CN101047223A - Thermoelectric material and thermoelectric conversion element using same - Google Patents
Thermoelectric material and thermoelectric conversion element using same Download PDFInfo
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- CN101047223A CN101047223A CN200610131001.5A CN200610131001A CN101047223A CN 101047223 A CN101047223 A CN 101047223A CN 200610131001 A CN200610131001 A CN 200610131001A CN 101047223 A CN101047223 A CN 101047223A
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Abstract
The thermoelectric material is represented by the following composition formula of (Tia1Zrb1Hfc1)xAyB100-x-y, in which element A is at least one element selected from the group consisting of Ni and Co, element B is at least one element selected from the group consisting of Sn and Sb, 0<=a1<=1, 0<=b1<=1, 0<=c1<=1, and a1+b1+c1=1 hold, and 30<=x<=35 and 30<=y<=35 hold, and the thermoelectric material comprises a phase having an MgAgAs type crystal structure as a major phase. In this thermoelectric material, the density of the thermoelectric material is more than 99.0% of the true density. When this thermoelectric material is used for either one or both of p-type elements and n-type elements, a thermoelectric conversion device having high thermoelectric conversion performance is realized.
Description
Technical field
The present invention relates to a kind of thermoelectric material, the thermoelectric conversion element that particularly uses the thermoelectric material of half Heusler compound and use this thermoelectric material with thermoelectric effect.
Background technology
In recent years, along with to the increasing of global environment problem thinking, utilize the thermoelectric cooling device (it is floride-free cooling device) of peltier effect noticeable day by day.In addition, consider global warming, in order to reduce emission amount of carbon dioxide, the thermoelectric power generation device that directly untapped waste thermal energy is changed into electric energy also begins noticeable.
Point out that in passing the performance index Z of thermoelectric material can be represented by following formula (1).
Z＝α
2·σ/κ(＝Pf/κ) (1)
In following formula (1), α represents the Seebeck coefficient of thermoelectric material, and σ represents conductivity, and κ represents thermal conductivity.Conductivity's inverse can be represented by the electricalresistivity.In addition, a α
2σ is called as output factor Pf.Z has the dimension opposite with temperature, and therefore, it is dimensionless number that performance index Z multiply by the ZT that absolute temperature T obtains.
This ZT value is called nondimensional performance index.This ZT value is relevant with the conversion efficiency of thermoelectric of thermoelectric material, and the material that has than big ZT value has higher conversion efficiency of thermoelectric.
As the formula (1), need thermoelectric material to have higher Seebeck coefficient α and lower electricalresistivity, that is, and higher output factor Pf and lower thermal conductivity κ.
Because some intermetallic compound with MgAgAs type crystal structure has characteristic of semiconductor, so they receive publicity as novel thermoelectric material.
Half Heusler compound (half Heusler compound) is a kind of intermetallic compound of the MgAgAs of having type crystal structure, and it presents characteristic of semiconductor.
Half Heusler compound is the cubic crystal compound, does not wherein comprise deleterious material fully or its content is reduced as small as possible.When representing the formation element of half Heusler compound by M, A and B, observing its structure is that elements A is embedded in the NaCl type lattice that is made of element M and B.Owing at room temperature have high Seebeck coefficient, cause people's attention in recent years because the global environment problem has half Heusler compound of said structure.
The pyroelecthc properties of half Heusler compound depends on the combination (for example, referring to the open No.2001-189495 of Japanese Unexamined Patent Application) that constitutes element according to reports.
For example, ZrNiSn has high Seebeck coefficient according to reports, for example at room temperature is-176 μ V/K, (for example referring to J.Phys.:Condensed Matter 11,1697-1709 (1999)).But, because ZrNiSn has high resistivity, be 11m Ω cm under the room temperature for example, and have high thermal conductivity, 8.8w/mK for example, so dimensionless performance index ZT is low, for example 0.01.
On the other hand, it is reported that the thermoelectric material HoPdSb that comprises rare earth element compares with ZrNiSn and has lower slightly thermal conductivity, for example 6W/mK (for example referring to Appl.Phys.Lett.74,1415 to 1417 pages (1999)).But, because HoPdSb has lower slightly Seebeck coefficient, for example be 150 μ V/K under the room temperature and have high resistivity that for example 9m Ω cm, so its dimensionless performance index ZT still keeps lowly, for example 0.01.In addition, also report Ho
0.5Er
0.5PdSb
1.05, Er
0.25Dy
0.75Pd
1.02Sb and Er
0.25Dy
0.75PdSb
1.05Have low dimensionless performance index, for example be respectively 0.04,0.03 and 0.02 under the room temperature.
So far, the thermoelectricity capability of known half Heusler compound changes with the combination that constitutes element.
But half relevant Heusler compound does not present sufficiently high thermoelectricity capability at present.
Need exploitation to use half Heusler compound to form and have the thermoelectric material of outstanding thermoelectricity capability, wherein do not comprise deleterious material fully or must reduce its content as far as possible for a short time.
Point out that in passing in known technology, the thermoelectric conversion element that utilizes peltier effect or Seebeck effect usually is to be made of p type element that comprises p type thermo-electric converting material and the n type element that comprises n type thermo-electric converting material, they alternately are connected in series each other.
As the thermo-electric converting material that uses under nearly room temperature at present, monocrystalline or polycrystalline Bi-Te based compound are frequently used because of its high efficiency.In addition, as being higher than the thermo-electric converting material that uses under the temperature of room temperature, also because its high efficiency is used the Pb-Te based compound.
