CN109022863A - A kind of based square cobalt mineral thermoelectric material and preparation method thereof for filling Ga - Google Patents
A kind of based square cobalt mineral thermoelectric material and preparation method thereof for filling Ga Download PDFInfo
- Publication number
- CN109022863A CN109022863A CN201810775076.XA CN201810775076A CN109022863A CN 109022863 A CN109022863 A CN 109022863A CN 201810775076 A CN201810775076 A CN 201810775076A CN 109022863 A CN109022863 A CN 109022863A
- Authority
- CN
- China
- Prior art keywords
- thermoelectric material
- preparation
- hours
- degrees celsius
- conductivity
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/007—Preparing arsenides or antimonides, especially of the III-VI-compound type, e.g. aluminium or gallium arsenide
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C12/00—Alloys based on antimony or bismuth
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
A kind of CoSb for filling Ga of the disclosure of the invention3Based square cobalt mineral thermoelectric material GaxCo4Sb12.3And preparation method thereof, belong to thermoelectric material field.The purpose of the present invention is to provide a kind of to form filled skutterudite by filling gallium simple substance (Ga) to improve CoSb3The method of based square cobalt mineral conducting material thermoelectricity performance.The thermoelectric material can adjust the parameters such as Seebeck coefficient, conductivity and thermal conductivity by changing the content of Metallic Gallium (Ga) to promote CoSb3The thermoelectricity capability of based square cobalt mineral material, and preparation process is simple, is suitble to large-scale production.
Description
Technical field
The invention belongs to thermoelectric material fields, and in particular to one kind by filling gallium simple substance (Ga) formation filled skutterudite come
Improve CoSb3The method of based square cobalt mineral conducting material thermoelectricity performance.
Background technique
Thermoelectric material can be realized mutually converting between thermal energy and electric energy, and it is a kind of potential for carrying out power generation using temperature difference
Using energy source method, the conversion furthermore with electricity to heat can carry out the accurate control of temperature, in sensor sum aggregate
At being had broad application prospects in circuit.
The energy conversion efficiency for influencing heat and power system has several factors, such as the type and performance of: thermoelement, heat
Loss, overall accuracy of equipment etc., wherein the factor of most critical is the performance of thermoelectric material.People commonly use nondimensional heat
Electric figure of merit zT measures the performance of thermoelectric material, expression formula are as follows:
Wherein, Τ indicates that absolute temperature, α indicate that Seebeck coefficient, σ indicate conductivity, and κ indicates thermal conductivity.
It can be seen that a good thermoelectric material should have biggish Seebeck coefficient and conductivity and to the greatest extent may be used
The small thermal conductivity of energy.However, being the presence of the pass that interdepends between three Seebeck coefficient of material, conductivity and thermal conductivity parameters
System: reduce the carrier concentration of material, Seebeck coefficient will increase, but conductivity can reduce, meanwhile, electron thermal conductivity
It is influenced by conductivity, changes one of parameter, other two parameter can also change, the optimization and heat of electronic transport performance
The optimization for transporting performance is coupled, therefore, it is desirable to optimize the thermoelectricity capability of material, Seebeck coefficient, conductivity and
These three parameters of thermal conductivity must necessarily be placed in be comprehensively considered together.
Thermoelectric material with Skutterudite crystal structure, also known as skutterudite material, initially in Norway small town
Skutterud is found with mineral forms, be a kind of general formula be MX3Compound (wherein, M represents metallic element, as Ir,
Co, Rh, Fe etc.；X represents V group element, such as P, As, Sb).Skutterudite is cubic lattice structure, is originally derived from CoAs3Mine
Object then expands in other compounds mutually of the same clan.One unit cell contains 8 AB3Molecule, totally 32 atoms, often
There are two biggish gaps in a structure cell, form filled skutterudite by filling atom in gap, and then reduce lattice
Thermal conductivity, and electron transport situation is substantially unaffected.Currently, the method for promoting skutterudite conducting material thermoelectricity performance mainly has: mixing
Miscellaneous (element replacement) reduces thermal conductivity by forming filled skutterudite material, handles material low-dimensionalization, synthesizes with micro-
The skutterudite material of stomata reduces thermal conductivity etc..
Summary of the invention
The purpose of the present invention is to provide a kind of to form filled skutterudite by filling gallium simple substance (Ga) to improve CoSb3Base
The method of skutterudite conducting material thermoelectricity performance.The thermoelectric material can adjust Sai Beike system by changing the content of Metallic Gallium (Ga)
The parameters such as number, conductivity and thermal conductivity promote CoSb3The thermoelectricity capability of based square cobalt mineral material, and preparation process is simple, is suitble to
Large-scale production.
Technical scheme is as follows:
A kind of based square cobalt mineral thermoelectric material Ga filling GaxCo4Sb12.3, the wherein value range of x are as follows: 0.1~0.25；It is logical
The content of Metallic Gallium (Ga) is overregulated to improve Seebeck coefficient, conductivity and the thermal conductivity of thermoelectric material.
Further, the thermoelectric material GaxCo4Sb12.3Preparation method, comprising the following steps:
Step 1: metal simple-substance Ga, Co, Sb stoichiometrically GaxCo4Sb12.3It weighs, after mixing, is packed into graphite
Crucible, then graphite crucible is fitted into and carries out vacuumizing tube sealing in quartz ampoule；
Step 2: the sealed silica envelope that step 1 is obtained is put into Muffle furnace, is warming up to 1100 degrees Celsius, heat preservation 10~15 is small
When；
Step 3: continuing the quartz ampoule after high-temperature fusion that step 2 obtains to put Muffle furnace into, it is Celsius to be warming up to 700
Degree, annealing heat preservation 100~120 hours；
Step 4: the block sample high-energy ball milling after the annealing that step 3 is obtained 3~6 hours；
Step 5: the stoichiometric ratio that step 4 is obtained is GaxCo4Sb12.3Powder carry out pressurization burning under vacuum conditions
Knot, obtains thermoelectric material GaxCo4Sb12.3。
Further, to avoid elemental metals from being oxidized, the weighing for the metal simple-substance being previously mentioned in step 1 is full of lazy
It is carried out in the glove box of property atmosphere；
Further, heating rate described in step 2 is 3 degrees celsius/minutes；
Further, heating rate described in step 3 is 5 degrees celsius/minutes；
Further, high-energy ball milling described in step 4 refers specifically to the ball milling in the high energy ball mill that revolving speed is 1450 revs/min
3~6 hours；
Further, pressure sintering mode described in step 5 is that hot pressed sintering or discharge plasma are sintered, the mold used
For graphite jig, added pressure size is 50~80MPa, and sintering time is 2~20 minutes.
Write out thermoelectric material Ga of the present inventionxCo4Sb12.3With conductivity is high, thermal conductivity is small, Seebeck coefficient is high, preparation side
Method prepares simple process, is suitble to large-scale production.
Detailed description of the invention
Fig. 1 is the Ga simple substance filled skutterudite Ga of different stoichiometric ratiosxCo4Sb12.3Scanning electron microscope (SEM) photograph.It (A) is implementation
The filled skutterudite Ga that example 1 obtainsxCo4Sb12.3The scanning electron microscope (SEM) photograph of thermoelectric material；(B) the filling side's cobalt obtained for embodiment 2
Mine GaxCo4Sb12.3The scanning electron microscope (SEM) photograph of thermoelectric material；(C) the filled skutterudite Ga obtained for embodiment 3xCo4Sb12.3Thermoelectricity material
The scanning electron microscope (SEM) photograph of material；(D) the filled skutterudite Ga obtained for embodiment 4xCo4Sb12.3The scanning electron microscope (SEM) photograph of thermoelectric material；Figure
In clearly cubic structure show that Examples 1 to 4 has successfully synthesized skutterudite thermoelectric material；
Fig. 2 is the filled skutterudite Ga that embodiment obtainsxCo4Sb12.3The X ray diffracting spectrum of thermoelectric material.(A),(B),
(C), (D) is respectively the filled skutterudite Ga that Examples 1 to 4 obtainsxCo4Sb12.3The X ray diffracting spectrum of thermoelectric material, due to
The Ga simple substance amount of filling is seldom, only occurs CoSb on map3The characteristic diffraction peak of skutterudite, in conjunction with Fig. 1 prove embodiment 1~
The sample of 4 preparations is filled skutterudite Ga reallyxCo4Sb12.3Thermoelectric material；
Fig. 3 is the filled skutterudite Ga that embodiment obtainsxCo4Sb12.3The conductivity versus temperature characteristic curve of thermoelectric material,
In " Ga0.1Co4Sb12.3”、“Ga0.15Co4Sb12.3”、“Ga0.2Co4Sb12.3”、“Ga0.25Co4Sb12.3" curve be respectively implement
The filled skutterudite Ga that example 1~4 obtainsxCo4Sb12.3The conductivity versus temperature characteristic curve of thermoelectric material.Preparation is shown in figure
Filled skutterudite GaxCo4Sb12.3The conductivity of thermoelectric material reaches as high as 286.68S/cm.
