CN107799774A - The method that crystalline flake graphite and micro crystal graphite are mixed with micro- swollen graphite material - Google Patents
The method that crystalline flake graphite and micro crystal graphite are mixed with micro- swollen graphite material Download PDFInfo
- Publication number
- CN107799774A CN107799774A CN201711043092.1A CN201711043092A CN107799774A CN 107799774 A CN107799774 A CN 107799774A CN 201711043092 A CN201711043092 A CN 201711043092A CN 107799774 A CN107799774 A CN 107799774A
- Authority
- CN
- China
- Prior art keywords
- graphite
- micro
- swollen
- crystalline flake
- mixed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of method that crystalline flake graphite and micro crystal graphite are mixed with micro- swollen 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 400 ~ 500 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, it is more beneficial for interelectric conduction, also li-ion electrode materials are more suitable for, the charge/discharge capacity that expansion forms micro- swollen graphite material afterwards is improved, improves its cycle performance and multiplying power discharging property.
Description
Technical field
The invention belongs to technical field of material, more particularly to a kind of crystalline flake graphite and micro crystal graphite mixing system
The method of standby micro- swollen graphite material.
Background technology
Lithium ion battery is due to high output voltage and energy density, good cyclical stability and environment-friendly etc. excellent
Point, most of consumer electronics product market is captured as the power resources of various electronic products, in recent years, with
Electronic product quickly update and the continuous development in electric car market, it is desirable to which lithium ion battery has lighter matter
Amount, smaller volume and higher power density.
The microdilatancy graphite compound between graphite layers extremely cheap as a kind of cost（GIC）, due to abundant more
Pore dimension structure, larger specific surface area, excellent thermoelectricity conductive performance, the advantages that good chemical stability, and recognized
For be a kind of great potential can large-scale application in lithium ion battery negative material.
Meanwhile the raw material for using native graphite to be prepared for raw material used in the technology of microdilatancy graphite material at present is general
For crystalloid flaky graphite, although crystalline flake graphite collective orientation is good, poor orientation is needed in the application of battery material,
The good graphite material of uniformity, micro crystal graphite particle is tiny, and aggregate poor orientation, homogenieity is good, and micro crystal graphite can replace squama
Piece graphite can be big as the raw material for preparing the more preferable expanded graphite of electrical property, charge efficiency, stability test and cycle performance
It is big to improve, but capacitance reduces, while the expansion effect of micro crystal graphite is bad, causes to expand micro crystal graphite as lithium-ion electric
The application of pole negative material is obstructed.If the advantages of crystalline flake graphite and micro crystal graphite can be combined, a kind of capacity is prepared
Novel slight expansion graphite material high, efficiency for charge-discharge is high and circulating ratio performance is good, the research to swollen graphite material micro- from now on
It is most important, while can also slow down the extensive low value-added predicament utilized of China's micro crystal graphite.
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 micro- swollen graphite material.
Another object of the present invention is to provide a kind of crystalline flake graphite and micro crystal graphite to be mixed with micro- swollen graphite material
Method.
Further object of the present invention is to provide application of micro- swollen graphite material as lithium ion battery negative material.
The purpose of the present invention is achieved by the following technical programs：
The method that crystalline flake graphite and micro crystal graphite are mixed with micro- swollen graphite material, 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 350 DEG C ~ 400 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 400 ~ 500 DEG C, obtain micro- swollen graphite material
Material.
Micro crystal graphite and crystalline flake graphite mixture puffing are prepared micro- swollen graphite material by the invention, in mechanical milling process
In, the crystalline flake graphite and micro crystal graphite of appropriate mass ratio are sufficiently mixed, and in mechanical milling process, part micro crystal graphite particle can enter
Crystalline flake graphite piece interlayer, is sufficiently mixed, and is heat-treated after mixing, and heat treatment can activate ball milling mixing material, while
Can handle sublimable impurity in raw material, carry out chemical graft processing after heat treatment immediately, can improve intercalation effect and
Efficiency, the expansion procedure after being more favorable to.
