CN106082190A - Graphene/carbon black composite granule Low Temperature Thermal expands ball-milling preparation method - Google Patents
Graphene/carbon black composite granule Low Temperature Thermal expands ball-milling preparation method Download PDFInfo
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- CN106082190A CN106082190A CN201610412097.6A CN201610412097A CN106082190A CN 106082190 A CN106082190 A CN 106082190A CN 201610412097 A CN201610412097 A CN 201610412097A CN 106082190 A CN106082190 A CN 106082190A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
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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
- C01B2204/32—Size or surface area
Abstract
The invention discloses graphene/carbon black composite granule Low Temperature Thermal expand ball-milling preparation method: 1) in ice-water bath, in concentrated sulphuric acid, graphite powder, sodium nitrate and potassium permanganate it is sequentially added under stirring condition, control reaction temperature and mixing time, add deionized water, heat and continue stirring, adding hydrogen peroxide makes solution become glassy yellow, filtered while hot, with HCl solution and deionized water wash until sulfate radical-free in filtrate；Filter cake is the driest；2) graphite oxide adds deionized water, ultrasonic in being placed in ultrasonic washing unit, configure graphene oxide solution；Conductive carbon powder is put into drying in oven, and the conductive carbon powder of drying joins in graphene oxide solution, ultrasonic disperse in ultrasonic washing unit, stirring, obtains graphene oxide/carbon black mixing dispersion soln, centrifugal, and washing is dried to powder；3) graphene oxide/carbon black mixed-powder, expands redox graphene through Low Temperature Thermal, prepares reduced graphene/carbon black mixt, mixture is placed in spheroidal graphite in ball mill, prepares the black powder body of high conductivity graphene/carbon.
Description
Technical field
The invention belongs to Graphene and electrochemical energy storage technical field, relate to a kind of graphene powder technology of preparing, specifically
It it is a kind of graphene/carbon black composite granule Low Temperature Thermal expansion-ball-milling preparation method.
Background technology
Graphene is a kind of SP that the mankind find in recent years22 dimension materials of hydridization, the thickness of single-layer graphene is
0.335nm, for material the thinnest, the hardest in known materials.Electronics transfer rate reaches the 1/300 of the light velocity.Unique performance
Lithium ion battery, ultracapacitor, solaode, medicine, desalinization, conductive fiber, conduction are widely used in it
The fields such as plastics, nano generator and photon sensor.
Application for a patent for invention number 201010273989.5 discloses the ultra-low temperature thermal expansion of a kind of graphene with high specific surface
Preparation method, they are under the conditions of 80 150 DEG C, graphite oxide generation volumetric expansion, and graphene oxide, concurrent heat are prepared in stripping
Reduction, is prepared for having graphene with high specific surface, and specific surface reaches 300 1200m2/g.Application for a patent for invention number
201210483568.4 disclose a kind of Graphene/carbon black composite material and preparation method and application, it in the solution will oxidation
Graphene is mixed homogeneously with white carbon black, obtains graphene oxide/white carbon black complex, under hot conditions, thermal reduction graphene oxide system
For going out Graphene/carbon black composite material.But preparation temperature is higher, temperature, at 700 900 DEG C, adds preparation of industrialization cost.
Though above-mentioned two technical schemes have respective advantage, but there is the defects such as complex process in both of which.
Summary of the invention
For solving the problems referred to above that prior art exists, the invention provides that a kind of preparation temperature is low, technique simply, easily grasp
The graphene/carbon black composite granule Low Temperature Thermal expansion-ball-milling preparation method made.
It is as follows that the present invention solves the technical scheme that its technical problem taked: graphene/carbon black composite granule Low Temperature Thermal is swollen
Swollen-ball-milling preparation method: utilize Low Temperature Thermal expanding method, prepares reduced graphene/carbon black complex, is utilizing ball-milling technology,
Obtain Graphene and the carbon black composite granule of uniform particle sizes, comprise the steps:
(1) preparation of graphite oxide
In ice-water bath, in concentrated sulphuric acid, under stirring, it is sequentially added into graphite powder, sodium nitrate and potassium permanganate, controls reaction temperature
Degree is 0～20 DEG C, is warmed up to 35 DEG C after reaction 0～60min, continues stirring 30min, is slowly added to deionized water, then heats
Continue stirring 30min to 70～90 DEG C, add hydrogen peroxide and make solution become glassy yellow, filtered while hot, and with 5% (wt.%)
HCl solution and deionized water wash until filtrate in sulfate radical-free be detected, finally by the filter cake (thing after filtration
Matter) the driest, save backup；
(2) preparation of graphene oxide/Carbon Black Composites
Deionized water is added in graphite oxide prepared by step (1), ultrasonic in sound wave cleaning machine, configure graphene oxide
Solution；Conductive carbon powder is put into drying in oven；The conductive carbon powder dried joins in graphene oxide solution, ultrasonic disperse half
Hour, mechanical agitation, obtain graphene oxide/carbon black mixing dispersion soln, centrifugal, washing, it is dried to powder, saves backup.
(3) preparation of the black composite granule of graphene/carbon
Method one: graphene oxide prepared by step (2)/carbon black mixed powder, is positioned in vacuum drying oven, evacuation
Under state, control reaction temperature, response time, thermal expansion redox graphene, prepare reduced graphene/carbon black composite wood
Material.Spheroidal graphite in ball mill, prepares the black composite granule of nano level graphene/carbon.
Method two: graphene oxide prepared by step (2)/carbon black mixed-powder, is positioned over the baking oven of inert gas shielding
In, control reaction temperature, response time, thermal expansion redox graphene, prepare reduced graphene/Carbon Black Composites.Ball
Spheroidal graphite in grinding machine, prepares the black composite granule of nano level graphene/carbon.
In step (1), ice-water bath temperature is 0～5 DEG C, graphite powder (C powder), sodium nitrate (NaNO2) and potassium permanganate
(KMnO4) mass ratio be 2:1:6, the solid-to-liquid ratio of graphite powder and concentrated sulphuric acid is 3g:23mL～1g:23mL, graphite powder with go from
The solid-to-liquid ratio of sub-water is 3g:110mL～1g:110mL.
In step (2), time prepared by graphene oxide, ultrasonic power is 0～150W, graphite oxide concentration be 0～
100mg/mL, ultrasonic washing unit water temperature is less than 10 DEG C.
In step (2), baking oven is vacuum drying oven, vacuum 0～1000Pa, dries temperature 30～80 DEG C, drying time 0～
24h.Graphite oxide is 0～100mg/mL:0～100mg/mL with the mass ratio of carbon black.When graphene oxide mixes with carbon black, super
Acoustic power is 0～150W, ultrasonic washing unit water temperature 0～10 DEG C.
In step (2), centrifugal, washing times 1～3 times, drying mode is vacuum drying or lyophilization, drying time 0
～24h.
In step (3) method one, vacuum drying oven vacuum 0～1000Pa, expansion temperature 120～220 DEG C, Bulking Time 0
～2h.
In step (3) method two, noble gas is nitrogen (N2), argon (Ar2) or gaseous mixture in one, air velocity 0
～800mL/min, vacuum drying oven vacuum 0～1000Pa, expansion temperature 120～220 DEG C, Bulking Time 0～2h.
In step (3), Ball-milling Time 0～24h, drum's speed of rotation 0～1000r/min.
The medicine have the advantages that
(1), in carbon black granules is dispersed in graphene oxide lamella in the present invention, increases the spacing of lamella, cause limellar stripping
Required energy reduces, it is easy to the stripping of graphite flake layer.Use Low Temperature Thermal expanding method redox graphene, preparation reduction
The black complex of graphene/carbon.
(2) utilize ball-milling technology, black for the graphene/carbon of multilamellar complex is carried out mechanical stripping, obtains uniform particle sizes, layer
The number black composite granule of less graphene/carbon, powder body conductivity is high.Compared with high-temperature heat expansion method, the present invention prepares graphite
The temperature of alkene/carbon black composite granule is low, and safety is higher, uniform particle sizes.
(3) preparation flow of the present invention is simple, less energy consumption, and technological operation is simple, it is simple to industrialized production.
(4) present invention uses the black composite granule of graphene/carbon prepared by Low Temperature Thermal expanding method-ball-milling technology, has stone
The ink conductivity of alkene conductive network high, two-dimentional own, carbon black high conductivity characteristic own can be applicable to lithium ion battery, super capacitor
The field such as device, electromagnetic shielding, intelligence wearing, militay space flight material.
Accompanying drawing explanation
Fig. 1 is the flow chart that graphene oxide/carbon black mixt prepares the black complex of graphene/carbon.
Detailed description of the invention
In order to ensure principle, technological innovation means that the present invention had, create novel characteristics, to realize purpose easy with effect
In grasp, below in conjunction with particularly relevant case study on implementation, present invention is expanded on further.
Embodiment 1
(1) prepared by graphene oxide
Reaction temperature is 0～5 DEG C, in 23mL concentrated sulphuric acid, is sequentially added into 1g graphite powder, 0.5g sodium nitrate and 3g permanganic acid
Potassium, mixed solution magnetic agitation 0～60min；It is warmed up to 35 DEG C, continues stirring 30min, be slowly added to 110mL deionized water；Add
Heat, to 90 DEG C, is kept stirring for 30min, adds 18mL hydrogen peroxide, filtered while hot；And with 5%HCl solution and deionized water wash
Until sulfate radical-free is detected, finally by filtration cakes torrefaction in filtrate；
(2) preparation of graphene oxide/Carbon Black Composites
Dose volume 100mL, the graphene oxide solution of mass fraction 1%, ultrasonic agitation 30min, magnetic agitation condition
Under, it is slowly added to 1g carbon black (drying) powder；Continuously stirred 30min；Centrifugal, washing, vacuum oven 12h, obtain oxygen
Functionalized graphene/Carbon Black Composites powder；
(3) preparation of the black composite granule of graphene/carbon
Take 100mg graphene oxide/carbon black mixed powder, be positioned in vacuum drying oven, vacuum 1000Pa, expansion temperature
It is 120 DEG C, Bulking Time 30min；Spheroidal graphite 12h in ball mill, rotating speed 600r/min, prepare nano level graphene/carbon black multiple
Close powder body.
Embodiment 2
(1) prepared by graphene oxide
Reaction temperature is 0～5 DEG C, in 23mL concentrated sulphuric acid, is sequentially added into 1g graphite powder, 0.5g sodium nitrate and 3g permanganic acid
Potassium, mixed solution magnetic agitation 0～60min；It is warmed up to 35 DEG C, continues stirring 30min, be slowly added to 110mL deionized water；Add
Heat, to 90 DEG C, is kept stirring for 30min, adds 18mL hydrogen peroxide, filtered while hot；And with 5%HCl solution and deionized water wash
Until sulfate radical-free is detected, finally by filtration cakes torrefaction in filtrate；
(2) preparation of graphene oxide/Carbon Black Composites
Dose volume 100mL, the graphene oxide solution of mass fraction 0.5%, ultrasonic agitation 30min, magnetic agitation bar
Under part, it is slowly added to 1g carbon black (drying) powder；Continuously stirred 30min；Centrifugal, washing, vacuum oven 24h, obtain
Graphene oxide/Carbon Black Composites powder；
(3) preparation of the black composite granule of graphene/carbon
Take 100mg graphene oxide/carbon black mixed powder, be positioned in vacuum drying oven, vacuum 1000Pa, expansion temperature
It is 120 DEG C, Bulking Time 30min；Spheroidal graphite 12h in ball mill, rotating speed 600r/min, prepare nano level graphene/carbon black multiple
Close powder body.
Embodiment 3
(1) prepared by graphene oxide
Reaction temperature is 0～5 DEG C, in 23mL concentrated sulphuric acid, is sequentially added into 1g graphite powder, 0.5g sodium nitrate and 3g permanganic acid
Potassium, mixed solution magnetic agitation 0～60min；It is warmed up to 35 DEG C, continues stirring 30min, be slowly added to 110mL deionized water；Add
Heat, to 90 DEG C, is kept stirring for 30min, adds 18mL hydrogen peroxide, filtered while hot；And with 5%HCl solution and deionized water wash
Until sulfate radical-free is detected, finally by filtration cakes torrefaction in filtrate；
(2) preparation of graphene oxide/Carbon Black Composites
Dose volume 100mL, the graphene oxide solution of mass fraction 1%, ultrasonic agitation 30min, magnetic agitation condition
Under, it is slowly added to 1g carbon black (drying) powder；Continuously stirred 30min；Centrifugal, washing, it is dried 12h in freezing baking oven, obtains oxygen
Functionalized graphene/Carbon Black Composites powder；
(3) preparation of the black composite granule of graphene/carbon
Take 100mg graphene oxide/carbon black mixed powder, be positioned in vacuum drying oven, vacuum 1000Pa, expansion temperature
It is 120 DEG C, Bulking Time 30min；Spheroidal graphite 12h in ball mill, rotating speed 600r/min, prepare nano level graphene/carbon black multiple
Close powder body.
