CN109599546A - Asphalt carbon-coated natural mixed graphite material and method for preparing lithium ion battery cathode by using same - Google Patents
Asphalt carbon-coated natural mixed graphite material and method for preparing lithium ion battery cathode by using same Download PDFInfo
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- CN109599546A CN109599546A CN201811477232.0A CN201811477232A CN109599546A CN 109599546 A CN109599546 A CN 109599546A CN 201811477232 A CN201811477232 A CN 201811477232A CN 109599546 A CN109599546 A CN 109599546A
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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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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 an asphalt carbon-coated natural mixed graphite material and a method for preparing a lithium ion battery cathode by using the same. The preparation process of the asphalt carbon-coated natural mixed graphite material comprises the following steps: ball-milling and mixing microcrystalline graphite and crystalline flake graphite to obtain mixed graphite powder; carrying out solvothermal reaction on the mixed graphite powder, asphalt liquid and an organic solvent to obtain a precursor material; and (3) performing pre-carbonization and carbonization treatment on the precursor material, and purifying by adopting acid to obtain the material. The method is simple, low in cost and suitable for large-scale production; the prepared asphalt carbon-coated natural mixed graphite material has the advantages of large average interlayer spacing, moderate specific surface area, good conductivity and the like, is used as a negative electrode material for preparing a lithium ion battery, shows good cycle stability and high specific capacity, and has a large-scale application prospect.
Description
Technical field
The present invention relates to a kind of carbon materials, and in particular to a kind of to be answered by one kind for constituting of pitch carbon coating mixing natural graphite
Carbon material is closed, the preparation method and the natural admixed graphite of pitch carbon coating of the natural admixed graphite material of pitch carbon coating are further related to
Application of the material as lithium ion battery negative material, belongs to battery technology field.
Background technique
Micro crystal graphite is one of natural graphite.Micro crystal graphite is the compact shape being made of small natural graphite crystal
Aggregate has the characteristics that high temperature resistant, heat transfer, conduction, acid and alkali-resistance and plasticity are good.China's micro crystal graphite is resourceful, looks into
Bright resource reserve reaches 3,458.1 ten thousand tons.The Hunan Province reserves whole nation first, the 74.7% of Zhan Quanguo, and mineral products are best in quality.But
Since development and utilization research is less, a large amount of micro crystal graphites is caused to be used as founding materials, refractory material, pencil and dyestuff etc. for a long time
In, low side carbon material, resources utilization degree is overall high.Wherein micro crystal graphite yield about 50% is used as fuel in the form of coal,
Significant wastage is caused to natural resources.
Graphite type material is always the negative electrode material of lithium secondary battery first choice, and current commercialized lithium secondary battery is generally adopted
Use natural flake graphite or artificial graphite as negative electrode material.But non-modified graphite there are specific capacities low, high rate performance
The disadvantages of difference and discharge platform are too low.Since crystal grain is tiny, orientation dispersion has the characteristics that nearly isotropy, has micro crystal graphite
Conducive to the fast transferring of ion, and micro crystal graphite also has Turbostratic, forms a large amount of defect, will obtain as negative electrode material
A large amount of active site is obtained, but its specific surface area is excessive, is easy to produce biggish irreversible capacity, first circle coulombic efficiency is low
Disadvantage.Accordingly, it is difficult to which micro crystal graphite is directly applied to power battery cathode material.
Summary of the invention
For micro crystal graphite in the prior art as defect present in lithium ion battery negative material use process, sheet
First purpose of invention is to be to provide that a kind of porosity is high, specific surface area is suitable for, the pitch carbon coating of good conductivity is natural
Admixed graphite material can be used for preparing the lithium ion battery negative material that stable circulation performance is good, the service life is long.
It is another object of the present invention to provide a kind of low raw-material cost, environmentally protective, degree of controllability is high, repeated
Well, it is easily industrialized the method for preparing the natural admixed graphite material of pitch carbon coating.
Third object of the present invention is to be to provide a kind of natural admixed graphite material of pitch carbon coating in lithium-ion electric
Application in pond, the natural admixed graphite material of pitch carbon coating have high, suitable, good conductivity of specific surface area of porosity etc. excellent
Point, the lithium ion battery of preparation have many advantages, such as that specific capacity is high, stable circulation performance is good, the service life is long.
