Flame and Heat Barrier Materials

Abstract

The present disclosure includes flame and thermal barrier laminates and devices containing the same. Some laminates have a reinforcement layer containing fiber, a flame-retardant layer having a flammability rating in accordance with UL94 5VA, UL94 5VB, or UL94 V-0, a porous insulation layer, and a heat-dissipating layer containing at least 90% by weight of metal or graphite, and the laminate thickness is 5 mm or less. TIFF2026503572000017.tif84162

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 63 / 481,124, filed January 23, 2023, and claims priority to International Application No. PCT / US2023 / 061100, filed January 23, 2023, which are incorporated by reference herein in their entireties.

[0002] A. Field of the Invention The present invention generally relates to laminates that can be used as flame and / or heat protection materials for any type of manufactured article. In some aspects, the laminates can be used to protect manufactured articles (such as batteries and / or electronic devices) from environments that may expose them to high temperatures (e.g., above 500°C) for a period of time (e.g., 1 to 90 minutes), and in some cases, the articles may also be impacted by ejecta (e.g., from battery thermal runaway). [Background technology]

[0003] B. Description of Related Art Modern society is becoming more electrified. One example of this is the rapid pace of electrification in the transportation sector. In particular, transportation vehicles such as cars, trains, and airplanes are moving away from combustion engine technology and instead being equipped with electric motors that rely on battery systems. These battery systems can be complex systems that rely on chemicals, chemical reactions, electronic components, and other materials to store and discharge electricity for the electric motors.

[0004] 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 used in typical transportation vehicles that primarily rely on combustion engine technology. A specific problem is that batteries used in electric vehicles can experience mechanical damage (e.g., vehicle accidents, wiring or electronic system malfunctions, etc.), be exposed to temperatures outside their operating range, or be subjected to rapid charge / discharge events, potentially resulting in a relatively large explosion, fire, and / or release of large amounts of corrosive chemical fumes compared to batteries used in vehicles that rely on combustion engines. Lithium-ion-based battery cells used in electric vehicles can ignite and / or explode at temperatures exceeding 500°C. In contrast, a vehicle fire resulting from a vehicle accident, for example, can generate heat exceeding 1,500°F (815°C). In the event of an accident and fire in an electric vehicle, a certain amount of time is required to extinguish the fire and / or exit and remove the vehicle before the battery ignites and / or explodes. As society becomes more electrified, particularly in transport infrastructure, and the energy density of batteries increases, the risk of electric vehicle fires and battery fires and explosions will also increase.

[0005] Traditional insulating materials, such as foams, polymers, and elastomers, have been used to provide some degree of thermal protection for electric vehicle battery systems. Unfortunately, these traditional materials still face limitations. For example, while polymer foams have low thermal conductivity, which reduces heat transfer, their thermal diffusivity—the thermal conductivity of a material divided by its density and specific heat capacity—tends to be higher than other insulating materials. The higher the thermal diffusivity (meaning a higher thermal conductivity relative to a material's specific heat capacity and density), the faster the temperature of such polymer foams tends to rise with continued heating, resulting in faster heat transfer. Other polymer and elastomeric materials may have lower thermal diffusivities than polymer foams but tend to have higher thermal conductivities. In addition, heat concentrated in one portion of such traditional insulating materials may not be distributed across its entire surface, accelerating heat transfer through the thickness of the material to the surface of the component it is designed to protect. Therefore, traditional insulating materials may not provide the desired level of thermal protection in some applications.

[0006] Furthermore, in some systems, insulating materials may be subject to severe space constraints. Because traditional insulating materials are typically relatively thick and / or stiff, such constraints limit the amount of traditional insulating material that can be included in a system, further limiting the thermal protection provided by the material or potentially rendering such materials unusable in the system. Compounding these constraints, polymers, elastomers, and foams often have relatively high coefficients of thermal expansion, further exacerbating the space constraints when these materials are heated. Summary of the Invention

[0007] A discovery has been made that provides a solution to at least one or more of the aforementioned problems associated with providing thermal protection to an article of manufacture, substrate, or system (e.g., an electric battery system). In one aspect, it has been discovered that a laminate including a flame-retardant layer having a flammability rating in accordance with at least one flammability standard (e.g., a UL94 5VB or UL94 5VA rating) and a porous thermal insulation (e.g., aerogel) layer can provide good thermal protection properties to the article of manufacture, substrate, or system (the terms "article of manufacture," "substrate," or "system" may be used interchangeably throughout this specification). In such a laminate, the synergy between the flame-retardant layer and the porous thermal insulation layer can provide thermal protection for the substrate in terms of heating rate and / or equilibrium temperature beyond what would be expected from the sum of their parts, particularly when the porous thermal insulation layer has a thin thickness (e.g., less than 0.5 mm). While not wishing to be bound by any particular theory, it is believed that the porous thermal insulation layer, having low thermal conductivity and low thermal diffusivity, effectively retards heat transfer from the flame-retardant layer and into the substrate.

[0008] For example, when attached to the surface of a substrate, the laminate of the present invention can maintain the temperature of the substrate (e.g., the surface temperature of the substrate) at or below 500°C when the laminate is exposed to temperatures exceeding 500°C, preferably between 500°C and 1,500°C, or more preferably between 700°C and 1,200°C, for 1 minute to 90 minutes, preferably at least 5 minutes. This is advantageous, for example, in that it provides a longer time before the substrate (e.g., the battery system of an electric vehicle) reaches a temperature at which it may fail. This can be particularly advantageous when used to protect the battery system of an electric vehicle after an accident, as it can provide more time for vehicle occupants to exit the vehicle before the electric vehicle battery ignites, explodes, and / or releases toxic chemicals. It can also provide more time for first responders (e.g., fire departments) to extinguish the fire before the electric vehicle battery ignites, explodes, and / or releases toxic chemicals. In particular, the laminates of the present invention can be relatively thin (e.g., 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) and / or relatively flexible (e.g., can be rolled (see, e.g., FIG. 9 ) and / or can have a bend radius). An advantage of the flexibility of the laminates of the present invention is that they can be used in applications with severe space constraints (e.g., electric vehicle battery systems and battery packs).

[0009] The laminates of the present invention may also be configured to mitigate ejecta, such as those that may result from a battery thermal runaway event, by including a (e.g., fibrous) reinforcing layer, an ejecta mitigation layer (e.g., fibrous, metallic, or ceramic), and / or a reinforced (e.g., fibrous) flame-retardant layer, and / or a porous insulating layer.

[0010] In one aspect of the present invention, a laminate is disclosed that includes a flame-retardant layer and a porous material layer (e.g., a foam layer or an aerogel layer, preferably an aerogel layer). The laminate can have opposing front and rear surfaces, and the flame-retardant layer can, but does not have to, define at least a majority of the front surface. The laminate can have a thickness of 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 less, or any range therein. In other aspects, the laminate can have a thickness of more than 25.4 mm (e.g., 26, 27, 28, 29, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 mm or more, or any range therein). In certain preferred aspects, the laminate has a thickness of 0.3 to 10 mm, 0.3 to 5 mm, or 0.3 mm to 3 mm. In certain aspects, the flame-retardant layer has a thickness of 0.05 mm to 0.8 mm. 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 thereof, such as 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 mm), preferably 0.05 mm and 0.254 mm.

[0011] 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 UL94 5VA or UL94 5VB. In certain aspects, the flame-retardant layer includes fibers (e.g., woven fibers and / or nonwoven fibers) and / or one or more of a metal hydroxide, an organic phosphate, an alumina hydroxide, an inorganic filler, and / or a metal oxide. In some aspects, the flame-retardant layer can be halogen-free. In some aspects, the flame-retardant layer can include a silicate (e.g., a phyllosilicate). In some specific aspects, the silicate can include mica. The flame-retardant layer can include at least 90 wt. % silicate, preferably mica, based on the total weight of the flame-retardant layer. In some aspects, the flame-retardant layer includes a ceramic. The ceramic can include inorganic and / or non-metallic materials (e.g., clay, kaolinate, aluminum oxide, silicon carbide, tungsten carbide, etc.) that can be exposed to high temperatures. 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 alumina, beryllia, ceria, zirconia, carbide, boride, nitride, or silicide, or any combination thereof. In some aspects, the flame-retardant layer can include at least 90 wt. % ceramic, based on the total weight of the flame-retardant layer.

[0012] In some aspects, the porous layer is an aerogel layer. In some aspects, the aerogel layer includes an organic polymer. In some aspects, the organic polymer is a thermoplastic polymer. In some aspects, the thermoplastic polymer is polyimide, polystyrene, polyester, polyamide, polyether, polyurethane, acrylic polymer, polyurea, polypyrrole, polythiophene, polyaniline, acrylic polymer, vinyl polymer, polysiloxane, polysulfide, polycarbonate, or copolymer, or a mixture thereof. In preferred embodiments, the thermoplastic polymer is polyimide, polyamic amide, or a mixture or copolymer thereof. In certain aspects, the aerogel layer includes at least 50%, 60%, 70%, 80%, 90%, or 95% thermoplastic polymer, preferably polyimide or polyamic amide. In other aspects, the polymeric aerogel layer includes less than 50%, 40%, 30%, 20%, 10%, or 5% thermoplastic polymer, preferably polyimide or polyamic amide. In some aspects, the aerogel layer has a decomposition temperature of 400°C or higher, preferably 400°C to 600°C.

[0013] The laminate of the present invention may include one or more adhesive layers. The one or more adhesive layers may be bonded to the porous layer. In one aspect, a first adhesive layer is disposed between the flame-retardant layer and the porous layer. The first adhesive layer may have a melting or decomposition temperature greater than 500°C, preferably greater than 600°C. In another aspect, a second adhesive layer may be disposed on the rear surface of the porous layer (the surface further 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. Prior to use, a removable or peelable liner layer may be disposed on the second adhesive layer. In certain aspects, the second adhesive layer may have a melting or decomposition temperature greater than 500°C, preferably greater than 600°C. In certain aspects, the adhesive layer may include a silicone adhesive compound and / or an epoxy compound.

[0014] The laminate of the present invention may include one or more heat spreading layers. In some aspects, the one or more heat spreading layers may have a thermal conductivity of at least 15 W / m·K, preferably 15 W / m·K to 2,500 W / m·K. In some aspects, the one or more heat spreading layers may include a 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 2,500 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, the one or more heat spreading layers can comprise at least 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, or more by weight of metal and / or graphite, based on the total weight of the heat spreading layer. In some aspects, the one or more heat spreading layers can have a thickness of 0.001 mm to 0.4 mm, preferably 0.01 mm to 0.05 mm, or any range or number therein (e.g., 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, or 0.25 mm).

[0015] In some aspects, one or more heat distribution layers can be bonded to the flame retardant layer and / or the porous layer. In some aspects, one or more heat distribution layers can be disposed between the flame retardant layer and the porous layer. In some aspects, a first adhesive layer can be disposed between the flame retardant layer and the heat distribution layer, and / or a second adhesive layer can be disposed between the heat distribution layer and the porous layer. In some aspects, no adhesive layer is disposed between the flame retardant layer and the porous layer. In some aspects, the first adhesive layer can be in direct contact with the flame retardant layer and the heat distribution layer, and the second adhesive layer can be in direct contact with the heat distribution layer and the porous layer. In some aspects, a third adhesive layer and, optionally, a liner layer can be used, where the third adhesive layer is disposed between the porous layer and any liner layer. In some aspects, the third adhesive layer can be in direct contact with the porous layer and any liner layer. In some aspects, the first, second, third, or other adhesive layer may each: (1) have a melting or decomposition temperature greater than 500° C.; (2) include a pressure-sensitive adhesive; and / or (3) include a silicone adhesive compound and / or an epoxy compound.

[0016] In some aspects, any one, any combination, or all of the flame-retardant layer, heat-dissipating layer, porous layer, first, second, third, or other adhesive layer, reinforcing layer, and / or ejecta mitigation layer (the latter two described below) can be perforated. In some aspects, the perforations can serve to allow gas (e.g., from evaporation or boiling of the adhesive layer) to escape from the laminate. In some aspects, the perforations are nanometers, micrometers, or millimeters in size. In some aspects, the perforation pattern can be random, grid-like, circular, or the like. In some particular embodiments, the pattern is grid-like. Without wishing to be bound by theory, it is believed that the perforations can be useful in venting the adhesive layer in the event of exposure to high temperatures or reduced pressure. Allowing escape can be useful to avoid foaming and / or delamination of the aerogel layer and / or the flame-retardant layer.

[0017] The laminate of the present invention may include one or more reinforcing layers. In some aspects, the one or more reinforcing layers may be attached to at least a portion of the flame-retardant layer and / or may be included in at least a portion of the volume of the flame-retardant layer. In some aspects, the one or more reinforcing layers may include 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 cellulosic fibers, or any combination thereof. In some aspects, the fibers are nonwoven or woven. Such reinforcing layers can increase the structural integrity of the entire laminate and can help mitigate potential ejecta that may occur during, for example, a battery thermal runaway event.

[0018] Indeed, during a battery thermal runaway event, a failed battery can produce heated ejecta, potentially compromising any thermal protection provided to the battery and / or adjacent components (e.g., multiple batteries), potentially triggering a cascade of component failures. Therefore, protection from such ejecta can be advantageous, as some laminates of the present invention provide by including a (e.g., fiber-reinforced) reinforcement layer, a (e.g., fiber-) reinforced flame-retardant and / or porous layer, and / or an ejecta mitigation layer (e.g., fibrous, metallic, or ceramic). In some aspects, such an ejecta mitigation layer can comprise at least 50%, e.g., at least 60, 70, 80, or 90%, metal. This metal can include, for example, titanium, stainless steel, nickel, molybdenum, and / or tantalum. In some aspects, such an ejecta mitigation layer can comprise fibers, such as any of the fibers described above in connection with the reinforcement layer, preferably woven but not necessarily woven. The ejecta mitigation layer of the laminate of the present invention may define at least a majority (up to and including all) of the front surface of the laminate.

[0019] Also disclosed in the context of the present invention is a device including one or more laminates of the present invention. The laminates can be coupled to the device such that the front surface of a first one of the laminates is positioned farther from the device than the rear surface of the first laminate. The device can be any type of device. In a preferred aspect, the device is one that may be exposed to high temperatures (e.g., greater than 500°C) during use. One example is a battery. In a preferred aspect, the battery can be a battery system or battery pack of an electric vehicle. The battery can be a secondary / rechargeable battery (e.g., a lithium-ion battery or a nickel-metal hydride battery). The vehicle can include one or more wheels and one or more electric motors, each configured to rotate at least one of the wheels. The battery can be in electrical communication with at least one of the electric motors. In another example, the device can be a bus bar for the battery. The bus bar can be in electrical communication with the battery. The laminates of the present invention can be coupled to a bus bar such that the front surface of the laminate is positioned farther from the bus bar than the rear surface of the laminate.

