CN103794790A - Lithium ion battery composite graphite negative electrode material and preparation method thereof - Google Patents
Lithium ion battery composite graphite negative electrode material and preparation method thereof Download PDFInfo
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- 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
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Abstract
The invention discloses a lithium ion battery composite graphite negative electrode material and a preparation method thereof. The preparation method comprises the following steps of 1, carrying out heating pre-treatment on natural spherical graphite at a temperature of 300-400 DEG C, 2, mixing the pre-treated natural spherical graphite, artificial graphite and a graphitization catalyst to obtain a uniform mixture, 3, kneading the mixture and a binder to obtain a kneaded material, 4, carrying out carbonization treatment, carrying out cooling and carrying out catalytic graphitization high-temperature treatment, and 5, carrying out crushing and grading. The preparation method is simple and feasible and is suitable for industrial production. The lithium ion battery composite graphite negative electrode material has good electrochemical properties, a discharge capacity more than 360mAh/g, high charging-discharging efficiency, good heavy current charging-discharging performances and good cycle performances, produces tiny expansion in charging and has good safety and good adaptability to an electrolyte and other additives. The lithium ion battery products prepared from the lithium ion battery composite graphite negative electrode material have stable properties and small batch difference.
Description
Technical field
The present invention relates to a kind of lithium ion battery composite graphite negative electrode material and preparation method thereof.
Background technology
In recent years, along with the microminiaturization 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.
Delanium product is good lithium ion battery negative material, has that current potential is low and flatness good, a feature such as high and processability is good than efficiency for charge-discharge great, the initial stage.But the reversible lithium storage capacity of Delanium is in 340mAh/g left and right, and capacity also has the space of rising.
In order to address the above problem, use native graphite to mix with Delanium, pitch etc. and the method processing such as catalyzed graphitization can improve lithium ion battery negative material quality effectively, not only can improve the reversible lithium storage capacity of graphite, and can improve the cycle performance of material.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.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.Japan Patent JP2003-173778 is by compound to melt kneading pitch and flakey native graphite, carry out mechanochemistry, graphitization processing, prepare spherical or oval composite graphite material, the composite particles that this composite material is made up of graphite core and graphite encasement.
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 composite 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 composite graphite negative electrode material chemical property is good, has high charge-discharge capacity and efficiency for charge-discharge, and high rate during charging-discharging is good, cycle performance is good, when charging, only have small expansion, fail safe is good, better to electrolyte and other additive adaptability, and use the prepared lithium ion battery product property of this composite 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.
The invention provides a kind of preparation method of lithium ion battery composite graphite negative electrode material, it comprises the steps: 1. spherical natural graphite to be carried out at 300 ~ 400 ℃ heat pre-treatment; 2. pretreated spherical natural graphite, Delanium and graphitization catalyst are mixed to obtain to compound; 3. mediate described compound and adhesive and obtain kneaded material; 4. charing processing, carries out catalyzed graphitization high-temperature process after cooling again; 5. pulverizing, classification.
Step 1. in, described spherical natural graphite can be selected the spherical natural graphite of the various routines in this area.The particle diameter of described spherical natural graphite can be the conventional particle diameter of this type of material of this area, and the volume average particle size of described spherical natural graphite is preferably 12 ~ 36 μ m; The D10 of described spherical natural graphite is preferably 6.0 ~ 25 μ m; The maximum particle diameter of described spherical natural graphite is preferably below 48.5 μ m.
Step 1. in, the conventional method that the method for described heat pre-treatment and condition are this area and condition.Described heat pre-treatment is generally spherical natural graphite to be placed in to heater heat, to remove volatile matter, moisture and the impurity in spherical natural graphite.The temperature of described heat pre-treatment is preferably 400 ℃.The time of described heat pre-treatment is preferably 2 ~ 6 hours, is more preferably 3 ~ 4 hours.By this area general knowledge, the atmosphere of described heat pre-treatment is inert atmosphere.
Step 2. in, described Delanium can be selected the Delanium of the various routines in this area.The particle diameter of described Delanium can be the conventional particle diameter of this type of material of this area, and the volume average particle size of described Delanium is preferably 14 ~ 17 μ m; The D10 of described Delanium is preferably 6.9 ~ 8.5 μ m; The maximum particle diameter of described Delanium is preferably below 36.8 μ m.
