CN102910623A - Modified graphene and preparation method thereof - Google Patents
Modified graphene and preparation method thereof Download PDFInfo
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- CN102910623A CN102910623A CN2012104209962A CN201210420996A CN102910623A CN 102910623 A CN102910623 A CN 102910623A CN 2012104209962 A CN2012104209962 A CN 2012104209962A CN 201210420996 A CN201210420996 A CN 201210420996A CN 102910623 A CN102910623 A CN 102910623A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 125000000524 functional group Chemical group 0.000 claims abstract description 92
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 239000000463 material Substances 0.000 claims abstract description 45
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 44
- 239000010439 graphite Substances 0.000 claims abstract description 44
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 23
- 238000003776 cleavage reaction Methods 0.000 claims description 20
- 230000007017 scission Effects 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 241000446313 Lamella Species 0.000 claims description 11
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 11
- 238000001149 thermolysis Methods 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 abstract description 4
- 230000001681 protective effect Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 20
- 229910019142 PO4 Inorganic materials 0.000 description 19
- 239000010452 phosphate Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 239000004593 Epoxy Chemical group 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WAKIWQDPYGMUCD-UHFFFAOYSA-N [N].NC1=CC=CC=N1 Chemical compound [N].NC1=CC=CC=N1 WAKIWQDPYGMUCD-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- -1 phosphate anion Chemical class 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of modified graphene, which comprises the following steps that: (1) graphite and materials with polar functional groups are uniformly mixed according to a mass ratio of 1:(0.1-50) at subzero 10 DEG C to 200 DEG C, and react at a certain temperature and within a certain time for one step or more steps, object polar functional groups are grafted onto graphitic sheet layers, the object polar functional groups comprise all the polar functional groups contained in the materials with the polar functional groups and/or polar functional groups generated by the reaction between the materials with the polar functional groups with the graphite; (2) the unreacted raw materials in Step (1) and/or impurities produced in the reaction are removed, and the graphite powder grafted with the object polar functional groups is obtained through drying and crushing; and (3) the graphite powder produced in Step (2) is heated and cleaved in protective gas, then the modified graphene grafted with the object polar functional groups on the sheet layers is obtained, and the mass percent of the goal polar functional groups in the modified graphene is 0.01-50%.
Description
Technical field
The invention belongs to Graphene and preparation field thereof, be specifically related to a kind of modified graphene and preparation method thereof.
Background technology
Graphene (Graphene) refers to be between the carbon atom a kind of plates that hexagonal annular is arranged, usually consisted of by the single or multiple lift graphite flake layer, can infinitely extend at two-dimensional space, can be described as proper two-dirnentional structure material, since the strong K of the peace moral of Univ Manchester UK sea nurse (Andre K.Geim) etc. since preparing this material with the mechanically peel method in 2004, its good performance just has been subject to people and has paid attention to widely.
Graphene has the outstanding advantages such as specific surface area is large, electrical and thermal conductivity performance is good, thermal expansivity is low, particularly: high specific surface area (calculated value: 2,630m
2/ g); High conductivity, carrier transport rate (200,000cm
2/ Vs); High heat conductance (5,000W/mK); High strength, and high Young's modulus (1,100GPa), breaking tenacity (125GPa).Therefore it possesses great utilization prospect in fields such as ultracapacitor and lithium ion batteries.
After containing an amount of polar functional group on the graphene sheet layer, the ultracapacitor that its assembling obtains can show the character of fake capacitance, therefore has higher capacity.The existing method for preparing Graphene mainly contains (1) micromechanics stripping method, (2) ultrahigh vacuum(HHV) Graphene epitaxial growth method, (3) oxidation-reduction method, (4) chemical Vapor deposition process (CVD), (5) solvent stripping method, (6) electrolytic process, (7) solvent-thermal method.All be difficult to realize large batch of Graphene production.This shows, prepare a kind of contain the modified graphene of multiple types polar functional group and develop a kind of method that can produce this Graphene in enormous quantities extremely urgent.
Summary of the invention
Technical problem to be solved by this invention is: remedy above-mentioned the deficiencies in the prior art, a kind of modified graphene and preparation method thereof is proposed, the preparation method is simple, can effectively control kind and the quantity of polar functional group on the graphene sheet layer of preparation, the modified graphene for preparing has the good electric chemical property.
Technical problem of the present invention is solved by following technical scheme:
A kind of preparation method of modified graphene comprises the steps:
(1) under-10 ℃ ~ 200 ℃, graphite and the material that contains polar functional group are mixed for 1:0.1 ~ 50 in mass ratio, under certain temperature of reaction and reaction times, by single step reaction or polystep reaction, the target polar functional group is grafted on the lamella of graphite, described target polar functional group comprises described polar functional group contained in the material of polar functional group and/or the described material of polar functional group and the polar functional group that the graphite reaction produces of containing of containing;
(2) remove the impurity that produces in the complete raw material of unreacted in the step (1) and/or the reaction, then dry, pulverize, obtain being grafted with the powdered graphite of target polar functional group;
(3) powdered graphite in the step (2) is placed shielding gas; the heating cleavage; obtain being grafted with on the lamella modified graphene of described target polar functional group, wherein, the mass percent that the content of described target polar functional group accounts for described modified graphene is 0.01 ~ 50%.
Preferably, in the step (1), when adopting single step reaction, temperature of reaction is 35 ℃ ~ 100 ℃.
Preferably, in the step (1), when adopting polystep reaction, the temperature of reaction in per step is respectively T1, T2 ... Tn, T1＜T2＜T3 wherein ...＜Tn, and have a temperature of reaction that goes on foot at least at 〉=35 ℃, n is the number of steps of reaction, n 〉=2.
When adopting polystep reaction, the temperature that progressively raises is reacted the grafting that is conducive to target functional group.
Preferably, the material that contains polar functional group described in the step (1) is selected from ammoniacal liquor, HNO
3, H
3PO
4, H
3AsO
4, KMnO
4, H
2SO
4, H
2SeO
4, H
6TeO
6, HF, HCl, HClO, HClO
3, HClO
4, HBrO
3, HBrO
4, H
5IO
6And HIO
3In a kind of or their combination or the zwitterion restructuring mixture that can be formed to few more than one materials.
Preferably, shielding gas is N described in the step (3)
2, a kind of in the gas that produces of rare gas element and the described material thermolysis that contains polar functional group or their combination.
Preferably, the pressure of shielding gas is 0.01Pa-100MPa described in the step (3).
Preferably, contain the gas that the described material thermolysis that contains polar functional group produces described in the step (3) in the shielding gas, the dividing potential drop of the gas that the described material thermolysis that contains polar functional group produces is 0.0001Pa ~ 50MPa.
Preferably, the temperature of the heating cleavage described in the step (3) is 80 ℃ ~ 3000 ℃.
Preferably, the reaction times described in the step (1) is 10min ~ 24h, and the time of heating cleavage is 1s ~ 48h in the step (3).
Preferably, in the step (1), when adopting polystep reaction, reactions steps was 3 steps, and temperature of reaction is followed successively by 0 ℃≤T1≤10 ℃, 30 ℃≤T2≤60 ℃, 80 ℃≤T3≤100 ℃, the reaction times is 10min ~ 10h, and the time of heating cleavage is 0.5-10 h in the step (3).
A kind of modified graphene that is prepared by the described method of above-mentioned any one is grafted with the target polar functional group on the graphene sheet layer, and the mass percent that the content of described target polar functional group accounts for described modified graphene is 0.01 ~ 50%.
Preferably, to account for the mass percent of described modified graphene be 0. 1 ~ 20% to the content of described target polar functional group.
Compared with prior art, the modified graphene of the present invention's preparation has the following advantages:
At first, use contains the compound of polar functional group with the graphite functionalization, thereby make the graphite flake layer surface grafting that the target polar functional group be arranged, be placed on again and carry out the pyrolysis reason in the shielding gas, thereby the modified graphene that suppresses this invention preparation of thermolysis of this target polar functional group has good chemical property, specific conductivity can reach 1000 s/cm, utilization has a extensive future, the modified graphene that is grafted with polar functional group is during as electrode material for super capacitor, the polar functional group of grafting can be so that its performance fake capacitance character, its fake capacitance can reach 200-600F/g, so it can give play to higher capacity; Simultaneously, the modified graphene and the polar solvent that are grafted with polar functional group have very excellent consistency, so it is during as the lithium ion battery conductive agent, can not exist and be difficult to the problem of disperseing in polar solvent.
Secondly, use the method to prepare modified graphene, can effectively control the kind of the target polar functional group that is grafted on the graphene sheet layer: owing to finally be grafted to the material of polar functional group contained in the material that uses when target polar functional group on the modified graphene lamella comes from functionalization graphite and use and the polar functional group of graphite reaction generation, therefore on graphite flake layer during grafting target polar functional group, can be by regulating kind and the functionalization time that adds the material that contains polar functional group, the pressure of shielding gas during the pyrolysis reason, the parameters such as cleavage temperature and time, kind and the quantity of target polar functional group in the modified graphene of simple and effective control preparation; Specifically: by controlling employed the contain kind of the material of polar functional group, temperature and the time of reaction; can effectively control kind and the total amount of the target polar functional group that is grafted on the graphite flake layer; simultaneously; in pyrolysis reason process; can effectively control the pressure of shielding gas in the temperature, time, reaction of cleavage reaction; thereby control is grafted to the decomposition amount of the target polar functional group on the modified graphene, finally reaches kind and the total amount of the target polar functional group of grafting on the control modified graphene.
The 3rd: the method prepares modified graphene, and technique is simple, with low cost, be easy to industrialized mass production.
Embodiment
Below in conjunction with preferred embodiment the present invention is explained in detail.
The invention provides a kind of preparation method of modified graphene, in one embodiment, comprise the steps:
(1) under-10 ℃ ~ 200 ℃, graphite and the material that contains polar functional group are mixed for 1:0.1 ~ 50 in mass ratio, under certain temperature of reaction and reaction times, by single step reaction or polystep reaction, the target polar functional group is grafted on the lamella of graphite, described target polar functional group comprises described polar functional group contained in the material of polar functional group and/or the described material of polar functional group and the polar functional group that the graphite reaction produces of containing of containing;
(2) remove the impurity that produces in the complete raw material of unreacted in the step (1) and/or the reaction, then dry, pulverize, obtain being grafted with the powdered graphite of target polar functional group;
(3) powdered graphite in the step (2) is placed shielding gas; the heating cleavage; obtain being grafted with on the lamella modified graphene of described target polar functional group, wherein, the mass percent that the content of described target polar functional group accounts for described modified graphene is 0.01 ~ 50%.
In some other preferred implementation, when adopting single step reaction in the step (1), temperature of reaction is 35 ℃ ~ 100 ℃.When adopting polystep reaction in the step (1), the temperature of reaction in per step is respectively T1, T2 ... Tn, T1＜T2＜T3 wherein ...＜Tn, and have a temperature of reaction that goes on foot at least at 〉=35 ℃, n is the number of steps of reaction, n 〉=2.
In further preferred embodiment:
The material that contains polar functional group described in the step (1) can be selected from ammoniacal liquor, HNO
3, H
3PO
4, H
3AsO
4, KMnO
4, H
2SO
4, H
2SeO
4, H
6TeO
6, HF, HCl, HClO, HClO
3, HClO
4, HBrO
3, HBrO
4, H
5IO
6And HIO
3In a kind of or their combination or the zwitterion restructuring mixture that can be formed to few more than one materials.
Shielding gas can be N described in the step (3)
2, a kind of in the gas that produces of rare gas element and the described material thermolysis that contains polar functional group or their combination.
The pressure of shielding gas is 0.01Pa-100MPa described in the step (3).
Contain the gas that the described material thermolysis that contains polar functional group produces described in the step (3) in the shielding gas, the dividing potential drop of the gas that the described material thermolysis that contains polar functional group produces is 0.0001Pa ~ 10MPa.
The temperature of the heating cleavage described in the step (3) is 80 ℃ ~ 3000 ℃.
Reaction times described in the step (1) is 10min ~ 24h, and the time of heating cleavage is 1s ~ 48h in the step (3).
In the step (1), when adopting polystep reaction, reactions steps was 3 steps, and temperature of reaction is followed successively by 0 ℃≤T1≤10 ℃, and 30 ℃≤T2≤60 ℃, 80 ℃≤T3≤100 ℃, the reaction times is 10min ~ 10h, and the time of heating cleavage is 0.5-10 h in the step (3).
