Flame and thermal barrier material

Abstract

The invention relates to a flame and heat barrier laminate and a device comprising the same. Some laminates have a reinforcement layer comprising fibers, a flame retardant layer having a flammability rating in accordance with UL94 5VA, UL94 5VB, or UL94 V-0, a porous thermal insulation layer, and a heat dispersion layer comprising at least 90% by weight of metal or graphite, wherein the laminate has a thickness of less than or equal to 5 mm.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 481,124, filed on January 23, 2023, and claims priority to International Patent Application No. PCT / US2023 / 061100, filed on January 23, 2023, the entire contents of which are incorporated herein by reference. Background of the Invention A. Field of the Invention

[0004] The present invention generally relates to laminates that can be used as fire and / or heat-resistant materials for various articles. In certain aspects, the laminates can be used to protect articles (e.g., batteries, electronic devices, and / or similar articles) from high temperature environments (e.g., greater than 500° C.) to which the articles may be subjected for a period of time (e.g., 1 minute to 90 minutes), and in some cases, from projectiles (e.g., caused by thermal runaway of a battery).

[0005] B. Description of Related Technology

[0006] The electrification trend in today's society is increasingly evident. For example, electrification in the transportation sector is advancing at a breakneck pace. Specifically, vehicles like cars, trains, and airplanes are gradually transitioning from internal combustion engine technology to electric motors that rely on battery systems. These battery systems can be complex, relying on chemicals, chemical reactions, electronic components, and other materials to store and release electrical energy for use by the electric motors.

[0007] One issue associated with battery systems used in electric vehicles is that they are larger and store and release significantly more energy than battery systems in conventional vehicles that primarily rely on internal combustion engine technology. Specifically, batteries used in electric vehicles can cause relatively larger explosions, larger fires, and / or release larger amounts of corrosive chemical fumes than batteries used in vehicles that rely on internal combustion engines if they are mechanically damaged (e.g., in a vehicle accident, wiring or electronic system failure, etc.), exposed to temperatures outside their operating range, or undergo rapid charge and / or discharge events. Lithium-ion-based batteries used in electric vehicles can catch fire and / or explode at temperatures exceeding 500°C. By comparison, vehicle fires, such as those caused by vehicle accidents, can generate heat as high as 1500°F (815°C). When an electric vehicle is involved in an accident and a fire occurs, there is a limited amount of time to extinguish the fire and / or evacuate the vehicle before the battery catches fire and / or explodes. With the increasing electrification of society, particularly transportation infrastructure, and the increasing energy density of batteries, the risk of electric vehicle fires and battery fires and explosions is likely to increase.

[0008] Traditional insulation materials, such as foams, polymers, and elastomers, have been used to provide some thermal protection for electric vehicle battery systems. However, these traditional materials still have limitations. For example, while polymer foams have low thermal conductivity to reduce heat transfer, their thermal diffusivity (i.e., the thermal conductivity of a material divided by its density and specific heat capacity) is often higher than that of other insulation materials. Due to the higher thermal diffusivity (meaning that its thermal conductivity is high relative to the material's specific heat capacity and density), the temperature of these polymer foams may rise faster, causing heat to transfer more quickly with continued heating. Other polymer and elastomeric materials may have lower thermal diffusivity than polymer foams, but often have higher thermal conductivity. In addition, when heat is concentrated in one part of these traditional insulation materials, it may not be evenly distributed across their surface, thereby accelerating the transfer of heat through the thickness of the material to the surface of the component it is designed to protect. As a result, traditional insulation materials may not provide the required level of thermal protection in some applications.

[0009] Furthermore, in some systems, insulation materials may be subject to severe spatial constraints. Because traditional insulation materials are typically thicker and / or stiffer, these limitations can restrict the amount of traditional insulation that can be included in a system, further limiting the thermal protection provided by the material or potentially precluding its use in the system. Compounding these limitations, polymers, elastomers, and foams typically have higher coefficients of thermal expansion, making these materials even more constrained when heated. SUMMARY OF THE INVENTION

[0011] A discovery provides a solution to at least one or more of the aforementioned problems of providing thermal protection to an article, substrate or system (e.g., an electric battery system). On the one hand, it has been found that a laminate can provide good thermal protection properties for an article, substrate or system (article, substrate or system are used interchangeably throughout this specification), the laminate comprising a flame retardant layer having a flammability rating that complies with at least one flammability standard (e.g., UL94 5VB or UL94 5VA rating) and a porous thermal insulation (e.g., aerogel) layer. In such a laminate, the synergistic effect between the flame retardant layer and the porous thermal insulation layer can provide thermal protection for the substrate, which may exceed the expected sum of these parts in terms of heating rate and / or equilibrium temperature of the substrate, especially when the porous thermal insulation layer is small (e.g., less than 0.5 mm). Without wishing to be bound by any particular theory, it is believed that the porous thermal insulation layer effectively delays heat transfer from the flame retardant layer to the substrate by virtue of its low thermal conductivity and low thermal diffusivity.

[0012] For example, the laminate of the present invention, when attached to the surface of a substrate, is capable of maintaining the temperature of the substrate (e.g., the surface temperature of the substrate) at or below 500°C during exposure of the laminate to a temperature above 500°C, preferably 500°C to 1500°C, more preferably 700°C to 1200°C, for 1 minute to 90 minutes, preferably at least 5 minutes. This has the advantage of providing more time, for example, before a substrate (e.g., an electric vehicle battery system) reaches a temperature at which it may fail. This is particularly advantageous when used to protect electric vehicle battery systems because it can provide more time for vehicle occupants to leave the vehicle after an accident and before the electric vehicle battery catches fire, explodes, and / or releases toxic chemicals. It can also provide more time for first responders (e.g., a fire department) to extinguish the fire before the electric vehicle battery catches fire, explodes, and / or releases toxic chemicals. Notably, the laminates of the present invention can be relatively thin (e.g., less than or equal to 25.4 millimeters (mm), 20 mm, 15 mm, 10 mm, 5 mm, 3 mm, 2 mm, 1 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, 0.1 mm, or less than 0.1 mm) and / or relatively more flexible (e.g., can be rolled (see, e.g., Figure 9 ) and / or have a bending radius. The flexibility of the laminates of the present invention is advantageous in that they can be used in space-constrained applications (eg, electric vehicle battery systems and battery packs).

[0013] The laminates of the present invention may also be configured to mitigate ejections, such as those generated by a battery thermal runaway event, by including a (e.g., fiber) reinforcement layer, a (e.g., fiber, metal, or ceramic) ejection mitigation layer, and / or one or more reinforced (e.g., by fibers) flame retardant layers, one or more porous insulation layers, and / or the like.

[0014] One aspect of the present invention discloses a laminate comprising a flame retardant layer and a porous material layer (e.g., a foam layer or an aerogel layer, preferably an aerogel layer). The laminate has opposing front and back surfaces, and the flame retardant layer may, but need not, constitute at least a majority of the front surface. The laminate may have a thickness less than or equal to 25.4 millimeters (mm), 24 mm, 23 mm, 22 mm, 21 mm, 20 mm, 19 mm, 18 mm, 17 mm, 16 mm, 15 mm, 14 mm, 13 mm, 12 mm, 11 mm, 10 mm, 9 mm, 8 mm, 7 mm, 6 mm, 5 mm, 4 mm, 3 mm, 2 mm, 1 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, 0.1 mm, or any range therebetween. In other aspects, the thickness of the laminate can be greater than 25.4mm (e.g., 26mm, 27mm, 28mm, 29mm, 30mm, 35mm, 40mm, 45mm, 50mm, 55mm, 60mm, 65mm, 70mm, 75mm, 80mm, 85mm, 90mm, 95mm or 100mm or more than 100mm or any range therebetween). In some preferred aspects, the thickness of the laminate is 0.3mm to 10mm, 0.3mm to 5mm or 0.3mm to 3mm. In some aspects, the thickness of the flame retardant layer is 0.05mm to 0.8mm. In certain aspects, the porous layer (e.g., aerogel layer) has a thickness of 0.05 mm to 1.0 mm (or any number or range therebetween, e.g., 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm), preferably 0.05 mm to 0.254 mm.

[0015] In some aspects, the flame retardant layer is not electrically insulating. In other aspects, the flame retardant layer is electrically insulating. In some aspects, the flame retardant layer and / or the entire laminate meets plastic flammability standards. In some specific aspects, the plastic flammability standard is UL945VA or UL945VB. In one specific aspect, the flame retardant layer comprises fibers (e.g., woven and / or non-woven fibers) and / or one or more of metal hydroxides, organophosphates, aluminum hydroxide, inorganic fillers, and / or metal oxides. In some aspects, the flame retardant layer may be halogen-free. In some aspects, the flame retardant layer may comprise a silicate (e.g., a layered silicate). In some specific aspects, the silicate may comprise mica. The flame retardant layer may comprise at least 90% by weight of a silicate, preferably mica, based on the total weight of the flame retardant layer. In some aspects, the flame retardant layer comprises ceramics. The ceramics may comprise inorganic and / or non-metallic materials that can withstand high temperatures (e.g., clay, kaolin, aluminum oxide, silicon carbide, tungsten carbide, etc.). In some aspects, the ceramic can include a metal oxide or a non-metal oxide or a combination thereof. In some aspects, the ceramic can include aluminum oxide, beryllium oxide, cerium oxide, zirconium oxide, carbide, boride, nitride or silicide, or any combination thereof. In some aspects, the flame retardant layer can include at least 90 weight percent of the ceramic based on the total weight of the flame retardant layer.

[0016] In some aspects, the porous layer is an aerogel layer. In some aspects, the aerogel layer comprises an organic polymer. In some aspects, the organic polymer is a thermoplastic polymer. In some aspects, the thermoplastic polymer is a polyimide, polystyrene, polyester, polyamide, polyether, polyurethane, acrylic polymer, polyurea, polypyrrole, polythiophene, polyaniline, acrylic polymer, vinyl polymer, polysiloxane, polysulfide, polycarbonate, or a copolymer thereof or a mixture thereof. In a preferred embodiment, the thermoplastic polymer is a polyimide, polyamide-amide, or a mixture or copolymer thereof. In specific aspects, the aerogel layer comprises at least 50%, 60%, 70%, 80%, 90% or 95% of a thermoplastic polymer, preferably a polyimide or polyamide-amide. In other aspects, the polymer aerogel layer comprises less than 50%, 40%, 30%, 20%, 10%, 5% or less than 5% of a thermoplastic polymer, preferably a polyimide or polyamide-amide. In certain aspects, the decomposition temperature of the aerogel layer is greater than or equal to 400°C, preferably 400°C to 600°C.

[0017] The laminate of the present invention may include one or more adhesive layers. One or more adhesive layers may be bonded to the porous layer. On the one hand, the first adhesive layer is disposed between the flame retardant layer and the porous layer. The first adhesive layer may have a melting temperature or decomposition temperature greater than 500°C, preferably greater than 600°C. On the other hand, the second adhesive layer may be disposed on the rear surface of the porous layer (the surface further away from the flame retardant layer). The first and / or second adhesive layers may be pressure-sensitive adhesive layers capable of attaching the rear surface of the porous layer to a substrate. Before use, a releasable or peelable liner may be disposed on the second adhesive layer. In some aspects, the second adhesive layer may have a melting temperature or decomposition temperature greater than 500°C, preferably greater than 600°C. In particular aspects, one or more adhesive layers may comprise a silicone adhesive compound and / or an epoxy resin compound.

[0018] The laminated material of the present invention may include one or more heat dissipation layers. In some aspects, one or more heat dissipation layers may have a thermal conductivity of at least 15 W / m·K, preferably 15 W / m·K to 2500 W / m·K. In some aspects, one or more heat dissipation layers may include metal or graphite or a combination thereof. The metal or graphite may have a thermal conductivity of at least 15 W / m·K, preferably 15 W / m·K to 2500 W / m·K. In some aspects, the metal may include copper, aluminum, molybdenum, tungsten, rhenium, tantalum, niobium, stainless steel, nickel or an alloy thereof. In some aspects, one or more heat dissipation layers may contain at least 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99% or more than 99% of metal and / or graphite based on the total weight of the heat dissipation layer. In certain aspects, the thickness of one or more heat dissipation layers is from 0.001 mm to 0.4 mm, preferably from 0.01 mm to 0.05 mm, or any range or number therebetween (e.g., 0.02 mm, 0.03 mm, 0.04 mm, 0.05 mm, 0.06 mm, 0.07 mm, 0.08 mm, 0.09 mm, 0.1 mm, 0.2 mm, or 0.25 mm).

[0019] In some aspects, one or more heat dissipation layers may be bonded to the flame retardant layer and / or the porous layer. In some aspects, one or more heat dissipation layers may be disposed between the flame retardant layer and the porous layer. In some aspects, a first adhesive layer may be disposed between the flame retardant layer and the heat dissipation layer, and / or a second adhesive layer may be disposed between the heat dissipation layer and the porous layer. In some aspects, an adhesive layer is not disposed between the flame retardant layer and the porous layer. In some aspects, the first adhesive layer may be in direct contact with the flame retardant layer and the heat dissipation layer, and the second adhesive layer may be in direct contact with the heat dissipation layer and the porous layer. In some aspects, a third adhesive layer may be used, as well as an optional backing layer, wherein the third adhesive layer is disposed between the porous layer and the optional backing layer. In some aspects, the third adhesive layer may be in direct contact with the porous layer and the optional backing layer. In certain aspects, the first, second, third, or other bonding layers can each: (1) have a melting temperature or decomposition temperature greater than 500°C; (2) comprise a pressure sensitive adhesive; and / or (3) include a silicone adhesive compound and / or an epoxy resin compound.

[0020] In some aspects, any one, any combination or all of flame retardant layer, heat dissipation layer, porous layer, first, second, third or other bonding layer, reinforcement layer and / or ejecta relief layer (latter two are introduced below) can be perforated. In some aspects, perforation can help to allow any gas (such as evaporation or boiling from bonding layer) to be discharged from laminate. In some aspects, the size of perforation is nanometer, micron or millimeter. In some aspects, the pattern of perforation can be random, grid-like, circular etc. In some specific embodiments, pattern is grid-like. Do not wish to be bound by theory, it is believed that perforation may help for the situation of releasing gas when one or more than one bonding layer is subjected to high temperature or decompression. Allowing gas release helps to avoid aerogel and / or flame retardant layer blistering and / or delamination.

[0021] The laminates of the present invention may include one or more reinforcement layers. In some aspects, the one or more reinforcement layers may be attached to at least a portion of the flame retardant layer and / or contained within at least a portion of the volume of the flame retardant layer. In some aspects, the one or more reinforcement layers may comprise fibers. Non-limiting examples of fibers include glass fibers, carbon fibers, aramid fibers, thermoplastic fibers, thermoset fibers, ceramic fibers, basalt fibers, rock wool fibers, steel fibers, or cellulose fibers, or any combination thereof. In some aspects, the fibers are non-woven fibers or woven fibers. In addition to increasing the overall structural integrity of the laminates, these reinforcement layers may also help mitigate ejecta that may occur, for example, during a battery thermal runaway event.

[0022] In fact, during battery thermal runaway, failed batteries may produce heated ejecta that may weaken any heat protection provided to the battery and / or adjacent components (e.g., batteries), potentially leading to a chain reaction of component failures. Therefore, it is advantageous to prevent such ejecta, as some laminates of the present invention do by including (e.g., fiber-reinforced) reinforcement layers, flame-retardant and / or porous layers that enhance (e.g., by fibers) and / or (e.g., fiber, metal, or ceramic) ejecta mitigation layers. In some aspects, this ejecta mitigation layer may comprise at least 50%, such as at least 60%, 70%, 80%, or 90% metal. The metal may comprise, for example, titanium, stainless steel, nickel, molybdenum, and / or tantalum. In some aspects, this ejecta mitigation layer may comprise fibers, such as any fibers described above for reinforcement layers, which are preferably woven but may be non-woven. In some laminates of the present invention, the ejecta mitigation layer may constitute at least a major portion of the front surface of the laminate, up to and including all of it.

[0023] Also disclosed in the context of the present invention is a device comprising one or more laminates of the present invention. One or more laminates may be bonded to a device such that the front surface of a first laminate of the one or more laminates is further away from the device than the rear surface of the first laminate. The device may be any type of device. In a preferred aspect, the device is a device that may be exposed to high temperatures (e.g., greater than 500° C.) during use. An example is a battery. In a preferred aspect, the battery may be an electric vehicle battery system or battery pack. The battery may be a secondary / rechargeable battery (e.g., a lithium-ion battery or a nickel metal hydride battery). The vehicle may include one or more wheels and one or more motors, each motor configured to rotate at least one wheel. The battery may be in electrical communication with at least one of the one or more motors. In another example, the device may be a busbar of a battery. The busbar may be in electrical communication with the battery. The laminate of the present invention may be bonded to the busbar such that the front surface of the laminate is further away from the busbar than the rear surface of the laminate.

[0024] In some aspects, the device can be a compression pad, a battery cell, a battery module, a battery pack, or a battery box. The compression pad, which may also be referred to as a battery pad gasket, can be positioned between battery cells to help accommodate dimensional changes in the battery cells as the battery cells are charged and / or in use. The compression pad can allow sufficient pressure to be applied to the battery pack to maintain thermal and / or electrical connections while also allowing for tolerances and / or expansion when the battery cells are charged or exposed to extreme temperatures. In some aspects, the compression pad can include a compressible material. In some aspects, the compressible material can be a foam (e.g., a polyurethane foam or a silicone foam). In some aspects, the compression pad is positioned between a first battery cell and a second battery cell. The laminate material of the present invention can cover a portion, a majority, or all of the outer surface of the compression pad.

[0025] In some aspects, the device can be a battery cell. The battery cell can be charged to provide electrical energy (e.g., to supply electrical energy to an electric motor) and can be discharged when in use or exposed to extreme temperatures or in a latent state. Multiple battery cells can be positioned adjacent to each other, and a compression pad can be positioned between each battery cell. The laminate of the present invention can cover a portion, a majority, or all of the outer surface of the battery cell.

[0026] In some aspects, the device can be a battery module. The battery module can include a plurality of battery cells. The laminated material of the present invention can cover a portion, a majority, or all of the outer surface of the battery module.

[0027] In certain aspects, the device may be a battery pack. The battery pack may include a plurality of battery modules. The laminated material of the present invention may be positioned between the battery modules of the battery pack. The laminated material of the present invention may cover a portion, a majority, or the entirety of the outer surface of the battery pack.

[0028] In some aspects, the device can be a battery box, battery housing or container. The battery box or container can encapsulate a portion, most of or all of the battery pack. The battery box can include an outer surface, an inner surface and an internal volume. The laminate of the present invention can cover at least a portion, most of or all of the outer surface of the battery box, at least a portion, most of or all of the inner surface, or both. In some preferred aspects, at least a portion, most of or all of the inner surface of the battery box is covered with one or more laminates of the present invention. In some aspects, the internal volume of the battery box includes a compression pad, a battery cell, a battery module or a battery pack or any combination thereof. In some aspects, the compression pad, battery cell, battery module, battery pack and / or battery box are contained in a vehicle, and the vehicle includes one or more electric motors. In some aspects, the vehicle can be a car, an aircraft, a train, a water vehicle or a spacecraft.

[0029] In some aspects, the device can be a cable. The cable can have a length and a width. The length can be longer than the width. In some aspects, the cable can be electrically conductive. In some aspects, the cable can have a conductive portion and an electrically insulating portion. In some aspects, the electrically insulating portion can surround a portion, a majority, or all of the conductive portion. In some aspects, the conductive portion can comprise a conductive metal (e.g., copper, gold, platinum, aluminum, steel, etc.). In some aspects, the cable can comprise a diameter of 0.0001 inch to 10 inches, preferably 0.001 inch to 1 inch, or any range or number therebetween (e.g., 0.0001 inch, 0.0002 inch, 0.0003 inch, 0.0004 inch, 0.0005 inch, 0.0006 inch, 0.0007 inch, 0.0008 inch, 0.0009 inch, 0.001 inch, 0.002 inch, 0.003 inch, 0.004 inch, 0.005 inch, 0.006 inch, In some aspects, the cable can be included in a missile, rocket, artillery, manned aircraft, unmanned aircraft, land vehicle, or marine vehicle. In some aspects, the vehicle can be a spacecraft or an aircraft.

[0030] Also disclosed within the context of the present invention is a method for thermally protecting a device using any of the laminates of the present invention. The method may include bonding the laminate to a surface of the device. The bonding may be performed using an adhesive. The laminate may be positioned relative to the device such that the front surface of the laminate is further away from the device than the back surface of the laminate. The laminate of the present invention is capable of maintaining the temperature of the device at or below 500°C while the front surface of the laminate is exposed to a temperature above 500°C, preferably 500°C to 1500°C (or 600°C, 700°C, 800°C, 900°C, 1000°C, 1200°C, 1300°C, 1400°C or any range therebetween), or more preferably 700°C to 1200°C (or 800°C, 900°C, 1000°C or 1100°C or any range therebetween) for 1 minute to 90 minutes (or 2 minutes, 3 minutes, 4 minutes, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 60 minutes, 70 minutes, 80 minutes or 90 minutes or any range therebetween), preferably for at least 5 minutes.

[0031] The term "aerogel" refers to a class of materials that are generally produced by forming a gel, removing a mobile interstitial solvent phase from the pores, and then replacing it with a gas or gas-like material. By controlling the gel and evaporation system, density, shrinkage, and pore collapse can be minimized. The aerogels of the present invention can include macropores, mesopores, and / or micropores. In preferred aspects, a majority (e.g., greater than 50%) of the pore volume of the aerogel can be composed of macropores. In other alternative aspects, a majority of the pore volume of the aerogel can be composed of mesopores and / or micropores, such that less than 50% of the pore volume of the aerogel is composed of macropores. In certain embodiments, the aerogels of the present invention can have a low bulk density (about 0.75 g / cm 3 or less than 0.75g / cm 3 , preferably about 0.01 g / cm 3 to about 0.5g / cm 3 ), high surface area (typically about 10m 2 / g to 1000m 2 / g and above 1000m 2 / g, preferably about 50m 2 / g to about 1000m 2 / g), high porosity (about 20% and greater than 20%, preferably greater than about 85%) and / or relatively large pore volume (greater than about 0.3 mL / g, preferably about 1.2 mL / g and greater than 1.2 mL / g).

[0032] The presence of macropores, mesopores, and / or micropores in the aerogels of the present invention can be determined by mercury intrusion porosimetry (MIP) and / or gas physical adsorption experiments. MIP testing can be used to measure mesopores and macropores (i.e., American Standard Test Method (ASTM) D4404-10, Standard Test Method for Pore Volume and Pore Volume Distribution of Soil and Rock by Mercury Intrusion Porosimetry). Gas physical adsorption experiments can be used to measure micropores (i.e., ASTM D1993-03 (2008), Standard Test Method for Surface Area of ​​Precipitated Silica by Multipoint BET Nitrogen Method).

[0033] The "decomposition temperature" of a material is the temperature at which 2%, 5%, or 10% of a sample of the material decomposes when the sample is placed in an environment heated to that temperature. The decomposition temperature can be determined by placing the sample in a thermogravimetric analyzer (TGA), heating the sample from ambient temperature in the TGA (e.g., at a rate of 10°C / min), and recording the temperature at which the sample mass decreases by 2%, 5%, or 10% of the initial mass.

[0034] The term "coupled" is defined as connected, although not necessarily directly and not necessarily mechanically. Two "coupled" items may be integral with one another or connected through one or more intermediate components or elements.

[0035] Unless the disclosure clearly requires it, quantifiers are not used in the definitions to mean one or more than one.

[0036] The term "substantially" is defined as meaning primarily, but not necessarily entirely, what is specified (and including what is specified; for example, substantially 90 degrees includes 90 degrees, and substantially parallel includes parallel) as understood by one of ordinary skill in the art. In any disclosed embodiment, the terms "substantially," "approximately," and "about" may be replaced with "within 10% of what is specified."

[0037] The phrase "and / or" means and or. By way of example, A, B, and / or C includes: A alone, B alone, C alone, the combination of A and B, the combination of A and C, the combination of B and C, or the combination of A, B, and C. In other words, "and / or" operates as an inclusive or.

[0038] The terms "comprise," "have," "include," and "contain" are open-ended linking verbs. Thus, a device that "comprises," "has," "includes," or "contains" one or more elements possesses those one or more elements, but is not limited to possessing only those one or more elements. Similarly, a method that "comprises," "has," "includes," or "contains" one or more steps possesses those one or more steps, but is not limited to possessing only those one or more steps.

[0039] The laminates of the present invention may "comprise," "consist essentially of," or "consist of" the particular ingredients, components, compositions, etc. disclosed in this specification. With respect to the transition phrase "consisting essentially of," in one non-limiting aspect, the fundamental and novel characteristic of the laminates of the present invention is their ability to provide thermal protection over time when a substrate is subjected to temperatures that could cause the substrate to fail (e.g., ignite, explode, rupture, deform, etc.).

[0040] One or more features of one embodiment may be applied to other embodiments even if not described or illustrated, unless expressly prohibited by the disclosure or the nature of the embodiments.

[0041] Certain details related to the above-described embodiments and other embodiments are described below.

[0042] BRIEF DESCRIPTION OF THE DRAWINGS

[0043] The following figures illustrate by way of example and not limitation. For the sake of brevity and clarity, not every feature of a given structure is labeled in every figure in which that structure appears. Identical reference numbers do not necessarily denote identical structures. Rather, identical reference numbers may be used to denote similar features or features having similar functions, even if they are non-identical.

[0044] Figure 1A and Figure 1B is a cross-sectional view of an embodiment of a laminate of the present invention having a flame retardant layer and a single aerogel layer attached to a surface of a substrate ( Figure 1A ) or a flame retardant layer and two aerogel layers ( Figure 1B ).

[0045] Figure 2 is a cross-sectional view of another embodiment of a laminate of the present invention having a liner removably disposed on the adhesive layer of the laminate, the liner forming at least a portion of the back surface of the laminate.

[0046] Figure 3 is a cross-sectional view of another embodiment of a laminate of the present invention having two flame retardant layers disposed on opposite sides of one or more aerogel layers, two aerogel layers being shown.

[0047] Figure 4 is a cross-sectional view of another embodiment of a laminate of the present invention having a reinforcement layer attached to the flame retardant layer of the laminate.

[0048] Figure 5 is a cross-sectional view of another embodiment of the laminate of the present invention having a heat dissipation layer disposed between the flame retardant layer and the aerogel layer of the laminate.

[0049] Figures 6A to 6C are cross-sectional views of other embodiments of laminates of the present invention, each laminate including one or more than one spray mitigation layer.

[0050] Figure 7 is a cross-sectional view of another embodiment of a laminate of the present invention, the laminate including a titanium layer.

[0051] Figure 8 is a cross-sectional view of another embodiment of a laminate of the present invention, the laminate including a vinyl layer.

[0052] Figure 9 is a perspective view of a roll of a laminate embodiment of the present invention.

[0053] Figure 10 is a schematic diagram of a vehicle having a battery comprising one or more embodiments of the laminate of the present invention.

[0054] Figure 11A is a schematic diagram of a cable comprising one or more embodiments of the laminate of the present invention.

[0055] Figure 11B It is along Figure 11A The line 11B-11B is intercepted Figure 11A Schematic cross-section of a cable.

[0056] Figure 12 is a schematic diagram of a setup for testing the heat and flame performance of laminates of the present invention.

[0057] Figure 13 is used for Figure 12 Schematic diagram of the laminate material of the test setup.

[0058] Figure 14 The thermal profiles are shown for a control (no barrier on a copper substrate), a flame retardant barrier (layer) on a copper substrate, a thermal insulation layer on a copper substrate, a laminate of the present invention on a copper substrate (one thermal insulation layer and one flame retardant layer), and another laminate of the present invention on a copper substrate (two thermal insulation layers and one flame retardant layer).

[0059] Figure 15 is a schematic diagram of another setup for testing the heat and flame performance of the laminates of the present invention.

[0060] Figure 16 and Figure 17 The thermal profiles of some of the laminates of the present invention are shown.

[0061] Figure 18 The thermal profile of some laminates of the present invention attached to mild steel panels is shown compared to the thermal profile of unprotected mild steel panels.

[0062] Figure 19 The thermal profile of some of the present invention laminates attached to a carbon fiber composite panel is shown compared to the thermal profile of an unprotected carbon fiber composite panel.

[0063] Figure 20 is a back view of a carbon fiber composite panel with the front side protected by a laminate of the present invention during exposure to a 1000°C flame for 25 minutes.

[0064] Figure 21 The thermal profile of a laminate of the present invention attached to an aluminum sheet substrate is shown.

[0065] Figure 22 is a back view of an aluminum sheet substrate having its front side protected by a laminate of the present invention during exposure to a 1000°C flame for 25 minutes.

[0066] Figure 23and Figure 24 The thermal profiles of some of the present laminates that included an ejecta mitigation layer are shown and compared to the thermal profiles of some of the present laminates that did not include an ejecta mitigation layer.

[0067] Figure 25 and Figure 26 are images of the hot and cold sides of some inventive laminates, excluding the ejecta mitigation layer, after exposure to a 1000°C flame for 10 minutes.

[0068] Figure 27 and Figure 28 are images of the hot and cold sides of some inventive laminates including an ejecta mitigation layer after exposure to a 1000°C flame for 10 minutes.

[0069] Figures 29 to 31 The thermal profiles of some laminates of the present invention comprising one or more than one ejecta mitigation layer are shown.

[0070] Figures 32 to 36 are images of the hot and cold sides of some laminates of the present invention including one or more ejecta mitigation layers after exposure to a 1000°C flame for 10 minutes.

[0071] Detailed description

[0072] The electrification of today's society has provided technological advances that offer alternatives to the internal combustion engine. However, with these advances come new challenges. For example, the use of electric vehicle battery systems in the transportation industry can reduce reliance on gasoline as a fuel. However, if the battery system is exposed to excessive temperatures (e.g., above 500°C), it can lead to a greater risk of explosion, fire, and / or toxic smoke release.

[0073] The present invention provides a solution to at least one of these problems. The solution includes a laminate that can provide good thermal protection and flexibility, both of which are beneficial properties in certain applications (e.g., electric vehicle battery systems). In one aspect, the present invention provides a laminate that includes a flame retardant layer and a thermal insulation layer, the flame retardant layer having a flammability rating that complies with at least one plastic flammability standard (e.g., UL94 5VB or UL94 5VA rating). The laminate of the present invention, when attached to a surface of a substrate, is capable of maintaining the temperature of the substrate (e.g., the surface temperature of the substrate) at or below 500°C when the laminate is exposed to a temperature above 500°C, preferably from 500°C to 1500°C, or more preferably from 700°C to 1200°C, for a period of 1 minute to 90 minutes, preferably at least 5 minutes.

[0074] The laminates of the present invention can also be thin (e.g., thickness equal to or less than 25.4 millimeters (mm), 20 mm, 15 mm, 10 mm, 5 mm, 3 mm, 2 mm, 1 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, 0.1 mm, or any range therebetween) and flexible (e.g., can be rolled up). Figure 9 ) and / or having a bending radius). The good thermal protection properties of the laminate of the present invention and its thin and flexible characteristics make it suitable for use as a cover or protective layer for batteries (such as electric vehicle batteries and battery systems with multiple batteries), battery bus bars, and various other articles in places where space is limited.

[0075] In some cases, a failed battery (e.g., one that enters thermal runaway) may release ejecta in addition to heat. To protect against such ejecta, it may be beneficial to provide reinforcement or ejecta mitigation in a heat barrier (e.g., for an adjacent component) so that the structural integrity of the barrier is not compromised by the ejecta, thereby allowing heat to break through earlier than expected. Some laminates of the present invention also address this need by including one or more (e.g., fiber-reinforced) reinforcement layers, (e.g., fiber) reinforced flame retardant layers and / or thermal insulation layers, and / or (e.g., fiber, metal, or ceramic) ejecta mitigation layers.

[0076] A. Barrier laminates for heat and fire protection

[0077] refer to Figure 1A and Figure 1B , showing a laminate 100. The laminate 100 can be attached to a surface of a substrate 10, the laminate having opposing front and back surfaces, 12 and 14, respectively. The laminate 100 can include one or more thermally insulating layers 16 (e.g., a porous layer, such as an aerogel layer), a flame retardant layer 18 that optionally constitutes at least a portion (e.g., at least a majority, up to and including all) of the front surface 12, and one or more adhesive layers 20, 22, and 24 for, for example, securing the one or more thermally insulating layers 16 and the flame retardant layer 18 to each other. Whether in the laminate 100 or in other laminates of the present invention, the one or more thermally insulating layers 16 can include a layer ( Figure 1A ), two such layers ( Figure 1B ) or more than two such layers (e.g., 3, 4, 5, 6, 7, 8, 9 or more than 9 insulation layers). Similarly, although the laminate 100 is depicted as including one flame retardant layer 18, other laminates of the present invention may include multiple flame retardant layers (e.g., 2, 3, 4, 5 or more than 5 flame retardant layers).

[0078] Therefore, the number of the adhesive layers 20, 22, and 24 can be 1, 2, 3, 4, 5, 6, 7, 8, 9, or more than 9. For example, the adhesive layer (e.g., 20) can bond the flame retardant layer 18 to the thermal insulation layer 16, and the adhesive layer (e.g., 24) can bond the thermal insulation layers 16 to each other when there are multiple thermal insulation layers 16. Figure 1B ), and / or the like. In addition, the adhesive layer (e.g., 22) can comprise substantially all of the back surface 14 of the laminate 100, allowing the laminate to be attached to the substrate 10. It should be understood that in certain embodiments, the laminate 100 need not include each or all of the one or more adhesive layers (e.g., 20, 22, 24) described above. For example, in one embodiment, the laminate 100 can include a single insulating layer (e.g., an aerogel layer) 16, a flame retardant layer 18, an adhesive layer 20, and an adhesive layer 24.

[0079] Each of the one or more thermal insulation layers 16 may have a power less than or equal to 0.05 Watts per meter-Kelvin, 0.045 Watts per meter-Kelvin, 0.040 Watts per meter-Kelvin, 0.035 Watts per meter-Kelvin, 0.030 Watts per meter-Kelvin, 0.025 Watts per meter-Kelvin, 0.020 Watts per meter-Kelvin, 0.015 Watts per meter-Kelvin, or 0.010 Watts per meter-Kelvin (W / m·K). Any one or between any two of the above (e.g., less than or equal to 0.025 W / m·K) thermal conductivity and / or less than or equal to 0.30 square millimeters per second, 0.20 square millimeters per second, 0.15 square millimeters per second, 0.125 square millimeters per second, 0.10 square millimeters per second, 0.09 square millimeters per second, 0.08 square millimeters per second, 0.07 square millimeters per second, 0.06 square millimeters per second or 0.05 square millimeters per second (mm 2 / s) or between any two of the above (e.g. less than or equal to 0.15 mm 2 / s or less than or equal to 0.10mm 2 / s) thermal diffusivity. As used herein, thermal conductivity and thermal diffusivity are measured at 25°C. In addition, each of the one or more thermal insulation layers 16 can be heat resistant and / or have a low coefficient of thermal expansion, so that the laminate 100 can withstand heating when in use and resist expansion in applications where the laminate is subject to severe spatial constraints. For example, each of the one or more thermal insulation layers 16 can have a decomposition temperature greater than or equal to any one of 400°C, 425°C, 450°C, 475°C, 500°C, 525°C, 550°C, 575°C or 600°C (e.g., greater than or equal to 450°C) or between any two of the above and / or less than or equal to 80 μm / m·K, 75 μm / m·K, 70 μm / m·K, 65 μm / m·K, 60 μm / m·K, 55 The thermal expansion coefficient (e.g., in at least one direction) is any one of μm / m·K, 50μm / m·K, 45μm / m·K, 40μm / m·K, 35μm / m·K, 30μm / m·K, 25μm / m·K, 20μm / m·K, 15μm / m·K, 10μm / m·K or 5μm / m·K, or between any two of the above (e.g., less than or equal to 80μm / m·K or less than or equal to 35μm / m·K).

[0080] To achieve these properties, at least one of the one or more insulating layers 16, up to and including each, can include a polymer aerogel layer. The polymer aerogel can be at least 90% by weight of an organic polymer, such as a polyimide, polyaramid, polyurethane, polyurea, and / or polyester. Each polymer aerogel layer can have micropores, mesopores, and / or macropores. Greater than or equal to any of the following, or between any two of the following values: 10%, 25%, 50%, 75%, or 95% of the pore volume of each aerogel layer can be comprised of micropores, mesopores, and / or macropores (e.g., comprised of micropores, comprised of mesopores, comprised of both micropores and mesopores, or comprised of macropores). The average pore size and / or median pore size of each aerogel layer can be greater than or equal to any of the following values, or between any two of the following values: 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 800 nm, 1000 nm, 2000 nm, 3000 nm, 4000 nm, or 5000 nm (for example, the average pore size can be from 100 nm to 500 nm, and the median pore size can be from 250 nm to 600 nm). The materials and preparation methods of the polymer aerogel layer will be further described in detail below.

[0081] In certain embodiments, for at least one (e.g., each) of the one or more insulating layers 16, the aerogel layer may include reinforcing fibers, which may be dispersed throughout the aerogel layer (e.g., as chopped or discontinuous fibers that are ordered (e.g., woven) or not arranged in sheets) or embedded in the aerogel layer (e.g., as woven, non-woven, or unidirectional sheets of fibers), optionally such that the volume of the fibers is greater than or equal to any of 0.1%, 10%, 20%, 30%, 40%, or 50% of the volume of the aerogel layer, or between any two values ​​thereof. However, one or more aerogel layers need not include fibers (e.g., to promote flexibility).

[0082] Suitable fibers include glass fibers, carbon fibers, aramid fibers, thermoplastic fibers, thermoset fibers, ceramic fibers, basalt fibers, rock wool fibers, steel fibers, cellulose fibers, and / or the like. The average monofilament cross-sectional area of ​​the fibers used for reinforcement may be greater than or equal to 7 μm. 2 , 15μm 2 , 30μm 2 , 60μm 2 , 100μm 2 , 200μm 2 , 300μm 2 , 400μm 2 , 500μm 2 , 600μm 2 , 700μm 2 or 800 μm 2 any value in the range of 1 to 20 μm, or between any two values ​​thereof; for example, for fibers having a circular cross-section, the average diameter of the fibers can be greater than or equal to any value in the range of 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm or 30 μm, or between any two values ​​thereof (for example, 5 μm to 24 μm, for example, 10 μm to 20 μm or 12 to 15 μm).

[0083] Non-limiting examples of thermoplastic polymers that can be used as polymer reinforcing fibers include polyethylene terephthalate (PET), polycarbonate (PC), polybutylene terephthalate (PBT), poly(1,4-cyclohexanedimethylene terephthalate) (PCCD), glycol-modified polycyclohexyl terephthalate (PCTG), polyphenylene oxide (PPO), polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polystyrene (PS), polymethyl methacrylate (PMMA), polyethyleneimine or polyetherimide (PEI) and its derivatives, thermoplastic elastomers (TPE), terephthalic acid (TPA) elastomers, poly(cyclohexanedimethylene terephthalate) (PCT), polyethylene naphthalate (PEN), polyamide (PA), polysulfone sulfonate (PSS), polysulfone sulfonate, polyetheretherketone (PEEK), polyetherketone ... ketone) (PEKK), acrylonitrile-butadiene-styrene copolymer (ABS), polyphenylene sulfide (PPS), copolymers thereof, polyester or derivatives thereof, polyamide or derivatives thereof (such as nylon), or blends thereof.

[0084] Non-limiting examples of thermosetting polymers that can be used as polymeric reinforcing fiber materials include unsaturated polyester resins, polyurethanes, polyoxybenzyl methylene glycol anhydride (e.g., Bakelite), urea-formaldehyde resins, diallyl phthalate, epoxy resins, epoxy vinyl esters, polyimides, cyanate esters of polycyanurates, dicyclopentadiene, phenolic resins, benzoxazines, copolymers thereof, or blends thereof.

[0085] While each of the one or more insulation layers 16 may comprise a polymer aerogel layer, in other embodiments, at least one, up to and including each, of the one or more insulation layers may comprise any suitable insulating material, such as a fiber layer. At least one, up to and including each, of the one or more insulation layers 16 may also comprise a fiber layer laminated to the polymer aerogel layer, optionally with the fiber layer positioned closer to the front surface 12 of the laminate 100 than the aerogel layer. The fibers in the fiber layer may be any of the fibers described above for aerogel fiber reinforcement (e.g., glass fibers and / or basalt fibers) and may be arranged in a variety of fiber structures. For example, the fibers may form a fiber matrix such as a felt, batting, fluff, mat, woven fabric, or non-woven fabric. The fibers may be arranged unidirectionally or omnidirectionally.

[0086] In some embodiments, the average single filament cross-sectional area of ​​the fibers used for reinforcement in the aerogel layer or fiber layer may be 5 μm 2 Up to 40000μm2 , and / or an average length of 20 mm to 100 mm.

[0087] To enable the laminate 100 to be used in space-constrained applications, each of the one or more insulation layers 16 (e.g., one or more aerogel layers) can be relatively thin. For example, at least one (e.g., each) thickness 26 ( Figure 1A ) may be less than or equal to any value of 50 mm, 25 mm, 20 mm, 15 mm, 10 mm, 5 mm, 4 mm, 3 mm, 2 mm, 1 mm, 0.9 mm, 0.8 mm, 0.7 mm, 0.6 mm, 0.5 mm, 0.4 mm, 0.3 mm, 0.2 mm, 0.15 mm, 0.1 mm or 0.05 mm, or between any two values ​​thereof (e.g., 0.10 mm to 0.20 mm, such as 0.165 mm).

[0088] The combination of one or more thermal insulation layers 16 and one or more flame retardant layers 18 can mitigate the spread of heat and flames and is used for heat and fire protection of the substrate surface 10. One or more flame retardant layers 18 each contain a flame retardant material, optionally further comprising non-woven fibers, paper, and fillers. Flame retardant materials include metal hydroxides, organic phosphates, metal phosphates, nitrogen-containing polymers, nitrogen-phosphorus compounds, talc, sulfonates or their salts, silica, silicates (e.g., mica, such as samica), hydrated oxides, organic polymers, nanoclays, organic clays, organic polymers, silicon-phosphorus-nitrogen compounds, metal oxides, ceramics (e.g., metal and / or non-metal oxides, aluminum oxide, beryllium oxide, cerium oxide, zirconium oxide, carbides, borides, nitrides, and / or silicides) and mixtures thereof. Non-limiting examples of metal hydroxides include aluminum trihydrate, magnesium oxide, and the like. Non-limiting examples of metal oxides include titanium oxide, aluminum oxide, zinc oxide, iron oxide, magnesium oxide, calcium oxide, and the like. Non-limiting examples of phosphates include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris(2-ethylhexyl) phosphate, tributoxyethyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl phosphate, trixylyl phosphate, tris(2-phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, diphenyl diphenyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, resorcinol bis(diphenyl phosphate), resorcinol bis(dixylyl phosphate), resorcinol bis(xylyl phosphate), ester), hydroquinone bis(dixylyl phosphate), bisphenol A bis(diphenyl phosphate), tetrakis(2,6-dimethylphenyl)1,3-phenylene bisphosphate, pentaerythritol phosphate alcohol, oligoethyl ethylene phosphate, tricresyl phosphate, tricresyl phosphate, isopropylphenyl phosphate, tert-butylphenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, isodecyl diphenyl phosphate, butyl diphenyl phosphate, dibutylphenyl phosphate, tributyl phosphate, tetraphenylresorcinol diphosphate, and tetraphenylbisphenol A diphosphate. In some embodiments, one or more flame retardant layers (e.g., 18) may comprise at least 90% by weight of a flame retardant material, such as at least 90% by weight of a silicate / ester, or at least 90% by weight of a ceramic.

[0089] Non-limiting examples of fillers include kaolin, talc, mica, calcium carbonate, alumina trihydrate, montmorillonite, smectite, bentonite, illite, chlorite, sepiolite, attapulgite, halloysite, vermiculite, laponite, rectorite, perlite, aluminum nitride, silicon carbide, boron nitride, and combinations thereof.

[0090] Each of the one or more flame retardant layers 18 may meet a plastic flammability standard (e.g., UL94 V-0, V-1, V-2, HB, 5VA, 5VB, etc.). The thickness 38 ( Figure 1Aand Figure 1B ) may be greater than any of 0.03mm, 0.04mm, 0.05mm, 0.10mm, 0.20mm, 0.30mm, 0.40mm, 0.50mm, 0.60mm, 0.70mm, 0.80mm, 0.90mm, 1.00mm, 1.20mm, 1.40mm, 1.60mm, 1.80mm, 2.00mm, 2.20mm, 2.40mm, 2.60mm, 2.80mm, 3.00mm, 3.20mm, 3.40mm, 3.60mm, 3.80mm, 4.00mm, 4.20mm, 4.40mm, 4.60mm, 4.80mm or 5.00mm, or between any two of the values ​​therein (e.g., 0.03mm to 5.0mm). In some cases, the flame retardant layer has a thickness ranging from 0.145 mm to 0.225 mm and has a UL94 5VA or UL94 5VB, preferably UL94 5VA flammability rating.The one or more flame retardant layers 18 may be electrically insulating or non-electrically insulating.

[0091] The one or more flame retardant layers 18 can each be a commercially available product. Non-limiting examples of commercially available flame retardant tapes or papers suitable for use as flame retardant layers include those sold under the Unifrax brand (e.g., FyreWrap LiB Papers and Film), Brand (e.g. 3M VHB tape, 3M FRB paper), Brand, U-Line brand, etc. In a specific embodiment, Unifrax brand FyreWrap LiB Paper (such as FX70 and IN70), Unifrax brand FyreWrap LiB Film (such as C1554), Flame Barrier FRB-WT series, Flame Barrier FRB-NT series (eg, FRB-BK, FRB-NT laminate, FRB-NC laminate, or FRB-NC series) (3M, St. Paul, MN, USA).

[0092] Each of the one or more flame-retardant layers 18 can be reinforced. For example, the flame-retardant layer can comprise woven and / or non-woven fibers. Non-limiting examples of fibers include aramid fibers, organic fibers, glass fibers, carbon fibers, thermoplastic fibers, thermoset fibers, basalt fibers, ceramic fibers, rock wool fibers, steel fibers, cellulose fibers, and / or the like. In embodiments where the flame-retardant layer is fiber-reinforced, the fibers can be included in at least a portion of the volume of the flame-retardant layer, for example, as a reinforcement layer.

[0093] As described above, when the laminate 100 includes multiple thermal insulation layers 16 and / or flame retardant layers 18, the laminate may include multiple adhesive layers (e.g., adhesive layers 20, 22, and 24), optionally including an adhesive layer (e.g., 22) that forms at least a portion of the back surface 14, so as to be bonded to the substrate 10 as described above. Such adhesive layers (e.g., 20, 24) may bond one or more thermal insulation layers 16, one or more flame retardant layers 18, one or more other layers described below, or a combination of these layers together. To this end, each adhesive layer may be disposed between layers of the other laminate and contact an adjacent layer of the other laminate (e.g., between two thermal insulation layers 16 or between one of the thermal insulation layers and a flame retardant layer).

[0094] As an example, two thermal insulation layers 16 can be bonded together and bonded to the flame retardant layer 18. In another example, a stack of the first flame retardant layer 18, the first thermal insulation layer 16, the second flame retardant layer 18, and the second thermal insulation layer 16 can be bonded together by adhesive layers (e.g., 20, 22, 24). Figure 1B For example, the adhesive layer 20 may be disposed between and in contact with the flame retardant layer 18 and one of the thermal insulation layers 16, and the adhesive layer 24 may be disposed between and in contact with two of the thermal insulation layers. To promote bonding without significantly increasing the thickness of the laminate, the thickness 28 of at least one (e.g., each) of the one or more adhesive layers (e.g., adhesive layers 20, 22, and 24) may be less than or equal to any one of 5.0 mm, 4.5 mm, 4.0 mm, 3.5 mm, 3.0 mm, 2.5 mm, 2.0 mm, 1.5 mm, or 1.0 mm, or between any two of these values ​​(e.g., 1.5 mm to 3.5 mm).

[0095] The adhesive layers (e.g., 20, 22, and 24) can be the same or different materials; for example, silicone adhesive compounds, acrylic adhesive compounds, rubber adhesive compounds, phenolic compounds, cyanate ester compounds, epoxy resin compounds, etc. In certain aspects, the adhesive layer can be an adhesive capable of maintaining adhesion at high temperatures (e.g., 500° C. or higher), non-limiting examples of which include FLEXcon Silicone Adhesive SA 6000SA 9000D Series (FLEXcon Company, Inc., Spencer, Massachusetts, USA), Alamo Tapes Epoxy Adhesive (Alamotape, San Antonio, Texas, USA), Avery FT 3010 (Avery Dennison Corporation, Painesville, Ohio, USA), and Adhesive Applications S1001-01 (Adhesive Applications, Inc., East Hampton, Massachusetts, USA).

[0096] At least one adhesive layer, up to and including all adhesive layers (e.g., 20, 22, and 24), may comprise a pressure sensitive adhesive, such as one comprising silicone, epoxy, acrylic, phenolic, cyanate ester, epoxy, and / or rubber, among others. When used in adhesive layer 22, such a pressure sensitive adhesive may facilitate application of the laminate 100 to the surface 10 to provide thermal protection (e.g., by simply pressing the laminate 100 against the surface). However, at least one of the one or more adhesive layers may comprise a different type of adhesive, such as a fluoropolymer film, a polyimide film, and a B-staged epoxy resin; examples include commercially available adhesives such as DuPont®. TM FEP film, HT and GPL, and TSU510S-A from Toyochem Co., LTD. (Tokyo, Japan). When such other adhesives are used, bonding can be achieved by stacking layers of the present laminate (e.g., 100) and applying heat and / or pressure (e.g., using a press) to the stack, optionally to a temperature exceeding the glass transition temperature of the adhesive layer. In some embodiments having multiple adhesive layers, some adhesive layers (e.g., 22) may comprise a pressure-sensitive adhesive, and other adhesive layers (e.g., 20 and 24) may comprise other types of adhesives as listed above.

[0097] The composition of one or more adhesive layers (e.g., 20, 22, and / or 24) can reduce the risk of delamination, for example, through heat resistance. For example, at least one (e.g., each) melting point or decomposition temperature of one or more adhesive layers can be greater than or equal to any of 350°C, 375°C, 400°C, 425°C, 450°C, 500°C, 550°C, or 600°C, or between any two values ​​therein. In addition, if a B-staged epoxy adhesive is used, at least one (e.g., each) glass transition temperature or melting point of one or more adhesive layers (20, 22, and 24) can be greater than or equal to any of 100°C, 150°C, 175°C, 200°C, 225°C, 250°C, or 275°C, or between any two values ​​therein. The composition of one or more adhesive layers (e.g., 20, 22, and / or 24) can be flame retardant.

[0098] By virtue of the above configuration, the laminate 100 can provide heat and fire protection in high temperature and flammable environments. For example, the thermal diffusivity of the laminate 100 can be less than or equal to 0.15 mm 2 / s, 0.125mm 2 / s、0.10mm 2 / s, 0.09mm 2 / s、0.08mm 2 / s、0.07mm2 / s、0.06mm 2 / s、0.05mm 2 / s or 0.04mm 2 / s, or between any two values ​​(e.g. less than or equal to 0.10 mm 2 / s, such as less than or equal to 0.075mm 2 / s), thereby mitigating heat transmission therethrough. The laminate 100 may have a flammability rating that meets UL 94 requirements. For example, the laminate may resist combustion by inhibiting the spread of flames at temperatures above 500°C for at least 5 minutes. The laminate may have a UL94 5VB or UL94 5VA rating. In some embodiments, the laminate may comply with FAR 25 Appendix F Part 1.

[0099] Furthermore, although the total thickness of the laminate 100 ( Figure 1A and Figure 1B The laminate 100 may be less than or equal to 25.4 mm, but as described above, the laminate may advantageously be relatively thin, such as less than or equal to any of 25.4 mm, 20 mm, 15 mm, 10 mm, 5 mm, 4 mm, 3 mm, or 2 mm, or between any two of these values ​​(e.g., less than or equal to 10 mm or less than or equal to 0.3 mm). This thinness may enable the laminate 100 to be used in small spaces, such as those commonly found in electric or hybrid vehicles and / or electronic components, while still providing the aforementioned heat and fire protection. Thus, the laminate 100 may provide better heat and fire protection than conventional thermal insulation / flame retardant materials in applications where size constraints may be present, where conventional materials may not be able to meet or may sacrifice heat or fire protection to meet size constraints.

[0100] Additional references Figure 2 , shows a laminate 200 that is substantially similar to the laminate 100, the main difference being that the laminate 200 includes a backing layer 32. As shown, the laminate 200 has not yet been attached to the substrate surface 10. In order to protect the second adhesive layer 22 before it is adhered to the substrate surface 10 (e.g., from contaminants that may impair its adhesion), the backing layer 32 is removably disposed on the second adhesive layer so that at least a portion (e.g., at least a majority, including all) of the back surface 14 of the laminate 200 is composed of the backing layer. The backing layer 32 may include, for example, a polymer film or a paper sheet and may be removed from the second adhesive layer 22, for example, by peeling it off from the laminate 200.

[0101] Additional references Figure 3 As mentioned above, the laminate of the present invention may include multiple flame retardant layers 18. Specifically, Figure 3The laminate material 300 includes two flame-retardant layers 18. One flame-retardant layer 18 can be disposed on one side of one or more thermal insulation layers 16, and the other flame-retardant layer can be disposed on the other side of the thermal insulation layers. The thickness of the flame-retardant layers 18 need not be the same; for example, the thickness of the flame-retardant layer 18 facing the flame can be any of 1.1 times, 1.2 times, 1.3 times, 1.4 times, 1.5 times, 1.6 times, 1.7 times, 1.8 times, 1.9 times, 2.0 times, 2.1 times, 2.2 times, 2.3 times, 2.4 times, 2.5 times, 2.6 times, 2.7 times, 2.8 times, 2.9 times, or 3.0 times the thickness of the flame-retardant layer 18 on the other side of the one or more thermal insulation layers 16, or any value between any two of these values ​​(e.g., approximately 2.6 times). Figure 3 Also shown are an adhesive layer (eg, 22) for securing the laminate to a substrate and a backing layer (eg, 32) for the adhesive layer, which are both optional.

[0102] Additionally or alternatively, reference Figure 4 Some laminates, such as laminate 400, include a separate reinforcement layer 60 that may include fibers of the types described above, whether woven and / or non-woven. More specifically, reinforcement layer 60 may be attached to at least a portion of flame retardant layer 18, such as via adhesive layer 20. Other laminates may include any suitable number of reinforcement layers (e.g., 60), which may be positioned at any suitable location within the laminate. In addition to providing general reinforcement to the laminate, such one or more reinforcement layers may also help to address ejecta that may be generated, such as during a battery thermal runaway event.

[0103] Now refer to Figure 5 , shows a laminate 500 that is substantially similar to laminate 100, with the primary difference being that laminate 500 includes a heat dissipation layer 62. Laminate 500 includes one heat dissipation layer 62 disposed between flame retardant layer 18 and aerogel layer 16. However, other laminates of the present invention may include any suitable number of heat dissipation layers (e.g., 62), which may be disposed at any suitable location within the laminate. Furthermore, in laminate 500, heat dissipation layer 62 is attached to flame retardant layer 18 and aerogel layer 16 via adhesive layers 20 and 22, respectively, although neither adhesive layer is required. Also, similar to any laminate of the present invention, laminate 500 may include an adhesive layer 24 for adhering the laminate to a substrate, which may optionally be protected by a backing layer (e.g., 32) prior to adhering, as described above.

[0104] The heat dissipation layer 62 may comprise a thermally conductive material, such as a metal (e.g., copper, aluminum, molybdenum, tungsten, rhenium, tantalum, niobium, stainless steel, nickel, or alloys thereof), graphite, and / or the like. More specifically, the heat dissipation layer 62 may comprise at least 90% by weight of a thermally conductive material, such as at least 90% by weight of a metal, or at least 90% by weight of graphite. The heat dissipation layer 60 may have a thermal conductivity of at least 15 W / m·K, preferably 15 W / m·K to 2500 W / m·K. The melting point or decomposition temperature thereof may also be at least 500°C, preferably a melting point of at least 1300°C, at least 1600°C, at least 1900°C, at least 2200°C, at least 2400°C, at least 2700°C, at least 3000°C, or at least 3300°C (e.g., and less than 3800°C or less than 3600°C). Generally speaking, such one or more heat dissipation layers can mitigate the formation of hot spots along one or more bottom layers in the laminate and the subsequent burning or charring of those bottom layers by spreading ambient heat throughout the laminate. The thickness 64 of the heat dissipation layer 62 may be greater than any value among 0.001mm, 0.002mm, 0.004mm, 0.006mm, 0.008mm, 0.01mm, 0.02mm, 0.04mm, 0.06mm, 0.08mm, 0.10mm, 0.12mm, 0.14mm, 0.16mm, 0.18mm, 0.20mm, 0.22mm, 0.24mm, 0.26mm, 0.28mm, 0.30mm, 0.32mm, 0.34mm, 0.36mm, 0.38mm or 0.40mm, or between any two values ​​therein (for example, 0.001mm to 4mm or 0.01mm to 0.08mm).

[0105] Although the laminate 500 is depicted as including one insulating layer 16, similar to other laminates of the present invention, the laminate 500 may include multiple insulating layers 16, optionally connected by adhesive layers such as 24. Furthermore, the laminate 500 is shown as including one flame retardant layer 18, but other embodiments may include multiple flame retardant layers 18, including one disposed above one or more insulating layers 16 and one disposed below one or more insulating layers 16.

[0106] Now refer to Figures 6A to 6C, some of the present invention laminates (600a to 600c) may include one or more ejecta mitigation layers 84 to address ejecta generated, for example, in a battery thermal runaway event. Such one or more ejecta mitigation layers 84 may include a fiber layer, which in this context may be referred to as a reinforcement layer. To this end, the one or more ejecta mitigation layers may include any of the fibers described above for reinforcement layers (e.g., basalt or glass fibers), specifically including silicon-based glass fibers, vermiculite-coated glass fibers, high silicon content glass fibers (e.g., quartz glass fibers), ceramic fibers (e.g., NEXTEL ceramic fibers 312, 440, 610, 729) (including alumina fibers), rock wool, or carbon fibers, whether woven or not. Likewise, the present invention laminate may not include a bottom flame retardant layer (e.g., Figure 6C ) and may not include a heat dissipation layer (e.g., 62). Also, similar to one or more porous insulation layers 16, multiple ejecta mitigation layers ( Figure 6B While the greatest benefit may be obtained by locating the ejecta mitigation layer above the heat sink layer, when present, this is not required.

[0107] In addition, refer to Figure 7 The laminate 700, the ejecta mitigation layer 84 may comprise a metal. The melting point of the metal may be above 1000°C, preferably above 1200°C. Such metals may include, for example, stainless steel, titanium, nickel, molybdenum, tantalum and / or similar metals. Such one or more layers may reflect heat back to the source and act as a thermal barrier. In a particularly advantageous embodiment, one ejecta mitigation layer 84 may be fiber-based and the other may be metal-based. In this case, the fiber-based ejecta mitigation layer 84 is preferably positioned closer to the flame-facing side than the metal-based ejecta mitigation layer 84 ( Figure 7 Regardless, the present laminates may include any suitable number (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9 or more) of ejecta mitigation layers, whether fiber-based and / or metal-based, and positioned at any suitable location in the laminate.

[0108] Now refer to Figure 8, a laminate 800 is shown. The laminate 800, like any other laminate of the present invention, may include a protective layer 86. The protective layer 86 may, for example, provide protection from the environment, including protection from rain, wind, sun, and / or the like. It may also provide protection for specific applications, including protection from jet fuel spray, arcing, mechanical wear, and / or the like. The protective layer 86 may comprise, for example, plastic, glass, or ceramic. Suitable thermoplastics include metal, polyester, PVC ("vinyl"), polyvinyl fluoride, polyvinylidene fluoride (PVDF), polyimide, aramid, polyethylene terephthalate (PET), polymers of the polycarbonate (PC) family, polybutylene terephthalate (PBT), poly(1,4-cyclohexanedicarboxylic acid-1,4-cyclohexanedimethanol ester) (PCCD), glycol-modified polycyclohexyl terephthalate (PCTG), polyphenylene oxide (PPO), polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polystyrene ( Suitable thermosetting plastics include polyaramide, polyimide, polybenzoxazole, polyurethane, polyurethane or polyetherimide (PS), polymethyl methacrylate (PMMA), polyethyleneimine or polyetherimide (PEI) and derivatives thereof, thermoplastic elastomers (TPE), terephthalic acid (TPA) elastomers, poly(cyclohexanedimethylene terephthalate) (PCT), polyethylene naphthalate (PEN), polyamide (PA), polysulfone sulfonate / ester (PSS), polysulfone sulfonate / ester, polyetheretherketone (PEEK), polyetherketoneketone (PEKK), acrylonitrile-butadiene-styrene (ABS), polyphenylene sulfide (PPS), copolymers thereof or blends thereof. Suitable thermosetting plastics include polyaramide, polyimide, polybenzoxazole, polyurethane or blends thereof.

[0109] Now refer to Figure 9 , laminate material of the present invention (for example 100 to 800) can be flexible.As an illustration, this type of laminate material can be provided with the roll 34 form with internal diameter 36, and described internal diameter is less than or equal to any value in 10cm, 8cm, 5cm, 4cm, 2cm, 1cm, 8mm, 5mm, 4mm, 2mm or 1mm, or between any two values ​​therein, and permanent deformation can not occur.This flexibility, even if do not reach this example level, can provide by the relatively small thickness of the material of the heat insulating layer, flame retardant layer, adhesive layer and other layers (if present) of laminate material and / or these layers (for example above-mentioned those).In roll 34, the part of laminate material front surface 12 can face the part of its rear surface 14.

[0110] In some embodiments, the laminate can protect the device or substrate from temperatures greater than 500°C. For example, a laminate of the present invention can be positioned relative to the device so that the flame retardant layer is positioned further away from the device than the back surface (e.g., back surface 14) of the laminate. When exposed to a temperature greater than 500°C to 1500°C for 1 to 90 minutes (preferably at least 5 minutes), the temperature of the device does not exceed 500°C during the time period. The exposure temperature range can be 500°C to 1500°C or 700°C to 1200°C, or 500°C, 600°C, 700°C, 800°C, 900°C, 1000°C, 1100°C, 1200°C, 1300°C, 1400°C, 1500°C, or any range or value therebetween. Of course, the present laminate is also suitable for applications involving exposure to lower temperatures (e.g., less than or equal to 100°C, 200°C, 300°C, or 400°C) and / or exposure to any of the above temperatures for shorter periods of time (e.g., less than or equal to 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 40, 50, or 60 seconds).

[0111] Devices that benefit from such thermal protection include, for example, batteries (e.g., lithium-ion batteries), busbars, and particularly electric or hybrid vehicles, or electrical assemblies containing batteries and motors that are exposed to high temperatures. The surface (e.g., 10) to which the laminate of the present invention may be attached may be the surface of a battery, such as a lithium-ion battery. The surface may also be a busbar or a non-conductive material.

[0112] For example, reference Figure 10 , a battery 66 including battery cells 68 is shown. The cells 68 can be grouped into battery modules 70, which can be assembled into battery packs 72. The battery 66 can also include a battery housing or case 74. To isolate the battery cells 68, battery modules 70, and / or battery packs 72 from vibration and / or accommodate expansion / contraction of the battery cells, battery modules, and / or battery packs, the battery 66 can also include one or more compression pads 76, which can be positioned between the battery cells, between the battery modules, between the battery pack and the battery case 74, and / or the like. The compression pads 76 can include, for example, a compressible material such as foam. The battery 66 can be contained in a vehicle 78, such as the automobile shown. The vehicle 78 can also be, for example, a motor vehicle (e.g., an internal combustion engine vehicle, an electric vehicle, a hybrid electric vehicle), an aircraft (e.g., an airplane, a jet, a helicopter, a drone, or an electric vertical take-off and landing (eVTOL) aircraft), a train, a motorcycle, a watercraft, a spacecraft, or the like.

[0113] However, such batteries 66 may be susceptible to thermal runaway events and / or other high temperature environments. To protect the batteries 66, the vehicle 78 in which the batteries are disposed, and / or the vehicle occupants, one or more laminates of the present invention may be employed. Illustratively, one of the laminates of the present invention may be disposed on the interior and / or exterior surfaces of at least one of the battery cells 68, the battery modules 70, the battery packs 72, the compression mats 76, and / or the battery case 74.

[0114] As another example, refer to Figure 11A and Figure 11B , a cable 80 is shown. The cable 80 may have a length 82 and a width or diameter 84, wherein the length is greater than the width (e.g., 10 times or more than 10 times the width). More specifically, the diameter 84 may be from 0.0003 inches to 10 inches, preferably from 0.001 inches to 1 inch. The cable 80 may be, but is not necessarily, electrically conductive. The cable may be contained in a vehicle (e.g., as described above), a missile, a rocket, an artillery piece, a manned aircraft, an unmanned aircraft, a land vehicle, a marine vehicle, or a spacecraft. Such cables may be exposed to high temperatures, and the laminates of the present invention may be used to mitigate this effect. For example, the cable 80 may comprise one or more laminates of the present invention (e.g., Figure 7 100) shown in B, which forms at least a part of the outer surface of the cable.

[0115] In addition to the above, non-limiting examples of articles that may comprise one or more laminates of the present invention include vehicles, trucks, trailers, trains, rail vehicles, aircraft, spacecraft, body panels or components for any of the foregoing, bridges, pipes, tubing, boats, ships, storage containers, tanks, furniture, windows, doors, railings, functional or decorative building elements, pipe railings, electrical components, conduits, beverage containers, food containers, foils, batteries (e.g., electric vehicle batteries, battery systems, battery housings), and battery bus bars.

[0116] B. Materials for the Polymer Aerogel Layer

[0117] The polymer aerogel layer may comprise an organic material, an inorganic material, or a mixture thereof. The organic aerogel may be made of polyacrylate, polystyrene, polyacrylonitrile, polyurethane, polyurea, polyimide, polyamide, polyaramid, polyfurfuryl alcohol, phenol furfuryl alcohol, melamine formaldehyde, resorcinol formaldehyde, cresol formaldehyde, phenol formaldehyde, polyvinyl alcohol dialdehyde, polycyanurate, polyacrylamide, various epoxy resins, agar, agarose, etc. In a specific embodiment, the aerogel is a polyimide aerogel.

[0118] Polyimides are a class of polymers with many desirable properties. Polyimide polymers contain a nitrogen atom in their polymer backbone, where the nitrogen atom is attached to two carbonyl carbon atoms, making the nitrogen atom relatively stable due to the adjacent carbonyl groups. The carbonyl groups contain a carbon, called a carbonyl carbon, which is double-bonded to an oxygen atom. Polyimides are generally considered to be AA-BB type polymers because two different monomers are typically used to produce polyimide polymers. Polyimides can also be made from AB type monomers. For example, aminodicarboxylic acid monomers can be polymerized to form AB type polyimides. If desired, monoamines and / or monoanhydrides can be used as end-capping agents.

[0119] One type of polyimide monomer is typically a diamine or diamine monomer. A diamine monomer can also be a diisocyanate, and it is understood that an isocyanate can be substituted for an amine in appropriate circumstances. It is known to those skilled in the art that other types of monomers can be used in place of diamine monomers. Another type of monomer is called an acid monomer, which is typically present in the form of a dianhydride. In this specification, the term "diacid monomer" is defined as including dianhydrides, tetraesters, diester acids, tetracarboxylic acids, or trimethylsilyl esters, all of which can react with a diamine to form a polyimide polymer. It is understood that a dianhydride can be appropriately substituted for a tetraester, diester acid, tetracarboxylic acid, or trimethylsilyl ester. It is known to those skilled in the art that other types of monomers can be used in place of a diacid monomer.

[0120] Because a diacid monomer has two anhydride groups, a different diamino monomer can react with each anhydride group, so a diacid monomer can be located between two different diamino monomers. A diamine monomer contains two amine functional groups; therefore, after the first amine functional group is attached to a diacid monomer, the second amine functional group is still available for attachment to another diacid monomer, which in turn is attached to another diamine monomer, and so on. This is how the polymer backbone is formed. The resulting polycondensation reaction forms polyamic acid.

[0121] Polyimide polymers are typically made from two different types of monomers, and different species of each type of monomer can be mixed. Thus, the reaction vessel can contain one, two, or more than two diacid monomers and one, two, or more than two diamino monomers. If long polymer chains are desired, the total molar amount of diacid monomers is kept approximately the same as the total molar amount of diamino monomers. Since more than one type of diamine or diacid can be used, the various monomer components of each polymer chain can be varied to produce polyimides with different properties. For example, a single diamine monomer AA can be reacted with two diacid comonomers B1B1 and B2B2 to form a polymer having the general formula (AA-B1B1) x -(AA-B2B2) y where x and y are determined by the relative incorporation of B1B1 and B2B2 into the polymer backbone. Alternatively, diamine comonomers A1A1 and A2A2 can be reacted with a single diacid monomer BB to form a polymer chain of the general formula (A1A1-BB) x-(A2A2-BB) y In addition, two diamine comonomers A1A1 and A2A2 can react with two diacid comonomers B1B1 and B2B2 to form a polymer chain of the general formula (A1A1-B1B1) w -(A1A1-B2B2) x -(A2A2-B1B1) y -(A2A2-B2B2) z A polymer chain comprising: wherein w, x, y, and z are determined by the relative incorporation of A1A1-B1B1, A1A1-B2B2, A2A2-B1B1, and A2A2-B2B2 into the polymer backbone. More than two diacid comonomers and / or more than two diamine comonomers can also be used. Thus, one or more diamine monomers can be polymerized with one or more diacids, with the general formula of the polymer being determined by varying the number and type of monomers used.

[0122] There are many examples of monomers that can be used to prepare polymer aerogels comprising polyamideamide polymers. In certain embodiments, the diamine monomer is a substituted or unsubstituted aromatic diamine, a substituted or unsubstituted alkyl diamine, or a diamine containing both aromatic and alkyl functional groups. A non-limiting list of possible diamine monomers includes 4,4'-oxydianiline (ODA), 3,4'-oxydianiline, 3,3'-oxydianiline, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, diaminobenzanilide, 3,5-diaminobenzoic acid, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis-(3-aminophenoxy)benzene, 1,4-bis-(4-aminophenoxy)benzene, 1,4-bis-(3-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]-hexafluoropropane, 2,2-bis(3-aminophenyl)-1,1,1, 3,3,3-Hexafluoropropane, 4,4'-isopropylidene diphenylamine, 1-(4-aminophenoxy)-3-(3-aminophenoxy)benzene, 1-(4-aminophenoxy)-4-(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(3-aminophenoxy)phenyl]sulfone, bis(4-[4-aminophenoxy]phenyl)ether, 2,2'-bis-(4-aminophenyl)-hexafluoropropane (6F-diamine), 2,2'-bis-(4-phenoxyaniline)isopropane, m-phenylenediamine, p-phenylenediamine, 1,2-diaminobenzene, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane Alkane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 2,6-diaminopyridine, bis(3-aminophenyl)diethylsilane, 4,4'-diaminodiphenyldiethylsilane, benzidine, dichlorobenzidine, 3,3'-dimethoxybenzidine, 4,4'-diaminobenzophenone, N,N-bis(4-aminophenyl)-n-butylamine, N,N-bis(4-aminophenyl)methylamine, 1,5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4-aminophenyl-3-aminobenzoate, N,N-bis(4 -aminophenyl) aniline, bis(p-β-amino-tert-butylphenyl) ether, p-bis-2-(2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl)benzene, 1,3-bis(4-aminophenoxy)benzene, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl ether phosphine oxide, 4,4'-diaminodiphenyl N-methylamine, 4,4'-diaminodiphenyl N-aniline, amino-terminated polydimethylsiloxane, amino-terminated polypropylene oxide, amino-terminated polybutylene oxide, 4,4'-methylenebis(2-methylcyclohexylamine), 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 4,4'-methylenedianiline, 2,2'-dimethylbenzidine (also known as 4,4'-diamino-2,2'-dimethylbiphenyl (DMB)), dianiline-p-xylene, 4,4'-bis(4-aminophenoxy)biphenyl, 3,3'-bis(4-aminophenoxy)biphenyl, 4,4'-(1,4-phenylenediisopropylidene)dianiline, and 4,4'-(1,3-phenylenediisopropylidene)dianiline, or a combination thereof. In a specific embodiment, the diamine monomer is ODA, 2,2'-dimethylbenzidine, or both.

[0123] A non-limiting list of possible dianhydride ("diacid") monomers includes hydroquinone dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 4,4'-(4,4'-isopropyl)-1-[1-[1-[1-dicarboxylic]-1-propene]-1-ol ... diphenoxy) bis(phthalic anhydride), 2,2-bis(3,4-dicarboxyphenyl) propane dianhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, bis(3,4-dicarboxyphenyl) sulfoxide dianhydride, polysiloxane-containing dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3,2',3'-benzophenonetetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic Acid dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)sulfide dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, In certain embodiments, the dianhydride monomer is BPDA, PMDA, or both.

[0124] In certain aspects, the molar ratio of anhydride to total diamine is 0.4: 1 to 1.6: 1, 0.5: 1 to 1.5: 1, 0.6: 1 to 1.4: 1, 0.7: 1 to 1.3: 1, or specifically 0.8: 1 to 1.2: 1. In other aspects, the molar ratio of dianhydride to polyfunctional amine (e.g., triamine) is 2: 1 to 140: 1, 3: 1 to 130: 1, 4: 1 to 120: 1, 5: 1 to 110: 1, 6: 1 to 100: 1, 7: 1 to 90: 1, or specifically 8: 1 to 80: 1. Monoanhydride groups may also be used. Non-limiting examples of monoanhydride groups include 4-amino-1,8-naphthalene dicarboxylic anhydride, endo-bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, citraconic anhydride, trans-1,2-cyclohexane dicarboxylic anhydride, 3,6-dichlorophthalic anhydride, 4,5-dichlorophthalic anhydride, tetrachlorophthalic anhydride, 3,6-difluorophthalic anhydride, 4,5-difluorophthalic anhydride, tetrafluorophthalic anhydride, malonic anhydride, octanoic ... The monoanhydride group may be phthalic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, 2,2-dimethylglutaric anhydride, 3,3-dimethylglutaric anhydride, 2,3-dimethylmaleic anhydride, 2,2-dimethylsuccinic anhydride, 2,3-diphenylmaleic anhydride, phthalic anhydride, 3-methylglutaric anhydride, methylsuccinic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, 2,3-pyrazinedicarboxylic anhydride or 3,4-pyridinedicarboxylic anhydride. Specifically, the monoanhydride group may be phthalic anhydride.

[0125] In another embodiment, the polymer composition used to prepare the polymer aerogel layer comprises a polyfunctional amine monomer having at least three primary amine functional groups. The polyfunctional amine can be a substituted or unsubstituted aliphatic polyfunctional amine, a substituted or unsubstituted aromatic polyfunctional amine, or a polyfunctional amine comprising a combination of an aliphatic and two aromatic groups, or a polyfunctional amine comprising a combination of an aromatic and two aliphatic groups. A non-limiting list of possible polyfunctional amines includes propane-1,2,3-triamine, 2-aminomethylpropane-1,3-diamine, 3-(2-aminoethyl)pentane-1,5-diamine, bis(hexamethylene)triamine, N',N'-bis(2-aminoethyl)ethane-1,2-diamine, N',N'-bis(3-aminopropyl)propane-1,3-diamine, 4-(3-aminopropyl)heptane-1,7-diamine, N',N'-bis(6- aminohexyl) hexane-1,6-diamine, benzene-1,3,5-triamine, cyclohexane-1,3,5-triamine, melamine, N-2-dimethyl-1,2,3-propanetriamine, diethylenetriamine, 1-methyl or 1-ethyl or 1-propyl or 1-benzyl substituted diethylenetriamine, 1,2-dibenzyldiethylenetriamine, lauryldiethylenetriamine, N-(2-hydroxypropyl)diethylenetriamine, N,N-bis(1-methylheptyl) )-N-2-dimethyl-1,2,3-propanetriamine, 2,4,6-tris(4-(4-aminophenoxy)phenyl)pyridine, N,N-dibutyl-N-2-dimethyl-1,2,3-propanetriamine, 4,4'-(2-(4-aminobenzyl)propane-1,3-diyl)diphenylamine, 4-((bis(4-aminobenzyl)amino)methyl)aniline, 4-(2-(bis(4-aminophenethyl)amino)ethyl)aniline, 4 , 4'-(3-(4-aminophenethyl)pentane-1,5-diyl)diphenylamine, 1,3,5-tris(4-aminophenoxy)benzene (TAPOB), 4,4',4"-methanetriyltriphenylamine, N,N,N',N'-tetrakis(4-aminophenyl)-1,4-phenylenediamine, polyoxypropylenetriamine, octa(aminophenyl)polyhedral oligomeric silsesquioxane, or a combination thereof. Specific examples of polyoxypropylenetriamines are available from Huntsman Corporation, The Woodlands, TX USA. T-403. In certain embodiments, the aromatic polyfunctional amine can be 1,3,5-tris(4-aminophenoxy)benzene or 4,4',4"-methanetriyltriphenylamine. In certain embodiments, the polyfunctional amine comprises three primary amine groups and one or more secondary and / or tertiary amine groups, such as N',N'-bis(4-aminophenyl)benzene-1,4-diamine.

[0126] Non-limiting examples of capping agents or capping groups include amines, maleimides, nadimides, acetylenes, biphenylenes, norbornenes, cycloalkyls, and N-propargyls, specifically those derived from agents including 5-norbornene-2,3-dicarboxylic anhydride (nadimides, NA), methylnadimides, hexachloronadimides, cis-4-cyclohexene-1,2-dicarboxylic anhydride, 4-amino-N-propargylphthalimide, 4-ethynylphthalic anhydride, and maleic anhydride.

[0127] The properties or performance of the final polymer are significantly affected by the choice of monomers used to produce it. Factors to consider when selecting monomers include the properties of the final polymer, such as flexibility, thermal stability, coefficient of thermal expansion (CTE), coefficient of hygroscopic expansion (CHE), and any other particularly desirable properties, as well as cost. Often, certain properties of a polymer can be identified as being important for a particular application. Other properties of the polymer may be less important or may have a wider range of acceptable values; therefore, many different monomer combinations can be used.

[0128] In some cases, the main chain of polymer can include substituents. These substituents (such as oligomers, functional groups etc.) can be directly bonded to the main chain or be connected to the main chain by a linking group (such as tether (tether) or flexible tether). In other embodiments, compound or particle can be incorporated into (such as blended and / or encapsulated in) polyimide structure and not covalently bound with the polyimide structure. In some cases, compound or particle can be incorporated into the polyamic acid reaction process. In some cases, particle can be assembled, thereby producing the polyimide with non-covalently bound compounds or particle regions in varying concentrations.

[0129] Specific properties of polyimides can be influenced by introducing certain compounds into the polyimide. Monomer selection is one way to influence specific properties. Another way to influence properties is by adding compounds or property-modifying moieties to the polyimide.

[0130] C. Preparation of polymer aerogel layers

[0131] Polymer aerogel films that can be used in at least some of the laminates of the present invention are commercially available. Non-limiting examples of such films include Blueshift Roll film (available from Blueshift Materials, Inc. (Spencer, Massachusetts)) and Membranes (available from Aerogel Technologies, LLC), with Blueshift being preferred in certain aspects. Roll film.

[0132] In addition, in addition to the methods discussed below, polymer aerogels (films, sizing materials, or monoliths, etc.) can be prepared using the methods described in patent publications WO 2014 / 189560 to Rodman et al., US2017 / 0355829 to Sakaguchi et al., US 2018 / 078512 to Yang et al., US2018 / 140804 to Sakaguchi et al., US2019 / 006184 to Irvin et al., international patent application PCT / US2019 / 029191 to Ejaz et al., U.S. Patent Publication No. 2017 / 0121483 to Poe et al., and / or U.S. Patent No. 9,963,571 to Sakaguchi et al., all of which are incorporated herein by reference in their entirety.

[0133] The following are non-limiting methods for preparing polymer aerogel layers suitable for use in the laminates of the present invention. These methods may include: (1) preparation of a polymer gel; (2) optional solvent exchange, (3) drying the polymer solution to form an aerogel; and (4) attaching the polymer aerogel film to a substrate.

[0134] 1. Formation of polymer gel

[0135] The first stage of aerogel synthesis can be the synthesis of a polymeric gel. For example, if a polyimide aerogel is desired, at least one acid monomer and at least one diamino monomer can be reacted in a reaction solvent to form polyamic acid. As mentioned above, a variety of acid monomers and diamino monomers can be used to synthesize polyamic acid. In one aspect, polyamic acid is contacted with an imidization catalyst in the presence of a chemical dehydrating agent to form a polymerized polyimide gel through an imidization reaction. "Imidization" is defined as converting a polyimide precursor into an imide. Any imidization catalyst that is suitable for driving a polyimide precursor into a polyimide state is suitable. Non-limiting examples of chemical imidization catalysts include pyridine, picoline, quinoline, isoquinoline, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), triethylenediamine, lutidine, N-methylmorpholine, triethylamine, tripropylamine, tributylamine, other trialkylamines, 2-methylimidazole, 2-ethyl-4-methylimidazole, imidazole, other imidazoles, and combinations thereof. Any dehydrating agent suitable for forming an imide ring from an amic acid precursor is suitable for use in the method of the present invention. Preferred dehydrating agents include at least one compound selected from the group consisting of acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, trifluoroacetic anhydride, phosphorus trichloride, and dicyclohexylcarbodiimide.

[0136] In one aspect of the present invention, one or more diamino monomers and one or more polyfunctional amine monomers are premixed in one or more solvents and then treated with one or more dianhydrides (e.g., diacid monomers) that are added sequentially in smaller amounts at predetermined time increments while monitoring viscosity. The desired viscosity range for the polymerized solution is 50 cP to 20,000 cP, or specifically 500 cP to 5,000 cP. Non-crosslinked aerogels can be prepared by conducting the reaction using incremental addition of dianhydrides while monitoring viscosity. For example, a triamine monomer (23 equivalents) can be added to a solvent to produce a 0.0081 molar solution. To this solution, a first diamine monomer (280 equivalents) is added, followed by a second diamine monomer (280 equivalents). Smaller amounts of dianhydrides (totaling 552 equivalents) are then added sequentially in predetermined time increments while monitoring viscosity. Dianhydrides can be added until the viscosity reaches 1,000 to 1,500 cP. For example, a first portion of dianhydride can be added, the reaction stirred (e.g., 20 minutes), a second portion of dianhydride added, and then a sample of the reaction mixture can be taken for viscosity analysis. After stirring for an additional period of time (e.g., 20 minutes), a third portion of dianhydride can be added, and a sample can be taken for viscosity analysis. After further stirring for a desired period of time (e.g., 10 to 12 hours), a monoanhydride (96 equivalents) can be added. After reaching the target viscosity, the reaction mixture can be stirred for a desired period of time (e.g., 10 to 12 hours) or the reaction can be determined to be complete.

[0137] The reaction temperature for gel formation can be determined by routine experiments based on the raw materials. In a preferred embodiment, the temperature can be greater than or equal to any of the following values ​​or between any two of the following values: 15°C, 20°C, 30°C, 35°C, 40°C and 45°C. After the desired time (e.g., about 2 hours), the product can be isolated (e.g., filtered) and then the nitrogen-containing hydrocarbon (828 equivalents) and dehydrating agent (1214 equivalents) can be added. The addition of the nitrogen-containing hydrocarbon and / or dehydrating agent can be carried out at any temperature. In certain embodiments, the nitrogen-containing hydrocarbon and / or dehydrating agent are added to the solution at 20°C to 28°C (e.g., room temperature) and stirred at this temperature for the desired time. In some cases, after the addition of the nitrogen-containing hydrocarbon and / or dehydrating agent, the solution temperature is raised to 150°C.

[0138] The reaction solvent may include dimethyl sulfoxide (DMSO), diethyl sulfoxide, N,N-dimethylformamide (DMF), N,N-diethylformamide, N,N-dimethylacetamide (DMAc), N,N-diethylacetamide, N-methyl-2-pyrrolidone (NMP), 1-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, 1,13-dimethyl-2-imidazolidinone, diethylene glycol dimethyl ether, o-dichlorobenzene, phenols, cresols, xylenols, catechol, butyrolactones, hexamethylphosphoramide, and mixtures thereof. The reaction solvent and other reactants may be selected based on compatibility with the materials and methods being applied; i.e., if the polymerized polyamide amide gel is to be cast onto a support membrane, injected into a moldable part, or poured into a shape for further processing into a workpiece. In a specific embodiment, the reaction solvent is DMSO.

[0139] In a non-limiting manner, the formation of macropores and smaller mesopores and micropores is mainly controlled by controlling the polymer / solvent dynamics during the gel formation process. By doing so, the pore structure can be controlled, and the amount and volume of macropores, mesopores and micropore units can be controlled. For example, compared with another curing additive such as triethylamine that improves the solubility of the resulting polymer, a curing additive such as 1,4-diazabicyclo[2.2.2]octane that reduces the solubility of the polymer formed during the polymerization process can produce a polymer gel containing more macropores. In another specific non-limiting example, when forming a polyimide aerogel, increasing the ratio of rigid amines (such as p-phenylenediamine (p-PDA)) to more flexible diamines (such as -ODA) incorporated into the polymer backbone can be beneficial to the formation of macropores rather than smaller mesopores and micropores.

[0140] Polymer solution can be optionally cast on the casting sheet covered by support film and continues for a period of time.Casting can comprise spin coating, gravure coating, three-roll coating, doctor blade roll coating, slot die extrusion, dip coating, Meyer rod coating or other technology.In one embodiment, casting sheet is polyethylene terephthalate (PET) casting sheet.After a period of time, the enhanced gel of polymerization is taken off from casting sheet and prepares to carry out solvent exchange process.In certain embodiments, cast film can be heated to high temperature in stages to remove solvent and also be referred to as imidization by cyclic dehydration reaction that the amic acid functional group in polyamic acid is converted into imide.In some cases, can by adding chemical dehydrating agent, catalyzer and / or heat in solution, polyamic acid is converted into polyimide.

[0141] In certain embodiments, the polyimide polymer can be produced by preparing a polyamic acid polymer in a reaction vessel. The polyamic acid is then formed into a sheet or film and subsequently treated with a catalyst or heat and a catalyst to convert the polyamic acid into a polyimide.

[0142] Wet gels used to prepare aerogels can be prepared by any known gel-forming technique, such as adjusting the pH and / or temperature of a dilute metal oxide sol to a point where gelation occurs.

[0143] 2. Optional solvent exchange

[0144] After the polymer gel is synthesized, it may be necessary in some cases to perform a solvent exchange, in which the reaction solvent is replaced with a more desirable second solvent. Thus, in one embodiment, a solvent exchange can be performed, in which the polymer gel is placed in a pressure vessel and immersed in a mixture comprising the reaction solvent and the second solvent. A high pressure environment is then established within the pressure vessel, forcing the second solvent into the polymer gel and displacing a portion of the reaction solvent. Alternatively, the solvent exchange step can be performed in a non-high pressure environment. Multiple rounds of solvent exchange may be necessary. In certain embodiments, solvent exchange is not necessary.

[0145] The time required to perform a solvent exchange varies depending on the type of polymer being exchanged and the reaction solvent and second solvent used. In one embodiment, each solvent exchange takes 1 to 168 hours or any length therebetween, including 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours or 23 hours, 24 hours, 25 hours, 50 hours, 75 hours, 100 hours, 125 hours, 150 hours, 155 hours, 160 hours, 165 hours, 166 hours, 167 hours or 168 hours. In another embodiment, each solvent exchange takes about 1 minute to 60 minutes, or about 30 minutes. Exemplary second solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 3-methyl-2-butanol, 3,3-dimethyl-2-butanol, 2-pentanol, 3-pentanol, 2,2-dimethylprop-1-ol, cyclohexanol, diethylene glycol, cyclohexanone, acetone, acetylacetone, 1,4-dioxane, ether, dichloromethane, trichloroethylene, chloroform, carbon tetrachloride, water and mixtures thereof. In certain non-limiting embodiments, the second solvent may have a suitable freezing point for carrying out a supercritical or subcritical drying step. For example, at an atmospheric pressure, the freezing point of tert-butanol is 25.5°C and the freezing point of water is 0°C. Alternatively, as described below, drying may be performed without using a supercritical or subcritical drying step, such as drying by evaporative drying technology.

[0146] The temperature and pressure used during the solvent exchange process can vary. The duration of the solvent exchange process can be adjusted by performing the solvent exchange at varying temperatures or atmospheric pressures, or both, provided that the pressure and temperature within the pressure vessel do not cause the first or second solvent to leave the liquid phase and transition to a gas, vapor, solid, or supercritical fluid phase. Generally, higher pressures and / or temperatures will shorten the time required to perform the solvent exchange, while lower temperatures and / or pressures will increase the time required to perform the solvent exchange.

[0147] 3. Cooling and drying

[0148] In one embodiment, after solvent exchange, the polymerized gel can be subjected to supercritical drying. In this case, the solvent in the gel can be removed by supercritical CO2 extraction.

[0149] In another embodiment, after solvent exchange, the polymerized gel can be subjected to subcritical drying. In this case, the gel can be cooled below the freezing point of the second solvent and subjected to a freeze-drying or lyophilization process to produce an aerogel. For example, if the second solvent is water, the polymerized gel is cooled to below 0°C. After cooling, the polymerized gel can be placed in a vacuum for a period of time to allow the second solvent to sublime.

[0150] In yet another embodiment, after solvent exchange, the polymerized gel can be subjected to subcritical drying and, optionally, heating after the majority of the second solvent has been removed by sublimation. In this case, the partially dried gel material is heated to a temperature near or above the boiling point of the second solvent for a period of time. This period can range from a few hours to several days, but a typical period is about four hours. During the sublimation process, a portion of the second solvent present in the polymerized gel is removed, leaving behind a gel that can have macropores, mesopores, or micropores, or any combination or all of these pore sizes. When the sublimation process is complete or nearly complete, an aerogel is formed.

[0151] In yet another embodiment, after solvent exchange, the polymerized gel can be dried under ambient conditions, for example, by removing the solvent under a flow of gas (e.g., air, anhydrous gas, an inert gas such as nitrogen (N2), etc.). In addition, passive drying techniques can be used, for example, by simply exposing the gel to ambient conditions without the use of a gas flow.

[0152] After cooling or drying, the film and sizing forms can be configured for use in the laminates of the present invention. For example, the film or sizing form can be processed (e.g., by cutting or grinding) into a desired shape, such as a square, rectangle, circle, triangle, irregular shape, random shape, etc. In addition, as described above, the film or sizing form can be secured to a support material with an adhesive. In an alternative embodiment, the support material can be incorporated into the matrix of the polymer aerogel, as discussed below.

[0153] 4. Incorporating the reinforcement layer into the polymer aerogel matrix

[0154] In addition to the aforementioned methods for attaching polymer aerogels to support materials using adhesives, an optional embodiment of the present invention may include incorporating support materials into a polymer matrix to form reinforced polymer aerogels without the use of adhesives. Notably, during the manufacture of unreinforced polymer aerogels, a reinforcing support film can be used as a carrier to support the gelled film during processing. During the rewinding process, the gelled film can be irreversibly pressed into the carrier film. Pressing the gelled film into the carrier film can significantly improve durability. Alternatively, during the aforementioned solvent casting step, the polymer solution can be cast into either the reinforcing material or the support material.

[0155] Substrate selection and direct casting can optimize (e.g., minimize) the thickness of the resulting reinforced aerogel material. This method can also be extended to the production of fiber-reinforced polymer aerogels—internal reinforced polyimide aerogels being an example. The method may include: (a) forming a polyamic acid solution from a mixture of dianhydride and diamine monomers in a polar solvent such as DMSO, DMAc, NMP, or DMF; (b) contacting the polyamic acid solution with the above-mentioned chemical curing agent and chemical dehydrating agent to initiate chemical imidization; (c) casting the polyamic acid solution onto a fiber support and allowing it to penetrate before gelation; (d) gelling the catalyzed polyamic acid solution around and into the fiber support during the chemical imidization process; (e) optionally performing a solvent exchange, which can facilitate drying; and (f) removing the transient liquid phase contained in the gel by supercritical, subcritical, or ambient drying to obtain an internally reinforced aerogel.

[0156] D. Non-Limiting Aspects of the Invention

[0157] The present invention may include the following non-limiting aspects.

[0158] Aspect 1: A laminate comprising: a flame retardant layer having a flammability rating in compliance with at least one plastic flammability standard; and an aerogel layer; wherein: the laminate has opposing front and back surfaces; the flame retardant layer constitutes at least a majority of the front surface; and the laminate has a thickness less than or equal to 25.4 millimeters (mm).

[0159] Aspect 2: The laminate according to aspect 1, wherein the thickness of the laminate is less than or equal to 10 mm, preferably less than or equal to 5 mm, more preferably less than or equal to 2 mm, or even more preferably from 0.3 mm to 2 mm.

[0160] Aspect 3: The laminate according to any one of aspects 1 or 2, wherein the thickness of the flame retardant layer is 0.05 mm to 0.8 mm.

[0161] Aspect 4: The laminate material of any of aspects 1 to 3, wherein the flame retardant layer is not electrically insulating.

[0162] Aspect 5: The laminate of any one of aspects 1 to 3, wherein the flame retardant layer is electrically insulating.

[0163] Aspect 6: The laminate according to any one of aspects 1 to 5, wherein the plastic flammability standard is UL94 5VA or UL94 5VB, and wherein the flammability rating of the flame retardant layer complies with UL94 5VA or UL94 5VB.

[0164] Aspect 7: The laminate according to any one of aspects 1 to 6, wherein the flammability rating of the laminate complies with the flammability standards for plastics, preferably UL94 5VB, more preferably UL94 5VA.

[0165] Aspect 8: The laminate of any of aspects 1 to 7, wherein the flame retardant layer comprises fibers.

[0166] Aspect 9: The laminate material of aspect 8, wherein the fibers are non-woven.

[0167] Aspect 10: The laminate of aspect 8, wherein the fibers are woven.

[0168] Aspect 11: The laminate of any of aspects 1 to 10, wherein the flame retardant layer comprises one or more than one of a metal hydroxide, an organic phosphate, an aluminum hydroxide, an inorganic filler, and / or a metal oxide.

[0169] Aspect 12: The laminate of any of aspects 1 to 11, wherein the flame retardant layer comprises a silicate.

[0170] Aspect 13: The laminate of aspect 12, wherein the silicate comprises mica, and wherein the flame retardant layer preferably comprises at least 90% by weight mica.

[0171] Aspect 14: The laminate of any of aspects 1 to 13, wherein the flame retardant layer comprises ceramic, and wherein the flame retardant layer preferably comprises at least 90% by weight ceramic.

[0172] Aspect 15: The laminate material of Aspect 14, wherein the ceramic comprises a metal oxide or a non-metal oxide or a combination thereof.

[0173] Aspect 16: The laminate material of aspect 15, wherein the ceramic comprises alumina, beryllia, ceria, zirconia, carbide, boride, nitride, or silicide, or any combination thereof.

[0174] Aspect 17: The laminate of any of aspects 1 to 16, wherein the flame retardant layer is halogen-free.

[0175] Aspect 18: The laminate of any of aspects 1 to 17, wherein the aerogel layer has a thickness of 0.05 mm to 0.254 mm.

[0176] Aspect 19: The laminate of any of aspects 1 to 18, wherein the aerogel layer is a polymer aerogel layer.

[0177] Aspect 20: The laminate of any of aspects 1 to 19, wherein the polymer aerogel layer comprises at least 50 wt% polyimide.

[0178] Aspect 21: The laminate material according to any one of aspects 1 to 20, wherein the decomposition temperature of the aerogel layer is greater than or equal to 400°C, preferably 400°C to 600°C.

[0179] Aspect 22: The laminate of any of aspects 1 to 21, comprising one or more adhesive layers bonded to the aerogel layer.

[0180] Aspect 23: The laminate of aspect 22, wherein a first adhesive layer of the one or more adhesive layers is disposed between the flame retardant layer and the aerogel layer.

[0181] Aspect 24: The laminate of aspect 23, wherein the first adhesive layer has a melting temperature or a decomposition temperature greater than 500°C.

[0182] Aspect 25: The laminate of aspect 23 or 24, wherein at least a portion of the back surface is comprised of: a second adhesive layer of the one or more adhesive layers; or a backing layer removably disposed on the second adhesive layer.

[0183] Aspect 26: The laminate of any of Aspects 22 to 25, wherein each of the one or more bonding layers comprises a pressure-sensitive adhesive.

[0184] Aspect 27: The laminate of any of Aspects 22 to 26, wherein each of the one or more bonding layers comprises a silicone adhesive compound and / or an epoxy resin compound.

[0185] Aspect 28: The laminate of any of aspects 1 to 27, wherein any one, any combination, or all of the flame retardant layer, the aerogel layer, and the adhesive layer are perforated.

[0186] Aspect 29: A laminate as described in any of Aspects 1 to 28, wherein when the laminate is attached to a substrate, the temperature of the substrate is capable of being maintained at or below 500°C when the front surface of the laminate is exposed to a temperature greater than 500°C, preferably from 500°C to 1500°C, or more preferably from 700°C to 1200°C for a period of 1 minute to 90 minutes, preferably at least 5 minutes.

[0187] Aspect 30: The laminate of any of aspects 1 to 29, wherein the laminate is provided in a roll such that a portion of the front surface of the laminate faces a portion of the back surface of the laminate.

[0188] Aspect 31: The laminate material according to any one of aspects 1 to 30, further comprising a heat dissipation layer.

[0189] Aspect 32: The laminate material according to aspect 31, wherein the heat dissipation layer comprises a metal having a thermal conductivity of at least 15 W / m·K, preferably 15 W / m·K to 2500 W / m·K.

[0190] Aspect 33: The laminate material of Aspect 32, wherein the metal comprises copper, aluminum, molybdenum, tungsten, rhenium, tantalum, niobium, stainless steel, nickel, or alloys thereof.

[0191] Aspect 34: The laminate of aspect 32 or 33, wherein the heat dissipation layer comprises at least 90% by weight of metal.

[0192] Aspect 35: The laminate material of Aspect 31, wherein the heat dissipation layer comprises graphite.

[0193] Aspect 36: The laminate material of Aspect 35, wherein the heat dissipation layer comprises at least 90% by weight of the graphite.

[0194] Aspect 37: The laminate material according to any one of aspects 31 to 36, wherein the heat dissipation layer has a thickness of 0.001 mm to 0.4 mm, preferably 0.01 mm to 0.05 mm.

[0195] Aspect 38: The laminate material of any of aspects 31 to 37, wherein the heat dissipation layer is disposed between the flame retardant layer and the aerogel layer.

[0196] Aspect 39: The laminate material according to aspect 38, comprising a first adhesive layer disposed between the flame retardant layer and the heat dissipation layer, and a second adhesive layer disposed between the heat dissipation layer and the aerogel layer.

[0197] Aspect 40: The laminate of aspect 39, wherein the first adhesive layer is in direct contact with the flame retardant layer and the heat dissipation layer, and the second adhesive layer is in direct contact with the heat dissipation layer and the aerogel layer.

[0198] Aspect 41: The laminate of aspect 39 or 40, further comprising a third adhesive layer and a backing layer, wherein the third adhesive layer is disposed between the aerogel layer and the backing layer.

[0199] Aspect 42: The laminate of aspect 41, wherein the third adhesive layer is in direct contact with the aerogel layer and the backing layer.

[0200] Aspect 43: The laminate of any of Aspects 39 to 42, wherein the first, second, and / or third adhesive layers: have a melting point or decomposition temperature greater than 500°C; comprise a pressure sensitive adhesive; and / or comprise a silicone adhesive compound and / or an epoxy resin compound.

[0201] Aspect 44: The laminate material of any one of aspects 31 to 43, wherein any one, any combination, or all of the flame retardant layer, the heat dissipation layer, the aerogel layer, and the first, second, and third adhesive layers are perforated.

[0202] Aspect 45: The laminate of any of Aspects 1 to 44, further comprising a reinforcement layer.

[0203] Aspect 46: The laminate of aspect 45, wherein the reinforcement layer is attached to at least a portion of the flame retardant layer.

[0204] Aspect 47: The laminate of aspect 45 or 46, wherein the reinforcement layer is contained within at least a portion of the volume of the flame retardant layer.

[0205] Aspect 48: The laminate material of any of Aspects 45 to 47, wherein the reinforcement layer comprises fibers.

[0206] Aspect 49: The laminate of aspect 48, wherein the fibers comprise glass fibers, carbon fibers, aramid fibers, thermoplastic fibers, thermoset fibers, ceramic fibers, basalt fibers, rock wool fibers, steel fibers, cellulose fibers, or any combination thereof.

[0207] Aspect 50: The laminate of aspect 48 or 49, wherein the fibers are non-woven fibers or woven fibers.

[0208] Aspect 51: A device comprising one or more laminates as described in any of Aspects 1 to 50, wherein a first laminate of the one or more laminates is bonded to the device such that a front surface of the first laminate is positioned further away from the device than a rear surface of the first laminate.

[0209] Aspect 52: The device of Aspect 51, wherein the device is a battery.

[0210] Aspect 53: The apparatus of Aspect 52, wherein the battery is contained in a vehicle, the vehicle comprising: one or more wheels; and one or more electric motors, each motor configured to rotate at least one wheel; wherein the battery is in electrical communication with at least one electric motor.

[0211] Aspect 54: A device as described in Aspect 52 or 53, further comprising: a busbar electrically connected to the battery; wherein one or more laminates include two or more laminates, and a second laminate in the one or more laminates is bonded to the busbar so that a front surface of the second laminate is positioned further away from the busbar than a rear surface of the second laminate.

[0212] Aspect 55: The device of any of Aspects 52 to 54, wherein the battery is a lithium-ion battery.

[0213] Aspect 56: The device of Aspect 51, wherein the device is a busbar.

[0214] Aspect 57: The device of aspect 51, wherein the device is a compression mat, a battery cell, a battery module, a battery pack, or a battery case.

[0215] Aspect 58: The device of aspect 57, wherein the device is a compression pad, and wherein the compression pad comprises a compressible material.

[0216] Aspect 59: The device of Aspect 58, wherein the compressible material comprises foam.

[0217] Aspect 60: The device of aspect 58 or 59, wherein the compression pad is positioned between the first battery cell and the second battery cell.

[0218] Aspect 61: The device of aspect 57, wherein the device is a battery cell.

[0219] Aspect 62: The device of aspect 57, wherein the device is a battery module comprising at least two battery cells, and wherein the one or more laminate materials are positioned between the two battery cells.

[0220] Aspect 63: The device of aspect 57, wherein the device is a battery pack comprising at least two battery modules, and wherein one or more of the laminates are positioned between the two battery modules.

[0221] Aspect 64: The device of Aspect 57, wherein the device is a battery case comprising an exterior surface, an interior surface, and an interior volume.

[0222] Aspect 65: The device of Aspect 64, wherein the one or more laminates cover at least a portion of the exterior surface, at least a portion of the interior surface, or both.

[0223] Aspect 66: The device of Aspect 64 or 65, wherein the interior volume is configured to accommodate a compression pad, a battery cell, a battery module, or a battery pack.

[0224] Aspect 67: The device of Aspect 66, wherein the internal volume comprises a compression pad, a battery cell, a battery module, a battery pack, or any combination thereof.

[0225] Aspect 68: The device of any of Aspects 57 to 67, wherein the compression pad, battery cell, battery module, battery pack, or battery cartridge is contained in a vehicle comprising one or more electric motors.

[0226] Aspect 69: The apparatus of Aspect 68, wherein the vehicle is a car, an aircraft, a train, a motorcycle, a watercraft, or a spacecraft.

[0227] Aspect 70: The device of Aspect 51, wherein the device is a cable.

[0228] Aspect 71: The apparatus of aspect 70, wherein the cable has a length and a width, and wherein the length is longer than the width.

[0229] Aspect 72: The device of Aspect 70 or 71, wherein the cable is conductive.

[0230] Aspect 73: The device of any of Aspects 70 to 72, wherein the cable comprises a diameter of 0.0003 inches to 10 inches, preferably 0.001 inches to 1 inch.

[0231] Aspect 74: The apparatus of any one of Aspects 70 to 73, wherein the cable is contained within a missile, rocket, artillery piece, manned aircraft, unmanned aircraft, land vehicle, sea vehicle, or space vehicle.

[0232] Aspect 75: The apparatus of Aspect 74, wherein the vehicle is a spacecraft or an aircraft.

[0233] Aspect 76: An apparatus as described in any of Aspects 51 to 75, wherein one or more laminates are capable of maintaining the temperature of the apparatus at or below 500°C when the front surface of the laminate is exposed to a temperature greater than 500°C, preferably 500°C to 1500°C, or more preferably 700°C to 1200°C for 1 minute to 90 minutes, preferably at least 5 minutes.

[0234] Aspect 77: A method for thermally protecting a device as described in any of aspects 51 to 76, the method comprising bonding the laminate material as described in any of aspects 1 to 50 to the device.

[0235] Aspect 78: The method of aspect 77, wherein the laminate is positioned relative to the device such that a front surface of the laminate is disposed further away from the device than a back surface of the laminate.

[0236] Aspect 79: The method of aspect 78, wherein the front surface of the laminate is subjected to a temperature of greater than 500°C to 1500°C for a period of 1 minute to 90 minutes, preferably at least 5 minutes, and the temperature of the device does not exceed 500°C during the period.

[0237] Aspect 80: The method of aspect 78, wherein the front surface of the laminate is subjected to a temperature of 700°C to 1200°C for a period of 1 minute to 90 minutes, preferably at least 5 minutes, and the temperature of the device does not exceed 500°C during the period.

[0238] Aspect 81: The laminate of any of aspects 1 to 50, wherein the flame retardant layer comprises a first flame retardant layer and a second flame retardant layer, and the first and second flame retardant layers are disposed on opposite sides of the aerogel layer.

[0239] Aspect 91: A laminate material comprising a reinforcement layer comprising fibers, a flame retardant layer having a flammability rating according to UL94 5VA, UL94 5VB, or UL94 V-0, a porous thermal insulation layer, and (e.g., optionally) a heat dissipation layer comprising at least 90% by weight of metal or graphite, wherein the thickness of the laminate material is less than or equal to 25.4 mm (e.g., less than or equal to 5 mm).

[0240] Aspect 92: The laminate of aspect 91, wherein the porous insulation layer comprises an aerogel layer.

[0241] Aspect 93: The laminate of Aspect 91 or 92, wherein the fibers of the reinforcement layer comprise glass fibers or basalt fibers.

[0242] Aspect 94: The laminate material of any of Aspects 91 to 93, wherein the fibers of the reinforcement layer are woven.

[0243] Aspect 95: The laminate material of any of aspects 91 to 94, wherein the laminate material has opposing front and back surfaces, and each of the reinforcement layer, the flame retardant layer, and the heat dissipation layer is located closer to the front surface than the aerogel layer.

[0244] Aspect 96: The laminate of any of aspects 91 to 95, wherein the flame retardant layer is located between the reinforcement layer and the aerogel layer.

[0245] Aspect 97: A laminate comprising a spray mitigation layer, a flame retardant layer having a flammability rating according to UL94 5VA, UL945VB, or UL94V-0, and a porous thermal insulation layer, wherein the laminate has opposing front and back surfaces and the spray mitigation layer constitutes at least a majority of the front surface.

[0246] Aspect 98: The laminate material of Aspect 97, wherein the porous insulating layer comprises an aerogel layer.

[0247] Aspect 99: The laminate of aspect 97 or 98, wherein the ejecta mitigation layer comprises at least 90% by weight metal.

[0248] Aspect 100: The laminate of Aspect 99, wherein the metal of the ejecta mitigation layer comprises titanium.

[0249] Aspect 101: The laminate of aspect 97 or 98, wherein the spray mitigation layer comprises fibers.

[0250] Aspect 102: The laminate of aspect 101, wherein the fibers of the ejecta mitigation layer comprise glass fibers or basalt fibers.

[0251] Aspect 103: The laminate of Aspect 101 or 102, wherein the fibers of the ejecta mitigation layer are woven.

[0252] Aspect 104: The laminate of any of aspects 91 to 103, wherein the flame retardant layer is based on an inorganic material.

[0253] Aspect 105: The laminate of any of aspects 91 to 104, wherein the flame retardant layer comprises paper.

[0254] Aspect 106: The laminate of any of aspects 91 to 105, wherein the flame retardant layer comprises at least 90% by weight silicate.

[0255] Aspect 107: The laminate of any of aspects 91 to 105, wherein the flame retardant layer comprises at least 90% by weight ceramic.

[0256] Aspect 108: The laminate of any of aspects 91 to 107, wherein the flame retardant layer has a thickness of 0.05 mm to 0.8 mm.

[0257] Aspect 109: The laminate of any of aspects 91 to 108, wherein the porous insulating layer comprises at least 50% by weight polyimide.

[0258] Aspect 110: The laminate of any of aspects 91 to 109, wherein the laminate has a flammability rating in accordance with UL94 5VA, UL94 5VB, or UL94 V-0.

[0259] Aspect 111: The laminate of any of aspects 91 to 110, comprising one or more adhesive layers bonded to the porous insulation layer, including a first adhesive layer disposed between the flame retardant layer and the porous insulation layer.

[0260] Aspect 112: The laminate of any of aspects 91 to 111, comprising a second flame retardant layer, wherein the flame retardant layer is disposed on opposite sides of the porous insulation layer.

[0261] Aspect 113: A device comprising the laminate of any of aspects 91 to 112, comprising the laminate bonded to the device.

[0262] Aspect 114: The device of aspect 113, wherein the device is a compression mat, a battery cell, a battery module, a battery pack, or a battery case.

[0263] Aspect 115: The device of Aspect 113, wherein the device is a conductive cable. Example

[0264] The present invention will be described in more detail by specific examples. The following examples are only for illustrative purposes and are not intended to limit the present invention in any way. Those of ordinary skill in the art will readily recognize multiple non-critical parameters that can be changed or modified to obtain substantially the same effect.

[0265] Example 1

[0266] (Flame and Heat Barrier Laminate Testing)

[0267] Materials. Copper rods measuring 12 inches by 1.6 inches by 0.2 inches were obtained from McMaster Carr. AeroZero (AZ) film (6.5 mils thick) was manufactured by Blueshift Materials Inc.; the flame retardant barrier material used was 3M FRBWT145 (5.8 mils thick), manufactured by 3M. Laminated test specimens were assembled using pressure-sensitive silicone adhesive SA6101LR manufactured by FLEXcon.

[0268] Test setup. The flame and heat barrier effectiveness of the sample was tested using a bare copper rod as the test substrate. The copper rod was clamped horizontally in a bracket. A thermocouple was secured to the center of the copper rod using Kapton tape. The test sample was wrapped around the copper rod before exposure to flame.

[0269] The test sample was wrapped around a 2-inch section of a 12-inch copper rod, with the tip of the thermocouple located directly below the test sample and in direct contact with the rod. The test sample was bonded to the rod with a silicone pressure-sensitive adhesive. A flame source (Bunsen burner) set at a flame temperature of 700°C was placed 1.5 inches from the test sample, with the flame in direct contact with the horizontally positioned test sample. The temperature from the thermocouple was recorded at 30-second intervals for 10 minutes.

[0270] Test configuration such as Figure 12As shown, the test setup 1200 includes a copper rod 40, test samples 42 and 44, a thermocouple 46, and a flame source 48. The flame and heat barrier test samples 42 and 44 are laminated as shown in FIG. Figure 13 Each sample included one or more AeroZero aerogel layers as one or more thermal insulation layers 16, wherein the one or more aerogel layers were directly attached to a copper rod 40 and a flame retardant layer 18 via adhesive layers 20 and 22. The flame retardant layer 18 faced the flame source 48. Several samples were tested, and their specific laminate structures are shown in Table 1.

[0271] Table 1: Laminated structures of flame and heat barrier test samples

[0272]

[0273] The thermal distribution curve of the tested sample is as follows Figure 14 Table 2 shows the temperature data of the copper rod for each sample after 5 and 10 minutes of exposure to the flame. These temperature data are compared with the control sample, which is a copper rod without a barrier. The test results show that when one or two thermal insulation layers (here, AeroZero film) are used in combination with a flame retardant layer (here, FRM WT-145), the copper rod temperature is significantly reduced, thereby demonstrating an unexpected synergistic effect between one or more thermal insulation layers and the flame retardant layer.

[0274] Table 2: Copper rod temperature when samples were exposed to flame

[0275]

[0276] Examples 2 to 7

[0277] (Flame and Heat Barrier Laminate Testing)

[0278] 1000°C flame test setup. Further testing of flame and heat barrier samples was performed using Figure 15Test setup 1500 was used as shown. Test setup 1500 was substantially similar to test setup 1200, with the following differences. Here, the flame height was 3 inches, the width was 2 inches, the temperature was 1000°C ± 30°C, and the base of the flame was 2.5 inches from the test sample 44. In addition, some tests did not use a test substrate, while other tests used test substrates including 8-inch × 8-inch aluminum plates, steel plates, and carbon fiber composite plates. In the tests using a test substrate, only a single sample 44 was bonded to the flame-contacting surface of the test substrate, rather than two samples 42 and 44. Finally, two thermocouples 46a and 46b were used. Thermocouple 46a was in direct contact with the flame to measure the flame temperature, while thermocouple 46b was placed on the non-flame-contacting surface (i.e., the cold side) of the laminated test sample (if a test substrate was not used) or on the test substrate. All thermal profiles described in Examples 2 to 7 are based on the temperature data recorded by thermocouple 46b.

[0279] Example 2

[0280] Flame and heat barrier laminate test samples having the laminate structure shown in Table 3 were exposed to a 1000°C flame for 600 seconds (10 minutes). The laminate test samples were not bonded to the test substrate. In this example, a laminate containing only a flame retardant layer ("FRB") was compared to a laminate in which the FRB was combined with a thermal barrier layer. The FRB tested was FRB model NT381 manufactured by 3M.

[0281] Table 3: Laminated structures of flame and heat barrier test samples

[0282]

[0283] The thermal distribution curves of the samples in Table 3 are as follows Figure 16 As shown, the laminate containing the FRB and the insulation layer not only has a lower primary heating rate than the laminate containing only the FRB, but also has a lower temperature after 5 minutes (312°C vs. 341°C).

[0284] Example 3

[0285] Flame and thermal barrier laminate test samples having the laminate structures shown in Table 4 were exposed to a 1000°C flame for 25 minutes. The laminate test samples were not bonded to the test substrate. In this example, one of the samples included an additional heat dissipation layer, a 0.05 mm thick graphite layer, positioned between the flame-facing FRB and one of the thermal insulation layers.

[0286] Table 4: Laminated structures of flame and heat barrier test samples

[0287]

[0288] The thermal distribution curves of the samples in Table 4 are as follows Figure 17 The data shows that adding a heat-distribution layer between the flame-facing FRB and the insulation further reduced the laminate's cold-side temperature. While the main heating rate of the laminate with the heat-distribution layer was similar to that of the laminate without the heat-distribution layer during the first three minutes or so, after three minutes, the laminate with the heat-distribution layer outperformed the laminate without the heat-distribution layer in terms of heating rate and other properties. Table 5 quantifies these improvements, listing the laminate's cold-side temperatures after 5, 10, and 25 minutes of flame exposure.

[0289] Table 5: Laminate cold side temperatures during flame exposure of samples

[0290]

[0291] Example 4

[0292] Flame and heat barrier laminate test samples of three different thicknesses (0.57 mm, 0.70 mm, and 1.17 mm) were bonded to 8 inch by 8 inch mild steel panels, 0.7 mm thick, and exposed to a 1000°C flame for 600 seconds (10 minutes). The layup structures of the laminate test samples are shown in Table 6.

[0293] Table 6: Laminated structures of flame and heat barrier test samples

[0294]

[0295] The thermal distribution curves of the samples in Table 6 are as follows Figure 18 The thermal profiles for an unbonded laminate consisting of steel plates ("no FRB") are also shown. The data show that as the laminate thickness increases, both the primary heating rate (measured within the first 200 seconds) and the maximum temperature (measured at 600 seconds) on the cold side of the substrate decrease. Notably, the maximum cold side temperature of the substrate remained below 350°C for both the 0.07 mm and 1.17 mm thick laminates during the 600 seconds (10 minutes) of flame exposure.

[0296] Example 5

[0297] Flame and heat barrier laminate test samples containing a 0.05 mm thick graphite heat-dissipating layer and those without such a heat-dissipating layer were bonded to an 8 inch x 8 inch carbon fiber composite panel, 1.0 mm thick, and exposed to a 1000°C flame for 25 minutes. The layup structures of the laminate test samples are shown in Table 7.

[0298] Table 7: Laminated structures of flame and heat barrier test samples

[0299]

[0300] The thermal distribution curve of the laminated material in Table 7 is as follows Figure 19 As shown, the thermal distribution curve of the control ("no FRB") composed of a carbon fiber composite plate with no bonded laminate is also shown. When not protected by the laminate, the carbon fiber composite plate begins to burn and produces thick smoke within 10 seconds of flame exposure. The temperature of the cold side of the carbon fiber composite plate quickly rises to 200°C within 40 seconds. The test was terminated due to excessive smoke and decomposition of the carbon fiber composite plate. When a flame and heat barrier laminate that does not include a heat distribution layer is used for protection, the main heating rate is significantly reduced: the cold side of the carbon fiber composite plate takes about 2 minutes to reach 200°C. And after 10 minutes of flame exposure, the maximum temperature of the cold side of the carbon fiber composite plate is 355°C, which does not continue to rise during the 25-minute test.

[0301] The flame and heat barrier laminate, including the heat distribution layer, demonstrated improved performance in both the main heating rate and maximum temperature on the cold side of the carbon fiber composite panel. Specifically, the main heating rate curve shifted slightly to the right, reaching 200°C after 2.8 minutes, and the maximum cold side temperature of the carbon fiber composite panel reached 333°C during the 25-minute flame exposure. Table 8 further quantifies these improvements, listing the substrate cold side temperatures after 5, 10, and 25 minutes of flame exposure.

[0302] Table 8: Substrate cold side temperatures when samples were exposed to flame

[0303]

[0304] like Figure 20 As shown in Table 7, no carbon fiber composite material burn-through occurred during the test of the two laminate materials.

[0305] Example 6

[0306] The 1.17 mm thick FRB / AeroZero / AeroZero / FRB flame and heat barrier laminate of Table 3 was bonded to an 8 inch x 8 inch aluminum panel, 0.025 mm (1 mil) thick, and exposed to a 1000°C flame for 25 minutes. The thermal profile of the laminate is shown in Table 3. Figure 21 As shown, the thermal profile includes a gradually increasing aluminum plate temperature that reaches a maximum temperature of 325°C during the 25-minute test period: well below the melting point of aluminum. Figure 22 As shown, no burn-through of the aluminum plate was observed during the test.

[0307] Example 7

[0308] The thermal conductivity of various flame and heat barrier laminates was tested according to ASTM C518, "Standard Test Method for Steady-State Thermal Transmission Properties by Means of the Heat Flow Meter Apparatus." The instrument used was a TA Instruments Fox50 heat flow meter. The laminate structures, thermal conductivities, and densities of the tested laminates are shown in Table 9.

[0309] Table 9: Properties of Flame and Heat Barrier Test Samples

[0310]

[0311] Example 8 to Example 9

[0312] (Flame and thermal barrier laminate testing including spray mitigation layers)

[0313] Materials. Flame and heat barrier laminates including ejecta mitigation layers were prepared, each including an aerogel layer, an FRB layer, and for some laminates, a graphite heat dissipation layer, wherein these layers were laminated to each other and to one or more ejecta mitigation layers using a pressure-sensitive silicone adhesive SA6101LR. The aerogel layer was a 6.5 mil thick AZ film, and the FRB layer was a 5.8 mil thick WT-145 or a 15 mil thick NT-381. Two ejecta mitigation layers were used. The first was a woven glass fiber layer with S2 glass fiber and a 6781 weave style produced by FibreGlast Development Corp. The second was a plain woven basalt fabric made of continuous basalt filament roving produced by Canadian Basalt. The properties of these ejecta mitigation layers are shown in Table 10.

[0314] Table 10: Properties of ejecta mitigation layers

[0315] Woven fiberglass Basalt fabric Thickness (mm) 0.25 0.11 <![CDATA[Grammage (g / m 2 )]]> 305 108 <![CDATA[Density (g / cm 3 )]]> 1.20 0.99

[0316] Measurement Methods. Laminate sample thickness was measured according to ASTM D374 / D374M-16 Method C: "Standard Test Methods for Thickness of Solid Electrical Insulation." For each laminate sample, five 2-inch diameter discs were cut from the laminate, and the thickness of each disc was measured at three locations. The sample thickness is reported as the average of 15 measurements. The micrometer used was a Mitutoyo Electronic Thickness Gauge (Model 547-526S).

[0317] Density was determined according to ASTM 202-17: "Standard Test Methods for Sampling and Testing Untreated Paper Used for Electrical Insulation." For each laminate sample, five 2-inch diameter discs were cut from the laminate. The mass of each disc was measured using an analytical balance and divided by the volume of the original disc to determine the density. The reported density is the average of five measurements.

[0318] The basis weight of each laminate sample was obtained by cutting ten 2-inch diameter discs from the laminate. The mass of each disc was measured using an analytical balance according to ASTM 202-17: "Standard Test Methods for Sampling and Testing Untreated Paper Used for Electrical Insulation" and divided by the surface area of ​​the disc to determine its basis weight. The average of the ten measurements was reported.

[0319] Thermal conductivity was measured using a FOX 50 heat flow meter according to ASTM C518-10: "Standard Test Method for Steady-State Thermal Transmission Properties by Means of the Heat Flow Meter Apparatus." 2-inch diameter discs were cut from the laminate and stacked together to create a 3-mm-thick, uniform surface. The stack was placed between the plates of the FOX 50 analyzer, with the hot and cold plates maintained at 35°C and 15°C, respectively. Therefore, thermal conductivity was measured at an average temperature of 25°C.

[0320] Flame Test Procedure. Each laminate sample tested was 8 inches by 8 inches and Figure 15 The test setup was devoid of test substrate 40. During the test, the gas flow rate of flame source 48 and the distance between the flame and sample laminate 44 were kept constant. Bottom thermocouple 46a recorded a temperature of 1000 ± 30°C during the test. Each test lasted 10 minutes, during which the cold side temperature of the laminate sample was recorded using thermocouple 46b.

[0321] Example 8

[0322] Test Sample Laminate Structures. The specific laminate structures of some of the tested laminate samples (S1 to S4) and the properties of these laminates are shown in Table 11. Laminate samples (S1 and S2) without a spray mitigation layer were included as controls.

[0323] Table 11: Laminated structures and properties of flame and heat barrier test samples

[0324]

[0325] Results. The thermal profiles of the laminated structure samples (S3 and S4) including the ejecta mitigation layer are shown in Figure 23 The thermal profiles of the laminate samples (S1 and S2) without the ejecta mitigation layer are shown in Figure 24 For each laminate sample, the cold side temperature of the laminate and the difference between the hot and cold side temperatures of the laminate at 5 and 10 minutes are reported in Table 12.

[0326] Table 12: Laminate Temperatures During Flame Exposure of Samples

[0327]

[0328] at last, Figures 25 to 28 The hot and cold sides of laminate samples S1 to S4 are shown respectively after 10 minutes of flame exposure.

[0329] Discussion. Figure 25 and Figure 26 As shown in Figure 2, the laminate samples without the ejecta mitigation layer (S1 and S2) cracked on the hot side after 10 minutes of flame exposure. On the other hand, the laminate samples including the ejecta mitigation layer maintained better structural integrity after 10 minutes of flame exposure. In fact, as Figure 27 and Figure 28 As shown, the laminate sample including the ejecta mitigation layer had no cracking on the hot side and only slight damage on the cold side, with no burn-through occurring.

[0330] The only difference between the laminate samples including the spray mitigation layer was that one laminate sample (S3) included a glass fiber spray mitigation layer on its hot side and the other laminate sample (S4) included a basalt fabric spray mitigation layer on its hot side. Although the thickness of the laminate with the glass fiber spray mitigation layer was greater than that of the laminate with the basalt fabric spray mitigation layer (1.50 mm compared to 1.29 mm due to the greater thickness of the glass fiber layer than the basalt fabric layer), the laminate with the basalt fabric spray mitigation layer had higher cold side temperature (282°C compared to 328°C at 5 minutes and 301°C compared to 350°C at 10 minutes) and heating rate ( Figure 23 ) performed better.

[0331] like Figure 24As shown in Table 12, the laminate with the basalt fabric ejecta mitigation layer (S4) outperformed the otherwise similar laminate sample (S2) that did not include the ejecta mitigation layer in cold side temperatures. In fact, adding the basalt fabric layer to S2 (making S4) reduced the cold side temperature from 299°C to 282°C after 5 minutes of flame exposure, and from 315°C to 301°C after 10 minutes of flame exposure.

[0332] Example 9

[0333] Testing Sample Laminate Structures Flame and heat barrier laminate samples having the laminate structures and properties shown in Table 13 were exposed to a 1000°C flame for 10 minutes.

[0334] Table 13: Laminated structures and properties of flame and heat barrier test samples

[0335]

[0336] The purpose of these tests was to further investigate the performance of basalt fabric ejecta mitigation layers, including when multiple such ejecta mitigation layers were included in a laminate (S7-S9), and to investigate the performance of laminates that included additional aerogel layers.

[0337] Results. The thermal distribution curve of the laminated material sample is shown in Figures 29 to 31 The cold side temperature and the difference between the cold side temperature and the hot side temperature of each laminate sample at 5 minutes and 10 minutes are reported in Table 14.

[0338] Table 14: Laminate Temperatures During Flame Exposure of Samples

[0339]

[0340] After 10 minutes of flame exposure, Figure 32 Showing the cold and hot sides of the S5, Figure 33 Showing the cold and hot sides of the S6, Figure 28 Showing the hot and cold sides of the S4, Figures 34 to 36 Showing the cold and hot sides of S7 to S9 respectively.

[0341] Results. The hot side structural integrity of the laminate samples was good ( Figure 32 、 Figure 33 、 Figure 28 and Figures 34 to 36 ), believed to be the result of the basalt fabric ejecta mitigation layer, only S7 ( Figure 34 ) and S8( Figure 35 ) cracks occurred. In terms of cold side structural integrity, the relatively thin laminate S5 consisting only of a basalt fabric spray mitigation layer and an aerogel layer showed combustion ( Figure 32); the cold side of the remaining laminate samples remained intact ( Figure 28 and Figures 33 to 36 ) and did not burn through. In fact, the aerogel layer on the cold side of S6 to S8 was almost intact. With the exception of S5, all basalt fabric ejecta mitigation layers remained connected to the laminate, which was sufficient to provide protection for the underlying layers.

[0342] With respect to temperature-based performance, an inverse relationship was generally observed between laminate thickness and laminate cold side temperature. This was demonstrated by comparing the cold side temperature of the thinner (0.28 mm thick) laminate S5 with the cold side temperatures of the thicker (1.11 mm to 1.40 mm thick) laminates S4 and S6 to S9. See also Figure 29 .

[0343] Laminate samples that included a double layer of basalt fabric spray relief layer showed improved cold side temperature performance compared to laminate samples with only a single layer of basalt fabric spray relief layer. As an illustration, S8 was otherwise similar to S6 but included an additional basalt fabric spray relief layer, and the heating rate and cold side temperature of S8 were significantly lower than the heating rate and cold side temperature of S6 (293°C compared to 338°C at 5 minutes, and 317°C compared to 354°C at 10 minutes). As a further illustration, S9 was otherwise similar to S4, where S9 included an additional basalt fabric spray relief layer, and S9 performed better than S4 in cold side temperature at 5 minutes (267°C compared to 282°C) and initial heating rate.

[0344] Furthermore, improved performance was observed for laminate samples that included more aerogel layers compared to the others. Laminate S8 had the same stackup structure as laminate S7 but included an additional aerogel layer. With only an approximately 10% increase in thickness, laminate S8 exhibited significantly lower heating rates and cold-side temperatures compared to laminate S7: 293°C compared to 365°C at 5 minutes and 317°C compared to 373°C at 10 minutes.

[0345] Example 10

[0346] (Flame and heat barrier laminates)

[0347] Table 15 contains a list of flame and thermal barrier laminates designed to mitigate battery thermal runaway events, suitable for use in battery-powered vehicles or equipment.

[0348] Table 15: Examples of flame and heat barrier laminates for mitigating battery thermal runaway

[0349]

[0350]

[0351] The above description and examples fully illustrate the structure and use of the exemplary embodiments. Although some embodiments have been described in specific detail or by reference to one or more specific embodiments, those skilled in the art may make many modifications to the disclosed embodiments without departing from the scope of the invention. Therefore, the exemplary embodiments of the apparatus and method are not intended to limit the specific forms disclosed. More specifically, they cover all modifications and alternatives within the scope of the claims, and embodiments other than those shown may include some or all of the features of the illustrated embodiments. For example, elements may be omitted or integrated into a single structure, and / or the connection method may be replaced. In addition, where appropriate, aspects of any of the above embodiments may be combined with aspects of any other embodiments to form other embodiments having comparable or different properties and / or functions, and solving the same or different problems. Similarly, it should be understood that the above benefits and advantages may be directed to one embodiment or to several embodiments.

[0352] The claims are not intended to include and should not be interpreted as including means-plus-function or step-plus-function limitations unless a claim explicitly recites such limitations using the phrase "means for..." or "step for..." respectively.

Claims

1. A laminate comprising: a reinforcement layer comprising fibers; a flame retardant layer having a flammability rating according to UL94 5VA, UL94 5VB, or UL94 V-0; porous insulation; and a heat dispersion layer comprising at least 90 wt. % metal or graphite; The thickness of the laminated material is less than or equal to 5 mm.

2. The laminate material of claim 1, wherein the porous insulation layer comprises an aerogel layer.

3. The laminate material according to claim 1 or 2, wherein the fibers of the reinforcement layer comprise glass fibers or basalt fibers.

4. A laminate material according to any one of claims 1 to 3, wherein the fibres of the reinforcement layer are woven.

5. The laminate according to any one of claims 1 to 4, wherein: The laminate has opposing front and back surfaces; and Each of the reinforcement layer, the flame retardant layer, and the heat distribution layer is located closer to the front surface than the aerogel layer.

6. The laminate according to any one of claims 1 to 5, wherein the flame retardant layer is located between the reinforcement layer and the aerogel layer.

7. A laminate comprising: ejecta mitigation layer; a flame retardant layer having a flammability rating according to UL94 5VA, UL94 5VB, or UL94 V-0; and porous insulation layer; in: The laminate has opposing front and back surfaces; and The ejecta mitigation layer constitutes at least a major portion of the front surface.

8. The laminate material of claim 7, wherein the porous insulating layer comprises an aerogel layer.

9. A laminate according to claim 7 or 8, wherein the ejecta mitigation layer comprises at least 90% by weight metal.

10. The laminate of claim 9, wherein the metal of the ejecta mitigation layer comprises titanium.

11. A laminate according to claim 7 or 8, wherein the spray mitigation layer comprises fibres.

12. The laminate of claim 11, wherein the fibers of the ejecta mitigation layer comprise glass fibers or basalt fibers.

13. A laminate according to claim 11 or 12, wherein the fibres of the spray mitigation layer are woven.

14. The laminate according to any one of claims 1 to 13, wherein the flame retardant layer is based on an inorganic material.

15. A laminate according to any one of claims 1 to 14, wherein the flame retardant layer comprises paper.

16. A laminate according to any one of claims 1 to 15 wherein the flame retardant layer comprises at least 90% by weight silicate.

17. A laminate according to any one of claims 1 to 15, wherein the flame retardant layer comprises at least 90% by weight of ceramic.

18. The laminate according to any one of claims 1 to 17, wherein the flame retardant layer has a thickness of 0.05 mm to 0.8 mm.

19. The laminate according to any one of claims 1 to 18, wherein the porous insulating layer comprises at least 50% by weight of polyimide.

20. The laminate according to any one of claims 1 to 19, wherein the laminate has a flammability rating in accordance with UL94 5VA, UL94 5VB or UL94 V-0.

21. The laminate material according to any one of claims 1 to 20, comprising one or more adhesive layers bonded to the porous insulation layer, the one or more adhesive layers comprising a first adhesive layer disposed between the flame retardant layer and the porous insulation layer.

22. The laminate material according to any one of claims 1 to 21, comprising a second flame retardant layer, wherein the flame retardant layers are provided on opposite sides of the porous insulating layer.

23. A device comprising the laminate according to any one of claims 1 to 22, the device comprising the laminate in combination with the device.

24. The device of claim 23, wherein the device is a compression mat, a battery cell, a battery module, a battery pack, or a battery case.

25. The device of claim 23, wherein the device is a conductive cable.

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