CN103855395A - Natural graphite negative electrode material of lithium ion battery and preparation method thereof - Google Patents

Natural graphite negative electrode material of lithium ion battery and preparation method thereof Download PDF

Info

Publication number
CN103855395A
CN103855395A CN201210516768.5A CN201210516768A CN103855395A CN 103855395 A CN103855395 A CN 103855395A CN 201210516768 A CN201210516768 A CN 201210516768A CN 103855395 A CN103855395 A CN 103855395A
Authority
CN
China
Prior art keywords
preparation
natural graphite
temperature
graphite
hours
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201210516768.5A
Other languages
Chinese (zh)
Other versions
CN103855395B (en
Inventor
杜旭
丁晓阳
乔永民
吴志红
李辉
李�杰
李虹
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Shanshan Technology Co Ltd
Original Assignee
Shanghai Shanshan Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Shanshan Technology Co Ltd filed Critical Shanghai Shanshan Technology Co Ltd
Priority to CN201210516768.5A priority Critical patent/CN103855395B/en
Publication of CN103855395A publication Critical patent/CN103855395A/en
Application granted granted Critical
Publication of CN103855395B publication Critical patent/CN103855395B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a preparation method and a natural graphite negative electrode material of a lithium ion battery prepared by the method. The method comprises the following steps: (1) preprocessing spherical natural graphite at high temperature of 500-600 DEG C for 4-6 hours; (2) uniformly mixing the spherical natural graphite in the step (1), a graphitized catalyst and petroleum asphalt to obtain a mixture; (3) carbonizing the mixture in the step (2), cooling, and performing high-temperature catalytic graphitization treatment; and (4) grading. The preparation method of the graphite negative electrode material is simple and feasible and is suitable for industrialization production. The graphite negative electrode material is large in discharge capacity and good in circulating performance; a button battery manufactured by the graphite negative electrode material is excellent in comprehensive performance.

Description

A kind of lithium ion battery natural graphite negative electrode material and preparation method thereof
Technical field
The present invention relates to a kind of lithium ion battery natural graphite negative electrode material and preparation method thereof.
Background technology
Along with microminiaturization and the universalness of electronic installation, more and more need more jumbo secondary cell.What attract people's attention especially is lithium ion battery, compared with NI-G or Ni-MH battery, uses lithium ion battery to have higher energy density.Although carried out broad research for improving battery capacity at present,, along with the raising that battery performance is required, need further to improve battery capacity.
Native graphite has very high capacitance (> 350mAh/g), but has structural unstable shortcoming.In the time improving squeeze pressure in order to obtain higher electrode density, graphite cathode particle is easy to be orientated abreast with collector, produces consistent orientation on whole electrode, owing to existing and inserting lithium in graphite, so the electrode obtaining is easy to expand.Electrode expands and makes cell active materials can reduce by loading in unit volume, produces the problem that battery capacity reduces.
U.S. Pat 2006001003 has reported that catalyzed graphitization processes the method for artificial graphite negative electrodes material, can improve fast charging and discharging performance and cycle performance, reduces but the method makes graphite negative electrodes material put into tap density, and it is large that specific area becomes.Japan Patent JP2000-182617 mixes the high crystalline graphite such as flakey native graphite with pitch, through pulverizing, charing, graphitization and make compound, can improve the deficiency of native graphite, first charge-discharge efficiency is high, cycle characteristics excellence, the large and coating excellence of capacity; But make compound through pulverizing, charing, graphitization, it is too much or inhomogeneous that pitch amount is mixed, and can have influence on the capacity of material etc.
Summary of the invention
It is low that technical problem to be solved by this invention is to have overcome existing graphite cathode material discharge capacity, and the defect that cycle performance is poor provides a kind of lithium ion battery natural graphite negative electrode material and preparation method thereof.Preparation method's simple possible of the present invention, be applicable to suitability for industrialized production, prepared natural graphite negative electrode material chemical property is good, and reversible lithium storage capacity is large, there is high charge-discharge capacity and efficiency for charge-discharge, high rate during charging-discharging is good, and cycle performance is good, only has small expansion when charging, fail safe is good, better to electrolyte and other additive adaptability, and use the prepared lithium ion battery product property of this natural graphite negative electrode material stable, between batch, almost there is no difference.