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 it expands
The change that process occurs is also different, and crystalline flake graphite expansion 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, more suitable
Cooperate to form the charge/discharge capacity of micro- swollen graphite material afterwards for li-ion electrode materials, raising expansion, improve its cycle performance
And multiplying power discharging property.
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 5 ~ 20 DEG C/min, the present invention
Using
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 400 ~ 500 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 micro- swollen graphite material in discharge outlet
Material.
Present invention additionally comprises crystalline flake graphite and micro crystal graphite be mixed with micro- swollen graphite material method be prepared it is micro-
Swollen graphite material.
Compared with the prior art, the beneficial effects of the present invention are：
（1）The present invention is mixed with micro- swollen graphite material using micro crystal graphite and crystalline flake graphite, and Chinese micro crystal graphite reserves are big,
It is cheap, it is mostly low value-added utilization, the present invention provides a kind of high value added utilization approach for micro crystal graphite.
（2）The present invention use micro crystal graphite and crystalline flake graphite as raw material, mixing material progress microdilatancy is handled to obtain micro-
Swollen graphite material, while high-volume and capacity ratio, graphite spacing is expanded, forms micro-nano pore space structure, prepared certain
Micro- swollen 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
Swollen process is also different, and crystalline flake graphite expansion process expands its piece interlamellar spacing, and micro crystal graphite then cotton-shaped, the scale of expanded formation
Cotton-shaped expansion micro crystal graphite between graphite is connected between crystalline flake graphite lamella, and cotton-shaped stone is mingled between this graphite flake layer
The structure of ink is more beneficial for interelectric conduction, is also more suitable for li-ion electrode materials, is formed after raising expansion micro- swollen
The charge/discharge capacity of graphite material, improve its cycle performance and multiplying power discharging property.
（4）Micro crystal graphite and crystalline flake graphite of the present invention are through causing graphite layers away from expansion and micro-nano hole after micro- swollen processing
Etc. internal flaw can effectively change in size of the buffer electrode material in discharge and recharge particularly high current charge-discharge, reduce pair
The destruction of electrode material, the increase of irreversible capacity is avoided, therefore micro- swollen graphite that the present invention is prepared possesses preferably
Cyclical 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 that embodiment 1 obtains micro- swollen graphite material scanning electron microscope (SEM) photograph.
Fig. 2 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 micro- swollen graphite material with micro crystal graphite and crystalline flake graphite, including step is as follows：Including graphite expansion
Stove, 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 350 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 400 DEG C, obtain micro- swollen graphite material
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 400 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
Micro- swollen graphite material.
The scanning electron microscope (SEM) photograph of the micro- swollen graphite material obtained in the present embodiment is as shown in figure 1, obtained micro- swollen graphite material
Pore size distribution range is 1~100nm, and specific surface area is 350 m2/ g, expansion multiple are 21 times, resistivity 1.32*10-3Ω
.m。
Embodiment 2
The present invention is mixed with micro- swollen graphite material with micro crystal graphite and crystalline flake graphite, including step is as follows：Including graphite expansion
Stove, 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 400 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 500 DEG C, obtain micro- swollen graphite material
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 500 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
Micro- swollen graphite material.
The result that morphological feature, structural analysis and the embodiment 1 of the micro- swollen graphite material obtained in the present embodiment are obtained
Essentially identical, obtained micro- swollen graphite material pore size distribution range is 1~100nm, specific surface area 606m2/ g, expansion multiple
For 23 times, resistivity 4.32*10-3Ω.m。
Embodiment 3
The present invention is mixed with micro- swollen graphite material with micro crystal graphite and crystalline flake graphite, including step is as follows：Including graphite expansion
Stove, 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 400 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 450 DEG C, obtain micro- swollen graphite material
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 450 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
Micro- swollen graphite material.
The result that morphological feature, structural analysis and the embodiment 1 of the micro- swollen graphite material obtained in the present embodiment are obtained
Essentially identical, obtained micro- swollen graphite material pore size distribution range is 1~100nm, specific surface area 623m2/ g, expansion multiple
For 18.1 times, resistivity 2.64*10-3Ω.m。
Embodiment 4
The present invention is mixed with micro- swollen graphite material with micro crystal graphite and crystalline flake graphite, including step is as follows：Including graphite expansion
Stove, 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 450 DEG C, obtain micro- swollen graphite material
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 450 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
Micro- swollen graphite material.
The result that morphological feature, structural analysis and the embodiment 1 of the micro- swollen graphite material obtained in the present embodiment are obtained
Essentially identical, obtained micro- swollen graphite material pore size distribution range is 1~100nm, specific surface area 492m2/ g, expansion multiple
For 18 times, resistivity 9.95*10-4Ω.m。
Embodiment 5
Referring to Fig. 2, 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.
Micro- swollen graphite material pore size distribution range that comparative example 1 obtains is 1~150nm, specific surface area 305m2/ g, it is swollen
Swollen multiple is 10 times, resistivity 9.95*10-2Ω.m。
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 400 DEG C carry out heating roasting 60s, obtain
Micro- swollen graphite material.
Micro- swollen graphite material pore size distribution range that comparative example 2 obtains is 1~150nm, specific surface area 290m2/ g, it is swollen
Swollen multiple is 12.9 times, resistivity 8.13*10-2Ω.m。
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.
Micro- swollen graphite material pore size distribution range that comparative example 3 obtains is 1~80nm, specific surface area 380m2/ g, expansion
Multiple is 2.1 times, resistivity 3.89*10-3Ω.m。
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.
Micro- swollen graphite material pore size distribution range that comparative example 4 obtains is 1~300nm, specific surface area 169m2/ g, it is swollen
Swollen multiple is 30.5 times, resistivity 8.14*10-3Ω.m。
Claims (8)
1. the method that crystalline flake graphite and micro crystal graphite are mixed with micro- swollen graphite material, 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 350 DEG C ~ 400 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 400 ~ 500 DEG C, obtain micro- swollen graphite material
Material.
2. crystalline flake graphite according to claim 1 and micro crystal graphite are mixed with the method for micro- swollen graphite material, its feature
It is, 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, and its carbon contains
Measure as 70 ~ 80%.
3. crystalline flake graphite according to claim 1 and micro crystal graphite are mixed with the method for micro- swollen graphite material, its feature
It is, 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.
4. crystalline flake graphite according to claim 1 and micro crystal graphite are mixed with the method for micro- swollen graphite material, its feature
It is, step S2 inert atmospheres are one kind in nitrogen, argon gas.
5. crystalline flake graphite according to claim 1 and micro crystal graphite are mixed with the method for micro- swollen graphite material, its feature
It is, compound described in step S2 heats in Muffle furnace, and the heating rate is 5 ~ 20 DEG C/min.
6. crystalline flake graphite according to claim 1 and micro crystal graphite are mixed with the method for micro- swollen graphite material, its feature
It is,
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. crystalline flake graphite according to claim 1 and micro crystal graphite are mixed with the method for micro- swollen graphite material, its feature
It is, 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 400 ~ 500 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 micro- swollen graphite material in discharge outlet
Material.
8. the method that the crystalline flake graphite and micro crystal graphite according to any one of claim 1 ~ 7 are mixed with micro- swollen graphite material
The micro- swollen graphite material being prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711043092.1A CN107799774A (en) | 2017-10-31 | 2017-10-31 | The method that crystalline flake graphite and micro crystal graphite are mixed with micro- swollen graphite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711043092.1A CN107799774A (en) | 2017-10-31 | 2017-10-31 | The method that crystalline flake graphite and micro crystal graphite are mixed with micro- swollen graphite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107799774A true CN107799774A (en) | 2018-03-13 |
Family
ID=61547677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711043092.1A Pending CN107799774A (en) | 2017-10-31 | 2017-10-31 | The method that crystalline flake graphite and micro crystal graphite are mixed with micro- swollen graphite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107799774A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010009980A (en) * | 2008-06-27 | 2010-01-14 | Yokohama City Univ | Negative electrode material for lithium ion battery and rapid charging/discharging lithium ion battery using the same |