Embodiment 4
(1) prepared by graphene oxide
Reaction temperature is 0～5 DEG C, in 23mL concentrated sulphuric acid, is sequentially added into 1g graphite powder, 0.5g sodium nitrate and 3g permanganic acid
Potassium, mixed solution magnetic agitation 0～60min；It is warmed up to 35 DEG C, continues stirring 30min, be slowly added to 110mL deionized water；Add
Heat, to 90 DEG C, is kept stirring for 30min, adds 18mL hydrogen peroxide, filtered while hot；And with 5%HCl solution and deionized water wash
Until sulfate radical-free is detected, finally by filtration cakes torrefaction in filtrate；
(2) preparation of graphene oxide/Carbon Black Composites
Dose volume 100mL, the graphene oxide solution of mass fraction 1%, ultrasonic agitation 30min, magnetic agitation condition
Under, it is slowly added to 1g white carbon black (drying) powder；Continuously stirred 30min；Centrifugal, washing, vacuum oven 12h, obtain oxygen
Functionalized graphene/Carbon Black Composites powder；
(3) preparation of the black composite granule of graphene/carbon
100mg graphene oxide/white carbon black mixed powder, is positioned in tube furnace, is passed through argon (Ar2) protection, gas velocity
Degree 400mL/min, expansion temperature is 220 DEG C, Bulking Time 5min；Spheroidal graphite 12h in ball mill, rotating speed 600r/min, preparation is received
The black composite granule of graphene/carbon of meter level.
Embodiment 5
(1) prepared by graphene oxide
Reaction temperature is 0～5 DEG C, in 23mL concentrated sulphuric acid, is sequentially added into 1g graphite powder, 0.5g sodium nitrate and 3g permanganic acid
Potassium, mixed solution magnetic agitation 0～60min；It is warmed up to 35 DEG C, continues stirring 30min, be slowly added to 110mL deionized water；Add
Heat, to 90 DEG C, is kept stirring for 30min, adds 18mL hydrogen peroxide, filtered while hot；And with 5%HCl solution and deionized water wash
Until sulfate radical-free is detected, finally by filtration cakes torrefaction in filtrate；
(2) preparation of graphene oxide/Carbon Black Composites
Dose volume 100mL, the graphene oxide solution of mass fraction 1%, ultrasonic agitation 30min, magnetic agitation condition
Under, it is slowly added to 1g white carbon black (drying) powder；Continuously stirred 30min；Centrifugal, washing, vacuum oven 12h, obtain oxygen
Functionalized graphene/Carbon Black Composites powder；
(3) preparation of the black composite granule of graphene/carbon
100mg graphene oxide/carbon black mixed powder, is positioned in tube furnace, is passed through argon (Ar2) protection, gas velocity
Degree 400mL/min, expansion temperature is 200 DEG C, Bulking Time 5min；Spheroidal graphite 12h in ball mill, rotating speed 800r/min, preparation is received
The black composite granule of graphene/carbon of meter level.
Embodiment 6
(1) prepared by graphene oxide
Reaction temperature is 0～5 DEG C, in 23mL concentrated sulphuric acid, is sequentially added into 1g graphite powder, 0.5g sodium nitrate and 3g permanganic acid
Potassium, mixed solution magnetic agitation 0～60min；It is warmed up to 35 DEG C, continues stirring 30min, be slowly added to 110mL deionized water；Add
Heat, to 90 DEG C, is kept stirring for 30min, adds 18mL hydrogen peroxide, filtered while hot；And with 5%HCl solution and deionized water wash
Until sulfate radical-free is detected, finally by filtration cakes torrefaction in filtrate；
(2) preparation of graphene oxide/Carbon Black Composites
Dose volume 100mL, the graphene oxide solution of mass fraction 0.5%, ultrasonic agitation 30min, magnetic agitation bar
Under part, it is slowly added to 1g carbon black (drying) powder；Continuously stirred 30min；Centrifugal, washing, vacuum oven 24h, obtain
Graphene oxide/Carbon Black Composites powder；
(3) preparation of the black composite granule of graphene/carbon
100mg graphene oxide/carbon black mixed powder, is positioned in tube furnace, is passed through argon (Ar2) protection, gas velocity
Degree 400mL/min, expansion temperature is 200 DEG C, Bulking Time 5min；Spheroidal graphite 12h in ball mill, rotating speed 800r/min, preparation is received
The black composite granule of graphene/carbon of meter level.
The uniform particle sizes of the black composite granule of graphene/carbon prepared by above-described embodiment 1-6, electric conductivity are preferable, electrical conductivity
Can reach more than 500S/cm, as lithium ion conducting agent, the specific capacity of battery can be significantly improved.As the coating of aluminium foil, aobvious
Write and reduce battery core dynamic internal resistance amplification, improve the pressure reduction concordance of set of cells, reduce polarization, improve multiplying power and gram volume.
Low Temperature Thermal expansion-the ball-milling preparation method of the black composite granule of graphene/carbon of the present invention, relates to energy storage electrochemical device
The preparation of middle conductive agent.In the present invention, first, solution is sufficiently mixed graphene oxide/carbon black, obtains a certain proportion of mixing
Thing；Again through vacuum drying, lyophilization or spray drying, obtain graphene oxide/carbon black mixed powder；Secondly, 120 250
Under the conditions of DEG C, thermal reduction graphene oxide, prepare reduced graphene/carbon black composite granule；Finally, utilize ball-milling technology, preparation
Uniform particle sizes, electric conductivity height, the black combined conductive agent of graphene/carbon of good dispersion.The conductivity of the black composite granule of graphene/carbon
Up to more than 500S/cm.Low Temperature Thermal expansion-the ball milling of the black composite granule of graphene/carbon that the present invention prepares can be widely applied to
The fields such as lithium ion battery, ultracapacitor, conductive plastics, conductive fiber.
The present invention focuses on preparing the black composite of graphene/carbon by Low Temperature Thermal expansion-ball-milling method, and is applied to lithium ion
The conductive agent of battery and the exploitation of aluminium foil coating.Other downstream application to its material, as ultracapacitor, solaode,
Conductive fiber, anti-corrosion material etc., application on the basis of the present invention is the most within the scope of the present invention.
Present invention illustrates and shows ultimate principle and principal character and advantages of the present invention.The engineering of the industry
Skilled person will appreciate that, the present invention is not restricted to the described embodiments, simply saying described in above-described embodiment and description
The bright principle of the invention, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, these
Changes and improvements both fall within scope of the claimed invention.
Claims (10)
1. graphene/carbon black composite granule Low Temperature Thermal expansion-ball-milling preparation method, its as follows:
1) in ice-water bath, in concentrated sulphuric acid, under stirring condition, it is sequentially added into graphite powder, sodium nitrate and potassium permanganate, controls reaction
Temperature and mixing time, be slowly added to deionized water, heats and continues stirring, add hydrogen peroxide and make solution become glassy yellow,
Filtered while hot, and with HCl solution and deionized water wash until sulfate radical-free in filtrate；It is finally that filter cake is the driest,
Stand-by；
2) step 1) prepare graphite oxide in add deionized water, ultrasonic in being placed in ultrasonic washing unit, configure graphite oxide
Alkene solution；Conductive carbon powder is put into drying in oven, and the conductive carbon powder of drying joins in graphene oxide solution, and ultrasound wave is clear
Ultrasonic disperse in washing machine, stirring, obtain graphene oxide/carbon black mixing dispersion soln, centrifugal, washing, it is dried to powder, standby
With；
3) step 2) prepare graphene oxide/carbon black mixed-powder, through thermal expansion redox graphene, be placed in ball mill
Spheroidal graphite, prepares the black composite granule of graphene/carbon.
2. graphene/carbon black composite granule Low Temperature Thermal expansion-ball-milling preparation method as claimed in claim 1, is characterized in that: step
Rapid 1), controlling reaction temperature is 0～20 DEG C, is warmed up to 35 DEG C after reaction 0～60min, continues stirring 30min；Add deionization
Water post-heating continues stirring 30min to 70～90 DEG C；The concentration of HCl solution is 5%.
