CN106976871A - A kind of method that utilization crystalline flake graphite prepares graphene - Google Patents
A kind of method that utilization crystalline flake graphite prepares graphene Download PDFInfo
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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
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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 method that utilization crystalline flake graphite prepares graphene, by crystalline flake graphite after ball milling, flotation, oxidation, reduction and drying, graphene is produced.The present invention, which prepares graphene, has purity high, the characteristics of specific surface area is greatly and the number of plies is few.
Description
Technical field
The present invention relates to a kind of method that utilization crystalline flake graphite prepares graphene.
Background technology
Crystalline flake graphite graphite crystal is in flakey；This is gone bad under the pressure of high intensity, has big scale and thin
Point of scale.The characteristics of crystalline flake graphite ore is that grade is not high, typically between 2~3% or 10~25%.Crystalline flake graphite is certainly
One of best ore of floatability in right boundary, high grade graphite concentrate can be obtained through excessive mill multiselect.Floatability, the profit of this kind of graphite
Slip, plasticity are more superior than other types graphite, therefore its industrial value is maximum.
《The research of crystalline flake graphite floatation process》Described in willow hair graphite common floatation process with once corase grind, six times again
Mill, eight times it is selected, then add one roughing once purging selection, chats returns step by step, the tediously long complexity of flow.
Crystalline flake graphite ore deposit is low due to grade, and purifying cost is high, is unfavorable for producing in enormous quantities.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of method that utilization crystalline flake graphite prepares graphene, this hair
The graphene purity of bright preparation is high, and specific surface area is big, and the number of plies is few.
In order to solve the above-mentioned technical problem, present invention employs following technical scheme：
A kind of method that utilization crystalline flake graphite prepares graphene, it is characterised in that follow the steps below：
1) slightly broken crystalline flake graphite ore deposit is prepared：Crystalline flake graphite ore deposit is added in disintegrating machine, it is thick broken, obtain slightly breaking crystalline flake graphite
Ore deposit；
2) ball milling slurry is prepared：To slightly break crystalline flake graphite ore deposit, 5040 dispersants and water according to mass ratio 40~60: 0.1~
0.5: 40~60 are added in one-level ball milling roller, are milled to 40~60 mesh and produce a slurry, a slurry is added into two
Level ball mill, is milled to 80~120 mesh, produces ball milling slurry；
3) crystalline flake graphite A and flotation slurry A are prepared：By step 2) prepare ball milling slurry 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, and flotation step is：
Flotation slurry A is squeezed into two grades of ball mill ball millings 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) crystalline graphite powder is prepared：By step 3) the crystalline flake graphite A for preparing and step 4) crystalline flake graphite for preparing merges dry
After dry, crystalline graphite powder is obtained；
6) organics removal and crude oxidation graphene is prepared：By step 5) prepare crystalline graphite powder be added to mass parts
In mixed liquor of the dilute sulfuric acid that the dust technology and mass fraction that number is 30% are 75% according to mass ratio 3: 7, 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 strata black thing and simultaneously filters, obtains
Crude oxidation graphene；
7) purification of graphite oxide alkene：By step 6) prepare crude oxidation graphene obtained after washing and drying aoxidize stone
Black alkene；
8) prereduction suspension is prepared：By step 7) prepare 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) rough graphene is prepared：Prereduction uniform suspension is applied on substrate, with infrared laser to substrate illumination
Graphene on 15~60min, substrate produces rough graphene；
10) reducing agent purifying graphene is removed：By rough graphene after washing and drying, graphene is produced；
The foaming agent is that polyoxyethylene sorbitan fatty acid ester, the basic sodium sulfonate of dodecane, sorbitol anhydride list are hard
One or more in resin acid fat, azodicarbonamide, pine-tree oil and unifor；
The reducing agent is the one or more in vitamin C, sodium borohydride and ethanol；
The substrate is the one or more in polytetrafluoroethylene (PTFE), silicon chip and Kynoar.
On the basis of above-mentioned technical proposal, the present invention can also do following improvement：
Further, step 1) described in the grade of crystalline flake graphite be 15~25%.
Further, step 2) milling material is ball milling steel ball in the one-level ball mill；Milling material in two grades of ball mills
It is ball milling rod iron.
