CN105731427A - Lithium ion battery graphite anode material and preparation method thereof - Google Patents
Lithium ion battery graphite anode material and preparation method thereof Download PDFInfo
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- CN105731427A CN105731427A CN201410767840.0A CN201410767840A CN105731427A CN 105731427 A CN105731427 A CN 105731427A CN 201410767840 A CN201410767840 A CN 201410767840A CN 105731427 A CN105731427 A CN 105731427A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 43
- 239000010439 graphite Substances 0.000 title claims abstract description 43
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000010405 anode material Substances 0.000 title abstract 3
- 238000000465 moulding Methods 0.000 claims abstract description 22
- 238000003763 carbonization Methods 0.000 claims abstract description 20
- 238000005087 graphitization Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 49
- 239000010426 asphalt Substances 0.000 claims description 20
- 238000010298 pulverizing process Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 8
- 230000001404 mediated effect Effects 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000011294 coal tar pitch Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 238000004898 kneading Methods 0.000 abstract description 40
- 229910021382 natural graphite Inorganic materials 0.000 abstract description 16
- 239000002245 particle Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 238000001513 hot isostatic pressing Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 230000004087 circulation Effects 0.000 description 17
- 239000010406 cathode material Substances 0.000 description 11
- 239000007770 graphite material Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 230000001105 regulatory effect Effects 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 10
- 238000003825 pressing Methods 0.000 description 10
- 238000005245 sintering Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000003245 coal Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 239000011302 mesophase pitch Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium ion battery graphite anode material and a preparation method thereof. The preparation method includes the steps of: 1) heating and kneading a mixture of natural graphite and an adhesive; 2) performing hot isostatic pressing moulding at 500-1000 DEG C under 50-100 MPa; 3) performing carbonization; 4) performing graphitization; and 5) crushing and classifying a product. The lithium ion battery graphite anode material has high tap density, large discharge capacity and good cycle performance, is reduced in internal pores of graphite particles, reduces expansion and is improved in cycle performance.
Description
Technical field
The present invention relates to field of lithium ion battery, particularly relate 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, uses lithium ion battery to have higher energy density.Although having been directed towards improving battery capacity at present and having carried out widely studied, 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).
Native graphite has significantly high capacitance (> 350mAh/g), there is structural instability in shortcoming, when improving squeeze pressure to obtain higher electrode density, graphite cathode granule is prone to and collector orientation abreast, whole electrode produces consistent orientation, 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, prior art is frequently used calcining and carries out the preparation of high-tap density graphite cathode material with the interpolation mode that combines of Colophonium.
Japan Patent JP2000-182617 is by contour for flake natural graphite crystalline graphite and Colophonium or mixed with resin, size-reduced, carbonization, graphitization and make complex, it is possible to improving the deficiency of native graphite, namely first charge-discharge efficiency is high, cycle characteristics is excellent, and capacity is big and coating is excellent.
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 above-mentioned graphite cathode material there is problems of when high-tap density uses, break due to graphite cathode material and expose the more surface area reacted with electrolyte, accelerate the reaction with electrolyte, cause the reduction of efficiency for charge-discharge, the problem simultaneously bringing poor stability；And big electric current (3C～5C) charge-discharge performance of these graphite cathode materials is not good, under 3C～5C discharge and recharge, capability retention is less than 70%.
Further, since high-tap density causes that granule is easily broken, serve as in the electrodes lithium ion tunnel space reduce, damage lithium ion mobility, cause 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 in the present invention is in that to overcome the defect that graphite negative material of lithium ion battery tap density in prior art is low, graphite granule internal void big, graphite cathode material cycle performance electric current bad, big (3C～5C) charge-discharge performance is not good, it is provided that a kind of lithium ion battery graphite cathode material and preparation method thereof.The preparation method of the present invention can improve the tap density of graphite cathode material, reduces graphite granule internal void, reduces and expands thus improving the cycle performance of material.
The present invention solves above-mentioned technical problem by the following technical programs:
The preparation method that the invention provides a kind of graphite negative material of lithium ion battery, it comprises the steps: 1. to be heated the mixture of native graphite Yu binding agent mediating；2. hip moulding；3. carbonization processes；4. graphitization processing；5. crushing and classification,；The temperature of described hip moulding is 500～1000 DEG C, and pressure is 50～100MPa.
Step 1. in, described native graphite can be various natural graphite starting material commonly used in the art, it is preferred that for spherical natural graphite.The median D50 of described native graphite is preferably 15～25 μm.
Step 1. in, described binding agent is preferably one or more in asphalt, coal tar pitch, phenolic resin and epoxy resin.
The mass ratio of described binding agent and described native graphite is preferably (1:9)～(5:5).
The temperature that described heating is mediated is preferably 100～180 DEG C.
Step 2. in, the time of described hip moulding is preferably 1～10 hour, is more preferably 1～3 hour.Step 2. in after hip moulding processes, it is possible to improve native graphite circulation expansion character and extend its service life cycle.
Step 3. in, the temperature that described carbonization processes is preferably 1100～2000 DEG C, and the time that described carbonization processes is preferably 1～10 hour.
Step 4. in, the method of described graphitization processing and condition can be method and the condition of this area ordinary graphiteization process, it is generally adopted the graphitization finishing stove of routine, the temperature of described graphitization processing is preferably 2800～3000 DEG C, and the time of described graphitization processing is preferably 24～48 hours.
Step 5. in, described crushing and classification is not particularly limited, and generally first carries out coarse pulverization, then carries out Crushing of Ultrafine, it is preferred that for being crushed to till the median D50 of product is 15～25 μm.Described coarse pulverization can use jaw crusher to carry out coarse pulverization.Crushing of Ultrafine can use the ultra-fine mechanical crusher crushing and classification of HHJ-10 laboratory that Weifang Zhengyuan Powder Engineering Equipment Co., Ltd. produces, the preferred grader main frame frequency of fine parameter is 5～100HZ, outer classification rotating speed is 1000～1500 revs/min, it is ensured that grain diameter and specific morphology disclosure satisfy that the requirement of the present invention preferably technical scheme.
The granule-morphology of the product of the present invention is re-compounded specific morphology: composite particles is inside and outside forms homogeneous hole, to reduce the Volumetric expansion in long circulating charge and discharge process.
Present invention also offers a kind of graphite negative material of lithium ion battery prepared by above-mentioned preparation method.
The negative material obtained by the preparation method of the present invention can efficiently solve current material Problems existing, described graphite be a kind of warp with can graphited binding agent is mediated and hip moulding processes natural graphite negative electrode material.Wherein native graphite is with binding agent heating kneading, hip moulding, carbonization process, graphitizable high temperature processes and crushing and classification process is simple and easy to do, and raw material sources are extensive and with low cost.Owing to have employed heating and mediating, the method such as hip moulding and crushing and classification, cause that the product tap density prepared is high, discharge capacity is big and good cycle, and its performance parameter is as shown in the table.
Meeting on the basis of this area general knowledge, 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: the graphite cathode material of the present invention, effectively improve processing characteristics, improve discharge capacity and cycle efficieny, efficiency for charge-discharge is high, small amount of expansion during charging, the high comprehensive performance of its button cell made, mainly has the advantage that 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 360mAh/g；3. discharge platform and platform conservation rate are higher；4. high rate during charging-discharging is better, and under 3C～5C discharge and recharge, capability retention is more than 80%；5. good cycle (500 circulations, capacity keeps >=89%)；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.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the graphite cathode material of the embodiment of the present invention 1.
Fig. 2 is the cycle performance curve of the graphite cathode material of the embodiment of the present invention 6.
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.
Embodiment 1
Asphalt is crushed to below 0.1mm, being alternately added 20kg spherical natural graphite (D50 is 19.1 μm) under stirring and 5kg asphalt powder mixes in kneading pot, carry out kneading process, the temperature of kneading is 100 DEG C, after kneading terminates, tablet machine is pressed into lamellar, pulverizes, put into molding in hot isostatic press, adopt argon gas medium, heat up pressurization, is incubated 1 hour, then Temperature fall under 500 DEG C of sintering temperatures and 50MPa pressure.Under the protection of nitrogen, and at the temperature of 1300 DEG C, carbonization processes 300 minutes, product is cooled to room temperature afterwards, then carries out graphitizable high temperature process (2800 DEG C) 48 hours.And carry out crushing and classification, first coarse pulverization, again Crushing of Ultrafine, regulating Crushing of Ultrafine grader main frame frequency is 15.35Hz, sets outer classification rotating speed as 1000 revs/min, prepares lithium ion battery negative high temperature insostatic pressing (HIP) graphite material.Half-cell capacity 362.5mAh/g, efficiency 92.8% first, 45 DEG C of circulation expansions 7.5% in 400 weeks.
The granule-morphology of the product of the present embodiment is re-compounded specific morphology: composite particles is inside and outside forms homogeneous hole, and to reduce the Volumetric expansion in long circulating charge and discharge process, specific granule-morphology asks for an interview accompanying drawing 1.
Embodiment 2
Asphalt is crushed to below 0.1mm, being alternately added 20kg spherical natural graphite (D50 is 19.5 μm) under stirring and 5kg asphalt powder mixes in kneading pot, carry out kneading process, the temperature of kneading is 120 DEG C, after kneading terminates, tablet machine is pressed into lamellar, pulverizes, put into molding in hot isostatic press, adopt argon gas medium, heat up pressurization, is incubated 1 hour, then Temperature fall under 500 DEG C of sintering temperatures and 50MPa pressure.Under the protection of nitrogen, and at the temperature of 1100 DEG C, carbonization processes 360 minutes, product is cooled to room temperature afterwards, then carries out graphitizable high temperature process (3000 DEG C) 48 hours.And carry out crushing and classification, first coarse pulverization, again Crushing of Ultrafine, regulating Crushing of Ultrafine grader main frame frequency is 5.26Hz, sets outer classification rotating speed as 1200 revs/min, prepares lithium ion battery negative high temperature insostatic pressing (HIP) graphite material.Half-cell capacity 363.1mAh/g, efficiency 93.2% first, 45 DEG C of circulation expansions 8.0% in 400 weeks.Granule-morphology is with embodiment 1.
Embodiment 3
Modified coal asphalt is crushed to below 0.1mm, being alternately added 12.5kg spherical natural graphite (D50 is 20.1 μm) under stirring and 12.5kg asphalt powder mixes in kneading pot, carry out kneading process, the temperature of kneading is 160 DEG C, after kneading terminates, tablet machine is pressed into lamellar, pulverizes, put into molding in hot isostatic press, adopt argon gas medium, heat up pressurization, is incubated 1 hour, then Temperature fall under 500 DEG C of sintering temperatures and 60MPa pressure.Under the protection of nitrogen, and at the temperature of 1500 DEG C, carbonization processes 180 minutes, product is cooled to room temperature afterwards, then carries out graphitizable high temperature process (3000 DEG C) 24 hours.And carry out crushing and classification, first coarse pulverization, again Crushing of Ultrafine, regulating Crushing of Ultrafine grader main frame frequency is 54Hz, sets outer classification rotating speed as 1300 revs/min, prepares lithium ion battery negative high temperature insostatic pressing (HIP) graphite material.Half-cell capacity 365.0mAh/g, efficiency 92.6% first, 45 DEG C of circulation expansions 6.7% in 400 weeks.Granule-morphology is with embodiment 1.
Embodiment 4
Modified coal asphalt is crushed to below 0.1mm, being alternately added 17.5kg spherical natural graphite (D50 is 15.2 μm) under stirring and 7.5kg asphalt powder mixes in kneading pot, carry out kneading process, the temperature of kneading is 180 DEG C, after kneading terminates, tablet machine is pressed into lamellar, pulverizes, put into molding in hot isostatic press, adopt argon gas medium, heat up pressurization, is incubated 3 hours, then Temperature fall under 800 DEG C of sintering temperatures and 80MPa pressure.Under the protection of nitrogen, and at the temperature of 1600 DEG C, carbonization processes 60 minutes, product is cooled to room temperature afterwards, then carries out graphitizable high temperature process (2900 DEG C) 36 hours.And carry out crushing and classification, first coarse pulverization, again Crushing of Ultrafine, regulating Crushing of Ultrafine grader main frame frequency is 100Hz, sets outer classification rotating speed as 1500 revs/min, prepares lithium ion battery negative high temperature insostatic pressing (HIP) graphite material.Half-cell capacity 366.7mAh/g, efficiency 93.0% first, 45 DEG C of circulation expansions 8.4% in 400 weeks.Granule-morphology is with embodiment 1.
Embodiment 5
Asphalt is crushed to below 0.1mm, being alternately added 17.5kg spherical natural graphite (D50 is 24.1 μm) under stirring and 7.5kg asphalt powder mixes in kneading pot, carry out kneading process, the temperature of kneading is 170 DEG C, after kneading terminates, tablet machine is pressed into lamellar, pulverizes, put into molding in hot isostatic press, adopt argon gas medium, heat up pressurization, is incubated 3 hours, then Temperature fall under 800 DEG C of sintering temperatures and 80MPa pressure.Under the protection of nitrogen, and at the temperature of 1100 DEG C, carbonization processes 600 minutes, product is cooled to room temperature afterwards, then carries out graphitizable high temperature process (3000 DEG C) 48 hours.And carry out crushing and classification, first coarse pulverization, again Crushing of Ultrafine, regulating Crushing of Ultrafine grader main frame frequency is 47.22Hz, sets outer classification rotating speed as 1000 revs/min, prepares lithium ion battery negative high temperature insostatic pressing (HIP) graphite material.Half-cell capacity 362.4mAh/g, efficiency 92.8% first, 45 DEG C of circulation expansions 7.3% in 400 weeks.Granule-morphology is with embodiment 1.
Embodiment 6
Asphalt is crushed to below 0.1mm, being alternately added 22.5kg spherical natural graphite (D50 is 18.5 μm) under stirring and 2.5kg asphalt powder mixes in kneading pot, carry out kneading process, the temperature of kneading is 160 DEG C, after kneading terminates, tablet machine is pressed into lamellar, pulverizes, put into molding in hot isostatic press, adopt argon gas medium, heat up pressurization, is incubated 3 hours, then Temperature fall under 800 DEG C of sintering temperatures and 80MPa pressure.Under the protection of nitrogen, and at the temperature of 1100 DEG C, carbonization processes 300 minutes, product is cooled to room temperature afterwards, then carries out graphitizable high temperature process (3000 DEG C) 48 hours.And carry out crushing and classification, first coarse pulverization, again Crushing of Ultrafine, regulating Crushing of Ultrafine grader main frame frequency is 15.67Hz, sets outer classification rotating speed as 1100 revs/min, prepares lithium ion battery negative high temperature insostatic pressing (HIP) graphite material.Half-cell capacity 366.1mAh/g, efficiency 92.4% first, 45 DEG C of circulation expansions 5.4% in 400 weeks.Granule-morphology is with embodiment 1.
Embodiment 7
It is alternately added 17.5kg spherical natural graphite (D50 is 19.1 μm) under stirring and 7.5kg epoxy powder mixes in kneading pot, carry out kneading process, the temperature mediated is 140 DEG C, mediates after terminating, is pressed into lamellar in tablet machine, pulverize, putting into molding in hot isostatic press, adopt argon gas medium, heat up pressurization, it is incubated 10 hours, then Temperature fall under 1000 DEG C of sintering temperatures and 100MPa pressure.Under the protection of nitrogen, and at the temperature of 1100 DEG C, carbonization processes 300 minutes, product is cooled to room temperature afterwards, then carries out graphitizable high temperature process (2800 DEG C) 30 hours.And carry out crushing and classification, first coarse pulverization, again Crushing of Ultrafine, regulating Crushing of Ultrafine grader main frame frequency is 49.38Hz, sets outer classification rotating speed as 1000 revs/min, prepares lithium ion battery negative high temperature insostatic pressing (HIP) graphite material.Half-cell capacity 363.6mAh/g, efficiency 92.6% first, 45 DEG C of circulation expansions 6.9% in 400 weeks.Granule-morphology is with embodiment 1.
Embodiment 8
It is alternately added in kneading pot and mixes under 20kg spherical natural graphite (D50 is 19.5 μm) and 5kg Phenolic resin powder (Wuxi City A Erzi Chemical Co., Ltd.) stirring, carry out kneading process, the temperature mediated is 160 DEG C, mediates after terminating, is pressed into lamellar in tablet machine, pulverize, putting into molding in hot isostatic press, adopt argon gas medium, heat up pressurization, it is incubated 10 hours, then Temperature fall under 1000 DEG C of sintering temperatures and 100MPa pressure.Under the protection of nitrogen, and at the temperature of 1100 DEG C, carbonization processes 300 minutes, product is cooled to room temperature afterwards, then carries out graphitizable high temperature process (2800 DEG C) 24 hours.And carry out crushing and classification, first coarse pulverization, again Crushing of Ultrafine, regulating Crushing of Ultrafine grader main frame frequency is 9.22Hz, sets outer classification rotating speed as 1000 revs/min, prepares lithium ion battery negative high temperature insostatic pressing (HIP) graphite material.Half-cell capacity 362.7mAh/g, efficiency 92.3% first, 45 DEG C of circulation expansions 7.1% in 400 weeks.Granule-morphology is with embodiment 1.
Comparative example 1
Asphalt is crushed to below 0.1mm, it is alternately added 17.5kg spherical natural graphite (D50 is 19.5 μm) under stirring and 7.5kg asphalt powder mixes in kneading pot, carry out kneading process, the temperature mediated is 150 DEG C, after kneading terminates, tablet machine is pressed into lamellar, pulverizes compound stalk forming.Under the protection of nitrogen, and at the temperature of 1100 DEG C, carbonization processes 120 minutes, afterwards product is cooled to room temperature.And carry out crushing and classification, first coarse pulverization, again Crushing of Ultrafine, regulating Crushing of Ultrafine grader main frame frequency is 16.41Hz, set outer classification rotating speed as 1000 revs/min, prepare graphite material at negative, half-cell capacity 345.2mAh/g, efficiency 87.6% first, 45 DEG C of circulation expansions 15.3% in 400 weeks.
Comparative example 2
Modified coal asphalt is crushed to below 0.1mm, it is alternately added 17.5 kilograms of spherical natural graphites (D50 is 15.2 μm) under stirring and 7.5 kilograms of asphalt powders mix in kneading pot, carry out kneading process, the temperature mediated is 120 DEG C, after kneading terminates, tablet machine is pressed into lamellar, pulverizes, put into molding in cold isostatic press.Under the protection of nitrogen, and at the temperature of 1600 DEG C, carbonization processes 60 minutes, afterwards product is cooled to room temperature.Carry out graphitizable high temperature process (3000 DEG C) 48 hours again.And carry out crushing and classification, first coarse pulverization, again Crushing of Ultrafine, regulating Crushing of Ultrafine grader main frame frequency is 15.64Hz, sets outer classification rotating speed as 1000 revs/min, prepares lithium ion battery negative cold isostatic pressing formed graphite material.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
Modified coal asphalt is crushed to below 0.1mm, being alternately added 12.5kg spherical natural graphite (D50 is 20.1 μm) under stirring and 12.5kg asphalt powder mixes in kneading pot, carry out kneading process, the temperature of kneading is 160 DEG C, after kneading terminates, tablet machine is pressed into lamellar, pulverizes, put into molding in hot isostatic press, adopt argon gas medium, heat up pressurization, is incubated 5 hours, then Temperature fall under 400 DEG C of sintering temperatures and 30MPa pressure.Under the protection of nitrogen, and at the temperature of 1500 DEG C, carbonization processes 180 minutes, product is cooled to room temperature afterwards, then carries out graphitizable high temperature process (3000 DEG C) 24 hours.And carry out crushing and classification, first coarse pulverization, again Crushing of Ultrafine, regulating Crushing of Ultrafine grader main frame frequency is 54Hz, sets outer classification rotating speed as 1300 revs/min, prepares lithium ion battery negative high temperature insostatic pressing (HIP) graphite material.Half-cell capacity 354.8mAh/g, efficiency 91.5% first, 45 DEG C of circulation expansions 11.4% in 400 weeks.
Used by the present invention, half-cell method of testing is: graphite sample, 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 of the embodiment of the present invention or comparative example 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 89.4%, as in figure 2 it is shown, test sample is embodiment 6 gained sample.
The performance parameter of each embodiment and comparative example is as shown in the table:
From data above it can be seen that the product tap density of comparative example 1 is low, discharging efficiency is low first, is 87.6%, and discharge capacity is only 345.2mAh/g, and circulation expands big, and under 3C～5C discharge and recharge, capability retention is low；The tap density that comparative example 2 isostatic cool pressing prepares negative material is low, and discharge capacity is low, and for 354.5mAh/g, and circulation expands big, and under 3C～5C discharge and recharge, capability retention is low；The tap density of comparative example 3 is low, and discharge capacity and efficiency are low first, and circulation expands big, and under 3C～5C discharge and recharge, capability retention is low；Adopting negative material prepared by the preparation method of the present invention, tap density can control more than or equal to 1.20g/cm3, discharge capacity up to capability retention under more than 360mAh/g, 3C～5C discharge and recharge more than 80%.
The product gram volume of the present invention and tap density 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, and porosity can reach 5～6%, is conducive to again suppressing lithium-ion battery system to produce ballooning, the security performance of battery good (130 DEG C/60 minutes, not quick-fried, do not rise)；Over-charging is better；Good cycle, after circulating 500 times, capability retention can reach 89.4%, uses the shortcoming of cycle performance difference to significantly improve effect for natural graphite negative electrode material at high-tap density, as shown in Figure 2.Electrolyte and other additive adaptability is better, and 0 DEG C of circulation in 10 weeks is without analysis lithium, and big electric current (3C～5C) charge-discharge performance is good, and capability retention is more than 80%.And existing product big electric current (3C～5C) discharge and recharge inferior pole piece analysis lithium, capability retention, about 50%, is only capable of under 2C discharge and recharge and uses.
Claims (10)
1. a preparation method for graphite negative material of lithium ion battery, it comprises the steps: 1. to be heated the mixture of native graphite Yu binding agent mediating；2. hip moulding；3. carbonization processes；4. graphitization processing；5. crushing and classification,；The temperature of described hip moulding is 500～1000 DEG C, and the pressure of described hip moulding is 50～100MPa.
2. preparation method as claimed in claim 1, it is characterised in that the median D50 of described native graphite is 15～25 μm；
Described binding agent is one or more in asphalt, coal tar pitch, phenolic resin and epoxy resin；
The mass ratio of described binding agent and described native graphite is (1:9)～(5:5).
3. preparation method as claimed in claim 1, it is characterised in that the temperature that described heating is mediated is 100～180 DEG C.
4. preparation method as claimed in claim 1, it is characterised in that the time of described hip moulding is 1～10 hour.
5. preparation method as claimed in claim 1, it is characterised in that the temperature that described carbonization processes is 1100～2000 DEG C, and the time that described carbonization processes is 1～10 hour.
6. preparation method as claimed in claim 1, it is characterised in that the temperature of described graphitization processing is 2800～3000 DEG C, and the time of described graphitization processing is 24～48 hours.
7. preparation method as claimed in claim 1, it is characterised in that described crushing and classification is for first carrying out coarse pulverization, then carries out Crushing of Ultrafine.
8. preparation method as claimed in claim 7, it is characterised in that described fine parameter is: grader main frame frequency is 5～100HZ, and outer classification rotating speed is 1000～1500 revs/min.
9. preparation method as claimed in claim 1, it is characterised in that described crushing and classification is be crushed to till the median D50 of product is 15～25 μm.
10. the graphite negative material of lithium ion battery that the preparation method according to any one of such as claim 1～9 prepares.
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