CN109704323A - Electrode material and secondary battery - Google Patents
Electrode material and secondary battery Download PDFInfo
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- CN109704323A CN109704323A CN201711012357.1A CN201711012357A CN109704323A CN 109704323 A CN109704323 A CN 109704323A CN 201711012357 A CN201711012357 A CN 201711012357A CN 109704323 A CN109704323 A CN 109704323A
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses an electrode material and a secondary battery. The electrode material is a graphitized carbon material, the graphitization degree of the graphitized carbon material is 93-97%, and the compaction density measured under the action force of 30000N is 1.40g/cm3‑1.85g/cm3. A lithium ion secondary battery using the electrode material can have both high capacity and good cycle stability.
Description
Technical field
The invention belongs to battery technology field, it is more particularly related to a kind of electrode material and use the material
Secondary cell.
Background technique
With becoming increasingly popular for electric car, the requirement to battery is also increasingly stringenter.Electric car is to course continuation mileage
It is required that it is higher and higher, cause the demand to battery core energy density also to correspondingly increase.Therefore it needs to provide tool for electrical core of power battery
There is the electrode material of more height ratio capacity.It is best for current comprehensive performance, most widely used lithium ion battery negative material stone
For ink, its specific capacity can effectively be improved by promoting its lattice degree of order (degree of graphitization).However, the graphite of high graphitization degree
It usually will affect the cycle performance and high rate performance of battery.
Therefore, how to guarantee lithium ion secondary battery under the premise of with height ratio capacity, combine cycle performance and
High rate performance is an insoluble problem.
Summary of the invention
In view of this, it is necessory to provide a kind of electrode for having both height ratio capacity, long circulation life and outstanding high rate performance
Material and the secondary cell for using the material.
In order to achieve the above object, this application provides a kind of electrode materials, are graphitized carbon material (usually powder
Material), while meeting degree of graphitization is 93%-97%, the compacted density under 30000N active force is 1.40g/cm3-
1.85g/cm3。
Inventors have found that the graphite of high graphitization degree is for the cycle performance of battery and the adverse effect reason of high rate performance
It is: in the production process of lithium ion battery, for the energy density for improving pole piece, improves the active contacts of pole piece, lead to
It often needs to carry out cold pressing treatment to pole piece；And the graphite quality of high graphitization degree is softer, and deformation is easy to happen after being cold-pressed, and causes
Hole between active material is blocked, especially pole piece, influences infiltration of the electrolyte to pole piece, and then influence battery
Cycle performance and high rate performance.
Inventor is it has furthermore been found that the degree of graphitization of graphitized carbon material and compacted density control in a certain range may be used
Unexpectedly to improve battery performance, especially energy density and cyclical stability.Specifically, inventor's discovery is when graphitization
It is 93%-97% that carbon material meets degree of graphitization simultaneously, and the compacted density under 30000N active force is 1.40g/cm3-
1.85g/cm3When, height ratio capacity, long circulation life and outstanding high rate performance are unexpectedly had both using the battery of the material.
Think after inventor's research: degree of graphitization reflects the crystal structure of material, and compacted density reflects the pole piece structure of material, together
When meet the material that degree of graphitization and compacted density require and have both suitable crystal structure and preferable pole piece structure, therefore will be above-mentioned
Material is applied in battery, the electrochemical performance (but the present invention is not limited by the above theoretical explanation) of battery.
Inventor is it has furthermore been found that controlling the average grain diameter specific surface area of above-mentioned electrode material in 0.5-3.0m2When/g,
Battery performance can further be improved.
Further research confirms, when degree of graphitization is lower than 93%, the specific capacity of material is lower；Degree of graphitization is higher than 97%
When, easy peeling off phenomenon in cyclic process leads to capacity attenuation, and its quality is excessively soft, under the same test conditions, compacting
Density is often excessively high；Compacted density (30000N) is less than 1.40g/cm3When, material will lead to the grain structure of material in cold pressing
It is easily destroyed, influences cycle performance, and the actual use densification of material is too low, causes energy density lower；Compacted density
(30000N) is greater than 1.85g/cm3When, the crushing resistance of material is poor, very sensitive to pressure, in cold pressing surface stress it is larger and
Cause duct to be destroyed, influence the infiltration of electrolyte, to influence the long-term cycle performance of battery.
