CN103311520B - A kind of lithium ion battery composite graphite negative electrode material and preparation method thereof - Google Patents
A kind of lithium ion battery composite graphite negative electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of lithium ion battery composite graphite negative electrode material, it comprises the steps: 1. spherical natural graphite, meso-phase graphite and graphitization catalyst mix homogeneously to be obtained compound；2. mediate compound and binding agent obtains kneaded material；3. carbonization processes, and carries out catalyzed graphitization high-temperature process after cooling again；4. pulverizing, classification,.The preparation method simple possible of the present invention, it is adaptable to industrialized production.Obtained composite graphite negative electrode material chemical property is good, discharge capacity is at more than 360mAh/g, there is high charge-discharge efficiencies, high rate during charging-discharging is good, and cycle performance is good, only has small expansion during charging, safety is good, preferable to electrolyte and other additive adaptability, and use the lithium ion battery product property obtained by this composite graphite negative electrode material stable, almost without difference between batch.
Description
Technical field
The present invention relates to a kind of lithium ion battery composite graphite negative electrode material and preparation method thereof.
Background technology
In recent years, along with the miniaturization of electronic installation, the secondary cell of more capacity is had increasing need for.Attract people's attention especially
Be lithium ion battery, compared with NI-G or Ni-MH battery, use lithium ion battery there is higher energy density.Although at present
Have been directed towards improving battery capacity and carried out widely studied, but, along with the raising to battery performance requirements, need to carry further
High battery capacity.
Native graphite has the highest capacitance (＞ 350mAh/g), but there is structural unstable shortcoming.When in order to
When obtaining higher electrode density and improve squeeze pressure, graphite cathode granule is prone to be orientated abreast with collector, whole
Produce consistent orientation on electrode, insert lithium owing to graphite existing, so the electrode obtained is prone to expand.Electrode expansion makes electricity
Pond active substance can reduce by loading in unit volume, produces the problem that battery capacity reduces.
Meso-phase graphite (i.e. carbonaceous mesophase spherules) product is excellent lithium ion battery negative material, have current potential low and
The feature such as flatness is good, higher than efficiency for charge-discharge great, the initial stage and processability is good.But the reversible lithium storage of meso-phase graphite
Capacity also has, at about 310mAh/g, capacity, the space risen.
In order to solve the problems referred to above, use native graphite to mix with meso-phase graphite, Colophonium etc. and catalyzed graphitization etc. just
Method processes can be effectively improved lithium ion battery negative material quality, not only can improve the reversible lithium storage capacity of graphite, and
And the cycle performance of material can be improved." " investigation of materials journal " Vol.21No.4 is P.404-408 " reports catalytic thermal treatment
Mesocarbon Microbeads For Lithium Ion Battery, alleviates the irreversible electrochemical reaction of carbon surface effectively.United States Patent (USP)
US2006001003 reports the method that catalyzed graphitization processes Delanium class negative material, can improve fast charging and discharging performance
And cycle performance.Contour for flake natural graphite crystalline graphite is mixed, through powder by Japan Patent JP2000-182617 with Colophonium
Broken, carbonization, graphitization and make complex, the deficiency of native graphite, i.e. first charge-discharge efficiency can be improved high, cycle characteristics
Excellence, capacity is big and coating is excellent.Japan Patent JP2003-173778 is multiple with flake natural graphite by melt kneading Colophonium
Closing, carry out mechanochemistry, graphitization processing, prepare spherical or oval composite graphite material, this composite is by graphite
Core and the composite particles of graphite coat shell composition.
In graphite cathode material disclosed in above-mentioned patent documentation, the graphite of flat pattern is prone at compound powder and electrode
Middle orientation, it is impossible to stoping electrode expansion, the lithium ion mobility causing material is poor, battery capacity is less than 355mAh/g, discharge and recharge
Efficiency is low.
Summary of the invention
It is low that the technical problem to be solved is to overcome existing graphite cathode material discharge capacity, cycle performance
The defect of difference, it is provided that a kind of lithium ion battery composite graphite negative electrode material and preparation method thereof.The preparation method letter of the present invention
Single feasible, it is adaptable to industrialized production, obtained composite graphite negative electrode material chemical property is good, has high charge-discharge capacity
And efficiency for charge-discharge, high rate during charging-discharging is good, and cycle performance is good, only has small expansion during charging, and safety is good, to electricity
Solve liquid and other additive adaptability is preferable, and use the lithium ion battery product obtained by this composite graphite negative electrode material
Matter is stable, almost without difference between batch.
The present invention solves above-mentioned technical problem by the following technical programs.
The invention provides the preparation method of a kind of lithium ion battery composite graphite negative electrode material, it comprises the steps:
1. spherical natural graphite, meso-phase graphite and graphitization catalyst mix homogeneously are obtained compound；2. mediate described compound and
Binding agent obtains kneaded material；3. carbonization processes, and carries out catalyzed graphitization high-temperature process after cooling again；4. pulverizing, classification,.
Step 1. in, described spherical natural graphite can be selected for the spherical natural graphite of the various routine in this area.Described ball
The particle diameter of shape native graphite can be the conventional particle size of this type of material of this area, the volume average particle size of described spherical natural graphite
D50 is preferably 12～36 μm.
Step 1. in, described meso-phase graphite can be selected for the meso-phase graphite of the various routine in this area.Described mesophase
The particle diameter of graphite can be the conventional particle size of this type of material of this area, and volume average particle size D50 of described meso-phase graphite is preferably
It is 10～30 μm.
Step 1. in, described graphitization catalyst can be selected for the graphitization catalyst of the various routine in this area, preferably
For carbide and/or the oxide of ferrum of silicon, it is more preferably SiC and/or Fe2O3。
Step 1. in, the mass ratio of described spherical natural graphite and meso-phase graphite is preferably 1: 1～19: 1, more preferably
It is 7: 3～9: 1.The consumption of described graphitization catalyst be preferably spherical natural graphite and the 1 of meso-phase graphite gross mass～
10%, it is more preferably 3～8%.
Step 1. in, the condition of described mixing and method are the conventional condition in this area and method, preferably use cantilever
Double-spiral conical mixer is carried out.The time of described mixing is preferably 1.5～3.0 hours.
Step 2. in, described binding agent refer in graphite cathode material field conventional can bond native graphite, in
Between phase graphite, and the binding agent of Delanium after graphitization, can be made, preferably asphalt and/or coal tar pitch.Institute
Asphalt, the coal tar pitch stated all can be selected for the asphalt of this area all size, coal tar pitch.Described binding agent is preferably
Middle fire stons oil asphalt and/or medium temperature coal pitch.The consumption of described binding agent can be the consumption that this area is conventional.Described compound with
The mass ratio of binding agent is preferably 1: 1～9: 1, is more preferably 3: 2～3: 1.
Step 2. in, the condition of described kneading and method are the conventional condition in this area and method.Kneading processes and can change
The processing characteristics of kind native graphite.The temperature of described kneading is preferably 100～180 DEG C.The time of described kneading is preferably 1
～10 hours.
Step 2. in, the most also carry out briquetting process after described kneading, in order to following process process.Described briquetting
The condition and the method that process can use the condition of the various routine in this area and method to carry out, such as extruded, mould molding or cold
Isostatic pressing, preferably briquetting becomes cylindrical or rectangle.
In a better embodiment of the present invention, after described kneading, before described briquetting processes, also carry out following
Operation: in tablet machine, described kneaded material is pressed into 2～5mm lamellars, is ground into the particle diameter powder at below 0.1mm.
Step 3. in, condition that described carbonization processes and method are the conventional condition in this area and method.At described carbonization
The temperature of reason is preferably 800～1500 DEG C.The time that described carbonization processes is preferably 2～6 hours.By common sense in the field,
The atmosphere that described carbonization processes is inert atmosphere.
Step 3. in, the condition of described cooling and method are the conventional condition in this area and method, are usually cooled to room
Temperature.
Step 3. in, the condition of described catalyzed graphitization high-temperature process and method are the conventional condition in this area and method.
The temperature of described catalyzed graphitization high-temperature process is preferably 2800～3200 DEG C.The time of described catalyzed graphitization high-temperature process
Preferably 24～48 hours.By common sense in the field, the atmosphere of described catalyzed graphitization high-temperature process is inert atmosphere.
Step 4. in, the condition of described pulverizing and method are the conventional condition in this area and method.Described pulverizing is preferable
Ground first carries out coarse pulverization, then carries out middle pulverizing, finally carries out Crushing of Ultrafine, to guarantee that grain diameter and specific morphology disclosure satisfy that this
The requirement of invention.The equipment of described coarse pulverization is preferably with jaw crusher；Grain diameter after described coarse pulverization is preferably
At below 30mm.The equipment of described middle pulverizing is preferably with plate-hammer crusher；Grain diameter after described middle pulverizing is preferable
Ground is at below 10mm.Described fine equipment is preferably with ultra-fine mechanical crusher；Grain diameter after described Crushing of Ultrafine
Preferably at below 1mm.
Step 4. in, the condition of described classification and method are the conventional condition in this area and method, the most first sieve
Divide and carry out Hydrodynamic Fractionation again.Described screening and the condition of Hydrodynamic Fractionation and method are condition and the side of this area routine
Method.250 mesh sieve extracting screen underflows are preferably crossed in described screening, more preferably use 250 mesh vibration type screening machines to carry out.Described stream
Mechanics classification preferably uses gas flow sizing machine to carry out.The frequency of described gas flow sizing machine is preferably 20～60Hz.Through institute
After stating classification, volume average particle size D50 of described composite graphite negative electrode material is 10～30 μm.
Present invention also offers a kind of lithium ion battery composite graphite negative electrode material prepared by above-mentioned preparation method.
Wherein, volume average particle size D50 of described composite graphite negative electrode material is 10～30 μm.Described composite graphite negative electrode
The specific surface area of material is 3.0～4.0m2/g.The true density of described composite graphite negative electrode material is at 2.20g/cm3Above.Described
The ash of composite graphite negative electrode material is at below 0.10wt%.
In the present invention, described room temperature is the ambient temperature that this area is conventional, preferably 5～40 DEG C.
On the basis of meeting common sense in the field, above-mentioned each optimum condition, can combination in any, obtain each preferable reality of the present invention
Example.
Agents useful for same of the present invention and raw material are the most commercially.
The most progressive effect of the present invention is:
1, the discharge capacity of the composite graphite negative electrode material of the present invention is big and good cycle, its button cell made
High comprehensive performance, mainly has the advantage that 1) chemical property is good, and discharge capacity is at more than 360mAh/g；2) discharge platform
And platform conservation rate is higher；3) high rate during charging-discharging is preferable；4) good cycle (300 times circulation, capacity keep >=
80%)；5) safety preferably (130 DEG C/60 minutes, the most quick-fried, do not rise)；6) preferable to electrolyte and other additive adaptability；
7) its product property prepared is stable, almost without difference between batch.
2, the preparation method simple possible of the present invention, it is adaptable to industrialized production.
Accompanying drawing explanation
Fig. 1 is the first charge-discharge curve chart of the composite graphite negative electrode material of the embodiment of the present invention 2.
Fig. 2 is the absorbency curve chart of the composite graphite negative electrode material of the embodiment of the present invention 2.
Fig. 3 is the cycle performance figure of the composite graphite negative electrode material of the embodiment of the present invention 2.
Detailed description of the invention
Further illustrate the present invention below by the mode of embodiment, but the most therefore limit the present invention to described reality
Execute among example scope.The experimental technique of unreceipted actual conditions in the following example, conventionally and condition, or according to business
Product description selects.
In following embodiment, the asphalt of use is the middle temperature of MQ-100 that Dalian bright strengthening work Materials Co., Ltd produces
Colophonium.The coal tar pitch used is the mid temperature pitch that Henan Bo Hai Chemical Co., Ltd. produces.The SiC used is that Linyi City gold covers carbon
The NAT6 carborundum that SiClx company limited produces.The native graphite used is the spherical sky that Shanghai Shanshan Science and Technology Co., Ltd produces
So graphite.The meso-phase graphite used is the CMS meso-phase graphite that Shanghai Shanshan Science and Technology Co., Ltd produces.
Embodiment 1
1. it is in 14.2 μm by native graphite 14kg, volume average particle size D50 that volume average particle size D50 is 19.3 μm
Between phase graphite 6kg and graphitization catalyst (SiC) 1.2kg add in cantilever double-spiral conical mixer and mix 2 hours, obtain mixing
Material；2. stirring is lower alternately joins in kneading pot by compound 20kg and asphalt 12kg, carries out kneading in 160 DEG C and processes 1
Hour, mediate after terminating, tablet machine is pressed into 2～5mm lamellars, is ground into the powder of below particle diameter 0.1mm, briquette forming；
3., under the protection of nitrogen, at a temperature of 1100 DEG C, carbonization processes 2 hours, afterwards product is cooled to room temperature, then at
2800 DEG C carry out 36 hours catalyzed graphitization high-temperature process；4. using jaw crusher to carry out coarse pulverization, grain diameter controls
Below 30mm；Using plate-hammer crusher to carry out middle pulverizing, grain diameter controls at below 10mm；Use ultra-fine mechanical crusher
Carrying out Crushing of Ultrafine, grain diameter controls at below 1mm；Using 250 mesh vibration type screening machine screenings, siftage uses air current classifying
Machine carries out classification, and the frequency of grading wheel is 48Hz, obtains the lithium ion battery composite stone that particle volume mean diameter D50 is 17.8 μm
Ink negative material.Recording its half-cell capacity is 362.5mAh/g, first charge-discharge efficiency 92.8%.
