CN103979527B - A kind of production method of mesophase spherule composite graphite negative electrode material - Google Patents
A kind of production method of mesophase spherule composite graphite negative electrode material Download PDFInfo
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- CN103979527B CN103979527B CN201410228049.2A CN201410228049A CN103979527B CN 103979527 B CN103979527 B CN 103979527B CN 201410228049 A CN201410228049 A CN 201410228049A CN 103979527 B CN103979527 B CN 103979527B
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Abstract
The invention provides a kind of production method of mesophase spherule composite graphite negative electrode material, take median as the MCMB of 15-20 μm is raw material A, take median as the native graphite of 4-8 μm is raw material B, with nanoscale micro mist pitch for raw material C.Get above-mentioned raw materials A, raw material A airflow pulverization method is ground into the micro mist of particle diameter≤8 μm.Get above-mentioned raw materials A and B in A/B=100/(30 ~ 200) ratio be uniformly mixed, then in (A+B)/C=100/(8 ~ 15) ratio add raw material C and carry out air-flow mixing.The material briquet finally will mixed, puts into sintering furnace and carbonizes at 1200 ~ 1500 DEG C, or carry out graphitization at 2800 ~ 3200 DEG C, or at 2800 ~ 3200 DEG C, carries out graphitization after first carbonizing at 1200 ~ 1500 DEG C.The invention has the advantages that: good cycle, capacity is high, efficiency is high, security performance is good.
Description
Technical field
The present invention relates to a kind of production method of mesophase spherule composite graphite negative electrode material, belong to technical field of lithium ion battery negative.
Background technology
Carbon anode lithium ion battery demonstrates good performance in safety and cycle life, and material with carbon element is inexpensive, nontoxic, and current commodity lithium ion battery extensively adopts carbon negative pole material.The advantages such as lithium ion battery has that operating voltage is high, discharging voltage balance, cryogenic property are good, specific energy is high, self discharge is little, memory-less effect, environmentally friendly and long service live are electrochemical educational circles study hotspots in recent years.Wherein, lithium ion battery negative material is the chief component of lithium ion battery, and negative material determines the key factor of performance of lithium ion battery especially.
Since first pitch coke was used as lithium ion battery negative material in 1989 by Japanese Sony Corporation, along with the fast development of lithium ion battery, the raw material sources of charcoal graphite cathode material also extend to MCMB, hard charcoal, Delanium and native graphite etc. in succession.But the electrical property that the serviceability due to the different charcoal graphite cathode material of raw material sources exists the certain defect that certain difference and charcoal graphite type material itself exist, and usually adopts various physics in industry, chemical means improves charcoal graphite type material.MCMB is a kind of material with very big potentiality to be exploited, and except having the general characteristic of graphite carbon negative material, it also has unique advantage in Structure and form.But MCMB uses as simple negative material, although its embedding lithium ability is higher than native graphite, reversible capacity is very low.The present invention adopts mechanical means to be destroyed by the original structure of MCMB, then carries out compound with native graphite and the compound graphite cathode material made, to play the embedding lithium ability of material, and improves reversible capacity.
Summary of the invention
The object of this invention is to provide a kind of production method of mesophase spherule composite graphite negative electrode material, to overcome the poor with compatibility of electrolyte of MCMB existence, the defect that reversible capacity is low, and the natural flaw that overcomes that the capacity that native graphite exists is low, poorly conductive, cycle life are short etc.
Technical scheme of the present invention: a kind of production method of mesophase spherule composite graphite negative electrode material, concrete production technology is:
A () take median as the MCMB of 15-20 μm is raw material A;
B () take median as the native graphite of 4-8 μm is raw material B;
C (), with nanometer asphalt micro mist for raw material C, median is≤90nm;
D raw material A is carried out graphitization processing by () at 2800 ~ 3200 DEG C;
E raw material A airslide disintegrating mill after graphitization processing is pulverized by (), be ground into the micro mist of particle diameter≤8 μm;
The raw material B of f raw material A micro mist that (e) step obtains by () and (b) step is in A/B=100/(30 ~ 200) ratio be uniformly mixed under normal temperature state, then in (A+B)/C=100/(8 ~ 15) ratio add raw material C and utilize airflow mixer to carry out air-flow mixing;
G material briquet that (f) step mixes by (), puts into sintering furnace at 1200 ~ 1500 DEG C, carries out charing process;
H () is cooled to after room temperature until material, carry out pulverizing, classification, removal of impurities, screening, product median controls at 13-20 μm.
Described raw material A is petroleum asphalt based or coal tar pitch base is obtaining the mesophase globule of homogeneous nucleation after thermal decomposition and thermal polycondensation reaction.
Described raw material C is petroleum asphalt or coal tar pitch.
Described being uniformly mixed adopts twin-screw or two ribbon agitating mode.
Beneficial effect of the present invention:
1, because the present invention carries out mechanical crushing process to MCMB, destroy its surface texture, utilize internal structural characteristic, play its de-lithium performance, therefore improve invertibity;
2, adopt native graphite and MCMB to carry out compound, the processing characteristics of material monolithic can be improved, improve tap density and compacted density;
3, adopt nanometer asphalt will carry out compression process to MCMB and native graphite as auxiliary material, contribute to the density improving briquetting on the one hand, be also that surface coating modification process is carried out to material on the other hand, make up the blemish of material;
4, in sum, the present invention carries out physics, chemical treatment and make compound graphite by utilizing MCMB, native graphite and pitch, reversible capacity and the cycle life of interphase material can be played greatly, and its production technology is simple, production efficiency is high, cost is low, and course of processing safety, can be used for suitability for industrialized production.
embodiment:
embodiment 1:
Take MCMB raw material A 20000g, under 2800 DEG C of conditions, carry out graphitization.
Take the raw material A 10000g after graphitization, carry out air-flow crushing, median requires to control at≤8 μm.
Take the raw material A 5000g and natural graphite starting material B5000g that crush, carry out being uniformly mixed 30 minutes under normal temperature state.
Take the mixture 8000g of raw material A and B, add asphalt stock C800g, under normal temperature state, carry out air-flow mixing 30min.
Take raw material A, the mixed material 8000g of B, C, carry out briquetting process, then block material is put into sintering furnace, at 1400 DEG C of temperature, carry out charing process.
Carried out pulverizing and reprocessing by block material after charing, described reprocessing comprises classification, removal of impurities, screening, requires that median controls at 13-20 μm.
Do experiment with LIR2430 type button cell, gained negative material discharge capacity is 360.7mAh/g, and discharging efficiency is 93.8%, as shown in table 1.
embodiment 2:
Take MCMB raw material A 20000g, under 2800 DEG C of conditions, carry out graphitization.
Take the raw material A 10000g after graphitization, carry out air-flow crushing, median requires to control at≤8 μm.
Take the raw material A 5000g and natural graphite starting material B3000g that crush, carry out being uniformly mixed 30 minutes under normal temperature state.
Take the mixture 8000g of raw material A and B, add asphalt stock C960g, under normal temperature state, carry out air-flow mixing 30min.
Take raw material A, the mixed material 8000g of B, C, carry out briquetting process, then block material is put into sintering furnace, at 1300 DEG C of temperature, carry out charing process.
Carried out pulverizing and reprocessing by block material after charing, described reprocessing comprises classification, removal of impurities, screening, requires that median controls at 13-20 μm.
Do experiment with LIR2430 type button cell, gained negative material discharge capacity is 352.6mAh/g, and discharging efficiency is 93.6%, as shown in table 1.
embodiment 3:
Take MCMB raw material A 20000g, under 3000 DEG C of conditions, carry out graphitization.
Take the raw material A 10000g after graphitization, carry out air-flow crushing, median requires to control at≤8 μm.
Take the raw material A 5000g and natural graphite starting material B4000g that crush, carry out being uniformly mixed 30 minutes under normal temperature state.
Take the mixture 8000g of raw material A and B, add asphalt stock C1200g, under normal temperature state, carry out air-flow mixing 30min.
Take raw material A, the mixed material 8000g of B, C, carry out briquetting process, then block material is put into sintering furnace, at 1400 DEG C of temperature, carry out charing process.
Carried out pulverizing and reprocessing by block material after charing, described reprocessing comprises classification, removal of impurities, screening, requires that median controls at 13-20 μm.
Do experiment with LIR2430 type button cell, gained negative material discharge capacity is 356.7mAh/g, and discharging efficiency is 93.7%, as shown in table 1.
embodiment 4:
Take MCMB raw material A 20000g, under 3000 DEG C of conditions, carry out graphitization.
Take the raw material A 10000g after graphitization, carry out air-flow crushing, median requires to control at≤8 μm.
Take the raw material A 5000g and natural graphite starting material B7500g that crush, carry out being uniformly mixed 30 minutes under normal temperature state.
Take the mixture 8000g of raw material A and B, add asphalt stock C960g, under normal temperature state, carry out air-flow mixing 30min.
Take raw material A, the mixed material 8000g of B, C, carry out briquetting process, then block material is put into sintering furnace, at 1400 DEG C of temperature, carry out charing process.
Carried out pulverizing and reprocessing by block material after charing, described reprocessing comprises classification, removal of impurities, screening, requires that median controls at 13-20 μm.
Do experiment with LIR2430 type button cell, gained negative material discharge capacity is 362.1mAh/g, and discharging efficiency is 93.6%, as shown in table 1.
embodiment 5:
Take MCMB raw material A 20000g, under 3100 DEG C of conditions, carry out graphitization.
Take the raw material A 10000g after graphitization, carry out air-flow crushing, median requires to control at≤8 μm.
Take the raw material A 5000g and natural graphite starting material B6000g that crush, carry out being uniformly mixed 30 minutes under normal temperature state.
Take the mixture 8000g of raw material A and B, add asphalt stock C800g, under normal temperature state, carry out air-flow mixing 30min.
Take raw material A, the mixed material 8000g of B, C, carry out briquetting process, then block material is put into sintering furnace, at 1300 DEG C of temperature, carry out charing process.
Carried out pulverizing and reprocessing by block material after charing, described reprocessing comprises classification, removal of impurities, screening, requires that median controls at 13-20 μm.
Do experiment with LIR2430 type button cell, gained negative material discharge capacity is 361.8mAh/g, and discharging efficiency is 93.8%, as shown in table 1.
embodiment 6:
Take MCMB raw material A 20000g, under 3100 DEG C of conditions, carry out graphitization.
Take the raw material A 10000g after graphitization, carry out air-flow crushing, median requires to control at≤8 μm.
Take the raw material A 5000g and natural graphite starting material B9000g that crush, carry out being uniformly mixed 30 minutes under normal temperature state.
Take the mixture 8000g of raw material A and B, add asphalt stock C640g, under normal temperature state, carry out air-flow mixing 30min.
Take raw material A, the mixed material 8000g of B, C, carry out briquetting process, then block material is put into sintering furnace, at 1400 DEG C of temperature, carry out charing process.
Carried out pulverizing and reprocessing by block material after charing, described reprocessing comprises classification, removal of impurities, screening, requires that median controls at 13-20 μm.
Do experiment with LIR2430 type button cell, gained negative material discharge capacity is 362.4mAh/g, and discharging efficiency is 94.0%, as shown in table 1.
embodiment 7:
Take MCMB raw material A 20000g, under 3000 DEG C of conditions, carry out graphitization.
Take the raw material A 10000g after graphitization, carry out air-flow crushing, median requires to control at≤8 μm.
Take the raw material A 5000g and natural graphite starting material B10000g that crush, carry out being uniformly mixed 30 minutes under normal temperature state.
Take the mixture 8000g of raw material A and B, add asphalt stock C1200g, under normal temperature state, carry out air-flow mixing 30min.
Take raw material A, the mixed material 8000g of B, C, carry out briquetting process, then block material is put into sintering furnace, at 1400 DEG C of temperature, carry out charing process.
Carried out pulverizing and reprocessing by block material after charing, described reprocessing comprises classification, removal of impurities, screening, requires that median controls at 13-20 μm.
Do experiment with LIR2430 type button cell, gained negative material discharge capacity is 362.3mAh/g, and discharging efficiency is 94.1%, as shown in table 1.
embodiment 8:
Take MCMB raw material A 20000g, under 3000 DEG C of conditions, carry out graphitization.
Take the raw material A 10000g after graphitization, carry out air-flow crushing, median requires to control at≤8 μm.
Take the raw material A 5000g and natural graphite starting material B9000g that crush, carry out being uniformly mixed 30 minutes under normal temperature state.
Take the mixture 8000g of raw material A and B, add asphalt stock C800g, under normal temperature state, carry out air-flow mixing 30min.
Take raw material A, the mixed material 8000g of B, C, carry out briquetting process, then block material is put into sintering furnace, at 1300 DEG C of temperature, carry out charing process.
Carried out pulverizing and reprocessing by block material after charing, described reprocessing comprises classification, removal of impurities, screening, requires that median controls at 13-20 μm.
Do experiment with LIR2430 type button cell, gained negative material discharge capacity is 363.4mAh/g, and discharging efficiency is 93.9%, as shown in table 1.
embodiment 9:
Take MCMB raw material A 20000g, under 3000 DEG C of conditions, carry out graphitization.
Take the raw material A 10000g after graphitization, carry out air-flow crushing, median requires to control at≤8 μm.
Take the raw material A 5000g and natural graphite starting material B8000g that crush, carry out being uniformly mixed 30 minutes under normal temperature state.
Take the mixture 8000g of raw material A and B, add asphalt stock C800g, under normal temperature state, carry out air-flow mixing 30min.
Take raw material A, the mixed material 8000g of B, C, carry out briquetting process, then block material is put into sintering furnace, at 1400 DEG C of temperature, carry out charing process.
Carried out pulverizing and reprocessing by block material after charing, described reprocessing comprises classification, removal of impurities, screening, requires that median controls at 13-20 μm.
Do experiment with LIR2430 type button cell, gained negative material discharge capacity is 361.9mAh/g, and discharging efficiency is 94.2%, as shown in table 1.
subordinate list 1 button cell test data summary sheet
。
Claims (4)
1. a production method for mesophase spherule composite graphite negative electrode material, concrete production technology is:
A () take median as the MCMB of 15-20 μm is raw material A;
B () take median as the native graphite of 4-8 μm is raw material B;
C (), with nanometer asphalt micro mist for raw material C, median is≤90nm;
D raw material A is carried out graphitization processing by () at 2800 ~ 3200 DEG C;
E raw material A airslide disintegrating mill after graphitization processing is pulverized by (), be ground into the micro mist of particle diameter≤8 μm;
The raw material B of f raw material A micro mist that (e) step obtains by () and (b) step is by weight A/B=100/(30 ~ 200) ratio be uniformly mixed under normal temperature state, then by weight (A+B)/C=100/(8 ~ 15) ratio add raw material C and utilize airflow mixer to carry out air-flow mixing;
G material briquet that (f) step mixes by (), puts into sintering furnace at 1200 ~ 1500 DEG C, carries out charing process;
H () is cooled to after room temperature until material, carry out pulverizing, classification, removal of impurities, screening, product median controls at 13-20 μm.
2. the production method of a kind of mesophase spherule composite graphite negative electrode material as claimed in claim 1, is characterized in that: described raw material A is petroleum asphalt based or coal tar pitch base is obtaining the mesophase globule of homogeneous nucleation after thermal decomposition and thermal polycondensation reaction.
3. the production method of a kind of mesophase spherule composite graphite negative electrode material as claimed in claim 1, is characterized in that: described raw material C is petroleum asphalt or coal tar pitch.
4. the production method of a kind of mesophase spherule composite graphite negative electrode material as claimed in claim 1, is characterized in that: described in be uniformly mixed and adopt twin-screw or two ribbon agitating mode.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104779396B (en) * | 2015-04-22 | 2017-01-11 | 大连宏光锂业股份有限公司 | Production method of lithium ion composite graphite cathode material |
| CN105884357B (en) * | 2016-04-13 | 2019-01-29 | 湖南省长宇新型炭材料有限公司 | It is a kind of for hot-forming graphite jig material and preparation method thereof |
| CN106169582B (en) * | 2016-08-23 | 2018-08-14 | 大连宏光锂业股份有限公司 | A kind of natural needle coke composite graphite negative electrode material production method |
| CN106935857A (en) * | 2017-03-17 | 2017-07-07 | 雅安乾润锂电池材料有限公司 | A kind of ultrafine graphite cathode material |
| CN111244398A (en) * | 2018-11-28 | 2020-06-05 | 上海杉杉科技有限公司 | Composite graphite negative electrode material, lithium ion battery, preparation method and application |
| CN111196737A (en) * | 2020-03-24 | 2020-05-26 | 辽宁科技学院 | Technological method for preparing compact calcium dialuminate refractory clinker by one-step method |
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| CN101740230A (en) * | 2009-12-09 | 2010-06-16 | 中南大学 | Carbon compound cathode material for ultracapacitor battery |
| CN102110813A (en) * | 2009-12-23 | 2011-06-29 | 上海杉杉科技有限公司 | Graphite material at negative pole of lithium ion battery and preparation method thereof |
| CN102651468A (en) * | 2012-05-03 | 2012-08-29 | 深圳市翔丰华科技有限公司 | Lithium ion battery graphite negative electrode material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101604748A (en) * | 2009-07-03 | 2009-12-16 | 中南大学 | The low temperature pyrogenation graphite covered by asphalt prepares the method for high multiplying power lithium ion capacitance cell negative electrode material |
| CN101740230A (en) * | 2009-12-09 | 2010-06-16 | 中南大学 | Carbon compound cathode material for ultracapacitor battery |
| CN102110813A (en) * | 2009-12-23 | 2011-06-29 | 上海杉杉科技有限公司 | Graphite material at negative pole of lithium ion battery and preparation method thereof |
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Address after: 116450 Haitang street, Huayuankou Economic Zone, Dalian, Liaoning Patentee after: Dalian Hongguang Lithium Industry Co.,Ltd. Address before: 116450 Haitang street, Huayuankou Economic Zone, Dalian, Liaoning Patentee before: DALIAN HONGGUANG LITHIUM INDUSTRY CO.,LTD. |