CN103395776B - Asphalt-based activated graphene sheet and preparation method thereof - Google Patents
Asphalt-based activated graphene sheet and preparation method thereof Download PDFInfo
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- CN103395776B CN103395776B CN201310332396.5A CN201310332396A CN103395776B CN 103395776 B CN103395776 B CN 103395776B CN 201310332396 A CN201310332396 A CN 201310332396A CN 103395776 B CN103395776 B CN 103395776B
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Abstract
The invention belongs to the field of carbon materials, and mainly relates to an asphalt-based activated graphene sheet and a preparation method thereof. The asphalt-based activated graphene sheet is prepared by processes of mixing, carbonizing, reaction milling, activating and pickling with the asphalt and an additive (aluminium powder or aluminium oxide) as raw materials. The preparation method is rich in raw material sources, low in preparation cost and simple in operations and can be industrialized easily. The asphalt-based activated graphene sheet has large specific surface area and high mesopore content.
Description
Technical field
The invention belongs to carbon materials field, be specifically related to a kind of asphaltic base activation graphene film and preparation method thereof.
Background technology
Graphene film is formed by single-layer graphene stacking, and thickness is the two-dimentional graphitic nanomaterials of nanoscale.Graphene film has individual layer, minority layer and multilayer, and its extreme case is single-layer graphene.The thickness limit of two-dimensional graphene sheet should be determined jointly depending on electronic structure sudden change and materialization effect sudden change, it is generally acknowledged that thickness is no more than 20nm.Due to the difference of dimension, the performance of two-dimensional graphene is different from carbon nanotube to a great extent, has the character of many uniquenesses.Because graphene film has nontoxic, that chemical and thermal property is excellent, electric conductivity is large, physical strength is large characteristic, the material based on graphene film is made to have industrial applicability widely, as can be used as sorbent material, drug conveying, support of the catalyst, Heat transmission media, and can be made into the electronic component with fine structure.Especially, along with updating of graphene film performance, graphene film becomes the leading of energy field gradually, is widely used in storing hydrogen, fuel cell, solar cell, lithium ion battery, ultracapacitor etc.
Compared with graphene film, activation graphene film has the mesopore content higher compared with large specific surface sum, is therefore more suitable for as stored energy active material, especially as the electrode materials of ultracapacitor.The preparation method that current preparation activation graphene film adopts has physical activation method, chemical activation method and thing to manage the chemical combined activation method of –, but all with the graphene film of costliness for raw material, therefore the cost of preparation activation Graphene remains high, and prospects for commercial application is dim.
Summary of the invention
The object of the present invention is to provide a kind of asphaltic base to activate graphene film and preparation method thereof, abundant raw material source, preparation cost are low, simple to operate, easily realize industrialization; Product specific surface area is large, and mesopore content is high.
For achieving the above object, the present invention adopts following technical scheme:
The preparation method of a kind of asphaltic base activation graphene film comprises the mixing of raw material, charing, reaction ball milling, activation, acid cleaning process.
(1) mixing of raw material
Basic raw material: one or several the mixture in coal-tar pitch, petroleum pitch, slag oil asphalt, synthetic asphalts;
Additive: aluminium powder or aluminum oxide;
Basic raw material and additive are sieve after 100:20 ~ 100:100 fully mixes in mass ratio;
Hybrid technique parameter is:
Raw material granularity: 100-300 order;
Additive purity: be greater than 99%;
(2) carbonize
The raw material that step (1) mixes is put into sintering oven, is incubated after being then warming up to preset temperature, be cooled to room temperature and take out;
Charring process parameter is:
Temperature rise rate: 5 DEG C/min –, 30 DEG C/min;
Preset temperature: 1300 DEG C – 1800 DEG C;
Soaking time: 0.1 h – 5 h;
Vacuum tightness: 1.0 × 10
-1pa – 1.0 × 10
4pa;
(3) reaction ball milling
Step (2) gained carbonizing production and KOH are carried out reaction ball milling process 1 – 10h for 1:1 ~ 1:4 puts into ball mill with the rotating speed of 100 – 600 revs/min in mass ratio;
(4) activate
Step (3) gained ball milling product is put into corundum crucible, is incubated after being then warming up to preset temperature in atmosphere furnace, cool to room temperature with the furnace and take out;
Activating process parameter is:
Temperature rise rate: 2 DEG C/min –, 10 DEG C/min;
Preset temperature: 700 DEG C – 900 DEG C;
Soaking time: 0.5 h – 5h;
Protective atmosphere: N
2or Ar;
Gas flow: 50 mL/min – 200 mL/min;
(5) pickling
Step (4) gained activation products are placed in dilute hydrochloric acid stir, it is neutral for being separated by filtration that rear deionized water fully washs to filtrate pH value, then puts into 120 DEG C of baking ovens and carries out dry 10 h;
Acid cleaning process parameter is:
Dilute hydrochloric acid pH value: 4 – 6;
The temperature of dilute hydrochloric acid: 25 DEG C – 80 DEG C;
The mass ratio of activation products and dilute hydrochloric acid: 1:2 ~ 1:5;
Churning time: 1 h – 5h;
Stirring velocity: 50 – 500 revs/min.
The specific surface area of obtained asphaltic base activation graphene film is 1500 ~ 3000m
2/ g, mesopore content is 30 ~ 60%.
Compared with prior art, the advantage that has of the present invention and effect are:
(1) abundant raw material, cheap.
(2) processing unit is simple, is easy to scale operation.
(3) specific surface area is high, and mesopore content is high.
Embodiment
embodiment 1
By coal-tar pitch and aluminium powder 100:20(mass ratio in mass ratio) take, put into sintering oven (vacuum tightness 1.0 × 10 after fully mixing 100 mesh sieves
3pa), be incubated 2h after being warming up to 1800 DEG C with 30 DEG C/min, be cooled to room temperature and take out carbonizing production.By carbonizing production and KOH in mass ratio 1:1 put into ball mill reaction ball milling 1h(rotational speed of ball-mill 100 revs/min after mixing).Ball milling product is put into corundum crucible, is then placed in atmosphere furnace, and pass into N
2, N
2flow is 50mL/min, keeps 2h after being warming up to 800 DEG C with 5 DEG C/min, cools to room temperature with the furnace and takes out.Activation products are placed in the hydrochloric acid (the mass ratio 1:2 of activation products and hydrochloric acid) that pH value is 4,1h(stirring velocity 500 revs/min is stirred) in 25 DEG C, it is neutral for being separated by filtration that rear deionized water fully washs to filtrate pH value, then be placed in 120 DEG C of baking ovens and carry out dry 10 h, namely obtain activation graphene film.Prepared activation graphene film has following performance: graphene film thickness 6 ~ 10nm, specific surface area 1500m
2/ g, mesopore content 42%.
embodiment 2
By coal-tar pitch and aluminum oxide powder 100:50(mass ratio in mass ratio) take, put into sintering oven (vacuum tightness 1.0 × 10 after fully mixing 150 mesh sieves
4pa), be incubated 2h after being warming up to 1600 DEG C with 5 DEG C/min, be cooled to room temperature and take out carbonizing production.By carbonizing production and KOH in mass ratio 1:3 put into ball mill reaction ball milling 5h(rotational speed of ball-mill 600 revs/min after mixing).Ball milling product is put into corundum crucible, is then placed in atmosphere furnace, and pass into Ar, Ar flow is 200mL/min, keeps 0.5h after being warming up to 900 DEG C with 2 DEG C/min, cools to room temperature with the furnace and takes out.Activation products are placed in the hydrochloric acid (the mass ratio 1:3 of activation products and hydrochloric acid) that pH value is 6,3h(stirring velocity 200 revs/min is stirred) in 80 DEG C, it is neutral for being separated by filtration that rear deionized water fully washs to filtrate pH value, then be placed in 120 DEG C of baking ovens and carry out dry 10 h, namely obtain activation graphene film.Prepared activation graphene film has following performance: graphene film thickness 3 ~ 5nm, specific surface area 2208m
2/ g, mesopore content 30%.
embodiment 3
By petroleum pitch and aluminium powder 100:100(mass ratio in mass ratio) take, put into sintering oven (vacuum tightness 1.0 × 10 after fully mixing 300 mesh sieves
-1pa), be incubated 5h after being warming up to 1300 DEG C with 10 DEG C/min, be cooled to room temperature and take out carbonizing production.By carbonizing production and KOH in mass ratio 1:3 put into ball mill reaction ball milling 2.5h(rotational speed of ball-mill 300 revs/min after mixing).Ball milling product is put into corundum crucible, is then placed in atmosphere furnace, and pass into Ar, Ar flow is 150mL/min, keeps 5h after being warming up to 800 DEG C with 10 DEG C/min, cools to room temperature with the furnace and takes out.Activation products are placed in the hydrochloric acid (the mass ratio 1:5 of activation products and hydrochloric acid) that pH value is 4,2h(stirring velocity 200 revs/min is stirred) in 60 DEG C, it is neutral for being separated by filtration that rear deionized water fully washs to filtrate pH value, then be placed in 120 DEG C of baking ovens and carry out dry 10 h, namely obtain activation graphene film.Prepared activation graphene film has following performance: graphene film thickness 1 ~ 3nm, specific surface area 2530m
2/ g, mesopore content 60%.
embodiment 4
By slag oil asphalt and aluminium powder 100:50(mass ratio in mass ratio) take, put into sintering oven (vacuum tightness 1.0 × 10 after fully mixing 150 mesh sieves
2pa), be incubated 3h after being warming up to 1600 DEG C with 15 DEG C/min, be cooled to room temperature and take out carbonizing production.By carbonizing production and KOH in mass ratio 1:4 put into ball mill reaction ball milling 10h(rotational speed of ball-mill 500 revs/min after mixing).Ball milling product is put into corundum crucible, is then placed in atmosphere furnace, and pass into N
2, N
2flow is 50mL/min, keeps 2.5h after being warming up to 700 DEG C with 10 DEG C/min, cools to room temperature with the furnace and takes out.Activation products are placed in the hydrochloric acid (the mass ratio 1:4 of activation products and hydrochloric acid) that pH value is 5,2h(stirring velocity 250 revs/min is stirred) in 50 DEG C, it is neutral for being separated by filtration that rear deionized water fully washs to filtrate pH value, then be placed in 120 DEG C of baking ovens and carry out dry 10 h, namely obtain activation graphene film.Prepared activation graphene film has following performance: graphene film thickness 1 ~ 3nm, specific surface area 2980m
2/ g, mesopore content 45%.
embodiment 5
By synthetic asphalts and aluminum oxide powder 100:40(mass ratio in mass ratio) take, put into sintering oven (vacuum tightness 1.0 × 10 after fully mixing 200 mesh sieves
3pa), be incubated 2h after being warming up to 1800 DEG C with 8 DEG C/min, be cooled to room temperature and take out carbonizing production.By carbonizing production and KOH in mass ratio 1:4 put into ball mill reaction ball milling 6h(rotational speed of ball-mill 300 revs/min after mixing).Ball milling product is put into corundum crucible, is then placed in atmosphere furnace, and pass into N
2, N
2flow is 200mL/min, keeps 1.5h after being warming up to 850 DEG C with 5 DEG C/min, cools to room temperature with the furnace and takes out.Activation products are placed in the hydrochloric acid (the mass ratio 1:3 of activation products and hydrochloric acid) that pH value is 4,2h(stirring velocity 200 revs/min is stirred) in 60 DEG C, it is neutral for being separated by filtration that rear deionized water fully washs to filtrate pH value, then be placed in 120 DEG C of baking ovens and carry out dry 10 h, namely obtain activation graphene film.Prepared activation graphene film has following performance: graphene film thickness 2 ~ 5nm, specific surface area 2060m
2/ g, mesopore content 35%.
embodiment 6
By coal-tar pitch and aluminium powder 100:100(mass ratio in mass ratio) take, put into sintering oven (vacuum tightness 1.0 × 10 after fully mixing 300 mesh sieves
1pa), be incubated 5h after being warming up to 1700 DEG C with 5 DEG C/min, be cooled to room temperature and take out carbonizing production.By carbonizing production and KOH in mass ratio 1:3 put into ball mill reaction ball milling 10h(rotational speed of ball-mill 600 revs/min after mixing).Ball milling product is put into corundum crucible, is then placed in atmosphere furnace, and pass into N
2, N
2flow is 100mL/min, keeps 1h after being warming up to 800 DEG C with 2 DEG C/min, cools to room temperature with the furnace and takes out.Activation products are placed in the hydrochloric acid (the mass ratio 1:4 of activation products and hydrochloric acid) that pH value is 4,2h(stirring velocity 50 revs/min is stirred) in 25 DEG C, it is neutral for being separated by filtration that rear deionized water fully washs to filtrate pH value, then be placed in 120 DEG C of baking ovens and carry out dry 10 h, namely obtain activation graphene film.Prepared activation graphene film has following performance: graphene film thickness 2 ~ 3nm, specific surface area 2550m
2/ g, mesopore content 52%.