Further, step 3) described in foaming agent be 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, step 4) flotation be 5 times.
The present invention has following advantageous effects：
1), because the specific surface area of graphite is big, secondary flocculation is readily formed in mechanical milling process, the present invention is by adding
5040 dispersants, can prevent graphene from flocculating, and reduce ball milling number of times, save the energy.
2), ball milling effect is good, but easily causes crystalline flake graphite and lost in grinding, and rod milling grinding effect is poor, but not
Easily 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 selection foaming agent is critically important, and foaming agent foaming is big then easily by other ore deposits
Thing 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 fat
Fat acid esters and pine-tree oil are according to 3: 1 composition, and foaming is fine and smooth, 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 is handled by the mixed liquor of dust technology and dilute sulfuric acid, while crystalline flake graphite is aoxidized, also aoxidizes squama
The organic matter taken out of during piece graphite flotation, while also dissolving some metal impurities；Be conducive to removing by washing, reach purifying
The purpose of graphene.
5), the present invention is by 5 flotation, and 3 edulcoration purifications, the graphene purity of production meets graphene up to 99.2
Battery request.
Embodiment
The present invention is further illustrated with reference to instantiation.
Embodiment one
1) slightly broken crystalline flake graphite ore deposit is prepared：Crystalline flake graphite ore deposit is added in disintegrating machine, it is thick broken, obtain slightly breaking crystalline flake graphite
Ore deposit；
2) ball milling slurry is prepared：Crystalline flake graphite ore deposit, 5040 dispersants and water will be slightly broken according to mass ratio 45: 0.2: 54.8 to add
Enter into one-level ball milling roller, be milled to 40~60 mesh and produce a slurry, a slurry is added to two grades of ball mills, ball milling
To 80~120 mesh, ball milling slurry is produced；
3) crystalline flake graphite A and flotation slurry A are prepared：By step 2) prepare ball milling slurry 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
Composition of the amount than 3: 1, the 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 is：
Flotation slurry A is squeezed into two grades of ball mill ball millings 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, the flotation 6h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite B and flotation slurry B floatingly selected；
Flotation slurry B is squeezed into two grades of ball mill ball millings 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, the flotation 5h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite C and flotation slurry C floatingly selected；
Flotation slurry C is squeezed into two grades of ball mill ball millings 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, the flotation 4h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite D and flotation slurry D floatingly selected；
Flotation slurry D is squeezed into two grades of ball mill ball millings 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, the flotation 3h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite E and flotation slurry E floatingly selected；
Flotation slurry E is squeezed into two grades of ball mill ball millings 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, the flotation 2h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite H and flotation slurry H floatingly selected；
5) crystalline graphite powder is prepared：By step 3) prepare crystalline flake graphite A and step 4) prepare crystalline flake graphite B to H close
And after drying, obtain crystalline graphite powder；
6) organics removal and crude oxidation graphene is prepared：By step 5) prepare crystalline graphite powder be added to mass parts
In mixed liquor of the dilute sulfuric acid that the dust technology and mass fraction that number is 30% are 75% according to mass ratio 3: 7, 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 strata black thing and simultaneously filters, obtains rough oxygen
Graphite alkene；
7) purification of graphite oxide alkene：By step 6) prepare crude oxidation graphene obtained after washing and drying aoxidize stone
Black alkene；
8) prereduction suspension is prepared：By step 7) prepare graphene oxide, reducing agent and water according to mass ratio 20: 7:
73 are added to vibrating dispersion 10min in ultrasonic container, and prereduction suspension is made；
9) rough graphene is prepared：Prereduction uniform suspension is applied on substrate, with infrared laser to substrate illumination
Graphene on 40min, substrate produces rough graphene；
10) reducing agent purifying graphene is removed：By rough graphene after washing and drying, graphene is produced.
Embodiment two
1) slightly broken crystalline flake graphite ore deposit is prepared：Crystalline flake graphite ore deposit is added in disintegrating machine, it is thick broken, obtain slightly breaking crystalline flake graphite
Ore deposit；
2) ball milling slurry is prepared：Crystalline flake graphite ore deposit, 5040 dispersants and water will be slightly broken according to mass ratio 45: 0.2: 54.8 to add
Enter into one-level ball milling roller, be milled to 40~60 mesh and produce a slurry, a slurry is added to two grades of ball mills, ball milling
To 80~120 mesh, ball milling slurry is produced；
3) crystalline flake graphite A and flotation slurry A are prepared：By step 2) prepare ball milling slurry 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
Composition of the amount than 3: 1, the 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 is：
Flotation slurry A is squeezed into two grades of ball mill ball millings 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, the flotation 6h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite B and flotation slurry B floatingly selected；
Flotation slurry B is squeezed into two grades of ball mill ball millings 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, the flotation 5h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite C and flotation slurry C floatingly selected；
Flotation slurry C is squeezed into two grades of ball mill ball millings 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, the flotation 4h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite D and flotation slurry D floatingly selected；
5) crystalline graphite powder is prepared：By step 3) prepare crystalline flake graphite A and step 4) prepare crystalline flake graphite B to D close
And after drying, obtain crystalline graphite powder；
6) organics removal and crude oxidation graphene is prepared：By step 5) prepare crystalline graphite powder be added to mass parts
In mixed liquor of the dilute sulfuric acid that the dust technology and mass fraction that number is 30% are 75% according to mass ratio 3: 7, 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 strata black thing and simultaneously filters, obtains rough oxygen
Graphite alkene；
7) purification of graphite oxide alkene：By step 6) prepare crude oxidation graphene obtained after washing and drying aoxidize stone
Black alkene；
8) prereduction suspension is prepared：By step 7) prepare graphene oxide, reducing agent and water according to mass ratio 20: 7:
73 are added to vibrating dispersion l0min in ultrasonic container, and prereduction suspension is made；
9) rough graphene is prepared：Prereduction uniform suspension is applied on substrate, with infrared laser to substrate illumination
Graphene on 40min, substrate produces rough graphene；
10) reducing agent purifying graphene is removed：By rough graphene after washing and drying, graphene is produced.
Embodiment three
1) slightly broken crystalline flake graphite ore deposit is prepared：Crystalline flake graphite ore deposit is added in disintegrating machine, it is thick broken, obtain slightly breaking crystalline flake graphite
Ore deposit；
2) ball milling slurry is prepared：Crystalline flake graphite ore deposit, 5040 dispersants and water will be slightly broken according to mass ratio 45: 0.2: 54.8 to add
Enter into one-level ball milling roller, be milled to 40~60 mesh and produce a slurry, a slurry is added to two grades of ball mills, ball milling
To 80~120 mesh, ball milling slurry is produced；
3) crystalline flake graphite A and flotation slurry A are prepared：By step 2) prepare ball milling slurry 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
Composition of the amount than 3: 1, the 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 is：
Flotation slurry A is squeezed into two grades of ball mill ball millings 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, the flotation 6h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite B and flotation slurry B floatingly selected；
Flotation slurry B is squeezed into two grades of ball mill ball millings 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, the flotation 5h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite C and flotation slurry C floatingly selected；
Flotation slurry C is squeezed into two grades of ball mill ball millings 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, the flotation 4h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite D and flotation slurry D floatingly selected；
Flotation slurry D is squeezed into two grades of ball mill ball millings 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, the flotation 3h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite E and flotation slurry E floatingly selected；
5) crystalline graphite powder is prepared：By step 3) prepare crystalline flake graphite A and step 4) prepare crystalline flake graphite B to E close
And after drying, obtain crystalline graphite powder；
6) organics removal and crude oxidation graphene is prepared：By step 5) prepare crystalline graphite powder be added to mass parts
In mixed liquor of the dilute sulfuric acid that the dust technology and mass fraction that number is 30% are 75% according to mass ratio 3: 7, 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 strata black thing and simultaneously filters, obtains rough oxygen
Graphite alkene；
7) purification of graphite oxide alkene：By step 6) prepare crude oxidation graphene obtained after washing and drying aoxidize stone
Black alkene；
8) prereduction suspension is prepared：By step 7) prepare graphene oxide, reducing agent and water according to mass ratio 20: 7:
73 are added to vibrating dispersion 10min in ultrasonic container, and prereduction suspension is made；
9) rough graphene is prepared：Prereduction uniform suspension is applied on substrate, with infrared laser to substrate illumination
Graphene on 40min, substrate produces rough graphene；
10) reducing agent purifying graphene is removed：By rough graphene after washing and drying, graphene is produced.
