CN100385719C - Lithium ion secondary battery negative pole material, producing method thereof and obtained battery - Google Patents

Lithium ion secondary battery negative pole material, producing method thereof and obtained battery Download PDF

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Publication number
CN100385719C
CN100385719C CNB2004100275689A CN200410027568A CN100385719C CN 100385719 C CN100385719 C CN 100385719C CN B2004100275689 A CNB2004100275689 A CN B2004100275689A CN 200410027568 A CN200410027568 A CN 200410027568A CN 100385719 C CN100385719 C CN 100385719C
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China
Prior art keywords
catalyst
negative material
graphitization
petroleum coke
negative
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Expired - Fee Related
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CNB2004100275689A
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Chinese (zh)
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CN1707830A (en
Inventor
杨绍斌
王建明
范军
刘甫先
刘秉东
廖钦林
谢根胜
郑华杰
陈杰
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ZHAOQING FENGHUA LITHIUM BATTERY CO Ltd
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ZHAOQING FENGHUA LITHIUM BATTERY CO Ltd
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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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention discloses a negative electrode material used for a lithium ion secondary battery. The negative electrode material is made from broken artificial graphite materials; the specific surface area of the negative electrode material is smaller than 4m<2>/g. The negative electrode material also contains elements which can be used as graphitization catalysts, and the content range of the catalyst elements in the negative electrode material is from 0.1 ppm to 300 ppm. The present invention also discloses a method for preparing a negative electrode material of a lithium ion secondary battery. The negative electrode material of a lithium ion secondary battery, which is produced by the method of the present invention has the advantages of small specific surface area, high specific capacity, good cycle performance, good safe performance, etc.

Description

Ion secondary battery cathode material lithium and gained battery
Technical field
The present invention relates to the employed negative material of lithium rechargeable battery, preparation method and resulting lithium rechargeable battery thereof.
Background technology
In recent years, lithium rechargeable battery is owing to have characteristics such as volume is little, in light weight, thereby obtained using widely in hand portable equipments such as mobile phone, compact video, notebook computer.Generally speaking, lithium rechargeable battery selects for use carbon materials as its negative material.The carbon element negative material can be divided into graphitization carbonaceous mesophase spherules material (being called for short MCMB class material, mesophase carbon microbead) and non-MCMB class material.Though MCMB class material irreversible capacity is little, its packing density is low, cost is high, thereby the use amount in box hat, aluminum hull and flexible package electricity core reduces significantly.Non-MCMB class material as broken Delanium and native graphite, because its packing density height, specific capacity is big and price is low, becomes the first-selected negative material of box hat, aluminum hull and flexible package electricity core gradually.
In the non-MCMB class material, it is following several that broken Delanium preparation methods has multiple, the most frequently used method to have: a kind of method is to be raw material with petroleum coke (comprising needle coke), pulverizes earlier, and direct graphitization sieves again then.The broken Delanium material degree of graphitization that this method is produced is low, be difficult to prepare the lithium ion battery of high power capacity, thereby production efficiency is low.Another kind method is that graphitization crushes and screens again then with the first compression molding of the petroleum coke of fragmentation (comprising needle coke).This method production efficiency height is a method commonly used now, but the Delanium specific area of this method preparation is big, and irreversible capacity is big, so battery capacity is difficult for guaranteeing.Also having a kind of method is that the method that graphite adopts carbon to coat is prepared material with carbon element, though this method can obtain the less broken Delanium material of surface area, manufacture craft is comparatively complicated.
Disclose cathode active material that a kind of rechargeable lithium battery uses and preparation method thereof among the Chinese patent application CN0111768 6.5, this cathode active material comprises crystalline carbon, and contains the dispersed elements as graphitization catalyst in the crystalline carbon; Its preparation method is: add graphitization catalyst in the carbon precursor, make the mixture coking 300-600 ℃ of following heat treatment then, make the coke carbonization again, make the carbide graphitization at last under 2800-3000 ℃.The raw material that this patent application is adopted is coal-based pitch, oil-based asphalt, mesophase pitch or tar, and preparation process comprises steps such as coking and carbonization, the technology relative complex, and energy consumption is relative with cost higher.
Therefore, be necessary to research and develop a kind of both easy, can prepare every performance again and meet the cathode material preparation method of making the high performance lithium ion battery requirement.
Summary of the invention
The purpose of this invention is to provide the ion secondary battery cathode material lithium that a kind of specific surface is little, specific volume is high, the residual quantity of catalyst is low and irreversible capacity is little, to make high performance lithium ion battery.
The negative material that lithium rechargeable battery provided by the present invention is used is a kind of Delanium material of fragmentation, and the specific area of this negative material is less than 4m 2/ g, and also contain the element that can be used as graphitization catalyst in this negative material, the content range of catalyst elements is controlled between the 0.1-300ppm, preferably is controlled to be 10-100ppm.
In above-mentioned negative material, the ratio of the X-ray diffraction peak intensity of the X-ray diffraction peak intensity of its (100) crystal face and its (002) crystal face preferably is controlled in the scope of 1-4; The ratio of the X-ray diffraction peak intensity of the X-ray diffraction peak intensity of its (101) crystal face and its (002) crystal face also preferably is controlled in the scope of 1-4.
In the above-mentioned negative material, contained catalyst elements is preferably B and/or Fe.
Another object of the present invention provides a kind of method for preparing above-mentioned ion secondary battery cathode material lithium.
Preparation method of the present invention in turn includes the following steps:
(1) the petroleum coke raw material such as pulverizes at preliminary treatment;
(2) add graphitization catalyst in the petroleum coke raw material after above-mentioned pulverizing;
(3) petroleum coke raw material above-mentioned adding catalyst, after pulverizing is carried out graphitization processing in nitrogen, argon gas or vacuum environment, under the temperature of 2400-3000 ℃; Graphitization time is 0.25-240h;
(4) reprocessing such as the material of gained after the above-mentioned graphitization processing is sieved.
Wherein, the breaking method of step (1) is preferably and carries out precomminution earlier, carries out the degree of depth again and pulverize; Precomminution can be jaw crusher pulverizing, high speed disintegrator pulverizing, rod milling pulverizing etc., and it can be comminution by gas stream, ball mill grinding etc. that the degree of depth is pulverized.
Raw materials used petroleum coke can be still formula Jiao, petroleum coke, retard petroleum coke, petroleum needle coke etc. in the step (1).
In step (2), the graphitization catalyst that is added is Fe system and/or B series catalysts; By weight percentage, the content of this catalyst in the petroleum coke raw material is 0.5-20% (is benchmark with the petroleum coke material), is preferably 1-15%; The Fe series catalysts can be FeCl 3, Fe 3O 4, Fe 2O 3, Fe (OH) 3In one or more, the B series catalysts can be B 2O 3And/or HBO 3The Fe series catalysts is preferably Fe 3O 4And/or Fe 2O 3The B series catalysts is preferably B 2O 3
In addition, more than when a kind of when the component of catalyst, the ratio between each component can be any ratio.
In step (2), graphitization catalyst can join in the petroleum coke in the wet mixing mode, also can join in the petroleum coke to do the mode of mixing; Wherein, the wet mixing mode is to utilize organic solvent, and petroleum coke and graphitization catalyst after pulverizing in the step (1) are mixed; Doing the mode of mixing is directly to utilize ball milling or alr mode, and the petroleum coke after pulverizing in the step (1) is mixed with graphitization catalyst.
In the step (3), graphited preferred temperature is 2600-2900 ℃, graphitization time 4-24h.
Screening reprocessing in the step (4) can be adopted directly and sieve, and sieves after sieving after the nodularization or pulverizing, and the screening mode can be an airflow screening, and vibrating sieving machine screening and hydraulic screen grade.
A further object of the present invention provides a kind of lithium rechargeable battery, and the negative plates of this lithium rechargeable battery is to adopt above-mentioned negative material to make.
Preparation method of the present invention has improved graphited degree, has improved every performance of ion cathode material lithium; And ion secondary battery cathode material lithium of the present invention has capacity height, advantage that surface area is little, can be used for preparing high performance lithium ion secondary battery.
Below, further specify the present invention in conjunction with the embodiments, but the present invention being not limited to these embodiment, any alternative or improvement that does not depart from spirit of the present invention is still the desired protection range of claims of the present invention.
Embodiment
Embodiment 1
Get petroleum coke, carry out high speed disintegrator successively and pulverize and comminution by gas stream, by 8% adding boron oxide catalyst, ball milling mixes, and in blanket of nitrogen, 2600 ℃ are carried out graphitization then, and screening obtains broken graphite cathode material.
Employing SBR is a binding agent, and CMC is that dispersant prepares the water-base cathode slurry, is applied on the Copper Foil, and roll-in is cut, the preparation negative plate.The anodal cobalt acid lithium material that adopts, PVDF are as binding agent, and NMP is that solvent prepares the anodal slurry of oiliness, be applied on the aluminium foil, roll-in is cut, the preparation positive plate, reel with barrier film, be loaded in the aluminum hull of 383450 models fluid injection, electrolyte consists of EC: DMC: DEC=1: 1: 1,1M LiPF6 seals agingly after opening changes into, make 383450 aluminum hulls electricity core.With electric core capacity (1C) electric current charge-discharge test capacity and cycle performance, specific area adopts the BET methods analyst in the physical chemistry Instrumental Analysis data, and crystal parameters and peak intensity are than adopting the X-ray diffractometer analysis.
Embodiment 2
Get petroleum needle coke, carry out high speed disintegrator successively and pulverize and ball mill grinding, by 8% adding boron oxide catalyst, ball milling mixes, and in blanket of nitrogen, 2700 ℃ are carried out graphitization, and screening obtains broken graphite cathode material.
Embodiment 3
Get petroleum coke and carry out high speed disintegrator pulverizing and ball mill grinding successively, air current classifying adds 7%Fe 3O 4Catalyst, ball milling mix, and in blanket of nitrogen, 2600 ℃ are carried out graphitization, sieve broken graphite cathode material.
Embodiment 4
Get petroleum coke, carry out high speed disintegrator successively and pulverize and comminution by gas stream, air current classifying adds 15%Fe 3O 4Catalyst do to mix, and in blanket of nitrogen, 2650 ℃ are carried out graphitization, sieve broken graphite cathode material.
Embodiment 5
Get petroleum needle coke, carry out high speed disintegrator successively and pulverize and ball mill grinding, add 12%Fe 2O 3With B catalyst, wherein Fe 2O 3And B 2O 3Add than being 1: 1, ball milling is done mixed, and in blanket of nitrogen, 2700 ℃ are carried out graphitization, sieve broken graphite cathode material.
Comparative Examples 1
Get petroleum needle coke through pulverizing, by 8% adding boron oxide catalyst, through after the compression molding, in blanket of nitrogen, 2700 ℃ are carried out graphitization, and crushing and screening gets graphite cathode material.
According to the electric performance test method of embodiment 1, embodiment 2-5 and Comparative Examples 1 are obtained ion secondary battery cathode material lithium test, obtain the physical analysis data of material equally.
The specific area electricity core capacity and the cycle performance of the ion secondary battery cathode material lithium of embodiment 1-5 and Comparative Examples 1 see Table 1.
Table 1
Sample number Specific area (m 2/g) Electricity core capacity (1C) 50 all cycle performances (%)
Embodiment 1 2.015 611 98.5
Embodiment 2 2.969 592 96.5
Embodiment 3 2.766 585 97.1
Embodiment 4 2.294 590 96.3
Embodiment 5 3.413 583 95.8
Comparative Examples 1 5.757 565 96.2
As seen from the above table, the negative material specific area of embodiment 1-5 is significantly less than the negative material of Comparative Examples 1, and electric core capacity (1C) also is better than the negative material of Comparative Examples 1.For 50 all cycle performances (%), though the numerical value of embodiment 5 will be a little less than Comparative Examples 6, the numerical value of embodiment 1-4 all is higher than Comparative Examples 1.Comprehensive three indexs illustrate that the lithium cell cathode material performance that has added the inventive method preparation is better than existing method.Wherein, the preparation method of embodiment 1 is a kind of preferred method.
The X-ray diffraction peak intensity data of (100), (101) and (002) crystal face see Table 2 among the foregoing description 1-5:
Table 2
Sample number I 100/I 102 I 101/I 002
Embodiment 1 1 2
Embodiment 2 2 4
Embodiment 3 2 3
Embodiment 4 2 2
Embodiment 5 1 2

Claims (5)

1. negative material that lithium rechargeable battery is used, this negative material are that raw material makes, broken Delanium material with the petroleum coke, and its specific area is less than 4m 2/ g is characterized in that, also containing in this negative material can be as the element of graphitization catalyst, and this catalyst elements is B and/or Fe, and the content range of described catalyst elements in described negative material is 0.1-300ppm.
2. negative material as claimed in claim 1 is characterized in that, the content range of described catalyst elements in described negative material is 10-100ppm.
3. negative material as claimed in claim 1 is characterized in that, this negative material is to adopt the method that in turn includes the following steps to make:
(1) the petroleum coke raw material is carried out pulverization process;
(2) add graphitization catalyst in the petroleum coke raw material after above-mentioned pulverizing;
(3) petroleum coke raw material above-mentioned adding catalyst, after pulverizing is carried out graphitization processing in nitrogen, argon gas or vacuum environment, under the temperature of 2400-3000 ℃;
(4) material with gained after the above-mentioned graphitization processing sieves processing.
4. negative material as claimed in claim 3 is characterized in that, the graphitization catalyst that adds in the described step (2) is B system and/or Fe series catalysts; By weight percentage, the content of this catalyst in the petroleum coke raw material is 0.5-20%; Described Fe series catalysts is FeCl 3, Fe 3O 4, Fe 2O 3, Fe (OH) 3In one or more, described B series catalysts is B 2O 3And/or HBO 3
5. a lithium rechargeable battery is characterized in that, the negative plates of this lithium rechargeable battery adopts and makes as the described negative material of one of claim 1-4.
CNB2004100275689A 2004-06-11 2004-06-11 Lithium ion secondary battery negative pole material, producing method thereof and obtained battery Expired - Fee Related CN100385719C (en)

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CN101087021B (en) * 2007-07-18 2014-04-30 深圳市贝特瑞新能源材料股份有限公司 Man-made graphite cathode material for lithium ion battery and its making method
US9406936B2 (en) * 2012-10-12 2016-08-02 Showa Denko K.K. Carbon material, carbon material for battery electrode, and battery
CN104218214B (en) * 2013-05-28 2018-02-23 福建杉杉科技有限公司 A kind of lithium ion battery negative material and preparation method thereof
CN103887504B (en) * 2013-12-19 2016-09-21 东莞市凯金新能源科技股份有限公司 A kind of lithium ion battery negative material and preparation method thereof
CN105938906B (en) * 2016-06-18 2019-06-07 湖南中科星城石墨有限公司 A kind of lithium ion battery artificial composite cathode material of silicon/carbon/graphite and preparation method thereof
CN116325231A (en) * 2021-02-05 2023-06-23 宁德时代新能源科技股份有限公司 Negative electrode active material, preparation method thereof, secondary battery and device

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CN1151617A (en) * 1995-08-18 1997-06-11 株式会社佩托卡 Carbon material for lithium secondary battery and process for producing the same
CN1225196A (en) * 1996-05-07 1999-08-04 东洋炭素株式会社 Cathode material for lithium ion secondary battery, method for manufacturing the same, and lithium ion secondary battery using the same
CN1244046A (en) * 1998-04-21 2000-02-09 索尼株式会社 Graphite powder as negative electrode of lithium secondary batteries
CN1324121A (en) * 2000-05-17 2001-11-28 三星Sdi株式会社 Cathode active material for lithium accumulator
US6344296B1 (en) * 1996-08-08 2002-02-05 Hitachi Chemical Company, Ltd. Graphite particles and lithium secondary battery using the same as negative electrode
JP2002270169A (en) * 2001-03-06 2002-09-20 Nippon Steel Corp Material for lithium secondary battery negative electrode, producing method thereof and lithium secondary battery

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1151617A (en) * 1995-08-18 1997-06-11 株式会社佩托卡 Carbon material for lithium secondary battery and process for producing the same
CN1225196A (en) * 1996-05-07 1999-08-04 东洋炭素株式会社 Cathode material for lithium ion secondary battery, method for manufacturing the same, and lithium ion secondary battery using the same
US6344296B1 (en) * 1996-08-08 2002-02-05 Hitachi Chemical Company, Ltd. Graphite particles and lithium secondary battery using the same as negative electrode
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