CN103872294A - Composite material of lithium ion battery, preparation method thereof and lithium ion battery - Google Patents
Composite material of lithium ion battery, preparation method thereof and lithium ion battery Download PDFInfo
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- CN103872294A CN103872294A CN201410117431.6A CN201410117431A CN103872294A CN 103872294 A CN103872294 A CN 103872294A CN 201410117431 A CN201410117431 A CN 201410117431A CN 103872294 A CN103872294 A CN 103872294A
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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
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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
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a composite material of a lithium ion battery, a preparation method thereof and the lithium ion battery. The composite material of the lithium ion battery is isotropic and comprises a carbon material which is used as a supporting skeleton and graphite particles which are embedded into the carbon material, wherein the carbon material is a product from thermal treatment of a binder; the graphite particles are formed by natural graphite or natural composite graphite which is formed by compounding natural graphite and auxiliary materials, and the mass of the graphite particles accounts for 50.0 to 99.9 percent of the total mass of the composite material. The composite material is high in orientation, high in capacity, high in rate capacity and long in service life; the preparation method is moderate in condition, simple in process and low in cost.
Description
Technical field
The present invention relates to technical field of lithium ion, relate in particular to a kind of composite material, its preparation method and lithium ion battery for lithium ion battery.
Background technology
Lithium ion battery has been applied to the various aspects of people's daily life as a kind of electrochemical power source system of technical maturity, and is employed on electrokinetic cell automobile.Although current application is wide, combination property preferably lithium ion battery there is good performance with composite material at aspects such as capacity, efficiency and absorbents, as secondary cell, orientation characteristic and the cycle performance of lithium ion battery also receive much concern.And at present in lithium ion battery this two aspects performance of the material that uses often undesirable, or this two aspects performance and other premium properties can not compatibilities.To on the good basis of guaranteed capacity, efficiency and absorbent, promote orientation characteristic and cycle performance, must improve graphite orientation.Mainly there is the shortcoming that process conditions harshness, technical sophistication and cost are higher in currently used lifting orientation technology, and the contribution that orientation characteristic is improved is limited.
Chinese invention patent application CN 102637859A discloses a kind of lithium ion battery and graphite cathode material thereof and preparation method thereof, the preparation method of described graphite cathode material comprises: the first step, adopts pitch and the coke granule kneading in vacuum tank that carbon content is 60%～80% to be bonded to hybrid particles; Second step, carries out carbonization treatment to hybrid particles, and the particle of the pitch that is then 30%～50% with carbon content after to carbonization carries out kneading and heat treatment in vacuum tank, and then particle is carried out to charing processing.The isotropism of the graphite cathode material that described method obtains still can not meet the demand as the lithium ion battery negative material of excellent orientation characteristic.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of composite material, its preparation method and lithium ion battery for lithium ion battery.Described composite material has high orientation, high power capacity, high rate capability and long circulation life; Described preparation method's mild condition, technique are simple and cost is lower.
For realizing object of the present invention, the present invention includes following content:
In first aspect, the invention provides a kind of lithium ion battery composite material, described composite material has isotropism, and it comprises that wherein said material with carbon element is the product after binding agent heat treatment as the graphite granule of the material with carbon element of support frame and embedding described material with carbon element inside; Described graphite granule is native graphite or the natural composite graphite that is composited by native graphite and auxiliary material, described graphite granule accounts for 50.0%～99.9% of described composite material gross mass, and for example 50.0%, 52.6%, 55.2%, 60.0%, 63.8%, 67.5%, 70.0%, 72.9%, 74.7%, 80.0%, 86.4%, 88.1%, 92.7%, 95.6% or 99.9% etc.
Preferably, described composite material utilizes the peak intensity I of (110) face that X-ray diffraction tries to achieve
110peak intensity I with (002) face
002ratio I
110/ I
002be more than 0.020, for example 0.020,0.021,0.023,0.024,0.025,0.026,0.029,0.035,0.039 or 0.040 etc.
Preferably, described auxiliary material is a kind or the combination of at least 2 kinds in Delanium, MCMB, needle coke, petroleum coke, boron and boron compound, phosphorus and phosphorus compound, silicon and silicon compound.The typical but non-limiting example of described combination has: the combination of Delanium and MCMB, the combination of Delanium and needle coke, the combination of needle coke and silicon compound, the combination of MCMB and boron compound.
Preferably, the addition of described auxiliary material is 0.1%～50.0% of described natural composite graphite gross mass, for example 0.2%, 0.5%, 0.8%, 1.2%, 2.0%, 4.0%, 7.0%, 10.0%, 30.0%, 42.0%, 46.0% or 48.0%.
Preferably, the median grain diameter D of described composite material
50be 3.000～30.000 μ m, be preferably 3.000～22.000 μ m, for example 3.667 μ m, 7.875 μ m, 14.342 μ m, 17.642 μ m, 20.817 μ m or 21.093 μ m.
Preferably, the specific area of described composite material is 1.000～15.000m
2/ g, more preferably 2.000～8.000m
2/ g, for example 2.119m
2/ g, 3.043m
2/ g, 3.852m
2/ g, 3.901m
2/ g, 4.219m
2/ g, 5.364m
2/ g, 6.676m
2/ g or 7.932m
2/ g.
Preferably, the tap density of described composite material is 0.200～1.200g/cc, more preferably 0.600～1.100g/cc, for example 0.619g/cc, 0.738g/cc, 0.897g/cc, 0.909g/cc, 0.987g/cc, 1.009g/cc, 1.020g/cc, 1.023g/cc or 1.070g/cc.Herein, the g/cc of unit, i.e. g/mL or g/cm
3.
Preferably, the imbibition time of described composite material under 1.650g/cc compacted density is below 80.0s, for example 11.1s, 19.7s, 35.2s, 40.6s, 42.4s, 55.4s, 69.6s or 75.0s.
Preferably, described composite material is more than 360.0mAh/g as the de-lithium specific capacity first of lithium ion battery negative pole active materials, for example 360.2mAh/g, 360.4mAh/g, 362.0mAh/g, 362.2mAh/g, 362.4mAh/g, 364.2mAh/g, 366.5mAh/g or 367.5mAh/g.
Preferably, described composite material is more than 92.0% as coulomb efficiency first of lithium ion battery negative pole active materials, for example 92.4%, 92.5%, 92.7%, 93.0%, 93.3% or 93.9%.
Preferably, described composite material is more than 95.0% as 50 weeks circulation volume conservation rates of lithium ion battery negative pole active materials, for example 96.1%, 96.4%, 96.9%, 97.0%, 97.7%, 98.2% or 98.8%.
Preferably, described composite material is more than 90.0% as 500 weeks circulation volume conservation rates of lithium ion battery negative pole active materials, for example 90.2%, 90.3%, 90.5%, 90.9%, 91.2%, 91.4%, 91.6% or 92.2%.
Preferably, it is more than 90.0% that described composite material is compared 1C multiplying power discharging capacity ratio as the 10C multiplying power discharging capacity of lithium ion battery negative pole active materials, for example 90.4%, 91.3%, 93.7%, 94.0%, 94.1%, 94.3%, 94.4% or 94.8%.
In second aspect, the invention provides a kind of method of preparing the composite material as described in first aspect, comprise the steps:
(1) graphite raw material is promoted to orientation processing and obtain graphite granule;
(2) use binding agent to carry out framework construction on described graphite granule surface and obtain powder;
(3) described powder is carried out to isotropism pressurized treatments and obtain block;
(4) described block is heat-treated;
(5) pulverize-classification-nodularization, remove magnetic and screening processing, obtain described composite material.
Preferably, the lifting orientation of described step (1) is treated to and pulverizes spheroidization processing, fusion treatment or ball-milling treatment.
Preferably, the feeding mode of described pulverizing spheroidization processing is batch (-type) or continous way, and more preferably batch (-type) is pulverized spheroidization processing.
Preferably, the disintegrating apparatus that described pulverizing spheroidization processing adopts is multi-functional particle disposal equipment, internal classification impact type pulverizing mill, low velocity impact formula nodularization pulverizer, ultra micro ball mill, micronizer, air-flow vortex formula pulverizer or pendulum type ring roll pulverizer.
Preferably, the pulverizing rotating speed of described pulverizing spheroidization processing is 50～8000rpm, and grinding time is 2～1200min, and pulverizing number of times is 1～10 time.
Preferably, it is 1 time that described batch (-type) is pulverized spheroidization number of processes, and the processing time is 1～60min, and pulverizing rotating speed is 1000～8000rpm, and classification rotating speed is 1000～8000rpm, and charging frequency is 5～80Hz, and air quantity is 5～50m
3/ min.
Preferably, the time of described fusion treatment is 20～800min, more preferably 20～300min.
Preferably, the rotating speed of described fusion treatment is 800～3000rpm, more preferably 800-2600rpm.
Preferably, the cavity gap of described fusion treatment is 0.1～2.0cm, more preferably 0.1～1.0cm.
Preferably, the temperature of described fusion treatment is 10～80 DEG C, more preferably 20～60 DEG C.
Preferably, the time of described ball-milling treatment is more than 5min, and instrument rotating speed is 200～4000rpm, and the ball of employing is zirconia ball or corundum ball, and diameter is 1～30mm.
Preferably, described step (2) adopt liquid phase mixes and be dried, liquid phase mix and spray be dried and solid phase kneading in a kind or the combination of at least 2 kinds of modes carry out framework construction.
Preferably, described liquid phase is mixed and is dried as carry out kneading or liquid phase under vacuum or non-vacuum condition dry after stirring.
Preferably, the described kneading time is 60～600min.
Preferably, described liquid phase is mixed and is sprayed to be dried and spray dry into adopting homogenizer liquid phase to mix rear employing spray dryer.
Preferably, the speed of agitator of described homogenizer is 3000～5000rpm, and mixing time is 120～180min.
Preferably, the inlet temperature of described spray dryer is 60～350 DEG C, and outlet temperature is 50～150 DEG C, and pressure is 10～100MPa, and charging frequency is 10～100Hz, and speed of agitator is 3000～5000rpm, and mixing time is 120～180min.
Preferably, the solvent that described liquid phase mixing is used is water and/or organic solvent.
Preferably, described organic solvent is a kind or the combination of at least 2 kinds in methyl alcohol, ethanol, ether, benzene, toluene and oxolane; The typical but non-limiting example of described combination has: the combination of methyl alcohol and ethanol, the combination of methyl alcohol and ether, the combination of benzene and toluene, the combination of toluene and oxolane, the combination of methyl alcohol, ethanol and ether.
Preferably, in described liquid phase mixing, the solid content of control mixing suspension-turbid liquid is 5%～70%(quality).
Preferably, described solid phase kneading is that VC mixes or merges.
Preferably, the time that described VC mixes is 3～60min, and temperature is 15～80 DEG C.
Preferably, the time of described fusion is 3～180min.
Preferably, described binding agent is a kind or the combination of at least 2 kinds in pitch, resin, macromolecular material and polymer; The typical but non-limiting example of described combination has: the combination of resin and high molecular polymer, the combination of pitch and resin, the combination of pitch and macromolecular material, the combination of resin and macromolecular material.
Preferably, described pitch is a kind or the combination of at least 2 kinds in coal tar pitch, petroleum asphalt, modified coal tar pitch and mesophase pitch, and softening point is 20～300 DEG C; The typical but non-limiting example of described combination has: the combination of coal tar pitch and petroleum asphalt, the combination of coal tar pitch and mesophase pitch, the combination of petroleum asphalt and modified coal tar pitch.
Preferably, described resin is that water-soluble resin or fusing point are the resin of 30～300 DEG C; Described fusing point is that the typical but non-limiting example of the resin of 30～300 DEG C has: polyethylene, polypropylene or polyvinyl chloride.
Preferably, described graphite granule and binding agent mass ratio are 50.0:50.0～99.9:0.1; Described graphite granule and the typical but non-limiting example of binding agent mass ratio have: 50.0:50.0,60.0:40.0,70.0:30.0,80.0:20.0 or 90.0:10.0.
Preferably, the isotropism pressurized treatments of described step (3) be extrusion molding processing, cold forming processing, hot moulding process and etc. a kind or the combination of at least 2 kind of static pressure in processing; The typical but non-limiting example of described combination has: the combination of static pressure processing is processed and waited to extrusion molding, cold forming process and etc. the combination of static pressure processing, hot moulding processing and etc. the combination of static pressure processing.
Preferably, the pressure of described isotropism pressurized treatments is 500～10000KN.
Preferably, the pressurized treatments temperature of described isotropism pressurized treatments is 20～500 DEG C.
Preferably, the pressurized treatments time of described isotropism pressurized treatments is 6～600min.
Preferably, the block compacted density that described isotropism pressurized treatments obtains is 0.800～2.000g/cc.
Preferably, in described step (4), heat treated temperature is 800～3300 DEG C, for example 800 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C, 1300 DEG C, 1600 DEG C, 2000 DEG C, 2500 DEG C, 2800 DEG C, 2900 DEG C, 3000 DEG C, 3200 DEG C or 3300 DEG C.
Preferably, described heat treated equipment is vacuum stirring bucket, vacuum kneading machine, agitator, kneading machine, roller kilns, pushed bat kiln, tunnel cave, tube furnace, box type furnace, rotary furnace, circular furnace or interior string stove.
Preferably, the heating rate in described heat treatment process be 20.0 DEG C/below min, more preferably 2.0～10.0 DEG C/min.
Preferably, the described heat treated time is 1.0～560.0h, more preferably 1.0～500.0h.
Preferably, in described step (5) equipment of pulverizings-classification-nodularization be selected from internal classification impact type pulverizing mill, low velocity impact formula nodularization pulverizer, ultra micro ball mill, micronizer, air-flow vortex formula pulverizer, pendulum type ring roll pulverizer, in point grader, segment grader, ball mill, fusion machine and sand mill.The said equipment can be used in combination, the typical but non-limiting example of described combination has: internal classification impact grinder, in point grader and the combination of merging machine, air-flow vortex formula pulverizer, in the combination of point grader and ball mill, the combination of low velocity impact formula nodularization pulverizer and segmentation grader.
Preferably, the described equipment except magnetic is for removing magnetic machine.
Preferably, the equipment of described screening is ultrasonic vibration sieve or airflow screen.
In the third aspect, the invention provides a kind of lithium ion battery, described lithium ion battery comprises the composite material as described in first aspect or method makes as described in second aspect composite material.
Beneficial effect of the present invention is: adopt the composite material that makes of the inventive method to utilize the peak intensity I of (110) face that X-ray diffraction tries to achieve
110peak intensity I with (002) face
002ratio I
110/ I
002value remains on more than 0.020, and orientation characteristic is outstanding; 50 weeks circulation volume conservation rates are all more than 95.0%, and 500 weeks circulation volume conservation rates are all more than 90.0%, and cycle performance is outstanding; De-lithium specific capacity is more than 360.0mAh/g first, and coulomb efficiency is that more than 92.0% volumetric properties is outstanding first; It is that more than 90.0% high rate performance is outstanding that 10C multiplying power discharging capacity is compared 1C multiplying power discharging capacity ratio.In a word, composite material of the present invention has high orientation, high power capacity, high rate capability and long circulation life.Described preparation method's production procedure is simple, technology controlling and process is accurate, with low cost, without harsh conditions and be easy to industrialization.
Embodiment
Below in conjunction with embodiment, embodiment of the present invention are described in detail.It will be understood to those of skill in the art that following examples are only the preferred embodiments of the present invention, so that understand better the present invention, thereby should not be considered as limiting scope of the present invention.For a person skilled in the art, the present invention can have various modifications and variations, within the spirit and principles in the present invention all, any amendment of doing, is equal to and replaces or improvement etc., within all should being included in protection scope of the present invention.
Experimental technique in following embodiment/comparative example, if no special instructions, is conventional method; Experiment material used, if no special instructions, is and is purchased available from routine biochemistry chemical reagent work.
Embodiment 1
Use internal classification formula pulverizing mill to pulverize spheroidization processing with continous way feeding mode native graphite, pulverizing rotating speed is 4000rpm, and the time is 2min, obtains graphite granule; By gained graphite granule and mesophase pitch in mass ratio 80.0:20.0 carry out VC and mix, incorporation time is 3min, temperature is 80 DEG C, obtains graphite-asphalt mixture; Graphite-asphalt mixture is carried out to extrusion modling processing, and pressure is 5000KN, and temperature is 20 DEG C, and the pressurized treatments time is 30min, and obtaining block compacted density is 1.500g/cc; Then wait static pressure processing, pressure is 8000KN, and temperature is 200 DEG C, and the pressurized treatments time is 180min, and obtaining block compacted density is 1.800g/cc; Obtained block is heat-treated in interior string stove, and in heat treatment process, heating rate is 3.0 DEG C/min, and treatment temperature is 3200 DEG C, and the processing time is 240.0h; Take out process after piece material, use successively internal classification impact grinder, in point grader, fusion machine, except magnetic machine, ultrasonic vibration sieve, it is processed, obtain lithium ion battery composite material.
Embodiment 2
Natural composite graphite (native graphite evenly mixes gained with Delanium by 80.0:20.0 mass ratio) is carried out to fusion treatment, and the processing time is 20min, and rotating speed is 2500rpm, and cavity gap is 0.5cm, and treatment temperature is 40 DEG C, obtains graphite granule; By graphite granule and softening point be 130 DEG C modified coal tar pitch in mass ratio 90.0:10.0 mix, hybrid mode is that liquid phase is mixed and sprays dry, solvent is the combination of fourth phase furans and ethanol, mixer rotating speed is 3000rpm, and mixing time is 120min, and suspension-turbid liquid solid content is 45%, spray dryer inlet temperature is 150 DEG C, outlet temperature is 80 DEG C, and pressure is 80MPa, obtains powder; Powder is carried out to hot moulding processing, and processing pressure is 6000KN, and treatment temperature is 100 DEG C, and the pressurized treatments time is 60min, and the block compacted density that obtains is 1.400g/cc; Then wait static pressure processing, pressure is 2000KN, and temperature is 20 DEG C, and the pressurized treatments time is 600min, and obtaining block compacted density is 1.800g/cc; Obtained block is heat-treated in roller kilns, and treatment temperature is 1600 DEG C, and heating rate is 5.0 DEG C/min, and the processing time is 24.0h; Then block is heat-treated in interior string stove, in processing procedure, heating rate is 3.0 DEG C/min, and treatment temperature is 3300 DEG C, and the processing time is 500.0h; Take out process after piece material, use successively air-flow vortex formula pulverizer, in point grader, ball mill, except magnetic machine, ultrasonic vibrating screen, it is processed, obtain lithium ion battery composite material.
Embodiment 3
Natural composite graphite (native graphite evenly mixes gained with MCMB by 55.0:45.0 mass ratio) is carried out to ball-milling treatment, and Ball-milling Time is 60min, and instrument rotating speed is 200rpm, and adopting the diameter of corundum ball is 8mm, obtains graphite granule; By gained graphite granule and high molecular polymer in mass ratio 85.0:15.0 to carry out liquid phase dry after stirring, obtain powder; Gained powder is carried out to cold forming processing, and pressure is 10000KN, and temperature is 25 DEG C, and the pressurized treatments time is 6min, and obtaining block compacted density is 1.600g/cc; Then wait static pressure processing, pressure is 8000KN, and temperature is 200 DEG C, and the pressurized treatments time is 180min, and obtaining block compacted density is 2.000g/cc; Gained block is placed in to tunnel cave and heat-treats, treatment temperature is 800 DEG C, and the heating rate in processing procedure is 5.0 DEG C/min, and the processing time is 36.0h; From tunnel cave, take out block, use successively low velocity impact formula nodularization pulverizer, segmentation grader, except magnetic machine, ultrasonic vibrating screen, it processed, obtain lithium ion battery composite material.
Embodiment 4
Adopt multi-functional particle disposal equipment to pulverize spheroidization processing with batch (-type) feeding mode natural composite graphite (native graphite evenly mixes gained with needle coke by 90.0:10.0 mass ratio), pulverizing rotating speed is 4000rpm, classification rotating speed is 4000rpm, charging frequency is 40Hz, and air quantity is 30m
3/ min, grinding time is 30min, obtains graphite granule; Gained graphite granule and coal tar pitch are merged in the ratio of 55.0:45.0, and time of fusion is 180min, obtains powder; Gained powder is carried out to hot moulding processing, and pressure is 500KN, and temperature is 200 DEG C, and the processing time is 300min, and gained block compacted density is 1.700g/cc; Gained block is placed in to roller kilns and heat-treats, heating rate is 10.0 DEG C/min, and treatment temperature is 1300 DEG C, and the processing time is 360.0h; Take out after block, use successively ultra micro ball mill, process except magnetic machine, airflow screen, obtain lithium ion battery composite material.
Embodiment 5
Adopt low velocity impact formula nodularization pulverizer to pulverize spheroidization processing with continous way feeding mode natural composite graphite (native graphite, needle coke evenly mix gained with boron carbide by 70.0:25.0:5.0 mass ratio), pulverizing rotating speed is 1000rpm, grinding time is 10min, pulverizing number of times is 10 times, obtains graphite granule; Gained graphite granule and resin are carried out after liquid phase stirs being dried in the ratio of 99.5:0.5 under vacuum condition, obtain powder; By the processing of gained powder extrusion molding, pressure is 5000KN, and temperature is 500 DEG C, and the processing time is 600min, and gained block compacted density is 1.800g/cc; Then wait static pressure processing, pressure is 10000KN, and temperature is 25 DEG C, and the processing time is 240min, and gained block compacted density is 2.000g/cc; Gained block is placed in to pushed bat kiln and heat-treats, heating rate is 3.0 DEG C/min, and treatment temperature is 1000 DEG C, and the processing time is 300.0h; Then block is placed in to tunnel cave and heat-treats, heating rate is 10.0 DEG C/min, and treatment temperature is 2700 DEG C, and the processing time is 200.0h; Take out after block, use successively micronizer, fusion machine, process except magnetic machine, ultrasonic vibration sieve, obtain lithium ion battery composite material.
Embodiment 6
Adopt air-flow vortex formula pulverizer to pulverize spheroidization processing with continous way feeding mode native graphite, pulverizing rotating speed is 500rpm, and grinding time is 1200min, and pulverizing number of times is 5 times, obtains graphite granule; Gained graphite granule and petroleum asphalt are carried out to kneading in the ratio of 70.0:30.0 under non-vacuum condition, and the kneading time is 300min, obtains powder; Gained powder is carried out to extrusion molding processing, and pressure is 6000KN, and temperature is 300 DEG C, and the processing time is 6min, and gained block compacted density is 0.800g/cc; Then wait static pressure processing, pressure is 10000KN, and temperature is 25 DEG C, and the processing time is 420min, and gained block compacted density is 1.900g/cc; Gained block is placed in to box type furnace and is warming up to 800 DEG C of processing 1.0h with the heating rate of 5.0 DEG C/min; Then be placed in circular furnace and heat-treat, heating rate is 3.0 DEG C/min, and treatment temperature is 1000 DEG C, and the processing time is 300.0h; Take out after block, use successively pendulum type ring roll pulverizer, process except magnetic machine, ultrasonic vibration sieve, obtain lithium ion battery composite material.
Embodiment 7
Adopt ultra micro ball mill to pulverize spheroidization processing with continous way feeding mode native graphite, ball kind is zirconia ball, and bulb diameter is 20mm, and pulverizing rotating speed is 4000rpm, and grinding time is 10min, and pulverizing number of times is 1 time, obtains graphite granule; Under non-vacuum condition, adopt homogenizer liquid phase to mix in the ratio of 90.0:10.0 with high molecular polymer gained graphite granule, use solvent is water, and suspension-turbid liquid solid content is 65%, and mixer rotating speed is 3000rpm, and mixing time is 120min; Then spray dry, inlet temperature is 350 DEG C, and outlet temperature is 150 DEG C, and pressure is 10Mpa, and charging frequency is 100Hz, and speed of agitator is 5000rpm, and mixing time is 180min, obtains powder; Gained powder is carried out to hot moulding processing, and processing pressure is 5000KN, and treatment temperature is 500 DEG C, and the processing time is 6min, and gained block compacted density is 0.800g/cc; Then be placed in rotary furnace, be warming up to 1200 DEG C of insulation 5.0h with the heating rate of 3.0 DEG C/min; Finally use successively sand mill, fusion machine, process except magnetic machine, ultrasonic vibration sieve, obtain lithium ion battery composite material.
Embodiment 8
Adopt micronizer to pulverize spheroidization processing with continous way feeding mode natural composite graphite (native graphite evenly mixes gained with petroleum coke by 60.0:40.0 mass ratio), pulverizing rotating speed is 1000rpm, grinding time is 600min, and pulverizing number of times is 4 times, obtains graphite granule; Gained graphite granule is mixed in the ratio VC of 75.0:25.0 with petroleum asphalt and mesophase pitch, and incorporation time is 60min, and temperature is 15 DEG C, obtains powder; Powder is carried out to hot moulding processing, and processing pressure is 2000KN, and temperature is 500 DEG C, and the time is 6min, and block compacted density is 0.800g/cc; Block is placed in to vacuum stirring bucket and is warming up to 800 DEG C of stirring 5.0h; Then be placed in tunnel cave and be warming up to 3000 DEG C of processing 240.0h with 10.0 DEG C/min heating rate; Then use successively air-flow vortex formula pulverizer, in point grader, process except magnetic machine, airflow screen, obtain lithium ion battery composite material.
Comparative example 1
Adopt pendulum type ring roll pulverizer to pulverize spheroidization processing with continous way feeding mode native graphite, pulverizing rotating speed is 50rpm, and grinding time is 480min, and pulverizing number of times is 1 time, obtains graphite granule; By gained graphite granule and resin and high molecular polymer in the ratio of 85.0:15.0 taking the mixed solvent of water and methyl alcohol as solvent, use homogenizer liquid phase to mix, gained suspension-turbid liquid solid content is 25%, and mixer rotating speed is 5000rpm, and mixing time is 180min; Then spray dry, inlet temperature control is 250 DEG C, and outlet temperature control is 120 DEG C, and pressure is 80Mpa, and charging frequency is 10Hz, and speed of agitator is 4000rpm, and mixing time is 180min, after spraying is dry, obtains powder; Powder is placed in to roller kilns and is warming up to 3300 DEG C of insulation 360.0h with the speed of 10.0 DEG C/min; Then use successively low velocity impact formula nodularization pulverizer, segmentation grader, process except magnetic machine, ultrasonic vibration sieve, obtain lithium ion battery composite material.
Comparative example 2
Natural composite graphite (native graphite evenly mixes gained with Delanium in 60.0:40.0 mass ratio) and mesophase pitch are merged in the ratio of 90.0:10.0, and time of fusion is 5min, obtains powder; Powder is carried out to extrusion modling processing, and processing pressure is 5000KN, and temperature is 20 DEG C, and the time is 600min, and gained block compacted density is 1.500g/cc; Block is placed in to tube furnace and is warming up to 1100 DEG C of insulation 48.0h with the speed of 2.0 DEG C/min; Then be placed in tunnel cave and be warming up to 3200 DEG C of insulation 360.0h with the heating rate of 8.0 DEG C/min; Finally use successively air-flow vortex formula pulverizer, in point grader, process except magnetic machine, airflow screen, obtain lithium ion battery composite material.
Each embodiment/comparative example gained lithium ion battery is carried out to following performance test with composite material, and test result is in table 2:
(1) granularity D
50:
Adopt Britain Malvern-Mastersizer2000 type laser particle size analyzer test lithium ion battery of the present invention composite material granularity D
50.
(2) specific area:
Adopt the BET method of nitrogen adsorption, the specific area of composite material for U.S. health tower Nova1000e specific area/pore analysis instrument test lithium ion battery of the present invention.
(3) tap density:
Adopt U.S. Quantachrome BOYNTON BEACH FL33426 type tap density instrument to carry out the tap density of No. 1000 machine method of slight test lithium ion battery of the present invention composite materials.
(4) I
110/ I
002value:
Adopt X ' pert PRO X-ray diffractometer test lithium ion battery of the present invention composite powder sample, then use X ' pert HighScore data processing software to process test data, draw I
110/ I
002.
(5) absorbent:
By lithium ion battery of the present invention with composite material and thickener, binding agent in mass ratio the ratio water system of 96.5:1.5:2.0 mix, then successively drying, levigate, sieve, film-making, imbibition test step, draw the imbibition time corresponding under one group of compacted density, and taking the imbibition time as ordinate, compacted density is abscissa mapping, reads the absorbent that imbibition time value corresponding under 1.650g/cc compacted density represents lithium ion battery of the present invention composite material after matched curve.
(6) electrochemical property test:
A, utilize lithium ion battery of the present invention composite material to prepare lithium ion simulated battery, specifically comprise the steps:
1. the composite material of preparing by the inventive method is made lithium ion battery negative pole active materials, sodium carboxymethylcellulose CMC is thickener; styrene butadiene rubber sbr is that binding agent is as electrode material; three is active material according to mass ratio: the mode of thickener: binding agent=96.5:1.5:2.0 is mixed; taking water as dispersion liquid, mixes well into pasty state with paste mixer, then uses coating machine coating on Copper Foil; coating thickness is 85～95 μ m, and it is the pole piece of 8.4mm that the rear punching of oven dry becomes diameter.
2. taking above-mentioned pole piece as work electrode, pour lithium slice is to electrode, and (anodal stainless steel gasket diameter is 8.4mm to adopt Celgard2400 type PE/PP/PE composite diaphragm in German Braun glove box, to be assembled into die type; Negative pole copper backing diameter is 11.4mm) simulated battery, H
2o and O
2bias voltage is all lower than 1.0ppm.Electrolyte adopts 1M LiPF
6the solution of/EC+EMC+DEC, wherein solvent ethylene carbonate EC, methyl ethyl carbonate EMC and diethyl carbonate DEC volume ratio are 3:3:4.
B, with Wuhan gold promise Land CT2001A charge-discharge test cabinet, in the voltage range of 0.001～1.500V, with the about 0.1C of 35.0mA/g() current density carry out the test of simulated battery charge-discharge performance.Method of testing and data are calculated as follows:
Embedding lithium specific capacity first: the quality with the current density initial charge of 0.1C to capacitance/negative electrode active material of 0.001V;
De-lithium specific capacity first: the quality that is discharged to first capacitance/negative electrode active material of 1.500V with the current density of 0.1C;
Coulomb efficiency first=de-lithium specific capacity/embedding lithium specific capacity * 100% first first
Charge ratio capacity, specific discharge capacity and the efficiency in composite material charge and discharge cycles prepared by the embodiment of the present invention 1 week several 1～3 is in table 1:
The charge and discharge cycles summary table of composite material for lithium ion battery prepared by table 1 embodiment 1
| Circulating cycle number | De-lithium specific capacity (mAh/g) | Embedding lithium specific capacity (mAh/g) efficiency (%) |
| 1 | 367.5 | 397.492.5 |
| 2 | 368.6 | 373.498.7 |
| 3 | 369.0 | 372.399.1 |
(7) full battery performance evaluation:
A, utilize lithium ion battery of the present invention composite material to prepare the full battery of lithium ion, specifically comprise the steps:
1. the composite material of preparing by the inventive method is made lithium ion battery negative pole active materials, and carbon black Super P is conductive agent, and styrene butadiene rubber sbr is binding agent, and carboxyl methyl cellulose is that thickener makes electrode material; Four is active material according to mass ratio: the mode of Super P:SBR:CMC=96.0:1.0:1.2:1.8 is mixed.Add appropriate deionized water, mix well into pasty state with paste mixer, then adopt coating machine coating on Copper Foil, after vacuumize, make the full battery cathode of lithium ion.
2. with cobalt acid lithium LiCoO
2, lithium nickelate LiNiO
2or spinel lithium manganate LiMn
2o
4for positive electrode; With 1M LiPF
6/ EC+EMC+DEC is electrolyte, and wherein the volume ratio of solvent ethylene carbonate EC, methyl ethyl carbonate EMC and diethyl carbonate DEC is 3:3:4; Taking Celgard2400 type PE/PP/PE composite membrane as barrier film; Adopt the production technology of conventional 18650 type cells to assemble full battery.
B, use Wuhan gold promise Land CT2001A charge-discharge test cabinet, in the voltage range of 3.0～4.2V, carry out charge-discharge test with different current densities.Performance evaluation and method of testing are as follows:
Capability retention performance evaluation:
Full battery, with 1C constant current charge-discharge, is circulated 500 weeks, taking second week capacity as benchmark, calculated each week capability retention since the 3rd week;
50 weeks capability retention=50 week de-lithium capacity/2nd week de-lithium capacity * 100%;
500 weeks capability retention=500 week de-lithium capacity/2nd week de-lithium capacity * 100%;
Capability retention value is larger, illustrates that the cycle performance of battery is better.
Battery high rate performance is evaluated:
To full battery with 0.5mA/cm
2the current density of (about 0.2C) is carried out constant current charge, then discharges with the discharging current of 1C, 5C, 10C, 15C, 20C respectively, and the discharge capacity of testing full battery changes, and calculates the capability retention of different discharge-rates:
10C/1C represents that 10C multiplying power discharging capacity compares the share of 1C multiplying power discharging capacity;
10C/1C value is larger, illustrates that the capability retention of different discharge-rates is higher, and the high rate performance of the full battery of 18650 type is better, and the chemical property of described composite material is better.
Each embodiment/the comparative example of table 2 is prepared gained lithium ion battery composite property test result
The test result of embodiment 1～8 shows: the I for preparing gained lithium ion battery composite material with the inventive method
110/ I
002value all remains on more than 0.020, and orientation characteristic is outstanding; 50 weeks circulation volume conservation rates are all more than 95.0%, and 500 weeks circulation volume conservation rates are all more than 90.0%, and cycle performance is outstanding.In addition, the present invention prepares the absorbent of gained lithium ion battery composite material, de-lithium specific capacity, high rate performance all maintain more excellent level first.As can be seen here, to prepare gained lithium ion battery composite property advantage remarkable in the present invention.
Comparative example 1, owing to not carrying out isotropism pressurized treatments, causes the I of material
110/ I
002value is lower than 0.020, and its cycle performance is also far away from embodiment 1～8.
Comparative example 2, owing to graphite raw material not being promoted to orientation processing, causes the I of resulting materials
110/ I
002value is lower than 0.020, and its first de-lithium specific capacity, coulomb efficiency, cycle performance be all not as good as embodiment 1～8 first.
Applicant's statement, the present invention illustrates detailed features of the present invention and method detailed by above-described embodiment, but the present invention is not limited to above-mentioned detailed features and method detailed, do not mean that the present invention must rely on above-mentioned detailed features and method detailed could be implemented.Person of ordinary skill in the field should understand, any improvement in the present invention is selected the selection of the equivalence replacement of component and the interpolation of auxiliary element, concrete mode etc., within all dropping on protection scope of the present invention and open scope to the present invention.
Claims (10)
1. a lithium ion battery composite material, is characterized in that, described composite material has isotropism, and it comprises that wherein said material with carbon element is the product after binding agent heat treatment as the graphite granule of the material with carbon element of support frame and embedding described material with carbon element inside; Described graphite granule is native graphite or the natural composite graphite that is composited by native graphite and auxiliary material, and described graphite granule accounts for 50.0%～99.9% of described composite material gross mass.
2. composite material according to claim 1, is characterized in that, described composite material utilizes the peak intensity I of (110) face that X-ray diffraction tries to achieve
110peak intensity I with (002) face
002ratio I
110/ I
002be more than 0.020.
3. composite material according to claim 1 and 2, is characterized in that, described auxiliary material is a kind or the combination of at least 2 kinds in Delanium, MCMB, needle coke, petroleum coke, boron and boron compound, phosphorus and phosphorus compound, silicon and silicon compound;
Preferably, the addition of described auxiliary material is 0.1%～50.0% of described natural composite graphite gross mass.
4. according to the composite material described in claim 1-3 any one, it is characterized in that the median grain diameter D of described composite material
50be 3.000～30.000 μ m, be preferably 3.000～22.000 μ m;
Preferably, the specific area of described composite material is 1.000～15.000m
2/ g, more preferably 2.000～8.000m
2/ g;
Preferably, the tap density of described composite material is 0.200～1.200g/cc, more preferably 0.600～1.100g/cc;
Preferably, the imbibition time of described composite material under 1.650g/cc compacted density is below 80.0s;
Preferably, described composite material is more than 360.0mAh/g as the de-lithium specific capacity first of lithium ion battery negative pole active materials;
Preferably, described composite material is more than 92.0% as coulomb efficiency first of lithium ion battery negative pole active materials;
Preferably, described composite material is more than 95.0% as 50 weeks circulation volume conservation rates of lithium ion battery negative pole active materials;
Preferably, described composite material is more than 90.0% as 500 weeks circulation volume conservation rates of lithium ion battery negative pole active materials;
Preferably, to compare 1C multiplying power discharging capacity ratio as the 10C multiplying power discharging capacity of lithium ion battery negative pole active materials be more than 90.0% to described composite material.
5. a method of preparing the composite material as described in claim 1-4 any one, comprises the steps:
(1) graphite raw material is promoted to orientation processing and obtain graphite granule;
(2) use binding agent to carry out framework construction on described graphite granule surface and obtain powder;
(3) described powder is carried out to isotropism pressurized treatments and obtain block;
(4) described block is heat-treated;
(5) pulverize-classification-nodularization, remove magnetic and screening processing, obtain described composite material.
6. method according to claim 5, is characterized in that, the lifting orientation of described step (1) is treated to pulverizes spheroidization processing, fusion treatment or ball-milling treatment;
Preferably, the feeding mode of described pulverizing spheroidization processing is batch (-type) or continous way, and more preferably batch (-type) is pulverized spheroidization processing;
Preferably, the disintegrating apparatus that described pulverizing spheroidization processing adopts is multi-functional particle disposal equipment, internal classification impact type pulverizing mill, low velocity impact formula nodularization pulverizer, ultra micro ball mill, micronizer, air-flow vortex formula pulverizer or pendulum type ring roll pulverizer;
Preferably, the pulverizing rotating speed of described pulverizing spheroidization processing is 50～8000rpm, and grinding time is 2～1200min, and pulverizing number of times is 1～10 time;
Preferably, it is 1 time that described batch (-type) is pulverized spheroidization number of processes, and the processing time is 1～60min, and pulverizing rotating speed is 1000～8000rpm, and classification rotating speed is 1000～8000rpm, and charging frequency is 5～80Hz, and air quantity is 5～50m
3/ min;
Preferably, the time of described fusion treatment is 20～800min, more preferably 20～300min;
Preferably, the rotating speed of described fusion treatment is 800～3000rpm, more preferably 800-2600rpm;
Preferably, the cavity gap of described fusion treatment is 0.1～2.0cm, more preferably 0.1～1.0cm;
Preferably, the temperature of described fusion treatment is 10～80 DEG C, more preferably 20～60 DEG C;
Preferably, the time of described ball-milling treatment is more than 5min, and instrument rotating speed is 200～4000rpm, and the ball of employing is zirconia ball or corundum ball, and diameter is 1～30mm.
7. according to the method described in claim 5 or 6, it is characterized in that, described step (2) adopt liquid phase mixes and be dried, liquid phase mix and spray be dried and solid phase kneading in a kind or the combination of at least 2 kinds of modes carry out framework construction;
Preferably, described liquid phase is mixed and is dried as carry out kneading or liquid phase under vacuum or non-vacuum condition dry after stirring;
Preferably, the described kneading time is 60～600min;
Preferably, described liquid phase is mixed and is sprayed to be dried and spray dry into adopting homogenizer liquid phase to mix rear employing spray dryer;
Preferably, the speed of agitator of described homogenizer is 3000～5000rpm, and mixing time is 120～180min;
Preferably, the inlet temperature of described spray dryer is 60～350 DEG C, and outlet temperature is 50～150 DEG C, and pressure is 10～100MPa, and charging frequency is 10～100Hz, and speed of agitator is 3000～5000rpm, and mixing time is 120～180min;
Preferably, the solvent that described liquid phase mixing is used is water and/or organic solvent;
Preferably, described organic solvent is a kind or the combination of at least 2 kinds in methyl alcohol, ethanol, ether, benzene, toluene and oxolane;
Preferably, in described liquid phase mixing, the solid content of control mixing suspension-turbid liquid is 5%～70%(quality);
Preferably, described solid phase kneading is that VC mixes or merges;
Preferably, the time that described VC mixes is 3～60min, and temperature is 15～80 DEG C;
Preferably, the time of described fusion is 3～180min;
Preferably, described binding agent is a kind or the combination of at least 2 kinds in pitch, resin, macromolecular material and polymer;
Preferably, described pitch is a kind or the combination of at least 2 kinds in coal tar pitch, petroleum asphalt, modified coal tar pitch and mesophase pitch, and softening point is 20～300 DEG C;
Preferably, described resin is that water-soluble resin or fusing point are the resin of 30～300 DEG C;
Preferably, described graphite granule and binding agent mass ratio are 50.0:50.0～99.9:0.1.
8. according to the method described in claim 5-7 any one, it is characterized in that, the isotropism pressurized treatments of described step (3) be extrusion molding processing, cold forming processing, hot moulding process and etc. a kind or the combination of at least 2 kind of static pressure in processing;
Preferably, the pressure of described isotropism pressurized treatments is 500～10000KN;
Preferably, the pressurized treatments temperature of described isotropism pressurized treatments is 20～500 DEG C;
Preferably, the pressurized treatments time of described isotropism pressurized treatments is 6～600min;
Preferably, the block compacted density that described isotropism pressurized treatments obtains is 0.800～2.000g/cc.
9. according to the method described in claim 5-8 any one, it is characterized in that, in described step (4), heat treated temperature is 800～3300 DEG C;
Preferably, described heat treated equipment is vacuum stirring bucket, vacuum kneading machine, agitator, kneading machine, roller kilns, pushed bat kiln, tunnel cave, tube furnace, box type furnace, rotary furnace, circular furnace or interior string stove;
Preferably, the heating rate in described heat treatment process be 20.0 DEG C/below min, more preferably 2.0～10.0 DEG C/min;
Preferably, the described heat treated time is 1.0～560.0h, more preferably 1.0～500.0h;
Preferably, in described step (5) equipment of pulverizings-classification-nodularization be selected from internal classification impact type pulverizing mill, low velocity impact formula nodularization pulverizer, ultra micro ball mill, micronizer, air-flow vortex formula pulverizer, pendulum type ring roll pulverizer, in point grader, segment grader, ball mill, fusion machine and sand mill;
Preferably, the described equipment except magnetic is for removing magnetic machine;
Preferably, the equipment of described screening is ultrasonic vibration sieve or airflow screen.
10. a lithium ion battery, is characterized in that, described lithium ion battery comprises the composite material as described in claim 1-4 any one or method makes as described in claim 5-9 any one composite material.
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| CN106602043A (en) * | 2017-02-10 | 2017-04-26 | 深圳市金润能源材料有限公司 | Silicon-carbon negative electrode material and preparation method thereof |
| CN109309194A (en) * | 2017-07-26 | 2019-02-05 | 中能中科（天津）新能源科技有限公司 | It is modified without cathode of lithium, preparation method and contains its lithium ion battery |
| CN111244450A (en) * | 2018-11-29 | 2020-06-05 | 贝特瑞新材料集团股份有限公司 | Natural graphite, modified natural graphite material prepared from natural graphite, preparation method and application |
| US20220020986A1 (en) * | 2020-07-20 | 2022-01-20 | China Steel Chemical Corporation | Electrode plate material of lithium-ion battery |
| CN114203978A (en) * | 2020-09-17 | 2022-03-18 | 湖南中科星城石墨有限公司 | High-capacity graphite negative electrode material and preparation method and application thereof |
| CN116178016A (en) * | 2021-11-29 | 2023-05-30 | 国家能源投资集团有限责任公司 | Low-orientation degree heat storage carbon material and preparation method thereof |
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| CN106602043A (en) * | 2017-02-10 | 2017-04-26 | 深圳市金润能源材料有限公司 | Silicon-carbon negative electrode material and preparation method thereof |
| CN106602043B (en) * | 2017-02-10 | 2019-05-17 | 深圳市金润能源材料有限公司 | Negative electrode material and preparation method thereof |
| CN109309194A (en) * | 2017-07-26 | 2019-02-05 | 中能中科（天津）新能源科技有限公司 | It is modified without cathode of lithium, preparation method and contains its lithium ion battery |
| CN111244450A (en) * | 2018-11-29 | 2020-06-05 | 贝特瑞新材料集团股份有限公司 | Natural graphite, modified natural graphite material prepared from natural graphite, preparation method and application |
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| US20220020986A1 (en) * | 2020-07-20 | 2022-01-20 | China Steel Chemical Corporation | Electrode plate material of lithium-ion battery |
| CN114203978A (en) * | 2020-09-17 | 2022-03-18 | 湖南中科星城石墨有限公司 | High-capacity graphite negative electrode material and preparation method and application thereof |
| CN114203978B (en) * | 2020-09-17 | 2024-05-17 | 湖南中科星城石墨有限公司 | High-capacity graphite anode material and preparation method and application thereof |
| CN116178016A (en) * | 2021-11-29 | 2023-05-30 | 国家能源投资集团有限责任公司 | Low-orientation degree heat storage carbon material and preparation method thereof |
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Application publication date: 20140618 |