CN107910432A - A kind of preparation method of powdered nano composite thermoelectric materials - Google Patents
A kind of preparation method of powdered nano composite thermoelectric materials Download PDFInfo
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- CN107910432A CN107910432A CN201711130258.3A CN201711130258A CN107910432A CN 107910432 A CN107910432 A CN 107910432A CN 201711130258 A CN201711130258 A CN 201711130258A CN 107910432 A CN107910432 A CN 107910432A
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Abstract
The present invention provides a kind of powdered nano composite thermoelectric materials preparation method, weigh graphene oxide and be put into deionized water, ultrasound is in transparent and homogeneous to liquid, then sequentially adds sodium tartrate, TeO2、KOH、Bi(NO3)3·5H2O, and stir；Again KBH is added into above-mentioned solution4, continue stirring reaction；Solution after stirring is transferred in hydrothermal reaction kettle and is heated, temperature is 80 200 DEG C；After reaction kettle cooled to room temperature, pour out in reaction kettle after product, first product is washed with deionized water, be in neutrality to supernatant pH, then washed product with absolute ethyl alcohol；The mixture of remaining product and a small amount of absolute ethyl alcohol is loaded into centrifuge tube, is put into supercentrifuge and centrifuges；Finally vacuum drying obtains a kind of powdered nano composite thermoelectric materials.Powdery graphite alkene/the Bi prepared by the method for the present invention2Te3Nano composite thermoelectric materials are widely used in thermoelectric material field.
Description
Technical field
The invention belongs to materialogy field, is related to a kind of thermoelectric material, specifically a kind of powdered nano combined heat
The preparation method of electric material.
Background technology
Energy deficiency is increasingly severe at present, and the discovery of thermoelectric material makes the hope it is seen that Resolving probiems.
Thermoelectric material is as a kind of novel energy material, it is possible to achieve mutually directly changes, therefore is now subjected between thermal energy and electric energy
Extensive concern.
Pyroelectric material performance index is generally weighed with dimensionless figure of merit ZT, its expression formula is as follows：
ZT=S2σT/k
Wherein：S is Seebeck coefficients；σ is electrical conductivity；K is thermal conductivity；T is thermodynamic temperature.Can be with above-mentioned formula
Find out, at the same with high conductivity, high Seebeck coefficients, lower thermal conductivity material just with high ZT values, and Seebeck systems
Mutually restricted between number, electrical conductivity and thermal conductivity, it is difficult to independent regulation and control, so it is difficult to improving the ZT values of material.
The low ZT values of thermoelectric material are still to restrict the main reason for its application is with promoting.Although Bi2Te3Based alloy thermoelectricity
Material can reach 1 or so, but the space that its ZT value is still improved near room temperature ZT values.By constantly exploring, researcher
It was found that Bi can be improved by lowering material dimension and the method for preparing composite material etc.2Te3The ZT of based alloy thermoelectric material
Value.
In recent years, graphene is because it is with excellent electric conductivity, high carrier mobility speed, excellent mechanical performance
Deng the research hotspot become instantly.Therefore if graphene/Bi can be prepared using appropriate method2Te3Base alloy composite materials,
Give full play to the high electrical conductivity of graphene, and Bi2Te3The Seebeck coefficients of this height of based alloy, it would be possible to further carry
High Bi2Te3Thermoelectricity capability.But current graphene/Bi2Te3The preparation method of nano composite thermoelectric materials is mainly that solution mixes
Conjunction and mechanical mixture, the graphene/Bi prepared using above two method2Te3Nano composite thermoelectric materials are easy to cause composite wood
Bi in material2Te3The oxidation of nanostructured, so as to influence the raising of composite material thermoelectricity capability.The present invention passes through hydro-thermal fabricated in situ
Method, a step successfully prepared a kind of powdery graphite alkene/Bi2Te3Composite thermoelectric material.This method can prevent compound
Bi in material preparation process2Te3The oxidation of nanostructured, to improve Bi2Te3Thermoelectricity capability provide a kind of new approaches.
The content of the invention
For above-mentioned technical problem of the prior art, the present invention provides a kind of powdered nano composite thermoelectric materials
Preparation method, the preparation method of this powdered nano composite thermoelectric materials will solve Bi of the prior art2Te3Base
The bad technical problem of the thermoelectricity capability of alloy.
The present invention provides a kind of powdered nano composite thermoelectric materials preparation method, include the following steps：
7) weigh graphene oxide to be put into deionized water, the mass volume ratio of graphene oxide and deionized water is 0.1
~8mg：80mL, ultrasound are in transparent and homogeneous to liquid, then sequentially add sodium tartrate, TeO2、KOH、Bi(NO3)3·5H2O,
The graphene oxide, TeO2And Bi (NO3)3·5H2The material ratio of O is 0.1~8mg：0.3~1g：0.6~2g；Wherein
The concentration of solution mesotartaric acid sodium is 0.1-0.15mol/L, and the concentration of KOH is 0.8-1.2mol/L；
1) KBH is added into above-mentioned solution again4, after addition, KBH in solution4Concentration be 0.25-0.35mol/L, continue
Stirring reaction 0.3-1h；
2) solution after stirring is transferred in hydrothermal reaction kettle and heats 10-30h, temperature is 80-200 DEG C；
3) by after reaction kettle cooled to room temperature, pour out in reaction kettle after product, product is washed with deionized water
Wash, be in neutrality to supernatant pH, after pouring out supernatant, then with absolute ethyl alcohol washed product at least twice；
4) pour out supernatant, by the mixture of remaining product and absolute ethyl alcohol load centrifuge tube, be left product with it is anhydrous
The quality volume of ethanol is 1g：5mL~30mL, is put into supercentrifuge and centrifuges 3~8 minutes, centrifugation rate 3000-8000
Rev/min；
5) it is dried in vacuo, drying temperature is 60-100 DEG C, drying time 6-8h, is obtained after the completion of dry a kind of powdered
Nano composite thermoelectric materials.
Further, in step 1), TeO2With Bi (NO3)3·5H2The molar ratio of O is 3:2.
Further, Bi of the graphene oxide in generation2Te3In content be 0.1-40%.
The present invention reaction principle be：In hydrothermal reaction process, under conditions of using reducing agent, Bi2Te3Nano junction
The generation of structure and the reduction of graphene oxide can synchronously complete, so that a step prepares graphene/Bi2Te3Nano combined thermoelectricity
Material.Since reaction is completed under a reducing atmosphere, so preventing Bi2Te3The oxidation of nanostructured, finally improves multiple
The thermoelectricity capability of condensation material.
The present invention is compared with prior art, its technological progress is significant.One-step synthesis of the present invention gone out graphene/
Bi2Te3Nano composite thermoelectric materials, the powdery graphite alkene/Bi prepared by the method for the present invention2Te3Nano combined thermoelectricity material
Material is widely used in thermoelectric power generation and refrigerating field.
Brief description of the drawings
Fig. 1 is using graphene/Bi synthesized by embodiment 12Te3Digital photograph (the stone in kind of nano composite thermoelectric materials
1%) black alkene content is.
Fig. 2 is using graphene/Bi synthesized by embodiment 12Te3The field emission scanning electron microscope of nano composite thermoelectric materials
Picture (graphene content is 1%).
Fig. 3 is using graphene/Bi synthesized by embodiment 12Te3Projection electron microscopic picture (the stone of nano composite thermoelectric materials
1%) black alkene content is.
Embodiment 1
Graphene content is 1% powdery graphite alkene/Bi2Te3The preparation method of nano composite thermoelectric materials
(1) dispensing：8mg graphene oxides will be weighed first is put into progress ultrasound in the beaker for filling 80mL deionized waters,
Ultrasound into beaker liquid formed transparent and homogeneous solution when terminate, then sequentially added into beaker 2g sodium tartrates,
0.4736gTeO2、4.48g KOH、0.9596g Bi(NO3)3·5H2O (add above-mentioned substance after, solution mesotartaric acid sodium it is dense
Spend for 0.13mol/L, the concentration of KOH is 1mol/L)；
(2) 1.2g KBH are added into above-mentioned solution again4(after addition, KBH in solution4Concentration be 0.28mol/L), stir
Mix reaction 1h；
(3) solution after stirring, which is put into hydrothermal reaction kettle, heats 24h, and heating-up temperature is 180 DEG C；
(4) wash, centrifuge：After reaction, the liquid in reaction kettle is transferred in beaker, it is repeatedly clear adds deionization
It is washed till liquid pH value in beaker to be in neutrality, is then cleaned 3 times repeatedly again with absolute ethyl alcohol；
(5) pour out supernatant, by the mixture of remaining product and absolute ethyl alcohol load centrifuge tube (remaining product with it is anhydrous
The quality volume of ethanol is 1g：10mL), it is put into supercentrifuge and centrifuges 5 minutes, rotating speed is 5000 revs/min；
(6) it is dry：Solid after centrifugation is put into vacuum drying chamber, 80 DEG C of dry 6h.
Embodiment 2
Graphene content is 0.5% powdery graphite alkene/Bi2Te3The preparation method of nano composite thermoelectric materials
(1) dispensing：2mg graphene oxides will be weighed first is put into progress ultrasound in the beaker for filling 40mL deionized waters,
Ultrasound into beaker liquid formed transparent and homogeneous solution when terminate, then sequentially added into beaker 1g sodium tartrates,
0.238gTeO2、2.24g KOH、0.4822g Bi(NO3)3·5H2O, (add above-mentioned substance after, solution mesotartaric acid sodium it is dense
Spend for 0.13mol/L, the concentration of KOH is 1mol/L)；
(2) 0.6g KBH are added into above-mentioned solution again4, (after addition, KBH in solution4Concentration be 0.28mol/L) stir
Mix reaction 0.5h；
(3) solution after stirring, which is put into hydrothermal reaction kettle, heats 24h, and heating-up temperature is 160 DEG C；
(4) wash, centrifuge：After reaction, the liquid in reaction kettle is transferred in beaker, it is repeatedly clear adds deionization
It is washed till liquid pH value in beaker to be in neutrality, is then cleaned 3 times repeatedly again with absolute ethyl alcohol；
(5) supernatant is poured out, the mixture of remaining product and absolute ethyl alcohol is loaded into centrifuge tube, (remaining product and nothing
The quality volume of water-ethanol is 1g：20mL) it is put into supercentrifuge and centrifuges 5 minutes, rotating speed is 5000 revs/min；
(6) it is dry：Solid after centrifugation is put into vacuum drying chamber, 80 DEG C of dry 8h.
Embodiment 3
Graphene content is 0.25% powdery graphite alkene/Bi2Te3The preparation method of nano composite thermoelectric materials
(1) dispensing：4mg graphene oxides will be weighed first is put into progress ultrasound in the beaker for filling 160mL deionized waters,
Ultrasound into beaker liquid formed transparent and homogeneous solution when terminate, then sequentially added into beaker 4g sodium tartrates,
0.9544gTeO2、8.96g KOH、1.9288g Bi(NO3)3·5H2O, (after adding above-mentioned substance, solution mesotartaric acid sodium
Concentration is 0.13mol/L, and the concentration of KOH is 1mol/L)；
(2) 2.4g KBH are added into above-mentioned solution again4(after addition, KBH in solution4Concentration be 0.28mol/L)；
(3) solution after stirring, which is put into hydrothermal reaction kettle, heats 24h, and heating-up temperature is 140 DEG C；
(4) wash, centrifuge：After reaction, the liquid in reaction kettle is transferred in beaker, it is repeatedly clear adds deionization
It is washed till liquid pH value in beaker to be in neutrality, is then cleaned 3 times repeatedly again with absolute ethyl alcohol；
(5) supernatant is poured out, the mixture of remaining product and absolute ethyl alcohol is loaded into centrifuge tube, (remaining product and nothing
The quality volume of water-ethanol is 1g：5mL) it is put into supercentrifuge and centrifuges 5 minutes, rotating speed is 3000 revs/min；
(6) it is dry：Solid after centrifugation is put into vacuum drying chamber, 60 DEG C of dry 8h.
Claims (3)
1. a kind of powdered nano composite thermoelectric materials preparation method, it is characterised in that include the following steps：
1) graphene oxide is weighed to be put into deionized water, the mass volume ratio of graphene oxide and deionized water for 0.1~
8mg：80mL, ultrasound are in transparent and homogeneous to liquid, then sequentially add sodium tartrate, TeO2、KOH、Bi(NO3)3·5H2O, institute
Graphene oxide, the TeO stated2And Bi (NO3)3·5H2The material ratio of O is 0.1~8mg：0.3~1g：0.6~2g；It is wherein molten
The concentration of liquid mesotartaric acid sodium is 0.1-0.15mol/L, and the concentration of KOH is 0.8-1.2mol/L；
2) KBH is added into above-mentioned solution again4, after addition, KBH in solution4Concentration be 0.25-0.35mol/L, continue to stir
React 0.3-1h；
3) solution after stirring is transferred in hydrothermal reaction kettle and heats 10-30h, temperature is 80-200 DEG C；
4) by after reaction kettle cooled to room temperature, pour out in reaction kettle after product, product is washed with deionized water, extremely
Supernatant pH is in neutrality, and after pouring out supernatant, then with absolute ethyl alcohol is washed product at least twice；
5) supernatant is poured out, the mixture of remaining product and absolute ethyl alcohol is loaded into centrifuge tube, is left product and absolute ethyl alcohol
Quality volume be 1g：5mL~30mL, is put into supercentrifuge and centrifuges 3~8 minutes, centrifugation rate for 3000-8000 turn/
Minute；
6) it is dried in vacuo, drying temperature is 60-100 DEG C, drying time 6-8h, and a kind of powdered nanometer is obtained after the completion of dry
Composite thermoelectric material.
A kind of 2. flexible nano composite thermoelectric material preparation method according to claim 1, it is characterised in that：In step 1)
In, TeO2With Bi (NO3)3·5H2The molar ratio of O is 3:2.
A kind of 3. powdered nano composite thermoelectric materials preparation method according to claim 1, it is characterised in that：Aoxidize stone
Bi of the black alkene in generation2Te3In content be 0.1-40%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109560186A (en) * | 2018-12-14 | 2019-04-02 | 东华大学 | A kind of N-type thermal electric film and its preparation and application |
| CN113526473A (en) * | 2021-07-30 | 2021-10-22 | 新沂市东方硕华光学材料有限公司 | Nonlinear optical material with high optical uniformity and preparation method thereof |
| CN115784173A (en) * | 2022-11-02 | 2023-03-14 | 常州大学 | One-dimensional CsAg 5 Te 3 Controllable preparation method of nano thermoelectric material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109560186A (en) * | 2018-12-14 | 2019-04-02 | 东华大学 | A kind of N-type thermal electric film and its preparation and application |
| CN109560186B (en) * | 2018-12-14 | 2020-08-11 | 东华大学 | N-type thermoelectric film and preparation and application thereof |
| CN113526473A (en) * | 2021-07-30 | 2021-10-22 | 新沂市东方硕华光学材料有限公司 | Nonlinear optical material with high optical uniformity and preparation method thereof |
| CN115784173A (en) * | 2022-11-02 | 2023-03-14 | 常州大学 | One-dimensional CsAg 5 Te 3 Controllable preparation method of nano thermoelectric material |
| CN115784173B (en) * | 2022-11-02 | 2024-01-23 | 常州大学 | One-dimensional CsAg 5 Te 3 Controllable preparation method of nano thermoelectric material |
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