3. graphene/carbon black composite granule Low Temperature Thermal expansion-ball-milling preparation method as claimed in claim 1 or 2, its feature
It is: step 1) in, ice-water bath temperature is 0～5 DEG C, and the mass ratio of graphite powder, sodium nitrate and potassium permanganate is 2:1:6, graphite powder
Being 3g:23mL～1g:23mL with the solid-to-liquid ratio of concentrated sulphuric acid, graphite powder is 3g:110mL～1g with the solid-to-liquid ratio of deionized water:
110mL。
Graphene/carbon black composite granule Low Temperature Thermal expansion the most according to claim 1-ball-milling preparation method, it is characterised in that:
Step 2) in, graphite oxide concentration 0～100mg/mL, ultrasonic power is 0～150W, ultrasonic washing unit water temperature 0～10 DEG C.
5., according to the black composite granule Low Temperature Thermal expansion of graphene/carbon described in claim 1 or 4-ball-milling preparation method, its feature exists
In: step 2) in, baking oven is vacuum drying oven, vacuum 0～1000Pa, drying temperature 30～80 DEG C, drying time 0～24h；Oxygen
Graphite is 0～100mg/mL:0～100mg/mL with the mass ratio of carbon black.
6., according to the black composite granule Low Temperature Thermal expansion of graphene/carbon described in claim 1 or 4-ball-milling preparation method, its feature exists
In: step 2) in, centrifugal, washing times 1～3 times, drying mode is vacuum drying or lyophilization, drying time 0～24h.
Graphene/carbon black composite granule Low Temperature Thermal expansion the most according to claim 1-ball-milling preparation method, it is characterised in that:
Step 3) select one of following two method to process:
Method one: step 2) prepare graphene oxide/carbon black mixed-powder, be positioned in vacuum drying oven, the state of evacuation
Under, control reaction temperature, response time, thermal expansion redox graphene；
Method two: step 2) prepare graphene oxide/carbon black mixed-powder, be positioned in the baking oven of inert gas shielding, control
Reaction temperature processed, the response time, thermal expansion redox graphene.
Graphene/carbon black composite granule Low Temperature Thermal expansion the most according to claim 7-ball-milling preparation method, it is characterised in that:
Step 3) in method one, vacuum drying oven vacuum 0～1000Pa, expansion temperature 120～220 DEG C, Bulking Time 0～2h.
Graphene/carbon black composite granule Low Temperature Thermal expansion the most according to claim 7-ball-milling preparation method, it is characterised in that:
Step 3) in method two, noble gas is nitrogen, argon or both gaseous mixtures, air velocity 0～800mL/min, vacuum is dried
Case vacuum 0～1000Pa, expansion temperature 120～220 DEG C, Bulking Time 0～2h.
10. according to the black composite granule Low Temperature Thermal expansion of graphene/carbon described in claim 7 or 9-ball-milling preparation method, its feature
It is: step 3) in method two, Ball-milling Time 0～24h, drum's speed of rotation 0～1000r/min.
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| CN106633169A (en) * | 2016-11-17 | 2017-05-10 | 复旦大学 | Carbon-black-filled polyimide-based compound aerogel material and preparation method thereof |
| CN106853965A (en) * | 2016-12-30 | 2017-06-16 | 绍兴文理学院 | A kind of preparation method of negative material Graphene and electrochemical property test method |
| CN107516740A (en) * | 2017-07-12 | 2017-12-26 | 常州第六元素材料科技股份有限公司 | A kind of carbon ink, graphene powder combined conductive agent and preparation method thereof, application |
| CN107516740B (en) * | 2017-07-12 | 2021-01-19 | 常州第六元素材料科技股份有限公司 | Carbon black and graphene powder composite conductive agent, and preparation method and application thereof |
| CN108899476A (en) * | 2018-07-17 | 2018-11-27 | 大同新成新材料股份有限公司 | A kind of preparation process of the graphene-based composite negative pole material of lithium battery |
| CN108899476B (en) * | 2018-07-17 | 2020-07-28 | 大同新成新材料股份有限公司 | Preparation process of lithium battery graphene-based composite negative electrode material |
| CN111410855A (en) * | 2019-12-31 | 2020-07-14 | 宁波德泰化学有限公司 | Preparation method of high-surface-activity/high-hydrophilicity dispersion type carbon black |
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Application publication date: 20161109 |