CN103811653B - Multi-cobalt p type skutterudite filled thermoelectric material and preparation method thereof - Google Patents
Multi-cobalt p type skutterudite filled thermoelectric material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a multi-cobalt p type skutterudite filled thermoelectric material. The multi-cobalt p type skutterudite filled thermoelectric material is a substance of which the molecular formula is EzFe2-xCo2+xSb12-yMy, wherein E is one or more of La, Ce, Pr, Nd, Eu, Yb, Ba, Sr and Ca, M is a composite dopant of Ge or Sn, z is greater than or equal to 0.2 and less than or equal to 0.8, x is greater than or equal to 0 and less than or equal to 1, and y is greater than 0 and less than or equal to 0.5. The preparation method comprises the steps of putting various raw materials such as E, Fe, Co, Sb and M in a quartz tube and sealing, putting the sealed quartz tube in a furnace for melting, and then quenching to form a solid-state material, taking out the quenched block, and then putting the quenched block back into the quartz tube for heating and annealing; grinding the annealed block into powder, carrying out pressure sintering of the powder into a block of a desired shape, and heating and annealing the sintered block. The multi-cobalt p type skutterudite filled thermoelectric material can be a skutterudite material based on EzFe2-xCo2+xSb12-yMy (x is greater than or equal to 0 and less than or equal to 1) with a low coefficient of thermal expansion, and thus has high thermoelectric properties (ZT is close to or greater than 1).
Description
Technical field
The invention belongs to new energy materialses field is and in particular to a kind of many cobalts p-type filling skutterudite thermoelectric material and its system
Preparation Method.
Background technology
At present, the shortage of one side carbon-containing energy and the becoming increasingly conspicuous of problem of environmental pollution, the heat that on the other hand burning produces
Can considerable part all be wasted with forms such as used heat.Thermoelectric generation utilizes the Seebeck effect (seebeck of thermoelectric material
Effect) heat energy is converted directly into electric energy, has the advantages that pollution-free, noiselessness, reliability are high and size is flexible, in used heat
Recycle, the exploitation aspect such as solar energy and underground heat has broad application prospects.Although the low conversion effect of existing thermoelectric material
Rate and higher cost, limit it and apply on a large scale, but the upsurge that the thermoelectricity being as starting in world wide is studied, thermoelectricity
Theoretical research deepens continuously, and has benefited from the development of material preparation technology simultaneously, and the performance of new thermoelectric materials is greatly improved.
The performance indications of thermoelectric material to be weighed by dimensionless thermoelectric figure of merit zt, zt=s2T/ (ρ k), wherein s are
Seebeck coefficient, ρ is resistivity, and k is thermal conductivity.Due to s, these three parameters of ρ, k have very strong relevance, therefore how real
The collaborative or independent regulation and control of existing electronics and phonon transport are the cores improving thermoelectricity capability that is to say, that meeting " phonon glasses-electricity
Sub- crystal " (pgec) concept (crc handbook of thermoelectrics, 1995).There is cage structure and contain heavy element
Filled-type skutterudite (skutterudite) thermoelectric material possess this characteristic (j.appl.phys., 1995,77,3777),
Show the higher thermal electricity figure of merit, and its best effort warm area is at 600 DEG C about, be extremely suitable for use in automobile tail gas pipe by engine
Waste heat is converted to vehicle-mounted electricity consumption, if it can enter being widely applied, situation about increasing year by year in current China automobile pollution
Under, the substantial amounts of energy will be saved.So far, skutterudite thermoelectric material at home and abroad receives extensive research, including different
The research of preparation technology, the research of different filling elements, and the research of different doped chemical.
The best p of thermoelectricity capability, N-shaped skutterudite broadly fall into e at presentzfe4-xcoxsb12(e is filling atom) series, respectively
For ezfe3cosb12And ezco4sb12, their highest thermoelectric figure of merit is respectively ztp=1.2 (intermetallics, 2010,
18,2435) and ztn=1.7 (j.am.chem.soc.2011,133,7837).However, regrettably, the heat of this two classes material
The coefficient of expansion differs greatly, and in use, can lead at thermoelectric material and the contact interface of external circuit due to thermal expansion system
Number mismatches and produces huge stress and form crackle, and (sci.adv.mater., 2011,3,621) was lost efficacy in detonator circuit open circuit.Right
In ezfe4-xcoxsb12Series, the thermal coefficient of expansion of 2≤x≤3 can be with N-shaped skutterudite (ezco4sb12) match, but this chemical combination
The best thermoelectricity capability of thing but only has ztmax=0.6 (intermetallics, 2011,19,1390).
Content of the invention
It is an object of the invention to provide a kind of many cobalts p-type filled skutterudite thermoelectricity material that can increase substantially thermoelectricity capability
Material and preparation method thereof.
Material of the present invention is a kind of molecular formula is ezfe2-xco2+xsb12-ymyMaterial, wherein to skutterudite cage
The element e that (20 face body lattice holes being made up of 12 sb) are filled with is in la, ce, pr, nd, eu, yb, ba, sr, ca
One or more, doped chemical m is one kind of ge or sn, or one of ge, sn and one or more of s, se, te,
And above-mentioned molecular formula meets 0.2≤z≤0.8,0≤x≤1,0≤y≤0.5.
The preparation method of material of the present invention, step is as follows:
1) adopt high-purity element simple substance be initial action raw material (purity >=99%), by regulation stoicheiometry weigh e,
The various raw material such as fe, co, sb and m, puts in quartz ampoule, and burns envelope quartz ampoule under vacuo.
2) quartz ampoule loading raw material is inserted in stove, be to slowly warm up to 900-1100 DEG C of melting, be incubated 6-12 hour.So
Quenching forms solid-state material afterwards.The medium of quenching adopts water (room temperature), frozen water (0 DEG C), salt solution (room temperature) or oil (room temperature).
3) block after quenching is taken out, be again placed in quartz ampoule, be heated to temperature 550-650 DEG C, anneal 2-3 days.
4) block after annealing is made powder, adoptable method has two kinds: method one, using mortar grinder；Method
Two, using planetary ball mill, ball milling 1-3 hour under 300-600 rev/min of moderate rotation.
5) by powder pressure sintering be required form block, sintering temperature be 500-610 DEG C, pressure be 50-70mpa；
If utilizing discharge plasma sintering, the sintered heat insulating time is 10-20 minute；If utilizing common hot-pressed sintering furnace, sinter
Temperature retention time is 1-4 hour.
6) block after sintering is heated to temperature 550-620 DEG C, anneals 1-3 days in vacuum or argon gas atmosphere.
The present invention compared with prior art has the advantage that
1. the present invention, by appropriate formula and suitable preparation technology, increases substantially and has the many of low thermal coefficient of expansion
The thermoelectricity capability of cobalt P-type skutterudite, its maximum thermoelectric figure of merit is close or larger than 1, makes the thermal coefficient of expansion of such P-type skutterudite
(≤10×10-6k-1) can match with N-shaped skutterudite.Existing thermoelectric figure of merit is too low: ztmax=0.6, the present invention passes through to mixing
While the interactive regulation and control of hetero atom and filling atom, introduce nanometer phase or the nano dot of in-situ endogenic, performance is transported to electroacoustic
It is optimized, improve thermoelectricity capability.
2. the present invention proposes to be suitable for the preparation technology of such material: hot pressed sintering after annealing, thus introducing in a large number in situ
Raw nanometer phase or nano dot, in the service temperature interval stable performance of material, required equipment is simple for the compound prepared,
Repeatable high, it is especially suitable for large-scale industrial production.
Brief description
Fig. 1 is the xrd collection of illustrative plates of prepared sample in the embodiment of the present invention 1,2,3.
Fig. 2 is the field emission scanning electron microscope photo figure of prepared sample section in the embodiment of the present invention 1,
A () is undoped p ge sample nd0.6fe2co2sb12Photo figure,
B () is doping ge sample nd0.6fe2co2sb11.7ge0.3Photo figure.
Fig. 3 is the transmission electron microscope photo figure of prepared sample in the embodiment of the present invention 1,
A () is to cover one layer of nano thin-film of grain surface and the nano particle figure being embedded in skutterudite grain surface,
B () is the Electronic Speculum high-resolution nano crystal grain enlarged drawing of (a) figure,
C () is the nanometer phasor being embedded in skutterudite particle.
Fig. 4 is the graph of a relation of the resistivity of prepared sample and undoped p sample and temperature in the embodiment of the present invention 1.
Fig. 5 is the graph of a relation of the Seebeck coefficient of prepared sample and undoped p sample and temperature in the embodiment of the present invention 1.
Fig. 6 is the graph of a relation of the thermal conductivity of prepared sample and undoped p sample and temperature in the embodiment of the present invention 1.
Fig. 7 is the graph of a relation of the thermoelectric figure of merit zt of prepared sample and undoped p sample and temperature in the embodiment of the present invention 1.
Fig. 8 is the graph of a relation of the thermoelectric figure of merit zt of prepared sample and temperature in the embodiment of the present invention 2.
Fig. 9 is the graph of a relation of the thermoelectric figure of merit zt of prepared sample and temperature in the embodiment of the present invention 3.
Figure 10 be the embodiment of the present invention 4 (curve a) and embodiment 5 (and in curve b) the thermoelectric figure of merit zt of prepared sample with
The graph of a relation of temperature.
Figure 11 is the embodiment of the present invention 6 (curve a), embodiment 7 (curve b) and embodiment 8 (prepared sample in curve c)
Thermoelectric figure of merit zt and temperature graph of a relation.
Figure 12 is the graph of a relation of the thermoelectric figure of merit zt of prepared sample and temperature in the embodiment of the present invention 9.
Specific embodiment
In order to be better understood from the present invention, below in conjunction with the accompanying drawings present disclosure is expanded on further by embodiment, but
Present disclosure is not limited solely to the following examples.
Embodiment 1: high thermoelectricity capability nd0.6fe2co2sb11.7ge0.3.
(1) by initial simple substance raw material nd (99%, particle), fe (99.9%, powder), co (99.8%, powder), sb
(99.99%, particle) and ge (99.999%, particle) are according to nd0.6fe2co2sb11.7ge0.3Stoichiometric proportion weigh 6g, put
Enter to vacuumize burning envelope quartz ampoule in quartz ampoule, quartz ampoule is placed in crucible puts in Muffle furnace afterwards, with 1 DEG C/min of liter
Warm speed is heated to 1050 DEG C and is incubated 8 hours, afterwards in ice quenching-in water.The block obtaining is removed and placed in quartz ampoule
Vacuum sealing, anneals 2 days at 610 DEG C, takes out cooling in the water of room temperature afterwards.In the glove box of applying argon gas, by obtain
Block underhand polish in mortar, to powder, the powder obtaining is loaded graphite jig, puts in discharge plasma sintering machine and add
Pressure is sintered to the block of required form, pressure 60mpa, 600 DEG C of sintering temperature, temperature retention time 15 minutes.Finally by after sintering
Block is annealed 60 hours for 600 DEG C in the tube furnace of logical argon hydrogen hybrid protection gas (95% argon gas 5% hydrogen).
(2) according to above-mentioned method, prepare unadulterated sample nd0.6fe2co2sb12, as the control sample of doped samples
Product.
(3) the curve a in Fig. 1 is the nd obtained by sps0.6fe2co2sb11.7ge0.3X-ray diffraction (xrd) figure of block,
Diffraction curve shows that this block is that skutterudite is single-phase.Can be seen that undoped p ge sample from the field emission scanning electron microscope picture of Fig. 2
nd0.6fe2co2sb12The grain surface of (Fig. 2 a) is smooth, and adulterate ge sample nd0.6fe2co2sb11.7ge0.3The crystal grain table of (Fig. 2 b)
The nanometer that face covers thin film and has 10-100nm mutually separates out.Fig. 3 is transmission electron microscope (tem) photo of this block, they
Illustrate the material of the different shape making thermal conductivity reduce.One layer of nanometer thin covering grain surface can be clearly apparent from Fig. 3 a
Film and the nano particle being embedded in skutterudite grain surface；The Electronic Speculum High-Resolution Map of Fig. 3 b is exaggerated nanocrystalline in Fig. 3 a
Grain, therefrom can find out the lattice defect in the presence of nanocrystal；Fig. 3 c represents the nanometer phase being embedded in skutterudite particle.
(4) block cutting is become the shape of requirement of experiment, such as cuboid and thin discs, using Seebeck coefficient and resistance
Test system (ulvac zem-2 and zem-3) test Seebeck coefficient s, electricalresistivityρ, using laser perturbation thermal conductivity instrument (ulvac
Tc-7000 and tc-9000) test thermal conductivity k.Fig. 4-Fig. 7 represent respectively electricalresistivityρ, Seebeck coefficient s, thermal conductivity k and
The curve that the zt value being calculated by these three parameters varies with temperature.Therefrom find out, the sample of ge doping is although resistivity has
Risen, but increased Seebeck coefficient, and significantly reduced thermal conductivity, so that thermoelectric figure of merit zt is significantly improved.
Embodiment 2: high thermoelectricity capability nd0.6fe1.8co2.2sb11.85ge0.15.
(1) by initial simple substance raw material nd (99%, particle), fe (99.9%, powder), co (99.8%, powder), sb
(99.99%, particle) and ge (99.999%, particle) are according to nd0.6fe1.8co2.2sb11.85ge0.15Stoichiometric proportion weigh
6g, puts into and vacuumizes burning envelope quartz ampoule in quartz ampoule, quartz ampoule is placed in crucible puts in Muffle furnace afterwards, with 0.7 DEG C/minute
The heating rate of clock is heated to 950 DEG C and is incubated 6 hours, afterwards in oil quenching.The block obtaining is taken out and is placed in quartz
Vacuum sealing in pipe, anneals 3 days at 580 DEG C, takes out cooling in the water of room temperature afterwards.In the glove box of applying argon gas, will
To block in mortar underhand polish to powder, the powder obtaining is loaded graphite jig, puts into discharge plasma sintering machine
Middle pressure sintering is the block of required form, pressure 50mpa, 550 DEG C of sintering temperature, temperature retention time 20 minutes.Finally will sinter
Block afterwards is annealed 48 hours for 550 DEG C in the tube furnace of logical argon hydrogen hybrid protection gas (95% argon gas 5% hydrogen).
(2) the curve b in Fig. 1 is the nd obtained by sps0.6fe1.8co2.2sb11.85ge0.15The xrd collection of illustrative plates of block.Diffraction
Curve shows that this block is pure skutterudite phase.
(3) block cutting is become the shape of requirement of experiment, such as cuboid and thin discs, using Seebeck coefficient and resistance
Test system (ulvac zem-2 and zem-3) test Seebeck coefficient s, electricalresistivityρ, using laser perturbation thermal conductivity instrument (ulvac
Tc-7000 and tc-9000) test thermal conductivity k.See Fig. 8 according to the zt value that test result calculations go out.Its thermoelectricity capability is much higher than
The nd of undoped p ge0.6fe2co2sb12(Fig. 7).
Embodiment 3: high thermoelectricity capability nd0.6fe2co2sb11.5sn0.45te0.05.
(1) by initial simple substance raw material nd (99%, particle), fe (99.9%, powder), co (99.8%, powder), sb
(99.99%, particle), sn (99.998%, silk) and te (99.999%, powder), according to nd0.6fe2co2sb11.5sn0.45te0.05
Stoichiometric proportion weigh 6g, put into vacuumize in quartz ampoule burning envelope quartz ampoule, quartz ampoule is placed in crucible puts into horse afterwards
Not in stove, it is heated to 1000 DEG C with 1 DEG C/min of heating rate and is incubated 8 hours, afterwards in ice quenching-in water.By obtain
Block takes out and is placed in vacuum sealing in quartz ampoule, anneals 3 days at 610 DEG C, takes out cooling in the oil of room temperature afterwards.In argon filling
In the glove box of gas, the block obtaining is put into tungsten-carbide ball grinding jar and seals, 300 revs/min of rotating speed in planetary ball mill
Clock, powder is loaded graphite jig and in common hot-pressed sintering furnace sintering, pressure 70mpa, sintering temperature to powder in 1 hour by ball milling
500 DEG C of degree, temperature retention time 2 hours.Finally by the block after sintering in logical argon hydrogen hybrid protection gas (95% argon gas 5% hydrogen)
Anneal 36 hours for 620 DEG C in tube furnace.
(2) the curve c in Fig. 1 is obtained nd after sintering0.6fe2co2sb11.5sn0.45te0.05The xrd collection of illustrative plates of block,
Diffraction curve shows that this block is that skutterudite is single-phase.
(3) cutting of sample and method of testing are same as Example 1.See Fig. 9 according to the zt value that test result calculations go out.
nd0.6fe2co2sb11.5sn0.45te0.05The thermoelectric figure of merit zt of block is far above the sample nd of no sn and te doping0.6fe2co2sb12
(see Fig. 7).
Embodiment 4: high thermoelectricity capability la0.6fe2co2sb11.7ge0.3.
(1) by initial simple substance raw material la (99%, particle), fe (99.9%, powder), co (99.8%, powder), sb
(99.99%, particle) and ge (99.999%, particle) are according to la0.6fe2co2sb11.7ge0.3Stoichiometric proportion weigh 6g, put
Enter to vacuumize burning envelope quartz ampoule in quartz ampoule, quartz ampoule is placed in crucible puts in Muffle furnace afterwards, with 1 DEG C/min of liter
Warm speed is heated to 900 DEG C and is incubated 12 hours, afterwards in salt quenching-in water.The block obtaining is removed and placed in quartz ampoule
Vacuum sealing, anneals 2 days at 650 DEG C, takes out cooling in the water of room temperature afterwards.In the glove box of applying argon gas, by obtain
Block underhand polish in mortar, to powder, the powder obtaining is loaded graphite jig, puts in discharge plasma sintering machine and add
Pressure is sintered to the block of required form, pressure 60mpa, 580 DEG C of sintering temperature, temperature retention time 15 minutes.Finally by after sintering
Block is annealed 24 hours for 550 DEG C in vacuum tube furnace.
(2) cutting of sample and method of testing are same as Example 1.See in Figure 10 according to the zt value that test result calculations go out
Curve a.la0.6fe2co2sb11.7ge0.3The thermoelectric figure of merit zt of block is better than unadulterated sample nd0.6fe2co2sb12(see figure
7).
Embodiment 5: high thermoelectricity capability ce0.6fe2co2sb11.7ge0.3.
(1) by initial simple substance raw material ce (99%, particle), fe (99.9%, powder), co (99.8%, powder), sb
(99.99%, particle) and ge (99.999%, particle) are according to ce0.6fe2co2sb11.7ge0.3Stoichiometric proportion weigh 6g, put
Enter to vacuumize burning envelope quartz ampoule in quartz ampoule, quartz ampoule is placed in crucible puts in Muffle furnace afterwards, with 1 DEG C/min of liter
Warm speed is heated to 1100 DEG C and is incubated 7 hours, afterwards in ice quenching-in water.The block obtaining is removed and placed in quartz ampoule
Vacuum sealing, anneals 2 days at 590 DEG C, takes out cooling in the frozen water of room temperature afterwards.In the glove box of applying argon gas, will obtain
Block put into tungsten-carbide ball grinding jar and seal, 600 revs/min of rotating speed in planetary ball mill, ball milling 1 hour to powder,
The powder obtaining is loaded graphite jig, putting into pressure sintering in discharge plasma sintering machine is the block of required form, pressure
55mpa, 610 DEG C of sintering temperature, temperature retention time 10 minutes.Finally by the block after sintering in logical argon hydrogen hybrid protection gas (95%
Argon gas 5% hydrogen) tube furnace in 590 DEG C anneal 24 hours.
(2) cutting of sample and method of testing are same as Example 1.See in Figure 10 according to the zt value that test result calculations go out
Curve b.ce0.6fe2co2sb11.7ge0.3The thermoelectric figure of merit zt of block is far above unadulterated sample nd0.6fe2co2sb12(see
Fig. 7).
Embodiment 6: high thermoelectricity capability yb0.2nd0.4fe2co2sb11.7ge0.3.
(1) preparation method is substantially the same manner as Example 1, and difference is: the nd element portions in embodiment 1 are changed to
Yb element, i.e. yb0.2nd0.4fe2co2sb11.7ge0.3.
(2) cutting of sample and method of testing are same as Example 1.See in Figure 11 according to the zt value that test result calculations go out
Curve a.yb0.2nd0.4fe2co2sb11.7ge0.3The thermoelectric figure of merit zt of block is far above unadulterated sample nd0.6fe2co2sb12
(see Fig. 7).
Embodiment 7: high thermoelectricity capability la0.3nd0.3fe2co2sb11.7ge0.3.
(1) preparation method is substantially the same manner as Example 1, and difference is: the nd element portions in embodiment 1 are changed to
La element, i.e. la0.3nd0.3fe2co2sb11.7ge0.3.
(2) cutting of sample and method of testing are same as Example 1.See in Figure 11 according to the zt value that test result calculations go out
Curve b.la0.3nd0.3fe2co2sb11.7ge0.3The thermoelectric figure of merit zt of block is better than unadulterated sample nd0.6fe2co2sb12
(see Fig. 7).
Embodiment 8: high thermoelectricity capability nd0.4ba0.1sr0.1fe2co2sb11.7ge0.3.
(1) preparation method is substantially the same manner as Example 1, and difference is: the nd element portions in embodiment 1 are changed to
Ba and sr element, i.e. nd0.4ba0.1sr0.1fe2co2sb11.7ge0.3.
(2) cutting of sample and method of testing are same as Example 1.See in Figure 11 according to the zt value that test result calculations go out
Curve c.nd0.4ba0.1sr0.1fe2co2sb11.7ge0.3The thermoelectric figure of merit zt of block is better than unadulterated sample
nd0.6fe2co2sb12(see Fig. 7).
Embodiment 9: ball milling prepares high thermoelectricity capability nd0.6fe2co2sb11.7ge0.3.
(1) its composition is same as Example 1.
(2) its preparation method is substantially the same manner as Example 3, and difference is: the speed setting of planetary ball mill is
400 revs/min.See Figure 10 according to the zt value that test result calculations go out.Its thermoelectric figure of merit zt outclass unadulterated sample
nd0.6fe2co2sb12(see Fig. 7), also above the sample (powder of hot pressed sintering derives from underhand polish) in embodiment 1.
Claims (4)
1. a kind of many cobalts p-type filling skutterudite thermoelectric material it is characterised in that: it be a kind of molecular formula be ezfe2-xco2+xsb12- ymyMaterial, wherein e is one or more of la, ce, pr, nd, eu, yb, ba, sr, ca, m be ge or sn one kind, or
One of ge, sn and one or more of s, se, te, and 0.2≤z≤0.8,0≤x≤1,0 ＜ y≤0.5.
2. many cobalts p-type filling skutterudite thermoelectric material of claim 1 preparation method it is characterised in that: methods described includes
Following steps:
1) adopt purity >=99% element simple substance be initial action raw material, by regulation stoicheiometry weigh e, fe, co, sb and
The various raw material of m, puts in quartz ampoule, and burns envelope quartz ampoule under vacuo；
2) quartz ampoule loading raw material is inserted in stove, be to slowly warm up to 900-1100 DEG C of melting, be incubated 6-12 hour, Ran Houcui
Fire forms solid-state material, and the medium of quenching adopts water, frozen water, salt solution or the oil of room temperature；
3) block after quenching is taken out, be again placed in quartz ampoule, be heated to temperature 550-650 DEG C, anneal 2-3 days；
4) block after annealing is made powder；
5) by powder pressure sintering be required form block, sintering temperature be 500-610 DEG C, pressure be 50-70mpa；
6) block after sintering is heated to temperature 550-620 DEG C, anneals 1-3 days in vacuum or argon gas atmosphere.
3. as claimed in claim 2 many cobalts p-type filling skutterudite thermoelectric material preparation method it is characterised in that: described step
Block after annealing is made powder by rapid 4), specially adopts planetary ball mill, with 300-600 in tungsten-carbide ball grinding jar
Rev/min moderate rotation, ball milling 1-3 hour.
4. as claimed in claim 2 many cobalts p-type filling skutterudite thermoelectric material preparation method it is characterised in that: described step
Powder pressure sintering is the block of required form by rapid 5), and sintering temperature is 500-610 DEG C, and pressure is 50-70mpa；It is specially
If utilizing discharge plasma sintering, the sintered heat insulating time is 10-20 minute；If utilizing common hot-pressed sintering furnace, sinter
Temperature retention time is 1-4 hour.
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| CN101350394A (en) * | 2008-09-11 | 2009-01-21 | 清华大学 | Pyroelectric material with quadruple skutterudite structure and preparation method thereof |
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| CN103811653A (en) | 2014-05-21 |
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