Inventor is it has furthermore been found that the degree of graphitization preferred scope of electrode material of the invention is 93-95%, in 30000N
Compacted density preferred scope under active force is 1.50g/cm3-1.70g/cm3.Further research confirms, specific surface area is less than
0.5m2When/g, the response area of material is too small, and electrochemical reaction speed is slow, causes the high rate performance of battery poor, under high magnification
Capacity retention ratio is lower.Specific surface area is greater than 3.0m2When/g, the response area of material is excessive, and rate of side reactions is fast, leads to battery
Capacity attenuation is fast in cyclic process, and cycle performance is poor.
Compared with prior art, electrode material provided by the invention, by controlling degree of graphitization and compacted density one
Determine in range, can effectively maintain stability and cellular structure of the material in cyclic process so that electrode pole active material it
Between contact interface keep complete, promote material circulation performance.By this material in the secondary battery, battery can be made to have
Under the premise of high capacity, cyclical stability is combined.It is that can not pass through based on existing theoretical and experience, the improvement of these performances
What the parameters such as degree of graphitization, compacted density were simply calculated or were predicted, but must be just detectable by a large amount of arduous experiments.
In the present invention, " graphitized carbon material " has the normally understood meaning of those skilled in the art institute, that is, is suitable for
Inside for battery electrode material is mainly in the carbon material of graphite laminated structure.Graphitized carbon material can be artificial graphite, day
The mixture of right graphite, carbonaceous mesophase spherules soft carbon, hard carbon and the above material or in which any two or more of mixtures.
Artificial graphite is usually the material for being handled and being obtained through high temperature graphitization for raw material with pitch coke, petroleum coke, metallurgical coke, coal tar etc.
Material.
In a preferred embodiment of the invention, the graphitized carbon material is artificial graphite or artificial graphite and natural
The mixture of graphite.In present invention further optimization embodiment, the artificial graphite be petroleum forging after needle coke or
The artificial graphite that needle coke is obtained through high temperature graphitization processing after coal measures forging.
In the present invention, the size of the degree of graphitization of the graphitized carbon material can carry out with method known in this field
Measurement, such as be measured with X-ray diffractometer (such as may refer to Qian Chongliang etc., " the graphitization of XRD determining carbon material
Degree ", " Zhongnan Polytechnic Univ's journal " the 3rd phase of volume 32, in June, 2001).The degree of graphitization of artificial graphite used in the present invention can
It is controlled with preparing by control the reaction conditions such as temperature, time of the graphitization reaction of artificial graphite.Natural graphite
Degree of graphitization then may be different with its place of production, purity etc..
On the other hand, the present invention also provides a kind of secondary cell (especially lithium ion secondary batteries) comprising on
State electrode material.Other than having used electrode material of the invention, the construction of these secondary cells and preparation method itself are public
Know.
On the other hand, it the invention further relates to a kind of method for preparing the electrode material, mainly comprises the steps that
(1) it is crushed: raw material being crushed and (carried out for example, by using airflow milling or roll mill), removal raw material is broken thin
Powder obtains the presoma that average grain diameter Dv50 is 5-15 μm；
(2) shaping: presoma in (1) is subjected to shaping, classification is handled, adjustment raw material particle size distribution；
(3) it is granulated: the presoma after shaping in (2) uniformly being mixed or be added without pitch with pitch, in protective atmosphere
Lower high-temperature stirring processing, products therefrom removal bulky grain obtain intermediate；
(4) it is graphitized: the intermediate after being granulated in (3) being put into graphitizing furnace (such as acheson furnace) and is carried out
2750-3250 DEG C of high temperature graphitization handles to obtain graphitization product.
It is broken for step (1), used in raw material, or mixtures thereof including but not limited to following material: raw petroleum
Coal-based needle coke after petroleum needle coke, raw coal-based needle coke, forging after petroleum coke, raw petroleum needle coke, forging after burnt, forging, pitch coke,
Metallurgical coke, anthracite, scale natural graphite, spherical natural graphite, soft carbon, hard carbon, MCMB (carbonaceous mesophase spherules).For broken
Method has no particular/special requirement, such as can be carried out using airflow milling or roll mill, as long as finally obtaining average grain diameter Dv50 is 5-
15 μm of presoma particle.Usual presoma diameter of particle is smaller, and the compacted density of final resulting materials is lower.
For step (2) shaping, Shape correction is the common processing method in artificial graphite preparation process, is ability
Known to field technique personnel.Shape correction is polished graphite raw material grain corner by trimmer, make its pattern become it is regular from
And it is convenient for subsequent graphitization processing；But Shape correction will lead to and more fine powder occurs, thus usually require at cooperation classification
Reason.Any reshaping machine or other shaping devices commonly used in the art can be used in Shape correction, and Chinese patent Shen also can be used
It please shaping device disclosed in CN201520275340.5, CN201410139952.1, CN201320354100.5 etc..Classification processing
Classifying screen commonly used in the art (sieve method), gravity selector, centrifugal separator etc. can be used to realize.It is classified the mesh of processing
Be to remove excessive and too small particle, adjust particle size distribution, therefore be preferably greater than by classification processing removing partial size
The bulky grain and partial size of Dv90 is less than the little particle of Dv10.
Dv50, Dv90, Dv10 described above have general sense well known in the art.The volume of Dv50 expression material granule
Granularity corresponding to 50% in distribution (particle size).Granularity corresponding to 90% in the volume distribution of Dv90 expression material granule
Less than the partial size (particle size).Granularity corresponding to 10% in the volume distribution of Dv10 expression material granule is less than the partial size
(particle size).Dv50, Dv90, Dv10 etc. can use laser particle size analyzer (such as Malvern Master Size 2000)
Easily measure.
For step (3) are granulated, heat treatment temperature is preferably 300-600 DEG C.The mass ratio of presoma and pitch is
100: (0-50) (pitch amount is added without pitch when being 0), be preferably 100: the dosage of (0-30), usual pitch are more, most
The compacted density of final product is lower.Preferred asphalt material is the powder of pitch that softening point is 100-280 DEG C after air-flow crushing
Body material, Dv50 are preferably 3-5 μm.In general, the softening point of pitch is higher, the compacted density of final product is lower.
For step (4) graphitization, the intermediate after being granulated in (3) is put into graphitizing furnace and carries out 2750-
3250 DEG C of high temperature graphitizations handle to obtain graphitized carbon material product.High temperature graphitization can be in such as acheson furnace
It carries out.Graphited temperature for example can be at 2750-3250 DEG C, and preferably 2850-3200 DEG C.In general, graphitization temperature is lower, most
The degree of graphitization of final product is lower, and compacted density is lower.
In order to further increase dynamic performance (the especially high rate performance of battery), the graphitized carbon material surface is also
There can be clad.Clad is usually amorphous carbon, such as selected from least one of carbon black, coke, soft carbon, hard carbon.It should
Amorphous carbon is usually 3-10% relative to the content of the electrode material total weight, preferably 5-9%.In some embodiments
In, the amorphous carbon be by polyvinyl butyral, pitch, furfural resin, epoxy resin or phenolic resin extremely
A kind of few material is through obtained from (high temperature) charing.For this purpose, after the method and step (4) for preparing electrode material of the invention
May include optional step (4 '):
(4 ') it coats: after evenly mixing by graphitization product and amorphous carbon presoma obtained in (4), in protectiveness gas
High temperature cabonization is under atmosphere to form clad.
Step (4 ') cladding described in amorphous carbon presoma be selected from polyvinyl butyral, pitch, furfural resin,
At least one of epoxy resin or phenolic resin material.The mass ratio for being graphitized product and amorphous carbon presoma is 100:
(0-50).In general, the dosage of amorphous carbon presoma is more, the degree of graphitization of final product is lower, and compacted density is lower.Carbonization
The temperature of processing for example can be 850-1250 DEG C (such as 900-1100 DEG C).When use pitch as amorphous carbon presoma
When, it is preferable to use softening point is the powder body material that 100-280 DEG C of pitch obtains after air-flow crushing, Dv50 is preferably 3-5 μ
m。
In order to improve product quality, the method for preparing electrode material of the invention can also include step (5):
(5) it sieves, remove magnetic: material obtained in (4) or (4 ') sieve and except magnetic.
Compared with the existing technology, the invention has the benefit that electrode material provided by the invention is with height ratio capacity
While with certain anti-pressure ability, preferable pore structure can be kept in pole piece cold pressure procedure, improves electrolysis
The wellability of liquid, so that the cycle life of battery and high rate performance be made to be obviously improved.
In the following with reference to the drawings and specific embodiments, to electrode material of the present invention, secondary cell and its advantages carry out into
One step is described in detail.
Detailed description of the invention
Fig. 1 shows the measurement process of electrode material compacted density of the invention.
