CN107845810A - A kind of soft or hard carbon of lithium ion battery is modified the preparation method of negative material - Google Patents
A kind of soft or hard carbon of lithium ion battery is modified the preparation method of negative material Download PDFInfo
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- CN107845810A CN107845810A CN201711011186.0A CN201711011186A CN107845810A CN 107845810 A CN107845810 A CN 107845810A CN 201711011186 A CN201711011186 A CN 201711011186A CN 107845810 A CN107845810 A CN 107845810A
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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 discloses the preparation method that a kind of soft or hard carbon of lithium ion battery is modified negative material, body step are as follows：（1）Mixing granulation,（2）Sieving approach,（3）Mixing,（4）High-temperature process,（5）Screening,（6）It is modified,（7）Secondary carbonization；The present invention is used as adhesive simultaneously using both soft carbon presoma and hard carbon presoma, kneading granulation is carried out under certain temperature and other conditions, graphite small particles are polymerize, make internal structure further careful, its bulk density is improved, then carries out high temperature graphitization, pitch and resin are transformed into pyrolytic carbon, form soft/hard carbon graphite composite system, modification it is soft/one layer of electric conductivity of coated with uniform of hard carbon composite negative pole material is good, chemical property is stable Ti3SiC2With conductive network, the lifting to the discharge capacity of graphite cathode material, discharging efficiency and cyclical stability is highly beneficial.
Description
Technical field
The present invention relates to technical field of lithium batteries, specially a kind of soft or hard carbon of lithium ion battery is modified the preparation of negative material
Method.
Background technology
Graphite type material has relatively low impulse electricity platform, and embedding lithium capacity is high, its lithium intercalation compound LiC6 theoretical embedding lithium
Capacity is 372mAh/g, and first charge-discharge efficiency is higher.People by study find, graphite in cyclic process first,
SEI films are formed due to being reacted with electrolyte, this layer film allows lithium ion to pass freely through, and prevents solvation lithium ion from entering
Enter, this layer of SEI film so formed on graphite surface be not it is prevented that graphite electrode is corroded further by electrolyte, dimension
Hold good cycle performance.But the formation of SEI films inevitably produces big irreversible capacity.Therefore, this can not
Inverse reaction is mainly relevant with the surface texture of solvent species and graphite.Corrosion of the electrolyte to graphite material is respectively occurring at two
Individual position occurs：One be graphite surface；Another is graphite layers, and the latter inserts mainly due to solvation lithium ion
Enter to graphite linings and ask, solvent reacts caused with graphite.It is known that graphite crystal is aeolotropic crystal, it has end
Face and basal plane, due to there is many high activity groups on end face, so end face is more active than basal plane a lot, irreversible reaction mostly occurs
On the end face of graphite.It is probably end face with electrolyte contacts, it is also possible to basal plane when graphite is as electrode.So no
Same structure and surface nature affects the electrochemical properties of graphite.It is desirable to by modifying graphite surface, that is, lead to
The method crossed physically or chemically carries out surface modification, so as to improve its chemical property.Many research workers are in graphite-like material
Make a large amount of beneficial explorations in terms of the surface modification of material and achieved very big effect, mainly there is surface oxidation, charcoal bag to cover, table
The methods of face deposited metal or metal oxide.
The surface oxidation of carbon material is to be modified most effective simplest method to graphite surface.Pertinent literature is reported to people
Its chemical property can be improved this has been introduced in graphite surface and received mainly due to aoxidizing by making graphite and carrying out the oxidation of appropriateness
Meter Wei Kong and passage, while the formation that yet forms both one layer of fine and close oxide layer nanometer micropore and passage can increase lithium ion
Embedded quantity, and therefore the formation of fine and close oxide layer can then reduce the decomposition of electrolyte, what its reversible capacity circulated first
Coulombic efficiency and cycle performance have different degrees of improvement.There is scholar to be changed using air oxidation to native graphite
Property, find modified through air oxidation, being charged and discharged capacity has an increase, but efficiency first reduces.
In 7th international lithium battery meeting, the research of nucleocapsid structure carbon material is reported first, it is this with native graphite
Spherical Jie's phase graphite and the Delanium of polyhedral are that compound material of the nuclear material using amorphous carbon as shell has concurrently
The advantages of coke and graphite, can be compatible with the electrolyte containing PC well, there is higher specific capacity, first time discharge and recharge storehouse
Logical sequence efficiency is more than 85%, but is investigated to cycle performance is not further.Hereafter, many researchers carry out again successively
The research of this respect.At present, the most frequently used method of people be with phenolic resin, epoxy resin, polyaniline, polythiophene, coal tar pitch,
The high-molecular compounds such as asphalt coat as shell to carbon material.Have for domestic natural flake graphite higher
Specific capacity, but the problems such as its poor compatibility, high magnification charge/discharge capacity difference with solvent, there is researcher to be pyrolyzed with epoxy resin
Carbon has carried out composite modified processing to graphite, by changing the surface state of graphite, is strengthened graphite layers adhesion,
Improve the compatibility of graphite material and solvent；The shape of graphite sheet-like particle is also changed simultaneously, mitigates it in film-forming process
In preferred orientation, be advantageous to insertion and abjection of the lithium ion in graphite pole piece, so as to improve the high magnification of graphite material
Charge/discharge capacity.The carbon composite of this nucleocapsid structure both has the property such as high reversible capacity and the low potential platform of graphite
Can, there is amorphous carbon material and solvent compatibility again and the features such as high-rate performance is good, so that modified composite
Chemical property greatly improve.But the shortcomings that resin-coating is, easily lumpd in preparation process, it is necessary to by composite
The negative material of suitable particle size distribution can be just obtained after crushing, this just inevitably destroys shell, it is difficult to accomplish that cladding is equal
Uniform holding shape, so that modified effect is deteriorated.How to avoid crushing, the excellent negative material of high-rate performance, which is made, is
One of the direction to be studied from now on.
Hard carbon material gos deep into Recent study, has many new hard carbon materials to be found again.Such as:Wang Q etc.
It was found that by hydrothermal method prepare the hard carbon ball (HCS1) containing micropore have splendid spherical morphology, controllable single point
Dissipate particle diameter and smooth surface.XRD shows that HCS1 is non-graphited with Raman spectrum.As the negative of lithium ion battery
Pole material, HCS1 reversible capacity are up to 430mAh/g, initial coulomb efficiency 73%.Its dynamic performance is more micro- than mesocarbon
This typical soft carbon material of ball (MCMB) is not bad.It is modified by surface, such as in hard carbon Surface coating tetraethoxysilane
(TEOS) HCS1 coulombic efficiency can, or using chemical vapor infiltration (CVD) in hard carbon surface precipitation acetylene be made significantly
Improve.In addition, nanometer SnSb alloying pellets are deposited on HCS1 surfaces, can effectively prevents alloying pellet electrochemical in charge and discharge process
Aggregation is learned, reversible capacity is greatly improved with cycle characteristics.Although hard carbon material has specific capacity height, good cycle etc.
Feature, but the electrode potential present in hard carbon material is too high, current potential hysteresis (i.e. intercalation potential, which is less than, takes off lithium current potential) and first
The shortcomings of irreversible capacity is big is circulated, the practicalization of hard carbon material is have impact on, fails commercial applications so far.
In the carbon material that people commonly use before the classification of the above three, the most stable with the performance of MCMB, high current is filled
Discharge performance is also relatively good, and better performance, but the price of MCMB will can be reached after being modified to its surface
Compare high, if modified cost will greatly increase, high cost will hinder it to be used for electric car negative material on a large scale.Firmly
The current commercial applications of carbons material it is also seldom, make it the defects of in terms of its large-scale production cost and itself electrical property
It is difficult to electric car negative material is may be used in the short time.Graphite type material is with its cheap price and its modified good
Performance would be possible to be applied on a large scale with negative material in electric car from now on.
The content of the invention
It is an object of the invention to make up the deficiencies in the prior art, there is provided it is a kind of by soft charcoal presoma and hard charcoal presoma with
The preparation method for soft/hard carbon composite negative pole material that graphite is common compound and is formed.
To achieve the above object, the present invention provides following technical scheme：
A kind of soft or hard carbon of lithium ion battery is modified the preparation method of negative material, comprises the following steps that：
(1) mixing granulation：By graphite, soft carbon presoma, hard carbon presoma according to a certain percentage, be added to heating and
In the kneading kettle of agitating device, heat temperature raising, then it is stirred continuously, stops heating after being well mixed, cool down and be stirred continuously, obtain
To powder A；
(2) sieving approach：Powder A is sieved, obtains minus sieve body B, and the bulky grain on sieve is crushed, is broken
The powder obtained after broken is sieved again, obtains minus sieve body C；
(3) mix：Powder B and powder C is subjected to mixed processing by the agitating device with mixed function, is well mixed
Afterwards, powder D is obtained；
(4) high-temperature process：Powder D is subjected to high temperature graphitization processing, obtains powder E；
(5) sieve：Powder E is sieved, obtains minus sieve body F, and the bulky grain sieved on a small quantity returns after broken
Return as the graphite raw material in step (1), recycled.
(6) it is modified：According to mol ratio Ti：Si：C=2~3：2~4：600~1000 weigh tetraethyl titanate, nano silica fume and
Powder F, under inert gas shielding, add dispersant and carry out spheroidal graphite or ultrasonic mixing processing, dry obtained powder G；
(7) secondary carbonization：Powder G is warming up to 1400~1600 DEG C of guarantors under hydrogen and the protection of inert gas mixed atmosphere
1~3h of temperature, be then cooled to 1200~1400 DEG C of 4~6h of insulation, be finally cooled to room temperature be required modification it is soft/hard carbon is multiple
Close negative material.
In step (1) of the present invention graphite be petroleum coke, it is needle coke, pitch coke, carbonaceous mesophase spherules, Delanium, natural
More than one or both of graphite, graphite average grain diameter D50 is 2~10 μm.
Soft charcoal presoma described in step (1) of the present invention includes selected from coal tar pitch and petroleum asphalt, mesophase pitch, Yi Jiyou
One or more kinds of mixtures obtained from pitch modification in condensation polycyclic polynuclear aromatic hydrocarbon, its softening point 70 DEG C~
Between 250 DEG C.
Hard charcoal presoma described in step (1) of the present invention is thermoplastic resin, including furane resins, Lauxite, phonetic
One or more kinds of mixtures in polyimide resin, phenolic resin, epoxy resin and polyformaldehyde methacrylate resin, its is soft
Change o'clock is between 50 DEG C~150 DEG C.
Graphite, soft carbon presoma, the weight ratio of hard carbon presoma are 100 in step (1) of the present invention:(20~50):(20~
50)。
Agitating and heating temperature in step (1) of the present invention is 100~600 DEG C, and mixing time is 1~12 hour.
The minus mesh collected in step (2) of the present invention and step (5) by screening, its average grain diameter D50 are 5~25 μm.
Dispersant in step (6) of the present invention for the mass fraction containing carboxymethyl cellulose or polyethylene glycol be 0.5~
3.0% ethanol solution；Drying process in the step (6) is dried in vacuo under 80~150 DEG C of temperature conditionss；
Inert gas in step (6) of the present invention and (7) is nitrogen, one or more mixed in hydrogen, helium
Close gas；The volumn concentration of hydrogen in the step (7) and the hydrogen in inert gas mixed atmosphere is 1~5%.
The raw material that the present invention uses are average grain diameter D50 for 2~10 μm of graphite, and the graphite that small particle is compared in selection is thin
Powder, have the characteristics that specific surface area is big, tap density is low.But just because its particle diameter is small, it is possible to shorten lithium ion and enter stone
Channel resistance between layer of ink, show more excellent high rate performance and cryogenic property.Heated by fine powder and organic carbon source
Mixed processing is carried out under environment, cladding, kneading, secondary granulation and other effects can be played, makes the fine powder of small particles in organic carbon source
Under cementation, second particle is formed, each diversity of material is solved the problems, such as, improves the tap density of material.
With prior art, the beneficial effects of the invention are as follows：
1st, the size of lithium ion battery negative material is directly related to the length of lithium ion diffusion path wherein, to electrode
High rate capability has a huge impact.When electrode material size is smaller, specific surface area is generally large, on the one hand, can make
The current density of electrode reduces, and reduces polarization of electrode effect；On the other hand more lithium ion mobility passages can be provided, contracted
Short migration path, diffusion impedance is reduced, so as to improve the high rate capability of electrode.Therefore, the less particle of particle diameter and nano junction
The material of structure, as lithium ion battery negative material when typically exhibit preferable high rate performance；
2nd, using both soft carbon presoma and hard carbon presoma simultaneously as adhesive, enter under certain temperature and other conditions
Row, which is mediated, to be granulated, and graphite small particles are polymerize, make internal structure further careful, improve its bulk density, then carry out high temperature
Graphitization, pitch and resin are transformed into pyrolytic carbon, form soft/hard carbon graphite composite system.
3rd, modification it is soft/one layer of electric conductivity of coated with uniform of hard carbon composite negative pole material is good, chemical property is stable
Ti3SiC2With conductive network, the lifting to the discharge capacity of graphite cathode material, discharging efficiency and cyclical stability has very much
Profit.
Embodiment
The technical scheme of this patent is described in more detail with reference to embodiment.
Embodiment 1
Using native graphite fine powder as raw material (average grain diameter D50 is 4.65 μm), asphalt (softening point is 100 DEG C) is soft
Carbon matrix precursor, phenolic resin are hard carbon presoma (softening point is 110 DEG C), and it is 10 that three's mass ratio, which is respectively,：3：3, add together
Enter reactor stirring, temperature is 320 DEG C, and mixing time is 6 hours, is cooled down afterwards.
The powder obtained after cooling is sieved by the screen cloth of 200 mesh, and the bulky grain on sieve is crushed, and is crushed
The powder obtained afterwards is sieved again, is afterwards stirred the powder under sieving, and carries out high temperature graphitization.
The powder obtained after graphitization is sieved by the screen cloth of 200 mesh again, takes minus sieve body, and by a small amount of sieve
Bulky grain returns after broken and is used as graphite raw material, is recycled.
According to mol ratio Ti:Si:C=2.5:2:800 weigh tetraethyl titanate, nano silica fume and above-mentioned minus sieve body, with matter
The ethanol solution for the polyethylene glycol that amount percentage composition is 2.0% is progress ball milling mixing processing under dispersant hydrogen shield.
The mixed slurry obtained carries out vacuum drying treatment under the conditions of 120 DEG C and obtains dried feed.
The dried feed obtained is risen to 1600 under the hydrogen hydrogen mixed atmosphere protection that hydrogen volume percentage composition is 3.5%
DEG C insulation 2h, then is incubated 5h, heating rate is 80 DEG C/min, and sintering feed naturally cools to room with stove under the conditions of being cooled to 1300 DEG C
Temperature, that is, obtain modified soft/hard carbon composite negative pole material.
Embodiment 2
Using native graphite fine powder as raw material (average grain diameter D50 is 6.25 μm), coal tar pitch (softening point is 150 DEG C) is soft carbon
Presoma, epoxy resin are hard carbon presoma (softening point is 100 DEG C), and it is 10 that three's mass ratio, which is respectively,：4：4, add together
Reactor stirs, and temperature is 450 DEG C, and mixing time is 7 hours, is cooled down afterwards.
The powder obtained after cooling is sieved by the screen cloth of 250 mesh, and the bulky grain on sieve is crushed, and is crushed
The powder obtained afterwards is sieved again, is afterwards stirred the powder under sieving, and carries out high temperature graphitization.
The powder obtained after graphitization is sieved by the screen cloth of 200 mesh again, takes minus sieve body, and by a small amount of sieve
Bulky grain returns after broken and is used as graphite raw material, is recycled.
According to mol ratio Ti:Si:C=3:2:1000 weigh tetraethyl titanate, nano silica fume and above-mentioned minus sieve body, with quality
The ethanol solution for the polyethylene glycol that percentage composition is 2.0% is progress ball milling mixing processing under dispersant hydrogen shield.Institute
The mixed slurry of acquisition carries out vacuum drying treatment under the conditions of 120 DEG C and obtains dried feed.
The dried feed obtained is risen to 1600 under the hydrogen hydrogen mixed atmosphere protection that hydrogen volume percentage composition is 3.5%
DEG C insulation 2h, then is incubated 5h, heating rate is 100 DEG C/min, and sintering feed naturally cools to stove under the conditions of being cooled to 1200 DEG C
Room temperature, that is, obtain modified soft/hard carbon composite negative pole material.
Embodiment 3
Using Delanium fine powder as raw material (average grain diameter D50 is 5.96 μm), asphalt (softening point is 250 DEG C) is to have
Machine carbon source, furane resins are hard carbon presoma (softening point is 90 DEG C), and it is 10 that three's mass ratio, which is respectively,：5：5, add together anti-
Kettle is answered to stir, temperature is 500 DEG C, and mixing time is 8 hours, is cooled down afterwards.
The powder obtained after cooling is sieved by the screen cloth of 200 mesh, and the bulky grain on sieve is crushed, and is crushed
The powder obtained afterwards is sieved again, is afterwards stirred the powder under sieving, and carries out high temperature graphitization.
The powder obtained after graphitization is sieved by the screen cloth of 200 mesh again, takes minus sieve body, and by a small amount of sieve
Bulky grain returns after broken and is used as graphite raw material, is recycled.
According to mol ratio Ti:Si:C=2:2:900 weigh tetraethyl titanate, nano silica fume and above-mentioned minus sieve body, with quality
The ethanol solution for the polyethylene glycol that percentage composition is 2.0% is progress ball milling mixing processing under dispersant hydrogen shield.Institute
The mixed slurry of acquisition carries out vacuum drying treatment under the conditions of 120 DEG C and obtains dried feed.
The dried feed obtained is risen to 1600 under the hydrogen hydrogen mixed atmosphere protection that hydrogen volume percentage composition is 3.5%
DEG C insulation 2h, then is incubated 5h, heating rate is 80 DEG C/min, and sintering feed naturally cools to room with stove under the conditions of being cooled to 1300 DEG C
Temperature, that is, obtain modified soft/hard carbon composite negative pole material.
Comparative example 1
Native graphite fine powder in embodiment 1 (average grain diameter D50 is 4.65 μm).
Comparative example 2
Native graphite fine powder in embodiment 2 (average grain diameter D50 is 6.25 μm).
Comparative example 3
Delanium fine powder in embodiment 3 (average grain diameter D50 is 5.96 μm).
Raw material in above-described embodiment and comparative example, specific targets parameter list 1.
Table 1
Electrochemical property test
To examine the capacity first of the raw material in embodiment and comparative example and first efficiency performance, with half-cell method of testing
Tested, with above example and the negative material of comparative example：Acetylene black：PVDF (Kynoar)=93：3：4 (weight
Than), add appropriate NMP (1-METHYLPYRROLIDONE) to be tuned into pulpous state, be coated on copper foil, be made within 8 hours through 110 DEG C of dryings of vacuum negative
Pole piece；Using metal lithium sheet as to electrode, electrolyte is 1mol/L LiPF6/EC+DEC+DMC=1：1：1, microporous polypropylene membrane is
Barrier film, it is assembled into battery.Charging/discharging voltage is 0~2.0V, charge-discharge velocity 0.2C, and energy test is carried out to battery performance, is surveyed
Test result is shown in Table 2.
To examine the cycle performance of the raw material in embodiment and comparative example, tested, used with the method for testing of full battery
The negative material of upper embodiment and comparative example：SP：SBR (solid content 50%)：CMC=94：2.5：1.5：2 (weight ratios), add suitable
Amount deionized water is well mixed to be tuned into pulpous state, is applied on copper foil, drying is vacuumized at 90 DEG C；By LiFePO4 powder：SP：KS-
6：PVDF=92：3.5：2：2.5 (weight ratios), after doing that solvent is well mixed with NMP and being sized mixing, it is applied on aluminium foil, at 100 DEG C
Under vacuumize drying；By dried positive and negative electrode pole piece by roll-in, cut-parts, winding, fluid injection, sealing, formation process, it is made
The type Soft Roll resultant battery (nominal capacity 2.5Ah) of LiFePO4 power type 4244130, barrier film Celgard2400, electrolyte
For 1M LiPF6/DMC：EC：DEC, the detection of cycle performance is carried out using battery check device, and test result is shown in Table 2.
Table 2
From table 1, table 2 as can be seen that the negative material properties obtained by each embodiment are superior to comparative example, in modification
The Ti that one layer of electric conductivity of coated with uniform of soft/hard carbon composite negative pole material is good, chemical property is stable3SiC2With conductive mesh
Network, the lifting to the discharge capacity of graphite cathode material, discharging efficiency and cyclical stability are highly beneficial.
Above content is to combine specific preferred embodiment further description made for the present invention, it is impossible to is assert
The specific implementation of the present invention is confined to these explanations.For general technical staff of the technical field of the invention,
On the premise of not departing from present inventive concept, some simple deduction or replace can also be made, should all be considered as belonging to the present invention's
Protection domain.
Claims (10)
1. a kind of soft or hard carbon of lithium ion battery is modified the preparation method of negative material, comprise the following steps that：
（1）Mixing granulation：By graphite, soft carbon presoma, hard carbon presoma according to a certain percentage, it is added to heating and stirring
In the kneading kettle of device, heat temperature raising, then it is stirred continuously, stops heating after being well mixed, cool down and be stirred continuously, obtain powder
Body A；
（2）Sieving approach：Powder A is sieved, obtains minus sieve body B, and the bulky grain on sieve is crushed, after crushing
Obtained powder is sieved again, obtains minus sieve body C；
（3）Mixing：Powder B and powder C is subjected to mixed processing by the agitating device with mixed function, after being well mixed,
Obtain powder D；
（4）High-temperature process：Powder D is subjected to high temperature graphitization processing, obtains powder E；
（5）Screening：Powder E is sieved, obtains minus sieve body F, is soft/hard carbon composite negative pole material obtained by the present invention
Material, and the bulky grain sieved on a small quantity returns after broken and is used as step（1）In graphite raw material, recycled；
（6）It is modified：According to mol ratio Ti：Si ：C=2~3：2~4：600~1000 weigh tetraethyl titanate, nano silica fume
With powder F, under inert gas shielding, add dispersant and carry out spheroidal graphite or ultrasonic mixing processing, dry obtained powder G；
（7）Secondary carbonization：Powder G is warming up to 1400~1600 DEG C of insulations 1 under hydrogen and the protection of inert gas mixed atmosphere
~3h, be then cooled to 1200~1400 0C and be incubated 4~6h, be finally cooled to room temperature be required modification it is soft/hard carbon is compound
Negative material.
2. the soft or hard carbon of a kind of lithium ion battery according to claim 1 is modified the preparation method of negative material, its feature exists
In：Step（1）Middle graphite is one kind in petroleum coke, needle coke, pitch coke, carbonaceous mesophase spherules, Delanium, native graphite
Or it is two or more, graphite average grain diameter D50 is 2~10 μm.
3. the soft or hard carbon of a kind of lithium ion battery according to claim 1 is modified the preparation method of negative material, its feature exists
In：Step（1）Described in soft charcoal presoma include selected from coal tar pitch and petroleum asphalt, mesophase pitch and by pitch modify and obtain
To condensation polycyclic polynuclear aromatic hydrocarbon in one or more kinds of mixtures, its softening point is between 70 DEG C~250 DEG C.
4. the soft or hard carbon of a kind of lithium ion battery according to claim 1 is modified the preparation method of negative material, its feature exists
In：Step（1）Described in hard charcoal presoma be thermoplastic resin, including furane resins, Lauxite, ethyl-amine resin, phenolic aldehyde
One or more kinds of mixtures in resin, epoxy resin and polyformaldehyde methacrylate resin, its softening point is at 50 DEG C
Between~150 DEG C.
5. the soft or hard carbon of a kind of lithium ion battery according to claim 1 is modified the preparation method of negative material, its feature exists
In：Step（1）Middle graphite, soft carbon presoma, the weight ratio of hard carbon presoma are 100:(20~50):(20~50).
6. the soft or hard carbon of a kind of lithium ion battery according to claim 1 is modified the preparation method of negative material, its feature exists
In：Step（1）In agitating and heating temperature be 100~600 DEG C, mixing time be 1~12 hour.
7. the soft or hard carbon of a kind of lithium ion battery according to claim 1 is modified the preparation method of negative material, its feature exists
In：Step（2）And step（5）The middle minus mesh collected by screening, its average grain diameter D50 are 5~25 μm.
8. the soft or hard carbon of a kind of lithium ion battery according to claim 1 is modified the preparation method of negative material, its feature exists
In：Step（6）In dispersant for the mass fraction containing carboxymethyl cellulose or polyethylene glycol be 0. 5~3. 0% anhydrous second
Alcoholic solution；The step（6）In drying process be to be dried in vacuo under 80~150 DEG C of temperature conditionss.
9. the soft or hard carbon of a kind of lithium ion battery according to claim 1 is modified the preparation method of negative material, its feature exists
In：The step（6）With（7）In inert gas be nitrogen, hydrogen, one or more mixed gas in helium.
10. the step（7）In hydrogen and the hydrogen in inert gas mixed atmosphere volumn concentration be 1 ~ 5%.
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| CN108807995A (en) * | 2018-08-03 | 2018-11-13 | 安徽科达洁能新材料有限公司 | A kind of lithium ion battery graphite cathode material and preparation method thereof |
| CN108933240A (en) * | 2018-06-26 | 2018-12-04 | 石家庄尚太科技有限公司 | A kind of preparation method and negative electrode material of high-density lithium ion battery negative electrode material |
| CN109748587A (en) * | 2018-12-29 | 2019-05-14 | 湖南中科星城石墨有限公司 | A kind of high capacity fast charge graphite cathode material and preparation method thereof |
| CN109761211A (en) * | 2018-12-10 | 2019-05-17 | 欣旺达电子股份有限公司 | Hard carbon material and hard carbon/graphite composite material preparation method |
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| CN110600715A (en) * | 2019-10-17 | 2019-12-20 | 石家庄尚太科技有限公司 | Graphite cathode composite material of lithium ion battery and preparation method thereof |
| CN110600715B (en) * | 2019-10-17 | 2021-06-04 | 石家庄尚太科技股份有限公司 | Graphite cathode composite material of lithium ion battery and preparation method thereof |
| CN113437292A (en) * | 2020-03-23 | 2021-09-24 | 中国石油化工股份有限公司 | Modified soft carbon negative electrode material and preparation method thereof |
| CN113451575B (en) * | 2020-03-24 | 2022-09-09 | 比亚迪股份有限公司 | Lithium ion battery cathode material, preparation method thereof, cathode and lithium ion battery |
| CN113451575A (en) * | 2020-03-24 | 2021-09-28 | 比亚迪股份有限公司 | Lithium ion battery cathode material, preparation method thereof, cathode and lithium ion battery |
| CN112768644A (en) * | 2020-04-16 | 2021-05-07 | 西安越遴新材料研究院有限公司 | Modification method for coating silicon-carbon composite negative electrode material interface by using modified asphalt |
| CN111620332A (en) * | 2020-06-08 | 2020-09-04 | 湖北亿纬动力有限公司 | Negative electrode material, preparation method thereof, negative plate and lithium ion battery |
| CN112028068A (en) * | 2020-09-03 | 2020-12-04 | 青海凯金新能源材料有限公司 | Artificial composite graphite and processing method thereof |
| CN112421001A (en) * | 2020-11-04 | 2021-02-26 | 成都爱敏特新能源技术有限公司 | High-rate double-layer coated graphite negative electrode material, lithium ion battery and preparation method of lithium ion battery |
| CN112421001B (en) * | 2020-11-04 | 2022-02-25 | 成都爱敏特新能源技术有限公司 | High-rate double-layer coated graphite negative electrode material, lithium ion battery and preparation method of lithium ion battery |
| CN113764640A (en) * | 2021-09-02 | 2021-12-07 | 大连宏光锂业股份有限公司 | Production method of high-compaction and fast-charging type lithium ion battery cathode material |
| CN114628650A (en) * | 2021-09-06 | 2022-06-14 | 万向一二三股份公司 | Material for improving quick charge performance of lithium ion battery and preparation method thereof |
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| CN114388806A (en) * | 2021-12-31 | 2022-04-22 | 宁波杉杉新材料科技有限公司 | Coating agent, modified graphite material, and preparation method and application thereof |
| CN116443869A (en) * | 2023-03-17 | 2023-07-18 | 乌海宝杰新能源材料有限公司 | Quick graphite charging negative electrode material for starting and stopping power supply and preparation method thereof |
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