CN106784767A - A kind of method that same stove prepares cathode of lithium battery graphite and carborundum - Google Patents
A kind of method that same stove prepares cathode of lithium battery graphite and carborundum Download PDFInfo
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- CN106784767A CN106784767A CN201611253088.3A CN201611253088A CN106784767A CN 106784767 A CN106784767 A CN 106784767A CN 201611253088 A CN201611253088 A CN 201611253088A CN 106784767 A CN106784767 A CN 106784767A
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- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- 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 provides a kind of method that same stove prepares cathode of lithium battery graphite material and carborundum, it is comprised the following steps：1) prepared by powder：Anthracite is crushed, powder body material is made；2) high temperature graphitization：By step 2) gained powder body material be placed in crucible, the crucible outside is with general decomposition graphite coat, constitute combustion chamber, insulation material, the reaction material of production carborundum and the combustion chamber will be successively loaded in acheson furnace, acheson furnace is powered, combustion chamber temperature is reached 1700~3300 DEG C, feeding is cooled down after calcining, respectively obtain graphite and carborundum.With anthracite as raw material, the lithium cell negative pole material prepared using the inventive method, with excellent electric property, and technological process economy is simple, with two kinds of materials of stove while output, greatlys save raw material auxiliary material and power consumption cost, realizes production energy-saving.
Description
Technical field
The present invention relates to cathode of lithium battery graphite material and the preparation method of carborundum, and in particular to prepared by a kind of same stove
The method of cathode of lithium battery graphite material and carborundum.
Background technology
Carbon material has the advantages that high-energy-density, high efficiency and long circulation life because of it, is widely used in lithium ion
Cell negative electrode material.At present, the preparing raw material of lithium ion battery negative material is prepared mainly with native graphite and Delanium two
Class.Though native graphite has the lithium ion to be embedded in/characteristic of deintercalation and excellent charge and discharge platform, the lithium ion of solvation can
To enter interlayer (solvent molecule with lithium ion altogether embedding), the interlamellar spacing for making graphite crystal expands, volumetric expansion, final delamination occurs
And new surface is formed, increase irreversible capacity first.Leafing destroys storage lithium structure simultaneously, and cycle life shortens.It is artificial
Graphite is that easy graphitized carbon is made after 2800-3000 DEG C of high-temperature process, and Delanium mainly has carbonaceous mesophase spherules
(MCMB), graphite fibre etc..MCMB is one of negative material of current small-scale lithium ion cell and electrokinetic cell large-scale use,
It has the disadvantage that irreversible capacity is higher, and capacity is less than native graphite.
In Delanium field, coal enriches the most as reserves in the world, cheap carbon containing mineral resource, negative preparing
Pole material aspect shows the advantage of uniqueness.Coal forms coke under conditions of air is completely cut off through high-temperature heating.Different coalification journeys
The coal of degree forms the coke of different indexs.Dahn once reported (J.D.Dahn, T zheng, Y.Liu, J.S.Xue, Science
270 (1995) 590.) coke that high-temperature retorting coal smoke is obtained has the characteristic of storage lithium ion, wherein in non-graphitic carbon,
High volatile bituminous coal shows preferably circulation and high rate performance because having minimum graphitization microstructure.But, this
The density of kind of coal is relatively low, causes its coking value lower, it is impossible to meet capacity requirement, and first charge-discharge coulombic efficiency also compared with
It is low.
Therefore a kind of carbon raw material is needed, the performances such as its reversible capacity, coulombic efficiency, and convenient for production, tool can be effectively improved
There are economic advantages higher.
Furthermore, the production process of lithium electro-graphitic negative material is and individually produces in the prior art, such as use internal thermal serial
Stove, generally requires to ensure product purity using sealing system, blanketing with inert gas, and need addition volume in preparation technology
Outer auxiliary material or inorganic acid carries out advance removal of impurities to material, and this causes that control of the existing method to production technology has higher wanting
Ask, and the discharge material for easily causing environmental pollution can be introduced, and the effective rate of utilization of resource is low, causes production cost higher.
Additionally, carborundum is also coal raw material normal material for producing after pyrolytic semlting, it has corrosion-resistant, high temperature resistant, strong
The characteristics such as degree is big, the good, shock resistance of heat conductivility, range of application is extremely wide.Although current China's carbofrax material yield is big,
But its production is also single stove production (such as using acheson furnace), due to the essence of the production that is powered, its also high, technological process of power consumption
Time-consuming, does not meet the important guiding thought of China's Energy Conservation.
