CN109755377A - A kind of skutterudite-base thermoelectrical material and preparation method thereof - Google Patents
A kind of skutterudite-base thermoelectrical material and preparation method thereof Download PDFInfo
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- CN109755377A CN109755377A CN201811542346.9A CN201811542346A CN109755377A CN 109755377 A CN109755377 A CN 109755377A CN 201811542346 A CN201811542346 A CN 201811542346A CN 109755377 A CN109755377 A CN 109755377A
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- 239000000463 material Substances 0.000 title claims abstract description 177
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000002585 base Substances 0.000 claims abstract description 98
- 229910018985 CoSb3 Inorganic materials 0.000 claims abstract description 47
- 230000005619 thermoelectricity Effects 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 4
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 58
- 238000003756 stirring Methods 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 21
- 239000011701 zinc Substances 0.000 claims description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052725 zinc Inorganic materials 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- 239000013049 sediment Substances 0.000 claims description 11
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- 239000004246 zinc acetate Substances 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 235000019698 starch Nutrition 0.000 claims 1
- 239000008107 starch Substances 0.000 claims 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 87
- 239000011787 zinc oxide Substances 0.000 abstract description 43
- 239000002105 nanoparticle Substances 0.000 abstract description 14
- 229960001296 zinc oxide Drugs 0.000 description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 23
- 238000000498 ball milling Methods 0.000 description 22
- 238000005245 sintering Methods 0.000 description 20
- 239000003708 ampul Substances 0.000 description 17
- 239000010453 quartz Substances 0.000 description 17
- UFIKNOKSPUOOCL-UHFFFAOYSA-N antimony;cobalt Chemical compound [Sb]#[Co] UFIKNOKSPUOOCL-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910017052 cobalt Inorganic materials 0.000 description 10
- 239000010941 cobalt Substances 0.000 description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 10
- 238000011068 loading method Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 4
- 239000004020 conductor Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000005679 Peltier effect Effects 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000009768 microwave sintering Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention provides a kind of skutterudite-base thermoelectrical materials and preparation method thereof, and the chemical formula of the thermoelectric material is as follows: MxCoSb3+ yZnO, in which: the value range of x is 0≤x≤0.4, and 0 < y≤3%, y is that ZnO accounts for MxCoSb3The mass percent of matrix；M is one of alkali metal, alkaline-earth metal and rare earth element of doping or a variety of.The present invention is by being evenly dispersed in skutterudite-base thermoelectrical material internal for suitable Zinc oxide nanoparticle, the selectivity scattering to low frequency phonon can be enhanced, to effectively reduce the lattice thermal conductivity of skutterudite-base thermoelectrical material, simultaneously because zinc oxide carrier mobility with higher, the Seebeck coefficient and conductivity that can guarantee thermoelectric material maintain in stable variation range, to be conducive to improve the thermoelectricity capability of skutterudite-base thermoelectrical material entirety.
Description
Technical field
The present invention relates to field of thermoelectric material technique, in particular to a kind of skutterudite-base thermoelectrical material and its preparation
Method.
Background technique
Thermoelectric generation technology is to carry out energy using the Seebeck effect and peltier effect of semiconductor material directly to convert
Technology, transfer efficiency depends primarily on dimensionless performance index ZT value (ZT=S2σ T/k, wherein S is Seebeck coefficient, and σ is
Conductivity, k are thermal conductivity, and T is absolute temperature).The ZT value of material is higher, and conversion efficiency of thermoelectric is higher.Using thermoelectric material system
The prototype part obtained has the characteristics that small in size, high reliablity, the service life is long, manufacturing process is simple and environmental-friendly, thus is expected to wide
It is general to be applied to the fields such as waste-heat power generation, aerospace power supply and health care refrigeration.
Skutterudite-base thermoelectrical material is presently believed to be applied to the optimal thermoelectric material in high temperature area.Skutterudite chemical combination
Object belongs to body-centered cubic structure, and the maximum feature of crystal structure is body position there are a sufficiently bulky hollow cage,
Other metallic atoms (such as rare earth or alkaline-earth metal) can be filled in the cage in a manner of weak binding and generate perturbation action
And the lattice thermal conductivity for greatly scattering phonon, material being greatly lowered, thus there is preferable comprehensive thermoelectricity capability.
The conventional method for improving skutterudite conducting material thermoelectricity performance is to reduce lattice thermal conductivity by means such as filling doping,
To improve the thermoelectricity capability of material.In the prior art, people are often reached by changing type and the loading of filling atom
Optimize the purpose of conducting material thermoelectricity performance, but since the reduction of lattice thermal conductivity is usually associated with significantly increasing for carrier concentration and
Deteriorate the Seebeck coefficient of material, the performance of skutterudite-base thermoelectrical material is difficult to further mention by changing packed factor merely
The performance raising of height, thermoelectric material is restricted.
Summary of the invention
In consideration of it, the invention proposes a kind of skutterudite-base thermoelectrical materials and preparation method thereof, it is intended to solve the prior art
The performance of middle thermoelectric material is difficult to by changing the type for filling atom and loading merely come the problem of raising.
First aspect present invention proposes a kind of skutterudite-base thermoelectrical material, and the chemical formula of the thermoelectric material is as follows:
MxCoSb3+ yZnO, in which: the value range of x is 0≤x≤0.4, and 0 < y≤3%, y is that ZnO accounts for MxCoSb3The quality hundred of matrix
Score；M is one of alkali metal, alkaline-earth metal and rare earth element of doping or a variety of.
Further, in above-mentioned skutterudite-base thermoelectrical material, the chemical formula of the thermoelectric material is MxCoSb3+ yZnO, x=
0.3, y=3%.
Further, in above-mentioned skutterudite-base thermoelectrical material, the M is at least one of Na, K, Ca, Mg, Yb and Ce.
First aspect present invention provide skutterudite-base thermoelectrical material, by by suitable Zinc oxide nanoparticle equably
It is dispersed in skutterudite-base thermoelectrical material internal, the selectivity scattering to low frequency phonon can be enhanced, thus the side's of effectively reducing cobalt
The lattice thermal conductivity of mine base thermoelectricity material, simultaneously because zinc oxide carrier mobility with higher, can guarantee thermoelectricity material
The Seebeck coefficient and conductivity of material maintain in stable variation range, so that it is whole to be conducive to raising skutterudite-base thermoelectrical material
The thermoelectricity capability of body.
Second aspect of the present invention provides a kind of preparation method of skutterudite-base thermoelectrical material, comprising the following steps:
Step S1, prepares nano zine oxide；Step S2 prepares MxCoSb3Solid-state material；Step S3, by certain mass score
Nano zine oxide and MxCoSb3Solid-state material is compound, and obtained nano zine oxide is distributed in CoSb3Base thermoelectricity material base is intracorporal
Skutterudite-base thermoelectrical material.
Further, in the preparation method of above-mentioned skutterudite-base thermoelectrical material, the nano zine oxide step for preparing includes:
Step (1), is respectively configured certain density zinc solution and alkaline solution；Zinc solution is heated simultaneously under the first preset temperature
It is lasting to stir, aqueous slkali is added dropwise thereto in whipping process, continues stirring a period of time after completion of dropwise addition；Step (2), Xiang Suoshu
Proper amount of surfactant is added dropwise in the suspension that step (1) obtains, continues stirring a period of time after completion of dropwise addition；Step (3), will
After suspension heating reaction a period of time that the step (2) obtains, it is separated by solid-liquid separation, obtains sediment, to sediment
It washed, be dried, obtain nano zine oxide.
Further, in the preparation method of above-mentioned skutterudite-base thermoelectrical material, the preparation MxCoSb3Solid-state material step
It include: according to MxCoSb3Stoichiometric ratio, be put into vacuum tank after weighing metal M, Co, Sb mixing, be to slowly warm up to the
Two preset temperatures make its melting, and quenching forms solid-state material after keeping the temperature a period of time.
Further, in the preparation method of above-mentioned skutterudite-base thermoelectrical material, the nano zine oxide and the MxCoSb3
It includes: the powder that the solid-state material is ground into certain particle size that solid-state material, which carries out compound step, weighs certain mass point
Several nano zine oxides are added thereto, and after mixed-powder is ground a period of time, are placed in vacuum environment, in the 4th preset temperature
It is sintered for a period of time under preset pressure, obtains nano zine oxide and be distributed in CoSb3The intracorporal skutterudite of base thermoelectricity material base
Base thermoelectricity material.
Further, in the preparation method of above-mentioned skutterudite-base thermoelectrical material, in the nano zine oxide and described
MxCoSb3Before solid-state material progress is compound, quenched solid-state material is heated to third preset temperature, makes annealing treatment one section
Time.
Further, in the preparation method of above-mentioned skutterudite-base thermoelectrical material, the zinc salt is zinc chloride, zinc acetate and nitre
At least one of sour zinc；The alkaline matter is at least one of sodium hydroxide and potassium hydroxide；The surfactant is ten
Six alkyl trimethyl ammonium bromides, lauryl sodium sulfate or dodecyl sodium sulfate.
Further, in the preparation method of above-mentioned skutterudite-base thermoelectrical material, Zn in the zinc salt2+In the lye
OH-Molar concentration rate be 1:(1.7-2.4).
Further, in the preparation method of above-mentioned skutterudite-base thermoelectrical material, first preset temperature is (50-80)
℃。
Further, in the preparation method of above-mentioned skutterudite-base thermoelectrical material, second preset temperature is (800-
1500)℃；Soaking time is (10-20) h.
Further, in the preparation method of above-mentioned skutterudite-base thermoelectrical material, the 4th preset temperature is (550-700)
℃；The preset pressure is (40-80) MPa.
Further, in the preparation method of above-mentioned skutterudite-base thermoelectrical material, the third preset temperature is (500-700)
℃；The annealing time is (25-60) h.
The preparation method for the skutterudite-base thermoelectrical material that second aspect of the present invention provides, using the regulation of nano-particles reinforcement
Means, in CoSb3A small amount of nano granular of zinc oxide is added in base thermoelectricity material, increases thermoelectric material and the scattering of low frequency phonon is come
Thermal conductivity is reduced, and Seebeck coefficient and conductivity is kept to maintain in stable variation range simultaneously, to improve thermoelectricity
The performance of material.
Detailed description of the invention
Fig. 1 is the flow chart of skutterudite-base thermoelectrical material preparation method provided in an embodiment of the present invention；
Fig. 2 is the Seebeck system of the compound front and back skutterudite base thermoelectricity material of nano granular of zinc oxide in the embodiment of the present invention 3
Number variation with temperature figure；
Fig. 3 be the embodiment of the present invention 3 in the compound front and back skutterudite base thermoelectricity material of nano granular of zinc oxide resistivity with
The variation diagram of temperature；
Fig. 4 be the embodiment of the present invention 3 in the compound front and back skutterudite base thermoelectricity material of nano granular of zinc oxide thermal conductivity with
The variation diagram of temperature；
Fig. 5 is the ZT value of the compound front and back skutterudite base thermoelectricity material of nano granular of zinc oxide in the embodiment of the present invention 3 with temperature
The variation diagram of degree.
Specific embodiment
The following is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principle of the present invention, some improvements and modifications can also be made, these improvement and modification are also considered as
Protection scope of the present invention.
First aspect present invention proposes a kind of skutterudite-base thermoelectrical material, and the chemical formula of the thermoelectric material is as follows:
MxCoSb3+ yZnO, in which: the value range of x is 0≤x≤0.4, and 0 < y≤3%, y is that ZnO accounts for MxCoSb3The quality hundred of matrix
Score；M is one of alkali metal, alkaline-earth metal and rare earth element of doping or a variety of.M can for Na, K, Ca, Mg, Yb and
At least one of Ce.
Specifically, x can be 0.1,0.2,0.3, y can be 1%, 1.5%, 2%, 3% etc.；Preferably, x=0.3,
Y=3%.Zinc oxide is a kind of direct broad-band gap oxide semiconductor of typical N-shaped, its forbidden bandwidth is about 3.2- at room temperature
2.4eV；And has very high fusing point (1975 DEG C), there is stronger stability at high temperature, be the half of a kind of high conductivity
Conductor material, carrier mobility also with higher.Since excessive zinc oxide will form brittlement phase inside thermoelectric material,
The mechanical property of thermoelectric material is reduced, while will also result in the unfavorable phenomenon that material hinders carrier transport, reduces the electricity of material
Conductance and Seebeck coefficient, so that the thermoelectricity capability of thermoelectric material declines, therefore, in the present embodiment, with MxCoSb3For
The mass fraction of doping zinc-oxide is preferably 3% in the thermoelectric material of matrix.
First aspect present invention provide skutterudite-base thermoelectrical material, by by suitable Zinc oxide nanoparticle equably
It is dispersed in skutterudite-base thermoelectrical material internal, the selectivity scattering to low frequency phonon can be enhanced, thus the side's of effectively reducing cobalt
The lattice thermal conductivity of mine base thermoelectricity material, simultaneously because zinc oxide carrier mobility with higher, can guarantee thermoelectricity material
The Seebeck coefficient and conductivity of material maintain in stable variation range, so that it is whole to be conducive to raising skutterudite-base thermoelectrical material
The thermoelectricity capability of body.
Second aspect of the present invention provides a kind of preparation method of skutterudite-base thermoelectrical material, comprising the following steps:
Step S1, prepares nano zine oxide.
The step of preparing nano zine oxide includes following sub-step:
Certain density zinc solution and alkaline solution is respectively configured in sub-step S11；By zinc solution in the first default temperature
It is heated under degree and continues to stir, aqueous slkali is added dropwise in whipping process thereto, continue stirring a period of time after completion of dropwise addition.
Wherein, zinc salt is at least one of zinc chloride, zinc acetate and zinc nitrate；The alkaline matter is sodium hydroxide and hydrogen
At least one of potassium oxide.Zn in the zinc salt2+With OH in the lye-Molar concentration rate be 1:(1.7-2.4).To zinc salt
The first preset temperature when being heated is (50-80) DEG C；Preferably 60 DEG C.It can be by the way of constant temperature water bath heating to zinc
Salt is heated.
When zinc salt is zinc chloride, and lye is sodium hydroxide solution, the zinc solution (example of certain molar concentration is prepared first
Such as 1.0molL-1Liquor zinci chloridi), then configure certain density lye (such as 2.4molL-1Sodium hydroxide it is molten
Liquid), zinc solution is placed in heated at constant temperature in (50-80) DEG C water-bath later and is kept stirring, during stirring, is dripped thereto
Add lye, after lye is added dropwise, temperature is kept to continue to stir (20-60) min.
Alkaline environment is the necessary condition for growing ZnO, and in alkaline solution of sodium hydroxide, the concentration of alkaline solution is higher,
The solubility of ZnO is also higher.ZnO crystalline solid is grown under certain condition after reaching saturation.
Key reaction mechanism is as follows:
The reason is that caused by there is stronger polarizability due to zinc ion, under certain reaction condition, metal
Polarizability is stronger, to O2-Attraction it is stronger, thus be not easy to be formed its hydroxide, or the hydroxide generated is unstable
And it is extremely easy in decomposition as corresponding oxide.
Sub-step S12 is added dropwise proper amount of surfactant in the suspension obtained to sub-step 11, continues to stir after completion of dropwise addition
Mix a period of time.
Specifically, surfactant can be cetyl trimethylammonium bromide, lauryl sodium sulfate (SDS) or ten
Dialkyl sulfonates.Preferably, surfactant is cetyl trimethylammonium bromide (CTAB).CTAB is cationic
Activating agent, ionizing resulting cation in water has very long hydrophobic chain, exists between the growth unit of zincite crystal
Stronger electrostatic interaction, compound easy to form and the surface for being adsorbed on zinc oxide nucleus.Hydrophilic group outwardly, hydrophobic group inwardly,
Space barrier layer is formed in the colloid surface of entire reaction system, the reunion of presoma is less likely to occur.And in dry mistake
Cheng Zhong, with the desorption of dampening, the surfactant molecule hydrophobic group around colloid in water enters water phase towards gas phase, hydrophilic group,
Colloid surface forms monomolecular film, reduces the contact surface of water and air, strongly reduces the surface tension of colloid, it is therefore prevented that group
The generation of poly- phenomenon.Therefore the addition of CTAB, which can be effectively prevented between the Zinc oxide nanoparticle to be formed, reunites.
When it is implemented, the mass concentration of surfactant can be (4-10) g/L, preferably (4-7) g/L.Surface is living
The dosage of property agent can be determined according to response situation.
Sub-step S13 was separated by solid-liquid separation, is obtained after the suspension heating reaction a period of time for obtaining sub-step 12
To sediment, sediment is washed, is dried, nano zine oxide is obtained.
Specifically, in order to enable solution thermally equivalent, the suspension that sub-step 12 obtains can be placed in micro-wave oven
Microwave heating reaction 3-10min may advantageously facilitate the zinc hydroxide that do not decompose and be converted into zinc oxide by microwave heating.
Then granularity is can be obtained into the nano oxygen of 50-150nm or so after centrifugation, deionized water cleaning, drying in sediment
Change zinc particle.
Step S2 prepares MxCoSb3Solid-state material.
Specifically, according to MxCoSb3Stoichiometric ratio, weighing metal M, (metal M can be Na, K, Yb, Ca, Mg, Ce
At least one of), be put into vacuum tank after Co, Sb mixing, being to slowly warm up to the second preset temperature makes its melting, heat preservation one
Quenching forms solid-state material after the section time.Second preset temperature is (800-1500) DEG C；Preferably (900-1200) DEG C
When it is implemented, several metal materials are put into quartz glass tube, and sealing is vacuumized to quartz ampoule, prevents material
Material aoxidizes under high temperature process environments later.The quartz ampoule for loading raw material is placed in furnace at high temperature later, slowly
It is warming up to (800-1500) DEG C melting, so that a variety of materials keep liquid to be uniformly mixed, quenching forms solid-state after keeping the temperature 10-20h
Material.
In order to refine crystal grain, improve tissue to improve the mechanical performance of material, in the nano zine oxide and described
MxCoSb3Before solid-state material progress is compound, quenched solid-state material is heated to third preset temperature, makes annealing treatment one section
Time.
Wherein, third preset temperature is (500-700) DEG C, preferably (550-650) DEG C；Annealing time is (25-60) h,
Preferably (30-60) h.
Step S3, by the nano zine oxide and M of certain mass scorexCoSb3Solid-state material is compound, and nano zine oxide is made
It is distributed in CoSb3The intracorporal skutterudite-base thermoelectrical material of base thermoelectricity material base.
Specifically, the solid-state material to be ground into the powder of certain particle size, the nano oxygen of certain mass score is weighed
Change zinc particle to be added thereto, after mixed-powder is ground a period of time, be placed in vacuum environment, in the 4th preset temperature and presets
It is sintered a period of time under pressure, obtains nano granular of zinc oxide Dispersed precipitate in CoSb3The intracorporal side's cobalt of base thermoelectricity material base
Mine base thermoelectricity material.Wherein, nano zine oxide accounts for CoSb3The mass fraction of base thermoelectricity material is (0-3%).Described 4th is default
Temperature is (550-700) DEG C, preferably (550-650) DEG C；The preset pressure is (40-80) MPa, preferably (50-70)
Mpa；Sintering time can be (10-30) min, preferably (10-20) min.
When it is implemented, first by the block skutterudite-base thermoelectrical material fragmentation prepared, be ground up, sieved to obtain the left side 100nm
Right powder, then the nano granular of zinc oxide of certain mass score is weighed, pass through the technique and skutterudite-base thermoelectrical material of ball milling
It is uniformly mixed.After ball milling, it is anti-that the mixed-powder prepared is carried out to discharge plasma sintering under the 4th preset temperature
Should a period of time, the compound CoSb3 base thermoelectricity material of nano ZnO particles can be obtained, wherein discharge plasma sintering can be with
For hot pressed sintering or microwave sintering.
In the step, when carrying out ball-milling treatment to the solid-state material and nano zine oxide mixed-powder, revolving speed is (250-
650) r/min, the time of ball milling are (4-12) h.Preferably, the revolving speed of ball milling is (300-600) r/min, and the time of ball milling is
(5-10)h。
In the step, to the broken of material, sieving, ball milling and sintering treatment process, on the one hand can increase substantially
On the other hand the mechanical property of composite material can be such that nano particle is distributed in thermoelectric material matrix more uniform.
The preparation method for the skutterudite-base thermoelectrical material that second aspect of the present invention provides, using the regulation of nano-particles reinforcement
Means, in CoSb3A small amount of nano granular of zinc oxide is added in base thermoelectricity material, increases thermoelectric material and the scattering of low frequency phonon is come
Thermal conductivity is reduced, and Seebeck coefficient and conductivity is kept to maintain in stable variation range simultaneously, to improve thermoelectricity
The performance of material.
Skutterudite-base thermoelectrical material and preparation method thereof of the invention is said below by several specific embodiments
It is bright.
Embodiment 1
The 1molL of 50ml is respectively configured-1The liquor zinci chloridi of concentration and the 1.7molL of 50ml-1Sodium hydroxide it is molten
Configured liquor zinci chloridi is placed in heated at constant temperature in 60 DEG C of water-bath and continues to stir, then into liquor zinci chloridi by liquid
Sodium hydroxide solution is added dropwise dropwise, temperature is kept to continue to stir 30min after dripping.
Then the CTAB of the 4g/L mass concentration of 30ml is added dropwise into suspension obtained above, continues to stir after completion of dropwise addition
Mix 30min.
Then suspension obtained in the previous step is placed in micro-wave oven, after heating reaction 3min, product is centrifuged
Processing, and cleaned with deionized water and repeatedly obtain sediment；It puts the precipitate at 80 DEG C and dries 12h, obtain nano zine oxide
Particle.
Using the raw material of Chun Du≤99% as initial feed, according to chemical formula Yb0.1CoSb3Stoichiometric ratio, successively
Metal 0.829gYb, 2.823gCo, 17.5gSb are weighed, mixing material is put into quartz glass tube, and quartz ampoule is vacuumized
Sealing.
The quartz ampoule for loading raw material is placed in heating furnace, 900 DEG C of meltings are to slowly warm up to, quenches formation after keeping the temperature 10h
Solid-state material；Then quenched quartz ampoule is again placed in furnace, is heated to 550 DEG C and is made annealing treatment, and keeps the temperature 30h.
Block solid-state material after annealing is ground into granularity in the powder of 100nm or so, weighing mass fraction is 1%
Nano granular of zinc oxide is added thereto, and mixed powder is placed in ball mill, ball milling speed 300r/min, Ball-milling Time 5h.
Powder after ball milling is fitted into graphite jig, is burnt under vacuum conditions using discharge plasma agglomerating plant
Knot, sintering temperature are 550 DEG C, sintering time 10min, sintering pressure 50MPa, obtain nano granular of zinc oxide disperse point
It is distributed in CoSb3The intracorporal skutterudite-base thermoelectrical material of base thermoelectricity material base.
Embodiment 2
The 1molL of 50ml is respectively configured-1The zinc acetate solution of concentration and the 2molL of 50ml-1Sodium hydroxide it is molten
Configured zinc acetate solution is placed in heated at constant temperature in 60 DEG C of water-bath and continues to stir, then into zinc acetate solution by liquid
Sodium hydroxide solution is added dropwise dropwise, temperature is kept to continue to stir 30min after dripping.
Then the CTAB of the 7g/L mass concentration of 30ml is added dropwise into suspension obtained above, continues to stir after completion of dropwise addition
Mix 30min.
Then suspension obtained in the previous step is placed in micro-wave oven, after heating reaction 6min, product is centrifuged
Processing, and cleaned with deionized water and repeatedly obtain sediment；It puts the precipitate at 80 DEG C and dries 12h, obtain nano zine oxide
Particle.
Using the raw material of Chun Du≤99% as initial feed, according to chemical formula Yb0.2Ca0.1CoSb3Stoichiometric ratio,
Metal 1.658gYb, 0.192gCa, 2.833gCo, 17.5gSb are successively weighed, mixing material is put into quartz glass tube, and
Sealing is vacuumized to quartz ampoule.
The quartz ampoule for loading raw material is placed in heating furnace, 1100 DEG C of meltings are to slowly warm up to, quenches formation after keeping the temperature 15h
Solid-state material；Then quenched quartz ampoule is again placed in furnace, is heated to 60 DEG C and is made annealing treatment, and keeps the temperature 40h.
Block solid-state material after annealing is ground into granularity in the powder of 100nm or so, weighing mass fraction is 2%
Nano granular of zinc oxide is added thereto, and mixed powder is placed in ball mill, ball milling speed 400r/min, Ball-milling Time 8h.
Powder after ball milling is fitted into graphite jig, is burnt under vacuum conditions using discharge plasma agglomerating plant
Knot, sintering temperature are 600 DEG C, sintering time 15min, sintering pressure 60MPa, obtain nano granular of zinc oxide disperse point
It is distributed in CoSb3The intracorporal skutterudite-base thermoelectrical material of base thermoelectricity material base.
Embodiment 3
The 1molL of 50ml is respectively configured-1The zinc nitrate solution of concentration and the 2.4molL of 50ml-1Sodium hydroxide it is molten
Configured zinc nitrate solution is placed in heated at constant temperature in 60 DEG C of water-bath and continues to stir, then into zinc nitrate solution by liquid
Sodium hydroxide solution is added dropwise dropwise, temperature is kept to continue to stir 30min after dripping.
Then the SDS of the 10g/L mass concentration of 30ml is added dropwise into suspension obtained above, continues to stir after completion of dropwise addition
Mix 30min.
Then suspension obtained in the previous step is placed in micro-wave oven, after heating reaction 10min, product is centrifuged
Processing, and cleaned with deionized water and repeatedly obtain sediment；It puts the precipitate at 80 DEG C and dries 12h, obtain nano zine oxide
Particle.
Using the raw material of Chun Du≤99% as initial feed, according to chemical formula Yb0.3Ca0.1Ce0.1CoSb3Chemistry meter
Ratio is measured, metal 2.487gYb, 0.192g Ca, 0.671gCe, 2.833g Co, 17.5g Sb is successively weighed, mixing material is put
Enter in quartz glass tube, and sealing is vacuumized to quartz ampoule.
The quartz ampoule for loading raw material is placed in heating furnace, 1200 DEG C of meltings are to slowly warm up to, quenches formation after keeping the temperature 20h
Solid-state material；Then quenched quartz ampoule is again placed in furnace, is heated to 650 DEG C and is made annealing treatment, and keeps the temperature 60h.
Block solid-state material after annealing is ground into granularity in the powder of 100nm or so, weighing mass fraction is 3%
Nano granular of zinc oxide is added thereto, and mixed powder is placed in ball mill, ball milling speed 600r/min, Ball-milling Time 10h.
Powder after ball milling is fitted into graphite jig, is burnt under vacuum conditions using discharge plasma agglomerating plant
Knot, sintering temperature are 650 DEG C, sintering time 20min, sintering pressure 70MPa, obtain nano granular of zinc oxide disperse point
It is distributed in CoSb3The intracorporal skutterudite-base thermoelectrical material of base thermoelectricity material base.
Embodiment 4
The 1molL of 50ml is respectively configured-1The liquor zinci chloridi of concentration and the 1.7molL of 50ml-1Sodium hydroxide it is molten
Configured liquor zinci chloridi is placed in heated at constant temperature in 60 DEG C of water-bath and continues to stir, then into liquor zinci chloridi by liquid
Sodium hydroxide solution is added dropwise dropwise, temperature is kept to continue to stir 30min after dripping.
Then the CTAB of the 6g/L mass concentration of 30ml is added dropwise into suspension obtained above, continues to stir after completion of dropwise addition
Mix 30min.
Then suspension obtained in the previous step is placed in micro-wave oven, after heating reaction 3min, product is centrifuged
Processing, and cleaned with deionized water and repeatedly obtain sediment；It puts the precipitate at 80 DEG C and dries 12h, obtain nano zine oxide
Particle.
Using the raw material of Chun Du≤99% as initial feed, according to chemical formula Yb0.1CoSb3Stoichiometric ratio, successively
Metal 0.829gYb, 2.833gCo, 17.5gSb are weighed, mixing material is put into quartz glass tube, and quartz ampoule is vacuumized
Sealing.
The quartz ampoule for loading raw material is placed in heating furnace, 1500 DEG C of meltings are to slowly warm up to, quenches formation after keeping the temperature 10h
Solid-state material；Then quenched quartz ampoule is again placed in furnace, is heated to 500 DEG C and is made annealing treatment, and keeps the temperature 25h.
Block solid-state material after annealing is ground into granularity in the powder of 150nm or so, weighing mass fraction is 1.5%
Nano granular of zinc oxide be added thereto, mixed powder is placed in ball mill, ball milling speed 250r/min, Ball-milling Time is
12h。
Powder after ball milling is fitted into graphite jig, is burnt under vacuum conditions using discharge plasma agglomerating plant
Knot, sintering temperature are 500 DEG C, sintering time 10min, sintering pressure 40MPa, obtain nano granular of zinc oxide disperse point
It is distributed in CoSb3The intracorporal skutterudite-base thermoelectrical material of base thermoelectricity material base.
Embodiment 5
The 1molL of 50ml is respectively configured-1The liquor zinci chloridi of concentration and the 1.7molL of 50ml-1Sodium hydroxide it is molten
Configured liquor zinci chloridi is placed in heated at constant temperature in 60 DEG C of water-bath and continues to stir, then into liquor zinci chloridi by liquid
Sodium hydroxide solution is added dropwise dropwise, temperature is kept to continue to stir 30min after dripping.
Then the CTAB of the 7g/L mass concentration of 30ml is added dropwise into suspension obtained above, continues to stir after completion of dropwise addition
Mix 30min.
Then suspension obtained in the previous step is placed in micro-wave oven, after heating reaction 3min, product is centrifuged
Processing, and cleaned with deionized water and repeatedly obtain sediment；It puts the precipitate at 80 DEG C and dries 12h, obtain nano zine oxide
Particle.
Using the raw material of Chun Du≤99% as initial feed, according to chemical formula Yb0.1CoSb3Stoichiometric ratio, successively
Metal 0.829gYb, 2.833gCo, 17.5gSb are weighed, mixing material is put into quartz glass tube, and quartz ampoule is vacuumized
Sealing.
The quartz ampoule for loading raw material is placed in heating furnace, 800 DEG C of meltings are to slowly warm up to, quenches formation after keeping the temperature 10h
Solid-state material；Then quenched quartz ampoule is again placed in furnace, is heated to 550 DEG C and is made annealing treatment, and keeps the temperature 30h.
Block solid-state material after annealing is ground into granularity in the powder of 50nm or so, weighing mass fraction is 1%
Nano granular of zinc oxide is added thereto, and mixed powder is placed in ball mill, ball milling speed 650r/min, Ball-milling Time 4h.
Powder after ball milling is fitted into graphite jig, is burnt under vacuum conditions using discharge plasma agglomerating plant
Knot, sintering temperature are 700 DEG C, sintering time 30min, sintering pressure 80MPa, obtain nano granular of zinc oxide disperse point
It is distributed in CoSb3The intracorporal skutterudite-base thermoelectrical material of base thermoelectricity material base.
By taking embodiment 3 as an example, the compound skutterudite-base thermoelectrical material of nano granular of zinc oxide of preparation is measured and calculated
Conductivity, Seebeck coefficient, thermal conductivity and ZT value variation with temperature relationship, while the cobalt antimony side to nano zine oxide before compound
The relationship that the related coefficient of cobalt ore sill varies with temperature is tested and is calculated, as a result as shown in Figure 1 to Figure 4.
As shown in Fig. 2, the compound cobalt antimony-based square cobalt mineral thermoelectric material of Zinc oxide nanoparticle is compared to multiple at identical temperature
Cobalt-stibium based thermoelectric material before conjunction, Seebeck coefficient are improved, such as at 500 DEG C, before Zinc oxide nanoparticle is compound
The absolute value of the Seebeck coefficient of cobalt antimony-based square cobalt mineral thermoelectric material afterwards increases to 182 μ V/K from 176 μ V/K；As shown in figure 3,
At identical temperature, the compound cobalt antimony-based square cobalt mineral thermoelectric material of Zinc oxide nanoparticle is compared to compound preceding cobalt-stibium based thermoelectric material
Material resistivity is improved, and conductivity reduces；As shown in figure 4, at identical temperature, the compound cobalt antimony base of Zinc oxide nanoparticle
Skutterudite thermoelectric material is reduced compared to compound preceding cobalt-stibium based thermoelectric material, thermal conductivity, such as at 500 DEG C, oxygen
The thermal conductivity for changing the cobalt antimony-based square cobalt mineral thermoelectric material of the compound front and back of zinc nanoparticles drops to 3.21W/mK from 4.08W/mK；Such as figure
Shown in 5, at identical temperature, the compound cobalt antimony-based square cobalt mineral thermoelectric material of Zinc oxide nanoparticle is compared to compound preceding cobalt antimony base
The thermoelectric figure of merit ZT of thermoelectric material is increased.Such as at 500 DEG C, the cobalt antimony base side of the compound front and back of Zinc oxide nanoparticle
The ZT value of cobalt ore thermoelectric material increases 1.01 from 0.86.
It can be seen from the above the thermal conductivity of the thermoelectric material of preparation of the embodiment of the present invention is reduced, Seebeck system
Number is improved, so that the thermoelectric figure of merit of thermoelectric material is improved, optimizes the thermoelectricity capability of material.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (14)
1. a kind of skutterudite-base thermoelectrical material, which is characterized in that the chemical formula of the thermoelectric material is as follows: MxCoSb3+ yZnO,
In: the value range of x is 0≤x≤0.4, and 0 < y≤3%, y is that ZnO accounts for MxCoSb3The mass percent of matrix；M is doping
One of alkali metal, alkaline-earth metal and rare earth element are a variety of.
2. skutterudite-base thermoelectrical material according to claim 1, which is characterized in that the chemical formula of the thermoelectric material is
MxCoSb3+ yZnO, x=0.3, y=3%.
3. skutterudite-base thermoelectrical material according to claim 1 or 2, which is characterized in that the M is Na, K, Ca, Mg, Yb
At least one of with Ce.
4. a kind of preparation method of skutterudite-base thermoelectrical material as claimed any one in claims 1 to 3, which is characterized in that
The following steps are included:
Prepare nano zine oxide；
Prepare MxCoSb3Solid-state material；
By the nano zine oxide and M of certain mass scorexCoSb3Solid-state material is compound, and obtained nano zine oxide is distributed in CoSb3
The intracorporal skutterudite-base thermoelectrical material of base thermoelectricity material base.
5. the preparation method of skutterudite-base thermoelectrical material according to claim 4, which is characterized in that the preparation nano oxygen
Changing zinc step includes:
Step (1), is respectively configured certain density zinc solution and alkaline solution；Zinc solution is added under the first preset temperature
Heat simultaneously continues to stir, and aqueous slkali is added dropwise in whipping process thereto, continues stirring a period of time after completion of dropwise addition；
Step (2) is added dropwise proper amount of surfactant in the suspension that Xiang Suoshu step (1) obtains, continues to stir after completion of dropwise addition
For a period of time；
Step (3) was separated by solid-liquid separation, is sunk after the suspension heating reaction a period of time for obtaining the step (2)
Starch is washed sediment, is dried, obtains nano zine oxide.
6. the preparation method of skutterudite-base thermoelectrical material according to claim 4, which is characterized in that the preparation MxCoSb3
Solid-state material step includes:
According to MxCoSb3Stoichiometric ratio, weigh metal M, Co, Sb mixing after be put into vacuum tank, be to slowly warm up to second
Preset temperature makes its melting, and quenching forms solid-state material after keeping the temperature a period of time.
7. the preparation method of skutterudite-base thermoelectrical material according to claim 4, which is characterized in that the nano zine oxide
With the MxCoSb3Solid-state material carries out compound step
The solid-state material is ground into the powder of certain particle size, the nano zine oxide for weighing certain mass score is added thereto,
It after mixed-powder is ground a period of time, is placed in vacuum environment, when being sintered one section under the 4th preset temperature and preset pressure
Between, it obtains nano zine oxide and is distributed in CoSb3The intracorporal skutterudite-base thermoelectrical material of base thermoelectricity material base.
8. the preparation method of skutterudite-base thermoelectrical material according to claim 6, which is characterized in that described nano oxidized
Zinc and the MxCoSb3Before solid-state material progress is compound, quenched solid-state material is heated to third preset temperature, is annealed
Processing a period of time.
9. the preparation method of skutterudite-base thermoelectrical material according to claim 5, which is characterized in that the zinc salt is chlorination
At least one of zinc, zinc acetate and zinc nitrate；The alkaline matter is at least one of sodium hydroxide and potassium hydroxide；The table
Face activating agent is cetyl trimethylammonium bromide, lauryl sodium sulfate or dodecyl sodium sulfate.
10. the preparation method of skutterudite-base thermoelectrical material according to claim 9, which is characterized in that Zn in the zinc salt2+
With OH in the lye-Molar concentration rate be 1:(1.7-2.4).
11. the preparation method of skutterudite-base thermoelectrical material according to claim 5, which is characterized in that described first is default
Temperature is (50-80) DEG C.
12. the preparation method of skutterudite-base thermoelectrical material according to claim 6, which is characterized in that described second is default
Temperature is (800-1500) DEG C；Soaking time is (10-20) h.
13. the preparation method of skutterudite-base thermoelectrical material according to claim 7, which is characterized in that the described 4th is default
Temperature is (550-700) DEG C；The preset pressure is (40-80) MPa.
14. the preparation method of skutterudite-base thermoelectrical material according to claim 8, which is characterized in that the third is default
Temperature is (500-700) DEG C；The annealing time is (25-60) h.
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