In order to achieve the above technical purposes, the present invention provides a kind of preparations of the natural admixed graphite material of pitch carbon coating
Method comprising following steps:
1) by micro crystal graphite and crystalline flake graphite ball milling mixing, mixing graphite powder is obtained；
2) mixing graphite powder and asphaltic liquid and organic solvent carry out solvent thermal reaction, obtain persursor material；
3) persursor material by be carbonized in advance with after carbonization treatment, using acid purification to get.
Technical solution of the present invention is first by being conducive to two for micro crystal graphite and crystalline flake graphite ball mill grinding and mixing together
Kind natural graphite is sufficiently mixed, so that part micro crystal graphite is embedded in crystalline flake graphite interlayer and is coated on flake graphite's surface.Again
Admixed graphite is mixed with pitch and organic solvent and carries out solvent thermal reaction and is drawn using the isotropism of natural micro crystal graphite
It leads pitch carbon coating admixed graphite and forms uniform and stable clad, especially during solvent thermal reaction, part bitumencarb
Change, in admixed graphite Surface Creation pitch carbon coating layer, and admixed graphite is connected to orderly scale by unordered micro crystal graphite
Admixed graphite kernel is constituted between graphite flake layer, the structure that micro crystal graphite is mingled between this Sheet Graphite is more advantageous to electronics
Between conduction and lithium ion storage.It is reacted by double carburization, to improve carbonizing degree.After double carburization reacts, then
Nitration mixture purification processes are carried out, which can be improved the porosity of admixed graphite, carbonize again if first purified, and asphaltic liquid holds
Filling easily during cladding to admixed graphite inner hole, porosity reduce, and purify again after being carbonized, and are equivalent in natural graphite
Ash content play the role of micropore template, the original internal capillary of admixed graphite can be retained after acid purification, increase admixed graphite
Pore structure.Therefore, the natural admixed graphite material conductivity of pitch carbon coating is good, and porosity is high, specific surface area is suitable for, duct phase
Mutually crosslinking, duct is abundant, can provide channel abundant for lithium ion and electrolyte transmission, swollen to volume caused by lithium ion deintercalation
Swollen contraction problem also can provide certain buffer function.
The mass ratio of preferred scheme, micro crystal graphite and crystalline flake graphite is 1:5~5:1；Micro crystal graphite and crystalline flake graphite are equal
Granularity is crushed to below 100 mesh.
Preferred scheme, the condition of the ball milling are as follows: ball material mass ratio is 20~40:1, and revolving speed is 300~500rpm,
Time is 2~12h.
Asphaltic liquid of the invention refers to liquid bitumen.
The mass ratio of preferred scheme, mixing graphite powder and asphaltic liquid is 1:10~10:1.
Preferred scheme, the organic solvent include formic acid, acetic acid, methanol, ethyl alcohol, ethylene glycol, isopropanol, butanol, second
At least one of nitrile, methylene chloride, chloroform, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone.
Preferably at least one of ethyl alcohol, isopropanol, N-Methyl pyrrolidone.
Preferred scheme, the condition of the solvent thermal reaction: temperature is 80~400 DEG C, and the time is 2~6 hours.
Preferred scheme, persursor material are placed under protective atmosphere, first at 350~750 DEG C, are carbonized 2~12 hours in advance,
Again at a temperature of 800~1200 DEG C, it is carbonized 2~12 hours.More preferably scheme, persursor material are placed under protective atmosphere, first
It at 450~750 DEG C, is carbonized 4~8 hours, then at a temperature of 900~1100 DEG C, is carbonized 4~8 hours in advance.
Preferred scheme, the acid purification process use HCl/HF nitration mixture.Using HCl/HF nitration mixture can depth removal it is mixed
The ash content in graphite is closed, carbon content is made to reach 99% or more.
More preferably scheme, the HCl/HF nitration mixture is by concentrated hydrochloric acid and dense hydrofluoric acid and water 0.8~1.5:1 by volume:
0.5~1 is mixed to get.Concentrated hydrochloric acid and dense hydrofluoric acid are commercially available technical grade conventional acid.
Preferred scheme, the acid purification process are as follows: carbonized product is placed in HCl/HF nitration mixture, in 80~100 DEG C of temperature
Under degree, impregnate 12~36 hours.It is purified, the ash content in admixed graphite can sufficiently be removed, ash content main component by nitration mixture
For SiO2、Al2O3、Fe2O3, the metal oxides such as MgO.After peracid purifies, the natural admixed graphite of pitch carbon coating is using conventional
Washing and alcohol wash, can be with ultrasonic wave added in washing process.
