CN104058390A - Preparation method for graphene - Google Patents
Preparation method for graphene Download PDFInfo
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- CN104058390A CN104058390A CN201310087411.4A CN201310087411A CN104058390A CN 104058390 A CN104058390 A CN 104058390A CN 201310087411 A CN201310087411 A CN 201310087411A CN 104058390 A CN104058390 A CN 104058390A
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Abstract
The invention discloses graphene and a preparation method thereof. The preparation method comprises the following steps: (1) providing a metal substrate, cleaning the metal substrate, putting the metal substrate into the reaction chamber of chemical vapor deposition equipment, introducing protective gas into the reaction chamber after sealing, stopping introduction of protective gas and carrying out vacuum-pumping so as to allow the reaction chamber to be in a vacuum state; (2) heating the metal substrate to 400 to 500 DEG C, starting an ultraviolet source, allowing the ultraviolet source to irradiate the surface of the metal substrate, introducing a carbon-containing fluid, carrying out a heat-preserved reaction for 10 to 100 min, stopping introduction of the carbon-containing fluid and stopping heating after completion of the reaction, carrying out cooling to room temperature, opening the chemical vapor deposition equipment and taking the metal substrate out so as to obtain the metal substrate with grown graphene on its surface; and (3) soaking the metal substrate with grown graphene on its surface in a corrosive liquid, removing the metal substrate, carrying out filtering, taking a filter residue and carrying out cleaning and drying so as to obtain graphene. The method adopts a chemical vapor phase process for deposition preparation of graphene on the substrate, guarantees the lamellar structure of graphene, simplifies preparation steps and has small energy consumption and low cost.
Description
Technical field
The present invention relates to the synthetic field of material, relate in particular to a kind of preparation method of Graphene.
Background technology
Graphene is between a kind of carbon atom, to be the two-dimensional sheet body that hexagonal annular is arranged, and the people such as the strong K sea nurse of peace moral (Andre K.Geim) of 2004 Nian You Univ Manchester UKs find first.Grapheme material has good conduction, heat conductivility and low thermal expansivity, and its theoretical specific surface area is up to 2630m
2/ g, thus be widely used in that effect transistor, liquid crystal are looked, battery, each field of sensor.
The method of preparing at present Graphene is mainly oxidation reduction process, be specially and first graphite made under the effect of strong acid or strong oxidizer to the graphite oxide of easily peeling off, then by ultrasonic method, form the graphene oxide of individual layer, finally by method of reducing such as strong reductant reduction, high-temperature heating treatment, microwave exposure processing, electrochemical reductions, mono-layer graphite oxide alkene is reduced to grapheme material again.This method cost is low, yield is high, easy to control, is applicable to suitability for industrialized production on a large scale.But because this method must be used strong acid or strong oxidizer in preparation process, the laminated structure of Graphene is destroyed, causes the performance of Graphene greatly to decline.How to overcome above-mentioned technological deficiency, develop new graphene preparation method, become one of the study hotspot in current Graphene field.
Summary of the invention
The object of the invention is to overcome above-mentioned technological deficiency, a kind of preparation method of Graphene is provided, the method adopts chemical gas-phase method to deposit and prepare Graphene on substrate, has both guaranteed the laminated structure of Graphene, has also simplified preparation method, and energy consumption is little, and cost is low.
On the one hand, the invention provides a kind of preparation method of Graphene, comprise the steps:
(1) provide metal substrate, put into the reaction chamber of chemical vapor depsotition equipment after cleaning, after sealing, in reaction chamber, passes into protective gas, stop passing into protective gas, vacuumize, making in reaction chamber is vacuum state;
(2) after being heated to 400～500 ℃, metal substrate opens ultraviolet source irradiation metal substrate surface, then the flow with 50～1000sccm passes into carbon containing fluid, insulation reaction 10～100 minutes, after question response finishes, stop passing into carbon containing fluid and stop heating, after being cooled to room temperature, open chemical vapor depsotition equipment, take out metal substrate, obtain the long metal substrate that has Graphene in surface;
(3) there is the metal substrate of Graphene to be dipped in corrosive fluid described surface length, remove metal substrate, leaching filter residue, dry after cleaning, obtain Graphene.
The present invention adopts the mode of ultraviolet catalytic to produce Graphene, and its principle is: when carbon containing fluid enters after reaction chamber, under high temperature and action of ultraviolet radiation, photodissociation forms carbon atom, is deposited on metal substrate, thereby forms Graphene.
Preferably, the described metal substrate of step (1) is iron foil, Copper Foil, cobalt paper tinsel or nickel foil.
Preferably, metal substrate described in step (1) clean, concrete operations are: metal substrate is dipped in acetone and carries out ultrasonic cleaning 10～30 minutes, then with ethanol and deionized water, carry out ultrasonic cleaning successively.
Preferably, step (1) passes into protective gas with the flow of 20～100sccm in reaction chamber; Vacuum state operating pressure in reaction chamber is 0.1～100Pa.
More preferably, described shielding gas is hydrogen, nitrogen or argon gas.
Preferably, described carbon containing fluid is at least one in methane, ethane, acetylene, propane, carbon monoxide and ethanol.
Preferably, the described corrosive fluid of step (3) is hydrochloric acid or the ferric chloride Solution of concentration 0.01～1mol/L.
Preferably, described in step (3), clean after dry concrete operations be: by the filter residue obtaining with washed with de-ionized water be placed in vacuum drying oven 80～100 ℃ dry 1～2 hour.
The present invention adopts chemical gas-phase method to deposit and prepare Graphene in metal substrate, Graphene is directly grown in metal substrate, and crystalline structure is complete, does not have the factor of destroying graphene-structured in preparation process, thereby the graphene sheet layer structural integrity making, specific conductivity is high.In addition, it is carbon atom by the photodissociation of carbon containing fluid that the present invention adopts the mode of ultraviolet catalytic, only need at 400～500 ℃, can complete, and has further reduced production energy consumption, and preparation method is simple, and cost is low, is applicable to suitability for industrialized production.
Than prior art, the preparation method of Graphene of the present invention has following beneficial effect:
(1) adopt chemical gas-phase method to deposit and prepare Graphene in metal substrate, Graphene is directly grown in metal substrate, and crystalline structure is complete, does not have the factor of destroying graphene-structured in preparation process, thereby the graphene sheet layer structural integrity making, specific conductivity is high;
(2) adopting the mode of ultraviolet catalytic is carbon atom by the photodissociation of carbon containing fluid, only need at 400～500 ℃, can complete, and has further reduced production energy consumption, and preparation method is simple, and cost is low, is applicable to suitability for industrialized production.
Accompanying drawing explanation
In order to be illustrated more clearly in technical scheme of the present invention, to the accompanying drawing of required use in embodiment be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the grapheme material of the embodiment of the present invention one preparation SEM figure under scanning electron microscope.
Embodiment
Below in conjunction with the accompanying drawing in embodiment of the present invention, the technical scheme in embodiment of the present invention is clearly and completely described.
A preparation method for Graphene, comprises the steps:
(1) provide metal substrate, put into the reaction chamber of chemical vapor depsotition equipment after cleaning, after sealing, in reaction chamber, passes into protective gas, stop passing into protective gas, vacuumize, making in reaction chamber is vacuum state;
(2) after being heated to 400～500 ℃, metal substrate opens ultraviolet source irradiation metal substrate surface, then the flow with 50～1000sccm passes into carbon containing fluid, insulation reaction 10～100 minutes, after question response finishes, stop passing into carbon containing fluid and stop heating, after being cooled to room temperature, open chemical vapor depsotition equipment, take out metal substrate, obtain the long metal substrate that has Graphene in surface;
(3) there is the metal substrate of Graphene to be dipped in corrosive fluid described surface length, remove metal substrate, leaching filter residue, dry after cleaning, obtain Graphene.
The present invention adopts the mode of ultraviolet catalytic to produce Graphene, and its principle is: when carbon containing fluid enters after reaction chamber, under high temperature and action of ultraviolet radiation, photodissociation forms carbon atom, is deposited on metal substrate, thereby forms Graphene.
The described metal substrate of step (1) is iron foil, Copper Foil, cobalt paper tinsel or nickel foil.
Cleaning of metal substrate described in step (1), concrete operations are: metal substrate is dipped in acetone and carries out ultrasonic cleaning 10～30 minutes, then with ethanol and deionized water, carry out ultrasonic cleaning successively.
Step (1) passes into protective gas with the flow of 20～100sccm in reaction chamber; Vacuum state operating pressure in reaction chamber is 0.1～100Pa.
Described shielding gas is hydrogen, nitrogen or argon gas.
The described ultraviolet source of step (3), the ultraviolet light wavelength of transmitting is 150～200nm.It is better to the degradation effect of carbon containing fluid that wavelength is less than the UV-light of 200nm.
Described carbon containing fluid is at least one in methane, ethane, acetylene, propane, carbon monoxide and ethanol.
The described corrosive fluid of step (3) is hydrochloric acid or the ferric chloride Solution of concentration 0.01～1mol/L.
After cleaning described in step (3), dry concrete operations are: by the filter residue obtaining with washed with de-ionized water be placed in vacuum drying oven 80～100 ℃ dry 1～2 hour.
The present invention adopts chemical gas-phase method to deposit and prepare Graphene in metal substrate, Graphene is directly grown in metal substrate, and crystalline structure is complete, does not have the factor of destroying graphene-structured in preparation process, thereby the graphene sheet layer structural integrity making, specific conductivity is high.In addition, it is carbon atom by the photodissociation of carbon containing fluid that the present invention adopts the mode of ultraviolet catalytic, only need at 400～500 ℃, can complete, and has further reduced production energy consumption, and preparation method is simple, and cost is low, is applicable to suitability for industrialized production.
Embodiment mono-
A preparation method for Graphene, comprises the steps:
(1) select Copper Foil as metal substrate, first be dipped in acetone soln ultrasonic cleaning 10 minutes, use successively again each ultrasonic cleaning of ethanol and deionized water 10 minutes, then metal substrate is put into chemical vapor depsotition equipment, sealing, the flow of 20sccm of usining passes into hydrogen as shielding gas, then opens air-bleed system, discharges the air in reaction chamber; When question response chamber operating pressure reaches 0.1Pa, metal substrate is heated to 500 ℃.
(2) in reaction chamber, place 185nm vacuum UV lamp, open ultra violet lamp metal substrate surface, then the flow with 50sccm passes into methane, insulation reaction 100 minutes, now methane is subject to be reduced into carbon atom under uv irradiating under hot conditions, and grow in metal substrate, finally on metal substrate surface, form a layer graphene; After reaction finishes, close air valve and the ultraviolet source of methane, and stop heating, continue to pass into hydrogen until metal substrate is cooled to room temperature; Close the air valve of shielding gas, close air-bleed system, open venting port, take out metal substrate, obtain the long metal substrate that has Graphene in surface;
(3) having the metal substrate of Graphene to put in the ferric chloride Solution of 1mol/L described surface length soaks, after being corroded completely, metal substrate filters described ferric chloride Solution, leaching filter residue, with deionized water rinsing 2 times, then filter residue is put into vacuum drying oven, with 100 ℃ dry 1 hour, obtain Graphene.
Embodiment bis-
A preparation method for Graphene, comprises the steps:
(1) select iron foil as metal substrate, first be dipped in acetone soln ultrasonic cleaning 30 minutes, use successively again each ultrasonic cleaning of ethanol and deionized water 30 minutes, then metal substrate is put into chemical vapor depsotition equipment, sealing, the flow of 50sccm of usining passes into helium as shielding gas, then opens air-bleed system, discharges the air in reaction chamber; When question response chamber operating pressure reaches 100Pa, metal substrate is heated to 400 ℃.
(2) in reaction chamber, place 150nm vacuum UV lamp, open ultra violet lamp metal substrate surface, then the flow with 200sccm passes into acetylene, insulation reaction 10 minutes, now acetylene is subject to be reduced into carbon atom under uv irradiating under hot conditions, and grow in metal substrate, finally on metal substrate surface, form a layer graphene; After reaction finishes, close air valve and the ultraviolet source of acetylene, and stop heating, continue to pass into helium until metal substrate is cooled to room temperature; Close the air valve of shielding gas, close air-bleed system, open venting port, take out metal substrate, obtain the long metal substrate that has Graphene in surface;
(3) having the metal substrate of Graphene to put in the hydrochloric acid soln of 0.5mol/L described surface length soaks, after being corroded completely, metal substrate filters described hydrochloric acid soln, leaching filter residue, with deionized water rinsing 2 times, then filter residue is put into vacuum drying oven, with 80 ℃ dry 2 hours, obtain Graphene.
Embodiment tri-
A preparation method for Graphene, comprises the steps:
(1) select cobalt paper tinsel as metal substrate, first be dipped in acetone soln ultrasonic cleaning 20 minutes, use successively again each ultrasonic cleaning of ethanol and deionized water 20 minutes, then metal substrate is put into chemical vapor depsotition equipment, sealing, the flow of 20sccm of usining passes into argon gas as shielding gas, then opens air-bleed system, discharges the air in reaction chamber; When question response chamber operating pressure reaches 50Pa, metal substrate is heated to 450 ℃.
(2) in reaction chamber, place 200nm vacuum UV lamp, open ultra violet lamp metal substrate surface, then the flow with 750sccm passes into ethane, insulation reaction 80 minutes, now ethane is subject to be reduced into carbon atom under uv irradiating under hot conditions, and grow in metal substrate, finally on metal substrate surface, form a layer graphene; After reaction finishes, close air valve and the ultraviolet source of ethane, and stop heating, continue to pass into argon gas until metal substrate is cooled to room temperature; Close the air valve of shielding gas, close air-bleed system, open venting port, take out metal substrate, obtain the long metal substrate that has Graphene in surface;
(3) having the metal substrate of Graphene to put in the ferric chloride Solution of 0.1mol/L described surface length soaks, after being corroded completely, metal substrate filters described ferric chloride Solution, leaching filter residue, with deionized water rinsing 3 times, then filter residue is put into vacuum drying oven, with 100 ℃ dry 1.5 hours, obtain Graphene.
Embodiment tetra-
A preparation method for Graphene, comprises the steps:
(1) select nickel foil as metal substrate, first be dipped in acetone soln ultrasonic cleaning 15 minutes, use successively again each ultrasonic cleaning of ethanol and deionized water 15 minutes, then metal substrate is put into chemical vapor depsotition equipment, sealing, the flow of 80sccm of usining passes into argon gas as shielding gas, then opens air-bleed system, discharges the air in reaction chamber; When question response chamber operating pressure reaches 10Pa, metal substrate is heated to 480 ℃.
(2) in reaction chamber, place 185nm vacuum UV lamp, open ultra violet lamp metal substrate surface, then the flow with 1000sccm passes into propane, insulation reaction 50 minutes, now propane is subject to be reduced into carbon atom under uv irradiating under hot conditions, and grow in metal substrate, finally on metal substrate surface, form a layer graphene; After reaction finishes, close air valve and the ultraviolet source of propane, and stop heating, continue to pass into argon gas until metal substrate is cooled to room temperature; Close the air valve of shielding gas, close air-bleed system, open venting port, take out metal substrate, obtain the long metal substrate that has Graphene in surface;
(3) having the metal substrate of Graphene to put in the ferric chloride Solution of 0.5mol/L described surface length soaks, after being corroded completely, metal substrate filters described ferric chloride Solution, leaching filter residue, with deionized water rinsing 3 times, then filter residue is put into vacuum drying oven, with 95 ℃ dry 1.2 hours, obtain Graphene.
Embodiment five
A preparation method for Graphene, comprises the steps:
(1) select Copper Foil as metal substrate, first be dipped in acetone soln ultrasonic cleaning 20 minutes, use successively again each ultrasonic cleaning of ethanol and deionized water 20 minutes, then metal substrate is put into chemical vapor depsotition equipment, sealing, the flow of 100sccm of usining passes into helium as shielding gas, then opens air-bleed system, discharges the air in reaction chamber; When question response chamber operating pressure reaches 1Pa, metal substrate is heated to 500 ℃.
(2) in reaction chamber, place 185nm vacuum UV lamp, open ultra violet lamp metal substrate surface, then the flow with 450sccm passes into carbon monoxide, insulation reaction 20 minutes, now carbon monoxide is subject to be reduced into carbon atom under uv irradiating under hot conditions, and grow in metal substrate, finally on metal substrate surface, form a layer graphene; After reaction finishes, close air valve and the ultraviolet source of carbon monoxide, and stop heating, continue to pass into helium until metal substrate is cooled to room temperature; Close the air valve of shielding gas, close air-bleed system, open venting port, take out metal substrate, obtain the long metal substrate that has Graphene in surface;
(3) having the metal substrate of Graphene to put in the ferric chloride Solution of 0.2mol/L described surface length soaks, after being corroded completely, metal substrate filters described ferric chloride Solution, leaching filter residue, with deionized water rinsing 3 times, then filter residue is put into vacuum drying oven, with 85 ℃ dry 1.8 hours, obtain Graphene.
Embodiment six
A preparation method for Graphene, comprises the steps:
(1) select nickel foil as metal substrate, first be dipped in acetone soln ultrasonic cleaning 30 minutes, use successively again each ultrasonic cleaning of ethanol and deionized water 30 minutes, then metal substrate is put into chemical vapor depsotition equipment, sealing, the flow of 50sccm of usining passes into hydrogen as shielding gas, then opens air-bleed system, discharges the air in reaction chamber; When question response chamber operating pressure reaches 80Pa, metal substrate is heated to 400 ℃.
(2) in reaction chamber, place 185nm vacuum UV lamp, open ultra violet lamp metal substrate surface, then the flow with 800sccm passes into ethanol, insulation reaction 100 minutes, now ethanol is subject to be reduced into carbon atom under uv irradiating under hot conditions, and grow in metal substrate, finally on metal substrate surface, form a layer graphene; After reaction finishes, close air valve and the ultraviolet source of ethanol, and stop heating, continue to pass into hydrogen until metal substrate is cooled to room temperature; Close the air valve of shielding gas, close air-bleed system, open venting port, take out metal substrate, obtain the long metal substrate that has Graphene in surface;
(3) having the metal substrate of Graphene to put in the ferric chloride Solution of 0.8mol/L described surface length soaks, after being corroded completely, metal substrate filters described ferric chloride Solution, leaching filter residue, with deionized water rinsing 3 times, then filter residue is put into vacuum drying oven, with 90 ℃ dry 1 hour, obtain Graphene.
Effect embodiment
The specific conductivity of the Graphene that employing four probe method test implementation example one～six makes, test result is as shown in table 1.
As can be seen from Table 1, the specific conductivity of the Graphene that the embodiment of the present invention makes is higher, is up to 6.1 * 10
6s/m.
The sign of the grapheme material that employing sem observation embodiment mono-makes, takes SEM figure, and result as shown in Figure 1, as can be seen from Figure 1, the Graphene surface opposed flattened that the embodiment of the present invention makes, there is fold part, thickness is about 1～3nm, width be several microns not etc.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (8)
1. a preparation method for Graphene, is characterized in that, comprises the steps:
(1) provide metal substrate, put into the reaction chamber of chemical vapor depsotition equipment after cleaning, after sealing, in reaction chamber, passes into protective gas, stop passing into protective gas, vacuumize, making in reaction chamber is vacuum state;
(2) after being heated to 400～500 ℃, metal substrate opens ultraviolet source irradiation metal substrate surface, then the flow with 50～1000sccm passes into carbon containing fluid, insulation reaction 10～100 minutes, after question response finishes, stop passing into carbon containing fluid and stop heating, be cooled to after room temperature, take out metal substrate, obtain the long metal substrate that has Graphene in surface;
(3) there is the metal substrate of Graphene to be dipped in corrosive fluid described surface length, remove metal substrate, leaching filter residue, dry after cleaning, obtain Graphene.
2. preparation method as claimed in claim 1, is characterized in that, the described metal substrate of step (1) is iron foil, Copper Foil, cobalt paper tinsel or nickel foil.
3. preparation method as claimed in claim 1, it is characterized in that, cleaning of metal substrate described in step (1), concrete operations are: metal substrate is dipped in acetone and carries out ultrasonic cleaning 10～30 minutes, then with ethanol and deionized water, carry out ultrasonic cleaning successively.
4. preparation method as claimed in claim 1, is characterized in that, step (1) passes into protective gas with the flow of 20～100sccm in reaction chamber; The vacuum state operating pressure of reaction chamber is 0.1～100Pa.
5. the preparation method as described in claim 1 or 4, is characterized in that, described shielding gas is hydrogen, nitrogen or argon gas.
6. preparation method as claimed in claim 1, is characterized in that, described carbon containing fluid is at least one in methane, ethane, acetylene, propane, carbon monoxide and ethanol.
7. preparation method as claimed in claim 1, is characterized in that, the described corrosive fluid of step (3) is hydrochloric acid or the ferric chloride Solution of concentration 0.01～1mol/L.
8. preparation method as claimed in claim 1, is characterized in that, after cleaning described in step (3), dry concrete operations are: by the filter residue obtaining with washed with de-ionized water be placed in vacuum drying oven 80～100 ℃ dry 1～2 hour.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104789941A (en) * | 2015-05-08 | 2015-07-22 | 北京化工大学 | Method for graphene chemical bonding coating by using chemical vapor deposition method |
| TWI571437B (en) * | 2015-11-23 | 2017-02-21 | 炬力奈米科技有限公司 | Method for growing graphene by chemical vapor deposition |
| US20170144888A1 (en) * | 2015-11-23 | 2017-05-25 | G-Force Nanotechnology Ltd. | Method for growing graphene by chemical vapor deposition |
| CN107117827A (en) * | 2017-06-29 | 2017-09-01 | 南陵县生产力促进中心 | The method of graphene is grown on a kind of glass substrate |
| CN107240702A (en) * | 2017-05-19 | 2017-10-10 | 北京理工大学 | A kind of preparation method of high-quality graphene paper tinsel collector |
| CN107416798A (en) * | 2017-06-29 | 2017-12-01 | 南陵县生产力促进中心 | A kind of preparation method for vulcanizing three-dimensional grapheme |
| CN107445147A (en) * | 2017-09-11 | 2017-12-08 | 张洪 | The preparation method and equipment of a kind of graphene |
| CN109179388A (en) * | 2018-10-31 | 2019-01-11 | 青岛科技大学 | A kind of method that carbon monoxide prepares graphene |
| CN109796008A (en) * | 2019-01-19 | 2019-05-24 | 东莞市长瑞精密设备制造有限公司 | A kind of graphene battery negative electrode material and its processing tooling |
| CN111675209A (en) * | 2020-06-02 | 2020-09-18 | 天津理工大学 | Method for growing vertical graphene film by using nitrogen and ethanol |
| CN113666365A (en) * | 2021-09-30 | 2021-11-19 | 萝北奥星新材料有限公司 | Method for preparing single-layer continuous graphene film by using hydrocarbon organic compound |
| CN113998694A (en) * | 2021-11-22 | 2022-02-01 | 上海大学 | Preparation method for obtaining large-size graphene by using solid carbon source |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104789941A (en) * | 2015-05-08 | 2015-07-22 | 北京化工大学 | Method for graphene chemical bonding coating by using chemical vapor deposition method |
| TWI571437B (en) * | 2015-11-23 | 2017-02-21 | 炬力奈米科技有限公司 | Method for growing graphene by chemical vapor deposition |
| US20170144888A1 (en) * | 2015-11-23 | 2017-05-25 | G-Force Nanotechnology Ltd. | Method for growing graphene by chemical vapor deposition |
| CN106756881A (en) * | 2015-11-23 | 2017-05-31 | 炬力奈米科技有限公司 | By the method for chemical vapor deposition growth Graphene |
| CN107240702A (en) * | 2017-05-19 | 2017-10-10 | 北京理工大学 | A kind of preparation method of high-quality graphene paper tinsel collector |
| CN107117827A (en) * | 2017-06-29 | 2017-09-01 | 南陵县生产力促进中心 | The method of graphene is grown on a kind of glass substrate |
| CN107416798A (en) * | 2017-06-29 | 2017-12-01 | 南陵县生产力促进中心 | A kind of preparation method for vulcanizing three-dimensional grapheme |
| CN107445147A (en) * | 2017-09-11 | 2017-12-08 | 张洪 | The preparation method and equipment of a kind of graphene |
| CN109179388A (en) * | 2018-10-31 | 2019-01-11 | 青岛科技大学 | A kind of method that carbon monoxide prepares graphene |
| CN109179388B (en) * | 2018-10-31 | 2020-05-08 | 青岛科技大学 | Method for preparing graphene from carbon monoxide |
| CN109796008A (en) * | 2019-01-19 | 2019-05-24 | 东莞市长瑞精密设备制造有限公司 | A kind of graphene battery negative electrode material and its processing tooling |
| CN109796008B (en) * | 2019-01-19 | 2020-07-03 | 东莞市长瑞精密设备制造有限公司 | Graphene battery negative electrode material and processing tool thereof |
| CN111675209A (en) * | 2020-06-02 | 2020-09-18 | 天津理工大学 | Method for growing vertical graphene film by using nitrogen and ethanol |
| CN113666365A (en) * | 2021-09-30 | 2021-11-19 | 萝北奥星新材料有限公司 | Method for preparing single-layer continuous graphene film by using hydrocarbon organic compound |
| CN113998694A (en) * | 2021-11-22 | 2022-02-01 | 上海大学 | Preparation method for obtaining large-size graphene by using solid carbon source |
| CN113998694B (en) * | 2021-11-22 | 2023-12-12 | 上海大学 | Preparation method for obtaining large-size graphene by using solid carbon source |
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Application publication date: 20140924 |