BARRIER ARTICLES FOR RECHARGEABLE ELECTRICAL ENERGY STORAGE SYSTEMS - Patent application

Abstract

The barrier article includes a multi-layer article including a plurality of core layers and a plurality of binder layers, at least one core layer includes a woven or nonwoven fiber mat or fabric, and at least one binder layer includes a silicone material. The plurality of core layers and the plurality of binder layers are arranged in an alternating manner. The barrier article is operatively adapted to survive or withstand at least 7 cycles of a torch and grit test. The barrier article can be flexible and can provide, for example, a thermal insulation and blast protection barrier in a rechargeable electrical energy storage system.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 267,354, filed January 31, 2022, and U.S. Provisional Patent Application No. 63 / 375,780, filed September 15, 2022, which are incorporated by reference in their entireties herein.

[0002] The present invention relates to the use of a multi-layer material as a barrier article in a rechargeable electrical energy storage system, for example comprising a plurality of individual rechargeable battery cells or battery cell modules or battery cell module packs.

[0003] The present invention also relates to electric vehicle batteries, and in particular to a blast resistant and thermal insulating barrier article for managing thermal runaway events in battery cells / modules / packs. The provided article may be particularly useful in, for example, automotive, aircraft, marine, and stationary power storage applications. [Background technology]

[0004] Rechargeable or reloadable batteries or rechargeable electrical energy storage systems including several single battery cells, e.g., lithium ion cells, are known and used in a number of technical fields, including, for example, powering mobile phones, portable computers, or electric cars, electric vehicles, or hybrid cars.

[0005] It is also known that rechargeable battery cells, such as lithium-ion cells, can suffer from internal overheating caused by events such as short circuits within the cell, improper cell use, manufacturing defects, or exposure to extreme external temperatures. This internal overheating can result in so-called "thermal runaway" when the reaction rate within the cell caused by high temperatures increases to a point where more heat is generated within the cell than can be extracted, and the generated heat leads to a further increase in the reaction rate and thus a further increase in the heat generated. In a standard lithium-ion (Li-ion) battery configuration, for example, the heat generated within such a defective cell can reach 500°C to 1000°C in localized hot spots.

[0006] Next generation electric vehicle EV batteries will have higher energy than batteries used today. High energy batteries, such as those described as 811 (NMC or Nickel-Manganese-Cobalt Ratio) or similar energy density, can fail catastrophically if punctured or overheated. When this occurs, the ensuing battery fire can reach temperatures of over 1200°C as well as release shrapnel at moderate to high speeds. Battery packs are typically housed in aluminum shells, but because aluminum melts at 660°C, the shell must be protected from the flame and shrapnel of a failed battery to give electric vehicle occupants time to escape in the event of such a failure. Battery packs can also be encased in fiber-reinforced polymer composites, which, like aluminum, can fail at high temperatures.

[0007] Although some materials exist that can survive high temperature flames (i.e., tens of minutes in flames over 1200°C without breaking), these materials cannot withstand the blast associated with a high energy battery thermal runaway event. The severe risks posed by thermal runaway propagation require the design of battery modules with blast resistant and insulating barriers to mitigate the effects of such thermal runaway and allow time for vehicle occupants to safely exit in the event of a fire.

[0008] WO 2021 / 144758, the entirety of which is incorporated herein by reference, describes thermal barrier articles and torch and grit tests useful for determining thermal runaway and blast resistance properties. Summary of the Invention

[0009] In view of the above, there remains a need for suitable materials and configurations that help provide thermal insulation and prevent or reduce damage to adjacent materials and areas from blast particles emitted from a failed battery pack, and that are easy to use in the assembly process and provide flexibility in designing rechargeable electrical energy storage systems.

[0010] The present invention provides a barrier article comprising a multi-layer material, the multi-layer material including alternating core layers and binder layers.

[0011] In a first embodiment, at least one core layer comprises a woven or nonwoven fibrous mat or fabric, the woven or nonwoven fibrous mat or fabric comprising inorganic fibers.

[0012] In another embodiment, at least one binder layer comprises a silicone material, which may include a silicone polymer and may include one or more filler materials or additives.

[0013] In another aspect, the core layer of the multi-layer material may be the same throughout the multi-layer material, hi another aspect, the core layer of the multi-layer material may include different materials in some or all of the multiple core layers.

[0014] In another embodiment, the binder layers of the multi-layer material may be the same throughout the multi-layer material. In another embodiment, the binder layers of the multi-layer material may comprise different materials in some or all of the multiple binder layers.

[0015] In another embodiment, the multiple core layers comprises at least three core layers.

[0016] In another embodiment, the multiple binder layers comprises at least two binder layers.

[0017] In another embodiment, the core layer comprises a woven or nonwoven fiber mat or fabric comprising a plurality of fibers selected from the group consisting of A-glass, C-glass, D-glass, E-glass, M-glass, R-glass, S-glass, ECR-glass, AR-glass, basalt fibers, silicate fibers (e.g., Astroquartz fibers), silicon carbide fibers, ceramic fibers (e.g., Nextel fibers), or other inorganic fibers.

[0018] In another embodiment, the thermal barrier article is operatively adapted to survive or withstand at least 7 cycles or blasts of a torch and grit test (T>). In addition, the thermal barrier article has a ratio of the number of T> blasts withstood divided by the thickness of the sample of at least 4.4. In another example, the thermal barrier article has a ratio of the number of T> blasts withstood divided by the thickness of the sample of at least 4.6.

[0019] In another embodiment, the thermal barrier article is flexible such that it can bend at least 0.5% in a three-point bend test (per ASTM D790) before breaking.

[0020] In another aspect, the present invention provides a battery compartment of an electric vehicle comprising at least one battery cell or assembly and a thermal barrier article as described above.

[0021] In another aspect, a method of preventing or at least mitigating further spread of blast debris into or out of an electric vehicle battery assembly includes providing at least one battery cell of the electric vehicle battery assembly with the thermal barrier article described above.

[0022] Protection from the hazards associated with sudden thermal runaway events in electric vehicle batteries is a significant technological challenge.

[0023] The present invention addresses the challenges of conventional materials by providing a blast and heat resistant barrier article that combines multiple core layers and multiple binder layers in an alternating arrangement, with at least one core layer containing a woven or nonwoven fibrous mat or fabric that includes inorganic fibers, and each binder layer comprising a silicone material. The core and binder layers create a blast and heat barrier article that is operably adapted to survive or withstand at least one cycle of a torch and grit test. In electric vehicle battery applications, the combination of the specified core and binder layers can provide blast protection and a high degree of thermal insulation during exposure to fire. [Brief description of the drawings]

[0024] The present invention will now be described in more detail with reference to the following figures, which illustrate certain embodiments of the invention. [Figure 1] 1 is a schematic cross-sectional view of a barrier article according to an embodiment of the present invention. [Diagram 2] 1 is a schematic diagram of an exemplary battery compartment of an electric vehicle.

[0025] Repeat use of reference characters in the specification and drawings is intended to represent the same or similar features or elements of the present disclosure. It is to be understood that those skilled in the art can devise numerous other modifications and embodiments that are within the scope and spirit of the principles of the present disclosure. The figures may not be drawn to scale.

[0026] definition As used herein, "Thickness" means the distance between opposing surfaces of a layer or barrier article.

[0027] "Flexible" means that the material is non-brittle and can bend at least 0.5% in a three-point bend test (per ASTM D790) before breaking. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0028] As used herein, the term "operably adapted" refers to a structure that is designed, configured, and / or dimensioned to perform an identified function or performance.

[0029] As used herein, the terms "preferred" and "preferably" refer to embodiments described herein that may offer certain advantages, under certain circumstances, although other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

[0030] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to an element followed by "a" or "the" may include one or more of the element and equivalents thereof known to those skilled in the art. Furthermore, the term "and / or" refers to one or all of the listed elements or a combination of any two or more of the listed elements.

[0031] It should be noted that the term "comprises" and variations thereof do not have a limiting meaning when these terms appear in the accompanying description. Furthermore, "a", "an", "the", "at least one" and "one or more" are used interchangeably herein. Relative terms such as left, right, front, rear, top, bottom, side, above, below, horizontal, and vertical may be used herein, when referring to a perspective seen in a particular view. However, these terms are used merely for ease of description and in no way limit the scope of the invention.

[0032] Throughout this specification, reference to "one embodiment," "a particular embodiment," "one or more embodiments," or "an embodiment" means that the particular feature, structure, material, or characteristic described with respect to that embodiment is included in at least one embodiment of the invention. Thus, the appearances of phrases such as "in one or more embodiments," "in a particular embodiment," "in one embodiment," or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment of the invention.

[0033] According to one embodiment of the present invention, the barrier article comprises a multi-layer material. The multi-layer material comprises an alternating arrangement of multiple core layers (A) and multiple binder layers (B) (e.g., A / B / A / B / A / B). In a first aspect, at least one core layer comprises a woven or nonwoven fibrous mat or fabric, and the woven or nonwoven fibrous mat or fabric comprises inorganic fibers. In addition, at least one binder layer comprises a silicone material. The silicone material may comprise a silicone polymer and may further comprise one or more filler materials or additives.

[0034] The multi-layer material according to the invention can be used, for example, to ensure the overall safety of a vehicle equipped with a rechargeable electric energy storage system. The multi-layer material may include at least four layers with alternating material compositions. When applied to electric or hybrid vehicles, the alternating materials should have a suitable total thickness to accommodate the potentially constrained deployment space while still providing sufficient thermal properties and blast resistance.

[0035] To more safely enclose the battery pack in the event of thermal runaway, the lid of the battery housing should be protected from flame and debris from a failed battery with a flame- and blast-resistant lining, sometimes referred to as "under-lid" material.

[0036] Suitable materials for use as thermal insulation barriers must withstand high temperatures and pressures accompanied by gas venting and particle blowing without too much damage. In addition, the material must provide thermal and electrical insulation properties even during and after high temperatures, pressures, and gas and / or particle bombardment.

[0037] The multilayer material according to the present invention can be flexible. By "flexible" it is meant that the material is non-brittle and can bend at least 0.5% in a three-point bending test (according to ASTM D790) before breaking. The flexibility of the multilayer material allows for a wider use of the material and a more effective application of the material, since the flexibility allows the material to bend, thus allowing more options for its application in rechargeable electrical energy storage systems.

[0038] The multilayer material according to the present invention may include inorganic fabrics including A-glass, C-glass, D-glass, E-glass, M-glass, R-glass, S-glass, ECR-glass, AR-glass, basalt fibers, silicate fibers (Astroquartz fibers), silicon carbide fibers, ceramic fibers (e.g., Nextel fibers), other inorganic fibers, or combinations thereof. The fibers may be chemically treated. The inorganic fabrics may be, for example, single layer cloths, knitted fabrics, interwoven fabrics, and crocheted fabrics, or multilayer fabrics including woven or nonwoven fabric layers bonded together by stitching, mechanical entanglement, or inorganic adhesives, or combinations thereof.

[0039] In another embodiment, one core layer can include a woven or nonwoven mat of fibrous material as described above, while another core layer can include inorganic particles or fibers, such as inorganic paper or board, for example, an inorganic insulating paper containing glass fibers and microfibers, such as 3M CEQUIN, available from 3M Company (St. Paul, Minn., USA).

[0040] Each core layer may have a thickness in the range of, for example, 0.04 to 1.5 mm, for example, 0.1 to 0.6 mm. Each core layer may also have a thickness in the range of 35 to 1,500 g / m 2 (gsm). The diameter of the individual filaments may range from about 4 to about 13 micrometers. The number of filaments per yarn may vary from about 5 to 1000. Typical weave patterns may include plain, basket, twill, leno, 4 harness satin, 8 harness satin, and others typical in the industry. The warp and weft yarns may be of the same or different configurations.

[0041] In some embodiments, the binder layer comprises a silicone material and one or more fillers or additives.For example, the filler can include inorganic materials such as glass, ceramic, clay, silicate, mineral, flame retardant, smoke suppressant, heat absorbing agent, rheology modifier, and combinations thereof.The filler can be in the form of beads, solid particles, ground powder, flakes, needles, rods, chopped fibers, hollow spheres, hollow tubes, and combinations thereof.

[0042] Examples of clays or aluminosilicates include, but are not limited to, kaolin clay, talc, mica, wollastonite, montmorillonite, smectite, bentonite, illite, chlorite, sepiolite, attapulgite, halloysite, laponite, rectorite, perlite, and combinations thereof. Suitable types of kaolin clay include, but are not limited to, wet kaolin clay, delaminated kaolin clay, calcined kaolin clay, and surface treated kaolin clay.

[0043] Examples of minerals include, but are not limited to, calcite, aragonite, limestone, quartz, sphalerite, colemanite, ferberite, fluorspar, gypsum, rutile, and apatite.

[0044] In one preferred embodiment, the inorganic particulate filler comprises glass beads, calcined kaolin clay, and mixtures thereof.

[0045] Optionally, flame retardant additives, smoke suppressant additives, rheology modifiers, endothermic fillers, and mixtures thereof (e.g., alumina trihydrate, magnesium hydroxide, polyphosphates, and silicone tackifying resins) may be added. The total thickness of the multi-layered material may be 0.5 to 23 mm. In some applications where thinner materials are used, the total thickness of the multi-layered material may be 0.7 to 5 mm. It is possible to adjust the thickness of the material depending on the application in which the material is used. As already mentioned, the material may be flexible to improve the ease of application of the material in the assembly process and to help withstand shock and vibration in an automotive or other environment.

[0046] At least one binder layer may comprise a silicone-based material, such as a layer of a silicone adhesive, contact adhesive, pressure sensitive adhesive (PSA), B-stageable adhesive, or structural adhesive. In a preferred embodiment, at least one binder layer comprises a silicone-based material. Silicone-based materials can be crosslinked by condensation, addition, peroxide, or high energy radiation (e.g., electron beam or gamma) curing.

[0047] In another embodiment, one or more of the silicone-based material layers can further include a combination of silicone units M, D, T, and Q. The silicone-based material layers can include a silicone resin (e.g., an MQ or TQ resin), particularly a resin with a low M content.

[0048] In one embodiment, the binder layer comprises a silicone PSA (crosslinked silicone with a tackifying resin).

[0049] In another embodiment, the binder layer comprises 100% silicone (eg, polydimethylsiloxane, polydiphenylsiloxane).

[0050] In another embodiment, the binder layer comprises a silicone-MQ blend having up to 40% Silicone MQ.

[0051] In another embodiment, the binder layer comprises a silicone-MQ blend having 60% or more Silicone MQ.

[0052] In another embodiment, the binder layer comprises a silicone MQ blend of about 50% MQ in a silicone polymer.

[0053] In another embodiment, at least one of the plurality of binder layers can include a blend of silicone and inorganic clays and minerals, such as kaolin, metakaolin, calcined kaolin, talc, mica, mullite, phlogopite, muscovite, montmorillonite, smectite, bentonite, illite, chlorite, sepiolite, attapulgite, halloysite, vermiculite, laponite, rectorite, perlite, fly ash, fumed silica, silica fume, quartz, titanium dioxide, boron nitride, iron oxide, and other inorganic materials.

[0054] In another embodiment, at least one of the binder layers can include a filler material comprising solid glass particles. The solid glass particles can include one or more of glass beads, glass flakes, chopped glass fibers, glass shards, and crushed glass powder. These solid glass particles can have an average particle size of about 2 to about 300 micrometers. In another embodiment, the solid glass particles can have an average particle size of about 10 to about 100 micrometers. In another embodiment, the solid glass particles can have an average particle size of about 10 to about 80 micrometers. In another embodiment, the solid glass particles can have an average particle size of about 10 to about 60 micrometers. The size range of these particles can be relatively monodisperse, or the particles can have a wide particle size distribution. It can be advantageous to use a bimodal or trimodal distribution of particle sizes to increase the filler loading. For high aspect ratio glass particles, such as glass flakes or chopped glass fibers, the average size of the largest dimension can be about 1 mm to about 8 mm.

[0055] In another embodiment, at least one of the binder layers may include carbon black.

[0056] In another embodiment, at least one of the plurality of binder layers can further include chopped inorganic fibers.

[0057] As will be apparent from the description herein, each of the multiple binder layers can have the same or different composition and / or can have the same or different thickness.

[0058] The binder layer / adhesive can be coated directly onto one of the core layers and optionally dried, or can be preformed into a free-standing laminate film adhesive that can be applied to the surface of one of the core layers prior to contacting the next core layer. In an alternative embodiment, one or more of the core layers can be in the form of a tape with an adhesive layer (e.g., a pressure sensitive adhesive layer) already disposed on the core layer material.

[0059] In one preferred embodiment, the at least two core layers comprise a woven or nonwoven fiberglass mat or fabric and the at least two binder layers comprise a silicone with inorganic filler.

[0060] In one preferred embodiment, the at least two core layers each comprise a woven or nonwoven glass fiber mat or cloth, at least one binder layer can comprise a silicone with inorganic filler, and another binder layer can comprise a PSA.

[0061] In one preferred embodiment, the at least four core layers each comprise a woven or nonwoven fiberglass mat or cloth, and the at least four binder layers comprise a silicone with inorganic filler.

[0062] In one preferred embodiment, the at least four core layers each comprise a woven or nonwoven glass fiber mat or cloth, the at least three binder layers each comprise a silicone with inorganic filler, and another binder layer comprises a PSA.

[0063] In one preferred embodiment, the at least two core layers each comprise a woven or nonwoven fiberglass mat or cloth, and the at least two binder layers each comprise a silicone with an MQ resin.

[0064] In one preferred embodiment, at least two core layers each comprise a woven or nonwoven fiberglass mat or cloth, at least two binder layers each comprise a silicone with an MQ resin, and another binder layer comprises a PSA.

[0065] In one preferred embodiment, the at least four core layers each comprise a woven or nonwoven fiberglass mat or cloth, and the at least four binder layers each comprise a silicone with an MQ resin.

[0066] In one preferred embodiment, the at least four core layers each comprise a woven or nonwoven fiberglass mat or cloth, the at least three binder layers each comprise a silicone with an MQ resin, and another binder layer comprises a PSA.

[0067] In one preferred embodiment, the at least four core layers each comprise a woven or nonwoven fiberglass mat or cloth, and the at least three binder layers each comprise a silicone with inorganic filler.

[0068] In one preferred embodiment, the at least four core layers each comprise a woven or nonwoven fiberglass mat or cloth, and the at least three binder layers each comprise a silicone with an MQ resin.

[0069] In one preferred embodiment, at least two core layers each comprise a woven or nonwoven glass fiber mat or cloth, at least one binder layer comprises a silicone pressure sensitive adhesive, and one binder layer comprises a blend of silicone and glass beads.

[0070] Embodiments of the present invention also relate to a rechargeable electrical energy storage system having at least one battery cell and a barrier article as described above.

[0071] Embodiments of multi-layer materials according to the present invention can be used, for example, as barrier articles that help increase the overall safety of vehicles equipped with rechargeable electrical energy storage systems.

[0072] The multi-layer material may be disposed within a rechargeable electrical energy storage system such that the core layer faces at least one battery cell / pack / module. The core layer is selected to have high resistance to temperature and other shocks as may occur during a thermal runaway event.

[0073] The rechargeable electrical energy storage system according to the invention may provide a barrier article arranged between at least one battery cell and the lid of the storage system. The barrier article may, for example, be fixed to the lid. Or a multi-layer material may be placed between the battery cell and the lid. The barrier article may be used in such a position as an insulating barrier for the lid or to protect the lid and any system or component arranged adjacent to the lid. It may also be used as an insulating barrier for any electrical components around the battery cell or battery pack, such as for example cables or bus bars. If the barrier article provides additional electrical insulation properties, it may also reduce / prevent short circuits due to deformation or other harm, for example heated electrical insulation around different battery systems. Another possibility is to arrange the barrier article so as to cover the burst plate of at least one battery cell. Of course, the barrier article may also be positioned in the rechargeable electrical energy storage system to meet all of the above-mentioned requirements. As already mentioned above, it may be advantageous to position the barrier article according to the invention so that the core layer faces the at least one battery cell, in particular so that the core layer faces the burst plate of the battery cell.

[0074] Additionally, the use of the barrier articles according to the present invention is not limited to use in any particular type of rechargeable electrical energy storage system, for example, they may be used in rechargeable electrical energy storage systems that include prismatic battery cells, pouch cells, or cylindrical cells.

[0075] Additionally, the use of the barrier articles according to the present invention is not limited to use in any particular type of vehicle.

[0076] Various embodiments of the present invention are described herein below and illustrated in the drawings, where like elements are designated with the same reference numerals.

[0077] Figure 1 shows a cross-sectional view of a barrier article 1 according to the present invention. The barrier article of Figure 1 includes multiple core layers 2 and multiple binder layers 3. In this example, the barrier article 1 includes three core layers 2 and two binder layers 3. In other embodiments, the barrier article can include 2, 4, 5, 6, 7, 8, 9, 10 (or more) alternating core layers and 2, 3, 4, 5, 6, 7, 8, 9 (or more) binder layers.

[0078] 2 is a schematic diagram of a rechargeable electrical energy storage system 5. The system includes prismatic battery cells 6, each equipped with a burst plate 7 for releasing potentially generated excess pressure through a vent hole, for example in case of a thermal runaway event. The cells 6 are disposed in a housing 8 (two walls, one front wall and one side wall, are shown as open, but are in fact closed). The housing is provided with a lid 9.

[0079] As already mentioned above, regulations require that rechargeable energy storage systems be constructed so as not to cause external fire. One area that needs to be protected is the area above the burst plate 7. The portion of the system located above the burst plate requires a thermal barrier to avoid battery burn-through and open flame on the outside of the system. In accordance with the present invention, a barrier article 1, shown in FIG. 1, is placed between the battery cells 6 / burst plate 7 and the lid 9.

[0080] The multi-layer material 1 may also be placed between the cells 6 and a side or bottom wall of the housing 8 (not shown).

[0081] The blast-resistant and thermal barrier articles described herein may, in some embodiments, be effective in mitigating the effects of thermal runaway propagation in Li-ion batteries. These articles may also have potential applications in other commercial and industrial applications, such as automotive, residential, industrial, marine, and aerospace applications, where people or surrounding structures need to be protected from the effects of flying debris or thermal fluctuations. For example, the blast-resistant and thermal barrier articles may be incorporated into major structural parts that run along or around a vehicle or building compartment structure to protect users and occupants. Such applications may include protection around battery modules, fuel tanks, and any other enclosures or compartments.

[0082] Further components, their construction, and test methods are described in the subsections below.

[0083] Furthermore, the particle size of the inorganic filler particles in the binder layer may only be limited by the thickness of the binder layer. Typically, the inorganic filler particles have a maximum particle size of about 8000 micrometers (μm) in at least one dimension. More typically, the inorganic filler particles have a particle size in the range of about 0.1 μm to about 2000 μm in at least one dimension. Even more typically, the inorganic filler particles have a particle size in the range of about 0.2 μm to about 50 μm in at least one dimension.

[0084] These layers, and successive layers, are shown in Figure 1 as being in flat contact with one another, however, it should be understood that the layers of barrier article 1 are flexible and the contact areas between the layers need not be flat, or even continuous.

[0085] The barrier article 1 of FIG. 1 can be placed in one or more locations within a battery module of an electric vehicle. Typically, multiple battery cells are structurally aligned and secured within a battery compartment. The battery cells can be of any shape (e.g., cylindrical or rectangular) or size. Gaps generally exist between each of the battery cells and / or between the battery cells and the walls of the battery compartment. The barrier article can be secured to a compartment lid or placed on the walls of the battery compartment.

[0086] Exemplary embodiments 1. A thermal barrier article comprising: a plurality of core layers, at least one of the core layers comprising a woven or nonwoven fiber mat or fabric; a plurality of binder layers, at least one of the binder layers comprising a silicone material, the plurality of core layers and the plurality of binder layers being arranged in alternating fashion; The thermal barrier article is operably adapted to survive or withstand at least 7 cycles of a torch and grit test (T>).

[0087] 2. The thermal barrier article of embodiment 1, wherein the woven or nonwoven fiber mat or fabric comprises a plurality of inorganic fibers.

[0088] 3. The thermal barrier article of embodiment 1 or 2, wherein the woven or nonwoven fiber mat or fabric comprises a plurality of fibers selected from the group consisting of A-glass, C-glass, D-glass, E-glass, M-glass, R-glass, S-glass, ECR-glass, AR-glass, basalt fibers, silicate fibers (e.g., Astroquartz fibers), silicon carbide fibers, ceramic fibers (e.g., Nextel fibers), or combinations thereof.

[0089] 4. The thermal barrier article of any one of embodiments 1-3, wherein each of the plurality of binder layers comprises a silicone polymer.

[0090] 5. The thermal barrier article of embodiment 4, wherein the silicone polymer further comprises a filler material or additive.

[0091] 6. The thermal barrier article of any one of embodiments 1-5, wherein the thermal barrier article has a thickness in the range of about 0.5 mm to about 10.0 mm.

[0092] 7. The thermal barrier article of any one of the preceding claims, comprising at least three core layers and at least two binder layers.

[0093] 8. The thermal barrier article of any one of the preceding claims, wherein each of the multiple core layers comprises the same material.

[0094] 9. The thermal barrier article of any one of the preceding claims, wherein at least two of the core layers comprise different materials.

[0095] 10. The thermal barrier article of any one of the preceding embodiments, wherein at least two of the binder layers comprise different materials.

[0096] 11. The thermal barrier article of any one of the preceding embodiments, comprising at least four core layers and at least three binder layers.

[0097] 12. The thermal barrier article of any one of the preceding embodiments, wherein each core layer has a thickness of from about 0.04 mm to about 1 mm.

[0098] 13. The thermal barrier article of any one of embodiments 1-12, wherein each core layer has a thickness of about 0.1 mm to about 0.6 mm.

[0099] 14. The thermal barrier article of any one of the preceding embodiments, wherein at least one binder layer comprises a solid glass particle filler material.

[0100] 15. The thermal barrier article of any one of the preceding embodiments, wherein the solid glass particle filler material has an average size of from about 10 micrometers to about 60 micrometers.

[0101] 16. The thermal barrier article of any one of the preceding claims, wherein the thermal barrier article has a ratio of T>blasts endured divided by sample thickness of at least 4.4.

[0102] 17. The thermal barrier article of any one of embodiments 1-5, operably adapted such that the thermal barrier article has a ratio of number of blasts survived to total thickness of at least 6.5.

[0103] 18. The thermal barrier article of any one of the preceding embodiments, wherein the barrier article is flexible such that it can bend at least 0.5% in a three-point bend test (per ASTM D790) before breaking.

[0104] 19. A battery compartment of an electric vehicle comprising at least one battery cell or assembly, wherein a thermal barrier article described in any one of embodiments 1-18 is disposed between the at least one battery cell or assembly and a lid.

[0105] 20. A method of preventing or at least mitigating further spread of blast debris into or from an electric vehicle battery assembly, comprising: A method comprising at least partially surrounding at least one battery cell or module of an electric vehicle battery assembly with the thermal barrier article of any one of embodiments 1-18.

[0106] 21. Use of a barrier article as an insulating and blast protection barrier in a rechargeable electrical energy storage system, the barrier article comprising: a plurality of core layers, at least one of the core layers comprising a woven or nonwoven fiber mat or fabric; a plurality of binder layers, at least one binder layer comprising a silicone material, the plurality of core layers and binder layers being arranged in alternating fashion; The thermal barrier article is operably adapted to survive or withstand at least 7 cycles of a torch and grit test (T>).

[0107] 22. The use of a barrier article according to embodiment 21, wherein the woven or nonwoven fiber mat or fabric comprises a plurality of inorganic fibers.

[0108] 23. The use of a barrier article according to embodiment 21 or 22, wherein the woven or nonwoven fiber mat or fabric comprises a plurality of fibers selected from the group consisting of A-glass, C-glass, D-glass, E-glass, M-glass, R-glass, S-glass, ECR-glass, AR-glass, basalt fibers, silicate fibers, silicon carbide fibers, ceramic fibers (e.g., Nextel fibers), or combinations thereof.

[0109] 24. The use of a barrier article according to any one of embodiments 21 to 23, wherein each of the binder layers comprises a silicone polymer.

[0110] 25. The use of a barrier article according to any one of embodiments 21 to 24, wherein the silicone polymer further comprises a filler material or an additive.

[0111] 26. The use of a barrier article according to any one of embodiments 21 to 25, wherein at least one binder layer comprises a solid glass particle filler material.

[0112] 27. The use of a barrier article according to any one of embodiments 21 to 26, wherein the solid glass particle filler material has an average size of from about 10 micrometers to about 60 micrometers.

[0113] 28. Use of a barrier article according to any one of embodiments 21 to 27, wherein the thermal barrier article has a ratio of T>blasts withstood divided by sample thickness of at least 4.4.

[0114] 29. The use of a barrier article according to any one of embodiments 21 to 28, wherein the thermal barrier article has a thickness in the range of about 0.5 mm to about 10.0 mm.

[0115] 30. The use of a barrier article according to any one of embodiments 21 to 29, comprising at least three core layers and at least two binder layers.

[0116] 31. The use of a barrier article according to any one of embodiments 21 to 30, wherein each of the multiple core layers comprises the same material.

[0117] 32. The use of a barrier article according to any one of embodiments 21 to 31, wherein at least two of the core layers comprise different materials.

[0118] 33. The use of a barrier article according to any one of embodiments 21 to 32, wherein at least two of the binder layers comprise different materials.

[0119] 34. The use of a barrier article according to embodiment 21 or 22, comprising at least four core layers and at least three binder layers.

[0120] 35. The use of a barrier article according to any one of embodiments 21 to 34, wherein the barrier article is flexible such that it can bend at least 0.5% in a three-point bending test (according to ASTM D790) before breaking.

[0121] Experiments and Examples

[0122] [Table 1]

[0123] Torch and Grit Testing For the torch and grit test (T>), each sample was mounted on an aluminum backing plate using mechanical clamps or adhesive tape. The sample was then placed in a horizontal sliding fixture in front of a Bethlehem Champion hydrogen torch (obtained from Bethlehem Apparatus Company Inc, Hellertown, PA, USA) at a distance of 60 mm (2.375 in.) from the sample surface to the hydrogen torch face. The torch temperature was set at 1200°C and measured by a K-type thermocouple 25.4 mm (1 in.) away from the torch face. The media blaster gun was loaded with 120 grit aluminum oxide unformed media and aligned with the center nozzle of the torch (nozzle 10 diameter = 0.185 in. to 0.188 in.) at the same distance (60 mm) from the sample. The media blaster gun was supplied with 172 kPa (25 psi) compressed air and the flow rate was controlled at 50 LPM when started for media blasting.

[0124] The test involved moving the sample into position and exposing it to the torch flame for 5 seconds before commencing the first media blast. One test cycle consisted of one 10 second media blast (with torch flame) and one 10 second exposure to the torch flame only for a total of 20 second test cycles. The test was stopped after the sample was exposed to 16 cycles or when the sample material was eroded away to expose the backing plate.

[0125] T> is a modified version of the torch and grit test described in WO 2021 / 144758(A1), which is incorporated by reference above.

[0126] Throughout this application and in the examples below, the terms "blast" and "cycle" of T> are used interchangeably. For example, if a sample survives 7 blasts of T>, it will survive 7 cycles of T>, and vice versa.

[0127] Insulation Flame Test One side of the specimen, measuring approximately 200 × 200 mm, was painted black with Flat Black Automotive High Heat Paint. The specimen was placed horizontally on a fixture, painted side up and unpainted side down, centered over the torch. The flame temperature at the point where the flame contacted the specimen was targeted to be 1200°C, as measured by a thermocouple placed on the underside of the specimen in the flame. The underside of the specimen was exposed to the flame for 10 minutes, while the topside was left at ambient conditions (approximately 22°C). The painted topside of the specimen exposed to ambient conditions was measured every 30 seconds by a fixed handheld IR thermometer (Westward model number 54TZ30) and videotaped with a FLIR camera (Teledyne FLIR T440 Thermal Imaging Camera, Teledyne FLIR LLC, flir.com). The maximum temperature at the center of the specimen, measured by the handheld IR thermometer, was recorded at 10 minutes. EXAMPLES

[0128] Comparative Example 1 (CE1): Nine layers of 3M™ Glass Cloth Electrical Tape 79 with an acrylic adhesive were laminated onto a 102×102 mm aluminum plate. Two CE1 specimens were prepared and subjected to T>. Both specimens of Comparative Example 1 withstood or survived 4 cycles (or blasts) of T>. Flame and particles reached the aluminum plate during the fifth blast. During the torch and grit tests, the burning of the acrylic adhesive was evident from large flames emanating from the surface and edges of the structure. Substantially the entire area facing the flame and blast was blackened as the organic adhesive burned from the flame, and the remaining layers of glass cloth that were not blasted in the center portion of the blast had separated.

[0129] Comparative Example 2 (CE2): Sylgard 184 was cured to a thickness of 1.56 mm, trimmed to a 102 x 102 mm square, and mounted onto a 102 x 102 mm aluminum plate using 3M™ Adhesive Transfer Tape 91022. Two Comparative Example 2 specimens were made, each surviving T>3 blasts. Flames and particles reached the aluminum plate during the fourth blast.

[0130] Comparative Example 3 (CE3): One layer of 3M™ Glass Cloth Electrical Tape 69 with Silicone Adhesive was adhered to one side of a silicone foam substrate. A second layer of 3M™ Glass Cloth Electrical Tape 69 with Silicone Adhesive was adhered to the opposite side of the silicone foam substrate. Two of these 3.79 mm thick structures were cut to 102 x 102 mm and adhered to a 102 x 102 mm aluminum plate with 91022 silicone transfer tape. Both Comparative Example 3 specimens survived T>3 blasts. Flames and particles reached the aluminum plate during the fourth blast.

[0131] Comparative Example 4 (CE4): 12 layers of 0.14 mm e-glass cloth were placed on top of each other and laser cut to a 102×102 mm square and fused together at the edges. This was tacked to the four corners of a 102×102 mm aluminum plate with 4 drops of Sylgard 184. The 4 drops of Sylgard 184 were far away from the center of the specimen where the torch and grit test was focused, ensuring that only the glass cloth was in the test area. Two structures were made in this manner, both Comparative Example 4 survived the torch and grit test for 6 blasts, with flames and particles reaching the aluminum panel during the 7th blast.

[0132] Comparative Example 5 (CE5): A mixture of 55.0% Sylgard 184 and 45.0% KaMin 70C was cured to a thickness of 1.49 mm, trimmed to a 102 x 102 mm square, and mounted onto a 102 x 102 mm aluminum plate with 3M™ Adhesive Transfer Tape 91022. Two Comparative Example 5 specimens were made and survived an average of T>4.5 blasts.

[0133] Comparative Example 6 (CE6): A mixture of 30.7 weight percent AK 1000000, 2.3 weight percent DDCBP-50, and 67.0 weight percent Spheriglass 3000 was cured to a thickness of 1.57 mm, trimmed to a 102×102 mm square, and mounted onto a 102×102 mm aluminum plate using 3M™ Adhesive Transfer Tape 91022. One Comparative Example 6 specimen was made and survived T>4 blasts. Flames and particles reached the aluminum plate during the fifth blast.

[0134] Comparative Example 7 (CE7): Eight layers of 3M 79 glass cloth electrical tape (acrylate adhesive) were adhesively bonded together to glass cloth to produce a total of 16 layers within an area of ​​(approximately) 200 x 200 mm. The resulting laminated structure was bendable and flexible. This structure was tested in the Insulation Flame Test. After 10 minutes exposure to flame, the ambient side of the structure was 362°C, with a temperature delta of 838°C relative to the torch side of the sample at 1200°C.

[0135] Example 1 (EX1): Nine layers of 3M™ Glass Cloth Electrical Tape 69 with silicone adhesive were laminated onto a 102×102 mm aluminum plate. Averaged over two tests, this 1.45 mm thick structure survived 12 blasts T>. During T>, there was little flaming of the silicone adhesive, in contrast to Comparative Example 1 with an organic adhesive, and more of the glass cloth retained its original white color after the test was completed.

[0136] Example 2 (EX2): A mixture of 55 weight percent Sylgard 184 and 45 weight percent KaMin 70C was blended together. A bead of this mixture was placed on one end of a layer of 0.14 mm e-glass cloth in a cross web, and another layer of 0.14 mm e-glass cloth was placed on top. The structure was pulled through a notch bar nip to spread the Sylgard 184 / KaMin 70C mixture evenly between the glass cloth layers, and then the structure was placed in an oven to cure the silicone. The result was a 1.50 mm thick interlaminate structure of glass cloth and Sylgard 184 / KaMin 70C. Two 102 x 102 mm sections were cut from this and laminated with 91022 silicone transfer tape onto 102 x 102 mm aluminum plates. On average over two tests, Example 2 survived T>7 blasts.

[0137] Example 3 (EX3): A mixture of 52.4 weight percent AK 1000000, 2.6 weight percent DDCBP-50, and 45 weight percent Burgess KE was blended together. A bead of this mixture was placed cross-web at one end of a layer of 0.14 mm e-glass cloth, and another layer of 0.14 mm e-glass cloth was placed on top. The structure was pulled through a notch bar nip to spread the filled silicone mixture evenly between the layers of glass cloth, and then the structure was placed in an oven to cure the silicone. The result was a 1.58 mm thick interlaminate structure of glass cloth and filled silicone. Two 102 x 102 mm sections were cut from this and laminated onto 102 x 102 mm aluminum plates with 91022 silicone transfer tape. Averaging over two tests, Example 3 survived an average of 10.5 blasts T>.

[0138] Example 4 (EX4): A mixture of 25.0 weight percent AK 1000000, 1.25 weight percent DDCBP-50, and 73.8 weight percent Spheriglass 3000 was blended together. A bead of this mixture was placed cross-web at one end of a layer of 0.14 mm e-glass cloth, and another layer of 0.14 mm e-glass cloth was placed on top. The structure was pulled through a notch bar nip to spread the filled silicone mixture evenly between the layers of glass cloth, and then the structure was placed in an oven to cure the silicone. The result was a 1.52 mm thick interlaminate structure of glass cloth and filled silicone. Two 102 x 102 mm sections were cut from this and laminated with 91022 silicone transfer tape onto 102 x 102 mm aluminum plates. Averaging over two tests, Example 4 survived an average of 12 blasts T>.

[0139] Example 5 (EX5): A mixture of 32.4 weight percent AK 1000000, 1.6 weight percent DDCBP-50, 22.0 weight percent KaMin 70C, and 44.0 weight percent Spheriglass 3000 was blended together. A bead of this mixture was placed on one end of a layer of 0.14 mm e-glass cloth in a cross web, and another layer of 0.14 mm e-glass cloth was placed on top. The structure was pulled through a notch bar nip to spread the filled silicone mixture evenly between the layers of glass cloth, and then the structure was placed in an oven to cure the silicone. The result was a 1.53 mm thick interlaminate structure of glass cloth and filled silicone. Two 102 x 102 mm sections were cut from this and laminated with 91022 silicone transfer tape onto 102 x 102 mm aluminum plates. Averaging over two tests, Example 5 survived an average of 11 blasts T>.

[0140] Example 6 (EX6): A mixture of 32.4 weight percent AK 1000000, 1.6 weight percent DDCBP-50, 22.0 weight percent Burgess KE, and 44.0 weight percent Spheriglass 3000 was blended together. A bead of this mixture was placed on one end of a layer of 0.14 mm e-glass cloth in a cross web, and another layer of 0.14 mm e-glass cloth was placed on top. The structure was pulled through a notch bar nip to spread the filled silicone mixture evenly between the layers of glass cloth, and then the structure was placed in an oven to cure the silicone. The result was a 1.56 mm thick interlaminate structure of glass cloth and filled silicone. Two 102 x 102 mm sections were cut from this and laminated with 91022 silicone transfer tape onto 102 x 102 mm aluminum plates. Averaging over two tests, Example 6 survived an average of 11.5 blasts T>.

[0141] Example 7 (EX7): A mixture of 90 weight percent Silopren 242-3 and 10 weight percent Satintone SP33 was blended together. A bead of this mixture was placed on one end of a layer of 0.14 mm e-glass cloth in a cross web. Another layer of 0.14 mm e-glass cloth was placed on top of this structure. Another bead of Silopren 242-3 / Satintone SP33 mixture was placed on top of a second layer of glass cloth. This procedure was repeated until there were six layers of glass cloth with five layers of beads of Silopren 242-3 / Satintone SP33 mixture between them. The structure was pulled through a notch bar nip to spread the Silopren 242-3 / Satintone SP33 mixture evenly between the glass cloth layers, and then the structure was placed in an oven to cure the silicone. The result was a 1.46 mm thick layer-by-layer structure of glass cloth and Silopren 242-3 / Satintone SP33. Two 102x102 mm sections were cut from this and laminated onto 102x102 mm aluminum plates with 91022 silicone transfer tape. Averaged over two tests, Example 7 survived T>7.5 blasts.

[0142] Example 8 (EX8): A mixture of 40 weight percent Sylgard 184 and 60 weight percent Mattex Pro was blended together. A bead of this mixture was placed on one end of a layer of 0.06 mm e-glass cloth in a cross web, and another layer of 0.06 mm e-glass cloth was placed on top. The structure was pulled through a notch bar nip to spread the Sylgard 184 / Mattex Pro mixture evenly between the layers of glass cloth, and then the structure was placed in an oven to cure the silicone. The result was a 1.60 mm thick interlaminate structure of glass cloth and Sylgard 184 / Mattex Pro. Two 102 x 102 mm sections were cut from this and laminated with 91022 silicone transfer tape onto 102 x 102 mm aluminum plates. Averaged over two tests, Example 8 survived a T> of 7.5 blasts.

[0143] Example 9 (EX9): A mixture of 47.2 weight percent Sylgard 184, 42.8 weight percent Suzorite 20S, and 10.0 weight percent Spheriglass 3000 was blended together. A bead of this mixture was placed on one end of a layer of 0.14 mm e-glass cloth in a cross web. Another layer of 0.14 mm e-glass cloth was placed on top of the structure. Another bead of Sylgard 184 / Suzorite 20S / Spheriglass 3000 mixture was placed on top of a second layer of glass cloth, and a third layer of glass cloth was placed on top of the structure. The structure was pulled through a notch bar nip to spread the Sylgard 184 / Suzorite 20S / Spheriglass 3000 mixture evenly between the layers of glass cloth, and then the structure was placed in an oven to cure the silicone. The result was a 1.64 mm thick laminated structure of glass cloth and Sylgard 184 / Suzorite 20S / Spheriglass 3000. Two 102 x 102 mm sections were cut from this and laminated with 91022 silicone transfer tape onto 102 x 102 mm aluminum plates. Averaged over two tests, Example 9 survived T>10 blasts.

[0144] Example 10 (EX10): A mixture of 55 weight percent Sylgard 184 and 45 weight percent KaMin 70C was blended together. A bead of this mixture was placed on one end of a layer of 0.14 mm e-glass cloth in a cross web. Another layer of 0.14 mm e-glass cloth was placed on top of this structure. Another bead of Sylgard 184 / KaMin 70C mixture was placed on top of a second layer of glass cloth. This procedure was repeated until there were 8 layers of glass cloth with 7 layers of Sylgard 184 / KaMin 70C mixture between them. The structure was pulled through a notch bar nip to spread the Sylgard 184 / KaMin 70C mixture evenly between the glass cloth layers, and then the structure was placed in an oven to cure the silicone. The result was a 1.53 mm thick layer-by-layer structure of glass cloth and Sylgard 184 / KaMin 70C. Two 102x102 mm sections were cut from this and laminated with 91022 silicone transfer tape onto 102x102 mm aluminum plates. Averaged over two tests, Example 10 survived T>7 blasts.

[0145] Example 11 (EX11): A mixture of 30.7 weight percent AK 1000000, 2.3 weight percent DDCBP-50, 60.0 weight percent Spheriglass 3000, and 7.0 weight percent KaMin 70C was blended together. A bead of this mixture was placed on one end of a layer of 0.14 mm e-glass cloth in a cross web, and a layer of 0.14 mm e-glass cloth was placed on top. The structure was pulled through a notch bar nip to spread the filled silicone mixture evenly between the layers of glass cloth, and then the structure was placed in an oven to cure the silicone. The result was a 1.56 mm thick interlaminate structure of glass cloth and filled silicone. Two 102 x 102 mm sections were cut from this and laminated onto 102 x 102 mm aluminum plates with 91022 silicone transfer tape. Averaging over two tests, Example 11 survived an average of 10.5 blasts T>.

[0146] Example 12 (EX12): A mixture of 30.7 weight percent AK 1000000, 2.3 weight percent DDCBP-50, 60.0 weight percent Spheriglass 3000 CP-01, and 7.0 weight percent KaMin 70C was blended together. A bead of this mixture was placed on one end of a layer of 0.14 mm e-glass cloth in a cross web, and a layer of 0.14 mm e-glass cloth was placed on top. The structure was pulled through a notch bar nip to spread the filled silicone mixture evenly between the layers of glass cloth, and then the structure was placed in an oven to cure the silicone. The result was a 1.54 mm thick interlaminate structure of glass cloth and filled silicone. Two 102 x 102 mm sections were cut from this and laminated with 91022 silicone transfer tape onto 102 x 102 mm aluminum plates. Averaging two tests, Example 12 survived an average of 9 blasts T>.

[0147] Example 13 (EX13): A mixture of 46.5 weight percent AK 1000000, 3.5 weight percent DDCBP-50, and 50 weight percent Spheriglass 3000 was blended together. A bead of this mixture was placed on one end of a layer of 0.14 mm e-glass cloth in a cross web, and a layer of 0.61 mm e-glass cloth was placed on top. The structure was pulled through a notch bar nip to spread the filled silicone mixture evenly between the layers of glass cloth, and then the structure was placed in an oven to cure the silicone. The result was a 0.93 mm thick interlaminate structure of glass cloth and filled silicone. Two 102 x 102 mm sections were cut from this and laminated onto 102 x 102 mm aluminum plates with 91022 silicone transfer tape. Averaging over two tests, Example 13 survived an average of 13.5 blasts T>.

[0148] Example 14 (EX14): A mixture of 46.5 weight percent AK 1000000, 3.5 weight percent DDCBP-50, and 50 weight percent Spheriglass 3000 was blended together. A bead of this mixture was placed on one end of a layer of 0.61 mm e-glass cloth in a cross web, and another layer of 0.61 mm e-glass cloth was placed on top. The structure was pulled through a notch bar nip to spread the filled silicone mixture evenly between the layers of glass cloth, and then the structure was placed in an oven to cure the silicone. The result was a 1.98 mm thick interlaminate structure of glass cloth and filled silicone. Two 102 x 102 mm sections were cut from this and laminated onto 102 x 102 mm aluminum plates with 91022 silicone transfer tape. Averaging over two tests, Example 14 survived an average of 16 blasts T>.

[0149] Example 15 (EX15): A mixture of 24.4 weight percent AK 1000000, 1.8 weight percent DDCBP-50, 53.8 weight percent Spheriglass 3000, 10.0 weight percent FR CROS 486, and 10.0 weight percent Zerogen 50 SP was blended together. A bead of this mixture was placed on one end of a layer of 0.14 mm e-glass cloth in a cloth web, and another layer of 0.14 mm e-glass cloth was placed on top. The structure was pulled through a notch bar nip to spread the filled silicone mixture evenly between the layers of glass cloth, and the structure was then placed in an oven to cure the silicone. The result was a 1.53 mm thick interlaminate structure of glass cloth and filled silicone. Two 102 x 102 mm sections were cut from this and laminated with 91022 silicone transfer tape onto a 102 x 102 mm aluminum plate. On average over two trials, Example 15 survived an average of T>9 blasts.

[0150] Example 16 (EX16): Eight layers of 3M 69 glass cloth electrical tape (silicone adhesive) were adhesively bonded together to glass cloth to produce a total of 16 layers within an area of ​​(approximately) 200 x 200 mm. The resulting laminated structure was bendable and flexible. This structure was tested in an insulation flame test. After 10 minutes of exposure to flame, the ambient temperature side of the structure was measured to be 263°C, with a temperature delta of 937°C relative to the torch side of the sample at 1200°C. This structure may be suitable as a thermal barrier for applications requiring an ambient temperature side of 300°C or less.

[0151] result Since samples may have different thicknesses, the results herein utilize a ratio parameter, where for a given sample, the number of T>blasts that survived or withstood is divided by the sample thickness. Table 2 below shows several surviving T>blasts / thickness ratios for Comparative Examples 1-6. Comparative Example 2 (a slab of crosslinked silicone) and Comparative Example 3 (a multi-layer structure with glass cloth, adhesive, and silicone foam) both survived three T>blasts. However, since Comparative Example 3 is more than twice the thickness of Comparative Example 2, its efficiency in withstanding T>blasts is much lower, and this characteristic is shown in the last column, where CE2 has a ratio parameter of 1.9 while CE3 has a value of only 0.8. All of the comparative example structures have relatively low surviving T>blasts / thickness ratios compared to the values ​​further shown in Table 3 below.

[0152] [Table 2]

[0153] Table 3 provides the composition, thickness, number of surviving torch and grit test blasts, and surviving T>blast / thickness ratios for Examples 1-15. The total thickness of all of these structures is less than 2 mm. The surviving T>blast / thickness ratios obtained for this wide range of compositions and number of layers are at least 4.6 for these examples, indicating that a variety of relatively thin structures, including core and binder layers, can provide suitable barrier properties against high temperature blasting.

[0154] [Table 3]

[0155] As is evident from Table 3, the use of the ratio of surviving T>blast number / thickness can help researchers identify suitable barrier article structures for space-constrained applications. Higher values ​​of this ratio provide a good indication of the suitability of a particular structure in space-constrained applications such as electric vehicle battery packs. While a particular structure may have an exceptionally high blast / thickness ratio, other considerations such as thermal insulation, cost, dielectric strength, or other related properties may favor a structure with a slightly lower blast / thickness ratio.

[0156] CE2, CE5, and CE6 are monolithic slabs of binder layers containing silicone with different fillers, and each of these comparative examples has a surviving T>blast number / thickness ratio of 3.0 or less. Comparative example 4, which contains multiple layers of glass cloth only, has a surviving T>blast number / thickness ratio of 4.2. The highest surviving T>blast number / thickness ratio for all comparative examples is 4.2. The lowest surviving T>blast number / thickness ratio for the examples described herein is 4.6. This demonstrates the synergistic properties of the multilayer structure containing the core layer and the filled silicone binder layer. This laminate system has a blast resistance that is greater than would be expected for the individual components.

[0157] The results in Table 3 show that all of the systems with both core and binder layers withstood T> better than the comparative examples. The systems including both core and binder layers had excellent resistance to high temperature flame and grit blasting, demonstrating their usefulness as protective layers in EV battery systems. The number of core layers in these examples ranged from 2 to 9, with more core layers possible. The thickness of the core layers ranged from 0.05 mm to 0.61 mm, demonstrating that more than one core thickness can be used in the structure. The amount of filler added in the silicone binder layer ranged from 10 to 73.8%, although more can be added, such as by utilizing a bimodal or trimodal distribution of filler sizes. The number of inorganic filler types in a single binder layer ranged from 1 to 3, although more can be added for additional properties.

[0158] Insulation flame testing showed that the ambient temperature side of Comparative Example 7 with acrylic adhesive rose to 362°C after 10 minutes of exposure to a 1200°C flame. The ambient temperature side of Example EX16 was only 263°C, demonstrating that this multi-layer structure with filled silicone can provide better insulation than the multi-layer structure with acrylic adhesive. Thus, the alternating structure of filled silicone binder layers and core layers can provide better blast resistance (CE1 vs. EX1) and better insulation properties.

[0159] All references, patents, and patent applications cited in the above patent application for Letters Patent are incorporated herein by reference in their entirety in a consistent manner. In the event of any inconsistency or discrepancy between any of the incorporated references and this application, the information in the foregoing description shall prevail. The foregoing description is intended to enable a person skilled in the art to practice the disclosure as set forth in the claims, and should not be construed as limiting the scope of the present disclosure, which is defined by the claims and all equivalents thereof.

Claims

1. 1. A thermal barrier article comprising: a plurality of core layers, at least one of the core layers comprising a woven or nonwoven fiber mat or fabric; a plurality of binder layers, at least one binder layer comprising a filled silicone material, the plurality of core layers and the plurality of binder layers being arranged in an alternating manner; The thermal barrier article has a ratio of the number of T> blasts it withstands divided by the thickness of the sample of at least 4.4 blast cycles / mm.

2. 10. The thermal barrier article of claim 1, wherein the woven or nonwoven fiber mat or fabric comprises a plurality of inorganic fibers.

3. 3. The thermal barrier article of claim 1 or 2, wherein the woven or nonwoven fiber mat or fabric comprises a plurality of fibers selected from the group consisting of A-glass, C-glass, D-glass, E-glass, M-glass, R-glass, S-glass, ECR-glass, AR-glass, basalt fibers, silicate fibers (e.g., Astroquartz fibers), silicon carbide fibers, ceramic fibers (e.g., Nextel fibers), or combinations thereof.

4. The thermal barrier article of claim 1 , wherein the filled silicone material comprises solid glass particles.

5. The thermal barrier article of claim 1, wherein the thermal barrier article has a thickness in the range of about 0.5 mm to about 10.0 mm.

6. The thermal barrier article of claim 1, wherein each core layer has a thickness of from about 0.04 mm to about 1 mm.

7. The thermal barrier article of claim 1, wherein the filled silicone material comprises inorganic clays and minerals.

8. The thermal barrier article of claim 1 , wherein the solid glass particle filler material has an average size of from about 10 micrometers to about 100 micrometers.

9. 10. The thermal barrier article of claim 1, wherein the thermal barrier article survives or is operatively adapted to withstand at least seven blast cycles in a torch and grit test.

10. 10. The thermal barrier article of claim 1, operably adapted such that the ratio of T> blasts withstood divided by sample thickness is at least 6.5 blast cycles / mm.

11. 10. The thermal barrier article of claim 1, wherein the barrier article is flexible such that it can bend at least 0.5% in a three-point bend test (per ASTM D790) before breaking.

12. A battery compartment of an electric vehicle including at least one battery cell or assembly, wherein the thermal barrier article of claim 1 is disposed between the at least one battery cell or assembly and a lid.

13. 1. A method of preventing or at least mitigating further spread of blast debris into or from an electric vehicle battery assembly, comprising: A method comprising at least partially surrounding at least one battery cell or module of an electric vehicle battery assembly with the thermal barrier article of claim 1.

14. 10. Use of a barrier article as a thermal insulation and blast protection barrier in a rechargeable electrical energy storage system, said barrier article comprising the thermal barrier article of claim 1.

15. A thermal barrier article comprising: a plurality of core layers, at least one core layer comprising a woven or nonwoven fiber mat or fabric, and at least one of the core layers comprising an outer surface; at least one binder layer, wherein the at least one binder layer comprises a filled silicone material; and an adhesive layer disposed on the at least one outer surface of the at least one core layer; Including, The thermal barrier article has a ratio of the number of T> blasts it withstands divided by the thickness of the sample of at least 4.4 blast cycles / mm.

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