CN106587017A - Porous graphene and preparation method thereof - Google Patents
Porous graphene and preparation method thereof Download PDFInfo
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- CN106587017A CN106587017A CN201611154095.8A CN201611154095A CN106587017A CN 106587017 A CN106587017 A CN 106587017A CN 201611154095 A CN201611154095 A CN 201611154095A CN 106587017 A CN106587017 A CN 106587017A
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- C01B2204/00—Structure or properties of graphene
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- C01P2006/16—Pore diameter
Abstract
The invention provides porous graphene and a preparation method thereof. The method comprises the following steps: I, mixing a carbon source and a flask template agent so as to obtain a carbon source-template agent composite, wherein in the carbon source-template agent composite, the carbon source covers the surface of the flask template agent; II, carbonizing the carbon source-template agent in the atmosphere of protective gas at 500-900 DEG C, and pickling and purifying a carbonized product so as to obtain flask porous carbon; and III, calcining the flask porous carbon in the atmosphere of protective gas at 1000-2000 DEG C, so that the porous graphene is obtained. According to the technical scheme provided by the invention, cheap raw materials are adopted, and the porous graphene is prepared in a large scale by virtue of heat treatment; and the method is simple to operate, low in cost and high in yield.
Description
Technical field
The present invention relates to a kind of porous graphene and preparation method thereof, belongs to novel porous technical field of graphene preparation.
Background technology
As a kind of new carbon, Graphene found from 2004 by Britain Geim et al. after (Science 2004；
306(5696):666-9), immediately become study hotspot.Graphene is a kind of two dimensional crystal material by monolayer carbon atomic building,
It is the elementary cell for constructing other dimension material with carbon elements.The special construction of Graphene gives its excellent electricity, calorifics and mechanical property
Can so that Graphene is all in nanometer electronic device, ultracapacitor, sensor, energy stores, transparency electrode and catalyst carrier etc.
It is multi-field to have broad application prospects.
In order to realize the practical application of Graphene, need on a large scale, repeatably to prepare high-quality grapheme material.
The method for preparing Graphene at present mainly includes micromechanics stripping method, supercritical fluid stripping method, reduction-oxidation graphite method, chemistry
Vapour deposition process, epitaxial growth method and solvent-thermal method etc..Wherein reduction-oxidation graphite method is that most popular batch prepares stone
The method of black alkene powder body material, the method carry out intercalation, stripping using Strong oxdiative process and obtain Graphene to graphite；Shooting flow
Body stripping method realizes the stripping of graphite flake layer using fluid force, obtains Graphene, is a kind of can to prepare Graphene in batches
Physical method.
Both of the above method is all, with graphite as raw material, to carry out stripping to graphite flake layer by physical chemistry means and obtain
Graphene, has the advantages that cost of material is low, easy batch production, but there is also the unmanageable problem of the Graphene number of plies.
As seen from the above：Although can realize prepared by the batch of graphite with chemical vapour deposition technique, yield is low,
Production cost is higher.
Therefore it provides a kind of preparation method of porous graphene becomes this area technical problem urgently to be resolved hurrily.
The content of the invention
To solve above-mentioned technical problem, it is an object of the invention to provide a kind of preparation method of porous graphene, the party
Method is simple to operate, low cost, can realize batch production.
To reach above-mentioned purpose, the invention provides a kind of preparation method of porous graphene, which comprises the following steps：
The first step, carbon source is mixed with lamellar template, obtains carbon source-template complex；In the carbon source-template
In complex, carbon source is coated on lamellar template surface；
Second step, carbon source-template complex is carbonized under 500-900 DEG C, shielding gas atmosphere, by carbonized product pickling
Purification, obtains flake porous charcoal；
3rd step, flake porous charcoal is calcined under 1000-2000 DEG C, shielding gas atmosphere, porous graphene is obtained.
The technical scheme that the present invention is provided first prepares flake porous Carbon Materials, and then flake porous Carbon Materials are carried out
High temperature forged is burnt, and obtains flake porous grapheme material, simple to operate, low cost, can realize batch production.
In the above-mentioned methods, it is preferable that the carbon source includes sucrose, starch, petroleum heavy component, decompression residuum, slurry oil
With the combination of one or more in slurry oil fraction products.
In the above-mentioned methods, it is preferable that in the first step, the method also includes adding the compound containing doped chemical
Step；It is highly preferred that after carbon source is mixed with the compound containing doped chemical, then mix with lamellar template；Or, will contain
After the compound for having doped chemical is mixed with lamellar template, then mix with carbon source.Compound of the addition containing doped chemical can
To prepare lamellar doping porous carbon material, and lamellar doping porous graphene is further prepared, wherein, the doping
Porous carbon material is referred to be replaced C atoms in the framing structure of C atomic buildings in material with carbon element or adds other primary colors, such as
Mix S, N, B.
In the above-mentioned methods, it is preferable that in second step, the time of the carbonization is 0.5-5h, more preferably 1-2h.
In the above-mentioned methods, it is preferable that in second step, the temperature of the carbonization is 600-900 DEG C, more preferably 650-
850℃。
In the above-mentioned methods, it is preferable that in the third step, the time of the calcining is 1-24h, more preferably 2-5h.
In the above-mentioned methods, it is preferable that in the third step, the temperature of the calcining is 1500-2000 DEG C, more preferably
1600-2000℃。
In the above-mentioned methods, it is preferable that the shielding gas includes the group of one or more in nitrogen, argon and helium
Close.
In the above-mentioned methods, it is preferable that the lamellar template include flake porous magnesium oxide, lamellar alkali magnesium sulfate and
The combination of one or more in flake magnesium hydroxide；Wherein, the flake porous magnesium oxide can be non-calcination processing,
Can be calcination processing (calcining heat is 550 DEG C, and calcination time is 1h), the lamellar alkali magnesium sulfate is existing any
Alkali magnesium sulfate crystal whisker, alkali magnesium sulfate crystal whisker that is any commercially available or preparing according to art methods are used equally to this
The technical scheme of bright offer.
In the above-mentioned methods, it is preferable that the lamellar template is 5 with the mass ratio of carbon source:(1-50).
In the above-mentioned methods, it is preferable that the compound containing doped chemical includes sulphuric acid, sulfate, nitric acid, nitric acid
Salt, phosphoric acid, phosphate, pyrophosphoric acid, sodium pyrophosphate, APP, tripolycyanamide, pyrroles, pyridine, thiophene, quinoline, boric acid and oxygen
Change the combination of one or more in boron.
In the above-mentioned methods, it is preferable that the compound containing doped chemical with the mass ratio of lamellar template is
8:(1-64)。
In the above-mentioned methods, it is preferable that when being carbonized and calcined, heated up with the speed of 15 DEG C/min.
In the above-mentioned methods, it is preferable that conventional equipment of the prior art can be adopted when being carbonized and calcined, it is excellent
Elect horizontal pipe furnace as.
In the above-mentioned methods, it is preferable that in second step, pickling is carried out using hydrochloric acid, pickling can remove remaining
The metal-oxide generated in shape template meter course of reaction；During pickling can adopt prior art, conventional method is grasped
Make, can be 1 according to mass ratio by concentrated hydrochloric acid and deionized water:(1-5) ratio mixing, the mass percent concentration of concentrated hydrochloric acid
Can be 37%, after being heated to boiling, flow back 0.5-3h.
Present invention also offers a kind of porous graphene prepared by said method.
In above-mentioned porous graphene, it is preferable that the specific surface area of the porous graphene is 200-3000m2/g；Aperture
For 1-100nm；The number of plies is 1-10.
In above-mentioned porous graphene, it is preferable that contain doped chemical in the porous graphene, with the porous graphite
The quality of alkene is 100% meter, and the content of the doped chemical is 0.001-40%；It is highly preferred that the doped chemical include boron,
The combination of one or more in nitrogen, sulfur and phosphorus.
Beneficial effects of the present invention：
Tradition prepares method (such as reduction-oxidation graphite method, chemical vapour deposition technique, the arc discharge method of porous graphene
Deng) have the shortcomings that high cost, yield poorly, complex operation, by comparison, the present invention provide technical scheme, using cheap
Carbonaceous material is presoma, prepares porous graphene with the method batch of high-temperature heat treatment, and simple to operate, low cost, yield are high；
Petroleum heavy component, decompression residuum, slurry oil, fraction products of slurry oil etc. are carried out by the technical scheme that the present invention is provided
Effectively utilizes, the porous graphene for finally preparing the energy storage and conversion aspect there is potential using value,
Which has good chemical property, can be made as lithium ion battery negative material and the electrode material of ultracapacitor
Standby porous graphene material；
The technical scheme that the present invention is provided can easily select various types of template and heteroatomic compound to prepare
Porous graphene or doping porous graphene are obtained, and easily scale can be amplified, so as to realize porous graphene material
Low cost batch production.
Description of the drawings
In Fig. 1, a, b calcine the low power of the porous charcoal after 60min, high power transmission under the conditions of 500 DEG C in being respectively embodiment 1
Electronic Speculum (TEM) picture；
In Fig. 2, A, B calcine the isothermal nitrogen adsorption of the porous charcoal after 60min under the conditions of 500 DEG C and take off in being respectively embodiment 1
Attached curve and pore size distribution curve figure；
In Fig. 3, a, b calcine the low power of the porous charcoal after 60min, high power transmission under the conditions of 900 DEG C in being respectively embodiment 2
Electronic Speculum (TEM) picture；
In Fig. 4, A, B calcine the isothermal nitrogen adsorption of the porous charcoal after 60min under the conditions of 900 DEG C and take off in being respectively embodiment 2
Attached curve and pore size distribution curve figure；
In Fig. 5, a, b calcine the low power of the porous graphene after 60min, high power under the conditions of 1200 DEG C in being respectively embodiment 1
Transmission electron microscope (TEM) picture；
In Fig. 6, A, B calcine the isothermal nitrogen of the porous graphene after 60min under the conditions of 1200 DEG C in being respectively embodiment 1
Adsorption/desorption curve and pore size distribution curve figure；
In Fig. 7, a, b calcine the low power of the porous graphene after 60min, high power under the conditions of 2000 DEG C in being respectively embodiment 2
Transmission electron microscope (TEM) picture；
In Fig. 8, A, B calcine the isothermal nitrogen of the porous graphene after 60min under the conditions of 2000 DEG C in being respectively embodiment 2
Adsorption/desorption curve and pore size distribution curve figure；
Conductivity maps of the Fig. 9 for PC500, PC900, PG1200 and PG2000；
Figure 10 is the high rate performance figure that PC500, PC900, PG1200 and PG2000 are used for that lithium ion battery test to be obtained；
Figure 11 is the CV curves that PC500, PC900, PG1200 and PG2000 are obtained for capacitor testing；
Figure 12 be PC500, PC900, PG1200 and PG2000 for capacitor testing obtain under different scanning rates
Capacity curve；
In Figure 13, a, b calcine the low of the sulfur doping porous graphene after 60min under the conditions of 1200 DEG C in being respectively embodiment 3
Again, high power transmission electron microscope (TEM) picture；
In Figure 14, A, B calcine the nitrogen of the sulfur doping porous graphene after 60min under the conditions of 1200 DEG C in being respectively embodiment 3
Gas isothermal adsorption desorption curve and pore size distribution curve figure；
In Figure 15, a, b calcine the low of the N doping porous graphene after 60min under the conditions of 1200 DEG C in being respectively embodiment 4
Again, high power transmission electron microscope (TEM) picture；
In Figure 16, A, B calcine the nitrogen of the N doping porous graphene after 60min under the conditions of 1200 DEG C in being respectively embodiment 4
Gas isothermal adsorption desorption curve and pore size distribution curve figure.
Specific embodiment
In order to be more clearly understood to the technical characteristic of the present invention, purpose and beneficial effect, now to skill of the invention
Art scheme carry out it is described further below, but it is not intended that to the present invention can practical range restriction.
