CN101355150B - Method for preparing graphitic carbon nanometer tube combination electrode material for lithium ion battery - Google Patents

Method for preparing graphitic carbon nanometer tube combination electrode material for lithium ion battery Download PDF

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CN101355150B
CN101355150B CN2008101507889A CN200810150788A CN101355150B CN 101355150 B CN101355150 B CN 101355150B CN 2008101507889 A CN2008101507889 A CN 2008101507889A CN 200810150788 A CN200810150788 A CN 200810150788A CN 101355150 B CN101355150 B CN 101355150B
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graphite
electrode material
combination electrode
mono
lithium ion
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CN101355150A (en
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王惠
任兆玉
李渭龙
王小芳
董发昕
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Northwest University
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Northwest University
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    • YGENERAL 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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    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a method for preparing a carbon nanotube composite electrode material by modifying graphite electrodes through a carbon nanotube and a single layer of graphite. The method comprises the following steps: (1) a precursor of a catalyst is prepared by an immersion method, and then is reduced to obtain a catalyst; (2) ethanol is cracked on the cracked catalyst and the cabon nanotube is grown in-situ; and (3) the product is mixed with acetylene black and a bonding agent to obtain a graphite carbon nanotube composite electrode material. The method allows the carbon nanotube to be grown on the surface of the graphite in situ, rather than takes the carbon nanotube as an addictive to be mixed in the graphite. The modifying method ensures that the carbon nanotube and the graphite are combined more closely and evenly microcosmically.

