CN106976871B - A method of graphene is prepared using crystalline flake graphite - Google Patents
A method of graphene is prepared using crystalline flake graphite Download PDFInfo
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- CN106976871B CN106976871B CN201710421098.1A CN201710421098A CN106976871B CN 106976871 B CN106976871 B CN 106976871B CN 201710421098 A CN201710421098 A CN 201710421098A CN 106976871 B CN106976871 B CN 106976871B
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- C01B2204/00—Structure or properties of graphene
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/30—Purity
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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Abstract
The present invention relates to a kind of methods for preparing graphene using crystalline flake graphite, by crystalline flake graphite to get graphene after ball milling, flotation, oxidation, reduction and drying.The present invention, which prepares graphene, has purity is high, large specific surface area and the few feature of the number of plies.
Description
Technical field
The present invention relates to a kind of methods for preparing graphene using crystalline flake graphite.
Background technique
Crystalline flake graphite graphite crystal is in flakey；This is to have big scale and thin made of going bad under high-intensitive pressure
Point of scale.The characteristics of crystalline flake graphite ore is that grade is not high, generally between 2~3% or 10~25%.Crystalline flake graphite is certainly
Best one of the ore of floatability in right boundary, high grade graphite concentrate can be obtained by excessively being ground multiselect.Floatability, the profit of this kind of graphite
Slip, plasticity are more superior than other types graphite, therefore its industrial value is maximum.
Record in " research of crystalline flake graphite floatation process " willow hair graphite the primary corase grinding of common floatation process, six times again
Mill, eight times it is selected, then plus one roughing once purging selection, chats return step by step, the tediously long complexity of process.
For crystalline flake graphite mine since grade is low, purifying is at high cost, is unfavorable for producing in enormous quantities.
Summary of the invention
The technical problem to be solved by the invention is to provide a kind of method for preparing graphene using crystalline flake graphite, this hairs
The graphene purity is high of bright preparation, large specific surface area, the number of plies are few.
In order to solve the above-mentioned technical problem, the invention adopts the following technical scheme:
A method of graphene is prepared using crystalline flake graphite, it is characterised in that is followed the steps below:
1) it prepares rough and torn crystalline flake graphite mine: crystalline flake graphite mine is added in crusher, it is rough and torn, obtain rough and torn crystalline flake graphite
Mine；
2) prepare ball milling slurry: by rough and torn crystalline flake graphite mine, 5040 dispersing agents and water according to mass ratio 40~60: 0.1~
0.5: 40~60 are added in level-one ball milling roller, are milled to 40~60 mesh up to a slurry, a slurry is added to two
Grade ball mill, is milled to 80~120 mesh to get ball milling slurry；
3) crystalline flake graphite A and flotation slurry A are prepared: by the ball milling slurry of step 2) preparation and foaming agent according to mass ratio
1000: 0.02~0.05 is added in flotation device, temperature be 60~80 DEG C under the conditions of 4~8h of flotation, obtain crystalline flake graphite A and
Flotation slurry A；
4) flotation: at least flotation is secondary, flotation step are as follows:
Flotation slurry A is squeezed into second level ball mill ball milling 5~20 minutes, by flotation slurry A and foaming agent according to mass ratio
1000: 0.02~0.05 is added in flotation device, temperature be 60~80 DEG C under the conditions of 1~8h of flotation, obtain crystalline flake graphite and
Flotation slurry；
5) it prepares crystalline graphite powder: the crystalline flake graphite of the crystalline flake graphite A of step 3) preparation and step 4) preparation being merged dry
After dry, crystalline graphite powder is obtained；
6) it removes organic matter and prepares crude oxidation graphene: crystalline graphite powder prepared by step 5) is added to mass parts
Number for 30% dust technologies and mass fraction be 75% mixed liquor of the dilute sulfuric acid according to mass ratio 3: 7 in, crystalline graphite powder and
The mass ratio of mixed liquor is 1: 100, and 1~6h is stirred under the conditions of temperature is 5~25 DEG C, removes upper layer black object and filters, obtains
Crude oxidation graphene；
7) crude oxidation graphene prepared by step 6) purification of graphite oxide alkene: is obtained into oxidation stone after washing and drying
Black alkene；
8) prepare prereduction suspension: by step 7) preparation graphene oxide, reducing agent and water according to mass ratio 15~
30: 5~15: 55~80 are added to 5~20min of vibrating dispersion in ultrasonic container, and prereduction suspension is made；
9) it prepares crude graphene: prereduction uniform suspension is applied on substrate, with infrared laser to substrate illumination
15~60min, the graphene on substrate is up to crude graphene；
10) reducing agent purifying graphene is removed: by crude graphene to get graphene after washing and drying；
The foaming agent is that polyoxyethylene sorbitan fatty acid ester, the basic sodium sulfonate of dodecane, sorbitol anhydride list are hard
One or more of resin acid rouge, azodicarbonamide, pine-tree oil and unifor；
The reducing agent is one or more of vitamin C, sodium borohydride and ethyl alcohol；
The substrate is one or more of polytetrafluoroethylene (PTFE), silicon wafer and Kynoar.
