CN107140632A - A kind of preparation method of the large-size graphene oxide sheet layer of high mechanical strength - Google Patents
A kind of preparation method of the large-size graphene oxide sheet layer of high mechanical strength Download PDFInfo
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- CN107140632A CN107140632A CN201710466829.4A CN201710466829A CN107140632A CN 107140632 A CN107140632 A CN 107140632A CN 201710466829 A CN201710466829 A CN 201710466829A CN 107140632 A CN107140632 A CN 107140632A
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Abstract
The present invention relates to a kind of preparation method of the large-size graphene oxide sheet of high mechanical strength layer, its step includes：First from addition potassium peroxydisulfate and phosphorus pentoxide, the concentrated sulfuric acid carries out pre-treatment to graphite, then under condition of ice bath with potassium permanganate to the further oxidation of graphite, temperature control is at 4~6 DEG C, through stirring after a while, dilution, deionized water is added immediately after whipping process and hydrogen peroxide is reacted, dilution temperature control is at 14~18 DEG C, eventually pass multiple centrifugation steps, the separation that concentration carries out graphene oxide layer for 5mol/L NaCl is added into the dispersion soln of above-mentioned graphene oxide, NaCl is dissolved to 30% saturation degree, solution separates out sediment；Solution left standstill is stayed overnight, and removes supernatant, that is, large-size graphene oxide sheet layer is made.This method safe preparation process is simple, can prepare 7~8 μm of large-size graphene oxide sheet layer and Size Distribution concentration, and lamella high mechanical strength, short preparation period has a good application prospect.
Description
Technical field
The invention belongs to the large scale of the preparation field, more particularly to a high mechanical strength of large-size graphene oxide sheet layer
The preparation method of graphene oxide layer.
Background technology
The performance of graphene oxide and its lateral dimension are closely related, and lateral dimension is smaller, and hydrophilic radical is relatively more, water
Dissolubility is better, and biocompatibility is stronger, and its bio-toxicity is also bigger；Lateral dimension is bigger, the oxygen-containing functional group on its surface then phase
To less, hydrophobicity is strong, and surface defect is also less, and its mechanical strength is so as to being strengthened.Temperature is dilute of graphite oxide of control
The essential condition of layer size, temperature is lower, and surface of graphene oxide degree of oxidation is smaller, and contained oxygenated functional group is fewer, then passes through
Cross the dilute lamella size of the graphite oxide obtained after ultrasound bigger.The research history of graphite oxide preparation method is remote, prepares at present
Graphene oxide mainly uses the various modification methods based on Hummers methods, but the graphene oxide sheet prepared by these methods
Layer size is small and is distributed in 0.1~3 μ m, it is necessary to carry out size separation to the dilute lamella of these graphite oxides.These are prepared
The modification method of graphene oxide is in KMnO4 80 DEG C can be heated in oxidation reaction and deionized water dilution or even at higher temperature
Degree, reaction is violent, with certain danger, and long preparation period, complex operation, yields poorly, prepared graphene oxide
Mechanical strength is low.Size Control is carried out so as to be separated to it to graphene oxide using sequence of differential centrifugation steps at present, but it is this
The separating effect of separation method is bad, the graphene oxide sheet for small size of still being adulterated in large-sized graphene oxide layer
Layer, need to be using salting out method to its further separation.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of large-size graphene oxide sheet layer of high mechanical strength
Preparation method, this method utilizes ice bath method, to KMnO4 Temperature conditionss in oxidation reaction and deionized water dilution are strictly controlled
System, graphene oxide is prepared by pre-oxidation, oxidation, and size point is carried out to graphene oxide using sequence of differential centrifugation steps and salting out method
From the final prepared dilute lamella size of graphite oxide is big, high mechanical strength, and short preparation period, simple to operate, and yield is high.
A kind of preparation method of the large-size graphene oxide sheet layer of high mechanical strength of the present invention, its step includes：
(1) is added into the concentrated sulfuric acid by potassium peroxydisulfate (K2S2O8) and phosphorus pentoxide (P2O5), ultrasonic 0.5h；Then, 78
The solution for adding native graphite after above-mentioned disperse under the conditions of~82 DEG C, is stirred in the case where temperature is kept for 78~82 DEG C with magnetic stirring apparatus
4.5h is mixed, is cooled to after room temperature, is diluted with deionized water, and is stood overnight；Supernatant is removed, with 0.2mm filters to precipitation
Thing carries out suction filtration, goes after the removal of impurity, puts the precipitate in and 12h is dried in vacuum drying chamber, and grinding obtains pre-oxidizing thing after drying；
(2) takes out above-mentioned dried pre-oxidation thing, is ground into powder, is stirred in the concentrated sulfuric acid for being then added to 120ml
Mix, this process temperature will be controlled at 4~6 DEG C；Take 15g potassium permanganate（KMnO4）, powder is ground into, is then slowly added into
Into the concentrated sulfuric acid, this process is carried out in ice bath, and temperature control is at 4~6 DEG C；Then it is temperature control is anti-in 33~37 DEG C of stirrings
2h is answered, then 250ml deionized waters are slowly added dropwise above-mentioned solution is diluted, also 2h is stirred under ice bath in dilution,
Temperature control is diluted at 14~18 DEG C, adds 0.7 L deionized waters, and be added immediately 20 mL30% hydrogen peroxide (H2O2), mix
Compound reacts generation bubble, and color becomes glassy yellow by brown；
(3) stays overnight said mixture solution left standstill, removes after supernatant, is diluted with 1L deionized waters, after dilution
Solution dispense to 35 50ml centrifuge tubes, centrifuge 10min in the centrifuge for being positioned over 10000RPM centrifugation rates, remove supernatant
Liquid；Centrifuged pellet thing A is inserted in beaker, then with concentration be 1：10 hydrochloric acid 1L dilution cleanings, by the precipitation after cleaning
Thing A is dispensed to 30 50ml centrifuge tubes, is centrifuged 10min in the centrifuge for being positioned over 10000RPM centrifugation rates, is removed supernatant；
By centrifuged pellet thing B, cleaned, sediment B after cleaning is dispensed to 30 50ml centrifuge tubes, addition is gone with deionized water
10min is centrifuged in ionized water, the centrifuge for being then placed into 10000RPM centrifugation rates；By centrifuged pellet thing C, spend
After ionized water dilution, ultrasonic 0.5h；
(4) adds the NaCl that concentration is 5mol/L into the dispersion soln of above-mentioned graphene oxide and carries out salt precipitation, NaCl
30% saturation degree is dissolved to, solution separates out sediment；Solution left standstill is stayed overnight, and removes supernatant, that is, large scale graphene oxide is made
Lamella.
Potassium peroxydisulfate, phosphorus pentoxide and native graphite mass ratio in the step (1) are 2.5: 2.5 : 3 .
Compared with prior art, the present invention has the advantages that：
The method preparation process of the present invention is simple, it is easy to operate, and can prepare 7~8 μm of large-size graphene oxide sheet layer,
Lamella high mechanical strength, and its short preparation period, have a good application prospect.
Brief description of the drawings
Fig. 1 is AFM (AFM) figure before the dilute lamella of large scale graphite oxide is saltoutd made from the present embodiment.
Fig. 2 is AFM (AFM) figure after the dilute lamella of large scale graphite oxide is saltoutd made from the present embodiment.
Embodiment
The present invention is expanded on further with reference to specific embodiment.
Embodiment 1
A kind of preparation method of the large-size graphene oxide sheet layer of high mechanical strength, its step is as follows：
(1) adds 2.5g potassium peroxydisulfates (K into the 12ml concentrated sulfuric acids2S2O8) and 2.5g phosphorus pentoxides (P2O5), ultrasound
0.5h；Then, the solution after 3g native graphites to be added to above-mentioned disperse under the conditions of 78~82 DEG C, keeps at 80 DEG C in temperature
Magnetic stirrer 4.5h is used, is cooled to after room temperature, is diluted with 500ml deionized waters, and stand overnight；Remove supernatant,
Suction filtration is carried out to sediment with 0.2mm filters, gone after the removal of impurity, puts the precipitate in and 12h is dried in 60 DEG C of vacuum drying chambers,
Grinding obtains pre-oxidizing thing after drying；
(2) takes out above-mentioned dried pre-oxidation thing, is ground into powder, is stirred in the concentrated sulfuric acid for being then added to 120ml
Mix, this process temperature will be controlled at 5 DEG C；Take 15g potassium permanganate（KMnO4）, powder is ground into, is then slowly added into dense
In sulfuric acid, this process is carried out in ice bath, and temperature control is at 6 DEG C；Then by temperature control at 35 DEG C stirring reaction 2h, then delay
The slow 250ml deionized waters that are added dropwise are diluted to above-mentioned solution, also to be stirred 2h in dilution under ice bath, be diluted temperature control
System adds 0.7L deionized waters, and be added immediately the hydrogen peroxide (H of 20 mL 30% at 18 DEG C2O2), mixture reacts,
Bubble is produced, color becomes glassy yellow by brown；
(3) stays overnight said mixture solution left standstill, removes after supernatant, is diluted with 1L deionized waters, after dilution
Solution dispense to 35 50ml centrifuge tubes, centrifuge 10min in the centrifuge for being positioned over 10000RPM centrifugation rates, remove supernatant
Liquid；Centrifuged pellet thing A is inserted in beaker, then with concentration be 1：10 hydrochloric acid 1L dilution cleanings, will be heavy after cleaning
Starch A is dispensed to 30 50ml centrifuge tubes, is centrifuged 10min in the centrifuge for being positioned over 10000RPM centrifugation rates, is removed supernatant
Liquid；By centrifuged pellet thing B, cleaned with deionized water, sediment B after cleaning is dispensed to 30 50ml centrifuge tubes, plus
Enter deionized water, 10min is centrifuged in the centrifuge for being then placed into 10000RPM centrifugation rates；By centrifuged pellet thing C,
After being diluted with deionized water, ultrasonic 0.5h；
(4) adds the NaCl that concentration is 5 mol/L into the dispersion soln of above-mentioned graphene oxide and carries out salt precipitation, NaCl
30% saturation degree is dissolved to, solution separates out sediment；Solution left standstill is stayed overnight, and removes supernatant, that is, large scale graphene oxide is made
Lamella.
It is dilute to large-size graphene oxide sheet layer table made from the present embodiment using AFM (AFM) graphite oxide
Face saltout preceding surface, saltout after surface be scanned, as shown in Figure 1 and Figure 2, from figure 1 it appears that large scale of the present invention,
The dilute lamella of graphite oxide saltout before surface topography；Show the dilute sheet surfaces of large scale graphite oxide of the present invention with big in Fig. 1
In 5um graphene oxide layer based on, and contain a small amount of dilute lamella of graphite oxide for being less than 5um；From figure 2 it can be seen that
The dilute lamella of large scale graphite oxide of the present invention saltout after surface topography；Show that large scale graphite oxide of the present invention is dilute in Fig. 2
Sheet surfaces are based on 7~8 μm of graphene oxide layer.
Claims (2)
1. a kind of high mechanical strength large-size graphene oxide sheet layer preparation method, it is characterised in that this method include with
Lower step：
（1）Added potassium peroxydisulfate (K into the concentrated sulfuric acid2S2O8) and phosphorus pentoxide (P2O5), ultrasonic 0.5h；Then, 78~
The solution for adding native graphite after above-mentioned disperse under the conditions of 82 DEG C, magnetic stirrer is used in the case where temperature is kept for 78~82 DEG C
4.5h, is cooled to after room temperature, is diluted with deionized water, and stands overnight；Supernatant is removed, with 0.2mm filters to sediment
Suction filtration is carried out, is gone after the removal of impurity, puts the precipitate in and 12h is dried in vacuum drying chamber, grinding obtains pre-oxidizing thing after drying；
（2）Above-mentioned dried pre-oxidation thing is taken out, powder is ground into, is then added in the 120ml concentrated sulfuric acid and stirs,
This process temperature will be controlled at 4~6 DEG C；Take 15g potassium permanganate（KMnO4）, powder is ground into, is then slowly added into dense
In sulfuric acid, this process is carried out in ice bath, and temperature control is at 4~6 DEG C；Then by temperature control at 33~37 DEG C stirring reaction
2h, then 250ml deionized waters are slowly added dropwise above-mentioned solution is diluted, 2h is also stirred in dilution under ice bath, it is dilute
Temperature control is released at 14~18 DEG C, 0.7 L deionized waters are added, and be added immediately 20 mL30% hydrogen peroxide (H2O2), mixing
Thing reacts generation bubble, and color becomes glassy yellow by brown；
（3）Said mixture solution left standstill is stayed overnight, removes after supernatant, is diluted with 1L deionized waters, after dilution
Solution is dispensed to 35 50ml centrifuge tubes, is centrifuged 10min in the centrifuge for being positioned over 10000RPM centrifugation rates, is removed supernatant
Liquid；Centrifuged pellet thing A is inserted in beaker, then with concentration be 1：10 hydrochloric acid 1L dilution cleanings, by the precipitation after cleaning
Thing A is dispensed to 30 50ml centrifuge tubes, is centrifuged 10min in the centrifuge for being positioned over 10000RPM centrifugation rates, is removed supernatant；
By centrifuged pellet thing B, cleaned, sediment B after cleaning is dispensed to 30 50ml centrifuge tubes, addition is gone with deionized water
10min is centrifuged in ionized water, the centrifuge for being then placed into 10000RPM centrifugation rates；By centrifuged pellet thing C, spend
After ionized water dilution, ultrasonic 0.5h；
（4）Concentration is added into the dispersion soln of above-mentioned graphene oxide and carries out salt precipitation for 5mol/L NaCl, NaCl is molten
Solution to 30% saturation degree, solution separates out sediment；Solution left standstill is stayed overnight, and removes supernatant, that is, large-size graphene oxide sheet is made
Layer.
2. a kind of preparation method of the large-size graphene oxide sheet layer of high mechanical strength according to claim 1, it is special
Levy and be, potassium peroxydisulfate, phosphorus pentoxide and the native graphite mass ratio of institute's art in above-mentioned steps (1) are 2.5: 2.5 :
3 。
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Cited By (3)
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| CN108933261A (en) * | 2018-07-17 | 2018-12-04 | 河南电池研究院有限公司 | A kind of nickel cobalt lithium aluminate/grapheme composite positive electrode material preparation method of cerium dopping |
| CN110697698A (en) * | 2019-11-28 | 2020-01-17 | 宁波石墨烯创新中心有限公司 | Graphene oxide and preparation method thereof |
| CN111704126A (en) * | 2020-05-14 | 2020-09-25 | 上海大学 | Reduction method of graphene oxide |
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| CN111704126A (en) * | 2020-05-14 | 2020-09-25 | 上海大学 | Reduction method of graphene oxide |
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