Specific embodiment
In order to be more clear goal of the invention of the invention, technical solution and advantageous effects, with reference to embodiments
The present invention is described in further detail with attached drawing.However, it should be understood that the embodiment of the present invention is just for the sake of this hair of explanation
It is bright, it is not intended to the limitation present invention, and the embodiment of the present invention is not limited to the embodiment provided in specification.In embodiment
The routinely condition production of experiment condition is not specified, or is made by the condition that material supplier is recommended.
Illustrate beneficial effects of the present invention with reference to embodiments.
One, the preparation process of graphitized carbon electrode material
Graphitized carbon electrode material used in following embodiment the preparation method is as follows:
(1) it is crushed: needle coke after the forging of raw material petroleum being crushed using airflow milling or roll mill, after removal raw material is broken
Fine powder, obtain equal partial size be Dv50 presoma；
(2) shaping: presoma in (1) is subjected to shaping, classification is handled, bulky grain and partial size of the removal partial size greater than Dv90
Little particle less than Dv10 is so as to adjust raw material particle size distribution；
(3) it is granulated: the presoma after shaping in (2) uniformly being mixed with pitch, at the lower 550 DEG C of stirrings of protective atmosphere
Reason, products therefrom removal bulky grain obtains intermediate, wherein the softening point of pitch used is 250 DEG C；
(4) it is graphitized: the intermediate after being granulated in (3) is put into progress high temperature graphitization processing in acheson furnace
Obtain graphitization product；
(4 ') it coats: after evenly mixing by graphitization product and pitch obtained in (4), in the lower 1050 DEG C of carbon of protective atmosphere
Change, wherein the mass ratio of graphitization product and pitch is 100: 6, the softening point of pitch is 250 DEG C (step is optional step)；
(5) it sieves, remove magnetic: material obtained in (4) or (4 ') being sieved, except magnetic, packaged spare.
In the above preparation method, the addition of pitch in presoma partial size in regulating step (1), step (3) can be passed through
Amount and step (4 ') control the compacted density of material；Meanwhile it can be controlled by the graphitization temperature in regulating step (4)
The degree of graphitization of material.
Two, performance test
1, the parametric measurement of electrode material
(1) degree of graphitization of electrode material is measured with X-ray diffractometer.
(2) compacted density of electrode material is tested by following procedure:
1) mold is calibrated: gasket and steel column being directly sequentially placed into groove, keep 30s, removal pressure after being pressurized to 30000N
Power waits the height H0 of reading steel column after 10s.
2) densification is tested: weigh graphitized carbon electrode material 1.00 ± 0.05g of powder, record weight data M (unit g),
Powder all pours into mold groove (groove area S=1.327cm2) in, it flats down and is pressed on powder by another steel plate washer,
Steel column flats down, and is pressed on gasket.30s is kept after being pressurized to 30000N, removal pressure waits the height of reading steel column after 10s
Spend H1.
Compacted density=M/ [(H1-H0) * S].
The above test process is schematically shown in fig. 1.
2, the gram volume measurement of electrode material
Electrode material, Super P (conductive agent), CMC (carboxymethyl cellulose), the SBR (butadiene-styrene rubber) of preparation press quality
Slurry is made than 94.5: 1.5: 1.5: 2.5, the slurry prepared is coated on copper foil, placement is toasted in a vacuum drying oven
It is spare as anode pole piece after 12h.It is to electrode with metal lithium sheet, Celgard film is diaphragm, is dissolved with LiPF6(1mol/L)
EC+DMC+DEC (ethylene carbonate, dimethyl carbonate, the diethyl carbonate of volume ratio 1: 1: 1) solution be electrolyte,
CR2430 type button cell is assembled into the glove box of argon gas protection.Battery pack stands 12h after installing, in 0.05C (i.e. in 1h
Bleed off the current value of theoretical capacity completely) discharge current under carry out constant-current discharge, until voltage be 50mV, then in 0.05C
Charging current under carry out constant-current charge, until final voltage is 2V, record the charging capacity that recycles for the first time.Charging capacity and work
Property material mass ratio, the gram volume of as prepared electrode material.
3, high rate performance is tested
Full battery is prepared first, in accordance with following steps:
1) preparation of anode pole piece:
By positive electrode active materials (LiNi0.5Co0.2Mn0.3O2), binder, conductive agent according to mass ratio be 97: 2: 1 ratio
Example is uniformly mixed with solvent is prepared into slurry (wherein, binder PVDF, conductive agent SuperP, solvent NMP), by slurry
Coated on aluminium collector, pole piece obtains anode pole piece after drying, cold pressing, slitting.
