CN104071777B - A kind of preparation method of Graphene - Google Patents
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Abstract
A kind of preparation method of Graphene.The present invention relates to technical field of new material preparation, particularly relate to a kind of preparation method of Graphene.The present invention is for solving the bad and mechanical means of existing machinery method productive rate not high, that lamellar spacing is wayward, prepared by unstable properties, chemical process Graphene performance and chemical process all exists supersound process and causes the production cycle long and the problem of the Graphene integrity difference of preparation.Method: first utilize high conductive graphite ball milling; Then ball milling is obtained powder pickling, and prepare expanded graphite; Again expanded graphite is oxidized, utilizes temperature variation to make limellar stripping, obtained graphene oxide; Then graphene oxide is reduced through ammonia hydrazine, final dry obtained graphene powder.The Graphene that preparation method of the present invention obtains needn't through ultrasonic stripping, and defect is few, can not destroy graphene-structured, keeps the integrity of graphene sheet layer preferably, and technique is simple, reduces costs, and suitable batch is produced.
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 strategic alliance standard " (Q/LM01CGS001-2013), only have carbon atomic layer thickness to characterize the carbon material being less than 10 layers and just can be called as grapheme material.Grapheme material has the excellent mechanical performance that higher electrical and thermal conductivity performance, thermostability are high, equal to carbon nanotube, and meanwhile, this material also has special Quantum Properties.Therefore just receive much attention from being born.
In current existing graphene preparation method, it is few that mechanical means obtains Graphene defect, but size is wayward and production efficiency is low; Graphene edge prepared by pure chemical process is often with dangling bonds, and simultaneously because need to experience long-time ultrasonic procedure, therefore obtained size is general less.These are all unfavorable for application and the popularization of Graphene.
With regard to mechanically peel, the method 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 etch microflute on high pyrolytic graphite, then with transparent adhesive tape repeatedly to taking off, and it is ultrasonic that the Graphene speckling with the different number of plies is put into acetone, makes it be separated with adhesive tape.The Graphene separated can be attracted on the silicon chip that placed in acetone.Graphite Powder 99 is put into liquid CO by the investigators such as Pu
2in, CO after 30min
2can graphite layers be diffused into, then through step-down, CO
2can undergoes rapid expansion be peeled off by few layer graphene from graphite.CatharinaKnieke etc. utilize ball milled, with sodium lauryl sulphate (SDS) for obtaining the graphene nanometer sheet of about 1nm 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, thus obtained graphene oxide (GO), then graphene oxide (GO) reduction is obtained the Graphene possessing high conductivity.Conventional graphite oxidation method comprises: Standenmaier method, Hummers method, Brodie method.Carbon fiber is put in superoxol and is oxidized by the investigators such as SridhaR, utilizes microwave heating and peels off the obtained Graphene containing oxy radical.Obtained Graphene puts into hydrazine and ultrasonic, removes oxy radical.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 CO
2; The Graphene specific surface area now obtained reaches 700 ~ 1500m
2/ g.
Epitaxial growth method is that SiC is decomposed, and Formed atom enters Ni layer or Si layer, and then Ni or Si layer matrix is lowered the temperature rapidly by heating Ni/SiC or SiC/Si, 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 obtains length >50 μm at Si (0001) matrix surface, width is the single-layer graphene of 3 μm.Now Graphene is 2000cm in the electronic mobility of 27K
2v
-1s
-1.
The investigators such as studies in China paper comprises, 08 year Physics Inst., Chinese Academy of Sciences king grace brother propose the method for stripping-embed again-expanding, have successfully prepared 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 developed the novel method that solvent thermal intercalation prepares Graphene.The method, is peeled off with the quadripole inducing action of strong polar organic solvent acetonitrile and graphene film for raw material with expanded graphite EG, dispersed graphite, makes the overall yield of Graphene bring up to 10% ~ 12%.
Being prepared in of Graphene domesticly also has many patents of invention, and preparation method is different.Publication number is that a kind of acidic solution that adopts that patent discloses of CN103570012A carries out pre-treatment to graphite, after raw material is added in actives solution, after ultrasonic, drying obtains graphene powder.The preparation process of the method needs ultrasonic, extends the production cycle, reduces 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, obtains the Graphene of large-size high-quality.Publication number be CN103130218A patent discloses a kind of method that ball milling prepares Graphene, the graphene film footpath that the method obtains is often uncontrollable and size is less.
Aforesaid method mechanically prepares Graphene, and to there is productive rate not high, and productive rate is generally 1% ~ 10%, and lamellar spacing is wayward, the problem of unstable properties; Though and with chemical preparation output height, because obtained grapheme material exists the existence of dangling bonds and other oxygen-containing functional groups, directly will material property be affected.And all need to carry out ultrasonic lift-off processing in mechanical means and chemical production processes Graphene, the treatment time is generally 1h ~ 4h, causes the production cycle long, and ultrasonic stripping can destroy graphene-structured cause prepare Graphene integrity poor, performance is bad.
Summary of the invention
The present invention is for solving the bad and mechanical means of existing machinery method productive rate not high, that lamellar spacing is wayward, prepared by unstable properties, chemical process Graphene performance and chemical process all exists supersound process and causes the production cycle long and the problem of the Graphene integrity difference of preparation, and provides a kind of preparation method of Graphene.
The preparation method of a kind of Graphene of the present invention carries out according to following steps:
One, graphite is carried out 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 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 the graphite after processing; Described graphite is of a size of 50 order ~ 200 orders;
Two, it is stir 15min ~ 30min in the salpeter solution of 48% ~ 68% that the graphite after step one being processed joins massfraction, then potassium permanganate is added, 60min ~ 90min is reacted under temperature is 10 ~ 20 DEG C of conditions, the pH value of the deionized water after extremely rinsing with deionized water rinsing solid matter after filtering is 6 ~ 7, obtains being oxidized intercalated graphite after drying; The quality of graphite after described step one processes is 1g:(3 ~ 5 with the ratio of the volume of salpeter solution) mL; Graphite after described step one processes and the mass ratio of potassium permanganate are 1:(0.3 ~ 0.5);
Three, the oxidation intercalated graphite obtained in step 2 is placed in retort furnace to heat-treat, thermal treatment temp is 1100 ~ 1200 DEG C, and heat treatment time is 80s ~ 100s, obtains expanded graphite;
Four, the expanded graphite that step 3 obtains being joined massfraction is not less than in the vitriol oil of 98%, stir 30min ~ 60min, then potassium permanganate is added and the speed that adds controlling potassium permanganate is 1g/min ~ 5g/min, be 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 mass ratio of the expanded graphite that described step 3 obtains and potassium permanganate is 1:(5 ~ 7);
Five, step 4 being obtained reaction solution transfers in reactor, add deionized water and the speed that adds controlling deionized water is 10g/min ~ 30g/min, then being heated to temperature is 100 ~ 105 DEG C, and reaction is 10min ~ 20min at temperature is 100 ~ 105 DEG C, then in reactor, drip the hydrogen peroxide that massfraction is 20% ~ 30%; Obtain golden solution; The ratio of the quality of the expanded graphite that volume and the step 3 of described deionized water obtain is (40 ~ 60) mL:1g; The ratio of the quality of the expanded graphite that volume and the step 3 of described hydrogen peroxide obtain is (18 ~ 22) mL:1g;
Six, drip in strong aqua and pH value to 8 ~ 9 in the golden solution obtained to step 5, filter at temperature is 40 ~ 50 DEG C, and clarify to filtrate with deionized water rinsing solid matter, then be dry under the condition of 30 ~ 40 DEG C in temperature, drying time is 8h ~ 24h, obtains desciccate;
Seven, the desciccate that step 6 obtains to be dissolved in organic solvent and to stir 30min ~ 50min, then be placed in liquid nitrogen and leave standstill 20min ~ 40min, being warming up to temperature is again 60 ~ 95 DEG C, then hydrazine hydrate is added, 1h ~ 3h is reacted at temperature is 60 ~ 95 DEG C, be 8 by deionized water rinsing to pH value after filtration, then dry, obtain Graphene; The ratio of the quality of the desciccate that volume and the step 6 of described hydrazine hydrate obtain is (0.8 ~ 1.5) mL:1g.
The Graphene that preparation method of the present invention obtains needn't through ultrasonic stripping, and defect is few, can not destroy graphene-structured, keeps the integrity of graphene sheet layer preferably, and technique is simple, reduces costs, and suitable batch is produced, and concrete advantage is as follows:
1, adopt high conductive graphite to be raw material, degree of graphitization is high, and genetic defects is few, in carbon atomic layer irregular pentagon and heptagon few, for 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 without the need to through ultrasonic, utilize in preparation process cold and heat succeed each other and small molecules effect atomic shell can be made to peel off, reduce energy consumption and production cycle, make the production cycle shorten 5h ~ 10h.
3, method of the present invention obtains Graphene size comparatively greatly, is of a size of 2 μm ~ 25 μm, and without the need to ultrasound destruction graphene film Rotating fields, lamella keeps more complete.
4, the organic solution in reaction process and ammonia hydrazine solution, liquid nitrogen can Reusabilities, and cost reduces, and cost reduces about 10% ~ 20%.
