CN1472831A - Cathode carbon material of lithium ion battery and preparing method thereof - Google Patents
Cathode carbon material of lithium ion battery and preparing method thereof Download PDFInfo
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- CN1472831A CN1472831A CNA031293794A CN03129379A CN1472831A CN 1472831 A CN1472831 A CN 1472831A CN A031293794 A CNA031293794 A CN A031293794A CN 03129379 A CN03129379 A CN 03129379A CN 1472831 A CN1472831 A CN 1472831A
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Abstract
A negative electrode carbon material of Li-ion battery, covers the surface of carbon material with the carbon composite that contains of the compound of boron and Li and has the core-shell structure; the method for preparation is as follows: adopt the compound of Li\compound of boron and carbon material as raw material, first dissolve the compound of boron in distilled water at the container to confect the boric acid solution, put the comminuting compound of Li and carbon material into the confected boric acid solution, stir it equally, dry by distillation, put the carbon material which is covered with the compound of boron and Li ion argon atmosphere to roast, through the natural cooling get the negative electrode carbon material of Li-ion battery.
Description
Technical field: the invention belongs to lithium ion battery negative pole carbon material and preparation method thereof.
Background technology: lithium ion battery realizes that one of key of small-sized, high capacity is the carbon materials as negative material, at present, for new, effectively negative pole constantly deeply carries out with the research of carbon materials.Graphite is the lithium ion battery negative material that a class has development prospect.Graphite is as the negative pole of lithium ion battery, compares with the material with carbon element of other structure that to have charge and discharge platform low, and voltage is stablized (0.0～0.2V vs.Li
+/ Li) advantage.But because the degree of graphitization of graphite is bigger, edge, the difference between the bottom surface of carbon crystallite are bigger, the reaction inhomogeneities is stronger, the reduction decomposition reaction of electrolyte mainly betides the marginal portion of crystallite, the fine and close character of the passivating film that is generated is relatively poor, in charging process, the common embedding of solvation lithium ion when inserting graphite layers, lithium ion easily takes place, the irreversible processs such as expansion, collapse that cause graphite linings take place, and make graphite material be unsuitable for directly the electrode material as lithium ion battery.Other non-graphite material with carbon element also all exists the low problem of first charge-discharge efficiency to some extent, makes that the lithium source is the large usage quantity of positive electrode in the battery enclosed system, and the production cost of battery is higher, is unfavorable for the large-scale industrial production of battery.
In order to obtain high performance used as negative electrode of Li-ion battery material with carbon element, in Chinese invention patent CN 1225196A, reported the method that the carbon materials piece that will contain boron or boron compound is heat-treated, improved the reversible specific capacity of native graphite to a certain extent, but further research report not aspect circulating and reversible performance repeatedly, only provided the test result of first charge-discharge, the deficiency of its circulating and reversible performance aspect makes it be difficult to reach requirement of actual application.
Summary of the invention: the lithium ion battery negative pole carbon material that the object of the present invention is to provide a kind of super quality and competitive price, by carbon materials being carried out coating modification, in the hope of obtaining a kind of carbon negative electrode material of lithium ion cell with height ratio capacity and excellent cycle reversibility with the boron lithium compound.
Another object of the present invention provides a kind of new method for preparing the lithium ion battery negative active material, and Zhi Bei negative active core-shell material is applied to lithium ion battery and has good charge-discharge characteristic in this way, and shortens the production time, reduces production costs.
The invention provides a kind of negative material of lithium ion battery, this negative material is the carbon composite with nucleocapsid structure, nuclear wherein is material with carbon element, shell is that a surface coated layer thickness is the mixture that contains boron carbide, lithium borate of 1-5 μ m, and the element lithium in this coating shell and the percentage by weight of boron are 0.2-0.4.
Lithium ion battery negative pole carbon material preparation method of the present invention is as follows:
It is raw material that the present invention adopts the compound of boron, the compound and the material with carbon element of lithium, and wherein the compound of boron is boric acid, diboron trioxide; The compound of lithium is lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate; Material with carbon element is electrographite, native graphite; The consumption of raw material according to the mol ratio of atom is: the ratio of Li: B: C=1-3: 2-6: 12-40 takes by weighing; In container, the compound of boron is dissolved at first that the preparation weight ratio is the BAS of 2-4% in the distilled water, with the compound and the material with carbon element of the lithium of the porphyrize of 200 mesh sieves add in the boric acid aqueous solution of preparation excessively, normal temperature stirs after 3-5 hour down, together be put in evaporating water in the baking oven together with container, the material with carbon element that has coated the boron lithium compound is placed in the alumina crucible, in the argon atmospher 700-1200 ℃ roast 6-10 hour, natural cooling makes product.
Characteristics of the present invention are, preparation technology is simple, and generated time is short, temperature is low, the synthetic a kind of new lithium ion secondary battery negative pole material with carbon element that can be used as, have bigger capacity and better cyclical stability than the related compound of reporting at present, have significant practical value and economic benefit.
Description of drawings: Fig. 1 represents the charging and discharging curve of material when charge-discharge magnification is 0.2C that embodiment 1 is prepared.
Embodiment:
Embodiment 1:
The consumption of raw material boride, lithium carbonate and material with carbon element according to the mol ratio of atom is: Li: B: C=1: 3: 18 ratio takes by weighing, wherein lithium carbonate 0.369 gram, boric acid 1.855 grams, electrographite 2.16 grams; At first in the 500ml beaker, boric acid is dissolved in preparation weight ratio in the distilled water and is 3% BAS, lithium carbonate and the material with carbon element of crossing the porphyrize of 200 mesh sieves are added in the BAS of preparation, normal temperature stirs after 4 hours down, together be put in evaporating water in the baking oven together with beaker, to coat the material with carbon element of boron lithium compound in alumina crucible, 750 ℃ of roasts are 6 hours in the argon atmospher, and natural cooling makes product.
Product with gained is a negative material, and acetylene black is conductive agent, and Kynoar (PVDF) is a bonding agent: the composition weight ratio of work electrode is: active material: acetylene black: bonding agent=8: 1: 1; With each component materials of electrode furnishing pasty state in N-methyl pyrrolidone (be called for short NMP) according to the above ratio, be evenly coated on the nickel sheet, (about 200Kg/cm pressurizes
2) moulding, 120 ℃ of oven dry of spending the night make the heavy 10mg/cm that generally is about of work electrode
2With the carbon electrode is work electrode, and metal lithium sheet is to electrode, and Celgard 2400 is a barrier film, ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1: 1)+1MLiPF
6Be electrolyte.Battery is assemblied in the glove box of applying argon gas and carries out, and water content is less than 1ppm.
In the voltage range of 0.0V～3.0V, with the test that the speed of 0.2C discharges and recharges on cell tester, test result such as Fig. 1.This material reversible capacity first is about 339mAh/g, and first charge-discharge efficiency is 95%, and through 200 circulations, reversible capacity is 326mAh/g, and capability retention is 96%.
Embodiment 2:
In Li: B: C=1: the ratio of 3: 24 (mol ratio) takes by weighing corresponding compounds: 0.369 gram lithium carbonate, 1.855 gram boric acid, 2.88 gram native graphites, and press the method preparation of embodiment 1 and test.The material of preparation, reversible capacity is about 345mAh/g first, and first charge-discharge efficiency is 90%, and through 200 circulations, reversible capacity is 322mAh/g, and capability retention is 93%.
Embodiment 3:
In Li: B: C=1: the ratio of 3: 30 (mol ratio) takes by weighing corresponding compounds: 0.369 gram lithium carbonate, 1.855 gram boric acid, 3.6 gram electrographites, and press the method preparation of embodiment 1 and test.The material of preparation, reversible capacity is about 352mAh/g first, and first charge-discharge efficiency is 88%, and through 200 circulations, reversible capacity is 321mAh/g, and capability retention is 91%.
Embodiment 4:
In Li: B: C=1: the ratio of 3: 30 (mol ratio) takes by weighing corresponding compounds: 0.369 gram lithium carbonate, 1.855 gram boric acid, 3.6 gram native graphites, and press the method preparation of embodiment 1 and test.The material of preparation, reversible capacity is about 330mAh/g first, and first charge-discharge efficiency is 94%, and through 200 circulations, reversible capacity is 3 12mAh/g, and capability retention is 94%.
Claims (5)
1, a kind of lithium ion battery negative pole carbon material, it is characterized in that this carbon material used as anode is the carbon composite with nucleocapsid structure, nuclear wherein is material with carbon element, shell is that a surface coated layer thickness is the mixture that contains boron carbide, lithium borate of 1-5 μ m, and the element lithium in this coating shell and the percentage by weight of boron are 0.2-0.4.
2, a kind of lithium ion battery negative pole carbon material according to claim 1, the nuclear that it is characterized in that carbon composite is the material with carbon element of electrographite, native graphite.
3, a kind of lithium ion battery negative material preparation method, it is characterized in that adopting the compound of boron, the compound and the material with carbon element of lithium is raw material, the consumption of raw material according to the mol ratio of atom is: the ratio of Li: B: C=1-3: 2-6: 12-40 takes by weighing; In container, the compound of boron is dissolved at first that the preparation weight ratio is the BAS of 2-4% in the distilled water, with the compound and the material with carbon element of the lithium of the porphyrize of 200 mesh sieves add in the boric acid aqueous solution of preparation excessively, normal temperature stirs after 3-5 hour down, together be put in evaporating water in the baking oven together with container, the material with carbon element that has coated the boron lithium compound is placed in the alumina crucible, in argon atmospher 700-1200 ℃ roast 6-10 hour, natural cooling makes product.
4, a kind of lithium ion battery negative material preparation method according to claim 3 is characterized in that adopting the compound of boron is boric acid, diboron trioxide.
5, a kind of lithium ion battery negative material preparation method according to claim 3, the compound that it is characterized in that lithium is lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB031293794A CN1206759C (en) | 2003-06-19 | 2003-06-19 | Cathode carbon material of lithium ion battery and preparing method thereof |
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| CN1206759C CN1206759C (en) | 2005-06-15 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006017986A1 (en) * | 2004-08-17 | 2006-02-23 | Byd Company Limited | Materials for negative electrodes of lithium ion batteries |
| US7629082B2 (en) | 2004-04-23 | 2009-12-08 | Lg Chem, Ltd. | Anode active material with improved electrochemical properties and electrochemical device comprising the same |
| CN101969122A (en) * | 2010-09-14 | 2011-02-09 | 东莞市迈科新能源有限公司 | Core-shell structured carbon for cathode material of lithium ion battery and preparation method thereof |
| CN105633407A (en) * | 2016-03-11 | 2016-06-01 | 中物院成都科学技术发展中心 | Surface modification method for carbon-based anode material for lithium-ion battery and carbon-based anode material |
| CN103066299B (en) * | 2013-01-08 | 2016-12-28 | 东莞新能源科技有限公司 | Native graphite of borosilicate coating modification and preparation method thereof |
| CN106532004A (en) * | 2016-12-10 | 2017-03-22 | 浙江大学 | Preparation method of carbon-coated nano boron composite material for negative electrode of lithium-ion battery |
| CN106784666A (en) * | 2016-12-10 | 2017-05-31 | 浙江大学 | For the preparation method of the carbon-coated nano boron lithium composite material of lithium-sulfur cell negative pole |
| CN108172757A (en) * | 2018-01-24 | 2018-06-15 | 中国工程物理研究院电子工程研究所 | A kind of high pressure Thermal Cell Cathode Material, high pressure thermal cell and preparation method thereof |
| CN111525097A (en) * | 2019-02-01 | 2020-08-11 | 沁新集团(天津)新能源技术研究院有限公司 | Negative electrode material, preparation method and application thereof |
-
2003
- 2003-06-19 CN CNB031293794A patent/CN1206759C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7629082B2 (en) | 2004-04-23 | 2009-12-08 | Lg Chem, Ltd. | Anode active material with improved electrochemical properties and electrochemical device comprising the same |
| US7754385B2 (en) | 2004-04-23 | 2010-07-13 | Lg Chem, Ltd. | Anode active material with improved electrochemical properties and electrochemical device comprising the same |
| CN1947283B (en) * | 2004-04-23 | 2013-06-12 | 株式会社Lg化学 | Anode active material with improved electrochemical properties and electrochemical device comprising the same |
| WO2006017986A1 (en) * | 2004-08-17 | 2006-02-23 | Byd Company Limited | Materials for negative electrodes of lithium ion batteries |
| CN101969122A (en) * | 2010-09-14 | 2011-02-09 | 东莞市迈科新能源有限公司 | Core-shell structured carbon for cathode material of lithium ion battery and preparation method thereof |
| CN103066299B (en) * | 2013-01-08 | 2016-12-28 | 东莞新能源科技有限公司 | Native graphite of borosilicate coating modification and preparation method thereof |
| CN105633407A (en) * | 2016-03-11 | 2016-06-01 | 中物院成都科学技术发展中心 | Surface modification method for carbon-based anode material for lithium-ion battery and carbon-based anode material |
| CN106532004A (en) * | 2016-12-10 | 2017-03-22 | 浙江大学 | Preparation method of carbon-coated nano boron composite material for negative electrode of lithium-ion battery |
| CN106784666A (en) * | 2016-12-10 | 2017-05-31 | 浙江大学 | For the preparation method of the carbon-coated nano boron lithium composite material of lithium-sulfur cell negative pole |
| CN106784666B (en) * | 2016-12-10 | 2019-04-02 | 浙江大学 | The preparation method of carbon-coated nano boron lithium composite material for lithium-sulfur cell cathode |
| CN108172757A (en) * | 2018-01-24 | 2018-06-15 | 中国工程物理研究院电子工程研究所 | A kind of high pressure Thermal Cell Cathode Material, high pressure thermal cell and preparation method thereof |
| CN108172757B (en) * | 2018-01-24 | 2020-10-09 | 中国工程物理研究院电子工程研究所 | High-voltage thermal battery negative electrode material, high-voltage thermal battery and preparation method of high-voltage thermal battery negative electrode material |
| CN111525097A (en) * | 2019-02-01 | 2020-08-11 | 沁新集团(天津)新能源技术研究院有限公司 | Negative electrode material, preparation method and application thereof |
| CN111525097B (en) * | 2019-02-01 | 2021-04-09 | 沁新集团(天津)新能源技术研究院有限公司 | Negative electrode material, preparation method and application thereof |
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|---|---|
| CN1206759C (en) | 2005-06-15 |
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