CN1393946A - Process for preparing carbon material used as negative electrode of Li-ion battery - Google Patents
Process for preparing carbon material used as negative electrode of Li-ion battery Download PDFInfo
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- CN1393946A CN1393946A CN01122691A CN01122691A CN1393946A CN 1393946 A CN1393946 A CN 1393946A CN 01122691 A CN01122691 A CN 01122691A CN 01122691 A CN01122691 A CN 01122691A CN 1393946 A CN1393946 A CN 1393946A
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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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invented method for preparing the charcoal material used for the negative pole of the lithium ion battery. With phenolic resin and coal tar being mixed, the said mixture is heated up and mixed round. Under the protection of nitrogen gas and the airtight condition, the reaction aggregation is carried out. With the aggregated matter being cooled naturally, the mother liquid is filtered out and the insoluble substance is extracted till colorless by use of pyridine. The product is obtained through drying, oxidizing, charring and grpahitizing procedures. The invention provides the features of wider source of raw materials, low cost, simple technique, high yield and high reversible capability of charging and discharging electricity.
Description
The invention belongs to a kind of charcoal preparation methods, relate in particular to a kind of preparation method who prepares carbon material used as negative electrode of Li-ion battery.
Coal tar and phenolic resins all are the persursor materials of preparation lithium ion battery negative, is that coal tar is generated the macromolecule pitches 350 ℃～500 ℃ following polymerizations with coal tar for the feedstock production lithium ion battery negative, again macromolecule pitch is carried out solvent extraction or oxidation processes, pitch after the processing carries out charing, graphitization processing, obtaining required raw material of wood-charcoal material at last, still is that the shortcoming of the raw material of wood-charcoal material of feedstock production is a complex process in preparation process with coal tar, utilization ratio of raw materials is low, the material yield is low, low and cycle performance is poor as the lithium ion battery negative reversible capacity.Phenolic resin carbon is that cost of material height, reversible capacity are low as the shortcoming of lithium ion battery negative.
The purpose of this invention is to provide the high lithium ion battery negative charcoal preparation methods of a kind of charge/discharge capacity.
Preparation method of the present invention is as follows:
With the phenolic resins of acetone solution and coal tar by weight being phenolic resins: coal tar=3～50: 100 mix after, add in the reactor, be warming up to 60～100 ℃, normal pressure stirred 1～10 hour, then under nitrogen protection, be warming up to 150～300 ℃, stirred again 1～10 hour, be warming up to 350～500 ℃ and under air-tight state reactive polymeric 0.5～15 hour;
2. behind the natural cooling, polymer is removed by filter mother liquor at 100～200 ℃, insoluble matter is extracted to colourless to remove residual mother liquor under 110 ℃ with pyridine, carry out drying then;
With the not fusant of drying at 200～300 ℃, oxidation is 1～15 hour under the air atmosphere, is warming up to 600～1200 ℃ of temperature charings through the product of oxidation under inert atmosphere protection, obtains carbonization product;
4. carbonization product is warming up to 1600～3000 ℃ under the high-purity argon gas protection and carries out graphitization processing, make the graphitization sample;
5. graphited sample is ground to 5 μ～50 μ m.
It is as follows that the present invention carries out the charge-discharge performance test process to the raw material of wood-charcoal material of preparation:
1. the preparation of carbon resistance rod sheet: ptfe emulsion and powdered carbon mixed roll on Copper Foil, carbon membrane thickness is 0.08～0.12 millimeter, then carbon membrane is carried out drying and removes solvent;
2. prepare three electrode Experimental cells: as work electrode, the lithium metal conduct is to electrode and auxiliary electrode with carbon membrane, and concentration is the LiPF of 1M
6(EC: DEC=1: 1 volume ratio) be electrolyte, polyethylene film is that barrier film is made battery to/ethylene carbonate (EC)/carbonic acid dihexyl (DEC);
3. Experimental cell is carried out the charge-discharge performance test: charging and discharging currents density is 20mAg
-1, 50mAg
-1, 100mAg
-1, the charging/discharging voltage excursion is 0.001～2.000 volt (with respect to lithium metal).
The prepared raw material of wood-charcoal material of the present invention is with 20mAg
-1, 50mAg
-1, 100mAg
-1The best result of reversible capacity first that discharges and recharges of electric current Wei 552mAhg
-1, 514mAhg
-1, 462mAhg
-1, the reversible capacity of the 20 circulation is respectively 465mAhg
-1, 442mAh
-1, 416mAhg
-1
The present invention has the following advantages:
1. raw material sources are extensive, low price.
2. technology is simple, the yield height of material.
3. the reversible capability of charging and discharging height of material.
Most preferred embodiment of the present invention is as follows:
Embodiment 1
Will with the phenolic resins of acetone solution and coal tar be by weight mix at 10: 100 after, add in the autoclave, rise to 80 ℃ with 0.3 ℃/minute speed from normal temperature, normal pressure stirred after 5 hours, rise to 180 ℃ with 2 ℃/minute speed, and under the nitrogen current protection, normal pressure stirred 5 hours, polyase 13 hour under 450 ℃ and air-tight state then, behind the polymerizate natural cooling, remove by filter mother liquor at 130 ℃, fusant is not extracted to colourless to remove residual mother liquor under 110 ℃ with pyridine, insoluble matter is carried out drying, and dry insoluble matter is at 280 ℃, oxidation is 10 hours under the air atmosphere; To rise to 700 ℃ of charings 2 hours through product speed with 10 ℃/minute under inert atmosphere protection of oxidation, obtain carbonization product; The gained carbonization product is ground to 5～50 μ m gets powdered carbon, mix with 10% ptfe emulsion then and roll on Copper Foil, make carbon membrane (carbon membrane thickness is about 0.08～12 millimeter), again carbon membrane is carried out drying and remove solvent, obtain carbon resistance rod, at last with carbon membrane as work electrode, lithium metal is as to electrode and auxiliary electrode, concentration is the LiPF of 1M
6(EC: DEC=1: 1 volume ratio) be electrolyte, polyethylene film is that barrier film is made battery to/ethylene carbonate (EC)/carbonic acid dihexyl (DEC), battery is carried out the constant current charge-discharge performance test, with 20mAg
-1, 50mAg
-1, 100mAg
-1The reversible capacity first that discharges and recharges of electric current be 542mAhg
-1, 474mAhg
-1, 416mAhg
-1, the reversible capacity of the 20 circulation is 465mAhg
-1, 424mAhg
-1, 376mAhg
-1
Embodiment 2
Will with the phenolic resins of acetone solution and coal tar be by weight mix at 50: 100 after, add in the autoclave, rise to 60 ℃ with 0.3 ℃/minute speed from normal temperature, normal pressure stirred after 10 hours, rise to 150 ℃ with 1 ℃/minute speed, and under the nitrogen current protection, normal pressure stirred 10 hours, polymerization 15 hours under 350 ℃ and air-tight state then, behind the polymerizate natural cooling, remove by filter mother liquor at 200 ℃, fusant is not extracted to colourless to remove residual mother liquor under 110 ℃ with pyridine, insoluble matter is carried out drying, and dry insoluble matter is at 200 ℃, oxidation is 15 hours under the air atmosphere; To rise to 1200 ℃ of charings 0.5 hour through product speed with 20 ℃/minute under inert atmosphere protection of oxidation, obtain carbonization product; The charing sample is ground to the particle of 5～50 μ m, is made into electrode then and carries out the constant current charge-discharge performance test, with 20mAg
-1, 50mAg
-1, 100mAg
-1The reversible capacity first that discharges and recharges of electric current be 292mAhg
-1, 254mAhg
-1, 211mAhg
-1, the reversible capacity of the 20 circulation is 267mAhg
-1, 230mAhg
-1, 183mAhg
-1
Embodiment 3
Will with the phenolic resins of acetone solution and coal tar be by weight mix at 3: 100 after, add in the autoclave, rise to 100 ℃ with 3 ℃/minute speed from normal temperature, normal pressure stirred after 1 hour, rise to 300 ℃ with 5 ℃/minute speed, and under the nitrogen current protection, normal pressure stirred 1 hour, under 500 ℃ and air-tight state polymerase 10 .5 hour then, behind the polymerizate natural cooling, remove by filter mother liquor at 100 ℃, fusant is not extracted to colourless to remove residual mother liquor under 110 ℃ with pyridine, insoluble matter is carried out drying, and dry insoluble matter is at 300 ℃, oxidation is 1 hour under the air atmosphere; To rise to 700 ℃ of charings 10 hours through product speed with 1 ℃/minute under inert atmosphere protection of oxidation, obtain carbonization product; The charing sample is ground to the particle of 5～50 μ m, is made into electrode then and carries out the constant current charge-discharge performance test, with 20mAg
-1, 50mAg
-1, 100mAg
-1The reversible capacity first that discharges and recharges of electric current be 392mAhg
-1, 368mAhg
-1, 337mAhg
-1, the reversible capacity of the 20 circulation is 367mAhg
-1, 344mAhg
-1, 308mAhg
-1
Embodiment 4
Will with the phenolic resins of acetone solution and coal tar be by weight mix at 10: 100 after, add in the autoclave, rise to 100 ℃ with 3 ℃/minute speed from normal temperature, normal pressure stirred after 1 hour, rise to 300 ℃ with 5 ℃/minute speed, and under the nitrogen current protection, normal pressure stirred 1 hour, polymerization 15 hours under 450 ℃ and air-tight state then, behind the polymerizate natural cooling, remove by filter mother liquor at 150 ℃, fusant is not extracted to colourless to remove residual mother liquor under 110 ℃ with pyridine, insoluble matter is carried out drying, and dry insoluble matter is at 300 ℃, oxidation is 10 hours under the air atmosphere; To rise to 700 ℃ of charings 1 hour through product speed with 10 ℃/minute under inert atmosphere protection of oxidation, obtain carbonization product; The charing sample is ground to the particle of 5～50 μ m, is made into electrode then and carries out the constant current charge-discharge performance test, with 20mAg
-1, 50mAg
-1, 100mAg
-1The reversible capacity first that discharges and recharges of electric current be 552mAhg
-1, 514mAhg
-1, 462mAhg
-1, the reversible capacity of the 20 circulation is 465mAhg
-1, 442mAhg
-1, 416mAhg
-1
Embodiment 5
Charing gained sample among the embodiment 4 is warming up to 1600 ℃ carries out graphitization processing under argon shield, the graphitization sample is with 20mAg
-1, 50mAg
-1, 100mAg
-1The reversible capacity first that discharges and recharges of electric current be 212mAhg
-1, 188mAhg
-1, 152mAhg
-1, the reversible capacity of the 20 circulation is 187mAhg
-1, 156mAhg
-1, 138mAhg
-1
Embodiment 6
Charing gained sample among the embodiment 4 is warming up to 2000 ℃ carries out graphitization processing under argon shield, the graphitization sample is with 20mAg
-1, 50mAg
-1, 100mAg
-1The reversible capacity first that discharges and recharges of electric current be 194mAhg
-1, 176mAhg
-1, 154mAhg
-1, the reversible capacity of the 20 circulation is 171mAhg
-1, 152mAhg
-1, 133mAhg
-1
Embodiment 7
Will with the phenolic resins of acetone solution and coal tar be by weight mix at 10: 100 after, add in the autoclave, rise to 80 ℃ with 0.3 ℃/minute speed from normal temperature, normal pressure stirred after 10 hours, rise to 150 ℃ with 1 ℃/minute speed, and under the nitrogen current protection, normal pressure stirred 10 hours, polymerization 2 hours under 450 ℃ and air-tight state then, behind the polymerizate natural cooling, remove by filter mother liquor at 120 ℃, fusant is not extracted to colourless to remove residual mother liquor under 110 ℃ with pyridine, insoluble matter is carried out drying, and dry insoluble matter is at 280 ℃, oxidation is 10 hours under the air atmosphere; To rise to 700 ℃ of charings 1 hour through product speed with 5 ℃/minute under inert atmosphere protection of oxidation, obtain carbonization product; The charing sample is ground to the particle of 5～50 μ m, is made into electrode then and carries out the constant current charge-discharge performance test, with 20mAg
-1, 50mAg
-1, 100mAg
-1The reversible capacity first that discharges and recharges of electric current be 502mAhg
-1, 462mAh
-1, 414mAhg
-1, the reversible capacity of the 20 circulation is 467mAhg
-1, 412mAhg
-1, 384mAhg
-1
Embodiment 8
Carbonization temperature among the embodiment 7 is become 600 ℃, and all the other are with embodiment 5.According to said method Zhi Bei raw material of wood-charcoal material is with 20mAg
-1, 50mAg
-1, 100mAg
-1The reversible capacity first that discharges and recharges of electric current be 442mAhg
-1, 351mAhg
-1, 298mAhg
-1, the reversible capacity of the 20 circulation is 357mAhg
-1, 294mAhg
-1, 247mAhg
-1
Embodiment 9
Charing gained sample among the embodiment 7 is warming up to 2600 ℃ carries out graphitization processing under argon shield, the graphitization sample is with 20mAg
-1, 50mAg
-1, 100mAg
-1The reversible capacity first that discharges and recharges of electric current be 265mAhg
-1, 243mAhg
-1, 208mAhg
-1, the reversible capacity of the 20 circulation is 246mAhg
-1, 224mAhg
-1, 195mAhg
-1
Embodiment 10
Charing gained sample among the embodiment 7 is warming up to 3000 ℃ carries out graphitization processing under argon shield, the graphitization sample is with 20mAg
-1, 50mAg
-1, 100mAg
-1The reversible capacity first that discharges and recharges of electric current be 332mAhg
-1, 293mAhg
-1, 252mAhg
-1, the reversible capacity of the 20 circulation is 307mAhg
-1, 279mAhg
-1, 248mAhg
-1
Claims (1)
1. the preparation method of a carbon material used as negative electrode of Li-ion battery is characterized in that step is as follows:
(1) with the phenolic resins of acetone solution and coal tar by weight being phenolic resins: coal tar=3～50: 100 mix after, add in the reactor, be warming up to 60～100 ℃, normal pressure stirred 1～10 hour, then under nitrogen protection, be warming up to 150～300 ℃, stirred again 1～10 hour, be warming up to 350～500 ℃ and under air-tight state reactive polymeric 0.5～15 hour;
(2) behind the natural cooling, polymer is removed by filter mother liquor at 100～200 ℃, insoluble matter is extracted to colourless to remove residual mother liquor under 110 ℃ with pyridine, carry out drying then;
(3) with the not fusant of drying at 200～300 ℃, oxidation is 1～15 hour under the air atmosphere, is warming up to 600～1200 ℃ of temperature charings through the product of oxidation under inert atmosphere protection, obtains carbonization product;
(4) carbonization product is warming up to 1600～3000 ℃ under the high-purity argon gas protection and carries out graphitization processing, make the graphitization sample;
(5) graphited sample is ground to 5 μ～50 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011226919A CN1157810C (en) | 2001-07-02 | 2001-07-02 | Process for preparing carbon material used as negative electrode of Li-ion battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011226919A CN1157810C (en) | 2001-07-02 | 2001-07-02 | Process for preparing carbon material used as negative electrode of Li-ion battery |
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|---|---|
| CN1393946A true CN1393946A (en) | 2003-01-29 |
| CN1157810C CN1157810C (en) | 2004-07-14 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502574A (en) * | 2011-10-17 | 2012-06-20 | 中国科学院山西煤炭化学研究所 | Preparation method of carbon anode plate material |
| CN102633251A (en) * | 2012-04-13 | 2012-08-15 | 西安交通大学 | Lithium ion battery cathode material prepared by blue carbon solid waste, and preparation method of lithium ion battery cathode material |
| CN106486641A (en) * | 2015-12-08 | 2017-03-08 | 宁波杉杉新材料科技有限公司 | A kind of lithium ion battery modified artificial graphite cathode and preparation method thereof |
| CN111029537A (en) * | 2018-10-10 | 2020-04-17 | 湖南晋烨高科股份有限公司 | Lithium battery negative electrode material, preparation method thereof and lithium battery negative electrode |
| CN111211315A (en) * | 2020-02-26 | 2020-05-29 | 中国科学院山西煤炭化学研究所 | Asphalt substrate layer carbon material and preparation method and application thereof |
| CN111263731A (en) * | 2017-10-26 | 2020-06-09 | 浦项化学株式会社 | Preparation method of porous carbon material by using coal tar generated in COG (chemical oxygen demand) process |
| CN113088263A (en) * | 2021-03-25 | 2021-07-09 | 渤瑞环保股份有限公司 | Method for preparing heat-conducting preform by blending heavy oil and waste plastic and application |
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|---|---|---|---|---|
| CN102569752A (en) * | 2010-12-10 | 2012-07-11 | 新乡远东电子科技有限公司 | Carbon modified material for lithium ion secondary battery cathode and preparation method for carbon modified material |
-
2001
- 2001-07-02 CN CNB011226919A patent/CN1157810C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102502574A (en) * | 2011-10-17 | 2012-06-20 | 中国科学院山西煤炭化学研究所 | Preparation method of carbon anode plate material |
| CN102502574B (en) * | 2011-10-17 | 2013-06-12 | 中国科学院山西煤炭化学研究所 | Preparation method of carbon anode plate material |
| CN102633251A (en) * | 2012-04-13 | 2012-08-15 | 西安交通大学 | Lithium ion battery cathode material prepared by blue carbon solid waste, and preparation method of lithium ion battery cathode material |
| CN106486641A (en) * | 2015-12-08 | 2017-03-08 | 宁波杉杉新材料科技有限公司 | A kind of lithium ion battery modified artificial graphite cathode and preparation method thereof |
| CN111263731A (en) * | 2017-10-26 | 2020-06-09 | 浦项化学株式会社 | Preparation method of porous carbon material by using coal tar generated in COG (chemical oxygen demand) process |
| US11369941B2 (en) | 2017-10-26 | 2022-06-28 | Posco Chemical Co., Ltd. | Method for preparing porous carbon material by using coal tar generated in COG process |
| CN111263731B (en) * | 2017-10-26 | 2022-12-23 | 浦项化学株式会社 | Preparation method of porous carbon material by using coal tar generated in COG (chemical oxygen demand) process |
| CN111029537A (en) * | 2018-10-10 | 2020-04-17 | 湖南晋烨高科股份有限公司 | Lithium battery negative electrode material, preparation method thereof and lithium battery negative electrode |
| CN111029537B (en) * | 2018-10-10 | 2023-05-26 | 湖南晋烨高科有限公司 | Lithium battery negative electrode material, preparation method thereof and lithium battery negative electrode |
| CN111211315A (en) * | 2020-02-26 | 2020-05-29 | 中国科学院山西煤炭化学研究所 | Asphalt substrate layer carbon material and preparation method and application thereof |
| CN111211315B (en) * | 2020-02-26 | 2023-02-28 | 中国科学院山西煤炭化学研究所 | Asphalt substrate layer carbon material and preparation method and application thereof |
| CN113088263A (en) * | 2021-03-25 | 2021-07-09 | 渤瑞环保股份有限公司 | Method for preparing heat-conducting preform by blending heavy oil and waste plastic and application |
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|---|---|
| CN1157810C (en) | 2004-07-14 |
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