WO2014204711A2 - Film composite à base d'oxyde de graphène - Google Patents
Film composite à base d'oxyde de graphène Download PDFInfo
- Publication number
- WO2014204711A2 WO2014204711A2 PCT/US2014/041681 US2014041681W WO2014204711A2 WO 2014204711 A2 WO2014204711 A2 WO 2014204711A2 US 2014041681 W US2014041681 W US 2014041681W WO 2014204711 A2 WO2014204711 A2 WO 2014204711A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- graphene oxide
- graphite sheet
- thermal management
- micron
- graphite
- Prior art date
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
- H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- a thermal management article includes graphite sheet from between about 10 micron and 100 micron thick and having an in-plane thermal conductivity at least 250 W/mK and having opposed major surfaces.
- a graphene oxide coating is disposed on at least one of the opposed major surfaces with a thickness from between about 0.1 micron to about 30 micron.
- a method of producing a thermal management article includes providing a graphite sheet having a thickness from between about 10 micron and about 100 micron and in-plane thermal conductivity of at least 250 W/mK and opposed major surfaces.
- a graphene oxide powder is dispersed in a solvent to form a graphene oxide suspension.
- the graphene oxide suspension is applied to the graphite sheet to form a graphene oxide coating less than 20 microns thick.
- Figure 1 is a side view of a composite thermal management article.
- Thermal management article is a composite article, including a graphite sheet or foil 12 and at least one coating layer 14.
- the coating layer 14 may be applied to a first major surface 16 of the graphite sheet 12.
- the coating layer 14 may be applied to both the first major surface 16 and to the opposed second major surface 18 of the flexible graphite layer 12.
- graphite sheet or graphite foil may be any graphite in the form of a sheet or foil that exhibits anisotropic thermal and/or electrical properties.
- exemplary graphite sheet may include compressed exfoliated graphite, pyrolytic graphite and heat treated graphitizable polymers.
- Compressed exfoliated graphite may be produced by treating particles of graphite, such as natural graphite flake, with an intercalant of, e.g. a solution of sulfuric and nitric acid. Upon exposure to high temperature, the intercalant within the graphite decomposes and volatilizes, causing the particles of intercalated graphite to expand in dimension as much as about 80 or more times its original volume in the direction perpendicular to the crystalline planes of the graphite.
- the exfoliated graphite particles are vermiform in appearance, and are therefore commonly referred to as worms.
- the worms may be compressed together into flexible sheets that, unlike the original graphite flakes, can be formed and cut into various shapes.
- Pyrolytic graphite commonly refers to the carbon materials produced through a gas- phase carbonization process.
- the gas-phase deposition of carbon occurs on a surface through the contact of hydrocarbons upon a substrate through the pyrolysis of hydrocarbons in the gas phase and deposition on the substrate surface.
- the large aromatic molecules produced by dehydrogenation and polymerization of hydrocarbons collide with the high-temperature substrate surface to form the deposit.
- Heat treated graphitizable polymers can be made from a polymer material heated to at least 2000°C.
- graphite films with high crystallinity can be created by the solid-state carbonization of graphitizable polymers, for example an aromatic polyimide film, followed by a high temperature heat treatment.
- the carbonization and heat treatment may take place as a two-step process, the first step at a substantially lower temperature than the second step.
- the first step of carbonizing a the graphitizable film which occurs by bringing the film to a temperature of at least about 600°C, up to about 1800°C, for a time sufficient to substantially carbonize the film.
- the graphitization process includes a higher temperature (i.e., at least 2000°C and up to about 3200°C) heat treatment with the temperature of the heat treatment resulting in alignment of the carbon atoms to nearly perfectly aligned carbon layers.
- the graphite sheet 12 advantageously has an in-plane thermal conductivity of greater than 250 W/mK, more advantageously greater than 400 W/mK, still more advantageously greater than 1000 W/mK, and still more advantageously greater than 1400 W/mK.
- graphite sheet has an in-plane thermal conductivity of from between 250 W/mK and 2000 W/mK.
- the graphite sheet has an in-plane thermal conductivity of from between about 250 W/mK and about 600 W/mK.
- the graphite sheet has an in-plane thermal conductivity of from between about 900 W/mK and about 1600 W/mK.
- Graphite sheet 12 advantageously has a thickness less than 100 microns, more advantageously less than 50 microns and still more advantageously less than 20 microns. In further embodiments, graphite sheet 12 has a thickness from between about 5 microns to about 3 millimeters. In further embodiments, graphite sheet 12 has a thickness from between about 10 microns and about 100 microns. In still further embodiments, the graphite sheet 12 has a thickness from between about 10 microns and about 50 microns. In certain
- the graphite sheet has a density of at least 1.0 grams/cc, still more
- the graphite sheet has a density of from between about 1.0 grams/cc and about 2.2 grams/cc. In still further embodiments, the graphite sheet has a density of from between about 1.4 grams/cc and about 2.0 grams/cc.
- Coating layer 14 is advantageously graphene oxide, which is a compound material comprised of carbon, oxygen, and hydrogen.
- the material is commonly synthesized from natural graphite, resulting in a brown-colored powder that generally retains the layer structure of graphite but with a larger and more irregular spacing.
- the structure and properties of graphite oxide depend on particular synthesis method and degree of oxidation. The material commonly conserves the layer structure the precursor graphite, but the layers tend to be generally buckled and the interlayer spacing is about 0.7 nanometers, which is approximately two times larger than that of graphite.
- coating layer 14 has a thickness from between about 0.1 microns and about 30 microns. In further embodiments coating layer 14 has a thickness from between about 1.0 microns and about 10 microns thick. In still further embodiments, the coating layer 14 is from between about 10 microns and about 20 microns thick. In still other embodiments, coating layer 14 has a thickness from between about 0.1 microns and about 5.0 microns. In further embodiments, the coating layer has a thickness advantageously less than 20 microns, more advantageously less than 10 microns and still more advantageously less than 5 microns.
- a chemical bonding agent may be used to bond together coating layer 14 and graphite sheet 12.
- suitable bonding agents might include, for example, a resin-hardener system or cement.
- coating layer 14 adheres to graphite sheet 12 in the absence of a bonding agent.
- the graphene oxide coating layer 14 is adhered to the graphite sheet by other mechanisms, such as dispersion forces (otherwise referred to as "van der Waals forces") and/or electrostatic forces. The strength of these forces is dependent on the distance between graphene oxide and the graphite sheet, as well as their respective geometry.
- the graphene oxide coating layer 14 is comprised of generally flat crystallites with a relatively large surface area to thickness ratio. This structure provides a large area for dispersion and electrostatic forces to enable adhesion. Further, the smoothness (lack of microscopic roughness) of the graphene oxide coating layer 14 allows the distance between layer 14 and the graphite sheet 12 to be minimized, enabling a strong adhesion.
- the graphene oxide is an electrical insulator wherein the individual graphene oxide layers are advantageously aligned substantially with the plane of the major surface to which it is attached. Accordingly, in one embodiment, the coating layer 14 is anisotropic, wherein it exhibits different properties in the in-plane direction verses the thru-plane direction.
- in-plane thermal conductivity may be from between about 2 W/mK to about 10 W/mK. In other embodiments, the in-plane thermal conductivity may be greater than about 2 W/mK.
- in-plane electrical conductivity, using a multi-meter, of the coating layer 14 is from between about 1.0 x 10 ⁇ 3 S/m to about 0.1 x 10 ⁇ 3 S/m. In other embodiments, the in-plane electrical conductivity of the coating layer 14 is from between about 0.8 x 10 ⁇ 3 S/m to about 0.3 x 10 ⁇ 3 S/m. In still further embodiments, the in-plane electrical conductivity of the coating layer 14 is advantageously less than about 1.5 x 10 ⁇ 3 S/m, still more advantageously less than about 1.0 x 10 "3 S/m, and still more advantageously less than about 0.5 x 10 "3 S/m.
- through-plane electrical conductivity, as measured using frequency sweeps, of coating layer 14 is from between about 1.0 x 10 "4 S/m to about 1.0 x 10 "5 S/m when measured at 106 Hz. In other embodiments, the through-plane electrical conductivity of coating layer 14 is from between about 2.0 x 10 "5 S/m to about 8.0 x 10 "5 S/m when measured at 106 Hz. In still further embodiments, the through-plane electrical conductivity of coating layer 14 is less than about 1.0 x 10 "4 S/m when measured at 106 Hz. In still further embodiments, the through-plane electrical conductivity of coating layer 14 is less than about 0.5 x 10 "4 S/m when measured at 106 Hz.
- through- plane electrical conductivity of coating layer 14 is from between about 10 "7 S/m to about 10 "11 S/m when measured at 10 "1 Hz. In still further embodiments, the through-plane electrical conductivity of coating layer 14 is less than about 1.0 x 10 "7 S/m and more advantageously less than about 1.0 x 10 "10 S/m when measured at 10 "1 Hz.
- the electrically insulating behavior results from a combination of the graphene oxide's sp3 bonding structure and the presence of air in the interlayer spaces.
- the above thermal management article may be produced in accordance with any one or more of the following methods.
- graphene oxide powder may be dispersed in water or another polar solvent in concentrations ranging from about 0.1 mg/ml to about 5 mg/ml. This powder may be dispersed in water or other polar solvents to generate a suspension containing single-layer graphene oxide sheets.
- dispersion of the graphene oxide sheets may be aided with sonication or any other suitable form of agitation.
- Graphene oxide in solution may then be assembled into a multi-layered film by any one or more of the following methods.
- the graphene oxide suspension is filtered over a fine-pored membrane having pore sizes from between about 100 nm to about 500 nm in diameter.
- the filtering process may be aided with the use of a vacuum.
- the thus formed graphene oxide multi-layer film may then be removed from the filter medium and applied to one or both major surfaces of graphite sheet 12.
- application of the graphene oxide film may be performed with or without the use of an adhesive.
- the graphene oxide coating layer 14 is arranged in a flat, aligned film with only trace solvent remaining between the coating layer 14 and graphite sheet 12.
- an electric field is applied the graphene oxide suspension (the individual graphene oxide sheets assume a negative charge when suspended in water).
- the single-layer graphene oxide sheets in the suspension move toward a conductive positively charged surface and deposit into a flat, aligned multi-layer film under the appropriate conditions.
- the graphene oxide film may then be transferred to the graphite sheet 12 (e.g., via a sacrificial layer).
- electrophoretic deposition is advantageously performed directly onto graphite sheet 12.
- the graphene oxide suspension may be sprayed onto one or both major surfaces of graphite sheet 12 to form a multi-layer graphene oxide coating layer 14.
- the graphite sheet 12 may be heated to encourage evaporation of the solvent, leaving behind the graphene oxide film.
- the graphene oxide suspension may be coated onto a substrate in a roller application or printing (e.g. gravure type printing) or the like. According to this method, achieving the desired thickness may require multiple coating and
- the substrate material may be heated to encourage evaporation of the solvent.
- the graphene oxide film may then be transferred to the graphite sheet 12 (e.g., via a sacrificial layer).
- the printing/rolling is advantageously performed directly onto graphite sheet 12.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Cette invention concerne un article de gestion thermique contenant une feuille de graphite ayant une épaisseur entre environ 10 et 100 microns et une conductivité thermique dans le plan d'au moins 250 W/mK. La feuille de graphite comporte un revêtement en oxyde de graphène ayant une épaisseur entre 0,1 et environ 30 microns.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201361837426P | 2013-06-20 | 2013-06-20 | |
US61/837,426 | 2013-06-20 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2014204711A2 true WO2014204711A2 (fr) | 2014-12-24 |
WO2014204711A3 WO2014204711A3 (fr) | 2015-05-28 |
Family
ID=52105476
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2014/041681 WO2014204711A2 (fr) | 2013-06-20 | 2014-06-10 | Film composite à base d'oxyde de graphène |
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WO (1) | WO2014204711A2 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016138478A1 (fr) * | 2015-02-26 | 2016-09-01 | P&T Global Solutions, Llc | Procédés se rapportant à une filtration d'eau isotopique |
US9475007B2 (en) | 2013-08-23 | 2016-10-25 | Energysolutions, Inc. | Methods relating to isotopic water filtration |
US10040702B2 (en) | 2013-08-23 | 2018-08-07 | Energysolutions, Inc. | Systems for isotopic water separation |
CN110137148A (zh) * | 2019-04-19 | 2019-08-16 | 苏州市达昇电子材料有限公司 | 一种复合导热石墨膜 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8936874B2 (en) * | 2008-06-04 | 2015-01-20 | Nanotek Instruments, Inc. | Conductive nanocomposite-based electrodes for lithium batteries |
US10049783B2 (en) * | 2010-02-19 | 2018-08-14 | Mike Foley | Utilizing nanoscale materials as dispersants, surfactants or stabilizing molecules, methods of making the same, and products produced therefrom |
US20110227000A1 (en) * | 2010-03-19 | 2011-09-22 | Ruoff Rodney S | Electrophoretic deposition and reduction of graphene oxide to make graphene film coatings and electrode structures |
CN203415567U (zh) * | 2010-09-21 | 2014-01-29 | 格拉弗技术国际控股有限公司 | 复合散热器 |
-
2014
- 2014-06-10 WO PCT/US2014/041681 patent/WO2014204711A2/fr active Application Filing
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9475007B2 (en) | 2013-08-23 | 2016-10-25 | Energysolutions, Inc. | Methods relating to isotopic water filtration |
US10040702B2 (en) | 2013-08-23 | 2018-08-07 | Energysolutions, Inc. | Systems for isotopic water separation |
US10226739B2 (en) | 2013-08-23 | 2019-03-12 | Energysolutions, Inc. | Methods relating to isotopic water filtration |
WO2016138478A1 (fr) * | 2015-02-26 | 2016-09-01 | P&T Global Solutions, Llc | Procédés se rapportant à une filtration d'eau isotopique |
CN110137148A (zh) * | 2019-04-19 | 2019-08-16 | 苏州市达昇电子材料有限公司 | 一种复合导热石墨膜 |
Also Published As
Publication number | Publication date |
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WO2014204711A3 (fr) | 2015-05-28 |
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