CN102522561A - Lithium ion battery cathode material and preparation method thereof - Google Patents
Lithium ion battery cathode material and preparation method thereof Download PDFInfo
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- CN102522561A CN102522561A CN2011104335922A CN201110433592A CN102522561A CN 102522561 A CN102522561 A CN 102522561A CN 2011104335922 A CN2011104335922 A CN 2011104335922A CN 201110433592 A CN201110433592 A CN 201110433592A CN 102522561 A CN102522561 A CN 102522561A
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a lithium ion battery cathode material and a preparation method thereof, belonging to the field of preparation of lithium ion battery cathode materials. The invention is characterized in that the material has a graphite or carbon core shell structure, graphitized high-quality anthracite is used in a core material and amorphous carbon is used in a shell material. The graphitized high-quality anthracite is treated at a temperature of 2800 to 3100 DEG C, a graphitization degree is greater than 80%, the content of fixed carbon is greater than 99.9%, and the granularity of the anthracite is in a range of 5 mu m to 50 mu m; the amorphous carbon is prepared from a precursor which comprises asphalt, emulsified bitumen, phenolic resin, furfural resin, epoxy resin or resin materials. The lithium ion battery cathode material prepared in the invention is characterized in that initial efficiency is greater than 90%, initial discharge capacity is greater than 350 mAh/g and a capacity retention rate is greater than 90% after 200 cycles.
Description
Technical field
The present invention relates to the lithium ion battery negative material preparation field, be specifically related to a kind ofly utilize natural anthracite modification to prepare lithium ion battery cathode material and its preparation method.
Background technology
From nineteen ninety sony company first since releasing lithium ion battery on the market; Lithium ion battery is that rechargeable battery is compared peculiar advantage with itself and ni-mh NI-G; Like high-energy-density, high working voltage, discharge and recharge life-span length, memory-less effect, environmental pollution is little, self-discharge rate is low etc.; Captured the market of commercial rechargeable battery rapidly, particularly as the power supply of miniature portable electrical equipment such as mobile phone, notebook computer, digital camera.In recent years; The research of lithium ion battery plus-negative plate material, electrolyte system and application are the domestic and international research emphasis; Electric motor car that particularly is accompanied by " low-carbon (LC) " theory and rises and hybrid vehicle etc., the performance to lithium ion battery has proposed new requirement especially.Low cost, height ratio capacity, high-power, long-life, high safety, environmental friendliness are lithium ion battery developing direction from now on.
Lithium ion battery develops so far, and the composition of positive electrode and capacity do not have big change basically, and main contribution is from negative material.The negative material of commercialization lithium ion battery use now is a material with carbon element, is main with Delanium.But see that from the low cost of material and the demand for development of high power capacity aboundresources, native graphite with low cost, that bulk density is high and specific capacity is big are development trends from now on.The efficient first and the reversible capacity that can effectively improve native graphite handled in modification through to native graphite.At present comparatively ripe to the research of natural flake graphite, can the efficient first of natural flake graphite be brought up to more than 90%, but reverse efficiency bring up to more than the 350mAh/g, satisfy the requirement of commercial applications.We can say that it is a development trend of lithium ion battery negative material that modified natural graphite replaces Delanium.
Native graphite is divided into two kinds of amorphous graphite (micro crystal graphite) and crystalline flake graphites.Micro crystal graphite is made up of the graphite microcrystal of different orientation, and crystallite size shows isotropism less than 1 μ, in charge and discharge cycles process middle level changes in spacing each to carrying out simultaneously, so cyclical stability is better.The crystalline flake graphite lamellar structure is more regular; Help the embedding of lithium ion and deviate from; Reversible capacity can reach 300～350mAh/g, but because expansion and contraction in the sheet interlayer charge and discharge process are unidirectional carrying out, thereby therefore cause coming off of lamella to influence cyclical stability easily.
The graphitization anthracite is thereby that high-quality anthracite is carried out the new type natural graphite material that graphitization processing obtains at 2800 ℃; Mechanism is similar owing to become a useful person; Therefore the graphitization anthracite has similar microstructure with natural micro crystal graphite, can be used for doing lithium ion battery negative material.The anthracitic cost of graphitization that adopts the production of serialization graphitizing furnace is compared native graphite and is had huge cost advantage for 6000～7000 yuan/ton less than 2000 yuan/ton.
Summary of the invention
The objective of the invention is to develop a kind of new type lithium ion battery negative material and preparation method thereof, the preparation method is simple, is suitable for suitability for industrialized production; The lithium ion battery negative material of preparation first efficient with can capacity high, good cycling stability; Prepare raw materials used aboundresources, cost is low.
The technical scheme that the present invention adopts is:
A kind of lithium ion battery negative material, its structure are graphite/silicon/charcoal core-shell structure, and inner nuclear material adopts graphited high-quality anthracite, and sheathing material is an amorphous carbon.Described graphitization high-quality anthracite is through 2800 ℃ of-3100 ℃ of processing, and degree of graphitization is greater than 80%, and fixed carbon content is greater than 99.9%, and particle size range is 5 μ m-50 μ m; Described amorphous carbon is by precursor charing gained, and precursor comprises resinae materials such as pitch, emulsified asphalt, phenolic resins, furfural resin, epoxy resin.
A kind of preparation method of lithium ion battery negative material is characterized in that, may further comprise the steps:
The first step is carried out graphitization processing in 2800 ℃-3100 ℃ with high-quality anthracite in graphitizing furnace;
Second step, the graphitization anthracite that obtains is pulverized and hierarchical processing, making the graphitization anthracite grain diameter scope that obtains is 5 μ m-50 μ m;
In the 3rd step, the method that adopts liquid phase to coat is coated on the charcoal precursor on the graphitization anthracite, and covering liquid comprises resin solution and asphalt emulsion, and precursor and graphitization anthracite mass ratio are (1-20): 100;
In the 4th step, mixed solution is carried out desolventizing handle;
The 5th step, to carry out charing and handle, charing sintering temperature scope is 900 ℃-1200 ℃.
The lithium ion battery negative material that the present invention obtained is characterized in that, efficient is greater than 90% first, and discharge capacity is greater than 350mAh/g first, through 200 circulation back capability retentions greater than 90%.
Embodiment
Below in conjunction with specific embodiment the present invention is further described.
Embodiment 1
A kind of lithium ion battery negative material, its raw material comprises anthracite and coal tar pitch, and described anthracite is the too western coal that originates from Ningxia Hui Autonomous Region's Shizuishan City Rujigou, and coal tar pitch is a mid temperature pitch.
A kind of preparation method of lithium ion battery negative material is characterized in that, may further comprise the steps:
The first step is carried out graphitization processing in 2800 ℃ with high-quality anthracite in graphitizing furnace, the graphitization anthracite fixed carbon content that is obtained is 99.9%, and degree of graphitization is 83%;
Second step, the graphitization anthracite that obtains is pulverized and hierarchical processing, making the graphitization anthracite grain diameter scope that obtains is 5 μ m-50 μ m, D
50Be 21.45 μ m;
In the 3rd step, the method that adopts liquid phase to coat is coated on the charcoal precursor on the graphitization anthracite, and coal tar pitch is dissolved in toluene solution as covering liquid, and coal tar pitch precursor and graphitization anthracite mass ratio are 1: 100;
In the 4th step, mixed solution is carried out desolventizing handle;
The 5th step, carry out charing and handle, the charing sintering temperature is 1200 ℃, protection gas is N
2
The lithium ion battery negative material that the present invention obtained, its first efficient be 92%, discharge capacity is 365mAh/g first, through 200 circulation back capability retentions greater than 90%.
Embodiment 2
A kind of lithium ion battery negative material, its raw material comprises anthracite and phenolic resins, and described anthracite is the too western coal that originates from Ningxia Hui Autonomous Region's Shizuishan City Rujigou, and phenolic resins is technical grade.
A kind of preparation method of lithium ion battery negative material is characterized in that, may further comprise the steps:
The first step is carried out graphitization processing in 3000 ℃ with high-quality anthracite in graphitizing furnace, the graphitization anthracite fixed carbon content that is obtained is 99.9%, and degree of graphitization is 83%;
Second step, the graphitization anthracite that obtains is pulverized and hierarchical processing, making the graphitization anthracite grain diameter scope that obtains is 5 μ m-50 μ m, D
50Be 21.45 μ m;
In the 3rd step, the method that adopts liquid phase to coat is coated on the charcoal precursor on the graphitization anthracite, and phenolic resins is dissolved in ethanolic solution as covering liquid, and phenolic resins precursor and graphitization anthracite mass ratio are 12: 100;
In the 4th step, mixed solution is carried out desolventizing handle;
The 5th step, carry out charing and handle, the charing sintering temperature is 1000 ℃, protection gas is N
2
The lithium ion battery negative material that the present invention obtained, its first efficient be 90%, discharge capacity is 356mAh/g first, through 200 circulation back capability retentions greater than 90%.
Embodiment 3
A kind of lithium ion battery negative material, its raw material comprises anthracite and polyvinyl alcohol, and described anthracite is the too western coal that originates from Ningxia Hui Autonomous Region's Shizuishan City Rujigou, and polyvinyl alcohol is a technical grade.
A kind of preparation method of lithium ion battery negative material is characterized in that, may further comprise the steps:
The first step is carried out graphitization processing in 3100 ℃ with high-quality anthracite in graphitizing furnace, the graphitization anthracite fixed carbon content that is obtained is 99.9%, and degree of graphitization is 83%;
Second step, the graphitization anthracite that obtains is pulverized and hierarchical processing, making the graphitization anthracite grain diameter scope that obtains is 5 μ m-50 μ m, D
50Be 21.45 μ m;
In the 3rd step, the method that adopts liquid phase to coat is coated on the charcoal precursor on the graphitization anthracite, and as covering liquid, phenolic resins precursor and graphitization anthracite mass ratio are 5: 100 with the water-soluble solution of polyvinyl alcohol;
In the 4th step, mixed solution is carried out desolventizing handle;
The 5th step, carry out charing and handle, the charing sintering temperature is 900 ℃, protection gas is N
2
The lithium ion battery negative material that the present invention obtained, its first efficient be 89.5%, discharge capacity is 350mAh/g first, through 200 circulation back capability retentions greater than 90%.
In sum, the present invention has used aboundresources, and cost is low; The preparation methods step is few, and device requirement is simple; The material that makes is efficient and specific discharge capacity height first, and characteristics such as good cycling stability are fit to carry out large-scale industrial production.
Claims (2)
1. a lithium ion battery negative material is characterized in that, the structure of said material is graphite or silicon/charcoal core-shell structure, and inner nuclear material adopts the graphitization high-quality anthracite, and sheathing material is an amorphous carbon; Said graphitization high-quality anthracite is through 2800 ℃ of-3100 ℃ of processing, and degree of graphitization is greater than 80%, and fixed carbon content is greater than 99.9%, and particle size range is 5 μ m-50 μ m; Said amorphous carbon is by precursor charing gained, and precursor comprises pitch, emulsified asphalt, phenolic resins, furfural resin, epoxy resin or resinous material.
2. the preparation method of a lithium ion battery negative material is characterized in that, said method comprising the steps of:
The first step is carried out graphitization processing in 2800 ℃-3100 ℃ with high-quality anthracite in graphitizing furnace;
Second step, the graphitization anthracite that obtains is pulverized and hierarchical processing, making the graphitization anthracite grain diameter scope that obtains is 5 μ m-50 μ m;
In the 3rd step, the method that adopts liquid phase to coat is coated on the charcoal precursor on the graphitization anthracite, and covering liquid comprises resin solution and asphalt emulsion, and precursor and graphitization anthracite mass ratio are (1-20): 100;
In the 4th step, mixed solution is carried out desolventizing handle;
The 5th step, to carry out charing and handle, charing sintering temperature scope is 900 ℃-1200 ℃.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104681786A (en) * | 2015-03-04 | 2015-06-03 | 深圳市贝特瑞新能源材料股份有限公司 | Coal-based anode material, preparation method and lithium-ion battery |
| CN106099105A (en) * | 2015-08-31 | 2016-11-09 | 三峡大学 | A kind of spherical porous artificial plumbago negative pole material |
| CN106486653A (en) * | 2015-12-08 | 2017-03-08 | 宁波杉杉新材料科技有限公司 | A kind of liquid phase coating modified graphite cathode material and preparation method thereof |
| CN107180958A (en) * | 2017-06-05 | 2017-09-19 | 三峡大学 | A kind of anthracite/silicon monoxide/amorphous carbon negative material and preparation method thereof |
| CN110407202A (en) * | 2019-02-19 | 2019-11-05 | 襄阳汉江高科新能源材料有限公司 | Graphite cathode material preparation method for sodium-ion battery |
| CN110797513A (en) * | 2018-08-03 | 2020-02-14 | 天津大学 | Graphite-hard carbon coated material and preparation method thereof |
| CN110931766A (en) * | 2019-12-18 | 2020-03-27 | 苏州大学 | Method for preparing air-stable lithium metal negative electrode by using natural coal powder |
| CN111146417A (en) * | 2019-12-24 | 2020-05-12 | 中国科学院山西煤炭化学研究所 | Spherical graphite negative electrode material of quick-charging lithium ion battery and preparation method thereof |
| CN111146418A (en) * | 2019-12-24 | 2020-05-12 | 中国科学院山西煤炭化学研究所 | High-energy-density lithium ion battery cathode material and preparation method thereof |
| CN112142060A (en) * | 2020-09-21 | 2020-12-29 | 陕西煤业化工技术研究院有限责任公司 | Coal-based silicon-carbon composite negative electrode material and preparation method thereof |
| CN114804877A (en) * | 2022-05-19 | 2022-07-29 | 李鑫 | Pulse current internal heating type intermediate temperature graphitized negative electrode material and manufacturing method thereof |
| CN115417405A (en) * | 2022-09-27 | 2022-12-02 | 贵州东岛新能源材料有限公司 | Preparation method of resistance material and negative electrode material for Acheson graphitizing furnace |
| WO2022257373A1 (en) * | 2021-06-10 | 2022-12-15 | 国家能源投资集团有限责任公司 | Negative electrode material, preparation method therefor and application thereof, and negative electrode plate and application |
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| CN1397598A (en) * | 2002-08-14 | 2003-02-19 | 清华大学 | Process for preparing carbon coated graphite microparticles |
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| CN1397598A (en) * | 2002-08-14 | 2003-02-19 | 清华大学 | Process for preparing carbon coated graphite microparticles |
| CN101651199A (en) * | 2009-07-27 | 2010-02-17 | 唐山金湾特碳石墨有限公司 | Lithium cell carbon cathode material and preparation method thereof |
| CN101665252A (en) * | 2009-09-23 | 2010-03-10 | 四川广汉士达炭素股份有限公司 | Method for subsidiarily producing graphitized anthracite by using graphitization furnace |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104681786A (en) * | 2015-03-04 | 2015-06-03 | 深圳市贝特瑞新能源材料股份有限公司 | Coal-based anode material, preparation method and lithium-ion battery |
| CN106099105A (en) * | 2015-08-31 | 2016-11-09 | 三峡大学 | A kind of spherical porous artificial plumbago negative pole material |
| CN106486653A (en) * | 2015-12-08 | 2017-03-08 | 宁波杉杉新材料科技有限公司 | A kind of liquid phase coating modified graphite cathode material and preparation method thereof |
| CN107180958A (en) * | 2017-06-05 | 2017-09-19 | 三峡大学 | A kind of anthracite/silicon monoxide/amorphous carbon negative material and preparation method thereof |
| CN110797513B (en) * | 2018-08-03 | 2022-04-05 | 天津大学 | Graphite-hard carbon coated material and preparation method thereof |
| CN110797513A (en) * | 2018-08-03 | 2020-02-14 | 天津大学 | Graphite-hard carbon coated material and preparation method thereof |
| CN110407202A (en) * | 2019-02-19 | 2019-11-05 | 襄阳汉江高科新能源材料有限公司 | Graphite cathode material preparation method for sodium-ion battery |
| CN110407202B (en) * | 2019-02-19 | 2023-06-30 | 湖北宝乾新能源材料有限公司 | Preparation method of graphite anode material for sodium ion battery |
| CN110931766B (en) * | 2019-12-18 | 2022-05-03 | 苏州大学 | Method for preparing air-stable lithium metal negative electrode by using natural coal powder |
| CN110931766A (en) * | 2019-12-18 | 2020-03-27 | 苏州大学 | Method for preparing air-stable lithium metal negative electrode by using natural coal powder |
| CN111146418A (en) * | 2019-12-24 | 2020-05-12 | 中国科学院山西煤炭化学研究所 | High-energy-density lithium ion battery cathode material and preparation method thereof |
| CN111146417A (en) * | 2019-12-24 | 2020-05-12 | 中国科学院山西煤炭化学研究所 | Spherical graphite negative electrode material of quick-charging lithium ion battery and preparation method thereof |
| CN112142060A (en) * | 2020-09-21 | 2020-12-29 | 陕西煤业化工技术研究院有限责任公司 | Coal-based silicon-carbon composite negative electrode material and preparation method thereof |
| CN112142060B (en) * | 2020-09-21 | 2022-04-19 | 陕西煤业化工技术研究院有限责任公司 | Coal-based silicon-carbon composite negative electrode material and preparation method thereof |
| WO2022257373A1 (en) * | 2021-06-10 | 2022-12-15 | 国家能源投资集团有限责任公司 | Negative electrode material, preparation method therefor and application thereof, and negative electrode plate and application |
| CN114804877A (en) * | 2022-05-19 | 2022-07-29 | 李鑫 | Pulse current internal heating type intermediate temperature graphitized negative electrode material and manufacturing method thereof |
| CN114804877B (en) * | 2022-05-19 | 2024-01-23 | 深圳市钢昱碳晶科技有限公司 | Pulse current internal heating type medium-temperature graphitized anode material and manufacturing method thereof |
| CN115417405A (en) * | 2022-09-27 | 2022-12-02 | 贵州东岛新能源材料有限公司 | Preparation method of resistance material and negative electrode material for Acheson graphitizing furnace |
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Application publication date: 20120627 |