Based on the above technical solution, the present invention can also be improved as follows:
Further, the grade of crystalline flake graphite described in step 1) is 15~25%.
Further, milling material is ball milling steel ball in step 2) the level-one ball mill；Milling material in second level ball mill
It is ball milling rod iron.
Further, foaming agent described in step 3) is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to quality
Composition than 3: 1；Ball milling slurry and foaming agent are according to mass ratio 1000: 0.03；70 DEG C of reaction temperature, reaction time 7h.
Further, the step 4) flotation is 5 times.
The present invention has following advantageous effects:
1), due to the large specific surface area of graphite, secondary flocculation is readily formed in mechanical milling process, the present invention passes through addition
5040 dispersing agents can prevent graphene from flocculating, and reduce ball milling number, energy saving.
2), ball milling effect is good, but crystalline flake graphite is be easy to cause to lose in grinding, and rod milling grinding effect is poor, but not
It is easy to cause the loss of crystalline flake graphite.The present invention is combined using ball milling and rod milling, it is possible to reduce the loss of crystalline flake graphite.
3), crystalline flake graphite has floatability, therefore selects foaming agent critically important, and foaming agent blistering is big to be then easy other mines
Object is taken out of, and the small then flotation time of bubble is long, and the present invention has found by many experiments, and foaming agent is polyoxyethylene sorbitan rouge
According to 3: 1 composition, blistering is fine and smooth for fat acid esters and pine-tree oil, and ball milling slurry and foaming agent are 1000 according to mass ratio:
0.03, flotation crystalline flake graphite alkene effect is good.
4), the present invention while aoxidizing crystalline flake graphite, also aoxidizes squama by the processing of the mixed liquor of dust technology and dilute sulfuric acid
The organic matter taken out of when piece graphite flotation, while also dissolving some metal impurities；Be conducive to remove by washing, reach purifying
The purpose of graphene.
5), the present invention passes through 5 flotation, 3 edulcoration purifications, and the graphene purity of production meets graphene up to 99.2
Battery request.
Specific embodiment
The present invention is further illustrated below with reference to specific example.
Embodiment one
1) it prepares rough and torn crystalline flake graphite mine: crystalline flake graphite mine is added in crusher, it is rough and torn, obtain rough and torn crystalline flake graphite
Mine；
2) it prepares ball milling slurry: rough and torn crystalline flake graphite mine, 5040 dispersing agents and water is added according to mass ratio 45: 0.2: 54.8
Enter into level-one ball milling roller, is milled to 40~60 mesh up to a slurry, a slurry is added to second level ball mill, ball milling
To 80~120 mesh to get ball milling slurry；
3) crystalline flake graphite A and flotation slurry A are prepared: by the ball milling slurry of step 2) preparation and foaming agent according to mass ratio
Be added in flotation device at 1000: 0.03, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to matter
Amount compares 3: 1 composition, and flotation 7h under the conditions of temperature is 70 DEG C obtains crystalline flake graphite A and flotation slurry A；
4) flotation: flotation 5 times, flotation step are as follows:
Flotation slurry A is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry A and foaming agent according to mass ratio 1000
: 0.03 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 6h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite B floatingly selected and flotation slurry B；
Flotation slurry B is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry B and foaming agent according to mass ratio 1000
: 0.03 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 5h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite C floatingly selected and flotation slurry C；
Flotation slurry C is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry C and foaming agent according to mass ratio 1000
: 0.03 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 4h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite D floatingly selected and flotation slurry D；
Flotation slurry D is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry D and foaming agent according to mass ratio 1000
: 0.03 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 3h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite E floatingly selected and flotation slurry E；
Flotation slurry E is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry E and foaming agent according to mass ratio 1000
: 0.03 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 2h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite H floatingly selected and flotation slurry H；
5) it prepares crystalline graphite powder: the crystalline flake graphite B to H of the crystalline flake graphite A of step 3) preparation and step 4) preparation is closed
And after drying, crystalline graphite powder is obtained；
6) it removes organic matter and prepares crude oxidation graphene: crystalline graphite powder prepared by step 5) is added to mass parts
Number for 30% dust technologies and mass fraction be 75% mixed liquor of the dilute sulfuric acid according to mass ratio 3: 7 in, crystalline graphite powder and
The mass ratio of mixed liquor is 1: 100, and 2h is stirred under the conditions of temperature is 15 DEG C, removes upper layer black object and filters, obtains crude oxygen
Graphite alkene；
7) crude oxidation graphene prepared by step 6) purification of graphite oxide alkene: is obtained into oxidation stone after washing and drying
Black alkene；
8) prereduction suspension is prepared: by graphene oxide, reducing agent and the water of step 7) preparation according to mass ratio 20: 7:
73 are added to vibrating dispersion 10min in ultrasonic container, and prereduction suspension is made；
9) it prepares crude graphene: prereduction uniform suspension is applied on substrate, with infrared laser to substrate illumination
40min, the graphene on substrate is up to crude graphene；
10) reducing agent purifying graphene is removed: by crude graphene to get graphene after washing and drying.
