CN106145063B - A kind of raising Cu2The method of Se base thermoelectricity material phase transition temperature - Google Patents
A kind of raising Cu2The method of Se base thermoelectricity material phase transition temperature Download PDFInfo
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Abstract
The invention discloses a kind of raising Cu2The method of Se base thermoelectricity material phase transition temperature, in Cu2The position Cu of Se mixes Cd element, specifically includes the following steps: 1) according to CdxCu2‑xThe stoichiometric ratio of Se (0.004≤x≤0.012) weighs each raw material, carries out tabletting after mixing；2) cylinder obtained by tabletting is subjected to vacuum sealing, then causes self-propagating reaction, after the reaction was completed, carry out natural cooling；3) reaction product obtained by step 2) is ground into fine powder, then carries out plasma activated sintering, obtains fine and close CdxCu2‑xSe block.Method of the present invention is simple, repeatability is high, can effectively improve Cu2The phase transition temperature of Se base thermoelectricity material is suitble to promote and apply.
Description
Technical field
The invention belongs to technical field of new material preparation, and in particular to a kind of raising Cu2Se base thermoelectricity material phase transition temperature
The method of degree.
Background technique
With gradually decreasing for fossil energy and getting worse for environmental pollution, Development of Novel, environmental-friendly can be again
The raw energy and energy conversion technology cause the great attention of countries in the world.Wherein, thermal energy is directly changed into the environment of electric energy
Coordination type thermoelectric generation technology is even more to be concerned by people.Thermoelectric generation technology utilizes the Seebeck of semiconductor material
(Seebeck) effect and Peltier (Peltier) effect realize that the direct conversion between thermal energy and electric energy, application mainly include
Thermoelectric power generation and thermoelectric cooling two ways.For traditional heat engine, have structure it is simple, without transmission parts, reliable
Property it is high, manufacturing process is simple, pollution-free and noiseless the features such as, in necks such as solar energy, industrial exhaust heat, waste heat of automotive exhaust gas power generations
Domain has a wide range of applications, to provide an important approach for alleviating energy crisis and solution environmental pollution.
The core of thermoelectric generation technology is thermoelectric material, and the performance of thermoelectric material determines the work effect of thermoelectric generation technology
Rate.The performance of thermoelectric material indicates by thermoelectric figure of merit ZT, ZT=S2α T/ κ, wherein S is Seebeck coefficient, and α is conductivity, κ
For thermal conductivity, T is absolute temperature.ZT value is bigger, and the conversion efficiency of thermoelectric of material is higher.Therefore, high performance thermoelectric material must
Must have high Seebeck coefficient, high conductivity and low thermal conductivity simultaneously.More high performance thermoelectric material is studied at present
It mainly include skutterudite (Skutterudite), Bi2Te3、PbTe、Mg2Si etc., but there are component reserves are dilute for these systems
Less, expensive, oxidizable or the disadvantages of be harmful to the human body, these factors all greatly restrict its as thermoelectric material can
Sustainable development.Therefore, abundant, inexpensive, the environmental-friendly high performance thermoelectric material of development reserves has very important meaning
Justice.
Cu2Se is a kind of ion-electron mixed type superionic conductors, has preferable electrical property and lower hot property, quilt
It is considered a kind of potentially with the thermoelectric material of " phonon liquid-electron crystal " characteristic, to widely be closed by people
Note.Simultaneously because Cu powder and Se powder abundance, cheap, there is it in heavy industrialization application aspect very big
Prospect.Currently, Cu2There are many preparation method of Se, and main includes melting annealing method, ball milling pressure sintering, solid reaction process, Low Temperature Wet
Chemical method and self-propagating high-temperature synthesis etc..Wherein, self-propagating high-temperature synthesis is supper-fast with its, low energy consumption, low cost
The characteristics of as researchers concern hot spot.
Cu2For Se as a kind of high temperature thermoelectric material, it is non-that excellent thermoelectricity capability has it in terms of thermoelectric power generation
Often big application prospect.But after temperature increases, Cu2Se can be the fast ion β phase of high temperature by the α phase transition of low-temperature stabilization.β-Cu2Se
It is unstable, Cu+It is extremely active, it easily migrates, and be easy to react with electrode material, to deteriorate its thermoelectricity capability.Cause
This, its phase transition temperature is elapsed toward high temperature area to improve its stability under high temperature and there is important practical application to anticipate
Justice.
Summary of the invention
The object of the present invention is to provide one kind, and Cu can be improved2The method of Se base thermoelectricity material phase transition temperature, this method letter
Single easy to operate, repeatable height is suitble to promote and apply.
To achieve the above object, a kind of the technical solution adopted by the present invention are as follows: raising Cu2Se base thermoelectricity material phase transition temperature
The method of degree, in Cu2The position Cu of Se mixes Cd element, specifically includes the following steps:
1) according to CdxCu2-xThe stoichiometric ratio of Se (0.004≤x≤0.012) weighs Cd powder, Cu powder and Se powder, mixing
Tabletting is carried out after uniformly, obtains cylinder raw material；
2) cylinder raw material obtained by step 1) is placed in reaction vessel and carries out vacuum sealing, then it is anti-to cause self- propagating for igniting
It answers, after the reaction was completed natural cooling, obtains ingot body product；
3) by ingot body product grind into powder obtained by step 2), plasma activated sintering is then carried out, fine and close Cu is obtained2Se
Base thermoelectricity material.
In above scheme, the mode for causing self-propagating reaction is direct flame ignition or other can quickly improve sample office
The mode of portion's temperature, such as electric current heating, metal heat transfer.
In above scheme, the plasma activated sintering technique are as follows: be less than 20Pa in vacuum degree and sintering pressure is 30
Under conditions of~50MPa, 500~700 DEG C are heated to the heating rate of 80~100 DEG C/min, keeps the temperature 3~5min.
In above scheme, in the tableting processes, cold pressure is 80~240MPa, and the dwell time is 10~15min.
In above scheme, the vacuum sealing procedure are as follows: first taken a breath with inert gas before sealing, it is close then to carry out vacuum
Envelope, until the air pressure in reaction vessel is≤100Pa.
In above scheme, the inert gas is argon gas.
In above scheme, the purity of the Cd powder, Cu powder and Se powder >=99.99wt%.
In above scheme, the reaction vessel used for holding raw material is quartz glass tube, but can be born heretofore described
The container of self-propagating reaction temperature all can, such as crucible, however it is not limited to which quartz glass tube is a kind of.
The Cu according to made from above scheme2Se base thermoelectricity material, chemical composition CdxCu2-xSe, wherein 0.004≤x≤
0.012。
The Cu according to made from above scheme2The phase transition temperature of Se base thermoelectricity material is 415~420K.
The principle of the present invention are as follows: the electronegativity difference of Cd atom and Se atom is greater than the electronegativity difference of Cu atom and Se atom,
It is easier Cd atom and Se atomistic binding；In addition, the atomic radius ratio Cu of Cd is big, make Cd after Cu incorporations, it can be preferably
It is filled in the clearance position of Se atom sublattice, to effectively block Cu+Migration, improve its stability.
There is the prior art to compare, the invention has the benefit that
1) present invention is by Cu2The position Cu of Se mixes Cd element, utilizes the bonding action and Cd of Cd atom and Se atom
Atom is in the filling effect in Se atom sublattice gap, effectively blocking Cu+Migration, improve gained Cu2The phase of Se base thermoelectricity material
Transition temperature.
2) Cu produced by the present invention2The phase transition temperature of Se base thermoelectricity material is 415~420K, to improve Cu2The phase of Se turns
Temperature provides a new way.
3) preparation method raw material of the invention is simple, low in cost, speed is fast, required instrument and equipment is few, easy to operate
And it is reproducible, it is suitble to large-scale industrial production.
Detailed description of the invention
The present invention will be further explained below with reference to the attached drawings, in attached drawing:
Fig. 1 is to improve Cu described in the embodiment of the present invention 12The process flow chart of Se base thermoelectricity material phase transition temperature.
Fig. 2 is the XRD spectrum of self-propagating reaction product in the embodiment of the present invention 1~3 and comparative example.
Fig. 3 is the XRD spectrum of the products therefrom after PAS in the embodiment of the present invention 1~3 and comparative example.
Fig. 4 is that hot-fluid of the products therefrom between 300~773K is bent after PAS in the embodiment of the present invention 1~3 and comparative example
Line.
Fig. 5 is the partial enlarged view of the products therefrom heat flow curve after PAS in the embodiment of the present invention 1~3 and comparative example.
Specific embodiment
In order to better understand the present invention, below with reference to the embodiment and attached drawing content that the present invention is furture elucidated, but this
The content of invention is not limited solely to the following examples.
In following embodiment, unless specific instructions, the reagent is commercially available chemical reagent or industrial products.
The purity of the Sb powder and Te powder >=99.9wt%, partial size≤200 mesh.
The raw material Cd powder, Cu powder, Se powder purity >=99.99wt%.
The container that raw material is held used in following embodiment is quartz glass tube, but can be born heretofore described from climing
Prolong the container of reaction temperature all can, such as crucible, so being not limited to quartz glass tube one kind.
The mode for causing self-propagating reaction in following embodiment is direct flame ignition, but can quickly improve sample part
The mode of temperature all can be with, such as electric current heating, metal heat transfer etc..
In following embodiment, the consistency is measured using Archimedes method.
The changes of heat flux curve is measured using differential scanning calorimetry, measures heat of the sample in temperature-rise period
Rheology, test temperature section are 27~500 DEG C (300~773K), and heating rate is 5~10 DEG C/min.
Embodiment 1
A kind of raising Cu2The method of Se base thermoelectricity material phase transition temperature, Cu2The chemical composition of Se base thermoelectricity material is
Cd0.004Cu1.996Fig. 1 is shown in Se, process flow, specifically includes the following steps:
1) the raw material Cd powder of high-purity, Cu powder, Se powder are weighed with the molar ratio of 0.004:1.996:1, after weighing
It is poured slowly into agate mortar and mixes, after hand-ground 10min, it is cold to carry out in the punching block of 10mm that powder is transferred to diameter
Pressure, cold pressure 80MPa, dwell time 15min obtain cylinder raw material；
2) gained cylinder raw material is demoulded and is taken out, be placed in quartz glass tube and carry out vacuum sealing, first use argon gas before sealing
Quartz glass tube is taken a breath 2~3 times, air pressure when sealing in quartz glass tube is < 100Pa, directly by means of flame after sealing
The flame of rifle removes fire after causing self-propagating reaction in quartz glass tube bottom priming immediately, will be quartzy after ingot body natural cooling
Glass tube, which is broken into pieces, takes out ingot body；
3) gained ingot body is placed in agate mortar and is ground into fine powder, weighed 4.1g powder and be placed in the graphite that diameter is 15mm
Plasma activated sintering is carried out in mold, under conditions of vacuum degree < 20Pa and sintering pressure are 30MPa, with 80 DEG C/min's
Heating rate is heated to 500 DEG C, keeps the temperature 5min, and natural cooling obtains the Cu2Se base thermoelectricity material block.
It takes out the fine powder that a small amount of step 3) grinding obtains and carries out XRD test, the results showed that after self-propagating reaction (SHS),
Gained ingot body is good single-phase Cu2Se (Fig. 2)；After plasma activated sintering (PAS), to gained Cu2Se base thermoelectricity material block
Body carries out XRD test, shows that products therefrom is good Cu2Se single-phase (Fig. 3), consistency is 99% or more.The present embodiment
The heat flow curve of products therefrom is shown in Fig. 4, shows gained Cu2The phase transition temperature of Se base thermoelectricity material is 415K (Fig. 5).
Embodiment 2
A kind of raising Cu2The method of Se base thermoelectricity material phase transition temperature, Cu2The chemical composition of Se base thermoelectricity material is
Cd0.008Cu1.992Fig. 1 is shown in Se, process flow, specifically includes the following steps:
1) the raw material Cd powder of high-purity, Cu powder, Se powder are weighed with the molar ratio of 0.008:1.992:1, after weighing
It is poured slowly into agate mortar and mixes, after hand-ground 12min, it is cold to carry out in the punching block of 15mm that powder is transferred to diameter
Pressure, cold pressure 160MPa, dwell time 12min obtain cylinder raw material；
2) gained cylinder raw material is demoulded and is taken out, be placed in quartz glass tube and carry out vacuum sealing, first use argon gas before sealing
Quartz glass tube is taken a breath 2~3 times, air pressure when sealing in quartz glass tube is < 100Pa, directly by means of flame after sealing
The flame of rifle removes fire after causing self-propagating reaction in quartz glass tube bottom priming immediately, will be quartzy after ingot body natural cooling
Glass tube, which is broken into pieces, takes out ingot body；
3) gained ingot body is placed in agate mortar and is ground into fine powder, weighed 4.1g powder and be placed in the graphite that diameter is 15mm
Plasma activated sintering is carried out in mold, under conditions of vacuum degree < 20Pa and sintering pressure are 35MPa, with 90 DEG C/min's
Heating rate is heated to 600 DEG C, keeps the temperature 4min, and natural cooling obtains the Cu2Se base thermoelectricity material block.
It takes out the fine powder that a small amount of step 3) grinding obtains and carries out XRD test, the results showed that after self-propagating reaction (SHS),
Gained ingot body is good single-phase Cu2Se (see Fig. 2)；After plasma activated sintering (PAS), to gained Cu2Se base thermoelectricity material
Block carries out XRD test, shows that products therefrom is good Cu2Se single-phase (Fig. 3), consistency is 99% or more.This implementation
The heat flow curve of example products therefrom is shown in Fig. 4, shows gained Cu2The phase transition temperature of Se base thermoelectricity material is 418K (Fig. 5).
Embodiment 3
A kind of raising Cu2The method of Se base thermoelectricity material phase transition temperature, Cu2The chemical composition of Se base thermoelectricity material is
Cd0.012Cu1.988Fig. 1 is shown in Se, process flow, specifically includes the following steps:
1) the raw material Cd powder of high-purity, Cu powder, Se powder are weighed with the molar ratio of 0.012:1.988:1, after weighing
It is poured slowly into agate mortar and mixes, after hand-ground 15min, it is cold to carry out in the punching block of 16mm that powder is transferred to diameter
Pressure, cold pressure 240MPa, dwell time 10min obtain cylinder raw material；
2) gained cylinder raw material is demoulded and is taken out, be placed in quartz glass tube and carry out vacuum sealing, first use argon gas before sealing
Quartz glass tube is taken a breath 2~3 times, air pressure when sealing in quartz glass tube is < 100Pa, directly by means of flame after sealing
The flame of rifle removes fire after causing self-propagating reaction in quartz glass tube bottom priming immediately, will be quartzy after ingot body natural cooling
Glass tube, which is broken into pieces, takes out ingot body；
3) gained ingot body is placed in agate mortar and is ground into fine powder, weighed 4.1g powder and be placed in the graphite that diameter is 15mm
Plasma activated sintering is carried out in mold, under conditions of vacuum degree < 20Pa and sintering pressure are 50MPa, with 100 DEG C/min's
Heating rate is heated to 700 DEG C, keeps the temperature 3min, and natural cooling obtains the Cu2Se base thermoelectricity material block.
It takes out the fine powder that a small amount of step 3) grinding obtains and carries out XRD test, the results showed that after self-propagating reaction (SHS),
Gained ingot body is good single-phase Cu2Se (see Fig. 2)；After plasma activated sintering (PAS), to gained Cu2Se base thermoelectricity material
Block carries out XRD test, shows that products therefrom is good Cu2Se single-phase (Fig. 3), consistency is 99% or more.This implementation
The heat flow curve of example products therefrom is shown in Fig. 4, shows gained Cu2The phase transition temperature of Se base thermoelectricity material is 419K (Fig. 5).
Comparative example
A kind of Cu2Se thermoelectric material, preparation method includes the following steps:
1) the raw material Cu powder of high-purity and Se powder are weighed with the molar ratio of 2:1, it is poured slowly into agate after weighing and grinds
It is mixed in alms bowl, after hand-ground 15min, powder is transferred in the punching block that diameter is 16mm and is cold-pressed, cold pressure is
240MPa, dwell time 10min obtain cylinder raw material；
2) gained cylinder raw material is demoulded and is taken out, be placed in quartz glass tube and carry out vacuum sealing, first use argon gas before sealing
Quartz glass tube is taken a breath 2~3 times, air pressure when sealing in quartz glass tube is < 100Pa, directly by means of flame after sealing
The flame of rifle removes fire after causing self-propagating reaction in quartz glass tube bottom priming immediately, will be quartzy after ingot body natural cooling
Glass tube, which is broken into pieces, takes out ingot body；
3) gained ingot body is placed in agate mortar and is ground into fine powder, weighed 4.1g powder and be placed in the graphite that diameter is 15mm
Plasma activated sintering is carried out in mold, under conditions of vacuum degree < 20Pa and sintering pressure are 50MPa, with 100 DEG C/min's
Heating rate is heated to 700 DEG C, keeps the temperature 3min, and natural cooling obtains the Cu2Se thermoelectric material block.
It takes out the fine powder that a small amount of step 3) grinding obtains and carries out XRD test, the results showed that after self-propagating reaction (SHS),
Gained ingot body is good single-phase Cu2Se (see Fig. 2)；After plasma activated sintering (PAS), to gained Cu2Se base thermoelectricity material
Block carries out XRD test, shows that products therefrom is good Cu2Se single-phase (Fig. 3), consistency is 99% or more.This implementation
The heat flow curve of example products therefrom is shown in Fig. 4, shows gained Cu2The phase transition temperature of Se thermoelectric material is 412K (Fig. 5).
The above results show that the present invention improves Cu2The effect of Se base thermoelectricity material phase transition temperature is obvious, to improve Cu2Se
Phase transition temperature provides a new approach, is also expected to optimize Cu simultaneously2The thermoelectricity capability of Se.In addition, original needed for the present invention
Expect rich reserves, cheap, nontoxic, pollution-free, required instrument and equipment is few, and the preparation process being related to is simple, supper-fast, energy consumption
Low, at low cost, favorable repeatability is suitble to large-scale industrial production.
The foregoing is merely the preferred embodiment of the present invention, it is noted that comes for those of ordinary skill in the art
It says, without departing from the concept of the premise of the invention, make several modifications and variations, these belong to protection model of the invention
It encloses.
Claims (9)
1. a kind of raising Cu2The method of Se base thermoelectricity material phase transition temperature, which is characterized in that in Cu2The position the Cu incorporation Cd member of Se
Element, specifically includes the following steps:
1) according to CdxCu2-xSe, wherein the stoichiometric ratio of 0.004≤x≤0.012 weighs Cd powder, Cu powder and Se powder, mixing is equal
Tabletting is carried out after even, obtains cylinder raw material；
2) cylinder raw material obtained by step 1) is subjected to vacuum sealing, then igniting causes self-propagating reaction, natural after the reaction was completed
It is cooling, obtain ingot body product；
3) by ingot body product grind into powder obtained by step 2), plasma activated sintering is then carried out, fine and close Cu is obtained2Se base heat
Electric material is that Cu2Se is single-phase.
2. the method according to claim 1, wherein cause self-propagating reaction mode be direct flame ignition,
Electric current heating or metal heat transfer.
3. the method according to claim 1, wherein the plasma activated sintering technique are as follows: in vacuum degree
Under conditions of being 30~50MPa less than 20Pa and sintering pressure, 500~700 are heated to the heating rate of 80~100 DEG C/min
DEG C, keep the temperature 3~5min.
4. being protected the method according to claim 1, wherein cold pressure is 80~240MPa in the tableting processes
The pressure time is 10~15min.
5. the method according to claim 1, wherein the vacuum sealing procedure are as follows: first use inertia before sealing
Then Gas scavenging carries out vacuum sealing, until the air pressure in reaction vessel is≤100Pa.
6. according to the method described in claim 5, it is characterized in that, the inert gas is argon gas.
7. the method according to claim 1, wherein the Cd powder, Cu powder and Se powder purity >=
99.99wt%.
8. improving Cu described in claim 12Cu made from the method for Se base thermoelectricity material phase transition temperature2Se base thermoelectricity material,
It is characterized in that, chemical composition CdxCu2-xSe, wherein 0.004≤x≤0.012.
9. Cu according to claim 82Se base thermoelectricity material, which is characterized in that its phase transition temperature is 415~420K.
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| CN101219779A (en) * | 2008-01-14 | 2008-07-16 | 重庆大学 | Method for producing selenide and telluride nano-material with composite base metal hydroxide solvent |
| CN103165809A (en) * | 2013-03-19 | 2013-06-19 | 武汉理工大学 | Self-propagating high-temperature rapid one-step synthesis thermoelectric material powder with nanostructure Cu2Se method |
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| CN101219779A (en) * | 2008-01-14 | 2008-07-16 | 重庆大学 | Method for producing selenide and telluride nano-material with composite base metal hydroxide solvent |
| CN103165809A (en) * | 2013-03-19 | 2013-06-19 | 武汉理工大学 | Self-propagating high-temperature rapid one-step synthesis thermoelectric material powder with nanostructure Cu2Se method |
| CN103910338A (en) * | 2013-06-07 | 2014-07-09 | 武汉理工大学 | Self-propagating high-temperature rapid one-step synthetic method for CuxMSnySe4 thermoelectric material powder |
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