[0020] In some aspects, the device may be a compression pad, a battery cell, a battery module, a battery pack, or a battery box. Compression pads, which may also be called battery pad cushions, may be placed between battery cells to help resist dimensional changes of the cells during charging and / or use. The compression pad may provide sufficient pressure to the battery pack to maintain thermal and / or electrical connection, while also allowing the battery cells to withstand and / or expand during charging or exposure to extreme temperatures. In some aspects, the compression pad may include a compressible material. In some aspects, the compressible material may be foam (e.g., polyurethane foam or silicone foam). In some aspects, the compression pad is placed between a first battery cell and a second battery cell. The laminate of the present invention may cover a portion, a majority, or all of the outer surface of the compression pad.

[0021] In some aspects, the device can be a battery cell. The battery cell can be charged to provide electrical energy (e.g., to power an electric motor) and can be discharged during use, when exposed to extreme temperatures, or when in a latent state. Multiple battery cells can be arranged side by side, with compression pads disposed between each battery cell. The laminate of the present invention can cover a portion, most, or all of the exterior surface of the battery cell.

[0022] In some aspects, the device can be a battery module. The battery module can include a plurality of battery cells. The laminate of the present invention can cover a portion, a majority, or all of the exterior surface of the battery module.

[0023] In some aspects, the device can be a battery pack. The battery pack can include a plurality of battery modules. The laminate of the present invention can be disposed between the battery modules of the battery pack. The laminate of the present invention can cover a portion, a majority, or all of the outer surface of the battery pack.

[0024] In some aspects, the device can be a battery box or battery casing or container. The battery box or container can enclose a portion, a majority, or all of the battery pack. The battery box can include an exterior surface, an interior surface, and an interior volume. The laminate of the present invention can cover at least a portion, a majority, or all of the exterior surface of the battery box, at least a portion, a majority, or all of the interior surface, or both. In some preferred aspects, at least a portion, a majority, or all of the interior surface of the battery box is covered with one or more laminates of the present invention. In some aspects, the interior volume of the battery box contains a compression pad, a battery cell, a battery module, or a battery pack, or any combination thereof. In some aspects, the compression pad, the battery cell, the battery module, the battery pack, and / or the battery box are included in a vehicle, and the vehicle includes one or more electric motors. In some aspects, the vehicle can be an automobile, an aircraft, a train, a ship, or a spacecraft.

[0025] In some aspects, the device can be a cable. The cable can have a length and a width. The length can be greater than the width. In some aspects, the cable can be electrically conductive. In some aspects, the cable can have an electrically conductive portion and an electrically insulating portion. In some aspects, the electrically insulating portion can encompass part, most, or all of the electrically conductive portion. In some aspects, the electrically conductive portion can include an electrically conductive metal (e.g., copper, gold, platinum, aluminum, steel, etc.). In some aspects, the cable has a diameter of 0.0001 inch to 10 inches, preferably 0.001 inch to 1 inch, or any range or number therein (e.g., diameters 0.0001, 0.0002, 0.0003, 0.0004, 0.0005, 0.0006, 0.0007, 0.0008, 0.0009, 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 inches). In certain aspects, the cable may be included in a missile, rocket, artillery piece, manned aircraft, unmanned aerial vehicle, ground vehicle, or sea vehicle. In certain aspects, the vehicle may be a spacecraft or aircraft.

[0026] Also disclosed in the context of the present invention is a method for thermally protecting a device using any one of the laminates of the present invention. The method may include bonding the laminate to a surface of the device. Bonding may be via an adhesive. The laminate may be positioned relative to the device such that the front surface of the laminate is positioned further from the device than the rear surface of the laminate. The laminate of the present invention is capable of maintaining the temperature of the device at or below 500°C when the front surface of the laminate is exposed to a temperature greater than 500°C, preferably between 500°C and 1,500°C (or 600, 700, 800, 900, 1,000, 1,200, 1,300, 1,400°C or any range therein), or more preferably between 700°C and 1,200°C (or 800, 900, 1,000, or 1,100°C or any range therein), for a period of between 1 minute and 90 minutes (or 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, or 90 minutes or any range therein), preferably for at least 5 minutes.

[0027] The term "aerogel" generally refers to a class of materials 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. 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 comprised of macropores. In other alternative aspects, a majority of the pore volume of the aerogel can be comprised of mesopores and / or micropores, such that less than 50% of the pore volume of the aerogel is comprised of macropores. In some embodiments, aerogels of the present invention have low bulk densities (about 0.75 g / cm). 3 or less, preferably about 0.01 g / cm 3 ~0.5g / cm 3 ), high surface area (typically about 10 m 2 / g~1,000m 2 / g or more, preferably about 50m 2 / g~1000m 2 / g), high porosity (greater than about 20%, preferably greater than about 85%), and / or relatively large pore volume (greater than about 0.3 mL / g, preferably greater than about 1.2 mL / g).

[0028] 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 physisorption experiments. MIP tests can be used to measure mesopores and macropores (i.e., American Standard Testing Method (ASTM) D4404-10, Standard Test Method for Determination of Pore Volume and Pore Volume Distribution of Soil and Rock by Mercury Intrusion Porosimetry). Gas physisorption experiments can be used to measure micropores (i.e., ASTM D1993-03 (2008) Standard Test Method for Precipitated Silica - Surface Area by Multipoint BET Nitrogen).

[0029] The "decomposition temperature" of a material is the temperature at which 2%, 5%, or 10% of a sample of the material will decompose when heated in an environment elevated to that temperature. The decomposition temperature can be measured 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 mass of the sample is 2%, 5%, or 10% lower than its initial mass as the decomposition temperature.

[0030] The term "coupled" is defined as connected, although not necessarily directly, and not necessarily mechanically. Two things that are "coupled" may be integral to one another, or may be connected to one another through one or more intermediate components or elements.

[0031] The terms "a" and "an" are defined as one or more, unless this disclosure expressly requires otherwise.

[0032] The term "substantially," as understood by one of ordinary skill in the art, is defined as largely, but not necessarily entirely, what is specified (and includes what is specified; e.g., substantially 90 degrees includes 90 degrees, and substantially parallel includes parallel). In any disclosed embodiment, the terms "substantially," "approximately," and "about" may be substituted with "within 10%" of what is specified.

[0033] The phrase "and / or" means and or or. By way of example, A, B, and / or C includes: A only, B only, C only, a combination of A and B, a combination of A and C, a combination of B and C, or a combination of A, B, and C. In other words, "and / or" operates as an inclusive or.

[0034] The terms "comprise" (and any form of "comprise," such as "comprises" and "comprising"), "have" (and any form of "has" and "having"), "include" (and any form of "includes," such as "includes" and "including"), and "contain" (and any form of "contains," such as "contains" and "containing") are open-ended linking verbs. Consequently, an apparatus that "comprises," "has," "includes," or "contains" one or more elements has those one or more elements, but is not limited to having only those one or more elements. Similarly, a method that "comprises," "has," "includes," or "contains" one or more steps has those one or more steps, but is not limited to having only those one or more steps.

[0035] The laminates of the present invention can "comprise," "consist essentially of," or "consist of" certain ingredients, components, compositions, etc. disclosed throughout this specification. With respect to the transitional phrase "consist essentially of," in one non-limiting aspect, a fundamental and novel feature of the laminates of the present invention is their ability to thermally protect a substrate over time when exposed to temperatures that could cause the substrate to fail (e.g., catch fire, explode, decompose, deform, etc.).

[0036] Unless expressly prohibited by the nature of this disclosure or the embodiments, features of one embodiment may be applied to other embodiments even if not described or illustrated.

[0037] Some details relating to the aforementioned aspects and others are set forth below. [Brief explanation of the drawings]

[0038] The following drawings are by way of example, and not limitation. For purposes of brevity and clarity, not all features of a given structure are always shown in every figure in which that structure appears. Identical reference numbers do not necessarily refer to identical structures. Rather, the same reference number may be used to refer to similar features or features with similar functionality, as well as non-identical reference numbers.

[0039] [Figure 1] 1A and 1B are cross-sectional views of embodiments of laminates of the present invention having a flame-retardant layer and a single aerogel layer (FIG. 1A) or a flame-retardant layer and two aerogel layers (FIG. 1B) attached to a substrate surface. [Figure 2] FIG. 2 is a cross-sectional view of another embodiment of a laminate of the present invention having a liner layer removably positioned on an adhesive layer of the laminate, the liner layer defining at least a portion of the rear surface of the laminate. [Figure 3] FIG. 2 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 (two shown) aerogel layers. [Figure 4] FIG. 2 is a cross-sectional view of another embodiment of a laminate of the present invention having a reinforcing layer attached to the flame retardant layer of the laminate. [Figure 5] FIG. 2 is a cross-sectional view of another embodiment of a laminate of the present invention having a heat dissipation layer disposed between the flame retardant layer of the laminate and the aerogel layer of the laminate. [Figure 6A] 1 is a cross-sectional view of another embodiment of a laminate of the present invention, each including one or more ejecta mitigation layers. [Figure 6B] See legend to Figure 6A. [Figure 6C] See legend to Figure 6A. [Figure 7] FIG. 2 is a cross-sectional view of another embodiment of a laminate of the present invention, including a titanium layer. [Figure 8] FIG. 2 is a cross-sectional view of another embodiment of a laminate of the present invention, including a vinyl layer. [Figure 9] 1 is a perspective view of a roll of one embodiment of a laminate of the present invention. [Figure 10]FIG. 1 is a schematic diagram of a vehicle having a battery comprising one or more embodiments of a laminate of the present invention. [Figure 11] 11A is a schematic diagram of a cable including one or more embodiments of a laminate of the present invention (FIG. 11A), and a cross-sectional schematic diagram of the cable of FIG. 11A taken along line 11B-11B of FIG. 11A (FIG. 11B). [Figure 12] FIG. 1 is a schematic diagram of a setup for testing the heat and flame properties of laminates of the present invention. [Figure 13] FIG. 13 is a schematic diagram of the laminate used in the test setup of FIG. 12. [Figure 14] Illustrated are thermal profiles 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). [Figure 15] FIG. 1 is another schematic diagram of a setup for testing the heat and flame properties of laminates of the present invention. [Figure 16] 1 shows the thermal profile of several laminates of the present invention. [Figure 17] 1 shows the thermal profile of several laminates of the present invention. [Figure 18] 1 shows the thermal profile of several laminates of the present invention adhered to a low carbon steel plate compared to the thermal profile of an unprotected low carbon steel plate. [Figure 19] 1 shows the thermal profile of several laminates of the present invention bonded to a carbon fiber composite plate compared to the thermal profile of an unprotected carbon fiber composite plate. [Figure 20] FIG. 1 is a view of the back side of a carbon fiber composite plate protected on the front side by one laminate of the present invention during 25 minutes of exposure to a 1,000° C. flame. [Figure 21] 1 shows the thermal profile of one laminate of the present invention adhered to an aluminum sheet substrate. [Figure 22] FIG. 1 is a view of the back side of an aluminum sheet substrate protected on the front side by one laminate of the present invention during 25 minutes exposure to a 1,000° C. flame. [Figure 23] 1 shows the thermal profile of several laminates of the present invention with a plume mitigation layer compared to the thermal profile of several laminates of the present invention without a plume mitigation layer. [Figure 24] 1 shows the thermal profile of several laminates of the present invention with a plume mitigation layer compared to the thermal profile of several laminates of the present invention without a plume mitigation layer. [Figure 25] 1 is a photograph of the hot and cold sides of several laminates of the present invention without an ejecta mitigation layer after 10 minutes of exposure to a 1,000° C. flame. [Figure 26] 1 is a photograph of the hot and cold sides of several laminates of the present invention without an ejecta mitigation layer after 10 minutes of exposure to a 1,000° C. flame. [Figure 27] 1 is a photograph of the hot and cold sides of several laminates of the present invention including an ejecta mitigation layer after 10 minutes of exposure to a 1,000° C. flame. [Figure 28] 1 is a photograph of the hot and cold sides of several laminates of the present invention including an ejecta mitigation layer after 10 minutes of exposure to a 1,000° C. flame. [Figure 29] 1 shows the thermal profiles of several laminates of the present invention that include one or more ejecta mitigation layers. [Figure 30] 1 shows the thermal profiles of several laminates of the present invention that include one or more ejecta mitigation layers. [Figure 31] 1 shows the thermal profiles of several laminates of the present invention that include one or more ejecta mitigation layers. [Figure 32] 1 is a photograph of the hot and cold sides of several laminates of the present invention including one or more ejecta mitigation layers after 10 minutes of exposure to a 1,000° C. flame. [Figure 33] 1 is a photograph of the hot and cold sides of several laminates of the present invention including one or more ejecta mitigation layers after 10 minutes of exposure to a 1,000° C. flame. [Figure 34]1 is a photograph of the hot and cold sides of several laminates of the present invention including one or more ejecta mitigation layers after 10 minutes of exposure to a 1,000° C. flame. [Figure 35] 1 is a photograph of the hot and cold sides of several laminates of the present invention including one or more ejecta mitigation layers after 10 minutes of exposure to a 1,000° C. flame. [Figure 36] 1 is a photograph of the hot and cold sides of several laminates of the present invention including one or more ejecta mitigation layers after 10 minutes of exposure to a 1,000° C. flame. DETAILED DESCRIPTION OF THE INVENTION

[0040] Detailed Description The electrification of modern society offers technological advancements that offer alternatives to combustion engines. However, with these advancements come new challenges. As one example, the use of battery systems in electric vehicles in the transportation industry can reduce reliance on gasoline as a fuel. However, these battery systems can lead to greater risks of explosion, fire, and / or toxic gas emissions, for example, if the battery system is exposed to excessive heat (e.g., above 500°C).

[0041] The present invention provides a solution to at least one of these problems. This solution includes a laminate material that can provide both good thermal protection and flexibility, both of which are desirable attributes in certain applications (e.g., battery systems for electric vehicles). In one aspect, the present invention provides a laminate including a flame-retardant layer and a heat-dissipating layer, each of which has a flammability rating in accordance with at least one plastic flammability standard (e.g., a UL94 5VB or UL94 5VA rating). When attached to a substrate surface, the laminate of the present invention can maintain the temperature of the substrate (e.g., the surface temperature of the substrate) at or below 500°C when the laminate is exposed to temperatures exceeding 500°C, preferably between 500°C and 1,500°C, or more preferably between 700°C and 1,200°C, for 1 minute to 90 minutes, preferably at least 5 minutes.