The present invention solves the problems of the technologies described above by the following technical programs.
One of technical scheme of the present invention is, a kind of preparation method of lithium ion battery natural graphite negative electrode material is provided, and it comprises the steps:
1. spherical natural graphite being carried out to High Temperature Pre at 500 ~ 600 ℃ of temperature processes 4 ~ 6 hours;
2. at 100 ~ 180 ℃ of temperature, spherical natural graphite by step in 1., mediate and stir 1-1.5 hour with graphitization catalyst and petroleum asphalt, mix to obtain compound;
3. the compound charing processing in 2. by step, carries out catalyzed graphitization high-temperature process after cooling again;
4. classification.
Step 1. in, described spherical natural graphite can be selected the spherical natural graphite of this area routine; The particle diameter of described spherical natural graphite can be the conventional particle diameter of this type of material of this area; Preferably, the volume average particle size D50 of described spherical natural graphite is 12 ~ 36 μ m.
Step 2. in, described graphitization catalyst can be selected the graphitization catalyst of this area routine; Preferably, the carbide that described graphitization catalyst is silicon, that better is SiC; Preferably, the consumption of described graphitization catalyst is 2 ~ 12% of spherical natural graphite gross mass, and better is 4 ~ 9% of spherical natural graphite gross mass, and described percentage is the mass percent that accounts for ball-type native graphite.
Step 2. in, the method for described mixing and condition are method and the condition of this area routine, preferably, described mixing adopts cantilever double helix cone-type mixer to carry out, better, the time of described mixing is 2.0 ~ 3.5 hours.
Step 2. in, described petroleum asphalt can be selected the petroleum asphalt of this area all size; Preferably, described petroleum asphalt is middle fire stons oil asphalt;
Wherein, described mid temperature pitch forms by aromatic compounds more than three rings with containing oxygen, nitrogenous, sulfur heterocyclic compound and a small amount of macromolecule carbon element material, and molecular weight ranges 200～2000, reaches as high as 3000, and softening point is 65～90 ℃.
The consumption of described petroleum asphalt is the consumption of this area routine; Preferably, described compound and the mass ratio of petroleum asphalt are (2:1) ~ (6:1), better is (3:1) ~ (4:1).
Step 3. in, the method for described charing processing and condition are method and the condition of this area routine; Preferably, the temperature of described charing processing is 800 ~ 1500 ℃; The time of described charing processing is 2 ~ 6 hours.By this area general knowledge, described charing is processed and is carried out in inert atmosphere, and preferably, described inert gas is nitrogen.
Step 3. in, described cooling method and condition are method and the condition of this area routine, preferably for being cooled to room temperature.In the present invention, described room temperature is the ambient temperature of this area routine, is preferably 5 ~ 30 ℃, and better is 25 ℃ ~ 26 ℃.
Step 3. in, the method for described catalyzed graphitization high-temperature process and condition are method and the condition of this area routine; Preferably, the temperature of described catalyzed graphitization high-temperature process is 2800 ~ 3200 ℃; The time of described catalyzed graphitization high-temperature process is 24 ~ 48 hours.By this area general knowledge, described catalyzed graphitization high-temperature process is carried out in inert atmosphere, and preferably, described inert gas is nitrogen.
Step 4. in, the method for described classification and condition are method and the condition of this area routine; Preferably carry out fluid mechanics classification for first sieving, wherein, the method for described screening and fluid mechanics classification and condition are method and the condition of this area routine again; Preferably, described screening 250 mesh sieve extracting screen underflows, better, adopt 250 order oscillatory type screening machines carry out; Preferably, described fluid mechanics classification adopts gas flow sizing machine to carry out; Better, the frequency of described gas flow sizing machine is 25 ~ 65Hz.After described classification, the volume average particle size D50 of described graphite cathode material is 10 ~ 30 μ m.
Two of technical scheme of the present invention is that a kind of lithium ion battery natural graphite negative electrode material being made by above-mentioned preparation method is provided.
Wherein, the volume average particle size D50 of described lithium ion battery natural graphite negative electrode material is 10 ~ 36 μ m.The specific area of described graphite cathode material is 3.0 ~ 4.0m 2/ g.The real density of described graphite cathode material is at 2.20g/cm 3above, be no more than 2.26g/cm 3.The ash content of described graphite cathode material is below 0.10wt%.