Fig. 4 is the filled skutterudite Ga that embodiment obtainsxCo4Sb12.3The Seebeck coefficient of thermoelectric material-temperature characterisitic is bent
Line, wherein " Ga0.1Co4Sb12.3”、“Ga0.15Co4Sb12.3”、“Ga0.2Co4Sb12.3”、“Ga0.25Co4Sb12.3" curve be respectively
The filled skutterudite Ga that Examples 1 to 4 obtainsxCo4Sb12.3Seebeck coefficient-temperature characteristics of thermoelectric material.It is shown in figure
Show the filled skutterudite Ga of preparationxCo4Sb12.3The Seebeck coefficient of thermoelectric material reaches as high as -336.4068uV/K.
Fig. 5 is the filled skutterudite Ga that embodiment obtainsxCo4Sb12.3Thermal conductivity-temperature characteristics of thermoelectric material,
In " Ga0.1Co4Sb12.3”、“Ga0.15Co4Sb12.3”、“Ga0.2Co4Sb12.3”、“Ga0.25Co4Sb12.3" curve be respectively implement
The filled skutterudite Ga that example 1~4 obtainsxCo4Sb12.3Thermal conductivity-temperature characteristics of thermoelectric material.Preparation is shown in figure
Filled skutterudite GaxCo4Sb12.3The minimum 2.792W/ of the thermal conductivity of thermoelectric material (mK).
Fig. 6 is the filled skutterudite Ga that embodiment obtainsxCo4Sb12.3The ZT- temperature characteristics of thermoelectric material, wherein
“Ga0.1Co4Sb12.3”、“Ga0.15Co4Sb12.3”、“Ga0.2Co4Sb12.3”、“Ga0.25Co4Sb12.3" curve be respectively embodiment 1
~4 obtained filled skutterudite GaxCo4Sb12.3The ZT- temperature characteristics of thermoelectric material.Filling side's cobalt of preparation is shown in figure
Mine GaxCo4Sb12.3The ZT of thermoelectric material reaches as high as 0.561.
Specific embodiment
Technical solution of the present invention is described in detail with reference to the accompanying drawings and examples.
Example 1
Step 1: metal simple-substance Ga, Co, Sb stoichiometrically Ga0.1Co4Sb12.3It weighs, after mixing, is packed into graphite
Crucible, then graphite crucible is fitted into and carries out vacuumizing tube sealing in quartz ampoule.To avoid elemental metals from being oxidized, mentioned in the step
To metal simple-substance weighing full of inert atmosphere glove box in carry out；
Step 2: the sealed silica envelope that step 1 is obtained is put into Muffle furnace, is warming up to 1100 degrees Celsius, heating rate 3
Degrees celsius/minute keeps the temperature 10 hours；
Step 3: continuing the quartz ampoule after high-temperature fusion that step 2 obtains to put Muffle furnace into, it is Celsius to be warming up to 700
Degree, heating rate are 5 degrees celsius/minutes, annealing heat preservation 100 hours；
Step 4: the block sample high-energy ball milling after the annealing that step 3 is obtained 3 hours；
Step 5: the stoichiometric ratio that step 4 is obtained is Ga0.1Co4Sb12.3Powder pressurize under vacuum conditions
Sintering, obtains thermoelectric material of the present invention.Pressure sintering mode is that hot pressed sintering or discharge plasma are sintered, and is used
Mold is graphite jig, and added pressure size is 70MPa, and sintering time is 5 minutes
The filled skutterudite Ga that example 1 obtains0.1Co4Sb12.3Thermoelectric material, conductivity reach 255.66S/ in 773K
Seebeck coefficient reaches -336.4uV/K when cm, 473K, the minimum 3.335W/ of thermal conductivity (mK) when 623K.
Example 2
Step 1: metal simple-substance Ga, Co, Sb stoichiometrically Ga0.15Co4Sb12.3It weighs, after mixing, is packed into stone
Black crucible, then graphite crucible is fitted into and carries out vacuumizing tube sealing in quartz ampoule.To avoid elemental metals from being oxidized, institute in the step
The weighing for the metal simple-substance mentioned carries out in the glove box full of inert atmosphere；
Step 2: the sealed silica envelope that step 1 is obtained is put into Muffle furnace, is warming up to 1100 degrees Celsius, heating rate 3
Degrees celsius/minute keeps the temperature 15 hours；
Step 3: continuing the quartz ampoule after high-temperature fusion that step 2 obtains to put Muffle furnace into, it is Celsius to be warming up to 700
Degree, heating rate are 5 degrees celsius/minutes, annealing heat preservation 110 hours；
Step 4: the block sample high-energy ball milling after the annealing that step 3 is obtained 6 hours；
Step 5: the stoichiometric ratio that step 4 is obtained is Ga0.15Co4Sb12.3Powder pressurize under vacuum conditions
Sintering, obtains thermoelectric material of the present invention.Pressure sintering mode is that hot pressed sintering or discharge plasma are sintered, and is used
Mold is graphite jig, and added pressure size is 60MPa, and sintering time is 5 minutes
The filled skutterudite Ga that example 2 obtains0.15Co4Sb12.3Thermoelectric material, conductivity reach in 773K
Seebeck coefficient reaches -324.56uV/K when 254.45S/cm, 473K, the minimum 2.822W/ of thermal conductivity (mK) when 573K.
Example 3
Step 1: metal simple-substance Ga, Co, Sb stoichiometrically Ga0.2Co4Sb12.3It weighs, after mixing, is packed into graphite
Crucible, then graphite crucible is fitted into and carries out vacuumizing tube sealing in quartz ampoule.To avoid elemental metals from being oxidized, mentioned in the step
To metal simple-substance weighing full of inert atmosphere glove box in carry out；
Step 2: the sealed silica envelope that step 1 is obtained is put into Muffle furnace, is warming up to 1100 degrees Celsius, heating rate 3
Degrees celsius/minute keeps the temperature 12 hours；
Step 3: continuing the quartz ampoule after high-temperature fusion that step 2 obtains to put Muffle furnace into, it is Celsius to be warming up to 700
Degree, heating rate are 5 degrees celsius/minutes, annealing heat preservation 120 hours；
Step 4: the block sample high-energy ball milling after the annealing that step 3 is obtained 4 hours；
Step 5: the stoichiometric ratio that step 4 is obtained is Ga0.2Co4Sb12.3Powder pressurize under vacuum conditions
Sintering, obtains thermoelectric material of the present invention.Pressure sintering mode is that hot pressed sintering or discharge plasma are sintered, and is used
Mold is graphite jig, and added pressure size is 80MPa, and sintering time is 5 minutes
The filled skutterudite Ga that example 3 obtains0.2Co4Sb12.3Thermoelectric material, conductivity reach 280.22S/ in 773K
Seebeck coefficient reaches -322.2uV/K when cm, 473K, the minimum 2.991W/ of thermal conductivity (mK) when 573K, finally, when 623K
ZT value reaches 0.561.With current metal simple-substance Ga single element filled skutterudite GaxCo4Sb12.3The thermoelectricity capability of material is compared, and is mentioned
2~3 times have been risen, warm thermoelectric material is suitable for.
