CN107651682A - A kind of preparation method of mixed expanded graphite - Google Patents
A kind of preparation method of mixed expanded graphite Download PDFInfo
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- CN107651682A CN107651682A CN201711043082.8A CN201711043082A CN107651682A CN 107651682 A CN107651682 A CN 107651682A CN 201711043082 A CN201711043082 A CN 201711043082A CN 107651682 A CN107651682 A CN 107651682A
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Abstract
The invention discloses a kind of preparation method of mixed expanded graphite material, using micro crystal graphite and crystalline flake graphite as raw material, carry out ball milling, then ball milling mixing material is placed in Muffle furnace calcining and activating under an inert atmosphere, then the compound after activation is subjected to chemical graft processing, obtains inflatable admixed graphite；Inflatable admixed graphite is put into graphite expansion stove and expanded at 800 ~ 900 DEG C, obtains micro- swollen graphite material.Micro- swollen graphite material produced by the present invention is mingled with the structure of cotton-shaped micro crystal graphite between crystalline flake graphite lamella, the structure for being mingled with cotton-shaped micro crystal graphite between this crystalline flake graphite lamella is more beneficial for interelectric conduction, it is more favorable to the absorption of ion, be advantageous to the study on the modification of follow-up expansion graphite, this structure the advantages of having crystalline flake graphite and micro crystal graphite concurrently simultaneously, overcome the shortcomings such as expansion crystalline flake graphite poor orientation, expansion micro crystal graphite expansion multiple be low.
Description
Technical field
The invention belongs to technical field of material, more particularly to the preparation method of mixed expanded graphite.
Background technology
Expanded graphite is a kind of carbon material.Expansible graphite is used as raw material, (is usually 700~1200 through high temperature
DEG C) processing when, insertion expanded graphite interlayer material drastically decompose, caused gas forms height in expansible graphite interlamination region
Press and expanded along c-axis direction high power, bulk density is by 0.7~1.8g/cm3It is changed into 0.003~0.03g/cm3, expansion multiple reaches
It is tens of to hundreds times.Porous and be in vermiform because intumesced graphite structure is loose, surface area is big, and surface energy is high, thus with excellent
Different liquid phase adsorption performance, good plasticity, preferable pliability, ductility and sealing, therefore be widely used in
The field such as environmental protection, machinery, chemical industry, Aero-Space, atomic energy.
At present, the raw material for using native graphite to be prepared for raw material used in the technology of expanded graphite meterial is generally crystalloid
Flaky graphite.Scaly graphite scale is big, aggregate favorable orientation.But in battery and electrode material for super capacitor, it is necessary to
The good graphite material of poor orientation, homogenieity, it is that Scaly graphite is often carried out spheroidization processing by this, but result is unsatisfactory.And
Micro crystal graphite particle is tiny, and aggregate poor orientation, homogenieity are good, and the expansion micro crystal graphite obtained after expanded processing has
More excellent electrical property.
Therefore, we can integrate two kinds of respective advantages of graphite, micro crystal graphite is mixed with micro crystal graphite expanded
Mixed expanded graphite is prepared, obtained mixed expanded graphite will possess more preferable chemical property, can also be used as preferably absorption
Material, specific surface area can also have greatly improved than before, yet there are no now on micro crystal graphite and crystalline flake graphite mixing
The research report of expanded graphite meterial technical method is prepared for raw material.
The content of the invention
The purpose of the present invention is the problem of presence for prior art, there is provided a kind of crystalline flake graphite and micro crystal graphite mixing system
The method of standby mixed expanded graphite material.
Another object of the present invention is to provide a kind of crystalline flake graphite and micro crystal graphite be mixed with to obtain it is mixed expanded
Graphite material.
The purpose of the present invention is achieved by the following technical programs：
A kind of preparation method of mixed expanded graphite, comprises the following steps：
S1. it is 2 ~ 3 to take crystalline flake graphite and micro crystal graphite mass ratio:1 carries out ball milling, is compound to the mesh of granularity 200 ~ 300；
S2. compound obtained by S1 is placed in Muffle furnace, is to slowly warm up to 400 DEG C ~ 450 DEG C under an inert atmosphere, insulation 10 ~
30min, it is stand-by to be air-cooled to room temperature；
S3. the compound after S2 is heat-treated carries out chemical graft processing, obtains inflatable admixed graphite；
S4. inflatable admixed graphite obtained by S3 is put into graphite expansion stove and expanded at 800 ~ 900 DEG C, obtain mixed expanded stone
Ink material.
Micro crystal graphite and crystalline flake graphite mixture puffing are prepared mixed expanded graphite material by the invention, in ball milling
During, the crystalline flake graphite and micro crystal graphite of appropriate mass ratio are sufficiently mixed, in mechanical milling process, part micro crystal graphite particle meeting
Into crystalline flake graphite piece interlayer, it is sufficiently mixed, is heat-treated after mixing, heat treatment can activate ball milling mixing material, together
When can also handle sublimable impurity in raw material, chemical graft processing is carried out after heat treatment immediately, intercalation effect can be improved
Fruit and efficiency, the expanding treatment process after being more favorable to.
Ball milling mixing material of the present invention is during expanding treatment, and crystalline flake graphite is different with the structure of micro crystal graphite, and its is expanded
The change that process occurs is also different, and crystalline flake graphite puffing process expands its piece interlamellar spacing, and micro crystal graphite then expanded formation
Cotton-shaped, cotton-shaped expansion micro crystal graphite of the compound between the structure after expanded is shown as crystalline flake graphite is connected to crystalline flake graphite piece
Between layer, the structure that cotton-shaped micro crystal graphite is mingled between this crystalline flake graphite lamella is more beneficial for interelectric conduction, also more
Be advantageous to the absorption of ion, be advantageous to the study on the modification of follow-up expansion graphite, while this structure has crystalline flake graphite and crystallite concurrently
The advantages of graphite, overcome the shortcomings such as expansion crystalline flake graphite poor orientation, expansion micro crystal graphite expansion multiple be low.
Preferably, crystalline flake graphite phosphorus content described in step S1 is not less than 85%, and the micro crystal graphite is Chenzhou City Shandong pool graphite
Powder, its carbon content are 70 ~ 80%.
Preferably, step S1 mechanical milling processes ratio of grinding media to material is 3 ~ 5:1, Ball-milling Time is 6 ~ 8h, and rotating speed is 200 ~ 300r/min.
Preferably, step S2 inert atmospheres are one kind in nitrogen, argon gas,
Preferably, compound described in step S2 heats in Muffle furnace, and the heating rate is 20 ~ 30 DEG C/min.
Preferably, chemical graft processing step includes described in step S3：
S31. it is 10~30 by liquid-solid ratio by mixed powder obtained by perchloric acid and step S2：1L/Kg is mixed evenly；
S32. it is 1 by the mass ratio of the mixed powder and potassium permanganate：2~8 add potassium permanganate, are stirred at room temperature uniformly
Afterwards, 30~60 DEG C are warming up to and continues 1~3.0h of stirring reaction；
S33. add deionized water the temperature in the reaction unit is increased to 60~100 DEG C, be further continued for stirring reaction 1~
3.0h；
S34. filter, then filtrate is washed, dried, obtains inflatable admixed graphite.
Preferably, step S4 carries out high-temperature expansion in graphite expansion stove and comprised the following steps：
S41. feed：Using conserving graphite expanding furnace, inflatable admixed graphite is put into burner hearth by charging aperture, the charging aperture
Temperature be 30 DEG C, dispensing speed is 2Kg/h；
S42. expand：The expansion temperature of burner hearth is 800 ~ 900 DEG C, by controlled wind speed come to control Bulking Time be 5s；
S43. discharge：After completing step S42, discharging opening temperature is 50 DEG C, then collects to obtain mixed expanded stone in discharge outlet
Ink material.
Present invention additionally comprises the mixed expanded graphite material that the preparation method using above-mentioned mixed expanded graphite is prepared.
Compared with the prior art, the beneficial effects of the present invention are：
（1）The present invention is mixed with mixed expanded graphite material, the storage of Chinese micro crystal graphite using micro crystal graphite and crystalline flake graphite
Amount is big, cheap, is mostly low value-added utilization, and the present invention provides a kind of high value added utilization approach for micro crystal graphite.
（2）The present invention uses micro crystal graphite and crystalline flake graphite as raw material, and carrying out expanding treatment to mixing material is mixed
Expanded graphite meterial, while high-volume and capacity ratio, graphite spacing is expanded, micro-nano pore space structure is formed, prepares height
The mixed expanded graphite material of multiple.
（3）Ball milling mixing material of the present invention is in expansion procedure, and crystalline flake graphite is different with the structure of micro crystal graphite, and its is swollen
The change that swollen process occurs is also different, and crystalline flake graphite expansion process expands its piece interlamellar spacing, and micro crystal graphite then expanded shape
Into cotton-shaped, cotton-shaped expansion micro crystal graphite of the compound between the structure after expanded is shown as crystalline flake graphite is connected to crystalline flake graphite
Between lamella, the structure that cotton-shaped micro crystal graphite is mingled between this crystalline flake graphite lamella is more beneficial for interelectric conduction,
The absorption of ion is more beneficial for, is advantageous to the study on the modification of follow-up expansion graphite, while this structure has crystalline flake graphite and micro- concurrently
The advantages of spar ink, overcome expansion crystalline flake graphite poor orientation, expansion micro crystal graphite expansion multiple is low, expansion effect is poor etc. lacks
Point.
（4）Micro crystal graphite and crystalline flake graphite of the present invention cause graphite layers away from expansion and micro-nano hole etc. after expanded
Portion's defect can effectively change in size of the buffer electrode material in discharge and recharge particularly high current charge-discharge, reduce to electrode
The destruction of material, the increase of irreversible capacity is avoided, therefore micro- swollen graphite that the present invention is prepared possesses preferable circulation
Stability and high rate performance, it can be used as the negative pole of lithium ion battery.
（5）High-temperature expansion method of the present invention, traditional high-temperature expansion method and graphite expansion stove are combined, using most
Good expansion temperature, and the stabilization of product can be effectively improved by the control to raw material and technological parameter around expansion temperature
Property.
（6）Raw material used in the method for the present invention is cheap, with short production cycle, have obvious social and economic benefits,
It is easily achieved industrialized production.
Brief description of the drawings
Fig. 1 is the high temperature graphite expansion furnace structure figure of embodiment 1 ~ 4.
Embodiment
The present invention is further illustrated with reference to specific embodiment.Following examples are only illustrative examples, not structure
Into inappropriate limitation of the present invention, the multitude of different ways that the present invention can be limited and covered by the content of the invention is implemented.It is unless special
Do not mentionlet alone bright, the present invention reagent, compound and the equipment that use is the art conventional reagent, compound and equipment.
Embodiment 1
The present invention is mixed with mixed expanded graphite material with micro crystal graphite and crystalline flake graphite, including step is as follows：Including graphite
Expansion furnace, using high-temperature expansion method, comprise the following steps：
S1. the micro crystal graphite raw material of phosphorus content 70% and the crystalline flake graphite raw material of phosphorus content 85%, crystalline flake graphite and micro crystal graphite are taken
Mass ratio is 2:1, crushing and grinding, to the mixing graphite powder that granularity is 300 mesh.
S2. compound obtained by S1 is placed in Muffle furnace, is to slowly warm up to 450 DEG C in a nitrogen atmosphere, be incubated 30min,
It is stand-by to be air-cooled to room temperature.
S3. the compound after S2 is heat-treated carries out chemical graft processing, obtains inflatable admixed graphite, wherein chemistry
Intercalation processing comprises the following steps that：
S31. it is 10 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：1L/Kg is mixed evenly；S32. microlite ink powder is pressed
The mass ratio of body and strong oxidizer is 2：1 adds strong oxidizer, after being stirred at room temperature uniformly, is warming up to 30 DEG C and continues stirring instead
Answer 3h；S33. adding deionized water makes the temperature in reaction unit be increased to 60 DEG C, is further continued for stirring reaction 3h；S34. filter,
Then washing drying is carried out to filtrate, obtains inflatable admixed graphite.
S4. inflatable admixed graphite obtained by S3 is put into graphite expansion stove and expanded at 800 DEG C, obtain mixed expanded stone
Ink material；Concretely comprise the following steps：
S41. feed：Using conserving graphite expanding furnace, inflatable admixed graphite is put into burner hearth by charging aperture, the charging aperture
Temperature be 30 DEG C, dispensing speed is 2Kg/h；S42. expand：The expansion temperature of burner hearth is 800 DEG C, is controlled by controlled wind speed
Bulking Time processed is 5s；S43. discharge：After completing step S42, discharging opening temperature is 50 DEG C, then collects to obtain in discharge outlet
Mixed expanded graphite material.
The scanning electron microscope (SEM) photograph of the mixed expanded graphite material obtained in the present embodiment is as shown in figure 1, what is obtained is mixed expanded
Graphite material pore size distribution range is 1~100nm, and specific surface area is 462 m2/ g, expansion multiple are 153 times.
Embodiment 2
The present invention is mixed with mixed expanded graphite material with micro crystal graphite and crystalline flake graphite, including step is as follows：Including graphite
Expansion furnace, using high-temperature expansion method, comprise the following steps：
S1. the micro crystal graphite raw material of phosphorus content 75% and the crystalline flake graphite raw material of phosphorus content 90%, crystalline flake graphite and micro crystal graphite are taken
Mass ratio is 2:1, crushing and grinding, to the mixing graphite powder that granularity is 200 mesh；
S2. compound obtained by S1 is placed in Muffle furnace, is to slowly warm up to 420 DEG C in a nitrogen atmosphere, be incubated 10min, air cooling
It is stand-by to room temperature.
S3. the compound after S2 is heat-treated carries out chemical graft processing, obtains inflatable admixed graphite, wherein chemistry
Intercalation processing comprises the following steps that：
S31. it is 15 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：1L/Kg is mixed evenly；S32. microlite ink powder is pressed
The mass ratio of body and potassium permanganate is 4：1 adds potassium permanganate, after being stirred at room temperature uniformly, is warming up to 40 DEG C and continues stirring instead
Answer 2h；S33. adding deionized water makes the temperature in reaction unit be increased to 70 DEG C, is further continued for stirring reaction 2h；S34. filter,
Then washing drying is carried out to filtrate, obtains inflatable admixed graphite.
S4. inflatable admixed graphite obtained by S3 is put into graphite expansion stove and expanded at 850 DEG C, obtain mixed expanded stone
Ink material；Concretely comprise the following steps：
S41. feed：Using conserving graphite expanding furnace, inflatable admixed graphite is put into burner hearth by charging aperture, the charging aperture
Temperature be 30 DEG C, dispensing speed is 2Kg/h；S42. expand：The expansion temperature of burner hearth is 850 DEG C, is controlled by controlled wind speed
Bulking Time processed is 5s；S43. discharge：After completing step S42, discharging opening temperature is 50 DEG C, then collects to obtain in discharge outlet
Mixed expanded graphite material.
What morphological feature, structural analysis and the embodiment 1 of the mixed expanded graphite material obtained in the present embodiment were obtained
As a result essentially identical, obtained mixed expanded graphite material pore size distribution range is 1~100nm, specific surface area 506m2/ g,
Expansion multiple is 174 times.
Embodiment 3
The present invention is mixed with mixed expanded graphite material with micro crystal graphite and crystalline flake graphite, including step is as follows：Including graphite
Expansion furnace, using high-temperature expansion method, comprise the following steps：
S1. the micro crystal graphite raw material of phosphorus content 75% and the crystalline flake graphite raw material of phosphorus content 85%, crystalline flake graphite and micro crystal graphite are taken
Mass ratio is 2.5:1, crushing and grinding, to the mixing graphite powder that granularity is 200 mesh；
S2. compound obtained by S1 is placed in Muffle furnace, is to slowly warm up to 430 DEG C in a nitrogen atmosphere, be incubated 10min, air cooling
It is stand-by to room temperature.
S3. the compound after S2 is heat-treated carries out chemical graft processing, obtains inflatable admixed graphite, wherein chemistry
Intercalation processing comprises the following steps that：
S31. it is 20 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：1L/Kg is mixed evenly；S32. microlite ink powder is pressed
The mass ratio of body and potassium permanganate is 6：1 adds potassium permanganate, after being stirred at room temperature uniformly, is warming up to 50 DEG C and continues stirring instead
Answer 2h；S33. adding deionized water makes the temperature in reaction unit be increased to 80 DEG C, is further continued for stirring reaction 2h；S34. filter,
Then washing drying is carried out to filtrate, obtains inflatable admixed graphite.
S4. inflatable admixed graphite obtained by S3 is put into graphite expansion stove and expanded at 900 DEG C, obtain mixed expanded stone
Ink material；Concretely comprise the following steps：
S41. feed：Using conserving graphite expanding furnace, inflatable admixed graphite is put into burner hearth by charging aperture, the charging aperture
Temperature be 30 DEG C, dispensing speed is 2Kg/h；S42. expand：The expansion temperature of burner hearth is 900 DEG C, is controlled by controlled wind speed
Bulking Time processed is 5s；S43. discharge：After completing step S42, discharging opening temperature is 50 DEG C, then collects to obtain in discharge outlet
Mixed expanded graphite material.
What morphological feature, structural analysis and the embodiment 1 of the mixed expanded graphite material obtained in the present embodiment were obtained
As a result essentially identical, obtained mixed expanded graphite material pore size distribution range is 1~100nm, specific surface area 523m2/ g,
Expansion multiple is 181 times.
Embodiment 4
The present invention is mixed with mixed expanded graphite material with micro crystal graphite and crystalline flake graphite, including step is as follows：Including graphite
Expansion furnace, using high-temperature expansion method, comprise the following steps：
S1. the micro crystal graphite raw material of phosphorus content 75% and the crystalline flake graphite raw material of phosphorus content 90%, crystalline flake graphite and micro crystal graphite are taken
Mass ratio is 3:1, crushing and grinding, to the mixing graphite powder that granularity is 300 mesh；
S2. compound obtained by S1 is placed in Muffle furnace, is to slowly warm up to 350 DEG C in a nitrogen atmosphere, be incubated 30min, air cooling
It is stand-by to room temperature.
S3. the compound after S2 is heat-treated carries out chemical graft processing, obtains inflatable admixed graphite, wherein chemistry is inserted
Layer processing comprises the following steps that：
S31. it is 20 by liquid-solid ratio by perchloric acid and micro crystal graphite powder：1L/Kg is mixed evenly；S32. microlite ink powder is pressed
The mass ratio of body and potassium permanganate is 6：1 adds potassium permanganate, after being stirred at room temperature uniformly, is warming up to 50 DEG C and continues stirring instead
Answer 2h；S33. adding deionized water makes the temperature in reaction unit be increased to 80 DEG C, is further continued for stirring reaction 2h；S34. filter,
Then washing drying is carried out to filtrate, obtains inflatable admixed graphite.
S4. inflatable admixed graphite obtained by S3 is put into graphite expansion stove and expanded at 880 DEG C, obtain mixed expanded stone
Ink material；Concretely comprise the following steps：
S41. feed：Using conserving graphite expanding furnace, inflatable admixed graphite is put into burner hearth by charging aperture, the charging aperture
Temperature be 30 DEG C, dispensing speed is 2Kg/h；S42. expand：The expansion temperature of burner hearth is 880 DEG C, is controlled by controlled wind speed
Bulking Time processed is 5s；S43. discharge：After completing step S42, discharging opening temperature is 50 DEG C, then collects to obtain in discharge outlet
Mixed expanded graphite material.
What morphological feature, structural analysis and the embodiment 1 of the mixed expanded graphite material obtained in the present embodiment were obtained
As a result essentially identical, obtained mixed expanded graphite material pore size distribution range is 1~100nm, specific surface area 497m2/ g,
Expansion multiple is 178 times.
Embodiment 5
Referring to Fig. 1, the graphite expansion stove used for the high-temperature expansion process of embodiment 1 to 4, graphite expansion stove includes body of heater 1, charging
Then device 2, drawing mechanism 3 and control device, raw material are collected by feeding device 2 to body of heater 1 by drawing mechanism 3；Discharging
Device 3 is located above body of heater, and feeding device 2 is located at below body of heater；Heater 11 is provided with body of heater 1, using Resistant heating,
The inner bottom part of body of heater 1 is additionally provided with air-flow shower nozzle 4, and air-flow shower nozzle 4 also includes source of the gas 41, airflow line 42 and control damper 43, gas
Source 41 is air, and connects airflow line 42, and airflow line 42 connects air-flow shower nozzle 4, and control damper 43 is located at airflow line
In 42, the top of air-flow shower nozzle 4 is provided with feeding device 2, specifically includes processor 5 and control using feed screw, control device
Device, processor 5 are provided with and control panel and be connecteds with controller, and controller includes the first controller 53, second controller 52 and the
Three controllers 51, the first controller 53 are connected with the control damper 43 of air-flow shower nozzle 4, second controller 52 and feeding device 2
Connection, the 3rd controller 51 are connected with heater 11；
Wherein, processor 5 uses microprocessor, and the first controller uses air inlet valve-driving circuit, and second controller is using charging
Valve-driving circuit, the 3rd controller use heat driven circuit.
Cooling device 7 is additionally provided between drawing mechanism 3 and body of heater 1, cooling device 7 includes heat exchanger tube 71 and water cooling tube 72,
One end connection body of heater 1 of heat exchanger tube 71, other end connection drawing mechanism 3, heat exchanger tube 71 and horizontal angle are 45 DEG C~90
DEG C, water cooling tube 72 is arranged on heat exchanger tube 71 in the shape of a spiral；
Drawing mechanism 3 includes multiple reserves storehouses 31 and connecting pipe 32, and the one end of connecting pipe 32 is connected with heat exchanger tube 71, and is provided with
Cyclone separator 33, the other end are connected with exhaust outlet 34, be additionally provided with connecting pipe 32 multiple subtubes 35 respectively with reserves storehouse
31 connections；Connecting pipe and 32 horizontal angles are 45 DEG C~90 DEG C；
Agitator 8 is additionally provided with body of heater 1, agitator 8 is spiral agitator, is coordinated by motor and ball-screw so that stir
Mix device 8 and upper and lower linear motion is done in body of heater 1, so as to drive the airflow reflux in body of heater 1.
Wherein：The temperature of discharging opening is controlled by cooling device, and heater 6 also is provided with to control in charging aperture
The temperature of charging aperture processed, specific the present embodiment can be heated using resistance wire 61 to the discharge pipe in feeding device.
Can control time and the temperature of expansion by control panel, specifically processor by control the first controller and
Second controller controls air velocity and charging rate, so as to control the reaction time that intercalated graphite expands, the 3rd controller
The temperature of heater can be controlled, the intellectuality of graphite expansion is realized, reaches and be precisely controlled.
Graphite expansion stove is placed using two floors, and the processing sequence according to raw material is heat exchanger tube and connection from the bottom up
Pipeline and horizontal line have certain angle, by the cooperation of gravity and wind speed, that is, solve expanded graphite and get stuck problem, improve anti-
Yield is answered, while also solves space compared to being disposed vertically.
Graphite expansion stove adds agitator 8 in body of heater 1 so that the air-flow in body of heater 1 forms convection current, ensure that intercalation stone
Ink is heated evenly, so as to which the expanded reaction efficiency of intercalated graphite be significantly increased..
Comparative example 1
Comparative example 1 is with the difference of embodiment 1：Comparative example 1 is not provided with step S2, and other steps are same as Example 1.
The mixed expanded graphite material pore size distribution range that comparative example 1 obtains is 1~150nm, specific surface area 298m2/
G, expansion multiple are 116 times.
Comparative example 2
Comparative example 2 is with the difference of embodiment 1：The step S4 of comparative example 1 is different, and other steps are same as Example 1, specifically
For：
S4. will obtained by S3 in the inflatable electric furnace of admixed graphite under nitrogen atmosphere 850 DEG C carry out heating roasting 60s, obtain
Mixed expanded graphite material.
The mixed expanded graphite material pore size distribution range that comparative example 2 obtains is 1~150nm, specific surface area 360m2/
G, expansion multiple are 101 times.
Comparative example 3
Comparative example 3 is with the difference of embodiment 1：The micro crystal graphite raw material of all phosphorus content 70% of raw material of comparative example 3 crushes
Grinding, to the graphite powder that granularity is 300 mesh.Other steps are same as Example 1.
The mixed expanded graphite material pore size distribution range that comparative example 3 obtains is 1~80nm, specific surface area 391m2/ g,
Expansion multiple is 5.6 times.
Comparative example 4
Comparative example 4 is with the difference of embodiment 1：The crystalline flake graphite raw material of all phosphorus content 85% of raw material of comparative example 4 crushes
Grinding, to the graphite powder that granularity is 300 mesh.Other steps are same as Example 1.
The mixed expanded graphite material pore size distribution range that comparative example 4 obtains is 1~300nm, specific surface area 196m2/
G, expansion multiple are 138 times.
Claims (8)
1. a kind of preparation method of mixed expanded graphite, it is characterised in that comprise the following steps：
S1. it is 2 ~ 3 to take crystalline flake graphite and micro crystal graphite mass ratio:1 carries out ball milling, is compound to the mesh of granularity 200 ~ 300；
S2. compound obtained by S1 is placed in Muffle furnace, is to slowly warm up to 400 DEG C ~ 450 DEG C under an inert atmosphere, insulation 10 ~
30min, it is stand-by to be air-cooled to room temperature；
S3. the compound after S2 is heat-treated carries out chemical graft processing, obtains inflatable admixed graphite；
S4. inflatable admixed graphite obtained by S3 is put into graphite expansion stove and expanded at 800 ~ 900 DEG C, obtain mixed expanded stone
Ink material.
2. the preparation method of mixed expanded graphite according to claim 1, it is characterised in that crystalline flake graphite described in step S1 contains
Carbon amounts is not less than 85%, and the micro crystal graphite is Chenzhou City Shandong pool graphite powder, and its carbon content is 70 ~ 80%.
3. the preparation method of mixed expanded graphite according to claim 1, it is characterised in that step S1 mechanical milling process ratios of grinding media to material
For 3 ~ 5:1, Ball-milling Time is 6 ~ 8h, and rotating speed is 200 ~ 300r/min.
4. the preparation method of mixed expanded graphite according to claim 1, it is characterised in that step S2 inert atmospheres are nitrogen
One kind in gas, argon gas.
5. the preparation method of mixed expanded graphite according to claim 1, it is characterised in that compound is in horse described in step S2
Not heated in stove, the heating rate is 20 ~ 30 DEG C/min.
6. the preparation method of mixed expanded graphite according to claim 1, it is characterised in that
Chemical graft processing step includes described in step S3：
S31. it is 10~30 by liquid-solid ratio by mixed powder obtained by perchloric acid and step S2：1L/Kg is mixed evenly；
S32. it is 1 by the mass ratio of the mixed powder and potassium permanganate：2~8 add potassium permanganate, are stirred at room temperature uniformly
Afterwards, 30~60 DEG C are warming up to and continues 1~3.0h of stirring reaction；
S33. add deionized water the temperature in the reaction unit is increased to 60~100 DEG C, be further continued for stirring reaction 1~
3.0h；
S34. filter, then filtrate is washed, dried, obtains inflatable admixed graphite.
7. the preparation method of mixed expanded graphite according to claim 1, it is characterised in that step S4 is in graphite expansion stove
High-temperature expansion is carried out to comprise the following steps：
S41. feed：Using conserving graphite expanding furnace, inflatable admixed graphite is put into burner hearth by charging aperture, the charging aperture
Temperature be 30 DEG C, dispensing speed is 2Kg/h；
S42. expand：The expansion temperature of burner hearth is 800 ~ 900 DEG C, by controlled wind speed come to control Bulking Time be 5s；
S43. discharge：After completing step S42, discharging opening temperature is 50 DEG C, then collects to obtain mixed expanded stone in discharge outlet
Ink material.
8. the mixed expanded graphite that the preparation method of the mixed expanded graphite according to any one of claim 1 ~ 7 is prepared
Material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108821278A (en) * | 2018-08-21 | 2018-11-16 | 大同新成新材料股份有限公司 | A method of expanded graphite is prepared using graphene composite material |
| CN113753888A (en) * | 2021-10-21 | 2021-12-07 | 青岛洛唯新材料有限公司 | Expandable graphite and preparation method and production system thereof |
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