[0042] The laminates of the present invention can also be thin (e.g., 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, or any range therein), flexible (e.g., rollable (FIG. 9)), and / or have a bend radius. The good thermal protection properties of the laminates of the present invention, along with their thin and flexible properties, allow them to be used in locations with severe space constraints, such as as covers or protective layers for batteries (e.g., electric vehicle batteries and battery systems having multiple batteries), battery bus bars, and a wide range of other articles of manufacture.

[0043] In some instances, a failed battery (e.g., one that goes into thermal runaway) may release not only heat but also ejecta. To protect against such ejecta, it may be advantageous to have reinforcement or ejecta mitigation in the thermal protection barrier (e.g., for adjacent components) so that the structural integrity of the barrier is not compromised by the ejecta, causing premature heat breakthrough. 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 and / or thermal insulation layers, and / or (e.g., fibrous, metallic, or ceramic) ejecta mitigation layers.

[0044] A. Heat and Flame Barrier Protection Laminate 1A and 1B, a laminate 100 is shown. The laminate 100 can be attached to a surface of a substrate 10, the laminate having opposing front and rear surfaces 12 and 14. The laminate 100 can include one or more thermal insulation layers 16 (e.g., a porous layer such as an aerogel layer), a flame-retardant layer 18 that can define at least a portion (e.g., at least a majority, up to all) of the front surface 12, and one or more adhesive layers 20, 22, and 24, for example, to secure the thermal insulation layer 16 and the flame-retardant layer 18 to one another. The thermal insulation layer 16 can include one such layer ( FIG. 1A ), two such layers ( FIG. 1B ), or more (e.g., 3, 4, 5, 6, 7, 8, 9, or more thermal insulation layers) in the laminate 100 or other laminates of the invention. Similarly, although 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., two, three, four, five, or more insulating layers).

[0045] Thus, the number of adhesive layers 20, 22, and 24 can be 1, 2, 3, 4, 5, 6, 7, 8, 9, or more. By way of example, an adhesive layer (e.g., 20) can adhere the flame-retardant layer 18 to the thermal insulation layer 16, and / or an adhesive layer (e.g., 24) can adhere the thermal insulation layers 16 together if there are multiple layers ( FIG. 1B ), etc. Furthermore, an adhesive layer (e.g., 22) can define substantially the entire rear surface 14 of the laminate 100, allowing the laminate to be attached to the substrate 10. Specifically, in some embodiments, the laminate 100 need not have each or all of the above-mentioned adhesive layers (e.g., 20, 22, 24). For example, in one embodiment, the laminate 100 can include a single thermal insulation layer (e.g., aerogel layer) 16, a flame-retardant layer 18, an adhesive layer 20, and an adhesive layer 24.

[0046] The thermal insulation layers 16 each have a thermal conductivity of less than or equal to any one of 0.05, 0.045, 0.040, 0.035, 0.030, 0.025, 0.020, 0.015, or 0.010 Watts per meter Kelvin (W / m K), or between any two (e.g., less than or equal to 0.025 W / m K), and / or a thermal conductivity of less than or equal to 0.30, 0.20, 0.15, 0.125, 0.10, 0.09, 0.08, 0.07, 0.06, or 0.05 millimeters per second (mm 2 / s) or between any two (e.g., 0.15 mm 2 / s or less or 0.10 mm 2 / s or less). As used herein, thermal conductivity and thermal diffusivity are each measured at 25° C. Additionally, each of the insulating layers 16 may be heat resistant and / or have a low coefficient of thermal expansion so that the laminate 100 can withstand heating during use and expansion in applications where the laminate is subject to severe space constraints. For example, each of the insulating layers 16 may have a decomposition temperature of any one or more of 400, 425, 450, 475, 500, 525, 550, 575, or 600°C, or between any two of these (e.g., 450°C or more), and / or a thermal expansion coefficient (e.g., in at least one direction) of any one or less of 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5 μm / m·K, or between any two of these (e.g., 80 μm / m·K or less or 35 μm / m·K or less).

[0047] To achieve such properties, at least one (and up to each) of the insulating layers 16 can include a layer of polymeric aerogel. The amount of polymeric aerogel can be at least 90% by weight of an organic polymer, such as polyimide, polyaramid, polyurethane, polyurea, and / or polyester. Each polymeric aerogel layer can have micropores, mesopores, and / or macropores. Any one or more of 10%, 25%, 50%, 75%, or 95% of the pore volume of each aerogel layer, or any two or more of these, can be composed of micropores, mesopores, and / or macropores (e.g., micropores, mesopores, micropores and mesopores, or macropores). The mean pore size and / or median pore size of each aerogel layer can be any one or more of 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 800, 1,000, 2,000, 3,000, 4,000, or 5,000 nm, or between any two (e.g., the mean pore size can be 100-500 nm, and the median pore size can be 250-600 nm). The materials and fabrication process for the polymer aerogel layers are described in further detail below.

[0048] In some embodiments, for at least one (e.g., each) of the insulation layers 16, the aerogel layer can include reinforcing fibers, which can be dispersed throughout the aerogel layer (e.g., as ordered (e.g., woven) fibers, or staple fibers, or discontinuous fibers not arranged in a sheet) or embedded in the aerogel layer (e.g., as a woven fiber sheet, a nonwoven fiber sheet, or a unidirectional fiber sheet), optionally such that the volume of the fibers is any one or more of 0.1%, 10%, 20%, 30%, 40%, or 50% of the volume of the aerogel layer, or any two between. However, the aerogel layer need not include fibers (e.g., to promote flexibility).

[0049] Suitable fibers include glass fibers, carbon fibers, aramid fibers, thermoplastic fibers, thermoset fibers, ceramic fibers, basalt fibers, rock wool fibers, steel fibers, and / or cellulose fibers. The average filament cross-sectional area of ​​the fibers used for reinforcement is 7, 15, 30, 60, 100, 200, 300, 400, 500, 600, 700, or 800 μm. 2 or between any two; for example, for fibers having a circular cross-section, the average diameter of the fibers can be any one or more of 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 μm, or between any two (e.g., 5-24 μm, such as 10-20 μm or 12-15 μm).

[0050] Non-limiting examples of thermoplastic polymers that may be used for the polymeric reinforcing fibers include polyethylene terephthalate (PET), polycarbonate (PC), polybutylene terephthalate (PBT), poly(1,4-cyclohexylidenecyclohexane-1,4-dicarboxylate) (PCCD), glycol-modified polycyclohexyl terephthalate (PCTG), poly(phenylene oxide) (PPO), polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polystyrene (PS), polymethyl methacrylate (PMMA), polyethyleneimine or polyetherimide (PEI), and and its derivatives, thermoplastic elastomers (TPE), terephthalic acid (TPA) elastomers, poly(cyclohexanedimethylene terephthalate) (PCT), polyethylene naphthalate (PEN), polyamide (PA), polysulfone sulfonate (PSS), sulfonate of polysulfone, polyether ether ketone (PEEK), polyether ketone (PEKK), acrylonitrile butyldiene styrene (ABS), polyphenylene sulfide (PPS), copolymers thereof, polyester or derivatives thereof, polyamide or derivatives thereof (e.g., nylon), or mixtures thereof.

[0051] Non-limiting examples of thermosetting polymers that may be used as materials for the polymeric reinforcing fibers include unsaturated polyester resins, polyurethanes, polyoxybenzyl methylene glycol anhydrides (e.g., Bakelite), urea formaldehyde, diallyl phthalate, epoxy resins, epoxy vinyl esters, polyimides, cyanate esters of polycyanurates, dicyclopentadiene, phenols, benzoxazines, copolymers thereof, or mixtures thereof.

[0052] While each of the insulation layers 16 can include a layer of polymeric aerogel, in other embodiments, at least one (and up to each) of the insulation layers can be any suitable insulating material, such as a layer of fiber. At least one (and up to each) of the insulation layers 16 can also optionally include a layer of fiber laminated to the layer of polymeric aerogel, such that the fiber layer is positioned closer to the front surface 12 of the laminate 100 than the aerogel layer. The fibers in the fiber layer can be any of those previously described with respect to aerogel fiber reinforcement (e.g., glass fiber and / or basalt fiber) and can be arranged in various fibrous structures. For example, the fibers can form a fiber matrix, such as a felt, a lofty batting, a mat, a woven fabric, or a nonwoven fabric. The fibers can be oriented unidirectionally or omnidirectionally.

[0053] In some embodiments, the fibers used as reinforcement in the aerogel layer or fiber layer are 5 μm 2 ~40,000μm 2 and / or an average length of 20 mm to 100 mm.

[0054] To enable use of the laminate 100 in applications with tight space constraints, each of the insulating layers 16 (e.g., aerogel layers) can be relatively thin. For example, the thickness 26 (FIG. 1A) of at least one (e.g., each) of the insulating layers 16 can be equal to or less than any one of 50, 25, 20, 15, 10, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.15, 0.1, or 0.05 mm, or between any two (e.g., 0.10-0.20 mm, such as 0.165 mm).

[0055] The combination of the thermal insulation layer 16 and the flame-retardant layer 18 can protect the substrate surface 10 from heat and flame by reducing the spread of heat and flame. Each of the flame-retardant layers 18 can include flame-retardant materials, optionally with nonwoven 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, organoclays, organic polymers, silicon-phosphorus-nitrogen compounds, metal oxides, ceramics (e.g., metal and / or non-metal oxides, alumina, beryllia, ceria, zirconia, carbides, borides, nitrides, and / or silicides), and mixtures thereof. Non-limiting examples of metal hydroxides include alumina trihydrate and magnesium oxide. Non-limiting examples of metal oxides include titanium oxide, aluminum oxide, zinc oxide, iron oxide, magnesium oxide, and calcium oxide, etc. Non-limiting examples of phosphates include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, tributoxyethyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl phosphate, trixylenyl phosphate, tris(2-phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, resorcinol bis(diphenyl phosphate), resorcinol bis(dixylenyl phosphate), resorcinol bis(dicresyl phosphate), hydroquinone bis(dixylenyl phosphate), biphenyl phosphate, bis(diphenyl phosphate), ... These include bisphenol A bis(diphenyl phosphate), tetrakis(2,6-dimethylphenyl) 1,3-phenylene bisphosphate, pentaerythritol phosphate alcohol, oligomeric ethyl ethylene phosphate, tricresyl phosphate, trixylenyl phosphate, isopropyl phenyl phosphate, tert-butylphenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, isodecyl diphenyl phosphate, butyl diphenyl phosphate, dibutyl phenyl phosphate, tributyl phosphate, tetraphenyl resorcinol diphosphate, and tetraphenyl bisphenol-A diphosphate.In some embodiments, the flame retardant layer (eg, 18) can comprise at least 90% by weight of flame retardant material, for example, at least 90% by weight of silicate, or at least 90% by weight of ceramic.

[0056] Non-limiting examples of fillers include kaolin clay, 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.

[0057] The flame retardant layers 18 may each conform to plastic flammability standards (e.g., UL94 V-0, V-1, V-2, HB, 5VA, and 5VB, etc.). The thickness 38 of a given flame-retardant layer 18 (FIGS. 1A and 1B) can be greater than or between any two of the following: 0.03, 0.04, 0.05, 0.10, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80, 0.90, 1.00, 1.20, 1.40, 1.60, 1.80, 2.00, 2.20, 2.40, 2.60, 2.80, 3.00, 3.20, 3.40, 3.60, 3.80, 4.00, 4.20, 4.40, 4.60, 4.80, 5.00 mm (e.g., 0.03 mm to 5.0 mm). In some cases, the flame retardant layer has a thickness in the range of 0.145 mm to 0.225 mm and has a flammability rating of UL94 5VA or UL94 5VB, preferably UL94 5VA. The flame retardant layer 18 can be electrically insulating or non-electrically insulating.

[0058] Flame-retardant layers 18 can each be a commercially available product. Non-limiting examples of commercially available flame-retardant tapes or papers suitable as flame-retardant layers include those sold under the Unifrax brand (e.g., FyreWrap LiB Papers and Films), 3M® brand (e.g., 3M VHB Tape, 3M FRB Paper), Scotch® brand, and U-Line brand. In some specific embodiments, Unifrax brand FyreWrap LiB Paper (e.g., FX70 and IN70), Unifrax brand FyreWrap LiB Film (e.g., C1554), 3M® Flame Barrier FRB-WT series, 3M® Flame Barrier FRB-NT series (e.g., FRB-BK, FRB-NT Laminate, FRB-NC Laminate, or FRB-NC series) (3M, St. Paul, Minnesota) can be used.

[0059] Each flame-retardant layer 18 can be reinforced. For example, the flame-retardant layer can include woven and / or nonwoven 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, and / or cellulosic fibers. 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, in the form of a reinforcing layer.

[0060] As noted above, when laminate 100 includes multiple 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 with adhesive layer (e.g., 22) defining at least a portion of rear surface 14 to enable adhesion to substrate 10, as previously described. Such adhesive layers (e.g., 20, 24) may bond together insulation layer 16, flame-retardant layer 18, other layers described below, or combinations of such layers. To do so, each of the adhesive layers may be disposed between and in contact with adjacent ones of the other laminate layers (e.g., between two of the insulation layers 16 and / or between one of the insulation layers and the flame-retardant layer).

[0061] As one example, two insulation layers 16 can be glued together and bonded to a flame-retardant layer 18. In another example, a stack of a first flame-retardant layer 18, a first insulation layer 16, a second flame-retardant layer 18, and a second insulation layer 16 can be glued together with adhesive layers (e.g., 20, 22, 24). As shown in FIG. 1B, adhesive layer 20 is disposed between and in contact with the flame-retardant layer 18 and one of the insulation layers 16, and adhesive layer 24 is disposed between and in contact with two of the insulation layers. To promote adhesion without adding substantial thickness to the laminate, the thickness 28 of at least one (e.g., each) of the adhesive layers (e.g., adhesive layers 20, 22, and 24) can be equal to or less than any one of 5.0, 4.5, 4.0, 3.5, 3.0, 2.5, 2.0, 1.5, or 1.0 mm, or between any two (e.g., between 1.5 and 3.5 mm).

[0062] The adhesive layers (e.g., 20, 22, 24) can be the same or different materials, such as silicone adhesive compounds, acrylic adhesive compounds, rubber adhesive compounds, phenolic compounds, cyanate ester compounds, and / or epoxy resin compounds. In certain aspects, the adhesive layers can be adhesives capable of maintaining adhesion at high temperatures (e.g., 500°C or higher), non-limiting examples of which include FLEXcon Silicone Adhesive SA 6000 SA 9000D series (FLEXcon Company, Inc., Spencer, Massachusetts), Alamo Tapes Epoxy Adhesives (Alamotape, San Antonio, Texas), Avery FT 3010 (Avery Dennison Corporation, Painesville, Ohio), and Adhesive Applications S1001-01 (Adhesive Applications, Inc., Easthampton, Massachusetts).