Example IV
1) slightly broken crystalline flake graphite ore deposit is prepared：Crystalline flake graphite ore deposit is added in disintegrating machine, it is thick broken, obtain slightly breaking crystalline flake graphite
Ore deposit；
2) ball milling slurry is prepared：Crystalline flake graphite ore deposit, 5040 dispersants and water will be slightly broken according to mass ratio 45: 0.2: 54.8 to add
Enter into one-level ball milling roller, be milled to 40~60 mesh and produce a slurry, a slurry is added to two grades of ball mills, ball milling
To 80~120 mesh, ball milling slurry is produced；
3) crystalline flake graphite A and flotation slurry A are prepared：By step 2) prepare ball milling slurry 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
Composition of the amount than 3: 1, the 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 is：
Flotation slurry A is squeezed into two grades of ball mill ball millings 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, the flotation 6h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite B and flotation slurry B floatingly selected；
Flotation slurry B is squeezed into two grades of ball mill ball millings 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, the flotation 5h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite C and flotation slurry C floatingly selected；
Flotation slurry C is squeezed into two grades of ball mill ball millings 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, the flotation 4h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite D and flotation slurry D floatingly selected；
Flotation slurry D is squeezed into two grades of ball mill ball millings 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, the flotation 3h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite E and flotation slurry E floatingly selected；
Flotation slurry E is squeezed into two grades of ball mill ball millings 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, the flotation 2h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite H and flotation slurry H floatingly selected；
Flotation slurry H is squeezed into two grades of ball mill ball millings 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, the flotation 1h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite I and flotation slurry I floatingly selected；
5) crystalline graphite powder is prepared：By step 3) prepare crystalline flake graphite A and step 4) prepare crystalline flake graphite B to I close
And after drying, obtain crystalline graphite powder；
6) organics removal and crude oxidation graphene is prepared：By step 5) prepare crystalline graphite powder be added to mass parts
In mixed liquor of the dilute sulfuric acid that the dust technology and mass fraction that number is 30% are 75% according to mass ratio 3: 7, 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 strata black thing and simultaneously filters, obtains rough oxygen
Graphite alkene；
7) purification of graphite oxide alkene：By step 6) prepare crude oxidation graphene obtained after washing and drying aoxidize stone
Black alkene；
8) prereduction suspension is prepared：By step 7) prepare graphene oxide, reducing agent and water according to mass ratio 20: 7:
73 are added to vibrating dispersion 10min in ultrasonic container, and prereduction suspension is made；
9) rough graphene is prepared：Prereduction uniform suspension is applied on substrate, with infrared laser to substrate illumination
Graphene on 40min, substrate produces rough graphene；
10) reducing agent purifying graphene is removed：By rough graphene after washing and drying, graphene is produced.
Embodiment five
1) slightly broken crystalline flake graphite ore deposit is prepared：Crystalline flake graphite ore deposit is added in disintegrating machine, it is thick broken, obtain slightly breaking crystalline flake graphite
Ore deposit；
2) ball milling slurry is prepared：Crystalline flake graphite ore deposit, 5040 dispersants and water will be slightly broken according to mass ratio 45: 0.2: 54.8 to add
Enter into one-level ball milling roller, be milled to 40~60 mesh and produce a slurry, a slurry is added to two grades of ball mills, ball milling
To 80~120 mesh, ball milling slurry is produced；
3) crystalline flake graphite A and flotation slurry A are prepared：By step 2) prepare ball milling slurry 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
Composition of the amount than 3: 1, the 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 is：
Flotation slurry A is squeezed into two grades of ball mill ball millings 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, the flotation 6h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite B and flotation slurry B floatingly selected；
Flotation slurry B is squeezed into two grades of ball mill ball millings 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, the flotation 5h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite C and flotation slurry C floatingly selected；
Flotation slurry C is squeezed into two grades of ball mill ball millings 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, the flotation 4h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite D and flotation slurry D floatingly selected；
Flotation slurry D is squeezed into two grades of ball mill ball millings 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, the flotation 3h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite E and flotation slurry E floatingly selected；
Flotation slurry E is squeezed into two grades of ball mill ball millings 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, the flotation 2h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite H and flotation slurry H floatingly selected；
5) crystalline graphite powder is prepared：By step 3) prepare crystalline flake graphite A and step 4) prepare crystalline flake graphite B to H close
And after drying, obtain crystalline graphite powder；
6) organics removal and crude oxidation graphene is prepared：By step 5) prepare crystalline graphite powder be added to mass parts
In mixed liquor of the dilute sulfuric acid that the dust technology and mass fraction that number is 30% are 75% according to mass ratio 3: 7, 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 strata black thing and simultaneously filters, obtains rough oxygen
Graphite alkene；
7) purification of graphite oxide alkene：By step 6) prepare crude oxidation graphene obtained after washing and drying aoxidize stone
Black alkene；
8) prereduction suspension is prepared：By step 7) prepare graphene oxide, reducing agent and water according to mass ratio 20: 7:
73 are added to vibrating dispersion 10min in ultrasonic container, and prereduction suspension is made；
9) rough graphene is prepared：Prereduction uniform suspension is applied on substrate, with infrared laser to substrate illumination
Graphene on 40min, substrate produces rough graphene；
10) reducing agent purifying graphene is removed：By rough graphene after washing and drying, graphene is produced.
Embodiment 6
1) slightly broken crystalline flake graphite ore deposit is prepared：Crystalline flake graphite ore deposit is added in disintegrating machine, it is thick broken, obtain slightly breaking crystalline flake graphite
Ore deposit；
2) ball milling slurry is prepared：Crystalline flake graphite ore deposit, 5040 dispersants and water will be slightly broken according to mass ratio 45: 0.2: 54.8 to add
Enter into one-level ball milling roller, be milled to 40~60 mesh and produce a slurry, a slurry is added to two grades of ball mills, ball milling
To 80~120 mesh, ball milling slurry is produced；
3) crystalline flake graphite A and flotation slurry A are prepared：By step 2) prepare ball milling slurry 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
Composition of the amount than 3: 1, the 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 is：
Flotation slurry A is squeezed into two grades of ball mill ball millings 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, the flotation 6h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite B and flotation slurry B floatingly selected；
Flotation slurry B is squeezed into two grades of ball mill ball millings 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, the flotation 5h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite C and flotation slurry C floatingly selected；
Flotation slurry C is squeezed into two grades of ball mill ball millings 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, the flotation 4h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite D and flotation slurry D floatingly selected；
Flotation slurry D is squeezed into two grades of ball mill ball millings 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, the flotation 3h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite E and flotation slurry E floatingly selected；
Flotation slurry E is squeezed into two grades of ball mill ball millings 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, the flotation 2h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite H and flotation slurry H floatingly selected；
5) crystalline graphite powder is prepared：By step 3) prepare crystalline flake graphite A and step 4) prepare crystalline flake graphite B to H close
And after drying, obtain crystalline graphite powder；
6) organics removal and crude oxidation graphene is prepared：By step 5) prepare crystalline graphite powder be added to mass parts
In mixed liquor of the dilute sulfuric acid that the dust technology and mass fraction that number is 30% are 75% according to mass ratio 3: 7, 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 strata black thing and simultaneously filters, obtains rough oxygen
Graphite alkene；
7) purification of graphite oxide alkene：By step 6) prepare crude oxidation graphene obtained after washing and drying aoxidize stone
Black alkene；
8) prereduction suspension is prepared：By step 7) prepare graphene oxide, reducing agent and water according to mass ratio 20: 7:
73 are added to vibrating dispersion 10min in ultrasonic container, and prereduction suspension is made；
9) rough graphene is prepared：Prereduction uniform suspension is applied on substrate, with infrared laser to substrate illumination
Graphene on 40min, substrate produces rough graphene；
10) reducing agent purifying graphene is removed：By rough graphene after washing and drying, graphene is produced.
Embodiment 7
1) slightly broken crystalline flake graphite ore deposit is prepared：Crystalline flake graphite ore deposit is added in disintegrating machine, it is thick broken, obtain slightly breaking crystalline flake graphite
Ore deposit；
2) ball milling slurry is prepared：Crystalline flake graphite ore deposit, 5040 dispersants and water will be slightly broken according to mass ratio 45: 0.2: 54.8 to add
Enter into one-level ball milling roller, be milled to 40~60 mesh and produce a slurry, a slurry is added to two grades of ball mills, ball milling
To 80~120 mesh, ball milling slurry is produced；
3) crystalline flake graphite A and flotation slurry A are prepared：By step 2) prepare ball milling slurry 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
Composition of the amount than 3: 1, the 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 is：
Flotation slurry A is squeezed into two grades of ball mill ball millings 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, the flotation 6h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite B and flotation slurry B floatingly selected；
Flotation slurry B is squeezed into two grades of ball mill ball millings 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, the flotation 5h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite C and flotation slurry C floatingly selected；
Flotation slurry C is squeezed into two grades of ball mill ball millings 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, the flotation 4h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite D and flotation slurry D floatingly selected；
Flotation slurry D is squeezed into two grades of ball mill ball millings 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, the flotation 3h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite E and flotation slurry E floatingly selected；
Flotation slurry E is squeezed into two grades of ball mill ball millings 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, the flotation 2h under the conditions of temperature is 70 DEG C, collect the crystalline flake graphite H and flotation slurry H floatingly selected；
5) crystalline graphite powder is prepared：By step 3) prepare crystalline flake graphite A and step 4) prepare crystalline flake graphite B to H close
And after drying, obtain crystalline graphite powder；
6) organics removal and crude oxidation graphene is prepared：By step 5) prepare crystalline graphite powder be added to mass parts
In mixed liquor of the dilute sulfuric acid that the dust technology and mass fraction that number is 30% are 75% according to mass ratio 3: 7, 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 strata black thing and simultaneously filters, obtains rough oxygen
Graphite alkene；
7) purification of graphite oxide alkene：By step 6) prepare crude oxidation graphene obtained after washing and drying aoxidize stone
Black alkene；
8) prereduction suspension is prepared：By step 7) prepare graphene oxide, reducing agent and water according to mass ratio 20: 7:
73 are added to vibrating dispersion 10min in ultrasonic container, and prereduction suspension is made；
9) rough graphene is prepared：Prereduction uniform suspension is applied on substrate, with infrared laser to substrate illumination
Graphene on 40min, substrate produces rough graphene；
10) reducing agent purifying graphene is removed：By rough graphene after washing and drying, graphene is produced.
Embodiment 8
1) slightly broken crystalline flake graphite ore deposit is prepared：Crystalline flake graphite ore deposit is added in disintegrating machine, it is thick broken, obtain slightly breaking crystalline flake graphite
Ore deposit；
2) ball milling slurry is prepared：Crystalline flake graphite ore deposit, 5040 dispersants and water will be slightly broken according to mass ratio 50: 0.3: 49.7 to add
Enter into one-level ball milling roller, be milled to 40~60 mesh and produce a slurry, a slurry is added to two grades of ball mills, ball milling
To 80~120 mesh, ball milling slurry is produced；
3) crystalline flake graphite A and flotation slurry A are prepared：By step 2) prepare ball milling slurry 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 bars in temperature
Flotation 8h under part, obtains crystalline flake graphite A and flotation slurry A；
4) flotation：Flotation 5 times, flotation step is：
Flotation slurry A is squeezed into two grades of ball mill ball millings 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 and flotation slurry B floatingly selected；
Flotation slurry B is squeezed into two grades of ball mill ball millings 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 and flotation slurry C floatingly selected；
Flotation slurry C is squeezed into two grades of ball mill ball millings 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 and flotation slurry D floatingly selected；
Flotation slurry D is squeezed into two grades of ball mill ball millings 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 and flotation slurry E floatingly selected；
Flotation slurry E is squeezed into two grades of ball mill ball millings 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 and flotation slurry H floatingly selected；
5) crystalline graphite powder is prepared：By step 3) prepare crystalline flake graphite A and step 4) prepare crystalline flake graphite B to H close
And after drying, obtain crystalline graphite powder；
6) organics removal and crude oxidation graphene is prepared：By step 5) prepare crystalline graphite powder be added to mass parts
In mixed liquor of the dilute sulfuric acid that the dust technology and mass fraction that number is 30% are 75% according to mass ratio 3: 7, 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 strata black thing and simultaneously filters, obtains rough
Graphene oxide；
7) purification of graphite oxide alkene：By step 6) prepare crude oxidation graphene obtained after washing and drying aoxidize stone
Black alkene；
8) prereduction suspension is prepared：By step 7) prepare graphene oxide, reducing agent and water according to mass ratio 30: 9:
61 are added to vibrating dispersion 10min in ultrasonic container, and prereduction suspension is made；
9) rough graphene is prepared：Prereduction uniform suspension is applied on substrate, with infrared laser to substrate illumination
Graphene on 40min, substrate produces rough graphene；
10) reducing agent purifying graphene is removed：By rough graphene after washing and drying, graphene is produced.
Beneficial effects of the present invention are further illustrated with reference to experimental data：
1st, material to be tested is tested
1 materials and methods：
1.1 material to be tested：The present invention does effect to embodiment 7 with embodiment 1 and compared.
1.2 experimental design：Experiment is divided into 7 groups, and 2 is parallel, prepares graphene according to embodiment 1 to the method for embodiment 7 respectively,
It is 5kg to extract crystalline flake graphite ore deposit used every time.
1.3 testing inspection：The graphene number of plies, graphene specific surface area, graphene yield and organic carbon content, wherein using
AFM (AFM) is determined to the graphene number of plies；Using scientific and technological (Beijing) Co., Ltd production 3H- of Bei Shide instruments
The full-automatic N2 adsorption specific surface instrument of 2000A types determines graphene specific surface area；Gravimetric method weighs graphene yield；Potassium bichromate holds
Amount method detects organic carbon.
Organic carbon Method And Principle
With quantitative potassium bichromate-sulfuric acid solution, in a heated condition, make to have organic oxidation of coal in graphene, it is unnecessary
Potassium bichromate with ferrous sulfate standard liquid titrate, while making blank test by additive of silica.Before oxidation
Rear oxidation agent consumption, 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 the 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 is to embodiment 4 as can be seen from Table 1, in addition to flotation number of times is different, and other operations are consistent, float
The yield of the embodiment 2 of three times and the embodiment 3 of flotation four times and the yield of embodiment 1 difference of flotation five times are selected than larger, and
Less, other index difference less, illustrate embodiment 2 for embodiment 4 that flotation is six times and the embodiment l yield difference of flotation five times
With the flotation of embodiment 3 not exclusively, although the slightly above embodiment l of embodiment 4, ball milling of increase and flotation, production cost
Increase is a lot, therefore embodiment l resultant effects are optimal.
Embodiment 1, embodiment 5, embodiment 6 and embodiment 7 as can be seen from Table 1, except flotation slurry and foaming agent add
Enter ratio different outer, other operations are consistent, and embodiment 5 is compared in addition to yielding poorly with embodiment 1, and other index difference are not
Greatly, illustrate that the flotation of embodiment 5 is incomplete；Embodiment 6 and the yield of embodiment 7 are apparently higher than embodiment 1, but the graphene number of plies, ratio
Surface area and organic carbon content differ greatly, and illustrate that embodiment 6 and the flotation of embodiment 7 introduce the slag insoluble in acid, comprehensive
The technical scheme of comparing embodiment 1 is optimal.
