CN106116587A - A kind of Emission in Cubic Ca2si thermoelectric material and preparation method thereof - Google Patents
A kind of Emission in Cubic Ca2si thermoelectric material and preparation method thereof Download PDFInfo
- Publication number
- CN106116587A CN106116587A CN201610455051.2A CN201610455051A CN106116587A CN 106116587 A CN106116587 A CN 106116587A CN 201610455051 A CN201610455051 A CN 201610455051A CN 106116587 A CN106116587 A CN 106116587A
- Authority
- CN
- China
- Prior art keywords
- cubic
- ball
- emission
- thermoelectric material
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C04B35/58—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/58085—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicides
-
- 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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/401—Alkaline earth metals
-
- 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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/428—Silicon
-
- 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
- C04B2235/658—Atmosphere during thermal treatment
- C04B2235/6581—Total pressure below 1 atmosphere, e.g. vacuum
Abstract
The invention discloses a kind of Emission in Cubic Ca2Si thermoelectric material and preparation method thereof, the method comprises the following steps: (1), by Ca powder and Si powder mix homogeneously under Ar protective atmosphere in proportion, obtains mixture；(2) mixture, mill ball and stainless steel jar mill and electronic balance are put in the glove box being filled with an atmospheric pressure Ar, in glove box after accurate weighing, put in ball grinder, by ball grinder good seal, avoid oxygen to enter, from glove box, then take out ball grinder；(3) by ready ball grinder in step (2), put in ball mill and carry out ball milling with certain rotating speed, make powder fully react；(4) powder completely reacted in step (3) is taken out, load in the stainless steel mould of required specification, use the mode of vacuum plasma sintering to carry out vacuum-sintering tabletting, obtain Emission in Cubic Ca2Si lamellar or bulk thermoelectric material.The advantages such as it is simple that the present invention has technique, processing ease, low cost, the Emission in Cubic Ca of gained2Si lamellar or bulk material, product purity is higher, is tightly combined, and has preferable industrialization prospect.
Description
Technical field
The present invention relates to thermoelectricity field of functional materials, be specifically related to a kind of Emission in Cubic Ca2Si thermoelectric material and preparation side thereof
Method.
Background technology
Thermoelectric material is a kind of to be capable of heat energy and environmental type functional material that electric energy is the most mutually changed；With heat
The thermoelectric device that electric material makes has that size is little, light weight, without any mechanical rotation part, work noiseless, use the longevity
Life is long, there is not the advantages such as environmental pollution problem, can be widely applied to the necks such as thermoelectric generator, thermoelectric refrigerator and sensor
Territory.High performance thermoelectric material is one of hot subject of current international material research field.The performance of thermoelectric material is mainly by nothing
Dimension quality factor ZT value characterizes: ZT=T σ α2/ κ, wherein T is absolute temperature, and σ is the electrical conductivity of material, and α is Seebeck system
Number, κ is thermal conductivity.
At present unit's its excellent performance of procatarxis such as Ga, As, In, Pb, Te and be widely used in manufacturing semi-conducting material and partly leading
Body device, but these element major parts are poisonous, and resource faces exhaustion.The elements such as Fe, Si, Ca reserves on earth are big,
Harmless to organism.Alkaline earth metal silicide Ca2Si material, its direct band gap is about 0.31eV, the longest by resource longevity
Ca, Si are elementary composition, can recycle, pollution-free to the earth, and due to calcium silicon compound Ca2Si has with existing silicon-based technologies
Excellent compatibility it is considered to be the most promising novel environmental close friend's semi-conducting material, at solaode and thermoelectricity
The fields such as conversion have potential application prospect.
At present, owing to Ca atom has a highest vapour pressure, therefore Ca atom be easy to from silicon substrate evaporation thus not
It is beneficial to the phase counterdiffusion of Ca and Si, forms the silicide of Ca.And the existence of the multiple phase of Ca-Si system, Ca atomic deposition serves as a contrast at Si
Ca is grown at the end2During Si, Ca can be concurrently formed5Si3, CaSi, CaSi2Deng the silicide of calcium, therefore in silicon face epitaxial growth
Ca2Si is extremely difficult.Ca2Si has two kinds of crystal structures: simple orthorhombic structure and cubic structure.The wherein sky of simple orthorhombic structure
Between group be P, lattice paprmeter is a=0.7667nm, b=0.4799nm, c=0.9002nm, comprises 4 Ca in structure cell2Si molecule, 12
Individual atom, Ca atom is on two non-equivalent positions.The lattice paprmeter of cubic structure is a=0.7016nm, and structure cell also comprises 4
Individual Ca2Si molecule, 12 atom Ca atoms are also on two non-equivalent positions.Either Ca2The X-ray diffraction XRD of Si powder
Analyze, or the cohesive energy calculation of two kinds of structures, result all shows, simple orthorhombic structure is stable phase, and Emission in Cubic Ca2Si's
Unstability makes it prepare and application is greatly limited, and present invention incorporates mechanical alloying method and the high pressure of low temperature
Plasma discharging vaccum sintering process, enables material to carry out the vacuum environment of reaction more high pressure low temperature at a lower temperature
Under sinter into densification Emission in Cubic Ca2Si, is expected to one of thermoelectric material being applied to middle warm area, can be widely applied to each neck
Territory.Currently, with respect to Emission in Cubic Ca2The most nearly no report of Si thermoelectric material.
Summary of the invention
Present invention aims to the deficiencies in the prior art, it is provided that a kind of Emission in Cubic Ca2Si thermoelectric material and system thereof
Preparation Method.Preparation manipulation technique is simple, product component is easy to control for this, obtained Emission in Cubic Ca2Si thermoelectric material is expected to application
One of thermoelectric material in middle warm area, can be widely applied to every field.
For solving the problems referred to above, the present invention adopts the following technical scheme that
A kind of Emission in Cubic Ca2The preparation method of Si thermoelectric material, comprises the following steps:
(1) Ca powder and Si powder are pressed mol ratio mix homogeneously under Ar protective atmosphere of 2.0 ~ 2.5:1, obtains mixture；
(2) mixture, mill ball and stainless steel jar mill and the electronic balance of step (1) are put into and be filled with an atmospheric pressure Ar
Glove box in, in glove box after accurate weighing, put in ball grinder, by ball grinder good seal, it is to avoid oxygen enter, then
Ball grinder is taken out from glove box；
(3) by ready ball grinder in step (2), put in ball mill with the rotating speed of 500 ~ 2000 rpm carry out ball milling 5 ~
100 h, make powder fully react；
(4) powder completely reacted in step (3) is taken out, load in the stainless steel mould of required specification, use vacuum plasma
The mode of sintering, is warming up to 100 ~ 500 DEG C under the pressure of 50 ~ 600 MPa and keeps 10 ~ 120 min to carry out vacuum-sintering pressure
Sheet, obtains Emission in Cubic Ca2Si lamellar or bulk thermoelectric material.
In step (2), ball material mass ratio is: 2 ~ 16:1.
In step (2), the particle diameter of mill ball is 0.2 ~ 1.5 cm, uses acetone, ethanol to carry out ultrasound wave successively clear before using
Washing, ultrasonic waves for cleaning total time is 10 ~ 30 min.
In step (4), sintering heating rate is 5 ~ 20 DEG C/min.
The present invention compared with prior art has the advantage that
1) Cryomilling and plasma discharging vaccum sintering process are combined by the present invention, and technique is simple, processing ease, and
And reaction temperature is relatively low, it is difficult to oxidation reaction and the Ca that Ca atom occurs2The decomposition of Si phase, composition is controlled；
2) sintering process of the present invention supports the use into stainless steel mould, it is possible to bear higher sintering pressure at a lower temperature
Power, efficiently controls oxidation and the volatilization of Ca in general sintering process, and therefore product composition is purer, and density is higher, final thing phase
Structure is Emission in Cubic Ca2Si；
3) material to the present invention carries out XRD diffraction analysis and shows, this thing is Emission in Cubic Ca mutually2Si (see Fig. 1)；By to SEM
The analysis of photo draws end product consistency preferably (see Fig. 3), can show that final Ca, Si compare about 2:1 by spectrogram from EDS
(seeing Fig. 4).
Accompanying drawing explanation
Fig. 1 is the XRD spectrum of the embodiment of the present invention 1 correspondence；
Fig. 2 is discharge plasma sintering schematic diagram；
Fig. 3 is the scanning electron microscope pattern of the block thermoelectric material of the embodiment of the present invention 1 correspondence；
The transmission electron microscope pattern of the block thermoelectric material of Fig. 4 embodiment 1 correspondence.
Specific implementation method
Below by embodiment, technical scheme is described in detail, but the protected content of the present invention is not limited only to
This.
Embodiment 1
A kind of Emission in Cubic Ca2The preparation method of Si thermoelectric material, comprises the following steps:
(1) Ca powder and Si powder are pressed the mol ratio of 2.0:1 mix homogeneously under Ar protective atmosphere, obtain mixture；
(2) step (1) gained mixture, mill ball and stainless steel jar mill and electronic balance are put into it is filled with an atmospheric pressure
In the glove box of Ar, wherein ball material mass ratio is 3:1 configuration, in glove box after accurate weighing, puts in ball grinder, by ball milling
Tank good seal, it is to avoid oxygen enters, then takes out ball grinder from glove box；
(3) by ready ball grinder in step (2), put in ball mill and carry out ball milling 5 h with the rotating speed of 2000 rpm, make powder
End fully reaction；
(4) being taken out by powder completely reacted in step (3), loading diameter of bore is in 10 mm stainless steel moulds, uses vacuum etc.
The mode of ion sintering, is warming up to 300 DEG C under the pressure of 300 MPa and keeps 120 min to carry out vacuum-sintering tabletting, heat up
Speed is 5 DEG C/min, obtains Emission in Cubic Ca2Si disc-shaped thermoelectric material.
In stainless-steel vacuum ball grinder, the particle diameter of mill ball is 0.2 cm, uses acetone, ethanol to surpass before using successively
Sound wave cleans, and ultrasonic waves for cleaning total time is 30 min.
Embodiment 2
A kind of Emission in Cubic Ca2The preparation method of Si thermoelectric material, comprises the following steps:
(1) Ca powder and Si powder are pressed the mol ratio of 2.3:1 mix homogeneously under Ar protective atmosphere, obtain mixture；
(2) mixture, mill ball and stainless steel jar mill and the electronic balance of step (1) gained are put into and be filled with an air
In the glove box of pressure Ar, wherein ball material mass ratio is 16:1 configuration, in glove box after accurate weighing, puts in ball grinder, will
Ball grinder good seal, it is to avoid oxygen enters, then takes out ball grinder from glove box；
(3) by ready ball grinder in step (2), put in ball mill and carry out ball milling 100 h with the rotating speed of 500 rpm, make
Powder fully reacts；
(4) powder completely reacted in step (3) is taken out, load in the stainless steel mould of hollow a size of 12 mm × 6 mm, adopt
By the mode of vacuum plasma sintering, under the pressure of 50 MPa, it is warming up to 500 DEG C keeps 20 min to carry out vacuum-sintering pressure
Sheet, heating rate is 10 DEG C/min, obtains Emission in Cubic Ca2Si bulk thermoelectric material.
In stainless-steel vacuum ball grinder, the particle diameter of mill ball is 1.5 cm, uses acetone, ethanol to surpass before using successively
Sound wave cleans, and ultrasonic waves for cleaning total time is 10 min.
Embodiment 3
A kind of Emission in Cubic Ca2The preparation method of Si thermoelectric material, comprises the following steps:
(1) Ca powder and Si powder are pressed the mol ratio of 2.5:1 mix homogeneously under Ar protective atmosphere, obtain mixture；
(2) described mixture, mill ball and stainless steel jar mill and electronic balance are put into it is filled with the hands of an atmospheric pressure Ar
In casing, wherein ball material mass ratio is 8:1 configuration, in glove box after accurate weighing, puts in ball grinder, is sealed by ball grinder
Good, it is to avoid oxygen enters, from glove box, then take out ball grinder；
(3) by stainless-steel vacuum ball grinder ready in step (2), put in ball mill the rotating speed with 2000 rpm and carry out ball
Grind 50 h, make powder fully react；
(4) powder completely reacted in step (3) is taken out, load in the mm stainless steel mould of hollow 10 mm × 10, use vacuum
The mode of plasma agglomeration, is warming up to 100 DEG C under the pressure of 600 MPa and keeps 60 min to carry out vacuum-sintering tabletting, heat up
Speed is 8 DEG C/min, obtains the Emission in Cubic Ca that the length of side is 10mm2Si bulk thermoelectric material.
In stainless-steel vacuum ball grinder, mill ball particle diameter is 1.0 cm, uses acetone, ethanol to carry out successively ultrasonic before using
Ripple cleans, and ultrasonic waves for cleaning total time is 20 min.
The electrical property of sample corresponding in table 1 embodiment
The foregoing is only presently preferred embodiments of the present invention, all equalizations done according to scope of the present invention patent change and repair
Decorations, all should belong to the covering scope of the present invention.
Claims (5)
1. an Emission in Cubic Ca2The preparation method of Si thermoelectric material, it is characterised in that: comprise the following steps:
(1) Ca powder and Si powder are pressed mol ratio mix homogeneously under Ar protective atmosphere of 2.0 ~ 2.5:1, obtains mixture；
(2) mixture, mill ball and stainless steel jar mill and the electronic balance of step (1) are put into and be filled with an atmospheric pressure Ar
Glove box in, in glove box after accurate weighing, put in ball grinder, by ball grinder good seal, it is to avoid oxygen enter, then
Ball grinder is taken out from glove box；
(3) by ready ball grinder in step (2), put in ball mill with the rotating speed of 500 ~ 2000 rpm carry out ball milling 5 ~
100 h, make powder fully react；
(4) powder completely reacted in step (3) is taken out, load in the stainless steel mould of required specification, use vacuum plasma
The mode of sintering, is warming up to 100 ~ 500 DEG C under the pressure of 50 ~ 600 MPa and keeps 10 ~ 120 min to carry out vacuum-sintering pressure
Sheet, obtains Emission in Cubic Ca2Si lamellar or bulk thermoelectric material.
Emission in Cubic Ca the most according to claim 12The preparation method of Si thermoelectric material, it is characterised in that: ball in step (2)
Material mass ratio is: 2 ~ 16:1.
Emission in Cubic Ca the most according to claim 12The preparation method of Si thermoelectric material, it is characterised in that: step is ground in (2)
The particle diameter of abrading-ball is 0.2 ~ 1.5 cm, uses acetone, ethanol to carry out ultrasonic waves for cleaning, ultrasonic waves for cleaning total time before using successively
It is 10 ~ 30 min.
Emission in Cubic Ca the most according to claim 12The preparation method of Si thermoelectric material, it is characterised in that: step (4) is burnt
Knot heating rate is 5 ~ 20 DEG C/min.
5. the Emission in Cubic Ca that a preparation method as described in any one of claim 1-4 prepares2Si thermoelectric material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610455051.2A CN106116587A (en) | 2016-06-22 | 2016-06-22 | A kind of Emission in Cubic Ca2si thermoelectric material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610455051.2A CN106116587A (en) | 2016-06-22 | 2016-06-22 | A kind of Emission in Cubic Ca2si thermoelectric material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106116587A true CN106116587A (en) | 2016-11-16 |
Family
ID=57470428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610455051.2A Pending CN106116587A (en) | 2016-06-22 | 2016-06-22 | A kind of Emission in Cubic Ca2si thermoelectric material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106116587A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108218425A (en) * | 2018-01-24 | 2018-06-29 | 福州大学 | A kind of cubic phase Ca of Sb doping2Ge base thermoelectricity materials and preparation method thereof |
| CN108358208A (en) * | 2018-04-28 | 2018-08-03 | 福州大学 | A kind of preparation method of the silicide of nanometer calcium |
| CN108502887A (en) * | 2018-04-28 | 2018-09-07 | 福州大学 | A kind of preparation method of the silicide of chemical method synthesis calcium |
| CN108565330A (en) * | 2018-04-28 | 2018-09-21 | 福州大学 | A kind of preparation method of the silicide of the calcium as thermoelectric material |
| CN110354959A (en) * | 2019-08-07 | 2019-10-22 | 江西省科学院应用物理研究所 | A kind of anaerobic ball grinding method and device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002285274A (en) * | 2001-03-27 | 2002-10-03 | Daido Steel Co Ltd | Mg-Si BASED THERMOELECTRIC MATERIAL AND PRODUCTION METHOD THEREFOR |
| CN101589480A (en) * | 2006-12-20 | 2009-11-25 | 昭和Kde株式会社 | Thermo-electric converting materials, process for producing the same, and thermo-electric converting element |
| CN102897768A (en) * | 2012-09-06 | 2013-01-30 | 中国科学院青海盐湖研究所 | Preparation method for Mg2Si thermoelectricity material |
-
2016
- 2016-06-22 CN CN201610455051.2A patent/CN106116587A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002285274A (en) * | 2001-03-27 | 2002-10-03 | Daido Steel Co Ltd | Mg-Si BASED THERMOELECTRIC MATERIAL AND PRODUCTION METHOD THEREFOR |
| CN101589480A (en) * | 2006-12-20 | 2009-11-25 | 昭和Kde株式会社 | Thermo-electric converting materials, process for producing the same, and thermo-electric converting element |
| CN102897768A (en) * | 2012-09-06 | 2013-01-30 | 中国科学院青海盐湖研究所 | Preparation method for Mg2Si thermoelectricity material |
Non-Patent Citations (4)
| Title |
|---|
| C. WEN ET AL.: "Electrical Properties of Ca2Si Sintered Compact Synthesized by Spark Plasma Sintering", 《PHYSICS PROCEDIA》 * |
| YOSHIFUMI WARASHINA ET AL.: "Growth of Ca-Germanide and Ca-Silicide Crystals by Mechanical Alloying", 《JOURNAL OF SURFACE SCIENCE AND NANOTECHNOLOGY》 * |
| 朱鸿民等: "《冶金研究 2010年》", 31 December 2010, 冶金工业出版社 * |
| 程继贵等: "《第十五届华东五省一市粉末冶金技术交流会论文集》", 31 January 2014, 合肥工业大学出版社, * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108218425A (en) * | 2018-01-24 | 2018-06-29 | 福州大学 | A kind of cubic phase Ca of Sb doping2Ge base thermoelectricity materials and preparation method thereof |
| CN108218425B (en) * | 2018-01-24 | 2020-11-27 | 福州大学 | Sb-doped cubic phase Ca2Ge-based thermoelectric material and preparation method thereof |
| CN108358208A (en) * | 2018-04-28 | 2018-08-03 | 福州大学 | A kind of preparation method of the silicide of nanometer calcium |
| CN108502887A (en) * | 2018-04-28 | 2018-09-07 | 福州大学 | A kind of preparation method of the silicide of chemical method synthesis calcium |
| CN108565330A (en) * | 2018-04-28 | 2018-09-21 | 福州大学 | A kind of preparation method of the silicide of the calcium as thermoelectric material |
| CN110354959A (en) * | 2019-08-07 | 2019-10-22 | 江西省科学院应用物理研究所 | A kind of anaerobic ball grinding method and device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106116587A (en) | A kind of Emission in Cubic Ca2si thermoelectric material and preparation method thereof | |
| CN102931335B (en) | A kind of Graphene is combined thermoelectric material of cobalt stibide based skutterudite and preparation method thereof | |
| CN102556941B (en) | A kind of cobaltosic oxide nano linear array, its preparation method and the purposes as lithium ion battery negative | |
| CN108374198B (en) | A kind of monocrystalline Bi2Te3The preparation method of thermoelectric material | |
| CN104046876B (en) | A kind of Graphene/Cu2AX3Type thermoelectric composite material and preparation method | |
| CN105200520B (en) | One kind prepares Bi2(SexTe1‑x)3The method of single crystal nanoplate | |
| CN102386321A (en) | Nanometer thermoelectric powder material preparing method | |
| CN111793824B (en) | Surface-modified high-nickel cathode material and preparation method and application thereof | |
| CN104477991A (en) | Preparation method of low-thermal-conductivity CuSbS<2+x> thermoelectric material | |
| CN104263986A (en) | Ultrafast preparation method of high-performance SnTe based thermoelectric material | |
| CN101435029A (en) | Rapid preparation of high performance nanostructured filling type skutterudite thermoelectric material | |
| CN109650435A (en) | A kind of copper sulfide base thermoelectrical composite material and preparation method thereof | |
| CN107887495A (en) | An a kind of step prepares Cu2The method of Se/BiCuSeO composite thermoelectric materials | |
| CN106098922B (en) | A kind of Cu doping Emission in Cubic Ca2Si thermoelectric materials | |
| CN110408989B (en) | Oxide thermoelectric material BiCuSeO monocrystal and preparation method thereof | |
| CN103555986B (en) | Method for preparing (Bi0.8Sb0.2)2Te3 nano thermoelectric material | |
| CN108615806B (en) | A kind of N-type SnSe thermoelectric material and preparation method thereof | |
| CN107240637B (en) | A kind of cubic phase Cu3SbS3Base thermoelectricity material and preparation method thereof | |
| CN103811653B (en) | Multi-cobalt p type skutterudite filled thermoelectric material and preparation method thereof | |
| CN106129241A (en) | Solid reaction process prepares the method for stacking faults chalcogenide thermoelectric material | |
| CN105932148B (en) | A kind of Ag doping Emission in Cubic Ca2Si thermoelectric materials | |
| CN108258110A (en) | A kind of method for preparing SiGe thermoelectric materials | |
| CN105859299A (en) | Na-doped cubic phase Ca2Si thermoelectric material and preparation method thereof | |
| CN103409656A (en) | Thermoelectric material Mg2Sn and preparation method thereof | |
| CN104946918A (en) | New method for quickly preparing AgInSe2 based thermoelectric material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161116 |