The present invention also provides a kind of modified graphene that is prepared by the described method of above-mentioned any embodiment, be grafted with the target polar functional group on the graphene sheet layer, and the mass percent that the content of described target polar functional group accounts for described modified graphene is 0.01 ~ 50%.Preferably, to account for the mass percent of described modified graphene be 0. 1 ~ 20% to the content of described target polar functional group.
Below the present invention will be described in detail by embodiment more specifically.
Embodiment 1
Step (1): adopt polystep reaction, namely in 1 ℃ of environment, 10g graphite, 400 g phosphoric acid are mixed, afterwards at 35 ℃ of lower stirring reaction 50min, 98 ℃ of lower reactions 2 hours, phosphate radical is grafted on the lamella of graphite;
Step (2): add entry in the reaction product that makes to step (1), then constantly washing until can't detect phosphate anion in the washings, then dry, pulverize, obtain being grafted with the powdered graphite of phosphate radical;
Step (3): the powdered graphite that step (2) is prepared places and contains the 95%(volume fraction) nitrogen and 5%(volume fraction) atmosphere of phosphuret-(t)ed hydrogen, regulating atmosphere pressure is 0.1 MPa, the heating cleavage are 3 hours under 400 ℃, prepare the modified graphene that is grafted with phosphate radical on the graphene sheet layer, the massfraction that phosphate radical accounts for modified graphene is 9%, and the capacitance of this material can reach 245 F/g.
Embodiment 2
Be to change the phosphoric acid in the step (1) into nitric acid with the difference of embodiment 1, phosphuret-(t)ed hydrogen in the step (3) changes ammonia into simultaneously, prepare the modified graphene that is grafted with amino, pyridine nitrogen, pyrroles's nitrogen on the graphene sheet layer, the massfraction that amino, pyridine nitrogen, pyrroles's nitrogen account for respectively modified graphene is 5%, 2% and 3%, and the capacitance of this material can reach 455 F/g.
Embodiment 3
Be to change 60 ℃ into 35 ℃ in the step (1) with the difference of embodiment 1.Prepare the modified graphene that is grafted with phosphate radical on the graphene sheet layer, the massfraction that phosphate radical accounts for modified graphene is 10%, and the capacitance of this material can reach 265 F/g.
Embodiment 4
Be to change 98 ℃ in the step (1) lower reactions into 98 ℃ of lower reactions 10 hours in 2 hours with the difference of embodiment 1.Prepare the modified graphene that is grafted with phosphate radical on the graphene sheet layer, the massfraction that phosphate radical accounts for modified graphene is 20%, and the capacitance of this material can reach 304 F/g.
Embodiment 5
Be the pressure in the step (3) is adjusted to 100 MPa with the difference of embodiment 1.Prepare the modified graphene that is grafted with phosphate radical on the graphene sheet layer, the massfraction that phosphate radical accounts for modified graphene is 8%, and the capacitance of this material can reach 254 F/g.
Embodiment 6
Be the pressure in the step (3) is adjusted to 0.01 Pa with the difference of embodiment 1.Prepare the modified graphene that is grafted with phosphate radical on the graphene sheet layer, the massfraction that phosphate radical accounts for modified graphene is 9%, and the capacitance of this material can reach 246 F/g.
Embodiment 7
Be that with the difference of embodiment 1 temperature regulation with the heating cleavage in the step (3) is 3000 ℃, prepare the modified graphene that is grafted with phosphate radical on the graphene sheet layer, the massfraction that phosphate radical accounts for modified graphene is 0.5%, and the capacitance of this material can reach 86 F/g.
Embodiment 8
Be that with the difference of embodiment 1 Timing with the heating cleavage in the step (3) is 24 h, prepare the modified graphene that is grafted with phosphate radical on the graphene sheet layer, the massfraction that phosphate radical accounts for modified graphene is 4%, and the capacitance of this material can reach 153 F/g.
Embodiment 9
Be to change the atmosphere in the step (3) into the 50%(volume fraction with the difference of embodiment 1) argon gas and 50%(volume fraction) phosphuret-(t)ed hydrogen, prepare the modified graphene that is grafted with phosphate radical on the graphene sheet layer, the massfraction that phosphate radical accounts for modified graphene is 50%, and the capacitance of this material can reach 612 F/g.
Embodiment 10
Step (1): in 0 ℃ of environment, 100g graphite, 4000g sulfuric acid are mixed, saltpetre to the potassium permanganate that wherein adds 500 g and 50g, afterwards at 30 ℃ of lower stirring reaction 150min, 90 ℃ of lower reactions 3 hours, with carboxyl, hydroxyl, epoxy functionality is grafted on the lamella of graphite;
Step (2): add entry in the reaction product that makes to step (1), then constantly wash until can't detect sulfate radical, MnO4, nitrate ion, drying, pulverizing in the washings, obtain being grafted with carboxyl, hydroxyl, the powdered graphite of epoxy functionality;
Step (3): the powdered graphite that step (2) is prepared places and contains the 95%(volume fraction) atmosphere of nitrogen and 5% water vapour (volume fraction), regulating pressure is 0.1 MPa, prepare graphite flake layer at 600 ℃ of lower heating cleavage 1h and be grafted with carboxyl, hydroxyl, the modified graphene of epoxy functionality, the massfraction that carboxyl, hydroxyl, epoxy group(ing) account for respectively modified graphene is 4%, 3% and 3%, and the capacitance of this material can reach 278 F/g.
Embodiment 11
Step (1): in-10 ℃ of environment, 10 g graphite, 400 g HClO are mixed, afterwards at 40 ℃ of lower stirring reaction 50min, 190 ℃ of lower reactions 5 hours are grafted to chlorine element functional group on the lamella of graphite in encloses container;
Step (2): add entry in the reaction product that makes to step (1), then constantly washing obtains being grafted with the powdered graphite of chlorine element functional group until can't detect hypochlorite ion, drying, pulverizing in the washings;
Step (3): the powdered graphite that step (2) is prepared places and contains the 85%(volume fraction) nitrogen and 15%(volume fraction) atmosphere of hydrogenchloride, pressure is 100 MPa in the stove, 900 ℃ of lower heating cleavage 10min, in safety stove, discharge pressure, prepare the modified graphene that is grafted with chlorine element functional group on the graphite flake layer, the massfraction that chlorine element functional group accounts for modified graphene is 13%, and the capacitance of this material can reach 158 F/g.
Embodiment 12
Step (1): adopt single step reaction, 35 ℃ lower, 10 g graphite, 400 g HClO are mixed reaction 5 hours, chlorine element functional group is grafted on the lamella of graphite;
Step (2): add entry in the reaction product that makes to step (1), then constantly washing obtains being grafted with the powdered graphite of chlorine element functional group until can't detect hypochlorite ion, drying, pulverizing in the washings;
Step (3): the powdered graphite that step (2) is prepared places and contains the 85%(volume fraction) nitrogen and 15%(volume fraction) atmosphere of hydrogenchloride, pressure is 100 MPa in the stove, 2000 ℃ of lower heating cleavage 1h, in safety stove, discharge pressure, prepare the modified graphene that is grafted with chlorine element functional group on the graphite flake layer, the massfraction that chlorine element functional group accounts for modified graphene is 3%, and the capacitance of this material can reach 98 F/g.In sum, adopt first grafting target polar functional group on graphite flake layer, and then expanded pyrolysis reason can prepare grafting target polar functional group kind and the controlled modified graphene with good electric chemical property of quantity in protective atmosphere.
Above content is the further description of the present invention being done in conjunction with concrete preferred implementation, can not assert that implementation of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, make some being equal to substitute or obvious modification, and performance or purposes are identical, all should be considered as belonging to protection scope of the present invention.
Claims (10)
1. the preparation method of a modified graphene is characterized in that, comprises the steps:
(1) under-10 ℃ ~ 200 ℃, graphite and the material that contains polar functional group are mixed for 1:0.1 ~ 50 in mass ratio, under certain temperature of reaction and reaction times, by single step reaction or polystep reaction, the target polar functional group is grafted on the lamella of graphite, described target polar functional group comprises described polar functional group contained in the material of polar functional group and/or the described material of polar functional group and the polar functional group that the graphite reaction produces of containing of containing;
(2) remove the impurity that produces in the complete raw material of unreacted in the step (1) and/or the reaction, then dry, pulverize, obtain being grafted with the powdered graphite of target polar functional group;
(3) powdered graphite in the step (2) is placed shielding gas; the heating cleavage; obtain being grafted with on the lamella modified graphene of described target polar functional group, wherein, the mass percent that the content of described target polar functional group accounts for described modified graphene is 0.01 ~ 50%.
