CN104071777A - Preparation method of graphene - Google Patents
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- CN104071777A CN104071777A CN201410276180.6A CN201410276180A CN104071777A CN 104071777 A CN104071777 A CN 104071777A CN 201410276180 A CN201410276180 A CN 201410276180A CN 104071777 A CN104071777 A CN 104071777A
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Abstract
The invention provides a preparation method of graphene, relating to the technical field of new material preparation and aiming to solve the problems that existing mechanical methods are low in yields, the lamella thickness is not easy to control, the properties are not stable, graphene prepared by chemical methods has poor properties, both mechanical and chemical methods adopt ultrasonic treatment, thus causing long production cycle, and prepared graphene has poor integrity. The method comprises the following steps: firstly, ball-milling graphite with high thermal conductivity; secondly, pickling the powder obtained after ball-milling and preparing expanded graphite; thirdly, oxidizing expanded graphite and stripping the lamella by utilizing temperature change, thus preparing graphene oxide; and fourthly, reducing graphene oxide with hydrogen hydrazine and finally carrying out drying, thus preparing graphene powder. The preparation method has the advantages that graphene prepared by the preparation method is free from ultrasonic stripping and has few detects; the graphene structure can not be destroyed and the integrity of the graphene lamella is better maintained; and the preparation method is simple in process, has the effect of reducing the cost and is suitable for volume production.
Description
Technical field
The present invention relates to technical field of new material preparation, particularly relate to a kind of preparation method of Graphene.
Background technology
Graphene is a kind of New Two Dimensional material.According to " Chinese Graphene industrial technology innovation strategy alliance standard " (Q/LM01CGS001-2013), the carbon material that only has carbon atomic layer thickness sign to be less than 10 layers just can be called as grapheme material.Grapheme material has the excellent mechanical property that higher electrical and thermal conductivity performance, thermostability are high, equal to carbon nanotube, and meanwhile, this material also has special Quantum Properties.Therefore from being born, just receive much attention.
In current existing graphene preparation method, it is few that mechanical means makes Graphene defect, but size is wayward and production efficiency is low; Graphene edge prepared by pure chemical process, often with dangling bonds, because need to experience long-time ultrasonic procedure, therefore makes size generally less simultaneously.These are all unfavorable for application and the popularization of Graphene.
With regard to mechanically peel, the method for utilizing External Force Acting to peel off single or multiple lift Graphene from graphite raw material is called mechanically peel method.The investigators such as Geim are etching microflute on high pyrolytic graphite, then with transparent adhesive tape repeatedly to taking off, and it is ultrasonic that the Graphene that speckles with the different numbers of plies is put into acetone, and it is separated with adhesive tape.The Graphene of separating can be attracted in acetone with on the silicon chip placing.Graphite Powder 99 is put into liquid CO 2 by the investigators such as Pu, and after 30min, CO2 can diffuse into graphite layers, then pass through step-down, and CO2 can expand and make few layer graphene peel off [24] from graphite rapidly.Catharina Knieke etc. utilizes ball milled, obtains the graphene nanometer sheet of 1nm left and right taking sodium lauryl sulphate (SDS) after tensio-active agent ball milling 5h.
Chemical stripping method is generally that graphite type material (as high graphite, carbon fiber, carbon nanotube) is oxidized and is peeled off, thereby be worth graphene oxide (GO), then graphene oxide (GO) reduction obtained possessing the Graphene of high conductivity.Conventional graphite oxidation method comprises: Standenmaier method, Hummers method, Brodie method.The investigators such as Sridha R are put in carbon fiber in superoxol and are oxidized, and utilize microwave heating peel value must contain the Graphene of oxy radical.Make Graphene and put into hydrazine ultrasonic, remove oxy radical [26].The investigators such as Schniepp utilize the strong oxidizers such as concentrated hydrochloric acid to mix with graphite, make it fully to react with graphite; Graphite is put into the container containing argon gas, be heated to rapidly 1050 DEG C, lamella is separated, wherein oxy radical oxidation forms CO2; The Graphene specific surface area now obtaining reaches 700～1500m2/g.
Chemical synthesis is that to utilize phenyl ring or other aroma systems be core, and the hydrogen atom that the carbon on phenyl ring is all substituted on it by linked reaction forms new aromatic nucleus.Carry out with reaction, thereby system is increased, thus the synthetic Graphene with larger two-dirnentional structure.The investigators such as Choucair first prepare intermediate material using ethanol and sodium as raw material, subsequently by the processing such as cracking and ultrasonic dispersion, make the Graphene of gram magnitude.
Epitaxial growth method is by heating Ni/SiC or SiC/Si, and SiC is decomposed, and Formed atom enters Ni layer or Si layer, and then Ni or Si layer matrix are lowered the temperature rapidly, and carbon atom can be separated out at Ni layer or Si layer surface due to supersaturation, forms Graphene.The investigators such as Emtsev utilize that the method makes length >50 μ m at Si (0001) matrix surface, width is the single-layer graphene of 3 μ m.Now Graphene is 2000cm2V-1S-1 in the electronic mobility of 27K.
Domestic research paper comprises, the investigators such as the 08 year king of Physics Inst., Chinese Academy of Sciences grace brother have proposed to peel off-embed-and the method for expanding, successfully prepare high-quality Graphene.They characterize Graphene and deep crystal structure analysis by transmission electron microscopy.The investigators such as Chinese Academy of Sciences's mathematics and system science researcher Ming Ping soldier predict that the ideal tensile strength of Graphene is 110～121GPa.For improving the productive rate of Graphene, the investigators such as Hou have been developed the novel method that solvent thermal intercalation is prepared Graphene.The method is taking expanded graphite EG as raw material, with the quadripole inducing action of strong polar organic solvent acetonitrile and graphene film peel off, dispersed graphite, make the overall yield of Graphene bring up to 10%～12%.
The preparation of Graphene also has many patents of invention at home, and preparation method is different.Publication number is that the patent of CN103570012A discloses a kind of employing acidic solution graphite is carried out to pre-treatment, after raw material is added in actives solution, the dry graphene powder that obtains after ultrasonic.The preparation process of the method needs ultrasonic, has extended the production cycle, has reduced efficiency and energy consumption is larger; Publication number is that the patent utilization improvement Hummers method of CN200910187298 is peeled off graphite oxide by ultrasonic, has obtained the Graphene of large-size high-quality.Publication number is that the patent of CN103130218A discloses a kind of method that ball milling is prepared Graphene, and the graphene film footpath that the method obtains is often uncontrollable and size is less.
Aforesaid method prepares Graphene with mechanical means and exists productive rate not high, and productive rate is generally 1%～10%, and lamellar spacing is wayward, the problem of unstable properties; Though and high by chemical preparation output, there is the existence of dangling bonds and other oxygen-containing functional groups because making grapheme material, directly will affect material property.And all need to carry out ultrasonic lift-off processing in mechanical means and chemical preparation Graphite During The Process alkene, the treatment time is generally 1h～4h, causes the production cycle long, and ultrasonic peel off can destroy graphene-structured cause preparation Graphene integrity poor, performance is bad.
Summary of the invention
Bad and the mechanical means of the present invention is that existing machinery method productive rate is not high, lamellar spacing is wayward in order to solve, prepared by unstable properties, chemical process Graphene performance and chemical process all exist supersound process to cause the poor problem of Graphene integrity of long and preparation of production cycle, and a kind of preparation method of Graphene is provided.
The preparation method of a kind of Graphene of the present invention carries out according to following steps:
One, graphite is carried out to ball milling, ratio of grinding media to material is (3～5): 1, Ball-milling Time is 0.5h～2h, then the graphite after ball milling being joined to massfraction is in 10%～38% hydrochloric acid soln, stir 10min～20min and remove surface impurity, the pH value of the deionized water after extremely rinsing with the graphite after deionized water rinsing removal of impurities is again neutral, finally dries, and obtains graphite after treatment; Described graphite is of a size of 50 order～200 orders;
Two, graphite after treatment step 1 being joined to massfraction is to stir 15min～30min in 48%～68% salpeter solution, then add potassium permanganate, be to react 60min～90min under 10～20 DEG C of conditions in temperature, the pH value of the deionized water after extremely rinsing with deionized water rinsing solid matter after filtering is 6～7, after being dried, obtains being oxidized intercalated graphite; The described quality of step 1 graphite after treatment and the ratio of the volume of salpeter solution are 1g:(3～5) mL; The mass ratio of described step 1 graphite after treatment and potassium permanganate is 1:(0.3～0.5);
Three, the oxidation intercalated graphite obtaining in step 2 is placed in to retort furnace and heat-treats, thermal treatment temp is 1100～1200 DEG C, and heat treatment time is 80s～100s, obtains expanded graphite;
Four, expanded graphite step 3 being obtained joins massfraction and is not less than in 98% the vitriol oil, stir 30min～60min, then the speed that adds that adds potassium permanganate and control potassium permanganate is 1g/min～5g/min, be to react 100min～140min under the condition of-5～0 DEG C in temperature, obtain reaction solution; The quality of the expanded graphite that described step 3 obtains is 1g:(35～45 with the ratio of the volume of the vitriol oil) mL; The expanded graphite that described step 3 obtains and the mass ratio of potassium permanganate are 1:(5～7);
Five, step 4 being obtained to reaction solution transfers in reactor, the speed that adds that adds deionized water and control deionized water is 10g/min～30g/min, then being heated to temperature is 100～105 DEG C, and be that at 100～105 DEG C, reaction for 10min～20min, then is 20%～30% hydrogen peroxide to dripping massfraction in reactor in temperature; Obtain golden yellow solution; The ratio of the quality of the expanded graphite that the volume of described deionized water and step 3 obtain is (40～60) mL:1g; The ratio of the quality of the expanded graphite that the volume of described hydrogen peroxide and step 3 obtain is (18～22) mL:1g;
Six, in the golden yellow solution obtaining to step 5, drip in strong aqua and pH value to 8～9, be to filter at 40～50 DEG C in temperature, and clarify with deionized water rinsing solid matter to filtrate, then under being the condition of 30～40 DEG C, temperature dries, drying time is 8h～24h, obtains desciccate;
Seven, desciccate step 6 being obtained is dissolved in organic solvent and stirs 30min～50min, then be placed in liquid nitrogen and leave standstill 20min～40min, being warming up to temperature is 60～95 DEG C again, then add hydrazine hydrate, be to react 1h～3h at 60～95 DEG C in temperature, after filtration, be 8 by deionized water rinsing to pH value, then dry, obtain Graphene; The ratio of the quality of the desciccate that the volume of described hydrazine hydrate and step 6 obtain is (0.8～1.5) mL:1g.
The Graphene that preparation method of the present invention makes needn't pass through ultrasonic peeling off, and defect is few, can not destroy graphene-structured, keep preferably the integrity of graphene sheet layer, and technique is simple, reduces costs, and suitable batch is produced, and concrete advantage is as follows:
1, adopting high conductive graphite is raw material, and degree of graphitization is high, and genetic defects is few, and in carbon atomic layer, irregular pentagon and heptagon are few, for the follow-up Graphene of preparing provides good basis.
2, after ball milling, in high conductive graphite, weak connection portion is broken up, preparation process is ultrasonic without process, utilize colding and heat succeed each other in preparation process can make atomic shell peel off with small molecules effect, reduced energy consumption and production cycle, make the production cycle shorten 5h～10h.
3, to make Graphene size larger for method of the present invention, is of a size of 2 μ m～25 μ m, and without ultrasound destruction graphene sheet layer structure, it is more complete that lamella keeps.
4, the organic solution in reaction process and ammonia hydrazine solution, liquid nitrogen can Reusabilities, cost, cost approximately 10%～20%.
5, preparation method's technique of the present invention is simple, can carry out suitability for industrialized production.
Brief description of the drawings
Fig. 1 is the XRD figure of test one Graphene preparing; Wherein a is that graphite, b are that expanded graphite, c are Graphene;
Fig. 2 is the SEM photo of test one Graphene preparing;
Fig. 3 is the SEM photo of test one Graphene preparing;
Fig. 4 is the SEM photo of test one Graphene preparing;
Fig. 5 is the SEM photo of test one Graphene preparing;
Fig. 6 is the atomic force microscope thickness phenogram of test one Graphene preparing;
Fig. 7 is the Raman spectrogram of test one Graphene preparing.
Embodiment
Embodiment one: the preparation method of a kind of Graphene of present embodiment carries out according to following steps:
One, graphite is carried out to ball milling, ratio of grinding media to material is (3～5): 1, Ball-milling Time is 0.5h～2h, then the graphite after ball milling being joined to massfraction is in 10%～38% hydrochloric acid soln, stir 10min～20min and remove surface impurity, the pH value of the deionized water after extremely rinsing with the graphite after deionized water rinsing removal of impurities is again neutral, finally dries, and obtains graphite after treatment; Described graphite is of a size of 50 order～200 orders;
Two, graphite after treatment step 1 being joined to massfraction is to stir 15min～30min in 48%～68% salpeter solution, then add potassium permanganate, be to react 60min～90min under 10～20 DEG C of conditions in temperature, the pH value of the deionized water after extremely rinsing with deionized water rinsing solid matter after filtering is 6～7, after being dried, obtains being oxidized intercalated graphite; The described quality of step 1 graphite after treatment and the ratio of the volume of salpeter solution are 1g:(3～5) mL; The mass ratio of described step 1 graphite after treatment and potassium permanganate is 1:(0.3～0.5);
Three, the oxidation intercalated graphite obtaining in step 2 is placed in to retort furnace and heat-treats, thermal treatment temp is 1100～1200 DEG C, and heat treatment time is 80s～100s, obtains expanded graphite;
Four, expanded graphite step 3 being obtained joins massfraction and is not less than in 98% the vitriol oil, stir 30min～60min, then the speed that adds that adds potassium permanganate and control potassium permanganate is 1g/min～5g/min, be to react 100min～140min under the condition of-5～0 DEG C in temperature, obtain reaction solution; The quality of the expanded graphite that described step 3 obtains is 1g:(35～45 with the ratio of the volume of the vitriol oil) mL; The expanded graphite that described step 3 obtains and the mass ratio of potassium permanganate are 1:(5～7);
Five, step 4 being obtained to reaction solution transfers in reactor, the speed that adds that adds deionized water and control deionized water is 10g/min～30g/min, then being heated to temperature is 100～105 DEG C, and be that at 100～105 DEG C, reaction for 10min～20min, then is 20%～30% hydrogen peroxide to dripping massfraction in reactor in temperature; Obtain golden yellow solution; The ratio of the quality of the expanded graphite that the volume of described deionized water and step 3 obtain is (40～60) mL:1g; The ratio of the quality of the expanded graphite that the volume of described hydrogen peroxide and step 3 obtain is (18～22) mL:1g;
Six, in the golden yellow solution obtaining to step 5, drip in strong aqua and pH value to 8～9, be to filter at 40～50 DEG C in temperature, and clarify with deionized water rinsing solid matter to filtrate, then under being the condition of 30～40 DEG C, temperature dries, drying time is 8h～24h, obtains desciccate;
Seven, desciccate step 6 being obtained is dissolved in organic solvent and stirs 30min～50min, then be placed in liquid nitrogen and leave standstill 20min～40min, being warming up to temperature is 60～95 DEG C again, then add hydrazine hydrate, be to react 1h～3h at 60～95 DEG C in temperature, after filtration, be 8 by deionized water rinsing to pH value, then dry, obtain Graphene; The ratio of the quality of the desciccate that the volume of described hydrazine hydrate and step 6 obtain is (0.8～1.5) mL:1g.
The Graphene that the preparation method of present embodiment makes needn't pass through ultrasonic peeling off, and defect is few, can not destroy graphene-structured, keep preferably the integrity of graphene sheet layer, and technique is simple, reduces costs, and suitable batch is produced, and concrete advantage is as follows:
1, adopting high conductive graphite is raw material, and degree of graphitization is high, and genetic defects is few, and in carbon atomic layer, irregular pentagon and heptagon are few, for the follow-up Graphene of preparing provides good basis.
2, after ball milling, in high conductive graphite, weak connection portion is broken up, preparation process is ultrasonic without process, utilize colding and heat succeed each other in preparation process can make atomic shell peel off with small molecules effect, reduced energy consumption and production cycle, make the production cycle shorten 5h～10h.
3, to make Graphene size larger for the method for present embodiment, is of a size of 2 μ m～25 μ m, and without ultrasound destruction graphene sheet layer structure, it is more complete that lamella keeps.
4, the organic solution in reaction process and ammonia hydrazine solution, liquid nitrogen can Reusabilities, cost, cost approximately 10%～20%.
5, preparation method's technique of present embodiment is simple, can carry out suitability for industrialized production.
Embodiment two: present embodiment is different from embodiment one: the ratio of grinding media to material described in step 1 is 4:1, Ball-milling Time is 1h～1.5h.Other step and parameter are identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two: the graphite described in step 1 is of a size of 100 order～150 orders.Other step and parameter are identical with embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three: the ratio of the quality of step 1 graphite after treatment described in step 2 and the volume of salpeter solution is 1g:4mL.Other step and parameter are identical with one of embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to four: in step 2, the mass ratio of step 1 graphite after treatment and potassium permanganate is 1:0.4.Other step and parameter are identical with one of embodiment one to four.
Embodiment six: present embodiment is different from one of embodiment one to five: the drying parameter described in step 2 is: temperature is 30～40 DEG C, the time is 4h～24h.Other step and parameter are identical with one of embodiment one to five.
Embodiment seven: present embodiment is different from one of embodiment one to six: the quality of the expanded graphite that the step 3 described in step 4 obtains is 1g:40mL with the ratio of the volume of the vitriol oil.Other step and parameter are identical with one of embodiment one to six.
Embodiment eight: present embodiment is different from one of embodiment one to seven: the expanded graphite that the step 3 described in step 4 obtains and the mass ratio of potassium permanganate are 1:6.Other step and parameter are identical with one of embodiment one to seven.
Embodiment nine: present embodiment is different from one of embodiment one to eight: the ratio of the quality of the expanded graphite that the volume of the deionized water described in step 5 and step 3 obtain is 50mL:1g.Other step and parameter are identical with one of embodiment one to eight.
Embodiment ten: present embodiment is different from one of embodiment one to nine: the ratio of the quality of the expanded graphite that the volume of the hydrogen peroxide described in step 5 and step 3 obtain is 20mL:1g.Other step and parameter are identical with one of embodiment one to nine.
Embodiment 11: present embodiment is different from one of embodiment one to ten: the ratio of the quality of the desciccate that the volume of the hydrazine hydrate described in step 7 and step 6 obtain is 1mL:1g.Other step and parameter are identical with one of embodiment one to ten.
Embodiment 12: present embodiment is different from one of embodiment one to 11: the organic solvent described in step 7 is one or more the mixture in dimethyl formamide, methyl alcohol, ethanol, acetone, polyvinyl alcohol.Other step and parameter are identical with one of embodiment one to 11.
Embodiment 13: present embodiment is different from one of embodiment one to 12: the drying parameter described in step 7 is: temperature is 30～40 DEG C, the time is 4h～8h.Other step and parameter are identical with one of embodiment one to 12.
With following verification experimental verification beneficial effect of the present invention:
The preparation method of a kind of Graphene of test one, this experiment carries out according to the following steps:
One, 5g graphite is carried out to ball milling, ratio of grinding media to material is 3:1, Ball-milling Time is 0.5h, then the graphite after ball milling being joined to massfraction is to stir 30min in 10% hydrochloric acid soln, the pH value of the deionized water after extremely rinsing with the graphite after deionized water rinsing removal of impurities is again 7, finally dry, obtain graphite after treatment; Described graphite is of a size of 50 orders;
Two, graphite after treatment step 1 being joined to 20mL massfraction is to stir 15min in 48% salpeter solution, then add 1g potassium permanganate, be to react 90min under 10 DEG C of conditions in temperature, the pH value of the deionized water after extremely rinsing with deionized water rinsing solid matter after filtering is 7, after being dried, obtains being oxidized intercalated graphite;
Three, the oxidation intercalated graphite obtaining in step 2 is placed in to retort furnace and heat-treats, thermal treatment temp is 1100 DEG C, and heat treatment time is 80s, obtains expanded graphite;
Four, it is in 98% the vitriol oil that expanded graphite step 3 being obtained joins massfraction, stirs 30min, and the speed that adds that then adds potassium permanganate and control potassium permanganate is 1g/min, is to react 120min under the condition of 0 DEG C in temperature, obtains reaction solution; The quality of the expanded graphite that described step 3 obtains is 1g:40mL with the ratio of the volume of the vitriol oil; The expanded graphite that described step 3 obtains and the mass ratio of potassium permanganate are 1:6;
Five, step 4 being obtained to reaction solution transfers in reactor, the speed that adds that adds deionized water and control deionized water is 10g/min, then being heated to temperature is 100 DEG C, and is that at 100 DEG C, reaction for 10min, then is 20% hydrogen peroxide to dripping massfraction in reactor in temperature; Obtain golden yellow solution; The ratio of the quality of the expanded graphite that the volume of described deionized water and step 3 obtain is 40mL:1g; The ratio of the quality of the expanded graphite that the volume of described hydrogen peroxide and step 3 obtain is 20mL:1g;
Six, in the golden yellow solution obtaining to step 5, drip in strong aqua and pH value to 8～9, be to filter at 40 DEG C in temperature, and clarify with deionized water rinsing solid matter to filtrate, then under temperature is the condition of 30 DEG C, dry, drying time is 8h, obtains desciccate;
Seven, desciccate step 6 being obtained is dissolved in dimethyl formamide solution and stirs 30min, then be placed in liquid nitrogen and leave standstill 30min, being warming up to temperature is 60 DEG C again, then add hydrazine hydrate, and be to react 1h at 60 DEG C in temperature, after filtration, be 8 by deionized water rinsing to pH value, then dry, obtain Graphene; The ratio of the quality of the desciccate that the volume of described hydrazine hydrate and step 6 obtain is 1mL:1g.
Drying parameter described in step 2 is: temperature is 30 DEG C, and the time is 4h.
Drying parameter described in step 7 is: temperature is 30 DEG C, and the time is 4h.
