CN102208616A - Preparation method of carbon-coated transition metal nano hollow particle - Google Patents
Preparation method of carbon-coated transition metal nano hollow particle Download PDFInfo
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Abstract
The invention provides a preparation method of a carbon-coated transition metal nano hollow particle. The method comprises the following steps: based on a Kirkendall effect, carrying out dissolving and mixing, high temperature co-pyrolysis and insulation in-situ reduction on an aromatic hydrocarbon compound with oxygen-containing groups and a transition metal compound so as to obtain the carbon coated metal nano hollow particle. The hollow structure shell layer prepared by the method consists of carbon and a nano metal composite material; and the nano particles are evenly distributed, the diameter range of the nano particle is 20nm-80nm, and the thickness of the carbon-coated layer is 2.2nm-4.3nm.
Description
Technical field
The present invention relates to a kind of carbon encapsulated material, particularly a kind of carbon coats the preparation method of transition metal simple substance hollow nano particle.
Background technology
It is the novel hollow structure nano composite material of a class that carbon coats transition metal hollow nano particle.Because nano metal material coated by the carbon shell, can avoid the problem that the hollow nano metallic can not stable existence in air; Owing to the existence of carbon coating layer, can improve the performance that recycles of composite material in addition, thereby have broad application prospects at ion secondary battery cathode material lithium.
The hollow preparation of nanomaterials mainly contains masterplate method and non-masterplate method at present.Wherein the subsequent treatment of template (comprising soft template method and hard template method) need be removed template, if template does not eliminate totally, might cause negative effect to the character of material as impurity, and this makes the application of this method be subjected to certain restriction; The method for preparing the hollow nano material based on the Ke Kendaer effect belongs to non-masterplate method, Yadong Yin etc. utilizes this method at first to synthesize cobalt oxide and cobalt sulfide hollow nano particle, and to made detailed explaining [Yin.Y et al based on the Reaction Mechanisms of Ke Kendaer effect, Formation of hollownanocrystals through the nanoscale Kirkendall effect, Science 2004:304:711].Nam etc. pass through face-centered cube cobalt oxide (CoO) at oleamide (C
18H
35NH
2) in pyrolysis synthesized face-centered cubic cobalt simple substance hollow nano particle [Nam.K.M et al, Single-crystalline hollowface-centered-cubic cobalt nanoparticles from solid face-centered-cubic cobalt oxidenanoparticles, Angew.Chem.Int.Ed.2008:47:9504], because it is the hollow structure nano cobalt granule of this method preparation does not have the carbon shell to coat, very easily oxidized and can not stable in the airly exist.
1993, U.S. Rouff etc. and Japanese Tomita etc. have found at first that in arc evaporation graphite cigarette ash carbon coats structure [the Ruoff.R et al of carbonization bright-coloured, Single-crystal metals encapsulated in carbonnanoparticles, Scienee, 1993:259:346; Tomita M et al, LaC
2Encapsulated in graphitenanoparticle.Jap, J.Appl.Phys., 1993:32:L280].People actively improve arc-discharge technique subsequently, and developed the CVD method gradually, infusion process, the synthetic method of the carbon-coated nano metal that pyrolysismethod etc. are new, employing pyrolysismethods such as Zhou carry out oxidation processes to airborne carbon-clad metal simple substance at a certain temperature and prepare carbon coated iron oxide hollow nano particle, and its electric property as lithium ion battery negative material done studied [Zhou.J et al, Oxidation conversion of carbon-encapsulated metalnanoparticles to hollow nanoparticles, Chem.Mater.2009:21:3730; Zhou.J et al, Carbon-encapsulated metal oxide hollow nanoparticles and metal oxide hollownanoparticles:A general synthesis strategy and its application to lithium-ionbatteries, Chem.Mater. 2009:21:2935].Do not coat the report of transition metal hollow nano structural composite material at present as yet relevant for preparation carbon.
Summary of the invention
The present invention is directed to the problems referred to above of prior art, provide a kind of carbon to coat the preparation method of transition metal hollow nano particle.Make by following step:
1: 3～1: 0.5 oxy radical aromatic compound of weight ratio and transistion metal compound are dissolved in the acetone; mechanical agitation to acetone volatilizees fully; then the gained solid is placed autoclave; add the high temperature resistant dimethicone of 60～100ml; under inert atmosphere protection; progressively be warming up to 420-540 ℃ from room temperature and carry out pyrolytic reaction; cool to 400 ℃ of insulation 4～8h then; products therefrom through organic solvent extraction, filtration and drying, is promptly got carbon and coats transition metal hollow nano particle.
The further preferred version of the present invention is: described oxy radical aromatic compound is selected from and contains a kind of in hydroxyl, carbonyl or the carboxylic model aromatic compound on the phenyl ring.
The further preferred version of the present invention is: described transistion metal compound is selected from and contains a kind of in cyclopentadienyl, carbonyl, acetylacetone based transistion metal compound, transition metal nitrate or the acetate.
The further preferred version of the present invention is: described organic solvent is selected from a kind of in ethanol, acetone, benzene, oxolane or the pyridine.
The further preferred version of the present invention is: the model aromatic compound that contains hydroxyl, carbonyl or carboxyl on the described phenyl ring is selected from a kind of in the oxygen element group aromatic compound of containing that phenol, resorcinol, phloroglucin, glucose, phenolic resins or other have hydroxyl, carboxyl.
The further preferred version of the present invention is: described cyclopentadienyl transistion metal compound is selected from a kind of in ferrocene, cobaltocene or the dicyclopentadienyl nickel.
The further preferred version of the present invention is: described carbonyl transistion metal compound is selected from a kind of in carbonyl iron, carbonyl cobalt or the carbonyl nickel.
The further preferred version of the present invention is: described acetylacetone based transistion metal compound is selected from a kind of in chromium acetylacetonate, acetylacetone,2,4-pentanedione platinum or the palladium acetylacetonate.
The further preferred version of the present invention is: described transition metal acetate is selected from a kind of in cobalt acetate, nickel acetate or the ferric acetate.
The further preferred version of the present invention is: described transition metal nitrate is selected from a kind of in ferric nitrate, cobalt nitrate or the nickel nitrate.
The further preferred version of the present invention is: resulting product particle diameter scope is 20nm～80nm, and carbon coating layer is 2.2nm～4.3nm.
The present invention reacts in the liquid phase environment that dimethicone provides, and can avoid reactant because of inhomogeneous product size, structure and modal difference and the minimizing agraphitic carbon content of causing that be heated.By the time of control insulation reduction reaction, can also prepare carbon-clad metal oxide nano particles, shell and core isolating construction nano particle and carbon-clad metal simple substance hollow nano particle in addition, realize the controlledly synthesis of material.And characteristics such as this method synthesis route is simple, reaction condition is gentle, raw material sources are abundant, the metal types selectable range is wide have commercial applications prospect well.
Description of drawings
Accompanying drawing 1 is carbon-encapsulated iron hollow nano particle X-ray diffraction (XRD) figure.
Accompanying drawing 2 is carbon-encapsulated iron hollow structure nano particle transmission electron microscope (TEM) figure.
Accompanying drawing 3 is carbon-encapsulated iron hollow structure nano particle high resolution transmission electron microscopy (HRTEM) figure.
Embodiment
The present invention is described in detail below in conjunction with drawings and Examples:
Embodiment 1
By weight taking by weighing 10g resorcinol and 20g ferrocene at 1: 2 and being dissolved in the acetone; mechanical agitation to acetone volatilizees fully; then the gained solid is placed in the autoclave; and add the 60ml high-temperature silicon oil as reaction medium; under continuously and smoothly's mechanical agitation and nitrogen protection; slowly lower the temperature when progressively being warming up to 420 ℃,, obtain the copyrolysis product 400 ℃ of insulations 6 hours.
As solvent product is carried out thermosol extracting repeatedly with benzinum and pyridine, until the filtrate achromaticity and clarification.Dry behind the suction filtration, promptly get carbon-encapsulated iron hollow nano granular materials.
The analysis showed that as accompanying drawing 1X-x ray diffraction (XRD) the product metal-back composition of layer that obtains is that (α-Fe), the carbon shell has higher density and orderly degree of alignment to iron simple substance; Show as accompanying drawing 2 transmission electron microscopes (TEM) and accompanying drawing 3 high resolution transmission electron microscopies (HRTEM) analysis result, product have a tangible hollow structure, grain diameter is between 20～60nm, the average thickness of carbon-encapsulated iron shell is 4.0nm.
Embodiment 2
Method of operation is with embodiment 1; difference is to take by weighing 10g phloroglucin and 30g cobaltocene by weight 1: 3 and be dissolved in the acetone; add the high temperature resistant dimethicone of 100ml as reaction medium; under inert atmosphere protection; progressively be warming up to 540 ℃ from room temperature and carry out pyrolytic reaction; cool to 400 ℃ of insulation 8h then, obtain carbon coating cobalt hollow nano granular materials at last, have the less metal simple-substance particle of particle diameter in the part shell nano particle.Confirm that through X-ray diffraction and transmission electron microscope (TEM) photo the average thickness of carbon-clad metal shell is about 2.2nm, metal ingredient is mainly cobalt simple substance, and the less particle size distribution in core is 35～50nm.
Embodiment 3
Method of operation is with embodiment 1; difference is to take by weighing 20g phenol and 10g palladium acetylacetonate by weight 1: 0.5 and be dissolved in the acetone; add the high temperature resistant dimethicone of 80ml; under inert atmosphere protection; progressively be warming up to 500 ℃ from room temperature and carry out pyrolytic reaction; cool to 400 ℃ of insulation 4h then, the carbon that obtains the agraphitic carbon content showed increased at last coats palladium hollow nano granular materials.Confirm that through X-ray diffraction and transmission electron microscope (TEM) photo the average thickness of carbon-clad metal shell is about 4.3nm, the nano particle diameter range is 25nm～40nm, and metal ingredient is mainly the simple substance palladium.
Method of operation is with embodiment 1, and difference is that originally for the reduction reaction time is 4 hours, all the other conditions are constant, obtain the nano particle of carbon-clad metal shell and core metal oxide isolating construction at last 400 ℃ of insulations.Confirm that through X-ray diffraction and transmission electron microscope (TEM) photo the thickness of carbon-clad metal shell is 3.5nm, metal ingredient is mainly iron simple substance (α-Fe); Shell and gap, core are grain 3.0nm; The core particle size distribution is 15～50nm, and main component is metal oxide (α-Fe
3O
4).
Embodiment 5
Method of operation is with embodiment 1, and difference is, takes by weighing 10g by weight 1: 1.5 and analyzes pure glucose and 15g carbonyl nickel and be dissolved in the acetone.Reaction finally obtains carbon-coating nickel simple substance hollow nano-particle material, and X-ray diffraction and transmission electron microscope (TEM) photo shows: the metal-back composition of layer is a nickel simple substance, and particle diameter is between 30～80nm, and the thickness of carbon-clad metal shell is 4.5nm.
Embodiment 6
Method of operation is with embodiment 1, and difference is, takes by weighing 10g phenolic resins and 10g ferric acetate by weight 1: 1 and is dissolved in the acetone.Reaction finally obtains carbon-encapsulated iron simple substance hollow nano-particle material, and transmission electron microscope (TEM) photo shows: the carbon shell is arranged the ordering degree and is improved, and fine and close more.
More than preferred embodiment of the present invention is specified, but the present invention is not limited to described embodiment, those of ordinary skill in the art also can make all modification that is equal to or replacement under the prerequisite of spirit of the present invention, modification that these are equal to or replacement all are included in the application's claim institute restricted portion.
Claims (11)
1. a carbon coats the preparation method of transition metal hollow nano particle, it is characterized in that making by following method:
1: 3～1: 0.5 oxy radical aromatic compound of weight ratio and transistion metal compound are dissolved in the acetone; mechanical agitation to acetone volatilizees fully; then the gained solid is placed autoclave; add the high temperature resistant dimethicone of 60～100ml; under inert atmosphere protection; progressively be warming up to 420-540 ℃ from room temperature and carry out pyrolytic reaction; cool to 400 ℃ of insulation 4～8h then; products therefrom through organic solvent extraction, filtration and drying, is promptly got carbon and coats transition metal hollow nano particle.
2. carbon coats the preparation method of transition metal hollow nano particle according to claim 1, it is characterized in that: described oxy radical aromatic compound is selected from and contains a kind of in hydroxyl, carbonyl or the carboxylic model aromatic compound on the phenyl ring.
According to claim 1 carbon coat transition metal hollow nano particle the preparation method, it is characterized in that: described transistion metal compound is selected from and contains a kind of in cyclopentadienyl, carbonyl, acetylacetone based transistion metal compound, transition metal nitrate or the acetate.
4. carbon coats the preparation method of transition metal hollow nano particle according to claim 1, it is characterized in that: described organic solvent is selected from a kind of in ethanol, acetone, benzene, oxolane or the pyridine.
5. coat the preparation method of transition metal hollow nano particle according to the described carbon of claim 2, it is characterized in that: the model aromatic compound that contains hydroxyl, carbonyl or carboxyl on the described phenyl ring is selected from a kind of in the oxygen element group aromatic compound of containing that phenol, resorcinol, phloroglucin, glucose, phenolic resins or other have hydroxyl, carboxyl.
6. coat the preparation method of transition metal hollow nano particle as carbon as described in the claim 3, it is characterized in that: described cyclopentadienyl transistion metal compound is selected from a kind of in ferrocene, cobaltocene or the dicyclopentadienyl nickel.
7. coat the preparation method of transition metal hollow nano particle as carbon as described in the claim 3, it is characterized in that: described carbonyl transistion metal compound is selected from a kind of in carbonyl iron, carbonyl cobalt or the carbonyl nickel.
8. coat the preparation method of transition metal hollow nano particle as carbon as described in the claim 3, it is characterized in that: described acetylacetone based transistion metal compound is selected from a kind of in chromium acetylacetonate, acetylacetone,2,4-pentanedione platinum or the palladium acetylacetonate.
9. coat the preparation method of transition metal hollow nano particle as carbon as described in the claim 3, it is characterized in that: described transition metal acetate is selected from a kind of in cobalt acetate, nickel acetate or the ferric acetate.
10. coat the preparation method of transition metal hollow nano particle as carbon as described in the claim 3, it is characterized in that: described transition metal nitrate is selected from a kind of in ferric nitrate, cobalt nitrate or the nickel nitrate.
11. the carbon for preparing as method as described in the claim 1～10 coats transition metal hollow nano particle, it is characterized in that: the nano particle diameter range is 20nm～80nm, and carbon coating layer is 2.2nm～4.3nm.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103623824A (en) * | 2012-08-23 | 2014-03-12 | 华东师范大学 | Magnetic iron-carbon composite material, preparation method and application thereof |
| CN104078653A (en) * | 2014-07-23 | 2014-10-01 | 吉林大学 | Carbon-coated transition metal oxide or transition metal nanoparticle composite electrode material adopting cellular structure and preparation method thereof |
| CN104282951A (en) * | 2013-07-09 | 2015-01-14 | 中国科学院上海硅酸盐研究所 | Sodium cell and positive pole material |
| CN104451942A (en) * | 2014-11-14 | 2015-03-25 | 大连交通大学 | Hollow-structure carbon-coated tin dioxide nanofiber material as well as preparation method and application of hollow-structure carbon-coated tin dioxide nanofiber material |
| CN106115795A (en) * | 2016-06-23 | 2016-11-16 | 上海交通大学 | A kind of preparation method of functionalized carbon coated magnetic nanoparticle |
| CN107442111A (en) * | 2016-05-30 | 2017-12-08 | 中国科学院长春应用化学研究所 | Carbon-clad metal nanocube material and preparation method thereof |
| CN108788181A (en) * | 2018-07-10 | 2018-11-13 | 哈尔滨理工大学 | A method of the nucleocapsid carbon gold-covered nano particle of the regular spherical morphology of synthesis |
| CN109304202A (en) * | 2017-07-28 | 2019-02-05 | 中国石油化工股份有限公司 | A kind of nanocomposite of carbon coating transition metal and its application |
| CN109616626A (en) * | 2018-11-15 | 2019-04-12 | 上海海事大学 | A kind of low temperature magnanimity preparation method that carbon coated ferriferrous oxide is nanocrystalline |
| CN110707327A (en) * | 2019-10-13 | 2020-01-17 | 浙江大学 | Preparation of modified porous carbon material based on cobaltocene and application of modified porous carbon material in lithium-sulfur battery |
| CN113823785A (en) * | 2021-09-18 | 2021-12-21 | 山东省科学院新材料研究所 | Hollow mesoporous carbon shell coated metal nanosphere and super-assembly preparation method and application thereof |
| CN113839104A (en) * | 2020-06-24 | 2021-12-24 | 比亚迪股份有限公司 | Lithium battery cathode and lithium battery |
| CN114512729A (en) * | 2020-11-16 | 2022-05-17 | 比亚迪股份有限公司 | Nanomaterial for negative electrode protection layer, negative electrode protection slurry, lithium negative electrode and lithium battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1507972A (en) * | 2002-12-18 | 2004-06-30 | 北京化工大学 | Method for preparing carbon-coated metal nano crystal |
-
2011
- 2011-05-09 CN CN2011101188565A patent/CN102208616A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1507972A (en) * | 2002-12-18 | 2004-06-30 | 北京化工大学 | Method for preparing carbon-coated metal nano crystal |
Non-Patent Citations (2)
| Title |
|---|
| 《中国优秀硕士学位论文全文数据库》 20110115 付伯承 "碳包覆纳米四氧化三铁颗粒的合成与结构研究" 第20-27页 1-11 , 第01期 * |
| 付伯承: ""碳包覆纳米四氧化三铁颗粒的合成与结构研究"", 《中国优秀硕士学位论文全文数据库》 * |
Cited By (21)
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| CN103623824B (en) * | 2012-08-23 | 2015-10-28 | 华东师范大学 | A kind of Armco magnetic iron carbon composite and its preparation method and application |
| CN103623824A (en) * | 2012-08-23 | 2014-03-12 | 华东师范大学 | Magnetic iron-carbon composite material, preparation method and application thereof |
| CN104282951A (en) * | 2013-07-09 | 2015-01-14 | 中国科学院上海硅酸盐研究所 | Sodium cell and positive pole material |
| CN104282951B (en) * | 2013-07-09 | 2016-10-19 | 中国科学院上海硅酸盐研究所 | Sode cell and positive electrode thereof |
| CN104078653A (en) * | 2014-07-23 | 2014-10-01 | 吉林大学 | Carbon-coated transition metal oxide or transition metal nanoparticle composite electrode material adopting cellular structure and preparation method thereof |
| CN104451942A (en) * | 2014-11-14 | 2015-03-25 | 大连交通大学 | Hollow-structure carbon-coated tin dioxide nanofiber material as well as preparation method and application of hollow-structure carbon-coated tin dioxide nanofiber material |
| CN107442111B (en) * | 2016-05-30 | 2020-04-07 | 中国科学院长春应用化学研究所 | Carbon-coated metal nanocube material and preparation method thereof |
| CN107442111A (en) * | 2016-05-30 | 2017-12-08 | 中国科学院长春应用化学研究所 | Carbon-clad metal nanocube material and preparation method thereof |
| CN106115795A (en) * | 2016-06-23 | 2016-11-16 | 上海交通大学 | A kind of preparation method of functionalized carbon coated magnetic nanoparticle |
| CN109304202A (en) * | 2017-07-28 | 2019-02-05 | 中国石油化工股份有限公司 | A kind of nanocomposite of carbon coating transition metal and its application |
| CN108788181A (en) * | 2018-07-10 | 2018-11-13 | 哈尔滨理工大学 | A method of the nucleocapsid carbon gold-covered nano particle of the regular spherical morphology of synthesis |
| CN108788181B (en) * | 2018-07-10 | 2021-07-06 | 哈尔滨理工大学 | Method for synthesizing core-shell structure carbon-coated gold nanoparticles with regular spherical morphology |
| CN109616626A (en) * | 2018-11-15 | 2019-04-12 | 上海海事大学 | A kind of low temperature magnanimity preparation method that carbon coated ferriferrous oxide is nanocrystalline |
| CN109616626B (en) * | 2018-11-15 | 2022-02-15 | 上海海事大学 | Low-temperature macro preparation method of carbon-coated ferroferric oxide nanocrystal |
| CN110707327B (en) * | 2019-10-13 | 2020-10-23 | 浙江大学 | Preparation of modified porous carbon material based on cobaltocene and application of modified porous carbon material in lithium-sulfur battery |
| CN110707327A (en) * | 2019-10-13 | 2020-01-17 | 浙江大学 | Preparation of modified porous carbon material based on cobaltocene and application of modified porous carbon material in lithium-sulfur battery |
| CN113839104A (en) * | 2020-06-24 | 2021-12-24 | 比亚迪股份有限公司 | Lithium battery cathode and lithium battery |
| CN113839104B (en) * | 2020-06-24 | 2023-12-12 | 比亚迪股份有限公司 | Lithium battery cathode and lithium battery |
| CN114512729A (en) * | 2020-11-16 | 2022-05-17 | 比亚迪股份有限公司 | Nanomaterial for negative electrode protection layer, negative electrode protection slurry, lithium negative electrode and lithium battery |
| CN114512729B (en) * | 2020-11-16 | 2023-07-14 | 比亚迪股份有限公司 | Nanomaterial, negative electrode protection slurry, lithium negative electrode and lithium battery |
| CN113823785A (en) * | 2021-09-18 | 2021-12-21 | 山东省科学院新材料研究所 | Hollow mesoporous carbon shell coated metal nanosphere and super-assembly preparation method and application thereof |
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Application publication date: 20111005 |