2. the preparation method of modified graphene according to claim 1 is characterized in that: in the step (1), when adopting single step reaction, temperature of reaction is 35 ℃ ~ 100 ℃; When adopting polystep reaction, the temperature of reaction in per step is respectively T1, T2 ... Tn, T1＜T2＜T3 wherein ...＜Tn, and have a temperature of reaction that goes on foot at least at 〉=35 ℃, n is the number of steps of reaction, n 〉=2.
3. the preparation method of modified graphene according to claim 1 and 2, it is characterized in that: the material that contains polar functional group described in the step (1) is selected from ammoniacal liquor, HNO
3, H
3PO
4, H
3AsO
4, KMnO
4, H
2SO
4, H
2SeO
4, H
6TeO
6, HF, HCl, HClO, HClO
3, HClO
4, HBrO
3, HBrO
4, H
5IO
6And HIO
3In a kind of or their combination or the zwitterion restructuring mixture that can be formed to few more than one materials.
4. the preparation method of modified graphene according to claim 1 and 2, it is characterized in that: shielding gas is N described in the step (3)
2, a kind of in the gas that produces of rare gas element and the described material thermolysis that contains polar functional group or their combination.
5. the preparation method of modified graphene according to claim 4, it is characterized in that: the pressure of shielding gas is 0.01Pa-100MPa described in the step (3).
6. the preparation method of modified graphene according to claim 4; it is characterized in that: contain the gas that the described material thermolysis that contains polar functional group produces described in the step (3) in the shielding gas, the dividing potential drop of the gas that the described material thermolysis that contains polar functional group produces is 0.0001Pa ~ 50MPa.
7. the preparation method of modified graphene according to claim 1 and 2, it is characterized in that: the temperature of the heating cleavage described in the step (3) is 80 ℃ ~ 3000 ℃.
8. the preparation method of the described modified graphene of any one according to claim 1 and 2, it is characterized in that: the reaction times described in the step (1) is 10min ~ 24h, the time of heating cleavage is 1s ~ 48h in the step (3).
9. the preparation method of modified graphene according to claim 1 and 2, it is characterized in that: in the step (1), when adopting polystep reaction, reactions steps was 3 steps, temperature of reaction is followed successively by 0 ℃≤T1≤10 ℃, and 30 ℃≤T2≤60 ℃, 80 ℃≤T3≤100 ℃, reaction times is 10min ~ 10h, and the time of heating cleavage is 0.5-10 h in the step (3).
10. the modified graphene for preparing of the described method of any one according to claim 1-9, it is characterized in that: be grafted with described target polar functional group on the graphene sheet layer, and the mass percent that the content of described target polar functional group accounts for described modified graphene is 0.01 ~ 50%, and the mass percent that the content of preferred described target polar functional group accounts for described modified graphene is 0.1 ~ 20%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387226A (en) * | 2013-07-05 | 2013-11-13 | 清华大学深圳研究生院 | Preparation method for graphene |
| CN106276867A (en) * | 2016-07-21 | 2017-01-04 | 绍兴文理学院 | The photoelectric modified graphene of a kind of enhancing |
| CN109227791A (en) * | 2018-08-31 | 2019-01-18 | 徐培培 | A kind of waterproof pluwood |
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Non-Patent Citations (2)
| Title |
|---|
| BIN SHEN ETAL: "Synthesis of graphene by low-temperature exfoliation and reduction of graphite oxide under ambient atmosphere", 《J. MATER. CHEM. C》 * |
| MEIHUA JIN ETAL: "Synthesis and systematic characterization of functionalized graphene sheets generated by thermal exfoliation at low temperature", 《J. PHYS. D: APPL. PHYS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387226A (en) * | 2013-07-05 | 2013-11-13 | 清华大学深圳研究生院 | Preparation method for graphene |
| CN106276867A (en) * | 2016-07-21 | 2017-01-04 | 绍兴文理学院 | The photoelectric modified graphene of a kind of enhancing |
| CN109227791A (en) * | 2018-08-31 | 2019-01-18 | 徐培培 | A kind of waterproof pluwood |
| CN109227791B (en) * | 2018-08-31 | 2021-04-02 | 贵港市鼎源木业有限公司 | Waterproof plywood |
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| CN102910623B (en) | 2015-01-07 |
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