CN102593434B - Composite graphite particles for lithium secondary battery and preparation method thereof - Google Patents
Composite graphite particles for lithium secondary battery and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of composite graphite particles for lithium secondary battery, it comprises the steps: 1. to heat mediates spherical natural graphite particle, graphited adhesive and graphitization catalyst can obtain kneaded material; 2. the block formed body obtaining kneaded material is pressed into; 3., under inert gas shielding, carry out charing process in 800 ~ 1500 DEG C, be cooled to room temperature; 4., under inert gas shielding, catalyzed graphitization high-temperature process is carried out in 2800 ~ 3200 DEG C; 5. pulverize rear classification or sieve.The invention still further relates to a kind of composite graphite particles for lithium secondary battery obtained by this method.The compacted density of composite graphite particles for lithium secondary battery of the present invention is high, and discharge capacity is large, good cycle, and compacted density is higher, and chemical property is good, discharge platform and platform conservation rate higher, high rate during charging-discharging is better, and fail safe is better.
Description
Technical field
The present invention relates to a kind of composite graphite particles for lithium secondary battery 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 extensive research for raising battery capacity at present, along with the raising to battery performance requirements, need to improve battery capacity further.
As cathode material of lithium ion battery, have studied the such as granular material such as metal or graphite at present.Along with the increase of battery capacity, special needs can with higher electrode density (such as 1.7g/cm
3or higher than 1.7g/cm
3) negative material that uses.
Native graphite has very high capacitance (> 350mAh/g), there is structural instability in shortcoming, when in order to obtain higher electrode density improve squeeze pressure time, graphite cathode particle is easy to and collector orientation abreast, whole electrode produces consistent orientation, owing to producing the graphite inserting lithium, so the electrode obtained is easy to expand.Electrode expansion makes cell active materials can reduce by loading in unit volume, produces the problem that battery capacity reduces.
In order to solve the problem, the composite graphite particles that the graphite using calcining to mix with pitch etc. obtains.
Japan Patent JP2000-182617 is by contour for flake natural graphite crystalline graphite and pitch or mixed with resin, through pulverizing, charing, graphitization and make compound, can improve the deficiency of native graphite, namely first charge-discharge efficiency is high, cycle characteristics is excellent, and capacity is large and coating is excellent.
Japan Patent JP2002-373656 will have the mesophase pitch melting mixing that height-oriented powdered graphite and softening point are 250 ~ 400 DEG C, then pulverizing, classification, calcining, graphitization and make compound, this negative material combines the high power capacity of graphite and the excellent specific property of mesophase pitch, shows high efficiency and bulk density.
When graphite cathode material high compacted density uses, Problems existing is, breaks and expose the more surface area reacted with electrolyte due to graphite cathode material, accelerates, with the reaction of electrolyte, to cause the reduction of efficiency for charge-discharge.
In addition, because high compacted density causes particle easily broken, serve as in the electrodes lithium ion tunnel space reduce, damage lithium ion mobility, cause part throttle characteristics to decline.
Therefore, in order to improve the discharge capacity of lithium ion battery, not only need to increase the capacity of active material, and need to make negative material to use under more high compacted density, and expansion when suppressing battery charging, maintain efficiency for charge-discharge and part throttle characteristics.
Japan Patent JP2003-173778 is by melt kneading pitch and flake natural graphite compound, 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 coat shell, this material reduces irreversible capacity when high compacted density uses, and improves cycle performance.By mechanochemistry process graphite granule, can control to react with electrolyte, because graphite core is combined densification with coating layer, so when high compacted density uses, this composite particles also breaks hardly, therefore there is above excellent specific property.
In graphite cathode material disclosed in above-mentioned patent documentation, the graphite of flat pattern is easy to orientation in the powder and electrode of compound, when with high compacted density (1.65g/cm
3when using above), can not stop electrode expansion, cause the lithium ion mobility of material poor, battery capacity is lower than 355mAh/g, and charging and discharging efficiency is low.
Summary of the invention
Technical problem to be solved by this invention is the compacted density further increasing composite graphite particles for lithium secondary battery, thus improve the cycle performance of material, because herein is provided a kind of composite graphite particles for lithium secondary battery with high compacted density and preparation method thereof.The lithium secondary battery obtained by composite graphite particles of the present invention has high charge/discharge capacity and efficiency for charge-discharge, only has expansion in a small amount during charging.
The invention provides a kind of preparation method of composite graphite particles for lithium secondary battery, it comprises the steps: 1. to heat mediates spherical natural graphite particle, graphited adhesive and graphitization catalyst can obtain kneaded material; 2. the block formed body obtaining kneaded material is pressed into; 3., under inert gas shielding, carry out charing process in 800 ~ 1500 DEG C, be cooled to room temperature; 4., under inert gas shielding, catalyzed graphitization high-temperature process is carried out in 2800 ~ 3200 DEG C; 5. pulverize rear classification or sieve.
Step 1. in, described native graphite can select the native graphite of the various routine in this area, and the particle diameter of described native graphite can be the conventional particle size of this type of material of this area, is preferably 12 ~ 36 μm.
Step 1. in, described can to refer to conventionally in graphite cathode material field can bond native graphite by graphited adhesive, and can make the adhesive of Delanium after graphitization, be preferably one or more in petroleum asphalt, coal tar pitch, phenolic resins, epoxy resin, furane resins and furfural resin.The particle diameter of described petroleum asphalt or coal tar pitch is preferably below 0.1mm.Petroleum asphalt of the present invention, coal tar pitch, phenolic resins, epoxy resin, furane resins and furfural resin all can select the petroleum asphalt of this area all size, coal tar pitch, phenolic resins, epoxy resin, furane resins and furfural resin.
Step 1. in, described graphitization catalyst is preferably one or more in the carbide of following element and oxide: silicon, iron, tin or boron are more preferably the carbide of silicon and/or the oxide of iron.
Step 1. in, described heating mediate process can improve native graphite high compacted density under processing characteristics, its concrete operation method can adopt the method for this area routine to carry out, and mediates or liquid phase is mediated and all can as solid phase.Liquid phase mediate refer to can graphited adhesive be heated to liquid after and native graphite and graphitization catalyst carry out kneading process.Solid phase is mediated and is referred to graphited adhesive, native graphite and graphitization catalyst to be mixed together heat temperature raising, carries out kneading process.Mediating due to liquid phase to avoid heating-up temperature too high causing to volatilize and polycondensation by graphited adhesive, and therefore preferred liquid phase is mediated.The heating-up temperature that heating in the present invention is mediated can be selected according to this area conventional method, be generally lower than described can graphited adhesive crosslinking temperature and described can more than the softening point temperature of graphited adhesive 10 ~ 80 DEG C, described heating-up temperature is preferably 160 ~ 180 DEG C.Heating kneading time short meeting causes material to lump, and mixes uneven, and heating kneading time length can cause adhesive volatilization loss, and can not form the formed body of kneaded material, described heating kneading time is preferably 1 ~ 2 hour.
Step 1. in, the consumption of described adhesive is preferably 10 ~ 30% of natural graphite particles quality.The consumption of described graphitization catalyst is preferably 1 ~ 10% of natural graphite particles quality, is more preferably 3 ~ 8% of natural graphite particles quality.
In the present invention one preferably execution mode, after 1. step terminates, after also being pulverized by described kneaded material compressing tablet, carry out step 2..Wherein, compressing tablet is for the ease of carrying, keeping and metering, and can by the uniformity of compressing tablet inspection mixing and caking property, and described compressing tablet is preferably for being pressed into the tablet of thickness 2 ~ 5mm.Described pulverizing can adopt the disintegrating process of the various routine in this area to carry out, and pulverizes preferably for being ground into the particle that particle diameter is 5 ~ 100 μm described in the present invention.
Step 2. in, the described bulk that is pressed into is conveniently follow-up graphitization processing, and the method for the various routine in this area can be adopted to carry out, as extrusion modling, mould molding or cold isostatic compaction.
Step 3. in, the time of described charing process can be selected according to this area conventional method, is preferably 2 ~ 6 hours.
Step 4. in, described catalyzed graphitization high-temperature process can adopt this area conventional method to carry out, and preferably carries out in graphitization finishing stove.The time of described catalyzed graphitization high-temperature process can be selected according to this area conventional method, is preferably 24 ~ 48 hours.
Step 5. in, described pulverizing is preferably for first carrying out coarse crushing carries out Crushing of Ultrafine again, to guarantee that grain diameter and specific morphology can meet requirement of the present invention.Described coarse crushing be generally by step 4. in block material to be crushed to lumpiness be 50 ~ 70 millimeters.Described coarse crushing can use the various conventional coarse crushing equipment in this area, preferably uses jaw crusher to carry out.The powder that it is particle diameter less than 0.10 millimeter that described Crushing of Ultrafine refers to the block material pulverizing through coarse crushing, can use the various conventional micro-crushing equipment in this area, the ultra-fine mechanical crusher of the HHJ-10 preferably using Weifang Zhengyuan Powder Engineering Equipment Co., Ltd. to produce is pulverized.Described classification or to sieve be to remove residual coarse granule, the coarse grained particle diameter of removal can carry out routine and select according to the needs producing lithium rechargeable battery, general removal is greater than 250 object coarse granules.The present invention by step 5. in pulverizing make initiation material---the primary particle of globular graphite particle and graphite granule section have towards the specific morphology in various direction (as shown in Figure 4) on the surface of composite graphite particles, can improve discharge and recharge acceptance further thus, and electrolyte is to the immersion liquid of pole plate.
Present invention also offers a kind of composite graphite particles for lithium secondary battery obtained by above-mentioned preparation method, its performance parameter is as shown in table 1 below:
Table 1
Room temperature described in the present invention is 5 ~ 40 DEG C.
In the present invention, above-mentioned optimum condition can combination in any on the basis meeting this area general knowledge, obtains each preferred embodiment of the present invention.
Raw material of the present invention and reagent are all commercially.
Positive progressive effect of the present invention is:
1, the compacted density of composite graphite particles of the present invention is high, and the large and good cycle of discharge capacity, the high comprehensive performance of its button cell made, mainly contains following advantage: 1. compacted density is higher, and under water-based system, compacted density can reach 1.70g/cm
3above; 2. chemical property is good, and discharge capacity is at more than 360mAh/g; 3. discharge platform and platform conservation rate higher; 4. high rate during charging-discharging is better; 5. good cycle (300 circulations, capacity keeps>=80%); 6. fail safe better (130 DEG C/60 minutes, not quick-fried, do not rise); 7. to electrolyte and other additive adaptability better; 8. product property is stablized, and does not almost have 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 particles of the embodiment of the present invention 2.
Fig. 2 is the absorbency curve of the composite graphite particles of the embodiment of the present invention 2.
Fig. 3 is the cycle performance figure of the composite graphite particles of the embodiment of the present invention 2.
Fig. 4 is the scanning electron microscope (SEM) photograph of the composite graphite particles of the embodiment of the present invention 2.
Embodiment
Further illustrate the present invention by embodiment below, but the present invention is not limited, the raw material in embodiment is conventional commercial product.
Described petroleum asphalt is the MQ-100 mid temperature pitch that Dalian bright strengthening work Materials Co., Ltd produces;
Described coal tar pitch is the mid temperature pitch that Henan Bo Hai Chemical Co., Ltd. produces;
Described phenolic resins is 2130 phenolic resins that Wuxi City A Erzi Chemical Co., Ltd. produces;
Described epoxy resin is 128 epoxy resin that Wuxi City A Erzi Chemical Co., Ltd. produces;
Described furfural resin is the FL type furfural resin that Wuhan Yuancheng Technology Development Co., Ltd. produces;
Described furane resins are the GM type furane resins that the bright Chemical Co., Ltd. in Wuxi produces.
Embodiment 1
Petroleum asphalt is crushed to below 0.1mm, alternately adds spherical natural graphite (D50 is 19.1 μm) 200kg and asphalt powder 60kg, graphitization catalyst (SiO under stirring
2) mix in 16kg to kneading pot, carry out kneading process 1 hour in 160 DEG C, mediate after terminating, in tablet press machine, be pressed into sheet (4mm), be ground into the particle that particle diameter is less than 100 μm, compound stalk forming.Under the protection of nitrogen; and at the temperature of 1100 DEG C, carbonize process 2 hours; afterwards product is cooled to room temperature; 36 hours catalyzed graphitization high-temperature process are carried out again in 2800 DEG C; use jaw crusher coarse crushing to 50 ~ 70 millimeter; Crushing of Ultrafine is carried out with the wheel speed of 8000 revs/min again with ultra-fine mechanical crusher; coarse granule is screened out by 250 objects; obtained grain diameter D50 is the composite graphite particles for lithium secondary battery of 17.8 μm; its half-cell capacity 362.5mAh/g, efficiency 92.8% first.
Embodiment 2
Petroleum asphalt is crushed to below 0.1mm, alternately add under stirring in spherical natural graphite (D50 is 19.5 μm) 200kg and asphalt powder 20kg, graphitization catalyst (SiC) 6kg to kneading pot and mix, kneading process is carried out 1 hour in 160 DEG C, after kneading terminates, sheet (3mm) is pressed in tablet press machine, be ground into the particle that particle diameter is less than 100 μm, compound stalk forming.Under the protection of nitrogen; and at the temperature of 800 DEG C, carbonize process 6 hours; afterwards product is cooled to room temperature; 48 hours catalyzed graphitization high-temperature process are carried out again in 3000 DEG C; use jaw crusher coarse crushing to 50 ~ 70 millimeter; Crushing of Ultrafine is carried out with the wheel speed of 8000 revs/min again with ultra-fine mechanical crusher; coarse granule is screened out by 250 objects; obtained grain diameter D50 is 18.3 μm of composite graphite particles for lithium secondary batteries; its half-cell capacity 363.1mAh/g, efficiency 93.2% first.
Embodiment 3
Pitch powder is broken to below 0.1mm, alternately adds spherical natural graphite (D50 is 20.1 μm) 200kg and asphalt powder 40kg, graphitization catalyst (SiO under stirring
2) mix in 10kg to kneading pot, carry out kneading process 1 hour in 160 DEG C, mediate after terminating, in tablet press machine, be pressed into sheet (5mm), be ground into the particle that particle diameter is less than 100 μm, compound stalk forming.Under the protection of nitrogen; and at the temperature of 1500 DEG C, carbonize process 3 hours; afterwards product is cooled to room temperature; 48 hours catalyzed graphitization high-temperature process are carried out again in 3200 DEG C; use jaw crusher coarse crushing to 50 ~ 70 millimeter; Crushing of Ultrafine is carried out with the wheel speed of 8000 revs/min again with ultra-fine mechanical crusher; coarse granule is screened out by 250 objects; obtained grain diameter D50 is 17.4 μm of composite graphite particles for lithium secondary batteries; its half-cell capacity 365.0mAh/g, efficiency 92.6% first.
Embodiment 4
Pitch powder is broken to below 0.1mm, alternately adds spherical natural graphite (D50 is 12.2 μm) 200kg and asphalt powder 50kg, graphitization catalyst (Fe under stirring
2o
3) mix in 2kg to kneading pot, carry out kneading process 1 hour in 160 DEG C, mediate after terminating, in tablet press machine, be pressed into sheet (5mm), be ground into the particle that particle diameter is less than 100 μm, compound stalk forming.Under the protection of nitrogen; and at the temperature of 1000 DEG C, carbonize process 4 hours; afterwards product is cooled to room temperature; 48 hours catalyzed graphitization high-temperature process are carried out again in 2800 DEG C; use jaw crusher coarse crushing to 50 ~ 70 millimeter; Crushing of Ultrafine is carried out with the wheel speed of 8000 revs/min again with ultra-fine mechanical crusher; coarse granule is screened out by 250 objects; obtained grain diameter D50 is 10.6 μm of composite graphite particles for lithium secondary batteries; its half-cell capacity 366.7mAh/g, efficiency 93.0% first.
Embodiment 5
Petroleum asphalt is crushed to below 0.1mm, alternately adds spherical natural graphite (D50 is 36.1 μm) 200kg and asphalt powder 40kg, graphitization catalyst (B under stirring
2o
3) mix in 20kg to kneading pot, carry out kneading process 1 hour in 170 DEG C, mediate after terminating, in tablet press machine, be pressed into sheet (2mm), be ground into the particle that particle diameter is less than 100 μm, compound stalk forming.Under the protection of nitrogen; and at the temperature of 1100 DEG C, carbonize process 2 hours; afterwards product is cooled to room temperature; 24 hours catalyzed graphitization high-temperature process are carried out again in 3200 DEG C; use jaw crusher coarse crushing to 50 ~ 70 millimeter; Crushing of Ultrafine is carried out with the wheel speed of 8000 revs/min again with ultra-fine mechanical crusher; coarse granule is screened out by 250 objects; obtained grain diameter D50 is 30.4 μm of composite graphite particles for lithium secondary batteries; its half-cell capacity 362.4mAh/g, efficiency 92.8% first.
Embodiment 6
Petroleum asphalt is crushed to below 0.1mm, alternately add under stirring in spherical natural graphite (D50 is 18.5 μm) 200kg and asphalt powder 30kg, graphitization catalyst (SiC) 10kg to kneading pot and mix, kneading process is carried out 1 hour in 160 DEG C, after kneading terminates, sheet (2mm) is pressed in tablet press machine, be ground into the particle that particle diameter is less than 100 μm, compound stalk forming.Under the protection of nitrogen; and at the temperature of 900 DEG C, carbonize process 5 hours; afterwards product is cooled to room temperature; 48 hours catalyzed graphitization high-temperature process are carried out again in 3200 DEG C; use jaw crusher coarse crushing to 50 ~ 70 millimeter; Crushing of Ultrafine is carried out with the wheel speed of 8000 revs/min again with ultra-fine mechanical crusher; coarse granule is screened out by 250 objects; obtained grain diameter D50 is 16.8 μm of composite graphite particles for lithium secondary batteries; its half-cell capacity 366.1mAh/g, efficiency 92.4% first.
Embodiment 7
Pitch powder is broken to below 0.1mm, alternately adds spherical natural graphite (D50 is 19.1 μm) 200kg and asphalt powder 20kg, graphitization catalyst (SnO under stirring
2) mix in 6kg to kneading pot, carry out kneading process 1 hour in 160 DEG C, mediate after terminating, in tablet press machine, be pressed into sheet (5mm), be ground into the particle that particle diameter is less than 100 μm, compound stalk forming.Under the protection of nitrogen; and at the temperature of 1100 DEG C, carbonize process 2 hours; afterwards product is cooled to room temperature; 48 hours catalyzed graphitization high-temperature process are carried out again in 3200 DEG C; use jaw crusher coarse crushing to 50 ~ 70 millimeter; Crushing of Ultrafine is carried out with the wheel speed of 8000 revs/min again with ultra-fine mechanical crusher; coarse granule is screened out by 250 objects; obtained grain diameter D50 is 17.1 μm of composite graphite particles for lithium secondary batteries; its half-cell capacity 363.6mAh/g, efficiency 92.6% first.
Embodiment 8
Spherical natural graphite (D50 is 19.5 μm) 200kg and Phenolic resin powder 50kg, graphitization catalyst (SiO
2) 16kg alternately joins in kneading pot and mix under stirring, carry out kneadings process 1 hour, after kneading terminates, be pressed into sheet (5mm), be ground into the particle that particle diameter is less than 100 μm, compound stalk forming in tablet press machine in 180 DEG C.Under the protection of nitrogen; and at the temperature of 1100 DEG C, carbonize process 120 minutes; afterwards product is cooled to room temperature; 48 hours catalyzed graphitization high-temperature process are carried out again in 2800 DEG C; use jaw crusher coarse crushing to 50 ~ 70 millimeter; Crushing of Ultrafine is carried out with the wheel speed of 8000 revs/min again with ultra-fine mechanical crusher; coarse granule is screened out by 250 objects; obtained grain diameter D50 is 17.9 μm of composite graphite particles for lithium secondary batteries; its half-cell capacity 362.7mAh/g, efficiency 92.3% first.
Embodiment 9
Spherical natural graphite (D50 is 19.5 μm) 200kg and furane resins powder 50kg, graphitization catalyst (SiC) 10kg alternately join in kneading pot under stirring and mix, kneading process is carried out 1.5 hours in 160 DEG C, after kneading terminates, sheet (5mm) is pressed in tablet press machine, be ground into the particle that particle diameter is less than 100 μm, compound stalk forming.Under the protection of nitrogen; and at the temperature of 1000 DEG C, carbonize process 180 minutes; afterwards product is cooled to room temperature; 32 hours catalyzed graphitization high-temperature process are carried out again in 3000 DEG C; use jaw crusher coarse crushing to 50 ~ 70 millimeter; Crushing of Ultrafine is carried out with the wheel speed of 8000 revs/min again with ultra-fine mechanical crusher; coarse granule is screened out by 250 objects; obtained grain diameter D50 is 19.3 μm of composite graphite particles for lithium secondary batteries; its half-cell capacity 360.2mAh/g, efficiency 94.0% first.
Embodiment 10
Spherical natural graphite (D50 is 18.5 μm) 200kg and furfural resin powder 60kg, graphitization catalyst (SiC) 10kg alternately join in kneading pot under stirring and mix, kneading process is carried out 2 hours in 170 DEG C, after kneading terminates, sheet (5mm) is pressed in tablet press machine, be ground into the particle that particle diameter is less than 100 μm, compound stalk forming.Under the protection of nitrogen; and at the temperature of 1100 DEG C, carbonize process 120 minutes; afterwards product is cooled to room temperature; 48 hours catalyzed graphitization high-temperature process are carried out again in 2800 DEG C; use jaw crusher coarse crushing to 50 ~ 70 millimeter; Crushing of Ultrafine is carried out with the wheel speed of 8000 revs/min again with ultra-fine mechanical crusher; coarse granule is screened out by 250 objects; obtained grain diameter D50 is 18.9 μm of composite graphite particles for lithium secondary batteries; its half-cell capacity 364.1mAh/g, efficiency 91.7% first.
Comparative example 1
Petroleum asphalt is crushed to O.1mm; alternately add under stirring in spherical natural graphite (D50 is 16.5 μm) 200kg and asphalt powder 20kg to reactor and mix; carry out hot coated process; after coated end under the protection of nitrogen; and at the temperature of 1100 DEG C, carbonize process 120 minutes; afterwards product is cooled to room temperature, with additive (SiO
2) 10kg carries out 48 hours catalyzed graphitization high-temperature process (3200 DEG C) after alternately adding in cantilever double-spiral conical mixer mixing again, 250 objects are used to screen out coarse granule, obtained grain diameter D50 is 19.4 μm of graphite cathode materials, its half-cell capacity 367.0mAh/g, efficiency 89.7% first.
Comparative example 2
Petroleum asphalt is crushed to below 0.1mm, alternately add under stirring in spherical natural graphite (D50 is 19.5 μm) 200kg and asphalt powder 20kg to kneading pot and mix, kneading process is carried out 1 hour in 160 DEG C, after kneading terminates, sheet (2mm) is pressed in tablet press machine, be ground into the particle that particle diameter is less than 100 μm, briquette forming.Under the protection of nitrogen; and at the temperature of 1100 DEG C, carbonize process 120 minutes; afterwards product is cooled to room temperature; use jaw crusher coarse crushing to 50 ~ 70 millimeter; carry out Crushing of Ultrafine with ultra-fine mechanical crusher with the wheel speed of 8000 revs/min again, screen out coarse granule by 250 objects, obtained grain diameter D50 is 19.2 μm of graphite cathode materials; its half-cell capacity 345.2mAh/g, efficiency 91.3% first.
Comparative example 3
Pitch powder is broken to below 0.1mm, alternately add under stirring in spherical natural graphite (D50 is 27.1 μm) 200kg and asphalt powder 20kg to kneading pot and mix, kneading process is carried out 1 hour in 160 DEG C, after kneading terminates, sheet (5mm) is pressed in tablet press machine, be ground into the particle that particle diameter is less than 100 μm, briquette forming.Under the protection of nitrogen; and at the temperature of 1100 DEG C, carbonize process 120 minutes; afterwards product is cooled to room temperature; graphitizable high temperature process in 48 hours is carried out again in 3200 DEG C; use jaw crusher coarse crushing to 50 ~ 70 millimeter; Crushing of Ultrafine is carried out with the wheel speed of 8000 revs/min again with ultra-fine mechanical crusher; coarse granule is screened out by 250 objects; obtained grain diameter D50 is 25.6 μm of composite graphite particles for lithium secondary batteries; its half-cell capacity 365.3mAh/g, efficiency 87.6% first.
Effect example
(1) carry out particle diameter, real density, compacted density, specific area and ash respectively to the graphite cathode material in embodiment 1 ~ 10 and comparative example 1 ~ 3 to grade test, the results are shown in Table 2.The instrument title that test uses and model are: particle diameter, laser fineness gage MS2000; Real density, super constant temperature water tank SC-15; Ash content, high-temperature electric resistance furnace SX2-2.5-12; Compacted density, pole piece milling train JZL235X35-B111; Specific area, specific surface area measuring instrument NOVA2000.
(2) adopt half-cell method of testing to carry out the test of discharge capacity and efficiency first to the graphite cathode material in embodiment 1 ~ 10 and comparative example 1 ~ 3, the results are shown in table 2.
Half-cell method of testing is: graphite sample, 1-METHYLPYRROLIDONE containing 6 ~ 7% Kynoar and 2% conductive black in 91.6: 6.6: 1.8 ratio mix, be applied on Copper Foil, the pole piece coated being put into temperature is that 110 DEG C of vacuum drying chamber vacuumizes 4 hours are for subsequent use.Simulated battery is assemblied in the German Braun glove box of applying argon gas and carries out, electrolyte is 1MLiPF6+EC: DEC: DMC=1: 1: 1 (volume ratio), metal lithium sheet is to electrode, electrochemical property test carries out on U.S. ArbinBT2000 type cell tester, charging/discharging voltage scope is 0.005 to 1.0V, and charge-discharge velocity is 0.1C.
(3) composite graphite particles for lithium secondary battery of full battery testing method to embodiment 2 is adopted to test.Full battery testing method is: using the composite graphite particles of embodiment 2 as negative pole, using cobalt acid lithium as positive pole, 1M-LiPF6EC: DMC: EMC=1: 1: 1 (volume ratio) solution is done electrolyte assembling and is helped battery, test 1C charge and discharge 300 weeks rear capability retentions can reach 86.1%, show good cycle, result as shown in Figure 3.
(4) be: discharge platform (3.6V) >=75% that the 100 weeks platforms that circulate keep >=95% to other relevant item test result of resultant battery that the composite graphite particles for lithium secondary battery by embodiment 1 ~ 10 is made; Multiplying power discharging 3C capacity >=50%; 300 circulations, capacity keeps >=80%; Overcharge, high temperature short circuit, the security performance measuring stability such as thermal shock be good, not on fire, do not explode, surface temperature is no more than 150 DEG C; Better to electrolyte and other additive adaptability, do not analyse lithium; Product is stablized, and does not almost have difference between batch; Over-charging is better; Pole piece processability is good.
Table 2
As can be seen from data above, the discharging efficiency of comparative example 1 is low, is only 89.7%; The discharge capacity of comparative example 2 is low, is only 345.2mAh/g, and compacted density is low; The compacted density of comparative example 3 is low.Adopt the composite graphite particles for lithium secondary battery that described in this patent prepared by method, specific area can control at 3.0 ~ 4.0m
2/ g, discharge capacity can reach more than 360mAh/g, and compacted density is not less than 1.70g/cm
3; Gram volume and compacted density higher, reduce the loss of irreversible capacity, improve energy density, reduce the consumption of positive pole; Specific area controls in suitable scope, can ensure that particle surface pore is flourishing, and be conducive to again suppressing lithium-ion battery system to produce ballooning, the security performance of battery is good; Over-charging is better; Pole piece processability is good, compacted density 1.70g/cm
3the lower imbibition time will be less than 180 seconds; Desirable voltage platform, discharge voltage can reach plateau very soon, as shown in Figure 1; Absorbency is good, as shown in Figure 2; Good cycle, the capability retention after 300 times that circulates can reach 86.1%, as shown in Figure 3; The primary particle of the spherical graphite granule of raw material and graphite granule section have towards the specific morphology in various direction (as shown in Figure 4) on the surface of composite graphite particles, can improve discharge and recharge acceptance further thus, and electrolyte is to the immersion liquid of pole plate.
Claims (16)
1. a preparation method for composite graphite particles for lithium secondary battery, is characterized in that: it comprises the steps: 1. to heat mediates spherical natural graphite particle, graphited adhesive and graphitization catalyst can obtain kneaded material; Described can graphited adhesive be one or more in petroleum asphalt, coal tar pitch, phenolic resins, epoxy resin, furane resins and furfural resin; The particle diameter of described petroleum asphalt or coal tar pitch is below 0.1mm, and the temperature of described heating is 160 ~ 180 DEG C, after 1. step terminates, carries out step 2. again after also being pulverized by described kneaded material compressing tablet; Described compressing tablet is be pressed into the tablet that thickness is 2 ~ 5mm; 2. the block formed body obtaining kneaded material is pressed into; 3., under inert gas shielding, carry out charing process in 800 ~ 1500 DEG C, be cooled to room temperature; 4., under inert gas shielding, catalyzed graphitization high-temperature process is carried out in 2800 ~ 3200 DEG C; 5. pulverize rear classification or sieve.
2. the preparation method of composite graphite particles for lithium secondary battery as claimed in claim 1, is characterized in that: step 1. in, the particle diameter of described native graphite is 12 ~ 36 μm.
3. the preparation method of composite graphite particles for lithium secondary battery as claimed in claim 1, is characterized in that: step 1. in, described graphitization catalyst is one or more in the carbide of following element and oxide: silicon, iron, tin or boron.
4. the preparation method of the composite graphite particles for lithium secondary battery according to any one of claims 1 to 3, is characterized in that: step 1. in, kneading time is 1 ~ 2 hour.
5. the preparation method of the composite graphite particles for lithium secondary battery according to any one of claims 1 to 3, is characterized in that: step 1. in, described can the consumption of graphited adhesive be 10 ~ 30% of natural graphite particles quality; The consumption of described graphitization catalyst is 1 ~ 10% of natural graphite particles quality.
6. the preparation method of composite graphite particles for lithium secondary battery as claimed in claim 5, is characterized in that: the consumption of described graphitization catalyst is 3 ~ 8% of natural graphite particles quality.
7. the preparation method of composite graphite particles for lithium secondary battery as claimed in claim 1, is characterized in that: the described pulverizing in after also being pulverized by described kneaded material compressing tablet is for being ground into the particle that particle diameter is 5 ~ 100 μm.
8. the preparation method of composite graphite particles for lithium secondary battery as claimed in claim 1 or 2, is characterized in that: step 2. described in be pressed into and blockly adopt extrusion modling, mould molding or cold isostatic compaction.
9. the preparation method of the composite graphite particles for lithium secondary battery according to any one of claims 1 to 3, is characterized in that: step 3. in, the time of described charing process is 2 ~ 6 hours; Step 4. in, described catalyzed graphitization high-temperature process is carried out in graphitization finishing stove; The time of described catalyzed graphitization high-temperature process is 24 ~ 48 hours.
10. the preparation method of composite graphite particles for lithium secondary battery as claimed in claim 4, is characterized in that: step 3. in, the time of described charing process is 2 ~ 6 hours; Step 4. in, described catalyzed graphitization high-temperature process is carried out in graphitization finishing stove; The time of described catalyzed graphitization high-temperature process is 24 ~ 48 hours.
The preparation method of 11. composite graphite particles for lithium secondary batteries as claimed in claim 5, is characterized in that: step 3. in, the time of described charing process is 2 ~ 6 hours; Step 4. in, described catalyzed graphitization high-temperature process is carried out in graphitization finishing stove; The time of described catalyzed graphitization high-temperature process is 24 ~ 48 hours.
The preparation method of 12. composite graphite particles for lithium secondary batteries according to any one of claims 1 to 3, it is characterized in that: step 5. described in pulverizing for first carrying out coarse crushing carries out Crushing of Ultrafine again, described coarse crushing be by step 4. in block material to be crushed to particle diameter be 50 ~ 70mm; Described Crushing of Ultrafine is the powder pulverized by the block material through coarse crushing as below particle diameter 0.10mm; Described classification or to sieve be greater than 250 object coarse granules to remove residual particle diameter.
The preparation method of 13. composite graphite particles for lithium secondary batteries as claimed in claim 4, it is characterized in that: step 5. described in pulverizing for first carrying out coarse crushing carries out Crushing of Ultrafine again, described coarse crushing be by step 4. in block material to be crushed to particle diameter be 50 ~ 70mm; Described Crushing of Ultrafine is the powder pulverized by the block material through coarse crushing as below particle diameter 0.10mm; Described classification or to sieve be greater than 250 object coarse granules to remove residual particle diameter.
The preparation method of 14. composite graphite particles for lithium secondary batteries as claimed in claim 5, it is characterized in that: step 5. described in pulverizing for first carrying out coarse crushing carries out Crushing of Ultrafine again, described coarse crushing be by step 4. in block material to be crushed to particle diameter be 50 ~ 70mm; Described Crushing of Ultrafine is the powder pulverized by the block material through coarse crushing as below particle diameter 0.10mm; Described classification or to sieve be greater than 250 object coarse granules to remove residual particle diameter.
The preparation method of 15. composite graphite particles for lithium secondary batteries as claimed in claim 9, it is characterized in that: step 5. described in pulverizing for first carrying out coarse crushing carries out Crushing of Ultrafine again, described coarse crushing be by step 4. in block material to be crushed to particle diameter be 50 ~ 70mm; Described Crushing of Ultrafine is the powder pulverized by the block material through coarse crushing as below particle diameter 0.10mm; Described classification or to sieve be greater than 250 object coarse granules to remove residual particle diameter.
The composite graphite particles for lithium secondary battery that 16. preparation methods according to any one of claim 1 ~ 15 obtain.
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| CN112670464B (en) * | 2020-04-21 | 2022-02-18 | 宁波杉杉新材料科技有限公司 | Graphite negative electrode material, lithium ion battery and preparation method and application of graphite negative electrode material |
| CN114203979A (en) * | 2020-09-17 | 2022-03-18 | 湖南中科星城石墨有限公司 | Graphite negative electrode material and preparation method and application thereof |
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