Step 2. in, described graphitization catalyst can be selected the graphitization catalyst of the various routines in this area, is preferably the carbide of silicon, is more preferably SiC.The volume average particle size of described graphitization catalyst is preferably 3.5 ~ 7.5 μ m, is more preferably 4.0 ~ 5.5 μ m.
Step 2. in, the mass ratio of described spherical natural graphite and Delanium is preferably 1:1 ~ 5:1, is more preferably 1:1 ~ 4:1.The consumption of described graphitization catalyst is preferably 1 ~ 10% of spherical natural graphite and Delanium gross mass, is more preferably 3 ~ 8%.
Step 2. in, the condition of described mixing and method are condition and the method for this area routine, preferably adopt cantilever double helix cone-type mixer to carry out.The time of described mixing is preferably 2.0 ~ 3.5 hours.
Step 3. in, described adhesive refer in graphite cathode material field conventional can bonding native graphite, Delanium, and after graphitization, can make the adhesive of Delanium, be preferably petroleum asphalt and/or coal tar pitch.Described petroleum asphalt, petroleum asphalt, the coal tar pitch that coal tar pitch all can be selected this area all size.Described adhesive is more preferably middle fire stons oil asphalt and/or medium temperature coal pitch.The consumption of described adhesive can be the consumption of this area routine.The mass ratio of described compound and adhesive is preferably 5:3 ~ 9:1, is more preferably 3:1 ~ 5:1.
Step 3. in, the condition of described kneading and method are condition and the method for this area routine.Mediate and process the processing characteristics that can improve native graphite.The temperature of described kneading is preferably 100 ~ 180 ℃.The time of described kneading is preferably 1 ~ 10 hour.
Step 3. in, after described kneading, preferably also carry out briquetting processing, so that following process processing.The condition of described briquetting processing and method can adopt the condition of the various routines in this area and method to carry out, and as extrusion modling, mould molding or cold isostatic compaction, preferably briquetting becomes cylindrical or rectangle.
In a preferred embodiments of the present invention, after described kneading, before described briquetting processes, also carry out following operation: in tablet press machine, described kneaded material is pressed into 2 ~ 5mm sheet, is ground into the powder of particle diameter below 0.1mm.
Step 4. in, the condition of described charing processing and method are condition and the method for this area routine.The temperature of described charing processing is preferably 800 ~ 1500 ℃.The time of described charing processing is preferably 2 ~ 6 hours.By this area general knowledge, the atmosphere of described charing processing is inert atmosphere.
Step 4. in, described cooling condition and method are condition and the method for this area routine, are generally and are cooled to room temperature.
Step 4. in, the condition of described catalyzed graphitization high-temperature process and method are condition and the method for this area routine.The temperature of described catalyzed graphitization high-temperature process is preferably 2800 ~ 3200 ℃.The time of described catalyzed graphitization high-temperature process is preferably 24 ~ 48 hours.By this area general knowledge, the atmosphere of described catalyzed graphitization high-temperature process is inert atmosphere.
Step 5. in, the condition of described pulverizing and method are condition and the method for this area routine.Coarse crushing is preferably first carried out in described pulverizing, then carries out middle pulverizing, finally carries out Crushing of Ultrafine, to guarantee that grain diameter and specific morphology can meet requirement of the present invention.The equipment of described coarse crushing preferably uses jaw crusher; Grain diameter after described coarse crushing is preferably below 30mm.The equipment of described middle pulverizing preferably uses plate-hammer crusher; Grain diameter after described middle pulverizing is preferably below 10mm.Described fine equipment preferably uses ultra-fine mechanical crusher; Grain diameter after described Crushing of Ultrafine is preferably below 1mm.
Step 5. in, the condition of described classification and method are condition and the method for this area routine, preferably first sieve and carry out fluid mechanics classification again.The condition of described screening and fluid mechanics classification and method are condition and the method for this area routine.250 mesh sieve extracting screen underflows are preferably crossed in described screening, more preferably adopt 250 order oscillatory type screening machines to carry out.Described fluid mechanics classification preferably adopts gas flow sizing machine to carry out.The frequency of described gas flow sizing machine is preferably 20 ~ 60Hz.After described classification, the volume average particle size of described composite graphite negative electrode material is 10 ~ 31 μ m.
The present invention also provides a kind of lithium ion battery composite graphite negative electrode material being made by above-mentioned preparation method.
Wherein, the volume average particle size of described composite graphite negative electrode material is 10 ~ 31 μ m.The specific area of described composite graphite negative electrode material is 3.0 ~ 4.0m
2/ g.The real density of described composite graphite negative electrode material is at 2.20g/cm
3above.The ash content of described composite graphite negative electrode material is below 0.10wt%.
In the present invention, described room temperature is the ambient temperature of this area routine, is preferably 5 ~ 40 ℃.
In the present invention, by this area general knowledge, described D10 refers to corresponding particle diameter when the cumulative particle sizes percentile of particle reaches 10%.
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 large and good cycle of the discharge capacity of composite graphite negative electrode material of the present invention, 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 360mAh/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 the present invention, is applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the first charge-discharge curve of the composite graphite negative electrode material of the embodiment of the present invention 2.
Fig. 2 is the absorbency curve of the composite graphite negative electrode material of the embodiment of the present invention 2.
Fig. 3 is the cycle performance figure of the composite 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 following embodiment, the MQ-100 mid temperature pitch that the petroleum asphalt of use is produced for Dalian bright strengthening work Materials Co., Ltd.The mid temperature pitch that the coal tar pitch using is produced for Henan Bo Hai Chemical Co., Ltd..The NAT6 carborundum that the SiC using produces for Linyi Jinmeng Silicon Carbide Co., Ltd., its volume average particle size is at 3.5 ~ 7.5 μ m.The spherical natural graphite that the native graphite using is produced for Shanghai Shanshan Science and Technology Co., Ltd; Wherein, the D10 of spherical natural graphite is at 6.0 ~ 25 μ m, and maximum particle diameter is at 25.0 ~ 48.5 μ m.The Delanium that the Delanium using is produced for Shanghai Shanshan Science and Technology Co., Ltd; Wherein, the D10 of Delanium is at 6.9 ~ 8.5 μ m, and maximum particle diameter is at 28.5 ~ 36.8 μ m.
Embodiment 1
1. the native graphite that by volume average particle size is 19.3 μ m is placed in heater, heats and within 3 hours, carry out heat pre-treatment in nitrogen atmosphere at 400 ℃; 2. be that the Delanium 6kg of 14.0 μ m and graphitization catalyst (SiC) 1.2kg add in cantilever double helix cone-type mixer and mix 2 hours by native graphite 14kg after treatment, volume average particle size, obtain compound; 3. under stirring, alternately compound 20kg and petroleum asphalt 12kg are joined in kneading pot, mediate and process 1 hour in 160 ℃, after kneading finishes, be pressed into 2 ~ 5mm sheet in tablet press machine, be ground into the powder below particle diameter 0.1mm, it is cylindrical that briquetting becomes; 4. under the protection of nitrogen, at the temperature of 1100 ℃, charing is processed 2 hours, afterwards product is cooled to room temperature, then carries out 36 hours catalyzed graphitization high-temperature process in 2800 ℃; 5. use jaw crusher to carry out coarse crushing, grain diameter is controlled at below 30mm; Use plate-hammer crusher to carry out middle pulverizing, grain diameter is controlled at below 10mm; Use ultra-fine mechanical crusher to carry out Crushing of Ultrafine, grain diameter is controlled at below 1mm; 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 is the lithium ion battery composite graphite negative electrode material of 17.8 μ m.Recording its half-cell capacity is 361.5mAh/g, first charge-discharge efficiency 92.5%.
Embodiment 2
1. the native graphite that by volume average particle size is 17.8 μ m is placed in heater, heats and within 4 hours, carry out heat pre-treatment in nitrogen atmosphere at 400 ℃; 2. be that the Delanium 10kg of 15.5 μ m and graphitization catalyst (SiC) 1.2kg add in cantilever double helix cone-type mixer and mix 2 hours by native graphite 10kg after treatment, volume average particle size, obtain compound; 3. under stirring, alternately compound 20kg and petroleum asphalt 3kg are joined in kneading pot, mediate and process 1 hour in 160 ℃, after kneading finishes, in tablet press machine, be pressed into 2 ~ 5mm sheet, be ground into the powder below particle diameter 0.1mm, briquetting rectangularity; 4. under the protection of nitrogen, and at the temperature of 800 ℃, charing is processed 6 hours, afterwards product is cooled to room temperature, then carries out 48 hours catalyzed graphitization high-temperature process in 3000 ℃; 5. use jaw crusher to carry out coarse crushing, grain diameter is controlled at below 30mm; Use plate-hammer crusher to carry out middle pulverizing, grain diameter is controlled at below 5 ~ 10mm; Use ultra-fine mechanical crusher to carry out Crushing of Ultrafine, grain diameter is controlled at below 1mm; 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 is the lithium ion battery composite graphite negative electrode material of 16.3 μ m.Record its half-cell capacity 363.3mAh/g, first charge-discharge efficiency 93.0%.
Embodiment 3
1. the native graphite that by volume average particle size is 12.1 μ m is placed in heater, heats and within 4 hours, carry out heat pre-treatment in nitrogen atmosphere at 400 ℃; 2. be that the Delanium 5kg of 16.7 μ m and graphitization catalyst (SiC) 1.2kg add in cantilever double helix cone-type mixer and mix 2 hours by native graphite 15kg after treatment, volume average particle size, obtain compound; 3. under stirring, alternately compound 20kg and petroleum asphalt 4kg are joined in kneading pot, mediate and process 10 hours in 100 ℃, after kneading finishes, be pressed into 2 ~ 5mm sheet in tablet press machine, be ground into the powder below particle diameter 0.1mm, it is cylindrical that briquetting becomes; 4. under the protection of nitrogen, and at the temperature of 1500 ℃, charing is processed 3 hours, afterwards product is cooled to room temperature, then carries out 48 hours catalyzed graphitization high-temperature process in 3200 ℃; 5. use jaw crusher to carry out coarse crushing, grain diameter is controlled at below 30mm; Use plate-hammer crusher to carry out middle pulverizing, grain diameter is controlled at below 10mm; Use ultra-fine mechanical crusher to carry out Crushing of Ultrafine, grain diameter is controlled at below 1mm; 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 is the lithium ion battery composite graphite negative electrode material of 14.4 μ m.Record its half-cell capacity 364.0mAh/g, first charge-discharge efficiency 92.4%.
Embodiment 4
1. the native graphite that by volume average particle size is 12.1 μ m is placed in heater, heats and within 4 hours, carry out heat pre-treatment in nitrogen atmosphere at 400 ℃; 2. be that the Delanium 10kg of 14.7 μ m and graphitization catalyst (SiC) 1.2kg add in cantilever double helix cone-type mixer and mix 2 hours by native graphite 19kg after treatment, volume average particle size, obtain compound; 2. under stirring, alternately compound 20kg and coal tar pitch 5kg are joined in kneading pot, mediate and process 5 hours in 140 ℃, after kneading finishes, be pressed into 2 ~ 5mm sheet in tablet press machine, be ground into the powder below particle diameter 0.1mm, it is cylindrical that briquetting becomes; 3. under the protection of nitrogen, and at the temperature of 1000 ℃, charing is processed 4 hours, afterwards product is cooled to room temperature, then carries out 48 hours catalyzed graphitization high-temperature process in 2800 ℃; 4. use jaw crusher to carry out coarse crushing, grain diameter is controlled at below 30mm; Use plate-hammer crusher to carry out middle pulverizing, grain diameter is controlled at below 10mm; Use ultra-fine mechanical crusher to carry out Crushing of Ultrafine, particle is controlled at below 1mm; 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 60Hz, and making particle volume average grain diameter is the lithium ion battery composite graphite negative electrode material of 13.6 μ m.Record its half-cell capacity 365.3mAh/g, first charge-discharge efficiency 93.2%.
Embodiment 5
1. the native graphite that by volume average particle size is 35.8 μ m is placed in heater, heats and within 4 hours, carry out heat pre-treatment in nitrogen atmosphere at 300 ℃; 2. be that the Delanium 6kg of 14.2 μ m and graphitization catalyst (SiC) 0.28kg add in cantilever double helix cone-type mixer and mix 2 hours by native graphite 14kg after treatment, volume average particle size, obtain compound; 2. under stirring, alternately compound 20kg and petroleum asphalt 8kg are joined in kneading pot, mediate and process 1 hour in 180 ℃, after kneading finishes, be pressed into 2 ~ 5mm sheet in tablet press machine, be ground into the powder below particle diameter 0.1mm, it is cylindrical that briquetting becomes; 3. under the protection of nitrogen, and at the temperature of 1100 ℃, charing is processed 2 hours, afterwards product is cooled to room temperature, then carries out 24 hours catalyzed graphitization high-temperature process in 3200 ℃; 4. use jaw crusher to carry out coarse crushing, grain diameter is controlled at below 30mm; Use plate-hammer crusher to carry out middle pulverizing, grain diameter is controlled at below 10mm; Use ultra-fine mechanical crusher to carry out Crushing of Ultrafine, grain diameter is controlled at below 1mm; 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 is the lithium ion battery composite graphite negative electrode material of 30.4 μ m.Record its half-cell capacity 362.4mAh/g, first charge-discharge efficiency 92.6%.
Comparative example 1
Native graphite 14kg, the volume average particle size that is 19.3 μ m by volume average particle size is that the Delanium 6kg of 14.2 μ m and graphitization catalyst (SiC) 1.2kg add in cantilever double helix cone-type mixer and mix 2 hours, 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 room temperature, 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 is the lithium ion battery composite graphite negative electrode material of 19.4 μ m.Record its half-cell capacity 365.0mAh/g, first charge-discharge efficiency 89.5%.
Comparative example 2
The native graphite that by volume average particle size is 19.3 μ m carries out High Temperature Pre processing in 4 hours at 600 ℃; The Delanium 6kg that is 14.2 μ m by native graphite 14kg after treatment and volume average particle size adds in cantilever double helix cone-type mixer and mixes 2 hours, obtains composite 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, in tablet press machine, be pressed into 2 ~ 5mm sheet, be ground into the powder below particle diameter 0.1mm, briquette forming; Under the protection of nitrogen, and at the temperature of 1100 ℃, charing is processed 2 hours, afterwards product is cooled to room temperature; Use jaw crusher to carry out coarse crushing, grain diameter is controlled at below 30mm; Use plate-hammer crusher to carry out middle pulverizing, grain diameter is controlled at below 10mm; Use ultra-fine mechanical crusher to carry out Crushing of Ultrafine, grain diameter is controlled at below 1mm; 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 is the lithium ion battery composite graphite negative electrode material of 19.2 μ m.Record its half-cell capacity 344.2mAh/g, first charge-discharge efficiency 90.5%.
Effect embodiment
(1) composite graphite negative electrode material in embodiment 1 ~ 5 and comparative example 1 ~ 2 is carried out respectively to particle diameter, real density, a specific area and ash index test that grades, the results are shown in Table 1.Instrument title and model that test is used are: volume average particle size, 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.
(2) adopt half-cell method of testing to carry out the test of discharge capacity and first charge-discharge efficiency to the composite graphite negative electrode material in embodiment 1 ~ 5 and comparative example 1 ~ 2, the results are shown in table 1.Half-cell method of testing is: composite graphite negative electrode material, the 1-METHYLPYRROLIDONE that contains 6 ~ 7% Kynoar and 2% conductive black mix in the ratio of 91.6:6.6:1.8, 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 1M LiPF6+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 each embodiment of table 1 and comparative example's composite graphite negative electrode material
As can be seen from Table 1, comparative example 1 and comparative example's 2 discharging efficiency is on the low side; Comparative example 2 discharge capacity is low, is only 344.2mAh/g.And the discharge capacity of each sample of embodiment 1 ~ 5 is all more than 360mAh/g, and first charge-discharge efficiency is all more than 92%.
(3) adopt full battery testing method to test the lithium ion battery composite graphite negative electrode material of embodiment 2.Full battery testing method is: using lithium ion battery 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, the imbibition time under high compacted density 1.70g/cm3 is less than 180 seconds, as shown in Figure 2; Its good cycle, the capability retention after 300 times that circulates can reach 89.1%, as shown in Figure 3.
(4) other relevant item test result of the finished product battery of the lithium ion battery composite graphite negative electrode material by embodiment 1 ~ 5 being made is: discharge platform (3.6V) >=75%, and the 100 weeks platforms that circulate keep >=95%; Multiplying power discharging 3C capacity >=50%; 300 circulations, Capacitance reserve >=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.
Visible, to adopt preparation method of the present invention to prepare lithium ion battery composite graphite negative electrode material, 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.
Claims (10)
1. a preparation method for lithium ion battery composite graphite negative electrode material, it comprises the steps: 1. spherical natural graphite to be carried out at 300 ~ 400 ℃ heat pre-treatment; 2. pretreated spherical natural graphite, Delanium and graphitization catalyst are mixed to obtain to compound; 3. mediate described compound and adhesive and obtain kneaded material; 4. charing processing, carries out catalyzed graphitization high-temperature process after cooling again; 5. pulverizing, classification.
2. preparation method as claimed in claim 1, is characterized in that, step 1. in, the volume average particle size of described spherical natural graphite is 12 ~ 36 μ m; The D10 of described spherical natural graphite is 6.0 ~ 25 μ m; The maximum particle diameter of described spherical natural graphite is below 48.5 μ m; And/or, step 2. in, the volume average particle size of described Delanium is 14 ~ 17 μ m; The D10 of described Delanium is 6.9 ~ 8.5 μ m; The maximum particle diameter of described Delanium is below 36.8 μ m; And/or, step 2. in, the mass ratio of described spherical natural graphite and Delanium is 1:1 ~ 5:1; And/or, step 2. in, the carbide that described graphitization catalyst is silicon; And/or, step 2. in, the volume average particle size of described graphitization catalyst is 3.5 ~ 7.5 μ m; And/or, step 2. in, the consumption of described graphitization catalyst is 1 ~ 10% of spherical natural graphite and Delanium gross mass; And/or, step 3. in, described adhesive is petroleum asphalt and/or coal tar pitch; And/or, step 3. in, the mass ratio of described compound and adhesive is 5:3 ~ 9:1.
3. preparation method as claimed in claim 2, is characterized in that, step 2. in, the mass ratio of described spherical natural graphite and Delanium is 1:1 ~ 4:1; And/or, step 2. in, the consumption of described graphitization catalyst is 3 ~ 8% of spherical natural graphite and Delanium gross mass; And/or, step 2. in, described graphitization catalyst is SiC; And/or, step 2. in, the volume average particle size of described graphitization catalyst is 4.0 ~ 5.5 μ m; And/or, step 3. in, described adhesive is middle fire stons oil asphalt and/or medium temperature coal pitch; And/or, step 3. in, the mass ratio of described compound and adhesive is 3:1 ~ 5:1.
4. the preparation method as described in claim 1 ~ 3 any one, is characterized in that, step 2. in, described mixing adopts cantilever double helix cone-type mixer to carry out; And/or, step 2. in, the time of described mixing is 2.0 ~ 3.5 hours.
5. the preparation method as described in claim 1 ~ 3 any one, is characterized in that, step 1. in, the time of described heat pre-treatment is 2 ~ 6 hours; And/or, step 3. in, the temperature of described kneading is 100 ~ 180 ℃; And/or, step 3. in, the time of described kneading is 1 ~ 10 hour; And/or, step 3. in, after described kneading, also carry out briquetting processing; And/or, step 4. in, the temperature of described charing processing is 800 ~ 1500 ℃; And/or, step 4. in, the time of described charing processing is 2 ~ 6 hours; And/or, step 4. in, the temperature of described catalyzed graphitization high-temperature process is 2800 ~ 3200 ℃; And/or, step 4. in, the time of described catalyzed graphitization high-temperature process is 24 ~ 48 hours; And/or, step 5. in, described pulverizing is for first carrying out coarse crushing, then carries out middle pulverizing, finally carries out Crushing of Ultrafine; And/or, step 5. in, described being classified as first sieved and carried out fluid mechanics classification again.
6. preparation method as claimed in claim 5, is characterized in that, step 1. in, the time of described heat pre-treatment is 3 ~ 4 hours; And/or, step 3. in, described briquetting is treated to briquetting and becomes cylindrical or rectangle; And/or, step 3. in, after described kneading, before described briquetting processes, also carry out following operation: in tablet press machine, described kneaded material is pressed into 2 ~ 5mm sheet, is ground into the powder of particle diameter below 0.1mm.
7. preparation method as claimed in claim 5, is characterized in that, the equipment of described coarse crushing uses jaw crusher, and the grain diameter after described coarse crushing is below 30mm; And/or the equipment of described middle pulverizing uses plate-hammer crusher, the grain diameter after described middle pulverizing is below 10mm; And/or described fine equipment uses ultra-fine mechanical crusher, the grain diameter after described Crushing of Ultrafine is below 1mm.
8. preparation method as claimed in claim 5, is characterized in that, described screening was 250 mesh sieve extracting screen underflows; And/or described fluid mechanics classification adopts gas flow sizing machine to carry out.
9. preparation method as claimed in claim 8, is characterized in that, described screening adopts 250 order oscillatory type screening machines to carry out; And/or the frequency of described gas flow sizing machine is 20 ~ 60Hz.
10. the lithium ion battery composite graphite negative electrode material being made by claim 1 ~ 9 any one preparation method.
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