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. a preparation method for asphaltic base activation graphene film, is characterized in that: comprise the following steps:
(1) mixing of raw material
Basic raw material: one or several the mixture in coal-tar pitch, petroleum pitch, slag oil asphalt, synthetic asphalts;
Additive: aluminium powder or aluminum oxide;
Basic raw material and additive are sieve after 100:20 ~ 100:100 fully mixes in mass ratio;
Hybrid technique parameter is:
Raw material granularity: 100-300 order;
Additive purity: be greater than 99%;
(2) carbonize
The raw material that step (1) mixes is put into sintering oven, is incubated after being then warming up to preset temperature, be cooled to room temperature and take out;
Charring process parameter is:
Temperature rise rate: 5 DEG C/min –, 30 DEG C/min;
Preset temperature: 1300 DEG C – 1800 DEG C;
Soaking time: 0.1 h – 5 h;
Vacuum tightness: 1.0 × 10
-1pa – 1.0 × 10
4pa;
(3) reaction ball milling
Step (2) gained carbonizing production and KOH are carried out reaction ball milling process 1 – 10h for 1:1 ~ 1:4 puts into ball mill with the rotating speed of 100 – 600 revs/min in mass ratio;
(4) activate
Step (3) gained ball milling product is put into corundum crucible, is incubated after being then warming up to preset temperature in atmosphere furnace, cool to room temperature with the furnace and take out;
Activating process parameter is:
Temperature rise rate: 2 DEG C/min –, 10 DEG C/min;
Preset temperature: 700 DEG C – 900 DEG C;
Soaking time: 0.5 h – 5h;
Protective atmosphere: N
2or Ar;
Gas flow: 50 mL/min – 200 mL/min;
(5) pickling
Step (4) gained activation products are placed in dilute hydrochloric acid stir, it is neutral for being separated by filtration that rear deionized water fully washs to filtrate pH value, then puts into 120 DEG C of baking ovens and carries out dry 10 h;
Acid cleaning process parameter is:
Dilute hydrochloric acid pH value: 4 – 6;
The temperature of dilute hydrochloric acid: 25 DEG C – 80 DEG C;
The mass ratio of activation products and dilute hydrochloric acid: 1:2 ~ 1:5;
Churning time: 1 h – 5h;
Stirring velocity: 50 – 500 revs/min;
The specific surface area of obtained asphaltic base activation graphene film is 1500 ~ 3000m
2/ g, mesopore content is 30 ~ 60%.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641111B (en) * | 2013-12-26 | 2015-12-30 | 安徽工业大学 | A kind of ultracapacitor preparation method of classifying porous grapheme material |
| CA3189208A1 (en) * | 2014-08-08 | 2016-02-11 | Olanrewaju W. Tanimola | Methods for synthesis of graphene derivatives and functional materials from asphaltenes, graphene derivatives, 2d materials and applications of use |
| CN105502363B (en) * | 2015-12-25 | 2018-02-09 | 安徽工业大学 | A kind of preparation method of the graphene nanometer sheet of ultracapacitor fold |
| CN105480971B (en) * | 2016-01-29 | 2017-07-04 | 福州大学 | A kind of preparation method of asphaltic base three-dimensional meso-hole grapheme material |
| CN105752970B (en) * | 2016-03-30 | 2017-12-05 | 福州大学 | A kind of preparation method of carbon nano tube/graphene compound |
| CN107417965A (en) * | 2017-09-14 | 2017-12-01 | 南通迅达橡塑制造有限公司 | A kind of preparation method of rubber-plastics material graphene composite flame-retardant agent |
| CN108976618A (en) * | 2018-08-08 | 2018-12-11 | 南通迅达橡塑制造有限公司 | A kind of graphene modified EPT rubber composite material and preparation method thereof |
| CN113443622B (en) * | 2020-08-19 | 2023-09-22 | 福建省鑫森炭业股份有限公司 | Method for loading nano metal oxide or nano metal material by porous carbon |
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| CN102874800B (en) * | 2012-09-29 | 2015-10-07 | 常州第六元素材料科技股份有限公司 | A kind of activation Graphene, Its Preparation Method And Use |
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| CN102381701A (en) * | 2011-08-01 | 2012-03-21 | 福州大学 | Method for numerously preparing asphalt-based graphene material with low cost |
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