2 technical schemes of comparative descriptions embodiment 1 are optimal more than, i.e. flotation five times, and foaming agent is polyoxyethylene sorbitan
Span and pine-tree oil are according to the composition of mass ratio 3: 1, and the mass ratio of flotation slurry and foaming agent is 1000:
0.03。
Claims (5)
1. a kind of method that utilization crystalline flake graphite prepares graphene, it is characterised in that follow the steps below：
1) slightly broken crystalline flake graphite ore deposit is prepared：Crystalline flake graphite ore deposit is added in disintegrating machine, it is thick broken, obtain slightly breaking crystalline flake graphite ore deposit；
2) ball milling slurry is prepared：Crystalline flake graphite ore deposit, 5040 dispersants and water will slightly be broken according to mass ratio 40~60: 0.1~0.5:
40~60 are added in one-level ball milling roller, are milled to 40~60 mesh and produce a slurry, a slurry is added into two grades of balls
Grinding machine, is milled to 80~120 mesh, produces ball milling slurry；
3) crystalline flake graphite A and flotation slurry A are prepared：By step 2) prepare ball milling slurry and foaming agent according to mass ratio 1000:
0.02~0.05 is added in flotation device, 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, and flotation step is：
Flotation slurry A is squeezed into two grades of ball mill ball millings 5~20 minutes, by flotation slurry A and foaming agent according to mass ratio 1000:
0.02~0.05 is added in flotation device, 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：By step 3) prepare crystalline flake graphite A and step 4) prepare crystalline flake graphite merge dry after,
Obtain crystalline graphite powder；
6) organics removal and crude oxidation graphene is prepared：By step 5) crystalline graphite powder for preparing is added to mass fraction and 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 strata black thing and simultaneously filters, obtains rough
Graphene oxide；
7) purification of graphite oxide alkene：By step 6) prepare crude oxidation graphene obtain graphite oxide after washing and drying
Alkene；
8) prereduction suspension is prepared：By step 7) prepare 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) rough graphene is prepared：Prereduction uniform suspension is applied on substrate, with infrared laser to substrate illumination 15~
Graphene on 60min, substrate produces rough graphene；
10) reducing agent purifying graphene is removed：By rough graphene after washing and drying, graphene is produced；
The foaming agent is polyoxyethylene sorbitan fatty acid ester, the basic sodium sulfonate of dodecane, sorbitol anhydride monostearate
One or more in fat, azodicarbonamide, pine-tree oil and unifor；
The reducing agent is the one or more in vitamin C, sodium borohydride and ethanol；
The substrate is the one or more in polytetrafluoroethylene (PTFE), silicon chip and Kynoar.
2. the method for preparing graphene using crystalline flake graphite as claimed in claim 1, it is characterised in that：Step 1) described in squama
The grade of piece graphite is 15~25%.
3. the method for preparing graphene using crystalline flake graphite as claimed in claim 1, it is characterised in that：Step 2) one-level
Milling material is ball milling steel ball in ball mill；Milling material is ball milling rod iron in two grades of ball mills.
4. the method for preparing graphene using crystalline flake graphite as claimed in claim 1, it is characterised in that：Step 3) described in rise
Infusion is the composition of polyoxyethylene sorbitan fatty acid ester and pine-tree oil according to mass ratio 3: 1；Ball milling slurry and foaming
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 claimed in claim 1, it is characterised in that：Step 4) flotation
For 5 times.
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| GB2568499A (en) * | 2017-11-17 | 2019-05-22 | Graphene Star Ltd | Improvements in or relating to organic material |
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| CN104003382A (en) * | 2014-06-17 | 2014-08-27 | 鸡西市同泰石墨制品有限公司 | Method for chemically purifying and continuously producing high-purity graphite |
| CN104961123A (en) * | 2015-06-18 | 2015-10-07 | 湖南大学 | Natural graphite ore stripping and purifying method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104003382A (en) * | 2014-06-17 | 2014-08-27 | 鸡西市同泰石墨制品有限公司 | Method for chemically purifying and continuously producing high-purity graphite |
| CN104961123A (en) * | 2015-06-18 | 2015-10-07 | 湖南大学 | Natural graphite ore stripping and purifying method |
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| CN107445151A (en) * | 2017-09-07 | 2017-12-08 | 南京汉尔斯生物科技有限公司 | Graphene, Graphene electrodes and preparation method thereof |
| GB2568499A (en) * | 2017-11-17 | 2019-05-22 | Graphene Star Ltd | Improvements in or relating to organic material |
| GB2568499B (en) * | 2017-11-17 | 2019-12-18 | Graphene Star Ltd | A method for producing graphene |
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