CN108346781A - A kind of high power capacity high-pressure solid high power lithium ion cell negative material and negative electrode slurry - Google Patents
A kind of high power capacity high-pressure solid high power lithium ion cell negative material and negative electrode slurry Download PDFInfo
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- CN108346781A CN108346781A CN201710059203.1A CN201710059203A CN108346781A CN 108346781 A CN108346781 A CN 108346781A CN 201710059203 A CN201710059203 A CN 201710059203A CN 108346781 A CN108346781 A CN 108346781A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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 present invention relates to field of lithium ion battery, disclosing a kind of high power capacity high-pressure solid high power lithium ion cell negative material and negative electrode slurry, negative material has nucleocapsid, and wherein nuclear material is artificial graphite, and shell material is unformed charcoal.The negative material power of the nucleocapsid of the present invention is high, and capacity is high, and capacity can reach 365mAh/g（0.5C discharges）, compacted density is high, can reach 1.65g/cm3More than.In addition, negative material particle of the present invention is small, negative material adhesive force on a current collector and uniformity are good, using the negative material of the present invention as the cathode of lithium ion battery, can reduce contact internal resistance of the negative material with copper foil.
Description
Technical field
The present invention relates to field of lithium ion battery more particularly to a kind of high power capacity high-pressure solid high power lithium ion cell cathode
Material and negative electrode slurry.
Background technology
With energy environment protection realize gradual reinforcement, in recent years new-energy automobile obtained significant progress.Wherein, electronic
Automobile is one of Main way.And in the power battery of electric vehicle, lithium ion battery occupies very important status.
The cathode of current lithium-ion-power cell on the market, negative material is mainly graphite.
As disclosed a kind of lithium ion battery negative material application No. is 201210092946.6 Chinese invention patent
Preparation method, the lithium ion battery negative material are obtained by the way that graphitic carbon material is placed in plasma processing apparatus handle
.The present invention also provides a kind of negative electrode of lithium ion battery and lithium ion batteries.The lithium ion battery negative material obtained, it is right
Electrolyte has good wellability.The wellability of negative electrode of lithium ion battery made from the lithium ion battery negative material also obtains
Improve to corresponding.To ensure infiltration of the cathode to electrolyte under the conditions of the compacted density of negative electrode of lithium ion battery is higher
Degree reaches the unit volume loading for improving negative electrode of lithium ion battery graphitic carbon material, and improves lithium ion battery energy in turn
The purpose of metric density.
That there are negative material capacity is low for the cathode of the lithium-ion-power cell of the prior art, compacted density is low, power is low
Disadvantage limits the performance of lithium ion battery.In addition existing negative material particle is big, cathode is on copper foil adhesive force and
The poor problem of even property, and then the internal resistance of cell can be caused higher, the poor problem of performance.
Invention content
In order to solve the above technical problem, the present invention provides a kind of high power capacity high-pressure solid high power lithium ion cell cathode
Material and negative electrode slurry.The negative material power of the nucleocapsid of the present invention is high, and capacity is high, and capacity can reach 365mAh/g
（0.5C discharges）, compacted density is high, can reach 1.65g/cm3More than.In addition, negative material particle of the present invention is small, negative material
Adhesive force and uniformity on a current collector is good, using the negative material of the present invention as the cathode of lithium ion battery, can reduce
Contact internal resistance of the negative material with copper foil.
The specific technical solution of the present invention is：A kind of high power capacity high-pressure solid high power lithium ion cell negative material, it is described
Negative material is in granular form, and has nucleocapsid structure, wherein nuclear material is artificial graphite, and shell material is unformed charcoal.
The negative material power of the nucleocapsid of the present invention is high, and capacity is high, and capacity can reach 365mAh/g（0.5C discharges）,
Compacted density is high, can reach 1.65g/cm3（Traditional negative material is generally 1.3-1.4 g/cm3）More than.In addition, the present invention is negative
Pole material granule is small, and negative material adhesive force on a current collector and uniformity are good, using the negative material of the present invention as lithium from
The cathode of sub- battery can reduce contact internal resistance of the negative material with copper foil.
The preparation method of negative material includes the following steps：
1）By mosaic coke and pitch 10-30 in mass ratio:1 mixes at 65-75 DEG C, is heated to 380-400 after mixing
DEG C carry out heat polymerization 3-5h.
2）By step 1）Product carry out low-temperature treatment to remove light component, wherein temperature is 380-450 DEG C, vacuum degree
It is -0.10 to -0.08MPa, time 1-2h.
3）By step 2）Product at 2600-2800 DEG C graphitization processing 5-10h, obtain artificial graphite.
4）Soft carbon or hard carbon are added into the artificial graphite, it is molten to be added to polymer precursor under atmosphere of inert gases
Organic liquid phase cladding processing is carried out in liquid, is obtained carbon polymer cladding organic double compound, is then carried out at 800-1800 DEG C high
Warm calcination processing, constant temperature keep 6-36h, obtain charcoal cladding negative material.
5）Charing process, carbonization temperature 800-1200 are carried out under atmosphere of inert gases to charcoal cladding negative material
DEG C, carbonization time 4-6h；Then carbonizing production is crushed, is classified by grain size after crushing, obtain negative material.
It is the aggregate of negative material that the present invention, which selects mosaic Jiaozhuo, and mosaic coke belongs to one kind of coke, and mosaic is burnt
It is different from the property of traditional needle coke, compared with needle coke, there is higher capacity, compacted density and power-performance.With
After pitch carries out thermal polymerization together, then low temperature modification processing, the individual particle structure for the specified particle diameter that then high-temperature heat treatment obtains
Artificial graphite, high rate during charging-discharging is good, is prepared into fine and close small particle artificial graphite base material, has high power capacity, high pressure
The characteristics of real density, high power performance.
The advantages of negative material is：
1, short grained negative material can shorten lithium ion diffusion length, increase electrolyte wetted area, reduce pole piece OI values,
To effectively promote the multiplying power and power-performance of material.
2, there is coarse surface with pure artificial graphite, electrochemical reaction activity is higher, increases the consumption of electrolyte, and
After unformed charcoal cladding artificial graphite, cladding rear surface is relatively smooth, and surface forms amorphous carbon coating, reduces active site；Simultaneously
The electrode reaction resistance of material can be greatly lowered, the power of material and cryogenic property is made to get a promotion.
3, after cycling, internal structure can become loose not fine and close to pure artificial graphite, and can avoid this feelings after coating
Condition, fine and close internal structure and smooth surface texture can effectively extend the cycle life of lithium battery.
Carried out on the basis of individual particle artificial graphite it is granule modified, it is unformed by liquid phase coating on artificial graphite surface
Charcoal makes it have nucleocapsid structure, it is therefore an objective to further improve interface resistance, hoisting power characteristic.Using liquid phase coating, cladding
Uniformly, carbon residue is low.
Preferably, the grain size of the negative material is d50≤6μm。
Preferably, step 3）In, the graphitization processing time is 7h.
Preferably, step 4）In, artificial graphite is 1 with the mass ratio of soft carbon or hard carbon:0.1-10, the high-temperature calcination
The temperature of processing is 1300 DEG C, and thermostatic hold-time is for 24 hours.
Preferably, step 4）In, the polybenzazole precursor liquid solution is Water-soluble phenolic resin solution.
A kind of negative electrode slurry includes the raw material of following parts by weight：90-97 parts of negative material, 0.2-3 parts of cathode conductive agent,
1-6 parts of negative electrode binder；400-1000 parts of solvent.
Preferably, the negative electrode binder is 1 by mass ratio:The carboxymethyl cellulose and butadiene-styrene rubber group of 0.5-1.5
At wherein the butadiene-styrene rubber is the styrol copolymer that grain size is less than 0.2 μm, the pH values of butadiene-styrene rubber are 6.5-7.5.
It is good with the bonding effect of collector after above-mentioned negative electrode binder and other specific components in the present invention are compound, no
It is easy to fall off.
Preferably, negative electrode slurry further includes carbon/3-5 parts of silicon composite sol.
Carbon/silicon composite sol can form solid skeletal in solidification, which has loose pore passage structure, the pore passage structure
The infiltration of electrolyte is not only contributed to, electric conductivity is enhanced, reduces internal resistance, and the firm work of auxiliary can be played to active material
With negative material after solidification is not easy to crack, falls off, high with the adhesive fastness of collector.
Preferably, the preparation method of the carbon/Ludox is as follows：
a）By ethyl orthosilicate, absolute ethyl alcohol, toluene 8-10 in mass ratio:100:0.1-0.2 is mixed, obtained solution A；By 0.5-
Glacial acetic acid, absolute ethyl alcohol and the water 20-30 in mass ratio of 1.5mol/L:100:6-8 is mixed, obtained solution B；To solution A
Supersonic oscillations processing is carried out at 50-60 DEG C, and solution B is added drop-wise to its 3-4 times of quality with the rate of 0.5-1.0 mL/s
In solution A；0.01-0.03 times of the sodium bicarbonate that quality is solution A is added while solution B is added dropwise into solution A, is dripped
2-4h is stirred after finishing, Ludox is made.
b）It is another to take nano carbon sol to be mixed with the Ludox and stir conjunction uniformly, obtain carbon silicon mass ratio 1-3:1 carbon/silicon
Complex sol.
Ludox prepared by the above method is mixed in specific proportions with nano carbon sol, in Ludox preparation process,
Pore-foaming agent is added, more pore passage structures can be formed after colloidal sol solidification, be further conducive to the infiltration of electrolyte, enhancing is led
Electrically, internal resistance is reduced.
Obtained negative electrode slurry is coated in collection liquid surface, negative electrode slurry is first made to carry out aging, aging energy after roll-in
The loose pore passage structure under its collosol state can be kept after enough curing negative electrode slurry as possible, is heated up again after aging molding
Dry, solvent moment volatilization, shaping structures, loose pore passage structure is retained.
It is compared with the prior art, the beneficial effects of the invention are as follows：
The negative material power of the nucleocapsid of the present invention is high, and capacity is high, and capacity can reach 365mAh/g（0.5C discharges）, compacting
Density is high, can reach 1.65g/cm3More than.In addition, negative material particle of the present invention is small, the attachment of negative material on a current collector
Power and uniformity are good, using the negative material of the present invention as the cathode of lithium ion battery, can reduce negative material and copper foil
Contact internal resistance.
Description of the drawings
Fig. 1 is the EIS performance data comparison diagrams of negative material of the present invention and comparative example；
Fig. 2 is the DCR performance data comparison diagrams of the negative material and comparative example of the present invention；
Fig. 3 is the discharge-rate performance data comparison diagram of battery and comparative example made from the negative material of the present invention；
Fig. 4 is battery lancing test temperature profile made from the negative material of the present invention.
Specific implementation mode
With reference to embodiment, the invention will be further described.
Embodiment 1
A kind of high power capacity high-pressure solid high power lithium ion cell negative material, the negative material are in granular form, grain size d50≤
6 μm, and there is nucleocapsid structure, wherein nuclear material is artificial graphite, and shell material is unformed charcoal.The preparation method of negative material
Include the following steps：
1）By mosaic coke and pitch in mass ratio 20:1 mixes at 70 DEG C, is heated to 390 DEG C of progress hot polymerizations after mixing
Close reaction 4h.
2）By step 1）Product carry out low-temperature treatment to remove light component, wherein temperature be 410 DEG C, vacuum degree be-
0.09MPa, time 1.5h.
3）By step 2）Product at 2700 DEG C graphitization processing 7h, obtain artificial graphite.
4）The soft carbon that 5 times of its quality is added into the artificial graphite, water-soluble phenolic is added under atmosphere of inert gases
In urea formaldehyde solution carry out organic liquid phase cladding processing, obtain carbon polymer cladding organic double compound, then at 1300 DEG C into
Row high-temperature calcination is handled, and constant temperature keeps for 24 hours, obtaining charcoal cladding negative material.
5）Charing process is carried out under atmosphere of inert gases to charcoal cladding negative material, carbonization temperature is 1000 DEG C,
Carbonization time is 5h；Then carbonizing production is crushed, is classified by grain size after crushing, obtain negative material.
Embodiment 2
A kind of high power capacity high-pressure solid high power lithium ion cell negative material, the negative material are in granular form, grain size d50≤
6 μm, and there is nucleocapsid structure, wherein nuclear material is artificial graphite, and shell material is unformed charcoal.The preparation method of negative material
Include the following steps：
1）By mosaic coke and pitch in mass ratio 10:1 mixes at 65 DEG C, is heated to 380 DEG C of progress hot polymerizations after mixing
Close reaction 5h.
2）By step 1）Product carry out low-temperature treatment to remove light component, wherein temperature be 380 DEG C, vacuum degree be-
0.10 MPa, time 2h.
3）By step 2）Product at 2600 DEG C graphitization processing 10h, obtain artificial graphite.
4）The hard carbon that 0.1 times of its quality is added into the artificial graphite, water solubility is added under atmosphere of inert gases
In phenol resin solution carry out organic liquid phase cladding processing, obtain carbon polymer cladding organic double compound, then at 800 DEG C into
Row high-temperature calcination is handled, and constant temperature keeps 36h, obtains charcoal cladding negative material.