Meeting on the basis of this area general knowledge, above-mentioned each optimum condition, can combination in any, obtains the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material be commercially available obtaining all.
Positive progressive effect of the present invention is:
1, the discharge capacity of graphite cathode material of the present invention is large, good cycle, and the high comprehensive performance of its button cell of making, mainly contains following advantage: 1) chemical property is good, and discharge capacity is more than 350mAh/g; 2) discharge platform and platform conservation rate are higher; 3) high rate during charging-discharging is better; 4) good cycle (300 circulations, Capacitance reserve >=80%); 5) better (130 ℃/60 minutes, not quick-fried, do not rise) of fail safe; 6) better to electrolyte and other additive adaptability; 7) its product property making is stable, almost there is no difference between batch.
2, preparation method's simple possible of graphite cathode material of the present invention, is applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the first charge-discharge curve of the natural graphite negative electrode material of the embodiment of the present invention 2.
Fig. 2 is the absorbency curve of the natural graphite negative electrode material of the embodiment of the present invention 2.
Fig. 3 is the cycle performance figure of the natural graphite negative electrode material of the embodiment of the present invention 2.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to conventional method and condition, or selects according to catalogue.
In the present invention, described raw material and manufacturer thereof and model see the following form:
The manufacturer of the each raw material of table 1 and model
Raw material Manufacturer and model
Native graphite Shanghai Shanshan Science and Technology Co., Ltd's spherical natural graphite
SiC The NAT6 of Linyi Jinmeng Silicon Carbide Co., Ltd. carborundum
Petroleum asphalt The Dalian bright strengthening work MQ-100 of Materials Co., Ltd mid temperature pitch
Coal tar pitch Henan Bo Hai Chemical Co., Ltd. mid temperature pitch
Embodiment 1
1. the native graphite 20kg that by volume average particle size D50 is 19.3 μ m carries out the preliminary treatment of 500 ℃, and the processing time is 4 hours; 2. be that the native graphite 20kg of 19.3 μ m and graphitization catalyst (SiC) 0.8kg add in cantilever double helix conical agitator and mix 2 hours by volume average particle size D50 after treatment, obtain compound; Under stirring, alternately compound 20.8kg and petroleum asphalt 4kg are joined in kneading pot, mediate stir process 1.5 hours in 100 ℃; 3. under the protection of nitrogen, at the temperature of 1100 ℃, charing is processed 2 hours, afterwards product is cooled to 5 ℃ of room temperatures, then carries out 36 hours catalyzed graphitization high-temperature process in 2800 ℃; 4. use 250 order oscillatory type screening machine screenings, screenings adopts gas flow sizing machine to carry out classification, and the frequency of grading wheel is 48Hz, and obtaining particle volume average grain diameter D50 is the graphite negative material of lithium ion battery of 20.6 μ m.Recording its half-cell capacity is 362.5mAh/g, first charge-discharge efficiency 91.1%.
Embodiment 2
1. the native graphite 20kg that by volume average particle size D50 is 17.8 μ m carries out the preliminary treatment of 600 ℃, and the processing time is 5 hours; 2. be that native graphite 20kg graphitization catalyst (SiC) 0.8kg of 17.8 μ m adds in cantilever double helix conical agitator and mixes 2 hours by volume average particle size D50 after treatment, obtain compound; Under stirring, alternately compound 20kg and petroleum asphalt 3kg are joined in kneading pot, mediate and process 1 hour in 160 ℃; 3. under the protection of nitrogen, and at the temperature of 800 ℃, charing is processed 6 hours, afterwards product is cooled to 30 ℃ of room temperatures, then carries out 48 hours catalyzed graphitization high-temperature process in 3000 ℃; 5. use 250 order oscillatory type screening machine screenings, screenings adopts gas flow sizing machine to carry out classification, and the frequency of grading wheel is 35Hz, and obtaining particle volume average grain diameter D50 is the graphite negative material of lithium ion battery of 18.4 μ m.Record its half-cell capacity 363.5mAh/g, first charge-discharge efficiency 92.4%.
Embodiment 3
1. the native graphite 20kg that by volume average particle size D50 is 12.1 μ m carries out the preliminary treatment of 500 ℃, and the processing time is 4 hours; 2. be that the native graphite 20kg of 12.1 μ m and graphitization catalyst (SiC) 1.2kg add in cantilever double helix conical agitator and mix 3 hours by volume average particle size D50 after treatment, obtain compound; Under stirring, alternately compound 21.2kg and petroleum asphalt 4kg are joined in kneading pot, mediate and process 1.5 hours in 100 ℃; 3. under the protection of nitrogen, and at the temperature of 1500 ℃, charing is processed 3 hours, afterwards product is cooled to 26 ℃ of room temperatures, then carries out 48 hours catalyzed graphitization high-temperature process in 3200 ℃; 4. use 250 order oscillatory type screening machine screenings, screenings adopts gas flow sizing machine to carry out classification, and the frequency of grading wheel is 45Hz, and obtaining particle volume average grain diameter D50 is the graphite negative material of lithium ion battery of 13.2 μ m.Record its half-cell capacity 365.2mAh/g, first charge-discharge efficiency 93.5%.
Embodiment 4
1. the native graphite 20kg that by volume average particle size D50 is 35.8 μ m carries out the preliminary treatment of 500 ℃, and the processing time is 4 hours; 2. be that the native graphite 20kg of 35.8 μ m and graphitization catalyst (SiC) 1.8kg add in cantilever double helix conical agitator and mix 3.5 hours by volume average particle size D50, obtain compound; Under stirring, alternately compound 21.8kg and petroleum asphalt 8kg are joined in kneading pot, mediate and process 1 hour in 180 ℃; 3. under the protection of nitrogen, and at the temperature of 1100 ℃, charing is processed 2 hours, afterwards product is cooled to 24 ℃ of room temperatures, then carries out 24 hours catalyzed graphitization high-temperature process in 3200 ℃; 4. use 250 order oscillatory type screening machine screenings, screenings adopts gas flow sizing machine to carry out classification, and the frequency of grading wheel is 20Hz, and making particle volume average grain diameter D50 is the graphite negative material of lithium ion battery of 36.2 μ m.Record its half-cell capacity 366.3mAh/g, first charge-discharge efficiency 92.1%.
Embodiment 5
1. the native graphite 20kg that by volume average particle size D50 is 17.8 μ m carries out the preliminary treatment of 600 ℃, and the processing time is 5 hours; 2. be that native graphite 20kg graphitization catalyst (SiC) 0.4kg of 17.8 μ m adds in cantilever double helix conical agitator and mixes 2 hours by volume average particle size D50 after treatment, obtain compound; Under stirring, alternately compound 20kg and petroleum asphalt 3kg are joined in kneading pot, mediate and process 1 hour in 160 ℃; 3. under the protection of nitrogen, and at the temperature of 800 ℃, charing is processed 6 hours, afterwards product is cooled to 25 ℃ of room temperatures, then carries out 48 hours catalyzed graphitization high-temperature process in 3000 ℃; 5. use 250 order oscillatory type screening machine screenings, screenings adopts gas flow sizing machine to carry out classification, and the frequency of grading wheel is 35Hz, and obtaining particle volume average grain diameter D50 is the graphite negative material of lithium ion battery of 18.5 μ m.Record its half-cell capacity 365.3mAh/g, first charge-discharge efficiency 92.4%.
Embodiment 6
1. the native graphite 20kg that by volume average particle size D50 is 35.8 μ m carries out the preliminary treatment of 500 ℃, and the processing time is 4 hours; 2. be that the native graphite 20kg of 35.8 μ m and graphitization catalyst (SiC) 2.4kg add in cantilever double helix conical agitator and mix 3.5 hours by volume average particle size D50, obtain compound; Under stirring, alternately compound 21.8kg and petroleum asphalt 8kg are joined in kneading pot, mediate and process 1 hour in 180 ℃; 3. under the protection of nitrogen, and at the temperature of 1100 ℃, charing is processed 2 hours, afterwards product is cooled to 26 ℃ of room temperatures, then carries out 24 hours catalyzed graphitization high-temperature process in 3200 ℃; 4. use 250 order oscillatory type screening machine screenings, screenings adopts gas flow sizing machine to carry out classification, and the frequency of grading wheel is 20Hz, and making particle volume average grain diameter D50 is the graphite negative material of lithium ion battery of 36.4 μ m.Record its half-cell capacity 366.2mAh/g, first charge-discharge efficiency 92.6%.
Comparative example 1
In this embodiment, native graphite is without High Temperature Pre treatment step.
The native graphite that is 19.3 μ m by volume average particle size D50 does not do High Temperature Pre processing, directly adds in cantilever double helix conical agitator and mixes 2 hours with 14kg and graphitization catalyst (SiC) 1.2kg, obtains compound; Under stirring, alternately compound 20kg and petroleum asphalt 8kg are joined in reactor, carry out the coated processing of heat, after coated end, at the temperature of 1100 ℃, charing is processed 2 hours, afterwards product is cooled to 27 ℃ of room temperatures, carry out 48 hours catalyzed graphitization high-temperature process in 3200 ℃ again, use 250 order oscillatory type screening machine screenings, making particle volume average grain diameter D50 is the graphite negative material of lithium ion battery of 19.3 μ m.Record its half-cell capacity 360.4mAh/g, first charge-discharge efficiency 87.7%.
Comparative example 2
In this embodiment, native graphite does not do catalyzed graphitization high-temperature process.
The native graphite that is 19.3 μ m by 14kg volume average particle size D50 carries out 600 ℃ of High Temperature Pres to be processed 4 hours; Again 14kg native graphite after treatment is added in cantilever double helix conical agitator and mixed 2 hours, obtain graphite raw material; Under stirring, alternately composite graphite raw material 20kg and petroleum asphalt 8kg are joined in kneading pot, mediate and process 1 hour in 160 ℃, after kneading finishes, under the protection of nitrogen, and at the temperature of 1100 ℃, charing is processed 2 hours, afterwards product is cooled to 26 ℃ of room temperatures; Use 250 order oscillatory type screening machine screenings, screenings adopts gas flow sizing machine to carry out classification, and the frequency of grading wheel is 48Hz, and making particle volume average grain diameter D50 is the graphite negative material of lithium ion battery of 19.1 μ m.Record its half-cell capacity 344.3mAh/g, first charge-discharge efficiency 90.2%.
Comparative example 3
In this embodiment, binding agent is coal tar pitch.
The native graphite that is 24.6 μ m by 14kg volume average particle size D50 carries out 600 ℃ of High Temperature Pres to be processed 4 hours, be that the native graphite 20kg of 24.6 μ m and graphitization catalyst (SiC) 1.2kg add in cantilever double helix conical agitator and mix 2 hours again by volume average particle size D50 after treatment, obtain graphite raw material; Under stirring, alternately graphite raw material 21.2kg and coal tar pitch 5kg are joined in kneading pot, mediate and process 1 hour in 180 ℃, after kneading finishes, under the protection of nitrogen, and charing is processed 2 hours at the temperature of 1100 ℃, afterwards product is cooled to 25 ℃ of room temperatures, then carries out 48 hours catalyzed graphitization high-temperature process in 3200 ℃; Use 250 order oscillatory type screening machine screenings, screenings adopts gas flow sizing machine to carry out classification, and the frequency of grading wheel is 45Hz, and making particle volume average grain diameter D50 is the graphite negative material of lithium ion battery of 25.4 μ m.Record its half-cell capacity 365.3mAh/g, first charge-discharge efficiency 86.7%.
Effect embodiment 1
(1) graphite cathode material in embodiment 1 ~ 4 and comparative example 1 ~ 3 is carried out respectively to the grade test of an index test and discharge capacity, first charge-discharge efficiency of particle diameter, real density, specific area and ash, the results are shown in Table 2.
Instrument title and model that test is used are:
Volume average particle size D50, laser fineness gage MS2000;
Real density, super constant temperature water tank SC-15;
Ash content, high-temperature electric resistance furnace SX2-2.5-12;
Specific area, specific surface area measuring instrument NOVA2000.
Assay method national standard:
Tap density GB/T5162-2006/ISO3953:1993;
Real density GBT 8330-2008;
Specific area GB/T 19587-2004.
Half-cell method of testing is: composite graphite negative electrode material, the 1-METHYLPYRROLIDONE that contains 6 ~ 7% Kynoar and 2% the conductive black in mass ratio ratio of 91.6:6.6:1.8 mix, be applied on Copper Foil, it is that 110 ℃ of vacuum drying chamber vacuumizes 4 hours are for subsequent use that the pole piece coating is put into temperature.Simulated battery is assemblied in the German Braun glove box of applying argon gas and carries out, electrolyte is 1MLiPF6+EC:DEC:DMC=1:1:1(volume ratio), metal lithium sheet is to electrode, electrochemical property test carries out on U.S. ArbinBT2000 type cell tester, charging/discharging voltage scope is 0.005 to 1.0V, and charge-discharge velocity is 0.1C.
The performance parameter of the graphite cathode material of the each embodiment of table 2 and comparative example
Figure BDA00002531561600091
As can be seen from Table 2, the discharge capacity of each sample of embodiment 1 ~ 6 is all more than 360mAh/g, and first charge-discharge efficiency is all more than 91%.
Comparative example 1 is that native graphite does not do high-temperature process, and embodiment 1 ~ 4 each first charge-discharge efficiency is more than 91%, and the first charge-discharge efficiency of comparative example 1 only has 87.7%, and first charge-discharge efficiency is on the low side.
Comparative example 2 is that native graphite does not do catalyzed graphitization high-temperature process, and embodiment 1 ~ 4 each discharge capacity is more than 362mAh/g, and the discharge capacity of comparative example 1 only has 344.3mAh/g, and discharge capacity is low.
Comparative example 3 binding agents are coal tar pitch, and the binding agent of embodiment 1 ~ 6 is petroleum asphalt, and its first charge-discharge efficiency is more than 91%, and the first charge-discharge efficiency of comparative example 3 only has 86.7%, and first charge-discharge efficiency is on the low side.
Visible, to adopt preparation method of the present invention to prepare graphite negative material of lithium ion battery, specific area is controlled at 3.0 ~ 4.0m 2/ g, can guarantee the prosperity of particle surface pore, is conducive to again suppress lithium-ion battery system and produces ballooning, and the security performance of battery is good; More than discharge capacity can reach 360mAh/g; Reduce the loss of irreversible capacity, improved energy density, reduced anodal consumption; Pole piece processability is good, high compacted density 1.70g/cm 3under the imbibition time be less than 180 seconds.
(2) adopt full battery testing method to test the graphite cathode material of embodiment 2.Full battery testing method is: using composite graphite negative electrode material as negative pole, using cobalt acid lithium as positive pole, 1M-LiPF6EC:DMC:EMC=1:1:1(volume ratio) solution does electrolyte assembling and helps battery, carries out electric performance test.
Result shows, sample has desirable voltage platform, and discharge voltage can reach plateau very soon, as shown in Figure 1; Its absorbent excellence, high compacted density 1.70g/cm 3under the imbibition time be less than 180 seconds, as shown in Figure 2; Its good cycle, the capability retention after 300 times that circulates can reach 86.1%, as shown in Figure 3.
(3) to other relevant item test result of the finished product battery of being made by the graphite negative material of lithium ion battery of embodiment 1 ~ 6 be: discharge platform (3.6V) >=75%, the 100 weeks platforms that circulate keep >=95%; Multiplying power discharging 3C capacity >=50%; 300 circulations, capability retention >=80%; Overcharge, the security performance measuring stability such as high temperature short circuit, thermal shock is good, not on fire, do not explode, surface temperature is no more than 150 ℃; Better to electrolyte and other additive adaptability, do not analyse lithium; Product is stable, almost there is no difference between batch.

Claims (10)

1. a preparation method for lithium ion battery natural graphite negative electrode material, is characterized in that: it comprises the steps:
1. spherical natural graphite being carried out to High Temperature Pre at 500 ~ 600 ℃ of temperature processes 4 ~ 6 hours;
2. at 100 ~ 180 ℃ of temperature, spherical natural graphite by step in 1., mediate and stir 1-1.5 hour with graphitization catalyst and petroleum asphalt, mix to obtain compound;
3. the compound charing processing in 2. by step, carries out catalyzed graphitization high-temperature process after cooling again;
4. classification.
2. preparation method as claimed in claim 1, is characterized in that: the volume average particle size D50 of described spherical natural graphite is 12 ~ 36 μ m.
3. preparation method as claimed in claim 1, is characterized in that: the carbide that described graphitization catalyst is silicon is preferably SiC; Better, the consumption of described graphitization catalyst is 2 ~ 12% of spherical natural graphite gross mass, and further better is 4 ~ 9% of spherical natural graphite gross mass, and described percentage is the mass percent that accounts for ball-type native graphite.
4. preparation method as claimed in claim 1, is characterized in that: step 2. in, described mixing adopts cantilever double helix cone-type mixer to carry out, preferably, the time of described mixing is 2.0 ~ 3.5 hours.
5. preparation method as claimed in claim 1, is characterized in that: step 2. in, described petroleum asphalt is middle fire stons oil asphalt;
Preferably, described compound and the mass ratio of petroleum asphalt are (2:1) ~ (6:1), better is (3:1) ~ (4:1).
6. preparation method as claimed in claim 1, is characterized in that: step 3. in, the temperature of described charing processing is 800 ~ 1500 ℃; The time of described charing processing is 2 ~ 6 hours; Described charing is processed and is carried out in inert atmosphere, and preferably, described inert gas is nitrogen;
Step 3. in, described being cooled to is cooled to room temperature, preferably, described room temperature is 5 ~ 30 ℃, better, described room temperature is 25 ℃ ~ 26 ℃;
Step 3. in, the temperature of described catalyzed graphitization high-temperature process is 2800 ~ 3200 ℃; The time of described catalyzed graphitization high-temperature process is 24 ~ 48 hours; Described catalytic graphite high-temperature process is carried out in inert atmosphere, and preferably, described inert gas is nitrogen.
7. preparation method as claimed in claim 1, is characterized in that: step 4. in, described classification carry out again fluid mechanics classification for first sieving.
8. preparation method as claimed in claim 7, is characterized in that: described screening 250 mesh sieve extracting screen underflows, preferably, adopt 250 order oscillatory type screening machines carry out; Described fluid mechanics classification adopts gas flow sizing machine to carry out; Preferably, the frequency of described gas flow sizing machine is 25 ~ 65Hz; After described classification, the volume average particle size D50 of described graphite cathode material is 10 ~ 30 μ m.
9. the lithium ion battery natural graphite negative electrode material making as claim 1 ~ 8 preparation method.
10. lithium ion battery natural graphite negative electrode material as claimed in claim 9, is characterized in that: its volume average particle size D50 is 10 ~ 36 μ m, and specific area is 3.0 ~ 4.0m 2/ g, real density is at 2.20g/cm 3above, be no more than 2.26g/cm 3, ash content is below 0.10wt%.
CN201210516768.5A 2012-12-05 2012-12-05 A kind of natural graphite cathode material of lithium ion battery and preparation method thereof Active CN103855395B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210516768.5A CN103855395B (en) 2012-12-05 2012-12-05 A kind of natural graphite cathode material of lithium ion battery and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210516768.5A CN103855395B (en) 2012-12-05 2012-12-05 A kind of natural graphite cathode material of lithium ion battery and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103855395A true CN103855395A (en) 2014-06-11
CN103855395B CN103855395B (en) 2017-07-21

Family

ID=50862779

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210516768.5A Active CN103855395B (en) 2012-12-05 2012-12-05 A kind of natural graphite cathode material of lithium ion battery and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103855395B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105024075A (en) * 2014-12-18 2015-11-04 上海杉杉科技有限公司 Negative electrode material for quickly rechargeable graphite lithium-ion battery and preparation method of negative electrode material
CN105304870A (en) * 2015-09-22 2016-02-03 江西正拓新能源科技有限公司 Secondary granulation lithium ion battery cathode material and preparation method thereof
CN106505198A (en) * 2015-09-25 2017-03-15 宁波杉杉新材料科技有限公司 A kind of graphite negative material of lithium ion battery and preparation method thereof
CN107871854A (en) * 2016-09-27 2018-04-03 宁波杉杉新材料科技有限公司 A kind of preparation method of graphite negative material of lithium ion battery second particle
CN110828824A (en) * 2019-11-26 2020-02-21 湖南中科星城石墨有限公司 Long-life natural graphite negative electrode material and preparation method thereof
CN114914408A (en) * 2021-02-10 2022-08-16 中国石油化工股份有限公司 Silicon-carbon composite material and preparation method and application thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101224882B (en) * 2007-01-16 2011-12-07 深圳市比克电池有限公司 Artificial graphite surface modifying method and lithium battery anode material produced thereby
CN101087021B (en) * 2007-07-18 2014-04-30 深圳市贝特瑞新能源材料股份有限公司 Man-made graphite cathode material for lithium ion battery and its making method