Embodiment two
1) it prepares rough and torn crystalline flake graphite mine: crystalline flake graphite mine is added in crusher, it is rough and torn, obtain rough and torn crystalline flake graphite
Mine；
2) it prepares ball milling slurry: rough and torn crystalline flake graphite mine, 5040 dispersing agents and water is added according to mass ratio 45: 0.2: 54.8
Enter into level-one ball milling roller, is milled to 40~60 mesh up to a slurry, a slurry is added to second level ball mill, ball milling
To 80~120 mesh to get ball milling slurry；
3) crystalline flake graphite A and flotation slurry A are prepared: by the ball milling slurry of step 2) preparation and foaming agent according to mass ratio
Be added in flotation device at 1000: 0.03, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to matter
Amount compares 3: 1 composition, and flotation 7h under the conditions of temperature is 70 DEG C obtains crystalline flake graphite A and flotation slurry A；
4) flotation: flotation 3 times, flotation step are as follows:
Flotation slurry A is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry A and foaming agent according to mass ratio 1000
: 0.03 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 6h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite B floatingly selected and flotation slurry B；
Flotation slurry B is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry B and foaming agent according to mass ratio 1000
: 0.03 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 5h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite C floatingly selected and flotation slurry C；
Flotation slurry C is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry C and foaming agent according to mass ratio 1000
: 0.03 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 4h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite D floatingly selected and flotation slurry D；
5) it prepares crystalline graphite powder: the crystalline flake graphite B to D of the crystalline flake graphite A of step 3) preparation and step 4) preparation is closed
And after drying, crystalline graphite powder is obtained；
6) it removes organic matter and prepares crude oxidation graphene: crystalline graphite powder prepared by step 5) is added to mass parts
Number for 30% dust technologies and mass fraction be 75% mixed liquor of the dilute sulfuric acid according to mass ratio 3: 7 in, crystalline graphite powder and
The mass ratio of mixed liquor is 1: 100, and 2h is stirred under the conditions of temperature is 15 DEG C, removes upper layer black object and filters, obtains crude oxygen
Graphite alkene；
7) crude oxidation graphene prepared by step 6) purification of graphite oxide alkene: is obtained into oxidation stone after washing and drying
Black alkene；
8) prereduction suspension is prepared: by graphene oxide, reducing agent and the water of step 7) preparation according to mass ratio 20: 7:
73 are added to vibrating dispersion l0min in ultrasonic container, and prereduction suspension is made；
9) it prepares crude graphene: prereduction uniform suspension is applied on substrate, with infrared laser to substrate illumination
40min, the graphene on substrate is up to crude graphene；
10) reducing agent purifying graphene is removed: by crude graphene to get graphene after washing and drying.
Embodiment three
1) it prepares rough and torn crystalline flake graphite mine: crystalline flake graphite mine is added in crusher, it is rough and torn, obtain rough and torn crystalline flake graphite
Mine；
2) it prepares ball milling slurry: rough and torn crystalline flake graphite mine, 5040 dispersing agents and water is added according to mass ratio 45: 0.2: 54.8
Enter into level-one ball milling roller, is milled to 40~60 mesh up to a slurry, a slurry is added to second level ball mill, ball milling
To 80~120 mesh to get ball milling slurry；
3) crystalline flake graphite A and flotation slurry A are prepared: by the ball milling slurry of step 2) preparation and foaming agent according to mass ratio
Be added in flotation device at 1000: 0.03, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to matter
Amount compares 3: 1 composition, and flotation 7h under the conditions of temperature is 70 DEG C obtains crystalline flake graphite A and flotation slurry A；
4) flotation: flotation 4 times, flotation step are as follows:
Flotation slurry A is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry A and foaming agent according to mass ratio 1000
: 0.03 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 6h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite B floatingly selected and flotation slurry B；
Flotation slurry B is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry B and foaming agent according to mass ratio 1000
: 0.03 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 5h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite C floatingly selected and flotation slurry C；
Flotation slurry C is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry C and foaming agent according to mass ratio 1000
: 0.03 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 4h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite D floatingly selected and flotation slurry D；
Flotation slurry D is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry D and foaming agent according to mass ratio 1000
: 0.03 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 3h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite E floatingly selected and flotation slurry E；
5) it prepares crystalline graphite powder: the crystalline flake graphite B to E of the crystalline flake graphite A of step 3) preparation and step 4) preparation is closed
And after drying, crystalline graphite powder is obtained；
6) it removes organic matter and prepares crude oxidation graphene: crystalline graphite powder prepared by step 5) is added to mass parts
Number for 30% dust technologies and mass fraction be 75% mixed liquor of the dilute sulfuric acid according to mass ratio 3: 7 in, crystalline graphite powder and
The mass ratio of mixed liquor is 1: 100, and 2h is stirred under the conditions of temperature is 15 DEG C, removes upper layer black object and filters, obtains crude oxygen
Graphite alkene；
7) crude oxidation graphene prepared by step 6) purification of graphite oxide alkene: is obtained into oxidation stone after washing and drying
Black alkene；
8) prereduction suspension is prepared: by graphene oxide, reducing agent and the water of step 7) preparation according to mass ratio 20: 7:
73 are added to vibrating dispersion 10min in ultrasonic container, and prereduction suspension is made；
9) it prepares crude graphene: prereduction uniform suspension is applied on substrate, with infrared laser to substrate illumination
40min, the graphene on substrate is up to crude graphene；
10) reducing agent purifying graphene is removed: by crude graphene to get graphene after washing and drying.
Example IV
1) it prepares rough and torn crystalline flake graphite mine: crystalline flake graphite mine is added in crusher, it is rough and torn, obtain rough and torn crystalline flake graphite
Mine；
2) it prepares ball milling slurry: rough and torn crystalline flake graphite mine, 5040 dispersing agents and water is added according to mass ratio 45: 0.2: 54.8
Enter into level-one ball milling roller, is milled to 40~60 mesh up to a slurry, a slurry is added to second level ball mill, ball milling
To 80~120 mesh to get ball milling slurry；
3) crystalline flake graphite A and flotation slurry A are prepared: by the ball milling slurry of step 2) preparation and foaming agent according to mass ratio
Be added in flotation device at 1000: 0.03, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to matter
Amount compares 3: 1 composition, and flotation 7h under the conditions of temperature is 70 DEG C obtains crystalline flake graphite A and flotation slurry A；
4) flotation: flotation 6 times, flotation step are as follows:
Flotation slurry A is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry A and foaming agent according to mass ratio 1000
: 0.03 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 6h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite B floatingly selected and flotation slurry B；
Flotation slurry B is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry B and foaming agent according to mass ratio 1000
: 0.03 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 5h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite C floatingly selected and flotation slurry C；
Flotation slurry C is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry C and foaming agent according to mass ratio 1000
: 0.03 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 4h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite D floatingly selected and flotation slurry D；
Flotation slurry D is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry D and foaming agent according to mass ratio 1000
: 0.03 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 3h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite E floatingly selected and flotation slurry E；
Flotation slurry E is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry E and foaming agent according to mass ratio 1000
: 0.03 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 2h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite H floatingly selected and flotation slurry H；
Flotation slurry H is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry H and foaming agent according to mass ratio 1000
: 0.03 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 1h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite I floatingly selected and flotation slurry I；
5) it prepares crystalline graphite powder: the crystalline flake graphite B to I of the crystalline flake graphite A of step 3) preparation and step 4) preparation is closed
And after drying, crystalline graphite powder is obtained；
6) it removes organic matter and prepares crude oxidation graphene: crystalline graphite powder prepared by step 5) is added to mass parts
Number for 30% dust technologies and mass fraction be 75% mixed liquor of the dilute sulfuric acid according to mass ratio 3: 7 in, crystalline graphite powder and
The mass ratio of mixed liquor is 1: 100, and 2h is stirred under the conditions of temperature is 15 DEG C, removes upper layer black object and filters, obtains crude oxygen
Graphite alkene；
7) crude oxidation graphene prepared by step 6) purification of graphite oxide alkene: is obtained into oxidation stone after washing and drying
Black alkene；
8) prereduction suspension is prepared: by graphene oxide, reducing agent and the water of step 7) preparation according to mass ratio 20: 7:
73 are added to vibrating dispersion 10min in ultrasonic container, and prereduction suspension is made；
9) it prepares crude graphene: prereduction uniform suspension is applied on substrate, with infrared laser to substrate illumination
40min, the graphene on substrate is up to crude graphene；
10) reducing agent purifying graphene is removed: by crude graphene to get graphene after washing and drying.