The present invention also provides a kind of natural admixed graphite materials of pitch carbon coating, are obtained by above-mentioned preparation method.
Preferred scheme, the natural admixed graphite material of pitch carbon coating have core-shell structure, and shell is pitch carbon-coating,
Kernel is natural admixed graphite, and the specific surface area of the natural admixed graphite material of pitch carbon coating is 1~50m2/g。
The present invention also provides a kind of applications of the natural admixed graphite material of pitch carbon coating, negative as lithium ion battery
Pole material application.
Existing method can be used in the preparation method of negative electrode of lithium ion battery of the invention, for example, the drip that the present invention is obtained
The green natural admixed graphite material of carbon coating is mixed with conductive agent and binder, is coated in copper foil current collector by rubbing method, system
Obtain negative electrode of lithium ion battery.
The natural admixed graphite material of pitch carbon coating prepared by the present invention prepares the side of lithium ion battery as negative electrode material
Method and method for testing performance: weighing the natural admixed graphite material of above-mentioned pitch carbon coating, and addition 10wt.% Super P, which is used as, to be led
Electric agent, 10wt.% polyvinyladine floride (PVDF) is used as binder, ground that few N-Methyl pyrrolidone is sufficiently added later
(NMP) it is mixed to form uniform black paste slurry, these slurries are coated in copper foil current collector as test electrode, with gold
Belonging to lithium piece, electrode assembling becomes button cell as a comparison, uses electrolyte system for 1M LiPF6/EC:DEC(1:1).It surveys
Trying charging and discharging currents density used in cycle performance is 100mA/g.
Compared with prior art, present invention has the advantage that
1, the present invention is using pitch and micro crystal graphite and crystalline flake graphite as raw material, using the pre- carbon of solvent thermal reaction combination low temperature
Change and the techniques such as high temperature cabonization prepare the natural admixed graphite material of pitch carbon coating, simple process, low raw-material cost is conducive to
Industrialized production.
2, the natural admixed graphite material of pitch carbon coating of the invention, the pitch carbon-coating of shell have preferable mechanical strong
Degree, can alleviate volume expansion problem during lithium ion is embedded in and deviates between admixed graphite, improve graphite material
Cyclical stability, and kernel is connected to structure between orderly crystalline flake graphite lamella by the micro crystal graphite of order-disorder Turbostratic
At, the structure that micro crystal graphite is mingled between this Sheet Graphite is more advantageous to the storage of interelectric conduction and lithium ion, because
This admixed graphite has good electric conductivity and high storage lithium characteristic.The defect that the Turbostratic of admixed graphite is formed simultaneously, can
A large amount of active site is provided for lithium ion storage.
3, the order-disorder Turbostratic of micro crystal graphite is formed in the natural admixed graphite material of pitch carbon coating of the invention
A large amount of micropores, and by first cladding pitch again pickling purification method it is micro- to retain ash content and the original inside of admixed graphite
Hole, these micropores abundant together constitute lithium ion and electrolyte transmission channel.Pitch carbon coating admixed graphite, reduces mixed
The specific surface area for closing graphite reduces irreversible capacity loss, improves first circle coulombic efficiency.
4, the natural admixed graphite material of pitch carbon coating of the invention is applied in lithium ion battery, has high circulation steady
Qualitative, the advantages that having extended cycle life.
Specific embodiment
Invention is further described in detail With reference to embodiment, rather than limits the claims in the present invention
Protection scope.
Embodiment 1
The natural micro crystal graphite of 10g, 5g crystalline flake graphite is taken to be sieving through 100 mesh mesh screens through ball milling, ball material quality in mechanical milling process
Than for 30:1, revolving speed 400rpm, time 6h, gained powder tapping density is 0.98g/cm3；With 6g asphaltic liquid and appropriate second
Alcohol, which is placed in together in closed container, carries out heating stirring, and heating temperature is dry after being 350 DEG C, 4 hours, by the pitch after drying
Cladding admixed graphite composite material is put into porcelain boat, in quartz tube furnace, nitrogen protection is passed through, with 450 DEG C of pre- carbon of progress low temperature
Change 4 hours, then again with 900 DEG C progress high temperature cabonization 4 hours；After being cooled to room temperature, gained admixed graphite carbon material is spent
It is dried in vacuo 6 hours at ion water washing 3 times, 80 DEG C, with concentrated hydrochloric acid: dense hydrofluoric acid: deionized water is that 5:3:2 is made into 100ml
The mixed acid solution is poured into the pitch-coating admixed graphite composite material, is heated with magnetic stirring apparatus by mixed acid solution
Stirring, whipping temp are 80 DEG C, and the time of nitration mixture processing is 12 hours；With deionized water filtration washing 3 times, then with 100ml without
Water-ethanol carries out sonic oscillation cleaning, and removal remains in the ash impurities in micropore, and the sonic oscillation time is 2 hours；Then again
It is secondary to use deionized water filtration washing 3 times；It is put into baking oven and keeps the temperature 6 hours for 60 DEG C；It obtains bitumencarb and coats natural admixed graphite
Carbon negative pole material.
The natural admixed graphite material of 80wt% pitch carbon coating manufactured in the present embodiment is weighed, 10wt.% Super is added
For P as conductive agent, 10wt.% polyvinyladine floride (PVDF) is used as binder, ground that few N- methylpyrrole is sufficiently added later
Alkanone (NMP) is mixed to form uniform black paste slurry, these slurries are coated in copper foil current collector as test electrode,
With metal lithium sheet, electrode assembling becomes R2025 button cell as a comparison, uses electrolyte system for 1M LiPF6/EC:
DEC(1:1).Under the current density of 500mA/g, test loop performance；It is close in the different electric current such as 1000mA/g, 2000mA/g
The high rate performance of the lower test battery of degree.Resulting test result shows that the lithium cell negative pole of this example preparation has good electrochemistry
Performance: under the current density of 500mA/g, after 300 circle of circulation, being still able to maintain the specific capacity of 348mA/g, after circulation 2000 is enclosed,
Still keep 97% capacity；Under the power-discharging density of 1000mA/g and 2000mA/g, remain to keep respectively 336mAh/g and
The specific capacity of 319mAh/g.
Embodiment 2
The natural micro crystal graphite of 10g, 5g crystalline flake graphite is taken to be sieving through 100 mesh mesh screens through ball milling, ball material quality in mechanical milling process
Than for 40:1, revolving speed 300rpm, time 8h, gained powder tapping density is 0.98g/cm3；With 5g asphaltic liquid and appropriate second
Alcohol, which is placed in together in closed container, carries out heating stirring, and heating temperature is dry after being 350 DEG C, 4 hours, by the pitch after drying
Cladding admixed graphite composite material is put into porcelain boat, in quartz tube furnace, nitrogen protection is passed through, with 450 DEG C of pre- carbon of progress low temperature
Change 6h, then again with 900 DEG C progress high temperature cabonization 4 hours；After being cooled to room temperature, by gained admixed graphite carbon material deionization
It is dried in vacuo 6 hours at water washing 3 times, 80 DEG C, with concentrated hydrochloric acid: dense hydrofluoric acid: deionized water is that 5:3:2 is made into 100ml nitration mixture
Solution, which is poured into the pitch-coating admixed graphite composite material, carries out heating stirring with magnetic stirring apparatus,
Whipping temp is 80 DEG C, and the time of nitration mixture processing is 12 hours；With deionized water filtration washing 3 times, then with 100ml dehydrated alcohol
Sonic oscillation cleaning is carried out, removal remains in the ash impurities in micropore, and the sonic oscillation time is 2 hours；Then it spends again
Ionized water filtration washing 3 times；It is put into baking oven and keeps the temperature 6 hours for 60 DEG C；It obtains bitumencarb and coats natural admixed graphite Carbon anode
Material.
The natural admixed graphite material of 80wt% pitch carbon coating manufactured in the present embodiment is weighed, 10wt.% Super is added
For P as conductive agent, 10wt.% polyvinyladine floride (PVDF) is used as binder, ground that few N- methylpyrrole is sufficiently added later
Alkanone (NMP) is mixed to form uniform black paste slurry, these slurries are coated in copper foil current collector as test electrode,
With metal lithium sheet, electrode assembling becomes R2025 button cell as a comparison, uses electrolyte system for 1M LiPF6/EC:
DEC (1:1), under the current density of 500mA/g, test loop performance；It is close in the different electric current such as 1000mA/g, 2000mA/g
The high rate performance of the lower test battery of degree.Resulting test result shows that the lithium cell negative pole of this example preparation has good electrochemistry
Performance: under the current density of 500mA/g, after 300 circle of circulation, being still able to maintain the specific capacity of 349mA/g, after circulation 2000 is enclosed,
Still keep 96% capacity；Under the power-discharging density of 1000mA/g and 2000mA/g, remain to keep respectively 331mAh/g and
The specific capacity of 314mAh/g.
Embodiment 3
The natural micro crystal graphite of 10g, 10g crystalline flake graphite ball milling is taken to be sieving through 100 mesh mesh screens, ball material mass ratio in mechanical milling process
For 20:1, revolving speed 300rpm, time 4h, gained powder tapping density is 1.00g/cm3；With 6g asphaltic liquid and ethanol in proper amount
It is placed in closed container together and carries out heating stirring, heating temperature is dry after being 350 DEG C, 4 hours, by the pitch packet after drying
It covers micro crystal graphite composite material and is put into porcelain boat, in quartz tube furnace, be passed through nitrogen protection, be carbonized 4 in advance with 400 DEG C of progress low temperature
Hour, then again with 900 DEG C progress high temperature cabonization 6 hours；After being cooled to room temperature, by gained micro crystal graphite carbon material deionization
It is dried in vacuo 6 hours at water washing 3 times, 80 DEG C, with concentrated hydrochloric acid: dense hydrofluoric acid: deionized water is that 5:4:1 is made into 100ml nitration mixture
Solution, which is poured into the pitch-coating admixed graphite composite material, carries out heating stirring with magnetic stirring apparatus,
Whipping temp is 80 DEG C, and the time of nitration mixture processing is 12 hours；With deionized water filtration washing 3 times, then with 100ml dehydrated alcohol
Sonic oscillation cleaning is carried out, removal remains in the ash impurities in micropore, and the sonic oscillation time is 2 hours；Then it spends again
Ionized water filtration washing 3 times；It is put into baking oven and keeps the temperature 6 hours for 60 DEG C；It obtains bitumencarb and coats natural admixed graphite Carbon anode
Material.
The natural admixed graphite material of 80wt% pitch carbon coating manufactured in the present embodiment is weighed, 10wt.%Super P is added
As conductive agent, 10wt.% polyvinyladine floride (PVDF) is used as binder, ground that few N- crassitude is sufficiently added later
Ketone (NMP) is mixed to form uniform black paste slurry, these slurries are coated in copper foil current collector and are used as test electrode, with
Electrode assembling becomes R2025 button cell to metal lithium sheet as a comparison, uses electrolyte system for 1M LiPF6/EC:DEC
(1:1), under the current density of 500mA/g, test loop performance；In the different current density such as 1000mA/g, 2000mA/g
The high rate performance of lower test battery.Resulting test result shows that the lithium cell negative pole of this example preparation has good electrochemistry
Can: under the current density of 500mA/g, after 300 circle of circulation, it is still able to maintain the specific capacity of 345mA/g, after circulation 2000 is enclosed, still
Keep 96% capacity；Under the power-discharging density of 1000mA/g and 2000mA/g, remain to keep 332mAh/g and 317mAh/ respectively
The specific capacity of g.
Comparative example 1
15g natural flake graphite is taken to be sieving through 100 mesh mesh screens through ball milling, ball material mass ratio is 30:1 in mechanical milling process, is turned
Speed is 400rpm, and time 6h, gained powder tapping density is 1.01g/cm3；It is put into porcelain boat with 6g asphaltic liquid, in quartz tube type
In furnace, be passed through nitrogen protection, be carbonized in advance 4 hours with 450 DEG C of progress low temperature, then again with 900 DEG C progress high temperature cabonization 4 hours；
After being cooled to room temperature, gained graphitic carbon material is washed with deionized at 3 times, 80 DEG C and is dried in vacuo 6 hours, with concentrated hydrochloric acid:
Dense hydrofluoric acid: deionized water is that 5:3:2 is made into 100ml mixed acid solution, which is poured into the pitch-coating and mixes stone
In black composite material, heating stirring is carried out with magnetic stirring apparatus, whipping temp is 80 DEG C, and the time of nitration mixture processing is 12 hours；
With deionized water filtration washing 3 times, then sonic oscillation being carried out with 100ml dehydrated alcohol and is cleaned, removal remains in the ash in micropore
Divide impurity, the sonic oscillation time is 2 hours；Then it uses deionized water filtration washing 3 times again；It is put into 60 DEG C of heat preservations 6 in baking oven
Hour；Obtain bitumencarb coated graphite carbon negative pole material.
80wt% bitumencarb coated graphite material manufactured in the present embodiment is weighed, 10wt.%Super P is added as conductive
Agent, 10wt.% polyvinyladine floride (PVDF) is used as binder, ground that few N-Methyl pyrrolidone (NMP) is sufficiently added later
It is mixed to form uniform black paste slurry, these slurries are coated in copper foil current collector as test electrode, with lithium metal
Electrode assembling becomes R2025 button cell to piece as a comparison, uses electrolyte system for 1M LiPF6/ EC:DEC (1:1),
Under the current density of 500mA/g, test loop performance；Electricity is tested under the different current density such as 1000mA/g, 2000mA/g
The high rate performance in pond.Resulting test result shows: under the current density of 500mA/g, after 300 circle of circulation, being able to maintain
The specific capacity of 327mA/g keeps 87% capacity after circulation 2000 is enclosed；In the power-discharging density of 1000mA/g and 2000mA/g
Under, the specific capacity of 318mAh/g and 289mAh/g can be kept respectively.It is compared with embodiment 1, the material of comparative example preparation is without crystallite
Graphite, reduces the active site of bitumencarb coated graphite cathode, and cycle performance and high rate performance are all deteriorated.
Comparative example 2
The natural micro crystal graphite of 10g, 5 crystalline flake graphites are taken to be sieving through 100 mesh mesh screens through ball milling, ball material mass ratio in mechanical milling process
For 30:1, revolving speed 400rpm, time 6h, gained powder tapping density is 0.99g/cm3；With 6g asphaltic liquid and ethanol in proper amount
It is placed in closed container together and carries out heating stirring, heating temperature is dry after being 350 DEG C, 4 hours, by gained admixed graphite carbon
Material is washed with deionized at 3 times, 80 DEG C and is dried in vacuo 6 hours, with concentrated hydrochloric acid: dense hydrofluoric acid: deionized water 5:3:2
It is made into 100ml mixed acid solution, which is poured into the pitch-coating admixed graphite composite material, magnetic stirring apparatus is used
Heating stirring is carried out, whipping temp is 80 DEG C, and the time of nitration mixture processing is 12 hours；With deionized water filtration washing 3 times, then use
100ml dehydrated alcohol carries out sonic oscillation cleaning, and removal remains in the ash impurities in micropore, and the sonic oscillation time is 2 small
When；Then it uses deionized water filtration washing 3 times again；It is put into baking oven and keeps the temperature 6 hours for 60 DEG C.Pitch-coating after drying is mixed
It closes graphite composite material and is put into porcelain boat, in quartz tube furnace, be passed through nitrogen protection, be carbonized in advance with 450 DEG C of progress low temperature 4 small
When, then again with 900 DEG C progress high temperature cabonization 4 hours；After being cooled to room temperature；It obtains bitumencarb and coats natural admixed graphite carbon
Negative electrode material.
The natural admixed graphite material of 80wt% pitch carbon coating manufactured in the present embodiment is weighed, 10wt.% Super is added
For P as conductive agent, 10wt.% polyvinyladine floride (PVDF) is used as binder, ground that few N- methylpyrrole is sufficiently added later
Alkanone (NMP) is mixed to form uniform black paste slurry, these slurries are coated in copper foil current collector as test electrode,
With metal lithium sheet, electrode assembling becomes R2025 button cell as a comparison, uses electrolyte system for 1M LiPF6/EC:
DEC (1:1), under the current density of 500mA/g, test loop performance；It is close in the different electric current such as 1000mA/g, 2000mA/g
The high rate performance of the lower test battery of degree.Resulting test result shows: under the current density of 500mA/g, after 300 circle of circulation,
After keeping the specific capacity of 368mA/g, circulation 2000 to enclose, 84% capacity can be kept；In the electric discharge of 1000mA/g and 2000mA/g
Under density, the specific capacity of 267mAh/g and 190mAh/g can be kept respectively.It is compared with embodiment 1, the material hole of comparative example preparation
Gap rate reduces, and microcellular structure is reduced, and cycle performance and high rate performance are all deteriorated.
Comparative example 3
The natural micro crystal graphite of 10g is taken to be sieving through 100 mesh mesh screens through ball milling, ball material mass ratio is 30:1 in mechanical milling process, is turned
Speed is 400rpm, and time 6h, gained powder tapping density is 0.98g/cm3；It is put into porcelain boat with 10g asphaltic liquid, in quartz ampoule
In formula furnace, it is passed through nitrogen protection, is carbonized in advance 4 hours with 450 DEG C of progress low temperature, it is then small with 900 DEG C of progress high temperature cabonizations 4 again
When；After being cooled to room temperature, gained micro crystal graphite carbon material is washed with deionized at 3 times, 80 DEG C and is dried in vacuo 6 hours, with
Concentrated hydrochloric acid: dense hydrofluoric acid: deionized water is that 5:3:2 is made into 100ml mixed acid solution, which is poured into the pitch packet
It covers in microcrystalline graphite material, carries out heating stirring with magnetic stirring apparatus, whipping temp is 80 DEG C, and the time of nitration mixture processing is 12 small
When；With deionized water filtration washing 3 times, then sonic oscillation being carried out with 100ml dehydrated alcohol and is cleaned, removal remains in micropore
Ash impurities, sonic oscillation time are 2 hours；Then it uses deionized water filtration washing 3 times again；It is put into 60 DEG C of heat preservations in baking oven
6 hours；Obtain bitumencarb cladding micro crystal graphite carbon negative pole material.
Use pitch carbon coating micro crystal graphite carbon negative pole material manufactured in the present embodiment for working electrode, lithium be to electrode,
It is assembled into R2025 button cell, under the current density of 500mA/g, test loop performance；In 1000mA/g, 2000mA/g etc.
The high rate performance of battery is tested under different current densities.Resulting test result shows that the lithium cell negative pole of this example preparation has
Good chemical property: under the current density of 500mA/g, after 300 circle of circulation, it is able to maintain the specific capacity of 335mA/g, is recycled
After 2000 circles, 87% capacity is kept；Under the power-discharging density of 1000mA/g and 2000mA/g, can keep respectively 320mAh/g and
The specific capacity of 299mAh/g.It is compared with embodiment 1, the material specific surface area of comparative example preparation is excessive, and the degree of disorder is excessively high, micropore
Structure is excessively abundant, and cycle performance and high rate performance are all deteriorated.
Comparative example 4
The natural micro crystal graphite of 10g, 10g crystalline flake graphite ball milling is taken to be sieving through 100 mesh mesh screens, ball material mass ratio in mechanical milling process
For 30:1, revolving speed 400rpm, time 6h, gained powder tapping density is 1.00g/cm3；With 6g asphaltic liquid and ethanol in proper amount
It is placed in closed container together and carries out heating stirring, heating temperature is dry after being 350 DEG C, 4 hours, by the pitch packet after drying
It covers micro crystal graphite composite material and is put into porcelain boat, in quartz tube furnace, be passed through nitrogen protection, it is small with 900 DEG C of progress high temperature cabonizations 6
When；After being cooled to room temperature, gained micro crystal graphite carbon material is washed with deionized at 3 times, 80 DEG C and is dried in vacuo 6 hours, with
Concentrated hydrochloric acid: dense hydrofluoric acid: deionized water is that 5:4:1 is made into 100ml mixed acid solution, which is poured into the pitch packet
It covers in admixed graphite composite material, carries out heating stirring with magnetic stirring apparatus, whipping temp is 80 DEG C, and the time of nitration mixture processing is
12 hours；With deionized water filtration washing 3 times, then sonic oscillation being carried out with 100ml dehydrated alcohol and is cleaned, removal remains in micropore
In ash impurities, the sonic oscillation time be 2 hours；Then it uses deionized water filtration washing 3 times again；60 DEG C are put into baking oven
Heat preservation 6 hours；It obtains bitumencarb and coats natural admixed graphite carbon negative pole material.
The natural admixed graphite material of 80wt% pitch carbon coating manufactured in the present embodiment is weighed, 10wt.% Super is added
For P as conductive agent, 10wt.% polyvinyladine floride (PVDF) is used as binder, ground that few N- methylpyrrole is sufficiently added later
Alkanone (NMP) is mixed to form uniform black paste slurry, these slurries are coated in copper foil current collector as test electrode,
With metal lithium sheet, electrode assembling becomes R2025 button cell as a comparison, uses electrolyte system for 1M LiPF6/EC:
DEC (1:1), under the current density of 500mA/g, test loop performance；It is close in the different electric current such as 1000mA/g, 2000mA/g
The high rate performance of the lower test battery of degree.Resulting test result shows that the lithium cell negative pole of this example preparation has good electrochemistry
Performance: under the current density of 500mA/g, after 300 circle of circulation, being still able to maintain the specific capacity of 331mA/g, after circulation 2000 is enclosed,
Still keep 85% capacity；Under the power-discharging density of 1000mA/g and 2000mA/g, 312mAh/g and 292mAh/ can be kept respectively
The specific capacity of g.It is compared with embodiment 3, comparative example 4 has lacked the pre- Carbonation process of low temperature, and admixed graphite and pitch fail in low temperature
Lower sufficiently fusion cladding, voidage and microcellular structure are reduced, and cycle performance and high rate performance are all deteriorated.
Better embodiment of the invention is explained in detail above, but the protection scope of the claims in the present invention is not
It is only limitted to above-described embodiment.
Claims (10)
1. a kind of preparation method of the natural admixed graphite material of pitch carbon coating, it is characterised in that: the following steps are included:
1) by micro crystal graphite and crystalline flake graphite ball milling mixing, mixing graphite powder is obtained；
2) mixing graphite powder and asphaltic liquid and organic solvent carry out solvent thermal reaction, obtain persursor material；
3) persursor material by be carbonized in advance with after carbonization treatment, using acid purification to get.
2. a kind of preparation method of the natural admixed graphite material of pitch carbon coating according to claim 1, it is characterised in that:
The mass ratio of micro crystal graphite and crystalline flake graphite is 1:5~5:1；Micro crystal graphite and crystalline graphite powder are milled to granularity in 100 mesh
Below；The condition of the ball milling are as follows: ball material mass ratio is 20~40:1, and revolving speed is 300~500rpm, and the time is 2~12h.
3. a kind of preparation method of the natural admixed graphite material of pitch carbon coating according to claim 1, it is characterised in that:
The mass ratio of mixing graphite powder and asphaltic liquid is 1:10~10:1；The organic solvent includes formic acid, acetic acid, methanol, ethyl alcohol, second
Glycol, isopropanol, butanol, acetonitrile, methylene chloride, chloroform, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- methyl
At least one of pyrrolidones.
4. a kind of preparation method of the natural admixed graphite material of pitch carbon coating according to claim 1 or 3, feature exist
In: the condition of the solvent thermal reaction: temperature is 80~400 DEG C, and the time is 2~6 hours.
5. a kind of preparation method of the natural admixed graphite material of pitch carbon coating according to claim 1, it is characterised in that:
Persursor material is placed under protective atmosphere, first at 350~750 DEG C, is carbonized 2~12 hours in advance, then in 800~1200 DEG C of temperature
Under, it is carbonized 2~12 hours.
6. a kind of preparation method of the natural admixed graphite material of pitch carbon coating according to claim 1, it is characterised in that:
The acid purification process uses HCl/HF nitration mixture；The HCl/HF nitration mixture is by concentrated hydrochloric acid and dense hydrofluoric acid and water by volume 0.8
~1.5:1:0.5~1 is mixed to get.
7. a kind of preparation method of the natural admixed graphite material of pitch carbon coating according to claim 1 or 6, feature exist
In: the acid purification process are as follows: carbonized product is placed in HCl/HF nitration mixture, at a temperature of 80~100 DEG C, dipping 12~36 is small
When.
8. a kind of natural admixed graphite material of pitch carbon coating, it is characterised in that: by the preparation of any one of claim 1~7
Method obtains.
9. the natural admixed graphite material of a kind of pitch carbon coating according to claim 8, it is characterised in that: the bitumencarb
Natural admixed graphite material is coated with core-shell structure, shell is pitch carbon-coating, and kernel is natural admixed graphite, pitch carbon coating
The specific surface area of natural admixed graphite material is 1~50m2/g。
10. a kind of application of the natural admixed graphite material of pitch carbon coating described in claim 8 or 9, it is characterised in that: as
Lithium ion battery negative material application.
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