CN106981565B - High stability Cu2-xSe composite thermoelectric material and preparation method thereof - Google Patents
High stability Cu2-xSe composite thermoelectric material and preparation method thereof Download PDFInfo
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- CN106981565B CN106981565B CN201710098778.4A CN201710098778A CN106981565B CN 106981565 B CN106981565 B CN 106981565B CN 201710098778 A CN201710098778 A CN 201710098778A CN 106981565 B CN106981565 B CN 106981565B
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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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- 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
Abstract
A kind of Cu with high stability2‑xThe preparation method of Se thermoelectric composite material, comprising: 1) by Cu2‑xSe block materials are ground；2) inorganic salt solution is prepared；3) Cu that will be obtained in step 1)2‑xSe little particle is mixed with the inorganic salt solution that step 2) is prepared；4) Cu containing inorganic salt solution for obtaining step 3)2‑xThe drying of Se little particle；5) little particle for obtaining step 4) is sintered, and obtains compact block, i.e. the Cu2-xSe thermoelectric material of acquisition structural stability raising.The present invention also provides a kind of Cu obtained by the above method2‑xSe thermoelectric composite material.
Description
Technical field
The present invention relates to one kind to belong to new energy materials field, in particular to a kind of high stability Cu2-xThe compound thermoelectricity material of Se
Material and preparation method thereof.
Background technique
Now, the environmental problem as caused by the consumption of traditional energy is got worse, especially PM2.5 pollution, positive to threaten
The health of more and more people.Meanwhile there is also huge waste in traditional energy consumption, industrial waste heat has been tended not to
Effect utilizes.Thermal energy may be implemented in thermoelectric material and the direct of electric energy mutually converts, and low temperature in industrial waste heat, underground heat etc. may be implemented
The direct generation of electricity of heat source is the effective means for solving the gentle solution environmental pollution of energy waste.Cu2-xSe is that high temperature is most potential
One of thermoelectric material, with other PbTe, Bi2Te3Contour performance thermoelectric material is compared, Cu2-xSe material component Cu and Se are on ground
Reserves relative abundance and no pollution to the environment on ball.As the thermoelectric material haveing excellent performance, Cu2-xThe electrothermal module of Se production exists
Easily-deformable disadvantage under high temperature, significantly impacts its application.Therefore, Cu is solved2-xSe material at high temperature bending deformation improves its height
Warm structural stability solves the problems, such as thermo-electric device stable military service at high temperature, is the key that expand its application.
Summary of the invention
In view of this, it is necessary to provide a kind of high stability Cu2-xSe composite thermoelectric material and preparation method thereof.
A kind of Cu with high stability2-xThe preparation method of Se composite thermoelectric material, includes the following steps:
1) by Cu2-xSe block materials are ground；
2) inorganic salt solution is prepared；
3) Cu that will be obtained in step 1)2-xSe little particle is mixed with the inorganic salt solution that step 2) is prepared；
4) Cu containing inorganic salt solution for obtaining step 3)2-xThe drying of Se little particle；
5) little particle for obtaining step 4) is sintered, and obtains compact block, the i.e. Cu2-xSe of acquisition structural stability raising
Thermoelectric material.
As further improved, the range of x is 0 to 1.
As further improved, in the step 1), after grinding Cu2-xSe partial size is in 10nm~1mm.
As further improved, in step 1), the atmosphere of grinding is air atmosphere or inert gas atmosphere.
As further improved, in step 2), in the inorganic salt solution inorganic salts include sulfate, nitrate,
Chlorate, acetate and its mixture, the solvent in the solution includes water, alcohol, ether, acetone and its mixture.
As further improved, in step 2), the concentration of the inorganic salt solution is 0.01mol/L~1mol/L.
It is described by Cu in step 3) as further improved2-xSe little particle and the inorganic salts that step 2) is prepared are molten
The step of liquid mixes includes: by Cu2-xSe little particle immerses in inorganic salt solution or to Cu2-xIt is molten that Se little particle sprays inorganic salts
Liquid.
As further improved, in step 4), drying course selection drying or in inert atmosphere protection in air
Lower drying, the temperature of drying are room temperature~700 DEG C.
As further improved, in step 5), sintering processing selects hot pressed sintering or discharge plasma sintering.
As further improved, in step 5), the temperature of sintering is 300 DEG C~700 DEG C, and the pressure of sintering is
10MPa~300MPa.
The invention further relates to a kind of according to above method high stability Cu obtained2-xSe composite thermoelectric material.
Compared with prior art, the beneficial effects of the present invention are: Cu can not influenced or influenced less2-xSe conducting material thermoelectricity
Under the premise of energy, Cu is avoided2-xSe material at high temperature bending deformation improves its thermal structure stability, promotes Cu2-xThe quotient of Se material
Industry application.In addition, preparation process of the invention also has the characteristics that method is simple, low in cost.
Detailed description of the invention
Fig. 1 is the Cu obtained after grinding2-xThe short grained structural schematic diagram of Se.
Fig. 2 is the Cu after drying2-xThe structural schematic diagram of Se powder particle.
Fig. 3 passes through the fine and close Cu after plasma activated sintering2-xThe structural schematic diagram of Se composite thermoelectric material.
Main element symbol
Nothing
Specific embodiment
Below in conjunction with drawings and embodiments to high stability Cu of the invention2-xSe composite thermoelectric material and its preparation
Method makees specific introduce.
Fig. 1-3 is please referred to, the embodiment of the present invention provides a kind of Cu with high stability2-xThe system of Se composite thermoelectric material
Preparation Method includes the following steps:
1) by Cu2-xSe block materials are ground；
2) inorganic salt solution is prepared；
3) Cu that will be obtained in step 1)2-xSe little particle is mixed with the inorganic salt solution that step 2) is prepared；
4) Cu containing inorganic salt solution for obtaining step 3)2-xThe drying of Se little particle；
5) little particle for obtaining step 4) is sintered, and obtains compact block, the i.e. Cu2-xSe of acquisition structural stability raising
Thermoelectric material.
In step 1), it is preferred that the range of x is 0 to 1.It is furthermore preferred that the range of x is 0 to 0.5.Cu after grinding2- xSe partial size is in 10nm~1mm, preferably are as follows: 100nm~100 μm, more preferably: 50 μm~100 μm.It is appreciated that Cu2-xSe's
Partial size is too small to will lead to conducting material thermoelectricity performance decline, also particle can be made to be easy to be bonded together；Partial size is excessive to be unfavorable for improving material
The stability of material, and be unfavorable for forming good contact with inorganic salts.In addition, the atmosphere of the grinding can for air atmosphere or
Inert gas atmosphere.
In step 2), in the inorganic salt solution inorganic salts include sulfate, nitrate, chlorate, acetate and its
Mixture.Preferably chlorate, such as iron chloride, copper chloride, zinc chloride.More preferably copper chloride.Solvent in the solution
Including water, alcohol, ether, acetone and its mixture.The concentration of the inorganic salt solution is 0.01mol/L~1mol/L.Experiment
Show that each solvent all has more preferred range.When solvent is water, concentration is about 0.05mol/L~0.2mol/L.
It is described by Cu in step 3)2-xThe step of Se little particle is mixed with the inorganic salt solution that step 2) is prepared include:
By Cu2-xSe little particle immerses in inorganic salt solution or to Cu2-xSe little particle sprays inorganic salt solution.
In step 4), drying course selection is dried or is dried under inert atmosphere protection, the temperature of drying in air
For room temperature~700 DEG C.
In step 5), sintering processing selects hot pressed sintering or discharge plasma sintering.Hot pressed sintering speed is slower, electric discharge
Plasma agglomeration speed is fast, high-efficient.Therefore preferably discharge plasma sintering.The temperature of sintering is 300 DEG C~700 DEG C, preferably
, the temperature of sintering is 600 DEG C~700 DEG C.When pressure is too small, the density of agglomerated material is lower, and pressure is excessive to will lead to density
Too high its thermoelectricity capability of influence.Therefore the pressure of sintering be 10MPa~300MPa, it is preferred that the pressure of sintering be 60MPa~
100MPa.It is furthermore preferred that the pressure of sintering is 60MPa~70MPa.The time of sintering is 5 minutes~30 minutes.After sintering
Preferably, 5 minutes~30 minutes are kept the temperature under vacuum conditions, vacuum degree is preferably smaller than 100Pa.It is inorganic during sintering
Salt will form oxide tight in Cu2-xSe particle surrounding, playing prevents Cu2-xThe deformation of Se grains, and prevent Cu2- xThe effect that Se is decomposed.
Referring to figure 3., the embodiment of the present invention further relates to a kind of according to above method high stability Cu obtained2-xSe is multiple
Close thermoelectric material.
Embodiment 1
The Cu1.9Se block materials for weighing 5g, are ground, grain diameter is at 50-100 μm using agate mortar；It prepares
The CuCl of 0.1mol/L2Aqueous solution 50ml；By ground Cu2-xSe powder particle immerses prepared CuCl2In solution, and fill
Divide mixing；By mixed Cu2-xSe powder is heated to 50 degrees Celsius in quartz ampoule, the lower drying of argon atmosphere protection；It will dry
Powder particle afterwards is fitted into the graphite jig that diameter is 20mm, is put into discharge plasma sintering system and is sintered.Sintering pressure
60MPa, 600 DEG C of sintering temperature, vacuum are less than 10Pa, heat preservation 15 minutes.Compact block material is obtained, i.e. acquisition structural stability
The Cu of raising2-xSe thermoelectric material.
In addition, those skilled in the art can also do other variations in spirit of that invention, certainly, these are smart according to the present invention
The variation that mind is done should all be included in the interior of scope of the present invention.
Claims (9)
1. a kind of high stability Cu2-xThe preparation method of Se composite thermoelectric material, which comprises the steps of:
1) by Cu2-xSe block materials are ground；
2) inorganic salt solution is prepared；
3) Cu that will be obtained in step 1)2-xSe little particle is mixed with the inorganic salt solution that step 2) is prepared；
4) Cu containing inorganic salt solution for obtaining step 3)2-xThe drying of Se little particle；
5) little particle for obtaining step 4) is sintered, and obtains compact block, the i.e. Cu of acquisition structural stability raising2-xSe thermoelectricity
Material；Wherein, the range of x is 0 to 1, the Cu after grinding2-xSe partial size is in 10nm~1mm.
2. preparation method according to claim 1, which is characterized in that in the step 1), the atmosphere of grinding is air gas
Atmosphere or inert gas atmosphere.
3. preparation method according to claim 1, which is characterized in that inorganic in the inorganic salt solution in step 2)
Salt includes or mixtures thereof sulfate, nitrate, chlorate, the solvent in the solution include water, alcohol, ether, acetone or
Its mixture.
4. preparation method according to claim 1, which is characterized in that in step 2), the concentration of the inorganic salt solution
For 0.01mol/L~1mol/L.
5. preparation method according to claim 1, which is characterized in that described by acquisition in step 1) in step 3)
Cu2-xThe step of Se little particle is mixed with the inorganic salt solution that step 2) is prepared includes: by Cu2-xIt is molten that Se little particle immerses inorganic salts
In liquid or to Cu2-xSe little particle sprays inorganic salt solution.
6. preparation method according to claim 1, which is characterized in that in step 4), drying course is selected in air
Drying is dried under inert atmosphere protection, and the temperature of drying is room temperature~700 DEG C.
7. preparation method according to claim 1, which is characterized in that in step 5), sintering processing selects hot pressed sintering
Or discharge plasma sintering.
8. preparation method according to claim 1, which is characterized in that in step 5), the temperature of sintering is 300 DEG C~
700 DEG C, the pressure of sintering is 10MPa~300MPa.
9. a kind of high stability Cu2-xSe composite thermoelectric material, the high stability Cu2-xSe composite thermoelectric material is by claim
The described in any item preparation methods of 1-8 obtain.
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| CN107910431A (en) * | 2017-10-27 | 2018-04-13 | 北京石油化工学院 | One kind regulation and control Cu2The method of Se base block thermoelectric material performances |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102709351A (en) * | 2012-06-05 | 2012-10-03 | 山东建筑大学 | Cuprous sulfide film with preferred orientation growth |
| CN105642884A (en) * | 2016-01-21 | 2016-06-08 | 合肥工业大学 | Preparation method for Bi-Te-based thermoelectric material with core-shell structure |
| CN105765748A (en) * | 2013-09-12 | 2016-07-13 | 科学与工业研究委员会 | Nanostructured copper-selenide with high thermoelectric figure-of-merit and process for the preparation thereof |
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| US9306145B2 (en) * | 2012-03-09 | 2016-04-05 | The Trustees Of Boston College | Methods of synthesizing thermoelectric materials |
| KR101635638B1 (en) * | 2013-10-17 | 2016-07-01 | 주식회사 엘지화학 | Thermoelectric materials and their manufacturing method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102709351A (en) * | 2012-06-05 | 2012-10-03 | 山东建筑大学 | Cuprous sulfide film with preferred orientation growth |
| CN105765748A (en) * | 2013-09-12 | 2016-07-13 | 科学与工业研究委员会 | Nanostructured copper-selenide with high thermoelectric figure-of-merit and process for the preparation thereof |
| CN105642884A (en) * | 2016-01-21 | 2016-06-08 | 合肥工业大学 | Preparation method for Bi-Te-based thermoelectric material with core-shell structure |
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