CN107793155B - Ultra-fast preparation of Cu2Method for Se bulk thermoelectric material - Google Patents
Ultra-fast preparation of Cu2Method for Se bulk thermoelectric material Download PDFInfo
- Publication number
- CN107793155B CN107793155B CN201610806167.6A CN201610806167A CN107793155B CN 107793155 B CN107793155 B CN 107793155B CN 201610806167 A CN201610806167 A CN 201610806167A CN 107793155 B CN107793155 B CN 107793155B
- Authority
- CN
- China
- Prior art keywords
- thermoelectric material
- powder
- ultra
- preparation
- raw materials
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/547—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on sulfides or selenides or tellurides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/65—Reaction sintering of free metal- or free silicon-containing compositions
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/666—Applying a current during sintering, e.g. plasma sintering [SPS], electrical resistance heating or pulse electric current sintering [PECS]
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a method for preparing Cu at ultra-fast speed for the first time2The method for making Se block thermoelectric material uses Cu powder and Se powder as raw material, and firstly the raw materials are uniformly mixed, then the obtained material is undergone the process of mixingThe mixed raw materials are put into a graphite die and placed in plasma activated sintering equipment to prepare single-phase compact Cu in the plasma activated stage of the plasma activated sintering process2Se bulk thermoelectric material Cu2The reaction synthesis and densification process of the Se compound are completed in one step. The process related by the invention is ultra-simple, the preparation time is ultra-short, and the prepared Cu2The Se block thermoelectric material has excellent performance, and ZT is in the range of 773-873K>1.2 is Cu2The scale preparation and large-scale application of the Se compound lay a good foundation.
Description
Technical Field
The invention belongs to the technical field of thermoelectric material preparation, and particularly relates to ultra-fast preparation of Cu2A method of Se bulk thermoelectric material.
Background
The thermoelectric conversion technology directly converts heat energy and electric energy into each other by utilizing thermoelectric materials, has the characteristics of small system volume, high reliability, no emission of pollutants, wide applicable temperature range, effective utilization of low-density energy and the like, and has wide application in the fields of recycling of industrial waste heat and automobile exhaust waste heat, high-precision temperature control, special power technology and the like. The conversion efficiency of thermoelectric material is determined by nondimensional thermoelectric figure of merit ZT (ZT ═ alpha)2σ T/κ, where α is Seebeck coefficient, σ is electrical conductivity, κ is thermal conductivity, and T is absolute temperature). The larger the ZT, the higher the thermoelectric conversion efficiency of the material. The high performance thermoelectric materials currently under investigation are generally Te-based, e.g., PbTe and Bi2Te3. The large-scale commercial application and sustainable development of the Te-based thermoelectric material are greatly restricted by the factors that the Te element is scarce in the earth and expensive and is also a main component element of the solar cell. Therefore, it is of great significance to develop high-performance thermoelectric materials with abundant reserves and low price and to find a low-cost ultra-fast preparation method.
Cu in recent years2Se compounds are of great interest to researchers for their excellent thermoelectric properties because they are typical "phonon liquids" exhibiting a transverse wave damping effect such that they have extremely low lattice thermal conductivity. Meanwhile, the Cu and Se are rich in source and low in priceSo that Cu2Se compounds have great potential for large-scale commercial production. At present Cu2The Se compound is mainly prepared by a long-time solid-phase reaction method, a melting annealing method and a self-propagating combustion synthesis technology, and a block body can be obtained only by further sintering densification. Meanwhile, the problem that the high-temperature treatment cannot be solved all the time is that Se volatilizes, so that the control of components is difficult. Therefore, it is urgent to find a technology that is simple, energy-saving, green and environment-friendly, and simultaneously avoids high-temperature treatment.
Disclosure of Invention
The invention aims to provide a method for preparing Cu at ultra-fast speed2The Se block thermoelectric material has simple technological process and short preparation period, and the prepared Cu has high heat conductivity2The Se block thermoelectric material has excellent performance and is Cu2The scale preparation and large-scale application of the Se compound lay a good foundation.
In order to achieve the purpose, the invention adopts the technical scheme that: ultra-fast preparation of Cu2A process for preparing Se block as thermoelectric material includes such steps as mixing Cu powder and Se powder, Plasma Activating Sinter (PAS) to obtain compact Cu powder2A bulk thermoelectric material of Se.
In the scheme, the time of the plasma activation stage is 30-60 s.
In the scheme, the molar ratio of the Cu powder to the Se powder is (1.8-2) to (1-1.1).
In the above scheme, the parameters of the plasma activation stage are as follows: pulse current of 10-200A, pulse voltage of 1-5V, ON/OFF pulse time of 15-300ms, axial pressure of 30-80MPa, protective atmosphere of vacuum condition, and N2Or Ar gas.
According to the scheme, the single-phase compact Cu can be prepared in 60s, especially 30s2A bulk thermoelectric material of Se.
Cu prepared according to the scheme2The Se block thermoelectric material has excellent performance, and ZT is in the range of 773-873K>1.2。
Cu prepared according to the above scheme2The density of the Se block thermoelectric material is more than 95%, a target product is obtained in one step, the densification of the material is realized, the subsequent resistance heating step of a plasma activated sintering process is not needed, the preparation process can be effectively simplified, and the sintering energy consumption is obviously reduced.
Based on the above, the present invention may be modified, replaced or changed in various forms according to the common technical knowledge and means in the field without departing from the basic technical idea of the present invention.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention discloses a method for preparing Cu directly by using plasma activation stage at ultra-fast speed for the first time2According to the method for the Se block thermoelectric material, a target product can be obtained within 30s, densification is realized in one step, and the complex processes of preparing raw material powder (compound powder) in the early stage and sintering densification in the later stage in the traditional method are avoided; the related process is ultra-simple, the preparation time is ultra-short, and the energy consumption can be obviously reduced.
2) Cu prepared by the invention2The Se bulk thermoelectric material shows excellent performance, and ZT is in the range of 773-873K>1.2. Is Cu2The scale preparation and large-scale application of the Se compound lay a good foundation.
Drawings
FIG. 1 is an XRD pattern of the product obtained in example 1.
FIG. 2 is a field emission scanning electron micrograph of a fresh cross section of the product of example 1 b.
FIG. 3 is a plot of the dimensionless thermoelectric figure of merit ZT versus temperature for the product obtained in example 1.
Figure 4 is the XRD pattern of the product obtained in example 2.
Figure 5 is the XRD pattern of the product obtained in example 3.
Detailed Description
For a better understanding of the present invention, the following examples are included to further illustrate the present invention, but the present invention is not limited to the following examples.
In the following examples, the Cu powder and Se powder used were commercially available products, and the purity was 4N.
Example 1
Ultra-fast preparation of Cu2The method for preparing the Se bulk thermoelectric material comprises the following specific steps:
1) weighing Cu powder and Se powder as raw materials according to a molar ratio of 2:1, wherein 5 groups of the raw materials are 5g, and the raw materials are respectively numbered as a, b, c, d and e;
2) putting each group of raw materials into an agate mortar respectively, and grinding for 20min to obtain uniform mixed powder (mixed raw materials);
3) respectively putting the mixed powder (a, b, c, d, e) into a graphite mold with the diameter of 16mm, compacting, and respectively putting the graphite mold into a Plasma Activated Sintering (PAS) device to activate for 30s (plasma activation stage) to prepare products a, b, c, d, e (Cu)2Se bulk thermoelectric material); wherein the parameters of each sample in the plasma activation stage are set as follows:
a: pulse current 60A, pulse voltage 2V, ON/OFF pulse time 30ms, axial pressure 50MPa, vacuum condition;
b: pulse current 80A, pulse voltage 2V, ON/OFF pulse time 30ms, axial pressure 50MPa, vacuum condition;
c: the pulse current is 100A, the pulse voltage is 2V, the ON/OFF pulse time is 30ms, the axial pressure is 50MPa, and the vacuum condition is realized;
d: pulse current 110A, pulse voltage 3V, ON/OFF pulse time 30ms, axial pressure 50MPa, vacuum condition;
e: pulse current 125A, pulse voltage 3V, ON/OFF pulse time 30ms, axial pressure 50MPa, vacuum condition.
The products obtained in this example were subjected to phase analysis (XRD analysis), and as shown in FIG. 1, the obtained products a, b, c, d, and e were all single-phase Cu2A Se compound. The density of the product is tested by an Archimedes method to find that the density is over 95 percent, which shows that the process not only obtains the target product in a short time, but also realizes the densification in one step. FIG. 2 is a FESEM (field emission scanning Electron microscope) photograph of a fresh cross section of a product b, i.e., in a local areaThere are particles of several tens of nanometers to several micrometers in size. Such a multi-scale structure will effectively scatter phonons, reduce thermal conductivity and thus improve thermoelectric performance. FIG. 3 is a graph of the dimensionless thermoelectric figure of merit of the obtained products a, b, c, d, e as a function of temperature, when the pulse current is 80A, the thermoelectric performance is superior, and ZT is in the range of 773-873K>1.2。
Example 2
Ultra-fast preparation of Cu2Method of Se bulk thermoelectric material (ON/OFF pulse time 50ms, 100ms and 200ms respectively) with the following steps:
1) taking Cu powder and Se powder as raw materials, weighing the Cu powder and the Se powder according to a molar ratio of 2:1, and weighing 3 groups, wherein each group is 5g and is respectively numbered as A1, B1 and C1;
2) putting each part of raw materials into an agate mortar respectively, and grinding for 20min to obtain uniform mixed powder (mixed raw materials);
3) respectively putting the mixed powder (A1, B1 and C1) into graphite molds with phi 16mm, compacting, and respectively putting the graphite molds into a Plasma Activated Sintering (PAS) device to activate for 30s (plasma activation stage) to obtain products A1, B1 and C1(Cu 1, B1 and C1)2Se bulk thermoelectric material); wherein the control parameters in the plasma activation phase are set as: under the vacuum condition of less than 10Pa, axial pressure is 50MPa, pulse current is 80A, pulse voltage is 2V A1 groups, ON/OFF pulse time is 50ms, B1 groups are 100ms, and C1 groups are 200 ms.
The products obtained in this example were subjected to phase analysis (XRD analysis), and as shown in FIG. 4, the obtained products A1, B1 and C1 were all single-phase Cu2A Se compound. The density of the product is tested by an Archimedes method to find that the density is over 95 percent, which shows that the process not only obtains the target product in a short time, but also realizes the densification in one step.
Example 3
Ultra-fast preparation of Cu2Method for Se bulk thermoelectric material (atmosphere N respectively)2And Ar), the specific steps are as follows:
1) taking Cu powder and Se powder as raw materials, weighing the Cu powder and the Se powder according to a molar ratio of 2:1, and weighing 2 groups, wherein each group is 5g and is respectively numbered as A2 and B2;
2) putting each part of raw materials into an agate mortar respectively, and grinding for 20min to obtain uniform mixed powder (mixed raw materials);
3) respectively putting the mixed powder (A2, B2) into graphite molds with phi 16mm, compacting, respectively putting the graphite molds into a Plasma Activated Sintering (PAS) device, and activating for 30s (plasma activation stage) to obtain products A2, B2 (Cu)2Se bulk thermoelectric material); wherein the control parameters in the plasma activation phase are set as: axial pressure is 50MPa, pulse current is 80A, pulse voltage is 2V, and ON/OFF pulse time is 30 ms; protective atmosphere of group A2 is N2And Ar gas is used for the group B2.
The products obtained in this example were subjected to phase analysis (XRD analysis), and as shown in FIG. 5, each of the obtained products A2 and B2 was single-phase Cu2A Se compound. The density of the product is tested by an Archimedes method to find that the density is over 95 percent, which shows that the process not only obtains the target product in a short time, but also realizes the densification in one step.
Of course, the technical proposal of the invention can be realized by weighing the elementary powders Cu and Se as reactants according to the molar ratio of (1.9-2) to (1-1.1) and adjusting the stoichiometric ratio of the two powders within the range;
the above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and changes can be made without departing from the inventive concept of the present invention, and these modifications and changes are within the protection scope of the present invention.
Claims (2)
1. Ultra-fast preparation of Cu2The method for preparing Se block thermoelectric material is characterized by that it uses Cu powder and Se powder as raw material, and mixes them uniformly, then places them into plasma activating sintering equipment, and makes them undergo the process of plasma activating sintering process to obtain the compact Cu2A bulk thermoelectric material of Se;
the parameters of the plasma activation stage are as follows: pulse current of 10-200A, pulse voltage of 1-5V, ON/OFF pulse time of 15-300ms, and axial directionThe pressure is 30-80MPa, the time is 30-60s, the protective atmosphere is vacuum condition, N2Or Ar gas.
2. The ultra-fast Cu preparation method according to claim 12The method for preparing the Se bulk thermoelectric material is characterized in that the molar ratio between the Cu powder and the Se powder is (1.8-2) to (1-1.1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610806167.6A CN107793155B (en) | 2016-09-07 | 2016-09-07 | Ultra-fast preparation of Cu2Method for Se bulk thermoelectric material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610806167.6A CN107793155B (en) | 2016-09-07 | 2016-09-07 | Ultra-fast preparation of Cu2Method for Se bulk thermoelectric material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107793155A CN107793155A (en) | 2018-03-13 |
| CN107793155B true CN107793155B (en) | 2020-01-14 |
Family
ID=61530892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610806167.6A Active CN107793155B (en) | 2016-09-07 | 2016-09-07 | Ultra-fast preparation of Cu2Method for Se bulk thermoelectric material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107793155B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109439939B (en) * | 2018-11-15 | 2020-05-05 | 安徽工业大学 | Rapid preparation method of CuSe block thermoelectric material |
| CN109250692B (en) * | 2018-11-30 | 2022-09-02 | 武汉理工大学 | Autocatalysis low-temperature rapid synthesis of Cu 2 Method for preparing Se-based thermoelectric material |
| CN115353145B (en) * | 2022-08-26 | 2023-11-24 | 中国矿业大学 | Sn (Ba, ca) TiO prepared by vacuum plasma field assisted sol-gel technology 3 Method for preparing powder |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130078478A (en) * | 2011-12-30 | 2013-07-10 | 한국전기연구원 | Fabrication method for te-based thermoelectric materials containing twins formed by addition of dopant and nano particle sintering |
| CN102674842A (en) * | 2012-05-14 | 2012-09-19 | 北京科技大学 | Cu-S-Se ternary thermoelectric material and preparation method thereof |
| CN103909264B (en) * | 2013-06-07 | 2016-05-11 | 武汉理工大学 | A kind of high-performance Cu with nano-pore structure2Se block thermoelectric material and fast preparation method thereof |
| KR101624306B1 (en) * | 2013-09-09 | 2016-05-25 | 주식회사 엘지화학 | Method for manufacturing thermoelectric materials |
| WO2015037014A1 (en) * | 2013-09-12 | 2015-03-19 | Council Of Scientific & Industrial Research | Nanostructured copper-selenide with high thermoelectric figure-of-merit and process for the preparation thereof |
| CN104646671B (en) * | 2015-01-04 | 2016-09-21 | 武汉理工大学 | A kind of supper-fast preparation Cu2the method of Se base thermoelectric power generating component |
| CN104878234B (en) * | 2015-06-17 | 2017-06-13 | 武汉理工大学 | It is a kind of to prepare Ag from homogenizing is quick2The method of Se block thermoelectric materials |
| CN105272258B (en) * | 2015-06-17 | 2017-11-17 | 武汉理工大学 | A kind of Cu2The supper-fast synthetic method of X block thermoelectric materials |
-
2016
- 2016-09-07 CN CN201610806167.6A patent/CN107793155B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107793155A (en) | 2018-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101786162B (en) | Preparation method of bismuth telluride based bulk nano crystalline thermoelectric material | |
| CN103011838B (en) | Preparation method of BiCuSeO-based pyroelectric oxide powder | |
| CN107793155B (en) | Ultra-fast preparation of Cu2Method for Se bulk thermoelectric material | |
| CN101694010B (en) | Preparation method of layered nanostructured InSb pyroelectric material | |
| CN105671344B (en) | One step prepares high-performance CoSb3The method of base thermoelectricity material | |
| CN107793154B (en) | Ultra-fast preparation of Cu2Method for Se/BiCuSeO block composite thermoelectric material | |
| CN105256161B (en) | A kind of Ag2The unburned densification preparation technology of Se block thermoelectric materials | |
| CN110078476B (en) | Al-doped BiCuSeO-based thermoelectric material and preparation method thereof | |
| CN105895795A (en) | Method for preparing composite tin selenide based thermoelectric material | |
| Madre et al. | High thermoelectric performance in Bi2-xPbxBa2Co2Oy promoted by directional growth and annealing | |
| CN105272258A (en) | Super-rapid synthesis method for Cu<2>X block thermoelectric material | |
| CN107794387B (en) | A kind of supper-fast preparation β-Zn4Sb3The method of base block thermoelectric material | |
| CN101913869B (en) | Oxide thermoelectric material capable of being sintered at low temperature and preparation method thereof | |
| CN103555986A (en) | Method for preparing (Bi0.8Sb0.2)2Te3 nano thermoelectric material | |
| CN109087987B (en) | α -MgAgSb based nano composite thermoelectric material and preparation method thereof | |
| CN109250692B (en) | Autocatalysis low-temperature rapid synthesis of Cu 2 Method for preparing Se-based thermoelectric material | |
| CN1614054B (en) | Cobalt antimonide based thermoelectric composite material and its preparation | |
| CN107792838B (en) | Ultra-fast preparation of Ag2Method for producing X-block thermoelectric material | |
| CN112216783B (en) | Preparation method of Ga-Ti doped ZnO block thermoelectric material | |
| CN110112281B (en) | Al-doped Cu-vacancy BiCuSeO-based thermoelectric material and preparation method thereof | |
| CN109205576B (en) | Room-temperature ultra-fast preparation method of copper-based chalcogenide solid solution | |
| CN107324292A (en) | A kind of supper-fast preparation high-performance Cu2The method of Se block thermoelectric materials | |
| CN104218143B (en) | A kind of preparation method of BiAgSeTe base thermoelectricity materials | |
| CN111690985B (en) | Quantum dot doped cuprous sulfide polycrystalline material and preparation method thereof | |
| CN112279652A (en) | Rapid non-equilibrium preparation method for Mg-Si-Sn-Sb based thermoelectric material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |