CN109087987A - A kind of α-MgAgSb base nano composite thermoelectric materials and preparation method thereof - Google Patents
A kind of α-MgAgSb base nano composite thermoelectric materials and preparation method thereof Download PDFInfo
- Publication number
- CN109087987A CN109087987A CN201810709524.6A CN201810709524A CN109087987A CN 109087987 A CN109087987 A CN 109087987A CN 201810709524 A CN201810709524 A CN 201810709524A CN 109087987 A CN109087987 A CN 109087987A
- Authority
- CN
- China
- Prior art keywords
- mgagsb
- snte
- composite thermoelectric
- nano composite
- powder
- 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
- 239000000463 material Substances 0.000 title claims abstract description 76
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910005642 SnTe Inorganic materials 0.000 claims abstract description 42
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000002086 nanomaterial Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 63
- 238000005245 sintering Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 15
- 238000000137 annealing Methods 0.000 claims description 13
- 238000009768 microwave sintering Methods 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 239000004567 concrete Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000005619 thermoelectricity Effects 0.000 abstract description 14
- 239000012535 impurity Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 239000002019 doping agent Substances 0.000 abstract description 2
- 238000010348 incorporation Methods 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000005457 optimization Methods 0.000 description 6
- 238000004663 powder metallurgy Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 241000549556 Nanos Species 0.000 description 1
- 241000209094 Oryza Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention belongs to the preparation technical fields of thermoelectric material, disclose a kind of α-MgAgSb base nano composite thermoelectric materials and preparation method thereof, wherein, the composite thermoelectric material is the incorporation SnTe nano material in undoped α-MgAgSb thermoelectric material, thus obtains α-MgAgSb base nano composite thermoelectric materials.The present invention is improved by composition to dopant and corresponding preparation method, by mixing nano combined narrow band gap p-type SnTe semiconductor into single-phase α-MgAgSb material, a kind of α-MgAgSb system nano composite thermoelectric materials have been prepared, the thermoelectricity capability of α-MgAgSb sill greatly improved, α-MgAgSb thermoelectric material compared to conventional impurity promotes significant effect, has good industrialized production and application prospect.
Description
Technical field
The invention belongs to the preparation technical fields of thermoelectric material, nano combined more particularly, to a kind of α-MgAgSb base
Thermoelectric material and preparation method thereof, the composite thermoelectric material are a kind of α-MgAgSb system novel nanos with novel ingredients design
Composite thermoelectric material.
Background technique
The maximal efficiency of its energy of the thermo-electric generation of thermoelectric material conversion is limited to the thermoelectric figure of merit ZT of thermoelectric material:
Based on above formula, the Seebeck coefficient (S) of material under thermoelectric figure of merit ZT, with the operating temperature, conductivity (σ) and
Thermal conductivity (κ) is related, in the parameter that these three are mutually coupled, S2σ characterizes the electronic transport ability of material, referred to as power because
Sub (Power factor, write a Chinese character in simplified form PF), and κ characterizes the thermotransport ability of material.Therefore, it is converted to obtain maximum energy
Efficiency, scientific research personnel are intended to have extremely low thermal conductivity again while thermoelectric material possesses high electronic transport ability.
MgAgSb (hereinafter referred to as MAS) alloy has complicated phase transformation, is respectively present high-temperature-phase γ-MgAgSb, medium temperature phase β-
MgAgSb and room temperature phase α-MgAgSb, but only room temperature phase α-MgAgSb shows good thermoelectricity capability.α-MgAgSb
Based alloy has component earth's crust rich reserves, is a kind of very potential nearly room-temperature zone thermoelectricity the advantages of haveing excellent performance
Material.For α-MgAgSb material, α-MgAgSb matrix that existing high melt method and mechanical alloying method are prepared (see
①Ying,P.,Li,X.,Wang,Y.,Yang,J.,Fu,C.,Zhang,W.,Zhu,T,et al.Advanced
Functional Materials, 2017,27 (1), 1604145;②Liu,Z.,Wang,Y.,Mao,J.,Geng,H.,
Shuai, J., Wang, Y., Ren, Z, et al.Advanced Energy Materials, 2016,6 (7), 1502269.), when
Before there are following main problems: (1) α-MgAgSb conductivity is lower, and power factor is lower.(2) current conventional impurity means
Promotion amplitude to the power factor of α-MgAgSb is about 10%~20%, and effect is not significant.(3) conventional impurity element
Such as Pb, La, Yb element have the shortcomings that toxicity it is big, not environmentally, high cost.Therefore, a kind of energy conservation and environmental protection, low cost are looked for simultaneously
And guarantee have the α-MgAgSb system nano composite thermoelectric materials of excellent thermoelectricity capability extremely important.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the purpose of the present invention is to provide a kind of α-MgAgSb Ji Na
Rice composite thermoelectric material and preparation method thereof, wherein particularly by dopant composition and corresponding preparation method change
Into a kind of α-has been prepared by mixing nano combined narrow band gap p-type SnTe semiconductor into single-phase α-MgAgSb material
MgAgSb system nano composite thermoelectric materials, greatly improved the thermoelectricity capability of α-MgAgSb sill, obtain with high electricity
The thermoelectric material of transport capability, the α-MgAgSb thermoelectric material compared to conventional impurity promote significant effect, have very
Good industrialized production and application prospect.
To achieve the above object, according to one aspect of the present invention, a kind of nano combined thermoelectricity of α-MgAgSb base is provided
Material, which is characterized in that the composite thermoelectric material is the incorporation SnTe nano material in undoped α-MgAgSb thermoelectric material,
Thus α-MgAgSb base nano composite thermoelectric materials are obtained.
As present invention further optimization, in the α-MgAgSb base nano composite thermoelectric materials, Mg element and SnTe
The molar ratio of the two is (1-x): x, x≤0.04;
Preferably, described its chemical composition of undoped α-MgAgSb thermoelectric material meets the atomic ratio of Mg, Ag, Sb three
It is 1: 1: 1;The partial size of the SnTe nano material is no more than 100nm, preferably 20~50nm.
It is another aspect of this invention to provide that the present invention provides a kind of preparations of α-MgAgSb base nano composite thermoelectric materials
Method, which is characterized in that specifically includes the following steps:
(1) stoichiometrically (MgAgSb) by MgAgSb powder and SnTe nanometer powder1-x(SnTe)xIt is mixed after proportion
Uniformly obtain composite powder, then by this it is compound be fitted into mold, in vacuum sintering funace under the protection of inert gas
It is compact formed to carry out hot pressed sintering, sintering temperature is 450 DEG C~500 DEG C, and soaking time is not less than 30min, the pressure of holding stage
By force be not less than 120MPa, thus obtain it is compact formed after block;
Wherein, x≤0.04;
(2) block that the step (1) obtains is placed in vacuum microwave sintering furnace, is passed through inert gas guarantor
Shield, progress microwave sintering annealing at least 5 days is then handled at 270 DEG C~300 DEG C, inside can be obtained and be mixed with SnTe nanometers
α-MgAgSb base the nano composite thermoelectric materials of material.
As present invention further optimization, in the step (1), the MgAgSb powder is preferably prepared as follows
It obtains:
Mg elemental powders, Ag elemental powders and Sb elemental powders by purity not less than 99.9% press atomic ratio Mg: Ag: Sb
=1: 0.97: 0.99 proportion, is fitted into graphite crucible, is placed in vacuum microwave sintering furnace, be filled with inertia mobility atmosphere, so
After be warming up to 950 DEG C~1000 DEG C heat preservation at least 20min and carry out microwave meltings, obtain initial melted ingot after cooling, then, will be described
MgAgSb powder can be obtained after grinding in initial melted ingot.
As present invention further optimization, the microwave melting preferably keeps the temperature 40min at 950 DEG C.
As present invention further optimization, in the step (1), sintering used by the hot pressed sintering is compact formed
Temperature is 450 DEG C, soaking time 30min, and holding stage pressure is 240Mpa.
As present invention further optimization, in the step (2), the microwave sintering annealing is specifically at 270 DEG C
Isothermal annealing 5 days.
As present invention further optimization, in the step (1), the SnTe nanometer powder preferably uses hydro-thermal method
It is prepared, the concrete processing procedure of hydro-thermal method is as follows:
By SnCl2·2H2O, Te powder, KOH and KBH4Four by uniformly mixing juxtaposition after the molar ratio weighing of 1:1:8:2
In autoclave, it is subsequently poured into N, reaction kettle sealing is put into baking oven by N- dimethylformamide, and hydro-thermal is anti-at 150 DEG C
It answers 12 hours, is centrifuged after cooling, SnTe nanometer powder can be obtained in drying;Preferably, the partial size of these SnTe nano materials is not
More than 100nm, more preferably 20~50nm.
The present invention prepares synthesis α-MgAgSb system nano composite thermoelectric materials, with α-prepared by existing high melt
MgAgSb sill is compared, can obtain it is following the utility model has the advantages that
(1) present invention is on the basis of prepare single-phase α-MgAgSb, nano combined SnTe, and obtaining a kind of α-MgAgSb is to receive
Rice composite thermoelectric material, the nano composite thermoelectric materials are made of nano material inside it, and chemical composition meets
(MgAgSb)1-x(SnTe)x.The present invention also by preferably being controlled doping ratio x, makes x≤0.04, further ensures
The thermoelectricity capability of α-MgAgSb base nano composite thermoelectric materials;By taking x is 0.03 as an example, under 548K (MgAgSb)0.97(SnTe)0.03
Its electricalresistivityρ of sample is 1.462 × 10-5Ω .m, thermal conductivity κ are 1.090W/mK, and Seebeck coefficient α is 164.97 μ V/K, power
The factor is 1861 μ Wm-1K-2, maximum thermoelectric figure of merit ZT is 0.94, improves 50% He respectively compared to single-phase α-MgAgSb matrix
47%.
(2) α-MgAgSb system nano composite thermoelectric materials of present invention preparation synthesis break conventional impurity means, benefit
With nano combined narrow band gap p-type semiconductor material, to the promotion significant effect of power factor.
(3) α-MgAgSb system's nano composite thermoelectric materials of present invention preparation synthesis are based on microwave technology principle, in material
Inside generates heating, and manufacturing cycle is greatly shortened, with energy conservation and environmental protection, low cost and the thermoelectricity capability for promoting 47%, tool
There is good thermo-electric device application prospect.
The present invention prepares α-MgAgSb base nano composite thermoelectric materials using microwave sintering process, and to microwave sintering work
Conditional parameter used by skill (such as treatment temperature and time) optimizes, and can reduce energy consumption, shorten α-MgAgSb base nanometer
The preparation time of composite thermoelectric material provided a kind of nano composite thermoelectric materials preparation side of efficient α-MgAgSb system to 5 days
Method.
The present invention further preferably uses microwave melting technique to prepare α-MgAgSb sill, its treatment temperature of microwave melting is
950 DEG C~1000 DEG C, the present invention also passes through the atomic ratio proportion of control Mg elemental powders, Ag elemental powders and Sb elemental powders,
Mg elemental powders, Ag elemental powders and Sb elemental powders will be matched by atomic ratio Mg: Ag: Sb=1:0.97:0.99, be led to
It crosses using slight excess of Mg, the volatilization of Mg in subsequent processes can be made up, it is ensured that obtain single-phase α-MgAgSb compound
(single-phase α-MgAgSb compound generally refers to the α-MgAgSb main phase content in product and is not less than 95%), can further really
Protect its thermoelectricity capability of α-MgAgSb base nano composite thermoelectric materials obtained.
Detailed description of the invention
In Fig. 1, (a) is the X-ray diffractogram of the SnTe nanometer powder of hydro-thermal method preparation, (b) is contained for compound difference SnTe
The X-ray diffractogram of the α-MgAgSb pyroelectric material of amount.
Fig. 2 is relational graph of the composite thermoelectric material resistivity with composite S nTe content and temperature change.
Fig. 3 is relational graph of the composite thermoelectric material Seebeck coefficient with composite S nTe content and temperature change.
Fig. 4 is relational graph of the composite thermoelectric material thermal conductivity with composite S nTe content and temperature change.
(a), (b) are respectively composite thermoelectric material power factor, thermoelectric figure of merit with composite S nTe content and temperature change in Fig. 5
The relational graph of change.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
α-MgAgSb base nano composite thermoelectric materials in the present invention specifically pass through first for preparation method is summarized
To the progress microwave melting of original composition material, the pure phase SnTe nanometer powder that compound different content is synthetically prepared based on hydro-thermal method,
Then by hot pressed sintering densification molding, then by the block progress microwave annealing processing of sinter molding, α-is eventually formed
MgAgSb system nano composite thermoelectric materials.
The following are specific embodiments:
Embodiment 1
(1) first by the SnCl of 10mmol2·2H2O, the KBH of the Te powder of 10mmol, the KOH and 20mmol of 80mmol4
Uniformly mixing is placed in the autoclave of 100ml after precise, is subsequently poured into the N of 90ml, N- dimethylformamide will be anti-
Kettle sealing is answered to be put into baking oven.Holding temperature is 150 DEG C, and soaking time is 12 hours, is centrifuged product after cooling, does
It is dry, obtain SnTe nanometer powder.
(2) then high-purity (>=99.9%) raw material powder is matched by atomic ratio Mg: Ag: Sb=1: 0.97: 0.99, is passed through
Microwave melting-furnace is cold-and grinding technics obtains MgAgSb powder.It is packed into dedicated powder metallurgy steel die, carries out hot pressed sintering
It is compact formed, entire sintering process argon atmosphere protection.
Specifically may is that each metal simple-substance raw material powder by high-purity (>=99.9%) by atomic ratio Mg: Ag: Sb=1:
0.97: 0.99 proportion, is fitted into high purity graphite crucible, is placed in vacuum microwave sintering furnace, be filled with inertia mobility atmosphere, fastly
Speed is warming up to 950 DEG C, and heating rate 20 DEG C/min, soaking time 40min, furnace is cold to obtain initial melted ingot.Above-mentioned melted ingot is ground
Alloy powder later be packed into dedicated powder metallurgy steel die or sintered-carbide die (for example, can by the ingot casting of acquisition into
Row concussion ball mill grinding, is then put into stainless steel mould for powder, the shape of mold can adjust according to actual needs, such as can
Think disk mold etc.), progress hot pressed sintering is compact formed in vacuum sintering funace, and 450 DEG C of sintering temperature, heating rate
10 DEG C/min, keep the temperature 30min, holding stage pressure 240MPa, entire sintering process argon atmosphere protection.
(3) block after will be compact formed is placed in microwave agglomerating furnace, is passed through inert gas shielding, 270 DEG C (i.e.
543K) isothermal annealing 5 days obtain α-MgAgSb basis material (i.e. single-phase α-MgAgSb material).Thermoelectricity capability is surveyed at 548K
Examination, the electricalresistivityρ of matrix sample are 2.282 × 10-5Ω .m, thermal conductivity κ are 1.072W/mK, and Seebeck coefficient α is 168.52 μ
V/K, thermoelectric figure of merit ZT are 0.64.
Embodiment 2
(1) first by the SnCl of 10mmol2·2H2O, the KBH of the Te powder of 10mmol, the KOH and 20mmol of 80mmol4
Uniformly mixing is placed in the autoclave of 100ml after precise, is subsequently poured into the N of 90ml, N- dimethylformamide will be anti-
Kettle sealing is answered to be put into baking oven.Holding temperature is 150 DEG C, and soaking time is 12 hours, is centrifuged product after cooling, does
It is dry, obtain SnTe nanometer powder.
(2) then high-purity (>=99.9%) raw material powder is matched by atomic ratio Mg: Ag: Sb=1: 0.97: 0.99, is passed through
Microwave melting-furnace is cold-and grinding technics obtains MgAgSb powder.According to stoichiometric ratio (MgAgSb)0.99(SnTe)0.01It is accurate to claim
MgAgSb and SnTe nanometer powder is measured, obtains composite powder after evenly mixing;It is packed into dedicated powder metallurgy steel die, is carried out
Hot pressed sintering is compact formed, entire sintering process argon atmosphere protection.
(3) block after will be compact formed is placed in microwave agglomerating furnace, is passed through inert gas shielding, 270 DEG C of isothermals
Annealing 5 days obtains α-MgAgSb basis material.Thermoelectricity capability is tested at 548K, and the electricalresistivityρ of matrix sample is 3.59 ×
10-5Ω .m, thermal conductivity κ are 1.021W/mK, and Seebeck coefficient α is 184.34 μ V/K, and thermoelectric figure of merit ZT is 0.6.
Embodiment 3
(1) first by the SnCl of 10mmol2·2H2O, the KBH of the Te powder of 10mmol, the KOH and 20mmol of 80mmol4
Uniformly mixing is placed in the autoclave of 100ml after precise, is subsequently poured into the N of 90ml, N- dimethylformamide will be anti-
Kettle sealing is answered to be put into baking oven.Holding temperature is 150 DEG C, and soaking time is 12 hours, is centrifuged product after cooling, does
It is dry, obtain SnTe nanometer powder.
(2) then high-purity (>=99.9%) raw material powder is matched by atomic ratio Mg: Ag: Sb=1: 0.97: 0.99, is passed through
Microwave melting-furnace is cold-and grinding technics obtains MgAgSb powder.According to stoichiometric ratio (MgAgSb)0.98(SnTe)0.02It is accurate to claim
MgAgSb and SnTe nanometer powder is measured, obtains composite powder after evenly mixing;It is packed into dedicated powder metallurgy steel die, is carried out
Hot pressed sintering is compact formed, entire sintering process argon atmosphere protection.
(3) block after will be compact formed is placed in microwave agglomerating furnace, is passed through inert gas shielding, 270 DEG C of isothermals
Annealing 5 days obtains α-MgAgSb basis material.Thermoelectricity capability is tested at 548K, and the electricalresistivityρ of matrix sample is 2.211 ×
10-5Ω .m, thermal conductivity κ are 1.053W/mK, and Seebeck coefficient α is 172.66 μ V/K, and thermoelectric figure of merit ZT is 0.70.
Embodiment 4
(1) first by the SnCl of 10mmol2·2H2O, the KBH of the Te powder of 10mmol, the KOH and 20mmol of 80mmol4
Uniformly mixing is placed in the autoclave of 100ml after precise, is subsequently poured into the N of 90ml, N- dimethylformamide will be anti-
Kettle sealing is answered to be put into baking oven.Holding temperature is 150 DEG C, and soaking time is 12 hours, is centrifuged product after cooling, does
It is dry, obtain SnTe nanometer powder.
(2) then high-purity (>=99.9%) raw material powder is matched by atomic ratio Mg: Ag: Sb=1: 0.97: 0.99, is passed through
Microwave melting-furnace is cold-and grinding technics obtains MgAgSb powder.According to stoichiometric ratio (MgAgSb)0.97(SnTe)0.03It is accurate to claim
MgAgSb and SnTe nanometer powder is measured, obtains composite powder after evenly mixing;It is packed into dedicated powder metallurgy steel die, is carried out
Hot pressed sintering is compact formed, entire sintering process argon atmosphere protection.
(3) block after will be compact formed is placed in microwave agglomerating furnace, is passed through inert gas shielding, 270 DEG C of isothermals
Annealing 5 days obtains α-MgAgSb basis material.Thermoelectricity capability is tested at 548K, and the electricalresistivityρ of matrix sample is 1.462 ×
10-5Ω .m, thermal conductivity κ are 1.090W/mK, and Seebeck coefficient α is 164.97 μ V/K, and thermoelectric figure of merit ZT is 0.94.
Embodiment 5
(1) first by the SnCl of 10mmol2·2H2O, the KBH of the Te powder of 10mmol, the KOH and 20mmol of 80mmol4
Uniformly mixing is placed in the autoclave of 100ml after precise, is subsequently poured into the N of 90ml, N- dimethylformamide will be anti-
Kettle sealing is answered to be put into baking oven.Holding temperature is 150 DEG C, and soaking time is 12 hours, is centrifuged product after cooling, does
It is dry, obtain SnTe nanometer powder.
(2) then high-purity (>=99.9%) raw material powder is matched by atomic ratio Mg: Ag: Sb=1: 0.97: 0.99, is passed through
Microwave melting-furnace is cold-and grinding technics obtains MgAgSb powder.According to stoichiometric ratio (MgAgSb)0.96(SnTe)0.04It is accurate to claim
MgAgSb and SnTe nanometer powder is measured, obtains composite powder after evenly mixing;It is packed into dedicated powder metallurgy steel die, is carried out
Hot pressed sintering is compact formed, entire sintering process argon atmosphere protection.
(3) block after will be compact formed is placed in microwave agglomerating furnace, is passed through inert gas shielding, 270 DEG C of isothermals
Annealing 5 days obtains α-MgAgSb basis material.Thermoelectricity capability is tested at 548K, and the electricalresistivityρ of matrix sample is 1.309 ×
10-5Ω .m, thermal conductivity κ are 1.16W/mK, and Seebeck coefficient α is 153.8 μ V/K, and thermoelectric figure of merit ZT is 0.85.
The present invention is carried out example verifying, each operation with regard to different microwave smelting times (20min~40min) respectively
Condition is as shown in table 1.
Table 1
The present invention is also carried out example with regard to Parameter Conditions employed in different microwave meltings, sintering annealing respectively and tests
Card, the operating condition of each embodiment are as shown in table 2.
Table 2
Inert atmosphere of the present invention can also use other inert gases other than argon gas.Institute of the present invention
Its partial size of SnTe nanometer powder used be less than 100nm, preferably 20 to 50nm;In addition to using the method system in above-described embodiment
Outside standby SnTe nanometer powder, it can also be prepared with reference to other preparation methods in the prior art, as long as its partial size is less than
100nm.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (8)
1. a kind of α-MgAgSb base nano composite thermoelectric materials, which is characterized in that the composite thermoelectric material is in undoped α-
SnTe nano material is mixed in MgAgSb thermoelectric material, thus obtains α-MgAgSb base nano composite thermoelectric materials.
2. α-MgAgSb base nano composite thermoelectric materials as described in claim 1, which is characterized in that the α-MgAgSb base nanometer
In composite thermoelectric material, the molar ratio of both Mg element and SnTe are (1-x): x, x≤0.04;
Preferably, the atomic ratio that described its chemical composition of undoped α-MgAgSb thermoelectric material meets Mg, Ag, Sb three is 1:
1:1;The partial size of the SnTe nano material is no more than 100nm, preferably 20~50nm.
3. a kind of preparation method of α-MgAgSb base nano composite thermoelectric materials, which is characterized in that specifically includes the following steps:
(1) stoichiometrically (MgAgSb) by MgAgSb powder and SnTe nanometer powder1-x(SnTe)xIt is uniformly mixed after proportion
To composite powder, then by this it is compound be fitted into mold, in vacuum sintering funace under the protection of inert gas carry out heat
Densified sintering product molding is pressed, sintering temperature is 450 DEG C~500 DEG C, and soaking time is not less than 30min, and the pressure of holding stage is not low
In 120MPa, thus obtain it is compact formed after block;
Wherein, x≤0.04;
(2) block that the step (1) obtains is placed in vacuum microwave sintering furnace, is passed through inert gas shielding, so
Progress microwave sintering annealing at least 5 days is handled at 270 DEG C~300 DEG C afterwards, inside can be obtained and be mixed with SnTe nano material
α-MgAgSb base nano composite thermoelectric materials.
4. the preparation method of α-MgAgSb base nano composite thermoelectric materials as claimed in claim 3, which is characterized in that the step
(1) in, the MgAgSb powder is preferably prepared as follows to obtain:
Mg elemental powders, Ag elemental powders and Sb elemental powders by purity not less than 99.9% press atomic ratio Mg: Ag: Sb=1:
0.97: 0.99 proportion, is fitted into graphite crucible, is placed in vacuum microwave sintering furnace, be filled with inertia mobility atmosphere, then rise
Temperature carries out microwave melting to 950 DEG C~1000 DEG C heat preservation at least 20min, obtains initial melted ingot after cooling, then, will be described initial
MgAgSb powder can be obtained in melted ingot after grinding.
5. the preparation method of α-MgAgSb base nano composite thermoelectric materials as claimed in claim 4, which is characterized in that the microwave
Melting preferably keeps the temperature 40min at 950 DEG C.
6. the preparation method of α-MgAgSb base nano composite thermoelectric materials as claimed in claim 3, which is characterized in that the step
(1) in, sintering temperature used by the hot pressed sintering is compact formed is 450 DEG C, soaking time 30min, holding stage pressure
It is by force 240Mpa.
7. the preparation method of α-MgAgSb base nano composite thermoelectric materials as claimed in claim 3, which is characterized in that the step
(2) in, the microwave sintering annealing is specifically isothermal annealing 5 days at 270 DEG C.
8. the preparation method of α-MgAgSb base nano composite thermoelectric materials as claimed in claim 3, which is characterized in that the step
(1) in, the SnTe nanometer powder preferably uses hydro-thermal method to be prepared, and the concrete processing procedure of hydro-thermal method is as follows:
By SnCl2·2H2O, Te powder, KOH and KBH4Four by uniformly mixing is placed in height after the molar ratio weighing of 1:1:8:2
It presses in reaction kettle, is subsequently poured into N, reaction kettle sealing is put into baking oven, the hydro-thermal reaction 12 at 150 DEG C by N- dimethylformamide
Hour, it is centrifuged after cooling, SnTe nanometer powder can be obtained in drying;Preferably, the partial size of these SnTe nano materials is no more than
100nm, more preferably 20~50nm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810709524.6A CN109087987B (en) | 2018-07-02 | 2018-07-02 | α -MgAgSb based nano composite thermoelectric material and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810709524.6A CN109087987B (en) | 2018-07-02 | 2018-07-02 | α -MgAgSb based nano composite thermoelectric material and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109087987A true CN109087987A (en) | 2018-12-25 |
CN109087987B CN109087987B (en) | 2020-07-24 |
Family
ID=64836901
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810709524.6A Active CN109087987B (en) | 2018-07-02 | 2018-07-02 | α -MgAgSb based nano composite thermoelectric material and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109087987B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115347109A (en) * | 2022-08-18 | 2022-11-15 | 哈尔滨工业大学 | Method for preparing thermoelectric refrigerating device by utilizing MgAgSb based thermoelectric material with superfine crystal and porous structure |
CN115490519A (en) * | 2022-09-27 | 2022-12-20 | 华中科技大学 | AgMnSbTe 3 High-entropy semiconductor material and preparation thereof |
WO2024152449A1 (en) * | 2023-01-16 | 2024-07-25 | 哈尔滨工业大学 | Preparation method for high-thermal-stability and low-contact-resistance barrier layer based on mgagsb-based thermoelectric material |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101350394A (en) * | 2008-09-11 | 2009-01-21 | 清华大学 | Pyroelectric material with quadruple skutterudite structure and preparation method thereof |
CN105671344A (en) * | 2014-11-21 | 2016-06-15 | 武汉理工大学 | Method for preparing high-performance CoSb3-based thermoelectric materials by one step |
CN105970070A (en) * | 2016-06-23 | 2016-09-28 | 浙江大学 | P-type alpha-MgAgSbSn thermoelectric material with high optimum value and preparation method |
-
2018
- 2018-07-02 CN CN201810709524.6A patent/CN109087987B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101350394A (en) * | 2008-09-11 | 2009-01-21 | 清华大学 | Pyroelectric material with quadruple skutterudite structure and preparation method thereof |
CN105671344A (en) * | 2014-11-21 | 2016-06-15 | 武汉理工大学 | Method for preparing high-performance CoSb3-based thermoelectric materials by one step |
CN105970070A (en) * | 2016-06-23 | 2016-09-28 | 浙江大学 | P-type alpha-MgAgSbSn thermoelectric material with high optimum value and preparation method |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115347109A (en) * | 2022-08-18 | 2022-11-15 | 哈尔滨工业大学 | Method for preparing thermoelectric refrigerating device by utilizing MgAgSb based thermoelectric material with superfine crystal and porous structure |
CN115347109B (en) * | 2022-08-18 | 2023-05-02 | 哈尔滨工业大学 | Method for preparing thermoelectric refrigeration device by using MgAgSb-based thermoelectric material with superfine crystal and porous structure |
CN115490519A (en) * | 2022-09-27 | 2022-12-20 | 华中科技大学 | AgMnSbTe 3 High-entropy semiconductor material and preparation thereof |
WO2024152449A1 (en) * | 2023-01-16 | 2024-07-25 | 哈尔滨工业大学 | Preparation method for high-thermal-stability and low-contact-resistance barrier layer based on mgagsb-based thermoelectric material |
US12052920B1 (en) | 2023-01-16 | 2024-07-30 | Harbin Institute Of Technology | Preparation method of contact material with high thermal stability and low contact resistance based on MgAgSb-based thermoelectric material |
Also Published As
Publication number | Publication date |
---|---|
CN109087987B (en) | 2020-07-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103700759B (en) | A kind of nano composite structure Mg 2si base thermoelectricity material and preparation method thereof | |
CN108238796B (en) | Copper seleno solid solution thermoelectric material and preparation method thereof | |
CN109087987A (en) | A kind of α-MgAgSb base nano composite thermoelectric materials and preparation method thereof | |
CN103130200B (en) | Thermoelectricity material compound and preparation method thereof | |
CN113421959B (en) | N-type bismuth telluride-based room temperature thermoelectric material and preparation method thereof | |
CN108461619A (en) | A kind of preparation method of Se doping skutterudite thermoelectric material | |
CN104263980A (en) | Method for rapidly preparing high-performance ZrNiSn block thermoelectric material | |
CN108374198A (en) | A kind of monocrystalline Bi2Te3The preparation method of thermoelectric material | |
CN105895795A (en) | Method for preparing composite tin selenide based thermoelectric material | |
CN111640853B (en) | By Sb and Cu 2 Method for improving thermoelectric performance of n-type PbTe by Te co-doping | |
CN107845724A (en) | A kind of low cost environment friendly SnS base thermoelectricity materials and preparation method thereof | |
CN110078476A (en) | A kind of Al doping BiCuSeO base thermoelectricity material and preparation method thereof | |
CN108950278A (en) | A kind of method that microwave heating prepares BiCuSeO thermoelectric block body material | |
CN104032194A (en) | Co-doped Mg-Si-Sn based thermo-electric material and preparation method thereof | |
CN101734730A (en) | Inter-metallic compound material with near-zero thermal expansion character and anti-perovskite structure | |
CN105219995B (en) | A kind of preparation method of n type thermoelectric material NbCoSb | |
CN102051513A (en) | Metal selenide thermoelectric material for intermediate temperate and preparation process thereof | |
CN106191522B (en) | A kind of method that laser efficiently prepares skutterudite thermoelectric material | |
CN105244435A (en) | Novel n-type thermoelectric material NbVTaCoSb and preparation method thereof | |
CN108198934A (en) | A kind of composite thermoelectric material and preparation method thereof | |
CN103409656B (en) | Thermoelectric material Mg2Sn and preparation method thereof | |
CN108950347A (en) | A kind of preparation method of MgAgSb pyroelectric material | |
CN108640683B (en) | A kind of preparation method of nano composite thermoelectric materials | |
CN106098922A (en) | A kind of Cu doping Emission in Cubic Ca2si thermoelectric material | |
CN111162160A (en) | P-type cubic phase Ge-Se-based 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 |