But as the Se (selenium) of the dopant of Bi-Te based compound, and Pb (lead) is harmful and poisonous, and considers that the global environment problem also is disadvantageous.
So far, as wherein not including a kind of of harmful substances or the as far as possible little thermo-electric converting material that must reduce its content, (for example for example can mention the basic thermo-electric converting material of half Heusler with MgAgAs type crystalline phase, referring to J.Phys.:Condensed Matter 11,1697-1709 (1999) and Proc.18thInternational Conference on Thermoelectrics 344-347 (1999)).
In relevant half Heusler base thermo-electric converting material, suppress the amount of the harmful substance of its use the least possible.
But the thermoelectric conversion performance of relevant half Heusler base thermo-electric converting material does not reach the par of Bi-Te sill.
Therefore, need be different from the thermo-electric converting material of Bi-Te base and Pb-Te sill, it is harmful to performance and toxicity and has high thermoelectric transfer characteristic.
Summary of the invention
Consider above-mentioned situation and envision the present invention, the thermoelectric conversion element that the purpose of this invention is to provide a kind of thermoelectric material and use this thermoelectric material, the half Heusler compound that use presents higher dimensionless performance index ZT forms this thermoelectric material, and this index is to obtain to high relatively level and the abundant thermal conductivity that reduces by improving the output factor.
Another object of the present invention provides a kind of have high thermoelectric transfer characteristic and harmless and nontoxic thermo-electric converting material and the thermoelectric conversion element that uses this thermo-electric converting material.
Can realize these and other target according to the present invention, provide by following composition formula (Ti on the one hand
A1Zr
B1Hf
C1)
xA
yB
100-x-yThe thermoelectric material of expression, wherein elements A is the element of at least a Ni of being selected from and Co, element B is the element of at least a Sn of being selected from and Sb, 0≤a1≤1,0≤b1≤1,0≤c1≤1, and a1+b1+c1=l sets up (hold), and 30≤x≤35, and set up 30≤y≤35, and its comprise have the MgAgAs type crystal structure as principal phase, wherein the density of this thermoelectric material is greater than 99.0% of real density.
On the other hand, also provide a kind of thermoelectric material, it is by following composition formula (Ln
d(Ti
A2Zr
B2Hf
C2)
1-d)
xA
yB
100-x-yExpression, wherein element Ln is the element of at least a Y of being selected from and rare earth element, and elements A is the element of at least a Ni of being selected from and Co, and element B is the element of at least a Sn of being selected from and Sb, 0≤a2≤1,0≤b2≤1,0≤c2≤1, and a2+b2+c2=1 sets up, set up 0＜d≤0.3, and 30≤x≤35 and 30≤y≤35 set up, and its comprise have the MgAgAs type crystal structure as principal phase, wherein the density of this thermoelectric material is greater than 90.0% of real density.
Another aspect provides a kind of by following composition formula ((Ti
A1Zr
B1Hf
C1)
xNi
ySn
100-x-y)
1-pA
pThe thermoelectric material of expression, wherein elements A is the element of at least a C of being selected from, N and O, and 0＜a1＜1,0＜b1＜1,0＜c1＜1, and a1+b1+c1=1 sets up 30≤x≤35 and 30≤y≤35 establishments, and 0.05＜p＜0.1 sets up, and its comprise have the MgAgAs type crystal structure as principal phase.
Another aspect provides a kind of thermoelectric material, and it is by following composition formula ((Ln
d(Ti
A2Zr
B2Hf
C2)
1-d)
xNi
ySn
100-x-y)
1-pA
pExpression, wherein elements A is the element of at least a C of being selected from, N and O, element Ln is at least a element that is selected from Y and rare earth element, 0≤a2≤1,0≤b2≤1,0≤c2≤1, and a2+b2+c2=1 sets up, and set up 0＜d≤0.3, and set up 30≤x≤35 and 30≤y≤35, and 0.05＜p＜0.1 sets up, and its comprise have the MgAgAs type crystal structure as principal phase.
In the preferred embodiment of above-mentioned aspect, at least a among Ti, Zr and the Hf can be partly by at least a element substitution that is selected from V, Nb, Ta, Cr, Mo and W.Elements A can be partly by at least a element substitution that is selected from Mn, Fe and Cu.Element B can be partly by at least a element substitution that is selected from Si, Mg, As, Bi, Ge, Pb, Ga and In.
Another aspect of the present invention can realize above-mentioned purpose by a kind of thermoelectric conversion element is provided, and this device comprises:
At least one comprises the p type element of p type thermoelectric material; With
At least one comprises the n type element of n type thermoelectric material, and p type element and n type element alternately are connected in series each other,
Wherein at least one of p type thermoelectric material and n type thermoelectric material is by following composition formula (Ti
A1Zr
B1Hf
C1)
xA
yB
100-x-yExpression, wherein elements A is the element of at least a Ni of being selected from and Co, element B is the element of at least a Sn of being selected from and Sb, 0≤a1≤1,0≤b1≤1,0≤c1≤1, and a1+b1+c1=1 sets up, 30≤x≤35 and 30≤y≤35 set up, and p type and n type thermoelectric material at least a comprise have the MgAgAs type crystal structure as principal phase, wherein the density of thermoelectric material is greater than 99.0% of real density.
On the other hand, also provide a kind of thermoelectric conversion element, this device comprises:
At least one comprises the p type element of p type thermoelectric material; With
At least one comprises the n type element of n type thermoelectric material, and p type element and n type element alternately are connected in series each other,
Wherein p type thermoelectric material and n type thermoelectric material is at least a by following composition formula (Ln
d(Ti
A2Zr
B2Hf
C2)
1-d)
xA
yB
100-x-yExpression, wherein element Ln is at least a element that is selected from Y and rare earth element, elements A is the element of at least a Ni of being selected from and Co, element B is the element of at least a Sn of being selected from and Sb, 0≤a2≤1,0≤b2≤1,0≤c2≤1, and a2+b2+c2=1 sets up, set up 0＜d≤0.3, and 30≤x≤35 and 30≤y≤35 set up, and p type and n type thermoelectric material at least a comprise have the MgAgAs type crystal structure as principal phase, wherein the density of thermoelectric material is greater than 99.0% of real density.
Another aspect also provides a kind of thermoelectric conversion element, and this device comprises:
At least one comprises the p type element of p type transition heat electric material; With
At least one comprises the n type element of n type transition heat electric material, and p type element and n type element alternately are connected in series each other,
Wherein p type thermo-electric converting material and n type thermo-electric converting material is few a kind of by following composition formula (Ti
A1Zr
B1Hf
C1)
xNi
ySn
100-x-yExpression, wherein elements A is the element of at least a C of being selected from, N and O, 0＜a1＜1,0＜b1＜1,0＜c1＜1 and a1+b1+c1=1 set up, and set up 30≤x≤35 and 30≤y≤35,0.05＜p＜0.1, and p type and n type thermoelectric material at least a comprise have the MgAgAs type crystal structure as principal phase.
On the other hand, also provide a kind of thermoelectric conversion element, this device comprises:
At least one comprises the p type element of p type thermo-electric converting material; With
At least one comprises the n type element of n type thermo-electric converting material, and p type element and n type element alternately are connected in series each other,
Wherein p type thermo-electric converting material and n type thermo-electric converting material is at least a by following composition formula ((Ln
d(Ti
A2Zr
B2Hf
C2)
1-d)
xNi
ySn
100-x-y)
1-pA
pExpression, wherein elements A is the element of at least a C of being selected from, N and O, element Ln is at least a element that is selected from Y and rare earth element, 0≤a2≤1,0≤b2≤1,0≤c2≤1, set up with a2+b2+c2=1, set up 0＜d≤0.3, and set up 30≤x≤35 and 30≤y≤35,0.05＜p＜0.1 sets up, and p type thermoelectric material and n type thermoelectric material at least a comprise have the MgAgAs type crystal structure as principal phase.
In the preferred embodiment of above-mentioned aspect, at least a among Ti, Zr and the Hf can be partly by at least a element substitution that is selected from V, Nb, Ta, Cr, Mo and W.Elements A can be partly by at least a element substitution that is selected from Mn, Fe and Cu.Element B can be partly by at least a element substitution that is selected from Si, Mg, As, Bi, Ge, Pb, Ga and In.
The thermoelectric conversion element that has this material of above-mentioned performance and structure according to thermoelectric material of the present invention and use, this thermoelectric material can present high dimensionless performance index ZT by the high relatively output factor and abundant low thermal conductivity, and does not comprise deleterious material fully or reduce its content as small as possible.In addition, by using this thermoelectric material, can easily make high performance thermoelectric conversion element and thermo-electric conversion module, therefore, the present invention can be used for industrial circle highly beneficially.
In addition, according to These characteristics of the present invention, this thermo-electric converting material, thermoelectric conversion element and thermo-electric conversion module are harmless and nontoxic, and have high performance, and therefore, the present invention can be applied to industrial circle highly beneficially.
By the following explanation of reference preferred embodiment and embodiment, character of the present invention and other performance characteristics will be more obvious.
Description of drawings
Fig. 1 is the cross sectional representation that shows according to the structure of thermoelectric conversion element of the present invention;
Fig. 2 shows the sintering temperature of thermoelectric material of embodiment 1 and the diagram of the relation between density/real density percentage; With
Fig. 3 shows a pair of p N-type semiconductor N be included in the thermoelectric conversion element shown in Figure 1 and the zoomed-in view of n N-type semiconductor N.
Embodiment
The thermoelectric material of first embodiment according to an aspect of the present invention will be described below.
At first, will the definition of the term that uses among the present invention be described.
Among the present invention, principal phase is meant the crystalline phase that has the maximum volume mark in the crystalline phase that forms thermoelectric material.
In addition, among the present invention, real density is meant by fusing being formed and wherein not existing the volume and weight of sample of the thermoelectric material in space to carry out the density that actual measurement obtains fully.
From formula (1) (Z=α
2σ/κ (=Pf/ κ)) as can be seen, because output factor Pf increases and thermal conductivity κ reduces, thereby thermoelectric material presents higher dimensionless performance index ZT and more outstanding performance.The output factor Pf of thermoelectric material and its thermal conductivity κ depend on and for example constitute element, crystal structure and histological structure (texture conformation).
The present inventor finds, when the density that makes intermetallic compound during near real density with MgAgAs type crystal structure, output factor Pf (=α 2/ ρ), Seebeck coefficient and conductivity obtain improvement, and compare with the low situation of density of material and can access high performance index.
That is be having the MgAgAs type crystal structure according to the thermoelectric material of first embodiment, and the density of thermoelectric material is greater than 99.0% of real density, as principal phase and with half Heusler compound of following composition formula (2) expression.
(Ti
a1Zr
b1Hf
c1)
xA
yB
100-x-y (2)
In above-mentioned composition formula (2), elements A is the element of at least a Ni of being selected from and Co; Element B is the element of at least a Sn of being selected from and Sb; 0≤a1≤1,0≤b1≤1,0≤c1≤1, and a1+b1+c1=1,30≤x≤35, and 30≤y≤35.
In thermoelectric material by composition formula (2) expression, when the formation element is represented by M, A and B, at least a element among Ti, Zn and the Hf as the M position.These elements can reduce thermal conductivity κ.
In addition, when at least two kinds of elements of Ti, Zn and Hf were used as M position element, because the inconsistent dispersion that may produce phonon of atomic radius and atomic wts, the result can significantly reduce thermal conductivity κ.
In addition, the present inventor finds, in the thermoelectric material by composition formula (2) expression, when all Ti, Zr and Hf element during as the element of M position, can effectively improve Seebeck coefficient α.It is believed that in by the thermoelectric material that comprises all Ti, Zr and Hf in the thermoelectric material of composition formula (2) expression, near the electron density distribution Fermi surface has taken place to change significantly.
When the crystalline phase that is different from the MgAgAs crystalline phase is separated out, may reduce Seebeck coefficient α under some situation.Therefore, the composition y of the composition x of element M and A element is preferably set to 30≤x≤35 and 30≤y≤35 respectively.In addition, the composition y of the composition x of element M and elements A more preferably is set at 33≤x≤34,33≤y≤34 respectively.
In addition, be to have the half Heusler compound of MgAgAs type crystalline phase by the thermoelectric material of composition formula (2) expression, and prepare this compound and make density surpass 99.0% of real density as principal phase.Therefore, compare with half general Heusler compound, the thermoelectric material of being represented by composition formula (2) has enough low thermal conductivity κ except that high relatively routine output factor Pf.As a result, the thermoelectric material by composition formula (2) expression can have high dimensionless performance index ZT.
Then, with the thermoelectric material of describing according to second embodiment of the present invention.
That is be to have with the MgAgAs type crystal structure according to the thermoelectric material of second embodiment, and the density of thermoelectric material is greater than 99.0% of real density, as principal phase and by half Heusler compound of following composition formula (3) expression.
(Ln
d(Ti
a2Zr
b2Hf
c2)
1-d)
xA
yB
100-x-y (3)
In above-mentioned composition formula (3), element Ln is at least a element that is selected from Y and rare earth element; Elements A is at least a element that is selected from Ni and Co; Element B is at least a element that is selected from Sn and Sb; 0≤a2≤1,0≤b2≤1,0≤c2≤1, and a2+b2+c2=1; 0＜d≤0.3; 30≤x≤35,30≤y≤35.
The present inventor finds, when at least a element that is selected from Y and rare earth element when the element M of half Heusler compound MAB (M=Ti, Zr and Hf) of composition formula (2) expression partly substitutes, this element has greater than any the atomic radius among Ti, Zr and the Hf, can improve thermal conductivity κ.
That is, find that element Ln (being selected from least a element of Y and rare earth element) is the effective element that reduces thermal conductivity.
As element Ln, comprise in the periodic table from atomic number being that 57 La is all rare earth elements of 71 Lu to atomic number.Consider fusing point and atomic radius, preferred especially Er, Gd and Nd are as element Ln.
Even also can obtain to reduce this thermal conductivity κ effect by a small amount of Ln.But, in order further to reduce thermal conductivity κ, the ratio of components of the total amount of Ln and Ln and M (Ti, Zr and Hf) is preferably set to 0.1 atomic percentage or bigger.When the ratio of components of Ln during, be different from the crystalline phase of MgAgAs type crystalline phase, for example LnSn greater than 30 atomic percentages
3Take place mutually obviously to separate out, the result can reduce Seebeck coefficient α in some cases.
Therefore, d is preferably set to 0＜d≤0.3, and more preferably is set at 0.001≤d≤0.3.
In the thermoelectric material by composition formula (3) expression, as the situation by composition formula (2) expression, x and y are preferably set to 30≤x≤35 and 30≤y≤35 respectively.This reason is that the crystalline phase that is different from MgAgAs type crystal is separated out when x and y are outside above-mentioned scope, and the possibility of result reduces Seebeck coefficient α in some cases.
Usually, in half Heusler compound, when the sum of valence electron is approximately 18, can observe high Seebeck coefficient.For example, the outer shell electronic configuration of ZrNiSn is expressed as Zr (5d
26s
2), Ni (3d
84s
2) and Sn (5s
25p
2) and valence electron add up to 18.Sum as the valence electron of said circumstances TiNiSn and HfNiSn also is 18.
On the other hand, shown in composition formula (3), when element M (Ti, Zr and Hf) was partly substituted by rare earth element, the sum of valence electron that comprises half Heusler compound of rare earth element (except Ce, Eu and Yb) may depart from 18 in some cases, and this rare earth element has by (5d
16s
2) expression the outer shell electronic configuration.
But, the departing from of sum that can correct valence electron by the suitable adjustment of x and y.
In composition formula (2) and (3), at least a element M ' part that element M (Ti, Zr and Hf) can be selected from V, Nb, Ta, Cr, Mo and W substitutes.Element M ' can be used alone or be used in combination.
When element M is substituted by element M ' part, can regulate sum, and therefore can improve Seebeck coefficient α and/or reduce the electricalresistivity as the valence electron of the MgAgAs type crystalline phase of principal phase.
In addition, to make that the sum of valence electron is controlled in approximate 18 the time when this element M ' with rare earth element is used, and can improve Seebeck coefficient α.
But, the element M that is used to substitute ' amount be preferably set to 30 atomic percentages of element M (Ti, Zr and Hf) or still less.When the element M that is used to substitute ' amount during greater than 30 atomic percentages, the crystalline phase that is different from MgAgAs type crystalline phase is separated out, the possibility of result reduces Seebeck coefficient α in some cases.
In composition formula (2) and (3), at least a elements A ' part that elements A (Ni and Co) can be selected from Mn, Fe, Co and Cu substitutes this elements A ' can be used alone or be used in combination.
When elements A is substituted by elements A ' part, for example, can regulate sum, and therefore can improve Seebeck coefficient α and/or reduce the electricalresistivity as the valence electron of the MgAgAs type crystalline phase of principal phase.
But, the elements A that is used to substitute ' amount be preferably set to 50 atomic percentages of elements A or still less.In fact, under the situation that elements A is partly substituted by Cu, when the amount of Cu is superfluous, may suppress the growth of MgAgAs type crystal in some cases, therefore the amount of the Cu that is used to substitute more preferably is set at 30 atomic percentages or littler.
In composition formula (2) and (3), at least a element B ' part that element B (Sn and Sb) can be selected from Si, Mg, As, Bi, Ge, Pb, Ga and In substitutes this element B ' can be used alone or be used in combination.
When element B is substituted by number of elements B ' part, for example, can regulate sum, and therefore can improve Seebeck coefficient α and/or reduce the electricalresistivity as the valence electron of the MgAgAs type crystalline phase of principal phase.
But, consider harmfulness, toxicity and material cost, element B ' more preferably be selected from Si and Bi.In addition, be used to the element B that substitutes ' amount more preferably be set at 30 atomic percentages of element B or still less.When the element B that is used to substitute ' amount during greater than 30 atomic percentages, the crystalline phase that is different from MgAgAs type crystalline phase is separated out, the possibility of result has reduced Seebeck coefficient α in some cases.
Then, will method that make thermoelectric material according to the present invention be described.
At first, form the alloy of the element as shown in composition formula (2) or (3) that comprises scheduled volume, for example, by arc-melting or high frequency fusing.When forming alloy, also can use the liquid hardening method, for example single-roller method, double roller therapy, spining disk method or gas atomization.Advantageously use the liquid hardening method to form to constitute the thin crystalline phase of alloy or enlarge the solid solution tagma of the element of crystalline phase inside, this method also plays the effect that reduces thermal conductivity κ.
When needs, can heat-treat the alloy of formation like this.By this heat treatment,, therefore can further improve thermoelectricity capability owing to make alloy form single-phase and controlled the diameter of crystal grain.In order to prevent alloy oxidation, preferably in the inert gas atmosphere that comprises Ar etc., melt, step such as liquid hardening, heat treatment.
Then, after alloy being pulverized, thus obtained powdery alloy is carried out global formation by methods such as sintering process, pressure sintering, SPS methods by ball mill, Blang's grinding machine and stamping mill etc.In order to prevent alloy oxidation, preferably in the inert gas atmosphere that comprises Ar etc., carry out global formation.
Then, will be described in further detail in the thermoelectric material by composition formula (2) and (3) expression, be used in scope, regulating the method for density greater than 99.0% real density.
For example, describe a kind of situation, wherein the predetermined molding time that continues 1 hour by pressure sintering under briquetting pressure P and forming temperature T is made thermoelectric material by the alloy of powdery.
Under the above-mentioned situation, when moulding pressure P and forming temperature T satisfied following formula (4), density surpassed 99.0% and can produce and have the more thermoelectric material of excellent properties.
P＞-0.35T+450 (4)
In following formula (4), P represents briquetting pressure (MPa), and T represent forming temperature (℃).
On the other hand, when P≤-when 0.35T+450 set up, the density of formed body was 99.0% or littler.When the density of formed body be real density 99.0% or more hour, reduced output factor Pf (=α
2/ ρ), Seebeck coefficient α and conductivity.
Therefore, when control moulding pressure P and forming temperature T, can in 99.0% scope, regulate density by the thermoelectric material of composition formula (2) or (3) expression greater than real density.
Optional shape and size to formed body are selected.For example, can be to have the cylindrical shape of 0.5-10mm external diameter and 1-30mm thickness or have the rectangular shape that 0.5-10mm takes advantage of the square of 0.5-10mm and 1-30mm thickness.
Then, the formed body that is obtained is machined to required shape.The shape and size of formed body are selected.For example, can be to have the cylindrical shape of 0.5-10mm external diameter and 1-30mm thickness or have the rectangular shape that 0.5-10mm takes advantage of the square of 0.5-10mm and 1-30mm thickness.
Then, will the embodiment of the thermoelectric conversion element that uses thermoelectric material of the present invention be described.
Fig. 1 is the schematic cross-sectional view that illustrates according to the structure of thermoelectric conversion element of the present invention.
Thermoelectric conversion element 10 has the structure that comprises following key element: each all comprise the thermoelectric material of making by the p N-type semiconductor N (p type thermoelectric material) p type element 1, each all comprises the n type element 2 of the thermoelectric material of being made by the n N-type semiconductor N (n type thermoelectric material), alternately connect the electrode 3 of p type element 1 and n type element 2 and the dielectric substrate 4 of coated electrode 3.
In this thermoelectric conversion element 10, one or two in p type element 1 and the n type element 2 is to use and forms according to the thermoelectric material by composition formula (2) or (3) expression of the present invention.When use only forms p type element 1 or n type element 2 according to thermoelectric material of the present invention, use Bi-Te base or Pb-Te base thermoelectricity material to form the element of other type.
Therefore, owing to will export the factor and bring up to high relatively level, and thermal conductivity κ fully reduced, so can form thermoelectric conversion element 10 by the thermoelectric material that use has the half Heusler compound of higher dimensionless performance index ZT.Therefore, the result compares with the switching device that the thermoelectric material that uses relevant half Heusler compound forms, and thermoelectric conversion element 10 has significantly high performance.
[embodiment]
Reference example is described according to thermoelectric material of the present invention.
Table 1 shows the result of embodiment 1 and is used for the result of the comparative example 1 of comparison purpose.
Embodiment shown in the table 11 is described as representative embodiment.As raw material, prepare to have 99.9% purity Ti, have 99.9% purity Zr, have the Hf of 99.9% purity, the Sn that has the Ni of 99.99% purity and have 99.99% purity, and weighing is to obtain by (Ti
0.3Zr
0.35Hf
0.35) alloy represented of NiSn.The raw material of weighing mixed and the arc furnace of packing in water cooling copper burner hearth after, be evacuated down to 2 * 10
-3The vacuum level of Pa.
Then, the high-purity Ar gas that introducing has 99.999% purity under 0.04Mpa carries out arc-melting then to form the Ar atmosphere that reduces pressure.After the fusing, water-cooled copper burner hearth is quenched, to obtain metal derby.With this metal derby vacuum seal 10
-4In the quartz ampoule of Pa or littler high vacuum levels and 1150 ℃ of heat treatments 2 hours.Then this metal derby is ground into 45 μ m or littler size.The mould that use has a 20mm internal diameter carries out moulding with the pressure of 50MPa to the powdery alloy that obtains.The formed body of Xing Chenging is filled in the carbon molding jig with 20mm inside diameter and then at 1200 ℃ of pressure with 80Mpa sintering 1 hour in Ar atmosphere, obtains to have the dish type sintered body of about 20mm diameter thus thus.This sintered body is considered to be substantially free of the material in space.
Then,, use the external diameter and the thickness of this sintered body of miking, obtain the volume of sintered body thus in order to obtain the accurate density of this sintered body.Find from measurement result,, therefore obtained to have the sintered body of approximate real density because the density of the sintered body of the present embodiment is 99.9% of real density.
By using powder x x ray diffraction method to confirm that this sintered body mainly is made of MgAgAs type crystalline phase.By using the ICP emission spectrum that the analysis of the composition of this sintered body has been confirmed to obtain approximate predetermined composition.
Estimate the thermoelectricity capability of thus obtained sintered body by following method.
(a) electricalresistivity
Sintered body is cut into has 1.5mm * 0.5mm * sample of 18mm size and forming after the electrode thereon, measure by the direct current four-end method.
(b) Seebeck coefficient α
Sintered body is cut into have 5mm * 1.5mm * sample of 0.5mm size after, the temperature difference that applies 2 ℃ by the two ends at sample is measured electromotive force, obtains Seebeck coefficient α thus.
(c) thermal conductivity κ
Sintered body is cut into after the sample of thickness of external diameter with 10mm and 2.0mm, uses the laser scintigraphy to measure thermal diffusivity.In addition, obtain specific heat by the DSC method.During this is measured, use the density of the sintered body of above-mentioned acquisition.According to thus obtained data, calculate thermal conductivity κ (lattice thermal conductivity).
By using electricalresistivity, Seebeck coefficient α and the thermal conductivity κ that so obtains, obtain dimensionless performance index ZT from formula (1).Show electricalresistivity, Seebeck coefficient α, thermal conductivity κ and dimensionless performance index ZT under 300K and the 700K below.
300K electricalresistivity 8.62 * 10
-3Ω cm
Seebeck coefficient α-333 μ V/K
Thermal conductivity κ 3.2W/mK
ZT 0.12
700K electricalresistivity 2.35 * 10
-3Ω cm
Seebeck coefficient α-323 μ V/K
Thermal conductivity κ 2.6W/mK
ZT 1.20
Below, comparative example 1 is described.
Obtain sintered body in the mode identical with embodiment 1, difference is the sintering that carried out in Ar atmosphere under the pressure of 780 ℃ temperature and 30Mpa 1 hour.The density of this sintered body is 69.1% (comparative example 1) of real density.
In the table 1, show percentage [(d/do) * 100], thermal conductivity κ, output factor Pf and the dimensionless performance index ZT of density (d)/real density (do).
Among Fig. 2, show the percentage and the (Ti of density/real density
0.3Zr
0.35Hf
0.35) relation between the sintering temperature of NiSn.
Can be clear from table 1,99.9% the thermoelectric material (embodiment 1) that has MgAgAs type crystalline phase, density and be a real density and density are that 69.1% thermoelectric material (comparative example 1) of real density is compared and had high dimensionless performance index ZT.
Table 1
| Form | (d/do) ×100％ | 300K | 700K | |||||
| κ(W/mk) | Pf(mW/mK 2) | ZT | κ(W/mK) | Pf(mW/mK 2) | ZT | |||
| Embodiment 1 | (Ti 0.3Zr 0.35Hf 0.35)NiSn | 99.9 | 3.2 | 1.29 | 0.12 | 2.6 | 4.4 | 1.20 |
| Comparative example 1 | (Ti 0.3Zr 0.35Hf 0.35)NiSn | 69.1 | 2.0 | 0.83 | 0.12 | 1.8 | 2.4 | 0.93 |
To another embodiment according to thermo-electric converting material of the present invention be described with reference to figure 1 and Fig. 3.
As what above mention in the first embodiment, the performance index Z of thermo-electric converting material can represent with following formula (1 ').
Z＝α
2/(ρκ) (1’)
In following formula (1 '), α represents the Seebeck coefficient of thermo-electric converting material, and ρ represents resistivity, and κ represents thermal conductivity.Therefore Z has the dimension in contrast to temperature, is dimensionless number by multiply by the ZT that performance index Z obtains with absolute temperature.
This ZT value is called as the dimensionless performance index.The ZT value is relevant with the conversion efficiency of thermoelectric of thermo-electric converting material, and the material with bigger ZT value has higher conversion efficiency of thermoelectric.
Shown in (1 '), in order to obtain having the thermo-electric converting material of high ZT value, Seebeck coefficient α that need be more higher, lower electricalresistivity and lower thermal conductivity κ.
As wherein do not contain hazardous substance fully or thermo-electric converting material that its content reduces as small as possible in a kind of, the present inventor furtherd investigate comprise have the MgAgAs type crystal structure (hereinafter referred to as " MgAgAs type crystalline phase ") to improve half Heusler sill of its performance.
As a result, find to have when being at least a element that is selected among C, N and the O of principal phase and comprising and the half Heusler sill represented by following chemical combination formula (2 ') thermo-electric converting material that can realize having high ZT value with MgAgAs type crystalline phase when forming.Therefore, as a result of obtained the present invention.
((Ti
a1Zr
b1Hf
c1)
xNi
ySn
100-x-y)
1-pA
p (2’)
In above-mentioned chemical combination formula (2 '), elements A is at least a element that is selected among C, N and the O; 0＜a1＜1,0＜b1＜1,0＜c1＜1, and a1+b1+c1=1 sets up; Set up 30≤x≤35 and 30≤y≤35, and set up 0.05＜p＜0.1.
Among the present invention, principal phase is illustrated in all crystalline phases of constituting thermo-electric converting material and the amorphous phase has the maximum volume mark mutually.
In thermo-electric converting material, because as element mutually of the same clan in the periodic table but in Ti, Zr that atomic weight and atomic radius differ from one another and Hf be included in, therefore can reduce thermal conductivity κ significantly by chemical combination formula (2 ') expression.
The ratio of components p of at least a element that is selected from C, N and O in the thermo-electric converting material of being represented by chemical combination formula (2 ') at first, will be described.
In the time of at least a element that is selected from C, N and O is included in by the thermo-electric converting material of chemical combination formula (2 ') expression, form carbide, nitride and/or oxide, and the reduction of the volume fraction of principal phase, so Seebeck coefficient α reduces.
On the other hand, owing to carbide, nitride and/or oxide are separated out at the place, grain boundary of MgAgAs type crystalline phase, so thermal conductivity κ significantly reduces.
Therefore, because this remarkable reduction of this thermal conductivity κ, conversion efficiency of thermoelectric is brought up to certain content of above-claimed cpd, in addition, surpasses above-mentioned certain level even work as content, makes p＞0.05 set up, and conversion efficiency of thermoelectric can seriously not reduce yet.
Because C, N and O are easy to be included as impurity usually during the production process of thermo-electric converting material, therefore be difficult to it accurately is controlled at low ratio of components.In addition, when not carrying out this control, ratio of components p may tend to satisfy p＞0.05 in many cases.
Therefore, when setting by the ratio of components p of the thermo-electric converting material of chemical combination formula (2 ') expression when satisfying p＞0.05, in thermo-electric converting material by chemical combination formula (2 ') expression, when obtaining to reduce the effect of thermal conductivity κ, can guarantee productivity ratio by at least a element that is selected from C, N and O.
In addition, consider the effect that reduces thermal conductivity κ by C, N and O, ratio of components p is set at 0.05＜p＜0.1.
As described below, be difficult to satisfy p≤0.05.
Actively being contained in method in the thermo-electric converting material as at least a element that wherein will be selected from C, N and O, for example, can be the compound that wherein will comprise C, N and O (for example ZrC, TiC, TiN, LaN and Sm
2O
3) join the method in the raw material, or the method for wherein in the atmosphere of the gas that comprises C, N and O or its chemical compound gas (for example nitrogen, oxygen, methane gas and ammonia), heat-treating.
But, in the method that is used for comprising above-mentioned element, when the ratio of components p of the element of at least a C of being selected from, N and O is controlled in when being limited to p≤0.05 for example low-level, owing to must accurately control the amount of gas in content of additive or the atmosphere, therefore the very time-consuming and effort of this method, so productivity ratio reduction.
In addition, as the method that wherein element of at least a C of being selected from, N and O actively is contained in the thermo-electric converting material, for example, can mention a kind of method, wherein by in the alloy melting step, using the high-frequency induction melting method of crucible from crucible material (for example aluminium oxide, zirconia or magnesium oxide), some above-mentioned element to be joined wherein.
But, even by element adding method, when being controlled at, ratio of components is limited to for example low-level following time of p≤0.05, must accurately control crucible material, because be difficult to produce cheap crucible with good productivity ratio, therefore said method has also reduced productivity ratio as mentioned above.