Embodiment five
1) it prepares rough and torn crystalline flake graphite mine: crystalline flake graphite mine is added in crusher, it is rough and torn, obtain rough and torn crystalline flake graphite
Mine；
2) it prepares ball milling slurry: rough and torn crystalline flake graphite mine, 5040 dispersing agents and water is added according to mass ratio 45: 0.2: 54.8
Enter into level-one ball milling roller, is milled to 40~60 mesh up to a slurry, a slurry is added to second level ball mill, ball milling
To 80~120 mesh to get ball milling slurry；
3) crystalline flake graphite A and flotation slurry A are prepared: by the ball milling slurry of step 2) preparation and foaming agent according to mass ratio
Be added in flotation device at 1000: 0.02, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to matter
Amount compares 3: 1 composition, and flotation 7h under the conditions of temperature is 70 DEG C obtains crystalline flake graphite A and flotation slurry A；
4) flotation: flotation 5 times, flotation step are as follows:
Flotation slurry A is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry A and foaming agent according to mass ratio 1000
: 0.02 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 6h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite B floatingly selected and flotation slurry B；
Flotation slurry B is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry B and foaming agent according to mass ratio 1000
: 0.02 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 5h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite C floatingly selected and flotation slurry C；
Flotation slurry C is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry C and foaming agent according to mass ratio 1000
: 0.02 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 4h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite D floatingly selected and flotation slurry D；
Flotation slurry D is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry D and foaming agent according to mass ratio 1000
: 0.02 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 3h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite E floatingly selected and flotation slurry E；
Flotation slurry E is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry E and foaming agent according to mass ratio 1000
: 0.02 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 2h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite H floatingly selected and flotation slurry H；
5) it prepares crystalline graphite powder: the crystalline flake graphite B to H of the crystalline flake graphite A of step 3) preparation and step 4) preparation is closed
And after drying, crystalline graphite powder is obtained；
6) it removes organic matter and prepares crude oxidation graphene: crystalline graphite powder prepared by step 5) is added to mass parts
Number for 30% dust technologies and mass fraction be 75% mixed liquor of the dilute sulfuric acid according to mass ratio 3: 7 in, crystalline graphite powder and
The mass ratio of mixed liquor is 1: 100, and 2h is stirred under the conditions of temperature is 15 DEG C, removes upper layer black object and filters, obtains crude oxygen
Graphite alkene；
7) crude oxidation graphene prepared by step 6) purification of graphite oxide alkene: is obtained into oxidation stone after washing and drying
Black alkene；
8) prereduction suspension is prepared: by graphene oxide, reducing agent and the water of step 7) preparation according to mass ratio 20: 7:
73 are added to vibrating dispersion 10min in ultrasonic container, and prereduction suspension is made；
9) it prepares crude graphene: prereduction uniform suspension is applied on substrate, with infrared laser to substrate illumination
40min, the graphene on substrate is up to crude graphene；
10) reducing agent purifying graphene is removed: by crude graphene to get graphene after washing and drying.
Embodiment 6
1) it prepares rough and torn crystalline flake graphite mine: crystalline flake graphite mine is added in crusher, it is rough and torn, obtain rough and torn crystalline flake graphite
Mine；
2) it prepares ball milling slurry: rough and torn crystalline flake graphite mine, 5040 dispersing agents and water is added according to mass ratio 45: 0.2: 54.8
Enter into level-one ball milling roller, is milled to 40~60 mesh up to a slurry, a slurry is added to second level ball mill, ball milling
To 80~120 mesh to get ball milling slurry；
3) crystalline flake graphite A and flotation slurry A are prepared: by the ball milling slurry of step 2) preparation and foaming agent according to mass ratio
Be added in flotation device at 1000: 0.04, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to matter
Amount compares 3: 1 composition, and flotation 7h under the conditions of temperature is 70 DEG C obtains crystalline flake graphite A and flotation slurry A；
4) flotation: flotation 5 times, flotation step are as follows:
Flotation slurry A is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry A and foaming agent according to mass ratio 1000
: 0.04 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 6h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite B floatingly selected and flotation slurry B；
Flotation slurry B is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry B and foaming agent according to mass ratio 1000
: 0.04 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 5h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite C floatingly selected and flotation slurry C；
Flotation slurry C is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry C and foaming agent according to mass ratio 1000
: 0.04 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 4h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite D floatingly selected and flotation slurry D；
Flotation slurry D is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry D and foaming agent according to mass ratio 1000
: 0.04 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 3h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite E floatingly selected and flotation slurry E；
Flotation slurry E is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry E and foaming agent according to mass ratio 1000
: 0.04 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 2h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite H floatingly selected and flotation slurry H；
5) it prepares crystalline graphite powder: the crystalline flake graphite B to H of the crystalline flake graphite A of step 3) preparation and step 4) preparation is closed
And after drying, crystalline graphite powder is obtained；
6) it removes organic matter and prepares crude oxidation graphene: crystalline graphite powder prepared by step 5) is added to mass parts
Number for 30% dust technologies and mass fraction be 75% mixed liquor of the dilute sulfuric acid according to mass ratio 3: 7 in, crystalline graphite powder and
The mass ratio of mixed liquor is 1: 100, and 2h is stirred under the conditions of temperature is 15 DEG C, removes upper layer black object and filters, obtains crude oxygen
Graphite alkene；
7) crude oxidation graphene prepared by step 6) purification of graphite oxide alkene: is obtained into oxidation stone after washing and drying
Black alkene；
8) prereduction suspension is prepared: by graphene oxide, reducing agent and the water of step 7) preparation according to mass ratio 20: 7:
73 are added to vibrating dispersion 10min in ultrasonic container, and prereduction suspension is made；
9) it prepares crude graphene: prereduction uniform suspension is applied on substrate, with infrared laser to substrate illumination
40min, the graphene on substrate is up to crude graphene；
10) reducing agent purifying graphene is removed: by crude graphene to get graphene after washing and drying.
Embodiment 7
1) it prepares rough and torn crystalline flake graphite mine: crystalline flake graphite mine is added in crusher, it is rough and torn, obtain rough and torn crystalline flake graphite
Mine；
2) it prepares ball milling slurry: rough and torn crystalline flake graphite mine, 5040 dispersing agents and water is added according to mass ratio 45: 0.2: 54.8
Enter into level-one ball milling roller, is milled to 40~60 mesh up to a slurry, a slurry is added to second level ball mill, ball milling
To 80~120 mesh to get ball milling slurry；
3) crystalline flake graphite A and flotation slurry A are prepared: by the ball milling slurry of step 2) preparation and foaming agent according to mass ratio
Be added in flotation device at 1000: 0.05, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to matter
Amount compares 3: 1 composition, and flotation 7h under the conditions of temperature is 70 DEG C obtains crystalline flake graphite A and flotation slurry A；
4) flotation: flotation 5 times, flotation step are as follows:
Flotation slurry A is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry A and foaming agent according to mass ratio 1000
: 0.05 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 6h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite B floatingly selected and flotation slurry B；
Flotation slurry B is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry B and foaming agent according to mass ratio 1000
: 0.05 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 5h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite C floatingly selected and flotation slurry C；
Flotation slurry C is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry C and foaming agent according to mass ratio 1000
: 0.05 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 4h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite D floatingly selected and flotation slurry D；
Flotation slurry D is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry D and foaming agent according to mass ratio 1000
: 0.05 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 3h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite E floatingly selected and flotation slurry E；
Flotation slurry E is squeezed into second level ball mill ball milling 10 minutes, by flotation slurry E and foaming agent according to mass ratio 1000
: 0.05 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3
: 1 composition, flotation 2h under the conditions of temperature is 70 DEG C collect the crystalline flake graphite H floatingly selected and flotation slurry H；
5) it prepares crystalline graphite powder: the crystalline flake graphite B to H of the crystalline flake graphite A of step 3) preparation and step 4) preparation is closed
And after drying, crystalline graphite powder is obtained；
6) it removes organic matter and prepares crude oxidation graphene: crystalline graphite powder prepared by step 5) is added to mass parts
Number for 30% dust technologies and mass fraction be 75% mixed liquor of the dilute sulfuric acid according to mass ratio 3: 7 in, crystalline graphite powder and
The mass ratio of mixed liquor is 1: 100, and 2h is stirred under the conditions of temperature is 15 DEG C, removes upper layer black object and filters, obtains crude oxygen
Graphite alkene；
7) crude oxidation graphene prepared by step 6) purification of graphite oxide alkene: is obtained into oxidation stone after washing and drying
Black alkene；
8) prereduction suspension is prepared: by graphene oxide, reducing agent and the water of step 7) preparation according to mass ratio 20: 7:
73 are added to vibrating dispersion 10min in ultrasonic container, and prereduction suspension is made；
9) it prepares crude graphene: prereduction uniform suspension is applied on substrate, with infrared laser to substrate illumination
40min, the graphene on substrate is up to crude graphene；
10) reducing agent purifying graphene is removed: by crude graphene to get graphene after washing and drying.
Embodiment 8
1) it prepares rough and torn crystalline flake graphite mine: crystalline flake graphite mine is added in crusher, it is rough and torn, obtain rough and torn crystalline flake graphite
Mine；
2) it prepares ball milling slurry: rough and torn crystalline flake graphite mine, 5040 dispersing agents and water is added according to mass ratio 50: 0.3: 49.7
Enter into level-one ball milling roller, is milled to 40~60 mesh up to a slurry, a slurry is added to second level ball mill, ball milling
To 80~120 mesh to get ball milling slurry；
3) crystalline flake graphite A and flotation slurry A are prepared: by the ball milling slurry of step 2) preparation and foaming agent according to mass ratio
Be added in flotation device at 1000: 0.05, and the foaming agent is polyoxyethylene sorbitan fatty acid ester, is 75 DEG C of items in temperature
Flotation 8h under part obtains crystalline flake graphite A and flotation slurry A；
4) flotation: flotation 5 times, flotation step are as follows:
Flotation slurry A is squeezed into second level ball mill ball milling 12 minutes, by flotation slurry A and foaming agent according to mass ratio 1000
: 0.05 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester, under the conditions of temperature is 75 DEG C
Flotation 7h collects the crystalline flake graphite B floatingly selected and flotation slurry B；
Flotation slurry B is squeezed into second level ball mill ball milling 12 minutes, by flotation slurry B and foaming agent according to mass ratio 1000
: 0.05 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester, under the conditions of temperature is 70 DEG C
Flotation 5h collects the crystalline flake graphite C floatingly selected and flotation slurry C；
Flotation slurry C is squeezed into second level ball mill ball milling 12 minutes, by flotation slurry C and foaming agent according to mass ratio 1000
: 0.05 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester, under the conditions of temperature is 70 DEG C
Flotation 4h collects the crystalline flake graphite D floatingly selected and flotation slurry D；
Flotation slurry D is squeezed into second level ball mill ball milling 12 minutes, by flotation slurry D and foaming agent according to mass ratio 1000
: 0.05 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester, under the conditions of temperature is 70 DEG C
Flotation 4h collects the crystalline flake graphite E floatingly selected and flotation slurry E；
Flotation slurry E is squeezed into second level ball mill ball milling 12 minutes, by flotation slurry E and foaming agent according to mass ratio 1000
: 0.05 is added in flotation device, and the foaming agent is polyoxyethylene sorbitan fatty acid ester, under the conditions of temperature is 60 DEG C
Flotation 2h collects the crystalline flake graphite H floatingly selected and flotation slurry H；
5) it prepares crystalline graphite powder: the crystalline flake graphite B to H of the crystalline flake graphite A of step 3) preparation and step 4) preparation is closed
And after drying, crystalline graphite powder is obtained；
6) it removes organic matter and prepares crude oxidation graphene: crystalline graphite powder prepared by step 5) is added to mass parts
Number for 30% dust technologies and mass fraction be 75% mixed liquor of the dilute sulfuric acid according to mass ratio 3: 7 in, crystalline graphite powder and
The mass ratio of mixed liquor is 1: 100, and 1.5h is stirred under the conditions of temperature is 20 DEG C, removes upper layer black object and filters, obtains crude
Graphene oxide；
7) crude oxidation graphene prepared by step 6) purification of graphite oxide alkene: is obtained into oxidation stone after washing and drying
Black alkene；
8) prereduction suspension is prepared: by graphene oxide, reducing agent and the water of step 7) preparation according to mass ratio 30: 9:
61 are added to vibrating dispersion 10min in ultrasonic container, and prereduction suspension is made；
9) it prepares crude graphene: prereduction uniform suspension is applied on substrate, with infrared laser to substrate illumination
40min, the graphene on substrate is up to crude graphene；
10) reducing agent purifying graphene is removed: by crude graphene to get graphene after washing and drying.
Beneficial effects of the present invention are further illustrated below with reference to experimental data:
1, material to be tested is tested
1 materials and methods:
1.1 materials to be tested: the present invention does effect to embodiment 7 with embodiment 1 and compares.
1.2 experimental designs: experiment is divided into 7 groups, and 2 is parallel, prepares graphene according to embodiment 1 to 7 method of embodiment respectively,
Extracting crystalline flake graphite mine used every time is 5kg.
1.3 testing inspections: graphene number of plies, graphene specific surface area, graphene yield and organic carbon content, wherein using
Atomic force microscope (AFM) measures graphene number of plies；Using Bei Shide instrument, scientific and technological (Beijing) Co., Ltd produces 3H-
The full-automatic N2 adsorption specific surface instrument of 2000A type measures graphene specific surface area；Gravimetric method weighs graphene yield；Potassium bichromate holds
Amount method detects organic carbon.
Organic carbon Method And Principle
Make the organic oxidation of coal for having in graphene in a heated condition with quantitative potassium bichromate-sulfuric acid solution, it is extra
Potassium bichromate titrated with ferrous sulfate standard solution, while making blank test by additive of silica.Before oxidation
Oxidant consumption amount afterwards calculates organic carbon content.
This experiment is consistent except the different outer other conditions of the embodiment of use.
2 results and analysis
Embodiment 1 is to embodiment 7, and processing is compared, as a result such as table 1.
Table 1 manages graphene number of plies, specific surface area, yield and organic carbon everywhere
| The number of plies (nm) | Specific surface area (m2/g) | Yield (kg) | Organic carbon content (%) | |
| Embodiment 1 | 1.8 | 456.82 | 0.76 | 99.2 |
| Embodiment 2 | 1.6 | 453.75 | 0.59 | 99.4 |
| Embodiment 3 | 1.9 | 451.71 | 0.64 | 98.8 |
| Embodiment 4 | 2.1 | 456.85 | 0.77 | 98.9 |
| Embodiment 5 | 1.4 | 458.75 | 0.70 | 99.0 |
| Embodiment 6 | 5.9 | 431.71 | 0.84 | 88.3 |
| Embodiment 7 | 20.6 | 407.6 | 0.88 | 83.5 |
Embodiment 1 to embodiment 4 as can be seen from Table 1, other than flotation number is different, other operations are consistent, float
The yield and flotation five times 1 yield of embodiment for selecting embodiment 2 and flotation four times embodiments 3 three times differ bigger, and
The embodiment 4 and flotation five times embodiment l yield difference that flotation is six times are little, and other index difference are little, illustrate embodiment 2
It is incomplete with 3 flotation of embodiment, although the slightly above embodiment l of embodiment 4, increase a ball milling and flotation, production cost
Increase very much, therefore embodiment l resultant effect is best.
Embodiment 1, embodiment 5, embodiment 6 and embodiment 7 as can be seen from Table 1, in addition to flotation slurry and foaming agent add
It is different outer to enter ratio, other operations are consistent, and embodiment 5 is compared other than low output with embodiment 1, and other index difference are not
Greatly, illustrate that 5 flotation of embodiment is incomplete；Embodiment 6 and 7 yield of embodiment are apparently higher than embodiment 1, but graphene number of plies, ratio
Surface area and organic carbon content differ greatly, and illustrate that embodiment 6 and 7 flotation of embodiment introduce the slag insoluble in acid, comprehensive
The technical solution of comparing embodiment 1 is best.
Best by 1 technical solution of the above two o'clock comparative descriptions embodiment, i.e. flotation five times, foaming agent is polyoxyethylene sorbitan
According to the composition of mass ratio 3: 1, the mass ratio of flotation slurry and foaming agent is 1000 for Span and pine-tree oil:
0.03。
Claims (5)
1. a kind of method for preparing graphene using crystalline flake graphite, it is characterised in that follow the steps below:
1) it prepares rough and torn crystalline flake graphite mine: crystalline flake graphite mine is added in crusher, it is rough and torn, obtain rough and torn crystalline flake graphite mine；
2) ball milling slurry is prepared: by rough and torn crystalline flake graphite mine, 5040 dispersing agents and water according to mass ratio 40~60: 0.1~0.5:
40~60 are added in level-one ball milling roller, are milled to 40~60 mesh up to a slurry, a slurry is added to second level ball
Grinding machine is milled to 80~120 mesh to get ball milling slurry；
3) crystalline flake graphite A and flotation slurry A are prepared: by the ball milling slurry of step 2) preparation and foaming agent according to mass ratio 1000:
0.02~0.05 is added in flotation device, and 4~8h of flotation under the conditions of temperature is 60~80 DEG C obtains crystalline flake graphite A and flotation
Slurry A；
4) flotation: at least flotation is secondary, flotation step are as follows:
Flotation slurry A is squeezed into second level ball mill ball milling 5~20 minutes, by flotation slurry A and foaming agent according to mass ratio 1000:
0.02~0.05 is added in flotation device, and 1~8h of flotation under the conditions of temperature is 60~80 DEG C obtains crystalline flake graphite and flotation material
Slurry；
5) crystalline graphite powder is prepared: after the crystalline flake graphite of the crystalline flake graphite A of step 3) preparation and step 4) preparation are merged drying,
Obtain crystalline graphite powder；
6) remove organic matter and prepare crude oxidation graphene: crystalline graphite powder prepared by step 5), which is added to mass fraction, is
In mixed liquor of the dilute sulfuric acid that 30% dust technology and mass fraction is 75% according to mass ratio 3: 7, crystalline graphite powder and mixing
The mass ratio of liquid is 1: 100, and 1~6h is stirred under the conditions of temperature is 5~25 DEG C, removes upper layer black object and filters, obtains crude
Graphene oxide；
7) crude oxidation graphene prepared by step 6) purification of graphite oxide alkene: is obtained into graphite oxide after washing and drying
Alkene；
8) prereduction suspension is prepared: by graphene oxide, reducing agent and the water of step 7) preparation according to mass ratio 15~30: 5
~15: 55~80 are added to 5~20min of vibrating dispersion in ultrasonic container, and prereduction suspension is made；
9) prepare crude graphene: prereduction uniform suspension be applied on substrate, with infrared laser to substrate illumination 15~
60min, the graphene on substrate is up to crude graphene；
10) reducing agent purifying graphene is removed: by crude graphene to get graphene after washing and drying；
The foaming agent is polyoxyethylene sorbitan fatty acid ester, neopelex, sorbitol anhydride monostearate
One or more of rouge, azodicarbonamide, pine-tree oil and unifor；
The reducing agent is one or more of vitamin C, sodium borohydride and ethyl alcohol；
The substrate is one or more of polytetrafluoroethylene (PTFE), silicon wafer and Kynoar.
2. the method for preparing graphene using crystalline flake graphite as described in claim 1, it is characterised in that: squama described in step 1)
The grade of piece graphite is 15~25%.
3. the method for preparing graphene using crystalline flake graphite as described in claim 1, it is characterised in that: the step 2) level-one
Milling material is ball milling steel ball in ball milling roller；Milling material is ball milling rod iron in second level ball mill.
4. the method for preparing graphene using crystalline flake graphite as described in claim 1, it is characterised in that: risen described in step 3)
Infusion is the composition of polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3: 1；Ball milling slurry and blistering
Agent is according to mass ratio 1000: 0.03；70 DEG C of reaction temperature, reaction time 7h.
5. the method for preparing graphene using crystalline flake graphite as described in claim 1, it is characterised in that: the step 4) flotation
It is 5 times.
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| CN104961123A (en) * | 2015-06-18 | 2015-10-07 | 湖南大学 | Natural graphite ore stripping and purifying method |
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