5）Charing process is carried out under atmosphere of inert gases to charcoal cladding negative material, carbonization temperature is 800 DEG C, charcoal
The change time is 6h；Then carbonizing production is crushed, is classified by grain size after crushing, obtain negative material.
Embodiment 3
A kind of high power capacity high-pressure solid high power lithium ion cell negative material, the negative material are in granular form, grain size d50≤
6 μm, and there is nucleocapsid structure, wherein nuclear material is artificial graphite, and shell material is unformed charcoal.The preparation method of negative material
Include the following steps：
1）By mosaic coke and pitch in mass ratio 30:1 mixes at 65 DEG C, is heated to 400 DEG C of progress hot polymerizations after mixing
Close reaction 3h.
2）By step 1）Product carry out low-temperature treatment to remove light component, wherein temperature be 450 DEG C, vacuum degree be-
0.08MPa, time 1h.
3）By step 2）Product at 2800 DEG C graphitization processing 5h, obtain artificial graphite.
4）The soft carbon that 10 times of its quality is added into the artificial graphite, water-soluble phenolic is added under atmosphere of inert gases
In urea formaldehyde solution carry out organic liquid phase cladding processing, obtain carbon polymer cladding organic double compound, then at 1800 DEG C into
Row high-temperature calcination is handled, and constant temperature keeps 6h, obtains charcoal cladding negative material.
5）Charing process is carried out under atmosphere of inert gases to charcoal cladding negative material, carbonization temperature is 1200 DEG C,
Carbonization time is 4h；Then carbonizing production is crushed, is classified by grain size after crushing, obtain negative material.
Embodiment 4
A kind of negative electrode slurry includes the raw material of following parts by weight：95 parts of the negative material of embodiment 1,1.5 parts of cathode conductive agent,
3.5 parts of negative electrode binder；700 parts of solvent.
Wherein, the negative electrode binder is 1 by mass ratio:1 carboxymethyl cellulose and butadiene-styrene rubber composition, wherein described
Butadiene-styrene rubber is the styrol copolymer that grain size is less than 0.2 μm, and the pH values of butadiene-styrene rubber are 6.5-7.5.
Embodiment 5
A kind of negative electrode slurry includes the raw material of following parts by weight：90 parts of the negative material of embodiment 2,3 parts of cathode conductive agent are born
2 parts of very viscous mixture, 5 parts of carbon/silicon composite sol, 400 parts of solvent.
Wherein, the negative electrode binder is 1 by mass ratio:0.5 carboxymethyl cellulose and butadiene-styrene rubber composition, wherein institute
It is the styrol copolymer that grain size is less than 0.2 μm to state butadiene-styrene rubber, and the pH values of butadiene-styrene rubber are 6.5-7.5.
The preparation method of the carbon/Ludox is as follows：
a）By ethyl orthosilicate, absolute ethyl alcohol, toluene in mass ratio 9:100:0.15 mixing, obtained solution A；By the ice of 1mol/L
Acetic acid, absolute ethyl alcohol and water in mass ratio 25:100:7 are mixed, obtained solution B；Ultrasonic wave is carried out at 55 DEG C to solution A
Solution B is added drop-wise to the rate of 0.75mL/s in the solution A of its 3.5 times of quality by oscillation treatment；Be added dropwise solution B while to
0.02 times of the sodium bicarbonate that quality is solution A is added in solution A, 3h is stirred after being added dropwise, and Ludox is made.
b）It is another to take nano carbon sol to be mixed with the Ludox and stir conjunction uniformly, obtain carbon silicon mass ratio 2:1 carbon/silicon is multiple
Close colloidal sol.
Embodiment 6
A kind of negative electrode slurry includes the raw material of following parts by weight：95.8 parts of the negative material of embodiment 3, cathode conductive agent 0.2
Part, 1 part of negative electrode binder, 3 parts of carbon/silicon composite sol, 1000 parts of solvent.
Wherein, the negative electrode binder is 1 by mass ratio:1.5 carboxymethyl cellulose and butadiene-styrene rubber composition, wherein institute
It is the styrol copolymer that grain size is less than 0.2 μm to state butadiene-styrene rubber, and the pH values of butadiene-styrene rubber are 6.5-7.5.
The preparation method of the carbon/Ludox is as follows：
a）By ethyl orthosilicate, absolute ethyl alcohol, toluene in mass ratio 10:100:0.2 mixing, obtained solution A；By 1.5mol/L's
Glacial acetic acid, absolute ethyl alcohol and water in mass ratio 30:100:8 are mixed, obtained solution B；Ultrasound is carried out at 60 DEG C to solution A
Solution B is added drop-wise to the rate of 1.0 mL/s in the solution A of its 4 times of quality by wave oscillation treatment；Be added dropwise solution B while to
0.03 times of the sodium bicarbonate that quality is solution A is added in solution A, 4h is stirred after being added dropwise, and Ludox is made.
b）It is another to take nano carbon sol to be mixed with the Ludox and stir conjunction uniformly, obtain carbon silicon mass ratio 3:1 carbon/silicon is multiple
Close colloidal sol.
Embodiment 7
A kind of negative electrode slurry includes the raw material of following parts by weight：94.8 parts of the negative material of embodiment 1, cathode conductive agent 0.2
Part, 1 part of negative electrode binder, 4 parts of carbon/silicon composite sol, 1000 parts of solvent.
Wherein, the negative electrode binder is 1 by mass ratio:1.5 carboxymethyl cellulose and butadiene-styrene rubber composition, wherein institute
It is the styrol copolymer that grain size is less than 0.2 μm to state butadiene-styrene rubber, and the pH values of butadiene-styrene rubber are 6.5-7.5.
The preparation method of the carbon/Ludox is as follows：
a）By ethyl orthosilicate, absolute ethyl alcohol, toluene in mass ratio 8:100:0.1 mixing, obtained solution A；By 0.5mol/L's
Glacial acetic acid, absolute ethyl alcohol and water in mass ratio 20:100:6 are mixed, obtained solution B；Ultrasound is carried out at 50 DEG C to solution A
Solution B is added drop-wise to the rate of 0.5 mL/s in the solution A of its 3 times of quality by wave oscillation treatment；Be added dropwise solution B while to
0.01 times of the sodium bicarbonate that quality is solution A is added in solution A, 2h is stirred after being added dropwise, and Ludox is made.
b）It is another to take nano carbon sol to be mixed with the Ludox and stir conjunction uniformly, obtain carbon silicon mass ratio 1:1 carbon/silicon is multiple
Close colloidal sol.
EIS performance tests
The negative material of the present invention is carried out in negative material of the present invention doped with the negative material of different proportion needle coke
EIS performance datas compare, and the results are shown in Figure 1.In figure, 1 indicates that needle coke doping is 0%, and 2 expression needle coke dopings are
10%, 3 indicate that needle coke doping is 20%, and 4 indicate that needle coke doping is 40%, and 1 indicates pure needle coke.It can be seen that with
The doping for needle coke is more, and negative material impedance is lower, therefore performance is better.
DCR performance tests
The negative material of the present invention and the negative material of the needle coke doped with 10% in negative material of the present invention are subjected to direct current
Resistive performance is tested, and the results are shown in Figure 2.In figure, 1 indicates that needle coke doping is 0%, and 2 indicate that needle coke doping is 10%.
It can be seen that 1 D.C. resistance is lower, performance is more preferable.
Discharge-rate performance test
The negative electrode slurry of embodiment 4 is applied in lithium ion battery, which includes the component of following mass parts：
94 parts of NCA（6:2:2）, 2 parts of nanotube, 2 parts of conductive carbon black, 2 parts of positive electrode binder；Diaphragm is PP diaphragms.To this
Battery carries out discharge-rate test（4.4V）, as shown in figure 3, difference lies in the needles doped with 10% in negative material for comparative example
Shape is burnt.It can be seen that 1 high rate performance is more preferable.
Lancing test
By the present invention since lithium ion battery is made in the NCA positive electrodes cooperation of negative material and 622, and carry out lancing test.
The temperature curve of test process is as shown in figure 4, test result is to pass through.
Raw materials used in the present invention, equipment is unless otherwise noted the common raw material, equipment of this field；In the present invention
Method therefor is unless otherwise noted the conventional method of this field.
The above is only presently preferred embodiments of the present invention, is not imposed any restrictions to the present invention, every according to the present invention
Technical spirit still falls within the technology of the present invention side to any simple modification, change and equivalent transformation made by above example
The protection domain of case.
Claims (9)
1. a kind of high power capacity high-pressure solid high power lithium ion cell negative material, it is characterised in that：The negative material is in particle
Shape has nucleocapsid structure, and wherein nuclear material is artificial graphite, and shell material is unformed charcoal；The preparation method of negative material includes
Following steps：
1）By mosaic coke and pitch 10-30 in mass ratio:1 mixes at 65-75 DEG C, is heated to 380-400 after mixing
DEG C carry out heat polymerization 3-5h；
2）By step 1）Product carry out low-temperature treatment to remove light component, wherein temperature be 380-450 DEG C, vacuum degree be-
0.10 to -0.08MPa, time 1-2h；
3）By step 2）Product at 2600-2800 DEG C graphitization processing 5-10h, obtain artificial graphite；
4）Soft carbon or hard carbon are added into the artificial graphite, are added under atmosphere of inert gases in polybenzazole precursor liquid solution
Organic liquid phase cladding processing is carried out, carbon polymer cladding organic double compound is obtained, then carrying out high temperature at 800-1800 DEG C forges
Burning processing, constant temperature keep 6-36h, obtain charcoal cladding negative material；
5）Charing process is carried out under atmosphere of inert gases to charcoal cladding negative material, carbonization temperature is 800-1200 DEG C,
Carbonization time is 4-6h；Then carbonizing production is crushed, is classified by grain size after crushing, obtain negative material.
2. a kind of high power capacity high-pressure solid high power lithium ion cell negative material as described in claim 1, which is characterized in that institute
The grain size for stating negative material is d50≤6μm。
3. a kind of high power capacity high-pressure solid high power lithium ion cell negative material as described in claim 1, which is characterized in that step
Rapid 3）In, the graphitization processing time is 7h.
4. a kind of high power capacity high-pressure solid high power lithium ion cell negative material as described in claim 1, which is characterized in that step
Rapid 4）In, artificial graphite is 1 with the mass ratio of soft carbon or hard carbon:The temperature of 0.1-10, the high-temperature calcination processing are 1300 DEG C,
Thermostatic hold-time is for 24 hours.
5. a kind of high power capacity high-pressure solid high power lithium ion cell negative material as described in claim 1, which is characterized in that step
Rapid 4）In, the polybenzazole precursor liquid solution is Water-soluble phenolic resin solution.
6. a kind of high power capacity high-pressure solid high power lithium ion cell negative material containing as described in one of claim 1-5 is negative
Pole slurry, it is characterised in that include the raw material of following parts by weight：90-97 parts of negative material, 0.2-3 parts of cathode conductive agent, cathode
1-6 parts of adhesive；400-1000 parts of solvent.
7. a kind of negative electrode slurry as claimed in claim 6, which is characterized in that the negative electrode binder is 1 by mass ratio:0.5-
1.5 carboxymethyl cellulose and butadiene-styrene rubber composition, wherein the butadiene-styrene rubber is that grain size is styrene copolymerized less than 0.2 μm
The pH values of object, butadiene-styrene rubber are 6.5-7.5.
8. a kind of negative electrode slurry as claimed in claim 6, which is characterized in that further include carbon/3-5 parts of silicon composite sol.
9. a kind of negative electrode slurry as claimed in claim 8, which is characterized in that the preparation method of the carbon/Ludox is as follows：
a）By ethyl orthosilicate, absolute ethyl alcohol, toluene 8-10 in mass ratio:100:0.1-0.2 is mixed, obtained solution A；By 0.5-
Glacial acetic acid, absolute ethyl alcohol and the water 20-30 in mass ratio of 1.5mol/L:100:6-8 is mixed, obtained solution B；To solution A
Supersonic oscillations processing is carried out at 50-60 DEG C, and solution B is added drop-wise to its 3-4 times of quality with the rate of 0.5-1.0 mL/s
In solution A；0.01-0.03 times of the sodium bicarbonate that quality is solution A is added while solution B is added dropwise into solution A, is dripped
2-4h is stirred after finishing, Ludox is made；
b）It is another to take nano carbon sol to be mixed with the Ludox and stir conjunction uniformly, obtain carbon silicon mass ratio 1-3:1 carbon/silicon is compound
Colloidal sol.
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| CN201710059203.1A CN108346781A (en) | 2017-01-23 | 2017-01-23 | A kind of high power capacity high-pressure solid high power lithium ion cell negative material and negative electrode slurry |
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| CN113097479A (en) * | 2021-03-30 | 2021-07-09 | 吴耀帮 | Preparation method of quick-charging type lithium ion battery negative electrode powder and application of quick-charging type lithium ion battery negative electrode powder in lithium ion battery |
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