CN1624956A - Production method of carbon nagtive electrode material of lithium ion cell - Google Patents
Production method of carbon nagtive electrode material of lithium ion cell Download PDFInfo
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- CN1624956A CN1624956A CNA2004100099367A CN200410009936A CN1624956A CN 1624956 A CN1624956 A CN 1624956A CN A2004100099367 A CNA2004100099367 A CN A2004100099367A CN 200410009936 A CN200410009936 A CN 200410009936A CN 1624956 A CN1624956 A CN 1624956A
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Abstract
This invention discloses a manufacturing method of the lithium battery carbon negative pole. It uses oil graphite or coal graphite as materials, carries out polyreaction under the temperature of 400-460deg.C, sample and use polarizing microscope to observe at the final phase of reaction, as the middle contact reaching to 20-80%, stop the reaction, cool and crush to obtain raw material A. Use the carbon powder, the natural graphite powder and artificial graphite powder with average aperture of 10-25 mum or their mixture as the raw material B. Use the organic solutions such as heavy oil, absorber petrol and anthracene oil as the raw material C. Mix the above raw materials based on the proportion of A/B=5-70/95-30, (A+B)/C=20-70/80-30 under the temperature of 150-200deg.C, then carry out heat process at the stirring state under the temperature of 400-600deg.C, carburize under the temperature of 900-1200deg.C, graphitize under the temperature of 2600-3000deg.C. The advantages are high content and long cycling service life.
Description
Technical field
The invention belongs to the lithium ion battery negative material technical field, a kind of carbon negative electrode material of lithium ion cell production method is provided especially, be applicable to suitability for industrialized production.
Background technology
In recent years, lithium ion battery has obtained application more and more widely.In the development process of lithium-ion electric pool technology, battery quality constantly is improved, and production cost constantly descends.Negative material has played great role in to the contribution of lithium ion battery technological progress.The negative material that obtains super quality and competitive price by surface treatment method has become one of main direction of negative material exploitation, has also obtained remarkable progress in practicality.Although the surface-treated practical approach is a lot, the technological development of this respect still has very big potentiality.
Lithium ion battery negative material remains graphite type material in actual applications and occupies an leading position.Delanium and native graphite respectively have merits and demerits as negative material, and Delanium has the advantage of stable circulation, but generally will be lower than native graphite on capacity.Though native graphite has the high advantage of capacity, capacity attenuation is its deadly defect soon in cyclic process.The surface treatment method of negative material is for the raising capacity and improve cycle performance certain effect is all arranged, no matter therefore for native graphite or artificial plumbago negative pole material, process for treating surface all is in important status in process of production, has a lot all relevant with process for treating surface about the patent of invention of negative material.JP2000357506 coats charcoal or graphite powder with cracking graphite, can not obtain thicker coating layer with this method for coating, will be restricted for the cycle performance that improves native graphite.Method pitch-coating charcoal or graphite powder that JP10294111 mixes by heat carry out not melt processed in oxidizing atmosphere, prevent that particle is molten also.The not melt processed technology here is higher to equipment requirements, is not easy to reduce production costs.JP2000348720 mesophase pitch coated graphite also will carry out not melt processed.JP2000203817 does coating with the amorphous charcoal to graphite, way is that organic substance is dissolved in the solvent, again graphite granule is dispersed in the solution, after removing solvent, carry out drying and heat treatment, can not get thicker coating layer in this way equally for native graphite, thereby be difficult to make cycle performance to be improved at all.Purpose of the present invention is exactly to overcome the shortcoming that negative material process of surface treatment in the past can't realize that vast scale coats or technology is too complicated, obtains high solids content pitch by degree of depth polymerization, realizes coating at high proportion with high solids content pitch.The effect that method for coating is reached is more obvious, and technology is also simpler.
Summary of the invention
The object of the present invention is to provide a kind of carbon negative electrode material of lithium ion cell production method, realize coating at high proportion powdered carbon or graphite powder.
The present invention proposes and prepare the method that coats pitch and application thereof.Can coat various powdered carbons or graphite powder with this pitch, all even process of coating layer is controlled easily, use solvent that the coating process is carried out under liquid situation.
Concrete production technology of the present invention is as follows:
1 is raw material with petroleum asphalt or coal tar pitch, carries out polymerization reaction under 400～460 ℃ of temperature, observes by sampling, determines the system reaction process, and cessation reaction when phase content reaches 20～80% in the middle of the system is preferably irreversible mutually in the middle of formed.Pulverize after the cooling and obtain coating raw material A.
Described petroleum asphalt can be ethylene residue.Coal tar pitch can be mid temperature pitch, modified coal tar pitch, pitch or the by-product pitch that produces when producing mesophase ball.
When polymerization, with phase growing state in the middle of the polarized light microscope observing system, system should be in flow regime during cessation reaction.
2 is raw material B with powdered carbon, natural graphite powder or graphous graphite powder and composition thereof, and the particle diameter D50 of raw material B is preferably between 10～30 μ m.Powdered carbon can be the pitch coke powder, also can be petroleum coke powder.Petroleum coke powder can be a coking powder, also can be to forge the back coke powder.Mixture can be to be mixed by any two or three of described powder.With the organic solvent is raw material C, and organic solvent is preferably heavy aromatic hydrocarbon solvent, as heavy oil, washing oil etc.
3 press A/B=5～70/95～30 with the three kinds of raw materials of A, B, C under above, (A+B)/C=20～70/80～30 mixes, under 150～200 ℃, carry out liquid-phase mixing, under stirring and 400～600 ℃ of temperature, heat-treat, stir and preferably adopt twin-screw or two ribbon alr mode.Under 900～1200 ℃ of temperature, carry out charing and handle, under 2600～3000 ℃ of temperature, carry out graphitization processing.When A/ (A+B)=10～70%, be preferably under 2600～3000 ℃ of temperature and carry out graphitization processing.
The present invention has the following advantages:
1 the present invention can increase substantially the ratio that coats pitch, and the electrical property of native graphite is improved at all.
2 can make the grain shape of Delanium and surface state obtain significant improvement, improve the bulk density of negative pole piece of battery, reduce irreversible capacity loss.
3 production technologies are simple, and the production efficiency height reduces the negative material production cost.
Embodiment
Embodiment 1:
The ethylene residue of 300 grams, polyase 13 is 60 minutes under 420 ℃ of temperature, and the middle phase content of observation system reaches 25% under the petrographic microscope, cessation reaction, the cooling back is pulverized and is obtained raw material A.
Take by weighing raw material A 100 grams, native graphite B 400 grams, solvent naphtha 300 grams.
Three kinds of raw materials are mixed, and dissolving is 120 minutes under 200 ℃ of temperature.Temperature is raised to 450 ℃ again, under strong mixing, kept 240 minutes.Continue slowly to be warming up to 600 ℃, kept 180 minutes, under 2700 ℃ of temperature, carry out graphitization.
Do experiment with button cell, gained negative material discharge capacity first is 355mAh/g, and discharging efficiency is 95% first.300 times circulation back capacity keeps 90%.
Embodiment 2:
The modified coal tar pitch of 300 grams, polymerization is 180 minutes under 430 ℃ of temperature, and phase content reached 40% in the middle of petrographic microscope was observed down, cessation reaction, the cooling back is pulverized and is obtained raw material A.
Take by weighing raw material A 100 grams, Delanium B 200 grams, washing oil 600 grams.
Three kinds of raw materials are mixed, and dissolving is 120 minutes under 200 ℃ of temperature.Temperature is raised to 440 ℃ again, under strong mixing, kept 180 minutes.Continue slowly to be warming up to 600 ℃, kept 150 minutes.Under 2800 ℃ of temperature, carry out graphitization.
Do experiment with button cell, gained negative material discharge capacity first is 335mAh/g, and discharging efficiency is 96% first.
Embodiment 3:
The mid temperature pitch of 300 grams, polymerization is 180 minutes under 450 ℃ of temperature, and phase content reached 70% in the middle of petrographic microscope was observed down, and the cooling back is pulverized and is obtained raw material A.
Take by weighing raw material A 140 grams, petroleum coke coke powder B 60 grams, pyridine solvent 700 grams.
Three kinds of raw materials are mixed, and dissolving is 120 minutes under 200 ℃ of temperature.Temperature is raised to 450 ℃ again, under strong mixing, kept 240 minutes.Continue slowly to be warming up to 500 ℃, kept 210 minutes, under 900 ℃, carry out charing and handle, under 2900 ℃ of temperature, carry out graphitization.
Do experiment with button cell, gained negative material discharge capacity first is 340mAh/g, and discharging efficiency is 96% first.
Embodiment 4:
The petroleum asphalt of 300 grams, polymerization is 210 minutes under 420 ℃ of temperature, and phase content reached 35% in the middle of petrographic microscope was observed down, and the cooling back is pulverized and is obtained raw material A.
Take by weighing raw material A 25 grams, native graphite B 275 grams, carbolineum solvent 150 grams.
Three kinds of raw materials are mixed, and dissolving is 120 minutes under 200 ℃ of temperature.Temperature is raised to 420 ℃ again, under strong mixing, kept 210 minutes.Continue slowly to be warming up to 600 ℃, kept 210 minutes, under 1200 ℃ of temperature, carry out charing.
Do experiment with button cell, gained negative material discharge capacity first is 350mAh/g, and discharging efficiency is 94% first.
Claims (3)
1, a kind of carbon negative electrode material of lithium ion cell production method is characterized in that: concrete production technology is:
A, be raw material with petroleum asphalt or coal tar pitch, under 400～460 ℃ of temperature, carry out polymerization reaction, in course of reaction, use the middle phase growing state of polarized light microscope observing system, cessation reaction when phase content reaches 20～80% in the middle of the system, system should be in flow regime during cessation reaction, pulverizes after the cooling to obtain coating raw material A;
B, be raw material B with powdered carbon, natural graphite powder or graphous graphite powder and composition thereof, the particle diameter D of raw material B
50Be between 10～30 μ m, mixture is mixed by any 2～3 kinds of described powder, is raw material C with the organic solvent;
C, the three kinds of raw materials of A, B, C under above are pressed A/B=5～70/95～30, (A+B)/C=20～70/80～30 mixes, and carries out liquid-phase mixing under 150～200 ℃, under stirring and 400～600 ℃ of temperature, heat-treat; Under 900～1200 ℃ of temperature, carry out charing and handle, under 2600～3000 ℃ of temperature, carry out graphitization processing.
2, according to the described production method of claim 1, it is characterized in that: described powdered carbon is pitch coke powder or petroleum coke powder; Described petroleum coke powder is coking powder or forges the back coke powder; Described organic solvent is heavy aromatic hydrocarbon solvent such as heavy oil or washing oil.
3, according to the described production method of claim 1, it is characterized in that: stir and adopt twin-screw or two ribbon alr mode; When A/ (A+B)=10～70%, be preferably under 2600～3000 ℃ of temperature and carry out graphitization processing.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186292A (en) * | 2006-11-22 | 2008-05-28 | 辽宁工程技术大学 | Method for preparing carbon cathode material and lithium iron battery using the material |
| CN100420627C (en) * | 2006-08-14 | 2008-09-24 | 长沙市海容电子材料有限公司 | Graphite material with shell-core structure and preparation method thereof |
| CN101108918B (en) * | 2007-08-16 | 2010-06-30 | 湛江市新蓄能源科技有限公司 | High softening point bitumen used as lithium ion battery negative pole coating layer material and manufacture thereof |
| CN102104141A (en) * | 2010-12-25 | 2011-06-22 | 雷铁军 | Method for preparing graphite anode material of membrane-structural lithium ion battery by hot coating method |
| CN101707246B (en) * | 2009-04-03 | 2011-12-21 | 湖州创亚动力电池材料有限公司 | Method for preparing carbon cathode material of lithium ion battery, carbon cathode material and lithium ion battery |
| CN102473915A (en) * | 2010-06-30 | 2012-05-23 | 松下电器产业株式会社 | Negative electrode for nonaqueous electrolyte secondary battery |
| CN103296255A (en) * | 2013-06-09 | 2013-09-11 | 东莞市比比克电子科技有限公司 | Manufacturing process of cathode material of lithium-ion battery |
| CN103346326A (en) * | 2013-07-08 | 2013-10-09 | 辽宁弘光科技(集团)有限公司 | Preparation method for carbon cathode material of lithium ion battery |
| CN103482606A (en) * | 2013-09-23 | 2014-01-01 | 辽宁弘光科技(集团)有限公司 | Production method for intermediate phase carbon anode material |
| CN105623694A (en) * | 2015-12-23 | 2016-06-01 | 山东晨阳新型碳材料股份有限公司 | Production method of intermediate-phase asphalt coke |
| CN103441251B (en) * | 2013-08-22 | 2017-12-05 | 大连宏光锂业股份有限公司 | The production method of compound coating carbon negative electrode material of lithium ion cell |
| CN109082301A (en) * | 2018-09-06 | 2018-12-25 | 中钢集团鞍山热能研究院有限公司 | A kind of production technology and its process units of negative electrode material coke |
| CN112750988A (en) * | 2019-10-29 | 2021-05-04 | 宝武炭材料科技有限公司 | Liquid-coated oil composition and preparation method and application thereof |
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| CN107871859A (en) * | 2016-09-27 | 2018-04-03 | 上海杉杉科技有限公司 | A kind of preparation method of Hyperhemodynamics lithium ion battery negative material |
-
2004
- 2004-12-02 CN CNB2004100099367A patent/CN1278437C/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100420627C (en) * | 2006-08-14 | 2008-09-24 | 长沙市海容电子材料有限公司 | Graphite material with shell-core structure and preparation method thereof |
| CN101186292A (en) * | 2006-11-22 | 2008-05-28 | 辽宁工程技术大学 | Method for preparing carbon cathode material and lithium iron battery using the material |
| CN101108918B (en) * | 2007-08-16 | 2010-06-30 | 湛江市新蓄能源科技有限公司 | High softening point bitumen used as lithium ion battery negative pole coating layer material and manufacture thereof |
| CN101707246B (en) * | 2009-04-03 | 2011-12-21 | 湖州创亚动力电池材料有限公司 | Method for preparing carbon cathode material of lithium ion battery, carbon cathode material and lithium ion battery |
| CN102473915A (en) * | 2010-06-30 | 2012-05-23 | 松下电器产业株式会社 | Negative electrode for nonaqueous electrolyte secondary battery |
| CN102104141A (en) * | 2010-12-25 | 2011-06-22 | 雷铁军 | Method for preparing graphite anode material of membrane-structural lithium ion battery by hot coating method |
| CN103296255B (en) * | 2013-06-09 | 2016-05-11 | 东莞市卓高电子科技有限公司 | A kind of lithium ion battery negative material manufacturing process |
| CN103296255A (en) * | 2013-06-09 | 2013-09-11 | 东莞市比比克电子科技有限公司 | Manufacturing process of cathode material of lithium-ion battery |
| CN103346326A (en) * | 2013-07-08 | 2013-10-09 | 辽宁弘光科技(集团)有限公司 | Preparation method for carbon cathode material of lithium ion battery |
| CN103441251B (en) * | 2013-08-22 | 2017-12-05 | 大连宏光锂业股份有限公司 | The production method of compound coating carbon negative electrode material of lithium ion cell |
| CN103482606B (en) * | 2013-09-23 | 2015-06-17 | 大连宏光锂业股份有限公司 | Production method for intermediate phase carbon anode material |
| CN103482606A (en) * | 2013-09-23 | 2014-01-01 | 辽宁弘光科技(集团)有限公司 | Production method for intermediate phase carbon anode material |
| CN105623694A (en) * | 2015-12-23 | 2016-06-01 | 山东晨阳新型碳材料股份有限公司 | Production method of intermediate-phase asphalt coke |
| CN105623694B (en) * | 2015-12-23 | 2018-09-11 | 济宁碳素集团有限公司 | A kind of production method of mesophase pitch coke |
| CN109082301A (en) * | 2018-09-06 | 2018-12-25 | 中钢集团鞍山热能研究院有限公司 | A kind of production technology and its process units of negative electrode material coke |
| CN109082301B (en) * | 2018-09-06 | 2023-12-26 | 中钢集团鞍山热能研究院有限公司 | Production process and production device of anode material coke |
| CN112750988A (en) * | 2019-10-29 | 2021-05-04 | 宝武炭材料科技有限公司 | Liquid-coated oil composition and preparation method and application thereof |
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| CN1278437C (en) | 2006-10-04 |
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