The content of the invention
In order to overcome above-mentioned problems of the prior art, prepare cathode of lithium battery the invention provides a kind of same stove and use
The method of graphite material and carborundum.
The present invention realizes above-mentioned purpose using following technical scheme：
A kind of method that same stove prepares cathode of lithium battery graphite material and carborundum, it is comprised the following steps：
1) prepared by powder
Anthracite is crushed, powder body material is made；
2) high temperature graphitization
By step 1) gained powder body material be placed in crucible, to furnace foundation bottom, burner/stove tail wall and removable furnace wall
Filling insulation material, the reaction material for producing carborundum and the crucible, some crucibles after filler in the acheson furnace of plate
It is arranged on the burner of the acheson furnace/stove tail wall direction, the periphery of the crucible is wrapped completely with general decomposition graphite
Cover, constitute combustion chamber layer, the combustion chamber layer is located at the middle part of the acheson furnace；The periphery of the combustion chamber layer is complete by the reaction material
Full cladding, the periphery of the reaction material is coated completely by the insulation material of fit the furnace foundation bottom, wall and wallboard inwall；By Ai Qi
Inferior stove is powered, and combustion chamber temperature is reached 1700~3300 DEG C, and feeding is cooled down after calcining, respectively obtains graphite and carborundum.
Acheson furnace of the invention is acheson furnace customary in the art, preferably with following structure：
The body of heater 1 of the acheson furnace has furnace foundation bottom 2, and the furnace foundation bottom is fluted body, and in the opening of the groove
End face 201a and 201b that two ends at end Ju You not stretch out, the cross section of the groove at the furnace foundation bottom is for opening is big
The small upside-down trapezoid in bottom.Two end face 201a and 201b at the furnace foundation bottom are supported by pillar 6a and 6b respectively, the furnace foundation bottom
Bottom is provided with the multiple pillars 5 for supporting it, and the pillar 6a and 6b and multiple pillars 5 make the furnace foundation bottom hanging
In ground.Moveable furnace wall plate 4a and 4b are provided with described two end face 201a and 201b at the furnace foundation bottom, described
Two other side at furnace foundation bottom is installed with the burner wall 3a and stove tail wall 3b and the stove for blocking the furnace foundation underseal
The height of head wall and stove tail wall is all higher than the height of movable hearth furnace the wallboard 4a and 4b, to form a surrounding sealing
The cavity that top opens.
Wherein, the movable hearth furnace wallboard is by cast iron framework and is filled in refractory brick therein and constitutes, and is stayed in filling
There is air-vent.The burner wall and stove tail wall are respectively by positioned at upper and lower refractory brickwork and the electrically conductive graphite being located therein
Electrode 7a and 7b are constituted.The body of heater unless otherwise indicated, with refractory brick configuration.
Preferred feeding manner is：
1) fed from the acheson furnace top, lay certain thickness insulation material to the furnace foundation bottom first, then existed
The separated material of two pieces of height parallel to the furnace wall plate and higher than the burner wall is inserted into the stove base groove respectively
I, the material baffle I are isometric with the furnace wall plate for plate, then loaded between the material baffle I and furnace wall plate with the furnace wall plate etc.
Insulation material high；
2) certain thickness reaction material is laid between two pieces of material baffle I, then between two pieces of material baffle I, respectively described
Stove base groove is inserted into two pieces of material baffle II parallel with the furnace wall plate and higher than the burner wall, the material baffle
II is identical with the length of the furnace wall plate；
3) in certain thickness general decomposition graphite is laid in the reaction material completed between two pieces of material baffle II, thereon
Equideparture set several along burner stove tail wall line it is in one line be filled with step 2) gained powder crucible, then proceed to
The general decomposition graphite of filling is to the crucible by the general decomposition graphite coat so that the general graphite that decomposes in crucible upper strata has
Certain thickness, forms combustion chamber layer；
4) continue to load reaction material between material baffle I and II, until the upper limb in combustion chamber layer is flushed；
5) take out and remove except two pieces of material baffle II, the certain thickness reaction material between two pieces of material baffle I so that the reaction bed of material exists
Section at the slot opening of furnace foundation bottom is in up-narrow and down-wide trapezoidal；
6) take out and remove except two pieces of thermal insulation board I, the top down from the trapezoidal reaction material is according to the trapezoidal insulation material
Profile lays insulation material so that section of the outer eaves of the insulation material that the step is laid at the slot opening of furnace foundation bottom, in the stove
Also up-narrow and down-wide trapezoidal shape is constituted on wallboard, the top of the insulation material is contour with the burner stove tail wall.
After final charging, described several crucible word orders are in the burner/stove tail wall direction, the earthenware of acheson furnace
The general graphite that decomposes in the periphery of crucible is coated completely, constitutes combustion chamber layer, and the combustion chamber layer is located at the middle part of the acheson furnace；It is described
The periphery of combustion chamber is coated completely by the reaction material, and the periphery of the reaction material is fitted in the furnace foundation bottom, wall and wallboard
The insulation material of wall is coated completely.
Heretofore described combustion chamber layer constitutes the resistance material in carborundum production, the reaction material for producing carborundum
Constitute the insulation material for the production of lithium electro-graphitic negative material.
Preferably, step 1) pulverizing process before may also include anthracite precalcining, the step of forming calcining and chat, preferably
Precalcining is carried out using can-type calcine furnace or electric heating calcining furnace, powder is carried out after forming can-type calcine furnace or electric heating calcining material
It is broken；It is preferred that the precalcining temperature is 1000~2000 DEG C；The precalcination time is 8~30h.
Alleged can-type calcine furnace (being commonly called as general forge furnace) of the invention is commonly used in the art, and it is spread out of with refractory brick wall with flues
Heat indirectly heat carbon raw material.
Alleged electric heating calcining furnace (being commonly called as electric forge furnace) of the invention is also commonly used in the art, and it is converted to by electric energy
Heat energy is heated, and calcined material plays a part of resistance heater simultaneously.
Preferably, step 1) in the gained index that has of powder body material be：
D10=5~10 μm；D50=11~24 μm；D90=25~55 μm；Dmax≤80μm；
Wherein, DnThe equivalent diameter (average grain diameter) of the largest particles when cumulative distribution is n% in expression distribution curve, it
Physical significance to be particle diameter account for n% less than the particle of the equivalent diameter.
In the present invention, as long as the particle diameter of the powder is in the range of These parameters, can just be used for follow-up lithium cell negative pole material
The production of material, will not be because influenceing the electric property of final products with numerical value different in the range of limiting.
Preferably, the reaction material of the production carborundum includes carbon raw material and silicon raw material, wherein carbon and element silicon
Mol ratio is 0.5-0.8.
Preferably, the carbon raw material includes anthracite and petroleum coke, and the silicon raw material includes quartz sand.
Preferably, the insulation material be anthracite, quartz sand, petroleum coke, graphite and reaction material reaction after evaporate it is poly-
One or more in the inorganic contaminants of collection, the inorganic contaminants include silica, alundum (Al2O3), calcium oxide.
Insulation material of the invention mainly produces the waste material of carborundum and graphite when institute output, and unreacted can be included in the waste material
Complete anthracite, quartz sand, petroleum coke and graphite etc., do not determine specific into being grouped into when using.
Preferably, step 3) described in calcination time be 8~80h.
Preferably, the general decomposition graphite can be the Delanium of generation in native graphite or carborundum production.
Carborundum can decompose reaction at too high a temperature, form gaseous silicon and solid artificial stone ink.The present invention
Combustion chamber temperature is high, and the carborundum near combustion chamber may again be decomposed after being formed by high temperature, so as to constitute into the general decomposition stone of combustion chamber
A part for ink.
Preferably, step 1) and step 2) in the anthracite with graphite is broken, needle coke, native graphite, carbon fiber, in
Between one or more in phase carbosphere or thermal decomposed resins carbon replace or, needle coke broken with graphite, native graphite, carbon fiber,
One or more combination in carbonaceous mesophase spherules or thermal decomposed resins carbon is used as raw material.
Preferably, the anthracite is Taixi anthracite.
Taixi anthracite alleged by the present invention refers to the anthracite that Ningxia Shizuishan City Rujigou coalfield produces.
The performance parameter of the inventive method products obtained therefrom and the unnecessary relation of crucible number for using, can be according to this area
The size of the acheson furnace known, and reality product yield demand, the number and its and sic raw material of any selection crucible
Ratio.
The beneficial effects of the present invention are：
When in the present invention with anthracite as raw material, low cost, environment harmful components are few：
1. the raw materials for production of pair three negative material producers are investigated, it is found that factory is entered by different negative material producers former
Material composition and price differ larger.It is calcined coke, Shanghai China fir China fir wherein to share new energy with Shanghai China fir Taxodiaceae Ji Jin factories raw material
Shuo Nengjin factories raw material is low-sulfur green coke.As shown in Table 1, equal sulfur-bearing in existing calcined coke and low-sulfur green coke, will in subsequent production
The discharge of the disagreeableness sulfurous pollutants of generation environment, and it is expensive, cause production that there is higher cost.Raw material of the invention
It is cheap, production cost is substantially reduced, and the bad composition of environment is free of in raw material, reduce the environment brought in production process
Pollution hidden trouble.
The negative material preparing raw material index of table 1 and price
2., because anthracitic density is higher than bituminous coal, after high temperature carbonization, it is on gram volume, cycle life, high rate performance
Have the performance advantage of graphitized carbon and ungraphitised carbon concurrently simultaneously, extension enriches the raw material for preparing cathode of lithium battery graphite material
Species.
3. the present invention need not be malleation using pressure in extra auxiliary material, and reaction system of the present invention, it is not necessary to use
Protective gas, technological process economy is simple.
4. the present invention produces cathode of lithium battery graphite material and carborundum with stove, can produce following good effect：1) ether
Western anthracite is raw material, due to the characteristic of raw material itself, larger stove can be produced to hinder, thus caloric value is larger, product graphite
Change degree is higher；2) furnace body temperature can be further improved as insulation material while carborundum is as product, is effectively reduced into
This improves the quality of another product (graphitization anthracite) simultaneously；3) two kinds of materials are loaded and output with stove, two kinds of lifes of material
Production. art unites two into one, and power consumption and production time are greatly reduced relative to the production of single stove, and have saved the use of auxiliary material, compared with
Power consumption cost is lacked, it is achieved thereby that production energy-saving.
5. also can use his material to replace anthracite to be raw material in the present invention, lithium cell negative pole material and carborundum produced with stove,
While production energy-saving, lithium cell negative pole graphite material suitable with the product electric property that existing graphitizing furnace is produced can be also obtained
Material.
Brief description of the drawings
Fig. 1 is the general flow chart of production technology of the present invention.
Fig. 2 is the generalized section of acheson furnace Facad structure used in optimal implementation of the invention.
Before Fig. 3 is charging used in of the invention optimal implementation (on) and after feeding (under) acheson furnace side structure
Generalized section.
Fig. 4 is the generalized section of acheson furnace combustion chamber used in optimal implementation of the invention.
Wherein reference is：1. body of heater；2. furnace foundation bottom；201a/201b. furnace foundation basal cross sections end；3a. burner walls；
3b. stove tail walls；4a/4b. movable hearth furnace wallboards；5. pillar；6a/6b. pillars；7a/7b. electrically conductive graphite electrodes；8. insulation material
Layer；9. the bed of material is reacted；10. combustion chamber layer；11. crucibles.
Specific embodiment
With reference to embodiments and accompanying drawing the present invention is described in detail, but it is not construed as limitation of the present invention.
Using anthracite for Shenhua Ningxia Coal Industry Group goes out in Ningxia Shizuishan City Rujigou coalfield in the embodiment of the present invention
The Taixi anthracite of product, product index：Ash content 3.46%, fugitive constituent 8.91%；Quartz sand comes from Qinghai Renhe quartz sand factory, two
Silica content 99.14%；Insulation material is Shenhua Ningxia Coal Industry Group production carborundum and the waste material of graphite institute output, and it is included
The complete anthracite of unreacted, quartz sand and graphite etc..
The instrument that the present invention is used includes：
Air-flow vortex pulverizing mill：Zhejiang new century disintegrating apparatus Co., Ltd, XQCM-30；
Laser particle analyzer：American-European gram instrument company, LS-609 types.
Acheson furnace used by the present embodiment is that Shenhua is self-built, with following structure：The body of heater 1 of the acheson furnace has stove
Substrate 2, the furnace foundation bottom is fluted body, and the end face that Ju You do not stretch out in two ends of the openend of the groove
201a and 201b, the cross section of the groove at the furnace foundation bottom is the opening small upside-down trapezoid in bottom, the bottom of the trapezoidal groove greatly
The length in portion is 2200mm, and the length of openend is 3100mm.Two end face 201a and 201b at the furnace foundation bottom are respectively by propping up
Post 6a and 6b are supported, and furnace foundation bottom bottom is provided with the multiple pillars 5 for supporting it, the pillar 6a and 6b and multiple institutes
Stating pillar 5 makes the furnace foundation bottom be suspended on ground.It is provided with removable on described two end face 201a and 201b at the furnace foundation bottom
Dynamic furnace wall plate 4a and 4b, the burner wall for blocking the furnace foundation underseal is installed with two other side at the furnace foundation bottom
The height of 3a and stove tail wall 3b and the burner wall and stove tail wall is all higher than the height of movable hearth furnace the wallboard 4a and 4b
Degree, the cavity that top opens to form a surrounding sealing.Wherein, the furnace foundation bottom is along burner wall and stove tail wall direction
30m long.
Wherein, the movable hearth furnace wallboard is by cast iron framework and is filled in refractory brick therein and constitutes, and is stayed in filling
There is air-vent.The burner wall and stove tail wall are respectively by positioned at upper and lower refractory brickwork and the electrically conductive graphite being located therein
Electrode 7a and 7b are constituted.The body of heater unless otherwise indicated, with refractory brick configuration.
Crucible, the processing of commission Ningxia Yong Weitansu companies, external diameter 450mm, internal diameter 410mm, square graphite crucible.
Embodiment 1：
1) Taixi anthracite is calcined 18 hours through can-type calcine furnace in 1200 ± 50 DEG C, obtains pot type calcining material, gained
The ratio resistance of pot type calcining material is 1246 μ Ω m, and fugitive constituent is 1.18%, and ash content is 3.49%.
2) by step 1) gained pot type calcining material through air-flow vortex pulverizing mill crush, be made powder body material.Using laser grain
Degree instrument is detected that the specific particle size parameters of gained powder are as shown in table 2.
3) production of anthracitic graphitization and carborundum is carried out using the acheson furnace described in accompanying drawing 2-4.By step
2) gained powder loads crucible, and crucible is housed in stove.
By Taixi anthracite and quartz sand by 0.64 carbon element silicon molar ratio ingredient, reaction material is mixed to form.
From acheson furnace top charging, first to the insulation material that furnace foundation bottom laying 700mm is thick, then respectively
Two pieces are inserted into parallel to the furnace wall plate and higher than institute to the stove base groove at 580mm away from furnace wall the plate 4a and 4b
The thermal insulation board I, the thermal insulation board I for stating the height of burner wall are isometric with the furnace wall plate, then in the thermal insulation board I and furnace wall
The insulation material contour with the furnace wall plate is loaded between plate；
The reaction material of 900mm is laid between two pieces of thermal insulation board I, then between two pieces of thermal insulation board I, respectively heat-insulated away from two pieces
At plate I 700mm to the stove base groove be inserted into two pieces it is parallel with the furnace wall plate and higher than the burner wall every
II, the thermal insulation board II are identical with the length of the furnace wall plate for hot plate, two plate spacing 650mm；
In the thick general decomposition graphite of 200mm is laid in the reaction material completed between two pieces of thermal insulation board II, thereon etc.
Anomaly set 30 along burner stove tail wall line it is in one line be filled with step 2) gained powder crucible, then proceed to filling
It is general decomposition graphite to the crucible by the general decomposition graphite coat so that crucible upper strata it is general decompose graphite thickness be
150mm, forms combustion chamber layer；
Continue to load reaction material between thermal insulation board I and II, until the upper limb in combustion chamber layer is flushed；
Take out and remove except two pieces of thermal insulation board II, the thick reaction materials of 950mm are loaded between two pieces of thermal insulation board I so that the 950mm is thick
Section of the reaction material at the slot opening of furnace foundation bottom be in up-narrow and down-wide trapezoidal, the trapezoidal top 700mm wide；
Take out and remove except two pieces of thermal insulation board I, the top down from the trapezoidal reaction material is according to the outer of the trapezoidal insulation material
Shape lays insulation material so that section of the outer eaves of the insulation material that the step is laid at the slot opening of furnace foundation bottom, in the furnace wall
Also up-narrow and down-wide trapezoidal shape, the trapezoidal top 700mm wide, the top of the insulation material and the burner stove are constituted on plate
Tail wall is contour.
After final charging, 30 crucible word orders are in the burner/stove tail wall direction, the crucible of acheson furnace
The general graphite that decomposes in periphery coat completely, constitute combustion chamber layer, combustion chamber layer is located at the middle part of the acheson furnace；The stove
The periphery of core is coated completely by the reaction material, and the periphery of the reaction material is by the furnace foundation bottom, wall and the wallboard inwall of fitting
Insulation material coat completely.
4) power transmission calcining, makes power transmission power that the 50% of rated transformer power is reached after power transmission half an hour, and power transmission half is small
Up to after one hour, power transmission power reaches the 100% of rated transformer power, final to control combustion chamber temperature for 2800 ± 200 DEG C,
Calcining 62h.
5) to be cooled to pull down insulation material with hook machine to room temperature after power transmission terminates, the carborundum for obtaining being generated by reaction material is produced
Product；And rear shovel walks the general decomposition graphite around crucible, crucible is taken out, obtained loaded on the lithium electro-graphitic negative material in crucible.
6) parameters obtained is listed in table to be detected to step 4 products obtained therefrom using the method in GB GB-24533-2009
In 3.
Embodiment 2：
1) Taixi anthracite is calcined 20 hours through electric heating calcining furnace in 1700 ± 100 DEG C, obtains electric heating calcining material, gained
The ratio resistance of electric heating calcining material is 600 μ Ω m, and fugitive constituent is 0.25%, and ash content is 5.3%.
2) by step 1) gained electric heating calcining material through air-flow vortex pulverizing mill crush, be made powder body material.Using laser grain
Degree instrument is detected that the specific particle size parameters of gained powder are as shown in table 2.
3) using and step 3 in embodiment 1)-step 6) identical method is to the present embodiment step 2) gained powder body material
Calcined in acheson furnace, with stove produce carborundum, and detect gained lithium electro-graphitic negative material chemical property, institute
Parameter is obtained to be listed in Table 3 below.
Embodiment 3：
1) Taixi anthracite is crushed through air-flow vortex pulverizing mill, is made powder body material.Examined using laser particle analyzer
Survey, it is specific as shown in table 2.
2) using and step 3 in embodiment 1)-step 6) identical method is to the present embodiment step 1) gained powder body material
Calcined in acheson furnace, with stove produce carborundum, and detect gained lithium electro-graphitic negative material chemical property, institute
Parameter is obtained to be listed in Table 3 below.
The Taixi anthracite of table 2, embodiment 2 and in embodiment 3 resulting material size distribution
Table 3 is prepared by raw material with Taixi anthracite, the general material and the gained electric heating of embodiment 3 calcining material forged of the gained of embodiment 2
The properties of product of lithium electro-graphitic negative material
From table 3, the index of products obtained therefrom has reached the Delanium class (oil of national regulations in embodiment 1-3
Burnt base) class standard of negative material II.
Embodiment 4：
As raw material, made respectively with the graphite that Qingdao Shuo Feng graphite products Co., Ltd provides broken (fixed carbon content 99.5%)
With method and condition described in embodiment 3, cathode of lithium battery graphite material and carborundum, gained cathode of lithium battery are prepared with stove
The performance of graphite material is as shown in table 4：
Table 4 is with the properties of product of graphite is broken and needle coke is prepared as raw material lithium electro-graphitic negative material
Comparative example 1：
Graphitization is carried out using internal thermal tandem graphitization furnace is broken to graphite, the internal thermal tandem graphitization furnace has existing skill
Conventional use of construction, specially horizontal type structure in art, body of heater generally rectangle, are enclosed by furnace body wall and formed, the body of heater
Partition wall is provided with the walls, and body of heater is divided into 30 independent bodies of heater longitudinally concatenated by electrode column by it, is provided with equipped with stone in each body of heater
The broken crucible of ink.Crucible outside is coated with insulation material coke.Resistance material, electric current is not used directly to be produced by electrode column in the method
Raw high temperature, graphitization calcining 12h is carried out in 2800 ± 200 DEG C, and the performance of gained lithium cell negative pole material is as follows after calcining：
Table 5 is with the performance of graphite is broken and needle coke is produced as raw material cathode of lithium battery graphite material
With Taixi anthracite as raw material prepare lithium cell negative pole material using same stove preparation method of the invention when, products obtained therefrom
With excellent chemical property, and cost of material is more cheap, reduces cost.And two kinds of products output simultaneously, energy consumption and
Production time substantially reduces.Additionally, with single stove production lithium cell negative pole material technique compared with, with stove production lithium cell negative pole material and
Carborundum, while production energy-saving, can also obtain lithium electro-graphitic negative material suitable with the product electric property that single stove is produced.
