CN101552333B - Method of preparing carbon anode active material of lithium-ion battery - Google Patents
Method of preparing carbon anode active material of lithium-ion battery Download PDFInfo
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- CN101552333B CN101552333B CN2009100975195A CN200910097519A CN101552333B CN 101552333 B CN101552333 B CN 101552333B CN 2009100975195 A CN2009100975195 A CN 2009100975195A CN 200910097519 A CN200910097519 A CN 200910097519A CN 101552333 B CN101552333 B CN 101552333B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 39
- 239000006183 anode active material Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000002407 reforming Methods 0.000 claims abstract description 50
- 238000005087 graphitization Methods 0.000 claims abstract description 46
- 238000003763 carbonization Methods 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 37
- 238000009826 distribution Methods 0.000 claims abstract description 33
- 239000011280 coal tar Substances 0.000 claims abstract description 18
- 239000003208 petroleum Substances 0.000 claims abstract description 13
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 4
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 51
- 239000002245 particle Substances 0.000 claims description 41
- 239000003595 mist Substances 0.000 claims description 38
- 238000010298 pulverizing process Methods 0.000 claims description 30
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 239000011859 microparticle Substances 0.000 abstract 2
- 244000228957 Ferula foetida Species 0.000 abstract 1
- 210000001699 lower leg Anatomy 0.000 abstract 1
- 239000000047 product Substances 0.000 description 48
- 238000005056 compaction Methods 0.000 description 17
- 239000012299 nitrogen atmosphere Substances 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- 238000002156 mixing Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000010439 graphite Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000011295 pitch Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000011849 charcoal-based material Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
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- 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 relates to a method of preparing carbon anode active material of lithium-ion battery. The prepartion method includes following steps: a materials selection step, selecting heavy productsof coal tar processing, heavy products of petroleum processing, heavy products of hydrocarbon polycondensation or, one or multiple of their low-temperature carbonization products as materials; a crus hing step, crushing materials obtained from the material selection step into micro-particles with an average grain diameter of 3-80 Mum and granularity distribution range of 0-160 Mum; a thermal chemistry reforming step, in inert atmosphere, the micro-particles obtained by the crushing step is thermal chemistry reformed in moving state; a carbonization or carbonization, graphitization step, products from the thermal chemistry reforming step is proceeded with carbonization or carbonization, graphitization. The lithium-ion battery of carbon anode active material prepared by using the invention is provided with advantages of stable quality, excellent circulation performance, outstanding antidamping ability, high volume electrochemicalspecific capacity.
Description
Technical field
The present invention relates to a kind of preparation method of carbon anode active material of lithium-ion battery.
Background technology
At present, the practicability lithium ion battery negative material is still with based on the charcoal based material, by sources or base belong to and dividing, mainly contain Delanium and native graphite two big classes.Hard carbon class material is early to be found the negative electrode active material with better cycle characteristics, and these characteristics are subjected to the influence of charge-discharge magnification hardly, but owing to have the higher significant deficiency of irreversible capacity loss, thereby never drop into and use.
In the existing typical carbon anode active material manufacturing technology, a kind of technology that native graphite is carried out two sections modifications is arranged, promptly at first handle the native graphite raw material, make it the apparent density raising and its pattern is improved with mechanical means; Then, in liquid state or molten state heavy arene, flood, carry out extract and separate, washing, heat treatment again.This method can be improved the serious deficiency of graphite type material decay, but the relative class of Delanium preferably material with cycle performance is compared gap in addition, and the regeneration removal process of washing, separation and the solvent of intermediate product can increase manufacturing cost simultaneously.By contrast, proposed to utilize aromatic hydrocarbons and asphalt pyrolysis steam by gas-phase permeation graphite type material to be carried out the direct chemical modification processing method in the typical technology in addition, the effect on the antidamping ability that improves negative electrode active material is comparatively obvious.But these methods have also been brought the problem that cost increases and the quality homogeneity is difficult to guarantee respectively.The patent No. is that 02804165.8 Chinese patent has proposed method that several selected material forming-heat treatments-pulverizing-post forming-secondary heat treatment-secondary is pulverized, make the structure and the surface state of negative electrode active material that bigger improvement arranged, electrochemical specific capacity and antidamping ability are improved synchronously, but long manufacturing process and more manufacturing procedure are brought difficulty to cost control.
Summary of the invention
The preparation method who the purpose of this invention is to provide the good carbon anode active material of lithium-ion battery of a kind of cycle performance.
Above-mentioned technical purpose of the present invention is achieved by the following technical programs:
A kind of preparation method of carbon anode active material of lithium-ion battery may further comprise the steps:
The step of selecting materials: select coal tar processing heavy product, PETROLEUM PROCESSING heavy product, hydro carbons polycondensation reaction heavy product and their low-temperature carbonization product any one or multiplely be raw material for standby; The fugitive constituent that makes described raw material is V
m, described raw material fixed carbon is C
w, described feature of raw material value satisfies relational expression 0.79≤1-V
m/ C
w≤ 0.97.
Pulverising step: through pulverizing to such an extent that average grain diameter is 3～80 μ m, particle size distribution is the particulate of 0～160 μ m by the step gained raw material of selecting materials;
The heat chemistry reforming step: under inert atmosphere, pulverising step gained particulate is reformed through heat chemistry under motion state;
Graphitization or first charing be the graphitization step again: through the product of heat chemistry reforming step through graphitization or first charing graphitization again.
Described graphitization or first charing be again in the graphitization step, can also can carry out graphitization again after the first charing by direct graphitization through the product of chemical reforming step.
The different phase that the present invention is based on the conversion of heavy hydrocarbon heat chemistry will produce cracking, polycondensation is the dynamics and the designed a kind of method of thermodynamic characteristics of multiple balance-consecutive reaction of master.In heat treatment process, under the complex phase state, raw material will experience multiple physicochemical change repeatedly, reform so that finish its chemical composition, interior tissue, edge layer structure and surface state, pass through secondary mechanical processing and graphitization or first charing graphitization more then, and then realize the conversion once more on its composition, structure, edge layer and surface and the typing of physicochemical characteristics, thereby stably become carbon anode active material with excellent cycle performance.
As preferably, the raw material in the step of selecting materials of the present invention is solid-state.
Preferred as technique scheme, described heat chemistry reforming step and graphitization or first charing also include the normal temperature pulverising step again between the graphitization step, described normal temperature pulverising step be with heat chemistry reforming step products therefrom be cooled to pulverize behind the normal temperature micro mist, the average grain diameter that makes described micro mist is 3～38 μ m, and particle size distribution is 0～90 μ m.
In the described heat chemistry reforming step, preferred 380～900 ℃ of temperature, pressure is preferred-0.1Mpa～6.0Mpa.
If the raw material in the described step of selecting materials is C
wLow-temperature carbonization product, the C of coal tar processing heavy part of 〉=89%
wIn the low-temperature carbonization product of PETROLEUM PROCESSING heavy part of removing residual catalyst of 〉=80% one or both, then in described heat chemistry reforming step, temperature is preferably 420～780 ℃, and pressure is preferably less than 2.6Mpa, and the heat chemistry reformation time is preferably 6～18 hours.
As preferably, in the described heat chemistry reforming step, the heat chemistry reformation time is 3～26 hours.
As preferably, in the graphitization step, carbonization temperature is 1000～1800 ℃ again for described graphitization or first charing, and graphitization temperature is 2400～3000 ℃.Further preferred as such scheme, graphitization temperature is 2600～2900 ℃.
In sum, the present invention has following beneficial effect:
1, meets 0.79≤(1-V
m/ C
wAbundant and the acquisition easily of the described raw material sources of)≤0.97 eigenvalue requirements;
2, relative prior art, manufacturing process of the present invention simply helps accomplishing scale production and cost control;
3, lithium ion battery stable in properties, the cycle performance of the carbon anode active material of use the present invention manufacturing are good, the antidamping ability outstanding, the volume electrochemical specific capacity is higher;
4, the processing characteristics of products obtained therefrom of the present invention is better, and has supporting preferably adaptability with other various materials.
Embodiment
This specific embodiment only is an explanation of the invention; it is not a limitation of the present invention; those skilled in the art can make the modification that does not have creative contribution to present embodiment as required after reading this specification, but as long as all are subjected to the protection of Patent Law in claim scope of the present invention.
Embodiment 1
The selected characteristic value is 0.91, and C
WThe low-temperature carbonization product of=89% coal tar processing heavy product and the low-temperature carbonization mixture of products of PETROLEUM PROCESSING heavy product are raw material.Above-mentioned raw materials is solid-state, and above-mentioned solid feed is pulverized in the air-flowing type disintegrating apparatus, and the average grain diameter of pulverizing the gained particulate is about 50 μ m, and its particle size distribution is 0～160 μ m.Is 580 ℃ with the gained particulate in temperature, in the nitrogen atmosphere, carries out heat chemistry under the condition of pressure 1.0Mpa and reforms 8.0 hours.The heat chemistry reforming step is carried out in back-mixing formula thermopnore, and all processes that particulate is reformed in heat chemistry all is kept in motion.After heat chemistry is reformed, be ground into micro mist with the mechanical type disintegrating apparatus after heat chemistry reforming step products therefrom is cooled to 60 ℃, the particle diameter of control pulverizing gained micro mist is about 38 μ m, particle size distribution is 0～90 μ m.Above-mentioned micro mist is carried out charing at 1200 ℃, after the charing, carry out graphitization at 2800 ℃ again, promptly get carbon anode active material of lithium-ion battery of the present invention.Utilize lithium ion battery that this material makes after measured its first discharge capacity be 336mAh/g, stock's efficient is 93.8% first, its compaction capacity is 1.50g/cm
3, the conservation rate in 300 weeks of circulating is 90.8%.
The low-temperature carbonization product of the coal tar processing heavy product in the present embodiment is the low-temperature carbonization product of mid temperature pitch, and the low-temperature carbonization product of described PETROLEUM PROCESSING heavy product is a cracking of ethylene residual oil low-temperature carbonization product.
Embodiment 2
The selected characteristic value is 0.91, and C
WThe low-temperature carbonization thing of the maltha in=91% the coal tar processing is a raw material.Above-mentioned raw materials is solid-state, and above-mentioned solid feed is pulverized in the air-flowing type disintegrating apparatus, and the average grain diameter of pulverizing the gained particulate is about 3 μ m, and its particle size distribution is 0～160 μ m.Is 600 ℃ with the gained particulate in temperature, in the nitrogen atmosphere, carries out heat chemistry under the condition of pressure 2.0Mpa and reforms 6.5 hours.The heat chemistry reforming step is carried out in the revolution bed, and the part process that particulate is reformed in heat chemistry is kept in motion.After heat chemistry is reformed, be ground into micro mist with the mechanical type disintegrating apparatus after heat chemistry reforming step products therefrom is cooled to 50 ℃, the particle diameter of control pulverizing gained micro mist is about 28 μ m, particle size distribution is 0～90 μ m.Above-mentioned micro mist is carried out charing at 1200 ℃, after the charing, carry out graphitization at 2800 ℃ again, promptly get carbon anode active material of lithium-ion battery of the present invention.Utilize lithium ion battery that this material makes after measured its first discharge capacity be 332mAh/g, stock's efficient is 94.4% first, its compaction capacity is 1.47g/cm
3, the conservation rate in 300 weeks of circulating is 89.4%.
Embodiment 3
The selected characteristic value is 0.91, and C
WMaltha low-temperature carbonization product in=91% the coal tar processing is a raw material.Above-mentioned raw materials is solid-state, and above-mentioned solid feed is pulverized in the air-flowing type disintegrating apparatus, and the average grain diameter of pulverizing the gained particulate is about the particulate of 80 μ m, and its particle size distribution is 0～160 μ m.Is 720 ℃ with the gained particulate in temperature, in the nitrogen atmosphere, carries out heat chemistry under the condition of pressure 0.6Mpa and reforms 16.0 hours.The heat chemistry reforming step is carried out in back-mixing formula thermopnore, and all processes that particulate is reformed in heat chemistry all is kept in motion.Above-mentioned heat chemistry reformate directly carrying out graphitization at 2800 ℃, is promptly got carbon anode active material of lithium-ion battery of the present invention.Utilize lithium ion battery that this material makes after measured its first discharge capacity be 330mAh/g, stock's efficient is 94.5% first, its compaction capacity is 1.45g/cm
3, the conservation rate in 300 weeks of circulating is 89.8%.
Embodiment 4
The selected characteristic value is 0.85, and C
WThe low-temperature carbonization product of the decompression residuum in=81% the PETROLEUM PROCESSING be raw material.Above-mentioned raw materials is solid-state, and above-mentioned solid feed is pulverized in the air-flowing type disintegrating apparatus, and the average grain diameter of pulverizing the gained particulate is about 27 μ m, and its particle size distribution is 0～160 μ m.Is 490 ℃ with the gained particulate in temperature, in the nitrogen atmosphere, carries out heat chemistry under the condition of pressure 1.0Mpa and reforms 8.0 hours.The heat chemistry reforming step is carried out in back-mixing formula fluid bed, and all processes that particulate is reformed in heat chemistry all is kept in motion.After heat chemistry is reformed, be ground into micro mist with the mechanical type disintegrating apparatus after heat chemistry reforming step products therefrom is cooled to 25 ℃, the particle diameter of control pulverizing gained micro mist is about 20 μ m, particle size distribution is 0～90 μ m.Above-mentioned micro mist is carried out charing at 1300 ℃, after the charing, carry out graphitization at 2600 ℃ again, promptly get carbon anode active material of lithium-ion battery of the present invention.Utilize lithium ion battery that this material makes after measured its first discharge capacity be 335mAh/g, stock's efficient is 95.2% first, its compaction capacity is 1.43g/cm
3, the conservation rate in 300 weeks of circulating is 96.8%.
Embodiment 5
The selected characteristic value is 0.85, and C
WThe low-temperature carbonization product of=83% the petroleum streams fluidized catalytic cracking circulation slurry oil that has removed catalyst is a raw material.Above-mentioned raw materials is solid-state, and above-mentioned solid feed is pulverized in the air-flowing type disintegrating apparatus, and the average grain diameter of pulverizing the gained particulate is about 32 μ m, and its particle size distribution is 0～160 μ m.Is 520 ℃ with the gained particulate in temperature, in the nitrogen atmosphere, carries out heat chemistry under the condition of pressure 2.0Mpa and reforms 5.5 hours.The heat chemistry reforming step is carried out in back-mixing formula thermopnore, and all processes that particulate is reformed in heat chemistry all is kept in motion.After heat chemistry is reformed, be ground into micro mist with the mechanical type disintegrating apparatus after heat chemistry reforming step products therefrom is cooled to 40 ℃, the average grain diameter of control pulverizing gained micro mist is about 10 μ m, particle size distribution is 0～90 μ m.Above-mentioned micro mist is carried out charing at 1300 ℃, carry out graphitization at 2700 ℃ then, promptly get carbon anode active material of lithium-ion battery of the present invention.Utilize lithium ion battery that this material makes after measured its first discharge capacity be 339mAh/g, stock's efficient is 95.7% first, its compaction capacity is 1.49g/cm
3, the conservation rate in 300 weeks of circulating is 92.7%.
Embodiment 6
The selected characteristic value is 0.85, and C
WThe low-temperature carbonization thing of=86% the heavy-oil catalytic circulation slurry oil that has removed catalyst is a raw material.Above-mentioned raw materials is solid-state, and above-mentioned solid feed is pulverized in the mechanical type disintegrating apparatus, and the average grain diameter of pulverizing the gained particulate is about 18 μ m, and its particle size distribution is 0～160 μ m.Is 680 ℃ with the gained particulate in temperature, in the nitrogen atmosphere, carries out heat chemistry under the condition of pressure 0.6Mpa and reforms 12.0 hours.The heat chemistry reforming step is carried out in having the fixed bed of forcing material continuous motion function, and all processes that particulate is reformed in heat chemistry all is kept in motion.Heat chemistry is carried out graphitization at 2800 ℃ after reforming again, promptly gets carbon anode active material of lithium-ion battery of the present invention.Utilize lithium ion battery that this material makes after measured its first discharge capacity be 345mAh/g, stock's efficient is 95.5% first, its compaction capacity is 1.55g/cm
3, the conservation rate in 300 weeks of circulating is 90.7%.
Embodiment 7
The selected characteristic value is 0.92, and C
WThe low-temperature carbonization product of the mid temperature pitch of=92% coal tar processing is a raw material.Above-mentioned raw materials is solid-state, and above-mentioned solid feed is pulverized in the air-flowing type disintegrating apparatus, and the average grain diameter of pulverizing the gained particulate is about 34 μ m, and its particle size distribution is 0～160 μ m.Is 530 ℃ with the gained particulate in temperature, in the nitrogen atmosphere, carries out heat chemistry under the condition of pressure 0.8Mpa and reforms 10.0 hours.The heat chemistry reforming step is carried out in back-mixing formula thermopnore, and all processes that particulate is reformed in heat chemistry all is kept in motion.After heat chemistry is reformed, be ground into micro mist with the mechanical type disintegrating apparatus after heat chemistry reforming step products therefrom is cooled to 20 ℃, the particle diameter of control pulverizing gained micro mist is about 38 μ m, particle size distribution is 0～90 μ m.Above-mentioned micro mist is carried out charing at 1000 ℃, carry out graphitization at 2900 ℃ then, promptly get carbon anode active material of lithium-ion battery of the present invention.Utilize lithium ion battery that this material makes after measured its first discharge capacity be 335mAh/g, stock's efficient is 94.3% first, its compaction capacity is 1.49g/cm
3, the conservation rate in 300 weeks of circulating is 92.5%.
Embodiment 8
The selected characteristic value is 0.87, and C
WThe low-temperature carbonization product of the cracking of ethylene residual oil in=80% the PETROLEUM PROCESSING is a raw material.Above-mentioned raw materials is solid-state, and above-mentioned solid feed is pulverized in the air-flowing type disintegrating apparatus, and the average grain diameter of pulverizing the gained particulate is about 34 μ m, and its particle size distribution is 0～160 μ m.Is 530 ℃ with the gained particulate in temperature, in the nitrogen atmosphere, carries out heat chemistry under the condition of pressure 0.8Mpa and reforms 10.0 hours.The heat chemistry reforming step is carried out in back-mixing formula thermopnore, and all processes that particulate is reformed in heat chemistry all is kept in motion.After heat chemistry is reformed, be ground into micro mist with the mechanical type disintegrating apparatus after heat chemistry reforming step products therefrom is cooled to 20 ℃, the average grain diameter of control pulverizing gained micro mist is about 38 μ m, particle size distribution is 0～90 μ m.Above-mentioned micro mist is carried out charing at 1000 ℃, after the charing, carry out graphitization at 2600 ℃ again, promptly get carbon anode active material of lithium-ion battery of the present invention.Utilize lithium ion battery that this material makes after measured its first discharge capacity be 337mAh/g, stock's efficient is 87.2% first, its compaction capacity is 1.58g/cm
3, the conservation rate in 300 weeks of circulating is 84.9%.
Embodiment 9
The selected characteristic value is 0.89, and C
W=91% mixture is a raw material, and described mixture is made up of the low-temperature carbonization product of the maltha in the coal tar processing that waits weight portion and the low-temperature carbonization product of the decompression residuum in the PETROLEUM PROCESSING.Above-mentioned raw materials is solid-state, and above-mentioned solid feed is pulverized in the air-flowing type disintegrating apparatus, and the average grain diameter of pulverizing the gained particulate is about 38 μ m, and its particle size distribution is 0～160 μ m.Is 620 ℃ with the gained particulate in temperature, in the nitrogen atmosphere, carries out heat chemistry under the condition of pressure 0.1Mpa and reforms 10.0 hours.The heat chemistry reforming step is carried out in back-mixing formula thermopnore, and all processes that particulate is reformed in heat chemistry all is kept in motion.After heat chemistry is reformed, be ground into micro mist with the mechanical type disintegrating apparatus after heat chemistry reforming step products therefrom is cooled to 20 ℃, the particle diameter of control pulverizing gained micro mist is about 38 μ m, particle size distribution is 0～90 μ m.Above-mentioned micro mist is carried out charing at 1200 ℃, after the charing, carry out graphitization at 2800 ℃ again, promptly get carbon anode active material of lithium-ion battery of the present invention.Utilize lithium ion battery that this material makes after measured its first discharge capacity be 339mAh/g, stock's efficient is 92.6% first, its compaction capacity is 1.45g/cm
3, the conservation rate in 300 weeks of circulating is 91.6%.
Embodiment 10
The selected characteristic value is 0.87 and C
WThe mixture that=91% the low-temperature carbonization product by the low-temperature carbonization product of the maltha in the 30% coal tar processing and the mid temperature pitch in the processing of 70% coal tar is formed is a raw material.Above-mentioned raw materials is solid-state, and above-mentioned solid feed is pulverized in the air-flowing type disintegrating apparatus, and the average grain diameter of pulverizing the gained particulate is about 38 μ m, and its particle size distribution is 0～160 μ m.Is 620 ℃ with the gained particulate in temperature, in the nitrogen atmosphere, carries out heat chemistry under the condition of pressure 0.6Mpa and reforms 10.0 hours.The heat chemistry reforming step is carried out in back-mixing formula thermopnore, and all processes that particulate is reformed in heat chemistry all is kept in motion.Heat chemistry is carried out graphitization with it at 2800 ℃ after reforming, and promptly gets carbon anode active material of lithium-ion battery of the present invention.Utilize lithium ion battery that this material makes after measured its first discharge capacity be 332mAh/g, stock's efficient is 93.6% first, its compaction capacity is 1.38g/cm
3, the conservation rate in 300 weeks of circulating is 89.4%.
Embodiment 11
The selected characteristic value is 0.90 and C
WThe mixture that 〉=86% the low-temperature carbonization product by the low-temperature carbonization product of the maltha in the 70% coal tar processing and the mid temperature pitch in the processing of 30% coal tar is formed is a raw material.Above-mentioned raw materials is solid-state, and above-mentioned solid feed is pulverized in the air-flowing type disintegrating apparatus, and the average grain diameter of pulverizing the gained particulate is about 38 μ m, and its particle size distribution is 0～160 μ m.Is 620 ℃ with the gained particulate in temperature, in the nitrogen atmosphere, carries out heat chemistry under the condition of pressure 0.2Mpa and reforms 10.0 hours.The heat chemistry reforming step is carried out in back-mixing formula thermopnore, and all processes that particulate is reformed in heat chemistry all is kept in motion.Heat chemistry is carried out graphitization with it at 2800 ℃ after reforming, and promptly gets carbon anode active material of lithium-ion battery of the present invention.Utilize lithium ion battery that this material makes after measured its first discharge capacity be 328mAh/g, stock's efficient is 92.4% first, its compaction capacity is 1.51g/cm
3, the conservation rate in 300 weeks of circulating is 88.5%.
Embodiment 12
The selected characteristic value is 0.88 and C
W=96% the low-temperature carbonization product composition mixture by the heavy-oil catalytic clarified oil in the PETROLEUM PROCESSING of the low-temperature carbonization product of the mid temperature pitch in the 50% coal tar processing and 50% is a raw material.Above-mentioned raw materials is solid-state, and above-mentioned solid feed is pulverized in the air-flowing type disintegrating apparatus, and the average grain diameter of pulverizing the gained particulate is about 50 μ m, and its particle size distribution is 0～160 μ m.Is 590 ℃ with the gained particulate in temperature, in the nitrogen atmosphere, carries out heat chemistry under the condition of pressure 0.2Mpa and reforms 12.0 hours.The heat chemistry reforming step is carried out in back-mixing formula thermopnore, and all processes that particulate is reformed in heat chemistry all is kept in motion.After heat chemistry is reformed, be ground into micro mist with the mechanical type disintegrating apparatus after heat chemistry reforming step products therefrom is cooled to 30 ℃, the particle diameter of control pulverizing gained micro mist is about 3 μ m, particle size distribution is 0～90 μ m.Above-mentioned micro mist is carried out charing at 1200 ℃, after the charing, carry out graphitization at 2800 ℃ again, promptly get carbon anode active material of lithium-ion battery of the present invention.Utilize lithium ion battery that this material makes after measured its first discharge capacity be 335mAh/g, stock's efficient is 90.1% first, its compaction capacity is 1.55g/cm
3, the conservation rate in 300 weeks of circulating is 84.3%.
Embodiment 13
The selected characteristic value is 0.92 and C
WThe carbonizing production of low temperature distillation coal tar processing heavy part of=88% is a raw material.Above-mentioned raw materials is solid-state, and above-mentioned solid feed is pulverized in the air-flowing type disintegrating apparatus, and the average grain diameter of pulverizing the gained particulate is about 68 μ m, and its particle size distribution is 0～160 μ m.Is 650 ℃ with the gained particulate in temperature, in the nitrogen atmosphere, carries out heat chemistry under the condition of pressure 0.2Mpa and reforms 10.0 hours.The heat chemistry reforming step is carried out in back-mixing formula thermopnore, and all processes that particulate is reformed in heat chemistry all is kept in motion.Heat chemistry is carried out graphitization with it at 2800 ℃ after reforming, and promptly gets carbon anode active material of lithium-ion battery of the present invention.Utilize lithium ion battery that this material makes after measured its first discharge capacity be 337mAh/g, stock's efficient is 93.8% first, its compaction capacity is 1.48g/cm
3, the conservation rate in 300 weeks of circulating is 89.7%.
Embodiment 14
The selected characteristic value is 0.93 and C
WThe low-temperature carbonization product of the modified coal tar pitch in=92% the coal tar processing is a raw material.Above-mentioned raw materials is solid-state, and above-mentioned solid feed is pulverized in the air-flowing type disintegrating apparatus, and the average grain diameter of pulverizing the gained particulate is about 18 μ m, and its particle size distribution is 0～160 μ m.Is 620 ℃ with the gained particulate in temperature, in the nitrogen atmosphere, carries out heat chemistry under the condition of pressure 0.2Mpa and reforms 10.0 hours.The heat chemistry reforming step is carried out in back-mixing formula thermopnore, and all processes that particulate is reformed in heat chemistry all is kept in motion.Heat chemistry is carried out graphitization with it at 2800 ℃ after reforming, and promptly gets carbon anode active material of lithium-ion battery of the present invention.Utilize lithium ion battery that this material makes after measured its first discharge capacity be 330mAh/g, stock's efficient is 93.1% first, its compaction capacity is 1.45g/cm
3, the conservation rate in 300 weeks of circulating is 90.2%.
Embodiment 15
The selected characteristic value is 0.87, and C
WThe low-temperature carbonization product of=80% Petropols processing heavy residue is a raw material.Above-mentioned raw materials is solid-state, and above-mentioned solid feed is pulverized in the air-flowing type disintegrating apparatus, and the average grain diameter of pulverizing the gained particulate is about 27 μ m, and its particle size distribution is 0～160 μ m.Is 560 ℃ with the gained particulate in temperature, in the nitrogen atmosphere, carries out heat chemistry under the condition of pressure 1.0Mpa and reforms 8.0 hours.The heat chemistry reforming step is carried out in back-mixing formula thermopnore, and all processes that particulate is reformed in heat chemistry all is kept in motion.After heat chemistry is reformed, be ground into micro mist with the mechanical type disintegrating apparatus after heat chemistry reforming step products therefrom is cooled to 25 ℃, the particle diameter of control pulverizing gained micro mist is about 24 μ m, particle size distribution is 0～90 μ m.Above-mentioned micro mist is carried out charing at 1600 ℃, after the charing, carry out graphitization at 2700 ℃ again, promptly get carbon anode active material of lithium-ion battery of the present invention.Utilize lithium ion battery that this material makes after measured its first discharge capacity be 339mAh/g, stock's efficient is 94.6% first, its compaction capacity is 1.43g/cm
3, the conservation rate in 300 weeks of circulating is 92.2%.
Embodiment 16
The selected characteristic value is 0.85, and C
WThe low-temperature carbonization product of the decompression residue in=80 the PETROLEUM PROCESSING is a raw material.Above-mentioned raw materials is solid-state, and above-mentioned solid feed is pulverized in the air-flowing type disintegrating apparatus, and the average grain diameter of pulverizing the gained particulate is about 27 μ m, and its particle size distribution is 0～160 μ m.Is 490 ℃ with the gained particulate in temperature, in the nitrogen atmosphere, carries out heat chemistry under the condition of pressure 1.0Mpa and reforms 8.0 hours.The heat chemistry reforming step is carried out in back-mixing formula thermopnore, and all processes that particulate is reformed in heat chemistry all is kept in motion.After heat chemistry is reformed, be ground into micro mist with the mechanical type disintegrating apparatus after heat chemistry reforming step products therefrom is cooled to 25 ℃, the particle diameter of control pulverizing gained micro mist is about 20 μ m, particle size distribution is 0～90 μ m.Above-mentioned micro mist is carried out graphitization at 2700 ℃, promptly get carbon anode active material of lithium-ion battery of the present invention.Utilize lithium ion battery that this material makes after measured its first discharge capacity be 336mAh/g, stock's efficient is 93.3% first, its compaction capacity is 1.42g/cm
3, the conservation rate in 300 weeks of circulating is 93.3%.
Embodiment 17
The selected characteristic value is 0.86, and C
WThe low-temperature carbonization product of=80% unsaturated polyester (UP) processing heavy residue is a raw material.Above-mentioned raw materials is solid-state, and above-mentioned solid feed is pulverized in the mechanical type disintegrating apparatus, and the average grain diameter of pulverizing the gained particulate is about 27 μ m, and its particle size distribution is 0～160 μ m.Is 560 ℃ with the gained particulate in temperature, in the nitrogen atmosphere, carries out heat chemistry under the condition of pressure 0.2Mpa and reforms 15.0 hours.The heat chemistry reforming step is carried out in back-mixing formula thermopnore, and all processes that particulate is reformed in heat chemistry all is kept in motion.After heat chemistry is reformed, be ground into micro mist with the mechanical type disintegrating apparatus after heat chemistry reforming step products therefrom is cooled to 25 ℃, the particle diameter of control pulverizing gained micro mist is about 24 μ m, particle size distribution is about 0～90 μ m.Above-mentioned micro mist is carried out charing at 1600 ℃, after the charing, carry out graphitization at 2700 ℃ again, promptly get carbon anode active material of lithium-ion battery of the present invention.Utilize lithium ion battery that this material makes after measured its first discharge capacity be 327mAh/g, stock's efficient is 92.4% first, its compaction capacity is 1.45g/cm
3, the conservation rate in 300 weeks of circulating is 85.3%.
Claims (10)
1. the preparation method of a carbon anode active material of lithium-ion battery may further comprise the steps successively:
(1) step of selecting materials: select coal tar processing heavy product, PETROLEUM PROCESSING heavy product, hydro carbons polycondensation reaction heavy product and their low-temperature carbonization product any one or multiplely be raw material for standby; The fugitive constituent that makes described raw material is V
m, the fixed carbon in the described raw material is C
w, described feature of raw material value satisfies relational expression 0.79≤1-V
m/ C
w≤ 0.97, V wherein
mAnd C
wAll according to as analysed basis, percentage meter, C
w〉=80%;
(2) pulverising step: by the step gained raw material of selecting materials through pulverizing to such an extent that average grain diameter is 3～80 μ m; Particle size distribution is the particulate of 0～160 μ m;
(3) heat chemistry reforming step: under inert atmosphere, pulverising step gained particulate is reformed through heat chemistry under whole process or part period motion state;
(4) graphitization or first charing graphitization step again: through the product of heat chemistry reforming step through graphitization or first charing graphitization again.
2. the preparation method of carbon anode active material of lithium-ion battery according to claim 1, it is characterized in that: described heat chemistry reforming step and graphitization or first charing also include the normal temperature pulverising step again between the graphitization step, described normal temperature pulverising step be with heat chemistry reforming step products therefrom be cooled to pulverize behind the normal temperature micro mist, the average grain diameter that makes described micro mist is 3～38 μ m, and particle size distribution is 0～90 μ m.
3. the preparation method of carbon anode active material of lithium-ion battery according to claim 1, it is characterized in that: in the described heat chemistry reforming step, temperature is 380～900 ℃, and pressure is-0.1Mpa～6.0Mpa.
4. the preparation method of carbon anode active material of lithium-ion battery according to claim 1, it is characterized in that: in the described heat chemistry reforming step, the heat chemistry reformation time is 3～26 hours.
5. the preparation method of carbon anode active material of lithium-ion battery according to claim 1, it is characterized in that: the raw material in the described step of selecting materials is solid-state.
6. the preparation method of carbon anode active material of lithium-ion battery according to claim 1 is characterized in that: in the graphitization step, carbonization temperature is 1000～1800 ℃ again for graphitization or first charing, and graphitization temperature is 2400～3000 ℃.
7. the preparation method of carbon anode active material of lithium-ion battery according to claim 1, it is characterized in that: the raw material in the described step of selecting materials is C
wThe low-temperature carbonization product and the C of coal tar processing heavy part of 〉=89%
w〉=80% removes one or both in the low-temperature carbonization product of PETROLEUM PROCESSING heavy part of residual catalyst.
8. the preparation method of carbon anode active material of lithium-ion battery according to claim 7, it is characterized in that: in the heat chemistry reforming step, temperature is 420～780 ℃, and pressure is less than 2.6Mpa, and the heat chemistry reformation time is 6～18 hours.
9. the preparation method of carbon anode active material of lithium-ion battery according to claim 1, it is characterized in that: in the described graphitization step, graphitization temperature is 2600～2900 ℃.
10. the preparation method of carbon anode active material of lithium-ion battery according to claim 2, it is characterized in that: the average grain diameter of micro mist is 5～36 μ m in the described pulverising step.
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| CN102424376A (en) * | 2011-09-09 | 2012-04-25 | 湖州创亚动力电池材料有限公司 | Production method and product of lithium-ion power battery rate cathode material |
| WO2013058349A1 (en) * | 2011-10-21 | 2013-04-25 | 昭和電工株式会社 | Graphite material, carbon material for battery electrode, and battery |
| CN109449367B (en) * | 2018-10-09 | 2022-05-17 | 合肥国轩电池材料有限公司 | Lithium ion battery cathode material and preparation method thereof |
| CN111170300B (en) * | 2020-02-17 | 2023-09-12 | 中钢集团鞍山热能研究院有限公司 | Production process and device of high-performance anode material |
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| CN1259546A (en) * | 1999-01-04 | 2000-07-12 | 北京化工大学 | Prepn. method of mesophase asphalt carbon microsphere |
| CN101383412A (en) * | 2008-10-07 | 2009-03-11 | 雷钧 | Composite negative pole of lithium ion power cell and preparation thereof |
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| CN101383412A (en) * | 2008-10-07 | 2009-03-11 | 雷钧 | Composite negative pole of lithium ion power cell and preparation thereof |
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