JP5458689B2 (en) * 2008-06-25 2014-04-02 三菱化学株式会社 Non-aqueous secondary battery composite graphite particles, negative electrode material containing the same, negative electrode and non-aqueous secondary battery
CN102485648B (en) * 2010-12-03 2014-08-06 上海杉杉科技有限公司 Modified graphite, composite graphite material containing the modified graphite and their preparation methods and application
CN102593434B (en) * 2011-01-11 2015-11-25 上海杉杉科技有限公司 Composite graphite particles for lithium secondary battery and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105024075A (en) * 2014-12-18 2015-11-04 上海杉杉科技有限公司 Negative electrode material for quickly rechargeable graphite lithium-ion battery and preparation method of negative electrode material
CN105304870A (en) * 2015-09-22 2016-02-03 江西正拓新能源科技有限公司 Secondary granulation lithium ion battery cathode material and preparation method thereof
CN106505198A (en) * 2015-09-25 2017-03-15 宁波杉杉新材料科技有限公司 A kind of graphite negative material of lithium ion battery and preparation method thereof
CN107871854A (en) * 2016-09-27 2018-04-03 宁波杉杉新材料科技有限公司 A kind of preparation method of graphite negative material of lithium ion battery second particle
CN110828824A (en) * 2019-11-26 2020-02-21 湖南中科星城石墨有限公司 Long-life natural graphite negative electrode material and preparation method thereof
CN110828824B (en) * 2019-11-26 2021-06-11 湖南中科星城石墨有限公司 Long-life natural graphite negative electrode material and preparation method thereof
CN114914408A (en) * 2021-02-10 2022-08-16 中国石油化工股份有限公司 Silicon-carbon composite material and preparation method and application thereof
CN114914408B (en) * 2021-02-10 2024-06-11 中国石油化工股份有限公司 Silicon-carbon composite material and preparation method and application thereof

Also Published As

Publication number Publication date
CN103855395B (en) 2017-07-21

Similar Documents

Publication Publication Date Title
CN102593434B (en) Composite graphite particles for lithium secondary battery and preparation method thereof
CN104143635B (en) A kind of artificial plumbago negative pole material and preparation method thereof
CN105236395B (en) A kind of composite artificial graphite negative material production method
CN104218214B (en) A kind of lithium ion battery negative material and preparation method thereof
CN102485648B (en) Modified graphite, composite graphite material containing the modified graphite and their preparation methods and application
CN103311519B (en) A kind of composite hard carbon cathode material and its production and use
CN102479942B (en) A kind of hard carbon cathode material and its production and use
CN106532053A (en) Graphite anode material for lithium ion batteries and preparation method thereof
CN109921018A (en) The preparation method of sodium-ion battery high capacity biomass hard charcoal negative electrode material
CN103311520B (en) A kind of lithium ion battery composite graphite negative electrode material and preparation method thereof
CN106532044A (en) Lithium secondary battery composite graphite and preparation method thereof
CN106981632A (en) High magnification fills the preparation method of graphite soon
CN103794790A (en) Lithium ion battery composite graphite negative electrode material and preparation method thereof
CN104143641B (en) A kind of interphase negative material and preparation method thereof
CN103855395A (en) Natural graphite negative electrode material of lithium ion battery and preparation method thereof
CN106252662A (en) A kind of preparation method of low bulk graphite
CN111370654B (en) Composite graphite negative electrode material, lithium ion battery and preparation method and application thereof
CN106395811B (en) Preparation method of low-expansion long-cycle natural graphite
CN105731427A (en) Lithium ion battery graphite anode material and preparation method thereof
CN109626352A (en) A kind of high multiplying power lithium ion battery class hard carbon graphite cathode material and preparation method thereof
CN106486652A (en) A kind of graphite negative material of lithium ion battery and preparation method thereof
CN102110813B (en) Graphite material at negative pole of lithium ion battery and preparation method thereof
CN105047928A (en) High-tap-density graphite anode material and preparation method thereof
CN105742636A (en) Graphite negative electrode material for lithium-ion battery and preparation method of graphite negative electrode material
CN103219520B (en) Graphite cathode material of lithium ion battery and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant