CN106098923A - A kind of argyrodite thermoelectric material and preparation method thereof - Google Patents
A kind of argyrodite thermoelectric material and preparation method thereof Download PDFInfo
- Publication number
- CN106098923A CN106098923A CN201610578274.8A CN201610578274A CN106098923A CN 106098923 A CN106098923 A CN 106098923A CN 201610578274 A CN201610578274 A CN 201610578274A CN 106098923 A CN106098923 A CN 106098923A
- Authority
- CN
- China
- Prior art keywords
- thermoelectric material
- argyrodite
- preparation
- temperature
- quartz ampoule
- 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
-
- 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
-
- 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
Abstract
The present invention relates to a kind of argyrodite thermoelectric material, its chemical formula is Ag8Sn1‑xNbxSe6, x=0～0.05；The preparation method of this thermoelectric material is with simple substance as raw material, dispensing is carried out by the stoichiometric proportion of described chemical formula, after Vacuum Package, frit reaction quenching and heat-treatment quenching, grind into powder, carrying out vacuum high-temperature hot pressed sintering, the block materials obtained after Slow cooling is argyrodite thermoelectric material.Compared with prior art, the present invention has prepared the high performance thermoelectric material of low heat conduction height thermoelectricity capability, the method exploring the thermoelectric material preparing high-compactness, high mechanical properties and high thermoelectricity capability, this thermoelectric material has extremely low lattice thermal conductivity (0.2～0.4W/m K) in the range of total temperature, when temperature is 900K, thermoelectricity peak value reaches 1.2, average thermoelectricity high-quality zT when 300～850Kave～0.8, it is the thermoelectric material of a class great potential.
Description
Technical field
The invention belongs to novel energy resource material technology field, be specifically related to a kind of low heat conduction high performance argyrodite thermoelectricity material
Material and preparation method thereof.
Background technology
Energy crisis and environmental pollution are to have become the two large problems that the world is urgently to be resolved hurrily.Environmental pollution and energy crisis day
Benefit is serious, precarious in the mode that oil and coal supply for main energy sources, and the development and utilization of cleaning Renewable resource is
Solve the basic demand of energy environment issues.Thermoelectric power source material, realizes heat energy by the carrier transport in semi-conducting material
Mutual with two kinds of form energy of electric energy is changed, because the feature such as noiselessness, pollution-free, environmental friendliness is it is considered to be a class is green
Color sustainable energy transition material, powers in space flight and aviation, industrial afterheat recovery, automobile exhaust heat utilize and obtained extensively
Application.
The conversion efficiency of thermoelectric material is generally weighed by dimensionless thermoelectricity thermoelectricity high-quality zT, zT=S2σ T/ κ, wherein: T
For absolute temperature, S is Seebeck coefficient；σ is electrical conductivity；κ is thermal conductivity, has electron thermal conductivity κEWith lattice thermal conductivity κLTwo
It is grouped into.Due to Seebeck coefficient S, conductivityσ, electron thermal conductivity κEBy carrier concentration phase mutual coupling between three parameters
Closing, a certain parameter of the most single optimization can not improve overall thermoelectric figure of merit.Lattice thermal conductivity, as independent parameter, passes through shape
The means of the lattice thermal conductivity that formation of nanostructured, lattice defect or increase lattice anharmonicity vibration reduce material are in the news,
And finally realize the lifting of thermoelectricity capability.Meanwhile, explore and develop and there is the new material of low lattice thermal conductance be increasingly becoming thermoelectricity
One of main flow direction of investigation of materials.Crystal structure is complicated, relatively big and distortion of lattice the material of molal weight has tended to intrinsic
Relatively low lattice thermal conductivity, is to develop low the main of heat conduction thermoelectric material to instruct thinking.
Argyrodite is the natural minerals that a class is distributed in earth formation, and classes of compounds is rich and varied, general chemistry
Formula is expressed as AgI 8MV XVI 6(M=Si, Ge, Sn and X=S, Se, Te).Argyrodite compound not only has ion conductor
Character and crystal structure is extremely complex, meet the primary condition of thermoelectric material needs.Ag8SiTe6、Ag8GeTe6Existing document
Report has extremely low lattice thermal conductivity, is considered the thermoelectric material with potentiality to be exploited.But, such mechanical strength
Low, sample is very easy to fragmentation in preparation process, and suitable preparation condition is difficult to determine, strongly limit argyrodite at thermoelectricity
The development in field.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and provide a kind of consistency high, mechanical
Argyrodite thermoelectric material of intensity heat conduction preferable, low height thermoelectricity capability and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of argyrodite thermoelectric material, its chemical formula is Ag8Sn1-xNbxSe6, x=0～0.05.
Preferably, described x=0.01～0.05, carrier concentration is of a relatively high.
It is further preferred that during described x=0.05, electric property realizes optimizing, it is thus achieved that higher power factor.
The preparation method of a kind of argyrodite thermoelectric material, comprises the following steps:
(1) Vacuum Package: with purity more than 99.99% simple substance as raw material, carry out according to the stoichiometric proportion of chemical formula
Dispensing, mix homogeneously final vacuum is encapsulated in quartz ampoule；
(2) frit reaction quenching: being heated by quartz ampoule, make raw material react in the molten state, then quench cooling,
Obtain the first ingot casting；
(3) heat-treatment quenching: by the first ingot casting Vacuum Package in quartz ampoule, carries out heat treatment, and then quench cooling,
To the second ingot casting；
(4) pressure sintering: by the second ingot casting grind into powder, be placed in graphite jig, carry out vacuum high-temperature hot pressed sintering,
The block materials obtained after Slow cooling is described argyrodite thermoelectric material.
Preferably, in step (2) with 150～300K/h speed by quartz ampoule from room temperature to 1073～1273K also
Insulation 6～12h, makes raw material react in the molten state.
It is further preferred that in step (2), by quartz ampoule from room temperature to 1173K.
Preferably, in step (3), quartz ampoule from room temperature to 800～1000K and is protected by speed with 150～300K/h
Temperature 2～4 days, carries out heat treatment.
It is further preferred that in step (3), by quartz ampoule from room temperature to 900K, and be incubated 3 days, carry out heat treatment.
Preferably, in step (4), by the second ingot casting grind into powder, it is placed in graphite jig, uses sensing heating, with
The ramp of 100～300K/min to 800～1000K, regulation pressure be 50～70MPa, and constant temperature and pressure process 20～
30min, carries out vacuum high-temperature hot pressed sintering, is then down to room temperature with the speed Slow cooling of 20～30K/min, prepares sulfur silver germanium
Ore deposit thermoelectric material.
It is further preferred that in step (4), the temperature of sintering is 900K, sintering pressure is 65MPa.
Preferably, the Absolute truth reciprocal of duty cycle of the vacuum described in step (1), step (3) and step (4) is no more than 10-1Pa。
Compared with prior art, the method have the advantages that
(1) by raw materials melt-heat treatment-high temperature hot pressing condition being carried out exploration optimization, it is thus achieved that low heat conduction high pyroelectricity
The Ag of energy8SnSe6Block materials, and further by doping niobium (Nb), optimize dosed carrier concentration, obtain the height of zT～1.2
Performance Ag8Sn1-xNbxSe6Block materials.
(2) under preparation condition described in the present invention, it is possible to prepare high-compactness, high mechanical properties and high thermoelectricity capability
Ag8Sn1-xNbxSe6Thermoelectric material.Ag8Sn1-xNbxSe6Material has the relatively low velocity of sound, therefore has in the range of total temperature
Extremely low lattice thermal conductivity (0.2～0.4W/m K).Ag8Sn1-xNbxSe6When temperature is 900K, thermoelectricity peak value reaches 1.2,
Temperature range interval is average thermoelectricity high-quality zT when being 300K～850Kave～0.8, it is the thermoelectric material of a class great potential.
(3) present invention is to Ag8Sn1-xNbxSe6The preparation method of block materials is explored, to raw materials melt-heat
Reason-high temperature hot pressing condition carries out exploring and optimizes, and slow cooling releasable material stress after high temperature hot pressing obtains the block that mechanical strength is high
Body material, this preparation method is to exploitation new sulfur silver germanium mineralising compound (AgI 8MV XVI 6), explore the inherent mechanism of low thermal conductance, deep
Enter to study thermoelectricity capability and there is directive significance.
Accompanying drawing explanation
Fig. 1 is the Ag of different carrier concentration8Sn1-xNbxSe6The graph of a relation of hall mobility (μ) and temperature；
Fig. 2 is the Ag of different carrier concentration8Sn1-xNbxSe6The graph of a relation of resistivity (ρ) and temperature；
Fig. 3 is the Ag of variable concentrations carrier concentration8Sn1-xNbxSe6The graph of a relation of Seebeck coefficient (S) and temperature；
Fig. 4 is the Ag of variable concentrations carrier concentration8Sn1-xNbxSe6Overall thermal conductance (κ) and lattice thermal conductivity (κL) with warm
The graph of a relation of degree；
Fig. 5 is the Ag8Sn of variable concentrations carrier concentration1-xNbxSe6The graph of a relation of zT value and temperature；
Fig. 6 is the Ag of variable concentrations carrier concentration8Sn1-xNbxSe6At the evenly heat that temperature range is 300～800K
Electricity figure of merit zTavgValue and PbTe and CoSb3Average thermoelectric figure of merit.
Detailed description of the invention
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
A kind of argyrodite thermoelectric material, its chemical formula is Ag8Sn1-xNbxSe6, x=0～0.05, passes through in the present embodiment
(as x=0, chemical formula is Ag to take x=0,0.01,0.02,0.03 and 0.058SnSe6, when x=0.01,0.02,0.03 and
When 0.05, i.e. optimize carrier concentration by the Nb of doping variable concentrations), according to following preparation method, obtain different current-carrying
The Ag of sub-concentration8Sn1-xNbxSe6Bulk material:
(1) according to different x values, by consisting of Ag8Sn1-xNbxSe6The stoichiometric proportion of (x=0～0.05) weighs purity
Simple substance stock silver Ag more than 99.99%, stannum Sn, niobium Nb, selenium Se, be positioned over raw material quartz ampoule, and encapsulate stone under vacuo
Ying Guan.
(2) quartz ampoule placing raw material is hung in high temperature Muffle furnace, be to slowly warm up to the speed of 150～300K/h
1073～1273K, and it is incubated 6～12h, rapid quenching cooling afterwards obtains the first ingot casting；This step of the present embodiment select with
The speed of 200K/h is to slowly warm up to 1173K, is incubated 8h at a temperature of 1173K.
(3) the first ingot casting after the high-temperature fusion quenching obtained step (2) carries out heat treatment, with 150～300K/h
Speed is to slowly warm up to 800～1000K, is incubated 2～4 days, and rapid quenching cooling afterwards obtains the second ingot casting；Being somebody's turn to do of the present embodiment
Step selects to be to slowly warm up to 900K with the speed of 200K/h, is incubated 3 days.
(4) by the second ingot casting grind into powder obtained by step (3), powder is placed in graphite jig, uses sensing
Heating, the ramp with 100～300K/min to 577～677K, regulation pressure be 50～70MPa, and constant temperature 20～
30min, carries out vacuum high-temperature hot pressed sintering, is then slowly cooled to room temperature with the speed of 20～30K/min, obtains Ag8Sn1- xNbxSe6Block materials, is described argyrodite thermoelectric material；This step of the present embodiment selects the speed with 200K/min
Rate is warming up to 900K, and regulation pressure is 65MPa, and constant temperature 25min, carries out vacuum high-temperature hot pressed sintering, then with 25K/min's
Speed is slowly cooled to room temperature.
As x=0, chemical formula is Ag8SnSe6, although sample preparation condition is consistent, but the unstability of material itself,
So different Ag8SnSe6Sample carrier concentration numerical value there are differences, therefore as x=0, the carrier concentration of corresponding sample is not
With；As x=0.01, the carrier concentration of thermoelectric material is 7.2 × 1018cm-3；As x=0.02, the current-carrying of thermoelectric material
Sub-concentration is 7.6 × 1018cm-3；As x=0.03, the carrier concentration of thermoelectric material is 6.9 × 1018cm-3；Work as x=0.05
Time, the carrier concentration of thermoelectric material is 7.0 × 1018cm-3。
The Ag of different carrier concentrations8Sn1-xNbxSe6Hall mobility (μ) and temperature relation as shown in Figure 1；From figure
In it can be seen that hall mobility variation with temperature trend is μ～T-1.5, disclose and transport performance mechanism by acoustic phonon scattering
Taking as the leading factor, the thermoelectric material of excellent performance the most all meets phonon acoustic scattering mechanism.
The Ag of different carrier concentrations8Sn1-xNbxSe6The relation of resistivity (ρ) and temperature as in figure 2 it is shown, the figure of this figure
Example is identical with Fig. 1；It can be seen that under the resistivity of low carrier concentration sample rises after a height of appearance first rises with temperature
The trend of fall is because, at high temperature, few sub-effect occurs.Along with the increase of the doping content of Nb, carrier concentration increases, resistivity
Variation tendency with temperature rise and increase, the lifting to thermoelectricity capability is favourable.
The Ag of variable concentrations carrier concentration8Sn1-xNbxSe6Seebeck coefficient (S) and temperature relation as shown in Figure 3；
Seebeck coefficient is that positive number indicates that this material is n-type material, consistent with Hall carrier concentration test result.Low carrier concentration
The Seebeck coefficient value with tem-perature of sample rises downward trend after a height of appearance first rises and is because, at high temperature, few son effect occurs
Should.Along with the increase of the doping content of Nb, carrier concentration increases, and the variation tendency of Seebeck coefficient rises with temperature and increases
Adding, the lifting to thermoelectricity capability is favourable.
The overall thermal conductance (κ) of the Ag8Sn1-xNbxSe6 of variable concentrations carrier concentration and lattice thermal conductivity (κL) and temperature
Relation is as shown in Figure 4；It can be seen that in full Range of measuring temp, Ag8Sn1-xNbxSe6All show extremely low crystalline substance
Lattice thermal conductivity (0.2～0.4W/m K), high thermoelectricity capability is had contributed much by lower thermal conductivity.
The Ag of variable concentrations carrier concentration8Sn1-xNbxSe6ZT value and temperature relation as shown in Figure 5；By doping
Nb, optimizes carrier concentration, is that 850K is in temperature, dimensionless thermoelectric figure of merit peak value～1.2, it was demonstrated that Ag8Sn1-xNbxSe6It is one
The thermoelectric material of class excellent performance.
The Ag of variable concentrations carrier concentration8Sn1-xNbxSe6At the average thermoelectric figure of merit that temperature range is 300～800K
zTavgValue and PbTe and CoSb3Average thermoelectric figure of merit as shown in Figure 6, be followed successively by x=0 (2.2 × 10 from left to right18cm-3)、x
=0 (3.3 × 1018cm-3), x=0.1 (7.2 × 1018cm-3), x=0.2 (7.6 × 1018cm-3), x=0.3 (6.9 × 1018cm-3), x=0.5 (7.0 × 1018cm-3), x=0 (4.2 × 1018cm-3), x=0 (4.0 × 1018cm-3), x=0 (4.7 × 1018cm-3) corresponding Ag8Sn1-xNbxSe6The average thermoelectric figure of merit of sample and PbTe and CoSb3Average thermoelectric figure of merit.During x=0, current-carrying
Sub-concentration is different, is because Ag8SnSe6Intrinsic material unstability, there is some difference for different sample room carrier concentrations.From
It can be seen that Ag in figure8Sn1-xNbxSe6With typical heat electric material PbTe, CoSb3Average thermoelectric figure of merit there is comparability.
Claims (10)
1. an argyrodite thermoelectric material, it is characterised in that its chemical formula is Ag8Sn1-xNbxSe6, x=0～0.05.
A kind of argyrodite thermoelectric material the most according to claim 1, it is characterised in that described x=0.01～0.05.
A kind of argyrodite thermoelectric material the most according to claim 2, it is characterised in that described x=0.05.
The preparation method of a kind of argyrodite thermoelectric material the most as claimed in claim 1, it is characterised in that include following step
Rapid:
(1) Vacuum Package: with purity more than 99.99% simple substance as raw material, carry out dispensing according to the stoichiometric proportion of chemical formula,
Mix homogeneously final vacuum is encapsulated in quartz ampoule；
(2) frit reaction quenching: being heated by quartz ampoule, make raw material react in the molten state, then quench cooling, obtains
First ingot casting；
(3) heat-treatment quenching: by the first ingot casting Vacuum Package in quartz ampoule, carries out heat treatment, and then quench cooling, obtains
Two ingot castings；
(4) pressure sintering: by the second ingot casting grind into powder, be placed in graphite jig, carries out vacuum high-temperature hot pressed sintering, slowly
The block materials obtained after cooling is described argyrodite thermoelectric material.
The preparation method of a kind of argyrodite thermoelectric material the most according to claim 4, it is characterised in that in step (2)
Quartz ampoule from room temperature to 1073～1273K and is incubated 6～12h by the speed with 150～300K/h, makes raw material in molten
React under state.
The preparation method of a kind of argyrodite thermoelectric material the most according to claim 5, it is characterised in that in step (2),
By quartz ampoule from room temperature to 1173K.
The preparation method of a kind of argyrodite thermoelectric material the most according to claim 4, it is characterised in that in step (3)
Quartz ampoule from room temperature to 800～1000K and is incubated 2～4 days by the speed with 150～300K/h, carries out heat treatment.
The preparation method of a kind of argyrodite thermoelectric material the most according to claim 7, it is characterised in that in step (3),
By quartz ampoule from room temperature to 900K, and it is incubated 3 days, carries out heat treatment.
The preparation method of a kind of argyrodite thermoelectric material the most according to claim 4, it is characterised in that in step (4),
By the second ingot casting grind into powder, being placed in graphite jig, use sensing heating, the ramp with 100～300K/min is extremely
800～1000K, regulation pressure is 50～70MPa, and constant temperature and pressure processes 20～30min, carries out vacuum high-temperature hot pressed sintering,
Then it is down to room temperature with the speed Slow cooling of 20～30K/min, prepares argyrodite thermoelectric material.
The preparation method of a kind of argyrodite thermoelectric material the most according to claim 9, it is characterised in that step (4)
In, the temperature of sintering is 900K, and sintering pressure is 65MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610578274.8A CN106098923A (en) | 2016-07-21 | 2016-07-21 | A kind of argyrodite thermoelectric material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610578274.8A CN106098923A (en) | 2016-07-21 | 2016-07-21 | A kind of argyrodite thermoelectric material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106098923A true CN106098923A (en) | 2016-11-09 |
Family
ID=57448997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610578274.8A Pending CN106098923A (en) | 2016-07-21 | 2016-07-21 | A kind of argyrodite thermoelectric material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106098923A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106711317A (en) * | 2016-11-22 | 2017-05-24 | 同济大学 | Sulfur-group lead-compound thermoelectric material and preparation method thereof |
| CN107235477A (en) * | 2017-07-04 | 2017-10-10 | 中国科学院上海硅酸盐研究所 | A kind of N-type high-performance argyrodite thermoelectric material and preparation method thereof |
| CN107359231A (en) * | 2017-06-08 | 2017-11-17 | 同济大学 | A kind of new low heat conduction argyrodite thermoelectric material and preparation method thereof |
| CN108346736A (en) * | 2017-10-16 | 2018-07-31 | 同济大学 | A kind of high-performance silver tellurium compound thermoelectric semiconductor material and preparation method thereof |
| CN108598252A (en) * | 2018-06-07 | 2018-09-28 | 上海大学 | Argyrodite type thermoelectric material and preparation method thereof |
| CN108821771A (en) * | 2018-05-29 | 2018-11-16 | 桂林电子科技大学 | A kind of preparation method of high thermoelectricity capability silver selenium ternary compound polycrystalline bulk material |
| CN109970083A (en) * | 2017-12-27 | 2019-07-05 | 现代自动车株式会社 | N doping sulfide-based solid electrolyte for all-solid-state battery |
| CN110098310A (en) * | 2018-01-30 | 2019-08-06 | 中国科学院宁波材料技术与工程研究所 | A kind of SnSe base thermoelectricity material orientation polycrystalline preparation method |
| CN111116201A (en) * | 2020-01-07 | 2020-05-08 | 北京科技大学 | Preparation method of GeS-based thermoelectric material |
| EP4292982A1 (en) | 2022-06-14 | 2023-12-20 | Akademia Gorniczo-Hutnicza im. Stanislawa Staszica w Krakowie | Gamma-argyrodite structure material for thermoelectric conversion and the method of obtaining the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101556986A (en) * | 2009-05-20 | 2009-10-14 | 南京大学 | Multi-state resistive switching material, thin film prepared therewith, multi-sate resistive switching memory element and application of memory element in memory device |
| CN101821199A (en) * | 2007-10-08 | 2010-09-01 | 锡根大学 | Lithium argyrodite |
| CN102931336A (en) * | 2012-10-19 | 2013-02-13 | 深圳大学 | Germanium telluride (GeTe) based composite thermoelectric material and preparation method thereof |
| CN103872237A (en) * | 2012-12-07 | 2014-06-18 | 中国科学院上海硅酸盐研究所 | Copper-sulfur-based high-performance thermoelectric material and preparation method thereof |
-
2016
- 2016-07-21 CN CN201610578274.8A patent/CN106098923A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101821199A (en) * | 2007-10-08 | 2010-09-01 | 锡根大学 | Lithium argyrodite |
| CN101556986A (en) * | 2009-05-20 | 2009-10-14 | 南京大学 | Multi-state resistive switching material, thin film prepared therewith, multi-sate resistive switching memory element and application of memory element in memory device |
| CN102931336A (en) * | 2012-10-19 | 2013-02-13 | 深圳大学 | Germanium telluride (GeTe) based composite thermoelectric material and preparation method thereof |
| CN103872237A (en) * | 2012-12-07 | 2014-06-18 | 中国科学院上海硅酸盐研究所 | Copper-sulfur-based high-performance thermoelectric material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| LI WEN,ET AL: "Low Sound Velocity Contributing to the High Thermoelectric Performance of Ag<sub>8</sub>SnSe<sub>6</sub>", 《ADV. SCI.》 * |
| ZHANG XIAO,ET AL: "Thermoelectric properties of n-type Nb-doped Ag<sub>8</sub>SnSe<sub>6</sub>", 《J. APPL. PHYS.》 * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106711317B (en) * | 2016-11-22 | 2019-06-11 | 同济大学 | A kind of sulfur family leaded object thermoelectric material and preparation method thereof |
| CN106711317A (en) * | 2016-11-22 | 2017-05-24 | 同济大学 | Sulfur-group lead-compound thermoelectric material and preparation method thereof |
| CN107359231A (en) * | 2017-06-08 | 2017-11-17 | 同济大学 | A kind of new low heat conduction argyrodite thermoelectric material and preparation method thereof |
| CN107359231B (en) * | 2017-06-08 | 2019-12-27 | 同济大学 | Low-heat-conduction Geranite thermoelectric material and preparation method thereof |
| CN107235477A (en) * | 2017-07-04 | 2017-10-10 | 中国科学院上海硅酸盐研究所 | A kind of N-type high-performance argyrodite thermoelectric material and preparation method thereof |
| CN108346736A (en) * | 2017-10-16 | 2018-07-31 | 同济大学 | A kind of high-performance silver tellurium compound thermoelectric semiconductor material and preparation method thereof |
| CN109970083B (en) * | 2017-12-27 | 2022-09-20 | 现代自动车株式会社 | Nitrogen-doped sulfide-based solid electrolyte for all-solid battery |
| US11637313B2 (en) | 2017-12-27 | 2023-04-25 | Hyundai Motor Company | Nitrogen-doped sulfide-based solid electrolyte for all-solid batteries |
| US11631891B2 (en) | 2017-12-27 | 2023-04-18 | Hyundai Motor Company | Nitrogen-doped sulfide-based solid electrolyte for all-solid batteries |
| CN109970083A (en) * | 2017-12-27 | 2019-07-05 | 现代自动车株式会社 | N doping sulfide-based solid electrolyte for all-solid-state battery |
| US11575154B2 (en) | 2017-12-27 | 2023-02-07 | Hyundai Motor Company | Nitrogen-doped sulfide-based solid electrolyte for all-solid batteries |
| CN110098310A (en) * | 2018-01-30 | 2019-08-06 | 中国科学院宁波材料技术与工程研究所 | A kind of SnSe base thermoelectricity material orientation polycrystalline preparation method |
| CN110098310B (en) * | 2018-01-30 | 2023-11-14 | 中国科学院宁波材料技术与工程研究所 | Preparation method of SnSe-based thermoelectric material oriented polycrystal |
| CN108821771B (en) * | 2018-05-29 | 2020-06-09 | 桂林电子科技大学 | Preparation method of silver-selenium ternary compound polycrystalline block material with high thermoelectric performance |
| CN108821771A (en) * | 2018-05-29 | 2018-11-16 | 桂林电子科技大学 | A kind of preparation method of high thermoelectricity capability silver selenium ternary compound polycrystalline bulk material |
| CN108598252A (en) * | 2018-06-07 | 2018-09-28 | 上海大学 | Argyrodite type thermoelectric material and preparation method thereof |
| CN111116201A (en) * | 2020-01-07 | 2020-05-08 | 北京科技大学 | Preparation method of GeS-based thermoelectric material |
| EP4292982A1 (en) | 2022-06-14 | 2023-12-20 | Akademia Gorniczo-Hutnicza im. Stanislawa Staszica w Krakowie | Gamma-argyrodite structure material for thermoelectric conversion and the method of obtaining the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106098923A (en) | A kind of argyrodite thermoelectric material and preparation method thereof | |
| CN108238796B (en) | Copper seleno solid solution thermoelectric material and preparation method thereof | |
| CN103872237B (en) | Copper-sulfur-based high-performance thermoelectric material and preparation method thereof | |
| JP6266099B2 (en) | High performance P-type thermoelectric material having reversible phase transition and method for producing the same | |
| CN106830940A (en) | A kind of GeTe base high-performances thermoelectric material and preparation method thereof | |
| CN105671344B (en) | One step prepares high-performance CoSb3The method of base thermoelectricity material | |
| CN103130200B (en) | Thermoelectricity material compound and preparation method thereof | |
| CN107799646A (en) | A kind of alloy thermoelectric semiconductor material and preparation method thereof | |
| CN107235477A (en) | A kind of N-type high-performance argyrodite thermoelectric material and preparation method thereof | |
| CN111640853B (en) | By Sb and Cu 2 Method for improving thermoelectric performance of n-type PbTe by Te co-doping | |
| CN103236493B (en) | TmCuTe2Compound and its preparation and use | |
| CN109534303A (en) | A kind of high performance low temperature thermoelectric material and preparation method thereof | |
| CN107195767B (en) | Five yuan of N-type thermoelectric materials of one kind and preparation method thereof | |
| CN110408989B (en) | Oxide thermoelectric material BiCuSeO monocrystal and preparation method thereof | |
| CN105449093B (en) | A kind of selenium tin compound semiconductor core/glass-clad composite material thermoelectric fiber and preparation method thereof with high thermoelectric figure of merit | |
| CN107359231B (en) | Low-heat-conduction Geranite thermoelectric material and preparation method thereof | |
| CN105990510B (en) | A kind of copper seleno high performance thermoelectric material and preparation method thereof | |
| CN113421959A (en) | N-type bismuth telluride-based room temperature thermoelectric material and preparation method thereof | |
| CN101857928A (en) | P-type Zn4Sb3 based thermoelectric material and preparation method thereof | |
| CN111312888A (en) | Method for improving SnTe thermoelectric performance by doping Bi, Cu and Cd | |
| CN103811653A (en) | Multi-cobalt p type skutterudite filled thermoelectric material and preparation method thereof | |
| CN101857929A (en) | Zinc antimony based porous p-type thermoelectric material and preparation method thereof | |
| CN106676322B (en) | A kind of environmentally friendly sulfur family stannide thermoelectric material and preparation method thereof | |
| CN101533888B (en) | Method for preparing Yb14MnSb11 semiconductor thermoelectric material | |
| CN108520915A (en) | A kind of high-performance PbTe-SnTe alloy base thermoelectricity materials and preparation method thereof |
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 |
Application publication date: 20161109 |
|
| RJ01 | Rejection of invention patent application after publication |