CN112086552B - Composite CoSb3 skutterudite-based thermoelectric material and preparation method thereof - Google Patents
Composite CoSb3 skutterudite-based thermoelectric material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 165
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229910018985 CoSb3 Inorganic materials 0.000 title description 5
- 229910018989 CoSb Inorganic materials 0.000 claims abstract description 103
- 229910052751 metal Inorganic materials 0.000 claims abstract description 69
- 239000002184 metal Substances 0.000 claims abstract description 69
- 239000011343 solid material Substances 0.000 claims abstract description 33
- 238000005245 sintering Methods 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000011159 matrix material Substances 0.000 claims abstract description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- 229910052709 silver Inorganic materials 0.000 claims description 26
- 239000004332 silver Substances 0.000 claims description 26
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 13
- 238000000137 annealing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 238000010791 quenching Methods 0.000 claims description 10
- 230000000171 quenching effect Effects 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 238000013329 compounding Methods 0.000 claims description 9
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- 238000000034 method Methods 0.000 claims description 9
- 239000011812 mixed powder Substances 0.000 claims description 9
- 239000007853 buffer solution Substances 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000007766 cera flava Substances 0.000 claims description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 5
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 5
- 238000002490 spark plasma sintering Methods 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- UFIKNOKSPUOOCL-UHFFFAOYSA-N antimony;cobalt Chemical compound [Sb]#[Co] UFIKNOKSPUOOCL-UHFFFAOYSA-N 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000956 alloy Substances 0.000 abstract description 4
- 229910045601 alloy Inorganic materials 0.000 abstract description 4
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 235000013871 bee wax Nutrition 0.000 description 15
- 239000012166 beeswax Substances 0.000 description 15
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- 238000006243 chemical reaction Methods 0.000 description 6
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- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RFXSFVVPCLGHAU-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1 RFXSFVVPCLGHAU-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
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- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
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- 229910052700 potassium Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 230000005679 Peltier effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
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- 230000005484 gravity Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
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- 239000007769 metal material Substances 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
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- 239000004065 semiconductor Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/853—Thermoelectric active materials comprising inorganic compositions comprising arsenic, antimony or bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
- B22F2009/245—Reduction reaction in an Ionic Liquid [IL]
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- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Optics & Photonics (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention provides a composite CoSb 3 Skutterudite-based thermoelectric material and its preparation method, comprising: preparing nano hollow metal balls; preparation M x CoSb 3 A solid material; mixing a certain mass fraction of nano hollow metal balls with M x CoSb 3 After mixing the solid materials, sintering in a vacuum environment to prepare nano hollow metal spheres distributed in CoSb 3 Composite CoSb in matrix of thermoelectric material 3 Skutterudite-based thermoelectric material. According to the invention, the micro-nano hollow metal balls are adopted to be compounded with the cobalt-antimony-based alloy, so that on one hand, the scattering effect of phonons is enhanced by introducing the micro-nano porous structure, and therefore, the lattice heat conductivity of the skutterudite-based thermoelectric material is effectively reduced, and on the other hand, the electric conductivity of the skutterudite-based thermoelectric material is ensured not to be obviously changed, so that the thermoelectric figure of merit ZT of the skutterudite-based thermoelectric material is improved, and the thermoelectric performance of the skutterudite-based thermoelectric material is optimized.
Description
Technical Field
The invention relates to the technical field of thermoelectric materials, in particular to a composite CoSb 3 Skutterudite-based thermoelectric material and a preparation method thereof.
Background
The thermoelectric conversion technique is Seebeck utilizing semiconductor materialEffect and peltier effect of direct energy interconversion, the conversion efficiency of both thermal and electrical energy is mainly dependent on the nondimensional performance index ZT value of the thermoelectric material (zt=s 2 σT/k, where S is the Seebeck coefficient, σ is the electrical conductivity, k is the thermal conductivity, and T is the absolute temperature). The higher the ZT value of the material, the higher the thermoelectric conversion efficiency. The original device prepared by adopting the thermoelectric material with high ZT value has the characteristics of smaller volume, higher reliability, longer service life, simple manufacturing process, environmental friendliness and the like, so that the original device is expected to be widely applied to the fields of waste heat power generation, aerospace power supply, medical health refrigeration and the like.
Skutterudite-based thermoelectric materials are currently considered to be the most ideal thermoelectric materials for use in the medium-high temperature region. Skutterudite belongs to a body-centered cubic structure, and the crystal structure is characterized in that a hollow cage with a large volume exists at the body center, other metal atoms (such as rare earth or alkaline earth metal) can be filled in the cage in a weak bonding mode to form a skutterudite compound, and the filled metal atoms can generate a disturbance effect in the cage to greatly scatter phonons and greatly reduce the heat conductivity of the material, so that the skutterudite-based thermoelectric material compound has better comprehensive thermoelectric performance. In addition, on the basis of filling other metal atoms, the solid micro-nano scale metal particles as a second filling item can increase phonon scattering of the solid micro-nano scale metal particles to further reduce the heat conductivity, but the migration speed of carriers in the thermoelectric material is also reduced, so that the electric conductivity of the material is reduced, and the thermoelectric performance of the material is inhibited from being improved.
Disclosure of Invention
In view of this, the present invention proposes a composite CoSb 3 The skutterudite-based thermoelectric material and the preparation method thereof aim to solve the problem that the thermoelectric performance of the existing thermoelectric material is difficult to comprehensively improve.
The first aspect of the invention provides a composite CoSb3 skutterudite-based thermoelectric material, which has the following chemical formula: m is M x CoSb 3 +ya, wherein: a is a nano hollow metal sphere, x is more than 0 and less than or equal to 0.4, y is more than 0 and less than or equal to 3, and y is M x CoSb 3 Mass percent of matrixThe method comprises the steps of carrying out a first treatment on the surface of the M is one or more of doped alkali metal, alkaline earth metal, rare earth element, aluminum element and iron element.
Further, the above composite CoSb 3 Skutterudite-based thermoelectric material, wherein the thermoelectric material has a chemical formula as follows: x=0.2, y=2.3%.
Further, the above composite CoSb 3 In the skutterudite-based thermoelectric material, the conductivity of the nano hollow metal sphere is more than or equal to 5 multiplied by 10 5 S/m。
Further, the above composite CoSb 3 In the skutterudite-based thermoelectric material, the nano hollow metal spheres are nano hollow Ag spheres, nano hollow Au spheres or nano hollow Cu spheres.
According to the composite CoSb3 skutterudite-based thermoelectric material provided by the first aspect of the invention, the scattering effect of phonons is enhanced by introducing nano hollow metal spheres with micro-nano porous structures, so that the lattice thermal conductivity of the skutterudite-based thermoelectric material is effectively reduced; on the other hand, the nano hollow metal spheres have higher carrier mobility, so that the electric conductivity of the skutterudite-based thermoelectric material is kept unchanged or slightly improved while the thermal conductivity of the thermoelectric material is reduced, and the thermoelectric figure of merit ZT of the skutterudite-based thermoelectric material is improved, so that the thermoelectric performance of the skutterudite-based thermoelectric material is optimized.
In a second aspect, the present invention provides a composite CoSb 3 The preparation method of the skutterudite-based thermoelectric material comprises the following steps: preparing nano hollow metal balls; preparation M x CoSb 3 A solid material; will have a certain mass fraction
Nano hollow metal sphere and M x CoSb 3 After mixing the solid materials, sintering in a vacuum environment to prepare nano hollow metal spheres distributed in CoSb 3 Composite CoSb in matrix of thermoelectric material 3 Skutterudite-based thermoelectric material.
Further, the above composite CoSb 3 In the preparation method of skutterudite-based thermoelectric material, the prepared nano hollow metal spheres are nano hollow silver spheres, and the preparation method comprises the following steps: step (1), preparing a mixed solution of potassium bromide and cetyltrimethylammonium bromide, wherein the potassium bromide substanceThe mass concentration is 10-18mmol/L, and the mass concentration of the cetyl trimethyl ammonium bromide is 0-4mmol/L; adding appropriate amount of Cera flava into the mixed solution until the mass concentration of Cera flava is 2-6g/L, heating in water bath at 60-80deg.C for 1-4 hr, cooling to room temperature, and emulsifying; adding a proper amount of a benzenediol solution with the mass concentration of 40-80mmol/L into the emulsion, mixing, placing in a dark environment, and sequentially adding a citric acid buffer solution with the pH value of 3-4 and a silver nitrate solution with the mass concentration of 0.5-2mol/L into the mixed solution; and (3) pouring the mixed solution obtained in the step (2) into an ethanol solution at 60-80 ℃, collecting precipitate, cleaning and drying to obtain the nano hollow silver spheres.
Further, the above composite CoSb 3 In the preparation method of skutterudite-based thermoelectric material, M is prepared x CoSb 3 The solid material steps include: according to M x CoSb 3 Weighing the stoichiometric ratio of the metal M, co and Sb, mixing, putting into a vacuum container, slowly heating to a first preset temperature to melt, preserving heat for a period of time, and quenching to form M x CoSb 3 Solid state material.
Further, the above composite CoSb 3 In the preparation method of skutterudite-based thermoelectric material, the nano hollow metal spheres and the M are arranged in the nano hollow metal spheres x CoSb 3 Before the solid material is compounded, M after quenching x CoSb 3 Heating the solid material to a second preset temperature, and annealing for a period of time to obtain stable M x CoSb 3 Solid state material.
Further, the above composite CoSb 3 In the preparation method of skutterudite-based thermoelectric material, the nano hollow metal sphere and the M x CoSb 3 The step of compounding the solid material comprises: grinding the solid material into powder with certain granularity, weighing nano hollow metal balls with certain mass fraction, adding the nano hollow metal balls into the powder, grinding the mixed powder for a period of time, and performing spark plasma sintering at a third preset temperature and preset pressure to obtain nano hollow metal balls distributed in CoSb 3 Composite CoSb in matrix of thermoelectric material 3 Skutterudite oreA thermoelectric material.
Further, the above composite CoSb 3 In the preparation method of the skutterudite-based thermoelectric material, the first preset temperature is (800-1500); the heat preservation time is (10-20) h.
Further, the above composite CoSb 3 In the preparation method of the skutterudite-based thermoelectric material, the second preset temperature is (500-700); the annealing time is (25-60) h.
Further, the above composite CoSb 3 In the preparation method of the skutterudite-based thermoelectric material, the third preset temperature is (600-750); the preset pressure is (20-70) MPa.
According to the preparation method of the composite CoSb3 skutterudite-based thermoelectric material, provided by the second aspect, the micro-nano hollow metal balls are adopted to be compounded with the cobalt-antimony base alloy, so that on one hand, the scattering effect of phonons is enhanced by introducing the micro-nano porous structure, and therefore, the lattice heat conductivity of the skutterudite-based thermoelectric material is effectively reduced, and on the other hand, the electric conductivity of the material is ensured not to be obviously changed, so that the thermoelectric figure of merit ZT of the skutterudite-based thermoelectric material is improved, and the thermoelectric performance of the skutterudite-based thermoelectric material is optimized.
Drawings
FIG. 1 shows a composite CoSb provided in an embodiment of the present invention 3 A flow chart of a preparation method of skutterudite-based thermoelectric material;
FIG. 2 is a graph showing the change in resistivity with temperature of skutterudite-based thermoelectric materials prepared in example 1 and comparative example 1 of the present invention;
FIG. 3 is a graph showing the Seebeck coefficient with temperature of skutterudite-based thermoelectric materials prepared in example 1 and comparative example 1 of the present invention;
FIG. 4 is a graph showing the thermal conductivity of skutterudite-based thermoelectric materials prepared in example 1 and comparative example 1 according to the present invention as a function of temperature;
FIG. 5 is a graph showing the ZT value of skutterudite-based thermoelectric materials prepared in example 1 and comparative example 1 according to the present invention, as a function of temperature;
FIG. 6 is a graph showing the ZT value of skutterudite-based thermoelectric materials prepared in example 2 and comparative example 2 according to the present invention, as a function of temperature;
fig. 7 is a graph showing the ZT value with temperature of skutterudite-based thermoelectric materials prepared in example 3 and comparative example 3 of the present invention.
Detailed Description
The following description is of the preferred embodiments of the present invention, and it should be noted that it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the principle of the invention, and these changes and modifications are also considered to be the scope of the invention.
The first aspect of the invention provides a composite CoSb 3 Skutterudite-based thermoelectric material having a chemical formula as follows: m is M x CoSb 3 +yA, A is a nano hollow metal sphere, x is more than 0 and less than or equal to 0.4, y is more than 0 and less than or equal to 3, and y is M of the nano hollow metal sphere x CoSb 3 Mass percent of the matrix; m is one or more of doped alkali metal, alkaline earth metal, rare earth element, aluminum element and iron element. M may be at least one of Na, K, ca, mg, yb, ce, al and Fe.
Specifically, the value range of x is preferably 0.1-0.3, for example, x can be 0.1, 0.2 or 0.3, and y can be controlled within a certain range to ensure that the nano hollow metal balls can be uniformly dispersed in the prepared thermoelectric material, and the nano hollow metal balls can be prevented from being connected with each other so as to improve the heat conductivity of the composite material. The value range of y is preferably 1.ltoreq.y.ltoreq.3%, for example, y may be 1%, 1.5%, 2%, 2.3%, 3%, etc.; preferably, x=0.2 and y=2.3%.
When M is a combination of plural elements, the stoichiometric number of each element satisfies 0 < x.ltoreq.0.4, and the stoichiometric numbers of each element may be the same or different.
In order to prevent the conductivity of the skutterudite-based thermoelectric material obtained by compounding the two materials from being lowered, the conductivity of A is greater than that of the matrix skutterudite thermoelectric material, preferably, the conductivity of the nano hollow metal spheres is 5×10 or more 5 The S/m, for example, can be nano hollow Ag spheres, nano hollow Au spheres or nano hollow Cu spheres.
Further preferably, the nano hollow metal spheres are nano hollow Ag spheres. M is doped into the crystal lattice of skutterudite, so that disturbance effect can be generated to greatly scatter phonons, thereby reducing the heat conductivity of skutterudite material and improving the thermoelectric performance of skutterudite material; when the nano hollow Ag balls are mixed in skutterudite material, on one hand, the nano hollow Ag balls are doped as a second phase, and a large number of interfaces can further scatter phonons so as to reduce the heat conductivity; on the other hand, the hollow structure of the thermoelectric material can enable a plurality of micro-nano holes to exist in the thermoelectric material, and the micro-nano holes can enable phonons to be further scattered in the skutterudite material, so that the lattice heat conductivity is further reduced. Meanwhile, silver is used as a material with high electrical conductivity, a large number of carriers can be provided, the carrier migration speed is high, the problem of carrier mobility reduction caused by the existence of a porous material is solved, and the electrical conductivity of the thermoelectric material is kept unchanged or slightly improved while the thermal conductivity of the thermoelectric material is reduced. Compared with the prior art, the thermoelectric material with the porous structure can inhibit the migration of carriers while reducing the thermal conductivity of the material, so that the thermoelectric performance of the material is improved.
The first aspect of the invention provides the composite CoSb 3 The skutterudite-based thermoelectric material is prepared by compounding micro-nano hollow metal spheres with cobalt-antimony base alloy, and on one hand, the scattering effect of phonons is enhanced by introducing nano hollow metal with a micro-nano porous structure, so that the lattice thermal conductivity of the skutterudite-based thermoelectric material is effectively reduced; on the other hand, the nano hollow metal spheres have higher carrier mobility, so that the electric conductivity of the skutterudite-based thermoelectric material is kept unchanged or slightly improved while the thermal conductivity of the thermoelectric material is reduced, and the thermoelectric figure of merit ZT of the skutterudite-based thermoelectric material is improved, so that the thermoelectric performance of the skutterudite-based thermoelectric material is optimized.
In a second aspect, the present invention provides a composite CoSb 3 The preparation method of the skutterudite-based thermoelectric material comprises the following steps:
and S1, preparing the nano hollow metal ball.
Specifically, in this embodiment, the nano hollow metal ball may be a nano hollow Ag ball, a nano hollow Au ball or a nano hollow Cu ball, and the preparation methods of the nano hollow Au ball and the nano hollow Cu ball may be any method in the prior art, and in this embodiment, the nano hollow silver ball is taken as an example, and the preparation steps include the following sub-steps:
s11, preparing a mixed solution of potassium bromide and cetyltrimethylammonium bromide, wherein the mass concentration of the potassium bromide is 10-18mmol/L, and the mass concentration of the cetyltrimethylammonium bromide is 0-4mmol/L; adding appropriate amount of Cera flava into the mixed solution until the mass concentration of Cera flava is 2-6g/L, heating in water bath at 60-80deg.C for 1-4 hr, cooling to room temperature, and emulsifying.
In the step, beeswax with moderate phase transition temperature is selected as a disperse phase, and added into a solution of hexadecyl trimethyl ammonium bromide with the temperature of 75 ℃, and the ultrasonic treatment can conveniently lead the liquid beeswax and water to form O/W type emulsion.
And S12, adding a proper amount of a benzenediol solution with the mass concentration of 40-80mmol/L into the emulsion, mixing, placing in a dark environment, and sequentially adding a citric acid buffer solution with the pH value of 3-4 and a silver nitrate solution with the mass concentration of 0.5-2mol/L into the mixed solution. The amounts of the substances of the citric acid buffer and silver nitrate may be determined according to the specific reaction system. The nano hollow silver balls with different particle sizes can be obtained by selecting the benzenediol, the citric acid buffer solution and the silver nitrate with different dosages, and the nano hollow silver balls with different particle sizes are filled into skutterudite materials according to a preset proportion, so that phonons with different frequency ranges can be scattered, and the purpose of reducing the heat conductivity is further achieved. It should be noted that the solutions of ortho, meta, and hydroquinone can be used as the dispersed phase.
In this step, agNO is added to the emulsion after the addition of the benzenediol during the ultrasound process 3 Solution, adjusting pH value of system by citric acid buffer solution to make Ag + Combine with Br-to produce negatively charged AgBr "seeds" and adsorb onto positively surface charged emulsion droplets. In the whole ultrasonic process, the whole emulsion system naturally exists in the airAnd cooling, and solidifying the liquid beeswax to form solid balls coated with broad seeds when the liquid beeswax is cooled to a certain temperature. Finally, under low light conditions, hydroquinone is used to reduce the "seeds" into particles according to the typical "photographic" principle. These initially reduced particles can self-catalyze the reduction of the positive charge around them to simple substances, gradually making the solid beeswax surface shell thick, forming particles of core-shell structure.
And S13, pouring the mixed solution obtained in the step S12 into an ethanol solution at 60-80 ℃, collecting precipitate, cleaning and drying to obtain the nano hollow silver spheres.
Specifically, since beeswax is dissolved in hot ethanol, the whole reaction system is poured into hot ethanol, and demulsifies on the one hand, so that the solid beeswax core melts and dissolves out from the pores of the shell layer on the other hand. After a period of treatment, the nano hollow silver spheres settle to the bottom of the system under the action of gravity, while the beeswax floats to the surface of the liquid due to the lower density and meets the cold air to separate out in lamellar. The silver hollow microsphere at the bottom and the beeswax at the surface layer are respectively collected, so that the preparation of the monodisperse hollow silver microsphere and the recovery of the used template are achieved. And (3) repeatedly washing the collected black precipitate with deionized water and absolute ethyl alcohol, and drying to obtain the nano hollow silver particles.
Step S2, preparing M x CoSb 3 Solid state material.
Specifically, according to M x CoSb 3 Weighing metal M (the metal M can be at least one of Na, K, ca, mg, yb, ce, al and Fe), co and Sb, mixing, putting into a vacuum container, slowly heating to a first preset temperature to melt, preserving heat for a period of time, and quenching to form a solid material. The first preset temperature is (800-1500); preferably (900-1200) DEG C
In the concrete implementation, several metal materials are put into a quartz glass tube, and the quartz tube is vacuumized and sealed to prevent the oxidation of the materials in the subsequent high-temperature treatment environment. And then placing the quartz tube loaded with the raw materials into a furnace at a high temperature, slowly heating to (800-1500) DEG C for melting, so that various materials are uniformly mixed in a liquid state, preserving the heat for 10-20 hours, and quenching to form a solid material.
To refine the grains, improve the structure to improve the mechanical properties of the material, the nano hollow metal spheres and the M x CoSb 3 Heating the quenched solid material to a second preset temperature before compounding the solid material, and annealing for a period of time to obtain stable M x CoSb 3 Solid state material.
Wherein the second preset temperature is (500-700) DEG C, preferably (550-650); the annealing time is (25-60) h, preferably (30-60) h.
Step S3, mixing the nano hollow metal balls with a certain mass fraction with M x CoSb 3 After mixing the solid materials, sintering in a vacuum environment to prepare nano hollow metal spheres distributed in CoSb 3 Composite CoSb in matrix of thermoelectric material 3 Skutterudite-based thermoelectric material.
Specifically, in order to refine the grain size, enhance the scattering ability for phonons to reduce the thermal conductivity of thermoelectric materials, it is necessary to crush and grind the solid materials into powder with a particle size of 40 μm or less, since the melting point of silver is lower than that of preparation M x CoSb 3 Quenching temperature at the time of solid material, therefore, at the time of feeding M x CoSb 3 Grinding the solid material, adding hollow nano silver balls, grinding for a period of time, and performing spark plasma sintering at a third preset temperature and preset pressure to obtain nano hollow metal balls distributed in CoSb 3 Composite CoSb in matrix of thermoelectric material 3 Skutterudite-based thermoelectric material. Wherein the nano hollow metal balls occupy CoSb 3 The mass fraction of the matrix material is (0-3%). The third preset temperature is (600-750) DEG C, preferably (650-730); the preset pressure is (20-70) MPa, preferably (30-60) MPa; the sintering time may be (10-30) min, preferably (10-20) min.
In specific implementation, the prepared powder ground by the thermoelectric material based on the block skutterudite and the nano hollow metal ball particles are placed in a ball mill, inert gas is filled, and in order to prevent the various hollow particles from agglomerating together, the ball milling speed is optimizedBall milling for 2-6 hours at the temperature of 300-600r/min, and performing spark plasma sintering reaction on the prepared mixed powder for a period of time at a third preset temperature to obtain the nano hollow metal sphere particle composite CoSb 3 The base thermoelectric material, wherein the spark plasma sintering can also be hot press sintering or microwave sintering. Wherein, in order to ensure that the nano hollow silver balls can keep a complete hollow shape in skutterudite base material, the sintering temperature is preferably 700 ℃, the sintering pressure is preferably 40Mpa, the sintering reaction time is preferably 10min, wherein, the discharge plasma sintering can also be hot press sintering or microwave sintering.
In the step, the processing technology of crushing, sieving, ball milling and sintering the material can greatly improve the mechanical property of the composite material on one hand and can lead the nano hollow silver ball particles to be distributed more uniformly in the thermoelectric material matrix on the other hand.
The method for preparing the skutterudite-based thermoelectric material of the present invention is described below with reference to several specific examples and comparative examples.
The raw materials used in the implementation of the invention are all commercial products.
Example 1
Preparing a mixed solution of potassium bromide and cetyltrimethylammonium bromide, wherein the mass concentration of the potassium bromide is 10mmol/L, the mass concentration of the cetyltrimethylammonium bromide is 1mmol/L, adding beeswax, heating in a water bath at 60 ℃ for 1h after the mass concentration of the beeswax is 2g/L, and emulsifying after cooling to room temperature;
stirring the emulsion for 1h, adding a proper amount of a benzene diphenol solution with the mass concentration of 40mmol/L into the emulsion, mixing the mixture, placing the mixture in a dark environment for standby, sequentially adding a citric acid buffer solution with the pH value of 3 and a proper amount of a silver nitrate solution with the mass concentration of 0.5mol/L into the mixture, and continuously stirring the mixture for 1 h;
pouring the obtained mixed solution into an ethanol solution at 60 ℃, collecting black precipitate generated in the steps, washing with deionized water and absolute ethanol successively, and drying to obtain the nano hollow silver spheres;
adopting a raw material with the purity of not less than 99 percent as an initial raw material according to the chemical formula Yb 0.3 Ca 0.2 CoSb 3 According to the stoichiometric ratio of (1), sequentially weighing 2.130g of metal Yb, 0.328g of Ca, 2.422g of Co and 15g of Sb, putting the mixed material into a quartz glass tube, and vacuumizing and sealing the quartz tube;
placing the quartz tube loaded with raw materials into a furnace at high temperature, slowly heating to 900 ℃ for melting, preserving heat for 10 hours, and quenching to form M x CoSb 3 A solid material; then placing the quenched quartz tube in a furnace again, heating to 550 ℃, and carrying out annealing treatment for 30 hours;
annealing the annealed block M x CoSb 3 Grinding the solid material into powder, weighing 1% of hollow nano silver by mass, adding the hollow nano silver into the powder, placing the mixed powder into a ball mill, and ball-milling and mixing the mixed powder for 2 hours at a ball milling speed of 300 r/min;
and (3) loading the ball-milled powder into a graphite mold, and sintering in a vacuum environment by using a discharge plasma sintering device, wherein the sintering temperature is 650 ℃, the sintering time is 10min, and the sintering pressure is 30MPa. The obtained hollow nano silver ball powder is dispersed and distributed in CoSb 3 Composite CoSb in matrix materials 3 Skutterudite-based thermoelectric material.
Example 2
Preparing a mixed solution of potassium bromide and cetyltrimethylammonium bromide, wherein the mass concentration of the potassium bromide is 18mmol/L, the mass concentration of the cetyltrimethylammonium bromide is 2mmol/L, adding beeswax, heating in a water bath at 70 ℃ for 1h after the mass concentration of the beeswax is 3g/L, cooling to room temperature, and emulsifying;
stirring the emulsion for 2 hours, adding a proper amount of a benzene diphenol solution with the mass concentration of 45mmol/L into the emulsion, mixing the mixture, placing the mixture in a dark environment for standby, sequentially adding a citric acid buffer solution with the pH value of 3 and a silver nitrate solution with the mass concentration of 0.5mol/L into the mixture, and continuously stirring the mixture for 1 hour;
pouring the obtained mixed solution into an ethanol solution with the temperature of 70 ℃, collecting black precipitate generated in the steps, washing with deionized water and absolute ethanol successively, and drying to obtain the nano hollow silver spheres;
adopting a raw material with the purity of not less than 99 percent as an initial raw material according to the chemical formula Yb 0.2 Ca 0.2 Al 0.1 CoSb 3 Sequentially weighing 1.420g of Yb, 0.328g of Ca, 0.011g of Al, 2.422g of Co and 15g of Sb of metal, putting the mixed material into a quartz glass tube, and vacuumizing and sealing the quartz tube;
placing the quartz tube loaded with raw materials into a furnace at high temperature, slowly heating to 1000 ℃ for melting, preserving heat for 20h, and quenching to form M x CoSb 3 A solid material; then placing the quenched quartz tube in a furnace again, heating to 600 ℃, and annealing for 40 hours;
annealing the annealed block M x CoSb 3 Grinding the solid material into powder, weighing 3% of hollow nano silver by mass, adding the hollow nano silver into the powder, placing the mixed powder into a ball mill, and ball-milling and mixing the mixed powder for 2 hours at a ball milling speed of 400 r/min;
and (3) loading the ball-milled powder into a graphite mold, and sintering in a vacuum environment by using a discharge plasma sintering device, wherein the sintering temperature is 700 ℃, the sintering time is 10min, and the sintering pressure is 40MPa. The obtained hollow nano silver ball powder is dispersed and distributed in CoSb 3 Composite CoSb in matrix materials 3 Skutterudite-based thermoelectric material
Example 3
Preparing a mixed solution of potassium bromide and cetyltrimethylammonium bromide, wherein the mass concentration of the potassium bromide is 15mmol/L, the mass concentration of the cetyltrimethylammonium bromide is 4mmol/L, adding beeswax, heating in a water bath at 80 ℃ for 1h after the mass concentration of the beeswax is 6g/L, cooling to room temperature, and emulsifying;
stirring the emulsion for 2 hours, adding a proper amount of a benzene diphenol solution with the mass concentration of 80mmol/L into the emulsion, mixing the mixture, placing the mixture in a dark environment for standby, sequentially adding a citric acid buffer solution with the pH value of 4 and a silver nitrate solution with the mass concentration of 2mol/L into the mixture, and continuously stirring the mixture for 1 hour;
pouring the obtained mixed solution into an ethanol solution with the temperature of 70 ℃, collecting black precipitate generated in the steps, washing with deionized water and absolute ethanol successively, and drying to obtain the nano hollow silver spheres;
adopting a raw material with the purity of not less than 99 percent as an initial raw material according to the chemical formula Yb 0.2 Ca 0.2 Al 0.1 Fe 0.2 Co 0.8 Sb 3 Sequentially weighing 1.420g of Yb, 0.328g of Ca, 0.111g of Al, 0.460g of Fe, 1.938g of Co and 15g of Sb of metal, putting the mixed material into a quartz glass tube, and vacuumizing and sealing the quartz tube;
placing the quartz tube loaded with raw materials into a furnace at high temperature, slowly heating to 1200 ℃ for melting, preserving heat for 30h, and quenching to form M x CoSb 3 A solid material; then placing the quenched quartz tube in a furnace again, heating to 650 ℃, and annealing for 40 hours;
annealing the annealed block M x CoSb 3 Grinding the solid material into powder, weighing hollow nano silver with the mass fraction of 2.3%, adding the hollow nano silver into the powder, placing the mixed powder into a ball mill, and ball-milling and mixing the mixed powder for 2 hours at the ball milling speed of 600 r/min;
and (3) loading the ball-milled powder into a graphite mold, and sintering in a vacuum environment by using a discharge plasma sintering device, wherein the sintering temperature is 730 ℃, the sintering time is 20min, and the sintering pressure is 60MPa. The obtained hollow nano silver ball powder is dispersed and distributed in CoSb 3 Composite CoSb in matrix materials 3 Skutterudite-based thermoelectric material.
Comparative example 1
Compared with the example 1, the preparation process of the nano hollow silver spheres is lack, and the nano hollow silver spheres and M x CoSb 3 The solid material is compounded into Yb 0.3 Ca 0.2 CoSb 3 Skutterudite-based thermoelectric material.
Comparative example 2
The difference from example 2 is that the commercial solid nano silver particles and M are selected x CoSb 3 Compounding solid materials to prepare composite skutterudite-based thermoelectric materials, wherein solid nano silver particles and CoSb 3 The process of compounding the thermoelectric material was the same as in example 2.
Comparative example 3
The difference from example 3 is that the commercial solid nano silver particles and M are selected x CoSb 3 Compounding solid materials to prepare composite skutterudite-based thermoelectric materials, wherein solid nano silver particles and CoSb 3 The process of compounding the thermoelectric material was the same as in example 3.
Composite CoSb prepared in the above examples 1 to 3 and comparative examples 1 to 3 3 Thermoelectric performance of skutterudite-based thermoelectric materials was tested and the results are shown in fig. 2 to 7. Wherein:
the relationship between the electric conductivity, seebeck coefficient, thermal conductivity and ZT value of the skutterudite-based thermoelectric material prepared in example 1 and comparative example 1 with respect to temperature was measured and calculated, and the results are shown in fig. 2 to 4:
as can be seen from fig. 2, at the same temperature, compared with the cobalt-antimony-based skutterudite thermoelectric material prepared in comparative example 1, the cobalt-antimony-based skutterudite thermoelectric material compounded by the nano hollow silver sphere particles has lower resistivity, and the conductivity of the cobalt-antimony-based skutterudite thermoelectric material filled with the nano hollow silver sphere particles is obviously improved, and the ZT value is also increased accordingly; as can be seen from fig. 3, at the same temperature, the seebeck coefficient of the cobalt-antimony-based skutterudite thermoelectric material compounded by the nano hollow silver sphere particles is not greatly changed compared with the cobalt-antimony-based thermoelectric material prepared in comparative example 1; as can be seen from fig. 4, at the same temperature, the thermal conductivity of the cobalt-antimony-based skutterudite thermoelectric material compounded by the nano hollow metal sphere particles is reduced compared with that of the cobalt-antimony-based thermoelectric material prepared in comparative example 1, for example, the thermal conductivity of the cobalt-antimony-based skutterudite thermoelectric material before and after the nano hollow metal sphere particle is compounded is reduced from 0.028 to 0.025 at 500 ℃; as can be seen from fig. 5, the thermoelectric figure of merit ZT of the nano hollow metal sphere particle-composited cobalt-antimony-based skutterudite thermoelectric material is increased compared with that of the cobalt-antimony-based thermoelectric material prepared in comparative example 1 at the same temperature. For example, at 450 ℃, the ZT value of the cobalt-antimony-based skutterudite thermoelectric material compounded by the nano hollow silver sphere particles reaches 1.16, and the ZT value of the cobalt-antimony-based skutterudite thermoelectric material not compounded by the nano hollow silver spheres is only 0.92.
From the above, it can be seen that the thermal conductivity of the thermoelectric material prepared in example 1 of the present invention is reduced while the electrical conductivity is improved, and the thermoelectric figure of merit of the thermoelectric material is improved while the seebeck coefficient is slightly reduced, thereby optimizing the thermoelectric performance of the material.
The ZT values of skutterudite-based thermoelectric materials prepared in example 2 and comparative example 2 were measured with respect to temperature, respectively, and the results are shown in fig. 6:
as can be seen from fig. 6, the thermoelectric figure of merit ZT of the nano hollow metal sphere particle-composited cobalt-antimony-based skutterudite thermoelectric material was increased compared with that of the cobalt-antimony-based thermoelectric material prepared in comparative example 2 at the same temperature. For example, at 450 ℃, the ZT value of the cobalt-antimony-based skutterudite thermoelectric material compounded by the nano hollow metal sphere particles reaches 1.2, and the thermoelectric figure of merit ZT of the cobalt-antimony-based thermoelectric material compounded by the solid nano silver particles is only 0.93.
The ZT values of skutterudite-based thermoelectric materials prepared in example 3 and comparative example 3 were measured with respect to temperature, respectively, and the results are shown in fig. 7:
as can be seen from fig. 7, at the same temperature, the thermoelectric figure of merit ZT of the cobalt-antimony-based skutterudite thermoelectric material composited with the nano hollow metal sphere particles was increased compared with that of the solid nano silver particle composited cobalt-antimony-based thermoelectric material prepared in comparative example 3. For example, at 450 ℃, the ZT value of the cobalt-antimony-based skutterudite thermoelectric material compounded by the nano hollow metal sphere particles reaches 1.18, and the thermoelectric figure of merit ZT of the cobalt-antimony-based thermoelectric material compounded by the solid nano silver particles is only 0.97.
In summary, the embodiment of the invention prepares the composite CoSb 3 The skutterudite-based thermoelectric material is compounded by adopting micro-nano hollow metal spheres and cobalt-antimony-based alloy, on one hand, the scattering effect of phonons is enhanced by introducing a micro-nano porous structure, so that the lattice heat conductivity of the skutterudite-based thermoelectric material is effectively reduced, and on the other hand, the electric conductivity of the skutterudite-based thermoelectric material is ensured not to be obviously changed, so that the thermoelectric figure of merit ZT of the skutterudite-based thermoelectric material is improved, and the thermoelectric performance of the skutterudite-based thermoelectric material is optimized.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (12)
1. Composite CoSb 3 Skutterudite-based thermoelectric material characterized by having the following chemical formula: m is M x CoSb 3 +ya, wherein: a is a nano hollow metal sphere, x is more than 0 and less than or equal to 0.4, y is more than 0 and less than or equal to 3, and y is M x CoSb 3 Mass percent of the matrix; m is one or more of doped alkali metal, alkaline earth metal, rare earth element, aluminum element and iron element; the nano hollow metal balls are distributed on CoSb 3 Composite CoSb is formed in matrix of base thermoelectric material 3 Skutterudite-based thermoelectric material.
2. The composite CoSb of claim 1 3 Skutterudite-based thermoelectric material characterized in that the thermoelectric material has a chemical formula as follows: x=0.2, y=2.3%.
3. The composite CoSb of claim 1 3 The skutterudite-based thermoelectric material is characterized in that the conductivity of the nano hollow metal sphere is more than or equal to 5 multiplied by 10 5 S/m。
4. A composite CoSb of claim 1 or 3 3 The skutterudite-based thermoelectric material is characterized in that the nano hollow metal spheres are nano hollow Ag spheres, nano hollow Au spheres or nano hollow Cu spheres.
5. A composite CoSb as claimed in any one of claims 1 to 4 3 The preparation method of the skutterudite-based thermoelectric material is characterized by comprising the following steps of:
preparing nano hollow metal balls;
preparation M x CoSb 3 A solid material;
mixing a certain mass fraction of nano hollow metal balls with M x CoSb 3 After mixing the solid materials, sintering in a vacuum environment to prepare nano hollow metal spheres distributed in CoSb 3 Composite CoSb in matrix of thermoelectric material 3 Skutterudite-based thermoelectric material.
6. The composite CoSb according to claim 5 3 The preparation method of the skutterudite-based thermoelectric material is characterized in that the prepared nano hollow metal spheres are nano hollow silver spheres, and the preparation steps comprise:
step (1), preparing a mixed solution of potassium bromide and cetyltrimethylammonium bromide, wherein the mass concentration of the potassium bromide is 10-18mmol/L, and the mass concentration of the cetyltrimethylammonium bromide is 0-4mmol/L; adding appropriate amount of Cera flava into the mixed solution until the mass concentration of Cera flava is 2-6g/L, heating in water bath at 60-80deg.C for 1-4 hr, cooling to room temperature, and emulsifying;
adding a proper amount of a benzenediol solution with the mass concentration of 40-80mmol/L into the emulsified solution, mixing, placing in a dark environment, and sequentially adding a citric acid buffer solution with the pH value of 3-4 and a silver nitrate solution with the mass concentration of 0.5-2mol/L into the mixed solution;
and (3) pouring the mixed solution obtained in the step (2) into an ethanol solution at 60-80 ℃, collecting precipitate, cleaning and drying to obtain the nano hollow silver spheres.
7. The composite CoSb according to claim 5 3 A method for preparing skutterudite-based thermoelectric material, characterized in that M is prepared x CoSb 3 The solid material steps include:
according to M x CoSb 3 Weighing the stoichiometric ratio of the metal M, co and Sb, mixing, putting into a vacuum container, slowly heating to a first preset temperature to melt, preserving heat for a period of time, and quenching to form M x CoSb 3 Solid state material.
8. The composite CoSb of claim 7 3 The preparation method of skutterudite-based thermoelectric material is characterized in that the nano hollow metal spheres and the M x CoSb 3 Before the solid material is compounded, M after quenching x CoSb 3 Heating the solid material to a second preset temperature, and annealing for a period of time to obtain stable M x CoSb 3 Solid state material.
9. The composite CoSb according to claim 5 3 The preparation method of skutterudite-based thermoelectric material is characterized in that the nano hollow metal sphere and the M x CoSb 3 The step of compounding the solid material comprises:
grinding the solid material into powder with certain granularity, weighing nano hollow metal balls with certain mass fraction, adding the nano hollow metal balls into the powder, grinding the mixed powder for a period of time, and performing spark plasma sintering at a third preset temperature and preset pressure to obtain nano hollow metal balls distributed in CoSb 3 Composite CoSb in matrix of thermoelectric material 3 Skutterudite-based thermoelectric material.
10. The composite CoSb of claim 7 3 The preparation method of the skutterudite-based thermoelectric material is characterized in that the first preset temperature is (800-1500); the heat preservation time is (10-20) h.
11. The composite CoSb of claim 8 3 The preparation method of the skutterudite-based thermoelectric material is characterized in that the second preset temperature is (500-700); the annealing time is (25-60) h.
12. The composite CoSb of claim 9 3 The preparation method of the skutterudite-based thermoelectric material is characterized in that the third preset temperature is (600-750); the preset pressure is (20-70) MPa.
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