CN103456958A - Preparation method of high-energy density type artificial graphite cathode material - Google Patents
Preparation method of high-energy density type artificial graphite cathode material Download PDFInfo
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- CN103456958A CN103456958A CN2013104286639A CN201310428663A CN103456958A CN 103456958 A CN103456958 A CN 103456958A CN 2013104286639 A CN2013104286639 A CN 2013104286639A CN 201310428663 A CN201310428663 A CN 201310428663A CN 103456958 A CN103456958 A CN 103456958A
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Abstract
The invention discloses a preparation method of a high-energy density type artificial graphite cathode material, which is characterized by comprising the following steps: grinding coke powder and performing high-temperature purification at 1,800-2,000 DEG EC to obtain a high-purity raw material; uniformly mixing the high-purity raw material with the resin easy to be carbonized and graphitized; heating to 150-600 DEG C, stirring so that the coke is sufficiently soaked in the resin, and then cooling; carbonizing at 1,000-1,300 DEG C, and graphitizing at 2,800-3,000 DEG C under the condition of introducing chlorine gas or Freon; finally, cooling and sieving to obtain the high-energy density type artificial graphite cathode material. By adopting the method disclosed by the invention, the obtained artificial graphite cathode material has the advantages of high graphitization degree, small specific surface area, denser structure, high tap density, high pole piece compaction density and large reversible discharge capacity.
Description
Technical field
The invention belongs to chemical power source lithium ion battery negative material technical field, particularly relate to the preparation method of high-energy-density type artificial plumbago negative pole material.
Technical background
Lithium ion battery has the advantages such as operating voltage is high, energy density is high, efficiency for charge-discharge is high, self discharge is little, memory-less effect, be widely used in the fields such as mobile phone, portable computer, electric tool, energy storage device, electric automobile, be considered to desirable secondary power supply of 21 century.
Negative material is one of critical material of lithium ion battery, and carbon negative pole material is at present unique lithium ion battery negative material that obtains the heavy industrialization application, mainly comprises native graphite, Delanium and MCMB etc.Native graphite, because cycle performance is poor, is difficult to the demand of satisfying the market; Although MCMB has excellent cycle performance, its capacity is on the low side; And artificial plumbago negative pole material has excellent cycle performance and higher capacity simultaneously, price also has stronger competitiveness, and the share in market increases year by year.
Artificial plumbago negative pole material be mainly used in smart mobile phone, dull and stereotyped IT, the super utmost point this etc. high-end 3C Product battery, the application aspect electric automobile power battery also increases gradually.In recent years, in order to promote stand-by time and course continuation mileage, 3C Product battery and electrokinetic cell develop to the high-energy-density type gradually, as the intelligent mobile phone battery energy density has reached 550Wh/L, estimate will approach 650Wh/L after 2 years, far above the 350Wh/L of regular handset battery before 5 years, this will ask for help and make graphite cathode material and must have higher specific discharge capacity and tap density, with the lifting of the energy density that realizes battery system.
But there are following shortcoming in existing Delanium and technology of preparing thereof:
1) raw materials such as green coke, calcined coke, pitch generally contain the influential impurity of graphitization, as ash content, sulphur content etc., cause material to have a large amount of lattice defects, degree of graphitization is low, capacity is only 335-350mAh/g, can't meet the demand of high-energy-density type lithium ion battery;
2) existence of the impurity such as a large amount of volatile matters, ash content, sulphur content in raw material, also can cause material to have the faults of construction such as a large amount of crackles, hole, and specific area increases, and causes the material first charge-discharge efficiency low, and tap density is low.
3), in order to control the material specific area, existing technique generally coats the uniform amorphous carbon material of one deck on the Delanium surface.But amorphous carbon density is usually lower, make on the contrary tap density reduce, the pole piece compacted density is generally less than 1.55g/cm
3, energy content of battery density reduces.
4) the amorphous carbon layer graphitization that also has the part technology that material surface is coated, to improve the material tap density, but twice graphitization energy consumption is huge, and contain the impurity such as the graphited quinoline insolubles of difficulty or ease in the pitch usually used as the coating layer carbon source, the material degree of graphitization is low.
Summary of the invention
The present invention, for solving the above-mentioned problems in the prior art, provides a kind of preparation method of high-energy-density type artificial plumbago negative pole material.
The preparation method that the present invention is a kind of high-energy-density type artificial plumbago negative pole material, is characterized in that, comprises the following steps:
After coke is pulverized at 1800-2000 ℃ of lower high temperature purification, the high pure raw material obtained; Again by the mixed with resin of the described high pure raw material that obtains and easy carbonized graphite evenly after, be warming up to 150-600 ℃ of stirring and make described resin form after abundant dipping cooling to described coke; Subsequently, first 1000-1300 ℃ of lower carbonization, then under the condition that passes into chlorine or freon 2800-3000 ℃ of lower graphitization, finally cooling, sieving makes high-energy-density type artificial plumbago negative pole material.
In technique scheme, described coke is oil green coke, coal tar pitch Jiao, needle coke or calcined coke; The resin of described easy carbonized graphite is one or more in acetenyl silane resin, fragrant polyimide type resin, polyaniline resin, polyoxadiazoles resin, poly-aryl ethane resin or polyethersulfone ketone resin, and the mass ratio of wherein said high pure raw material and described resin is 1:0.05-0.25.
Above-mentioned coke is pulverized rear particle diameter (D
50) be 5-30 μ m, that better is 10-20 μ m.
Advantage and beneficial effect that the present invention has are:
1. coke is pulverized to laggard row high temperature purification, especially cleansing temp is up to 1800-2000 ℃, most volatile matter, sulphur content, ash content can have been removed, and selected impregnating agent high-purity resin that is easier carbonized graphite, not containing impurity components such as quinoline insolubleses, gained negative material degree of graphitization is high, and reversible discharge capacity is higher than 360mAh/g;
2. after high temperature purification, the high pure raw material obtained is carried out to the resin-dipping processing, then, through carbonized graphite, the hole occurred while making high temperature purification, crackle etc. are made up, the material specific area is low, and first charge-discharge efficiency is high.And after the impregnating resin graphitization, make material structure more fine and close, and the material tap density is high, and the pole piece compacted density is large.
Embodiment
Below by specific embodiment, the present invention is described in detail, following embodiment is only for the present invention is described, but the practical range be not intended to limit the present invention.
Embodiment 1: petroleum coke powder is broken to granularity (D
50) be 12 μ m particles, then under 1800 ℃, carry out high temperature purification.By the high pure raw material after purifying and acetenyl silane resin in mass ratio 1:0.1 mix, insert in stirred autoclave and be heated to 300 ℃, constant temperature 4h, realize the abundant dipping of resin to raw material.Cooling rear sample passes into graphitization under the condition of chlorine 1000 ℃ of carbonizations, 2800 ℃, after screening both high-energy-density type artificial plumbago negative pole material.Resulting materials discharge capacity 361mAh/g, first charge-discharge efficiency 92%, tap density 1.05g/cm
3, pole piece compacted density 1.72g/cm
3.
Embodiment 2: the coal tar pitch coke powder is broken to granularity (D
50) be 15 μ m particles, then under 1900 ℃, carry out high temperature purification.By the high pure raw material after purifying and polyethersulfone ketone resin in mass ratio 1:0.15 mix, insert in stirred autoclave and be heated to 400 ℃, constant temperature 2h, realize the abundant dipping of resin to raw material.Cooling rear sample passes into graphitization under the condition of chlorine 1100 ℃ of carbonizations, 2900 ℃, after screening both high-energy-density type artificial plumbago negative pole material.Resulting materials discharge capacity 363mAh/g, first charge-discharge efficiency 91%, tap density 1.01g/cm
3, pole piece compacted density 1.70g/cm
3.
Embodiment 3: after-smithing petroleum coke is crushed to granularity (D
50) be 17 μ m particles, then under 2000 ℃, carry out high temperature purification.By the high pure raw material after purifying, acetenyl silane resin and polyethersulfone ketone resin in mass ratio 1:0.15:0.05 mix, insert in stirred autoclave and be heated to 450 ℃, constant temperature 2h, realize the abundant dipping of resin to raw material.Cooling rear sample passes into graphitization under the condition of chlorine 1200 ℃ of carbonizations, 3000 ℃, after screening both high-energy-density type artificial plumbago negative pole material.Resulting materials discharge capacity 364mAh/g, first charge-discharge efficiency 92%, tap density 1.07g/cm
3, pole piece compacted density 1.75g/cm
3.
Comparative Examples: petroleum coke powder is broken to granularity (D
50) be 12 μ m particles, then under 1200 ℃, carry out carbonization treatment.Raw material after carbonization is carried out to graphitization processing and obtains Delanium material, 3000 ℃ of graphitization temperatures passing under the chlorine condition.By Delanium and high temperature petroleum asphalt (270 ℃ of softening points) in mass ratio 1:0.1 mix, insert in stirred autoclave and be heated to 500 ℃, constant temperature 4h, realize the abundant coating dipping of hard pitch to raw material.Cooling rear sample, 1200 ℃ of carbonizations, had both obtained the artificial plumbago negative pole material that amorphous carbon material coats modification after screening.Resulting materials discharge capacity 350mAh/g, first charge-discharge efficiency 91%, tap density 0.85g/cm
3, pole piece compacted density 1.61g/cm
3.
Claims (3)
1. the preparation method of a high-energy-density type artificial plumbago negative pole material, is characterized in that, comprises the following steps:
After coke is pulverized at 1800-2000 ℃ of lower high temperature purification, the high pure raw material obtained; Again by the mixed with resin of the described high pure raw material that obtains and easy carbonized graphite evenly after, be warming up to 150-600 ℃ of stirring and make described resin form after abundant dipping cooling to described coke; Subsequently, first 1000-1300 ℃ of lower carbonization, then under the condition that passes into chlorine or freon 2800-3000 ℃ of lower graphitization, finally cooling, sieving makes high-energy-density type artificial plumbago negative pole material.
2. the preparation method of a kind of high-energy-density type artificial plumbago negative pole material according to claim 1, is characterized in that, described coke is oil green coke, coal tar pitch Jiao, needle coke or calcined coke; The resin of described easy carbonized graphite is one or more in acetenyl silane resin, fragrant polyimide type resin, polyaniline resin, polyoxadiazoles resin, poly-aryl ethane resin or polyethersulfone ketone resin, and the mass ratio of wherein said high pure raw material and described resin is 1:0.05-0.25.
3. the preparation method of a kind of high-energy-density type artificial plumbago negative pole material according to claim 1, is characterized in that, the particle diameter D after described coke is pulverized
50for 5-30 μ m.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104401974A (en) * | 2014-10-24 | 2015-03-11 | 中国海洋石油总公司 | Preparation method of high capacity carbon cathode material for lithium ion batteries |
| CN106159235A (en) * | 2016-08-26 | 2016-11-23 | 宁波杉杉新材料科技有限公司 | A kind of preparation method of graphite negative material of lithium ion battery |
| CN106505184A (en) * | 2016-10-10 | 2017-03-15 | 新乡市博瑞达电源材料有限公司 | A kind of polynary coating modification lithium ion battery negative material and preparation method thereof |
| CN108190879A (en) * | 2017-12-25 | 2018-06-22 | 惠州Tcl金能电池有限公司 | Modified artificial graphite and preparation method thereof and lithium ion battery |
| CN112875695A (en) * | 2021-01-29 | 2021-06-01 | 广东凯金新能源科技股份有限公司 | Artificial graphite as resistance material and preparation method thereof |
| CN113753882A (en) * | 2021-08-16 | 2021-12-07 | 山西沁新能源集团股份有限公司 | Preparation method of artificial graphite negative electrode material |
| CN114709393A (en) * | 2022-04-11 | 2022-07-05 | 深圳市翔丰华科技股份有限公司 | Preparation method of negative electrode material for sodium ion battery |
| CN116375015A (en) * | 2023-03-16 | 2023-07-04 | 湖北斯诺新材料科技有限公司 | Preparation method and application of artificial graphite material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1481041A (en) * | 2002-07-31 | 2004-03-10 | ���µ�����ҵ��ʽ���� | Lithium secondary cell |
| CN1796334A (en) * | 2004-12-27 | 2006-07-05 | 陈瑾惠 | Carbon/Carbon Composite material and mfg. method thereof |
| CN1885598A (en) * | 2006-07-10 | 2006-12-27 | 深圳市贝特瑞电子材料有限公司 | Composite carbon negative electrode material of lithium ion power battery and its preparation method |
-
2013
- 2013-09-18 CN CN2013104286639A patent/CN103456958A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1481041A (en) * | 2002-07-31 | 2004-03-10 | ���µ�����ҵ��ʽ���� | Lithium secondary cell |
| CN1796334A (en) * | 2004-12-27 | 2006-07-05 | 陈瑾惠 | Carbon/Carbon Composite material and mfg. method thereof |
| CN1885598A (en) * | 2006-07-10 | 2006-12-27 | 深圳市贝特瑞电子材料有限公司 | Composite carbon negative electrode material of lithium ion power battery and its preparation method |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104401974A (en) * | 2014-10-24 | 2015-03-11 | 中国海洋石油总公司 | Preparation method of high capacity carbon cathode material for lithium ion batteries |
| CN104401974B (en) * | 2014-10-24 | 2016-06-15 | 中国海洋石油总公司 | A kind of preparation method of lithium ion battery high power capacity carbon negative pole material |
| CN106159235A (en) * | 2016-08-26 | 2016-11-23 | 宁波杉杉新材料科技有限公司 | A kind of preparation method of graphite negative material of lithium ion battery |
| CN106505184A (en) * | 2016-10-10 | 2017-03-15 | 新乡市博瑞达电源材料有限公司 | A kind of polynary coating modification lithium ion battery negative material and preparation method thereof |
| CN108190879A (en) * | 2017-12-25 | 2018-06-22 | 惠州Tcl金能电池有限公司 | Modified artificial graphite and preparation method thereof and lithium ion battery |
| CN112875695A (en) * | 2021-01-29 | 2021-06-01 | 广东凯金新能源科技股份有限公司 | Artificial graphite as resistance material and preparation method thereof |
| CN113753882A (en) * | 2021-08-16 | 2021-12-07 | 山西沁新能源集团股份有限公司 | Preparation method of artificial graphite negative electrode material |
| CN114709393A (en) * | 2022-04-11 | 2022-07-05 | 深圳市翔丰华科技股份有限公司 | Preparation method of negative electrode material for sodium ion battery |
| CN116375015A (en) * | 2023-03-16 | 2023-07-04 | 湖北斯诺新材料科技有限公司 | Preparation method and application of artificial graphite material |
| CN116375015B (en) * | 2023-03-16 | 2024-02-20 | 湖北斯诺新材料科技有限公司 | Preparation method and application of artificial graphite material |
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Application publication date: 20131218 |