5, preparation method's technique of the present invention is simple, can carry out suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the Graphene that test one prepares; Wherein a is graphite, b is expanded graphite, c is Graphene;
Fig. 2 is the SEM photo of the Graphene that test one prepares;
Fig. 3 is the SEM photo of the Graphene that test one prepares;
Fig. 4 is the SEM photo of the Graphene that test one prepares;
Fig. 5 is the SEM photo of the Graphene that test one prepares;
Fig. 6 is the atomic force microscope thickness phenogram of the Graphene that test one prepares;
Fig. 7 is the Raman spectrogram of the Graphene that test one prepares.
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 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 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 the graphite after processing; Described graphite is of a size of 50 order ~ 200 orders;
Two, it is stir 15min ~ 30min in the salpeter solution of 48% ~ 68% that the graphite after step one being processed joins massfraction, then potassium permanganate is added, 60min ~ 90min is reacted under temperature is 10 ~ 20 DEG C of conditions, the pH value of the deionized water after extremely rinsing with deionized water rinsing solid matter after filtering is 6 ~ 7, obtains being oxidized intercalated graphite after drying; The quality of graphite after described step one processes is 1g:(3 ~ 5 with the ratio of the volume of salpeter solution) mL; Graphite after described step one processes and the mass ratio of potassium permanganate are 1:(0.3 ~ 0.5);
Three, the oxidation intercalated graphite obtained in step 2 is placed in retort furnace to heat-treat, thermal treatment temp is 1100 ~ 1200 DEG C, and heat treatment time is 80s ~ 100s, obtains expanded graphite;
Four, the expanded graphite that step 3 obtains being joined massfraction is not less than in the vitriol oil of 98%, stir 30min ~ 60min, then potassium permanganate is added and the speed that adds controlling potassium permanganate is 1g/min ~ 5g/min, be 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 mass ratio of the expanded graphite that described step 3 obtains and potassium permanganate is 1:(5 ~ 7);
Five, step 4 being obtained reaction solution transfers in reactor, add deionized water and the speed that adds controlling deionized water is 10g/min ~ 30g/min, then being heated to temperature is 100 ~ 105 DEG C, and reaction is 10min ~ 20min at temperature is 100 ~ 105 DEG C, then in reactor, drip the hydrogen peroxide that massfraction is 20% ~ 30%; Obtain golden solution; The ratio of the quality of the expanded graphite that volume and the step 3 of described deionized water obtain is (40 ~ 60) mL:1g; The ratio of the quality of the expanded graphite that volume and the step 3 of described hydrogen peroxide obtain is (18 ~ 22) mL:1g;
Six, drip in strong aqua and pH value to 8 ~ 9 in the golden solution obtained to step 5, filter at temperature is 40 ~ 50 DEG C, and clarify to filtrate with deionized water rinsing solid matter, then be dry under the condition of 30 ~ 40 DEG C in temperature, drying time is 8h ~ 24h, obtains desciccate;
Seven, the desciccate that step 6 obtains to be dissolved in organic solvent and to stir 30min ~ 50min, then be placed in liquid nitrogen and leave standstill 20min ~ 40min, being warming up to temperature is again 60 ~ 95 DEG C, then hydrazine hydrate is added, 1h ~ 3h is reacted at temperature is 60 ~ 95 DEG C, be 8 by deionized water rinsing to pH value after filtration, then dry, obtain Graphene; The ratio of the quality of the desciccate that volume and the step 6 of described hydrazine hydrate obtain is (0.8 ~ 1.5) mL:1g.
The Graphene that the preparation method of present embodiment obtains needn't through ultrasonic stripping, and defect is few, can not destroy graphene-structured, keeps the integrity of graphene sheet layer preferably, and technique is simple, reduces costs, and suitable batch is produced, and concrete advantage is as follows:
1, adopt high conductive graphite to be raw material, degree of graphitization is high, and genetic defects is few, in carbon atomic layer irregular pentagon and heptagon few, for 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 without the need to through ultrasonic, utilize in preparation process cold and heat succeed each other and small molecules effect atomic shell can be made to peel off, reduce energy consumption and production cycle, make the production cycle shorten 5h ~ 10h.
3, the method for present embodiment obtains Graphene size comparatively greatly, is of a size of 2 μm ~ 25 μm, and without the need to ultrasound destruction graphene film Rotating fields, lamella keeps more complete.
4, the organic solution in reaction process and ammonia hydrazine solution, liquid nitrogen can Reusabilities, and cost reduces, and cost reduces about 10% ~ 20%.
5, preparation method's technique of present embodiment is simple, can carry out suitability for industrialized production.
Embodiment two: present embodiment and embodiment one unlike: the ratio of grinding media to material described in step one is 4:1, and Ball-milling Time is 1h ~ 1.5h.Other step and parameter identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: the graphite described in step one is of a size of 100 order ~ 150 orders.Other step and parameter identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: the quality of graphite after step one described in step 2 processes is 1g:4mL with the ratio of the volume of salpeter solution.Other step and parameter identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: in step 2 step one process after graphite and the mass ratio of potassium permanganate be 1:0.4.Other step and parameter identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: the drying parameter described in step 2 is: temperature is 30 ~ 40 DEG C, and the time is 4h ~ 24h.Other step and parameter identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six unlike: 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 identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: the mass ratio of the expanded graphite that the step 3 described in step 4 obtains and potassium permanganate is 1:6.Other step and parameter identical with one of embodiment one to seven.
Embodiment nine: the ratio of the quality of the expanded graphite that one of present embodiment and embodiment one to eight obtain unlike volume and the step 3 of: the deionized water described in step 5 is 50mL:1g.Other step and parameter identical with one of embodiment one to eight.
Embodiment ten: the ratio of the quality of the expanded graphite that one of present embodiment and embodiment one to nine obtain unlike volume and the step 3 of: the hydrogen peroxide described in step 5 is 20mL:1g.Other step and parameter identical with one of embodiment one to nine.
Embodiment 11: the ratio of the quality of the desciccate that one of present embodiment and embodiment one to ten obtain unlike volume and the step 6 of: the hydrazine hydrate described in step 7 is 1mL:1g.Other step and parameter identical with one of embodiment one to ten.
Embodiment 12: one of present embodiment and embodiment one to ten one unlike: the organic solvent described in step 7 is the mixture of one or more in dimethyl formamide, methyl alcohol, ethanol, acetone, polyvinyl alcohol.Other step and parameter identical with one of embodiment one to ten one.
Embodiment 13: one of present embodiment and embodiment one to ten two unlike: the drying parameter described in step 7 is: temperature is 30 ~ 40 DEG C, and the time is 4h ~ 8h.Other step and parameter identical with one of embodiment one to ten two.
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 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 massfraction is 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 the graphite after processing; Described graphite is of a size of 50 orders;
Two, it is stir 15min in the salpeter solution of 48% that the graphite after step one being processed joins 20mL massfraction, then 1g potassium permanganate is added, 90min is reacted under temperature is 10 DEG C of conditions, the pH value of the deionized water after extremely rinsing with deionized water rinsing solid matter after filtering is 7, obtains being oxidized intercalated graphite after drying;
Three, the oxidation intercalated graphite obtained in step 2 is placed in retort furnace to heat-treat, thermal treatment temp is 1100 DEG C, and heat treatment time is 80s, obtains expanded graphite;
Four, the expanded graphite that step 3 obtains being joined massfraction is in the vitriol oil of 98%, stirs 30min, then adds potassium permanganate and the speed that adds controlling potassium permanganate is 1g/min, is react 120min under the condition of 0 DEG C, obtains reaction solution in temperature; 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 mass ratio of the expanded graphite that described step 3 obtains and potassium permanganate is 1:6;
Five, step 4 being obtained reaction solution transfers in reactor, add deionized water and the speed that adds controlling deionized water is 10g/min, then being heated to temperature is 100 DEG C, and reaction is 10min at temperature is 100 DEG C, then in reactor, drip the hydrogen peroxide that massfraction is 20%; Obtain golden solution; The ratio of the quality of the expanded graphite that volume and the step 3 of described deionized water obtain is 40mL:1g; The ratio of the quality of the expanded graphite that volume and the step 3 of described hydrogen peroxide obtain is 20mL:1g;
Six, drip in strong aqua and pH value to 8 ~ 9 in the golden solution obtained to step 5, filtering at temperature is 40 DEG C, and clarify to filtrate with deionized water rinsing solid matter, is then dry under the condition of 30 DEG C in temperature, drying time is 8h, obtains desciccate;
Seven, the desciccate that step 6 obtains to be dissolved in dimethyl formamide solution and to stir 30min, then be placed in liquid nitrogen and leave standstill 30min, being warming up to temperature is again 60 DEG C, then hydrazine hydrate is added, and 1h is reacted at temperature is 60 DEG C, be 8 by deionized water rinsing to pH value after filtration, then dry, obtain Graphene; The ratio of the quality of the desciccate that volume and the step 6 of described hydrazine hydrate 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 ball milling, ratio of grinding media to material is 5:1, Ball-milling Time is 2h, then graphite after ball milling being joined massfraction is 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 the graphite after processing; Described graphite is of a size of 200 orders;
Two, it is stir 25min in the salpeter solution of 48% that the graphite after step one being processed joins 20mL massfraction, then 1g potassium permanganate is added, 90min is reacted under temperature is 20 DEG C of conditions, the pH value of the deionized water after extremely rinsing with deionized water rinsing solid matter after filtering is 7, obtains being oxidized intercalated graphite after drying;
Three, the oxidation intercalated graphite obtained in step 2 is placed in retort furnace to heat-treat, thermal treatment temp is 1100 DEG C, and heat treatment time is 80s, obtains expanded graphite;
Four, the expanded graphite that step 3 obtains being joined massfraction is in the vitriol oil of 98%, stirs 30min, then adds potassium permanganate and the speed that adds controlling potassium permanganate is 2g/min, is react 120min under the condition of-1 DEG C, obtains reaction solution in temperature; 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 mass ratio of the expanded graphite that described step 3 obtains and potassium permanganate is 1:6;
Five, step 4 being obtained reaction solution transfers in reactor, add deionized water and the speed that adds controlling deionized water is 25g/min, then being heated to temperature is 105 DEG C, and reaction is 20min at temperature is 105 DEG C, then in reactor, drip the hydrogen peroxide that massfraction is 30%; Obtain golden solution; The ratio of the quality of the expanded graphite that volume and the step 3 of described deionized water obtain is 60mL:1g; The ratio of the quality of the expanded graphite that volume and the step 3 of described hydrogen peroxide obtain is 20mL:1g;
Six, drip in strong aqua and pH value to 8 ~ 9 in the golden solution obtained to step 5, filtering at temperature is 45 DEG C, and clarify to filtrate with deionized water rinsing solid matter, is then dry under the condition of 30 DEG C in temperature, drying time is 8h, obtains desciccate;
Seven, the desciccate that step 6 obtains to be dissolved in dehydrated alcohol and to stir 60min, then be placed in liquid nitrogen and leave standstill 30min, being warming up to temperature is again 95 DEG C, then hydrazine hydrate is added, and 3h is reacted at temperature is 90 DEG C, be 8 by deionized water rinsing to pH value after filtration, then dry, obtain Graphene; The ratio of the quality of the desciccate that volume and the step 6 of described hydrazine hydrate 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 ball milling, ratio of grinding media to material is 4:1, Ball-milling Time is 1.5h, then graphite after ball milling being joined massfraction is 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 the graphite after processing; Described graphite is of a size of 150 orders;
Two, it is stir 40min in the salpeter solution of 48% that the graphite after step one being processed joins 20mL massfraction, then 1g potassium permanganate is added, 90min is reacted under temperature is 15 DEG C of conditions, the pH value of the deionized water after extremely rinsing with deionized water rinsing solid matter after filtering is 7, obtains being oxidized intercalated graphite after drying;
Three, the oxidation intercalated graphite obtained in step 2 is placed in retort furnace to heat-treat, thermal treatment temp is 1100 DEG C, and heat treatment time is 80s, obtains expanded graphite;
Four, the expanded graphite that step 3 obtains being joined massfraction is in the vitriol oil of 98%, stirs 30min, then adds potassium permanganate and the speed that adds controlling potassium permanganate is 3g/min, is react 120min under the condition of-5 DEG C, obtains reaction solution in temperature; 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 mass ratio of the expanded graphite that described step 3 obtains and potassium permanganate is 1:6;
Five, step 4 being obtained reaction solution transfers in reactor, add deionized water and the speed that adds controlling deionized water is 15g/min, then being heated to temperature is 105 DEG C, and reaction is 15min at temperature is 102 DEG C, then in reactor, drip the hydrogen peroxide that massfraction is 30%; Obtain golden solution; The ratio of the quality of the expanded graphite that volume and the step 3 of described deionized water obtain is 50mL:1g; The ratio of the quality of the expanded graphite that volume and the step 3 of described hydrogen peroxide obtain is 20mL:1g;
Six, drip in strong aqua and pH value to 8 ~ 9 in the golden solution obtained to step 5, filter at temperature is 95 DEG C, and with the clarification of deionized water rinsing solid matter filtrate, be then dry under the condition of 30 DEG C in temperature, drying time is 8h, obtains desciccate;
Seven, the desciccate that step 6 obtains to be dissolved in methyl alcohol and to stir 60min, then be placed in liquid nitrogen and leave standstill 60min, being warming up to temperature is again 95 DEG C, then hydrazine hydrate is added, and 2h is reacted at temperature is 85 DEG C, be 8 by deionized water rinsing to pH value after filtration, then dry, obtain Graphene; The ratio of the quality of the desciccate that volume and the step 6 of described hydrazine hydrate 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 ball milling, ratio of grinding media to material is 3:1, Ball-milling Time is 2h, then graphite after ball milling being joined massfraction is 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 the graphite after processing; Described graphite is of a size of 50 orders;
Two, it is stir 25min in the salpeter solution of 48% that the graphite after step one being processed joins 20mL massfraction, then 1g potassium permanganate is added, 90min is reacted under temperature is 10 DEG C of conditions, the pH value of the deionized water after extremely rinsing with deionized water rinsing solid matter after filtering is 7, obtains being oxidized intercalated graphite after drying;
Three, the oxidation intercalated graphite obtained in step 2 is placed in retort furnace to heat-treat, thermal treatment temp is 1100 DEG C, and heat treatment time is 80s, obtains expanded graphite;
Four, the expanded graphite that step 3 obtains being joined massfraction is in the vitriol oil of 98%, stirs 30min, then adds potassium permanganate and the speed that adds controlling potassium permanganate is 4g/min, is react 120min under the condition of-4 DEG C, obtains reaction solution in temperature; 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 mass ratio of the expanded graphite that described step 3 obtains and potassium permanganate is 1:6;
Five, step 4 being obtained reaction solution transfers in reactor, add deionized water and the speed that adds controlling deionized water is 20g/min, then being heated to temperature is 102 DEG C, and reaction is 15min at temperature is 102 DEG C, then in reactor, drip the hydrogen peroxide that massfraction is 30%; Obtain golden solution; The ratio of the quality of the expanded graphite that volume and the step 3 of described deionized water obtain is 50mL:1g; The ratio of the quality of the expanded graphite that volume and the step 3 of described hydrogen peroxide obtain is 20mL:1g;
Six, drip in strong aqua and pH value to 8 ~ 9 in the golden solution obtained to step 5, filtering at temperature is 45 DEG C, and clarify to filtrate with deionized water rinsing solid matter, is then dry under the condition of 30 DEG C in temperature, drying time is 8h, obtains desciccate;
Seven, the desciccate that step 6 obtains to be dissolved in methyl alcohol and to stir 40min, then be placed in liquid nitrogen and leave standstill 40min, being warming up to temperature is again 85 DEG C, then hydrazine hydrate is added, and 3h is reacted at temperature is 90 DEG C, be 8 by deionized water rinsing to pH value after filtration, then dry, obtain Graphene; The ratio of the quality of the desciccate that volume and the step 6 of described hydrazine hydrate 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 ball milling, ratio of grinding media to material is 5:1, Ball-milling Time is 1h, then graphite after ball milling being joined massfraction is 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 the graphite after processing; Described graphite is of a size of 180 orders;
Two, it is stir 10min in the salpeter solution of 48% that the graphite after step one being processed joins 20mL massfraction, then 1g potassium permanganate is added, 90min is reacted under temperature is 10 DEG C of conditions, the pH value of the deionized water after extremely rinsing with deionized water rinsing solid matter after filtering is 7, obtains being oxidized intercalated graphite after drying;
Three, the oxidation intercalated graphite obtained in step 2 is placed in retort furnace to heat-treat, thermal treatment temp is 1100 DEG C, and heat treatment time is 80s, obtains expanded graphite;
Four, the expanded graphite that step 3 obtains being joined massfraction is in the vitriol oil of 98%, stirs 30min, then adds potassium permanganate and the speed that adds controlling potassium permanganate is 1g/min, is react 120min under the condition of 0 DEG C, obtains reaction solution in temperature; 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 mass ratio of the expanded graphite that described step 3 obtains and potassium permanganate is 1:6;
Five, step 4 being obtained reaction solution transfers in reactor, add deionized water and the speed that adds controlling deionized water is 20g/min, then being heated to temperature is 100 DEG C, and reaction is 15min at temperature is 100 DEG C, then in reactor, drip the hydrogen peroxide that massfraction is 30%; Obtain golden solution; The ratio of the quality of the expanded graphite that volume and the step 3 of described deionized water obtain is 50mL:1g; The ratio of the quality of the expanded graphite that volume and the step 3 of described hydrogen peroxide obtain is 20mL:1g;
Six, drip in strong aqua and pH value to 8 ~ 9 in the golden solution obtained to step 5, filtering at temperature is 45 DEG C, and clarify to filtrate with deionized water rinsing solid matter, is then dry under the condition of 30 DEG C in temperature, drying time is 8h, obtains desciccate;
Seven, the desciccate that step 6 obtains to be dissolved in methyl alcohol and to stir 40min, then be placed in liquid nitrogen and leave standstill 30min, being warming up to temperature is again 95 DEG C, then hydrazine hydrate is added, and 3h is reacted at temperature is 95 DEG C, be 8 by deionized water rinsing to pH value after filtration, then dry, obtain Graphene; The ratio of the quality of the desciccate that volume and the step 6 of described hydrazine hydrate 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 ball milling, ratio of grinding media to material is 3:1, Ball-milling Time is 40min, then graphite after ball milling being joined massfraction is 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 the graphite after processing; Described graphite is of a size of 80 orders;
Two, it is stir 25min in the salpeter solution of 48% that the graphite after step one being processed joins 20mL massfraction, then 1g potassium permanganate is added, 90min is reacted under temperature is 10 DEG C of conditions, the pH value of the deionized water after extremely rinsing with deionized water rinsing solid matter after filtering is 7, obtains being oxidized intercalated graphite after drying;
Three, the oxidation intercalated graphite obtained in step 2 is placed in retort furnace to heat-treat, thermal treatment temp is 1100 DEG C, and heat treatment time is 80s, obtains expanded graphite;
Four, the expanded graphite that step 3 obtains being joined massfraction is in the vitriol oil of 98%, stirs 30min, then adds potassium permanganate and the speed that adds controlling potassium permanganate is 5g/min, is react 120min under the condition of 0 DEG C, obtains reaction solution in temperature; 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 mass ratio of the expanded graphite that described step 3 obtains and potassium permanganate is 1:6;
Five, step 4 being obtained reaction solution transfers in reactor, add deionized water and the speed that adds controlling deionized water is 15g/min, then being heated to temperature is 100 DEG C, and reaction is 15min at temperature is 100 DEG C, then in reactor, drip the hydrogen peroxide that massfraction is 30%; Obtain golden solution; The ratio of the quality of the expanded graphite that volume and the step 3 of described deionized water obtain is 50mL:1g; The ratio of the quality of the expanded graphite that volume and the step 3 of described hydrogen peroxide obtain is 20mL:1g;
Six, drip in strong aqua and pH value to 8 ~ 9 in the golden solution obtained to step 5, filtering at temperature is 50 DEG C, and clarify to filtrate with deionized water rinsing solid matter, is then dry under the condition of 30 DEG C in temperature, drying time is 8h, obtains desciccate;
Seven, the desciccate that step 6 obtains to be dissolved in methyl alcohol and to stir 40min, then be placed in liquid nitrogen and leave standstill 45min, being warming up to temperature is again 95 DEG C, then hydrazine hydrate is added, and 3h is reacted at temperature is 95 DEG C, be 8 by deionized water rinsing to pH value after filtration, then dry, obtain Graphene; The ratio of the quality of the desciccate that volume and the step 6 of described hydrazine hydrate 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 adopting philips to produce carries out XRD detection to the Graphene that test one prepares, and utilize Cu target, voltage is 40kV, electric current is 30mA, sweep angle 10 ~ 90 °, sweep velocity: 2deg/min, obtains diffracting spectrum as shown in Figure 1; Wherein a is graphite, b is expanded graphite, c is Graphene, presents obvious amorphous peak as can be seen from Figure 1 with graphite-phase than the Graphene that test one prepares.
(2) model is adopted to be that TecnaiG2F30 type scanning electronic microscope scans the Graphene that test one prepares, obtain Graphene SEM scanned photograph as shown in Figure 2-5, as can be seen from the figure the Graphene that test one prepares presents naturally curls shape, and this is determined by Graphene self property.
(3) the DimensionFastScanTM atomic power Scanning Probe Microscopy adopting German Brooker company to produce carries out atomic force microscope thickness sign (AFM) to the Graphene that test one prepares, 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 comparatively large, and sheet footpath is of a size of 2 μm ~ 25 μm obtained Graphene thinner thicknesses simultaneously, and thickness is no more than 3nm.
(4) the Renishaw Raman spectrometer adopting Britain's Reinshaw to produce detects the Graphene that test one prepares, and obtain Raman spectrum spectrogram as shown in Figure 7, 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 the vibration of the atom pairs of carboatomic ring sp2 hydridization in graphene, stretching motion produces, and this is closely related with the Raman active mould of the E2g of the atom of the carbon atom centering of sp2 hydridization; 2D peak is that the phonon that two momentum are contrary produces in the process participating in double resonance Raman.The Graphene of the different number of plies is at 2700cm
-1the position of neighbouring absorption peak is different, and along with the minimizing of the Graphene number of plies, 2D peak, as lower wave number direction Yu Dong, namely shows as and is moved to the left.The 2D peak of single-layer graphene appears at 2680cm
-1near.D peak is then defect peak, is because the double resonance scattering of irregular five-ring, seven-membered ring produces.
Fig. 7 shows: the Graphene 2D peak that test one prepares is higher, and lamella is thinner; D peak is lower, i.e. defect peak, shows that obtained Graphene quality is 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 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 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 the graphite after processing; Described graphite is of a size of 50 order ~ 200 orders;
Two, it is stir 15min ~ 30min in the salpeter solution of 48% ~ 68% that the graphite after step one being processed joins massfraction, then potassium permanganate is added, 60min ~ 90min is reacted under temperature is 10 ~ 20 DEG C of conditions, the pH value of the deionized water after extremely rinsing with deionized water rinsing solid matter after filtering is 6 ~ 7, obtains being oxidized intercalated graphite after drying; The quality of graphite after described step one processes is 1g:(3 ~ 5 with the ratio of the volume of salpeter solution) mL; Graphite after described step one processes and the mass ratio of potassium permanganate are 1:(0.3 ~ 0.5);
Three, the oxidation intercalated graphite obtained in step 2 is placed in retort furnace to heat-treat, thermal treatment temp is 1100 ~ 1200 DEG C, and heat treatment time is 80s ~ 100s, obtains expanded graphite;
Four, the expanded graphite that step 3 obtains being joined massfraction is not less than in the vitriol oil of 98%, stir 30min ~ 60min, then potassium permanganate is added and the speed that adds controlling potassium permanganate is 1g/min ~ 5g/min, be 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 mass ratio of the expanded graphite that described step 3 obtains and potassium permanganate is 1:(5 ~ 7);
Five, step 4 being obtained reaction solution transfers in reactor, add deionized water and the speed that adds controlling deionized water is 10g/min ~ 30g/min, then being heated to temperature is 100 ~ 105 DEG C, and reaction is 10min ~ 20min at temperature is 100 ~ 105 DEG C, then in reactor, drip the hydrogen peroxide that massfraction is 20% ~ 30%; Obtain golden solution; The ratio of the quality of the expanded graphite that volume and the step 3 of described deionized water obtain is (40 ~ 60) mL:1g; The ratio of the quality of the expanded graphite that volume and the step 3 of described hydrogen peroxide obtain is (18 ~ 22) mL:1g;
Six, drip in strong aqua and pH value to 8 ~ 9 in the golden solution obtained to step 5, filter at temperature is 40 ~ 50 DEG C, and clarify to filtrate with deionized water rinsing solid matter, then be dry under the condition of 30 ~ 40 DEG C in temperature, drying time is 8h ~ 24h, obtains desciccate;
Seven, the desciccate that step 6 obtains to be dissolved in organic solvent and to stir 30min ~ 50min, then be placed in liquid nitrogen and leave standstill 20min ~ 40min, being warming up to temperature is again 60 ~ 95 DEG C, then hydrazine hydrate is added, 1h ~ 3h is reacted at temperature is 60 ~ 95 DEG C, be 8 by deionized water rinsing to pH value after filtration, then dry, obtain Graphene; The ratio of the quality of the desciccate that volume and the step 6 of described hydrazine hydrate obtain is (0.8 ~ 1.5) mL:1g.
2. the preparation method of a kind of Graphene according to claim 1, it is characterized in that the ratio of grinding media to material described in step one is 4:1, 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 one is of a size of 100 order ~ 150 orders.
4. the preparation method of a kind of Graphene according to claim 3, is characterized in that the quality of graphite after step one process described in step 2 is 1g:4mL with the ratio of the volume of salpeter solution; Graphite after step one processes and the mass ratio of potassium permanganate are 1:0.4.
5. the preparation method of a kind of Graphene according to claim 3, it is characterized in that the drying parameter described in step 2 is: temperature is 30 ~ 40 DEG C, 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 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; The mass ratio of the expanded graphite that step 3 obtains and potassium permanganate is 1:6.
7. the preparation method of a kind of Graphene according to claim 3, is characterized in that 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; The ratio of the quality of the expanded graphite that volume and the step 3 of described hydrogen peroxide obtain is 20mL:1g.
8. the preparation method of a kind of Graphene according to claim 3, is characterized in that 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.
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 the mixture of one or more in dimethyl formamide, methyl alcohol, ethanol, acetone, polyvinyl alcohol.
10. the preparation method of a kind of Graphene according to claim 3, it is characterized in that the drying parameter described in step 7 is: temperature is 30 ~ 40 DEG C, the time is 4h ~ 8h.
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| CN106082194B (en) * | 2016-06-17 | 2018-06-29 | 西北师范大学 | A kind of method for preparing bigger serface and the less graphene of the number of plies |
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| CN113131029A (en) * | 2019-12-30 | 2021-07-16 | 江苏天奈科技股份有限公司 | Method for recycling and regenerating graphene from graphite cathode of lithium ion battery |
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