CN109103323A - A method of Sb is replaced by filling Ga, Te and improves based square cobalt mineral conducting material thermoelectricity performance - Google Patents
A method of Sb is replaced by filling Ga, Te and improves based square cobalt mineral conducting material thermoelectricity performance Download PDFInfo
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- CN109103323A CN109103323A CN201810775036.5A CN201810775036A CN109103323A CN 109103323 A CN109103323 A CN 109103323A CN 201810775036 A CN201810775036 A CN 201810775036A CN 109103323 A CN109103323 A CN 109103323A
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- 238000011049 filling Methods 0.000 title claims abstract description 27
- 230000005619 thermoelectricity Effects 0.000 title abstract description 12
- 229910052500 inorganic mineral Inorganic materials 0.000 title abstract description 10
- 239000011707 mineral Substances 0.000 title abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 title abstract description 9
- 239000010941 cobalt Substances 0.000 title abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title abstract description 9
- 238000000034 method Methods 0.000 title abstract description 9
- 239000004020 conductor Substances 0.000 title abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 52
- 239000000126 substance Substances 0.000 claims abstract description 52
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 17
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 16
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 16
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 10
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims description 31
- 239000002184 metal Substances 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000005245 sintering Methods 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000010439 graphite Substances 0.000 claims description 18
- 229910002804 graphite Inorganic materials 0.000 claims description 18
- 239000003708 ampul Substances 0.000 claims description 12
- 238000000137 annealing Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 12
- 239000010453 quartz Substances 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 238000000713 high-energy ball milling Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 230000004927 fusion Effects 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 2
- 229910018985 CoSb3 Inorganic materials 0.000 abstract description 8
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 239000002305 electric material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
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- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Powder Metallurgy (AREA)
Abstract
The disclosure of the invention is a kind of to be replaced Sb by filling Ga and improves CoSb3The method of based square cobalt mineral conducting material thermoelectricity performance belongs to thermoelectric material field and its prepares neighborhood.The purpose of the present invention is to provide a kind of to form filling replacement skutterudite by filling gallium simple substance (Ga), tellurium simple substance (Te) replacement part antimony simple substance (Sb) 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 the amount of content and tellurium simple substance (Te) replacement antimony simple substance (Sb) of change 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 passes through filling gallium simple substance (Ga), tellurium simple substance (Te) replacement
Part antimony simple substance (Sb) forms filling replacement skutterudite to 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 one kind to replace part antimony simple substance by filling gallium simple substance (Ga), tellurium simple substance (Te)
(Sb) filling replacement skutterudite is formed to improve CoSb3The method of based square cobalt mineral conducting material thermoelectricity performance.The thermoelectric material can pass through
Change Metallic Gallium (Ga) content and tellurium simple substance (Te) replacement antimony simple substance (Sb) amount come adjust Seebeck coefficient, conductivity and
The parameters such as 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:
The thermoelectric material that one kind passing through filling gallium simple substance (Ga), tellurium simple substance (Te) replacement part antimony simple substance (Sb)
GaxCo4Sb12.3-yTey, it is characterised in that the value that wherein value of x is 0.2, y is 0.6~0.9；By adjusting Metallic Gallium
(Ga) loading and tellurium simple substance (Te) replaces the amount of antimony simple substance (Sb) to improve thermoelectric material GaxCo4Sb12.3-yTeySai Bei
Gram coefficient, conductivity and thermal conductivity.
Further, the thermoelectric material Ga0.2Co4Sb12.3-yTeyPreparation method, comprising the following steps:
Step 1: metal simple-substance Ga, Co, Sb, Te stoichiometrically Ga0.2Co4Sb12.3-yTeyIt weighs, after mixing,
It 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, keeps the temperature 10 hours；
Step 3: the quartz ampoule after high-temperature fusion that step 2 obtains is put into cold water under conditions of 1100 degrees Celsius
Quenching, then proceedes to put Muffle furnace into, is warming up to 700 degrees Celsius, annealing heat preservation 100 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 Ga0.2Co4Sb12.3-yTeyPowder carry out under vacuum conditions
Pressure sintering obtains thermoelectric material of the present invention.
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.In addition, to guarantee that every kind of metal simple-substance is equal
It can melt completely, of short duration heat preservation 10 minutes near the fusing point of each metal simple-substance；
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
5 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 75MPa, and sintering time is 5 minutes.
The present invention replaces the amount of antimony simple substance (Sb) by the content and tellurium simple substance (Te) that change Metallic Gallium (Ga) to adjust match
The parameters such as seebeck coefficient, conductivity and thermal conductivity promote CoSb3The thermoelectricity capability of based square cobalt mineral material, and preparation process letter
It is single, it is suitble to large-scale production, obtained hot spot material Ga0.2Co4Sb12.3-yTeyWith conductivity is high, thermal conductivity is small, Sai Beike system
The high advantage of number.
Detailed description of the invention
Fig. 1 is that stoichiometric ratio is Ga0.2Co4Sb11.4Te0.9Thermoelectric material scanning electron microscope (SEM) photograph.Clearly cube knot in figure
Structure has synthesized skutterudite thermoelectric material with showing this Success in Experiment；
Fig. 2 is that skutterudite Ga is replaced in the filling that embodiment obtains0.2Co4Sb12.3-yTeyThe X-ray diffractogram of thermoelectric material
Spectrum.(A), (B), (C), (D) are respectively the filling replacement skutterudite Ga that Examples 1 to 4 obtains0.2Co4Sb12.3-yTeyThermoelectricity material
The X ray diffracting spectrum of material, since the loading of Ga simple substance is seldom, and the amount of Te simple substance replacement Sb is also seldom, therefore on map
Only there is CoSb3The characteristic diffraction peak of skutterudite proves that sample prepared by Examples 1 to 4 is filling replacement really in conjunction with Fig. 1
Skutterudite Ga0.2Co4Sb12.3-yTeyThermoelectric material；
Fig. 3 is that skutterudite Ga is replaced in the filling that embodiment obtains0.2Co4Sb12.3-yTeyThe conductivity versus temperature of thermoelectric material is special
Linearity curve, wherein " Ga0.2Co4Sb11.7Te0.6”、“Ga0.2Co4Sb11.6Te0.7”、“Ga0.2Co4Sb11.5Te0.8”、
“Ga0.2Co4Sb11.4Te0.9" curve be respectively Examples 1 to 4 obtain filling replacement skutterudite Ga0.2Co4Sb12.3-yTeyHeat
The conductivity versus temperature characteristic curve of electric material.
Fig. 4 is that skutterudite Ga is replaced in the filling that embodiment obtains0.2Co4Sb12.3-yTeySeebeck coefficient-temperature of thermoelectric material
Characteristic curve is spent, wherein " Ga0.2Co4Sb11.7Te0.6”、“Ga0.2Co4Sb11.6Te0.7”、“Ga0.2Co4Sb11.5Te0.8”、
“Ga0.2Co4Sb11.4Te0.9" curve be respectively Examples 1 to 4 obtain filling replacement skutterudite Ga0.2Co4Sb12.3-yTeyHeat
Seebeck coefficient-temperature characteristics of electric material.
Fig. 5 is that skutterudite Ga is replaced in the filling that embodiment obtains0.2Co4Sb12.3-yTeyThe thermal conductivity of thermoelectric material-temperature is special
Linearity curve, wherein " Ga0.2Co4Sb11.7Te0.6”、“Ga0.2Co4Sb11.6Te0.7”、“Ga0.2Co4Sb11.5Te0.8”、
“Ga0.2Co4Sb11.4Te0.9" curve be respectively Examples 1 to 4 obtain filling replacement skutterudite Ga0.2Co4Sb12.3-yTeyHeat
Thermal conductivity-temperature characteristics of electric material.
Fig. 6 is that skutterudite Ga is replaced in the filling that embodiment obtains0.2Co4Sb12.3-yTeyThe ZT- temperature characterisitic of thermoelectric material is bent
Line, wherein " Ga0.2Co4Sb11.7Te0.6”、“Ga0.2Co4Sb11.6Te0.7”、“Ga0.2Co4Sb11.5Te0.8”、
“Ga0.2Co4Sb11.4Te0.9" curve be respectively Examples 1 to 4 obtain filling replacement skutterudite Ga0.2Co4Sb12.3-yTeyHeat
The ZT- temperature characteristics of electric material.
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, Te stoichiometrically Ga0.2Co4Sb11.7Te0.6It weighs, after mixing,
It 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, step
The weighing for the metal simple-substance being previously mentioned in 1 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 10 hours, attached in the fusing point of each metal simple-substance to guarantee that every kind of metal simple-substance can melt completely
Nearly of short duration heat preservation 10 minutes；
Step 3: the quartz ampoule after high-temperature fusion that step 2 obtains is put into cold water under conditions of 1100 degrees Celsius
Quenching, then proceedes to put Muffle furnace into, is warming up to 700 degrees Celsius, and heating rate is 5 degrees celsius/minutes, and annealing heat preservation 100 is small
When；
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 Ga0.2Co4Sb11.7Te0.6Powder carry out under vacuum conditions
Pressure sintering obtains thermoelectric material of the present invention, and pressure sintering mode is that hot pressed sintering or discharge plasma are sintered, and makes
Mold is graphite jig, and added pressure size is 75MPa, and sintering time is 5 minutes.
Skutterudite Ga is replaced in the filling that example 1 obtains0.2Co4Sb11.7Te0.6Thermoelectric material, conductivity highest in room temperature
For 957.4 S/cm, Seebeck coefficient reaches -240.68uV/K when 723K, the minimum 2.75W/ of thermal conductivity (mK) when 723K.
Example 2
Step 1: metal simple-substance Ga, Co, Sb, Te stoichiometrically Ga0.2Co4Sb11.6Te0.7It weighs, after mixing,
It 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, step
The weighing for the metal simple-substance being previously mentioned in 1 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 10 hours, attached in the fusing point of each metal simple-substance to guarantee that every kind of metal simple-substance can melt completely
Nearly of short duration heat preservation 10 minutes；
Step 3: the quartz ampoule after high-temperature fusion that step 2 obtains is put into cold water under conditions of 1100 degrees Celsius
Quenching, then proceedes to put Muffle furnace into, is warming up to 700 degrees Celsius, and heating rate is 5 degrees celsius/minutes, and annealing heat preservation 100 is small
When；
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 Ga0.2Co4Sb11.6Te0.7Powder carry out under vacuum conditions
Pressure sintering obtains thermoelectric material of the present invention, and pressure sintering mode is that hot pressed sintering or discharge plasma are sintered, and makes
Mold is graphite jig, and added pressure size is 75MPa, and sintering time is 5 minutes.
Skutterudite Ga is replaced in the filling that example 2 obtains0.2Co4Sb11.6Te0.7Thermoelectric material, conductivity highest in room temperature
For 1124.24S/cm, Seebeck coefficient reaches -231.71uV/K when 723K, the minimum 2.834W/ of thermal conductivity (mK) when 723K.
Example 3
Step 1: metal simple-substance Ga, Co, Sb, Te stoichiometrically Ga0.2Co4Sb11.5Te0.8It weighs, after mixing,
It 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, step
The weighing for the metal simple-substance being previously mentioned in 1 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 10 hours, attached in the fusing point of each metal simple-substance to guarantee that every kind of metal simple-substance can melt completely
Nearly of short duration heat preservation 10 minutes；
Step 3: the quartz ampoule after high-temperature fusion that step 2 obtains is put into cold water under conditions of 1100 degrees Celsius
Quenching, then proceedes to put Muffle furnace into, is warming up to 700 degrees Celsius, and heating rate is 5 degrees celsius/minutes, and annealing heat preservation 100 is small
When；
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 Ga0.2Co4Sb11.5Te0.8Powder carry out under vacuum conditions
Pressure sintering obtains thermoelectric material of the present invention, and pressure sintering mode is that hot pressed sintering or discharge plasma are sintered, and makes
Mold is graphite jig, and added pressure size is 75MPa, and sintering time is 5 minutes.
Skutterudite Ga is replaced in the filling that example 3 obtains0.2Co4Sb11.5Te0.8Thermoelectric material, conductivity highest in room temperature
For 1230.75S/cm, Seebeck coefficient reaches -215.87uV/K when 773K, the minimum 2.765W/ of thermal conductivity (mK) when 673K.
Example 4
Step 1: metal simple-substance Ga, Co, Sb, Te stoichiometrically Ga0.2Co4Sb11.4Te0.9It weighs, after mixing,
It 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, step
The weighing for the metal simple-substance being previously mentioned in 1 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 10 hours, attached in the fusing point of each metal simple-substance to guarantee that every kind of metal simple-substance can melt completely
Nearly of short duration heat preservation 10 minutes；
Step 3: the quartz ampoule after high-temperature fusion that step 2 obtains is put into cold water under conditions of 1100 degrees Celsius
Quenching, then proceedes to put Muffle furnace into, is warming up to 700 degrees Celsius, and heating rate is 5 degrees celsius/minutes, and annealing heat preservation 100 is small
When；
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 Ga0.2Co4Sb11.4Te0.9Powder carry out under vacuum conditions
Pressure sintering obtains thermoelectric material of the present invention, and pressure sintering mode is that hot pressed sintering or discharge plasma are sintered, and makes
Mold is graphite jig, and added pressure size is 75MPa, and sintering time is 5 minutes.
Skutterudite Ga is replaced in the filling that example 4 obtains0.2Co4Sb11.4Te0.9Thermoelectric material, conductivity highest in room temperature
For 1309.73 S/cm, Seebeck coefficient reaches -207.05 uV/K when 873K, thermal conductivity minimum 2.766W/ when 673K
(mK).Finally, ZT value when 873K reaches 1.41.It is suitable with the thermoelectricity capability of current dual element filled skutterudite material, it is applicable in
In warm thermoelectric material.
Claims (7)
1. one kind passes through the thermoelectric material of filling gallium simple substance (Ga), tellurium simple substance (Te) replacement part antimony simple substance (Sb)
GaxCo4Sb12.3-yTey, it is characterised in that the value that wherein value of x is 0.2, y is 0.6~0.9；By adjusting Metallic Gallium
(Ga) loading and tellurium simple substance (Te) replaces the amount of antimony simple substance (Sb) to improve thermoelectric material GaxCo4Sb12.3-yTeySai Bei
Gram coefficient, conductivity and thermal conductivity.
2. a kind of thermoelectric material Ga as described in claim 10.2Co4Sb12.3-yTeyPreparation method, comprising the following steps:
Step 1: metal simple-substance Ga, Co, Sb, Te stoichiometrically Ga0.2Co4Sb12.3-yTeyIt 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, keeps the temperature 10 hours；
Step 3: the quartz ampoule after high-temperature fusion that step 2 obtains being put into cold water under conditions of 1100 degrees Celsius and is quenched
Fire then proceedes to put Muffle furnace into, is warming up to 700 degrees Celsius, annealing heat preservation 100 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 Ga0.2Co4Sb12.3-yTeyPowder pressurize under vacuum conditions
Sintering, obtains thermoelectric material of the present invention.
3. the thermoelectric material Ga to count such as claim 20.2Co4Sb12.3-yTeyPreparation method, it is characterised in that avoid simple substance
Metal is oxidized, and the weighing for the metal simple-substance being previously mentioned in step 1 carries out in the glove box full of inert atmosphere.
4. the thermoelectric material Ga to count such as claim 20.2Co4Sb12.3-yTeyPreparation method, it is characterised in that described in step 2
Heating rate be 3 degrees celsius/minutes.In addition, to guarantee that every kind of metal simple-substance can melt completely, in each metal simple-substance
Of short duration heat preservation 10 minutes near fusing point.
5. the thermoelectric material Ga to count such as claim 20.2Co4Sb12.3-yTeyPreparation method, it is characterised in that described in step 3
Heating rate be 5 degrees celsius/minutes.
6. the thermoelectric material Ga to count such as claim 20.2Co4Sb12.3-yTeyPreparation method, it is characterised in that described in step 4
High-energy ball milling refers specifically in the high energy ball mill that revolving speed is 1450 revs/min ball milling 5 hours.
7. the thermoelectric material Ga to count such as claim 20.2Co4Sb12.3-yTeyPreparation method, it is characterised in that described in step 5
Pressure sintering mode is that hot pressed sintering or discharge plasma are sintered, and the mold used is graphite jig, added pressure size
For 75MPa, sintering time is 5 minutes.
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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 |
| CN112978684A (en) * | 2021-02-05 | 2021-06-18 | 武汉理工大学 | Intra-crystalline porous high-performance skutterudite thermoelectric material and preparation method thereof |
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| CN1916211A (en) * | 2006-08-29 | 2007-02-21 | 中国科学院上海硅酸盐研究所 | Filling in thermoelectric material of cobalt stibide based skutterudite by alkali-metal atom, and preparation method |
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