CN103794765A - Lithium ion battery graphite negative electrode material and preparation method thereof - Google Patents
Lithium ion battery graphite negative electrode material and preparation method thereof Download PDFInfo
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- H01—ELECTRIC ELEMENTS
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- 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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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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Abstract
The invention discloses a lithium ion battery graphite negative electrode material and a preparation method thereof. The preparation method of the lithium ion battery graphite negative electrode material comprises the following steps of (1) heating and kneading a mixture containing natural graphite and asphalt, and smashing the mixture, an average particle size (D50) of the natural graphite being 5-10 [mu]m and a mass ratio of the natural graphite to the asphalt being 50:50-90:10; (2) carrying out heat treatment at a temperature of 300-700 DEG C and under protection of an inert gas; and (3) graphitizing. The average particle size (D50) of the lithium ion battery graphite negative electrode material is between 10 [mu]m and 25 [mu]m; and a specific surface area is below 2.0 m<2>/g. First discharge capacity of a battery manufactured by using the lithium ion battery graphite negative electrode material is higher than 360 mAh/g; first charge-discharge efficiency is over 90%; and a discharge rate (2C/0.2C) is above 90%. A product has high discharge capacity, high charge-discharge efficiency, and good rate capability.
Description
Technical field
The present invention relates to graphite cathode material field, relate in particular to a kind of graphite negative material of lithium ion battery and preparation method thereof.
Background technology
Lithium ion battery compared with original battery, high with its energy density, have extended cycle life, the feature such as memory-less effect, universal rapidly at aspects such as mobile phone, notebook computer and electric tools.Along with various products constantly increase small-size light-weight and requirement multi-functional, long-time driving, product also improves day by day to the capacity requirement of lithium ion battery, and the raising of capacity of lithium ion battery at present mainly depends on the development and improvement of negative material.Therefore, for a long time, improve lithium ion battery negative material specific capacity, reduce irreversible capacity first, improve multiplying power property, be always research and development emphasis.
The native graphite that ion secondary battery cathode material lithium uses has desirable layer structure, there is very high discharge capacity (approaching theoretical capacity 372mAh/g), cost is low but it exists structural instability, easily cause the common embedding of solvent molecule, its synusia in charge and discharge process is come off, cause cycle performance of battery poor, poor stability.
Therefore,, for overcoming the deficiency of native graphite performance, prior art is all that native graphite is carried out to modification.Japan Patent JP10294111 carries out low temperature with pitch to graphite Carbon Materials and is coated, and must not melt and process and slight pulverizing after being coated, and this method is difficult to accomplish be coated evenly.Japan Patent JP11246209 floods graphite and hard charcoal particle at 10～300 ℃ of temperature in pitch or tar, then carry out separated from solvent and heat treatment, this method is difficult to form the bitumen layer with certain thickness height polymerization at graphite and hard carbon surface, will be restricted for the raising of native graphite structural stability.Japan Patent JP2000003708 carries out rounding with mechanical means to graphite material, then in heavy oil, tar or pitch, floods, then separates and wash, and sees merely close with JP 11246209 from method for coating.Japan Patent JP2000182617 adopts native graphite etc. and pitch or resin or the charing altogether of its mixture, and this method can reduce graphite material specific area, but on covered effect, is difficult to reach better control.Japan Patent JP2000243398 is that the atmosphere of utilizing asphalt pyrolysis to produce is carried out surface treatment to graphite material, and this method is unlikely, and make the to be modified form of material is greatly improved, thereby the raising of electrical property is restricted.Japan Patent JP2002042816 is coated by chemical vapor deposition (CVD) method take aromatic hydrocarbons as raw material or is coated with pitch phenolic resins, and this and JP2000182617 and JP2000283398 have similarity in effect.