The preparation method of a kind of Graphene of test two, this experiment carries out according to the following steps:
One, 5g graphite is carried out to ball milling, ratio of grinding media to material is 5:1, Ball-milling Time is 2h, then graphite after ball milling being joined to massfraction is to stir 35min in 10% hydrochloric acid soln, the pH value of the deionized water after extremely rinsing with the graphite after deionized water rinsing removal of impurities is again 7, finally dry, obtain graphite after treatment; Described graphite is of a size of 200 orders;
Two, graphite after treatment step 1 being joined to 20mL massfraction is to stir 25min in 48% salpeter solution, then add 1g potassium permanganate, be to react 90min under 20 DEG C of conditions in temperature, the pH value of the deionized water after extremely rinsing with deionized water rinsing solid matter after filtering is 7, after being dried, obtains being oxidized intercalated graphite;
Three, the oxidation intercalated graphite obtaining in step 2 is placed in to retort furnace and heat-treats, thermal treatment temp is 1100 DEG C, and heat treatment time is 80s, obtains expanded graphite;
Four, it is in 98% the vitriol oil that expanded graphite step 3 being obtained joins massfraction, stirs 30min, and the speed that adds that then adds potassium permanganate and control potassium permanganate is 2g/min, is to react 120min under the condition of-1 DEG C in temperature, obtains reaction solution; The quality of the expanded graphite that described step 3 obtains is 1g:40mL with the ratio of the volume of the vitriol oil; The expanded graphite that described step 3 obtains and the mass ratio of potassium permanganate are 1:6;
Five, step 4 being obtained to reaction solution transfers in reactor, the speed that adds that adds deionized water and control deionized water is 25g/min, then being heated to temperature is 105 DEG C, and is that at 105 DEG C, reaction for 20min, then is 30% hydrogen peroxide to dripping massfraction in reactor in temperature; Obtain golden yellow solution; The ratio of the quality of the expanded graphite that the volume of described deionized water and step 3 obtain is 60mL:1g; The ratio of the quality of the expanded graphite that the volume of described hydrogen peroxide and step 3 obtain is 20mL:1g;
Six, in the golden yellow solution obtaining to step 5, drip in strong aqua and pH value to 8～9, be to filter at 45 DEG C in temperature, and clarify with deionized water rinsing solid matter to filtrate, then under temperature is the condition of 30 DEG C, dry, drying time is 8h, obtains desciccate;
Seven, desciccate step 6 being obtained is dissolved in dehydrated alcohol and stirs 60min, then be placed in liquid nitrogen and leave standstill 30min, being warming up to temperature is 95 DEG C again, then add hydrazine hydrate, and be to react 3h at 90 DEG C in temperature, after filtration, be 8 by deionized water rinsing to pH value, then dry, obtain Graphene; The ratio of the quality of the desciccate that the volume of described hydrazine hydrate and step 6 obtain is 1.5mL:1g.
Drying parameter described in step 2 is: temperature is 30 DEG C, and the time is 4h.
Drying parameter described in step 7 is: temperature is 40 DEG C, and the time is 8h.
The preparation method of a kind of Graphene of test three, this experiment carries out according to the following steps:
One, 5g graphite is carried out to ball milling, ratio of grinding media to material is 4:1, Ball-milling Time is 1.5h, then graphite after ball milling being joined to massfraction is to stir 20min in 38% hydrochloric acid soln, the pH value of the deionized water after extremely rinsing with the graphite after deionized water rinsing removal of impurities is again 7, finally dry, obtain graphite after treatment; Described graphite is of a size of 150 orders;
Two, graphite after treatment step 1 being joined to 20mL massfraction is to stir 40min in 48% salpeter solution, then add 1g potassium permanganate, be to react 90min under 15 DEG C of conditions in temperature, the pH value of the deionized water after extremely rinsing with deionized water rinsing solid matter after filtering is 7, after being dried, obtains being oxidized intercalated graphite;
Three, the oxidation intercalated graphite obtaining in step 2 is placed in to retort furnace and heat-treats, thermal treatment temp is 1100 DEG C, and heat treatment time is 80s, obtains expanded graphite;
Four, it is in 98% the vitriol oil that expanded graphite step 3 being obtained joins massfraction, stirs 30min, and the speed that adds that then adds potassium permanganate and control potassium permanganate is 3g/min, is to react 120min under the condition of-5 DEG C in temperature, obtains reaction solution; The quality of the expanded graphite that described step 3 obtains is 1g:40mL with the ratio of the volume of the vitriol oil; The expanded graphite that described step 3 obtains and the mass ratio of potassium permanganate are 1:6;
Five, step 4 being obtained to reaction solution transfers in reactor, the speed that adds that adds deionized water and control deionized water is 15g/min, then being heated to temperature is 105 DEG C, and is that at 102 DEG C, reaction for 15min, then is 30% hydrogen peroxide to dripping massfraction in reactor in temperature; Obtain golden yellow solution; The ratio of the quality of the expanded graphite that the volume of described deionized water and step 3 obtain is 50mL:1g; The ratio of the quality of the expanded graphite that the volume of described hydrogen peroxide and step 3 obtain is 20mL:1g;
Six, in the golden yellow solution obtaining to step 5, drip in strong aqua and pH value to 8～9, be to filter at 95 DEG C in temperature, and clarify with deionized water rinsing solid matter filtrate, then under temperature is the condition of 30 DEG C, dry, drying time is 8h, obtains desciccate;
Seven, desciccate step 6 being obtained is dissolved in methyl alcohol and stirs 60min, then be placed in liquid nitrogen and leave standstill 60min, being warming up to temperature is 95 DEG C again, then add hydrazine hydrate, and be to react 2h at 85 DEG C in temperature, after filtration, be 8 by deionized water rinsing to pH value, then dry, obtain Graphene; The ratio of the quality of the desciccate that the volume of described hydrazine hydrate and step 6 obtain is 1mL:1g.
Drying parameter described in step 2 is: temperature is 30 DEG C, and the time is 5h.
Drying parameter described in step 7 is: temperature is 40 DEG C, and the time is 8h.
