CN105742636A - Graphite negative electrode material for lithium-ion battery and preparation method of graphite negative electrode material - Google Patents
Graphite negative electrode material for lithium-ion battery and preparation method of graphite negative electrode material Download PDFInfo
- Publication number
- CN105742636A CN105742636A CN201410749026.6A CN201410749026A CN105742636A CN 105742636 A CN105742636 A CN 105742636A CN 201410749026 A CN201410749026 A CN 201410749026A CN 105742636 A CN105742636 A CN 105742636A
- Authority
- CN
- China
- Prior art keywords
- ion battery
- kneading
- preparation
- graphite negative
- lithium ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a graphite negative electrode material for a lithium-ion battery and a preparation method of the graphite negative electrode material. The method comprises the following steps: (1) kneading treatment, namely kneading green coke powder and a binder to obtain a kneaded object; (2) hot isostatic pressing treatment, namely carrying out hot isostatic pressing treatment on the kneaded object to obtain a kneaded object forming body, wherein the hot isostatic pressing treatment temperature is 1,000-2,000 DEG C; the hot isostatic pressing treatment pressure is 50-100MPa and the hot isostatic pressing treatment time is 1-10 hours; (3) graphitizing treatment; and (4) crushing and classification. The invention further discloses the graphite negative electrode material for the lithium-ion battery prepared by the method. According to the graphite negative electrode material for the lithium-ion battery, the processability of the lithium-ion battery can be effectively improved; the discharge capacity and the cycle efficiency are improved; the battery prepared from the negative electrode material is excellent in overall performance; and meanwhile, the preparation method disclosed by the invention is simple, convenient and feasible, wide in raw material source and low in cost.
Description
Technical field
The present invention relates to a kind of graphite negative material of lithium ion battery and preparation method thereof.
Background technology
In recent years, along with the microminiaturization of electronic installation, the secondary cell of Large Copacity low bulk is had increasing need for.What attract people's attention especially is lithium ion battery, compared with NI-G or Ni-MH battery, has higher energy density.Although currently for improving, capacity of lithium ion battery is existing to be studied widely, but, along with the raising to battery performance requirements, it is necessary to reduce the expansion of battery core while improving battery capacity further.
As cathode material of lithium ion battery, have studied the such as granular material such as metal or graphite at present.Increase along with battery capacity, it is accordingly required in particular to can with higher tap density (such as 1.20g/cm3Or 1.20g/cm3The negative material used above).
Delanium also exists poor processability, expands the shortcoming that bounce-back is big, and when improving squeeze pressure to obtain higher electrode density, graphite cathode granule is easily broken, owing to producing to insert the graphite of lithium, so the electrode obtained is prone 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 problems referred to above, existing bibliographical information uses the graphite that calcining mixes with Colophonium etc. to obtain high-tap density graphite cathode material.
Japan Patent JP2002-373656 will have height-oriented powdered graphite and the mesophase pitch melting mixing that softening point is 250～400 DEG C, then pulverizing, classification, calcining, graphitization and make complex, 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 there is problems of when high compacted density uses, breaking due to graphite cathode material and exposing has the more surface area of high response with electrolyte, thus accelerating the reaction with electrolyte, causes the reduction of efficiency for charge-discharge.
Further, since high compacted density causes that graphite granule is easily broken, the space serving as lithium ion tunnel in the electrodes is reduced, and damages lithium ion mobility, causes that part throttle characteristics declines.
Therefore, in order to improve the discharge capacity of lithium ion battery, not only need to increase the capacity of active substance, and need to improve the tap density of negative material, and expansion when suppressing battery to charge, maintain efficiency for charge-discharge and part throttle characteristics.
Summary of the invention
The technical problem to be solved is to overcome existing graphite negative material of lithium ion battery when high compacted density uses, break due to graphite cathode material and expose, with electrolyte, there is the more surface area of high response, thus accelerating to react with electrolyte, cause that efficiency for charge-discharge reduces；And high compacted density is easily caused graphite granule and crushes, the space serving as lithium ion tunnel in the electrodes is reduced, and damages lithium ion mobility, causes degradation defect under part throttle characteristics, and provides a kind of graphite negative material of lithium ion battery and preparation method thereof.The graphite negative material of lithium ion battery of the present invention, it is possible to be effectively improved lithium ion battery processing characteristics, improves discharge capacity and cycle efficieny；Adopt the battery that the graphite negative material of lithium ion battery of the present invention prepares, high comprehensive performance；Meanwhile, the preparation method of the graphite negative material of lithium ion battery of the present invention is simple and easy to do, and raw material sources are extensive, and cost is low.