Summary of the invention
Technical problem solved by the invention is the graphite cathode material poor stability in order to overcome existing asphalt modification, the defect that battery capacity is not high, and a kind of graphite negative material of lithium ion battery and preparation method thereof is provided.Preparation method's productive rate of the present invention is high, and operation is simple, and the product graphite negative material of lithium ion battery making high rate performance in obtaining high power capacity also improves.
The present invention solves the problems of the technologies described above by the following technical programs.
The preparation method who the invention provides a kind of graphite negative material of lithium ion battery, it comprises the steps:
(1) the mixture heating that includes native graphite and pitch is mediated, pulverize; Wherein, the average grain diameter D50 of described native graphite is 5 ~ 10 μ m, and the mass ratio of described native graphite and described pitch is 50:50 ~ 90:10;
(2), under inert gas shielding, heat-treat in 300 ~ 700 ℃;
(3) graphitization.
In step (1), described native graphite is preferably potato shape and/or spherical.The average grain diameter D50 of described native graphite is preferably 6 ~ 8 μ m.
In step (1), described pitch can be the conventional pitch using in this area, and in the present invention, described pitch is preferably petroleum asphalt and/or coal tar pitch.The average grain diameter D50 of described pitch is preferably 2 ~ 10 μ m.
In step (1), the mass ratio of described native graphite and described pitch is preferably 60:40 ~ 80:20.
In step (1), described mixture also can include the conventional graphitization catalyst using in this area, and described graphitization catalyst is preferably the carbide of silicon and/or the oxide of iron, and better is carborundum and/or iron oxide.Described graphitization catalyst and the mass ratio of native graphite are preferably 1:50 ~ 7:90, and that better is 3:100 ~ 3:50.
In step (1), the hybrid mode of described mixture preferably, for adopting cantilever double helix cone-type mixer to mix, can alternately add native graphite and pitch when reinforced, to guarantee to mix unanimously; Wherein, the rotating speed of described cantilever double helix cone-type mixer is preferably 35 ~ 37rpm; The time of described mixing is preferably 2 ~ 3 hours.Preferably, after adopting cantilever double helix cone-type mixer to mix, then mix in kneading pot.
Described heating kneading processing can make graphite granule, and modification is bonding equably, its concrete operation method can adopt the method for this area routine to carry out, by the mixture heat temperature raising of above-mentioned native graphite and pitch, mediate processing, for example in kneading pot, mediate processing.
In step (1), the temperature that described heating is mediated is preferably 100 ~ 180 ℃.The time that described heating is mediated is preferably 1 ~ 10 hour, and heating short meeting of kneading time causes material caking, mixes inhomogeneously, and heating kneading time length can cause binder pitch volatilization loss, affects adhesive effect.
In step (1), described pulverizing is preferably for adopting machine hammer piece type crusher to pulverize, and pulverizing is evenly bonding in order to guarantee particle.
In step (2), described inert gas is preferably nitrogen and/or argon gas.
In step (2), described heat treated temperature is preferably 400 ~ 600 ℃.The described heat treated time is preferably 12 ~ 24 hours.
In step (3), described graphitizing method can be the conventional method for graphitizing using in this area, and in the present invention, graphited temperature is preferably 2400 ~ 2800 ℃.The graphited time is preferably 20 ~ 60 hours.
In the present invention, after described graphitization step, also can comprise sieve classification step.
Wherein, the method for described sieve classification can be this area conventional method, preferably for adopting oscillatory type screening machine and/or the classification of ultrasonic type screening machine.Guarantee that by sieve classification the average grain diameter D50 of particle reaches 10 ~ 25 μ m, pattern, the function of product can be better.
The present invention also provides a kind of graphite negative material of lithium ion battery being made by above-mentioned preparation method.
The graphite negative material of lithium ion battery obtaining by above-mentioned preparation method, its average grain diameter D50 can be between 10 ~ 25 μ m, and specific area can be at 2.0m
2below/g, in the present invention, in the button cell that preferably graphite negative material of lithium ion battery is made, carry out performance test, discharge capacity is more than 360mAh/g first, first charge-discharge efficiency is more than 90%, and discharge-rate (2C/0.2C) is more than 90%, and product discharge capacity and efficiency for charge-discharge are high, good rate capability, its performance parameter is as shown in table 1.