Claims (10)
1. a kind of method that same stove prepares cathode of lithium battery graphite material and carborundum, it is comprised the following steps：
1) prepared by powder
Anthracite is crushed, powder body material is made；
2) high temperature graphitization
By step 1) gained powder body material be placed in crucible, to furnace foundation bottom, burner/stove tail wall and movable hearth furnace wallboard
Filling insulation material, the reaction material for producing carborundum and the crucible in acheson furnace, some crucibles are set after filler
It is placed on the burner of the acheson furnace/stove tail wall direction, the periphery of the crucible is coated completely with general decomposition graphite, structure
Into combustion chamber layer, the combustion chamber layer is located at the middle part of the acheson furnace；Wrapped completely by the reaction material periphery of the combustion chamber layer
Cover, the periphery of the reaction material is coated completely by the insulation material of fit the furnace foundation bottom, wall and wallboard inwall；By acheson furnace
It is powered, combustion chamber temperature is reached 1700~3300 DEG C, feeding is cooled down after calcining, respectively obtains graphite and carborundum.
2. method according to claim 1, it is characterised in that step 1) pulverizing process before may also include anthracite is pre-
Calcining, forms the step of calcining material, and preferably using can-type calcine furnace or electric heating calcining furnace carries out precalcining, forms pot type calcining
Crushed after material or electric heating calcining material；It is preferred that the precalcining temperature is 1000~2000 DEG C；The precalcination time is 8
~30h.
3. method according to claim 1 and 2, it is characterised in that step 1) in the index that has of gained powder body material be：
D10=5~10 μm；D50=11~24 μm；D90=25~55 μm；Dmax≤80μm。
4. the method according to foregoing any one claim, it is characterised in that the reaction material of the production carborundum includes carbon
The mol ratio of raw material and silicon raw material, wherein carbon and element silicon is 0.5-0.8.
5. method according to claim 4, it is characterised in that the carbon raw material includes anthracite and petroleum coke, the silicon is former
Material includes quartz sand.
6. the method according to foregoing any one claim, it is characterised in that the insulation material is anthracite, quartz sand, stone
One or more in the inorganic contaminants of aggregation, the inorganic contaminants are evaporated after the reaction of oil coke, graphite and reaction material
Including silica, alundum (Al2O3), calcium oxide.
7. the method according to foregoing any one claim, it is characterised in that step 3) described in calcination time be 8~
80h。
8. the method according to foregoing any one claim, it is characterised in that the general decomposition graphite can be natural stone
The Delanium produced in ink or carborundum production.
9. the method according to foregoing any one claim, it is characterised in that step 1) and step 2) in the anthracite
Replace for one or more with graphite is broken, in needle coke, native graphite, carbon fiber, carbonaceous mesophase spherules or thermal decomposed resins carbon or
Person is broken with graphite, combine for one or more in needle coke, native graphite, carbon fiber, carbonaceous mesophase spherules or thermal decomposed resins carbon
Used as raw material.
10. the method according to any one in claim 1-9, it is characterised in that the anthracite is Taixi anthracite.
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| CN109626369A (en) * | 2019-01-31 | 2019-04-16 | 吴建云 | A kind of application of graphitizing furnace about roasting technique |
| CN111232970A (en) * | 2018-11-28 | 2020-06-05 | 上海杉杉科技有限公司 | Graphite negative electrode material, lithium ion battery, preparation method and application |
| CN111362260A (en) * | 2018-12-26 | 2020-07-03 | 宁波杉杉新材料科技有限公司 | High-compaction graphite negative electrode material of lithium ion battery and preparation method of high-compaction graphite negative electrode material |
| WO2022257372A1 (en) * | 2021-06-10 | 2022-12-15 | 国家能源投资集团有限责任公司 | Graphite negative electrode material, preparation method therefor and use thereof |
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