2) preparation of cathode pole piece:
It is according to mass ratio by negative electrode active material (electrode material of above-mentioned preparation), binder SBR, carboxymethyl cellulose
97: 1.8: 1.2 ratio is uniformly mixed with aqueous solvent is prepared into slurry, and slurry is coated on copper current collector, and pole piece is by drying
Cathode pole piece is obtained after dry, cold pressing, slitting.
3) preparation of electrolyte:
Ethylene carbonate (EC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC) are mixed according to volume ratio 3: 6: 1
It closes, then by sufficiently dry lithium salts LiPF6It is dissolved in mixed organic solvents according to the ratio of 1mol/L, is configured to be electrolysed
Liquid.
4) isolation film:
Using 12 microns of PP/PE composite isolated film.
5) assembling of full battery:
Battery core is made in above-mentioned anode pole piece, cathode pole piece and isolation film, then battery core is fitted into battery packages shell, it
After inject electrolyte, using chemical conversion, stand etc. techniques be made full battery.
Then full battery high rate performance is measured as steps described below:
In 25 DEG C of environment, charge-discharge test is carried out, 1.0C (i.e. bleeding off the current value of theoretical capacity in 1h completely)
Discharge current under carry out constant-current discharge, until voltage be 2.8V.Then under the charging current of 1.0C constant-current charge to voltage
For 4.2V, continuing constant-voltage charge to electric current is 0.05C, and battery is fully charged state at this time.After the battery core completely filled is stood 5min,
Constant-current discharge is the actual capacity under the 1.0C of battery core to 2.8V, discharge capacity at this time under the discharge current of 1.0C, is denoted as C0.
Then by battery core, in 1C constant-current charge to 4.2V, then constant-voltage charge to electric current is 0.05C, stands 5min, 2C is permanent
Stream is discharged to 2.8V, and record discharge capacity C1 is 2C discharge capacity.
2C rate capability conservation rate=(discharge capacity/1C discharge capacity of 2C) × 100%.
4, cycle performance is tested:
First, in accordance with the step 1) -5 in above-mentioned " 3, high rate performance test ") the preparation full battery, then according to following
Step measures full battery cycle performance:
In 25 DEG C of environment, by battery core under the charging current of 1C (i.e. bleeding off the current value of theoretical capacity in 1h completely)
Constant-current discharge is carried out, until voltage is 2.8V, battery core is completely to put state at this time.Then charge-discharge test is carried out, in the charging of 1C
For constant-current charge to 4.2V, constant-voltage charge to electric current is 0.05C under electric current, stands 5min, then 1C constant-current discharge is to 2.8V., record
The discharge capacity recycled for the first time；It then carries out continuing charge and discharge cycles.
Circulation volume conservation rate=(discharge capacity of n-th circulation/discharge capacity recycled for the first time) × 100%.
Embodiment 1
It is described using listed specific process parameter in table 1 first, in accordance with the preparation process of graphitized carbon electrode material " one, "
(presoma partial size, graphitization temperature etc.) prepares electrode material, then according to " two, performance test " the gained electricity of test respectively
The degree of graphitization of pole material, compacted density (30000N), gram volume, high rate performance and cycle performance, measured data are listed in table 2
In.
Embodiment 2-6
Embodiment 1 is repeated using technological parameter different listed by table 1, corresponding electrode material is made, and according to " two, performance
Degree of graphitization, compacted density (30000N), gram volume, high rate performance and the cyclicity of the electrode obtained material are tested in test " respectively
Can, measured data are listed in Table 2 below.
Comparative example 1-4
Electrode material is prepared substantially according to the preparation process of graphitized carbon electrode material " one, " is described, but set-up procedure
(1) technological parameters (being specifically shown in Table 1) such as the graphitization processing temperature in being crushed in average grain diameter and step (4) graphitization, thus
Degree of graphitization, compacted density are obtained different from the electrode material comparative example of embodiment, is then surveyed respectively according to " two, performance test "
Try degree of graphitization, compacted density (30000N), gram volume, high rate performance and the cycle performance of the electrode obtained material, measured number
According to being listed in Table 2 below.
Table 1, each embodiment and comparative example electrode material preparation process technological parameter
The electrode material the performance test results of table 2, each embodiment and comparative example
According to the data of table 2, comparative example 1-6 and comparative example 1-4 can be obtained, when degree of graphitization 93%-97% it
Between, and compacted density is in 1.40g/cm3-1.85g/cm3Between when, battery combines well under the premise of keeping high capacity
High rate performance and cycle performance.
According to the data of table 2, degree of graphitization has certain influence to the high rate performance of battery and cycle performance；Degree of graphitization exists
Effect is best when between 93%-95%.When degree of graphitization exceeds given range (93%-97%), such as comparative example 3-4, battery
High rate performance or cycle performance can decrease.
According to the data of table 2, compacted density has certain influence to the high rate performance of battery and cycle performance；Compacted density exists
1.50g/cm3-1.70g/cm3Between when effect it is best.When compacted density exceeds given range (1.40g/cm3-1.85g/cm3)
When, such as comparative example 1-2, the high rate performance or cycle performance of battery be can decrease.
In conclusion battery could keep Gao Rong only when degree of graphitization and compacted density while in given range
High rate performance and cycle performance are taken into account under the premise of amount.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula carries out change and modification appropriate.Therefore, the invention is not limited to the specific embodiments disclosed and described above, to this
Some modifications and changes of invention should also be as falling into the scope of the claims of the present invention.In addition, although this specification
In use some specific terms, these terms are merely for convenience of description, does not limit the present invention in any way.
Claims (10)
1. a kind of electrode material for secondary cell, it is characterised in that: the material is graphitized carbon material, degree of graphitization
For 93%-97%, and the compacted density that material measures under 30000N active force is 1.40g/cm3-1.85g/cm3。
2. electrode material according to claim 1, the material is selected from artificial graphite, natural graphite, carbonaceous mesophase spherules
At least one of soft carbon, hard carbon and any mixture of the above material.
3. electrode material according to claim 1 or 2, the degree of graphitization of the material is 93-95%, and is made in 30000N
Firmly the lower compacted density measured is 1.50g/cm3-1.70g/cm3。
4. electrode material according to claim 1 or 2, the specific surface area of the material is 0.5-3.0m2/g。
5. electrode material according to claim 1, the material surface has clad, and the clad is amorphous carbon.
6. electrode material according to claim 5, content of the amorphous carbon relative to the electrode material total weight
For 3-10%.
7. a kind of method for preparing the described in any item electrode materials of claim 1-4, comprising the following steps:
(1) be crushed: raw material is crushed, remove the broken fine powder of raw material, obtain average grain diameter Dv50 be 5-15 μm before
Drive body；
(2) shaping: shaping is carried out to presoma in (1), classification is handled, adjustment raw material particle size distribution；
(3) it is granulated: the presoma after shaping, classification in (2) uniformly being mixed or be added without pitch with pitch, in protective atmosphere
Lower high-temperature stirring processing, products therefrom removal bulky grain obtain intermediate；
(4) it is graphitized: the intermediate after being granulated in (3) being put into graphitizing furnace and is carried out at 2750-3250 DEG C of high temperature graphitization
Reason obtains graphitization product；
Wherein raw material described in step (1) is the petroleum needle after petroleum coke, raw petroleum needle coke, forging after raw petroleum coke, forging
Coal-based needle coke, pitch coke, metallurgical coke, anthracite, scale natural graphite, spherical natural stone after burnt, raw coal-based needle coke, forging
Or mixtures thereof ink, soft carbon, hard carbon and material of MCMB (carbonaceous mesophase spherules).
8. according to the method described in claim 7, it is characterized by: also comprising carrying out step (4 ') cladding later after step (4):
Graphitization product and amorphous carbon presoma obtained in (4) after evenly mixing, are subjected to 850-1250 under protective atmosphere
DEG C high temperature cabonization is to form clad, wherein the amorphous carbon presoma is selected from polyvinyl butyral, pitch, furfural
At least one of resin, epoxy resin or phenolic resin material.
9. method according to claim 7 or 8, it is characterised in that: also comprising being carried out to material obtained in (4) or (4 ')
Screening removes magnetic treatment.
10. a kind of secondary cell, including electrode material described in any one of claims 1 to 6.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110127687A (en) * | 2019-05-24 | 2019-08-16 | 深圳鸿鹏新能源科技有限公司 | Artificial graphite and its preparation method and application |
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| EP3923387A4 (en) * | 2019-12-03 | 2022-04-06 | Contemporary Amperex Technology Co., Limited | Artificial graphite, secondary battery, preparation method, and device |
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