The performance parameter of table 1 graphite negative material of lithium ion battery
As seen from the above table, graphite negative material of lithium ion battery of the present invention has reduced specific area effectively, has improved discharge capacity and discharging efficiency, the high comprehensive performance of its button cell of making.
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) preparation method's simple process of the present invention is easily gone, and raw material sources are extensive and cost is low.
(2) graphite negative material of lithium ion battery of the present invention has adopted the methods such as asphalt modification granulation processing, graphitization, and the product discharge capacity and the efficiency for charge-discharge that make are high, good rate capability.
Accompanying drawing explanation
Fig. 1 is the first charge-discharge curve of the graphite cathode material of the embodiment of the present invention 2.
Fig. 2 is the scanning electron microscope (SEM) photograph of the graphite cathode material of the embodiment of the present invention 2.
Fig. 3 is the high rate performance figure of the graphite cathode 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.
Native graphite is the QDC-80 native graphite that Qingdao Tai Neng graphite Co., Ltd produces.
Petroleum asphalt is the MQ-260 oil hard pitch that Dalian bright strengthening work Materials Co., Ltd produces.
Coal tar pitch is the modified coal tar pitch that Henan Bo Hai Chemical Co., Ltd. produces.
SiC is the GCF carborundum that Linyi Jin Meng carborundum Co., Ltd produces.
Embodiment 1
By native graphite (D50 be 6.0 μ m) 16kg, petroleum asphalt (D50 is that m) 4kg and graphitization catalyst (SiC) 0.8kg alternately add in cantilever double helix cone-type mixer and mix 2 hours 4.0 μ, under stirring, be added in kneading pot and mix, be heated to 160 ℃ and mediate processing 3 hours, after kneading finishes, in tablet press machine, be pressed into sheet, beater disintegrating machine is pulverized.Under the protection of nitrogen, and heat-treat granulation at 500 ℃, 12 hours heat treatment granulation time, afterwards product is cooled to room temperature, then carries out catalyzed graphitization processing in 48 hours in 2400 ℃, make graphite negative material of lithium ion battery.Its button cell capacity is 364.9mAh/g, and efficiency is 91.8% first, and discharge-rate (2C/0.2C) is 93.8%.
By native graphite (D50 be 6.0 μ m) 16kg, coal tar pitch (D50 is that m) 4kg and graphitization catalyst (SiC) 0.8kg alternately add in cantilever double helix cone-type mixer and mix 2 hours 6.4 μ, under stirring, be added in kneading pot and mix, be heated to 160 ℃ and mediate processing 5 hours, after kneading finishes, in tablet press machine, be pressed into sheet, beater disintegrating machine is pulverized.Under the protection of nitrogen, and heat-treat granulation at 500 ℃, 18 hours heat treatment granulation time, afterwards product is cooled to room temperature, then carries out catalyzed graphitization processing in 48 hours in 2400 ℃, make graphite negative material of lithium ion battery.Its button cell capacity is 363.7mAh/g, and efficiency is 90.8% first, and discharge-rate (2C/0.2C) is 94.0%.
Embodiment 3
By native graphite (D50 be 5.0 μ m) 10kg, petroleum asphalt (D50 is that m) 10kg and graphitization catalyst (SiC) 0.5kg alternately add in cantilever double helix cone-type mixer and mix 2 hours 4.0 μ, under stirring, be added in kneading pot and mix, be heated to 100 ℃ and mediate processing 10 hours, after kneading finishes, in tablet press machine, be pressed into sheet, beater disintegrating machine is pulverized.Under the protection of nitrogen, and heat-treat granulation at 700 ℃, 18 hours heat treatment granulation time, afterwards product is cooled to room temperature, then carries out catalyzed graphitization processing in 20 hours in 2500 ℃, make graphite negative material of lithium ion battery.Its button cell capacity is 360.2mAh/g, and efficiency is 91.3% first, and discharge-rate (2C/0.2C) is 92.1%.
By native graphite (D50 be 7.5 μ m) 14kg, petroleum asphalt (D50 is m) 6kg and graphitization catalyst (Fe of 4.0 μ
2o
3) 0.7kg alternately adds in cantilever double helix cone-type mixer and mix 2 hours, is added in kneading pot and mixes under stirring, is heated to 140 ℃ and mediates and process 5 hours, after mediating and finishing, is pressed into sheet in tablet press machine, beater disintegrating machine is pulverized.Under the protection of nitrogen, and heat-treat granulation at 600 ℃, 15 hours heat treatment granulation time, afterwards product is cooled to room temperature, then carries out catalyzed graphitization processing in 60 hours in 2800 ℃, make graphite negative material of lithium ion battery.Its button cell capacity is 360.5mAh/g, and efficiency is 91.2% first, and discharge-rate (2C/0.2C) is 93.2%.
Embodiment 5
By native graphite (D50 be 6.0 μ m) 14kg, petroleum asphalt (D50 is that m) 6kg and graphitization catalyst (SiC) 0.3kg alternately add in cantilever double helix cone-type mixer and mix 2 hours 2.1 μ, under stirring, be added in kneading pot and mix, be heated to 180 ℃ and mediate processing 1 hour, after kneading finishes, in tablet press machine, be pressed into sheet, beater disintegrating machine is pulverized.Under the protection of nitrogen, and heat-treat granulation at 300 ℃, 24 hours heat treatment granulation time, afterwards product is cooled to room temperature, then carries out catalyzed graphitization processing in 48 hours in 2400 ℃, make graphite negative material of lithium ion battery.Its button cell capacity is 362.2mAh/g, and efficiency is 91.8% first, and discharge-rate (2C/0.2C) is 93.0%.
Embodiment 6
By native graphite (D50 be 10.0 μ m) 18kg, coal tar pitch (D50 is that m) 2kg and graphitization catalyst (SiC) 0.9kg alternately add in cantilever double helix cone-type mixer and mix 2 hours 6.4 μ, under stirring, be added in kneading pot and mix, be heated to 160 ℃ and mediate processing 2 hours, after kneading finishes, in tablet press machine, be pressed into sheet, beater disintegrating machine is pulverized.Under the protection of nitrogen, and heat-treat granulation at 500 ℃, 20 hours heat treatment granulation time, afterwards product is cooled to room temperature, then carries out catalyzed graphitization processing in 48 hours in 2600 ℃, make graphite negative material of lithium ion battery.Its button cell capacity is 360.8mAh/g, and efficiency is 90.5% first, and discharge-rate (2C/0.2C) is 92.0%.
Embodiment 7
By native graphite (D50 be 6.0 μ m) 14kg, coal tar pitch (D50 is that m) 6kg and graphitization catalyst (SiC) 1.1kg alternately add in cantilever double helix cone-type mixer and mix 2 hours 9.9 μ, under stirring, be added in kneading pot and mix, be heated to 160 ℃ and mediate processing 2 hours, after kneading finishes, in tablet press machine, be pressed into sheet, beater disintegrating machine is pulverized.Under the protection of nitrogen, and heat-treat granulation at 400 ℃, 24 hours heat treatment granulation time, afterwards product is cooled to room temperature, then carries out catalyzed graphitization processing in 40 hours in 2400 ℃, make graphite negative material of lithium ion battery.Its button cell capacity is 361.2mAh/g, and efficiency is 91.0% first, and discharge-rate (2C/0.2C) is 93.8%.
Embodiment 8
By native graphite (D50 be 6.0 μ m) 14kg, petroleum asphalt (D50 be 4.0 μ m) 6kg alternately add in cantilever double helix cone-type mixer and mix 2 hours, under stirring, be added in kneading pot and mix, be heated to 160 ℃ and mediate processing 2 hours, after kneading finishes, in tablet press machine, be pressed into sheet, beater disintegrating machine is pulverized.Under the protection of nitrogen, and heat-treat granulation at 500 ℃, 18 hours heat treatment granulation time, afterwards product is cooled to room temperature, then carries out 48 hours graphitization processing in 2800 ℃, make graphite negative material of lithium ion battery.Its button cell capacity is 355.9mAh/g, and efficiency is 90.5% first, and discharge-rate (2C/0.2C) is 90.7%.
Comparative example 1
By native graphite, (D50 is that m) 14kg, graphitization catalyst (SiC) 0.7kg alternately add in cantilever double helix cone-type mixer and mix 2 hours 9.8 μ.Under the protection of nitrogen, and heat-treat at 500 ℃, heat treatment time 18 hours, is cooled to room temperature by product afterwards, then carries out catalyzed graphitization processing in 48 hours in 2400 ℃, makes graphite negative material of lithium ion battery.Its button cell capacity is 354.1mAh/g, and efficiency is 87.2% first, and discharge-rate (2C/0.2C) is 70.8%.
Comparative example 2
By native graphite (D50 be 15.8 μ m) 14kg, coal tar pitch (D50 is that m) 6kg and graphitization catalyst (SiC) 0.3kg alternately add in cantilever double helix cone-type mixer and mix 2 hours 6.4 μ, under stirring, be added in kneading pot and mix, be heated to 160 ℃ and mediate processing 2 hours, after kneading finishes, in tablet press machine, be pressed into sheet, beater disintegrating machine is pulverized.Under the protection of nitrogen, and heat-treat granulation at 500 ℃, 20 hours heat treatment granulation time, afterwards product is cooled to room temperature, then carries out catalyzed graphitization processing in 48 hours in 2600 ℃, make graphite negative material of lithium ion battery.Its button cell capacity is 364.7mAh/g, and efficiency is 90.0% first, and discharge-rate (2C/0.2C) is 82.4%.
Effect embodiment
(1) graphite cathode material in embodiment 1 ~ 8 and comparative example 1,2 is carried out respectively to an index test such as particle diameter, specific area, the results are shown in Table 2.Instrument title and model that test is used are: particle diameter, laser fineness gage MS2000; Specific area, specific surface area measuring instrument NOVA2000.
(2) adopt button cell method of testing to carry out discharge capacity and the test of efficiency first to the graphite cathode material in embodiment 1 ~ 8 and comparative example 1,2, the results are shown in table 2.
The present invention's button cell method of testing used is: in carboxymethyl cellulose (CMC) aqueous solution, add conductive black, then add graphite sample, finally add butadiene-styrene rubber (SBR), stir, on coating machine, slurry is coated in uniformly and on Copper Foil, makes pole piece.It is 110 ℃ of vacuum drying chamber vacuumizes 4 hours that the pole piece coating is put into temperature, takes out pole piece roll extrusion on roll squeezer, for subsequent use.Simulated battery is assemblied in the German Braun glove box of applying argon gas and carries out, and electrolyte is 1MLiPF6EC:DEC:DMC=1:1:1(volume ratio), metal lithium sheet is to electrode.Volume test is carried out on U.S. ArbinBT2000 type cell tester, and charging/discharging voltage scope is 0.005 to 2.0V, and charge-discharge velocity is 0.1C.
The present invention's discharge-rate method of testing used is: the graphite of the embodiment of the present invention or comparative example is made negative pole, and cobalt acid lithium is done anodal, 1MLiPF6EC:DMC:EMC=1:1:1(volume ratio) solution does electrolyte assembling and helps battery, test 1C ~ 3C discharge-rate.
Table 2 embodiment and comparative example's performance parameter
Data from table 2 can find out, discharge capacity and efficiency for charge-discharge in comparative example 1 are low, and the efficiency for charge-discharge of the native graphite that non-pitch-coating heating is mediated is only 87.2%, and discharge-rate (2C/0.2C) only reaches 70.8%; The average grain diameter D50 of the native graphite in comparative example 2 is greater than 10 μ m, and heating kneading effect is not good, and specific area is bigger than normal, and discharge-rate is low; The negative material that described in employing patent prepared by method, specific area reduces greatly, is less than 2.0m
2/ g, discharge capacity is greater than 360mAh/g, and efficiency for charge-discharge is greater than 90%, and discharge-rate (2C/0.2C) is more than 90%.
Claims (14)
1. a preparation method for graphite negative material of lithium ion battery, is characterized in that, it comprises the steps:
(1) the mixture heating that includes native graphite and pitch is mediated, pulverize; Wherein, the average grain diameter D50 of described native graphite is 5 ~ 10 μ m, and the mass ratio of described native graphite and described pitch is 50:50 ~ 90:10;
(2), under inert gas shielding, heat-treat in 300 ~ 700 ℃;
(3) graphitization.
2. the preparation method of graphite negative material of lithium ion battery as claimed in claim 1, is characterized in that, in step (1), described native graphite is potato shape and/or spherical.
3. the preparation method of graphite negative material of lithium ion battery as claimed in claim 1, is characterized in that, in step (1), the average grain diameter D50 of described native graphite is 6 ~ 8 μ m.
4. the preparation method of graphite negative material of lithium ion battery as claimed in claim 1, is characterized in that, in step (1), described pitch is petroleum asphalt and/or coal tar pitch, and the average grain diameter D50 of described pitch is 2 ~ 10 μ m.
5. the preparation method of graphite negative material of lithium ion battery as claimed in claim 1, is characterized in that, in step (1), the mass ratio of described native graphite and described pitch is 60:40 ~ 80:20.
6. the preparation method of graphite negative material of lithium ion battery as claimed in claim 1, is characterized in that, in step (1), described mixture also comprises graphitization catalyst.
7. the preparation method of graphite negative material of lithium ion battery as claimed in claim 6, is characterized in that, the carbide that described graphitization catalyst is silicon and/or the oxide of iron, and described graphitization catalyst and the mass ratio of native graphite are 1:50 ~ 7:90.
8. the preparation method of the graphite negative material of lithium ion battery as described in claim 6 or 7, is characterized in that, described graphitization catalyst is carborundum and/or iron oxide, and described graphitization catalyst and the mass ratio of native graphite are 3:100 ~ 3:50.
9. the preparation method of graphite negative material of lithium ion battery as claimed in claim 1, is characterized in that, in step (1), the hybrid mode of mixture, for adopting cantilever double helix cone-type mixer to mix, alternately adds native graphite and pitch when reinforced; The rotating speed of described cantilever double helix cone-type mixer is 35 ~ 37rpm; The time of described mixing is 2 ~ 3 hours.
10. the preparation method of graphite negative material of lithium ion battery as claimed in claim 1, it is characterized in that, in step (1), described heating is mediated and is carried out in kneading pot, the temperature that described heating is mediated is 100 ~ 180 ℃, and the time that described heating is mediated is 1 ~ 10 hour.
The preparation method of 11. graphite negative material of lithium ion batteries as claimed in claim 1, is characterized in that, in step (2), described heat treated temperature is 400 ~ 600 ℃, and the described heat treated time is 12 ~ 24 hours.
The preparation method of 12. graphite negative material of lithium ion batteries as claimed in claim 1, is characterized in that, in step (3), described graphited temperature is 2400 ~ 2800 ℃, and the described graphited time is 20 ~ 60 hours.
The preparation method of 13. graphite negative material of lithium ion batteries as claimed in claim 1, is characterized in that, after described graphitization step, also comprises sieve classification step.
The graphite negative material of lithium ion battery that 14. preparation methods as described in any one in claim 1 ~ 13 make.
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