CN1733649A - N type cobalt niobate oxide thermoelectric material and preparation method thereof - Google Patents

N type cobalt niobate oxide thermoelectric material and preparation method thereof Download PDF

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CN1733649A
CN1733649A CN 200510012221 CN200510012221A CN1733649A CN 1733649 A CN1733649 A CN 1733649A CN 200510012221 CN200510012221 CN 200510012221 CN 200510012221 A CN200510012221 A CN 200510012221A CN 1733649 A CN1733649 A CN 1733649A
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thermoelectric material
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oxide
preparation
oxide thermoelectric
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CN100357223C (en
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徐桂英
吴卿
贾斌
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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Abstract

The N-niobate cobalt oxide thermoelectric material and its preparation method relate to thermoelectric semiconductor material. Wherein, with method combined solid-phase synthesis and hyperpressure, using solid-phase metal oxide or metal elementary substance as raw material to syntheze required material at oxidizing atmosphere; smashing the material and cold briquetting; finally, sintering at high temperature. The oxide, Co0.66Nb1.33O4 say, belongs to tetragonal system with P42/mnm(136) symmetry, characterized conductibility 7701.3(omega cm)<-1>, Seebeck coefficient 39.95(muV/K), power factor 1229.129muW/(mK<2>), and dimensionless Q value 0.033-0.038, which has better performance and bright application future.

Description

A kind of N type cobalt niobate oxide thermoelectric material and preparation method thereof
Technical field
The present invention relates to the preparation method of a kind of oxide thermoelectricity (thermoelectricity) semiconductor material, particularly the preparation of N type niobic acid cobalt series oxide pyroelectric material.
Background technology
The thermoelectric material that has obtained practical application from the last century since the fifties is semiconductor material.Wherein the problem of Cun Zaiing is that conversion efficiency of thermoelectric is low.For the efficiency of conversion scientists that improves thermoelectric material has been carried out number of research projects, but never have big progress, the zero dimension figure of merit (ZT) of thermoelectric material is paced up and down about 1 always, makes the investigator of most this areas abandon their research direction midway.Although the nineties in last century, the material scholar of Japan proposed the gradient material notion, and this structure of theory expectation can make the conversion efficiency of thermoelectric of the thermoelectric material with gradient-structure reach about 23%, and makes the research with gradient-structure thermoelectric material become a very important research direction in current thermoelectric field.Yet great deal of research results finds that the key of restriction conversion efficiency of thermoelectric still is the conversion efficiency of thermoelectric of its each composition material, has begun the upsurge of the high-performance of a new round, the exploitation of novel thermoelectric material for this reason.Oxide compound series thermoelectric material arises at the historic moment under this big environment.
The oxide semiconductor stupalith is paid close attention to over nearly 10 years, and it has been carried out the novel medium and high temperature thermoelectric material of big quantity research.Tradition thinks that oxide ceramics is an isolator, and its specific conductivity is low, is not suitable for being applied to thermoelectric field.But in recent years, Japanese scholar is to NaCo 2O 4Research in find that it has good P type thermoelectricity capability, this has excited the research interest of people to the oxide semiconductor thermoelectric material, because with the alloy phase ratio, oxide compound has the oxidation of not being afraid of, use range is wide, series of advantages such as preparation technology is simple, and the raw material scope of selecting material is wide, cost is low make oxide pyroelectric material have wide practical use at aspects such as waste-heat power generations.But the thermoelectric quality factor Z of P type oxide ceramics is lower than the Z of traditional thermoelectric alloy system at present, its quality factor Z is about 7 * 10-4/K～1.3 * 10-3/K, especially the thermoelectricity capability of N type oxide ceramics is lower, than the low nearly order of magnitude of P type, and make searching high-performance N type oxide thermoelectricity pottery become important goal in research.
At present, the preparation oxide pyroelectric material adopts synthesis by solid state reaction usually, though this method can be prepared N type oxide compound, and technology is simple, and the highest thermoelectricity capability ZT value of N type oxide compound is about 0.02, can not satisfy the demand far away.
Summary of the invention
The invention provides the technology that a kind of ultra-high voltage legal system is equipped with N type cobalt niobate oxide thermoelectric material, with solid metallic oxide compound or metal simple-substance is starting materials, adopt solid reaction process, synthetic material requested under oxidizing atmosphere, pulverize the material after synthesizing then, and carry out coldmoulding, sintering under ultra-high voltage at last.Not only can prepare N type cobalt niobate oxide thermoelectric material easily by this method, and can improve the specific conductivity of N type cobalt niobate oxide series material greatly, make it become the thermoelectric material that application prospect is arranged.
N type cobalt niobate oxide thermoelectric material of the present invention, its molecular formula is Co 0.66Nb 1.33O 4, and be the doping phase with CoO.
N type cobalt niobate oxide thermoelectric material preparation method's concrete steps are as follows:
(1) press stoichiometric ratio with Niobium Pentxoxide, tricobalt tetroxide and cobalt metal are put into the nylon mixing tank, adopt ball milled mixing 10-12 hour, fully mixing;
(2) obtaining compound after 10-12 hour, in 20-25MPa coldmoulding, is put into retort furnace 100-200 ℃ of oven dry again, in air,, make raw material fully react synthetic in 900-1200 ℃ of constant temperature 2-4 hour;
(3) with the fragmentation of synthetic sample, granularity is below 200 orders;
(4) product after will pulverizing is again in 20-25MPa coldmoulding;
(5) molded product is put into the mould of ultra-high pressure sintering, under 5-9GPa, in 1000-1200 ℃ of sintering 1-3 minute.
Compared with prior art, the method that the present invention adopts solid phase synthesis and ultra-high voltage to combine can be prepared high performance N type niobic acid cobalt Co 0.66Nb 1.33O 4Oxide compound, this oxide compound belongs to tetragonal system, has P4 2/ mnm (136) symmetry, at 108 ℃, the specific conductivity that this thermoelectric material characterizes is 7701.3 (Ω * cm) -1, Seebeck coefficient is 39.95 (μ V/K), power factor is 1229.129 μ W/ (mK 2), zero dimension figure of merit ZT is 0.033-0.038, the highest thermoelectricity capability ZT value of the N type oxide compound that its thermoelectricity capability has been reported at present has a more substantial increase.
Description of drawings
Fig. 1 is synthetic Co 0.66Nb 1.33O 4The X-ray diffraction analysis result, wherein ●-Co 0.66Nb 1.33O 4, -CoO.
Embodiment
Embodiment 1:
(1) press stoichiometric ratio with Niobium Pentxoxide, tricobalt tetroxide and cobalt metal are put into the nylon mixing tank, adopt ball milled to mix 10 hours, with abundant mixing;
(2) with compound that previous step obtains 100 ℃ of oven dry after 10 hours in 20MPa coldmoulding, put into retort furnace again, in air, in 900 ℃ of constant temperature 2 hours, so that raw material fully reacts is synthetic;
(3) adopting the vibration-type crusher in crushing to cause granularity in the above-mentioned sample of synthetic is below 180 orders;
(4) product after will pulverizing is according to the dimensional requirement of super high pressure mould, in 20MPa coldmoulding;
(5) molded product is put into the mould of ultra-high pressure sintering, under 5GPa, in 1000 ℃ of sintering 3 minutes.
Embodiment 2:
(1) press stoichiometric ratio with Niobium Pentxoxide, tricobalt tetroxide and cobalt metal are put into the nylon mixing tank, adopt ball milled to mix 11 hours, with abundant mixing;
(2) compound that previous step obtains after 11 hours, in 22MPa coldmoulding, is put into retort furnace 150 ℃ of oven dry again, in air, in 1000 ℃ of constant temperature 3 hours, so that raw material fully reacts is synthetic;
(3) adopting the vibration-type crusher in crushing to cause granularity in the above-mentioned sample of synthetic is below 190 orders;
(4) will crush product and get dimensional requirement, in 22MPa coldmoulding according to super high pressure mould;
(5) molded product is put into the mould of ultra-high pressure sintering, under 7GPa, in 1100 ℃, sintering 2 minutes.
Embodiment 3:
(1) press stoichiometric ratio with Niobium Pentxoxide, tricobalt tetroxide and cobalt metal are put into the nylon mixing tank, adopt ball milled to mix 12 hours, with abundant mixing;
(2) compound that previous step obtains after 12 hours, in 25MPa coldmoulding, is put into retort furnace 200 ℃ of oven dry again, in air, in 1200 ℃ of constant temperature 4 hours, so that raw material fully reacts is synthetic;
(3) adopting the vibration-type crusher in crushing to cause granularity in the above-mentioned sample of synthetic is below 200 orders;
(4) product after will pulverizing gets dimensional requirement according to super high pressure mould, in 25MPa coldmoulding;
(5) molded product is put into the mould of ultra-high pressure sintering, under 9GPa, in 1200 ℃ of sintering 1 minute.
The material x x ray diffraction analysis x result that embodiment 1-3 prepares corresponds respectively to 1-1,1-2 and 1-3, as shown in Figure 1.Therefrom as seen remove the synthetic product Co of institute 0.66Nb 1.33O 4, also contain a certain amount of CoO outward, the effect of this CoO is equivalent to mix.Table 1 provides three groups of products at 108 ℃ of specific conductivity, Seebeck coefficient, power factor and zero dimension figure of merit ZT, and as seen the highest thermoelectricity capability ZT value of the present N type oxide compound of having reported of its thermoelectricity capability has a more substantial increase.
Table 1 specific conductivity, Seebeck coefficient, power factor test result
Sample number Specific conductivity (Ω * cm) -1 Seebeck coefficient (μ V/K) Power factor (μ w/mK 2) ZT
1-1 7701.30 -39.95 1229.13 0.038
1-2 8669.43 -29.98 1123.56 0.035
1-3 10231.16 -32.87 1067.40 0.033

Claims (2)

1, a kind of N type cobalt niobate oxide thermoelectric material is characterized in that, N type cobalt niobate oxide thermoelectric material molecular formula is Co 0.66Nb 1.33O 4, and be the doping phase with CoO.
2, the preparation method of the described N type of claim 1 cobalt niobate oxide thermoelectric material is characterized in that concrete steps are as follows:
1) press stoichiometric ratio with Niobium Pentxoxide, tricobalt tetroxide and cobalt metal are put into the nylon mixing tank, adopt ball milled mixing 10-12 hour, fully mixing;
2) obtaining compound after 10-12 hour, in 20-25MPa coldmoulding, is put into retort furnace 100-200 ℃ of oven dry again, in air,, make raw material fully react synthetic in 900-1200 ℃ of constant temperature 2-4 hour;
3) with synthetic sample fragmentation, granularity is below 200 orders;
4) product after will pulverizing is again in 20-25MPa coldmoulding;
5) molded product is put into the mould of ultra-high pressure sintering, under 5-9GPa, in 1000-1200 ℃ of sintering 1-3 minute.
CNB2005100122211A 2005-07-19 2005-07-19 N type cobalt niobate oxide thermoelectric material and preparation method thereof Expired - Fee Related CN100357223C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101669222B (en) * 2007-04-12 2012-08-01 住友化学株式会社 Thermoelectric conversion material, method for production thereof, and thermoelectric conversion element
CN109817967A (en) * 2019-01-22 2019-05-28 南京大学 A kind of preparation method of high capacity aluminium ion cell positive material

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08236818A (en) * 1995-03-01 1996-09-13 Denki Kagaku Kogyo Kk Thermoelectric material
JP2002270907A (en) * 2001-03-06 2002-09-20 Nec Corp Thermoelectric conversion material and device using the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101669222B (en) * 2007-04-12 2012-08-01 住友化学株式会社 Thermoelectric conversion material, method for production thereof, and thermoelectric conversion element
CN109817967A (en) * 2019-01-22 2019-05-28 南京大学 A kind of preparation method of high capacity aluminium ion cell positive material
CN109817967B (en) * 2019-01-22 2021-11-05 南京大学 Preparation method of high-capacity aluminum ion battery positive electrode material

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