[0063] At least one (up to and including each) of the adhesive layers (e.g., 20, 22, and 24) may include a pressure-sensitive adhesive, such as those containing silicone, epoxy, acrylic, phenolic, cyanate ester, epoxy resin, and / or rubber. Such a pressure-sensitive adhesive, when used in adhesive layer 22, may allow laminate 100 to be easily applied to surface 10 for thermal protection (e.g., by simply pressing laminate 100 onto the surface). However, at least one of the adhesive layers may include a different type of adhesive, such as a fluoropolymer film, a polyimide film, and a B-stage epoxy; examples include commercially available adhesives such as FEP Film, DuPont™'s Pyralux® HT and Pyralux® GPL, and Toyochem Co., LTD. (Tokyo, Japan)'s TSU510S-A. With such other adhesives, bonding can be achieved by stacking layers of a laminate of the invention (e.g., 100) and, optionally, applying heat and / or pressure to the stack (e.g., in a press) so that the temperature exceeds the glass transition temperature of the adhesive layers. In some embodiments having multiple adhesive layers, some of the adhesive layers (e.g., 22) may comprise a pressure-sensitive adhesive, while others (e.g., 20 and 24) may comprise another type of adhesive, such as those listed above.

[0064] The composition of the adhesive layers (e.g., 20, 22, and / or 24) can reduce the risk of delamination, for example, by providing heat resistance. For example, at least one (e.g., each) of the adhesive layers can have a melting or decomposition temperature of any one or more of 350, 375, 400, 425, 450, 500, 550, or 600°C, or any two therebetween. In addition, when a B-stage epoxy adhesive is used, at least one (e.g., each) of the adhesive layers (20, 22, and 24) can have a glass transition or melting temperature of any one or more of 100, 150, 175, 200, 225, 250, or 275°C, or any two therebetween. The composition of the adhesive layers (e.g., 20, 22, and / or 24) can be flame retardant.

[0065] The foregoing configuration allows the laminate 100 to provide heat and flame protection in high temperature and flammable environments. For example, the thermal diffusivity of the laminate 100 may be 0.15, 0.125, 0.10, 0.09, 0.08, 0.07, 0.06, 0.05, or 0.04 mm 2 / s or less, or between any two (e.g., 0.075 mm 2 / s etc. 0.10mm 2 / s or less), thereby reducing the propagation of heat therethrough. The flammability rating of the laminate 100 may meet the requirements of UL 94. For example, the laminate may be able to inhibit the spread of flame at temperatures above 500°C for at least 5 minutes, thereby resisting combustion. 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.

[0066] Furthermore, while the total thickness of laminate 100 (shown as 30 in FIGS. 1A and 1B ) can be 25.4 mm or less, the laminate can advantageously be relatively thin, as discussed above, for example, 25.4, 20, 15, 10, 5, 4, 3, or 2 mm or less, or any two between (e.g., 10 mm or less or 0.3 mm or less). Such thinness can enable laminate 100 to be used in small spaces common in vehicles, such as electric or hybrid vehicles, and / or electronic components, while still providing the heat and fire protection discussed above. Thus, laminate 100 can provide better heat and fire protection in size-constrained applications than conventional insulating / flame-retardant materials that may not fit the size constraints or that may sacrifice heat or fire protection to fit the size constraints.

[0067] 2, shown is a second laminate 200 that is substantially similar to laminate 100, with the primary exception that laminate 200 includes a liner layer 32. As shown, laminate 200 has not yet been attached to substrate surface 10. To protect second adhesive layer 22 (e.g., against contaminants that may impair its adhesive properties) prior to attachment to substrate surface 10, liner layer 32 may be removably disposed on second adhesive layer 22 such that at least a portion (e.g., at least a majority, including up to the entirety) of rear surface 14 of laminate 200 is defined by the liner layer. Liner layer 32 may include, for example, a polymer film or a paper sheet and may be removable from second adhesive layer 22, for example, by peeling it from laminate 200.

[0068] 3 , and as described above, a laminate of the present invention can include multiple flame-retardant layers 18. Specifically, laminate 300 of FIG. 3 includes two flame-retardant layers 18. One of the flame-retardant layers 18 can be positioned on one side of the insulation layer 16, and the other of the flame-retardant layers 18 can be positioned on the other side of the insulation layer 16. The flame-retardant layers 18 need not be the same thickness; for example, the flame-facing flame-facing flame-retardant layer 18 can have a thickness greater than, or between, any one of 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0 times (e.g., about 2.6 times) the thickness of the flame-retardant layer 18 on the opposite side of the insulation layer 16. FIG. 3 also shows that adhesive layers (eg, 22) for securing the laminate to a substrate, and liner layers (eg, 32) for the adhesive layers, are each optional.

[0069] Additionally or alternatively, with reference to FIG. 4 , some laminates, such as laminate 400, include a separate reinforcing layer 60, which may include woven and / or non-woven fibers of the types described above. More specifically, reinforcing layer 60 may be attached to at least a portion of flame-retardant layer 18, for example, via adhesive layer 20. Other laminates may include any suitable number of reinforcing layers (e.g., 60), each of which may be positioned in any suitable location in the laminate. In addition to providing general reinforcement to the laminate, such reinforcing layers may facilitate the handling of ejecta that may be produced, for example, during a battery thermal runaway event.

[0070] Referring now to FIG. 5, shown is a laminate 500 substantially similar to laminate 100, with the primary exception that laminate 500 includes a heat spreading layer 62. Laminate 500 includes one heat spreading 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 spreading layers (e.g., 62), which may be disposed in any suitable location in the laminate. Furthermore, in laminate 500, heat spreading layer 62 is attached to both flame-retardant layer 18 and aerogel layer 16 via adhesive layers 20 and 22, respectively, although neither adhesive layer is required. Also, as with any laminate of the present invention, laminate 500 may include adhesive layer 24 for adhering the laminate to a substrate, which may optionally be protected by a liner layer (e.g., 32) prior to such adhering, as described above.

[0071] The heat spreading layer 62 may include a thermally conductive material, such as a metal (e.g., copper, aluminum, molybdenum, tungsten, rhenium, tantalum, niobium, stainless steel, nickel, or alloys thereof) and / or graphite. More specifically, the heat spreading layer 62 may include at least 90% by weight of a thermally conductive material, such as at least 90% by weight of metal or at least 90% by weight of graphite. The heat spreading layer 60 may have a thermal conductivity of at least 15 W / m·K, preferably between 15 W / m·K and 2,500 W / m·K. They may also have a melting point or decomposition temperature of at least 500° C., preferably at least 1,300° C., at least 1,600° C., at least 1,900° C., at least 2,200° C., at least 2,400° C., at least 2,700° C., at least 3,000° C., or at least 3,300° C. (e.g., and less than 3,800° C. or less than 3,600° C.). Generally, such heat spreading layers can diffuse heat from the environment along the laminate, thereby reducing the occurrence of hot spots along underlying layers of the laminate and the resulting burning or charring of those underlying layers. The thickness 64 of the heat spreading layer 62 can be greater than any one of, or between any two of, 0.001, 0.002, 0.004, 0.006, 0.008, 0.01, 0.02, 0.04, 0.06, 0.08, 0.10, 0.12, 0.14, 0.16, 0.18, 0.20, 0.22, 0.24, 0.26, 0.28, 0.30, 0.32, 0.34, 0.36, 0.38, and 0.40 mm (e.g., 0.001 mm to 4 mm or 0.01 mm to 0.08 mm).

[0072] Although laminate 500, like other laminates of the present invention, is depicted as including one insulation layer 16, laminate 500 may include multiple insulation layers 16, optionally bonded with adhesive layers (e.g., 24). Additionally, while laminate 500 is shown including one flame retardant layer 18, other embodiments may include multiple flame retardant layers 18, including, for example, one disposed above and one disposed below insulation layer 16.

[0073] Referring now to Figures 6A-6C, some laminates of the present invention (600a-600c) may include one or more ejecta mitigation layers 84, for example, to address ejecta generated during a battery thermal runaway event. Such ejecta mitigation layers 84 may include a fiber layer and, in this context, may be characterized as a reinforcement layer. To this end, the ejecta mitigation layer 84 may include any of the fibers (e.g., basalt fiber or glass fiber) described above with respect to the reinforcement layer, specifically including woven or non-woven silica-based glass fiber, vermiculite-coated glass fiber, high-silica-content glass fiber (e.g., quartz glass fiber), ceramic fiber (e.g., NEXTEL ceramic fiber 312, 440, 610, 729) (including aluminum oxide fiber), rock wool, or carbon fiber. Again, laminates of the present invention may not include a lower flame-retardant layer (e.g., Figure 6C) or a heat-dissipating layer (e.g., 62). Also, multiple ejecta mitigation layers (FIG. 6B) may prove advantageous, as may the porous insulating layer 16. While greatest benefit may be obtained by placing the ejecta mitigation layer above the heat dissipation layer (if present), this is not required.

[0074] Moreover, with further reference to the laminate 700 of FIG. 7 , the ejecta mitigation layer 84 can include a metal. The metal can have a melting point above 1,000°C, preferably above 1,200°C. Such metals can include, for example, stainless steel, titanium, nickel, molybdenum, or tantalum. Such a layer reflects heat toward the heat source and functions as a thermal barrier. In particularly advantageous embodiments, one of the ejecta mitigation layers 84 can be fiber-based and another can be metal-based. In such a situation, the fiber-based ejecta mitigation layer 84 is preferably positioned closer to the flame-facing side than the metal-based ejecta mitigation layer 84 ( FIG. 7 ). In any event, the laminate of the present invention can include any suitable number of ejecta mitigation layers (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or more), whether fiber-based and / or metal-based, and can be positioned in any suitable location on the laminate.

[0075] 8, laminate 800 is shown. Laminate 800, like any other laminate of the present invention, can include a protective layer 86. Protective layer 86 provides protection from the environment, such as, for example, rain, wind, and / or sunlight. Protective layer 86 can also provide protection against application-specific conditions, such as jet fuel spray, electrical arcs, and / or mechanical abrasion. Protective layer 86 can include, for example, plastic, glass, or ceramic. Suitable thermoplastics include metals, polyesters, PVC ("vinyl"), polyvinyl fluoride, polyvinylidene fluoride (PVDF), polyimides, aramids, polyethylene terephthalate (PET), polycarbonate (PC) family polymers, polybutylene terephthalate (PBT), poly(1,4-cyclohexylidenecyclohexane-1,4-dicarboxylate) (PCCD), glycol-modified polycyclohexyl terephthalate (PCTG), poly(phenylene oxide) (PPO), polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polystyrene (PS), polymethyl Suitable thermosetting plastics include poly(methyl methacrylate) (PMMA), polyethyleneimine or polyetherimide (PEI) and their derivatives, thermoplastic elastomers (TPE), terephthalic acid (TPA) elastomers, poly(cyclohexanedimethylene terephthalate) (PCT), polyethylene naphthalate (PEN), polyamides (PA), polysulfone sulfonates (PSS), sulfonates of polysulfones, polyether ether ketone (PEEK), polyether ketone ketone (PEKK), acrylonitrile butyldiene styrene (ABS), polyphenylene sulfide (PPS), copolymers thereof, or mixtures thereof. Suitable thermosetting plastics include polyaramids, polyimides, polybenzoxazoles, polyurethanes, or mixtures thereof.

[0076] Referring now to FIG. 9, laminates of the present invention (e.g., 100-800) can be flexible. By way of example, such laminates can be processed into the shape of a roll 34 having an inner diameter 36 of 10 cm, 8 cm, 5 cm, 4 cm, 2 cm, 1 cm, 8 mm, 5 mm, 4 mm, 2 mm, or 1 mm or less, or between any two of these, without undergoing permanent deformation. Such flexibility, even if not at the level of this example, can be provided by the materials of the laminate's insulation, flame-retardant, adhesive, and other layers (if present), and / or the relatively thin thicknesses of those layers (e.g., as described above). When in the shape of a roll 34, a portion of the front surface 12 of the laminate can face a portion of its rear surface 14.

[0077] In some embodiments, the laminate can protect a device or substrate from temperatures exceeding 500°C. For example, one laminate of the present invention can be positioned relative to a device such that the flame-retardant layer is located farther from the device than the rear surface (e.g., rear surface 14) of the laminate. When exposed to temperatures of greater than 500°C to 1,500°C for 1 to 90 minutes (preferably at least 5 minutes), the temperature of the device does not exceed 500°C during that period. The exposure temperature can be in the range of 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 laminates of the present invention are also suitable for use in applications involving exposure to lower temperatures (e.g., up to 100°C, 200°C, 300°C, or 400°C) and / or for shorter periods of time (e.g., up to 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 40, 50, or 60 seconds) to any of the aforementioned temperatures.

[0078] Devices in which such thermal protection is advantageous include, for example, batteries (e.g., lithium-ion batteries), bus bars, and electric or hybrid vehicles or electrical components, including batteries and electric motors, that are particularly exposed to high-temperature environments. The surface (e.g., 10) to which one laminate of the present invention is attached can be the surface of a battery, such as a lithium-ion battery. The surface can also be a bus bar or a non-conductive material.

[0079] For example, referring to FIG. 10 , shown is a battery 66 including battery cells 68. The cells 68 can be grouped into battery modules 70, and the modules can be assembled into a battery pack 72. The battery 66 can further include a battery housing or box 74. To isolate the cells 68, modules 70, and / or packs 72 from vibration and / or to account for expansion / contraction of the cells, modules, and / or packs, the battery 66 can also include one or more compression pads 76, which can be disposed between multiple cells, multiple modules, and / or between the pack and box 74, etc. The compression pads 76 can include, for example, a compressible material such as foam. The battery 66 can be included in a vehicle 78, such as the illustrated automobile. The vehicle 78 can also be, for example, an automotive vehicle (e.g., an internal combustion engine vehicle, an electric vehicle, a hybrid electric vehicle), an aircraft (e.g., an airplane, a jet aircraft, a helicopter, an unmanned aerial vehicle, or an electric vertical take-off and landing (eVTOL) aircraft), a train, a motorcycle, a watercraft, a spacecraft, or the like.

[0080] However, such batteries 66 are susceptible to thermal runaway events and / or exposure to other high temperature environments. One or more laminates of the present invention can be implemented to protect the battery 66, the vehicle 78 in which the battery is located, and / or the vehicle occupants. Illustratively, one of the laminates of the present invention can be disposed on the interior and / or exterior surface of at least one of the cells 68, module 70, pack 72, compression pad 76, and / or box 74.

[0081] As another example, referring to FIGS. 11A and 11B, shown is a cable 80. Cable 80 can have a length 82 and a width or diameter 84, where the length is greater than the width (e.g., 10 times or more the width). Notably, diameter 84 can be 0.0003 inches to 10 inches, preferably 0.001 inches to 1 inch. Cable 80 can be, but need not be, electrically conductive. The cable can be included in a vehicle (e.g., as described above), a missile, a rocket, an artillery piece, a manned aircraft, an unmanned aircraft, a ground vehicle, a sea vehicle, or a spacecraft. Such cables can be exposed to high temperatures, which the laminates of the present invention can be used to mitigate. For example, cable 80 can include one or more laminates of the present invention (e.g., shown as 100 in FIG. 7B) forming at least a portion of the exterior surface of the cable.

[0082] Non-limiting examples of articles of manufacture that may comprise the laminates of the present invention include, in addition to those previously mentioned, vehicles, trucks, trailers, trains, railcars, aircraft, spacecraft, body panels or components for any of the foregoing, bridges, pipelines, pipes, piping, boats, ships, storage vessels, storage tanks, furniture, windows, doors, handrails, functional or decorative building parts, pipe railings, electrical components, conduits, beverage containers, food containers, foils, batteries (e.g., electric vehicle batteries, battery systems, battery casings), and battery bus bars.

[0083] B. Polymer aerogel layer material The polymer aerogel layer can comprise organic materials, inorganic materials, or a mixture thereof. Organic aerogels can be made from polyacrylates, polystyrenes, polyacrylonitriles, polyurethanes, polyureas, polyimides, polyamides, polyaramids, polyfurfural alcohols, phenol furfuryl alcohols, melamine formaldehyde, resorcinol formaldehyde, cresol formaldehyde, phenol formaldehyde, polyvinyl alcohol dialdehyde, polycyanurates, polyacrylamides, various epoxies, agar, and agarose, among others. In certain embodiments, the aerogel is a polyimide aerogel.

[0084] Polyimides are a type of polymer with many desirable properties. Polyimide polymers contain nitrogen atoms in the polymer backbone, linked to two carbonyl carbons, somewhat stabilized by adjacent carbonyl groups. The carbonyl groups contain a carbon, called the carbonyl carbon, which is double-bonded to an oxygen atom. Because two different classes of monomers are typically used to produce polyimide polymers, polyimides are typically considered AA-BB type polymers. Polyimides can also be prepared from AB type monomers. For example, aminodicarboxylic acid monomers can be polymerized to form AB type polyimides. Monoamines and / or monoanhydrides can be used as end-capping agents, if desired.

[0085] One class of polyimide monomers is typically diamines, or diamine monomers. It should be understood that diamine monomers can also be diisocyanates, and that isocyanates can be substituted for amines in this description, where appropriate. As known to those skilled in the art, there are other types of monomers that can be used in place of diamine monomers. These other types of monomers are called acid monomers, and are usually in the form of dianhydrides. In this description, the term "diacid monomers" is defined to include dianhydrides, tetraesters, diester acids, tetracarboxylic acids, or trimethylsilyl esters, all of which can react with diamines to produce polyimide polymers. Dianhydrides should be understood to mean tetraesters, diester acids, tetracarboxylic acids, or trimethylsilyl esters, which can be substituted where appropriate. As known to those skilled in the art, there are other types of monomers that can be used in place of diacid monomers.

[0086] Because a diacid monomer has two anhydride groups, a different diamino monomer can react with each anhydride group, and thus the diacid monomer can be located between two different diamino monomers. The diamine monomer contains two amine functional groups; therefore, after the first amine functional group is linked to one diacid monomer, the second amine functional group is available to link to yet another diacid monomer, which then links to another diamine monomer, and so on. In this way, a polymer backbone is formed. The resulting polycondensation reaction product forms a polyamic acid.

[0087] Polyimide polymers are typically formed from two different types of monomers, and different variations of each type of monomer can be mixed. Thus, one, two, or more diacid monomers can be included in the reaction vessel, as well as one, two, or more 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. Because multiple types of diamines or diacids can be used, the various monomer compositions 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 polyimide 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 be reacted with two diacid comonomers B1B1 and B2B2 to form polymer chains of the general formula (A1A1-B1B1): w -(A1A1-B2B2) x -(A2A2-B1B1) y -(A2A2-B2B2) z where 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, and the general formula of the polymer is determined by varying the amount and type of monomers used.

[0088] There are many examples of monomers that can be used to make polymer aerogels, including polyamic acid amide polymers. In some embodiments, the diamine monomer is a substituted or unsubstituted aromatic diamine, a substituted or unsubstituted alkyl diamine, or a diamine that can contain 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'-isopropylidenedianiline, 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)isopropylidene, meta-phenylenediamine, para-phenylenediamine, 1,2-diaminobenzene, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 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-beta-amino-t-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-xylenediamine, p-xylenediamine, 4,4'-diaminodiphenyl ether phosphine oxide, 4,4'-diaminodiphenyl N-methylamine, 4,4'- Diaminodiphenyl N-phenylamine, 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, and 4,4'-methylenebisbenzenamine, 2,2'-dimethylbenzidine, (also known as 4,4'-diamino-2,2'-dimethylbiphenyl (DMB)), bisaniline-p-xylidene, 4,4'-bis(4-aminophenoxy)biphenyl, 3,3'-bis(4 In certain embodiments, the diamine monomer is ODA, 2,2'-dimethylbenzidine, or both.

[0089] 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'-isopropylidenediphenoxy)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 dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride arboxylie) 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)hexafluoropropane, 2,6-dichloro Included are naphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene, 8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride and thiophene-2,3,4,5-tetracarboxylic dianhydride.In certain embodiments, the dianhydride monomer is BPDA, PMDA or both.

[0090] In some 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 particularly 0.8:1 to 1.2:1. In further 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 particularly 8:1 to 80:1. Monoanhydride groups can also be used. Non-limiting examples of monoanhydride groups include 4-amino-1,8-naphthalic anhydride, endo-bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, citraconic anhydride, trans-1,2-cyclohexanedicarboxylic anhydride, 3,6-dichlorophthalic anhydride, 4,5-dichlorophthalic anhydride, tetrachlorophthalic anhydride, 3,6-difluorophthalic anhydride, 4,5-difluorophthalic anhydride, tetrafluorophthalic anhydride, maleic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, and 2,2-dimethylglutaric anhydride. Examples of suitable anhydrides include 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, and 3,4-pyridinedicarboxylic anhydride. In particular, the monoanhydride group may be phthalic anhydride.

[0091] In another embodiment, the polymer composition used to prepare the polymeric aerogel layer includes a polyfunctional amine monomer having at least three primary amine functional groups. The polyfunctional amine may be a substituted or unsubstituted aliphatic polyfunctional amine, a substituted or unsubstituted aromatic polyfunctional amine, or a polyfunctional amine containing a combination of an aliphatic and two aromatic groups, or 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-aminopropyl)heptane-1,7-diamine, N',N'-bis(6-aminopropyl)ethane-1,2-diamine, 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-aminopropyl)ethane-1,2 ... (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 diethylenetriamines, 1,2-dibenzyldiethylenetriamine, lauryldiethylenetriamine, N-(2-hydroxypropyl)diethylenetriamine N,N-bis(l-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)dianiline, 4-((bis(4-aminobenzyl)amino)methyl)aniline, 4-(2-(bis(4-aminophenethyl)amino)ethoxy)aniline Examples of suitable aromatic polyfunctional amines include 1,3,5-tris(4-aminophenoxy)benzene (TAPOB), 4,4',4"-methanetriyltrianiline, N,N,N',N'-tetrakis(4-aminophenyl)-1,4-phenylenediamine, polyoxypropylene triamine, octa(aminophenyl) polyhedral oligomeric silsesquioxane, or a combination thereof. A specific example of a polyoxypropylene triamine is JEFFAMINE® T-403 from Huntsman Corporation, The Woodlands, TX USA. In certain embodiments, the aromatic polyfunctional amine may be 1,3,5-tris(4-aminophenoxy)benzene or 4,4',4"-methanetriyltrianiline.In some embodiments, the multifunctional amine comprises three primary amine groups and one or more secondary and / or tertiary amine groups, for example, N',N'-bis(4-aminophenyl)benzene-1,4-diamine.

[0092] Non-limiting examples of capping agents or groups include amine, maleimide, nadimide, acetylene, biphenylene, norbornene, cycloalkyl, and N-propargyl, and those derived from reagents including 5-norbornene-2,3-dicarboxylic anhydride (nadic anhydride, NA), methylnadic anhydride, hexachloronadic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, 4-amino-N-propargylphthalimide, 4-ethynylphthalic anhydride, and maleic anhydride, among others.

[0093] The characteristics or properties of the final polymer are greatly influenced by the choice of monomers used to produce the polymer. 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 hydraulic expansion (CHE), and any other properties that are particularly desirable, as well as cost. In many cases, certain important properties of a polymer for a particular application can be identified. Other properties of the polymer may be less important or may have a wide range of acceptable values; therefore, many different monomer combinations may be used.

[0094] In some examples, the backbone of the polymer may include a substituent. The substituent (e.g., an oligomer, a functional group, etc.) may be directly attached to the backbone or may be linked to the backbone through a linking group (e.g., a tether or a flexible tether). In other embodiments, compounds or particles may be incorporated (e.g., mixed and / or encapsulated) into the polyimide structure without being covalently bonded to the polyimide structure. In some examples, the incorporation of compounds or particles may be carried out during the polyamic acid reaction process. In some examples, the particles may aggregate, thereby producing polyimides having domains containing different concentrations of non-covalently bound compounds or particles.

[0095] Specific properties of polyimides can be influenced by incorporating 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.

[0096] C. Preparation of polymer aerogel layers Polymer aerogel films that may be used in at least some of the laminates of the present invention are commercially available. Non-limiting examples of such films include Blueshift AeroZero® rolled film (available from Blueshift Materials, Inc. (Spencer, Massachusetts)) and Airloy® film (available from Aerogel Technologies, LLC), with Blueshift AeroZero® rolled film being preferred in some aspects.

[0097] Additionally, and in addition to the processes described below, polymer aerogels (such as films, stock shapes, or monoliths) can be made using methods described in WO 2014 / 189560 to Rodman et al., US 2017 / 0355829 to Sakaguchi et al., US 2018 / 078512 to Yang et al., US 2018 / 140804 to Sakaguchi et al., and US 2019 / 006184 to Irvin et al., International Application PCT / US2019 / 029191 to Ejaz et al., U.S. Patent Application 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 by reference in their entireties.

[0098] The following provides non-limiting steps that can be used to make layers of polymeric aerogel suitable for use in the laminates of the present invention. These steps can include: (1) preparation of the polymer gel, (2) optional solvent exchange, (3) drying the polymer solution to form the aerogel, and (4) bonding the polymeric aerogel film to a substrate.

[0099] 1. Polymer gel formation The first stage in the synthesis of an aerogel can be the synthesis of a polymerized gel. For example, if a polyimide aerogel is desired, at least one acid monomer can be reacted with at least one diamino monomer in a reaction solvent to produce a polyamic acid. As previously mentioned, many acid monomers and diamino monomers can be used to synthesize a polyamic acid. In one aspect, the polyamic acid is contacted with an imidization catalyst in the presence of a chemical dehydrating agent to produce a polymerized polyimide gel via an imidization reaction. "Imidization" is defined as the conversion of a polyimide precursor to an imide. Any imidization catalyst suitable for driving the conversion of a polyimide precursor to a polyimide state is suitable. Non-limiting examples of chemical imidization catalysts include pyridine, methylpyridine, 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 use in forming imide rings from amic acid precursors is suitable for use in the methods 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.

[0100] 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, followed by the addition of one or more dianhydrides (e.g., diacid monomers) in small, sequential additions at predetermined time increments while monitoring the viscosity. The desired viscosity of the polymerization solution can range from 50 to 20,000 cP, or more specifically, from 500 to 5,000 cP. Non-crosslinked aerogels can be prepared by carrying out the reaction using incremental additions of dianhydrides while monitoring the viscosity. For example, a triamine monomer (23 equivalents) can be added to a solvent to obtain a 0.0081 molar solution. A first diamine monomer (280 equivalents) can be added to the solution, followed by a second diamine monomer (280 equivalents). Next, dianhydrides (552 equivalents total) can be added in small, sequential additions at predetermined time increments while monitoring the viscosity. The dianhydrides can be added until the viscosity reaches 1,000 to 1,500 cP. For example, a first portion of the dianhydride can be added, the reaction can be stirred (e.g., 20 minutes), a second portion of the dianhydride can be added, and then a sample of the reaction mixture can be analyzed for viscosity. After stirring for an additional time (e.g., 20 minutes), a third portion of the dianhydride can be added, and a sample can be taken for viscosity analysis. After further stirring for a desired period of time (e.g., 10-12 hours), the 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., 10-12 hours) or until the reaction is deemed complete.

[0101] The reaction temperature for gel formation can be determined by routine experimentation depending on the starting materials. In preferred embodiments, the temperature can be any one or more of 15°C, 20°C, 30°C, 35°C, 40°C, and 45°C, or between any two of these. After a desired time (e.g., about 2 hours), the product can be isolated (e.g., filtered), followed by the addition of a nitrogen-containing hydrocarbon (828 equivalents) and a dehydrating agent (1214 equivalents). The addition of the nitrogen-containing hydrocarbon and / or dehydrating agent can be carried out at any temperature. In some embodiments, the nitrogen-containing hydrocarbon and / or dehydrating agent is added to the solution at 20°C to 28°C (e.g., room temperature) and stirred at that temperature for the desired time. In some examples, after the addition of the nitrogen-containing hydrocarbon and / or dehydrating agent, the solution temperature is raised to 150°C.

[0102] Reaction solvents 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-pyrrolidinone, N-cyclohexyl-2-pyrrolidone, 1,13-dimethyl-2-imidazolidinone, diethylene glycol dimethoxy ether, o-dichlorobenzene, phenol, cresol, xylenol, catechol, butyrolactone, hexamethylphosphoramide, and mixtures thereof. The reaction solvent and other reactants can be selected based on their compatibility with the materials and methods used; that is, whether the polymerized polyamic acid amide gel is cast onto a support film, injected into a moldable part, or poured into a shape for further processing into a workpiece. In certain embodiments, the reaction solvent is DMSO.

[0103] In one non-limiting example, the formation of macropores, as opposed to small mesopores and micropores, can be controlled primarily by controlling the polymer / solvent dynamics during gel formation. This allows for control of the pore structure and the amount and volume of macroporous, mesoporous, and microporous cells. For example, a curing additive that reduces the solubility of the resulting polymer during polymerization, such as 1,4-diazabicyclo[2.2.2]octane, can produce a polymer gel with more macropores than another curing additive that improves the solubility of the resulting polymer, such as trimethylamine. In another specific, non-limiting example, when producing polyimide aerogels, the ratio of rigid amines (e.g., p-phenylenediamine (p-PDA)) incorporated into the polymer backbone to more flexible diamines (e.g., -ODA) can be increased to favor the formation of macropores over small mesopores and micropores.