Embodiment 1
A kind of preparation method of porous graphene is present embodiments provided, which comprises the following steps：
1) 10g slurry oils are weighed, liquid (60-90 DEG C) is heated to, 20g lamellar magnesium oxide is added, is stirred, be put into level
Tube furnace, then in stove is passed through argon (Ar), while horizontal stove rises to 500 DEG C with 15 DEG C/min heating rates, and keeps
60min, takes out gray product after furnace temperature naturally cools to room temperature；This product is placed in excessive dilute hydrochloric acid, and (dilute hydrochloric acid is by dense
Hydrochloric acid and deionized water are 1 according to mass ratio:3 are mixed to get, during wherein 37%) mass percent concentration of concentrated hydrochloric acid is, water
Backflow pickling 1h is boiled, last deionized water is washed till under the conditions of neutrality is placed in 80 DEG C and is dried, and obtains porous carbon material, and numbering is
PC500。
In Fig. 1, a, b are respectively the low power of obtained porous carbon material, high power TEM figure under the conditions of 500 DEG C.Can be with by figure
The porous charcoal for finding out preparation is sheet porous structural, finds out that the edge of materials is thicker by high power TEM, is typical unformed carbon materials
Material.According to specific surface and pore analysis (Fig. 2), porous carbon material specific surface area obtained in this kind of process conditions is 880.8m2/ g,
Average pore size is 3.7nm, and average pore sizes are 0.77m3/g。
2) obtained porous carbon material in step 1 is weighed, and is put into horizontal pipe furnace, then Ar is passed through in stove, while water
Open hearth rises to 1200 DEG C with 15 DEG C/min heating rates, and keeps 60min；The product for obtaining is placed in excessive dilute hydrochloric acid, and (this is dilute
Hydrochloric acid is 1 according to mass ratio by concentrated hydrochloric acid and deionized water:3 are mixed to get, and the mass percent concentration of wherein concentrated hydrochloric acid is
37%), in, decocting in water backflow pickling 1h, last deionized water are washed till under the conditions of neutrality is placed in 80 DEG C and are dried, and obtain porous stone
Black alkene material, numbering is PG1200.
In Fig. 5, a, b are respectively the low power of obtained porous graphene material, high power TEM figure under the conditions of 1200 DEG C, by scheming
It can be seen that the porous graphene for preparing is sheet porous structural, find out that the material is 3-5 layers by high power TEM.By specific surface and
Pore analysis (Fig. 6) understand that porous carbon material specific surface area obtained in this kind of process conditions is 696.3m2/ g, average pore size is
3.8nm, average pore sizes are 0.64m3/g。
Embodiment 2
A kind of preparation method of porous graphene is present embodiments provided, which comprises the following steps：
1) 10g slurry oils are weighed, liquid (60-90 DEG C) is heated to, 20g lamellar magnesium oxide is added, is stirred, be put into level
Tube furnace, then in stove is passed through argon (Ar), while horizontal stove rises to 900 DEG C with 15 DEG C/min heating rates, and keeps
60min, takes out gray product after furnace temperature naturally cools to room temperature；This product is placed in excessive dilute hydrochloric acid, and (dilute hydrochloric acid is by dense
Hydrochloric acid and deionized water are 1 according to mass ratio:3 are mixed to get, during wherein 37%) mass percent concentration of concentrated hydrochloric acid is, water
Backflow pickling 1h is boiled, last deionized water is washed till under the conditions of neutrality is placed in 80 DEG C and is dried, and obtains porous carbon material, and numbering is
PC900。
In Fig. 3, a, b are respectively the low power of obtained porous carbon material, high power TEM figure under the conditions of 900 DEG C.Can be with by figure
The porous charcoal for finding out preparation is sheet porous structural, finds out that the edge of materials is thicker by high power TEM, is typical unformed carbon materials
Material.According to specific surface and pore analysis (Fig. 4), the porous carbon material specific surface area is 738.0m2/ g, average pore size are 6.4nm,
Average pore sizes are 1.28m3/g。
2) obtained porous carbon material in 1g previous steps is weighed, and is put into horizontal pipe furnace, then Ar is passed through in stove, together
When horizontal stove rise to 2000 DEG C with 15 DEG C/min heating rates, and keep 60min；The product for obtaining is placed in into excessive dilute hydrochloric acid
In, decocting in water backflow pickling 1h, last deionized water are washed till under the conditions of neutrality is placed in 80 DEG C and are dried, and obtain porous graphene material
Material, numbering is PG2000.
In Fig. 7, a, b are respectively the low power of obtained porous graphene material, high power TEM figure under the conditions of 2000 DEG C, by scheming
It can be seen that the porous graphene for preparing is sheet porous structural, find out that the material is layer 2-3 by high power TEM.According to specific surface
And pore analysis (Fig. 8), porous graphene material specific surface area obtained in this kind of process conditions is 667.1m2/ g, average pore size
For 4.3nm, average pore sizes are 0.72m3/ g, compared with 1200 DEG C of porous graphene materials for obtaining, specific surface area, average hole
Footpath and pore volume change are little, illustrate that material is relatively stable.
Conductivity maps of the Fig. 9 for PC500, PC900, PG1200 and PG2000, as seen from the figure, with heat treatment temperature
Increase, degree of graphitization increase, the electrical conductivity of material increase；
Figure 10 is the high rate performance that PC500, PC900, PG1200 and PG2000 are used for that lithium ion battery negative test to be obtained
Figure, PG1200 is with higher specific capacity as seen from the figure；
Figure 11 is the CV curves that PC500, PC900, PG1200 and PG2000 are obtained for capacitor testing, can by curve chart
To find out the CV curves for obtaining rectangle closure figure preferably；
Figure 12 be PC500, PC900, PG1200 and PG2000 for capacitor testing obtain under different scanning rates
Capacity curve, as seen from Figure 12 the material prepared by embodiment 3 have higher specific capacity.
Embodiment 3
A kind of preparation method of sulfur doping porous graphene is present embodiments provided, which comprises the following steps：
10g slurry oils are weighed, liquid (60-90 DEG C) is heated to, 20g magnesium sulfate crystal whiskers is added, is stirred, be put into horizontal tube
Formula stove, is then passed through Ar in stove, while horizontal stove rises to 600 DEG C with 15 DEG C/min heating rates, and keeps 60min, treats stove
Temperature takes out gray product after naturally cooling to room temperature.This product is placed in excessive dilute hydrochloric acid, decocting in water backflow pickling 1h is finally used
Deionized water is washed till under the conditions of neutrality is placed in 80 DEG C and is dried, and obtains sulfur doping porous charcoal；Wherein, magnesium sulfate crystal whisker is referred to
MA,X；NING,G；QI,C；GAO,J,One-step synthesis of basic magnesium sulfate whiskers
Preparation method in by atmospheric pressure reflux.Particuology 2016,24,191-196 is obtained；
Further, the sulfur doping porous charcoal is carried out into 1200 DEG C of calcinings using the method for 1 step 2 of embodiment, obtains sulfur and mix
Miscellaneous porous graphene.
In Figure 13, a, b are respectively the low power of sulfur doping porous graphene obtained in said process, high power TEM figure, can by figure
To find out that the sulfur doping porous graphene of preparation is strip loose structure.
Tested from elementary analysiss, 1.58% (matter of sulfur-bearing in sulfur doping porous graphene obtained in this kind of process conditions
Amount fraction).From specific surface and pore analysis (Figure 14), the sulfur doping porous graphene specific surface area is 275.8m2/ g, puts down
Aperture is 10.5nm, and average pore sizes are 0.51m3/g。
Embodiment 4
A kind of preparation method of N doping porous graphene is present embodiments provided, which comprises the following steps：
10g slurry oils are weighed, liquid (60-90 degree) is heated to, adds 20g tripolycyanamide-magnesium oxide complex template (to be somebody's turn to do
Complex template is mixed to get with lamellar template magnesium oxide by the compound tripolycyanamide containing doped chemical, tripolycyanamide
Mass ratio with magnesium oxide is 1:1), stir, be put into horizontal pipe furnace, be then passed through Ar in stove, at the same horizontal stove with
15 DEG C/min heating rates rise to 600 DEG C, and keep 60min, after furnace temperature naturally cools to room temperature take out gray product.By this
Product is placed in excessive dilute hydrochloric acid, and decocting in water backflow pickling 1h, last deionized water are washed till under the conditions of neutrality is placed in 80 DEG C and do
It is dry, obtain N doping porous charcoal；
Further, the N doping porous charcoal is carried out into 1200 DEG C of calcinings using the method for 1 step 2 of embodiment, obtains nitrogen and mix
Miscellaneous porous graphene.
In Figure 15, a, b are respectively the low power of N doping porous graphene obtained in said process, high power TEM figure.Can by figure
To find out, the N doping porous graphene of preparation is sheet porous structural.
From according to elementary analysiss test, nitrogenous 0.56% in N doping porous graphene obtained in this kind of process conditions
(mass fraction).From specific surface and pore analysis (Figure 16), the N doping porous graphene specific surface area is 274.5m2/
G, average pore size are 7.7nm, and average pore sizes are 0.55m3/g。
Claims (10)
1. a kind of preparation method of porous graphene, which comprises the following steps：
The first step, carbon source is mixed with lamellar template, obtains carbon source-template complex；It is compound in the carbon source-template
In thing, carbon source is coated on lamellar template surface；
Second step, carbon source-template complex is carbonized under 500-900 DEG C, shielding gas atmosphere, will be carbonized product pickling pure
Change, obtain flake porous charcoal；
3rd step, flake porous charcoal is calcined under 1000-2000 DEG C, shielding gas atmosphere, porous graphene is obtained.
2. method according to claim 1, wherein, in the first step, the method also includes adding containing doped chemical
The step of compound；
Preferably, after mixed carbon source with the compound containing doped chemical, then mix with lamellar template；Or, will contain
After the compound of doped chemical is mixed with lamellar template, then mix with carbon source.
3. method according to claim 1 and 2, wherein, in second step, the time of the carbonization is 0.5-5h, preferably
For 1-2h；
It is highly preferred that the temperature of the carbonization is 600-900 DEG C, more preferably 650-850 DEG C.
4. the method according to any one of claim 1-3, wherein, in the third step, the time of the calcining is 1-24h,
Preferably 2-5h；
It is highly preferred that the temperature of the calcining is 1500-2000 DEG C, more preferably 1600-2000 DEG C.
5. the method according to any one of claim 1-4, wherein, the lamellar template include flake porous magnesium oxide,
The combination of one or more in lamellar basic magnesium carbonate and flake magnesium hydroxide.
6. the method according to any one of claim 1-5, wherein, the lamellar template is 5 with the mass ratio of carbon source:
(1-50)。
7. the method according to any one of claim 2-6, wherein, the compound containing doped chemical include sulphuric acid,
Sulfate, nitric acid, nitrate, phosphoric acid, phosphate, pyrophosphoric acid, sodium pyrophosphate, APP, tripolycyanamide, pyrroles, pyridine, thiophene
The combination of one or more in fen, quinoline, boric acid and boron oxide；
Preferably, the compound containing doped chemical and the mass ratio of lamellar template are 8:(1-64).
8. the porous graphene that a kind of method by described in any one of claim 1-7 is prepared.
9. porous graphene according to claim 8, wherein, the specific surface area of the porous graphene is 200-3000m2/
g；Aperture is 1-100nm；The number of plies is 1-10.
10. porous graphene according to claim 8 or claim 9, wherein, contain doped chemical in the porous graphene, with
The quality of the porous graphene is 100% meter, and the content of the doped chemical is 0.001-40%；
Preferably, the doped chemical includes the combination of one or more in boron, nitrogen, sulfur and phosphorus.
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| CN113148994A (en) * | 2021-05-19 | 2021-07-23 | 中国石油大学(北京) | Graphene and preparation method and application thereof |
| CN113148994B (en) * | 2021-05-19 | 2022-12-20 | 中国石油大学(北京) | Graphene and preparation method and application thereof |
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