Production process for highly conductive graphitic films
A process for producing a graphitic film comprising the steps of (a) mixing graphene platelets with a carbon precursor polymer and a liquid to form a slurry and forming the slurry into a wet film under the influence of an orientation-inducing stress field to align the graphene platelets on a solid substrate; (b) removing the liquid to form a precursor polymer composite film wherein the graphene platelets occupy a weight fraction of 1% to 99%; (c) carbonizing the precursor polymer composite film at a carbonization temperature of at least 300° C. to obtain a carbonized composite film; and (d) thermally treating the carbonized composite film at a final graphitization temperature higher than 1,500° C. to obtain the graphitic film. Preferably, the carbon precursor polymer is selected from the group consisting of polyimide, polyamide, polyoxadiazole, polybenzoxazole, polybenzobisoxazole, polythiazole, polybenzothiazole, polybenzobisthiazole, poly(p-phenylene vinylene), polybenzimidazole, polybenzobisimidazole, and combinations thereof.
1. A process for producing a graphitic film comprising the steps of:
(a) mixing graphene platelets with a carbon precursor polymer and a liquid to form a slurry or suspension and forming said slurry or suspension into a wet film under the influence of an orientation-inducing stress field to align said graphene platelets along planar directions of said wet film on a solid substrate, wherein the graphene platelets are selected from pristine graphene, oxidized graphene, reduced graphene oxide, fluorinated graphene, hydrogenated graphene, doped graphene, chemically functionalized graphene, or a combination thereof, and said carbon precursor polymer is selected from the group consisting of polyimide, polyamide, polyoxadiazole, polybenzoxazole, polybenzobisoxazole, polythiazole, polybenzothiazole, polybenzobisthiazole, poly(p-phenylene vinylene), polybenzimidazole, polybenzobisimidazole, and combinations thereof;
(b) removing said liquid from said wet film to form a precursor polymer composite film wherein the graphene platelets occupy a weight fraction of 1% to 99% based on the total dried precursor polymer composite weight;
(c) carbonizing the precursor polymer composite film at a carbonization temperature of at least 300° C. to obtain a carbonized composite film; and
(d) thermally treating the carbonized composite film at a final graphitization temperature higher than 1,500° C. to obtain the graphitic film.
2. The process of claim 1 , further comprising a step of compressing said carbonized composite film during or after said step (c) of carbonizing the precursor polymer composite film.
3. The process of claim 1 , further comprising a step of compressing said graphitic film during or after said step (d) of thermally treating the carbonized composite film.
4. The process of claim 1 , wherein the final graphitization temperature is lower than 2,500° C.
5. The process of claim 1 , wherein the carbonization temperature is lower than 1,000° C.
6. The process of claim 1 , wherein the graphene platelets comprise a single-layer graphene sheet or a multi-layer graphene platelet with a thickness less than 10 nm.
7. The process of claim 1 , wherein the graphene platelets comprise a multi-layer graphene platelet with a thickness less than 4 nm.
8. The process of claim 1 , wherein the graphene platelets comprise a single-layer pristine graphene sheet or a multi-layer pristine graphene platelet with a thickness less than 10 nm and said pristine graphene sheet or pristine graphene platelet contains no oxygen and is produced from a process that does not involve oxidation.
9. The process of claim 1 , wherein the carbonization temperature and/or the final graphitization temperature for obtaining said graphitic film having a thermal conductivity value from said graphene platelet-filled carbon precursor polymer composite is lower than a carbonization temperature and/or a final graphitization temperature required of producing a graphitic film having said conductivity value from the carbon precursor polymer alone without an added graphene platelet.
10. The process of claim 9 , wherein the carbonization temperature for carbonizing said graphene platelet-filled precursor polymer composite is lower than 1,000° C. and the carbonization temperature for said polymer alone is higher than 1,000° C.
11. The process of claim 9 , wherein the final graphitization temperature for producing said graphitic film from said graphene platelet-filled carbon precursor polymer composite is lower than 2,500° C. and the final graphitization temperature of a graphitic film obtained from said polymer alone and having a comparable conductivity is higher than 2,500° C.
12. The process of claim 1 , wherein said final graphitization temperature is less than 2,000° C. and said graphitic film has an inter-graphene spacing less than 0.338 nm, a thermal conductivity of at least 1,000 W/mK, and/or an electrical conductivity no less than 5,000 S/cm.
13. The process of claim 1 , wherein said final graphitization temperature is less than 2,200° C. and said graphitic film has an inter-graphene spacing less than 0.337 nm, a thermal conductivity of at least 1,200 W/mK, an electrical conductivity no less than 7,000 S/cm, a physical density greater than 1.9 g/cm3, and/or a tensile strength greater than 30 MPa.
14. The process of claim 1 , wherein said final graphitization temperature is less than 2,500° C. and said graphitic film has an inter-graphene spacing less than 0.336 nm, a thermal conductivity of at least 1,500 W/mK, an electrical conductivity no less than 10,000 S/cm, a physical density greater than 2.0 g/cm3, and/or a tensile strength greater than 35 MPa.
15. The process of claim 1 , wherein the graphitic film exhibits an inter-graphene spacing less than 0.337 nm and a mosaic spread value less than 1.0.
16. The process of claim 1 , wherein the graphitic film exhibits a degree of graphitization no less than 60% and/or a mosaic spread value less than 0.7.
17. The process of claim 1 , wherein the graphitic film exhibits a degree of graphitization no less than 90% and/or a mosaic spread value less than 0.4.
18. A process for producing a graphitic film comprising the steps of:
(a) mixing graphene sheets with a carbon precursor material and a liquid to form a slurry or suspension and forming said slurry or suspension into a wet film under the influence of an orientation-inducing stress field to align said graphene platelets along planar directions of said wet film;
(b) removing said liquid to form a graphene platelet-filled precursor composite film wherein the graphene platelets occupy a weight fraction of 1% to 99% based on the total precursor composite weight;
(c) carbonizing the precursor composite film at a carbonization temperature of at least 500° C. to obtain a carbonized composite film; and
(d) thermally treating the carbonized composite film at a final graphitization temperature higher than 1,500° C. to obtain the graphitic film;
wherein the graphene platelets are selected from pristine graphene, oxidized graphene, reduced graphene oxide, fluorinated graphene, hydrogenated graphene, doped graphene, chemically functionalized graphene, or a combination thereof, and the carbon precursor material has a carbon yield of less than 70%.
19. The process of claim 18 , further comprising a step of compressing said carbonized composite film during or after said step (c) of carbonizing the precursor composite film.
20. The process of claim 18 , further comprising a step of compressing said graphitic film during or after said step (d) of thermally treating the carbonized composite film.
21. The process of claim 18 , wherein said carbon precursor material has a carbon yield of less than 50%.
22. The process of claim 18 , wherein said carbon precursor material is selected from a monomer, an oligomer, an organic material, a polymer, or a combination thereof.
23. The process of claim 18 , wherein said carbon precursor material has a carbon yield of less than 30%.
24. A process for producing a graphitic film comprising the steps of:
(a) mixing expanded graphite flakes with a carbon precursor material and a liquid to form a slurry and forming said slurry into a wet film under the influence of an orientation-inducing stress field to align said expanded graphite flakes along planar directions of said wet film;
(b) removing said liquid to form an expanded graphite flake-filled precursor composite film wherein the expanded graphite flakes occupy a weight fraction of 1% to 99% based on the total precursor composite weight;
(c) carbonizing the precursor composite film at a carbonization temperature of at least 300° C. to obtain a carbonized composite film; and
(d) thermally treating the carbonized composite film at a final graphitization temperature higher than 1,500° C. to obtain the graphitic film having a mosaic spread value of 0.2-1.0.
25. The process of claim 24 , wherein said carbon precursor material is selected from the group consisting of polyimide, polyamide, polyoxadiazole, polybenzoxazole, polybenzobisoxazole, polythiazole, polybenzothiazole, polybenzobisthiazole, poly(p-phenylene vinylene), polybenzimidazole, polybenzobisimidazole, phenolic resin, poly(furfuryl alcohol), polyacrylonitrile, and combinations thereof.