Description

The preparation method of graphitic carbon nanometer tube combination electrode material for lithium ion battery
Technical field
The present invention relates to lithium ion battery graphite electrode material preparing technical field, specifically, relate to the method for utilizing carbon nano-tube, mono-layer graphite graphite electrode to be carried out modification.
Background technology
Lithium ion battery is the green high-capacity rechargeable battery of latest generation, is considered to 21 century to national economy and the significant new high-tech industry of people's lives.Yet along with the development of battery miniaturization, the exploitation of height ratio capacity, high cycle-index battery becomes more and more urgent.Graphite is as lithium ion battery negative material, and in use exist at present: poor with solvent compatibility, high-rate performance is poor, and the common embedding because of solvent molecule during first charge-discharge is peeled off graphite linings, and reduce electrode life.Therefore, need carry out modification to the graphite material surface handles.
The research of carbon nano-tube becomes the new direction that improves the research of carbon negative pole material lithium reserves.The theoretical research that the quantum-mechanical density functional theory of usefulness such as Zhou is done the electronic structure and the embedding lithium performance of carbon nano-tube, for replacing graphite, carbon nano-tube provides theoretical foundation (Zhou Z as electrode material, Zhao J J, Gao X P, Chen Z, Yan J, Schleyer P V, Morinaga M.Chem.Mater.2005,17,992).Usefulness CVD methods such as J.Y.Eom are prepared multi-walled carbon nano-tubes, and it is carried out purifying and etching processing, find that such material has good its reversible specific capacity of storage lithium ability to be respectively 351mAh/g and 681mAh/g, and electrode good cycling stability (J.Y.Eom, H.S.Kwon, J.Liu, O.Zhou, Carbon, 2004,42,2589).Also have the researcher to adopt the additive of carbon nano-tube as lithium ion battery negative material, make the capacity of charge and discharge first of negative material improve 29.4mAh/g and 45.1mAh/g respectively, through circulating 20 times, capacity is not seen decay (Zhang Wanhong, Fang Liang, Yue Min, Yu Zuolong, battery, 2006,01,53).As seen being introduced on the raising lithium battery performance of carbon nano-tube has very big effect.
Summary of the invention
The objective of the invention is to utilize the original position of carbon nano-tube, mono-layer graphite or add modification, a kind of lithium ion battery simple and convenient, with low cost method of modifying of graphite electrode material is provided.
Implementation procedure of the present invention is as follows:
A kind of preparation method of graphitic carbon nanometer tube combination electrode material for lithium ion battery comprises the steps:
(1) the catalyst precursor of usefulness immersion process for preparing 5mol%~40mol%Co/C, Ni/C, Mo-Co/C or Mo-Ni/C is then at Ar/H 2Mixed atmosphere in reduce catalyst for cracking, Mo and Co, the mol ratio of Mo and Ni is 1:1;
(2) ethanol cracking in-situ growing carbon nano tube on above-mentioned catalyst for cracking, the reaction temperature of ethanol cracking in-situ growing carbon nano tube is 450-800 ℃;
(3) product and acetylene black, adhesive are mixed, promptly get graphitic carbon nanometer tube combination electrode material.
A kind of lithium ion battery comprises the steps: with the preparation method of mono-layer graphite original position or interpolation modification (multilayer) graphitic carbon nanometer tube combination electrode material
(1) with the multilayer graphite part or all be converted into mono-layer graphite, at last with the graphite oxide reduction, the in-situ modified multilayer graphite of mono-layer graphite combination electrode material;
(2) ethanol cracking in-situ growing carbon nano tube on above-mentioned mono-layer graphite modification (multilayer) graphite material makes combination electrode material;
(3) will make product and acetylene black, adhesive mix through (1), (2) step, promptly get graphitic carbon nanometer tube combination electrode material.
Also can carry out chemical etching or mechanical ball milling to the oxide of mono-layer graphite of preparation and handle, make to occur many nano level micropores in the mono-layer graphite.
Also can adopt following method with the multilayer graphite part or all be converted into mono-layer graphite: (1) graphite immerses that oxidation can or all be converted into mono-layer graphite with the multilayer graphite part in the concentrated sulfuric acid or the red fuming nitric acid (RFNA); (2) graphite heating is immersed rapidly after 100-300 ℃ in the concentrated sulfuric acid or concentrated nitric acid solution below 10 ℃, add the surfactant sonic oscillation, the abundant oxidation of graphite is separated,, promptly form the mono-layer graphite of high yield again with the product reduction.
The basic functional principle of lithium ion battery (graphite cathode):
Anodal reaction: LiCoO 2====Li 1-xCoO 2+ xLi++xe -
Negative reaction: 6C+x Li ++ xe -====Li xC 6
Battery overall reaction: LiCoO 2+ 6C=====Li 1-xCoO 2+ Li xC 6
The present invention adopts through preliminary treatment mineral carbon load catalyst, and be the carbon nano-tube of carbon source original position oriented growth particular dimensions with ethanol, has obtained the long lithium ion battery of specific capacity height, life-span with original position oriented growth of carbon nanometer tube modified graphite combination electrode material.Since carbon nano-tube modification graphite combination electrode material be with the carbon nano-tube growth in situ at graphite surface, rather than carbon nano-tube is blended in the graphite simply as a kind of additive.Therefore, the electrode reversible specific capacity of making according to the material of the present invention preparation is greatly improved, recycle 1000 times after, specific capacity is stabilized in more than the 360mAh/g.
The present invention comes graphite electrode material is carried out the modification except utilizing carbon nano-tube, also comes (multilayer) graphite electrode material is carried out modification by mono-layer graphite Graphene.Mono-layer graphite also has more superior character, as bigger specific area, good electrical conductivity etc. except having the similar character of similar carbon nano-tube with it.Therefore, on the basis of modified graphite carbon nano-tube combination electrode material, the present invention proposes to use mono-layer graphite as one of composition original position or interpolation modification (multilayer) graphitic carbon nanometer tube combination electrode material, and this material can further improve the electric conductivity of original position oriented growth of carbon nanometer tube modified graphite combination electrode material with further raising cyclical stability.
Advantage of the present invention is as follows: (1) with the carbon nano-tube modification graphite cathode be by with the carbon nano-tube growth in situ at graphite surface, rather than carbon nano-tube is blended in the graphite as a kind of additive, therefore this method of modifying can make tightr on microcosmic, the combination equably of carbon nano-tube and graphite; (2) apart from (shown in Fig. 1 (d)), this helps the embedding of lithium ion and takes off embedding the carbon nano-tube interlamellar spacing of ethanol cracking preparation greater than graphite layers; (3) mono-layer graphite has excellent conducting performance, helps further improving battery capacity and life-span with its modified graphite electrode material.
Description of drawings
The SEM of the carbon nano-tube of growth in situ and TEM photo on the Ni/C catalyst of Fig. 1, immersion process for preparing; (a) carbon nano-tube of growth in situ on the graphite linings; (b) symbiosis of carbon nano-tube and carbon fiber on the graphite linings; (c) carbon nanotubes grown mostly is opening on the graphite linings; (d) Sheng Chang multi-walled carbon nano-tubes interlamellar spacing (0.35nm) is slightly larger than the interlamellar spacing (0.34nm) of graphite.
Fig. 2. the mono-layer graphite of the ultrasonic auxiliary graphite oxidation method preparation of thermal stress; (a) the graphite oxide nanometer sheet of ball milling not; (b) the cavernous graphite oxide of ball milling after 24 hours.
Fig. 3, (a) and (b) be respectively carbon nano-tube modification graphite (soft carbon) and the prepared material of active carbon (hard carbon) charge-discharge performance curve chart as the lithium ion battery of negative pole.
Embodiment
Embodiment 1:
(1) nitrate (catalyst) that takes by weighing a certain amount of (supporting body mass ratio 5%~40% by catalyst and its takes by weighing) Co, Ni or Mo is made into 50ml solution;
(2) the catalyst loading body graphite of respective amount is sneaked into (1) solution, heat in 90 ℃ of water-baths, the stirring that does not stop is until evaporate to dryness solution;
(3) solid of gained in (2) is put into 80 ℃ of oven dry of baking oven 12 hours, put into N again 2The back grind into powder is taken out in 500 ℃ of calcinings of the Muffle furnace of gas shiled 10 hours, and it is standby to put into drier;
(4) the complex catalyst precursor thing of preparation being put into the fixed bed-gas-phase apparatus (WFSM-3011 type) that flows, is 40ml/min (Ar:H at gas flow 2=1:1; Ar is carrier gas, H 2Be reducing gases) atmosphere under from room temperature linear temperature increase to 500 ℃, keep this temperature 60min to guarantee that the catalyst precursor Restore All is an active catalyst.
(5) ethanol cracking in-situ growing carbon nano tube on (4) described active catalyst, reaction temperature: 450-800 ℃, the reaction time: 5-60min.Obtain uniform diameter, controllable density, the growth in situ carbon nano-tube on graphite, as shown in Figure 1.
(6) product and acetylene black, adhesive are mixed, promptly get graphitic carbon nanometer tube combination electrode material.
Embodiment 2:
The key step of mono-layer graphite in-situ modified (multilayer) graphitic carbon nanometer tube combination electrode material preparation:
(1) graphite is immersed oxidation in the concentrated sulfuric acid or the red fuming nitric acid (RFNA), between the graphite laminate structure a large amount of functional groups can appear then, interaction between graphite linings and the layer will significantly diminish, the sandwich construction of graphite just part is converted into single layer structure, and then, promptly get the combination electrode material of mono-layer graphite in-situ modified (multilayer) graphite with the graphite oxide reduction;
(2) in-situ growing carbon nano tube (with embodiment 1) on (1) prepared material obtains mono-layer graphite (Graphene) in-situ modified (multilayer) graphitic carbon nanometer tube combination electrode material.
Embodiment 3:
Mono-layer graphite adds the key step of modification (multilayer) graphitic carbon nanometer tube combination electrode material preparation:
(1) graphite heating is immersed rapidly after 100-300 ℃ in the concentrated sulfuric acid or concentrated nitric acid solution below 10 ℃, add surfactant (as SDS) sonic oscillation, the abundant oxidation of graphite is separated, again product is reduced, promptly form the mono-layer graphite of high yield, shown in Fig. 2 (a);
(2) oxide of mono-layer graphite of preparation is carried out chemical etching or mechanical ball milling is handled, make to occur many nano level micropores in the mono-layer graphite, further increase the specific area of mono-layer graphite, be convenient to the embedding of lithium ion and take off embedding, shown in Fig. 2 (b);
What (3) will prepare is pure, through pretreated mono-layer graphite and (multilayer) graphite fully, mix equably, then in-situ growing carbon nano tube thereon; Perhaps, with the graphene/carbon nanotube composite material of preparation among purer mono-layer graphite and the embodiment 1 of preparation fully, mix equably, obtain carbon nano-tube and mono-layer graphite (Graphene) interpolation modification (multilayer) graphite combination electrode material.
Embodiment 4:
Discharge and recharge instrument with LAND CT2001A type, come the charge-discharge performance of the sample of test implementation example 1,2,3 preparations, concrete steps are as follows:
(1) mixes (weight ratio: 15:5:85), after high-speed stirred is even, make the negative material of pulpous state with pulverous negative electrode active material with acetylene black, binding agent.
(2) slurry of making is coated in equably the surface of Copper Foil, cathode pole piece is made in oven dry.
(3)---the top-down order of barrier film---negative plate---barrier film is put well, makes Battery Pole Core through coiling, again through injecting the electrolyte (LiPF of 1mol/L by positive plate (lithium metal) 6), technical process such as seal, promptly finish the assembling process of battery.
(4) with the battery charging/discharging apparatus battery that assembles in (3) is carried out charge-discharge test, discharge and recharge constant current, electric current and voltage scope 5V/1mA.Fig. 3 is the charge-discharge performance curve chart of the prepared material of carbon nano-tube modification graphite as the lithium ion battery of negative electrode active material.
By orthogonal test, the present invention has optimized the reaction condition among each embodiment, prepared have high power capacity (greater than 380mAh/g), the modified graphite composite material of long-life (high cycle-index is greater than 1500 times).We find that the principal element that influences electrode material capacity and life-spans two aspect is: the content of the distribution of carbon nano-tube and pattern, mono-layer graphite etc. by analyzing contrast.

Claims (6)

1. the preparation method of a graphitic carbon nanometer tube combination electrode material for lithium ion battery comprises the steps:
(1) be the catalyst precursor of 5%~40%Co/C, Ni/C, Mo-Co/C or Mo-Ni/C with the immersion process for preparing mass ratio, then at Ar/H 2Mixed atmosphere in reduce catalyst for cracking;
(2) ethanol cracking in-situ growing carbon nano tube on above-mentioned catalyst for cracking;
(3) product and acetylene black, adhesive are mixed, promptly get graphitic carbon nanometer tube combination electrode material.
2. the preparation method of graphitic carbon nanometer tube combination electrode material for lithium ion battery according to claim 1, it is characterized in that: the reaction temperature of ethanol cracking in-situ growing carbon nano tube is 450-800 ℃.
3. a lithium ion battery comprises the steps: with the mono-layer graphite original position or add the preparation method of modification multilayer graphitic carbon nanometer tube combination electrode material
(1) with the multilayer graphite part or all be oxidized to mono-layer graphite, at last with the graphite oxide reduction, the in-situ modified multilayer graphite of mono-layer graphite combination electrode material;
(2) ethanol cracking in-situ growing carbon nano tube on the in-situ modified multilayer graphite of above-mentioned mono-layer graphite combination electrode material;
(3) will make product and acetylene black, adhesive mix through (1), (2) step, promptly get graphitic carbon nanometer tube combination electrode material.
4. the preparation method of graphitic carbon nanometer tube combination electrode material for lithium ion battery according to claim 3, it is characterized in that: the oxide of mono-layer graphite of preparation is carried out chemical etching or mechanical ball milling is handled, make to occur many nano level micropores in the mono-layer graphite.
5. according to the preparation method of claim 3 or 4 described graphitic carbon nanometer tube combination electrode material for lithium ion battery, it is characterized in that: graphite immerses in the concentrated sulfuric acid or the red fuming nitric acid (RFNA) oxidation with the multilayer graphite part or all be oxidized to mono-layer graphite.
6. according to the preparation method of claim 3 or 4 described graphitic carbon nanometer tube combination electrode material for lithium ion battery, it is characterized in that: graphite heating is immersed rapidly after 100-300 ℃ in the concentrated sulfuric acid or concentrated nitric acid solution below 10 ℃, add the surfactant sonic oscillation, the abundant oxidation of graphite is separated, with the product reduction, promptly form mono-layer graphite again.
CN2008101507889A 2008-09-03 2008-09-03 Method for preparing graphitic carbon nanometer tube combination electrode material for lithium ion battery Expired - Fee Related CN101355150B (en)

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CN101712452B (en) * 2009-11-20 2012-07-11 哈尔滨工程大学 Composite material of nano graphite flakes, carbon nano tubes and transition metal oxides and preparation method
CN103682282B (en) * 2012-09-22 2016-08-31 微宏动力***(湖州)有限公司 Lithium ion battery graphite cathode material and preparation method thereof
CN103094529B (en) * 2013-01-30 2015-06-24 新乡远东电子科技有限公司 Preparation method of composite cathode material of helical carbon nanotube/graphite
CN106571245A (en) * 2015-10-10 2017-04-19 联创汽车电子有限公司 Method for producing expanded graphite carbon nanotube composite material and supercapacitor produced from expanded graphite carbon nanotube composite material
CN106410197B (en) * 2016-05-17 2019-02-01 江西鸿炭科技有限公司 A kind of preparation method of graphite cathode material used in lithium ion battery
CN109449419B (en) * 2018-11-05 2021-04-06 台州学院 CNT-graphite composite active material for lithium ion battery and preparation method thereof
CN109786722B (en) * 2019-02-26 2021-05-11 苏州第一元素纳米技术有限公司 Method for producing electrochemically active material
CN110203920A (en) * 2019-05-31 2019-09-06 西安航空职业技术学院 A kind of preparation method of chemical vapor deposition modified graphite

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