CN101414678B - Method for preparing lithium ion battery cathode material - Google Patents
Method for preparing lithium ion battery cathode material Download PDFInfo
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- CN101414678B CN101414678B CN2008101592932A CN200810159293A CN101414678B CN 101414678 B CN101414678 B CN 101414678B CN 2008101592932 A CN2008101592932 A CN 2008101592932A CN 200810159293 A CN200810159293 A CN 200810159293A CN 101414678 B CN101414678 B CN 101414678B
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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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Abstract
The invention relates to a method for preparing cathode materials for lithium ion batteries, and the materials for cathode are compounds of metal hydride and carbonaceous materials and are characterized in that the mixture of metal powder and carbonaceous materials is ball milled and then reacts with hydrogen to form the materials for cathodes, wherein the mass content of the metal powder of raw materials is from 80 to 95%, and the mass content of the carbonaceous materials is from 5 to 20%. The materials prepared by the method are metal hydride. When the materials are used as cathodes of lithium ion batteries, the lithium ions store lithium by the chemical conversion reaction by displacing hydrogen atoms in electrode materials, and the restriction of graphite cathode theoretical content.The method has the characteristics of high specific capacity, small drain current, long circulation content, simple preparation technology, etc. Moreover, the phenomenon of the insertion of organic bath does not occur, and the stability and the safety of graphite cathodes are improved.
Description
Technical field
The present invention relates to the preparation method of lithium ion battery negative material, particularly a kind of lithium ion battery metal hydride cathode preparation methods.
Background technology
At present, superior functions such as average output voltage height, specific energy are big because lithium ion battery has, discharging voltage balance, safe and long working life, the power supply that can be used as mobile electronic products such as mobile phone, notebook computer, field camera, camera, can also be as the power supply of DVD and electric bicycle, its application is boundless.What the commercial Li-ion batteries negative material adopted usually at present is the graphite-like material with carbon element, and its weak point is that its theoretical specific capacity has only 372mAh/g, thereby has limited the further raising of lithium ion battery specific capacity.
Summary of the invention
Technical problem to be solved by this invention is to overcome above-mentioned weak point, a kind of preparation method of new type of metal hydride lithium ion battery negative material is provided, its storage lithium mechanism is different from the storage lithium mechanism that forms graphite intercalation compound, has characteristics such as specific capacity height.
The preparation method of lithium ion battery negative material of the present invention, described negative material is the compound of metal hydride and carbonaceous material, it is characterized in that: generate negative material with hydrogen reaction behind the mixture process ball milling by metal powder and carbonaceous material, wherein the mass content of feed metal powder is 80-95%, and the mass content of carbonaceous material is 5-20%.
Negative material of the present invention, wherein metal hydride is a main active, carbonaceous material mainly plays the effect that disperses and conduct electricity.
Optimized technical scheme of the present invention is:
Described metal is one or both in titanium, nickel, magnesium, the lanthanum.When used metal was two kinds, wherein a kind of was metallic nickel, and the mass ratio of another kind of metal and nickel is 5:1-1:5.
Described carbonaceous material is a kind of in graphite, carbon black, carbon nano-tube, middle phase microballoon, the active carbon.
The ball milling time of the mixture of described metal powder and carbonaceous material is 20 hours, and ratio of grinding media to material is 10:1.
Described hydrogen reaction, the pressure of hydrogen are 2Mpa, and reaction temperature is 350 ℃, and the reaction time is 10 hours.
Product behind the hydrogen reaction needs to make the material average grain diameter less than 1 micron through ball milling 2 hours again.
A kind of preferred concrete preparation process of the present invention is:
(1) metal powder and carbonaceous material are added in the ball milling according to mass ratio, ratio of grinding media to material is 10:1, and the ball milling time is 20 hours;
(2) material behind the taking-up ball milling is put into the high-pressure metal container, feeds hydrogen, and the pressure of control hydrogen is 2Mpa, and reaction temperature is 350 ℃, and the reaction time is 10 hours;
(3) with hydrogen reaction after product need again to obtain negative material through ball milling 2 hours.
The invention has the beneficial effects as follows: the material that this method makes is the hydride of metal, make lithium ion battery negative with it, lithium ion reacts by the chemical conversion of displacement hydrogen atoms in electrode materials and stores up lithium, broken through the restriction of graphite cathode theoretical capacity, have specific capacity height, leakage current little, have extended cycle life, preparation technology is simple etc. characteristics.In addition, there is not the common insertion phenomenon of organic bath solvent, increased the stability and the fail safe of graphite cathode.
Embodiment:
Below in conjunction with embodiment the present invention is described, but does not limit the present invention.
Embodiment 1:
With mass ratio is titanium valve and the graphite powder ball milling of 9:1, and ratio of grinding media to material is 10:1, and the ball milling time is 20 hours, and the material behind the taking-up ball milling is put into the high-pressure metal container, feeds hydrogen.The pressure of control hydrogen is 2Mpa, and reaction temperature is 350 ℃, and the reaction time is 10 hours; Need obtain end product again through ball milling 2 hours (ratio of grinding media to material still is 10:1, down together) with the product behind the hydrogen reaction.Below can carry out routinely, be negative material with the product that makes, and acetylene black is conductive agent, and Kynoar (PVDF) is a bonding agent.The proportioning of battery cathode (weight ratio) is: active material (negative material behind the above-mentioned ball milling): acetylene black: bonding agent=85:5:10.Add a certain amount of N-methyl and adjoin pyrrolidone (NMP) and mix well into pasty state, be evenly coated on the Copper Foil of 10 micron thickness, roll oven dry and obtain work electrode.With the pour lithium slice is auxiliary electrode, and electrolyte is the organic electrolyte that contains lithium ion, and barrier film is a microporous polyethylene film, is assembled into button cell.In the voltage range of 0.01V-3.0V, on cell tester, carry out charge-discharge test with the speed of 0.05C.Reversible capacity is 648mAh/g first, and first charge-discharge efficiency is 79%, and through 50 circulations, reversible capacity is 406mAh/g, and coulombic efficiency is 95%.
Embodiment 2:
With mass ratio is nickel powder and the carbon powder ball milling of 8:2, and ratio of grinding media to material is 10:1, and the ball milling time is 20 hours, and the material behind the taking-up ball milling is put into the high-pressure metal container, feeds hydrogen.The pressure of control hydrogen is 2Mpa, and reaction temperature is 350 ℃, and the reaction time is 10 hours; Need again to obtain end product with product behind the hydrogen reaction through ball milling 2 hours.Below press embodiment 1 described conventional method preparation and test.Reversible capacity is 576mAh/g first, and first charge-discharge efficiency is 77%, and through 50 circulations, reversible capacity is 324mAh/g, and coulombic efficiency is 91%.
Embodiment 3:
With mass ratio is magnesium powder and the graphite powder ball milling of 9:1, and ratio of grinding media to material is 10:1, and the ball milling time is 20 hours, and the material behind the taking-up ball milling is put into the high-pressure metal container, feeds hydrogen.The pressure of control hydrogen is 2Mpa, and reaction temperature is 350 ℃, and the reaction time is 10 hours; Need again to obtain end product with product behind the hydrogen reaction through ball milling 2 hours.Below press embodiment 1 described conventional method preparation and test.Reversible capacity is 756mAh/g first, and first charge-discharge efficiency is 81%, and through 50 circulations, reversible capacity is 525mAh/g, and coulombic efficiency is 97%.
Embodiment 4:
With mass ratio is magnesium powder and the carbon nano-tube ball milling of 9:1, and ratio of grinding media to material is 10:1, and the ball milling time is 20 hours, and the material behind the taking-up ball milling is put into the high-pressure metal container, feeds hydrogen.The pressure of control hydrogen is 2Mpa, and reaction temperature is 350 ℃, and the reaction time is 10 hours; Need again to obtain end product with product behind the hydrogen reaction through ball milling 2 hours.Below press embodiment 1 described conventional method preparation and test.Reversible capacity is 771mAh/g first, and first charge-discharge efficiency is 82%, and through 50 circulations, reversible capacity is 557mAh/g, and coulombic efficiency is 97%.
Embodiment 5:
With mass ratio is the lanthanum powder and the middle ball milling of microballoon mutually of 19:1, and ratio of grinding media to material is 10:1, and the ball milling time is 20 hours, and the material behind the taking-up ball milling is put into the high-pressure metal container, feeds hydrogen.The pressure of control hydrogen is 2Mpa, and reaction temperature is 350 ℃, and the reaction time is 10 hours; Need again to obtain end product with product behind the hydrogen reaction through ball milling 2 hours.Below press embodiment 1 described conventional method preparation and test.Reversible capacity is 432mAh/g first, and first charge-discharge efficiency is 75%, and through 50 circulations, reversible capacity is 371mAh/g, and coulombic efficiency is 96%.
Embodiment 6:
With mass ratio is magnesium powder, nickel powder and the carbon nano-tube ball milling of 6:3:1, and ratio of grinding media to material is 10:1, and the ball milling time is 20 hours, and the material behind the taking-up ball milling is put into the high-pressure metal container, feeds hydrogen.The pressure of control hydrogen is 2Mpa, and reaction temperature is 350 ℃, and the reaction time is 10 hours; Need again to obtain end product with product behind the hydrogen reaction through ball milling 2 hours.Below press embodiment 1 described conventional method preparation and test.Reversible capacity is 735mAh/g first, and first charge-discharge efficiency is 81%, and through 50 circulations, reversible capacity is 573mAh/g, and coulombic efficiency is 96%.
Embodiment 7:
With mass ratio is magnesium powder, titanium valve and the carbon nano-tube ball milling of 3:6:1, and ratio of grinding media to material is 10:1, and the ball milling time is 20 hours, and the material behind the taking-up ball milling is put into the high-pressure metal container, feeds hydrogen.The pressure of control hydrogen is 2Mpa, and reaction temperature is 350 ℃, and the reaction time is 10 hours; Need again to obtain end product with product behind the hydrogen reaction through ball milling 2 hours.Below press embodiment 1 described conventional method preparation and test.Reversible capacity is 623mAh/g first, and first charge-discharge efficiency is 82%, and through 50 circulations, reversible capacity is 426mAh/g, and coulombic efficiency is 94%.
Embodiment 8:
With mass ratio is lanthanum powder, nickel powder and the carbon nano-tube ball milling of 1:5:1, and ratio of grinding media to material is 10:1, and the ball milling time is 20 hours, and the material behind the taking-up ball milling is put into the high-pressure metal container, feeds hydrogen.The pressure of control hydrogen is 2Mpa, and reaction temperature is 350 ℃, and the reaction time is 10 hours; Need again to obtain end product with product behind the hydrogen reaction through ball milling 2 hours.Below press embodiment 1 described conventional method preparation and test.Reversible capacity is 694mAh/g first, and first charge-discharge efficiency is 78%, and through 50 circulations, reversible capacity is 512mAh/g, and coulombic efficiency is 94%.
Claims (6)
1. the preparation method of a lithium ion battery negative material, wherein negative active core-shell material is the compound of metal hydride and carbonaceous material, it is characterized in that: generate negative active core-shell material with hydrogen reaction behind the mixture process ball milling by metal powder and carbonaceous material, wherein the mass content of feed metal powder is 80-95%, the mass content of carbonaceous material is 5-20%, described metal is one or both in titanium, nickel, magnesium, the lanthanum, and described carbonaceous material is a kind of in graphite, carbon black, carbon nano-tube, middle phase microballoon, the active carbon.
2. preparation method according to claim 1 is characterized in that described metal is two kinds, and wherein a kind of is metallic nickel, and the mass ratio of another kind of metal and nickel is 5: 1-1: 5.
3. preparation method according to claim 1, the ball milling time that it is characterized in that the mixture of described metal powder and carbonaceous material is 20 hours, ratio of grinding media to material is 10: 1.
4. preparation method according to claim 1, the mixture that it is characterized in that described metal powder and carbonaceous material through behind the ball milling with hydrogen reaction, the pressure of hydrogen is 2Mpa, reaction temperature is 350 ℃, the reaction time is 10 hours.
5. preparation method according to claim 1 is characterized in that product behind the hydrogen reaction needs to make the negative active core-shell material average grain diameter less than 1 micron through ball milling 2 hours again.
6. preparation method according to claim 1 is characterized in that concrete steps are:
(1) metal powder and carbonaceous material are added in the ball milling according to mass ratio, ratio of grinding media to material is 10: 1, and the ball milling time is 20 hours;
(2) material behind the taking-up ball milling is put into the high-pressure metal container, feeds hydrogen, and the pressure of control hydrogen is 2Mpa, and reaction temperature is 350 ℃, and the reaction time is 10 hours;
(3) with hydrogen reaction after product need again to obtain negative active core-shell material through ball milling 2 hours.
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| CN2008101592932A CN101414678B (en) | 2008-11-28 | 2008-11-28 | Method for preparing lithium ion battery cathode material |
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| CN2008101592932A CN101414678B (en) | 2008-11-28 | 2008-11-28 | Method for preparing lithium ion battery cathode material |
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| CN101414678B true CN101414678B (en) | 2011-06-15 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9225023B2 (en) | 2013-10-04 | 2015-12-29 | Toyota Motor Engineering & Manufacturing North America, Inc. | Fullerenes as high capacity cathode materials for a rechargeable magnesium battery |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2527959C1 (en) * | 2013-05-06 | 2014-09-10 | Федеральное государственное бюджетное учреждение науки институт физики им. Л.В. Киренского Сибирского отделения Российской академии наук | Method of obtaining magnesium hydride powders in high-frequency arc plasma |
| CN106941155B (en) * | 2017-03-14 | 2019-12-24 | 北京大学 | Rare earth hydride-carbon nano composite material and preparation method and application thereof |
| CN108520946B (en) * | 2018-03-28 | 2020-06-19 | 华南理工大学 | Magnesium-iron hydride-graphite composite electrode material and preparation method and application thereof |
| CN112357916B (en) * | 2020-12-11 | 2022-09-06 | 安徽工业大学 | Method for improving capacity of graphite electrode material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9225023B2 (en) | 2013-10-04 | 2015-12-29 | Toyota Motor Engineering & Manufacturing North America, Inc. | Fullerenes as high capacity cathode materials for a rechargeable magnesium battery |
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Inventor after: Xing Wei Inventor after: Zhuo Shuping Inventor after: Si Weijiang Inventor after: Gao Xiuli Inventor after: Yuan Xun Inventor before: Zhuo Shuping Inventor before: Xing Wei Inventor before: Si Weijiang Inventor before: Gao Xiuli Inventor before: Yuan Xun |
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Free format text: CORRECT: INVENTOR; FROM: ZHUO SHUPING XING WEI SI WEIJIANG GAO XIULI YUAN XUN TO: XING WEI ZHUO SHUPING SI WEIJIANG GAO XIULI YUAN XUN |
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Granted publication date: 20110615 Termination date: 20121128 |