| CN104157465A (en) * | 2014-08-22 | 2014-11-19 | 东莞市长安东阳光铝业研发有限公司 | Lithium ion capacitor |
| CN105355870A (en) * | 2015-10-22 | 2016-02-24 | 清华大学深圳研究生院 | Expanded graphite and nano-silicon composite material, preparation method thereof, electrode plate and battery |
| CN107285306A (en) * | 2017-08-04 | 2017-10-24 | 湖南国盛石墨科技有限公司 | A kind of method that micro crystal graphite prepares expansion micro crystal graphite |
-
2017
- 2017-10-31 CN CN201711043092.1A patent/CN107799774A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010009980A (en) * | 2008-06-27 | 2010-01-14 | Yokohama City Univ | Negative electrode material for lithium ion battery and rapid charging/discharging lithium ion battery using the same |
| CN104157465A (en) * | 2014-08-22 | 2014-11-19 | 东莞市长安东阳光铝业研发有限公司 | Lithium ion capacitor |
| CN105355870A (en) * | 2015-10-22 | 2016-02-24 | 清华大学深圳研究生院 | Expanded graphite and nano-silicon composite material, preparation method thereof, electrode plate and battery |
| CN107285306A (en) * | 2017-08-04 | 2017-10-24 | 湖南国盛石墨科技有限公司 | A kind of method that micro crystal graphite prepares expansion micro crystal graphite |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107285306A (en) | A kind of method that micro crystal graphite prepares expansion micro crystal graphite | |
| CN105870417B (en) | A kind of preparation method of sodium-ion battery tungsten disulfide/carbon nanometer tube negative pole composite | |
| CN107732205B (en) | Method for preparing sulfur-nitrogen co-doped carbon-coated nano flower-shaped lithium titanate composite negative electrode material | |
| CN104617281A (en) | Method for preparing sodium-ion battery antimony/nitrogen-doped carbon nanosheet negative electrode composite material | |
| CN103904307A (en) | Silicon-carbon composite material, preparation method and application thereof | |
| CN103151497A (en) | Preparation method of negative material for low-temperature lithium ion battery | |
| CN105460917A (en) | Nitrogen-doped carbon nanotube adopting hierarchical structure and preparation method | |
| CN109286015A (en) | A kind of hollow porous TiO2The preparation method and applications of nanocube material | |
| CN107359328A (en) | A kind of preparation method of lithium ion battery botryoidalis niobium oxide/carbon composite electrode material | |
| CN103413924A (en) | La1-xCaxCoO3 coated lithium ion battery cathode material LiNi1/3Co1/3Mn1/3O2 and preparation method thereof | |
| CN107516740A (en) | A kind of carbon ink, graphene powder combined conductive agent and preparation method thereof, application | |
| CN105789615A (en) | Modified lithium nickel cobalt manganese cathode material and preparation method thereof | |
| CN107381499A (en) | A kind of hollow porous nanometer α Fe2O3The preparation of hexagonal prismoid material and its application process | |
| CN104617270A (en) | Preparation method of spherical hollow lithium titanate/graphene composite material as lithium battery negative material | |
| CN106099092A (en) | A kind of preparation method of the copper vanadate for lithium ion battery negative material | |
| CN109065861A (en) | Asphaltic base porous carbon materials and preparation method thereof, silicon-carbon cathode material and secondary cell | |
| CN108807956A (en) | A kind of lithium ion battery nucleocapsid negative material and preparation method thereof | |
| CN107651682A (en) | A kind of preparation method of mixed expanded graphite | |
| CN101734710A (en) | Method for preparing zinc stannate semiconductor functional material | |
| CN107293708A (en) | The improved method that solvent-thermal method prepares graphene silicon composite | |
| CN107381566A (en) | A kind of method that micro crystal graphite prepares reexpansion micro crystal graphite | |
| CN114566727A (en) | Modification method for direct pyrogenic repair and regeneration of lithium iron phosphate positive electrode material | |
| CN109037679A (en) | Petroleum coke base porous carbon materials and preparation method thereof and silicon-carbon cathode material | |
| CN107799774A (en) | The method that crystalline flake graphite and micro crystal graphite are mixed with micro- swollen graphite material | |
| CN108063234A (en) | A kind of carbon nanotubes/application of micro- swollen graphite composite material as lithium ion battery negative material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| AD01 | Patent right deemed abandoned | ||
| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20210730 |