[0104] The polymer solution may be cast onto a cast sheet, optionally covered with a support film, for a period of time. Casting may include spin casting, gravure coating, three-roll coating, roll-type knife coating, slot-die extrusion, dip coating, Mayer rod coating, or other techniques. In one embodiment, the cast sheet is a polyethylene terephthalate (PET) cast sheet. After the period, the polymerized reinforced gel is removed from the cast sheet and prepared for the solvent exchange step. In some embodiments, the cast film may be heated to elevated temperatures in stages to remove the solvent and convert the amic acid functional groups in the polyamic acid to imides via a dehydration cycloreaction, also known as imidization. In some examples, polyamic acid may be converted to polyimide in solution by the addition of a chemical dehydrating agent, a catalyst, and / or heat.

[0105] In some embodiments, polyimide polymers can be produced by preparing a polyamic acid polymer in a reaction vessel, then forming the polyamic acid into a sheet or film, followed by treatment with a catalyst or heat and a catalyst to convert the polyamic acid to a polyimide.

[0106] The wet gel used to prepare the aerogel may be prepared by any known gel-forming technique, for example, by adjusting the pH and / or temperature of a dilute metal oxide solution to the point where gelation occurs.

[0107] 2. Optional Solvent Exchange After synthesizing a polymer gel, in certain instances, it may be desirable 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 by placing the polymer gel inside a pressure vessel and submerging it in a mixture containing the reaction solvent and the second solvent. A high-pressure atmosphere is then created inside the pressure vessel, which forces the second solvent into the polymer gel and displaces a portion of the reaction solvent. Alternatively, the solvent exchange step may be performed without using a high-pressure environment. Multiple solvent exchanges may be necessary. In some embodiments, solvent exchange is not required.

[0108] The time required to perform a solvent exchange will vary depending on the type of polymer undergoing the exchange and the reaction solvent and second solvent used. In one embodiment, each solvent exchange can take 1 to 168 hours, or any period therebetween, including 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, or 23, 24, 25, 50, 75, 100, 125, 150, 155, 160, 165, 166, 167, or 168 hours. In another embodiment, each solvent exchange can take approximately 1 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-dimethylpropan-1-ol, cyclohexanol, diethylene glycol, cyclohexanone, acetone, acetylacetone, 1,4-dioxane, diethyl ether, dichloromethane, trichloroethylene, chloroform, carbon tetrachloride, water, and mixtures thereof. In certain non-limiting embodiments, the second solvent can have a freezing point suitable for carrying out a supercritical or subcritical drying step. For example, at 1 atmosphere, tert-butyl alcohol has a freezing point of 25.5°C, and water has a freezing point of 0°C. Alternatively, as described below, drying can be carried out without a supercritical or subcritical drying step, such as by evaporative drying techniques.

[0109] The temperature and pressure used in the solvent exchange step may be varied. The duration of the solvent exchange step can be adjusted by conducting the solvent exchange at various temperatures or atmospheric pressures, or both, provided that the pressure and temperature within the pressure vessel do not cause either the first solvent or the second solvent to leave the liquid phase and become a gas, vapor, solid, or supercritical fluid. Generally, higher pressures and / or temperatures decrease the amount of time required to conduct the solvent exchange, and lower temperatures and / or pressures increase the amount of time required to conduct the solvent exchange.

[0110] 3. Cooling and drying In one embodiment, after solvent exchange, the polymerized gel can be exposed to supercritical drying. In this example, the solvent in the gel can be removed by supercritical CO2 extraction.

[0111] In another embodiment, after solvent exchange, the polymerized gel can be subjected to subcritical drying. In this example, 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 can be cooled to below 0°C. After cooling, the polymerized gel can be subjected to a vacuum for a period of time to sublimate the second solvent.

[0112] In yet another embodiment, after solvent exchange, the polymerized gel can be subjected to subcritical drying, optionally with heating, after most of the second solvent has been removed by sublimation. In this example, 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. The period can range from several hours to several days, with a typical period being about 4 hours. During the sublimation step, a portion of the second solvent present in the polymerized gel is removed, leaving behind a gel that may have macropores, mesopores, or micropores, or any combination thereof, or all of these pore sizes. After the sublimation step is complete, or nearly complete, the aerogel is formed.

[0113] 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, inert gas (e.g., nitrogen (N) gas), etc.). Additionally, passive drying techniques can be used, such as simply exposing the gel to ambient conditions without an airflow.

[0114] Once cooled or dried, the films and stock shapes can be configured for use in the laminates of the present invention. For example, the film or stock shape can be machined (e.g., by cutting or grinding) into a desired shape, such as a square, rectangle, circle, triangle, irregular, random, etc. Also, as previously described, the film or stock shape can be attached to a support material, such as with an adhesive. In an alternative embodiment, the support material can be incorporated into the matrix of a polymer aerogel, as described below.

[0115] 4. Incorporation of a reinforcing layer into a polymer aerogel matrix In addition to the methods described above regarding the use of adhesives to bond polymer aerogels to support materials, any embodiment of the present invention can include incorporating a support material into the polymer matrix to create reinforced polymer aerogels without the use of adhesives. Of note, during the production of unreinforced polymer aerogels, a reinforcing support film can be used as a carrier to support the gelled film during processing. During unwinding, the gelled film can be irreversibly pressed into the carrier film. Pressing the gelled film into the carrier film can provide substantial durability improvements. In another example, the polymer solution can be cast into the reinforcing or support material during the aforementioned solution casting step.

[0116] Substrate selection and direct casting can allow for optimization (e.g., minimization) of the thickness of the resulting reinforced aerogel material. This process can also be extended to the production of fiber-reinforced polymer aerogels, with internally reinforced polyimide aerogels provided as an example. The process can 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 chemical curing and dehydrating agents listed above to initiate chemical imidization; (c) casting the polyamic acid solution onto a fiber support and allowing it to infiltrate before gelation; (d) allowing the catalytic polyamic acid solution to gel around and within the fiber support during chemical imidization; (e) optionally, performing a solvent exchange to facilitate drying; and (f) removing the transient liquid phase contained within the gel by supercritical, subcritical, or ambient drying to obtain an internally reinforced aerogel.

[0117] D. Non-Limiting Aspects of the Invention The present invention can include the following non-limiting aspects.

[0118] Aspect 1: A laminate including a flame-retardant layer having a flammability rating in accordance with at least one Plastics Flammability Standard and an aerogel layer, the laminate having opposing front and rear surfaces; the flame-retardant layer defining at least a majority of the front surface; and a thickness of the laminate of 25.4 millimeters (mm) or less.

[0119] Aspect 2: The laminate of Aspect 1, wherein the thickness of the laminate is 10 mm or less, preferably 5 mm or less, more preferably 2 mm or less, or even more preferably 0.3 mm to 2 mm.

[0120] Aspect 3: The laminate of any one of Aspects 1 or 2, wherein the flame-retardant layer has a thickness of 0.05 mm to 0.8 mm.

[0121] Aspect 4: The laminate of any one of Aspects 1 to 3, wherein the flame-retardant layer is not electrically insulating.

[0122] Aspect 5: The laminate of any one of Aspects 1 to 3, wherein the flame-retardant layer is electrically insulating.

[0123] Aspect 6: The laminate of any one of Aspects 1 to 5, wherein the plastic flammability standard is UL94 5VA or UL94 5VB, and the flammability rating of the flame-retardant layer complies with UL94 5VA or UL94 5VB.

[0124] Aspect 7: The laminate of any one of aspects 1 to 6, wherein the flammability rating of the laminate complies with the Plastics Flammability Standard, preferably UL94 5VB, more preferably UL94 5VA.

[0125] Aspect 8: The laminate of any one of Aspects 1 to 7, wherein the flame-retardant layer comprises fibers.

[0126] Aspect 9: The laminate of aspect 8, wherein the fibers are nonwoven fibers.

[0127] Aspect 10: The laminate of Aspect 8, wherein the fibers are woven fibers.

[0128] Aspect 11: The laminate of any one of Aspects 1-10, wherein the flame-retardant layer comprises one or more of a metal hydroxide, an organic phosphate, an alumina hydroxide, an inorganic filler, and / or a metal oxide.

[0129] Aspect 12: The laminate of any one of Aspects 1 to 11, wherein the flame-retardant layer comprises a silicate.

[0130] Aspect 13: The laminate of Aspect 12, wherein the silicate comprises mica, and the flame-retardant layer preferably comprises at least 90% by weight of the mica.

[0131] Aspect 14: The laminate of any one of Aspects 1 to 13, wherein the flame retardant layer comprises a ceramic, and preferably comprises at least 90 wt. % of the ceramic.

[0132] Aspect 15: The laminate of Aspect 14, wherein the ceramic comprises a metal oxide or a non-metal oxide or a combination thereof.

[0133] Aspect 16: The laminate of Aspect 15, wherein the ceramic comprises alumina, beryllia, ceria, zirconia, a carbide, a boride, a nitride, or a silicide, or any combination thereof.

[0134] Aspect 17: The laminate of any one of Aspects 1 to 16, wherein the flame-retardant layer is halogen-free.

[0135] Aspect 18: The laminate of any one of Aspects 1 to 17, wherein the aerogel layer has a thickness between 0.05 mm and 0.254 mm.

[0136] Aspect 19: The laminate of any one of Aspects 1 to 18, wherein the aerogel layer is a polymer aerogel layer.

[0137] Aspect 20: The laminate of any one of Aspects 1 to 19, wherein the polymer aerogel layer comprises at least 50% by weight of polyimide.

[0138] Aspect 21: The laminate of any one of Aspects 1 to 20, wherein the aerogel layer has a decomposition temperature of 400°C or higher, preferably 400°C to 600°C.

[0139] Aspect 22: The laminate of any one of Aspects 1-21, including one or more adhesive layers bonded to the aerogel layer.

[0140] Aspect 23: The laminate of Aspect 22, wherein a first of the adhesive layers is disposed between the flame retardant layer and the aerogel layer.

[0141] Aspect 24: The laminate of Aspect 23, wherein the first adhesive layer has a melting or decomposition temperature greater than 500°C.

[0142] Aspect 25: The laminate of Aspect 23 or 24, wherein at least a portion of the rear surface is defined by a second one of the adhesive layers or a liner layer removably disposed on the second adhesive layer.

[0143] Aspect 26: The laminate of any of Aspects 22-25, wherein each of the adhesive layers comprises a pressure-sensitive adhesive.

[0144] Aspect 27: The laminate of any one of Aspects 22-26, wherein each of the adhesive layers comprises a silicone adhesive compound and / or an epoxy compound.

[0145] Aspect 28: The laminate of any of Aspects 1-27, wherein any one, any combination, or all of the flame retardant layer, the aerogel layer, and the adhesive layer are perforated.

[0146] Aspect 29: The laminate of any one of Aspects 1 to 28, wherein when attached to a substrate, the laminate is capable of maintaining the temperature of the substrate at or below 500°C when the front surface of the laminate is exposed to a temperature greater than 500°C, preferably between 500°C and 1,500°C, or more preferably between 700°C and 1,200°C, for a period of between 1 minute and 90 minutes, preferably at least 5 minutes.

[0147] Aspect 30: The laminate of any one of Aspects 1 to 29, wherein the laminate is disposed in a roll shape such that a portion of the front surface of the laminate faces a portion of the rear surface of the laminate.

[0148] Aspect 31: The laminate of any one of Aspects 1-30, further comprising a heat spreading layer.

[0149] Aspect 32. The laminate of Aspect 31, wherein the heat spreading layer comprises a metal having a thermal conductivity of at least 15 W / m·K, preferably between 15 W / m·K and 2,500 W / m·K.

[0150] Aspect 33: The laminate of Aspect 32, wherein the metal comprises copper, aluminum, molybdenum, tungsten, rhenium, tantalum, niobium, stainless steel, nickel, or an alloy thereof.

[0151] Aspect 34: The laminate of Aspect 32 or 33, wherein the heat spreading layer comprises at least 90% by weight of the metal.

[0152] Aspect 35: The laminate of Aspect 31, wherein the heat spreading layer comprises graphite.

[0153] Aspect 36: The laminate of Aspect 35, wherein the heat spreading layer comprises at least 90% by weight of the graphite.

[0154] Aspect 37: The laminate of 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.

[0155] Aspect 38: The laminate of any one of Aspects 31 to 37, wherein the heat dissipation layer is disposed between the flame-retardant layer and the aerogel layer.

[0156] Aspect 39: The laminate of Aspect 38, including a first adhesive layer disposed between the flame retardant layer and the heat spreading layer, and a second adhesive layer disposed between the heat spreading layer and the aerogel layer.

[0157] Aspect 40: The laminate of Aspect 39, wherein the first adhesive layer is in direct contact with the flame retardant layer and the heat spreading layer, and the second adhesive layer is in direct contact with the heat spreading layer and the aerogel layer.

[0158] Aspect 41: The laminate of Aspect 39 or 40, further comprising a third adhesive layer and a liner layer, the third adhesive layer being disposed between the aerogel layer and the liner layer.

[0159] Aspect 42: The laminate of Aspect 41, wherein the third adhesive layer is in direct contact with the aerogel layer and the liner layer.

[0160] Aspect 43: The laminate of any one of Aspects 39-42, wherein the first, second, and / or third adhesive layer has a melting temperature or decomposition temperature greater than 500°C; comprises a pressure-sensitive adhesive; and / or comprises a silicone adhesive compound and / or an epoxy compound.

[0161] Aspect 44: The laminate of any of Aspects 31-43, wherein any one, any combination, or all of the flame retardant layer, the heat dispersion layer, the aerogel layer, and the first, second, and third adhesive layers are perforated.

[0162] Aspect 45: The laminate of any one of Aspects 1-44, further comprising a reinforcing layer.

[0163] Aspect 46: The laminate of Aspect 45, wherein the reinforcing layer is attached to at least a portion of the flame retardant layer.

[0164] Aspect 47: The laminate of Aspect 45 or 46, wherein the reinforcing layer is included within at least a portion of the volume of the flame retardant layer.

[0165] Aspect 48: The laminate of any one of aspects 45 to 47, wherein the reinforcing layer includes fibers.

[0166] 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, cellulosic fibers, or any combination thereof.

[0167] Aspect 50: The laminate of Aspect 48 or 49, wherein the fibers are nonwoven fibers or woven fibers.

[0168] Aspect 51: A device including one or more stacks of any one of Aspects 1-50, wherein a first of the stacks is bonded such that a front surface of the first stack is positioned farther from the device than a rear surface of the first stack.

[0169] Aspect 52: The apparatus of Aspect 51, which is a battery.

[0170] Aspect 53: The apparatus of Aspect 52, wherein the battery is included in a vehicle, the vehicle including one or more wheels; and one or more electric motors each configured to rotate at least one of the wheels; and the battery is in electrical communication with at least one of the electric motors.

[0171] Aspect 54: The apparatus of Aspect 52 or 53, further including a busbar in electrical communication with the battery; and wherein the one or more stacks include two or more stacks, a second of the stacks being coupled to the busbar such that a front surface of the second stack is positioned farther from the busbar than a rear surface of the second stack.

[0172] Aspect 55: The device of any one of Aspects 52 to 54, wherein the battery is a lithium ion battery.

[0173] Aspect 56: The apparatus of Aspect 51, which is a busbar.

[0174] Aspect 57: The apparatus of Aspect 51, which is a compression pad, a battery cell, a battery module, a battery pack, or a battery box.

[0175] Aspect 58: The device of Aspect 57, wherein the compression pad is a compression pad, the compression pad comprising a compressible material.

[0176] Aspect 59: The device of Aspect 58, wherein the compressible material comprises foam.

[0177] Aspect 60: The device of Aspect 58 or 59, wherein the compression pad is disposed between the first battery cell and the second battery cell.

[0178] Aspect 61: The apparatus of Aspect 57, wherein the apparatus is a battery cell.

[0179] Aspect 62: The device of Aspect 57, which is a battery module including at least two battery cells, wherein one or more of the stacks are disposed between the two battery cells.

[0180] Aspect 63: The device of Aspect 57, wherein the battery pack includes at least two battery modules, and one or more of the stacks are disposed between the two battery modules.

[0181] Aspect 64: The apparatus of Aspect 57, wherein the battery box includes an exterior surface, an interior surface, and an interior volume.

[0182] Aspect 65: The device of Aspect 64, wherein one or more of the laminates cover at least a portion of the exterior surface, at least a portion of the interior surface, or both.

[0183] Aspect 66: The device of Aspect 64 or 65, wherein the interior volume is configured to contain the compression pad, the battery cell, the battery module, or the battery pack.

[0184] Aspect 67: The apparatus of Aspect 66, wherein the interior volume includes the compression pad, the battery cell, the battery module, the battery pack, or any combination thereof.

[0185] Aspect 68: The apparatus of any one of Aspects 57 to 67, wherein the compression pad, the battery cell, the battery module, the battery pack, or the battery box is included in a vehicle, and the vehicle includes one or more electric motors.

[0186] Aspect 69: The apparatus of Aspect 68, wherein the vehicle is an automobile, an aircraft, a train, a motorcycle, a watercraft, or a spacecraft.

[0187] Aspect 70: The apparatus of Aspect 51, which is a cable.

[0188] Aspect 71: The apparatus of Aspect 70, wherein the cable has a length and a width, the length being greater than the width.

[0189] Aspect 72: The apparatus of Aspect 70 or 71, wherein the cable is electrically conductive.

[0190] Aspect 73: The apparatus of any one of Aspects 70-72, wherein the cable comprises a diameter of 0.0003 inches to 10 inches, preferably 0.001 inches to 1 inch.

[0191] Aspect 74: The apparatus of any one of Aspects 70-73, wherein the cable is included in a missile, a rocket, a cannon, a manned aerial vehicle, an unmanned aerial vehicle, a ground vehicle, a sea vehicle, or a spacecraft.

[0192] Aspect 75: The apparatus of Aspect 74, wherein the vehicle is a spacecraft or an aircraft.

[0193] Aspect 76: The apparatus of any one of Aspects 51 to 75, wherein the one or more laminates are capable of maintaining a 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 between 500°C and 1,500°C, or more preferably between 700°C and 1,200°C, for a period of between 1 minute and 90 minutes, preferably at least 5 minutes.

[0194] Aspect 77: A method of thermally protecting a device of any one of Aspects 51-76, comprising bonding a laminate of any one of Aspects 1-50 to the device.

[0195] Aspect 78: The method of Aspect 77, wherein the stack is positioned relative to the device such that the front surface of the stack is positioned farther from the device than the rear surface of the stack.

[0196] Aspect 79: The method of Aspect 78, wherein the front surface of the laminate is exposed to a temperature of greater than 500°C to 1,500°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 that period.

[0197] Aspect 80: The method of Aspect 78, wherein the front surface of the laminate is exposed to a temperature of 700°C to 1,200°C for 1 minute to 90 minutes, preferably at least 5 minutes, and the temperature of the device does not exceed 500°C during that period.

[0198] Aspect 81: The laminate of any one of Aspects 1 to 50, wherein the flame-retardant layer includes a first flame-retardant layer and a second flame-retardant layer, the first and second flame-retardant layers being disposed on opposite sides of the aerogel layer.

[0199] Aspect 91: A reinforcing layer including fibers; a flame-retardant layer having a flammability rating according to UL94 5VA, UL94 5VB, or UL94 V-0; A porous insulation layer; a heat spreading layer (e.g., optional) comprising at least 90% by weight of metal or graphite; Including, A laminate having a thickness of 25.4 mm or less (e.g., 5 mm or less).

[0200] Aspect 92: The laminate of Aspect 91, wherein the porous insulating layer comprises an aerogel layer.

[0201] Aspect 93: The laminate of Aspect 91 or 92, wherein the fibers of the reinforcing layer include glass fibers or basalt fibers.

[0202] Aspect 94: The laminate of any one of aspects 91 to 93, wherein the fibers of the reinforcing layer are woven.

[0203] Aspect 95: The laminate has opposing front and rear surfaces; the reinforcing layer, the flame-retardant layer, and the heat-dispersing layer are each positioned closer to the front surface than the aerogel layer; A laminate of any one of aspects 91 to 94.

[0204] Aspect 96: The laminate of any one of Aspects 91 to 95, wherein the flame-retardant layer is positioned between the reinforcing layer and the aerogel layer.

[0205] Phase 97: Ejecta mitigation layer; a flame-retardant layer having a flammability rating according to UL94 5VA, UL94 5VB, or UL94 V-0; Porous insulation layer A laminate comprising: the laminate having opposing front and rear surfaces; the ejecta mitigation layer defines at least a majority of the front surface; Laminate.

[0206] Aspect 98: The laminate of Aspect 97, wherein the porous insulating layer comprises an aerogel layer.

[0207] Aspect 99: The laminate of Aspect 97 or 98, wherein the ejecta mitigation layer comprises at least 90% by weight metal.

[0208] Aspect 100: The laminate of Aspect 99, wherein the metal in the ejecta mitigation layer comprises titanium.

[0209] Aspect 101: The laminate of Aspect 97 or 98, wherein the ejecta mitigation layer comprises fibers.

[0210] Aspect 102: The laminate of aspect 101, wherein the fibers of the ejecta mitigation layer include fiberglass or basalt fibers.

[0211] Aspect 103: The laminate of Aspect 101 or 102, wherein the fibers of the ejecta mitigation layer are woven.

[0212] Aspect 104: The laminate of any one of Aspects 91 to 103, wherein the flame-retardant layer is inorganic.

[0213] Aspect 105: The laminate of any one of aspects 91 to 104, wherein the flame-retardant layer comprises paper.

[0214] Aspect 106: The laminate of any of Aspects 91-105, wherein the flame-retardant layer comprises at least 90% by weight of silicate.

[0215] Aspect 107: The laminate of any of Aspects 91-105, wherein the flame-retardant layer comprises at least 90% by weight ceramic.

[0216] Aspect 108: The laminate of any one of Aspects 91 to 107, wherein the flame-retardant layer has a thickness of 0.05 mm to 0.8 mm.

[0217] Aspect 109: The laminate of any one of Aspects 91-108, wherein the porous insulating layer comprises at least 50% by weight of polyimide.

[0218] Aspect 110: The laminate of any one of Aspects 91 to 109, wherein the flammability rating complies with UL94 5VA, UL94 5VB, or UL94 V-0.

[0219] Aspect 111: 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. The laminate of any one of aspects 91 to 110, including:

[0220] Aspect 112: The laminate of any one of aspects 91 to 111, including a second flame-retardant layer, the plurality of flame-retardant layers being disposed on opposing sides of the porous insulating layer.

[0221] Aspect 113: A device comprising the laminate of any of Aspects 91-112, the device comprising the laminate coupled to the device.

[0222] Aspect 114: The apparatus of aspect 113, which is a compression pad, a battery cell, a battery module, a battery pack, or a battery box.

[0223] Aspect 115: The apparatus of Aspect 113, wherein the apparatus is a conductive cable. [Example]

[0224] The present invention will now be described in detail by way of specific examples. The following examples are provided for illustrative purposes only and are not intended to limit the present invention in any way. Those skilled in the art will readily recognize a variety of non-critical parameters that can be changed or modified to achieve essentially the same results.

[0225] Example 1 (Flame and Thermal Barrier Laminate Testing) Materials. 12" x 1.6" x 0.2" copper rods were obtained from McMaster Carr. The AeroZero (AZ) film (6.5 mil thick) used was from Blueshift Materials Inc., and the flame retardant barrier material used was 3M FRB WT145 (5.8 mil thick) from 3M. Laminate test specimens were assembled using a pressure sensitive silicone adhesive, SA6101LR, from FLEXcon.

[0226] Test Setup. Flame and thermal barrier specimen effectiveness tests were performed using a bare copper rod as the test substrate. The copper rod was fixed horizontally to a support. A thermocouple was attached using Kapton tape to secure it to the center of the copper rod. The test specimen was wrapped around the copper rod prior to flame exposure.

[0227] The test sample was wrapped around 2 inches of a 12-inch copper rod, with the tip of the thermocouple directly contacting the copper rod directly below the test sample. The test sample was attached to the copper rod using a silicone pressure-sensitive adhesive. A flame source (Bunsen burner) with a flame temperature set at 700°C was positioned 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.

[0228] The test configuration is shown in Figure 12. As shown, the test setup 1200 included a copper rod 40, test specimens 42, 44, a thermocouple 46, and a flame source 48. The layups of the flame and thermal barrier test specimens 42, 44 are shown in Figure 13. Each included one or more AeroZero aerogel layers as the thermal insulation layer 16, with adhesive layers 20, 22 attaching the aerogel layers directly to the copper rod 40 and the flame retardant layer 18. The flame retardant layer 18 faced the flame source 48. Several specimens were tested, and their specific layups are listed in Table 1.

[0229] Table 1. Flame and thermal barrier test specimen layup TIFF2026503572000002.tif46136

[0230] The thermal profiles of the tested samples are shown in Figure 14. For each sample, the copper rod temperatures after 5 and 10 minutes of exposure to the flame are shown in Table 2. These temperatures were compared to a control sample, i.e., a copper rod without a barrier. This test showed that when one or two insulation layers (here, AeroZero film) were combined with a flame-retardant layer (here, FRM WT-145), the temperature of the copper rod was significantly reduced, thus demonstrating a surprising synergistic effect between the insulation and flame-retardant layers.

[0231] (Table 2) Temperature of copper rod during sample exposure to flame TIFF2026503572000003.tif41159

[0232] Examples 2 to 7 (Flame and Thermal Barrier Laminate Testing) 1000°C Flame Test Setup. Further testing of flame and thermal barrier samples was conducted using test setup 1500, shown in Figure 15. Test setup 1500 was substantially similar to test setup 1200, with the following exceptions: the flame was 3 inches high, 2 inches wide, had a temperature of 1000°C ± 30°C, and the base of the flame was positioned 2.5 inches away from the test sample 44. Additionally, some tests were conducted without a test substrate, while others were conducted with a test substrate comprising an 8-inch x 8-inch plate of aluminum, steel, and carbon fiber composite. In tests using a test substrate, instead of two samples 42 and 44, only one sample 44 was adhered to the flame-facing side of the test substrate. Finally, two thermocouples, 46a and 46b, were used. Thermocouple 46a was in direct contact with the flame to measure the flame temperature, and thermocouple 46b was placed on the laminate test sample (if no test substrate was used) or on the side of the test substrate facing away from the flame (i.e., "cold") All thermal profiles described in Examples 2-7 are based on the temperatures recorded by thermocouple 46b.

[0233] Example 2 Flame and thermal barrier laminate test specimens having the layups shown in Table 3 were exposed to a 1,000°C flame for 600 seconds (10 minutes). The laminate test specimens were not adhered to the test substrate. In this example, a laminate having only a flame retardant layer ("FRB") was compared to a laminate combining an FRB with a thermal insulation layer. The FRB tested was a FRB NT381 type manufactured by 3M.

[0234] Table 3: Flame and thermal barrier test specimen layup TIFF2026503572000004.tif31159

[0235] The thermal profiles of the samples in Table 3 are shown in Figure 16. As shown, the laminate containing the FRB and the thermal barrier exhibited both a lower initial heating rate and a lower temperature after 5 minutes (312°C vs. 341°C) than the laminate containing only the FRB.

[0236] Example 3 Flame and thermal barrier laminate test specimens having the layups shown in Table 4 were exposed to a 1,000°C flame for 25 minutes. The laminate test specimens were not adhered to the test substrate. In this example, one of the specimens included an additional heat dissipation layer (a 0.05 mm thick graphite layer) placed between the FRB facing the flame and one of the thermal insulation layers.

[0237] Table 4: Flame and thermal barrier test specimen layup TIFF2026503572000005.tif31159

[0238] The thermal profiles of the samples in Table 4 are shown in Figure 17. This data shows that adding a heat spreader layer between the FRB facing the flame and the thermal insulation layer further reduces the temperature of the cold side of the laminate. The primary heating rate of the laminate with the heat spreader layer was similar to that of the laminate without the heat spreader layer for about the first 3 minutes, but after 3 minutes, the laminate with the heat spreader layer outperformed the laminate without the heat spreader layer, including in terms of heating rate. These improvements are quantified in Table 5, which shows the cold side temperatures of the laminate at 5, 10, and 25 minutes of sample exposure to the flame.

[0239] Table 5: Laminate cold side temperatures during sample exposure to flame TIFF2026503572000006.tif31159

[0240] Example 4 Flame and thermal barrier laminate test specimens of three different thicknesses (0.57 mm, 0.70 mm, and 1.17 mm) were bonded to 0.7 mm thick 8 inch x 8 inch low carbon steel plates and exposed to a 1,000°C flame for 600 seconds (10 minutes). The laminate test specimen layups are shown in Table 6.

[0241] Table 6. Flame and Thermal Barrier Test Specimen Layup TIFF2026503572000007.tif33159

[0242] The thermal profiles of the samples in Table 6, along with the thermal profile of a control ("No FRB") consisting of a steel plate with no laminate attached, are shown in Figure 18. As the data show, both the primary heating rate (measured within the first 200 seconds) and the maximum temperature (measured at 600 seconds) of the cold side of the substrate decreased with increasing laminate thickness. In particular, for both the 0.70 mm and 1.17 mm thick laminates, the maximum temperature of the cold side of the substrate remained below 350°C during the 600 second (10 minute) flame exposure.

[0243] Example 5 Flame and thermal barrier laminate test specimens, including those with and without a 0.05 mm thick heat-dissipating graphite layer, were bonded to 1.0 mm thick 8 in. x 8 in. carbon fiber composite plates and exposed to a 1000°C flame for 25 minutes. The laminate test specimen layups are shown in Table 7.

[0244] Table 7. Flame and Thermal Barrier Test Specimen Layup TIFF2026503572000008.tif31159

[0245] Thermal profiles for the laminates in Table 7, along with a control ("No FRB") consisting of a carbon fiber composite plate with no laminate attached, are shown in Figure 19. Without the protective laminate, the carbon fiber composite plate began to burn within 10 seconds of exposure to the flame, generating a large amount of smoke. The temperature of the cold side of the carbon fiber composite plate rose rapidly, reaching 200°C within 40 seconds. The test was terminated due to the generation of large amounts of smoke and the decomposition of the carbon fiber composite plate. When protected with a flame and thermal barrier laminate without a heat dissipation layer, the initial heating rate was significantly reduced: it took approximately 2 minutes for the cold side of the carbon fiber composite plate to reach 200°C. Additionally, the maximum temperature of the cold side of the carbon fiber composite plate was 355°C after 10 minutes of flame exposure and did not increase further during the 25-minute test period.

[0246] The flame and thermal barrier laminate including the heat spreading layer showed improved performance with respect to both the primary heating rate and the maximum temperature of the cold side of the carbon fiber composite plate. In particular, the primary heating rate shifted slightly to the right, reaching 200°C after 2.8 minutes, and the maximum temperature of the cold side of the carbon fiber composite plate was 333°C during the 25 minute flame exposure. These improvements are further quantified in Table 8, which shows the substrate cold side temperatures at 5, 10, and 25 minutes of sample exposure to the flame.

[0247] Table 8: Substrate cold side temperatures during sample exposure to flame TIFF2026503572000009.tif31159

[0248] In addition, as shown in Figure 20, for both of the laminates in Table 7, no burn-through of the carbon fiber composite plate was observed during the test.

[0249] Example 6 A 1.17 mm thick FRB / AeroZero / AeroZero / FRB flame and thermal barrier laminate from Table 3 was bonded to an 8 inch by 8 inch aluminum sheet, 0.025 mm (1 mil) thick, and exposed to a 1,000°C flame for 25 minutes. The thermal profile of this laminate is shown in Figure 21. As shown, this thermal profile involves a gradual increase in the temperature of the aluminum sheet, reaching a maximum of 325°C during the 25 minute test: well below the melting point of aluminum. In fact, no burn-through of the aluminum sheet was observed during the test, which is shown in Figure 22.

[0250] Example 7 The thermal conductivity of several flame and thermal 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 Fox 50 heat flow meter manufactured by TA instruments. The layup, thermal conductivity, and density of the tested laminates are listed in Table 9.

[0251] Table 9. Flame and Thermal Barrier Test Sample Properties TIFF2026503572000010.tif68128

[0252] Examples 8-9 (Testing of Fire and Thermal Barrier Laminates Including Ejecta Mitigation Layers) Materials. Flame and thermal barrier laminates containing ejecta mitigation layers were prepared. Each laminate contained an aerogel layer, an FRB layer, and, for some laminates, a heat-dissipating graphite layer. These layers were laminated to each other and to one or more ejecta mitigation layers using pressure-sensitive silicone adhesive SA6101LR. The aerogel layer was 6.5 mil thick AZ film, and the FRB layer was 5.8 mil thick WT-145 or 15 mil thick NT-381. Two different ejecta mitigation layers were used. The first was a woven fiberglass layer manufactured by Fibre Glast Development Corp. with S2-glass fibers in a 6781 weave format. The second was a plain weave basalt fabric manufactured by Canadian Basalt, made from continuous rovings of basalt filaments. The properties of these ejecta mitigation layers are listed in Table 10.

[0253] (Table 10) Characteristics of the ejecta mitigation layer TIFF2026503572000011.tif32160

[0254] Measurement Method: The thickness of the sample laminates was measured by applying Method C of ASTM D374 / D374M-16, "Standard Test Method for Thickness of Solid Electrical Insulation." Five 2-inch diameter circles were cut from each sample laminate, and the thickness was measured at three points on each circle. The reported sample thickness is the average of these 15 measurements. The micrometer used was a Mitutoyo Electronic Thickness Gauge (No. 547-526S).

[0255] Density was calculated according to ASTM 202-17, "Standard Test Method for Sampling and Testing of Untreated Paper Used in Electrical Insulation." Five 2-inch diameter circles were cut from each sample laminate. The mass of each circle was measured using an analytical balance and divided by the volume of the circle to determine the density. The reported density is the average of these five measurements.

[0256] The basis weight of each sample laminate was obtained from ten 2-inch diameter circles cut from the laminate. The mass of each of these circles was measured using an analytical balance according to ASTM 202-17, "Standard Test Method for Sampling and Testing of Untreated Paper Used in Electrical Insulation," and divided by the surface area of ​​the circle to determine the basis weight. The reported basis weight is the average of these 10 measurements.

[0257] Thermal conductivity was obtained using a FOX 50 heat flow meter in accordance with ASTM C518-10, "Standard Test Method for Steady-State Heat Transfer Properties by Heat Flow Meter Apparatus." A 2-inch diameter circle was cut from each sample stack and stacked until a 3-mm thick stack with a uniform surface was obtained. The stack was placed between the plates of a FOX 50 analyzer. The hot and cold plate temperatures were maintained at 35°C and 15°C, respectively. Thus, thermal conductivity was measured at an average temperature of 25°C.

[0258] Flame Test Procedure. Each of the sample laminates tested was 8 inches by 8 inches, and the test setup of FIG. 15 was used without the test substrate 40. The gas flow rate to the flame source 48 and the distance between the flame and the test laminate 44 were maintained throughout the test. During the test, the bottom thermocouple 46a recorded a temperature of 1,000 ± 30°C. Each test was run for 10 minutes, during which time the cold side temperature of the test laminate was recorded using thermocouple 46b.

[0259] Example 8 Test Sample Layups. The specific layups of several laminates (S1-S4) tested, along with the properties of these laminates, are listed in Table 11. Test laminates (S1 and S2) without an ejecta mitigation layer were included for comparison purposes.

[0260] Table 11. Layup and properties of flame and thermal barrier test specimens TIFF2026503572000012.tif45163

[0261] Results. The thermal profiles of the sample stacks with ejecta layers (S3 and S4) are shown in Figure 23, and the thermal profiles of the sample stacks without ejecta layers (S1 and S2) are shown in Figure 24. For each of the test stacks, the temperature of the cold side of the stack and the difference between the temperature of the hot side and the temperature of the cold side of the stack at 5 and 10 minutes are shown in Table 12.

[0262] Table 12: Laminate temperatures during sample exposure to flame TIFF2026503572000013.tif58163

[0263] Finally, Figures 25-28 show the hot and cold sides of test laminates S1-S4, respectively, after 10 minutes of flame exposure.

[0264] Discussion: First, looking at Figures 25 and 26, the test laminates without the ejecta layer (S1 and S2) exhibited cracking on the hot side after 10 minutes of fire exposure. On the other hand, the test laminates with the ejecta layer maintained more structural integrity after 10 minutes of fire exposure. In fact, as shown in Figures 27 and 28, the test laminates with the ejecta layer exhibited no cracking on the hot side and minimal damage on the cold side with no burn-through.

[0265] The only difference between the test stacks containing ejecta layers was that one (S3) contained a fiberglass ejecta layer on its hot side, while the other (S4) contained a basalt fabric ejecta layer on its hot side. Although the laminate with the fiberglass ejecta layer was thicker than the laminate with the basalt fabric ejecta layer (1.50 mm vs. 1.29 mm, due to the thicker fiberglass layer than the basalt fabric layer), the laminate with the basalt fabric ejecta layer outperformed the laminate with the fiberglass ejecta layer in cold-side temperature (282°C vs. 328°C at 5 minutes, 301°C vs. 350°C at 10 minutes) and heating rate (Figure 23).

[0266] Furthermore, as can be seen from Figure 24 and Table 12, the laminate with the basalt fabric ejecta layer (S4) outperformed the similar sample laminate (S2) without the ejecta layer in terms of cold-side temperature. In fact, by adding the basalt fabric layer to S2 (S4), the cold-side temperature after 5 minutes of flame exposure decreased from 299°C to 282°C, and after 10 minutes of flame exposure decreased from 315°C to 301°C.

[0267] Example 9 Test Sample Lay-Ups: Flame and thermal barrier sample laminates having the lay-ups and properties shown in Table 13 were exposed to a 1,000°C flame for 10 minutes.

[0268] Table 13. Layup and properties of flame and thermal barrier test specimens TIFF2026503572000014.tif60163

[0269] The purpose of these tests was to further investigate the performance of the basalt fabric ejecta layers, including when multiple basalt fabric ejecta layers were included in the stack (S7-S9), and to investigate the performance of stacks containing additional aerogel layers.

[0270] Results. The thermal profiles of the sample laminates are shown in Figures 29-31, and the cold side temperatures and the difference between the hot side and cold side temperatures at 5 and 10 minutes for each of the test laminates are reported in Table 14.

[0271] Table 14: Laminate temperatures during sample exposure to flame TIFF2026503572000015.tif73161

[0272] After 10 minutes of flame exposure, Figure 32 shows the low and high temperature sides of S5, Figure 33 shows the low and high temperature sides of S6, Figure 28 shows the low and high temperature sides of S4, and Figures 34-36 show the low and high temperature sides of S7-S9, respectively.

[0273] Results. The structural integrity of the hot side of the sample stacks was good (Figures 32, 33, 28, and 34-36), likely the result of the basalt fabric ejecta layer; cracking only appeared in S7 (Figure 34) and S8 (Figure 35). Regarding the structural integrity of the cold side, only S5 (a relatively thin stack consisting of basalt fabric and aerogel layers) showed signs of burning (Figure 32); the cold sides of the other sample stacks remained intact with no burnout (Figures 28 and 33-36). In fact, the aerogel layers on the cold sides of S6-S8 were virtually undamaged. In all but S5, the basalt fabric ejecta layer remained well adhered to the stack, providing protection for the layers below.

[0274] Looking at performance based on temperature, it was generally observed that the thickness of the laminate was inversely proportional to the temperature of the cold side of the laminate. This can be seen by comparing the cold side temperature of the relatively thin (0.28 mm thick) laminate S5 with the cold side temperatures of the thicker (1.11-1.40 mm thick) laminates S4 and S6-S9. See also Figure 29.

[0275] Sample stacks containing two basalt fabric layers also showed improved cold-side temperatures compared to stacks containing only one basalt fabric layer. For example, S8 was similar to S6 except for the inclusion of an additional basalt fabric layer; its heating rate and cold-side temperature were significantly reduced compared to those of S6 (293°C vs. 338°C at 5 minutes, and 317°C vs. 354°C at 10 minutes). As a further example, S9 was similar to S4 except for the inclusion of an additional basalt fabric layer; S9 outperformed S4 in terms of cold-side temperature at 5 minutes (267°C vs. 282°C) and initial heating rate.

[0276] Additionally, improvements were observed in test laminates that contained more aerogel layers than the others. Laminate S8 had a similar layup to Laminate S7, except that it contained an additional aerogel layer. Laminate S8 showed a significant reduction in heating rate and cold-side temperature compared to Laminate S7 (293°C vs. 365°C at 5 minutes, and 317°C vs. 373°C at 10 minutes), despite only being approximately 10% thicker.

[0277] Example 10 (Flame and Thermal Barrier Laminates) Table 15 contains a list of flame and thermal barrier laminates made for use in mitigating battery thermal runaway events in battery powered vehicles or devices.

[0278] Table 15. Examples of Flame and Thermal Barrier Laminates for Mitigating Battery Thermal Runaway TIFF2026503572000016.tif98128

[0279] The foregoing specification and examples provide a complete description of the structure and use of exemplary embodiments. While certain embodiments have been described above in some detail or with reference to one or more individual embodiments, those skilled in the art may make numerous modifications to the disclosed embodiments without departing from the scope of the present invention. Therefore, it is not intended that the various exemplary embodiments of the apparatus and method be limited to the particular forms disclosed. Rather, they include all modifications and alternatives that fall within the scope of the claims, and embodiments other than those shown may include some or all of the features of the shown embodiments. For example, elements may be omitted or combined in a single structure and / or connections may be substituted. Furthermore, where appropriate, aspects of any of the above-described embodiments may be combined with aspects of any other of the above-described embodiments to form further embodiments having equivalent or different characteristics and / or functionality and addressing the same or different problems. Similarly, it will be understood that the benefits and advantages described above may relate to one embodiment or to several embodiments.

[0280] The claims are not intended to, and should not be construed as including, means-plus-function or step-plus-function limitations, unless such limitations are expressly recited in a given claim using the words "means" or "step," respectively.

Claims

1. a reinforcing layer including fibers; a flame-retardant layer having a flammability rating according to UL94 5VA, UL94 5VB, or UL94 V-0; A porous insulation layer; a heat dissipation layer containing at least 90% by weight of metal or graphite; Including, A laminate having a thickness of 5 mm or less.

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

3. 3. The laminate of claim 1 or 2, wherein the fibers of the reinforcing layer comprise glass fibers or basalt fibers.

4. The laminate of any one of claims 1 to 3, wherein the fibers of the reinforcing layer are woven.

5. the laminate has opposing front and rear surfaces; the reinforcing layer, the flame-retardant layer, and the heat-dispersing layer are each positioned closer to the front surface than the aerogel layer; The laminate according to any one of claims 1 to 4.

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

7. an ejecta mitigation layer; a flame-retardant layer having a flammability rating according to UL94 5VA, UL94 5VB, or UL94 V-0; Porous insulation layer A laminate comprising: the laminate having opposing front and rear surfaces; the ejecta mitigation layer defines at least a majority of the front surface; Laminate.

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

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

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

11. 9. The laminate of claim 7 or 8, wherein the ejecta mitigation layer comprises fibers.

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

13. 13. The laminate of claim 11 or 12, wherein the fibers of the ejecta mitigation layer are woven.

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

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

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

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

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

21. 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; 21. The laminate of any one of claims 1 to 20, comprising:

22. The laminate of any one of claims 1 to 21, comprising a second flame retardant layer, the plurality of flame retardant layers being disposed on opposite sides of the porous insulating layer.

23. 23. A device comprising the laminate of any one of claims 1 to 22, the device comprising the laminate bonded to said device.

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

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

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