CN106898689B - A kind of metal-doped tungsten disulfide thermoelectric material and preparation method - Google Patents
A kind of metal-doped tungsten disulfide thermoelectric material and preparation method Download PDFInfo
- Publication number
- CN106898689B CN106898689B CN201510962265.4A CN201510962265A CN106898689B CN 106898689 B CN106898689 B CN 106898689B CN 201510962265 A CN201510962265 A CN 201510962265A CN 106898689 B CN106898689 B CN 106898689B
- Authority
- CN
- China
- Prior art keywords
- metal
- thermoelectric material
- tungsten disulfide
- doped tungsten
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 73
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000005245 sintering Methods 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 7
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 7
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 239000004570 mortar (masonry) Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000003801 milling Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 230000005619 thermoelectricity Effects 0.000 abstract description 14
- 239000011812 mixed powder Substances 0.000 abstract description 2
- 230000005518 electrochemistry Effects 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002048 multi walled nanotube Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002305 electric material Substances 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 244000187801 Carpobrotus edulis Species 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 150000004772 tellurides Chemical class 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The present invention relates to a series of metal-doped tungsten disulfide thermoelectric materials and preparation method, the chemical general formula of metal-doped tungsten disulfide thermoelectric material is MxWS2, wherein M is one of Ti, V, Nb, Zr, Ta, Hf, Yb, Re or two or more, and x is that M metal accounts for WS2Molar fraction, and 0 x≤1 <;The preparation method of material includes: the discharge plasma sintering of solid powder mixing and material, metal and tungsten sulfide are weighed by certain mol proportion first, mechanical lapping mixing, then carries out discharge plasma sintering for mixed powder under suitable pressure and temperature, obtains M after sinteringxWS2Thermoelectric material.This thermoelectric material conductance with higher and Seebeck coefficient, have preferable thermoelectricity capability.The M simultaneouslyxWS2Material also can be applicable to the fields such as electrochemistry, photoelectrocatalysis, electronic device.
Description
Technical field
The present invention relates to a kind of new thermoelectric materials, i.e., metal-doped tungsten disulfide thermoelectric material and preparation method belong to
In thermoelectricity field.
Background technique
Thermoelectric material is a kind of material that thermal energy is converted into electric energy, and the performance of thermoelectric material can use thermoelectric figure of merit
ZT indicates, thermoelectric figure of merit ZT=S2σ T/K, power factor PF=S2σ, S represent Seebeck coefficient, and σ represents conductance, and T represents temperature
Degree, K represent thermal conductivity.Thermoelectric material requires have high conductance, high Seebeck coefficient, low thermal conductivity, so as to there is high thermoelectricity
Figure of merit ZT.Thermoelectric material research at present is most widely the tellurides containing heavy element, antimonide etc., although this kind of material has very
Good thermoelectricity capability, but the shortcomings that these materials is that toxicity is big, it is at high cost, earth content is low etc..Therefore research environment pollution
Small, small toxicity, at low cost, earth rich content thermoelectric material are the important research directions in thermoelectricity field.
Tungsten disulfide (WS2) it is a kind of semiconductor material with two-dimensional layered structure.Although WS2Seebeck coefficient ratio
It is higher, but WS2Conductance it is very poor, this leads to the thermoelectric property of tungsten disulfide itself and bad.Jong-Young in 2010
Kim etc. has studied WS2Thermoelectric property, research shows that WS2Seebeck coefficient can reach 500-600 μ V/K, and conductance only has
10-500S/m, Jonathan N.Coleman study group is prepared for WS within 20112- SWNT (single-walled carbon nanotube) film, it is this
Film conductance can reach 10000S/m, but Seebeck coefficient is very low, only 60-80 μ V/K, so that power factor only has 120 μ
W/(mK2).Seunghyun Baik in 2012 etc. is by multi-walled carbon nanotube (MWNT) and WS2It is compound, prepare a kind of compound thermoelectricity
Material can make WS after finding a small amount of MWNT incorporation2Conductance be improved, Seebeck coefficient reduce it is less, temperature exists
ZT reaches 0.22 when 800K.In addition to above-mentioned document, WS2Base thermoelectricity material is studied also seldom.
Summary of the invention
The technology of the present invention solves the problems, such as: overcoming the deficiencies of the prior art and provide a kind of metal-doped tungsten disulfide thermoelectricity
Material and preparation method, this thermoelectric material conductance with higher and Seebeck coefficient, have preferable thermoelectricity capability.
The technology of the present invention solution: a kind of metal-doped tungsten disulfide thermoelectric material, the chemistry of the thermoelectric material
General formula is MxWS2, wherein 0 x≤1 <, metal M is one of Ti, V, Ta, Nb, Zr, Hf, Yb and Re element or two kinds.
The mole percent of the metal M be 1%-30%, preferably after range be 10-20%.The Mole percent of metal M
Number all has a great impact for the conductance and thermal conductivity that regulate and control thermoelectric material, optimizes thermoelectric material simultaneously in preferred scope
Conductance and thermal conductivity.
The MxWS2In x preferred scope be 0.1≤x≤0.2.In specific x value, the power factor of thermoelectric material reaches
To maximum value.
The WS2Particle size range be 1-150 μm;The particle size range of the metal M is 40-150 μm.Partial size is for material
The sintered degree of orientation has a significant impact, and selected particle size range is conducive to the orientation of thermoelectric material when sintering, to be conducive to drop
Low-heat is led.
A kind of metal-doped tungsten disulfide thermoelectric material preparation method realizes that steps are as follows,
(1) solid powder mixes: according to certain molar ratio, weighing WS2With metal M, metal M be Ti, V, Ta, Nb, Zr,
One of Hf, Yb and Re element simple substance or two kinds, the two is mixed, is put into mortar, mechanical lapping is uniform, obtains
Mixing sample after grinding;
(2) mixture of powders is sintered: will be mixed sample, is put into graphite jig, then mold is put into sintering furnace, adds
Pressure, then vacuumizes, when vacuum reaches 5Pa, starts to warm up sintering, keeps the temperature a period of time after reaching sintering temperature, then ties
Beam sintering process starts to cool down, and obtains metal-sulfur tungsten composite thermoelectric material, i.e. MxWS2Thermoelectric material.
The WS2Mole percent with metal M is respectively 70-99%, 1%-30%.
Revolving speed 90rpm, milling time 90-180min when step (1) mechanical lapping.Revolving speed and milling time all can
Influence WS2With the mixture homogeneity of metal M.Under conditions of this step provides, WS can guarantee2It can sufficiently be mixed with metal M powder
It closes, and assay reproducibility is good.
Pressing force range is 30-100MPa in step (2) sintering process.The size of pressure will affect thermoelectric material
Consistency and the degree of orientation, under suitable pressure, the consistency of thermoelectric material can reach theoretical density after can guarantee sintering
95% or more, while keeping the orientation of thermoelectric material preferable, the degree of orientation reaches 0.8 or more.
Heating rate in the step (2) is 50-100 DEG C/min, and thermostat temperature is 1400-1500 DEG C, soaking time
10-60min.Temperature in sintering process will affect thermoelectric material MxWS2Consistency, heat can be made within the scope of 1400-1500 DEG C
The consistency of electric material reaches 95% or more theoretical density.
The sintering furnace is discharge plasma sintering furnace.
Resulting MxWS2Thermoelectric material degree of grain alignment is greater than 0.8.
The present invention has the advantages that
(1) present invention has obtained the better thermoelectric material M of the degree of orientation by introducing metalxWS2, make the thermal conductivity of specific direction
It reduces, to make MxWS2The ZT value of thermoelectric material is greatly improved, and ZT is increased to by 0.005 (temperature 1000K) before adulterating
0.22 (temperature 1000K) after doping.
(2) present invention passes through metal and WS2It is sintered, effectively increases WS2The conductance of material, before conductivity is by adulterating
10-200S/m be increased to doping after 4700-12000S/m, obtained MxWS2Thermoelectric material Seebeck coefficient is high,
Seebeck coefficient can reach 402 μ V/K, and power factor is largely increased, WS before adulterating2Power factor there was only 40 μ W/mK2,
MxWS2Power factor can achieve 760 μ W/mK2.The degree of orientation of crystal grain is improved after sintering, and the degree of orientation is greater than 0.8, makes
The thermal conductivity for obtaining specific direction reduces, to effectively increase the thermoelectricity capability of material.
(3) preparation method of the invention is simple, is easy a large amount of preparations, has expanded the field of thermoelectricity research.
(4) M of the inventionxWS2Material is also applied to electro-catalysis, photoelectrocatalysis, the fields such as electronic device.
Detailed description of the invention
Fig. 1 is WS of the present invention2The flow chart of preparation method;
Fig. 2 is 1 (Ti of present example0.1WS2), 2 (V of example0.2WS2) and 3 (Ta of example0.05WS2) thermal conductivity datagram;
Fig. 3 is 1 (Ti of present example0.1WS2), 2 (V of example0.2WS2) and 3 (Ta of example0.05WS2) conductance datagram;
Fig. 4 is 1 (Ti of present example0.1WS2), 2 (V of example0.2WS2) and 3 (Ta of example0.05WS2) Seebeck coefficient
Datagram;
Fig. 5 is 1 (Ti of present example0.1WS2), 2 (V of example0.2WS2) and 3 (Ta of example0.05WS2) power factor
(Power Factor) figure;
Fig. 6 is 1 (Ti of present example0.1WS2), 2 (V of example0.2WS2) and 3 (Ta of example0.05WS2) thermoelectric figure of merit (ZT)
Figure;
Fig. 7 is 1 (Ti of present example0.1WS2), 2 (V of example0.2WS2) and 3 (Ta of example0.05WS2) X-ray diffraction
(XRD) figure.
Specific embodiment
With reference to the accompanying drawing and the present invention is discussed in detail in specific embodiment.But embodiment below is only limitted to explain this hair
Bright, protection scope of the present invention should include the full content of claim, be not limited only to the present embodiment.
The present invention is prepared for a kind of new thermoelectric materials, chemical general formula MxWS2, wherein M be Ti, V, Nb, Ta, Zr, Hf,
One of element simple substances such as Yb and Re or two kinds, wherein x represents institute's doped chemical simple substance and WS2Molar ratio, the range of x
It is 1%-30%, x preferred scope is 0.1≤x≤0.2.
As shown in Figure 1, specific implementation method of the invention includes two processes, implementation steps are described as follows:
(1) first, in accordance with certain molar ratio, metal and WS the mixing of solid powder: are weighed2.Metal can be Ti, V,
The powder of the metal simple-substances such as Nb, Ta, Zr, Hf, Yb, Re, metal powder size used is 40-150 μm, WS2Size be 1-
150μm.By the metal after weighing and WS2, it is put into the agate mortar that internal diameter is 12cm, agate mortar is then placed on grinding
In machine, grinding condition is set, preferable grinding condition is revolving speed 90rpm, milling time 90-180min.By metal powder and WS2
Powder is uniformly mixed.
(2) sintering of mixture of powders: it is first 40mm, internal diameter 13.1mm in outer diameter, is highly the graphite mo(u)ld of 40mm
Add one layer of carbon paper in tool, then mixed powder is put into graphite jig, is 12.7mm with diameter, is highly the stone of 20mm
Powder is compacted by black pressure head, is added two layers of carbon felt in mold outer layer, is retained thermometer hole, mold is then put into discharge plasma sintering
In furnace (SPS).It is forced into certain pressure, pressure limit can be 30-100MPa, and the size of pressing force is to resulting thermoelectricity material
The performance of material has a major impact.Then start to vacuumize, this mainly prevents sample to be oxidized in sintering process, protects simultaneously
SPS instrument starts sintering procedure when vacuum reaches 5Pa.After starting sintering, electric current is gradually increased, current value is increased to by 0
1000-1500A, electric current are increased speed as 50-100A/min, so that mold is warming up to 1400-1500 DEG C by 20-30min, heating
Rate is 50-100 DEG C/min, and in 1400-1500 DEG C of heat preservation a period of time, soaking time can be 10-60min.Then terminate
Sintering procedure starts to cool down, and temperature-fall period can be to maintain pressure, gradually turns down electric current, can also be directly by pressure and electric current
0 is dropped to, mold Temperature fall is made.
Embodiment 1
The Ti of Ti dopingxWS2, it is specific the preparation method is as follows:
(1) solid mixes: in x=0.1, by Ti and WS2Molar ratio be 0.1 to weigh Ti and WS2Powder, Ti powder are
The gross mass of 325 mesh (45 μm), powder is 10g, then the two is put into agate mortar, with grinder under the conditions of 90rpm
Mechanical lapping 90min is carried out, the two is uniformly mixed.
(2) sample is sintered: uniformly mixed solid is put into the graphite jig that internal diameter is 13.1mm, then by mold
It is put into the furnace body of SPS sintering instrument, is forced into 50MPa, then vacuumizes, when vacuum reaches 5Pa, start to be sintered,
Electric current is gradually increased, 1500 DEG C is warming up to by 30min, keeps 10min, then start to cool down, close sintering procedure, lay down pressure
Electric current is adjusted to 0 by power, makes sample Temperature fall.
Embodiment 2
The V of V dopingxWS2, the preparation method is as follows:
(1) solid mixes: in x=0.2, by V and WS2Molar ratio be 0.2 to weigh V and WS2Powder, the size of V powder
Be 100-200 mesh, then powder be put into agate mortar, total powder quality 10g, with grinder under the conditions of 90rpm into
Row mechanical lapping 90min is uniformly mixed the two.
(2) sample is sintered: by uniformly mixed 10g solid, being put into outer diameter is 40mm, and internal diameter is the graphite jig of 13.1mm
In, then mold is put into sintering furnace body, plus-pressure 6.3KN makes pressure reach 50MPa, then starts to warm up, and passes through
40min is warming up to 1500 DEG C, then constant temperature 10min starts to cool down, and closes sintering procedure, lays down pressure, drop sample naturally
Temperature.
Embodiment 3
The Ta of Ta dopingxWS2, the preparation method is as follows:
(1) solid mixes: in x=0.05, by Ta and WS2Molar ratio be 0.05 to weigh Ta and WS2Powder makes herein
The size of Ta powder is 325 mesh, and the solid weighed up is put into mortar, is existed with grinder by total powder quality 10g
Mechanical lapping 90min is carried out under the conditions of 90rpm, is uniformly mixed the two.
(2) sample is sintered: by uniformly mixed 10g solid, being put into graphite jig, mold is then put into sintering furnace body
In, plus-pressure 6.3KN makes pressure reach 50MPa, is evacuated to 5Pa, then starts to warm up, and is warming up to 1500 by 30min
DEG C, then constant temperature 10min starts to cool down, close sintering procedure, lay down pressure, make sample Temperature fall.
Determination of conductive coefficients
Test case 1, example 2, example 3 thermoelectric material thermal coefficient, instrument includes: German NETZSCH
LFA 457, German NETZSCH STA 449F3, Range of measuring temp 323-1000K, the thermal coefficient measured such as Fig. 2 institute
Show, the thermal conductivity that pressure direction is parallel to after doping is reduced, and thermal coefficient is reduced with temperature, at room temperature example
1 and example 2 thermal coefficient in 7W/mK or so, the thermal coefficient of example 3 is 6.1W/mK.Example 1 leads at high temperature 1000K
Hot coefficient is 3.5W/mK, and the thermal coefficient of example 2 is 4.5W/mK, and the thermal coefficient of example 3 is 4.2W/mK.
Conductivity and the test of Seebeck coefficient
Electrical properties test is carried out after the sample of example 1, example 2, example 3 is cut, test equipment is Japanese ULVAC
ZEM-3, temperature range 323K-1000K, the conductivity measured and Seebeck coefficient are as shown in Figure 3 and Figure 4.It can be with by Fig. 3
See, conductivity is improved, and obtaining 1 conductance of thermoelectric material example after adulterating under high temperature 1000K can achieve 4700S/m, real
The conductance of example 2 can achieve 12000S/m, and the conductance of example 3 can achieve 8290S/m.Heat after adulterating as seen from Figure 4
The Seebeck coefficient of electric material is still higher, and in temperature 1000K, the Seebeck coefficient of example 1 can reach 402 μ V/K, example
2 Seebeck coefficient can reach 265 μ V/K, and the Seebeck coefficient of example 3 can reach 160 μ V/K.Fig. 5 is by example 1, example
2 and example 3 the power factor that is calculated of corresponding conductivity and Seebeck coefficient.As seen from Figure 5, after doping
The thermoelectric material M arrivedxWS2Power factor be improved, the power factor of example 1 can achieve 760 μ W/mK2, the function of example 2
The rate factor can achieve 840 μ W/mK2, the power factor of example 3 can achieve 212 μ W/mK2.Fig. 6 is by example 1,2 and of example
The thermoelectric figure of merit ZT figure that the corresponding thermal coefficient of example 3 and power factor calculate.The thermoelectric material M obtained after dopingxWS2ZT
It effectively improves, the ZT of example 1 can reach 0.22 when temperature is 1000K, and the ZT of example 2 can reach 0.17, the ZT energy of example 3
Reach 0.05.
The XRD structural characterization of material
X-ray diffraction characterization is carried out to the sample of example 1, example 2, example 3.Instrument is Dutch Panaco company
Empyrean, test results are shown in figure 7.By XRD characterization it can be seen that there is the characteristic peak of metal to go out in the sample of sintering
It is existing, there is the characteristic peak of titanium-tungsten in the XRD diagram of example 1, there is the feature of vanadium metal and tungsten metal in the XRD diagram of example 2
There is the characteristic peak of tantalum metal and tungsten metal at peak in the XRD diagram of example 3, illustrates the M obtained after oversinteringxWS2Thermoelectricity material
Contain metal phase in material.(00l) corresponding peak relative intensity after adulterating it can be seen from XRD simultaneously is improved, so that
Degree of grain alignment after doping is improved, and the orientation factor of (00l) of example 1 can reach 0.82.
In short, the present invention is by by metal and WS2It is sintered, it is compound then to obtain a kind of thermoelectricity containing metal phase
Material effectively increases the conductance of thermoelectric material, and it is higher to maintain Seebeck coefficient, so that MxWS2Power factor obtain
To large increase.The degree of orientation of crystal grain is improved after sintering, so that the thermal conductivity of specific direction reduces, to effectively increase
The thermoelectricity capability of material.
It should be noted that those skilled in the art are that this hair may be implemented completely according to the various embodiments described above of the present invention
Bright independent claims and the full scope of appurtenance, realize process and the same the various embodiments described above of method;And the present invention is not
It elaborates and partly belongs to techniques well known.
Above embodiments are provided just for the sake of the description purpose of the present invention, and are not intended to limit the scope of the invention.This
The range of invention is defined by the following claims.It does not depart from spirit and principles of the present invention and the various equivalent replacements made and repairs
Change, should all cover within the scope of the present invention.
Claims (11)
1. a kind of preparation method of metal-doped tungsten disulfide thermoelectric material, it is characterised in that: the chemistry of the thermoelectric material
General formula is MxWS2, wherein 0 x≤1 <, metal M is one of Ti, V, Ta, Nb, Zr, Hf, Yb and Re element or two kinds;Institute
The mole percent for stating metal M is 1%-30%;Realize that steps are as follows:
(1) solid powder mixes: according to certain molar ratio, weighing WS2It is Ti, V, Ta, Nb, Zr, Hf, Yb with metal M, metal M
And one of Re element simple substance or two kinds, the two is mixed, is put into mortar, mechanical lapping is uniform, is ground
Mixing sample afterwards;
(2) mixture of powders is sintered: sample will be mixed, be put into graphite jig, then mold is put into sintering furnace, pressurizeed,
It vacuumizes, when vacuum reaches 5Pa, starts to warm up sintering, keep the temperature a period of time after reaching sintering temperature, terminate sintering process,
Start to cool down, obtains metal-sulfur tungsten composite thermoelectric material, i.e. MxWS2Thermoelectric material.
2. the preparation method of metal-doped tungsten disulfide thermoelectric material according to claim 1, it is characterised in that: described
The mole percent of metal M is 10-20%.
3. the preparation method of metal-doped tungsten disulfide thermoelectric material according to claim 1, it is characterised in that: described
MxWS2In x be preferably 0.1≤x≤0.2.
4. the preparation method of metal-doped tungsten disulfide thermoelectric material according to claim 1, it is characterised in that: described
WS2Particle size range be 1-150 μm;The particle size range of the metal M is 40-150 μm.
5. metal-doped tungsten disulfide thermoelectric material preparation method according to claim 1, it is characterised in that: the WS2
Mole percent with metal M is respectively 70-99%, 1%-30%.
6. metal-doped tungsten disulfide thermoelectric material preparation method according to claim 1, it is characterised in that: the WS2
Particle size range be 1-150 μm, the particle size range of M is 40-150 μm.
7. metal-doped tungsten disulfide thermoelectric material preparation method according to claim 1, it is characterised in that: the step
Suddenly revolving speed 90rpm when (1) mechanical lapping, milling time 90-180min.
8. metal-doped tungsten disulfide thermoelectric material preparation method according to claim 1, it is characterised in that: the step
Suddenly pressing force range is 30-100MPa in (2) sintering process.
9. metal-doped tungsten disulfide thermoelectric material preparation method according to claim 1, it is characterised in that: the step
Suddenly the heating rate in (2) is 50-100 DEG C/min, and thermostat temperature is 1400-1500 DEG C, soaking time 10-60min.
10. metal-doped tungsten disulfide thermoelectric material preparation method according to claim 1, it is characterised in that: described
Sintering furnace be discharge plasma sintering furnace.
11. metal-doped tungsten disulfide thermoelectric material preparation method according to claim 1, it is characterised in that: gained
MxWS2Thermoelectric material degree of grain alignment is greater than 0.8.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510962265.4A CN106898689B (en) | 2015-12-18 | 2015-12-18 | A kind of metal-doped tungsten disulfide thermoelectric material and preparation method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510962265.4A CN106898689B (en) | 2015-12-18 | 2015-12-18 | A kind of metal-doped tungsten disulfide thermoelectric material and preparation method |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106898689A CN106898689A (en) | 2017-06-27 |
CN106898689B true CN106898689B (en) | 2019-10-11 |
Family
ID=59190504
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510962265.4A Active CN106898689B (en) | 2015-12-18 | 2015-12-18 | A kind of metal-doped tungsten disulfide thermoelectric material and preparation method |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106898689B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109256459B (en) * | 2017-07-12 | 2020-12-15 | 中国科学院大连化学物理研究所 | Multi-metal co-doped GeSe-based thermoelectric material and preparation method thereof |
CN110578110B (en) * | 2019-10-15 | 2021-08-27 | 河南科技大学 | Sulfide-based composite film layer, preparation method thereof and wear-resistant workpiece |
CN115188877A (en) * | 2022-07-27 | 2022-10-14 | 武汉理工大学 | Method for preparing flexible thermoelectric film with strong texture and high thermoelectric performance |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101479862A (en) * | 2006-06-26 | 2009-07-08 | 戴蒙得创新股份有限公司 | Increasing the seebeck coefficient of semiconductors by hpht sintering |
CN102272958A (en) * | 2009-01-09 | 2011-12-07 | 戴蒙得创新股份有限公司 | Affecting the thermoelectric figure of merit (zt) by high pressure, high temperature sintering |
CN103296192A (en) * | 2013-05-27 | 2013-09-11 | 河南理工大学 | Massive thermoelectric material preparation method |
WO2014001519A1 (en) * | 2012-06-28 | 2014-01-03 | The Provost, Fellows, Foundation Scholars, & The Other Members Of Board, Of The College Of The Holy & Undiv. Trinity Of Queen Elizabeth Near Dublin | Atomically thin crystals and films and process for making same |
-
2015
- 2015-12-18 CN CN201510962265.4A patent/CN106898689B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101479862A (en) * | 2006-06-26 | 2009-07-08 | 戴蒙得创新股份有限公司 | Increasing the seebeck coefficient of semiconductors by hpht sintering |
CN102272958A (en) * | 2009-01-09 | 2011-12-07 | 戴蒙得创新股份有限公司 | Affecting the thermoelectric figure of merit (zt) by high pressure, high temperature sintering |
WO2014001519A1 (en) * | 2012-06-28 | 2014-01-03 | The Provost, Fellows, Foundation Scholars, & The Other Members Of Board, Of The College Of The Holy & Undiv. Trinity Of Queen Elizabeth Near Dublin | Atomically thin crystals and films and process for making same |
CN103296192A (en) * | 2013-05-27 | 2013-09-11 | 河南理工大学 | Massive thermoelectric material preparation method |
Also Published As
Publication number | Publication date |
---|---|
CN106898689A (en) | 2017-06-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Liang et al. | Flexible thermoelectrics: from silver chalcogenides to full-inorganic devices | |
Jabar et al. | Achieving high thermoelectric performance through constructing coherent interfaces and building interface potential barriers in n-type Bi 2 Te 3/Bi 2 Te 2.7 Se 0.3 nanocomposites | |
Dou et al. | Enhanced thermopower and thermoelectric performance through energy filtering of carriers in (Bi2Te3) 0.2 (Sb2Te3) 0.8 bulk alloy embedded with amorphous SiO2 nanoparticles | |
Toprak et al. | The impact of nanostructuring on the thermal conductivity of thermoelectric CoSb3 | |
Lee et al. | Contrasting role of antimony and bismuth dopants on the thermoelectric performance of lead selenide | |
CN102931335B (en) | A kind of Graphene is combined thermoelectric material of cobalt stibide based skutterudite and preparation method thereof | |
CN106898689B (en) | A kind of metal-doped tungsten disulfide thermoelectric material and preparation method | |
Mawassi et al. | Improvement of superconducting parameters of Bi 1.8 Pb 0.4 Sr 2 Ca 2 Cu 3 O 10+ δ added with nano-Ag | |
Liu et al. | Thermoelectric properties of Bi 3+ substituted Co-based misfit-layered oxides | |
Tang et al. | Bi 2 Te 3 single crystals with high room-temperature thermoelectric performance enhanced by manipulating point defects based on first-principles calculation | |
Guan et al. | Effect of CaO-doped in NiMn 2 O 4–LaMnO 3 composite ceramics on microstructure and electrical properties | |
Pradhan et al. | Dielectric dispersion and impedance spectroscopy of yttrium doped BiFeO 3-PbTiO 3 electronic system | |
Ma et al. | Preparation and characterization for LaMnO 3 and 0.3 LaMnO 3–0.7 Y 2 O 3 high temperature bilayer structure NTC thermistors | |
Zhang et al. | Enhanced thermoelectric performance of Ba8Ga16Ge30 clathrate by modulation doping and improved carrier mobility | |
CN109650435A (en) | A kind of copper sulfide base thermoelectrical composite material and preparation method thereof | |
Cui et al. | Band structure and thermoelectric properties of Al-doped Mg 3− x Al x Sb 2 compounds | |
CN107123729A (en) | A kind of nanometer silicon carbide/P-type silicon germanium alloy base thermoelectrical composite material and preparation method thereof | |
Cui et al. | Fabrication of nano-grained negative temperature coefficient thermistors with high electrical stability | |
Zhao et al. | Effect of Y 2 O 3, Nd 2 O 3 or Sm 2 O 3 on the microstructure and electrical properties of ZnVMnNbO varistor ceramics | |
Yang et al. | Electrical properties and temperature sensitivity of B-substituted CuO-based ceramics for negative temperature coefficient thermistors | |
Hu et al. | Fabrication and thermosensitive characteristics of BaCoO 3− δ ceramics for low temperature negative temperature coefficient thermistor | |
Yu et al. | Significantly enhanced thermoelectric figure of merit of n-type Mg3Sb2-based Zintl phase compounds via co-doped of Mg and Sb site | |
Zhou et al. | The effect of samarium doping on structure and enhanced thermionic emission properties of lanthanum hexaboride fabricated by spark plasma sintering | |
CN109399580A (en) | A kind of quickly preparation CuFeSe2Method | |
Yang et al. | Dielectric properties and high-temperature dielectric relaxation of tungsten-bronze structure ceramics Ba 2 GdFeNbTa 3 O 15 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |