CN103872237B - Copper-sulfur-based high-performance thermoelectric material and preparation method thereof - Google Patents
Copper-sulfur-based high-performance thermoelectric material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 title abstract description 47
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 title abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 62
- 239000010949 copper Substances 0.000 claims description 66
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 238000005245 sintering Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000003708 ampul Substances 0.000 claims description 17
- 239000010453 quartz Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 238000010791 quenching Methods 0.000 claims description 14
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- 229910052802 copper Inorganic materials 0.000 claims description 12
- 230000000171 quenching effect Effects 0.000 claims description 12
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- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
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- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- 229910002899 Bi2Te3 Inorganic materials 0.000 description 1
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- 238000003723 Smelting Methods 0.000 description 1
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- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
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- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
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Abstract
The invention relates to a copper-sulfur-based high-performance thermoelectric material and a preparation method thereof, and particularly provides a novel p-type thermoelectric compound Cu(2-x)S or Cu2S(1-y)Ay (A is Se or Te) and a preparation method thereof. The compound is composed of Cu-S-(Se/Te), x equals 0.02-0.05, and y equals 0.2-0.4. The material is a semiconductor. Compared with traditional thermoelectric materials, the compound is simple, low in cost of raw materials, high in Seebeck coefficient, low in thermal conductivity, and excellent in thermal property, the thermoelectric figures of merit ZT of some components can reach 1 and above at 800K, and the compound has good thermoelectric application prospects.
Description
Technical field
The present invention relates to copper sulfenyl high performance thermoelectric material and preparation method thereof, in particular it relates to a kind of new
The p-type thermoelectric compound Cu of type2-xS1-yAy(for example, Cu2-xS and Cu2S1-yAy, in formula, A is Se or Te）And preparation method thereof, institute
That states p-type thermoelectric compound consists of Cu2-xS1-y（Se/Te）y, the wherein value for 0.02～0.05, y for the value of x is 0.2～0.4.
Copper sulfenyl high performance thermoelectric material of the present invention is a kind of quasiconductor, compared to traditional thermoelectric material, this change
The composition of compound is simple, and low in raw material price has higher Seebeck coefficient and extremely low thermal conductivity, thermoelectricity capability is excellent,
Part thermoelectric figure of merit ZT can reach in 800K 1.0 and more than, there is good thermoelectric applications prospect.
Technical background
Because the exhaustion of non-renewable energy resources and environment such as go from bad to worse at the appearance of thorny problem, the exploitation of new cleaning fuel
Using receiving much concern, thermo-electric converting material utilizes its Seebeck effect and paltie effect to can achieve the phase between heat energy and electric energy
Mutually change, be a kind of new clean energy resource, it may use that the temperature difference of nature and industrial waste heat, cogeneration, may be made as
The high refrigeration machine of noiseless, no actuating device, reliability.But, at present because the conversion efficiency of thermoelectric material is very low（Generally<
10%）, not yet enable large-scale commercialization, therefore, the thermoelectricity capability how improving thermoelectric material is one and of great value grinds
Study carefully problem.
The high low side temperature that the conversion efficiency of thermoelectric material is worked by material and material essence performance determine.For determine
Use environment, high low side temperature is generally to determine, so can only start with itself from optimizing material for improving conversion efficiency.Generally
Assess the quality of thermoelectric material energy conversion efficiency with dimensionless thermoelectric figure of merit ZT, its definition is：ZT=S2T σ/κ, wherein S
For thermoelectrical potential（Seebeck（Seekbeck）Coefficient）, T is absolute temperature, and σ is electrical conductivity, and κ is thermal conductivity.In order to obtain high heat
Electric conversion efficiency is it is desirable to material must have high thermoelectric figure of merit.
The thermoelectric material having started to apply at present mostly is metallic compound and its solid solution, such as Bi2Te3, SiGe, PbTe etc.,
But the requirement of the preparation condition of these thermoelectric materials is higher, need to carry out under certain shielding gas, and containing harmful weight
Metal, and because ZT value may each be about 1.0, so that the shortcomings of energy conversion efficiency is high.
In recent decades, researchers are by various means, such as doping, the dimension of reduction material（Make thin film, receive
Rice noodle, quantum dot etc.）And find the method such as noval chemical compound and achieve being substantially improved of thermoelectric material thermoelectricity capability, ZT value can reach
More than 1.5, it is that the scale of thermoelectric material should be used as further propulsion.
Copper sulfur-based compound Cu2-xS is a kind of new thermoelectric material, and its chemical formula is extremely simple, but its crystal structure and former
Sub- arranging situation is very complicated.As Cu2-xThere is solid phase phase transformation at two in S near 370K, 700K, and phase transition temperature and x value phase
Close.Below 370K is γ phase（Durleite（lowchalcocite）：L-chalc）, 370K to 700K is β phase（High vitreous copper
（high chalcocite）：H-chalc）, more than 700K is α phase.Low temperature γ phase（L-chalc）Phase structure extremely complex, to the greatest extent
Pipe has carried out the research of recent decades, and its crystal structure is not still very bright and clear so far, is widely considered to be rhombic system at present, each
96 Cu are contained in structure cell2S cell, but each Cu has well-determined position；High temperature β phase（H-chalc）For hexagonal crystal
System, contains two Cu in each structure cell2S cell, wherein S press Hexagonal array, and Cu is randomly dispersed in Wyckoff with certain probability
Position (in expression structure cell, atom of equal value is symmetric).High temperature β phase（H-chalc）It is fast-ionic conductor, there is very high moving
Shifting rate, but high temperature β phase（H-chalc）The reason become fast-ionic conductor and other fast-ionic conductors such as metal halogen compound
（AgCl、AgBr、AgI、CaF2）Difference, Cu2S has fast-ionic conductor characteristic and is not due to Frenkel disorder number under high temperature
Increase and lead to ion to be provided with high animal migration, and be because in Cu2It is available for position that Cu ion occupies than Cu ion in S
Number will many, Cu ion freely can migrate in different interstitial sites, so at relatively low temperature, Cu2S's
β phase（H-chalc）Just it is provided with the property of class I liquid I.
Cu2-xShow p-type electric-conducting behavior because of Cu room in S, and electrical conductivity increases with the increase of x value.When x is 0,
Meet the Cu of stoichiometric proportion2S shows quasiconductor behavior, because its energy gap is about 1.2eV, is the preferable material of solaode
Material, can form good contact with CdS again（Cu2S/CdS）, so to Cu2The research of S class material focuses mostly in terms of battery, right
The research of thermoelectricity capability is very few, reports that such material had larger thermoelectrical potential and very low thermal conductivity in only a small amount of document,
To Cu2-xThe thermoelectricity capability of S material is further studied and is optimized, presumably this Cu2-xS sill will have good thermoelectricity
Application prospect.
Experimental studies have found that intrinsic Cu2S has extremely low heat conductivity value, in the test temperature interval of 300～800K only
For 0.3～0.4Wm-1K-1, but too low due to its carrier concentration due to so that its conductivity value when close to 650K just not
Sufficient 100Sm-1, cannot have excellent thermoelectricity capability because the reason power factor (PF) is too small.So, based on such copper sulfenyl
Compound has so low thermal conductivity, attempts regulating and controlling the carrier concentration of this base thermoelectricity material by means such as doping, obtains
Preferably power factor（PF）, thus realizing the raising to its thermoelectricity capability.
Content of the invention
For this reason, the present invention provides a kind of p-type thermoelectric compound, the formula of described compound is Cu2-xS1-yAy, in formula, A selects
From Se and/or Te, between 0.02 to 0.05, y value is between 0.2 to 0.4 for x value.
Also, the present invention provides a kind of p-type thermoelectric compound, the formula of described compound is Cu2-xS or Cu2S1-yAy, in formula,
A is selected from Se and/or Te, and, between 0 to 0.05, y value is between 0 to 0.4 for x value.
In an embodiment of the invention, between 0.02 to 0.05, y value is between 0.2 to 0.3 for x value.
In an embodiment of the invention, between 0.02 to 0.05, y value is between 0.2 to 0.4 for x value.
On the other hand, the present invention provides a kind of method preparing p-type thermoelectric compound of the present invention, methods described bag
Include：
(1) with formula Cu2-xS or Cu2S1-yAyStoichiometric proportion（2-x）:(1-y):Y weighs each element simple substance respectively and makees
For initial feed；
(2) after mixing initial feed, Vacuum Package is in quartz ampoule；
(3) initial feed is melted；
(4) carry out Quenching Treatment, obtain block after quenching；
(5) block after described quenching is pulverized, and be packaged in quartz ampoule again after being cold-pressed into block and annealed
Process；With
(6) it is cooled to room temperature, obtain p-type thermoelectric compound.
In the present invention, methods described also includes p-type thermoelectric compound is pulverized, and discharges etc. in a mold
Ion pressure sintering, obtains the p-type thermoelectric compound shaping.
In an embodiment of the invention, described each element simple substance is respectively elemental copper, Sublimed Sulfur and simple substance Se
And/or Te.
In an embodiment of the invention, in step (2), described Vacuum Package adopts in argon gas atmosphere glove box
Plasma or flame gun are carried out.
In an embodiment of the invention, in step (2), after quartz ampoule evacuation, internal pressure is 1-10000Pa.
In an embodiment of the invention, in step (3), described being melted in vertical melting furnace is carried out：With 4.5
DEG C/min heating rate be warming up to 1150 DEG C, constant temperature melt 20 hours.
In an embodiment of the invention, in step (4), described quenching is carried out in mixture of ice and water.
In an embodiment of the invention, in step (5), described annealing process is carried out in tubular annealing stove：?
Anneal 5-7 days at 580 DEG C.
In an embodiment of the invention, described mould is graphite jig, and, mould inside and on push-down head
Place's spraying boron nitride（BN）To insulate；Sintering temperature is 390-420 DEG C, and pressure is 50-65MPa, sintering time 5-10 minute.
Another further aspect, the present invention provides application in thermoelectric device for the p-type thermoelectric compound of the present invention.Described thermoelectricity
Device includes thermoelectric power generation or the thermoelectric cooling unit in high temperature area, such as in vehicle exhaust and commercial production, particularly smelting
The thermoelectric power generation in high temperature area in golden industry or thermoelectric cooling unit.
In the present invention, this p-type thermoelectric compound is suitable to the thermoelectric power generation in high temperature area or the use of thermoelectric cooling, such as
In vehicle exhaust and commercial production, particularly in metallurgy industry, generated electricity using its high-temperature residual heat used heat, be can achieve low close
The effectively utilizes of degree thermal source, reach the purpose of energy-saving and emission-reduction to a certain extent.
Specifically, the invention provides a kind of new p-type thermoelectric compound and preparation method thereof, consisting of Cu2- xS1-y（Se/Te）y, between 0 to 0.05, y value is between 0 to 0.4 for wherein x value.
In the present invention, the Cu that described part regulates and controls through carrier concentration2-xS1-y（Se/Te）yThe thermoelectricity of compound
Figure of merit ZT can reach 1.0 in 800K and above it is adaptable to the application in high temperature area.And, described Cu2-xS1-y（Se/Te）yChange
Compound focus material has higher Seebeck coefficient and extremely low thermal conductivity.
Thermoelectric compound material C u of the present invention2-xS exists by typically opposite class I liquid I phase in version between 370-400K
Solid phase phase transformation；And there is another solid phase phase transformation between 650-700K.
The Seebeck coefficient of material of the present invention is gradually increased with the rising of temperature, and electrical conductivity is non-monotonic with the rising of temperature
Change, near solid phase phase transition temperature, the variation tendency of electrical conductivity changes.Meanwhile, thermal conductivity maintains relatively low water always
Put down so that its thermoelectric figure of merit can reach 1.0 about in 800K, thermoelectricity capability is preferable.
In addition, the raw material sources that adopted of preparation method of the present invention enrich, with low cost, production technology and production
Equipment is simple, and controllability and repeatability are all preferable.
Brief description
Fig. 1 is the schematic flow sheet of preparation method of the present invention.
Fig. 2 is thermoelectric compound in one embodiment of the present invention（Cu1.98S）Thermoelectricity capability.
Wherein, Fig. 2（a）It is the electrical conductivity of thermoelectric compound；Fig. 2（b）It is the Seebeck coefficient of thermoelectric compound；Fig. 2（c）
It is the thermal conductivity of thermoelectric compound, and Fig. 2（d）It is the thermoelectric figure of merit ZT of thermoelectric compound.
Fig. 3 is thermoelectric compound in another embodiment of the present invention（Cu1.95S）Thermoelectricity capability.
Wherein, Fig. 3（a）It is the electrical conductivity of thermoelectric compound；Fig. 3（b）It is the Seebeck coefficient of thermoelectric compound；Fig. 3（c）
It is the thermal conductivity of thermoelectric compound, and Fig. 3（d）It is the thermoelectric figure of merit ZT of thermoelectric compound.
Fig. 4 is thermoelectric compound in another embodiment of the present invention（Cu2S0.7Te0.3）Thermoelectricity capability.
Wherein, Fig. 4（a）It is the electrical conductivity of thermoelectric compound；Fig. 4（b）It is the Seebeck coefficient of thermoelectric compound；Fig. 4（c）
It is the thermal conductivity of thermoelectric compound, and Fig. 4（d）It is the thermoelectric figure of merit ZT of thermoelectric compound.
Fig. 5 is thermoelectric compound in another embodiment of the present invention（Cu2S0.6Se0.4）Thermoelectricity capability.
Wherein, Fig. 5（a）It is the electrical conductivity of thermoelectric compound；Fig. 5（b）It is the Seebeck coefficient of thermoelectric compound；Fig. 5（c）
It is the thermal conductivity of thermoelectric compound, and Fig. 5（d）It is the thermoelectric figure of merit ZT of thermoelectric compound.
Fig. 6 is thermoelectric compound in an embodiment of the present invention（Cu2S0.7Te0.3）The X-ray diffraction of powder（XRD）Figure
Spectrum.
Specific embodiment：
With reference to embodiment and accompanying drawing, the present invention is described in further detail.It should be noted that the present invention's is interior
Hold and be not limited to these specific embodiments.On the premise of without departing substantially from background of the present invention and spirit, those skilled in the art
Equivalencing and modification can be carried out on the basis of reading present disclosure, its content is also included within claimed
In the range of.
The invention provides a kind of new p-type thermoelectric compound and preparation method thereof, wherein：
● the compound synthesized by the present invention is Cu2-xS1-y（Se/Te）y, it is made up of element Cu and element S, Se/Te, x value
Between 0.02 to 0.05, y value is between 0.2 to 0.4.
● the preparation process of the present invention is to be realized by Vacuum Package, melting, quenching, annealing process, and Fig. 1 show this
The process chart of material preparation.
● the preparation method is that using pure element simple substance as initial feed, respectively elemental copper, Sublimed Sulfur and list
Matter Se/Te.Initial feed is with stoichiometric proportion（2-x）:1-y：Y is weighed, and is then sealed in quartz ampoule.
● Vacuum Package is carried out in argon gas atmosphere glove box, using plasma or flame gun packaged type, encapsulation
When quartz ampoule evacuation, internal pressure has 1-10000Pa.
● melting process is carried out in vertical melting furnace.It is warming up to 1150 DEG C with 4.5 DEG C/min of heating rate, constant temperature
Melting quenched in mixture of ice and water after 20 hours.
● annealing process is carried out in tubular annealing stove.First the block after quenching is clayed into power in agate mortar, then
It is cold-pressed into block, Vacuum Package, in quartz ampoule, is annealed 1 hour -7 days at 580 DEG C, cooled to room temperature with the furnace again.
● the block after annealing is milled to powder in agate mortar, then carries out plasma discharging pressure sintering.Using
Graphite jig, and mould inside and at push-down head spraying BN to insulate；Sintering temperature be 390-420 DEG C, pressure be 50 or
65MPa, sintering time 5-10 minute.
Embodiment 1：
Cu1.88S（x=0.02,y=0）
Simple substance raw material Cu and S is pressed 1.98:1 mol ratio weighing, is then packaged in quartz ampoule.With 4.5 DEG C/min
Heating rate is warming up to 1150 DEG C, raw material is melted 20 hours at 1150 DEG C, then quenches in mixture of ice and water.To quench again
The block obtaining after fire is pulverized in agate mortar, and powder is cold-pressed into bulk, is packaged in again in quartz ampoule, finally by it
Put in tube furnace and anneal 7 days at 580 DEG C, be then cooled to room temperature with stove.
The product obtaining after annealing is pulverized, carries out discharge plasma sintering（SPS sinters）, sintering temperature is 390-
420 DEG C, pressure is 50 or 65MPa, and sintering time is 5-10 minute, the final block materials obtaining densification.
As shown in Fig. 2 gained Cu1.98The thermoelectricity capability measurement of S block materials shows in institute temperature measuring area（300-800K）,
This material has very high Seebeck coefficient, and moderate electrical conductivity.And this material has abnormal low thermal conductivity：300-
In 800K temperature range, its numerical value ＜ 0.6Wm-1K-1.The ZT value being calculated this material according to performance measurement can in 800K
Reach 1.0.
Embodiment 2：
Cu1.95S（x=005,y=0）
Simple substance raw material Cu and S is pressed 1.95:1 mol ratio weighing, is then packaged in quartz ampoule.With 4.5 DEG C/min
Heating rate is warming up to 1150 DEG C, raw material is melted 20 hours at 1150 DEG C, then quenches in mixture of ice and water.To quench again
The block obtaining after fire is pulverized in agate mortar, and powder is cold-pressed into bulk, is packaged in again in quartz ampoule, finally by it
Put in tube furnace and anneal 7 days at 580 DEG C, be then cooled to room temperature with stove.
The product obtaining after annealing is pulverized, carries out discharge plasma sintering, sintering temperature is 390-420 DEG C, pressure
Power is 65MPa, and sintering time is 5-10 minute, the final block materials obtaining densification.
As shown in figure 3, gained Cu1.95The thermoelectricity capability measurement of S block materials shows its Seebeck system of sample of this composition
Number is slightly below Cu1.98S, and electrical conductivity is then slightly higher.And, the thermal conductivity of the sample of this composition is all higher than corresponding warm area is interior
Cu1.98S, but its heat conductivity value is also maintained at very low level：In 300-800K temperature range, its numerical value ＜ 0.8Wm-1K-1.Root
The ZT value being calculated the material of this composition according to performance measurement can be to 0.7 in 800K.
Embodiment 3：
Cu2S.07Te0.3（x=0,y=0.3）
Simple substance raw material Cu, S and Te are pressed 2:0.7:0.3 mol ratio weighing, is then packaged in quartz ampoule.With 4.5 DEG C/
The heating rate of minute is warming up to 1150 DEG C, raw material is melted 20 hours at 1150 DEG C, then quenches in mixture of ice and water.
Again the block obtaining after quenching is pulverized in agate mortar, powder is cold-pressed into bulk, is packaged in again in quartz ampoule,
After put it in tube furnace and to anneal 7 days at 580 DEG C, be then cooled to room temperature with stove.
The product obtaining after annealing is pulverized, carries out discharge plasma sintering, sintering temperature is 390-420 DEG C, pressure
Power is 50 or 65MPa, and sintering time is 5-10 minute, the final block materials obtaining densification.
As shown in figure 4, gained Cu2S0.7Te0.3The thermoelectricity capability measurement of block materials shows, the sample of this composition has relatively
Good thermoelectricity capability, its heat conductivity value is also maintained at a fairly low level：In 300-800K temperature range, its numerical value ＜
0.41Wm-1K-1.The ZT value being calculated the material of this composition according to performance measurement can be to 1.2 in 800K.
Embodiment 4：
Cu2S0.6Se0.4（X=0, y=0.4）
Simple substance raw material Cu, S and Se are pressed 2:0.6:0.4 mol ratio weighing, is then packaged in quartz ampoule.With 4.5 DEG C/
The heating rate of minute is warming up to 1150 DEG C, raw material is melted 20 hours at 1150 DEG C, then quenches in mixture of ice and water.
Again the block obtaining after quenching is pulverized in agate mortar, powder is cold-pressed into bulk, is packaged in again in quartz ampoule,
After put it in tube furnace and to anneal 7 days at 580 DEG C, be then cooled to room temperature with stove.
The product obtaining after annealing is pulverized, carries out discharge plasma sintering, sintering temperature is 390-420 DEG C, pressure
Power is 50 or 65MPa, and sintering time is 5-10 minute, the final block materials obtaining densification.
As shown in figure 5, gained Cu2S0.6Se0.4The thermoelectricity capability measurement of block materials shows, the pyroelectricity of this composition sample
Can be also preferable, but it is inferior to Cu2S0.7Te0.3.Its heat conductivity value is also maintained at a fairly low level：300-800K temperature range
Interior, its numerical value ＜ 0.48Wm-1K-1.The ZT value being calculated the material of this composition according to performance measurement can arrive in 800K
0.8.
Claims (12)
1. a kind of method preparing p-type thermoelectric compound, methods described includes：
(1) with formula Cu2-xS or Cu2S1-yAyStoichiometric proportion weigh each element simple substance respectively as initial feed, in formula, A
For Se and/or Te, 0 ＜ x≤0.05,0 ＜ y≤0.4；
(2) after mixing initial feed, Vacuum Package is in quartz ampoule；
(3) initial feed is melted；
(4) carry out Quenching Treatment, obtain block after quenching；
(5) block after described quenching is pulverized, and be packaged in quartz ampoule again after being cold-pressed into block and made annealing treatment；
(6) it is cooled to room temperature, obtain p-type thermoelectric compound.
2. the method for preparation p-type thermoelectric compound as claimed in claim 1 is it is characterised in that gained p-type thermoelectric compound grinds
Cheng Fen, and carry out plasma discharging pressure sintering in a mold, obtain the p-type thermoelectric compound shaping.
3. the method for preparation p-type thermoelectric compound as claimed in claim 1 is it is characterised in that described each element simple substance is respectively
Elemental copper, Sublimed Sulfur and simple substance Se and/or Te.
4. the method for preparation p-type thermoelectric compound as claimed in claim 1 is it is characterised in that in step (2), described vacuum seal
It is contained in using plasma or flame gun in argon gas atmosphere glove box to carry out.
5. the method for preparation p-type thermoelectric compound as claimed in claim 1 is it is characterised in that in step (2), quartz ampoule is taken out very
After sky, internal pressure is 1-10000Pa.
6. the method for preparation p-type thermoelectric compound as claimed in claim 1 is it is characterised in that in step (3), described is melted in
Carry out in vertical melting furnace：It is warming up to 1150 DEG C with 4.5 DEG C/min of heating rate, constant temperature melts 20 hours.
7. the method for preparation p-type thermoelectric compound as claimed in claim 1 is it is characterised in that in step (4), described quenching exists
Carry out in mixture of ice and water.
8. the method for preparation p-type thermoelectric compound as claimed in claim 1 is it is characterised in that in step (5), described lehr attendant
Skill is carried out in tubular annealing stove：Anneal 5-7 days at 580 DEG C.
9. as claimed in claim 2 preparation p-type thermoelectric compound method it is characterised in that described mould is graphite jig, and
And, mould inside and at push-down head spraying boron nitride to insulate；Sintering temperature is 390-420 DEG C, and pressure is 50-65MPa,
Sintering time 5-10 minute.
10. the p-type thermoelectric compound of a kind of claim 1-9 any one methods described preparation, the formula of described compound is
Cu2-xS or Cu2S1-yAy, in formula, A is Se and/or Te, 0 ＜ x≤0.05,0 ＜ y≤0.4；
Wherein, the thermoelectric figure of merit ZT of described p-type thermoelectric compound reach in 800K 1.0 and more than.
It is characterised in that x value is between 0.02 to 0.05, y value exists 11. p-type thermoelectric compounds as claimed in claim 10
Between 0.2 to 0.4.
12. p-type thermoelectric compounds as claimed in claim 10 it is characterised in that x value is between 0 to 0.03, y value 0.1 to
Between 0.4.
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| CN105990510B (en) * | 2015-02-04 | 2018-07-20 | 中国科学院上海硅酸盐研究所 | A kind of copper seleno high performance thermoelectric material and preparation method thereof |
| CN106033790B (en) * | 2015-02-15 | 2018-10-09 | 武汉理工大学 | A kind of Cu2-xSe/ graphene composite materials and preparation method thereof |
| CN104692448B (en) * | 2015-03-18 | 2017-01-25 | 武汉理工大学 | Synthesis method of dynamic load of Ag2S (Silver Sulfide)-based compound and reactive assistant thereof |
| CN104810465B (en) * | 2015-04-21 | 2017-05-17 | 电子科技大学 | Cu2-xS thermoelectric material preparation method |
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| CN108238796B (en) * | 2016-12-26 | 2019-11-15 | 中国科学院上海硅酸盐研究所 | Copper seleno solid solution thermoelectric material and preparation method thereof |
| CN106587135B (en) * | 2016-12-28 | 2017-12-29 | 中国科学院上海高等研究院 | Cu S base thermoelectricity materials of I doping and preparation method thereof |
| CN111244256B (en) * | 2018-11-28 | 2022-03-08 | 中国科学院上海硅酸盐研究所 | Silver sulfide-based inorganic thermoelectric material and preparation method and application thereof |
| LV15536A (en) * | 2019-04-26 | 2020-11-20 | Latvijas Universitātes Cietvielu Fizikas Institūts | High-speed visible light and infrared radiation sensor and manufacturing method thereof |
| CN110212080B (en) * | 2019-05-14 | 2021-03-05 | 清华大学 | Barium copper sulfur-based thermoelectric material and preparation method thereof |
| CN110407581B (en) * | 2019-06-28 | 2020-10-13 | 清华大学 | Copper-sulfur-based thermoelectric compound and preparation method thereof |
| CN111883642B (en) * | 2020-08-06 | 2022-08-16 | 重庆大学 | Cu 2-x S-based thermoelectric material and solvothermal preparation method |
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