CN108598252A - Argyrodite type thermoelectric material and preparation method thereof - Google Patents
Argyrodite type thermoelectric material and preparation method thereof Download PDFInfo
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- CN108598252A CN108598252A CN201810577403.0A CN201810577403A CN108598252A CN 108598252 A CN108598252 A CN 108598252A CN 201810577403 A CN201810577403 A CN 201810577403A CN 108598252 A CN108598252 A CN 108598252A
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- H10N10/851—Thermoelectric active materials comprising inorganic compositions
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Abstract
The invention discloses a kind of argyrodite type thermoelectric material and preparation method thereof, argyrodite type thermoelectric material chemical formula is Ag9‑ xCuyGaSe6, and any one in the stoichiometric ratio relationship characteristic with following elemental mole ratios example：As y=0,0≤x≤0.1；As y ≠ 0,0 x=y≤0.9 ＜.Argyrodite type thermoelectric material of the present invention has ultralow lattice thermal conductivity, thermoelectric figure of merit regulation and control can improve the ZT values of this material by single regulation and control Seebeck, the present invention is also replaced by reducing Ag and part Ag by Cu, to reduce carrier concentration, reduce conductivity, improve Seebeck coefficient, to improve argyrodite type thermoelectricity capability, the ideal novel argyrodite type thermoelectric material of thermoelectric material thermoelectric conversion efficiency is prepared, basis is carried out without transmission parts, noiseless, pollution-free reliable and stable thermal energy conversion for following realize.The method of the present invention is simple for process, easily controllable, at low cost.
Description
Technical field
The present invention relates to a kind of thermoelectric material and preparation method thereof, N-type thermoelectric material and preparation method thereof further relates to one kind
The electrical property of argyrodite type thermoelectric material regulates and controls method, is applied to function field of thermoelectric material technique.
Background technology
As global economy science and technology develops rapidly, non-renewable fossil energy consumption exponentially increases.Scientist's prediction is complete
Ball petroleum resources will be depleted in the year two thousand fifty, other fossil energies will run out of the latest in 2100, the exploitation profit of new energy
With extremely urgent.In addition to solar energy, wind energy, water energy etc., the huge energy that thermal energy is contained also results in the huge of scientists
Enthusiasm, for example, indoor/outdoor temperature-difference, the waste heat of factory, automobile exhaust emissions etc..The thermal energy electric energy conversion function of thermoelectric material is just
It is the most effective approach for realizing heat energy utilization.Thermoelectric material realizes the conversion of thermal energy electric energy by microcosmic carrier, realizes without biography
Dynamic component, noiseless, pollution-free reliable and stable thermal energy conversion.The breakthrough of thermoelectric material by be utilization of new energy resources another mileage
Upright stone tablet.
Germany scientist Seebeck in 1821 has found that Seebeck effect found to fill in French scientist Peltier in 1834
The back wash effect of Bake effect --- paltie effect is two basic theories of thermoelectric material.Seebeck effect is conductor both ends
There are the effect that the temperature difference generates voltage, paltie effect is the phenomenon that conductor electrical conductor generates temperature difference heat.Transfer efficiency heat
Electric figure of merit ZT is characterized, ZT=S2σ T/ κ, wherein S are Seebeck coefficient.σ is conductivity, and T is absolute temperature, and κ is overall thermal conductance
Rate.It is wherein interrelated between three physical parameter S Seebeck coefficients, conductivityσ and thermal conductivity κ of decision thermoelectric figure of merit, very
Difficulty by it is independent regulate and control some parameter therein realize being obviously improved for thermoelectric figure of merit, this is also few material bodies so far
The main reason for ZT values of system break through 2.Wherein κ=κe+κL。κe=L σ T, L are Lorentz constant, κLIt is lattice thermal conductivity.Work as κL
Lattice thermal conductivity is with respect to κeIt ignores when smaller.Thermoelectric figure of merit formula can be reduced to ZT=S2σ T/L σ T=S2/ L, thermoelectric figure of merit
Impact factor only it is related with S Seebecks.This situation is suitable only for κLOpposite κeWhen smaller, the σ when regulating and controlling S Seebecks and increasing
Become smaller, finally results in κLWith κeIt is close, and κLIt can not ignore.Existing thermoelectric material thermoelectric conversion efficiency is also undesirable.
Invention content
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
Argyrodite type thermoelectric material and preparation method thereof, argyrodite type thermoelectric material of the present invention have ultralow lattice thermal conductivity, thermoelectricity
Figure of merit regulation and control can improve the ZT values of this material by single regulation and control Seebeck, and the present invention is also by reducing Ag and part Ag quilts
Cu is replaced, and to reduce carrier concentration, is reduced conductivity, is improved Seebeck coefficient, to improve the argyrodite type heat
Electrical property prepares the ideal novel argyrodite type thermoelectric material of thermoelectric material thermoelectric conversion efficiency, and nothing is realized to be following
Basis is carried out in transmission parts, noiseless, pollution-free reliable and stable thermal energy conversion.
In order to achieve the above objectives, the present invention adopts the following technical scheme that：
A kind of argyrodite type thermoelectric material, chemical formula Ag9-xCuyGaSe6, and with following elemental mole ratios example
Any one in stoichiometric ratio relationship characteristic：
1) as y=0,0≤x≤0.1；
2) as y ≠ 0,0 x=y≤0.9 ＜.
As currently preferred technical solution, the chemical formula of argyrodite type thermoelectric material is Ag9-xCuyGaSe6, and have
There is any one of the stoichiometric ratio relationship characteristic of following elemental mole ratios example：
1) as y=0,0≤x≤0.1；
2) as y ≠ 0,0 x=y≤0.9 ＜.
As most preferred technique scheme of the present invention, x=0.1 and y=0 or x=y=0.9 have larger Seebeck and compared with
Low thermal conductivity.
It is preferred that the total thermal conductivity of argyrodite type thermoelectric material is 0.25~0.55W*m-1k-1；
It is preferred that the Seebeck coefficient of argyrodite type thermoelectric material is -80~-165uV/k；
It is preferred that argyrodite type thermoelectric material, in 823K, the ZT values of argyrodite type thermoelectric material are 0.85~1.5.
The present invention still further preferably argyrodite type thermoelectric material Seebeck coefficient be 150~165uV/k.
The present invention still further preferably argyrodite type thermoelectric material, in 823K, the ZT of argyrodite type thermoelectric material
Value is 1.3~1.5.
A kind of preparation method of argyrodite type thermoelectric material of the present invention, includes the following steps：
A. the stoichiometric ratio of target argyrodite type thermoelectric material each element to be prepared is pressed, purity of weighing respectively is not low
In 99.99% element simple substance as raw material, each raw material is mixed, and is packaged in vitreosil glass tube, it is spare；
B. the vacuum material quartz ampoule of the charging feedstock in the step a is placed in Muffle furnace, high temperature 1000~
1100 DEG C are heated mixed raw material, and carry out 24~48h of heat preservation under mixed raw material fused solution state, then 600
24~48h of annealing heat-treats is carried out at~700 DEG C obtains ingot casting after furnace cooling is cooled to room temperature；
C. the ingot casting prepared in the step b is crushed, and is ground into fine powder, be then placed into vacuum high-temperature high pressure stone
In black grinding tool, hot pressing is carried out into bulk material；
D. the block materials prepared in the step c are packaged in other vitreosil glass tube, and 500~
Annealing heat-treats 4~for 24 hours are carried out at 600 DEG C, are then shut off Muffle furnace power supply, furnace cooling is carried out and is down to room temperature, obtain required sulphur silver
Germanium mine type thermoelectric material.
As currently preferred technical solution, each raw material is mixed in the step a and is packaged in vitreosil glass
When in glass pipe, or when block materials are packaged in other vitreosil glass tube in the step d, packaging technology uses
The small tolerance flame gun of hydrogen-oxygen high temperature is only sealed to being heated at the encapsulation of vitreosil glass tube, is reduced to vitreosil glass tube
Interior sample heat effect reduces Se powder volatilization losses in encapsulation process.
As currently preferred technical solution, in the step b, 1000~1100 DEG C of high temperature is warming up to described in control
Heating rate be 1~5 DEG C/min.
As currently preferred technical solution, in the step c, when carrying out hot pressing into bulk material, use
Heat pressing process is that vacuum degree is not higher than 5Pa, and hot pressing pressure is 40~60Mpa, and hot pressing temperature is 450~600 DEG C, and constant temperature heat preservation is protected
The pressure time is 5~20min.
Annealing temperature 500~600 is warming up to described in control in the step d as currently preferred technical solution
DEG C heating rate be not more than 5 DEG C/min.
As currently preferred technical solution, in the step c, hot pressing is not less than sulphur at the density of bulk material
The 98% of silver-colored germanium mine type pyroelectric crystal material theoretical density.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage：
1. argyrodite type pyroelectric material Ag of the present invention9GaSe6With ultralow lattice thermal conductivity, thermoelectric figure of merit regulation and control can pass through
Single regulation and control Seebeck and improve the ZT values of this material；
2. the lattice thermal conductivity κ in 823k of argyrodite type thermoelectric material of the present inventionLIt is electronics thermal conductivity κeNearly 1/15, symbol
Close ZT=S2The scope of application of/L can obtain the new sulfur silver with ideal thermoelectric conversion efficiency by regulating and controlling Seebeck coefficient
Germanium mine type thermoelectric material；
3. the method for the present invention is that the Ag-Ga-Se type argyrodite type thermoelectric materials prepared are N-type semiconductor, fluid-like state knot
Cation-bit Ag in structure provides conduction electrons, and the present invention is replaced by the content and part Ag for reducing Ag by Cu, and current-carrying is reduced
Sub- concentration improves Seebeck coefficient, thermal conductivity is reduced, and then improve ZT, to improve argyrodite type thermoelectricity capability
4. the method for the present invention preparation process is simple, easily controllable, at low cost, can prepare thermoelectric material thermoelectric conversion efficiency compared with
For ideal novel argyrodite type thermoelectric material, realized without transmission parts, noiseless, pollution-free reliable and stable heat to be following
It can convert and carry out basis.
Description of the drawings
Fig. 1 is Ag prepared by the embodiment of the present invention one9GaSe6Conductivity vary with temperature curve.
Fig. 2 is Ag prepared by the embodiment of the present invention one9GaSe6Seebeck coefficient vary with temperature curve.
Fig. 3 is Ag prepared by the embodiment of the present invention one9GaSe6Total thermal conductivity vary with temperature curve.
Fig. 4 is Ag prepared by the embodiment of the present invention one9GaSe6ZT values vary with temperature curve.
Fig. 5 is Ag prepared by the embodiment of the present invention two8.9GaSe6Conductivity vary with temperature curve.
Fig. 6 is Ag prepared by the embodiment of the present invention two8.9GaSe6Seebeck coefficient vary with temperature curve.
Fig. 7 is Ag prepared by the embodiment of the present invention two8.9GaSe6Total thermal conductivity vary with temperature curve.
Fig. 8 is Ag prepared by the embodiment of the present invention two8.9GaSe6ZT values vary with temperature curve.
Fig. 9 is Ag prepared by the embodiment of the present invention three8.1Cu0.9GaSe6Conductivity vary with temperature curve.
Figure 10 is Ag prepared by the embodiment of the present invention three8.1Cu0.9GaSe6Seebeck coefficient vary with temperature curve.
Figure 11 is Ag prepared by the embodiment of the present invention three8.1Cu0.9GaSe6Total thermal conductivity vary with temperature curve.
Figure 12 is Ag prepared by the embodiment of the present invention three8.1Cu0.9GaSe6ZT values vary with temperature curve.
Specific implementation mode
Said program is described further below in conjunction with specific examples of the implementation, the preferred embodiment of the present invention is described in detail such as
Under：
Embodiment one
In the present embodiment, a kind of argyrodite type thermoelectric material, chemical formula Ag9GaSe6。
A kind of preparation method of argyrodite type thermoelectric material, which is characterized in that include the following steps：
A. chemical formula Ag is pressed9GaSe6Molar ratio 9:1:The silver, gallium, selenium pure metals that 6 proportioning purity are 99.99% are total
6g in glove box, inert gas is summarized and is poured into clean quartz glass tube as raw material, and the viscous sample of tube wall
Powder blows to glass bottom of the tube, fills in glass stopper in the middle part of the glass tube, waits to be sealed, and glass tube is sealed and connects and vacuum-pumping tube
Head, pumping inflation cycle 3 times, carries out gas washing, is finally evacuated to less than 3pa sealed silica envelopes again, is mixed by each raw material again
And when being packaged in vitreosil glass tube, packaging technology is heated with high temperature hydrogen-oxygen flame gun at glass stopper, softens quartz glass
It manages and Vacuum Package sample, using the small tolerance flame gun of hydrogen-oxygen high temperature, is only sealed to being heated at the encapsulation of vitreosil glass tube,
It reduces to the sample heat effect in vitreosil glass tube, reduces Se powder volatilization losses in encapsulation process；Each raw material is mixed,
And be packaged in vitreosil glass tube, it is spare；
B. the vacuum material quartz ampoule of the charging feedstock in the step a is placed in Muffle furnace, with the liter of 3 DEG C/min
Warm rate is warming up to 1000 DEG C of high temperature, is heated to mixed raw material, and is kept the temperature under mixed raw material fused solution state
For 24 hours, 700 DEG C then are cooled to the cooling rate of 3 DEG C/min again, carry out annealing heat-treats 48h, then stops heated at constant temperature,
After furnace cooling is cooled to room temperature, ingot casting is obtained；
C. the ingot casting prepared in the step b is crushed, and is ground into fine powder, be then placed into vacuum high-temperature high pressure stone
It in black grinding tool, is put into vacuum hotpressing stove, carries out hot pressing into bulk material；When carrying out hot pressing into bulk material, first take out
Vacuum rises to 550 DEG C to 5pa hereinafter, use hydraulic pressure for 60Mpa, according to the rate of 50 DEG C/min of sensing heating rate, and
Constant temperature and pressure, which is tried hard to keep, holds 5min, then removes hydraulic pressure and closes heating power supply, cooled to room temperature takes out bulk being inflated to normal pressure
Material；
D. the block materials prepared in the step c are Resealed in other vitreosil glass tube, is being incited somebody to action
When block materials are packaged in other vitreosil glass tube, pumping inflation cycle 3 times carries out gas washing, finally vacuumizes again
To less than 3pa sealed silica envelopes again, packaging technology uses the small tolerance flame gun of hydrogen-oxygen high temperature, only to the envelope of vitreosil glass tube
Sealing is heated at dress, is reduced to the sample heat effect in vitreosil glass tube, is reduced Se powder volatilization losses in encapsulation process；
Quartz glass tube is placed in Muffle furnace again, 550 DEG C of high temperature is warming up to the heating rate of 5 DEG C/min, is carried out at 12h annealing heat
Reason is then shut off Muffle furnace power supply, carries out furnace cooling and is down to room temperature, obtains required argyrodite type pyroelectric material Ag9GaSe6。
Experimental test and analysis：
After hot pressing block materials described in the present embodiment are annealed, after taking out polishing surface, then thermoelectricity capability survey is carried out
Amount.It show Ag referring to Fig. 1~Fig. 49GaSe6Thermoelectricity capability test result, conductivity 3.8 × 104~7 × 104S*m-1, plug
Seebeck coefficient is -120~-80uV/k, the minimum 0.55W/k*m of overall thermal conductance.Reach best ZT values 0.85 in 823k.
In the present embodiment, argyrodite type pyroelectric material Ag9GaSe6Bulk semiconductor material has relatively low thermal conductivity
0.55W·m-1k-1And moderate ZT values 0.85.Due to argyrodite pyroelectric material Ag9GaSe6With relatively low lattice thermal conductivity, thermoelectricity
Figure of merit regulation and control can improve the ZT values of this material by single regulation and control Seebeck.In N-type semiconductor Ag9GaSe6In, Ag atoms carry
For conduction electrons.Compared to one Ag of embodiment9GaSe6, the present embodiment carrier concentration is relatively low, and conductivity is relatively low.Seebeck coefficient compared with
Height, to improve the argyrodite thermoelectricity capability.
Embodiment two
The present embodiment and embodiment one are essentially identical, are particular in that：
In the present embodiment, a kind of argyrodite type thermoelectric material, chemical formula Ag8.9GaSe6。
A kind of preparation method of argyrodite type thermoelectric material, which is characterized in that include the following steps：
A. chemical formula Ag is pressed8.9GaSe6Molar ratio 8.9:1:The silver, gallium, selenium pure metals that 6 proportioning purity are 99.99%
Total 6g in glove box, inert gas is summarized and is poured into clean quartz glass tube as raw material, and the viscous sample of tube wall
Product powder blows to glass bottom of the tube, fills in glass stopper in the middle part of the glass tube, waits to be sealed, and glass tube is sealed and connects and vacuumizes
Tube head, pumping inflation cycle 3 times, carries out gas washing, is finally evacuated to less than 3pa sealed silica envelopes again, is mixed by each raw material again
When merging is packaged in vitreosil glass tube, packaging technology is heated with high temperature hydrogen-oxygen flame gun at glass stopper, softens quartzy glass
Glass pipe and Vacuum Package sample, it is only close to being heated at the encapsulation of vitreosil glass tube using the small tolerance flame gun of hydrogen-oxygen high temperature
Envelope reduces to the sample heat effect in vitreosil glass tube, reduces Se powder volatilization losses in encapsulation process；Each raw material is mixed
It closes, and is packaged in vitreosil glass tube, it is spare；
B. the vacuum material quartz ampoule of the charging feedstock in the step a is placed in Muffle furnace, with the liter of 3 DEG C/min
Warm rate is warming up to 1000 DEG C of high temperature, is heated to mixed raw material, and is kept the temperature under mixed raw material fused solution state
For 24 hours, 700 DEG C then are cooled to the cooling rate of 3 DEG C/min again, carry out annealing heat-treats 48h, then stops heated at constant temperature,
After furnace cooling is cooled to room temperature, ingot casting is obtained；
C. the ingot casting prepared in the step b is crushed, and is ground into fine powder, be then placed into vacuum high-temperature high pressure stone
It in black grinding tool, is put into vacuum hotpressing stove, carries out hot pressing into bulk material；When carrying out hot pressing into bulk material, first take out
Vacuum rises to 550 DEG C to 5pa hereinafter, use hydraulic pressure for 60Mpa, according to the rate of 50 DEG C/min of sensing heating rate, and
Constant temperature and pressure, which is tried hard to keep, holds 5min, then removes hydraulic pressure and closes heating power supply, cooled to room temperature takes out bulk being inflated to normal pressure
Material；
D. the block materials prepared in the step c are Resealed in other vitreosil glass tube, is being incited somebody to action
When block materials are packaged in other vitreosil glass tube, pumping inflation cycle 3 times carries out gas washing, finally vacuumizes again
To less than 3pa sealed silica envelopes again, packaging technology uses the small tolerance flame gun of hydrogen-oxygen high temperature, only to the envelope of vitreosil glass tube
Sealing is heated at dress, is reduced to the sample heat effect in vitreosil glass tube, is reduced Se powder volatilization losses in encapsulation process；
Quartz glass tube is placed in Muffle furnace again, 550 DEG C of high temperature is warming up to the heating rate of 5 DEG C/min, is carried out at 12h annealing heat
Reason is then shut off Muffle furnace power supply, carries out furnace cooling and is down to room temperature, obtains required argyrodite type pyroelectric material Ag8.9GaSe6。
Experimental test and analysis：
After hot pressing block materials described in the present embodiment are annealed, after taking out polishing surface, then thermoelectricity capability survey is carried out
Amount.It show Ag referring to Fig. 5~Fig. 88.9GaSe6Thermoelectricity capability test result, conductivity be 2.5 × 104~5.4 × 104S*
m-1, compare Ag9GaSe6Minimum 3.6 × 104S*m-1It is low.Seebeck coefficient is -150~-85uV/k.Because free electron with
The compound reduction carrier concentration in the vacancy Ag reduces conductivity, while overall thermal conductance is minimum drops to 0.37W/k*m, and ZT values are increased to
1.3。
In the present embodiment, argyrodite type pyroelectric material Ag8.9GaSe6Bulk semiconductor material is led with low-heat
0.37W·m-1k-1And higher ZT values 1.3.Due to argyrodite pyroelectric material Ag8.9GaSe6With low lattice thermal conductivity, thermoelectricity is excellent
Value regulation and control can improve the ZT values of this material by single regulation and control Seebeck.In N-type semiconductor Ag8.9GaSe6In, Ag atoms carry
For conduction electrons.Compared to one Ag of embodiment9GaSe6, the present embodiment by reduce Ag, reduce carrier concentration, reduce conductance
Rate improves Seebeck to improve the argyrodite thermoelectricity capability.
Embodiment three
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, a kind of argyrodite type thermoelectric material, chemical formula Ag8.1Cu0.9GaSe6。
A kind of preparation method of argyrodite type thermoelectric material, which is characterized in that include the following steps：
A. chemical formula Ag is pressed8.1Cu0.9GaSe6Molar ratio 8.1:0.9:1:6 proportioning purity be 99.99% silver, copper,
Gallium, the total 6g of selenium pure metals in glove boxes, inert gas are summarized and is poured into clean quartz glass tube as raw material, and
The sample powder that tube wall glues is blown to glass bottom of the tube, fills in glass stopper in the middle part of the glass tube, waits to be sealed, glass tube is sealed
And tube head is connect and vacuumizes, pumping inflation cycle 3 times carries out gas washing, is finally evacuated to again less than 3pa sealed silica envelopes again,
When mixing and being packaged in vitreosil glass tube by each raw material, packaging technology heats glass stopper with high temperature hydrogen-oxygen flame gun
Place softens quartz glass tube and Vacuum Package sample, using the small tolerance flame gun of hydrogen-oxygen high temperature, only to vitreosil glass tube
Sealing is heated at encapsulation, is reduced to the sample heat effect in vitreosil glass tube, and Se powder volatilization damage in encapsulation process is reduced
It loses；Each raw material is mixed, and is packaged in vitreosil glass tube, it is spare；
B. the vacuum material quartz ampoule of the charging feedstock in the step a is placed in Muffle furnace, with the liter of 3 DEG C/min
Warm rate is warming up to 1000 DEG C of high temperature, is heated to mixed raw material, and is kept the temperature under mixed raw material fused solution state
For 24 hours, 700 DEG C then are cooled to the cooling rate of 3 DEG C/min again, carry out annealing heat-treats 48h, then stops heated at constant temperature,
After furnace cooling is cooled to room temperature, ingot casting is obtained；
C. the ingot casting prepared in the step b is crushed, and is ground into fine powder, be then placed into vacuum high-temperature high pressure stone
It in black grinding tool, is put into vacuum hotpressing stove, carries out hot pressing into bulk material；When carrying out hot pressing into bulk material, first take out
Vacuum rises to 550 DEG C to 5pa hereinafter, use hydraulic pressure for 60Mpa, according to the rate of 50 DEG C/min of sensing heating rate, and
Constant temperature and pressure, which is tried hard to keep, holds 5min, then removes hydraulic pressure and closes heating power supply, cooled to room temperature takes out bulk being inflated to normal pressure
Material；
D. the block materials prepared in the step c are Resealed in other vitreosil glass tube, is being incited somebody to action
When block materials are packaged in other vitreosil glass tube, pumping inflation cycle 3 times carries out gas washing, finally vacuumizes again
To less than 3pa sealed silica envelopes again, packaging technology uses the small tolerance flame gun of hydrogen-oxygen high temperature, only to the envelope of vitreosil glass tube
Sealing is heated at dress, is reduced to the sample heat effect in vitreosil glass tube, is reduced Se powder volatilization losses in encapsulation process；
Quartz glass tube is placed in Muffle furnace again, 550 DEG C of high temperature is warming up to the heating rate of 5 DEG C/min, is carried out at 12h annealing heat
Reason is then shut off Muffle furnace power supply, carries out furnace cooling and is down to room temperature, obtains required argyrodite type thermoelectric material
Ag8.1Cu0.9GaSe6。
Experimental test and analysis：
After hot pressing block materials described in the present embodiment are annealed, after taking out polishing surface, then thermoelectricity capability survey is carried out
Amount.It show Ag referring to Fig. 9~Figure 128.1Cu0.9GaSe6Thermoelectricity capability test result, test temperature 323-823k, highest
ZT performance points are 1.5 in 823k.Seebeck coefficient is -165~-113uV/k.Conductivity 2.0 × 104~3.7 × 104S*m-1Phase
Compare Ag9GaSe6With Ag8.9GaSe6Minimum value will be low, so electronics thermal conductivity is small, also smaller is 0.29W/k*m to total thermal conductivity.
In addition it is applicable in the thinking that single regulation and control Seebeck improves ZT, the present embodiment Seebeck coefficient is up to -165uV/k, also reaches herein
To maximum ZT1.5.
In the present embodiment, argyrodite type pyroelectric material Ag8.1Cu0.9GaSe6Bulk semiconductor material has ultralow heat
Lead 0.29Wm-1k-1And high ZT values 1.5.Due to argyrodite pyroelectric material Ag8.1Cu0.9GaSe6With ultralow lattice thermal conductivity,
Thermoelectric figure of merit regulation and control can improve the ZT values of this material by single regulation and control Seebeck.In N-type semiconductor Ag8.1Cu0.9GaSe6
In, Ag atoms provide conduction electrons.Compared to one Ag of embodiment9GaSe6, the present embodiment by reduce Ag and part Ag replaced by Cu,
Carrier concentration is reduced, conductivity is reduced, improves Seebeck to improve the argyrodite thermoelectricity capability.
One~embodiment of embodiment three, the lattice thermal conductivity κ in 823k of prepared argyrodite thermoelectric materialLIt is electronics
Thermal conductivity κeNearly 1/15, meet ZT=S2The scope of application of/L.One~embodiment of embodiment, two the method is to pass through Ag9- xGaSe6It is N-type semiconductor, the cation-bit Ag in fluid-like state structure provides conduction electrons, compared with prior art, by reducing Ag
Content reduce carrier concentration, improve Seebeck coefficient, reduce thermal conductivity, to improve ZT.And the sulphur prepared by embodiment three
The lattice thermal conductivity κ in 823k of silver-colored germanium mine thermoelectric materialLIt is electronics thermal conductivity κeAlso nearly 1/15, meet ZT=S2The applicable model of/L
It encloses.Three the method for embodiment is to pass through Ag9-xCuyGaSe6It is N-type semiconductor, the cation-bit Ag in fluid-like state structure is provided
Conduction electrons, being replaced by Cu by the content and part Ag that reduce Ag reduces carrier concentration, improves Seebeck coefficient, reduces heat
It leads, to improve ZT.Argyrodite type thermoelectric material prepared by embodiment three reduces in ultralow lattice thermal conducting material and provides electricity
The content of the Ag of son increases vacancy.After electronics and vacancy are compound, conductance reduction also reduces electronics thermal conductivity, to greatly drop
Low overall thermal conductance.Seebeck coefficient increases simultaneously, and the variation of total power factor is little, achievees the purpose that improve ZT.In addition, Ag
Atom position can largely be dissolved Cu atoms, increase a large amount of defects, on the one hand reduce conductivity and increase Seebeck, another party is more
Strong phon scattering also greatly reduces thermal conductivity.
Combination attached drawing of the embodiment of the present invention is illustrated above, but the present invention is not limited to the above embodiments, it can be with
The purpose of innovation and creation according to the present invention makes a variety of variations, under the Spirit Essence and principle of all technical solutions according to the present invention
Change, modification, replacement, combination or the simplification made, should be equivalent substitute mode, as long as meeting the goal of the invention of the present invention,
Without departing from argyrodite type thermoelectric material of the present invention and preparation method thereof, technical principle and inventive concept, belong to this
The protection domain of invention.
Claims (10)
1. a kind of argyrodite type thermoelectric material, it is characterised in that：Its chemical formula is Ag9-xCuyGaSe6, and there is following element
Any one in the stoichiometric ratio relationship characteristic of molar ratio：
1) as y=0,0≤x≤0.1；
2) as y ≠ 0,0 x=y≤0.9 ＜.
2. argyrodite type thermoelectric material according to claim 1, it is characterised in that：Its chemical formula is Ag9-xCuyGaSe6, and
Any one of stoichiometric ratio relationship characteristic with following elemental mole ratios example：
1) as y=0,0≤x≤0.1；
2) as y ≠ 0,0 x=y≤0.9 ＜.
3. argyrodite type thermoelectric material according to claim 1 or claim 2, it is characterised in that：
Its total thermal conductivity is 0.25~0.55W*m-1k-1；
Alternatively, its Seebeck coefficient is -80~-165uV/k；
Alternatively, in 823K, the ZT values of the argyrodite type thermoelectric material are 0.85~1.5.
4. argyrodite type thermoelectric material according to claim 3, it is characterised in that：Its Seebeck coefficient be 150~
165uV/k。
5. argyrodite type thermoelectric material according to claim 3, it is characterised in that：In 823K, the argyrodite type
The ZT values of thermoelectric material are 1.3~1.5.
6. the preparation method of argyrodite type thermoelectric material described in a kind of claim 1, which is characterized in that include the following steps：
A. the stoichiometric ratio of target argyrodite type thermoelectric material each element to be prepared is pressed, purity of weighing respectively is not less than
99.99% element simple substance mixes each raw material as raw material, and is packaged in vitreosil glass tube, spare；
B. the vacuum material quartz ampoule of the charging feedstock in the step a is placed in Muffle furnace, in high temperature 1000~1100
DEG C mixed raw material is heated, and 24~48h of heat preservation is carried out under mixed raw material fused solution state, then 600~700
24~48h of annealing heat-treats is carried out at DEG C obtains ingot casting after furnace cooling is cooled to room temperature；
C. the ingot casting prepared in the step b is crushed, and is ground into fine powder, be then placed into vacuum high-temperature high-pressure graphite mill
In tool, hot pressing is carried out into bulk material；
D. the block materials prepared in the step c are packaged in other vitreosil glass tube, and 500~600
Annealing heat-treats 4~for 24 hours are carried out at DEG C, are then shut off Muffle furnace power supply, are carried out furnace cooling and are down to room temperature, obtain required argyrodite
Type thermoelectric material.
7. the preparation method of argyrodite type thermoelectric material according to claim 6, it is characterised in that：In the step a
When each raw material being mixed and being packaged in vitreosil glass tube, or in the step d block materials be packaged in it is other
When in vitreosil glass tube, packaging technology uses the small tolerance flame gun of hydrogen-oxygen high temperature, only the encapsulation to vitreosil glass tube
Place's heating sealing, reduces to the sample heat effect in vitreosil glass tube, reduces Se powder volatilization losses in encapsulation process.
8. the preparation method of argyrodite type thermoelectric material described according to claim 6 or 7, it is characterised in that：In the step b
In, the heating rate that 1000~1100 DEG C of high temperature is warming up to described in control is 1~5 DEG C/min.
9. the preparation method of argyrodite type thermoelectric material described according to claim 6 or 7, it is characterised in that：
In the step c, when carrying out hot pressing into bulk material, heat pressing process is used to be not higher than 5Pa, hot pressing for vacuum degree
Pressure is 40~60Mpa, and hot pressing temperature is 450~600 DEG C, and the constant temperature heat-insulation pressure keeping time is 5~20min；
Alternatively, in the step d, be warming up to described in control the heating rate of 500~600 DEG C of annealing temperature no more than 5 DEG C/
min。
10. the preparation method of argyrodite type thermoelectric material described according to claim 6 or 7, it is characterised in that：In the step
In c, hot pressing is not less than the 98% of argyrodite type pyroelectric crystal material theoretical density at the density of bulk material.
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| WO2023030025A1 (en) * | 2021-09-01 | 2023-03-09 | 上海屹锂新能源科技有限公司 | Preparation method for argyrodite-type solid electrolyte, and all-solid-state battery application thereof |
| EP4292982A1 (en) | 2022-06-14 | 2023-12-20 | Akademia Gorniczo-Hutnicza im. Stanislawa Staszica w Krakowie | Gamma-argyrodite structure material for thermoelectric conversion and the method of obtaining the same |
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| CN110690341A (en) * | 2019-09-27 | 2020-01-14 | 中国科学院合肥物质科学研究院 | Thermoelectric material and preparation method thereof |
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| WO2023030025A1 (en) * | 2021-09-01 | 2023-03-09 | 上海屹锂新能源科技有限公司 | Preparation method for argyrodite-type solid electrolyte, and all-solid-state battery application thereof |
| EP4292982A1 (en) | 2022-06-14 | 2023-12-20 | Akademia Gorniczo-Hutnicza im. Stanislawa Staszica w Krakowie | Gamma-argyrodite structure material for thermoelectric conversion and the method of obtaining the same |
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