CN102603270A - Method for preparing rare-earth element double-doped nanocrystalline In2O3 based thermoelectric ceramic material - Google Patents
Method for preparing rare-earth element double-doped nanocrystalline In2O3 based thermoelectric ceramic material Download PDFInfo
- Publication number
- CN102603270A CN102603270A CN2011104314926A CN201110431492A CN102603270A CN 102603270 A CN102603270 A CN 102603270A CN 2011104314926 A CN2011104314926 A CN 2011104314926A CN 201110431492 A CN201110431492 A CN 201110431492A CN 102603270 A CN102603270 A CN 102603270A
- Authority
- CN
- China
- Prior art keywords
- ceramic material
- nanocrystalline
- temperature
- thermoelectric
- in2o3
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to a method for preparing a rare-earth element double-doped nanocrystalline In2O3 based thermoelectric ceramic material. The method comprises the steps of: carrying out solid-phase low-temperature synthesis to obtain precursor powder based on In2O3, ZnO and lanthanide oxides as raw materials; and carrying out low-temperature spark plasma sintering (SPS) to obtain a ceramic block material. By means of the method, the In[2-2x]ZnxRxO3 (R is a lanthanide element and x is greater than or equal to 0.0025 and less than or equal to 0.04) nanocrystalline ceramic material can be simply, conveniently and accurately prepared; the carrier concentration and the main carrier type of the material are controlled through component doping elements and non-stoichiometric ratio, thus the thermoelectric property of the ceramic material is increased and the maximal ZT value of the ceramic material can be up to 0.40 at a temperature of 800 DEG C.
Description
Technical field
To be that a kind of REE is two mix nanocrystalline In in the present invention
2O
3The preparation method of base thermoelectric ceramic material belongs to material science,
Background technology
Thermoelectric material is directly to carry out the functional materials that heat energy and electric energy are changed each other.The thermo-electric device that utilizes the thermoelectric material body plan is referred to as thermoelectric cell existing under the condition of thermograde through the exportable electric energy of Seebeck (Seebeck) effect; On the other hand, thermo-electric device can also produce the effect that the temperature difference reaches electronic cooling through Peltier (Peltier) effect.Characteristics such as thermo-electric conversion has that device volume is little, safety is high, exhaust emission material, Applicable temperature scope be not wide are a kind of eco-friendly energy conversion techniques.Along with the development of material science and technology and to the attention of energy and environment problem; The thermoelectric energy study on the transformation become in recent years one increase rapidly, the active research field; High performance thermoelectric material and utilisation technology thereof worldwide receive increasing concern; And obtain some impressive progresses, the researchist of China correlative study mechanism is also making much influential in the world work aspect the thermoelectric material research.
The performance of thermoelectric material is generally used non-dimensional thermoelectric figure of merit ZT (ZT=α
2σ T/ κ, wherein α, σ, κ, T represent Seebeck coefficient, specific conductivity, thermal conductivity and the T of material respectively) represent.Good thermoelectric material should have high Seebeck coefficient absolute value, high specific conductivity and low thermal conductivity.The thermoelectric material of being studied at present comprises metal solid solution, alloy semiconductor and oxide pyroelectric material, and research emphasis concentrates on Bi for a long time
3Te
2Systems such as base alloy, filling type Skutterudites type alloy and Half-Heusler alloy, but this type alloy melting point low, contain objectionable impurities, when temperature is higher, be prone to oxidation etc. and limited it in the application aspect the thermoelectric power generation.Compare with the non-oxidized substance series material; Oxide-base ceramic thermoelectric transition material have stability at elevated temperature, heat-resisting, synthetic preparation easily, can be in advantages such as the medium-term and long-term uses of atmospheric environment; And pollution-free, nontoxicity, preparation technology are simple; Thermoelectric field has very big application potential in middle high-temperature zone, is suitable for utilizing low grade heat energy (like industrial exhaust heat, used heat, sun power etc.) to generate electricity.At present, the research of oxide pyroelectric material has formed a research direction with research and Practical significance.
In
2O
3As a kind of semi-conductor of broad stopband, to bring into play great potential in gas sensing, translucidus and photoelectron property field always, and obtaining paying close attention to widely, a large amount of research concentrates on the film of transparent conductor material.The D.B é rardan of France's research establishment, E.Guilmeau waits the people to utilize adulterated In such as traditional solid state sintering synthetic high valence elements Sn, Ti, Zr, Ta, Nb, Ge
2O
3The base pottery, research shows that carrier concentration can reach 10
-20Cm
-3More than, can reach maximum 0.9 * 10 during 800 ℃ of power factors
-3Wm
-1K
-2, ZT is about 0.3, and corresponding its thermal conductivity is 3Wm
-1K
-1About.[E.Guilmeau, D.B é rardan, Ch.Simon, A.Maignan, B.Raveau, D.Ovono Ovono, F.Delorme.J.Appl.Phys.106,053715 (2009); D.B é rardan, E.Guilmeau, A.Maignan, B.Raveau.Solid State Commun.146,97 (2008)] but In
2O
3Matrix is that thermal conductivity is higher relatively, is difficult to can improve its thermoelectric transmission performance on this basis again.
Summary of the invention
The present invention provides to above-mentioned prior art situation and designing just that a kind of REE is two mixes nanocrystalline In
2O
3The preparation method of base thermoelectric ceramic material; Its objective is through solid phase synthesis precursor powder and synthetic a series of zinc of discharge plasma sintering and the two In-O base thermoelectric ceramicses of mixing of lanthanon; Through alloying element and non-stoichiometric control; Regulate its carrier concentration and grain-size size, thus the thermoelectric transmission performance of controlled material.
The objective of the invention is to realize through following technical scheme:
This kind REE is two mixes nanocrystalline In
2O
3The preparation method of base thermoelectric ceramic material, it is characterized in that: the step of this method is:
(1) chemical ingredients that the thermoelectric ceramic material that adopts this method to prepare comprises is indium, zinc and lanthanon, and the mol ratio of indium, zinc and lanthanon is: 2-2X: X: X, and the span of X is: 0.0025≤X≤0.04;
(2) with In
2O
3, ZnO and lanthanide oxide be as raw material, takes by weighing by said ratio, mixes the back was accomplished the thing phase in 2～6 hours at 400～600 ℃ of sintering the one-tenth phase stage;
(3) with the goods granulation, heat up then, heat-up rate is 100～300 ℃/min, under 900～1100 ℃, utilizes graphite grinding tool discharge plasma sintering 4～10min of diameter 5～20cm;
(4) with goods 700～800 ℃ annealing 2～6h, can obtain new type double and mix nanocrystalline In
2O
3The base oxide thermoelectric ceramic material.
The preferred value of X of confirming the mol ratio of indium, zinc and lanthanon is 0.01 or 0.04.
Technical scheme of the present invention is utilized In
2O
3Excellent properties on electrical transmission through the ratio and the kind of regulation and control alloying element, can be regulated and control each parameter in this material system thermoelectricity capability, makes goods electrical transmission performance on the basis that little amplitude reduces, and has had lower thermal conductance transmission performance.Thereby overcome In
2O
3The inferior position that single-phase thermoelectricity capability is not high makes goods have higher electric property and lower heat conveyance performance and thermoelectric preferably transmission performance, is one type of new type high temperature oxide thermoelectricity stupalith with broad prospect of application.
Description of drawings
The XRD figure of product spectrum among Fig. 1 embodiment 1
The SEM image of product among Fig. 2 embodiment 1
The product power factor is with variation of temperature among Fig. 3 embodiment 1
The XRD figure of product spectrum among Fig. 4 embodiment 2
The SEM image of product among Fig. 5 embodiment 2
The product power factor is with variation of temperature among Fig. 6 embodiment 2
The XRD figure of product spectrum among Fig. 7 embodiment 3
The SEM image of product among Fig. 8 embodiment 3
The product power factor is with variation of temperature among Fig. 9 embodiment 3
The XRD figure of product spectrum among Figure 10 embodiment 4
The SEM image of product among Figure 11 embodiment 4
The product power factor is with variation of temperature among Figure 12 embodiment 4
The product thermoelectric figure of merit is with variation of temperature among Figure 13 embodiment 4
The XRD figure of product spectrum among Figure 14 embodiment 5
The SEM image of product among Figure 15 embodiment 5
The product power factor is with variation of temperature among Figure 16 embodiment 5
Embodiment
Below will do to detail further to technical scheme of the present invention through accompanying drawing and embodiment:
Embodiment 1:
According to In
1.98Nd
0.01Zn
0.01O
3The element proportioning, take by weighing In
2O
3, ZnO and Nd
2O
3, put into ball grinder 250rpm wet-milling 12 hours.Powder is taken out, put into the loft drier drying, temperature is 70 ℃, and the time is 12h.Become technology through pre-burning, sintering is 2 hours in 600 ℃ of air, accomplishes the one-tenth phase stage of material thing phase; Then, through granulation, dried powder becomes block with discharge plasma sintering; Mould diameter is 20mm, and heat-up rate is 200 ℃/min, 1000 ℃ of temperature; Pressure 50MPa, soaking time is 5min, obtains the In-O-1 stupalith.Its X-ray diffraction analysis (XRD) test result such as Fig. 1 show that thing is In mutually
2O
3Its grain-size size is about 300～400nm such as Fig. 2.Specific density 85%.700 ℃ of power factors are 5.3 * 10
-4Wm
-1K
-2, as shown in Figure 3; Its
Thermal conductivity is 2Wm
-1K
-1, corresponding ZT value is about 0.25.
Embodiment 2:
According to In
1.92Er
0.04Zn
0.04O
3The element proportioning, take by weighing In
2O
3, ZnO and Er
2O
3, put into ball grinder 250rpm wet-milling 12 hours.Powder is taken out, put into the loft drier drying, temperature is 70 ℃, and the time is 12h.Become technology through pre-burning, sintering is 2 hours in 600 ℃ of air, accomplishes the one-tenth phase stage of material thing phase; Then, through granulation, dried powder becomes block with discharge plasma sintering; Mould diameter is 20mm, and heat-up rate is 200 ℃/min, 1000 ℃ of temperature; Pressure 50MPa, soaking time is 5min, obtains the In-O-2 stupalith.Its X-ray diffraction analysis (XRD) test result such as Fig. 4 show that thing is In mutually
2O
3Its grain-size size is about 300～400nm such as Fig. 5.Specific density 95%.800 ℃ of power factors are 4.6 * 10
-4Wm
-1K
-2, as shown in Figure 6, thermal conductivity is 2Wm
-1K
-1, corresponding ZT value is about 0.2.
Embodiment 3:
According to In
1.92Tb
0.04Zn
0.04O
3The element proportioning, take by weighing In
2O
3, ZnO and Tb
2O
3, put into ball grinder 250rpm wet-milling 12 hours.Powder is taken out, put into the loft drier drying, temperature is 70 ℃, and the time is 12h.Become technology through pre-burning, sintering is 2 hours in 600 ℃ of air, accomplishes the one-tenth phase stage of material thing phase; Then, through granulation, dried powder becomes block with discharge plasma sintering; Mould diameter is 20mm, and heat-up rate is 200 ℃/min, 1000 ℃ of temperature; Pressure 50MPa, soaking time is 5min, obtains the In-O-3 stupalith.Its X-ray diffraction analysis (XRD) test result such as Fig. 7 show that thing is In mutually
2O
3Its grain-size size is about 300～400nm such as Fig. 8.Specific density 95%.800 ℃ of power factors are 5.8 * 10
-4Wm
-1K
-2, as shown in Figure 9; Its thermal conductivity is 2.4Wm
-1K
-1, corresponding ZT value is about 0.27.
Embodiment 4:
According to In
1.92Ce
0.04Zn
0.04O
3The element proportioning, take by weighing In
2O
3, ZnO and Ce
2O
3, put into ball grinder 250rpm wet-milling 12 hours.Powder is taken out, put into the loft drier drying, temperature is 70 ℃, and the time is 12h.Become technology through pre-burning, sintering is 2 hours in 600 ℃ of air, accomplishes the one-tenth phase stage of material thing phase; Then, through granulation, dried powder becomes block with discharge plasma sintering; Mould diameter is 20mm, and heat-up rate is 200 ℃/min, 1000 ℃ of temperature; Pressure 50MPa, soaking time is 5min, obtains the In-O-4 stupalith.Its X-ray diffraction analysis (XRD) test result such as Figure 10 show that thing is In mutually
2O
3With dephasign CeO
2Its grain-size size is about 200～400nm such as Figure 11.Specific density 96%.800 ℃ of power factors are 7.6 * 10
-4Wm
-1K
-2, thermal conductivity is 1.9Wm
-1K
-1, corresponding ZT value is about 0.4.Like Figure 12, shown in 13.
Embodiment 5:
According to In
1.92Pr
0.04Zn
0.04O
3The element proportioning, take by weighing In
2O
3, ZnO and Pr
2O
3, put into ball grinder 250rpm wet-milling 12 hours.Powder is taken out, put into the loft drier drying, temperature is 70 ℃, and the time is 12h.Become technology through pre-burning, sintering is 2 hours in 600 ℃ of air, accomplishes the one-tenth phase stage of material thing phase; Then, through granulation, dried powder becomes block with discharge plasma sintering; Mould diameter is 20mm, and heat-up rate is 200 ℃/min, 1000 ℃ of temperature; Pressure 50MPa, soaking time is 5min, obtains the In-O-5 stupalith.Its X-ray diffraction analysis (XRD) test result such as Figure 14 show that thing is In mutually
2O
3Its grain-size size is about 300～400nm such as Figure 15.Specific density 95%.800 ℃ of power factors are 3.2 * 10
-4Wm
-1K
-2, shown in figure 16; Thermal conductivity is 2.3Wm
-1K
-1, corresponding ZT value is about 0.12.
Compared with prior art, technical scheme of the present invention has the reaction times weak point, and sintering temperature is low, and is controlled to the grain-size of material simultaneously, can synthesize the ceramics sample of a series of different sizes sizes.And the agglomerating properties of sample improves a lot, and is that its ZT value can reach 0.4 under the 1073K at 800 ℃.
Claims (2)
1. a REE is two mixes nanocrystalline In
2O
3The preparation method of base thermoelectric ceramic material, it is characterized in that: the step of this method is:
(1) chemical ingredients that the thermoelectric ceramic material that adopts this method to prepare comprises is indium, zinc and lanthanon, and the mol ratio of indium, zinc and lanthanon is: 2-2X: X: X, and the span of X is: 0.0025≤X≤0.04;
(2) with In
2O
3, ZnO and lanthanide oxide be as raw material, takes by weighing by said ratio, mixes the back was accomplished the thing phase in 2～6 hours at 400～600 ℃ of sintering the one-tenth phase stage;
(3) with the goods granulation, heat up then, heat-up rate is 100～300 ℃/min, under 900～1100 ℃, utilizes graphite grinding tool discharge plasma sintering 4～10min of diameter 5～20cm;
(4) with goods 700～800 ℃ annealing 2～6h, can obtain new type double and mix nanocrystalline In
2O
3The base oxide thermoelectric ceramic material.
2. REE according to claim 1 is two mixes nanocrystalline In
2O
3The preparation method of base thermoelectric ceramic material is characterized in that: the value of X of confirming the mol ratio of indium, zinc and lanthanon is 0.01 or 0.04.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104314926A CN102603270A (en) | 2011-12-20 | 2011-12-20 | Method for preparing rare-earth element double-doped nanocrystalline In2O3 based thermoelectric ceramic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104314926A CN102603270A (en) | 2011-12-20 | 2011-12-20 | Method for preparing rare-earth element double-doped nanocrystalline In2O3 based thermoelectric ceramic material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102603270A true CN102603270A (en) | 2012-07-25 |
Family
ID=46521129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011104314926A Pending CN102603270A (en) | 2011-12-20 | 2011-12-20 | Method for preparing rare-earth element double-doped nanocrystalline In2O3 based thermoelectric ceramic material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102603270A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106711318A (en) * | 2017-02-27 | 2017-05-24 | 山东大学 | Oxide thermoelectric power generation module and system and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1675399A (en) * | 2002-08-02 | 2005-09-28 | 出光兴产株式会社 | Sputtering target, sintered body, conductive film produced using the same, organic EL element, and substrate used for the same |
| CN1775693A (en) * | 2005-11-22 | 2006-05-24 | 华东理工大学 | Method for preparing tin-doped indium oxide nano powder |
| CN101508560A (en) * | 2009-03-20 | 2009-08-19 | 清华大学 | Process for producing codoped In2O3 based pyroelectric material |
| WO2010058533A1 (en) * | 2008-11-20 | 2010-05-27 | 出光興産株式会社 | ZnO-SnO2-In2O3 BASED SINTERED OXIDE AND AMORPHOUS TRANSPARENT CONDUCTIVE FILM |
-
2011
- 2011-12-20 CN CN2011104314926A patent/CN102603270A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1675399A (en) * | 2002-08-02 | 2005-09-28 | 出光兴产株式会社 | Sputtering target, sintered body, conductive film produced using the same, organic EL element, and substrate used for the same |
| CN1775693A (en) * | 2005-11-22 | 2006-05-24 | 华东理工大学 | Method for preparing tin-doped indium oxide nano powder |
| WO2010058533A1 (en) * | 2008-11-20 | 2010-05-27 | 出光興産株式会社 | ZnO-SnO2-In2O3 BASED SINTERED OXIDE AND AMORPHOUS TRANSPARENT CONDUCTIVE FILM |
| CN101508560A (en) * | 2009-03-20 | 2009-08-19 | 清华大学 | Process for producing codoped In2O3 based pyroelectric material |
Non-Patent Citations (1)
| Title |
|---|
| 成波等: "Yb、Dy双掺杂CaMnO3陶瓷的热电性能研究-1", 《2011中国材料研讨会论文摘要集》, 17 May 2011 (2011-05-17) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106711318A (en) * | 2017-02-27 | 2017-05-24 | 山东大学 | Oxide thermoelectric power generation module and system and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | High‐performance pseudocubic thermoelectric materials from non‐cubic chalcopyrite compounds | |
| Kahraman et al. | Enhancement of mechanical and thermoelectric properties of Ca3Co4O9 by Ag addition | |
| CN108238796B (en) | Copper seleno solid solution thermoelectric material and preparation method thereof | |
| CN103928604B (en) | A kind of supper-fast method preparing N-shaped bismuth telluride-base high performance thermoelectric material | |
| Tkach et al. | Abnormal grain growth as a method to enhance the thermoelectric performance of Nb-doped strontium titanate ceramics | |
| CN101723669A (en) | Compound capable of being used for thermoelectric material and preparation method thereof | |
| Wang et al. | Effects of mesoporous silica addition on thermoelectric properties of Nb-doped SrTiO3 | |
| CN103872237A (en) | Copper-sulfur-based high-performance thermoelectric material and preparation method thereof | |
| Prasoetsopha et al. | Synthesis and thermoelectric properties of Ca 3 Co 4 O 9 prepared by a simple thermal hydro-decomposition method | |
| CN103011838A (en) | Preparation method of BiCuSeO-based pyroelectric oxide powder | |
| CN102643085A (en) | Bi Cu 1-x SeO-based oxide thermoelectric ceramic material and preparation method thereof | |
| CN105671344B (en) | One step prepares high-performance CoSb3The method of base thermoelectricity material | |
| Van et al. | Nanostructured oxide materials and modules for high-temperature power generation from waste heat | |
| Wang et al. | High-temperature thermoelectric properties of Cd1− xPrxO ceramics | |
| Zhang et al. | Influence of the phase transformation in NaxCoO2 ceramics on thermoelectric properties | |
| CN106145062B (en) | A kind of quick method for preparing antimony telluride thermoelectric material | |
| CN107793154B (en) | Ultra-fast preparation of Cu2Method for Se/BiCuSeO block composite thermoelectric material | |
| Ohta et al. | Preparation and Thermoelectric Properties of LaGd 1+ x S 3 and SmGd 1+ x S 3 | |
| Lu et al. | Improvement of thermoelectric properties of CuAlO2 by excess oxygen doping in annealing | |
| Nag et al. | Doping induced high temperature transport properties of Ca1− xGdxMn1− xNbxO3 (0≤ x≤ 0.1) | |
| CN107793155B (en) | Ultra-fast preparation of Cu2Method for Se bulk thermoelectric material | |
| CN101905972A (en) | Aluminum-doped zinc oxide-based thermoelectric material and preparation method thereof | |
| CN105140383B (en) | Compound PbSe base thermoelectricity materials for mixing Sr and Na and preparation method thereof | |
| Lü et al. | Electrical and thermal transport properties of CdO ceramics | |
| CN107032763A (en) | One kind prepares n-type CaMnO3The method of base thermoelectric ceramics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120725 |