Embodiment 2
1. it is in 20.5 μm by native graphite 10kg, volume average particle size D50 that volume average particle size D50 is 17.8 μm
Between phase graphite 10kg and graphitization catalyst (SiC) 1.2kg add in cantilever double-spiral conical mixer and mix 2 hours, obtain mixed
Close material；2. stirring is lower alternately joins in kneading pot by compound 20kg and asphalt 3kg, carries out kneading in 160 DEG C and processes 1
Hour, mediate after terminating, tablet machine is pressed into 2～5mm lamellars, is ground into the powder of below particle diameter 0.1mm, briquette forming；
3. under the protection of nitrogen, and at a temperature of 800 DEG C, carbonization processes 6 hours, afterwards product is cooled to room temperature, then at
3000 DEG C carry out 48 hours catalyzed graphitization high-temperature process；4. using jaw crusher to carry out coarse pulverization, grain diameter controls
Below 30mm；Using plate-hammer crusher to carry out middle pulverizing, grain diameter controls 5～below 10mm；Use ultra-fine machinery powder
Broken machine carries out Crushing of Ultrafine, and grain diameter controls at below 1mm；Using 250 mesh vibration type screening machine screenings, siftage uses air-flow
Grader carries out classification, and the frequency of grading wheel is 35Hz, obtains the lithium ion battery that particle volume mean diameter D50 is 18.3 μm multiple
Close graphite cathode material.Record its half-cell capacity 363.1mAh/g, first charge-discharge efficiency 93.2%.
Embodiment 3
1. it is in 29.8 μm by native graphite 15kg, volume average particle size D50 that volume average particle size D50 is 12.1 μm
Between phase graphite 5kg and graphitization catalyst (SiC) 1.2kg add in cantilever double-spiral conical mixer and mix 2 hours, obtain mixing
Material；2. stirring is lower alternately joins in kneading pot by compound 20kg and asphalt 4kg, carries out kneading in 100 DEG C and processes 10
Hour, mediate after terminating, tablet machine is pressed into 2～5mm lamellars, is ground into the powder of below particle diameter 0.1mm, briquette forming；
3. under the protection of nitrogen, and at a temperature of 1500 DEG C, carbonization processes 3 hours, afterwards product is cooled to room temperature, then
48 hours catalyzed graphitization high-temperature process are carried out in 3200 DEG C；4. using jaw crusher to carry out coarse pulverization, grain diameter controls
At below 30mm；Using plate-hammer crusher to carry out middle pulverizing, grain diameter controls at below 10mm；Use ultra-fine mechanical activation comminution
Machine carries out Crushing of Ultrafine, and grain diameter controls at below 1mm；Using 250 mesh vibration type screening machine screenings, siftage uses air-flow to divide
Level machine carries out classification, and the frequency of grading wheel is 45Hz, obtains the lithium ion battery that particle volume mean diameter D50 is 17.4 μm and is combined
Graphite cathode material.Record its half-cell capacity 365.0mAh/g, first charge-discharge efficiency 92.6%.
Embodiment 4
1. it is in 10.7 μm by native graphite 19kg, volume average particle size D50 that volume average particle size D50 is 12.1 μm
Between phase graphite 1kg and graphitization catalyst (Fe2O3) 1.2kg adds in cantilever double-spiral conical mixer and mix 2 hours, obtains mixed
Close material；2. stirring is lower alternately joins in kneading pot by compound 20kg and coal tar pitch 5kg, and carrying out kneading in 140 DEG C, to process 5 little
Time, mediate after terminating, tablet machine is pressed into 2～5mm lamellars, is ground into the powder of below particle diameter 0.1mm, briquette forming；③
Under the protection of nitrogen, and at a temperature of 1000 DEG C, carbonization processes 4 hours, afterwards product is cooled to room temperature, then at
2800 DEG C carry out 48 hours catalyzed graphitization high-temperature process；4. using jaw crusher to carry out coarse pulverization, grain diameter controls
Below 30mm；Using plate-hammer crusher to carry out middle pulverizing, grain diameter controls at below 10mm；Use ultra-fine mechanical crusher
Carrying out Crushing of Ultrafine, Grain size controlling is at below 1mm；Using 250 mesh vibration type screening machine screenings, siftage uses gas flow sizing machine to enter
Row classification, the frequency of grading wheel is 60Hz, prepares the lithium ion battery composite graphite that particle volume mean diameter D50 is 10.6 μm
Negative material.Record its half-cell capacity 366.7mAh/g, first charge-discharge efficiency 93.0%.
Embodiment 5
1. it is in 14.2 μm by native graphite 14kg, volume average particle size D50 that volume average particle size D50 is 35.8 μm
Between phase graphite 6kg and graphitization catalyst (SiC) 0.28kg add in cantilever double-spiral conical mixer and mix 2 hours, obtain mixed
Close material；2. stirring is lower alternately joins in kneading pot by compound 20kg and asphalt 8kg, carries out kneading in 180 DEG C and processes 1
Hour, mediate after terminating, tablet machine is pressed into 2～5mm lamellars, is ground into the powder of below particle diameter 0.1mm, briquette forming；
3. under the protection of nitrogen, and at a temperature of 1100 DEG C, carbonization processes 2 hours, afterwards product is cooled to room temperature, then
24 hours catalyzed graphitization high-temperature process are carried out in 3200 DEG C；4. using jaw crusher to carry out coarse pulverization, grain diameter controls
At below 30mm；Using plate-hammer crusher to carry out middle pulverizing, grain diameter controls at below 10mm；Use ultra-fine mechanical activation comminution
Machine carries out Crushing of Ultrafine, and grain diameter controls at below 1mm；Using 250 mesh vibration type screening machine screenings, siftage uses air-flow to divide
Level machine carries out classification, and the frequency of grading wheel is 20Hz, prepares the lithium ion battery that particle volume mean diameter D50 is 30.4 μm multiple
Close graphite cathode material.Record its half-cell capacity 362.4mAh/g, first charge-discharge efficiency 92.8%.