Lithium battery artificial plumbago negative pole material is carried out big quantity research by the present inventor, found that, adopt and mediate, hip treatment, graphitization processing and pulverizing, the preparation method of classification, the graphite granule of ad hoc structure can be prepared, in this, as graphite negative material of lithium ion battery, adopt hip treatment technique, at different directions, charcoal granule is applied identical pressure, while add flanging carbonization, the graphite granule hole that volatile component effusion results in is homogeneous, isotropism degree is good, compact structure, the lithium ion battery prepared has bigger charge/discharge capacity, efficiency for charge-discharge is high, small amount of expansion during charging, when using with high-tap density, can effectively solve above-mentioned technical problem, thus completing the present invention.
The preparation method that the invention provides a kind of graphite negative material of lithium ion battery, it comprises the steps of
(1) kneading processes: mediates coking powder and binding agent, obtains kneaded material；
(2) hip treatment: described kneaded material is carried out hip treatment, obtains kneaded material formed body；The temperature of described hip treatment is 1000～2000 DEG C, and the pressure of described hip treatment is 50～100MPa；The time of described hip treatment is 1～10 hour；
(3) graphitization processing；
(4) crushing and classification,.
In step (1), described coking powder can be the coking powder that this area is conventional, it is preferred that for petroleum coke and/or pitch coke.The particle diameter of described coking powder can be the particle diameter that this area coking powder is conventional, it is preferred that, its median particle diameter (D50) is 15～25 μm.
In step (1), described binding agent can be the binding agent that this area is conventional, it is preferred that for one or more in asphalt, coal tar pitch, phenolic resin and epoxy resin.Described coal tar pitch is preferably modified coal asphalt.Described modified coal asphalt can be the modified coal asphalt that this area is conventional, it is preferred that for the modified coal asphalt that Angang Stock Co., Ltd produces.When described binding agent is asphalt or coal tar pitch, it is preferred that re-use after being crushed to below 0.1mm.The consumption of described binding agent can be the consumption that this area is conventional, it is preferred that, the mass ratio of described binding agent and described coking powder is 1:9～9:1, and more preferably, the mass ratio of described binding agent and described coking powder is 1:9～5:5.
In step (1), the method of described kneading and condition can mediate conventional method and condition for this area, as long as being able to ensure that coking powder and binding agent mix homogeneously, coking powder is preferably alternately added in kneading pot with binding agent and mixes by the present invention.The temperature of described kneading can mediate conventional temperature for this area, it is preferred that is 100～180 DEG C.The time of described kneading can be preferably 1～10 hour for the time that this area kneading is conventional, is more preferably 3～5 hours.
In step (1), after described kneading, preferably also carry out tabletting process, in order to following process processes.Condition and method that described tabletting processes can adopt the condition of the various routine in this area and method to carry out, as being pressed into lamellar in tablet machine.
In step (1), after described kneading, before described tabletting processes, more preferably also can carry out operations described below: in tablet machine, described kneaded material is pressed into the tablet that thickness is 2～5mm, is ground into the granule that particle diameter is 5～100 μm.
In step (2), the temperature of described hip treatment is preferably 1500 DEG C～2000 DEG C.The time of described hip treatment is preferably 3～5 hours.Described hip treatment preferably carries out under inert atmosphere protection.The described gas in inert atmosphere can be the inert atmosphere gases that this area is conventional, it is preferred that for argon.In the present invention, the operation of hip treatment can improve graphite negative material of lithium ion battery circulation and expands and extend service life cycle.
In step (2), after described hip treatment terminates, it is preferred that, also carry out cooling process.The method of described cooling and condition can be method and the condition of this area routine, are generally and naturally cool to room temperature.
In step (3), the method for described graphitization processing and condition can be method and the condition of this area routine, and the temperature of described graphitization processing is preferably 2800～3000 DEG C.The time of described graphitization processing is preferably 24～48 hours.
In step (4), the operation of described crushing and classification, it does not have limit especially, it is preferred that first carry out coarse pulverization and carry out Crushing of Ultrafine again.Jaw crusher generally can be used to carry out coarse pulverization.During Crushing of Ultrafine, use the ultra-fine mechanical crusher crushing and classification of HHJ-10 laboratory that Weifang Zhengyuan Powder Engineering Equipment Co., Ltd. produces, adjust grading wheel rotating speed, guarantee that grain diameter and specific morphology disclosure satisfy that the requirement of the present invention, in the present invention, after the operation of described crushing and classification terminates, the median particle diameter of the graphite negative material of lithium ion battery granule obtained is generally 15～25 μm.
Present invention also offers a kind of graphite negative material of lithium ion battery prepared by above-mentioned preparation method.
The particle diameter (D50) of described graphite negative material of lithium ion battery is generally 15～25 μm；True density is general >=2.20g/cm3；Ash is generally≤0.10%；Tap density is general >=1.20g/cm3；Specific surface area is generally 2.5～3.5m2/g；Discharge capacity is generally >=355 first；Discharging efficiency is generally >=92% first.
In the present invention, described room temperature is the ambient temperature that this area is conventional, is generally 10～35 DEG C.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can combination in any, obtain the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material are all commercially.
The actively progressive effect of the present invention is in that:
(1) graphite negative material of lithium ion battery of the present invention, it is possible to be effectively improved lithium ion battery processing characteristics, improves discharge capacity and cycle efficieny.
(2) adopting the battery that the graphite negative material of lithium ion battery of the present invention prepares, high comprehensive performance, main manifestations is: 1. tap density is higher, more than or equal to 1.20g/cm3；2. chemical property is good, and discharge capacity is at more than 355mAh/g；3. discharge platform and platform conservation rate are higher；4. high rate during charging-discharging is better；5. good cycle (500 circulations, capacity keeps >=90%)；6. safety better (130 DEG C/60 minutes, not quick-fried, do not rise)；7. electrolyte and other additive adaptability is better；8. product property is stable, almost without difference between batch.
(3) preparation method of the graphite negative material of lithium ion battery of the present invention is simple and easy to do, and raw material sources are extensive, and cost is low.
Accompanying drawing explanation
Fig. 1 is the cycle performance curve of the graphite negative material of lithium ion battery that embodiment 2 prepares.
Detailed description of the invention
Mode by the examples below 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, conventionally and condition, or selects according to catalogue.
Part material source-information in following embodiment is as follows:
Asphalt is the MQ-260 high temperature asphalt that Dalian bright strengthening work Materials Co., Ltd produces.
Modified coal asphalt is the modified coal asphalt that Angang Stock Co., Ltd produces.
Phenolic resin is 2130 phenolic resin that Wuxi City A Erzi Chemical Co., Ltd. produces.
Epoxy resin is 128 epoxy resin that Wuxi City A Erzi Chemical Co., Ltd. produces.
Relating to the median particle diameter (D50) of raw material and graphite negative material of lithium ion battery in following embodiment, be all adopt laser diffraction granularity analytical tool Mastersizer2000 to measure, it is produced by Malvern Instr Ltd. of Britain.
Embodiment 1
Asphalt is crushed to below 0.1mm, is alternately added petroleum coke (D50 is 19.1 μm) under stirring, and asphalt powder mixes in kneading pot, wherein, the mass ratio of petroleum coke and asphalt is 8:2, carries out kneading process, wherein, the temperature of kneading is 140 DEG C；The time mediated is 4 hours.After kneading terminates, tablet machine is pressed into the tablet of 2～5mm, it is ground into the granule that particle diameter is 5～100 μm, putting in hot isostatic press and shape, adopt argon gas medium, heat up pressurization, it is incubated 1 hour under 1500 DEG C of sintering temperatures and 50MPa pressure, then Temperature fall, then carry out graphitizable high temperature process, process 36 hours at 2800 DEG C.And carry out crushing and classification, first use jaw crusher to carry out coarse pulverization, re-use the ultra-fine mechanical crusher crushing and classification of HHJ-10 laboratory, it is ensured that grain diameter and specific morphology disclosure satisfy that the requirement of the present invention.The graphite negative material of lithium ion battery granule finally prepared, its particle diameter (D50) is generally 15～25 μm, half-cell capacity 356.5mAh/g, efficiency 92.8% first, and the circulation at 45 DEG C in 400 weeks is expanded to 5.3%.
Embodiment 2
Asphalt is crushed to below 0.1mm, is alternately added petroleum coke (D50 is 19.5 μm) and asphalt powder mixes in kneading pot, wherein under stirring, the mass ratio of petroleum coke and asphalt is 8:2, carrying out kneading process, wherein, the temperature of kneading is 140 DEG C；The time mediated is 4 hours.After kneading terminates, tablet machine is pressed into the tablet of 2～5mm, it is ground into the granule that particle diameter is 5～100 μm, putting in hot isostatic press and shape, adopt argon gas medium, heat up pressurization, it is incubated 3 hours under 1000 DEG C of sintering temperatures and 50MPa pressure, then Temperature fall, then carry out graphitizable high temperature process, process 36 hours at 3000 DEG C.And carry out crushing and classification, first use jaw crusher to carry out coarse pulverization, re-use the ultra-fine mechanical crusher crushing and classification of HHJ-10 laboratory, it is ensured that grain diameter and specific morphology disclosure satisfy that the requirement of the present invention.The graphite negative material of lithium ion battery granule finally prepared, its particle diameter (D50) is generally 15～25 μm, half-cell capacity 358.1mAh/g, efficiency 93.2% first, and the circulation at 45 DEG C in 400 weeks is expanded to 5.0%.
Embodiment 3
Modified coal asphalt is crushed to below 0.1mm, is alternately added pitch coke (D50 is 20.1 μm) and modified coal asphalt powder mixes in kneading pot, wherein under stirring, the mass ratio of pitch coke and modified coal asphalt is 5:5, carrying out kneading process, wherein, the temperature of kneading is 180 DEG C；The time mediated is 2 hours.After kneading terminates, tablet machine is pressed into the tablet of 2～5mm, it is ground into the granule that particle diameter is 5～100 μm, putting in hot isostatic press and shape, adopt argon gas medium, heat up pressurization, it is incubated 1 hour under 1200 DEG C of sintering temperatures and 60MPa pressure, then Temperature fall, then carry out graphitizable high temperature process, process 48 hours at 3000 DEG C.And carry out crushing and classification, first use jaw crusher to carry out coarse pulverization, re-use the ultra-fine mechanical crusher crushing and classification of HHJ-10 laboratory, it is ensured that grain diameter and specific morphology disclosure satisfy that the requirement of the present invention.The graphite negative material of lithium ion battery granule finally prepared, its particle diameter (D50) is generally 15～25 μm, half-cell capacity 355.6mAh/g, efficiency 92.6% first, and the circulation at 45 DEG C in 400 weeks is expanded to 5.2%.
Embodiment 4
Modified coal asphalt is crushed to below 0.1mm, is alternately added pitch coke (D50 is 15.2 μm) and modified coal asphalt powder mixes in kneading pot, wherein under stirring, the mass ratio of pitch coke and modified coal asphalt is 1:9, carrying out kneading process, wherein, the temperature of kneading is 100 DEG C；The time mediated is 10 hours.After kneading terminates, tablet machine is pressed into the tablet of 2～5mm, it is ground into the granule that particle diameter is 5～100 μm, putting in hot isostatic press and shape, adopt argon gas medium, heat up pressurization, it is incubated 3 hours under 2000 DEG C of sintering temperatures and 80MPa pressure, then Temperature fall, then carry out graphitizable high temperature process, process 48 hours at 2900 DEG C.And carry out crushing and classification, first use jaw crusher to carry out coarse pulverization, re-use the ultra-fine mechanical crusher crushing and classification of HHJ-10 laboratory, it is ensured that grain diameter and specific morphology disclosure satisfy that the requirement of the present invention.The graphite negative material of lithium ion battery granule finally prepared, its particle diameter (D50) is generally 15～25 μm, half-cell capacity 356.7mAh/g, efficiency 93.0% first, and the circulation at 45 DEG C in 400 weeks is expanded to 4.0%.
Embodiment 5
Asphalt is crushed to below 0.1mm, is alternately added petroleum coke (D50 is 24.1 μm) and asphalt powder mixes in kneading pot, wherein under stirring, the mass ratio of petroleum coke and asphalt is 8:2, carrying out kneading process, wherein, the temperature of kneading is 150 DEG C；The time mediated is 10 hours.After kneading terminates, tablet machine is pressed into the tablet of 2～5mm, it is ground into the granule that particle diameter is 5～100 μm, putting in hot isostatic press and shape, adopt argon gas medium, heat up pressurization, it is incubated 3 hours under 1800 DEG C of sintering temperatures and 80MPa pressure, then Temperature fall, then carry out graphitizable high temperature process, process 24 hours at 3000 DEG C.And carry out crushing and classification, first use jaw crusher to carry out coarse pulverization, re-use the ultra-fine mechanical crusher crushing and classification of HHJ-10 laboratory, it is ensured that grain diameter and specific morphology disclosure satisfy that the requirement of the present invention.The graphite negative material of lithium ion battery granule finally prepared, its particle diameter (D50) is generally 15～25 μm, half-cell capacity 358.4mAh/g, efficiency 92.8% first, and the circulation at 45 DEG C in 400 weeks is expanded to 4.6%.
Embodiment 6
Asphalt is crushed to below 0.1mm, is alternately added petroleum coke (D50 is 18.5 μm) and asphalt powder mixes in kneading pot, wherein under stirring, the mass ratio of petroleum coke and asphalt is 9:1, carrying out kneading process, wherein, the temperature of kneading is 150 DEG C；The time mediated is 1 hour.After kneading terminates, tablet machine is pressed into the tablet of 2～5mm, it is ground into the granule that particle diameter is 5～100 μm and puts into shaping in hot isostatic press, adopt argon gas medium, heat up pressurization, is incubated 3 hours, then Temperature fall under 1200 DEG C of sintering temperatures and 80MPa pressure, carry out graphitizable high temperature process again, process 36 hours in 3000 DEG C.And carry out crushing and classification, first use jaw crusher to carry out coarse pulverization, re-use the ultra-fine mechanical crusher crushing and classification of HHJ-10 laboratory, it is ensured that grain diameter and specific morphology disclosure satisfy that the requirement of the present invention.The graphite negative material of lithium ion battery granule finally prepared, its particle diameter (D50) is generally 15～25 μm, half-cell capacity 357.2mAh/g, efficiency 92.4% first, and the circulation at 45 DEG C in 400 weeks is expanded to 4.9%.
Embodiment 7
Modified coal asphalt is crushed to below 0.1mm, is alternately added pitch coke (D50 is 19.1 μm) and modified coal asphalt powder mixes in kneading pot, wherein under stirring, the mass ratio of pitch coke and modified coal asphalt is 8:2, carrying out kneading process, wherein, the temperature of kneading is 150 DEG C；The time mediated is 5 hours.After kneading terminates, tablet machine is pressed into the tablet of 2～5mm, it is ground into the granule that particle diameter is 5～100 μm, putting in hot isostatic press and shape, adopt argon gas medium, heat up pressurization, it is incubated 10 hours under 1200 DEG C of sintering temperatures and 100MPa pressure, then Temperature fall, then carry out graphitizable high temperature process, process 36 hours at 2800 DEG C.And carry out crushing and classification, first use jaw crusher to carry out coarse pulverization, re-use the ultra-fine mechanical crusher crushing and classification of HHJ-10 laboratory, it is ensured that grain diameter and specific morphology disclosure satisfy that the requirement of the present invention.The graphite negative material of lithium ion battery granule finally prepared, its particle diameter (D50) is generally 15～25 μm, half-cell capacity 355.6mAh/g, efficiency 92.6% first, and the circulation at 45 DEG C in 400 weeks is expanded to 5.8%.
Embodiment 8
It is alternately added in kneading pot and mixes under pitch coke (D50 is 19.5 μm) and Phenolic resin powder (Wuxi City A Erzi Chemical Co., Ltd.) stirring, wherein, the mass ratio of pitch coke and phenolic resin is 8:2, carries out kneading process, wherein, the temperature of kneading is 150 DEG C；The time mediated is 2 hours.After kneading terminates, tablet machine is pressed into the tablet of 2～5mm, it is ground into the granule that particle diameter is 5～100 μm, putting in hot isostatic press and shape, adopt argon gas medium, heat up pressurization, it is incubated 10 hours under 1200 DEG C of sintering temperatures and 100MPa pressure, then Temperature fall, then carry out graphitizable high temperature process, process 36 hours at 2800 DEG C.And carry out crushing and classification, first use jaw crusher to carry out coarse pulverization, re-use the ultra-fine mechanical crusher crushing and classification of HHJ-10 laboratory, it is ensured that grain diameter and specific morphology disclosure satisfy that the requirement of the present invention.The graphite negative material of lithium ion battery granule finally prepared, its particle diameter (D50) is generally 15～25 μm, half-cell capacity 357.2mAh/g, efficiency 92.3% first, and the circulation at 45 DEG C in 400 weeks is expanded to 5.6%.
Comparative example 1 (being called for short DBL1)
Asphalt is crushed to below 0.1mm, is alternately added petroleum coke (D50 is 19.5 μm) and asphalt powder mixes in kneading pot, wherein under stirring, the mass ratio of petroleum coke and asphalt is 8:2, carrying out kneading process, wherein, the temperature of kneading is 140 DEG C；The time mediated is 10 hours.After kneading terminates, tablet machine is pressed into the tablet of 2～5mm, pulverizes briquetting die forming.Under the protection of nitrogen, and at the temperature of 1200 DEG C, carbonization processes 120 minutes, is cooled to room temperature afterwards.And carry out crushing and classification, first use jaw crusher to carry out coarse pulverization, re-use the ultra-fine mechanical crusher crushing and classification of HHJ-10 laboratory, it is ensured that grain diameter and specific morphology disclosure satisfy that the requirement of the present invention.The graphite negative material of lithium ion battery granule finally prepared, its particle diameter is generally 15～25 μm, half-cell capacity 345.2mAh/g, efficiency 87.6% first, and the circulation at 45 DEG C in 400 weeks is expanded to 10.3%.
Comparative example 2 (being called for short DBL2)
According to the operation of the embodiment of the present invention 3, being distinctive in that and the operation of hip treatment replaces with the operation that isostatic cool pressing processes, wherein, the pressure waiting calm pressure is 60MPa, and the time is 1 hour.The graphite negative material of lithium ion battery granule finally prepared, half-cell capacity 354.5mAh/g, efficiency 89.1% first, the circulation at 45 DEG C in 400 weeks is expanded to 12.0%.
Comparative example 3 (being called for short DBL3)
According to the operation of the embodiment of the present invention 3, being distinctive in that the temperature in hip treatment, pressure are different with the time, wherein, the temperature of high temperature insostatic pressing (HIP) is 800 DEG C, and pressure is 30MPa, and the time is 5 hours.The graphite negative material of lithium ion battery granule finally prepared, half-cell capacity 354.8mAh/g, efficiency 91.5% first, the circulation at 45 DEG C in 400 weeks is expanded to 9.4%.
Effect example
Used by the present invention, half-cell method of testing is: graphite material that the preparation method of the embodiment of the present invention 1～8 prepares, N-Methyl pyrrolidone containing 6～7% Kynoar and 2% conductive black mix homogeneously, being applied on Copper Foil, it is that in 110 DEG C of vacuum drying ovens, vacuum drying 4 hours is standby that the pole piece coated is put into temperature.Simulated battery is assemblied in the German Braun glove box of applying argon gas and carries out, electrolyte is 1MLiPF6+EC:DEC:DMC=1:1:1 (volume ratio), metal lithium sheet is to electrode, electrochemical property test carries out on U.S. ArbinBT2000 type cell tester, charging/discharging voltage ranges for 0.005 to 1.0V, and charge-discharge velocity is 0.1C.
The present invention full battery testing method used is: the graphite material that the embodiment of the present invention 1～8 or comparative example 1～3 prepare makes negative pole, cobalt acid lithium makes positive pole, 1M-LiPF6EC:DMC:EMC=1:1:1 (volume ratio) solution is done electrolyte assembling and is helped battery, test 500 weeks capability retentions of 1C charge and discharge are more than 90%, and the capability retention of the graphite cathode material that embodiment 2 prepares can reach 90.7% as shown in Figure 1.
The performance parameter of each embodiment and comparative example is as shown in the table:
As can be seen from the above table data, the tap density of comparative example 1 is low, and discharging efficiency is low first, for 345.2mAh/g, and circulation expands big, the tap density that comparative example 2 isostatic cool pressing prepares negative material is low, and discharge capacity is low, for 354.5mAh/g, and circulation expands big, the tap density of comparative example 3 is low, and discharge capacity and efficiency are low first, and circulation expands big；Adopting negative material prepared by the method for the invention, tap density can control more than or equal to 1.20g/cm3, discharge capacity is up to more than 355mAh/g.
Discharge capacity and the tap density of the graphite negative material of lithium ion battery obtained by the present invention are higher, reduce the loss of irreversible capacity, improve energy density, reduce the consumption of positive pole；Specific surface area controls in suitable scope, both can guarantee that particle surface pore was flourishing, is conducive to again suppressing lithium-ion battery system to produce ballooning, and the security performance of battery is good；Over-charging is better；Good cycle, after circulating 500 times, capability retention is more than 90%.
Claims (10)
1. the preparation method of a graphite negative material of lithium ion battery, it is characterised in that it comprises the steps of
(1) kneading processes: mediates coking powder and binding agent, obtains kneaded material；
(2) hip treatment: described kneaded material is carried out hip treatment, obtains kneaded material formed body；The temperature of described hip treatment is 1000～2000 DEG C, and the pressure of described hip treatment is 50～100MPa；The time of described hip treatment is 1～10 hour；
(3) graphitization processing；
(4) crushing and classification,.
2. preparation method as claimed in claim 1, it is characterised in that in step (1), described coking powder is petroleum coke and/or pitch coke；And/or, the median particle diameter of described coking powder is 15～25 μm；And/or, described binding agent is one or more in asphalt, coal tar pitch, phenolic resin and epoxy resin；Described coal tar pitch is preferably modified coal asphalt；And/or, the mass ratio of described binding agent and described coking powder is 1:9～9:1.
