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WO2025133814A1 - Revêtements inorganiques souples pour applications de barrière thermique résistant aux chocs - Google Patents

Revêtements inorganiques souples pour applications de barrière thermique résistant aux chocs Download PDF

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Publication number
WO2025133814A1
WO2025133814A1 PCT/IB2024/062396 IB2024062396W WO2025133814A1 WO 2025133814 A1 WO2025133814 A1 WO 2025133814A1 IB 2024062396 W IB2024062396 W IB 2024062396W WO 2025133814 A1 WO2025133814 A1 WO 2025133814A1
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WO
WIPO (PCT)
Prior art keywords
coating
water
article
dried
silicate
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Pending
Application number
PCT/IB2024/062396
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English (en)
Inventor
Dinh Ba Le
Matthew T. Johnson
Peter T. Dietz
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3M Innovative Properties Co
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3M Innovative Properties Co
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Publication of WO2025133814A1 publication Critical patent/WO2025133814A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • Ceramic inorganic coatings are currently being investigated for use in electric vehicles.
  • such coatings are typically very rigid and can fracture due to conformational change, such as bending, or exposure to sudden impact.
  • FIG. 1 is a schematic drawing of the Bend Test Method in the Examples
  • the coatings of the present disclosure generally comprise a filler and a hydrated alkali- rich silicate.
  • the filler comprises alumina, aluminosilicate, calcium silicate, titania, silicon carbide, silicon nitride, boron nitride, hexagonal boron nitride, zircon, kaolin clay, mica, vermiculite, graphite, or combinations thereof.
  • the alkali silicate has the formula [Li2O] x [Na2O] y [K2O] z [SiO2] where the sum of x, y and z is at least 0.35. Water is present in an amount where the mole ratio of water to alkali silicate is 4 to 20.
  • the coatings are typically applied to one or more surfaces of a substrate and hardened by drying.
  • the resultant article can be used to create a high impact resistant thermal barrier that operates at temperatures as high as 1800°C.
  • the article can be used as a thermal barrier between cells in a battery module within a battery pack, and/or as a thermal barrier between battery modules within a battery pack to reduce the potential for catastrophic thermal runaway events.
  • the article can be used as a protective inner surface of a battery pack casing (e.g., inner surface of lid).
  • alkali-rich silicates for the coatings disclosed herein have the formula [Li2O]x[Na2O] y [K2O]z[SiO2].
  • Alkali-rich refers to the sum of x, y and z being at least 0.35. In some embodiments of the present disclosure, the sum of x, y and z is at least 0.35, at least 0.40, at least 0.45, at least 0.50, at least 0.55, at least 0.60, at least 0.65, at least 0.70, at least 0.75, at least 0.80, at least 0.85, at least 0.90, at least 0.95, or at least 1.00.
  • the sum of x, y and z is 0.35 to 1, more particularly 0.35 to 0.70.
  • alkali-rich silicates and “alkali silicates” are used interchangeable herein.
  • the alkali silicates can be made up of only one alkali metal (e.g., sodium silicate, lithium silicate or potassium silicate). Alternatively, the alkali silicates can be made up of two or three alkali metals in silicate form.
  • x and z are each zero. In some other embodiments, x is zero. In yet some other embodiments, z is zero.
  • the alkali silicates are hydrated, which means water is present in both the coating and hardened coating formed by drying.
  • the molar ratio of water to alkali silicate in the coating is at least 4 but no greater than 20.
  • the hydration value is at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, at least 10, at least 11, at least 12, at least 13, at least 14, at least 15, at least 16, at least 17, at least 18, or at least 19 up to 20.
  • the hydration value is no greater than 20, no greater than 19, no greater than 18, no greater than 17, no greater than 16, no greater than 15, no greater than 14, no greater than 13, no greater than 12, no greater than 11, no greater than 10, no greater than 9, no greater than 8, no greater than 7, no greater than 6, or no greater than 5 down to 4. If the hydration values are less than 4, the coating is typically not spreadable, making application to a substrate difficult. If the hydration values are greater than 20, the components of the coating can separate out to form a nonuniform mixture, which can negatively impact the properties of the dried coating. In some embodiments, the hydration value is 4 to 20, more particularly 5 to 15, and even more particularly 6 to 9.
  • the hydrated alkali silicates can be made, for example, by combining a silicate solution with an alkali hydroxide in the proper proportions.
  • silicate as used herein, means a salt in which the anion contains both silicon and oxygen.
  • Silicates include metasilicates (SiCE 2 ) and orthosilicate (SiO/ ).
  • Exemplary alkali silicates for use in the silicate solution include sodium silicate, potassium silicate, lithium silicate, or combinations thereof.
  • the silicate solution comprises sodium silicate or potassium silicate.
  • the alkali hydroxide comprises sodium hydroxide, potassium hydroxide, lithium hydroxide, or combinations thereof.
  • the coating comprises 20 wt.% to 80 wt.% alkali silicate based upon the percentage of solids in the coating.
  • solids as used herein in the context of percentage of solids in the coating, means the components that remain in the coating after drying, excluding any remaining water. Solvents driven off during formation of the dried coating are not considered solids. Since any solvents and remaining water do not form part of the solids in the coating, the solids content will be approximately the same before and after a coating is dried.
  • the coating comprises at least 20 wt.%, at least 25 wt.%, at least 30 wt.%, at least 35 wt.%, at least 40 wt.%, at least 50 wt.%, at least 60 wt.%, or at least 70 wt.% alkali silicate based upon the percentage of solids in the coating.
  • the coating comprises up to 80 wt.%, up to 75 wt.%, up to 70 wt.%, up to 65 wt.%, up to 60 wt.%, up to 50 wt.%, or up to 40 wt.% alkali silicate based upon the percentage of solids in the coating.
  • the coating comprises 20 wt.% to 80 wt.%, more particularly 20 wt.% to 60 wt.%, even more particularly 30 or wt.% to 40 wt.% alkali silicate based upon the percentage of solids in the coating.
  • the coatings further comprises fillers.
  • Fillers can be used to enhance the mechanical properties of the dried coating. Suitable fillers include alumina, aluminosilicate, calcium silicate, titania, silicon carbide, silicon nitride, boron nitride, hexagonal boron nitride, zircon, kaolin clay, mica, vermiculite, graphite, or combinations thereof. In some embodiments, the coating comprises kaolin clay, mica or combinations thereof.
  • the coating comprises at least 20 wt.%, at least 25 wt.%, at least 30 wt.%, at least 35 wt.%, at least 40 wt.%, at least 50 wt.%, at least 60 wt.%, or at least 70 wt.% filler based upon the percentage of solids in the coating.
  • the coating comprises up to 80 wt.%, up to 75 wt.%, up to 70 wt.%, up to 65 wt.%, up to 60 wt.%, up to 50 wt.%, or up to 40 wt.% filler based upon the percentage of solids in the coating.
  • the coating comprises 20 wt.% to 80 wt.%, more particularly 40 wt.% to 80 wt.%, even more particularly 60 wt.% to 70 wt.% filler based upon the percentage of solids in the coating.
  • Coatings of the present disclosure may, optionally, include additives.
  • Exemplary additives include defoamers, surfactants, rheological modifiers, forming aids, pH-adjusting materials, plasticizers, or combinations thereof.
  • the coating comprises 0 wt.%, at least 0.5 wt.%, at least 1 wt.%, at least 1.5 wt.%, at least 2 wt.%, at least 2.5 wt.%, at least 3 wt.%, at least 3.5 wt.%, at least 4 wt.%, at least 4.5 wt.%, or at least 5 wt.% additives based upon the percentage of solids in the coating.
  • the coating comprises up to 10 wt.%, up to 9 wt.%, up to 8 wt.%, up to 7 wt.%, up to 6 wt.%, up to 5 wt.% , up to 4 wt.%, or up to 3 wt.% additives based upon the percentage of solids in the coating.
  • the coating comprises 0 wt.% to 10 wt.%, more particularly 0.5 wt.% to 10 wt.%, even more particularly 0.5 wt.% to 5 wt.%, and further 1 wt.% to 3 wt.% additives based upon the percentage of solids in the coating.
  • the additive includes sodium tetraborate.
  • the presence of water in the dried coatings can make the coatings more susceptible to moisture uptake and, in extreme cases, cause dissolution of the coating.
  • Chemical hardeners such as aluminum-based hardeners and zinc borate, can stabilize the coatings by crosslinking the silicate network.
  • such hardeners often lead to premature crosslinking that reduces shelf life of the coatings, necessitating a less favorable two-component application.
  • borates can decompose to boric acid when hydrated, which acid can also decrease the shelf life of the coating.
  • sodium tetraborate can improve moisture sensitivity of the dried coatings.
  • the sodium ion does not lead to premature crosslinking like the previously mentioned aluminum and zinc ions. Further, by adding alkali hydroxides during formation of the coating, the alkalinity of the coating neutralizes the acidity of the boric acid, thus maintaining shelflife of the coating slurry and reducing moisture sensitivity of the dried coating.
  • the above described water can provide the proper consistency for the coating. Therefore, in some preferable embodiments, the coating does not include additional solvents (i.e., the only solvent is water).
  • the above coatings can be applied to a substrate to create articles exhibiting high impact and high thermal transfer resistance in high temperature applications.
  • the substrates are typically flame resistant and may include flame resistant paper (e.g., inorganic paper or mica based paper), an inorganic fabric, or flame resistant boards (e.g., inorganic fiber boards or mica boards or sheets).
  • Inorganic fabrics may comprise E-glass fibers, R-glass fibers, ECR-glass fibers, basalt fibers, ceramic fibers, silicate fibers, NextelTM fibers, steel filaments, or combinations thereof.
  • the fibers in the inorganic fabric may be chemically treated.
  • the fabrics may, for example, be a woven or nonwoven mat, a felt, a cloth, a knitted fabric, a stitch bonded fabric, a crocheted fabric, an interlaced fabric, or combinations thereof.
  • Substrates may also include flame resistant polymers, including thermoplastic resins, thermosetting resins, or glass-fiber reinforced resins (e.g., polyester).
  • Substrates may further include metals or metal alloys, including aluminum, steel, or stainless steel. Substrates may comprise a single layer structure (e.g., sheets or foils) or a multi-layered structure comprising one or more of the forementioned materials. In some embodiments involving battery application, is it preferably that the substrate by non-conductive and light weight (e.g., nonmetals).
  • the articles are made by applying the coatings described herein to a substrate and drying the coating by reducing the amount of water present.
  • the coating can be applied to the substrate by conventional techniques, including by dispensing (e.g., flat stream coating), spraying, brushing, knife coating, nip coating, or dip coating, to a thickness, for example, of at least 0.5 mm.
  • the composition of the dried coating typically comprises less water but is not completely dehydrated.
  • the molar ratio of water to alkali silicate in the dried coating is at least 1.0, at least 1.5, at least 2.0, at least 2.5, at least 3.0, at least 3.5, at least 4.0, at least 4.5 up to 5 in the dried coating.
  • the hydration value is no greater than 5.0, no greater than 4.5, no greater than 4.0, no greater than 3.5, no greater than 3.0, no greater than 2.5, no greater than 2.0, or no greater than 1.5 down to 1.0 in the dried coating.
  • the coating loses its flexibility and can fracture due to conformation changes (e.g., bending) or exposure upon high impact particles. If the hydration values are greater than 5, the coating is not sufficiently hard to provide the desired mechanical properties.
  • the molar ratio of water to alkali silicate is 1 to 5, more particularly 1 to 3, and even more particularly 2 to 3. Therefore, the term “dried” as applied to the finished coating does not involve driving off all the water but, instead, refers to removing solvent (if present) and reducing, but not eliminating, the water in the dried coating.
  • the thickness of the dried coating will depend upon the desired application. For example, thinner coatings can be used for applications involving lower temperatures and/or lower potential particle blast forces. Thicker coatings would be used for higher temperature applications and/or higher potential particle blast forces. In some embodiments, the dried coating has a thickness in the range of 0. 1 mm to 6 mm.
  • the dried coating of the present disclosure can survive at least 1, at least 2, least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, at least 10, at least 11, at least 12, at least 13, at least 14, at least 15, or at least 16 blasts of abrasive media at 1200°C, as determined by the Torch and Grit Test in the Examples.
  • the dried coating can survive at least 8, more preferably at least 12, and even more preferably at least 16 blasts of abrasive media at 1200°C, as determined by the Torch and Grit Test in the Examples.
  • Articles of the present application may be used in a variety of high impact, high temperature applications.
  • articles of the present disclosure may be used as impact resistant thermal barriers disposed in the gap between battery cells in an electric vehicle battery (e.g., in a battery module or a batter pack) and/or between individual battery modules in a battery pack.
  • the coatings or articles of the present disclosure may be disposed on the inner surface of the casing of a battery pack (e.g., a battery module or a battery pack), including the inner surface of a compartment lid or the inner surface of vent passages for exhaust gas.
  • the coatings and articles of the present disclosure may be used to protect a wide variety of components used in high voltage equipment, such as busbars used for high current power distribution.
  • a hydrogen/oxygen torch (a customized hydrogen/oxygen burner obtained from Bethlehem Apparatus, Hellertown, PA having a central channel for particulates and a ring of outer ports for fuel and oxidizer feeds) was first equilibrated to a designed flame temperature of 1200°C, as measured by a thermocouple inserted into the flame cone one inch (2.54 cm) from the face of the torch (i.e. tip of the nozzle).
  • a test panel was prepared with a sample coating on one side of the panel and a high temperature black paint on the other side of the panel. The panel was oriented so that the side with the sample coating faced the torch flame.
  • Coatings were made by adding fdler to each of the alkali rich silicates in Examples 1 A- 12A using the reagents and quantities provided in Table 3.
  • the solutions were mixed by a high shear mixer (Speedmixer DAC 600 from Flack Tek Inc.).
  • Example 13 Dried Coating Subjected to Torch and Grit Test
  • Example 13 using the reagents and conditions provided in Table 5.
  • the coating thickness and results from the Torch and Grit Test are also provided in Table 5.
  • Coatings were made by adding fdler to silicate solutions using the reagents and quantities provided in Table 3.
  • the solutions were mixed by a high shear mixer (Speedmixer DAC 600 from Flack Tek Inc.).
  • the dried coatings in Comparative Examples 1C-4C were made by drying each of the coatings in Comparative Examples 1B-4B.
  • the coatings was spread onto a release liner using a round 3/8” outer diameter (OD) steel tube and 2.29 mm coating gap.
  • the coating was then air dried in a convection oven at 50°C for 24 hours followed by exposure to room air at 21 °C for 24 hours.
  • a free-standing coating was obtained by removing the release liner and cutting the dried coating into pieces for flexibility evaluation, e.g., 2.54 cm (1 inch) wide and 12.7 cm (5 inches) long.
  • the thickness of the dried coating and results of the 20° Bend Test are provided in Table 4.
  • Coating solution 3B was applied to four G10-FR4 panels using a round 3/8” outer diameter (OD) steel tube and 2.29 mm coating gap. The panels were dried for 24 hours, each at a different temperature: 80°C (Example 5 A); 100°C (Example 5B); 120°C (Example 5C); and 140°C (Example 5D). Pieces of dried coating were broken off and immersed in deionized water in closed vials for 24 hours at ambient temperature. Sample dissolution in the deionized water is indicated by cloudiness. Results are shown in FIG. 3.
  • the present disclosure provides, among other things, flexible coatings and articles containing the flexible coatings that can be used in high temperature applications where impact resistance and/or thermal transfer resistance are desired.
  • flexible coatings and articles containing the flexible coatings that can be used in high temperature applications where impact resistance and/or thermal transfer resistance are desired.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

Revêtement comprenant une charge, un silicate riche en alcali présentant la formule [Li2O]x[Na2O]y[K2O]z[SiO2], et de l'eau. La charge comprend de l'alumine, de l'aluminosilicate, du silicate de calcium, de l'oxyde de titane, du carbure de silicium, du nitrure de silicium, du nitrure de bore, du nitrure de bore hexagonal, du zircon, de l'argile de kaolin, du mica, de la vermiculite, du graphite ou des combinaisons de ceux-ci. La somme de x, y et z dans le silicate alcalin est d'au moins 0,35. Le rapport molaire entre l'eau et le silicate alcalin dans le revêtement est de 4:20. Des revêtements et des articles contenant les revêtements séchés peuvent être utilisés en tant que barrières thermiques résistant aux chocs dans des applications à haute température.
PCT/IB2024/062396 2023-12-21 2024-12-09 Revêtements inorganiques souples pour applications de barrière thermique résistant aux chocs Pending WO2025133814A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US202363613337P 2023-12-21 2023-12-21
US63/613,337 2023-12-21
US202463721619P 2024-11-18 2024-11-18
US63/721,619 2024-11-18

Publications (1)

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WO2025133814A1 true WO2025133814A1 (fr) 2025-06-26

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2699407A (en) * 1952-08-26 1955-01-11 Sherwin Williams Co Resinous composition method of coating metals therewith to increase hightemperature resistance thereof and article produced thereby
JPS57201568A (en) * 1981-06-04 1982-12-10 Kansai Paint Co Ltd Formation of paint film
JPS59138214A (ja) * 1983-01-26 1984-08-08 バイエル・アクチエンゲゼルシヤフト 発泡性防火組成物およびそれから製造された構造要素
KR20180033583A (ko) * 2015-07-30 2018-04-03 코닝 인코포레이티드 열적으로 강화된 소비자 전자제품 유리 및 이에 대한 시스템 및 방법
US20200147932A1 (en) * 2017-06-09 2020-05-14 Corning Incorporated Bendable laminated article including anisotropic layer
WO2020227924A1 (fr) * 2019-05-14 2020-11-19 Schott Glass Technologies (Suzhou) Co. Ltd. Substrat en verre mince à résistance à la flexion élevée et procédé de production associé

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2699407A (en) * 1952-08-26 1955-01-11 Sherwin Williams Co Resinous composition method of coating metals therewith to increase hightemperature resistance thereof and article produced thereby
JPS57201568A (en) * 1981-06-04 1982-12-10 Kansai Paint Co Ltd Formation of paint film
JPS59138214A (ja) * 1983-01-26 1984-08-08 バイエル・アクチエンゲゼルシヤフト 発泡性防火組成物およびそれから製造された構造要素
KR20180033583A (ko) * 2015-07-30 2018-04-03 코닝 인코포레이티드 열적으로 강화된 소비자 전자제품 유리 및 이에 대한 시스템 및 방법
US20200147932A1 (en) * 2017-06-09 2020-05-14 Corning Incorporated Bendable laminated article including anisotropic layer
WO2020227924A1 (fr) * 2019-05-14 2020-11-19 Schott Glass Technologies (Suzhou) Co. Ltd. Substrat en verre mince à résistance à la flexion élevée et procédé de production associé

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