Embodiment 6
1. it is in 14.2 μm by native graphite 10kg, volume average particle size D50 that volume average particle size D50 is 24.6 μm
Between phase graphite 10kg and graphitization catalyst (SiC) 2.0kg add in cantilever double-spiral conical mixer and mix 2 hours, obtain mixed
Close material；2. stirring is lower alternately joins in kneading pot by compound 20kg and asphalt 10kg, carries out kneading process in 160 DEG C
1 hour, mediate after terminating, tablet machine is pressed into 2～5mm lamellars, is ground into the powder of below particle diameter 0.1mm, briquette forming；
3. under the protection of nitrogen, and at a temperature of 900 DEG C, carbonization processes 5 hours, afterwards product is cooled to room temperature, then at
3200 DEG C carry out 48 hours catalyzed graphitization high-temperature process；4. using jaw crusher to carry out coarse pulverization, grain diameter controls
Below 30mm；Using plate-hammer crusher to carry out middle pulverizing, grain diameter controls at below 10mm；Use ultra-fine mechanical crusher
Carrying out Crushing of Ultrafine, grain diameter controls at below 1mm；Using 250 mesh vibration type screening machine screenings, siftage uses air current classifying
Machine carries out classification, and the frequency of grading wheel is 48Hz, prepares the lithium ion battery that particle volume mean diameter D50 is 16.8 μm and is combined
Graphite cathode material.Record its half-cell capacity 366.1mAh/g, first charge-discharge efficiency 92.4%.
Embodiment 7
1. it is in 20.5 μm by native graphite 12kg, volume average particle size D50 that volume average particle size D50 is 12.1 μm
Between phase graphite 8kg and graphitization catalyst (SiC) 1.2kg add in cantilever double-spiral conical mixer and mix 2 hours, obtain mixing
Material；2. stirring is lower alternately joins in kneading pot by compound 20kg and coal tar pitch 20kg, and carrying out kneading in 160 DEG C, to process 1 little
Time, mediate after terminating, tablet machine is pressed into 2～5mm lamellars, is ground into the powder of below particle diameter 0.1mm, briquette forming；③
Under the protection of nitrogen, and at a temperature of 1100 DEG C, carbonization processes 2 hours, afterwards product is cooled to room temperature, then at
3200 DEG C carry out 48 hours catalyzed graphitization high-temperature process；4. using jaw crusher to carry out coarse pulverization, grain diameter controls
Below 30mm；Using plate-hammer crusher to carry out middle pulverizing, grain diameter controls at below 10mm；Use ultra-fine mechanical crusher
Carrying out Crushing of Ultrafine, Grain size controlling is at below 1mm；Using 250 mesh vibration type screening machine screenings, siftage uses gas flow sizing machine to enter
Row classification, the frequency of grading wheel is 40Hz, prepares the lithium ion battery composite graphite that particle volume mean diameter D50 is 17.1 μm
Negative material.Record its half-cell capacity 363.6mAh/g, first charge-discharge efficiency 92.6%.
Embodiment 8
1. it is in 20.5 μm by native graphite 18kg, volume average particle size D50 that volume average particle size D50 is 17.8 μm
Between phase graphite 2kg and graphitization catalyst (SiC) 1.2kg add in cantilever double-spiral conical mixer and mix 2 hours, obtain mixing
Material；2. stirring is lower alternately joins in kneading pot by compound 20kg and asphalt 5kg, and carrying out kneading in 180 DEG C, to process 1 little
Time, mediate after terminating, tablet machine is pressed into 2～5mm lamellars, is ground into the powder of below particle diameter 0.1mm, briquette forming；③
Under the protection of nitrogen, and at a temperature of 1100 DEG C, carbonization processes 2 hours, afterwards product is cooled to room temperature, then at
2800 DEG C carry out 48 hours catalyzed graphitization high-temperature process；4. using jaw crusher to carry out coarse pulverization, grain diameter controls
Below 30mm；Using plate-hammer crusher to carry out middle pulverizing, grain diameter controls at below 10mm；Use ultra-fine mechanical crusher
Carrying out Crushing of Ultrafine, grain diameter controls at below 1mm；Using 250 mesh vibration type screening machine screenings, siftage uses air current classifying
Machine carries out classification, and the frequency of grading wheel is 48Hz, prepares the lithium ion battery that particle volume mean diameter D50 is 17.9 μm and is combined
Graphite cathode material.Record its half-cell capacity 362.7mAh/g, first charge-discharge efficiency 92.3%.
Comparative example 1
By the centre that native graphite 14kg that volume average particle size D50 is 19.3 μm, volume average particle size D50 are 14.2 μm
Phase graphite 6kg and graphitization catalyst (SiC) 1.2kg adds in cantilever double-spiral conical mixer and mixes 2 hours, obtains mixing
Material；Stirring is lower alternately to be joined in reactor by compound 20kg and asphalt 8kg, carries out hot cladding process, and cladding terminates
After at a temperature of 1100 DEG C carbonization process 2 hours, afterwards product is cooled to room temperature, carries out 48 hours then at 3200 DEG C
Catalyzed graphitization high-temperature process, uses 250 mesh vibration type screening machine screenings, and preparing particle volume mean diameter D50 is 19.4 μm
Lithium ion battery composite graphite negative electrode material.Record its half-cell capacity 367.0mAh/g, first charge-discharge efficiency 89.7%.
Comparative example 2
It is in 14.2 μm by native graphite 14kg and volume average particle size D50 that volume average particle size D50 is 19.3 μm
Between phase graphite 6kg add in cantilever double-spiral conical mixer and mix 2 hours, obtain composite graphite raw material；Stirring is lower alternately will
Composite graphite raw material 20kg and asphalt 8kg joins in kneading pot, carries out kneading in 160 DEG C and processes 1 hour, and kneading terminates
After, tablet machine is pressed into 2～5mm lamellars, is ground into the powder of below particle diameter 0.1mm, briquette forming；Protection at nitrogen
Under, and at a temperature of 1100 DEG C, carbonization processes 2 hours, afterwards product is cooled to room temperature；Use jaw crusher enters
Row coarse pulverization, grain diameter controls at below 30mm；Using plate-hammer crusher to carry out middle pulverizing, grain diameter controls at 10mm
Below；Using ultra-fine mechanical crusher to carry out Crushing of Ultrafine, grain diameter controls at below 1mm；Use 250 mesh vibration type screening machines
Screening, siftage uses gas flow sizing machine to carry out classification, and the frequency of grading wheel is 48Hz, prepares particle volume mean diameter D50
It it is the lithium ion battery composite graphite negative electrode material of 19.2 μm.Recording its half-cell capacity 345.2mAh/g, first charge-discharge is imitated
Rate 91.3%.
Comparative example 3
Native graphite 20kg and graphitization catalyst (SiC) 1.2kg that volume average particle size D50 is 24.6 μm are added outstanding
Arm double-spiral conical mixer mixes 2 hours, obtains composite graphite raw material；Stirring lower alternately by composite graphite raw material 20kg and
Coal tar pitch 5kg joins in kneading pot, in 180 DEG C carry out kneading process 1 hour, mediate terminate after, be pressed in tablet machine 2～
5mm lamellar, is ground into the powder of below particle diameter 0.1mm, briquette forming；Under the protection of nitrogen, and at a temperature of 1100 DEG C
Carbonization processes 2 hours, afterwards product is cooled to room temperature, carries out at 48 hours catalyzed graphitization high temperature then at 3200 DEG C
Reason；Using jaw crusher to carry out coarse pulverization, grain diameter controls at below 30mm；Plate-hammer crusher is used to carry out middle powder
Broken, grain diameter controls at below 10mm；Using ultra-fine mechanical crusher to carry out Crushing of Ultrafine, grain diameter controls at below 1mm.
Using 250 mesh vibration type screening machine screenings, siftage uses gas flow sizing machine to carry out classification, and the frequency of grading wheel is 45Hz, system
Obtain the lithium ion battery composite graphite negative electrode material that particle volume mean diameter D50 is 25.6 μm.Record its half-cell capacity
365.3mAh/g, first charge-discharge efficiency 87.6%.
Effect example
(1) composite graphite negative electrode material in embodiment 1～8 and comparative example 1～3 is carried out respectively particle diameter, true
Density, specific surface area and ash grade an index test, and the results are shown in Table 1.Test the instrument title used and model is: body
Long-pending mean diameter D50, laser fineness gage MS2000；True density, super constant temperature water tank SC-15；Ash, high-temperature electric resistance furnace SX2-
2.5-12；Specific surface area, specific surface area measuring instrument NOVA2000.
(2) use half-cell method of testing to the composite graphite negative electrode material in embodiment 1～8 and comparative example 1～3
Material carries out the test of discharge capacity and first charge-discharge efficiency, and result is listed in table 1.Half-cell method of testing is: composite graphite
Negative material, containing 6～7% Kynoar N-Methyl pyrrolidone and 2% conductive black by 91.6: 6.6: 1.8
Ratio mix homogeneously, is applied on Copper Foil, and it is to be vacuum dried 4 hours in 110 DEG C of vacuum drying ovens that the pole piece coated is put into temperature
Standby.Simulated battery is assemblied in the German Braun glove box of applying argon gas and carries out, and electrolyte is 1M LiPF6+EC: DEC: DMC
=1: 1: 1 (volume ratio), metal lithium sheet is that electrochemical property test is at U.S. ArbinBT2000 type cell tester to electrode
On carry out, charging/discharging voltage scope is 0.005 to 1.0V, and charge-discharge velocity is 0.1C.
The performance parameter of the composite graphite negative electrode material of each embodiment of table 1 and comparative example
As it can be seen from table 1 the discharging efficiency of comparative example 1 and comparative example 3 is on the low side；Comparative example's 2 puts
Capacitance is low, only 345.2mAh/g.And the discharge capacity of each sample of embodiment 1～8 is all at more than 360mAh/g and first
Secondary efficiency for charge-discharge is all more than 92%.
(3) use full battery testing method that the composite graphite negative electrode material of embodiment 2 is tested.Full battery testing side
Method is: using composite graphite negative electrode material as negative pole, using cobalt acid lithium as positive pole, 1M-LiPF6EC: DMC: EMC=1: 1: 1 (body
Long-pending than) solution makees electrolyte assembling and helps battery, carries out electric performance test.Result shows, sample has preferable voltage platform,
Discharge voltage quickly can reach plateau, as shown in Figure 1；Its absorbent is excellent, high compacted density 1.70g/cm3Under suction
The liquid time be less than 180 seconds, as shown in Figure 2；Its good cycle, after circulating 300 times, capability retention can reach 86.1%, such as figure
Shown in 3.
(4) to other continuous item of resultant battery being made up of the lithium ion battery composite graphite negative electrode material of embodiment 1～8
Range estimation test result is: discharge platform (3.6V) >=75%, circulates 100 weeks platforms and keeps >=95%；Multiplying power discharging 3C capacity >=
50%300 circulations, capacity keeps >=80%；Overcharge, high temperature short circuit, the security performance measuring stability such as thermal shock good, do not rise
Fire, does not explodes, and surface temperature is less than 150 DEG C；Preferable to electrolyte and other additive adaptability, do not analyse lithium；Product is stable,
Almost without difference between batch.
Visible, use lithium ion battery composite graphite negative electrode material prepared by preparation method of the present invention, specific surface area controls
3.0～4.0m2/ g, both can guarantee that particle surface pore was flourishing, was conducive to again suppression lithium-ion battery system to produce flatulence existing
As, the security performance of battery is good；Discharge capacity is up to more than 360mAh/g；Reduce the loss of irreversible capacity, improve energy
Metric density, reduces the consumption of positive pole；Pole piece processability is good, high compacted density 1.70g/cm3Under the imbibition time less than 180 seconds.
Claims (16)
1. a preparation method for lithium ion battery composite graphite negative electrode material, it comprises the steps: 1. by spherical natural stone
Ink, meso-phase graphite and graphitization catalyst mix homogeneously obtain compound；2. mediate described compound and binding agent obtains kneaded material；
3. described kneaded material is carried out carbonization process, after cooling, carry out catalyzed graphitization high-temperature process again；4. by step 3. products therefrom
Carry out pulverizing, classification,；
Step 2. described in binding agent be asphalt and/or coal tar pitch.
2. preparation method as claimed in claim 1, it is characterised in that volume average particle size D50 of described spherical natural graphite
It is 12～36 μm；Volume average particle size D50 of described meso-phase graphite is 10～30 μm；And/or, described spherical natural graphite and
The mass ratio of meso-phase graphite is 1:1～19:1.
3. preparation method as claimed in claim 2, it is characterised in that described spherical natural graphite and the quality of meso-phase graphite
Ratio is 7:3～9:1.
4. preparation method as claimed in claim 1 or 2, it is characterised in that described graphitization catalyst is the carbide of silicon
And/or the oxide of ferrum；And/or, the consumption of described graphitization catalyst is spherical natural graphite and meso-phase graphite gross mass
1～10%.
5. preparation method as claimed in claim 4, it is characterised in that described graphitization catalyst is SiC and/or Fe2O3；
And/or, the consumption of described graphitization catalyst is spherical natural graphite and the 3 of meso-phase graphite gross mass～8%.
6. preparation method as claimed in claim 1 or 2, it is characterised in that step 1. described in mixing use cantilever Double helix
Cone-type mixer is carried out；The time of described mixing is 1.5～3.0 hours.
7. preparation method as claimed in claim 1 or 2, it is characterised in that step 2. described in binding agent be the middle temperature of oil
Colophonium and/or coal mid temperature pitch；Described compound is 1:1～9:1 with the mass ratio of binding agent.
8. preparation method as claimed in claim 7, it is characterised in that the mass ratio of described compound and binding agent be 3:2～
3:1。
9. preparation method as claimed in claim 1 or 2, it is characterised in that step 2. described in the temperature mediated be 100～
180℃；The time of described kneading is 1～10 hour；And/or, step 2. described in kneading after also carry out briquetting process.
10. preparation method as claimed in claim 9, it is characterised in that step 2. described in kneading after also carry out at briquetting
Manage into cylindrical or rectangle.
11. preparation methoies as claimed in claim 9, it is characterised in that after described kneading, before described briquetting processes,
Also carry out operations described below: described kneaded material is pressed into 2～5mm lamellars in tablet machine, be ground into the particle diameter powder at below 0.1mm
End.
12. preparation methoies as claimed in claim 1 or 2, it is characterised in that step 3. described in carbonization process temperature be
800～1500 DEG C；The time that described carbonization processes is 2～6 hours；And/or, step 3. described in catalyzed graphitization high-temperature process
Temperature be 2800～3200 DEG C；The time of described catalyzed graphitization high-temperature process is 24～48 hours.
13. preparation methoies as claimed in claim 1 or 2, it is characterised in that step 4. described in pulverizing for first carrying out coarse powder
Broken, then carry out middle pulverizing, finally carry out Crushing of Ultrafine；And/or, step 4. in, described being classified as first carries out sieving flowing again
Mechanics classification.
14. preparation methoies as claimed in claim 13, it is characterised in that the equipment of described coarse pulverization uses jaw crusher,
Grain diameter after described coarse pulverization is at below 30mm；The equipment of described middle pulverizing uses plate-hammer crusher, described middle pulverizing
After grain diameter at below 10mm；Described fine equipment uses ultra-fine mechanical crusher, the granule after described Crushing of Ultrafine
Particle diameter is at below 1mm；And/or, step 4. in, described screening was 250 mesh sieve extracting screen underflows；Described Hydrodynamic Fractionation is adopted
Carry out with gas flow sizing machine；The frequency of described gas flow sizing machine is 20～60Hz.
15. preparation methoies as claimed in claim 14, it is characterised in that described screening uses 250 mesh vibration type screening machines to enter
OK.
16. 1 kinds of lithium ion battery composite graphite negative electrode materials prepared by claim 1～15 any one preparation method.
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| CN106104871B (en) * | 2014-03-25 | 2018-05-11 | 日立化成株式会社 | Lithium rechargeable battery and its anode, its negative material and manufacture method and negative material slurry |
| CN105024075A (en) * | 2014-12-18 | 2015-11-04 | 上海杉杉科技有限公司 | Negative electrode material for quickly rechargeable graphite lithium-ion battery and preparation method of negative electrode material |
| CN106486670A (en) * | 2015-11-17 | 2017-03-08 | 上海杉杉科技有限公司 | A kind of method that mesophase pitch Jiao prepares lithium cell cathode material |
| CN108328614B (en) * | 2017-12-28 | 2021-09-03 | 合肥国轩高科动力能源有限公司 | Graphite negative electrode material for quick-charging lithium ion battery and preparation method thereof |
| CN109103453A (en) * | 2018-08-17 | 2018-12-28 | 东莞市凯金新能源科技股份有限公司 | A kind of preparation method and its material of the graphite cathode material of catalyzed graphitization |
| CN111244449B (en) * | 2018-11-28 | 2022-04-08 | 上海杉杉科技有限公司 | Modified intermediate phase negative electrode material, lithium ion secondary battery, preparation method and application |
| CN112670464B (en) * | 2020-04-21 | 2022-02-18 | 宁波杉杉新材料科技有限公司 | Graphite negative electrode material, lithium ion battery and preparation method and application of graphite negative electrode material |
| CN111697267A (en) * | 2020-06-24 | 2020-09-22 | 宁德新能源科技有限公司 | Electrolyte solution, electrochemical device containing electrolyte solution, and electronic device |
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Effective date of registration: 20210201 Address after: 200131 building 10, No. 860, Xinyang Road, Lingang New District, China (Shanghai) pilot Free Trade Zone, Pudong New Area, Shanghai Patentee after: Shanghai Shanshan New Material Co.,Ltd. Address before: 315177 No.1 Jucai Road, Wangchun Industrial Park, Yinzhou District, Ningbo City, Zhejiang Province Patentee before: NINGBO SHANSHAN NEW MATERIAL TECHNOLOGY Co.,Ltd. Patentee before: SHANGHAI SHANSHAN TECH Co.,Ltd. |