3. preparation method as claimed in claim 1, it is characterised in that in step (1), the method for described kneading and condition be: is alternately added in kneading pot with binding agent by coking powder and mixes；And/or, the temperature of described kneading is 100～180 DEG C；And/or, the time of described kneading is 1～10 hour.
4. preparation method as claimed in claim 1, it is characterised in that in step (1), also carry out tabletting process after described kneading.
5. preparation method as claimed in claim 1, it is characterized in that, in step (1), after described kneading, before described tabletting processes, also carry out operations described below: in tablet machine, described kneaded material is pressed into the tablet that thickness is 2～5mm, is ground into the granule that particle diameter is 5～100 μm.
6. preparation method as claimed in claim 1, it is characterised in that in step (2), the temperature of described hip treatment is 1500 DEG C～2000 DEG C；And/or, the time of described hip treatment is 3～5 hours；And/or, described hip treatment carries out under inert atmosphere protection；The described gas in inert atmosphere is argon；And/or, in step (2), after described hip treatment terminates, also carry out cooling process.
7. preparation method as claimed in claim 1, it is characterised in that in step (3), the temperature of described graphitization processing is 2800～3000 DEG C；And/or, the time of described graphitization processing is 24～48 hours.
8. preparation method as claimed in claim 1, it is characterised in that in step (4), the operation of described crushing and classification is: first carries out coarse pulverization and carries out Crushing of Ultrafine again；After the operation of described crushing and classification terminates, the median particle diameter of the graphite negative material of lithium ion battery granule obtained is 15～25 μm.
9. the graphite negative material of lithium ion battery that the preparation method described in any one of claim 1～8 prepares.
10. graphite negative material of lithium ion battery as claimed in claim 9, it is characterised in that the median particle diameter of described graphite negative material of lithium ion battery is 15～25 μm；Its true density >=2.20g/cm3；Its ash≤0.10%；Its tap density >=1.20g/cm3；Its specific surface area is 2.5～3.5m2/g；It is discharge capacity >=355 first；It is discharging efficiency >=92% first.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410749026.6A CN105742636A (en) | 2014-12-09 | 2014-12-09 | Graphite negative electrode material for lithium-ion battery and preparation method of graphite negative electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410749026.6A CN105742636A (en) | 2014-12-09 | 2014-12-09 | Graphite negative electrode material for lithium-ion battery and preparation method of graphite negative electrode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105742636A true CN105742636A (en) | 2016-07-06 |
Family
ID=56238647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410749026.6A Pending CN105742636A (en) | 2014-12-09 | 2014-12-09 | Graphite negative electrode material for lithium-ion battery and preparation method of graphite negative electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105742636A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106430143A (en) * | 2016-08-26 | 2017-02-22 | 上海杉杉科技有限公司 | Preparing method of high- capacity intermediate phase coal micro powder |
| CN107161995A (en) * | 2017-06-24 | 2017-09-15 | 平顶山市天宝碳素制造有限公司 | A kind of preparation method of low-density and high-strength high purity graphite |
| CN107871866A (en) * | 2016-09-27 | 2018-04-03 | 宁波杉杉新材料科技有限公司 | A kind of preparation method of high magnification natural graphite negative electrode material |
| CN113023724A (en) * | 2021-02-26 | 2021-06-25 | 四川东岛新能源有限公司 | Preparation method of high-rate graphite negative electrode material for lithium ion power battery |
| CN113526956A (en) * | 2021-06-24 | 2021-10-22 | 湛江市聚鑫新能源有限公司 | Low-cost long-cycle graphite negative electrode material and preparation method and application thereof |
| CN115196630A (en) * | 2022-06-07 | 2022-10-18 | 谢艳 | Preparation method for improving tap density of carbon electrode material for energy storage device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033064A (en) * | 2006-03-07 | 2007-09-12 | 宁波杉杉新材料科技有限公司 | Method of preparing isotropic carbon material and prepared carbon material |
| CN102502594A (en) * | 2011-10-14 | 2012-06-20 | 上海理工大学 | Method for preparing isotropic graphite containing coal-based needle coke as aggregate |
| CN102557015A (en) * | 2010-12-31 | 2012-07-11 | 上海杉杉科技有限公司 | Carbon material with isotropic fine structure and preparation method for same |
| CN102593434A (en) * | 2011-01-11 | 2012-07-18 | 上海杉杉科技有限公司 | Composite graphite particles for lithium secondary battery and preparation method thereof |
-
2014
- 2014-12-09 CN CN201410749026.6A patent/CN105742636A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033064A (en) * | 2006-03-07 | 2007-09-12 | 宁波杉杉新材料科技有限公司 | Method of preparing isotropic carbon material and prepared carbon material |
| CN102557015A (en) * | 2010-12-31 | 2012-07-11 | 上海杉杉科技有限公司 | Carbon material with isotropic fine structure and preparation method for same |
| CN102593434A (en) * | 2011-01-11 | 2012-07-18 | 上海杉杉科技有限公司 | Composite graphite particles for lithium secondary battery and preparation method thereof |
| CN102502594A (en) * | 2011-10-14 | 2012-06-20 | 上海理工大学 | Method for preparing isotropic graphite containing coal-based needle coke as aggregate |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106430143A (en) * | 2016-08-26 | 2017-02-22 | 上海杉杉科技有限公司 | Preparing method of high- capacity intermediate phase coal micro powder |
| CN107871866A (en) * | 2016-09-27 | 2018-04-03 | 宁波杉杉新材料科技有限公司 | A kind of preparation method of high magnification natural graphite negative electrode material |
| CN107161995A (en) * | 2017-06-24 | 2017-09-15 | 平顶山市天宝碳素制造有限公司 | A kind of preparation method of low-density and high-strength high purity graphite |
| CN113023724A (en) * | 2021-02-26 | 2021-06-25 | 四川东岛新能源有限公司 | Preparation method of high-rate graphite negative electrode material for lithium ion power battery |
| CN113526956A (en) * | 2021-06-24 | 2021-10-22 | 湛江市聚鑫新能源有限公司 | Low-cost long-cycle graphite negative electrode material and preparation method and application thereof |
| CN115196630A (en) * | 2022-06-07 | 2022-10-18 | 谢艳 | Preparation method for improving tap density of carbon electrode material for energy storage device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107369823B (en) | Artificial graphite composite negative electrode material for lithium ion battery and preparation method thereof | |
| CN105731427B (en) | A kind of graphite negative material of lithium ion battery and preparation method thereof | |
| CN102593434B (en) | Composite graphite particles for lithium secondary battery and preparation method thereof | |
| CN104143635B (en) | A kind of artificial plumbago negative pole material and preparation method thereof | |
| CN103887502B (en) | A kind of Delanium lithium ion battery negative material and preparation method thereof | |
| CN110642247A (en) | Artificial graphite negative electrode material, preparation method thereof and lithium ion battery | |
| CN106058304A (en) | Artificial graphite negative electrode material used for lithium ion power batteries, and preparation method thereof | |
| CN104218214B (en) | A kind of lithium ion battery negative material and preparation method thereof | |
| CN105742636A (en) | Graphite negative electrode material for lithium-ion battery and preparation method of graphite negative electrode material | |
| CN103311520B (en) | A kind of lithium ion battery composite graphite negative electrode material and preparation method thereof | |
| CN113526500B (en) | Preparation method of high-performance artificial graphite anode material | |
| CN104143641B (en) | A kind of interphase negative material and preparation method thereof | |
| CN101908627B (en) | Cathode material of lithium ion secondary battery and preparation method thereof | |
| CN114597361A (en) | Artificial graphite composite negative electrode material for lithium ion battery and preparation method and application thereof | |
| CN103811717A (en) | Power lithium-ion battery negative electrode material with core-shell structure and preparation method thereof | |
| CN111244453B (en) | Artificial composite graphite negative electrode material, lithium ion battery, preparation method and application | |
| CN103794790A (en) | Lithium ion battery composite graphite negative electrode material and preparation method thereof | |
| CN103165869A (en) | Modified intermediate phase anode material, lithium ion secondary battery and preparation method and application | |
| CN105355841A (en) | High-capacity and high-rate lithium battery anode material and preparation method thereof | |
| CN105047928A (en) | High-tap-density graphite anode material and preparation method thereof | |
| CN115347176A (en) | Graphite-based composite negative electrode material and preparation method and application thereof | |
| CN104900878B (en) | Production method of artificial graphite anode material for high-capacity lithium ion battery | |
| CN103219520B (en) | Graphite cathode material of lithium ion battery and preparation method thereof | |
| CN113023724A (en) | Preparation method of high-rate graphite negative electrode material for lithium ion power battery | |
| CN111232969B (en) | Composite intermediate phase negative electrode material, lithium ion secondary battery, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160706 |
|
| RJ01 | Rejection of invention patent application after publication |