CN104733605B - A kind of preparation method of the thermoelectric material being separated comprising nano super-lattice and micron - Google Patents
A kind of preparation method of the thermoelectric material being separated comprising nano super-lattice and micron Download PDFInfo
- Publication number
- CN104733605B CN104733605B CN201510145896.7A CN201510145896A CN104733605B CN 104733605 B CN104733605 B CN 104733605B CN 201510145896 A CN201510145896 A CN 201510145896A CN 104733605 B CN104733605 B CN 104733605B
- Authority
- CN
- China
- Prior art keywords
- separated
- lattice
- thermoelectric material
- block
- graphite
- 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.)
- Active
Links
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A kind of preparation method of the thermoelectric material being separated comprising nano super-lattice and micron, belongs to field of material technology, carries out according to the following steps：（1）By Nd2O3、Li2O、TiO2And Nb2O5It is placed in ball grinder and is well mixed；（2）In 1100 ~ 1200 DEG C of calcinings；（3）It is placed in graphite crucible after grinding, under conditions of argon gas protection, heat treatment makes calcining materials that reduction reaction occur with graphite；（4）Grinding；（5）Isostatic pressing obtains block；Block is placed in graphite crucible, block is covered with heat treatment powder, high temperature sintering makes block that reduction reaction occur with graphite；It is cooled to normal temperature.The thermoelectric material of present invention synthesis has the microstructure that nanoscale superlattices, micro-meter scale are separated, and is a kind of rich potential new oxide thermoelectric material.
Description
Technical field
The invention belongs to field of material technology, more particularly to a kind of thermoelectricity material being separated comprising nano super-lattice and micron
The preparation method of material.
Background technology
Fossil energy is originated as current main energy sources, its non-renewable energy crisis brought and is used
The greenhouse effects caused by carbon dioxide are discharged in journey and causes increasing concern.According to statistics, about 2/3rds fossil
The energy of the energy is wasted in the form of used heat in use；If can be reclaimed to this part used heat, it is clear that to alleviating
Energy crisis and solve greenhouse effects and all have and be of great significance；In this context, thermoelectric material is used as can be real
The functional material that existing heat energy is directly converted with electric energy, received higher and higher attention in recent years.
Thermoelectric material realizes the mutual conversion of heat energy and electric energy based on Seebeck effect and paltie effect；Evaluate thermoelectricity
The parameter of material property is zero dimension thermoelectric figure of merit ZT；ZT=(Sσ2)T/k, wherein S, σ,kSeebeck coefficient is respectively with T
（Thermoelectrical potential）, electrical conductivity, thermal conductivity and absolute temperature；Seebeck coefficient is bigger, electrical conductivity is higher, thermal conductivity is lower means material
The thermoelectricity capability of material is better.
All the time, what is be used widely is generally have the alloy thermoelectric material compared with high zt, such as Bi2Ti3, PbTe etc.；
But, alloy material has poisonous, raw material shortcoming, thermo-chemical stability, is not suitable for large-scale application；In view of
This, in recent years, oxide material starts to cause the attention and attention of thermoelectric material researcher.
The composition of thermo-electric device generally requires two kinds of thermoelectric materials of p-type and N-type；In oxide pyroelectric material, as p-type
Stratiform cobaltatess NaxCoO2And Ca3Co4O9Preferable thermoelectricity capability is found to have, most high zt is even close to 1；And it is relative
N-type oxide pyroelectric material ZT values it is relatively low, thermal conductivity height is main cause.With the more SrTiO of current research3As a example by, its
Although electric property can compare favourably with alloy material, thermal conductivity is up to 11W/ (mK) at room temperature, is several times as much as closing
Gold compound such as Bi2Te32 ~ 3 W/ (mK)；The current main method for reducing thermal conductivity is using solid solution or nanosizing
Method, solid solution method thermal conductivity reduction limited extent, although and the method thermal conductivity reducing effect of nanosizing is bright
It is aobvious, but often because the counter productive that micro-nano particle interface is discontinuous and presence of defect causes electric property also to decline.Cause
This, seeks to reduce the new method of N-type oxide thermal conductivity or finds the new N-type oxide pyroelectric material with lower thermal conductivity
It is significant.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the thermoelectric material being separated comprising nano super-lattice and micron,
By designing the composition of N-type oxide pyroelectric material, by calcining, grinding, reduction, regrinding, briquetting and reduce again, institute
Oxide pyroelectric material has an excellent performance because comprising nano super-lattice and micron be separated and reducing material
There is provided possible in thermal conductivity, while again because the continuity at micro-nano structure interface can avoid the reduction of electric property.
The method of the present invention is carried out according to the following steps：
1st, Nd is prepared2O3、Li2O、TiO2And Nb2O5, the mol ratio of Nd, Li, Ti and Nb in whole materials is 0.55:
0.36:（1-x）:X, wherein 0<x≤0.15；Whole materials are placed in ball grinder and are well mixed, obtain mixed material；
2nd, mixed material is calcined into 10 ~ 12h at 1100 ~ 1200 DEG C, obtains calcining materials；
3rd, calcining materials are ground to granularity≤100 μm, are subsequently placed in graphite crucible, under conditions of argon gas protection,
1430 ± 5 DEG C of 3 ~ 5h of heat treatment are heated to, make calcining materials that reduction reaction occur with graphite, obtain heat-treated material；
4th, heat-treated material is ground to granularity≤100 μm, obtains heat treatment powder；
5th, by part heat treatment powder isostatic pressing, pressing pressure is 20 ~ 25MPa, obtains block；Block is placed in stone
In black crucible, block is covered with remaining heat treatment powder, be then heated to 1250 ~ 1300 DEG C of 10 ~ 12h of high temperature sintering, made
There is reduction reaction with graphite in block；Reaction is cooled to normal temperature after terminating, the lump material of acquisition be comprising nano super-lattice and
The thermoelectric material that micron is separated.
In above-mentioned step 5, reaction is first cooled to less than 650 DEG C after terminating with the speed of 100 ~ 150 DEG C/h, then natural
It is cooled to normal temperature.
The composition of the thermoelectric material being separated comprising nano super-lattice and micron that the above method is obtained is（Nd0.55Li0.36）
（Ti1-xNbx)O3, 0<x≤0.15.
The thermoelectric material being separated comprising nano super-lattice and micron that the above method is obtained in temperature range 30 ~ 450
In DEG C, conductivityσ is 2 ~ 55S/cm, and Seebeck coefficient is 61 ~ 212 μ V/K.
Method of the present invention process is simple, is suitable to batch production；Product prepared by the method is nano-structured with general
Method is compared, the coherent zero defect of micro-nano boundary in the invention；Compared with general film superlattices preparation structure, the superlattices
Structure is present among block, the thermal conductivity of materialkGlass is shown because of the presence that nano super-lattice and micron are separated
It is very popular for the thermal conductivity property of state, this application for material on pyroelectric technology；Specifically, in temperature model
30 ~ 450 DEG C are enclosed, its thermal conductivity maintains 1.8 ~ 2.2W/ (m κ) always, this approaches and is even below wide variety of alloy instantly
Thermoelectric material；Through calculating, the zero dimension thermoelectric figure of merit ZT of material in 450 DEG C of most high availables 0.07, for oxide system
For, this is a fairly good thermoelectricity capability；Therefore, material prepared by the method for being provided using the invention is in pyroelectric technology
Using the potentiality for above showing desirable.
Brief description of the drawings
Fig. 1 is the XRD of the thermoelectric material being separated comprising nano super-lattice and micron of preparation in the embodiment of the present invention；
In figure, A, B, C and D are respectively embodiment 1,2,3 and 4；（The diffraction pattern that XRD tests are obtained is with the standard card in JCPDS card bases
Piece contrasts to determine whether to prepare desired thing phase）
Fig. 2 is thermoelectric material FE-SEM and HR- comprising nano super-lattice and micron phase separation in the embodiment of the present invention 2
TEM schemes, in figure（a）For FE-SEM schemes,（b）For HR-TEM schemes.
Specific embodiment
The model RINT-2001 of the XRD equipment used in the embodiment of the present invention（Rigaku Corporation）.
The model JSM-7500F of the FE-SEM equipment used in the embodiment of the present invention（Japan Electron Optics
Laboratory Corporation）, the model EM-002B of the HR-TEM equipment of use（Topcon Corporation）.
The unit type that electrical conductivity and Seebeck coefficient test are used in the embodiment of the present invention is RZ-2001K（Ozawa
Scientific Corporation）.
The Nd used in the embodiment of the present invention2O3、Li2O、TiO2And Nb2O5It is commercial products, purity >=99.99%.
The equal pressing equipment used in the embodiment of the present invention is the small-sized cold isostatic press CIP15 of 15T（MTI
Corporation）.
Embodiment 1
Prepare Nd2O3、Li2O、TiO2And Nb2O5, the mol ratio of Nd, Li, Ti and Nb in whole materials is 0.55:0.36:
（1-x）:X, wherein x=0.02；Whole materials are placed in ball grinder and are well mixed, obtain mixed material；
Mixed material is calcined into 12h at 1100 DEG C, calcining materials are obtained；
Calcining materials are ground to granularity≤100 μm, are subsequently placed in graphite crucible, under conditions of argon gas protection, plus
Heat makes calcining materials that reduction reaction occur with graphite to 1430 ± 5 DEG C of heat treatment 3h, obtains heat-treated material；
Heat-treated material is ground to granularity≤100 μm, heat treatment powder is obtained；
By part heat treatment powder isostatic pressing, pressing pressure is 20MPa, obtains block；Block is placed in graphite earthenware
In crucible, block is covered with remaining heat treatment powder, be then heated to 1250 DEG C of high temperature sintering 12h, block is sent out with graphite
Raw reduction reaction；Reaction is first cooled to less than 650 DEG C after terminating with the speed of 100 DEG C/h, is then naturally cooling to normal temperature, obtains
Lump material be the thermoelectric material being separated comprising nano super-lattice and micron；
The composition of the thermoelectric material being separated comprising nano super-lattice and micron is（Nd0.55Li0.36）（Ti0.98Nb0.02)O3；
In 30 ~ 450 DEG C of temperature range, conductivityσ is 24 ~ 55S/cm, and Seebeck coefficient is 62 ~ 165 μ V/K.
Embodiment 2
Method is with embodiment 1, difference：
（1）Mol ratio is 0.55:0.36:（1-x）:X, wherein x=0.05；
（2）Mixed material is calcined into 11h at 1150 DEG C；
（3）It is heated to 1430 ± 5 DEG C of heat treatment 4h；
（4）The pressing pressure of isostatic pressing is 22MPa；It is heated to 1270 DEG C of high temperature sintering 11h；Reaction terminate after first with
The speed of 120 DEG C/h is cooled to less than 650 DEG C；
（5）The composition of the thermoelectric material being separated comprising nano super-lattice and micron is（Nd0.55Li0.36）
（Ti0.95Nb0.05)O3；In 30 ~ 450 DEG C of temperature range, conductivityσ is 23 ~ 54S/cm, and Seebeck coefficient is 61 ~ 188 μ V/K.
Embodiment 3
Method is with embodiment 1, difference：
（1）Mol ratio is 0.55:0.36:（1-x）:X, wherein x=0.10；
（2）Mixed material is calcined into 10h at 1200 DEG C；
（3）It is heated to 1430 ± 5 DEG C of heat treatment 5h；
（4）The pressing pressure of isostatic pressing is 25MPa；It is heated to 1300 DEG C of high temperature sintering 12h；Reaction terminate after first with
The speed of 150 DEG C/h is cooled to less than 650 DEG C；
（5）The composition of the thermoelectric material being separated comprising nano super-lattice and micron is（Nd0.55Li0.36）（Ti0.9Nb0.1)
O3；In 30 ~ 450 DEG C of temperature range, conductivityσ is 25 ~ 53S/cm, and Seebeck coefficient is 68 ~ 146 μ V/K.
Embodiment 4
Method is with embodiment 1, difference：
（1）Mol ratio is 0.55:0.36:（1-x）:X, wherein x=0.15；
（2）Mixed material is calcined into 11h at 1150 DEG C；
（3）It is heated to 1430 ± 5 DEG C of heat treatment 4h；
（4）The pressing pressure of isostatic pressing is 22MPa；It is heated to 1270 DEG C of high temperature sintering 11h；Reaction terminate after first with
The speed of 150 DEG C/h is cooled to less than 650 DEG C；
（5）The composition of the thermoelectric material being separated comprising nano super-lattice and micron is（Nd0.55Li0.36）
（Ti0.85Nb0.15)O3；In 30 ~ 450 DEG C of temperature range, conductivityσ is 2 ~ 10S/cm, and Seebeck coefficient is 92 ~ 212 μ V/K.
Claims (2)
1. a kind of preparation method of the thermoelectric material being separated comprising nano super-lattice and micron, it is characterised in that according to the following steps
Carry out：
（1）Prepare Nd2O3、Li2O、TiO2And Nb2O5, the mol ratio of Nd, Li, Ti and Nb in whole materials is 0.55:0.36:
（1-x）:X, wherein 0<x≤0.15；Whole materials are placed in ball grinder and are well mixed, obtain mixed material；
（2）Mixed material is calcined into 10 ~ 12h at 1100 ~ 1200 DEG C, calcining materials are obtained；
（3）Calcining materials are ground to granularity≤100 μm, are subsequently placed in graphite crucible, under conditions of argon gas protection, heating
To 1430 ± 5 DEG C of 3 ~ 5h of heat treatment, make calcining materials that reduction reaction occur with graphite, obtain heat-treated material；
（4）Heat-treated material is ground to granularity≤100 μm, heat treatment powder is obtained；
（5）It is 20 ~ 25MPa by part heat treatment powder isostatic pressing, pressing pressure, obtains block；Block is placed in graphite
In crucible, block is covered with remaining heat treatment powder, be then heated to 1250 ~ 1300 DEG C of 10 ~ 12h of high temperature sintering, make block
There is reduction reaction with graphite in material；Reaction is cooled to normal temperature after terminating, and the lump material of acquisition is comprising nano super-lattice and micro-
The thermoelectric material that rice is separated；The composition of the described thermoelectric material being separated comprising nano super-lattice and micron is
（Nd0.55Li0.36）（Ti1-xNbx)O3, 0<X≤0.15, in 30 ~ 450 DEG C of temperature range, conductivityσ is 2 ~ 55S/cm, Sai Bei
Gram coefficient is 61 ~ 212 μ V/K.
2. the preparation method of a kind of thermoelectric material being separated comprising nano super-lattice and micron according to claim 1,
It is characterized in that step（5）In, reaction is first cooled to less than 650 DEG C after terminating with the speed of 100 ~ 150 DEG C/h, then drops naturally
Temperature is to normal temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510145896.7A CN104733605B (en) | 2015-03-31 | 2015-03-31 | A kind of preparation method of the thermoelectric material being separated comprising nano super-lattice and micron |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510145896.7A CN104733605B (en) | 2015-03-31 | 2015-03-31 | A kind of preparation method of the thermoelectric material being separated comprising nano super-lattice and micron |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104733605A CN104733605A (en) | 2015-06-24 |
| CN104733605B true CN104733605B (en) | 2017-06-23 |
Family
ID=53457293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510145896.7A Active CN104733605B (en) | 2015-03-31 | 2015-03-31 | A kind of preparation method of the thermoelectric material being separated comprising nano super-lattice and micron |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104733605B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106007704A (en) * | 2016-05-25 | 2016-10-12 | 东北大学 | Block ceramic material with micron cubic particle structure and preparation method thereof |
| CN106935699A (en) * | 2016-12-28 | 2017-07-07 | 滁州玛特智能新材料科技有限公司 | Middle temperature quantum-well superlattice thick film thermoelectric material and its production method |
| CN109292830A (en) * | 2018-11-19 | 2019-02-01 | 西北师范大学 | The method of solid phase reaction preparation four oxygen seven of pure phase indium barium cobalt |
-
2015
- 2015-03-31 CN CN201510145896.7A patent/CN104733605B/en active Active
Non-Patent Citations (7)
| Title |
|---|
| Chessboard/Diamond Nanostructures and the A-site Deficient, Li<sub>1/2-3x</sub>Nd<sub>1/2+x</sub>Ti<sub>O</sub>3, Defect Perovskite Solid Solution;Withers Ray L., et al;《Chemistry of Materials》;20121218;第25卷(第2期);第190页摘要、第192页左栏第2部分实验 * |
| Enhanced thermoelectric properties of Nb-doped SrTiO<sub>3</sub> polycrystalline ceramic by titanate nanotube addition;Wang Ning, et al;《Journal of Alloys and Compounds》;20100707;第506卷(第1期);全文 * |
| Fabrication and thermoelectric properties of Mg<sub>2</sub>Si-based composites using reduction reaction with additives;Tani Jun-ichi,et al;《Intermetallics》;20121009;第32卷;全文 * |
| Frustrated Octahedral Tilting Distortion in the Incommensurately Modulated Li<sub>3x</sub>Nd<sub>2/3-x</sub>TiO<sub>3</sub> Perovskites;Abakumov Artem M.,et al;《Chemistry of Materials》;20130604;第25卷(第13期);全文 * |
| Glass-like thermal conductivity of Nd<sub>2/3-x</sub>Li<sub>3x</sub>TiO<sub>3</sub> bulk ceramics with nanochessboard superlattice structure;Ba Yaoshuai, et al;《Materials Letters》;20130201;第97卷;全文 * |
| Spontaneous Compositional Nanopatterning in Li-Containing Perovskite Oxides;Guiton Beth S. et al;《J. AM. CHEM. SOC.》;20081217;第130卷(第50期);全文 * |
| 烧结条件及掺杂对块体Nd<sub>0.55</sub>Li<sub>0.35</sub>TiO<sub>3</sub>结构及表面性质的影响;巴要帅,等;《2013年真空杂志编委会学术论文（摘要）集》;20130922;第1-2页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104733605A (en) | 2015-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102655204B (en) | Preparation method of sr-doping oxide BiCuSeO thermoelectric material | |
| Zhang et al. | Rapid reactive synthesis and sintering of textured Ca3Co4O9 ceramics by spark plasma sintering | |
| CN104733605B (en) | A kind of preparation method of the thermoelectric material being separated comprising nano super-lattice and micron | |
| TWI656667B (en) | Thermoelectric materials and their manufacturing method | |
| CN105671344B (en) | One step prepares high-performance CoSb3The method of base thermoelectricity material | |
| CN101913869B (en) | Oxide thermoelectric material capable of being sintered at low temperature and preparation method thereof | |
| CN101338386B (en) | Method for preparing TiNi Sn based thermoelectric compounds | |
| CN103236493A (en) | TmCuTe2 compound as well as preparation and use thereof | |
| CN104716254B (en) | A kind of preparation method of the thermoelectric material of room filling regulation electric property | |
| CN101613814A (en) | A kind of quick preparation n type Bi 2(Se xTe 1-x) 3The method of thermoelectric material | |
| JP2016530715A (en) | Thermoelectric material | |
| KR20150044794A (en) | Thermoelectric materials and their manufacturing method | |
| JP2016530716A (en) | Thermoelectric material | |
| CN106006738A (en) | Ni-doped CuCrO2-based oxide thermoelectric material and preparation method thereof | |
| CN101570321A (en) | Method for preparing BixSbyTe(3-z) thermoelectric material with high performance and nano structure | |
| KR101612492B1 (en) | Thermoelectric materials | |
| CN102168308A (en) | Method for preparing Ag-Pb-Sb-Te-Se thermoelectric material | |
| CN100532320C (en) | Lithium-sodium-cobalt-oxygen thermoelectric ceramic and preparation method thereof | |
| CN103626138A (en) | Preparation method of bismuth telluride nano thermoelectric material | |
| KR101624306B1 (en) | Method for manufacturing thermoelectric materials | |
| CN104944385A (en) | Novel method for quickly preparing high-performance CuInTe2-base thermoelectric material | |
| CN103043728A (en) | Barium cobalt thermoelectric material powder and preparation method thereof | |
| CN101692479B (en) | Method for preparing P-type high manganese-silicon thermoelectric material | |
| CN107275469A (en) | A kind of preparation method for the thermoelectric figure of merit and preparation efficiency for improving N-type BiTeSe semiconductors | |
| CN101523627A (en) | Thermoelectric material, method for producing the same, and thermoelectric converter |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |