CN104638099B - A kind of blocky graphite alkene/Runge-Kutta integration composite and preparation method thereof - Google Patents
A kind of blocky graphite alkene/Runge-Kutta integration composite and preparation method thereof Download PDFInfo
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- CN104638099B CN104638099B CN201510098806.3A CN201510098806A CN104638099B CN 104638099 B CN104638099 B CN 104638099B CN 201510098806 A CN201510098806 A CN 201510098806A CN 104638099 B CN104638099 B CN 104638099B
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Abstract
The present invention relates to a kind of blocky graphite alkene/Runge-Kutta integration composite and preparation method thereof, belongs to field of thermoelectric material technique.The composite：(w% Graphenes)/CoGexSe3‑x(1.0≤x≤2.0,0<W%<20%).It is of the invention that CoGe is obtained by raw material of metal simple-substance Co, Ge and Se firstxSe3‑x, then graphene oxide is prepared using chemical peeling, mill powdered rear and CoGexSe3‑xRear heat-treatment quenching is mixed in proportion, Graphene/CoGe is obtainedxSe3‑xComposite, high temperature high pressure process obtain fine and close, regular shape blocky graphite alkene/CoGexSe3‑xComposite.The thermoelectric material matrix of non-composite graphite alkene is compared, the material electric conductivity of the present invention is improved, and thermal conductivity declines, and its preparation method cost low-yield is high, is suitable to large-scale industrial production.
Description
Technical field
The present invention relates to a kind of blocky graphite alkene/Runge-Kutta integration composite and preparation method thereof, belongs to thermoelectric material technology
Field.
Background technology
Thermoelectric material is a kind of functional material that directly can mutually change heat energy and electric energy, and it is mainly used in aviation electricity
On source, refrigerator, have broad application prospects in terms of vehicle exhaust and industrial afterheat power generation, at present the Main Bottleneck of research
It is that conversion efficiency of thermoelectric is relatively low.Conversion efficiency of thermoelectric can be represented with dimensionless factor ZT, ZT=S2σ T/ κ, wherein T are absolute
Temperature；S is Seebeck coefficient；σ is electrical conductivity；κ is total thermal conductivity, including electron thermal conductivity and lattice thermal conductivity.
Skutterudite material has cage structure, therefore is also considered as one kind of Runge-Kutta integration.Its advantage is with high
Electrical conductivity and larger Seebeck coefficient, but its higher thermal conductivity limits conversion efficiency of thermoelectric.Current research is concentrated on
Strengthen the scattering to phonon by adulterating and filling to increase the quality fluctuation in lattice defect and lattice, so as to reduce thermal conductivity
Rate, but this method has limitation in controllable standby.As nano material has unusual characteristic, particularly with very
Little thermal conductivity, thus by conventional thermoelectric materials and nano material carry out it is compound become the new focus of research, such as study more
Yb2O3/ skutterudite composite, this kind of composite can substantially reduce the thermal conductivity of material, but while to destroy material good
Electric conductivity, so as to affect which to apply.
Graphene is a kind of tow -dimensions atom stratified material being made up of carbon atom, and its carbon atom is with sp2Hydridization constitutes six sides
Shape lattice.Due to its special structure, its band gap is zero, and with high electrical conductivity and Seebeck coefficient, therefore it is in thermoelectricity material
Material field has broad prospects.It is incorporated into Graphene as nano-second-phase in skutterudite matrix, new sound can be formed
Sub- scattering center, further reduces thermal conductivity, and there is Graphene excellent electronic transmission performance to be expected to the further side of optimization in addition
The electric property of cobalt ore, so as to improve its conversion efficiency of thermoelectric.There is presently no in terms of Graphene/skutterudite composite
Play-by-play.
The content of the invention
For problem above, the present invention proposes a kind of blocky graphite alkene/Runge-Kutta integration composite and preparation method thereof.
An object of the present invention is to provide a kind of compound structure for new residence thermoelectric material, the chemical group of this kind of composite
Into with larger regulation space, being easy to be optimized its thermoelectricity capability.
The present invention is adopted the following technical scheme that：
A kind of blocky graphite alkene/Runge-Kutta integration composite, it is characterised in that described composite has following chemistry logical
Formula：
(w% graphene oxides)/CoGexSe3-x
Wherein, 1.0≤x≤2.0,
W% be mass fraction shared by graphene oxide, 0<W%<20%.
It is yet another object of the invention to provide a kind of preparation method, the method is easily operated, readily available to be evenly distributed
Composite, and can produce in a large number.The method comprising the steps of：
(1) with metal simple-substance Co, Ge and Se as raw material, stoichiometrically Co：Ge：Se=1：x：3-x is weighed
And mix homogeneously, wherein 1.0≤x≤2.0；The raw material of mix homogeneously is sealing in quartz ampoule, selects the temperature being adapted to carry out
High-temperature process simultaneously quenches, and between 500-800 DEG C, the time is 1-5 days to heat treatment temperature, and CoGe is obtainedxSe3-x；
(2) chemical peeling is adopted to obtain thickness for 1-1.5 nanometers by raw material of crystalline flake graphite, it is long to be all higher than 1 with wide
The big lamella graphene oxide of micron, is vacuum dried between 60-80 DEG C, removes moisture and volatile matter, will subsequently be dried at
The graphene oxide managed is milled to powder；
(3) CoGe prepared by the powder graphene oxide of step (2) and step (1)xSe3-xBy certain mass than mixed
Close uniform and be sealing in quartz ampoule, wherein, graphene oxide/CoGexSe3-xThe mass fraction of middle graphene oxide is little more than 0
In 20%, heat treatment quenched after 1-3 days between 500-600 DEG C, the functional group of graphene oxide point in heat treatment process
Solution, graphene oxide is converted into Graphene, so as to obtain Graphene/CoGexSe3-xComposite；
(4) composite is carried out into high temperature high pressure process, pressure is 50-100MPa, and temperature is 500-600 DEG C, reaction
Time is 10-30 minutes, is derived from densification, regular shape blocky graphite alkene/CoGexSe3-xComposite.
The invention has the advantages that：
1st, mutually it is introduced into the Graphene of nanostructured as second in skutterudite, on the one hand optimizes the conductance of skutterudite
Rate, the nano-second-phase on the other hand being formed can scatter phonon in a large number, reduce thermal conductivity, so as to optimize thermoelectricity capability.
2nd, the chemical composition of composite has larger regulation space, is conducive to being optimized performance.
3rd, preparation method of the invention has the advantages that process is simple, with low cost, yield are high, is suitable to heavy industrialization
Production.
Description of the drawings
Fig. 1 is 5% Graphene/CoGe1.5Se1.5X-ray diffraction (XRD) figure of composite.
Fig. 2 is 5% Graphene/CoGe1.5Se1.5The Raman collection of illustrative plates of composite.
Specific embodiment
The present invention is further described with reference to instantiation, but the invention is not restricted to these embodiments.
Embodiment：5% Graphene/CoGe1.5Se1.5Composite and preparation method thereof.
(1) by metal Co (0.308 gram), Ge (0.571 gram), Se (0.621 gram) is weighed respectively, is sealing into after mix homogeneously
In quartz ampoule, the vacuum of quartz ampoule is at least 10-3mbar.Material is carried out into high annealing, annealing temperature is 500-800 DEG C,
Annealing time 1-5 days, then quenches to keep high-temperature-phase in ice-water bath.It is derived from the high CoGe of purity1.5Se1.5Chemical combination
Thing；
(2) by 3g crystalline flake graphites, (less than 20 DEG C) are slowly added into 360mL concentrated sulphuric acids and 40mL phosphoric acid (9 at room temperature：1)
Mixed liquor in, then 18g potassium permanganate is slowly added in mixed liquor, be warming up to after adding 50 DEG C heating 12h, washing and
Dialysis, obtains big lamella graphene oxide dispersion after supersound process；Dispersion liquid is dried under 50 DEG C of vacuum conditions, after being dried
Carrying out milling, it is stand-by to obtain powder graphene oxide；
(3) by 1.5 grams of CoGe1.5Se1.5With 0.075 gram of graphene oxide mix homogeneously and enclose in quartz ampoule, quartz ampoule
Vacuum be at least 10-3mbar.By material in 600 DEG C of heat treatments 3 days (graphene oxide is converted into Graphene), then in ice
Quench in water-bath, obtain 5% Graphene/CoGe1.5Se1.5Composite；
(4) composite is carried out into high temperature high pressure process, pressure is 50MPa, and temperature is 500 DEG C, and process time is 30 points
Clock, so as to obtain the block materials of densification.
Fig. 1 is 5% Graphene/CoGe in the embodiment of the present invention1.5Se1.5X-ray diffraction (XRD) figure of composite.Institute
There is the diffraction maximum can be with index as body-centered cubic structure, space group is Im3, it was demonstrated that resulting materials have the crystal structure of skutterudite
Feature, while also indicating that resulting materials do not have other impurities.Fig. 2 is 5% Graphene/CoGe in the embodiment of the present invention1.5Se1.5It is multiple
The Raman collection of illustrative plates of condensation material.This it appears that the characteristic peak (D peaks and G peaks) of Graphene from figure, it was demonstrated that contain in composite
There is Graphene.
The Runge-Kutta integration thermoelectric material obtained by above method is with low cost；Material has higher chemical stability, category
In medium and high temperature thermoelectric material, available wider range；Its thermoelectric figure of merit can reach 1, meet thermoelectric material application
Require.
Claims (1)
1. a kind of preparation method of blocky graphite alkene/Runge-Kutta integration composite, the composite have following chemical general formula：
(w% graphene oxides)/CoGexSe3-x
Wherein, 1.0≤x≤2.0,
W% accounts for the mass fraction of composite for graphene oxide, and 0<W%<20%；
Characterized in that, the method comprising the steps of：
(1) with metal simple-substance Co, Ge and Se as raw material, stoichiometrically Co：Ge：Se=1：x：3-x is weighed and is mixed
Close uniform, wherein 1.0≤x≤2.0；The raw material of mix homogeneously is sealing in quartz ampoule, height is carried out between 500-800 DEG C
Temperature is processed and is quenched, and the high-temperature process time is 1-5 days, and CoGe is obtainedxSe3-x；
(2) chemical peeling is adopted to obtain thickness for 1-1.5 nanometers by raw material of crystalline flake graphite, it is long to be all higher than 1 micron with wide
Big lamella graphene oxide, be vacuum dried between 60-80 DEG C, remove moisture and volatile matter, subsequently will be dried
Graphene oxide be milled to powder；
(3) CoGe prepared by the powder graphene oxide of step (2) and step (1)xSe3-xCompare mix homogeneously by certain mass
And be sealing in quartz ampoule, wherein, graphene oxide/CoGexSe3-xThe mass fraction of middle graphene oxide is less than more than 0
20%, heat treatment quenched after 1-3 days between 500-600 DEG C, obtained Graphene/CoGexSe3-xComposite；
(4) composite is carried out into high temperature high pressure process, pressure is 50-100MPa, and temperature is 500-600 DEG C, the response time
For 10-30 minutes, prepared described blocky graphite alkene/Runge-Kutta integration composite.
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Citations (3)
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|---|---|---|---|---|
| CN102593341A (en) * | 2012-03-14 | 2012-07-18 | 武汉理工大学 | Plumbum telluride (PbTe) or graphene nanocomposite material and preparing method thereof |
| CN102931335A (en) * | 2012-10-24 | 2013-02-13 | 东华大学 | Graphene compounded with stibine cobalt base skutterudite thermoelectric material and preparation method of material |
| CN104046876A (en) * | 2014-06-16 | 2014-09-17 | 济南大学 | Graphene/Cu2AX3 type thermoelectric composite material and preparation method thereof |
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| US7648552B2 (en) * | 2004-07-23 | 2010-01-19 | Gm Global Technology Operations, Inc. | Filled skutterudites for advanced thermoelectric applications |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102593341A (en) * | 2012-03-14 | 2012-07-18 | 武汉理工大学 | Plumbum telluride (PbTe) or graphene nanocomposite material and preparing method thereof |
| CN102931335A (en) * | 2012-10-24 | 2013-02-13 | 东华大学 | Graphene compounded with stibine cobalt base skutterudite thermoelectric material and preparation method of material |
| CN104046876A (en) * | 2014-06-16 | 2014-09-17 | 济南大学 | Graphene/Cu2AX3 type thermoelectric composite material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Prearation and Characterization of the Skutterudite-Related Phases CoGe1.5S1.5 and CoGe1.5Se1.5;R.Korenstein et al.;《Inorganic Chemistry》;19770930;第16卷(第9期);第2344-2346页 * |
| Transport properties of CoGe1.5Se1.5;G.S. Nolas et al.;《Physical Review B》;20031120;第68卷(第19期);参见Experimental Techniques节 * |
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