CN104310457A - Thermoelectric material capable of inhibiting Cu ion migration and method for inhibiting Cu ion migration in Cu-base thermoelectric material - Google Patents
Thermoelectric material capable of inhibiting Cu ion migration and method for inhibiting Cu ion migration in Cu-base thermoelectric material Download PDFInfo
- Publication number
- CN104310457A CN104310457A CN201410520197.1A CN201410520197A CN104310457A CN 104310457 A CN104310457 A CN 104310457A CN 201410520197 A CN201410520197 A CN 201410520197A CN 104310457 A CN104310457 A CN 104310457A
- Authority
- CN
- China
- Prior art keywords
- base thermoelectricity
- big current
- thermoelectricity material
- ion migration
- transition metal
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/12—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to a thermoelectric material capable of inhibiting Cu ion migration and a method for inhibiting Cu ion migration in a Cu-base thermoelectric material. The chemical composition of the thermoelectric material is Cu[2-m-n]TnX, wherein X is S or Se, T is an immovable transition metal element under the action of heavy current, 0<=m<=1, and 0<n<=0.5.
Description
Technical field
The present invention relates to thermoelectric material field, be specifically related to a kind of novel high-performance Cu base thermoelectricity material that can suppress Cu ion migration and preparation method thereof, also relate to a kind of method improving Cu base thermoelectricity material stability, more particularly, a kind of method that in the Cu of suppression sill, Cu ion moves under big current effect is related to.
Background technology
Thermoelectric generation technology received in recent years in the world as a kind of novel regeneration clean energy technology attractes attention widely.It utilizes the Seebeck effect of semiconductor material, directly heat energy and electric energy are changed mutually, have that the life-span is long, reliability is high, environmental friendliness, use temperature scope are wide, can effectively utilize the features such as low density energy, the recycling of used heat and waste heat of automotive exhaust gas more than industry, high precision temperature control device, and the high-technology field such as Military Power has significant advantage.
But traditional thermoelectric material is as Bi
2te
3, PbTe, SiGe etc. are often containing rare element (as Te and Ge) or toxic element (as Pb), therefore it is restricted (Chemistry of Materials2013 to a great extent being applied in of civil area, 25,2911).This makes to find cheap, that environment amenable novel high-performance thermoelectric material becomes thermoelectricity field hot research direction.
In recent years, the people such as Liu and He finds Cu sill Cu
2-mx (X=S or Se, m represent Cu vacancy content) has very excellent thermoelectricity capability, and its highest thermoelectric figure of merit is 1.7, can to compare favourably (Nature Materials2012,11,422 by conventional thermoelectric materials, Advanced Materials2014,26,3974).The earlier application CN103130200A of the applicant discloses a kind of Thermoelectricity material compound, and its chemical constitution is Cu
2-xse, wherein, 0≤x≤0.15, its thermal conductivity is low and have good thermoelectric figure of merit.Cu sill has with low cost, abundant raw material, the feature such as environmentally friendly, and therefore this compounds has attracted the extensive concern of thermoelectricity researchist, has shown very wide application prospect.
Restricting current Cu sill Cu
2-ma principal element of X (X=S or Se) large-scale application is the Cu ion migration behavior (J.Electron Materials2013,42,2014, Advanced Energy Materials2014,1301581) under big current effect.At high temperature, Cu
2-mx (X=S or Se) is fast-ionic conductor, wherein among the Cu atom tetrahedron that is randomly distributed in X atom host lattice and trihedron space, and there is directional migration behavior under big current effect.From the viewpoint of thermo-electric device practical application, the long service stability of Cu ion migration behavior to Cu sill thermo-electric device is totally unfavorable.The electric current that thermo-electric device produces under the temperature difference can drive the Cu ion in thermoelectric material to move along the sense of current, causes electric current to flow into the phenomenon of the poor Cu of end and the rich Cu of outflow of bus current end.This migration, by destroying the homogeneity of material, changes its carrier concentration, and then has a strong impact on the thermoelectricity capability of material.Particularly, when Cu ionic transporting quantity acquires a certain degree, when namely in material matrix, remaining Cu is not enough to maintain original crystalline structure, will there is crystal structure transition and even decompose in thing originally, cause the complete failure of thermo-electric device mutually.With Cu
2-mthe people such as S is example, Dennler find at room temperature to Cu
2s sample applies 24A/cm
2electric current, only namely there is obvious Cu simple substance enrichment phenomenon (Advanced Energy Materials2014,1301581) at outflow of bus current end after 24 hours.Be illustrated in figure 1 Cu under big current effect
2the time dependent schematic diagram of S material resistance.Due to Cu
2cu content in the resistance of S and material is closely related, so the change of its resistance can reflect the amplitude of Cu ion migration in material well.As shown in Figure 1, galvanization is after 5 seconds, Cu
2namely the resistance of S drop to 45% of initial resistance; Galvanization is after 2000 seconds, Cu
2namely the resistance of S drop to 10% of initial resistance.Further, in 60 seconds-2000 seconds regions, because crystalline structure is destroyed, Cu
2there is rapid fluctuation in the resistance of S.This Cu ion migration behavior under big current effect will have a strong impact on Cu
2the military service stability of S base thermo-electric device.For Cu
2-mse material, the people such as Brown also report similar phenomenon, namely under big current effect material due to the migratory behaviour of Cu ion rapid failure (J.Elect.Mater.2013,42,2014).Eighties of last century sixties, Minnesota Mining and Manufacturing Company and NASA jet power laboratory once proposed to utilize Cu
2- mx base thermo-electric device replaces traditional sige material for survey of deep space satellite provides power supply, but experience reaches vicennial research to be found still to solve the migration problem of above-mentioned Cu ion under big current effect, this plan is finally caused to be forced to stop (Thermoelectric generator testing and RTG degradation mechanisms evaluation.Progress report No.SAN-0959-T2, DOI:10.2172/5531078).Up to now, at Cu
2-min X (X=S or Se) material, also show successfully effectively to suppress the Cu ion migration behavior under big current effect without any open report.
In sum, a kind of effective means, in the urgent need to a kind of Cu base thermoelectricity material that effectively can suppress wherein Cu ion migration, is that is badly in need of to suppress Cu sill Cu in this area
2-mthe migratory behaviour of Cu ion under big current effect in X (X=S or Se).
Summary of the invention
In the face of the problems referred to above that prior art exists, the present invention aims to provide a kind of Cu base thermoelectricity material that effectively can suppress wherein Cu ion migration, and a kind of method suppressing Cu ion migration in Cu base thermoelectricity material.
A first aspect of the present invention provides Cu base thermoelectricity material, and the chemical constitution of described thermoelectric material is Cu
2-m-nt
nx, wherein, X is S or Se, T is immovable transition metal under big current effect, 0≤m≤1,0 < n≤0.5.
Thermoelectricity material compound provided by the invention is semi-conductor, compared to traditional Cu base thermoelectricity material, (thermal conductivity is low can not only to keep the original excellent thermoelectricity capability of material, there is good thermoelectric figure of merit ZT), and replace Cu due to transition metal T part immovable under being used in big current effect
2-mcu atom in X, impact even destroys the migrating channels of original Cu ion, and then effectively reduces Cu mobility of ions, improves the stability of material, has fabulous prospects for commercial application.
Preferably, 0.02≤m≤0.5; 0.01≤m≤0.25; T is at least one transition metal in Cr, Mn, Fe, Co, Ni and Zn.
Described big current can be 1 ~ 12A/cm
2, the initial resistance of relatively described Cu base thermoelectricity material, after the described big current 1000S of applying, the fall of the resistance of described Cu base thermoelectricity material is lower than 20%.
On the other hand, the present invention also provides a kind of method preparing above-mentioned Cu base thermoelectricity material compound, comprising:
Get that mol ratio is the copper of (2-m-n): n:1, T simple substance and X simple substance Vacuum Package is carried out to it;
Melting treatment 0.5 ~ 3000 hour at 700 ~ 1400 DEG C;
Anneal 1 ~ 3000 hour at 300 ~ 900 DEG C; And
300 ~ 800 DEG C, carry out hot pressed sintering or discharge plasma sintering under 10 ~ 500MPa.
In invention, Vacuum Package, preferably at rare gas element, such as, is carried out under argon shield.Vacuum Package can using plasma or flame gun packaged type.
Preparation method's raw material of the present invention is simple, cost is low and technical process simple, and controllability is high, reproducible, is applicable to scale production.Utilize the Cu that method provided by the present invention obtains
2-m-nt
nx material (0≤m≤1,0≤n≤0.5), the behavior of Cu ion migration is largely suppressed, and stability of material significantly improves, and can meet the demand of practical application.
Again on the one hand, the present invention also provides a kind of method suppressing Cu ion migration in Cu base thermoelectricity material, and under adopting big current effect, immovable transition metal T part replaces Cu base thermoelectricity material Cu
2-mcu atom in X consists of Cu to be formed
2-m-nt
nthe thermoelectric material of X, wherein, X is S or Se, 0≤m≤1,0 < n≤0.5.
Preferably, 0.02≤m≤0.5; 0.01≤m≤0.25; T is at least one transition metal in Cr, Mn, Fe, Co, Ni and Zn.
Method of modifying of the present invention replaces Cu by immovable transition metal T (T is at least one or more in transition metal Cr, Mn, Fe, Co, Ni or Zn) part under being used in big current effect
2-mcu atom in X, impact even destroys the migrating channels of original Cu ion, and then effectively reduces Cu mobility of ions, improves the stability of material.And the method should keep the original excellent thermoelectricity capability of material, and there is the features such as with low cost, technique is simple, reliability is high, be convenient to the preparation of extensive mass.
Accompanying drawing explanation
Fig. 1 illustrates at 573K temperature, Cu
2s reference substance is at big current effect (12A/cm
2) electrical resistance time variations schematic diagram, wherein R/R afterwards
0represent resistance relatively to change, R
0for sample initial resistance, R is the resistance of sample after big current logical time rating;
Fig. 2 illustrates material C u of the present invention
2-m-nt
nin X (X=S or Se), under big current effect, immovable T atom suppresses Cu ion migration principle schematic, and wherein open circles represents Cu atom; Filled circles represents T atom, and curve arrow represents Cu ion migration path;
Fig. 3 illustrates at 573K temperature, examples material Cu of the present invention
1.97fe
0.01s sample is at big current effect (12A/cm
2) electrical resistance time variations schematic diagram afterwards;
Fig. 4 illustrates at 573K temperature, examples material Cu of the present invention
1.96ni
0.02s sample is at big current effect (12A/cm
2) electrical resistance time variations schematic diagram afterwards;
Fig. 5 illustrates at 573K temperature, examples material Cu of the present invention
1.25fe
0.25s sample is at big current effect (12A/cm
2) electrical resistance time variations schematic diagram afterwards.
Embodiment
With reference to Figure of description, and further illustrate the present invention with the following embodiments, should be understood that Figure of description and following embodiment are only for illustration of the present invention, and unrestricted the present invention.
The invention provides a kind of prepare big current effect under there is the method for the Cu base thermoelectricity material of high stability, the method effectively can suppress Cu
2-mthe migration of Cu ion under big current effect in X (X=S or Se) material, improves the military service stability of Cu base thermoelectricity material, makes material meet the demand of thermo-electric device practical application.Method provided by the present invention, with low cost, technique is simple, is convenient to the preparation of extensive mass.Described method replaces Cu by transition metal T part immovable under being used in big current effect
2-mcu atom in X, forms Cu
2-m-ntnX material (0≤m≤1,0≤n≤0.5), wherein immovable transition metal T occupies Cu position, can affect and even destroy original Cu ionic transport passages, moving freely of restriction Cu ion, and then the mobility significantly reducing Cu ion, improve the stability of material.
Cu base thermoelectricity material Cu
2-mx (X=S or Se) has excellent thermoelectricity capability, but its Cu ion migration behavior decision serious under big current effect its there is low service reliability, because which limit the practical application of such material.For Cu
2-min X (X=S or Se), the understanding of Cu ion migration mechanism, the invention provides a kind of method that effectively can limit Cu ion migration, and under being namely used in big current effect, immovable transition metal T part replaces Cu
2-mcu atom in X, impact even destroys the migrating channels of original Cu ion, and then effectively reduces Cu mobility of ions, improves the stability of material.The Cu obtained
2-m-nt
nin X material, T atomic component replaces Cu
2-mcu atom in X, forms Cu
2-m-nt
nx material.
The chemical formula of the material obtained based on method provided by the present invention is Cu
2-m-nt
nx material, wherein m represents the Cu vacancy content in material, and its scope is 0≤m≤1; N represents the content of transition metal T, and its scope is 0≤n≤0.5.T can be selected from one or more in transition metal Cr, Mn, Fe, Co, Ni or Zn.
According to method provided by the present invention, under big current effect, immovable T atomic component replaces Cu
2-mcu atom in X, forms Cu
2-m-nt
nx material, the crystal positions of immovable T atom occupied by it produces " pinning " effect, stops the migration over these locations of Cu ion.Meanwhile, due to the difference of atomic radius, electronegativity and valence state, T atom also can affect the Periodic Potential distribution near position occupied by it, causes lattice distortion, and then suppresses the migration of Cu ion greatly.The principle schematic of the method as shown in Figure 2.
Based on method provided by the invention, the Cu obtained
2-m-nt
nx material can be prepared synthesis (preparation method can with reference to CN103130200) by melting-annealing-sintering technology, also can be prepared synthesis by magnetron sputtering, pulsed laser deposition, chemical vapour deposition, ion implantation technique.The Cu obtained
2-m-nt
nin X material, T atom is macroscopically uniformly distributed among sample.
Based on method provided by the invention, the Cu obtained
2-m-nt
nstoichiometrically load weighted Cu, T, X simple substance Vacuum Package, if be prepared synthesis by melting-annealing-sintering technology, in silica tube, can be carried out high-temperature fusion and annealing, be scattered in Cu uniformly to enable T atom by X material
2-m-nt
namong X material.Then annealed product being pulverized, sintering block into by there being pressure sintering technology.
Preferably, if use melting-annealing-sintering process, stoichiometrically weigh Cu, T, X simple substance, then by its Vacuum Package among silica tube, silica tube internal pressure is 0.1 ~ 40000Pa.Preferably, by the silica tube of Vacuum Package in 700 DEG C of-1400 DEG C of meltings 0.5 ~ 3000 hour; Then in 300 DEG C-900 DEG C annealing 1 ~ 3000 hour.The Cu of synthesis
2-m- nt
nx material is ground into powder, then selects the sintering processing such as hot pressed sintering or discharge plasma sintering to obtain compact mass Cu
2-m- nt
nx material (density >95%); Sintering temperature is 300 DEG C-800 DEG C; Sintering pressure is 10MPa-500MPa; Sintering time is 5min-1000min.
Utilize the Cu that method provided by the present invention obtains
2-m-nt
nx material (0≤m≤1,0≤n≤0.5), when introducing micro-T, namely obviously can weaken the Cu ion migration in material; When introducing volume T, then significantly can suppress the Cu ion migration in material, significantly improve the stability of material under big current effect.Specifically, under big current effect, T atom does not move, and the crystal positions occupied by it produces " pinning " effect, stops the migration over these locations of Cu ion.Meanwhile, due to the difference of atomic radius, electronegativity and valence state, T atom also can affect the Periodic Potential distribution near position occupied by it, causes lattice distortion, and then suppresses the migration of Cu ion greatly.
The present invention further such as following examples better the present invention to be described.
Embodiment 1
Cu
2-m-nfe
ns (m=0.02, n=0.01) material
By raw metal Cu, Fe, S according to 1.97:0.01:1 molar ratio ingredient, raw material is sealing in silica tube, extracting vacuum limit, limit argon plasma flame encapsulates, and fills a small amount of Ar gas shielded in silica tube.By the melting 30 hours at 1000 DEG C of mixed raw material.Room temperature is cooled to after melting completes.By the silica tube after melting 600 DEG C of annealing 120 hours, carry out discharge plasma sintering after the block obtained being worn into fine powder, sintering temperature is 400 DEG C, soaking time 5 minutes, and pressure is 50MPa.As shown in Figure 3, at 573K temperature, to Cu
1.97fe
0.01s sample applies big current (12A/cm
2) after the Changing Pattern of resistance that observes show, its resistance change amplitude is considerably slower than Cu
2s sample.This shows by Cu
2-mimmovable T atom under adding micro-big current effect in S sample, namely obviously can suppress the migration of Cu ion.Particularly, in whole Measuring Time section, resistance change is relatively milder, does not observe Cu
2the sharply change of the resistance occurred in S sample, namely containing the Cu of micro Fe atom
1.97fe
0.01the crystalline structure of S sample does not change under long-time big current effect, and stability of material significantly improves.
Embodiment 2
Cu
2-m-nni
ns (m=0.02, n=0.02) material
By raw metal Cu, Ni, S according to 1.96:0.02:1 molar ratio ingredient, raw material is sealing in silica tube, extracting vacuum limit, limit argon plasma flame encapsulates, and fills a small amount of Ar gas shielded in silica tube.By the melting 30 hours at 1000 DEG C of mixed raw material.Room temperature is cooled to after melting completes.By the silica tube after melting 550 DEG C of annealing 120 hours, carry out discharge plasma sintering after the block obtained being worn into fine powder, sintering temperature is 400 DEG C, soaking time 5 minutes, and pressure is 50MPa.As shown in Figure 4, at 573K temperature, to Cu
1.96ni
0.02s sample applies big current (12A/cm
2) after the Changing Pattern of resistance that observes show, its resistance change amplitude is considerably slower than Cu
2s, and in whole Measuring Time section, resistance change is relatively milder, does not observe Cu
2the sharply change of the resistance occurred in S sample, namely containing the Cu of micro-Ni atom
1.96ni
0.02the crystalline structure of S sample does not change under long-time big current effect, and stability of material significantly improves.
Embodiment 3
Cu
2-m-nfe
ns (m=0.5, n=0.25) material
By raw metal Cu, Fe, S according to 1.25:0.25:1 molar ratio ingredient, raw material is sealing in silica tube, extracting vacuum limit, limit argon plasma flame encapsulates, and fills a small amount of Ar gas shielded in silica tube.By the melting 30 hours at 1000 DEG C of mixed raw material.Room temperature is cooled to after melting completes.By the silica tube after melting 600 DEG C of annealing 120 hours, carry out discharge plasma sintering after the block obtained being worn into fine powder, sintering temperature is 400 DEG C, soaking time 5 minutes, and pressure is 50MPa.As shown in Figure 5, at 573K temperature, to Cu
1.25fe
0.25s sample applies big current (12A/cm
2) after the Changing Pattern of resistance that observes show, its resistance change amplitude is considerably slower than Cu
2s.At applying big current after 1000 seconds, material resistance only reduces by 5%; And after 60000 seconds, material resistance only reduces by 10%.This shows by Cu
2-mimmovable T atom under adding the big current effect of volume in S sample, significantly can suppress the migration of Cu ion, improves the stability of material under big current effect, makes it close to practical application request.
Industrial applicability: utilize the Cu that method provided by the present invention obtains
2-m-nt
nx material, the behavior of Cu ion migration is largely suppressed, and stability of material significantly improves, and can meet the demand of practical application.And method itself is with low cost, technique simple, be convenient to the preparation of extensive mass.
Claims (10)
1. a Cu base thermoelectricity material, is characterized in that, the chemical constitution of described thermoelectric material is Cu
2-m-nt
nx, wherein, X is S or Se, T is immovable transition metal under big current effect, 0≤m≤1,0 < n≤0.5.
2. Cu base thermoelectricity material according to claim 1, is characterized in that, 0.02≤m≤0.5.
3. Cu base thermoelectricity material according to claim 1 and 2, is characterized in that, 0.01≤m≤0.25.
4. the Cu base thermoelectricity material according to any one of claim 1-3, is characterized in that, T is at least one transition metal in Cr, Mn, Fe, Co, Ni and Zn.
5. the Cu base thermoelectricity material according to any one of claim 1-4, is characterized in that, described big current is 1-12 A/cm
2, the initial resistance of relatively described Cu base thermoelectricity material, after the described big current 1000S of applying, the fall of the resistance of described Cu base thermoelectricity material is lower than 30 %.
6. prepare a method for Cu base thermoelectricity material compound according to claim 1, it is characterized in that, comprising:
Get that mol ratio is the copper of (2-m-n): n:1, T simple substance and X simple substance Vacuum Package is carried out to it;
Melting treatment 0.5 ~ 3000 hour at 700 ~ 1400 DEG C;
Anneal 1 ~ 3000 hour at 300 ~ 900 DEG C; And
300 ~ 800 DEG C, carry out hot pressed sintering or discharge plasma sintering under 10 ~ 500MPa.
7. suppress a method for Cu ion migration in Cu base thermoelectricity material, it is characterized in that, under adopting big current effect, immovable transition metal T part replaces Cu base thermoelectricity material Cu
2-mcu atom in X consists of Cu to be formed
2-m-nt
nthe thermoelectric material of X, wherein, X is S or Se, 0≤m≤1,0 < n≤0.5.
8. method according to claim 7, is characterized in that, 0.02≤m≤0.5.
9. the method according to claim 7 or 8, is characterized in that, 0.01≤m≤0.25.
10. the method according to any one of claim 7-9, is characterized in that, T is at least one transition metal in Cr, Mn, Fe, Co, Ni and Zn.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410520197.1A CN104310457B (en) | 2014-09-30 | 2014-09-30 | Can suppress the thermoelectric material of Cu ion migration and suppress the method for Cu ion migration in Cu base thermoelectricity material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410520197.1A CN104310457B (en) | 2014-09-30 | 2014-09-30 | Can suppress the thermoelectric material of Cu ion migration and suppress the method for Cu ion migration in Cu base thermoelectricity material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104310457A true CN104310457A (en) | 2015-01-28 |
| CN104310457B CN104310457B (en) | 2016-05-18 |
Family
ID=52365811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410520197.1A Active CN104310457B (en) | 2014-09-30 | 2014-09-30 | Can suppress the thermoelectric material of Cu ion migration and suppress the method for Cu ion migration in Cu base thermoelectricity material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104310457B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109590481A (en) * | 2019-01-30 | 2019-04-09 | 北京科技大学 | A kind of Cu2-xMxThe high pressure method for preparing of Se alloy series thermoelectric material |
| CN109904305A (en) * | 2019-01-31 | 2019-06-18 | 桂林电子科技大学 | A kind of nickel doping Cu-S base thermoelectricity material of high thermoelectricity capability and preparation method thereof |
| CN110544741A (en) * | 2018-05-29 | 2019-12-06 | 中国科学院上海硅酸盐研究所 | method for improving service stability of fast ion conductor thermoelectric material |
| CN115101653A (en) * | 2022-07-08 | 2022-09-23 | 中南大学 | Manganese-selenium-doped copper-sulfur-based thermoelectric material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102363530A (en) * | 2011-08-03 | 2012-02-29 | 北京科技大学 | Preparation method of Cu1.8+xS binary thermoelectric material |
| CN102674270A (en) * | 2012-05-25 | 2012-09-19 | 武汉理工大学 | Method for preparing Cu2Se thermoelectric material by low-temperature solid-phase reaction |
| CN103130200A (en) * | 2011-11-25 | 2013-06-05 | 中国科学院上海硅酸盐研究所 | Thermoelectricity material compound and preparation method thereof |
| CN103526061A (en) * | 2013-08-01 | 2014-01-22 | 华南师范大学 | Regulation and control method for relative orientation of levels in layered microstructure of pyroelectric material |
-
2014
- 2014-09-30 CN CN201410520197.1A patent/CN104310457B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102363530A (en) * | 2011-08-03 | 2012-02-29 | 北京科技大学 | Preparation method of Cu1.8+xS binary thermoelectric material |
| CN103130200A (en) * | 2011-11-25 | 2013-06-05 | 中国科学院上海硅酸盐研究所 | Thermoelectricity material compound and preparation method thereof |
| CN102674270A (en) * | 2012-05-25 | 2012-09-19 | 武汉理工大学 | Method for preparing Cu2Se thermoelectric material by low-temperature solid-phase reaction |
| CN103526061A (en) * | 2013-08-01 | 2014-01-22 | 华南师范大学 | Regulation and control method for relative orientation of levels in layered microstructure of pyroelectric material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110544741A (en) * | 2018-05-29 | 2019-12-06 | 中国科学院上海硅酸盐研究所 | method for improving service stability of fast ion conductor thermoelectric material |
| CN109590481A (en) * | 2019-01-30 | 2019-04-09 | 北京科技大学 | A kind of Cu2-xMxThe high pressure method for preparing of Se alloy series thermoelectric material |
| CN109904305A (en) * | 2019-01-31 | 2019-06-18 | 桂林电子科技大学 | A kind of nickel doping Cu-S base thermoelectricity material of high thermoelectricity capability and preparation method thereof |
| CN115101653A (en) * | 2022-07-08 | 2022-09-23 | 中南大学 | Manganese-selenium-doped copper-sulfur-based thermoelectric material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104310457B (en) | 2016-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Masood et al. | Odyssey of thermoelectric materials: foundation of the complex structure | |
| Koshibae et al. | Thermopower in cobalt oxides | |
| Sawalha et al. | Electrical conductivity study in pure and doped ZnO ceramic system | |
| Austin et al. | Electronic transport phenomena in single-crystal NiO and CoO | |
| Wang et al. | Higher mobility in bulk semiconductors by separating the dopants from the charge-conducting band–a case study of thermoelectric PbSe | |
| CN104310457A (en) | Thermoelectric material capable of inhibiting Cu ion migration and method for inhibiting Cu ion migration in Cu-base thermoelectric material | |
| KR101995917B1 (en) | Power factor enhanced thermoelectric material and method of producing same | |
| KR102138527B1 (en) | Thermoelectric material with phase separation, thermoelectric device and method for manufacturing the same | |
| KR102067647B1 (en) | Manufacturing method of thermoelectric device and cooling thermoelectric moudule using the same | |
| CN102194989A (en) | Method for preparing thermoelectric material of ternary diamond structure | |
| Geisler et al. | Confinement-and strain-induced enhancement of thermoelectric properties in LaNiO 3/LaAlO 3 (001) superlattices | |
| Wang et al. | Characteristics of lattice thermal conductivity and carrier mobility of undoped PbSe-PbS solid solutions | |
| EP2899763B1 (en) | Novel compound semiconductor and use thereof | |
| Gong et al. | Fabrication and thermoelectric properties of Ca-Co-O ceramics with negative Seebeck coefficient | |
| Fleurial et al. | Skutterudites: a new class of promising thermoelectric materials | |
| JP2006165125A (en) | Thermoelectric material and its manufacturing method | |
| Uher | Thermoelectric properties of Skutterudites | |
| Artini et al. | Roadmap on thermoelectricity | |
| CN105990510B (en) | A kind of copper seleno high performance thermoelectric material and preparation method thereof | |
| Yang et al. | High-performance and stable (ag, cd)-containing znsb thermoelectric compounds | |
| CN103811653B (en) | Multi-cobalt p type skutterudite filled thermoelectric material and preparation method thereof | |
| US8865997B2 (en) | Thermoelectric material, method for fabricating the same, and thermoelectric module employing the same | |
| Furtado et al. | Microstructural evaluation of rare-earth-zinc oxide-based varistor ceramics | |
| KR20170069795A (en) | Half-heusler type thermoelectric material, method for manufacturing the same, thermoelectric element comprising the same | |
| Hwang et al. | Strong correlation between the crystal structure and the thermoelectric properties of pavonite homologue Cu x+ y Bi 5− y Ch 8 (Ch= S or Se) compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |