Method of preparing nitrogen-doped graphene and method of producing composite heat dispatching plate thereof
10494557 ยท 2019-12-03
Assignee
Inventors
Cpc classification
H01L23/373
ELECTRICITY
International classification
Abstract
The present invention relates to a method of preparing nitrogen-doped graphene, comprising: mixing at least one solid-state nitrogen containing precursor with a graphene to form a mixture, and sintering the mixture under a reducing atmosphere to obtain the nitrogen-doped graphene. The present invention further provides a method of producing a composite heat dispatching plate coated with nitrogen-doped graphene film, comprising: mixing a nitrogen-doped graphene obtained aforementioned with a polymer bonding agent to form a mixture slurry, coating the mixture slurry onto at least one surface of a metal substrate to form a composite material, drying the composite material, and obtaining the composite heat dispatching plate with a film of nitrogen-doped graphene. Structural defects of graphene lattices are reduced during doping process so that crystallinity and thermal conductivity are improved. Methods of the present invention may be conducted under normal pressure using commercially available solid-state nitrogen sources without adding polluting solvents to provide a safe, stable and cost effective preparation of composite heat dispatching material.
Claims
1. A method of preparing nitrogen-doped graphene for a heat dispatching plate, comprising the steps of: mixing at least one solid-state precursor containing nitrogen with a solid-state graphene to directly form a powder mixture by using a solid phase mixing method; and sintering said powder mixture under a reducing atmosphere to obtain said nitrogen-doped graphene, wherein said solid-state precursor containing nitrogen is an organic solid-state nitrogen source, and said organic solid-state nitrogen source is selected from at least one of the following: C.sub.6H.sub.5COONH.sub.4, HOC(CO.sub.2NH.sub.4)(CH.sub.2CO.sub.2NH.sub.4).sub.2, HCO.sub.2NH.sub.4, C.sub.11H.sub.7N, C.sub.10H.sub.6(CN).sub.2 and C.sub.12H.sub.7NO.sub.2.
2. The method of preparing nitrogen-doped graphene according to claim 1, wherein said solid-state precursor containing nitrogen is a combination of an organic solid-state nitrogen source and an inorganic solid-state nitrogen source; said organic solid-state nitrogen source is selected from at least one of the following: C.sub.6H.sub.12N.sub.4, C.sub.6H.sub.5COONH.sub.4, (NH.sub.4).sub.2CO.sub.3, HOC(CO.sub.2NH.sub.4)(CH.sub.2CO.sub.2NH.sub.4).sub.2, HCO.sub.2NH.sub.4, C.sub.11H.sub.7N, C.sub.3H.sub.3N.sub.6, C.sub.10H.sub.6(CN).sub.2 and C.sub.12H.sub.7NO.sub.2; and said inorganic solid-state nitrogen source is selected from at least one of NH.sub.4NO.sub.3 and other inorganic nitrate salts.
3. The method of preparing nitrogen-doped graphene according to claim 1, wherein said solid-state graphene is selected from at least one of monolayer graphene, multilayer graphene, reduced graphene oxide and graphene derivatives.
4. The method of preparing nitrogen-doped graphene according to claim 1, wherein said nitrogen-doped graphene has bonding configurations of Pyridinic N(398.1399.3 eV) and Graphitic N(401.1402.7 eV).
5. The method of preparing nitrogen-doped graphene according to claim 1, wherein a mass mixing ratio between said solid-state precursor containing nitrogen and said solid-state graphene is over 1.
6. The method of preparing nitrogen-doped graphene according to claim 1, wherein a mass mixing ratio between said solid-state graphene and said solid-state precursor containing nitrogen is between 1:1 and 1:30.
7. The method of preparing nitrogen-doped graphene according to claim 1, wherein a nitrogen content of said nitrogen-doped graphene is between 0.04 wt % and 5 wt %.
8. The method of preparing nitrogen-doped graphene according to claim 1, wherein said powder mixture is sintered under a temperature between 300 C. and 800 C.
9. The method of preparing nitrogen-doped graphene according to claim 1, wherein said powder mixture is sintered for 0.5 to 10 hours.
10. A method of producing a composite heat dispatching plate, comprising the steps of: mixing a nitrogen-doped graphene with a polymer bonding agent to form a mixture slurry, wherein said nitrogen-doped graphene is prepared by using any of the methods of claims 1, 3 to 9, wherein said nitrogen-doped graphene content in said mixture slurry is between 50 wt % and 93 wt %; coating said mixture slurry onto at least one surface of a metal substrate to form a composite material; drying said composite material; and obtaining said composite heat dispatching plate with a coating of nitrogen-doped graphene.
11. The method of producing a composite heat dispatching plate according to claim 10, wherein said polymer bonding agent is Carboxymethyl Cellulose.
12. The method of producing a composite heat dispatching plate according to claim 10, wherein said mixture slurry further comprising an electricity conductive agent, an adhesive agent, or a combination thereof.
13. The method of producing a composite heat dispatching plate according to claim 10, wherein said nitrogen-doped graphene content in said mixture slurry is between 89 wt % and 92 wt %.
14. The method of producing a composite heat dispatching plate according to claim 13, wherein said mixture slurry further comprises 8 wt % to 11 wt % of conductive graphite, Carboxymethyl cellulose and butadiene styrene rubber.
15. The method of producing a composite heat dispatching plate according to claim 10, wherein said metal substrate is a copper foil.
16. The method of producing a composite heat dispatching plate according to claim 10, wherein a thickness of said nitrogen doped graphene coating is between 15 um and 65 um.
17. The method of producing a composite heat dispatching plate according to claim 10, wherein said mixture slurry further comprises 7 wt % to 50 wt % of conductive graphite, Carboxymethyl Cellulose and butadiene styrene rubber.
18. A method of preparing nitrogen-doped graphene for a heat dispatching plate, comprising: mixing at least one solid-state precursor containing nitrogen with a solid-state graphene to directly form a powder mixture; and sintering said powder mixture under a reducing atmosphere to obtain said nitrogen-doped graphene, wherein said solid-state precursor containing nitrogen is an organic solid-state nitrogen source, and said organic solid-state nitrogen source is selected from at least one of the following: C.sub.6H.sub.5COONH.sub.4, HOC(CO.sub.2NH.sub.4)(CH.sub.2CO.sub.2NH.sub.4).sub.2, HCO.sub.2NH.sub.4, C.sub.11H.sub.7N, C.sub.10H.sub.6(CN).sub.2 and C.sub.12H.sub.7NO.sub.2.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The above and other objects, features and advantages of the present invention will be apparent from the following detailed description of the embodiments of the invention in conjunction with the accompanying drawings, in which:
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DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
(10) The present invention is explained in relation to its embodiments and experimental samples. Any person of ordinary skills in the art shall understand methods disclosed in the present invention and appreciate advantages and benefits other than mentioned therein. It is to be understood that many other possible modifications and variations can be made without departing from the spirit and scope of the invention as hereinafter claimed.
(11) The following description discloses a nitrogen-doped graphene (referred as N-graphene hereafter), a method of preparing the N-graphene, and embodiments of a testing device thereof. The description further discloses a composite heat dispatching plate coated with N-graphene and a method of producing thereof, as well as effects of various coating thicknesses, single or double sided coated, and facing direction of the film. It should be noted that drawings in the description are only schematic representatives of features of the present invention, and are not scaled to actual dimensions.
(12) The present invention provides an N-graphene, including the following chemical bonding configurations: Pyridinic N (398.1399.3 eV) and Graphitic N (401.1402.7 eV), wherein solid-state nitrogen sources may be organic or inorganic nitrogen sources, the organic nitrogen sources include C.sub.6H.sub.12N.sub.4(HMT), C.sub.6H.sub.5COONH.sub.4, (NH.sub.4).sub.2CO.sub.3, HOC(CO.sub.2NH.sub.4)(CH.sub.2CO.sub.2NH.sub.4).sub.2, HCO.sub.2NH.sub.4, C.sub.11H.sub.7N, C.sub.3H.sub.3N.sub.6, C.sub.10H.sub.6(CN).sub.2 and C.sub.12H.sub.7NO.sub.2, and the inorganic nitrogen sources include NH.sub.4NO.sub.3 and other inorganic nitrate salts.
(13) The method of preparing N-graphene of the present invention may also utilize graphene obtained from mechanical exfoliation or oxidation reduction; and then mix the graphene with the organic or inorganic nitrogen sources, dope nitrogen into structures of graphene, improve completeness of graphene lattices, and better crystallinity and thermal conductivity of the graphene. The graphene may be selected from at least one of monolayer graphene, multilayer graphene, graphene oxide, reduced graphene and graphene derivatives.
(14) With reference to
(15) With reference to Table 1 below, 1 (one) gram of graphene is analyzed for its nitrogen, oxygen and carbon contents using X-ray photoelectron spectroscopy (XPS). The results as indicated in column 1 of Table 1 are used as a basis for comparison for content analysis of embodiments 1 to 7. In addition, scanning electron microscope (SEM) image of the graphene as another basis for comparison is shown in
(16) Embodiment 1 of the present invention provides a structure of N-graphene and a preparing method thereof with the following steps: mixing 1 (one) gram of graphene and 1 (one) gram of solid-state Hexamethylenetetramine (HMT) (C.sub.6H.sub.12N.sub.4) thoroughly to form a mixture, grinding and placing above mixture in a crucible (or thoroughly mixing without grinding, not restricted thereto in the present invention), placing the crucible in a high temperature sintering furnace to sinter under the temperature of 800 C. and a H2/N2 reducing atmosphere for 8 (eight) hours, and finally removing the crucible and obtaining N-graphene from the furnace. The N-graphene may be in the form of powder or any other forms of solids, and not restricted in the present invention.
(17) With reference to Table 1, the N-graphene obtained in embodiment 1 is analyzed for nitrogen, oxygen and carbon contents using XPS, and the result is shown in column 2 of Table 1.
(18) Embodiments 2 to 7 of the present invention provide a structure of N-graphene and preparing methods thereof, wherein the steps, conditions and the type of solid-state nitrogen containing precursor are the same as embodiment 1. The differences in embodiment 2 to 7 are different masses of solid-state HMT are added. The mass ratios between graphene and solid-state EMT are 1:3, 1:5, 1:7, 1:10, 1:20 and 1:30 respectively. The nitrogen, oxygen and carbon contents in each of embodiment 2 to 7 are subsequently analyzed using XPS, and the results are as shown in Table 1 and bond energies thereof in
(19) With reference to Table 1, embodiment 6 is a result of additional 20 wt % solid-state HMT to the basis for comparison, wherein the nitrogen content is 3.92% higher as compared to the basis. With further reference to
(20) Embodiments 8 to 11 provide a structure of N-graphene and a preparing method thereof, wherein the steps and conditions of solid-state nitrogen containing precursor mixing ratio are the same as embodiment 1. The differences in embodiment 8 to 11 are different organic and/or inorganic solid-state nitrogen sources adding to them. The added organic and/or inorganic solid-state nitrogen sources are (NH.sub.4).sub.2CO.sub.3, NH.sub.4NO.sub.3, NCO.sub.2NH.sub.4 and C.sub.3H.sub.3N.sub.6 respectively, as indicated in Table 2.
(21) The nitrogen, oxygen and carbon contents of N-graphene of embodiments 8 to 11 are analyzed using XPS, and the results are shown as in Table 2.
(22) TABLE-US-00001 TABLE 1 graphene:HMT C wt. % O wt. % N wt. % Basis for 1:0 86.65 10.2 0 comparison Embodiment 1 1:1 80.78 12.19 3.27 Embodiment 2 1:3 77.7 14.05 3.04 Embodiment 3 1:5 78.81 14.32 2.41 Embodiment 4 1:7 81.62 11.85 3.34 Embodiment 5 1:10 82.37 10.51 4.61 Embodiment 6 1:20 80.13 12.75 3.92 Embodiment 7 1:30 82.63 11.9 3.53
(23) TABLE-US-00002 TABLE 2 Solid-state Embodiment nitrogen source C wt. % O wt. % N wt. % 8 (NH.sub.4).sub.2CO.sub.3 90.57 8.21 1.14 9 NH.sub.4NO.sub.3 91.78 8.22 0.04 10 HCO.sub.2NH.sub.4 92.37 6.25 1.3 11 C.sub.3H.sub.3N.sub.6 89.17 7.47 3.36
(24) Experimental samples 1 to 13 provide a structure of composite heat dispatching plate coated with graphene that is not nitrogen doped. With reference to
(25) Experimental sample 5 of the present invention provides a structure of a composite heat dispatching plate coated with graphene not being nitrogen doped, and a preparing method thereof, including following steps: preparing 1.5 g graphene, 0.1011 g CMC, 0.0506 g Super-P, 0.0337 g SBR, adding water as solvent and aforementioned ingredients orderly into a homogenizer mixer, mixing thoroughly to form a mixture slurry, applying the mixture slurry onto a copper foil 102, coating the mixture slurry onto the copper foil 102 using a coating applicator, placing the coated copper foil 102 into a high temperature furnace to remove water at the temperature 40 C. to 100 C. to obtain a composite material, measuring the thickness of the composite material, and pressing the composite material to 50 m with appropriate pressing rate to obtain the composite heat dispatching plate 100 coated with the graphene film not being nitrogen doped 101.
(26) With reference to
(27) With reference to Table 3, experimental sample 5 is the result of additional 40 wt % to experimental sample 1. Comparing to experimental sample 1, the coating thickness is 10 m thinner, but the heat dispatching performance is 1.27 C. higher. With further reference to
(28) Experimental samples 10 and 13 have the same graphene content of 60 wt %, the same proportions of KS-6, Super-P, CMC and SBR, and both have the graphene film not being nitrogen doped 101 coated on double sides. The only difference is coating thicknesses and the result is that the heat dispatching performance of experimental sample 13 is 0.7 C. higher than that of experimental 10. Therefore, a thicker graphene film not being nitrogen doped has higher graphene content and better heat dispatching performance as compared to a thinner graphene film not being nitrogen doped.
(29) Experimental samples 12 and 13 have the same graphene content of 60 wt %, the same proportions of KS-6, Super-P, CMC and SBR, and both have the same thickness of the graphene film not being nitrogen doped 101. The only difference is the coating method where experimental sample 12 being single side coated with the graphene film not being nitrogen doped 101 and experimental sample 13 being double sides coated. The result is that the heat dispatching performance of experimental sample 13 is 0.8 C. higher than that of experimental 12. Therefore, a double sides coating allows one side of the graphene film not being nitrogen doped 101 to absorb heats, and another side of the graphene film not being nitrogen doped 101 to dispatch heats. Therefore, the double sides coating has better heat dispatching performance as compared to the single side coating.
(30) TABLE-US-00003 TABLE 3 Single/ Copper Double Foil/Coating Experimental Graphene KS-6 Super-P CMC SBR Side thickness T1-T2 Sample (wt.) % (wt.) % (wt.) % (wt.) % (wt.) % coating (m) ( C.) 1 50 35 5 6 4 Single 35/25 0.03 2 60 25 5 6 4 Single 35/25 0.1 3 70 15 5 6 4 Single 35/25 0.3 4 80 5 5 6 4 Single 35/25 0.4 5 89 3 6 2 Single 35/15 1.3 6 89 3 6 2 Double 35/65 1.9 7 90 10 Single 35/25 0.3 8 92 8 Single 35/15 0.7 9 93 7 Single 35/15 0.34 10 60 25 5 6 4 Double 35/25 0.2 11 60 25 5 6 4 Double 35/25 0.6 12 60 25 5 6 4 Single 35/50 0.1 13 60 25 5 6 4 Double 35/50 0.9
(31) Embodiment 12 of the present invention provides a structure and a method of preparing a composite heat dispatching plate coated with N-graphene, wherein the preparing steps and conditions are similar to experimental sample 5, except embodiment 12 uses the same N-graphene obtained in embodiment 6. The N-graphene content is 89 wt % and the proportions of KS-6, Super-P, CMC and SBR, coating thickness, and coating method are the same. Table 4 indicates differences in heat dispatching performances between N-graphene and graphene not being nitrogen doped.
(32) With reference to
(33) Embodiments 13 and 14 of the present invention provide a structure and a method of preparing a composite heat dispatching plate coated with N-graphene, wherein the preparing steps and conditions are similar to experimental sample 5, except embodiments 13 and 14 use the same N-graphene obtained in embodiment 6. The N-graphene contents of embodiments 13 and 14 are 89 wt % and 92 wt % respectively. Proportions of Super-P, CMC and SBR of embodiment 13 are 3 wt %, 6 wt % and 2 wt % respectively. Proportions of Super-P, CMC and SBR of embodiment 14 are 0 wt %, 8 wt % and 0 wt % respectively. Embodiments 13 and 14 are both single side coated with the thickness of 15 m. Table 4 indicates different heat dispatching performances between different content proportions of N-graphene.
(34) With reference to
(35) It is further noted in results of experimental sample 5 and embodiments 12 to 14 in Table 4, the heat dispatching performances drop when the temperature of the heating chip 107 reaches 90 C. The reason being the high temperature causes N-graphene molecules to vibrate at a higher frequency, hence the contacting surface between the coated N-graphene film 101 and the copper foil 102 is reduced and causing the dropping heat dispatching performance. Even the heating chip 107 is heated to 90 C. as shown in embodiments 13-14, the temperature testing method of T1-T2 ( C.) in the present invention is positive, which is still better than the copper foil 102 using alone and can effectively enhance the ability of heat dispatching performance about 0.2-0.4 C.
(36) TABLE-US-00004 TABLE 4 Graphene or Single/ Copper N-graphene Heating Chip Double Foil/Coating N-graphene film Temperature Super-P CMC SBR side thickness T1-T2 film (wt.) % ( C.) (wt.) % (wt.) % (wt.) % coating (m) ( C.) Experimental No 89 75 3 6 2 Single 35/15 1.3 Sample 5 Embodiment Yes 89 75 3 6 2 Single 35/15 2.7 12 Embodiment Yes 89 90 3 6 2 Single 35/15 0.4 13 Embodiment Yes 92 90 8 Single 35/15 0.2 14
(37) With reference to
(38) The observation results of the thermal imaging camera show that the composite heat dispatching plate 100 coated with N-graphene film 101 increases heat radiation absorption and thermal conduction efficiency. With reference to