CN103613096B - Low-cost method for preparing graphene macroform - Google Patents
Low-cost method for preparing graphene macroform Download PDFInfo
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- CN103613096B CN103613096B CN201310650587.6A CN201310650587A CN103613096B CN 103613096 B CN103613096 B CN 103613096B CN 201310650587 A CN201310650587 A CN 201310650587A CN 103613096 B CN103613096 B CN 103613096B
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Abstract
The invention discloses a low-cost method for preparing a graphene macroform (a thin film, foams, fibers and fabric bodies thereof). A polyimide thin film, a carbon film, an organic foam material, foamy carbon, organic fibers (including a fabric body), carbon fibers (including a fabric body) and the like are taken as raw materials, magnesium powder, zinc powder, aluminum powder, silicon powder, tin powder, copper powder or a mixture are used as an additive, and the graphene macroform is directly prepared by processes of pre-oxidization, vacuum high-temperature treatment, acid-leaching, drying and the like. The method is high in product value, simple in process, environment-friendly, low in preparation cost and easy to industrially popularize, and has remarkable economic benefits and social benefits.
Description
Technical field
The invention belongs to high-performance carbon element preparation field, be specifically related to a kind of method that low cost prepares graphene macroform (film, foams, fiber and knitted body thereof).
Background technology
Graphene is that carbon atom is with SP
2hybrid structure is formed by connecting the netted monoatomic layer of honeycomb, and it is the thinnest known two dimensional crystal, is the basic building block of other carbon nanomaterial of composition.Graphene can obtain one dimension carbon nanotube by curling, and Graphene twists the closed soccerballene that just can form zero dimension.Due to the structure of Graphene uniqueness, it is made to have good electricity, calorifics and chemical property.Current Graphene has industrial applicability widely, as sorbent material, drug conveying, support of the catalyst, Heat transmission media, can be made into the electronic component with fine structure.Along with updating of Graphene performance, Graphene is widely used in storing hydrogen, fuel cell, solar cell, lithium ion battery, ultracapacitor etc.Common Graphene exists with the graphene powder form of little lamella.As everyone knows, the Graphene of this little lamella is easily reunited due to nano effect, and be difficult to manipulation in practice, this greatly hinders the industrial applications of Graphene.
A kind of macrostructure with certain form that graphene macroform and Graphene are formed by superposition or the overlap joint of lamella, generally can be divided into two-dimentional macroscopic body (film, fiber) and three-dimensional macro body (foams, fibrage body).Because Graphene can play the character of Graphene better after being assembled into macroscopic body, as the electronic mobility etc. of outstanding mechanical property, high heat conductance, high speed, and have good adsorptive power, therefore graphene macroform shows good application potential in fields such as ultracapacitor, battery, catalysis, biomedicines.Because some graphene nano level phenomenons are represented a macroscopic aspect by graphene macroform, this practical application that promotion Graphene is marched toward.The preparation method of current graphene macroform comprises chemical Vapor deposition process, filters construction from part, self-assembly method etc.But these methods are prepared graphene macroform and be there is the problems such as complex process, cost are high, environmental pollution, and are difficult to prepare graphene macroform in a large number.
Summary of the invention
A kind of low cost is the object of the present invention is to provide to prepare the method for graphene macroform (film, foams, fiber and knitted body thereof), value of the product is high, technique is simple, environmental protection, low, the easy industrialization promotion of preparation cost, there is significant economic benefit and social benefit.
For achieving the above object, the present invention adopts following technical scheme:
A kind of method that low cost prepares graphene macroform (film, foams, fiber and knitted body thereof) comprises the selection of raw material, preoxidation, vacuum high-temperature process, acidleach and drying process.
(1) selection of raw material
Raw material is the one of Kapton, carbon membrane, organic foam material, Carbon foam, organic fibre or Carbon fibe and knitted body thereof, and wherein knitted body is two and three dimensions material, carbon membrane is the one in asphalt-base carbon-film, intermediate phase pitch-based carbon membrane, polyimide-based carbon membrane, organic foam material is asphalt foam, mesophase pitch foams, phenolic resin foam, furane resin foam, poly-aryl ethane foam, Polybenzoxazine resin foam, polyimide foam, cyanate ester resin foam, one in bimaleimide resin foam, Carbon foam is asphalt base foam carbon, Mesophase Pitch-Derived Carbon Foam, phenolic resin based foam carbon, furane resin based foam carbon, poly-aryl ethane based foam carbon, Polybenzoxazine resin base Carbon foam, polyimide based foam carbon, cyanate ester resin based foam carbon, one in bimaleimide resin base Carbon foam, organic fibre is the one in pitch fibers, Mesophase Pitch Fibers, phenolic resin fibre, polyacrylonitrile fibre, viscose fiber, polyimide fiber, lignin fibre, Carbon fibe is the one in pitch-based carbon fiber, Mesophase Pitch-based Carbon Fibers, Phenolic resin based carbobn fiber, PAN-based carbon fiber, rayon-based carbon fiber, polyimide based carbon fiber, lignin-base Carbon fibe,
Additive be magnesium powder, zinc powder, aluminium powder, silica flour, glass putty, copper powder one or several;
The characteristic parameter of starting material and additive is:
Kapton thickness: 1 ~ 100 μm
Organic foam material porosity: 50% ~ 90%
Organic foam material percentage of open area: 60% ~ 100%
Carbon foam porosity: 60% ~ 95%
Carbon foam percentage of open area: 70% ~ 100%
Organic fibre diameter: 1 ~ 100 μm
Carbon fibe diameter: 0.1 ~ 50 μm
Additive purity: be greater than 99%
Additive granularity: 10 ~ 1000 orders
Additive and raw-material mass ratio: 1:100 ~ 100:100;
(2) preoxidation
Organic foam material, organic fibre or its knitted body are placed in loft drier and carry out pre-oxidation treatment; Kapton, carbon membrane, Carbon foam, Carbon fibe or its knitted body do not need through pre-oxidation treatment, directly enter step (3);
Pre-oxidation treatment processing parameter is:
Temperature: 200 DEG C ~ 400 DEG C
Oxidization time: 0.1h ~ 10h;
(3) vacuum high-temperature process
By additive spreading in crucible bottom, put into the starting material after step (2) process above, then move into after being warming up to preset temperature in vacuum oven and be incubated, be cooled to room temperature and take out;
Vacuum high-temperature treatment process parameter is:
Temperature rise rate: 1 DEG C/min ~ 100 DEG C/min
Temperature: 1000 DEG C ~ 3000 DEG C
Soaking time: 0.1 h ~ 10 h
Vacuum tightness: 1.0 × 10
-3pa ~ 1.0 × 10
5pa;
(4) acidleach
Step (3) products therefrom is placed in acid solution flood, then fully washs with deionized water and detect to without acid ion;
Acid leaching process parameter is:
Acid solution: the one in hydrochloric acid, formic acid, acetic acid, oxalic acid
PH value: 1 ~ 7
Dipping time: 1h ~ 10h;
(5) dry
Step (4) products therefrom is put into vacuum drying oven and carries out drying treatment;
Drying Technology Parameter is:
Time of drying: 1h ~ 10h
Drying temperature: 60 ~ 200 DEG C
Vacuum tightness: 1.0 × 10
1pa ~ 1.0 × 10
5pa.
Compared with prior art, the advantage that has of the present invention and effect are:
(1) preparation cost is low, and value of the product is high.
(2) processing unit is simple, environmental protection.
(3) scale operation is easy to.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscopic picture of the graphene film adopting embodiment 1 technique to prepare.
Fig. 2 is the scanning electron microscopic picture of the graphene film adopting embodiment 2 technique to prepare.
Fig. 3 is the scanning electron microscopic picture of the grapheme foam adopting embodiment 3 technique to prepare.
Fig. 4 is the scanning electron microscopic picture of the grapheme foam adopting embodiment 4 technique to prepare.
Fig. 5 is the scanning electron microscopic picture of the grapheme foam adopting embodiment 5 technique to prepare.
Fig. 6 is the scanning electron microscopic picture of the graphene fiber adopting embodiment 6 technique to prepare.
Fig. 7 is the scanning electron microscopic picture of the Graphene knitted body adopting embodiment 7 technique to prepare.
Embodiment
Be below several specific embodiment of the present invention, further illustrate the present invention, but the present invention be not limited only to this.
embodiment 1
By 100 object aluminium powder spreadings in crucible bottom, (aluminium powder and Kapton mass ratio are 1:100 to put into Kapton above, film thickness 25 μm), then crucible is moved in vacuum oven to heat up after 2200 DEG C with the temperature rise rate of 20 DEG C/min and keep 5h(vacuum tightness 1.0 × 10
-3pa), be cooled to room temperature to take out.Vacuum high-temperature process product is placed in pH value be 6 formic acid soak 1h, fully wash with deionized water and detect to without formate ion, be then placed on 80 DEG C of oven drying 1h(vacuum tightness 10 Pa), namely obtain graphene film.Prepared graphene film has following performance: specific conductivity 15000S/cm, horizontal direction thermal conductivity 1500W/mK, vertical direction thermal conductivity 30W/mK.
embodiment 2
By 500 object magnesium powder spreadings in crucible bottom, (aluminium powder and carbon membrane mass ratio are 10:100 to put into asphalt-base carbon-film above, film thickness 50 μm), then crucible is moved in vacuum oven to heat up after 2500 DEG C with the temperature rise rate of 50 DEG C/min and keep 1h(vacuum tightness 1.0 × 10
-1pa), be cooled to room temperature to take out.Vacuum high-temperature process product is placed in pH value be 4 acetic acid soak 5h, fully wash with deionized water and detect to without acetate ion, be then placed on 60 DEG C of oven drying 10h(vacuum tightness 133Pa), namely obtain graphene film.Prepared graphene film has following performance: specific conductivity 13000S/cm, horizontal direction thermal conductivity 1200W/mK, vertical direction thermal conductivity 25W/mK.
embodiment 3
Asphalt foam (porosity 50%, percentage of open area 60%) is placed in 200 DEG C of loft drier and carries out pre-oxidation treatment 10h, then put into the crucible (glass putty and asphalt foam mass ratio 50:100, glass putty granularity is 10 orders) of spreading glass putty in advance.Being moved into by crucible in vacuum oven heats up after 1500 DEG C with the temperature rise rate of 100 DEG C/min keeps 5h(vacuum tightness 1.0 × 10
2pa), be cooled to room temperature to take out.Vacuum high-temperature process product is placed in pH value be 2 hydrochloric acid soak 1h, fully wash to without Cl with deionized water
-detect, be then placed on 200 DEG C of oven drying 2h(vacuum tightnesss 1.0 × 10
5pa), namely grapheme foam is obtained.Prepared grapheme foam has following performance: density 0.08g/cm
3, compressive strength 0.5MPa, thermal conductivity 200W/mK.
embodiment 4
Phenolic resin based foam carbon (porosity 85%, percentage of open area 92%) is put into the crucible (magnesium powder and Carbon foam mass ratio 100:100) that spreading granularity is in advance 100 order magnesium powder, then being moved into by crucible in vacuum oven heats up after 1900 DEG C with the temperature rise rate of 30 DEG C/min keeps 3h(vacuum tightness 1.0 × 10
4pa), be cooled to room temperature to take out.Vacuum high-temperature process product is placed in pH value be 3 oxalic acid soak 2h, fully wash with deionized water and detect to without oxalic acid radical ion, be then placed on 100 DEG C of oven drying 4h(vacuum tightnesss 1.0 × 10
3pa), namely grapheme foam is obtained.Prepared grapheme foam has following performance: density 0.05g/cm
3, compressive strength 0.2MPa, thermal conductivity 300W/mK.
embodiment 5
Be that the polyacrylonitrile fibre of 30 μm is placed in 400 DEG C of loft drier and carries out pre-oxidation treatment 0.1h by diameter, then put into the crucible (zinc powder and asphalt foam mass ratio 1:100, zinc powder particle size is 1000 orders) of spreading zinc powder in advance.Crucible is moved into after being warming up to 1700 DEG C with the temperature rise rate of 10 DEG C/min in vacuum oven and keep 2h(vacuum tightness 1.0 × 10
3pa), be cooled to room temperature to take out.Vacuum high-temperature process product is placed in pH value be 6 formic acid soak 5h, fully wash with deionized water and detect to without formate ion, be then placed on 160 DEG C of oven drying 2h(vacuum tightnesss 1.0 × 10
2pa), namely graphene fiber is obtained.Prepared graphene fiber has following performance: density 0.5g/cm
3, tensile strength 200MPa, thermal conductivity 1200W/mK.
embodiment 6
It is the crucible (, than 10:100, copper powder particle size is 300 orders for copper powder and copper mass) that the PAN-based carbon fiber of 10 μm puts into spreading copper powder in advance by diameter.Crucible is moved into after being warming up to 3000 DEG C with the temperature rise rate of 20 DEG C/min in vacuum oven and keep 0.1h(vacuum tightness 1.0 × 10
-2pa), be cooled to room temperature to take out.Vacuum high-temperature process product is placed in pH value be 1 hydrochloric acid soak 1h, fully wash to without Cl with deionized water
-detect, be then placed on 80 DEG C of oven drying 10h(vacuum tightnesss 1.0 × 10
3pa), namely graphene fiber is obtained.Prepared graphene fiber has following performance: density 0.8g/cm
3, tensile strength 300MPa, thermal conductivity 1500W/mK.
embodiment 7
Pitch-based carbon fiber cloth is put into the crucible (silica flour and carbon fiber sheet mass ratio 10:100, silicon particle size is 200 orders) of spreading silica flour in advance.Crucible is moved into after being warming up to 1600 DEG C with the temperature rise rate of 100 DEG C/min in vacuum oven and keeps 1h(vacuum tightness 1Pa), be cooled to room temperature and take out.Vacuum high-temperature process product is placed in pH value be 2 hydrochloric acid soak 3h, fully wash to without Cl with deionized water
-detect, be then placed on 110 DEG C of oven drying 6h(vacuum tightnesss 1.0 × 10
3pa), namely graphene fiber is obtained.Prepared graphene fiber has following performance: density 0.4g/cm
3, tensile strength 120MPa, thermal conductivity 900W/mK.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (1)
1. low cost prepares a method for graphene macroform, it is characterized in that: described macroscopic body comprises film, foams and fiber and knitted body thereof, and preparation method comprises the selection of raw material, preoxidation, vacuum high-temperature process, acidleach and drying process;
Comprise the following steps:
(1) selection of raw material
Raw material is the one of Kapton, carbon membrane, organic foam material, Carbon foam, organic fibre or Carbon fibe and knitted body thereof, and wherein knitted body is two and three dimensions material; Carbon membrane is the one in asphalt-base carbon-film, intermediate phase pitch-based carbon membrane, polyimide-based carbon membrane; Organic foam material is the one in asphalt foam, mesophase pitch foams, phenolic resin foam, furane resin foam, poly-aryl ethane foam, Polybenzoxazine resin foam, polyimide foam, cyanate ester resin foam, bimaleimide resin foam; Carbon foam is the one in asphalt base foam carbon, Mesophase Pitch-Derived Carbon Foam, phenolic resin based foam carbon, furane resin based foam carbon, poly-aryl ethane based foam carbon, Polybenzoxazine resin base Carbon foam, polyimide based foam carbon, cyanate ester resin based foam carbon, bimaleimide resin base Carbon foam; Organic fibre is the one in pitch fibers, Mesophase Pitch Fibers, phenolic resin fibre, polyacrylonitrile fibre, viscose fiber, polyimide fiber, lignin fibre; Carbon fibe is the one in pitch-based carbon fiber, Mesophase Pitch-based Carbon Fibers, Phenolic resin based carbobn fiber, PAN-based carbon fiber, rayon-based carbon fiber, polyimide based carbon fiber, lignin-base Carbon fibe;
Additive be magnesium powder, zinc powder, aluminium powder, silica flour, glass putty, copper powder one or several;
The characteristic parameter of starting material and additive is:
Kapton thickness: 1 ~ 100 μm
Organic foam material porosity: 50% ~ 90%
Organic foam material percentage of open area: 60% ~ 100%
Carbon foam porosity: 60% ~ 95%
Carbon foam percentage of open area: 70% ~ 100%
Organic fibre diameter: 1 ~ 100 μm
Carbon fibe diameter: 0.1 ~ 50 μm
Additive purity: be greater than 99%
Additive granularity: 10 ~ 1000 orders
Additive and raw-material mass ratio: 1:100 ~ 100:100;
(2) preoxidation
Organic foam material, organic fibre or its knitted body are placed in loft drier and carry out pre-oxidation treatment; Kapton, carbon membrane, Carbon foam, Carbon fibe or its knitted body do not need through pre-oxidation treatment, directly enter step (3);
Pre-oxidation treatment processing parameter is:
Temperature: 200 DEG C ~ 400 DEG C
Oxidization time: 0.1h ~ 10h;
(3) vacuum high-temperature process
By additive spreading in crucible bottom, put into the starting material after step (2) process above, then move into after being warming up to preset temperature in vacuum oven and be incubated, be cooled to room temperature and take out;
Vacuum high-temperature treatment process parameter is:
Temperature rise rate: 1 DEG C/min ~ 100 DEG C/min
Temperature: 1000 DEG C ~ 3000 DEG C
Soaking time: 0.1 h ~ 10 h
Vacuum tightness: 1.0 × 10
-3pa ~ 1.0 × 10
5pa;
(4) acidleach
Step (3) products therefrom is placed in acid solution flood, then fully washs with deionized water and detect to without acid ion;
Acid leaching process parameter is:
Acid solution: the one in hydrochloric acid, formic acid, acetic acid, oxalic acid
PH value: 1 ~ 7
Dipping time: 1h ~ 10h;
(5) dry
Step (4) products therefrom is put into vacuum drying oven and carries out drying treatment;
Drying Technology Parameter is:
Time of drying: 1h ~ 10h
Drying temperature: 60 ~ 200 DEG C
Vacuum tightness: 1.0 × 10
1pa ~ 1.0 × 10
5pa.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864065A (en) * | 2014-03-10 | 2014-06-18 | 贵州新碳高科有限责任公司 | Method for improving thermal conductivity of graphene thin film |
| CN104151515B (en) * | 2014-08-13 | 2017-01-11 | 济南圣泉集团股份有限公司 | Graphene modified furan resin and preparation method thereof |
| CN105271177B (en) * | 2015-11-18 | 2017-10-20 | 福州大学 | A kind of preparation method of the multi-level foam carbon material of graphite alkylene |
| CN105609323A (en) * | 2016-03-17 | 2016-05-25 | 北京理工大学 | Porous nanocarbon slice |
| TW201739692A (en) * | 2016-04-21 | 2017-11-16 | 鴻準精密工業股份有限公司 | Graphene and method for making the same |
| CN109319764B (en) * | 2017-07-31 | 2022-05-06 | 哈尔滨工业大学 | Preparation method and application of lignin combustion synthesis graphene |
| CN111100291B (en) * | 2018-10-25 | 2021-08-31 | 中国科学院上海硅酸盐研究所 | Preparation method of polybenzoxazine-reinforced three-dimensional graphene foam |
| CN111825078B (en) * | 2019-04-22 | 2021-12-10 | 南京大学 | Method for preparing three-dimensional graphene foam material |
| CN110482531B (en) * | 2019-08-16 | 2022-08-30 | 中国科学院宁波材料技术与工程研究所 | Preparation method and product of polybenzoxazine resin-based graphene |
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| CN102134068A (en) * | 2011-04-24 | 2011-07-27 | 大连理工大学 | Preparation method of graphitic carbon foam with high aperture ratio |
| CN102381701A (en) * | 2011-08-01 | 2012-03-21 | 福州大学 | Method for numerously preparing asphalt-based graphene material with low cost |
| CN102491320B (en) * | 2011-11-28 | 2013-06-05 | 福州大学 | Pitch-based active carbon with superhigh specific surface area and preparation method thereof |
| CN103072982B (en) * | 2013-02-28 | 2015-02-04 | 福州大学 | Low-cost asphalt-based graphene sheet and preparation method thereof |
| CN103332686B (en) * | 2013-07-12 | 2015-03-11 | 中国科学院新疆理化技术研究所 | Preparation method of three-dimensional graphene-based foam material |
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