The preparation method of a kind of Graphene of test four, this experiment carries out according to the following steps:
One, 5g graphite is carried out to ball milling, ratio of grinding media to material is 3:1, Ball-milling Time is 2h, then graphite after ball milling being joined to massfraction is to stir 20min in 38% hydrochloric acid soln, the pH value of the deionized water after extremely rinsing with the graphite after deionized water rinsing removal of impurities is again 7, finally dry, obtain graphite after treatment; Described graphite is of a size of 50 orders;
Two, graphite after treatment step 1 being joined to 20mL massfraction is to stir 25min in 48% salpeter solution, then add 1g potassium permanganate, be to react 90min under 10 DEG C of conditions in temperature, the pH value of the deionized water after extremely rinsing with deionized water rinsing solid matter after filtering is 7, after being dried, obtains being oxidized intercalated graphite;
Three, the oxidation intercalated graphite obtaining in step 2 is placed in to retort furnace and heat-treats, thermal treatment temp is 1100 DEG C, and heat treatment time is 80s, obtains expanded graphite;
Four, it is in 98% the vitriol oil that expanded graphite step 3 being obtained joins massfraction, stirs 30min, and the speed that adds that then adds potassium permanganate and control potassium permanganate is 4g/min, is to react 120min under the condition of-4 DEG C in temperature, obtains reaction solution; The quality of the expanded graphite that described step 3 obtains is 1g:40mL with the ratio of the volume of the vitriol oil; The expanded graphite that described step 3 obtains and the mass ratio of potassium permanganate are 1:6;
Five, step 4 being obtained to reaction solution transfers in reactor, the speed that adds that adds deionized water and control deionized water is 20g/min, then being heated to temperature is 102 DEG C, and is that at 102 DEG C, reaction for 15min, then is 30% hydrogen peroxide to dripping massfraction in reactor in temperature; Obtain golden yellow solution; The ratio of the quality of the expanded graphite that the volume of described deionized water and step 3 obtain is 50mL:1g; The ratio of the quality of the expanded graphite that the volume of described hydrogen peroxide and step 3 obtain is 20mL:1g;
Six, in the golden yellow solution obtaining to step 5, drip in strong aqua and pH value to 8～9, be to filter at 45 DEG C in temperature, and clarify with deionized water rinsing solid matter to filtrate, then under temperature is the condition of 30 DEG C, dry, drying time is 8h, obtains desciccate;
Seven, desciccate step 6 being obtained is dissolved in methyl alcohol and stirs 40min, then be placed in liquid nitrogen and leave standstill 40min, being warming up to temperature is 85 DEG C again, then add hydrazine hydrate, and be to react 3h at 90 DEG C in temperature, after filtration, be 8 by deionized water rinsing to pH value, then dry, obtain Graphene; The ratio of the quality of the desciccate that the volume of described hydrazine hydrate and step 6 obtain is 1mL:1g.
Drying parameter described in step 2 is: temperature is 30 DEG C, and the time is 4h.
Drying parameter described in step 7 is: temperature is 40 DEG C, and the time is 8h.
The preparation method of a kind of Graphene of test five, this experiment carries out according to the following steps:
One, 5g graphite is carried out to ball milling, ratio of grinding media to material is 5:1, Ball-milling Time is 1h, then graphite after ball milling being joined to massfraction is to stir 30min in 38% hydrochloric acid soln, the pH value of the deionized water after extremely rinsing with the graphite after deionized water rinsing removal of impurities is again 7, finally dry, obtain graphite after treatment; Described graphite is of a size of 180 orders;
Two, graphite after treatment step 1 being joined to 20mL massfraction is to stir 10min in 48% salpeter solution, then add 1g potassium permanganate, be to react 90min under 10 DEG C of conditions in temperature, the pH value of the deionized water after extremely rinsing with deionized water rinsing solid matter after filtering is 7, after being dried, obtains being oxidized intercalated graphite;
Three, the oxidation intercalated graphite obtaining in step 2 is placed in to retort furnace and heat-treats, thermal treatment temp is 1100 DEG C, and heat treatment time is 80s, obtains expanded graphite;
Four, it is in 98% the vitriol oil that expanded graphite step 3 being obtained joins massfraction, stirs 30min, and the speed that adds that then adds potassium permanganate and control potassium permanganate is 1g/min, is to react 120min under the condition of 0 DEG C in temperature, obtains reaction solution; The quality of the expanded graphite that described step 3 obtains is 1g:40mL with the ratio of the volume of the vitriol oil; The expanded graphite that described step 3 obtains and the mass ratio of potassium permanganate are 1:6;
Five, step 4 being obtained to reaction solution transfers in reactor, the speed that adds that adds deionized water and control deionized water is 20g/min, then being heated to temperature is 100 DEG C, and is that at 100 DEG C, reaction for 15min, then is 30% hydrogen peroxide to dripping massfraction in reactor in temperature; Obtain golden yellow solution; The ratio of the quality of the expanded graphite that the volume of described deionized water and step 3 obtain is 50mL:1g; The ratio of the quality of the expanded graphite that the volume of described hydrogen peroxide and step 3 obtain is 20mL:1g;
Six, in the golden yellow solution obtaining to step 5, drip in strong aqua and pH value to 8～9, be to filter at 45 DEG C in temperature, and clarify with deionized water rinsing solid matter to filtrate, then under temperature is the condition of 30 DEG C, dry, drying time is 8h, obtains desciccate;
Seven, desciccate step 6 being obtained is dissolved in methyl alcohol and stirs 40min, then be placed in liquid nitrogen and leave standstill 30min, being warming up to temperature is 95 DEG C again, then add hydrazine hydrate, and be to react 3h at 95 DEG C in temperature, after filtration, be 8 by deionized water rinsing to pH value, then dry, obtain Graphene; The ratio of the quality of the desciccate that the volume of described hydrazine hydrate and step 6 obtain is 1mL:1g.
Drying parameter described in step 2 is: temperature is 30 DEG C, and the time is 4h.
Drying parameter described in step 7 is: temperature is 40 DEG C, and the time is 8h.
The preparation method of a kind of Graphene of test six, this experiment carries out according to the following steps:
One, 5g graphite is carried out to ball milling, ratio of grinding media to material is 3:1, Ball-milling Time is 40min, then graphite after ball milling being joined to massfraction is to stir 20min in 38% hydrochloric acid soln, the pH value of the deionized water after extremely rinsing with the graphite after deionized water rinsing removal of impurities is again 7, finally dry, obtain graphite after treatment; Described graphite is of a size of 80 orders;
Two, graphite after treatment step 1 being joined to 20mL massfraction is to stir 25min in 48% salpeter solution, then add 1g potassium permanganate, be to react 90min under 10 DEG C of conditions in temperature, the pH value of the deionized water after extremely rinsing with deionized water rinsing solid matter after filtering is 7, after being dried, obtains being oxidized intercalated graphite;
Three, the oxidation intercalated graphite obtaining in step 2 is placed in to retort furnace and heat-treats, thermal treatment temp is 1100 DEG C, and heat treatment time is 80s, obtains expanded graphite;
Four, it is in 98% the vitriol oil that expanded graphite step 3 being obtained joins massfraction, stirs 30min, and the speed that adds that then adds potassium permanganate and control potassium permanganate is 5g/min, is to react 120min under the condition of 0 DEG C in temperature, obtains reaction solution; The quality of the expanded graphite that described step 3 obtains is 1g:40mL with the ratio of the volume of the vitriol oil; The expanded graphite that described step 3 obtains and the mass ratio of potassium permanganate are 1:6;
Five, step 4 being obtained to reaction solution transfers in reactor, the speed that adds that adds deionized water and control deionized water is 15g/min, then being heated to temperature is 100 DEG C, and is that at 100 DEG C, reaction for 15min, then is 30% hydrogen peroxide to dripping massfraction in reactor in temperature; Obtain golden yellow solution; The ratio of the quality of the expanded graphite that the volume of described deionized water and step 3 obtain is 50mL:1g; The ratio of the quality of the expanded graphite that the volume of described hydrogen peroxide and step 3 obtain is 20mL:1g;
Six, in the golden yellow solution obtaining to step 5, drip in strong aqua and pH value to 8～9, be to filter at 50 DEG C in temperature, and clarify with deionized water rinsing solid matter to filtrate, then under temperature is the condition of 30 DEG C, dry, drying time is 8h, obtains desciccate;
Seven, desciccate step 6 being obtained is dissolved in methyl alcohol and stirs 40min, then be placed in liquid nitrogen and leave standstill 45min, being warming up to temperature is 95 DEG C again, then add hydrazine hydrate, and be to react 3h at 95 DEG C in temperature, after filtration, be 8 by deionized water rinsing to pH value, then dry, obtain Graphene; The ratio of the quality of the desciccate that the volume of described hydrazine hydrate and step 6 obtain is 1mL:1g.
Drying parameter described in step 2 is: temperature is 30 DEG C, and the time is 4h.
Drying parameter described in step 7 is: temperature is 35 DEG C, and the time is 6h.
(1) X ' the pert diffractometer that adopts philips to produce carries out XRD detection to testing a Graphene preparing, and utilizes Cu target, and voltage is 40kV, electric current is 30mA, 10～90 ° of sweep angles, sweep velocity: 2deg/min, obtains diffracting spectrum as shown in Figure 1; Does is wherein a that graphite, b are that expanded graphite, c are Graphene, as can be seen from Figure 1 with the test of graphite-phase ratio? the Graphene preparing presents obvious amorphous peak.
(2) adopting model is that Tecnai G2F30 type scanning electronic microscope scans testing a Graphene preparing, obtain Graphene SEM scanned photograph as shown in Figure 2-5, as can be seen from the figure test a Graphene preparing and present and naturally curl shape, this is to be determined by Graphene self property.
(3) the Dimension FastScanTM atomic power Scanning Probe Microscopy that adopts German Brooker company to produce carries out atomic force microscope thickness sign (AFM) to testing a Graphene preparing, and obtains atomic force microscope thickness phenogram as shown in Figure 6; Wherein the large figure in left side is graphene sheet layer size; Upper right side figure Graphene 3D solid figure; Lower right side figure is the sign of Graphene thickness; As can be seen from Figure 6, the sheet footpath of Graphene is larger, and sheet footpath is of a size of 2 μ m～25 μ m and makes Graphene thinner thickness simultaneously, and thickness is no more than 3nm.
(4) the Renishaw Raman spectrometer that adopts Britain's Reinshaw to produce detects testing a Graphene preparing, and obtains Raman spectrum spectrogram as shown in Figure 7, and from figure, 7 can find out at 1350cm
-1near there is D peak value, at 1580cm
-1near there is G peak value, at 2700cm
-1near there is 2D peak value, wherein G peak is that the vibration, stretching motion of the atom pairs of carboatomic ring sp2 hydridization in graphite individual layer produces, the Raman active mould of the E2g of the atom of the carbon atom centering of this and sp2 hydridization is closely related; 2D peak is that two contrary phonons of momentum produce in the process that participates in double resonance Raman.The Graphene of the different numbers of plies is at 2700cm
-1near the position of absorption peak is different, and along with the minimizing of the Graphene number of plies, 2D peak, shows as and is moved to the left in east as lower wave number direction.The 2D peak of single-layer graphene appears at 2680cm
-1near.D peak is defect peak, is because the double resonance scattering of irregular five-ring, seven-membered ring produces.
Fig. 7 shows: the test one Graphene 2D peak preparing is higher, and lamella is thinner; D peak is lower, i.e. defect peak, shows to make Graphene quality higher.
Claims (10)
1. a preparation method for Graphene, is characterized in that a kind of preparation method of Graphene carries out according to following steps:
One, graphite is carried out to ball milling, ratio of grinding media to material is (3～5): 1, Ball-milling Time is 0.5h～2h, then the graphite after ball milling being joined to massfraction is in 10%～38% hydrochloric acid soln, stir 10min～20min and remove surface impurity, the pH value of the deionized water after extremely rinsing with the graphite after deionized water rinsing removal of impurities is again neutral, finally dries, and obtains graphite after treatment; Described graphite is of a size of 50 order～200 orders;
Two, graphite after treatment step 1 being joined to massfraction is to stir 15min～30min in 48%～68% salpeter solution, then add potassium permanganate, be to react 60min～90min under 10～20 DEG C of conditions in temperature, the pH value of the deionized water after extremely rinsing with deionized water rinsing solid matter after filtering is 6～7, after being dried, obtains being oxidized intercalated graphite; The described quality of step 1 graphite after treatment and the ratio of the volume of salpeter solution are 1g:(3～5) mL; The mass ratio of described step 1 graphite after treatment and potassium permanganate is 1:(0.3～0.5);
Three, the oxidation intercalated graphite obtaining in step 2 is placed in to retort furnace and heat-treats, thermal treatment temp is 1100～1200 DEG C, and heat treatment time is 80s～100s, obtains expanded graphite;
Four, expanded graphite step 3 being obtained joins massfraction and is not less than in 98% the vitriol oil, stir 30min～60min, then the speed that adds that adds potassium permanganate and control potassium permanganate is 1g/min～5g/min, be to react 100min～140min under the condition of-5～0 DEG C in temperature, obtain reaction solution; The quality of the expanded graphite that described step 3 obtains is 1g:(35～45 with the ratio of the volume of the vitriol oil) mL; The expanded graphite that described step 3 obtains and the mass ratio of potassium permanganate are 1:(5～7);
Five, step 4 being obtained to reaction solution transfers in reactor, the speed that adds that adds deionized water and control deionized water is 10g/min～30g/min, then being heated to temperature is 100～105 DEG C, and be that at 100～105 DEG C, reaction for 10min～20min, then is 20%～30% hydrogen peroxide to dripping massfraction in reactor in temperature; Obtain golden yellow solution; The ratio of the quality of the expanded graphite that the volume of described deionized water and step 3 obtain is (40～60) mL:1g; The ratio of the quality of the expanded graphite that the volume of described hydrogen peroxide and step 3 obtain is (18～22) mL:1g;
Six, in the golden yellow solution obtaining to step 5, drip in strong aqua and pH value to 8～9, be to filter at 40～50 DEG C in temperature, and clarify with deionized water rinsing solid matter to filtrate, then under being the condition of 30～40 DEG C, temperature dries, drying time is 8h～24h, obtains desciccate;
Seven, desciccate step 6 being obtained is dissolved in organic solvent and stirs 30min～50min, then be placed in liquid nitrogen and leave standstill 20min～40min, being warming up to temperature is 60～95 DEG C again, then add hydrazine hydrate, be to react 1h～3h at 60～95 DEG C in temperature, after filtration, be 8 by deionized water rinsing to pH value, then dry, obtain Graphene; The ratio of the quality of the desciccate that the volume of described hydrazine hydrate and step 6 obtain is (0.8～1.5) mL:1g.
2. the preparation method of a kind of Graphene according to claim 1, is characterized in that the ratio of grinding media to material described in step 1 is 4:1, and Ball-milling Time is 1h～1.5h.
3. the preparation method of a kind of Graphene according to claim 1 and 2, is characterized in that the graphite described in step 1 is of a size of 100 order～150 orders.
4. the preparation method of a kind of Graphene according to claim 3, the ratio that it is characterized in that the quality of step 1 graphite after treatment described in step 2 and the volume of salpeter solution is 1g:4mL; The mass ratio of step 1 graphite after treatment and potassium permanganate is 1:0.4.
5. the preparation method of a kind of Graphene according to claim 3, is characterized in that the drying parameter described in step 2 is: temperature is 30～40 DEG C, and the time is 4h～24h.
6. the preparation method of a kind of Graphene according to claim 3, is characterized in that the quality of expanded graphite that the step 3 described in step 4 obtains and the ratio of the volume of the vitriol oil are 1g:40mL; The expanded graphite that step 3 obtains and the mass ratio of potassium permanganate are 1:6.
7. the preparation method of a kind of Graphene according to claim 3, the ratio of the quality of the expanded graphite that the volume that it is characterized in that the deionized water described in step 5 and step 3 obtain is 50mL:1g; The ratio of the quality of the expanded graphite that the volume of described hydrogen peroxide and step 3 obtain is 20mL:1g.
8. the preparation method of a kind of Graphene according to claim 3, the ratio of the quality of the desciccate that the volume that it is characterized in that the hydrazine hydrate described in step 7 and step 6 obtain is 1mL:1g.
9. the preparation method of a kind of Graphene according to claim 3, is characterized in that the organic solvent described in step 7 is one or more the mixture in dimethyl formamide, methyl alcohol, ethanol, acetone, polyvinyl alcohol.
10. the preparation method of a kind of Graphene according to claim 3, is characterized in that the drying parameter described in step 7 is: temperature is 30～40 DEG C, and the time is 4h～8h.
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| CN106564893A (en) * | 2016-11-10 | 2017-04-19 | 电子科技大学 | Hundred micron-order graphene oxide and preparation method thereof |
| CN107215868A (en) * | 2017-06-14 | 2017-09-29 | 黑龙江省宝泉岭农垦帝源矿业有限公司 | The method that the graphene product of high-purity is prepared using oxidation-reduction method Fast Purification |
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