Example 4
Step 1: metal simple-substance Ga, Co, Sb stoichiometrically Ga0.25Co4Sb12.3It weighs, after mixing, is packed into stone
Black crucible, then graphite crucible is fitted into and carries out vacuumizing tube sealing in quartz ampoule.To avoid elemental metals from being oxidized, institute in the step
The weighing for the metal simple-substance mentioned carries out in the glove box full of inert atmosphere；
Step 2: the sealed silica envelope that step 1 is obtained is put into Muffle furnace, is warming up to 1100 degrees Celsius, heating rate 3
Degrees celsius/minute keeps the temperature 14 hours；
Step 3: continuing the quartz ampoule after high-temperature fusion that step 2 obtains to put Muffle furnace into, it is Celsius to be warming up to 700
Degree, heating rate are 5 degrees celsius/minutes, annealing heat preservation 1000 hours；
Step 4: the block sample high-energy ball milling after the annealing that step 3 is obtained 5 hours；
Step 5: the stoichiometric ratio that step 4 is obtained is Ga0.25Co4Sb12.3Powder pressurize under vacuum conditions
Sintering, obtains thermoelectric material of the present invention.Pressure sintering mode is that hot pressed sintering or discharge plasma are sintered, and is used
Mold is graphite jig, and added pressure size is 50MPa, and sintering time is 5 minutes
The filled skutterudite Ga that example 4 obtains0.25Co4Sb12.3Thermoelectric material, conductivity reach in 773K
Seebeck coefficient reaches -334.93uV/K when 258.77S/cm, 473K, the minimum 2.792W/ of thermal conductivity (mK) when 573K.
Claims (7)
1. a kind of based square cobalt mineral thermoelectric material Ga for filling GaxCo4Sb12.3, the wherein value range of x are as follows: 0.1~0.25；Pass through
The content of Metallic Gallium (Ga) is adjusted to improve Seebeck coefficient, conductivity and the thermal conductivity of thermoelectric material.
2. a kind of thermoelectric material Ga as described in claim 1xCo4Sb12.3Preparation method, comprising the following steps:
Step 1: metal simple-substance Ga, Co, Sb stoichiometrically GaxCo4Sb12.3It weighs, after mixing, is packed into graphite crucible,
Graphite crucible is fitted into again and carries out vacuumizing tube sealing in quartz ampoule；
Step 2: the sealed silica envelope that step 1 is obtained is put into Muffle furnace, is warming up to 1100 degrees Celsius, keeps the temperature 10~15 hours；
Step 3: continuing the quartz ampoule after high-temperature fusion that step 2 obtains to put Muffle furnace into, be warming up to 700 degrees Celsius, move back
Fire heat preservation 100~120 hours；
Step 4: the block sample high-energy ball milling after the annealing that step 3 is obtained 3~6 hours；
Step 5: the stoichiometric ratio that step 4 is obtained is GaxCo4Sb12.3Powder carry out pressure sintering under vacuum conditions,
Obtain thermoelectric material GaxCo4Sb12.3。
3. thermoelectric material Ga as claimed in claim 2xCo4Sb12.3Preparation method, it is characterised in that avoid elemental metals
It is oxidized, the weighing for the metal simple-substance being previously mentioned in step 1 carries out in the glove box full of inert atmosphere.
4. thermoelectric material Ga as claimed in claim 2xCo4Sb12.3Preparation method, it is characterised in that heating described in step 2
Rate is 3 degrees celsius/minutes.
5. thermoelectric material Ga as claimed in claim 2xCo4Sb12.3Preparation method, it is characterised in that heating described in step 3
Rate is 5 degrees celsius/minutes.
6. thermoelectric material Ga as claimed in claim 2xCo4Sb12.3Preparation method, it is characterised in that high energy ball described in step 4
Mill refers specifically in the high energy ball mill that revolving speed is 1450 revs/min ball milling 3~6 hours.
7. thermoelectric material Ga as claimed in claim 2xCo4Sb12.3Preparation method, it is characterised in that described in step 5 pressurize burn
Knot mode is that hot pressed sintering or discharge plasma are sintered, and the mold used is graphite jig, added pressure size is 50~
80MPa, sintering time are 2~20 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810775076.XA CN109022863B (en) | 2018-07-16 | 2018-07-16 | Ga-filled skutterudite thermoelectric material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810775076.XA CN109022863B (en) | 2018-07-16 | 2018-07-16 | Ga-filled skutterudite thermoelectric material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109022863A true CN109022863A (en) | 2018-12-18 |
| CN109022863B CN109022863B (en) | 2020-09-25 |
Family
ID=64642472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810775076.XA Active CN109022863B (en) | 2018-07-16 | 2018-07-16 | Ga-filled skutterudite thermoelectric material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109022863B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112538579A (en) * | 2020-12-07 | 2021-03-23 | 安徽工业大学 | Method for reducing thermal conductivity of p-type Ce-filled iron-based skutterudite thermoelectric material |
| CN114497335A (en) * | 2022-01-20 | 2022-05-13 | 济南大学 | Skutterudite thermoelectric material electrode and connection method of skutterudite thermoelectric material and electrode |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101435029A (en) * | 2008-12-26 | 2009-05-20 | 武汉理工大学 | Rapid preparation of high performance nanostructured filling type skutterudite thermoelectric material |
-
2018
- 2018-07-16 CN CN201810775076.XA patent/CN109022863B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101435029A (en) * | 2008-12-26 | 2009-05-20 | 武汉理工大学 | Rapid preparation of high performance nanostructured filling type skutterudite thermoelectric material |
Non-Patent Citations (1)
| Title |
|---|
| 苏贤礼等: "Ga填充n型方钴矿化合物的结构及热电性能", 《物理学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112538579A (en) * | 2020-12-07 | 2021-03-23 | 安徽工业大学 | Method for reducing thermal conductivity of p-type Ce-filled iron-based skutterudite thermoelectric material |
| CN114497335A (en) * | 2022-01-20 | 2022-05-13 | 济南大学 | Skutterudite thermoelectric material electrode and connection method of skutterudite thermoelectric material and electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109022863B (en) | 2020-09-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108238796B (en) | Copper seleno solid solution thermoelectric material and preparation method thereof | |
| CN102931335B (en) | A kind of Graphene is combined thermoelectric material of cobalt stibide based skutterudite and preparation method thereof | |
| WO2010048900A1 (en) | Compound used for thermoelectric material and preparing method thereof | |
| CN108374198B (en) | A kind of monocrystalline Bi2Te3The preparation method of thermoelectric material | |
| JP7344531B2 (en) | Thermoelectric conversion material and its manufacturing method | |
| CN102031416A (en) | Composite material of skutterudite filling substrate and preparation method thereof | |
| CN106986315B (en) | A kind of p-type bismuth telluride thermoelectric material and preparation method suitable for low-temperature electricity-generating | |
| CN107235477A (en) | A kind of N-type high-performance argyrodite thermoelectric material and preparation method thereof | |
| CN107799646A (en) | A kind of alloy thermoelectric semiconductor material and preparation method thereof | |
| CN104498751A (en) | Preparation method of thermoelectric material of skutterudite | |
| CN107195767B (en) | Five yuan of N-type thermoelectric materials of one kind and preparation method thereof | |
| CN109022863A (en) | A kind of based square cobalt mineral thermoelectric material and preparation method thereof for filling Ga | |
| CN108417704B (en) | High-performance europium-doped PbTe-based thermoelectric material and preparation method thereof | |
| CN108649115B (en) | Five elements N-shaped thermoelectric material and preparation method based on the sintering phase transformation of crystal topological realization powder metallurgy | |
| CN108516526B (en) | High-performance PbTe-based solid solution thermoelectric material and preparation method thereof | |
| CN105990510B (en) | A kind of copper seleno high performance thermoelectric material and preparation method thereof | |
| CN103811653B (en) | Multi-cobalt p type skutterudite filled thermoelectric material and preparation method thereof | |
| CN109103323A (en) | A method of Sb is replaced by filling Ga, Te and improves based square cobalt mineral conducting material thermoelectricity performance | |
| CN103409656B (en) | Thermoelectric material Mg2Sn and preparation method thereof | |
| CN107359231A (en) | A kind of new low heat conduction argyrodite thermoelectric material and preparation method thereof | |
| CN101307392B (en) | Process for preparing CoSb3-based thermoelectric material by combining liquid quenching and spark plasma sintering | |
| CN101857929A (en) | Zinc antimony based porous p-type thermoelectric material and preparation method thereof | |
| CN111162160A (en) | P-type cubic phase Ge-Se-based thermoelectric material and preparation method thereof | |
| CN101307393A (en) | Process for preparing silicon-germanium-based thermoelectric material by liquid quenching cooperated with spark plasma sintering | |
| CN108511588A (en) | A kind of MnTe2Base novel thermoelectric material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |