CN103449415A - Preparation method of boron-doped graphene - Google Patents
Preparation method of boron-doped graphene Download PDFInfo
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- CN103449415A CN103449415A CN2012101765726A CN201210176572A CN103449415A CN 103449415 A CN103449415 A CN 103449415A CN 2012101765726 A CN2012101765726 A CN 2012101765726A CN 201210176572 A CN201210176572 A CN 201210176572A CN 103449415 A CN103449415 A CN 103449415A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 229910052796 boron Inorganic materials 0.000 claims abstract description 96
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 95
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 34
- 230000001681 protective effect Effects 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims description 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 20
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 5
- ZXNQLIVFWAFRKQ-UHFFFAOYSA-N [B].CC Chemical compound [B].CC ZXNQLIVFWAFRKQ-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 206010040844 Skin exfoliation Diseases 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- 230000035618 desquamation Effects 0.000 claims description 3
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000004506 ultrasonic cleaning Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ACZDXRVCACAKLV-UHFFFAOYSA-N [B].[C].[O] Chemical compound [B].[C].[O] ACZDXRVCACAKLV-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 238000004611 spectroscopical analysis Methods 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 150000001638 boron Chemical class 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004050 hot filament vapor deposition Methods 0.000 description 1
- 238000001182 laser chemical vapour deposition Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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Abstract
The invention discloses a preparation method of boron-doped graphene. The preparation method comprises the following steps of putting a substrate into a reaction chamber of a chemical vapor deposition device, heating the substrate to a temperature of 500-1300 DEG C, and in a gas protective atmosphere, alternately feeding a gaseous carbon source and a gaseous boron source into the reaction chamber, wherein each gas feeding process is carried out for 1-60min and the boron-doped graphene is produced on the surface of the substrate. The boron-doped graphene obtained by the preparation method has high boron content.
Description
Technical field
The present invention relates to a kind of preparation method of boron doped graphene and the preparation method of lithium ion battery.
Background technology
Graphene is as a kind of new carbon, since within 2004, being found, due to its two-dimentional unimolecular layer structure and excellent physical properties, as high theoretical specific surface area, excellent physical strength, good snappiness and high specific conductivity etc., and be widely used.And the derivative of Graphene also is subject to investigator's extensive concern, the Graphene derivative mainly contains nitrogen-doped graphene and boron doped graphene at present.Wherein the boron doped graphene, due to the outer few electronics of boron atom ratio carbon atom, is the doping of P-type, compare Graphene and have better energy-storage property, and the boron content of boron doped graphene is higher, and energy-storage property is better.
When at present prepared by the boron doped graphene, normally at high temperature the gaseous precursor of boron and carbon material are reacted and make the carbon on doped element replacement carbon material.Yet the contact area of gaseous precursor and carbon material is limited, thus the boron content of boron doped graphene of preparation all below 3%, content is lower.
Summary of the invention
Based on this, be necessary to provide the preparation method of the boron doped graphene that a kind of boron content is higher.
A kind of preparation method of boron doped graphene, comprise the steps:
Substrate is positioned over to the reaction chamber of chemical vapor depsotition equipment, heating described substrate, to make described substrate temperature be 500 ℃ ~ 1300 ℃; And
Under the protective gas atmosphere, alternately in described reaction chamber, pass into gaseous carbon source and gaseous boron source, continue 1min ~ 60min at every turn, generate the boron doped graphene at described substrate surface.
In embodiment, described protective gas is selected from least one in nitrogen and argon gas therein.
In embodiment, described gaseous carbon source is selected from least one in methane, ethane, ethene and acetylene therein.
In embodiment, described gaseous boron source is selected from least one in boron trichloride and ethane boron therein.
In embodiment, the flow in described gaseous carbon source and described gaseous boron source is 50mL/min ~ 300mL/min therein; Described gaseous carbon source and described gaseous boron source flow proportional be 1:0.5 ~ 1:3.
In embodiment, the flow of described protective gas is 50mL/min ~ 200mL/min therein.
In embodiment, pass into gaseous carbon source 5 times ~ 20 times in reaction chamber, and pass into the gaseous boron source 5 times ~ 20 times in reaction chamber therein.
In embodiment, described substrate is selected from least one in Copper Foil, iron foil and nickel foil therein.
In embodiment, after substrate is positioned over to described reaction chamber, in described reaction chamber, pass into protective gas therein, adopt mechanical pump, lobe pump and molecular pump are evacuated to 10 by reaction chamber step by step
-3below Pa, and keep 1 ~ 30min, stop afterwards passing into protective gas, the closure molecule pump, start described substrate is heated.
In embodiment, the preparation method of described boron doped graphene also comprises step therein: by described boron doped graphene from described substrate desquamation.
The preparation method of above-mentioned boron doped graphene generates Graphene when passing into carbon source, the part carbon atom that the boron atom replaces on the Graphene generated when passing into the boron source generates doped graphene, again pass into carbon source at doped graphene Surface Creation Graphene, can again be replaced passing into the boron source, so circulation, by alternately in reaction chamber, passing into carbon source and boron source, thereby can increase the contact area of the Graphene of boron source and generation, improve the probability that the boron source replaces the Graphene carbon atom, therefore in the boron doped graphene that prepared by the preparation method of this boron doped graphene, the content of boron is higher.
The accompanying drawing explanation
The preparation method's of the boron doped graphene that Fig. 1 is an embodiment schema;
The XPS collection of illustrative plates of the boron doped graphene that Fig. 2 is embodiment 1 preparation;
The XPS-B1s collection of illustrative plates of the boron doped graphene that Fig. 3 is embodiment 1 preparation.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement much to be different from alternate manner described here, those skilled in the art can be in the situation that do similar improvement without prejudice to intension of the present invention, so the present invention is not subject to the restriction of following public concrete enforcement.
Refer to Fig. 1, the preparation method of the boron doped graphene of an embodiment, comprise the steps:
Step S110, substrate is positioned over to the reaction chamber of chemical vapor depsotition equipment, it is 500 ℃ ~ 1300 ℃ that heated substrate makes substrate temperature.
Preferably, substrate is selected from least one in Copper Foil, iron foil and nickel foil.
Preferably, substrate was first used successively deionized water, ethanol and acetone ultrasonic cleaning post-drying before being positioned over reaction chamber.
Preferably, chemical vapor depsotition equipment is that hot-filament chemical vapor deposition equipment, radio-frequency plasma strengthen chemical vapor depsotition equipment, microwave plasma enhanced chemical vapor depsotition equipment, laser chemical vapor deposition equipment, low pressure chemical vapor deposition equipment or aumospheric pressure cvd equipment.
Preferably, after substrate is positioned over to reaction chamber, in reaction chamber, pass into protective gas, adopt mechanical pump, lobe pump and molecular pump are evacuated to 10 by reaction chamber step by step
-3below Pa, and keep 1 ~ 30min, stop afterwards passing into protective gas, the closure molecule pump, start substrate is heated.Protective gas is selected from least one in nitrogen and argon gas.
Step S120, under the protective gas atmosphere, alternately in reaction chamber, pass into gaseous carbon source and gaseous boron source, continue 1min ~ 60min at every turn, generate the boron doped graphene at substrate surface.
Preferably, protective gas is selected from least one in nitrogen and argon gas.
Preferably, the flow of protective gas is 50mL/min ~ 200mL/min.
Preferably, gaseous carbon source is selected from least one in methane, ethane, ethene and acetylene.
Preferably, the gaseous boron source is selected from least one in boron trichloride and ethane boron.
Preferably, the flow in gaseous carbon source and gaseous boron source is 50mL/min ~ 300mL/min.
Preferably, gaseous carbon source and gaseous boron source flow proportional be 1:0.5 ~ 1:3.
Preferably, alternate cycles 5 times ~ 20 times passes into gaseous carbon source 5 times ~ 20 times in reaction chamber, in reaction chamber, passes into the gaseous boron source 5 times ~ 20 times.
In this step, generate Graphene when passing into carbon source, the part carbon atom that the boron atom replaces on the Graphene generated when passing into the boron source generates doped graphene, again passes into carbon source at doped graphene Surface Creation Graphene, can again be replaced passing into the boron source, so circulation.
Step S130, by the boron doped graphene from substrate desquamation.
The preparation method of above-mentioned boron doped graphene, utilize chemical Vapor deposition process, generate Graphene when passing into carbon source, the part carbon atom that the boron atom replaces on the Graphene generated when passing into the boron source generates doped graphene, again pass into carbon source at doped graphene Surface Creation Graphene, can again be replaced passing into the boron source, so circulation, by alternately in reaction chamber, passing into carbon source and boron source, thereby can increase the contact area of the Graphene of boron source and generation, improve the probability that the boron source replaces the Graphene carbon atom, therefore the higher and uniform doping of the content of boron in the boron doped graphene that prepared by the preparation method of this boron doped graphene.
Below in conjunction with specific embodiment, further illustrate.
Embodiment 1
(1) by deionized water, ethanol, acetone ultrasonic cleaning post-drying for substrate;
(2) substrate is put into to reaction chamber, is filled with nitrogen, and adopt mechanical pump, lobe pump and molecular pump are evacuated to 10 by reaction chamber step by step
-3below Pa, and, after keeping 30 minutes, stop filling nitrogen, air to close closes molecular pump, starts heating;
(3) when underlayer temperature reaches 1000 ℃, 100ml/ minute) and argon gas (flow: 100ml/ minute), continue 30 minutes, stop passing into methane beginning is filled with methane (flow: to reaction chamber, then pass into boron trichloride (flow: 100ml/min minute), argon gas remains unchanged, and continues 30 minutes, so step methane and the boron trichloride of alternately being filled with, circulate 5 times, stop heating, naturally be down to room temperature, obtain the boron doped graphene.
Table 1
| Element | Carbon | Boron | Oxygen element |
| Content (%) | 78.7 | 18.2 | 3.1 |
Refer to table 1, table 1 is depicted as the mass content of each principal element that boron doped graphene that embodiment 1 obtains draws by X-ray photoelectron spectroscopic analysis (XPS) test.As can be seen from Table 1, the boron-containing quantity of the boron doped graphene of embodiment 1 preparation is higher, is 18.2%.
Refer to Fig. 2 and Fig. 3, in Fig. 2 and Fig. 3, the absorption peak of boron all, between 187eV-193eV, proves that the boron on the boron doped graphene has all mixed Graphene, rather than exists with the pure boron form.
Embodiment 2
(1) by deionized water, ethanol, acetone ultrasonic cleaning post-drying for substrate;
(2) substrate is put into to reaction chamber, is filled with nitrogen, and adopt mechanical pump, lobe pump and molecular pump are evacuated to 10 by reaction chamber step by step
-3below Pa, and, after keeping 30 minutes, stop filling nitrogen, air to close closes molecular pump, starts heating;
(3) when underlayer temperature reaches 900 ℃, 100ml/ minute) and argon gas (flow: 100ml/ minute), continue 15 minutes, stop passing into ethene beginning is filled with ethene (flow: to reaction chamber, then pass into boron trichloride (flow: 300ml/min minute), argon gas remains unchanged, and continues 15 minutes, so step gaseous carbon sources and the gas boron source of being filled with, circulate 10 times, stop heating, naturally be down to room temperature, obtain the boron doped graphene.
Table 2
| Element | Carbon | Boron | Oxygen element |
| Content (%) | 75.9 | 21.2 | 2.9 |
Refer to table 2, table 2 is depicted as the mass content of each principal element that boron doped graphene that embodiment 2 obtains draws by X-ray photoelectron spectroscopic analysis (XPS) test.As can be seen from Table 2, the boron-containing quantity of the boron doped graphene of embodiment 2 preparations is higher, is 21.2%.
Embodiment 3
(1) by deionized water, ethanol, acetone ultrasonic cleaning post-drying for substrate;
(2) substrate is put into to reaction chamber, is filled with nitrogen, and adopt mechanical pump, lobe pump and molecular pump are evacuated to 10 by reaction chamber step by step
-3below Pa, and, after keeping 20 minutes, stop filling nitrogen, air to close closes molecular pump, starts heating;
(3) when underlayer temperature reaches 500 ℃, 100ml/ minute) and argon gas (flow: 50ml/ minute), continue 20 minutes, stop passing into methane beginning is filled with methane (flow: to reaction chamber, then pass into boron trichloride (flow: 50ml/min minute), argon gas remains unchanged, and continues 20 minutes, so step methane and the boron trichloride of being filled with, circulate 20 times, stop heating, naturally be down to room temperature, obtain the boron doped graphene.
Table 3
| Element | Carbon | Boron | Oxygen element |
| Content (%) | 84.1 | 12.3 | 3.6 |
Refer to table 3, table 3 is depicted as the mass content of each principal element that boron doped graphene that embodiment 3 obtains draws by X-ray photoelectron spectroscopic analysis (XPS) test.As can be seen from Table 3, the boron-containing quantity of the boron doped graphene of embodiment 3 preparations is higher, is 12.3%.
Embodiment 4
(1) by deionized water, ethanol, acetone ultrasonic cleaning post-drying for substrate;
(2) substrate is put into to reaction chamber, is filled with nitrogen, and adopt mechanical pump, lobe pump and molecular pump are evacuated to 10 by reaction chamber step by step
-3below Pa, and, after keeping 30 minutes, stop filling nitrogen, air to close closes molecular pump, starts heating;
(3) when underlayer temperature reaches 1300 ℃, 150ml/ minute) and argon gas (flow: 200ml/ minute), continue 5 minutes, stop passing into methane beginning is filled with acetylene (flow: to reaction chamber, then pass into ethane boron (flow: 150ml/min minute), argon gas remains unchanged, and continues 5 minutes, so step acetylene and the boron trichloride of being filled with, circulate 20 times, stop heating, naturally be down to room temperature, obtain the boron doped graphene.
Table 4
| Element | Carbon | Boron | Oxygen element |
| Content (%) | 77.6 | 20.1 | 2.3 |
Refer to table 4, table 4 is depicted as the mass content of each principal element that boron doped graphene that embodiment 4 obtains draws by X-ray photoelectron spectroscopic analysis (XPS) test.As can be seen from Table 4, the boron-containing quantity of the boron doped graphene of embodiment 4 preparations is higher, is 20.1%.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. the preparation method of a boron doped graphene, is characterized in that, comprises the steps:
Substrate is positioned over to the reaction chamber of chemical vapor depsotition equipment, heating described substrate, to make described substrate temperature be 500 ℃ ~ 1300 ℃; And
Under the protective gas atmosphere, alternately in described reaction chamber, pass into gaseous carbon source and gaseous boron source, continue 1min ~ 60min at every turn, generate the boron doped graphene at described substrate surface.
2. the preparation method of boron doped graphene according to claim 1, is characterized in that, described protective gas is selected from least one in nitrogen and argon gas.
3. the preparation method of boron doped graphene according to claim 1, is characterized in that, described gaseous carbon source is selected from least one in methane, ethane, ethene and acetylene.
4. the preparation method of boron doped graphene according to claim 1, is characterized in that, described gaseous boron source is selected from least one of boron trichloride and ethane boron.
5. the preparation method of boron doped graphene according to claim 1, is characterized in that, the flow in described gaseous carbon source and described gaseous boron source is 50mL/min ~ 300mL/min; Described gaseous carbon source and described gaseous boron source flow proportional be 1:0.5 ~ 1:3.
6. the preparation method of boron doped graphene according to claim 1, is characterized in that, the flow of described protective gas is 50mL/min ~ 200mL/min.
7. the preparation method of boron doped graphene according to claim 1, is characterized in that, in reaction chamber, passes into gaseous carbon source 5 times ~ 20 times, and pass into the gaseous boron source 5 times ~ 20 times in reaction chamber.
8. the preparation method of boron doped graphene according to claim 1, is characterized in that, described substrate is selected from least one in Copper Foil, iron foil and nickel foil.
9. the preparation method of boron doped graphene according to claim 1, is characterized in that, after substrate is positioned over to described reaction chamber, in described reaction chamber, passes into protective gas, adopts mechanical pump, and lobe pump and molecular pump are evacuated to 10 by reaction chamber step by step
-3below Pa, and keep 1 ~ 30min, stop afterwards passing into protective gas, the closure molecule pump, start described substrate is heated.
10. the preparation method of boron doped graphene according to claim 1, is characterized in that, the preparation method of described boron doped graphene also comprises step: by described boron doped graphene from described substrate desquamation.
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| CN106145103A (en) * | 2016-08-10 | 2016-11-23 | 中国人民大学 | A kind of preparation method of two-dimensional layer hetero-junctions based on Graphene |
| CN106966797A (en) * | 2017-04-06 | 2017-07-21 | 浙江伟豪能源科技有限公司 | A kind of fertilizer specially for wheat for adding graphene and preparation method thereof |
| CN107010999A (en) * | 2017-04-06 | 2017-08-04 | 浙江伟豪能源科技有限公司 | A kind of preparation method for the modified graphene that can be applied to fertilizer |
| CN107221666A (en) * | 2017-06-28 | 2017-09-29 | 深圳市贝特瑞纳米科技有限公司 | Combination electrode material of Heteroatom doping graphene coated and preparation method thereof |
| CN108975319A (en) * | 2018-08-22 | 2018-12-11 | 恒力（厦门）石墨烯科技产业集团有限公司 | A kind of preparation method of P-type semiconductor graphene |
| CN109987597A (en) * | 2018-12-25 | 2019-07-09 | 宁波大学 | A kind of preparation method of anisotropic stacked graphene |
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| CN101289181A (en) * | 2008-05-29 | 2008-10-22 | 中国科学院化学研究所 | Doped graphene and preparation method thereof |
| CN102306781A (en) * | 2011-09-05 | 2012-01-04 | 中国科学院金属研究所 | Doped graphene electrode material, macro preparation method and application of doped graphene electrode material |
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| CN101289181A (en) * | 2008-05-29 | 2008-10-22 | 中国科学院化学研究所 | Doped graphene and preparation method thereof |
| CN102306781A (en) * | 2011-09-05 | 2012-01-04 | 中国科学院金属研究所 | Doped graphene electrode material, macro preparation method and application of doped graphene electrode material |
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| CN106145103A (en) * | 2016-08-10 | 2016-11-23 | 中国人民大学 | A kind of preparation method of two-dimensional layer hetero-junctions based on Graphene |
| CN106145103B (en) * | 2016-08-10 | 2018-06-26 | 中国人民大学 | A kind of preparation method of the two-dimensional layer hetero-junctions based on graphene |
| CN106966797A (en) * | 2017-04-06 | 2017-07-21 | 浙江伟豪能源科技有限公司 | A kind of fertilizer specially for wheat for adding graphene and preparation method thereof |
| CN107010999A (en) * | 2017-04-06 | 2017-08-04 | 浙江伟豪能源科技有限公司 | A kind of preparation method for the modified graphene that can be applied to fertilizer |
| CN107221666A (en) * | 2017-06-28 | 2017-09-29 | 深圳市贝特瑞纳米科技有限公司 | Combination electrode material of Heteroatom doping graphene coated and preparation method thereof |
| CN108975319A (en) * | 2018-08-22 | 2018-12-11 | 恒力（厦门）石墨烯科技产业集团有限公司 | A kind of preparation method of P-type semiconductor graphene |
| CN109987597A (en) * | 2018-12-25 | 2019-07-09 | 宁波大学 | A kind of preparation method of anisotropic stacked graphene |
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Application publication date: 20131218 |