CN104638099A - Blocky graphene/clathrate composite material and preparation method thereof - Google Patents
Blocky graphene/clathrate composite material and preparation method thereof Download PDFInfo
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- CN104638099A CN104638099A CN201510098806.3A CN201510098806A CN104638099A CN 104638099 A CN104638099 A CN 104638099A CN 201510098806 A CN201510098806 A CN 201510098806A CN 104638099 A CN104638099 A CN 104638099A
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Abstract
The invention relates to a blocky graphene/clathrate composite material and a preparation method thereof, and belongs to the technical field of thermoelectric materials. The composite material is (w% graphene)/CoGexSe3-x (s is greater than or equal to 1.0 and is smaller than or equal to 2.0, and w% is greater than 0 and is smaller than 20%). The method comprises the following steps: firstly preparing CoGexSe3-x with metal elementary substances Co, Ge and Se as raw materials; then preparing graphene oxide by using a chemical stripping method; grinding into powder, mixing with the CoGexSe3-x according to a proportion and then performing heat treatment quenching to obtain the graphene/CoGexSe3-x composite material; performing high-temperature high-pressure treatment to obtain the compact blocky graphene/CoGexSe3-x composite material with regular shape. Compared with the thermoelectric material matrix which is uncompounded with graphene, the material and the method have the advantages that the electric conductivity of the material is improved, the thermal conductivity is reduced, and the preparation method is low in cost and high in yield and is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of blocky graphite alkene/Runge-Kutta integration composite material and preparation method thereof, belong to field of thermoelectric material technique.
Background technology
Thermoelectric material is a kind of functional material heat energy and electric energy directly can changed mutually, it is mainly used on airplane power source, refrigerator, have broad application prospects in vehicle exhaust and industrial afterheat power generation, the Main Bottleneck of research is at present that conversion efficiency of thermoelectric is lower.Conversion efficiency of thermoelectric can represent with dimensionless factor ZT, ZT=S
2σ T/ κ, wherein T is absolute temperature; S is Seebeck coefficient; σ is conductivity; κ is total heat conductance, comprises electron thermal conductivity and lattice thermal conductivity.
Skutterudite material has cage structure, is therefore also considered to the one of Runge-Kutta integration.Its advantage has high conductivity and larger Seebeck coefficient, but its higher thermal conductivity limits conversion efficiency of thermoelectric.Current research concentrates on and strengthens scattering to phonon by adulterating and filling the quality fluctuation increased on lattice defect and lattice, thus reduces thermal conductivity, but this method has limitation on controlled synthesis.Because nano material has unusual characteristic, particularly have very little thermal conductivity, therefore conventional thermoelectric materials and nano material being carried out compound becomes and studies new focus, such as studies more Yb
2o
3/ skutterudite composite material, this kind of composite material can reduce the thermal conductivity of material greatly, but can destroy the good electric conductivity of material simultaneously, thus affects its application.
Graphene is a kind of tow-dimensions atom stratified material be made up of carbon atom, and its carbon atom is with sp
2hydridization composition hexagonal lattice.Due to the structure that it is special, its band gap is zero, has high conductivity and Seebeck coefficient, and therefore it has broad prospects in thermoelectric material field.Graphene is incorporated in skutterudite matrix as nano-second-phase, new phonon scattering centers can be formed, further reduction thermal conductivity, Graphene has the electric property that excellent electronic transmission performance is expected to optimize further skutterudite in addition, thus improves its conversion efficiency of thermoelectric.Play-by-play at present also not in Graphene/skutterudite composite material.
Summary of the invention
For above problem, the present invention proposes a kind of blocky graphite alkene/Runge-Kutta integration composite material and preparation method thereof.
An object of the present invention is to provide a kind of compound structure for new residence thermoelectric material, and the chemical composition of this kind of composite material has larger adjustment space, is convenient to be optimized its thermoelectricity capability.
The present invention adopts following technical scheme:
A kind of blocky graphite alkene/Runge-Kutta integration composite material, it is characterized in that, described composite material has following chemical general formula:
(w% graphene oxide)/CoGe
xse
3-x
Wherein, 1.0≤x≤2.0,
W% is mass fraction shared by graphene oxide, 0<w%<20%.
Another object of the present invention is to provide a kind of preparation method, and the method is easy to operation, is convenient to obtain the composite material be evenly distributed, and can produces in a large number.Said method comprising the steps of:
(1) with metal simple-substance Co, Ge and Se for raw material, stoichiometrically Co:Ge:Se=1:x:3-x carries out weighing and mixing, wherein 1.0≤x≤2.0; Be sealing in quartz ampoule by the raw material mixed, select the temperature be applicable to carry out high-temperature process and quench, heat treatment temperature is between 500-800 DEG C, and the time is 1-5 days, obtained CoGe
xse
3-x;
(2) adopting chemical peeling to take crystalline flake graphite as raw material acquisition thickness is 1-1.5 nanometer, length and the wide large lamella graphene oxide being all greater than 1 micron, vacuumize between 60-80 DEG C, removing moisture and volatile matter, be milled to Powdered by dried graphene oxide subsequently;
(3) by CoGe prepared by the Powdered graphene oxide of step (2) and step (1)
xse
3-xmix by certain mass ratio and be sealing in quartz ampoule, wherein, graphene oxide/CoGe
xse
3-xthe mass fraction of middle graphene oxide is greater than 0 and is less than 20%, quenches between 500-600 DEG C after heat treatment 1-3 days, and in heat treatment process, the functional group of graphene oxide decomposes, and graphene oxide is converted into Graphene, thus obtains Graphene/CoGe
xse
3-xcomposite material;
(4) composite material is carried out high temperature high pressure process, pressure is 50-100MPa, and temperature is 500-600 DEG C, and the reaction time is 10-30 minute, obtains blocky graphite alkene/CoGe that is fine and close, regular shape thus
xse
3-xcomposite material.
Tool of the present invention has the following advantages:
1, introduced in skutterudite as second-phase by the Graphene of nanostructure, optimize the conductivity of skutterudite on the one hand, the nano-second-phase formed on the other hand can a large amount of scattering phonon, reduces thermal conductivity, thus optimization thermoelectricity capability.
2, the chemical composition of composite material has larger adjustment space, is conducive to being optimized performance.
3, preparation method of the present invention has that technique is simple, with low cost, productive rate advantages of higher, is suitable for large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is 5% Graphene/CoGe
1.5se
1.5x-ray diffraction (XRD) figure of composite material.
Fig. 2 is 5% Graphene/CoGe
1.5se
1.5the Raman collection of illustrative plates of composite material.
Embodiment
Further describe the present invention below in conjunction with instantiation, but the invention is not restricted to these embodiments.
Embodiment: 5% Graphene/CoGe
1.5se
1.5composite material and preparation method thereof.
(1) metal Co (0.308 gram), Ge (0.571 gram), Se (0.621 gram) are weighed respectively, be sealing in quartz ampoule after mixing, the vacuum degree of quartz ampoule is at least 10
-3mbar.Material is carried out high annealing, and annealing temperature is 500-800 DEG C, annealing time 1-5 days, then quenches to keep high-temperature-phase in ice-water bath.Obtain the high CoGe of purity thus
1.5se
1.5compound;
(2) by 3g crystalline flake graphite, under room temperature, (less than 20 DEG C) slowly join in the mixed liquor of the 360mL concentrated sulfuric acid and 40mL phosphoric acid (9:1), then 18g potassium permanganate is slowly joined in mixed liquor, 50 DEG C of heating 12h are warming up to after adding, washing and dialysis, obtain large lamella graphene oxide dispersion after ultrasonic process; Dispersion liquid is dry under 50 DEG C of vacuum conditions, and carrying out after drying milling, it is stand-by to obtain Powdered graphene oxide;
(3) by 1.5 grams of CoGe
1.5se
1.5mix with 0.075 gram of graphene oxide and enclose in quartz ampoule, the vacuum degree of quartz ampoule is at least 10
-3mbar.By material in 600 DEG C of heat treatments 3 days (graphene oxide is converted into Graphene), then quench in ice-water bath, obtain 5% Graphene/CoGe
1.5se
1.5composite material;
(4) composite material is carried out high temperature high pressure process, pressure is 50MPa, and temperature is 500 DEG C, and the processing time is 30 minutes, thus obtains fine and close block materials.
Fig. 1 is 5% Graphene/CoGe in the embodiment of the present invention
1.5se
1.5x-ray diffraction (XRD) figure of composite material.All diffraction maximums can index be all body-centered cubic structure, and space group is Im3, proves that resulting materials has the crystal structure characteristic of skutterudite, also show that resulting materials does not have other impurity simultaneously.Fig. 2 is 5% Graphene/CoGe in the embodiment of the present invention
1.5se
1.5the Raman collection of illustrative plates of composite material.Obviously can find out the characteristic peak (D peak and G peak) of Graphene from figure, prove in composite material containing Graphene.
The Runge-Kutta integration thermoelectric material obtained by above method is with low cost; Material has higher chemical stability, belongs to medium and high temperature thermoelectric material, available wider range; Its thermoelectric figure of merit can reach 1, meets thermoelectric material application requirement.
Claims (2)
1. blocky graphite alkene/Runge-Kutta integration composite material, is characterized in that, described composite material has following chemical general formula:
(w% graphene oxide)/CoGe
xse
3-x
Wherein, 1.0≤x≤2.0,
W% is the mass fraction that graphene oxide accounts for composite material, 0<w%<20%.
2. a preparation method for blocky graphite alkene/Runge-Kutta integration composite material as claimed in claim 1, is characterized in that, said method comprising the steps of:
(1) with metal simple-substance Co, Ge and Se for raw material, stoichiometrically Co:Ge:Se=1:x:3-x carries out weighing and mixing, wherein 1.0≤x≤2.0; Be sealing in quartz ampoule by the raw material mixed, carry out high-temperature process and quench between 500-800 DEG C, the time is 1-5 days, obtained CoGe
xse
3-x;
(2) adopting chemical peeling to take crystalline flake graphite as raw material acquisition thickness is 1-1.5 nanometer, length and the wide large lamella graphene oxide being all greater than 1 micron, vacuumize between 60-80 DEG C, removing moisture and volatile matter, be milled to Powdered by dried graphene oxide subsequently;
(3) by CoGe prepared by the Powdered graphene oxide of step (2) and step (1)
xse
3-xmix by certain mass ratio and be sealing in quartz ampoule, wherein, graphene oxide/CoGe
xse
3-xthe mass fraction of middle graphene oxide is greater than 0 and is less than 20%, quenches between 500-600 DEG C after heat treatment 1-3 days, obtains Graphene/CoGe
xse
3-xcomposite material;
(4) composite material is carried out high temperature high pressure process, pressure is 50-100MPa, and temperature is 500-600 DEG C, and the reaction time is 10-30 minute, obtained described blocky graphite alkene/Runge-Kutta integration composite material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111430530A (en) * | 2020-04-16 | 2020-07-17 | 中南林业科技大学 | Thermoelectric device based on porphin-graphene nanoribbon coupling |
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|---|---|---|---|---|
| US20060016470A1 (en) * | 2004-07-23 | 2006-01-26 | Jihui Yang | Filled skutterudites for advanced thermoelectric applications |
| 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 |
-
2015
- 2015-03-06 CN CN201510098806.3A patent/CN104638099B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060016470A1 (en) * | 2004-07-23 | 2006-01-26 | Jihui Yang | Filled skutterudites for advanced thermoelectric applications |
| 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 |
|---|
| G.S. NOLAS ET AL.: "Transport properties of CoGe1.5Se1.5", 《PHYSICAL REVIEW B》 * |
| R.KORENSTEIN ET AL.: "Prearation and Characterization of the Skutterudite-Related Phases CoGe1.5S1.5 and CoGe1.5Se1.5", 《INORGANIC CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111430530A (en) * | 2020-04-16 | 2020-07-17 | 中南林业科技大学 | Thermoelectric device based on porphin-graphene nanoribbon coupling |
| CN111430530B (en) * | 2020-04-16 | 2022-09-23 | 中南林业科技大学 | Thermoelectric device based on porphin-graphene nanoribbon coupling |
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