CN104124332B - A kind of p-type FeNbTiSb thermoelectric materials of the high figure of merit and preparation method thereof - Google Patents
A kind of p-type FeNbTiSb thermoelectric materials of the high figure of merit and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of p-type FeNbTiSb thermoelectric materials of high figure of merit, raw material composition is FeNb1‑xTixSb, wherein, x=0.06~0.24.It is FeNb first by composition the invention also discloses the preparation method of described p-type FeNbTiSb thermoelectric materials1‑xTixSb chemical dosage ratio weighs raw material iron, niobium, titanium and antimony, smelting to obtain ingot casting under argon gas protection；Ingot casting is ground into particle, then sintered obtains described p-type FeNbTiSb thermoelectric materials.The preparation technology of the present invention is simple, with short production cycle, and production efficiency is high；The p-type FeNbTiSb thermoelectric materials high-temperature stability prepared is good, constitutes the element of the material in earth's crust rich content, industrialization cost is relatively low；Its maximum zT value reaches 1.1 in 1100K, and this is the peak performance obtained in current Half Heusler systems.
Description
Technical field
The present invention relates to semi-conductor thermoelectric material field, and in particular to a kind of p-type FeNbTiSb thermoelectric materials of high figure of merit
And preparation method thereof.
Background technology
Thermoelectric material is that a kind of carrier (electronics or hole) motion by material internal realizes that electric energy and heat energy are direct
The semi-conducting material mutually changed.When thermoelectric material two ends have the temperature difference, thermoelectric material can convert heat into electric energy output,
This is referred to as Seebeck effects；And after adding electric field at thermoelectric material two ends, thermoelectric material can convert electrical energy into heat energy,
One end heat release and the other end absorb heat, and are referred to as Petier effects, and both effects allow thermoelectric material generate electricity or making respectively
Be widely used background in terms of cold.
The TRT manufactured with thermoelectric material can be used as deep layer space device, field work, ocean lighthouse, nomadic people
The power supply that group uses, or for industrial exhaust heat, waste-heat power generation.The refrigerating plant small volume that is manufactured with thermoelectric material, it need not change
Medium is learned, Local cooling, the portable medical ultralow temperature of small-sized cooling case, computer chip and laser detector etc. is can be applied to
In terms of refrigerator, wider potential application field will include：Domestic refrigerator, cooling, automobile-used or household air conditioning device etc..With heat
The device of electric material manufacture has can set on demand without mechanical moving element, noiseless, without abrasion, simple in construction, volume profiles
The outstanding advantages such as meter.
The performance of thermoelectric material is characterized with " thermoelectric figure of merit "-zT：
ZT=(α2σT/κ)
α is the Seebeck coefficient of material, and σ is electrical conductivity, and T is absolute temperature, and κ is thermal conductivity.
A kind of good thermoelectric material should have high electrical conductivity and Seebeck coefficient and low thermal conductivity, high performance thermoelectricity
Requirement on devices has the N-type and P-type material that performance, structure match.
At present, high-temperature power generation thermoelectric material has important in fields such as auto industry, factory's Waste Heat Recovery, deep space satellites
Using.Typical high-temperature power generation thermoelectric material is SiGe alloys, and its n type material performance is higher, and zT values are about 1.0, but p-type material
Expect poor-performing, about 0.5.
In recent years, Half-Heusler systems are due to component rich content, and the advantages of electric property is good causes thermoelectricity
The concern of field scholar.Wherein, the zT values of N-type ZrNiSn bases Half-Heusler materials compare favourably up to 1.0 with N-type SiGe.
But the performance of p-type Half-Heusler materials is still relatively low, this is restrict that the system applies in terms of high-temperature power generation one big
Problem.
Rich reserves of the raw material of FeNbTiSb thermoelectric materials in the earth's crust, relative low price.But at present, to such heat
The research of electric material is seldom.
The content of the invention
The present invention provides a kind of new high figure of merit p-type FeNbTiSb thermoelectric materials and preparation method thereof, the p-type
The highest zT values of FeNbTiSb thermoelectric materials are about 1.1 in 1100K.
The invention discloses a kind of p-type FeNbTiSb thermoelectric materials of high figure of merit, raw material composition is FeNb1-xTixSb, its
In, x=0.06~0.24, x represents atomic percent.
Preferably, x=0.2~0.24；It is further preferred that x=0.2.
The invention also discloses the preparation method of the p-type FeNbTiSb thermoelectric materials, step is as follows：
(1) it is FeNb by composition1-xTixSb chemical dosage ratio weighs raw material iron, niobium, titanium and antimony, under argon gas protection, warp
Melting obtains ingot casting；
(2) ingot casting for obtaining step (1) is ground into particle, then sintered obtains described p-type FeNbTiSb thermoelectricity materials
Material.
Preferably, in step (1), raw material after smelting in suspension method melting 3 times through obtaining ingot casting.
Preferably, in step (2), the particle size diameter that ingot casting is ground into particle is 200nm~10.0 μm.
Preferably, in step (2), through discharge plasma sintering technique, sintering 10min under 850 DEG C, 65MPa, obtaining
Described p-type FeNbTiSb thermoelectric materials.
Compared with prior art, the invention has the advantages that：
The present invention is prepared for a kind of high figure of merit p-type FeNbTiSb thermoelectric materials, and its maximum zT value reaches 1.1 in 1100K,
This is the peak performance obtained in current Half-Heusler systems.
P-type FeNbTiSb thermoelectric materials prepared by the present invention, reserves of the element in the earth's crust contained by its material composition are rich
Richness, therefore, production cost relative moderate.
The high-temperature stability of p-type FeNbTiSb thermoelectric materials is good in the present invention, preparation technology is simple, with short production cycle, raw
Produce efficiency high.
Brief description of the drawings：
Fig. 1 is FeNb prepared by embodiment 10.8Ti0.2Sb XRD spectrum.
Fig. 2 is FeNb prepared by embodiment 10.8Ti0.2The thermogravimetric analysis figure of Sb samples.
Fig. 3 is the FeNb that embodiment is prepared1-xTixThe thermal conductivity κ (a) of Sb samples, conductivityσ (b), Seebeck systems
Number α (c) and power exponentα2σ (d) varies with temperature figure.
Fig. 4 is the FeNb that embodiment is prepared1-xTixThe zT values of Sb samples vary with temperature figure.
Embodiment：
The present invention is further elaborated with reference to embodiments.
Embodiment 1
Raw material is pressed into chemical dosage ratio FeNb0.8Ti0.2Sb is calculated after weighing, in the copper pipe for being placed in Ar gas shieldeds, using height
3 acquisition ingot castings of frequency method of smelting melt back, then crush ingot casting using mechanical ball mill method and obtain submicron order little particle,
Then 10min is sintered under the conditions of 850 DEG C, 65MPa using discharge plasma sintering method, obtains final sample.
Sample made from the present embodiment is carried out using RigakuD/MAX-2550PC type X-ray polycrystalline diffractometers (XRD)
Material phase analysis, as shown in figure 1, and confirm as FeNbSb based structures, i.e. cubic structure (F43m), space group number is No. 216.
According to the thermal diffusion coefficient measured using Netzsch LFA-457 type laser pulses thermal analyzer, using Netzsch
The specific heat of DSC-404 type difference specific heats instrument measurement and the density of material calculate and obtain thermal conductivity κ.Sample made from the present embodiment
Thermal conductivity in 1100K be κ=4.5Wm-1K-1。
The μ V/K of Seebeck coefficient α of the material in 1100K=204 are measured using Linses LSR-3 equipment, conductivityσ=
10.7×104S/m。
ZT=(α are pressed according to above-mentioned measured value2σ T/ κ) calculate, the zT values of sample made from the present embodiment in 1100K about
For 1.1.
Thermogravimetric analysis is carried out to sample under nitrogen and air atmosphere using DSCQ1000 equipment respectively, testing result is such as
Shown in Fig. 2, heating rate 10K/min, temperature range 300K-1200K.From 300K to 1000K, sample is in nitrogen and air atmosphere
Lower holding weight stabilization is enclosed, this shows that prepared sample high-temperature stability is fine.More than 1000K, sample is in nitrogen atmosphere
In remain in that stabilization, but under air atmosphere, weight increase, this is due to caused by surface oxidation.
Embodiment 2
Raw material is pressed into chemical dosage ratio FeNb0.76Ti0.24Sb is calculated after weighing, in the copper pipe for being placed in Ar gas shieldeds, using height
3 acquisition ingot castings of frequency method of smelting melt back, then crush ingot casting using mechanical ball mill method and obtain submicron order little particle,
Then 10min is sintered under the conditions of 850 DEG C, 65MPa using discharge plasma sintering method, obtains final sample.
The thermal conductivity of sample made from the present embodiment is κ=4.6Wm in 1100K-1K-1。
The μ V/K of Seebeck coefficient α of the material in 1100K=198 are measured using Linses LSR-3 equipment, conductivityσ=
11.3×104S/m。
ZT=(α are pressed according to above-mentioned measured value2σ T/ κ) calculate, the zT values of sample made from the present embodiment in 1100K about
For 1.06.
Embodiment 3
Raw material is pressed into chemical dosage ratio FeNb0.84Ti0.16Sb is calculated after weighing, in the copper pipe for being placed in Ar gas shieldeds, using height
3 acquisition ingot castings of frequency method of smelting melt back, then crush ingot casting using mechanical ball mill method and obtain submicron order little particle,
Then 10min is sintered under the conditions of 850 DEG C, 65MPa using discharge plasma sintering method, obtains final sample.
The thermal conductivity of sample made from the present embodiment is κ=4.8Wm in 1100K-1K-1。
The μ V/K of Seebeck coefficient α of the material in 1100K=219 are measured using Linses LSR-3 equipment, conductivityσ=
8.6×104S/m。
ZT=(α are pressed according to above-mentioned measured value2σ T/ κ) calculate, the zT values of sample made from the present embodiment in 1100K about
For 0.96.
Embodiment 4
Raw material is pressed into chemical dosage ratio FeNb0.88Ti0.12Sb is calculated after weighing, in the copper pipe for being placed in Ar gas shieldeds, using height
3 acquisition ingot castings of frequency method of smelting melt back, then crush ingot casting using mechanical ball mill method and obtain submicron order little particle,
Then 10min is sintered under the conditions of 850 DEG C, 65MPa using discharge plasma sintering method, obtains final sample.
The thermal conductivity of sample made from the present embodiment is κ=5.1Wm in 1100K-1K-1。
The μ V/K of Seebeck coefficient α of the material in 1100K=222 are measured using Linses LSR-3 equipment, conductivityσ=
6.7×104S/m。
ZT=(α are pressed according to above-mentioned measured value2σ T/ κ) calculate, the zT values of sample made from the present embodiment in 1100K about
For 0.72.
Embodiment 5
Raw material is pressed into chemical dosage ratio FeNb0.92Ti0.08Sb is calculated after weighing, in the copper pipe for being placed in Ar gas shieldeds, using height
3 acquisition ingot castings of frequency method of smelting melt back, then crush ingot casting using mechanical ball mill method and obtain submicron order little particle,
Then 10min is sintered under the conditions of 850 DEG C, 65MPa using discharge plasma sintering method, obtains final sample.
The thermal conductivity of sample made from the present embodiment is κ=5.8Wm in 1100K-1K-1。
The μ V/K of Seebeck coefficient α of the material in 1100K=246 are measured using Linses LSR-3 equipment, conductivityσ=
5.3×104S/m。
ZT=(α are pressed according to above-mentioned measured value2σ T/ κ) calculate, the zT values of sample made from the present embodiment in 1100K about
For 0.61.
Embodiment 6
Raw material is pressed into chemical dosage ratio FeNb0.94Ti0.06Sb is calculated after weighing, in the copper pipe for being placed in Ar gas shieldeds, using height
3 acquisition ingot castings of frequency method of smelting melt back, then crush ingot casting using mechanical ball mill method and obtain submicron order little particle,
Then 10min is sintered under the conditions of 850 DEG C, 65MPa using discharge plasma sintering method, obtains final sample.
The thermal conductivity of sample made from the present embodiment is κ=6.5Wm in 1000K-1K-1。
The μ V/K of Seebeck coefficient α of the material in 1100K=263 are measured using Linses LSR-3 equipment, conductivityσ=
5.1×104S/m。
ZT=(α are pressed according to above-mentioned measured value2σ T/ κ) calculate, the zT values of sample made from the present embodiment in 1000K about
For 0.54.
Thermoelectricity capability is analyzed：
The sample that embodiment 1-6 is prepared carries out thermoelectricity capability detection in different temperatures respectively, and Fig. 3 is FeNb1- xTixThe alternating temperature thermoelectricity capability figure of Sb samples.It can be seen that the thermal conductivity and Seebeck coefficients of sample are with x from Fig. 3 (a) -3 (d)
Increase persistently reduce, electrical conductivity then increases with x increase.According to zT=(α2σ T/ κ) it can be calculated the final zT of sample
Value, it is found that the zT values of all samples rise with temperature and increased (shown in Fig. 4), exist as most preferred sample x=0.2
Possess highest zT=1.1 during 1100K.Analysis finds that the reason for sample possesses highest zT is that it has most in 1100K
Low thermal conductivity (Fig. 3 a) and highest power factor (Fig. 3 d).
Claims (7)
1. the p-type FeNbTiSb thermoelectric materials of a kind of high figure of merit, it is characterised in that raw material composition is FeNb1-xTixSb, wherein, x
=0.16~0.24.
2. p-type FeNbTiSb thermoelectric materials according to claim 1, it is characterised in that x=0.2~0.24.
3. p-type FeNbTiSb thermoelectric materials according to claim 2, it is characterised in that x=0.2.
4. a kind of preparation method of p-type FeNbTiSb thermoelectric materials according to claims 1 to 3 any claim, its
It is characterised by, step is as follows：
(1) it is FeNb by composition1-xTixSb chemical dosage ratio weighs raw material iron, niobium, titanium and antimony, under argon gas protection, smelting
To ingot casting；
(2) ingot casting for obtaining step (1) is ground into particle, then sintered obtains described p-type FeNbTiSb thermoelectric materials.
5. preparation method according to claim 4, it is characterised in that in step (1), raw material is through smelting in suspension method melting 3
Ingot casting is obtained after secondary.
6. preparation method according to claim 4, it is characterised in that in step (2), the granularity that ingot casting is ground into particle is straight
Footpath is 200nm~10.0 μm.
7. preparation method according to claim 4, it is characterised in that in step (2), through discharge plasma sintering technique,
10min is sintered under 850 DEG C, 65MPa, described p-type FeNbTiSb thermoelectric materials are obtained.
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| EP2092579A2 (en) * | 2006-12-04 | 2009-08-26 | Arhus Universitet | Use of thermoelectric materials for low temperature thermoelectric purposes |
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| Enhanced phonon scattering by mass and strain field fluctuation in Nb substituted FeVSb half-Heusler thermoelectric materials;Chenguang Fu;《Journal of Applied Physics》;20121215;第112卷(第12期);摘要和实验部分 * |
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