distribution of the particulate superabsorbent polymer, the lower limit of the weight ratio in the fraction showing the maximum weight size (i.e., the weight ratio of the superabsorbent polymer belonging to the maximum weight size in the weight-based size distribution) may be approximately 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 71% by weight, 72% by weight, 73% by weight, or 74% by weight, and the upper limit may be approximately 95% by weight, 90% by weight, 85% by weight, 80% by weight, 79% by weight, 78% by weight, 77% by weight, 76% by weight, or 75% by weight. The weight ratio may be within a range that is greater than or greater than any one of the lower limits arbitrarily selected from the listed lower limits; or within a range that is greater than or greater than any one of the lower limits arbitrarily selected from the listed lower limits, and less than or equal to any one of the upper limits arbitrarily selected from the listed upper limits.

[0135] If the maximum weight size is excessively small, and / or the weight ratio in the fraction representing the maximum weight size is excessively small, the composite material may not be able to properly form the desired gel, potentially leading to reduced handling and storage properties, or failure to exhibit the desired digestive function. Therefore, an appropriate particulate superabsorbent polymer can be selected with this in mind.

[0136] If included, the lower limit of the weight ratio of the superabsorbent polymer to 100 parts by weight of the vaporizing substance may be approximately 0.01 parts by weight, 0.5 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, or 9 parts by weight, and the upper limit may be approximately 50 parts by weight, 45 parts by weight, 40 parts by weight, 35 parts by weight, 30 parts by weight, 29 parts by weight, 28 parts by weight, 27 parts by weight, 26 parts by weight, 25 parts by weight, 24 parts by weight, 23 parts by weight, 22 parts by weight, 21 parts by weight, 20 parts by weight, 19 parts by weight, 18 parts by weight, 17 parts by weight, 16 parts by weight, 15 parts by weight, 14 parts by weight, 13 parts by weight, 12 parts by weight, 11 parts by weight, 10 parts by weight, 9 parts by weight, 8 parts by weight, 7 parts by weight, 6 parts by weight, 5 parts by weight, 4 parts by weight, 3 parts by weight, or 2 parts by weight. The ratio may be within a range where it is less than or equal to any one upper limit arbitrarily selected from the listed upper limits; or within a range where it is greater than or equal to any one lower limit arbitrarily selected from the listed lower limits; or within a range where it is greater than or equal to any one lower limit arbitrarily selected from the listed lower limits, and less than or equal to any one upper limit arbitrarily selected from the listed upper limits.

[0137] The sealed space or composite material inside the fire extinguishing device may contain the aforementioned components and, if necessary, additional components.

[0138] This specification discloses a method for manufacturing the composite material. For example, the manufacturing method may include a step of polymerizing the precursor solution containing the inorganic gel precursor and the vaporizing substance.

[0139] The polymerization described above is a process in which relatively low molecular weight substances, such as monomers or oligomers, form a network to form high molecular weight components. In this case, the monomer or oligomer may be the precursor. Furthermore, there are no particular restrictions on the specific method by which the polymerization is carried out. For example, if the inorganic gel precursor is a condensing precursor described later, the polymerization process may be a so-called sol-gel process.

[0140] As the precursor, for example, a metal alkoxide can be used. Such a precursor is a condensation precursor and can form an inorganic gel via the sol-gel process. Specifically, examples of the metal alkoxide include one or more alkoxides selected from the group consisting of silicon, titanium, zirconium, niobium, tantalum, molybdenum, and tungsten. The lower limit of the number of carbon atoms in the alkoxide may be around 4, 6, 8, or 10, and the upper limit may be around 20, 18, 16, 14, 12, 10, or 8. The number of carbon atoms may be within a range that is greater than or exceeds any one of the lower limits arbitrarily selected from the listed lower limits, and less than or equal to any one of the upper limits arbitrarily selected from the listed upper limits. As the precursor, for example, a component called so-called water glass (sodium silicate) can be used, and such a component can form silica gel as an inorganic gel.

[0141] As the aforementioned vaporizing substance, components such as water can be used.

[0142] The composition of the precursor solution can be adjusted to form the desired inorganic gel and composite material.

[0143] For example, the content of the vaporized substance in the precursor solution can be adjusted. For example, the lower limit of the content of the vaporized substance in the precursor solution may be around 30% by weight, 40% by weight, 50% by weight, 60% by weight, or 65% by weight, and the upper limit may be around 95% by weight, 90% by weight, 85% by weight, 80% by weight, 75% by weight, 70% by weight, 65% by weight, or 60% by weight. The content may be greater than or greater than any one lower limit arbitrarily selected from the listed lower limits, and less than or equal to any one upper limit arbitrarily selected from the listed upper limits.

[0144] In the precursor solution, the lower limit of the weight ratio of the precursor to 100 parts by weight of the vaporizable substance may be approximately 0.001 parts by weight, 0.005 parts by weight, 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.15 parts by weight, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 1 part by weight, 3 parts by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, or 20 parts by weight, and the upper limit may be approximately 25 parts by weight, 20 parts by weight, 15 parts by weight, 10 parts by weight, 5 parts by weight, 4 parts by weight, 3 parts by weight, 2 parts by weight, 1 part by weight, or 0.5 parts by weight. The content may be greater than or greater than any one lower limit arbitrarily selected from the listed lower limits, and less than or equal to any one upper limit arbitrarily selected from the listed upper limits.

[0145] The precursor solution can be composed to exhibit a pH within a predetermined range. For example, the lower limit of the pH of the precursor solution may be around 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, or 7, and the upper limit may be around 14, 13, 12, 11, 10, 9, 8, or 7. The pH may be within a range where it is above or above any one lower limit arbitrarily selected from the listed lower limits, and below or below any one upper limit arbitrarily selected from the listed upper limits.

[0146] To adjust the pH, the precursor solution may further contain a catalyst. Such a catalyst may be one of the ionic compounds mentioned above. There are no particular restrictions on the type of catalyst that can be applied; for example, acid catalysts or base catalysts applicable to general sol-gel processes can be used. Examples of such acid catalysts include one or more selected from hydrochloric acid, sulfuric acid, sulfuric acid fluoride, nitric acid, phosphoric acid, acetic acid, hexafluorophosphate, p-toluenesulfonic acid, and trifluoromethanesulfonic acid, while examples of base catalysts include, but are not limited to, alkaline catalysts such as sodium hydroxide, ammonium hydroxide, or ammonium chloride.

[0147] The content of the catalyst can be controlled within a range that allows the aforementioned pH to be achieved. For example, in the precursor solution, the lower limit of the molar concentration of the catalyst relative to the vaporizable substance (i.e., the number of moles of catalyst present per 1 kg of vaporizable substance) may be around 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.5, 1, or 1.5, and the upper limit may be around 5, 4.5, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.8, 0.6, or 0.4. The molar concentration may be greater than or greater than any one lower limit arbitrarily selected from the listed lower limits, and less than or equal to any one upper limit arbitrarily selected from the listed upper limits.

[0148] The precursor solution may additionally contain ionic compounds in addition to the catalyst. Such ionic compounds can be added to adjust the molecular energy or intermolecular forces of the vaporizing substance, as described above, in order to form the desired inorganic gel. Examples of ionic compounds include the aforementioned freezing point adjusters or carbonization catalysts.

[0149] The content of all ionic compounds present in the precursor solution, including the catalyst, can be adjusted. Such adjustment of content controls the fluidity of the vaporized substance, and this controlled fluidity affects the polymerization efficiency of the precursor, allowing the desired inorganic gel to be formed at a specified polymerization temperature.

[0150] For example, the ionic compound is ΔT of the above formula 1. f It can be added so that it falls within the aforementioned predetermined range.

[0151] The precursor solution may contain any other necessary components besides those mentioned above. For example, the polymerization can be carried out in the presence of the inorganic fibers. The inorganic fibers also affect the polymerization efficiency of the precursor. In such cases, the precursor solution may contain the inorganic fibers mentioned above.

[0152] The lower limit of the weight ratio of the inorganic fiber to 100 parts by weight of the vaporizable substance in the precursor solution may be approximately 0.5 parts by weight, 1 part by weight, 5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, or 75 parts by weight, and the upper limit may be approximately 100 parts by weight, 95 parts by weight, 90 parts by weight, 85 parts by weight, 80 parts by weight, 75 parts by weight, 70 parts by weight, 65 parts by weight, 60 parts by weight, 55 parts by weight, 50 parts by weight, 45 parts by weight, 40 parts by weight, 35 parts by weight, 30 parts by weight, 25 parts by weight, or 20 parts by weight. The weight ratio may be within a range where it is greater than or exceeds any one of the lower limits arbitrarily selected from the listed lower limits, and at the same time less than or equal to any one of the upper limits arbitrarily selected from the listed upper limits.

[0153] The temperature for polymerization of the precursor solution can be controlled. Such a controlled temperature is ΔT f It works in conjunction with ionic compounds having a specific value to contribute to the formation of inorganic gels in the desired form.

[0154] For example, the lower limit of the polymerization temperature may be around 10°C, 15°C, 20°C, 25°C, 30°C, or 35°C, and the upper limit may be around 50°C, 45°C, 40°C, 35°C, 30°C, or 25°C. The polymerization temperature may be at or above any one of the lower limits arbitrarily selected from the listed lower limits, while simultaneously being below or below any one of the upper limits arbitrarily selected from the listed upper limits.

[0155] For the formation of the target composite material, polymerization of the precursor or the prepolymer of the precursor can be carried out in the presence of inorganic fibers. For this purpose, the polymerization can proceed in multiple stages. For example, the production method may include a first stage (primary polymerization) in which the precursor solution is polymerized to obtain a prepolymer, and a second stage (secondary polymerization) in which the precursor or prepolymer is polymerized in the presence of inorganic fibers to obtain an inorganic gel. The precursor solution applied to the primary polymerization does not have to contain the inorganic fibers. That is, the primary polymerization is carried out without inorganic fibers, and the second stage secondary polymerization can be carried out in the presence of inorganic fibers. That is, after primary polymerization, the polymer can be mixed with inorganic fibers and polymerization can proceed further. The precursor in the second stage may mean a precursor that did not participate in polymerization and form a prepolymer during primary polymerization.

[0156] The primary polymer or prepolymer may be, for example, an inorganic sol.

[0157] The polymerization temperature, polymerization time, and / or mixing conditions of the first stage can be adjusted.

[0158] The lower limit of the polymerization temperature in the first stage may be approximately 10°C, 15°C, 20°C, 25°C, 30°C, or 35°C, and the upper limit may be approximately 50°C, 45°C, 40°C, 35°C, 30°C, or 25°C. The polymerization temperature may be at or above any one of the lower limits arbitrarily selected from the listed lower limits, while simultaneously being below or below any one of the upper limits arbitrarily selected from the listed upper limits.

[0159] The first step can be carried out while stirring the precursor solution at an appropriate speed. In this process, the lower limit of the stirring speed may be around 100 rpm, 150 rpm, 200 rpm, 250 rpm, 300 rpm, 350 rpm, 400 rpm, 450 rpm, or 500 rpm, and the upper limit may be around 2,000 rpm, 1,500 rpm, 1,000 rpm, 800 rpm, 600 rpm, 400 rpm, or 300 rpm. The stirring speed may be greater than or greater than any one lower limit arbitrarily selected from the listed lower limits, and less than or equal to any one upper limit arbitrarily selected from the listed upper limits.

[0160] The lower limit of the time for the primary polymerization may be approximately 1 second, 5 seconds, 10 seconds, 30 seconds, 1 minute, 5 minutes, 10 minutes, or 15 minutes, and the upper limit may be approximately 60 minutes, 55 minutes, 50 minutes, 45 minutes, 40 minutes, 35 minutes, 30 minutes, 25 minutes, 20 minutes, 15 minutes, 10 minutes, 8 minutes, 6 minutes, 4 minutes, 2 minutes, 1 minute, or 30 seconds. The time may be greater than or greater than any one lower limit arbitrarily selected from the listed lower limits, and less than or less than any one upper limit arbitrarily selected from the listed upper limits.

[0161] By forming a primary polymer (prepolymer or a mixture of prepolymer and precursor) under the above conditions and proceeding with secondary polymerization, the desired composite material can be formed.

[0162] The primary polymer can be further subjected to secondary polymerization to form an inorganic gel. As mentioned above, secondary polymerization can be carried out in the presence of the inorganic fibers. That is, after primary polymerization, the inorganic fibers and the primary polymer can be mixed to satisfy the aforementioned ratio (ratio of inorganic fibers to 100 parts by weight of vaporizable substance), and then polymerization can be further carried out to effectively form the desired inorganic gel.

[0163] The aforementioned secondary polymerization can be carried out at an appropriate temperature.

[0164] For example, the lower limit of the polymerization temperature may be around 10°C, 15°C, 20°C, or 25°C, and the upper limit may be around 40°C, 35°C, 30°C, or 25°C. The temperature may be within a range where it is above or above any one of the lower limits arbitrarily selected from the listed lower limits, and below or below any one of the upper limits arbitrarily selected from the listed upper limits.

[0165] By maintaining the mixture of the primary polymer and inorganic fibers at the aforementioned temperature during secondary polymerization, the desired inorganic gel can be obtained.

[0166] The inorganic gel formed in this manner can be mixed with other components of the required composite material to produce the composite material. The components may be mixed with the inorganic gel after its production, or mixed into a precursor solution before the inorganic gel is produced, or at an appropriate point during the inorganic gel production process.

[0167] After manufacturing the composite material, it can be inserted into a case to form a fire extinguishing device. Alternatively, the composite material can be inserted into the case after manufacturing, and all or part of the manufacturing process of the composite material can be carried out within the case to form a fire extinguishing device. For example, the fire extinguishing device and the composite material can be manufactured simultaneously by pre-arranging inorganic fibers in the case, injecting a primary polymer, performing additional polymerization, and introducing additional components as needed after polymerization.

[0168] This specification also discloses electronic equipment or devices to which the fire extinguishing system is applied.

[0169] The type of electronic equipment or device is not particularly limited. For example, the composite material or fire extinguishing device can be applied to equipment or devices that pose a risk of abnormal heat generation, ignition, and / or explosion during operation, maintenance, and / or storage, and where such abnormal phenomena should be controlled.

[0170] A typical example of the aforementioned equipment or device is a battery. In particular, in battery modules composed of multiple battery cells, it is important to prevent abnormal heat generation, ignition, and / or explosion occurring in one battery cell from spreading to other adjacent battery cells.

[0171] This specification discloses a battery module including the fire extinguishing device.

[0172] Such a battery module may essentially include a number of battery cells; and the fire extinguishing device positioned between the battery cells.

[0173] As long as the fire extinguishing device is applied, the specific configuration of the battery module, such as the type of battery cell, is not particularly limited, and known materials can be used. For example, known pouch-type, rectangular, or cylindrical battery cells can be used as the battery cells.

[0174] The method for manufacturing the battery module is not particularly limited. For example, a method can be used in which a fire extinguishing device similar in form to a battery cell is manufactured as described above, and then the fire extinguishing device is positioned at the required location during the manufacturing process of the battery module. [Effects of the Invention]

[0175] This specification discloses composite materials and fire extinguishing devices that are applied to products or elements that are in or potentially in an abnormal state and that can effectively respond to said abnormal state. For example, the composite materials, etc., are applied to articles containing multiple such products or elements and can respond to abnormal heat generation, explosions, and ignition occurring in any one of the elements or products, and can prevent or minimize the propagation of such heat generation, explosions, and ignition to adjacent elements or products. The composite materials, etc., also exhibit excellent handling and storage stability. This specification can also provide applications for the composite materials, etc. [Brief explanation of the drawing]

[0176] [Figure 1] This is an exemplary cross-sectional view of a battery module to which a fire extinguishing system has been applied. [Figure 2] This is an illustrative diagram illustrating the operating principle of a fire extinguishing system. [Figure 3] This is an illustrative diagram illustrating the operating principle of a fire extinguishing system. [Figure 4] This diagram illustrates the process of manufacturing a fire extinguishing device in an example. [Modes for carrying out the invention]

[0177] The composite materials, etc. will be described in detail below with reference to the examples, but the scope of the composite materials, etc. is not limited by the examples below.

[0178] 1. Convection Exam A fire extinguishing device (width x height x thickness = 9cm x 12cm x 3mm) was positioned between two aluminum plates, and insulation material was laminated onto one of the two aluminum plates to create a laminate in which the insulation material, aluminum plate, fire extinguishing device, and aluminum plate were sequentially laminated. For the aluminum plate, a plate with a thickness of approximately 3mm was used, and for the insulation material, mineral wool (KCC, insulation board No. 1) with a thickness of approximately 2mm was used. Next, both sides of the laminate were pressed together and fixed with a jig at a pressure of approximately 350kPa. A temperature sensor (k-type thermocouple, Fluke IR thermometers model 566) was positioned on the insulation material side of the laminate, and the temperature was measured with the temperature sensor while applying a flame toward the aluminum plate on the opposite side. The flame was applied using two cans of butane gas (220g capacity can-type butane gas (unused product)) and a torch, at a distance of approximately 2 inches from the aluminum plate. The temperature was measured using the temperature sensor while the flame was applied for about 5 minutes, and evaluated according to the following criteria.

[0179] <Evaluation Criteria> Pass: If the temperature sensor's measured temperature is maintained below 200°C. NG: If the temperature sensor measures a temperature of 200°C or higher, or if the aluminum dish is observed to melt.

[0180] 2. Chain ignition test Rectangular batteries were arranged at approximately 3mm intervals, with a fire extinguishing device positioned between them. CATL products (120Ah, 3.2V, size = thickness x width x height = 48 x 174 x 165) were used as rectangular batteries and were applied to the test in a 100% charged state. In the above arrangement, battery ignition was induced in one rectangular battery according to the SAE J2464:2009 standard, and it was checked whether chain ignition to other cells occurred. The ignition of the aforementioned battery was induced by penetrating the rectangular battery with a nail approximately 5mm in diameter at a speed of 25mm / sec (nail penetration method).

[0181] <Evaluation Criteria> Pass: If no fire occurs in any battery cell other than the one that has been penetrated by the nail. NG: If fire occurs in a battery cell other than the one pierced by the nail.

[0182] 3. Evaluation of thermal conductivity Thermal conductivity was evaluated using Hot Disk's TPS2200 equipment, in accordance with the ISO22007-2 standard.

[0183] 4. Measurement of molecular weight The molecular weight of starch was evaluated using the following method.

[0184] (1) Manufacturing of the mobile phase Mobile phase A was prepared by filtering 1000 mL of a 150 mM NaNO3 aqueous solution containing 0.02 wt% NaN3 using a solvent clarification system (Millipore Millisolve Kit, MilliporeSigma).

[0185] (2) Preparation of sample solution A 25 mg sample was taken from the sample whose molecular weight was to be measured, mixed with 5 mL of a 150 mM NaNO3 aqueous solution containing 0.02 wt% NaN3, heated at 80°C for 20 hours, and then filtered through a 0.4 μm Nylon Syringe Filter to prepare the sample solution.

[0186] (3) GPC (Gel Permeation Chromatography) / MALS (Multi-Angle Light Scattering Detection) conditions The molecular weight was evaluated using the sample solution and mobile phase A in the following manner. Measurement instrument: Agilent GPC (Agilent 1200 series, US) Stationary phase: Shodex OH-Pak 804 column and Shodex OH-Pak 80 column linked together Mobile phase: A; 0.02% NaN3, 150mM NaNO3 aqueous solution = 100 (v / v%) Flow rate: 0.4mL / min Stationary phase temperature: 25℃ Injection volume: 100μl (0.45μm filtered) Analysis time: 120 minutes

[0187] 5. Measurement of amylopectin and amylose content The amylopectin and amylose content of starch was evaluated according to the method described in the paper (Potato Research 31 (1988) 241-246).

[0188] First, approximately 5 mg of starch was dissolved in approximately 1 mL of sterile water to prepare the sample (Step 1), and then heated in a water bath at 95°C for approximately 15 minutes (Step 2).

[0189] Next, approximately 20 μl of the sample was placed in a cuvette (step 3), and approximately 980 μl of iodine solution was added and mixed (step 4).

[0190] Next, the absorbance of the sample mixed with the iodine solution was measured and recorded at wavelengths of 525 nm and 700 nm (Step 5). The absorbance was measured using the KLAB OPTIZEN POP model.

[0191] Approximately 20 μl of water was placed in another cuvette, and 980 μl of iodine solution was added and mixed (Step 6). The absorbance of the solution from Step 6 at wavelengths of 525 nm and 700 nm was measured and recorded, as in Step 5 (Step 7).

[0192] The absorbance obtained in step 7 was subtracted from the absorbance obtained in step 5, and the ratio (%) of amylose was confirmed according to formula C below (step 8). [Formula C] PA = 3.039 - U / L - 19.192

[0193] In equation C, PA is the percentage of amylose, U is determined by equation D below, and L is determined by equation E below. [Formula D] U = 7.154 × OD 700 / OD 525 [Formula E] L = 3.048 × OD 700 / OD 525

[0194] In formulas D and E, OD 700 This is the value obtained by subtracting the absorbance at 700 nm measured in step 7 from the absorbance at 700 nm measured in step 5, and OD 525 This value is obtained by subtracting the absorbance at 525 nm measured in step 7 from the absorbance at 525 nm measured in step 5.

[0195] 6. Evaluation of WVTR (Water Vapor Transmission Rate) The WVTR of the fire extinguishing system case was evaluated according to ASTM F1249 standards under conditions of 38°C and 100% relative humidity.

[0196] 7. Evaluation of solubility Solubility was evaluated based on the ASTM E1148-02 standard. The amount of sample that could be maximally dissolved in 100g of water at room temperature (approximately 25°C) or 0°C was evaluated according to the aforementioned standard, and the solubility was confirmed.

[0197] 8. Evaluation of compressive strength The compressive strength of the composite material was evaluated using the Instron Compression test kit D90, based on the ISO 604 standard. With the composite material positioned flat, it was compressed using a jig, and a Compression SS curve was obtained with compression strain (%) on the x-axis and compression stress corresponding to the compression strain on the y-axis. The compression stress at the point where the compression strain (%) reached 60% was defined as the compressive strength. During the evaluation, the compression speed was set to approximately 1.3 mm / min, and the preload was set to approximately 10 kN.

[0198] 9. Thickness shrinkage rate The thickness of the composite material was evaluated using TESA's μ-HITE equipment. A Flat Face Probe with a diameter of approximately 5 mm was used as the probe type, and the thickness was measured with a force of approximately 0.63 N in Single Probing Mode. With the test specimen (the object to be measured for thickness) positioned flat on the equipment, the thickness was measured at three points on the specimen, and the arithmetic mean of the measured thicknesses was calculated and designated as the thickness. After dividing the test specimen into three equal parts, the midpoints of each of the three divided regions were designated as the three points. The test specimen to be measured for thickness was cut to a length of approximately 9 cm and 12 cm in both width and length.

[0199] The initial thickness (T1) of the composite material was measured using the method described above. After applying the fire extinguishing device to the "1. Convection Test," the composite material was removed from the fire extinguishing device and its thickness (T2) was measured.

[0200] The thicknesses T1 and T2 were substituted into the following formula A, and the thickness shrinkage rate ΔT was measured. [Formula A] △T = 100 × (T2-T1) / T1

[0201] 10. Evaluation of storage stability The fire extinguishing device was stored in an oven at a temperature of approximately 35°C for 1,000 hours, and the weight change before and after storage in the oven was measured. A weight change of 1% or more was evaluated as NG, and a weight change of less than 1% or no weight change was evaluated as PASS.

[0202] Example 1. Manufacturing of composite materials A silica sol was produced by mixing distilled water, liquid sodium silicate, hydrochloric acid aqueous solution (hydrochloric acid concentration: approximately 33% by weight), monoammonium phosphate (NH4H2PO4), potassium acetate, and starch to create a mixture.

[0203] As the starch used, corn starch with a weight-average molecular weight of approximately 51,000,000 g / mol and a weight ratio of amylose to amylopectin (amylose:amylopectin) of approximately 25:75 was used. As the liquid sodium silicate used, No. 3 (KS) (No. 3 KS) from YOUNG IL CHEMICAL Co., Ltd. was used (Na2O content: approximately 9-10% by weight, SiO2 content: approximately 28-30% by weight, sodium silicate molar ratio (=1.032 (SiO2 weight) / (Na2O weight)): approximately 3.1-3.3).

[0204] The solubility of monoammonium phosphate (N) (NH4H2PO4) in water at 25°C is approximately 29 g. The solubility of potassium acetate in 100 g of water at 0°C is approximately 216 g, and its solubility in 100 g of water at 25°C is approximately 268.6 g.

[0205] The mixing was carried out so that the weight ratio (W:S:A:N:K:T) of the distilled water (W), SiO2 (S) in the liquid sodium silicate, hydrochloric acid aqueous solution (A), monoammonium phosphate (N), potassium acetate (K), and starch (T) was approximately 64:2:2.6:4.5:25:0.7.

[0206] The pH of the mixture was approximately 5 to 6.

[0207] In the aforementioned mixture, the molar concentration of hydrochloric acid relative to distilled water was approximately 0.36, the molar concentration of monoammonium phosphate was approximately 0.6, and the molar concentration of potassium acetate was approximately 3.87.

[0208] In the aforementioned mixture, the following ΔT of formula 1 is obtained by the hydrochloric acid f The value is approximately 1.33, and the ΔT of the following formula 1 due to monoammonium phosphate is approximately 1.33. f The value is approximately 2.21, and the ΔT of the following formula 1 due to potassium acetate is approximately 2.21. f The average was approximately 14.41, and the total was approximately 17.96. [Formula 1] △T f = K f × M × I In Equation 1, K f The ratio is approximately 1.86 K / m, where M is the molar concentration of each ionic compound, and I is the number of moles of ions generated when 1 mole of the ionic compound completely dissociates.

[0209] The silica sol was prepared by stirring the mixture at a speed of approximately 500 rpm for approximately 15 minutes at room temperature (approximately 23°C).

[0210] Ceramic paper (WOOREE REFRACTORIES, thickness: approx. 3mm, density: approx. 0.2g / cm³) is placed on a conveyor belt equipped with gel casting equipment. 3 The ceramic paper was positioned and impregnated with the silica sol using spike rollers. Subsequently, the composite material was manufactured by further gelation at room temperature (approximately 25°C) while moving the conveyor belt to form silica gel. During the manufacture of the composite material, the ratio W:P of the weight of water (W) in the silica sol to the weight of the ceramic paper (P) was set to approximately 100:23.

[0211] The water content in the composite material was approximately 56.38% by weight, the inorganic gel (silica gel) content was approximately 1.76% by weight, and the inorganic fiber (ceramic paper) content was approximately 12.97% by weight.

[0212] Manufacturing of fire extinguishing systems The composite material was inserted into an aluminum can (case) used in the manufacture of prismatic batteries, and the opening was sealed to manufacture a fire extinguishing device. The aluminum can was made of an aluminum alloy, and the WVTR of the case was approximately 0 g / m². 2 The process took approximately one day. As shown in Figure 4, two heat conductive layers (2001, 2002) were inserted into the aluminum can (1001), the composite material was placed between the two heat conductive layers (2001, 2002), and then the lid (1002) was placed over it to manufacture the fire extinguishing device. The composite material was cut and applied so as to occupy at least 80% of the volume of the space inside the can. For the heat conductive layers (2001, 2002), a copper film (thickness approximately 15 μm) with a thermal conductivity of approximately 401 W / mK was used. For the rectangular battery case, a case with a width of approximately 9 cm, a height of approximately 12 cm, and a thickness of approximately 3 mm was used.

[0213] Example 2. A silica sol was produced by mixing distilled water, liquid sodium silicate, an aqueous NaOH solution (NaOH concentration: approximately 35% by weight), an aqueous acetic acid solution (acetic acid concentration: approximately 33% by weight), monoammonium phosphate (NH4H2PO4), ammonium sulfate, and starch to create a mixture.

[0214] The same substances as in Example 1 were used as the starch and liquid sodium silicate.

[0215] The solubility of ammonium sulfate in 100g of water at 0°C is approximately 70.6g, and its solubility in 100g of water at 25°C is approximately 76g.

[0216] The mixing was carried out so that the weight ratio (W:S:B:A:N:K:T) of the distilled water (W), SiO2 (S) in the liquid sodium silicate, NaOH aqueous solution (B), acetic acid aqueous solution (A), monoammonium phosphate (N), ammonium sulfate (K), and starch (T) was approximately 64:2:0.09:1:4.5:16:0.7.

[0217] The pH of the aforementioned mixture was approximately 6 to 8.

[0218] In the aforementioned mixture, the molar concentration of NaOH relative to distilled water was approximately 0.01, the molar concentration of acetic acid was approximately 0.26, the molar concentration of monoammonium phosphate was approximately 0.61, and the molar concentration of ammonium sulfate was approximately 1.89.

[0219] In the mixture, the ΔT of formula 1 due to the NaOH f The ratio is approximately 0.04, and the ΔT of formula 1 due to acetic acid is approximately 0.04. f The ratio is approximately 0.96, and the ΔT of formula 1 due to monoammonium phosphate is approximately 0.96. f The value is approximately 2.27, and the ΔT of formula 1 due to ammonium sulfate is approximately 2.27. f The ratio was approximately 10.55, and the total was approximately 13.82.

[0220] The silica sol was prepared by stirring the mixture at a speed of approximately 500 rpm for approximately 15 minutes at room temperature (approximately 23°C).

[0221] The composite material and fire extinguishing device were manufactured in the same manner as in Example 1, except that the silica sol was used.

[0222] However, the WVTR content of the can (case) used in the manufacture of the aforementioned fire extinguishing device is approximately 0.11 g / m³. 2 A case suitable for a day was used, and an aluminum film with a thermal conductivity of approximately 235 W / mK and a thickness of approximately 100 μm was used as the thermal conductive layer.

[0223] In the aforementioned composite material, the water content was approximately 62.13% by weight, the inorganic gel (silica gel) content was approximately 1.94% by weight, and the inorganic fiber (ceramic paper) content was approximately 14.29% by weight.

[0224] Comparative Example 1. Manufacturing of composite materials A silica sol was produced by mixing distilled water, liquid sodium silicate, hydrochloric acid aqueous solution (hydrochloric acid concentration: approximately 33% by weight), monoammonium phosphate (NH4H2PO4), potassium acetate, and starch to create a mixture.

[0225] The same substances as in Example 1 were used as the starch and liquid sodium silicate.

[0226] The mixing was carried out so that the weight ratio (W:S:A:N:K:T) of the distilled water (W), SiO2 (S) in the liquid sodium silicate, hydrochloric acid aqueous solution (A), monoammonium phosphate (N), potassium acetate (K), and starch (T) was approximately 50:16:2:4.5:25:0.7.

[0227] The pH of the mixture was approximately 5 to 6.

[0228] In the aforementioned mixture, the molar concentration of hydrochloric acid relative to distilled water was approximately 0.35, the molar concentration of monoammonium phosphate was approximately 0.76, and the molar concentration of potassium acetate was approximately 4.96.

[0229] In the mixture, the hydrochloric acid causes ΔT of formula 1 f The value is approximately 1.31, and the ΔT of formula 1 due to the monoammonium phosphate is approximately 1.31. f The value is approximately 2.83, and the ΔT of formula 1 due to potassium acetate is approximately 2.83. f The ratio was approximately 18.46, and the total was approximately 22.6.

[0230] The silica sol was prepared by stirring the mixture at a speed of approximately 500 rpm for approximately 15 minutes at room temperature (approximately 23°C).

[0231] Ceramic paper (WOOREE REFRACTORIES, thickness: approx. 3mm, density: approx. 0.2g / cm³) is placed on a conveyor belt equipped with gel casting equipment. 3 The ceramic paper was positioned and impregnated with the silica sol using spike rollers. Subsequently, the composite material was manufactured by further gelation at room temperature (approximately 25°C) while moving the conveyor belt to form silica gel. During the manufacture of the composite material, the ratio W:P of the weight of water (W) in the silica sol to the weight of the ceramic paper (P) was set to approximately 100:23.

[0232] The water content in the composite material was approximately 45.58% by weight, the inorganic gel (silica gel) content was approximately 14.59% by weight, and the inorganic fiber (ceramic paper) content was approximately 10.48% by weight.

[0233] Manufacturing of fire extinguishing systems A fire extinguishing device was manufactured in the same manner as in Example 1, using an aluminum can (case) used in the manufacture of prismatic batteries, the composite material, and a thermal conductive layer. The aluminum can was made of an aluminum alloy, and the WVTR of the case was approximately 0 g / m². 2 The duration was approximately one day. As the thermal conductive layer, a copper film with a thermal conductivity of approximately 401 W / mK (thickness approximately 300 μm) was used.

[0234] Comparative Example 2. Distilled water (W), monoammonium phosphate (N) (NH4H2PO4), potassium acetate (K), and starch (T) were mixed in a weight ratio of 65:4.5:25:0.7 (W:N:K:T). The same starch as in Example 1 was used. The mixture was placed on ceramic paper (WOOREE REFRACTORIES, thickness: approximately 3 mm, density: approximately 0.2 g / cm³).3 A composite material was manufactured by impregnating it with ( ). During the manufacture of the composite material, the ratio of the weight of water (W) to the weight of the ceramic paper (P) W:P was set to approximately 100:23. Subsequently, a fire extinguishing device was manufactured using the composite material in the same manner as in Example 1.

[0235] Comparative Example 3. A silicone foam pad (L2Y), which is used as an insulating material instead of composite material, was applied, and a fire extinguishing device was manufactured in the same manner as in Example 1.

[0236] The evaluation results for the examples and comparative examples are shown in Table 1 below. [Table 1]

[0237] The compressive strength (before) in Table 1 refers to the compressive strength (C) measured for composite materials manufactured using the method described in "8. Compressive Strength Evaluation" above. f1 The compressive strength (after) is (MPa), and the compressive strength (after) is obtained by applying the fire extinguishing device into which the composite material has been introduced to the "1. Convection test", removing the composite material from the fire extinguishing device, and evaluating the compressive strength (C) using the same method. f2 )(MPa). In Table 1, the ratio is the compressive strength C f2 Compressive strength C f1 The value C divided by f2 / C f1 That is the case.

[0238] From the results in Table 1, the composite material of the example has the ratio C f2 / C f1 The composite material exhibits a high value. This means that even when the environment to which the composite material is applied becomes abnormal and strong pressure is applied to the composite material along with high temperature, the composite material can stably maintain its shape. Consequently, the composite material of the example showed a low thickness shrinkage rate. Such results indicate that the composite material can effectively cope with abnormal conditions.

[0239] On the other hand, in Comparative Example 1, where the proportion of inorganic gel (silica gel) in the composite material was high, measuring the compressive strength was difficult, but a large thickness shrinkage rate was observed. This means that under abnormal conditions, the shape of the composite material is easily destroyed, and the fire extinguishing function cannot be effectively performed.

[0240] Furthermore, in the case of Comparative Example 2, which does not contain an inorganic gel, the C level is low. f2 / C f1 Comparative Example 3, which corresponds to a general silicone pad, also showed a low C ratio and high thickness shrinkage rate. f2 / C f1 It showed a ratio and a high rate of thickness shrinkage.

Claims

1. Vaporizing substances; and Contains inorganic gel, A composite material in which the ratio of compressive strength at 60% compression before and after a convection test is 1.2 or higher.

2. The composite material according to claim 1, wherein the compressive strength at 60% compression before the convection test is in the range of 0.1 to 5 MPa.

3. The composite material according to claim 1, wherein the absolute value of the thickness shrinkage rate after the convection test is 10% or less.

4. The composite material according to claim 1, wherein the vaporizing substance has a boiling point in the range of 80°C to 120°C.

5. The composite material according to claim 1, wherein the vaporizing substance is water.

6. The composite material according to claim 1, wherein the content of volatile substances is in the range of 40 to 90% by weight.

7. The composite material according to claim 1, comprising 30 parts by weight or less of inorganic gel per 100 parts by weight of a volatile substance.

8. The composite material according to claim 1, further comprising inorganic fibers.

9. The composite material according to claim 8, comprising 5 to 150 parts by weight of inorganic fibers per 100 parts by weight of a volatile substance.

10. The composite material according to claim 8, wherein the inorganic gel is attached to the inorganic fibers, or the inorganic gel and inorganic fibers are intertwined with each other.

11. The composite material according to claim 1, further comprising an ionic compound.

12. The triangle T in equation 1 below f The composite material according to claim 11, wherein the value is in the range of 5 to 50: [Formula 1] △T f = K f × M × I In Equation 1, K f is the freezing point depression constant of the vaporized substance, M is the molar concentration of the ionic compound relative to the vaporized substance, and I is the number of moles of ions produced when 1 mole of the ionic compound dissociates.

13. The composite material according to claim 11, wherein the solubility of the ionic compound in 100 g of water at 25°C is 10 g or more.

14. The composite material according to claim 11, wherein the ionic compound is one or more selected from the group consisting of formate, acetate, carbonate, and sulfate.

15. The composite material according to claim 1, further comprising a carbonizable organic substance.

16. The composite material according to claim 15, further comprising a carbonization catalyst.

17. Cases; and A fire extinguishing device comprising a composite material according to any one of claims 1 to 16 present in the aforementioned case.

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