In addition, as the method that wherein element of at least a C of being selected from, N and O actively is contained in the thermo-electric converting material, for example, can mention a kind of method, wherein the concentration of C, N and O in the controlled atmospher gas in fusing, pulverizing or the sintering step of for example manufacturing process.
But, even the method by this controlled concentration is limited to for example low-level following time of p≤0.05 when ratio of components is controlled at, in above-mentioned steps, be evacuated down to high vacuum levels after, the also concentration of controlled atmospher gas accurately.Therefore, must provide big production equipment, therefore reduce productivity ratio.
For example, in this concentration control method, when p is set at p＞0.05, be not evacuated down to high vacuum levels, can produce conversion efficiency of thermoelectric and ratio of components p and be 0.05 or the littler suitable material of material, and p be 0.05 or littler material reduced productivity ratio.
Therefore, in thermo-electric converting material by chemical combination formula (2 ') expression, for the element that uses at least a C of being selected from, N and O to reduce the effect of thermal conductivity κ, consider productivity ratio, the ratio of components p of the element of at least a C of being selected from, N and O is set at 0.05＜p＜0.1.
Then, will describe by symbol x and y in the thermo-electric converting material of chemical combination formula (2 ') expression.
When a large amount of crystalline phases that are different from MgAgAs type crystalline phase are separated out, may reduce Seebeck coefficient α in some cases.Therefore, in the thermo-electric converting material by chemical combination formula (2 ') expression, x and y are set at 30≤x≤35,30≤y≤35 respectively.In addition, x and y more preferably are set at 33≤x≤34,33≤y≤34 respectively.
The element that comprises at least a C of being selected from, N and O by the thermo-electric converting material of chemical combination formula (2 ') expression.The element of at least a C of being selected from, N and O has significantly reduced the thermal conductivity by the thermo-electric converting material of chemical combination formula (2 ') expression, has therefore improved conversion efficiency of thermoelectric.
In addition, in thermo-electric converting material, the ratio of components p of the element of at least a C of being selected from, N and O is set at 0.05＜p by chemical combination formula (2 ') expression.Therefore, when making the thermo-electric converting material of representing by chemical combination formula (2 '), needn't accurately control ratio of components p.Because C, N and O are easy to be included as impurity usually during the production process of thermo-electric converting material, therefore be difficult to accurately be controlled at low ratio of components.Therefore, in the time needn't accurately controlling this ratio of components p, highly beneficial to productivity ratio with the upper limit of strictness.
Therefore, although the thermo-electric converting material of being represented by chemical combination formula (2 ') is harmless and nontoxic material, can obtains improveing the effect of conversion efficiency of thermoelectric by the element of at least a C of being selected from, N and O, and in addition, can produce with good productivity ratio.
Another embodiment according to thermo-electric converting material of the present invention will be described below.
The present inventor has further furtherd investigate atomic radius greater than any one rare earth element among Ti, Zr and the Hf.
Find in the selected free Y of M of half Heusler compound MNiSn (wherein M=Ti, Zr and Hf) therein and the thermo-electric converting material that at least a element in the rare earth element partly substitutes, when comprising the element of at least a C of being selected from, N and O, can improve thermal conductivity κ significantly, and obtain high ZT value.
That is, shown in following chemical combination formula (3 '), comprise the element of at least a C of being selected from, N and O according to the thermo-electric converting material of this embodiment.
((Ln
d(Ti
a2Zr
b2Hf
c2)
1-d)
xNi
ySn
100-x-y)
1-pA
p (3’)
In above-mentioned chemical combination formula (3 '), elements A is the element of at least a C of being selected from, N and O; Element Ln is at least a element that is selected from Y and rare earth element; 0≤a2≤1,0≤b2≤1,0≤c2≤1, and a2+b2+c2=1 sets up; Set up 0＜d≤0.3; Set up 30≤x≤35 and 30≤y≤35; And set up p＞0.05.
When the M of half Heusler compound MNiSn (wherein M=Ti, Zr and Hf) during greater than being selected from least a element in Y and the rare earth element and partly substituting of Ti, Zr and Hf, can be improved thermal conductivity κ by atomic radius.
Be that element Ln (element of at least a Y of being selected from and rare earth element) is the effective element that reduces the thermal conductivity κ of thermo-electric converting material.
In element Ln, be that 57 La is that the element of 71 Lu all comprises as rare earth element to atomic number from atomic number in the periodic table.In addition, when considering fusing point and atomic radius, preferred especially Er, Gd and Nd are as element Ln.
Promptly allow to also to obtain to reduce the effect of thermal conductivity κ by oligo-element Ln.But, preferably Ln is set at 0.1 atomic percentage or bigger to the ratio of components d of Ln, Ti, Zr and Hf summation.When the ratio of components d of element Ln is during greater than 30 atomic percentages, be different from the crystalline phase of MgAgAs type crystalline phase, for example LnSn
3Phase is separated out significantly, and the result may reduce Seebeck coefficient α in some cases.
Therefore, preferably ratio of components d is set at 0＜d≤0.3, and more preferably is set at 0.001≤d≤0.3.
In addition, equally therein in the thermo-electric converting material that the M element of half Heusler compound MNiSn (wherein M=Ti, Zr and Hf) is partly substituted by Ln, when comprising the element of at least a C of being selected from, N and O, can significantly reduce thermal conductivity κ, and therefore improve conversion efficiency of thermoelectric.
When comprising the element of at least a C of being selected from, N and O in the thermo-electric converting material that wherein the M element of half Heusler compound MNiSn (wherein M=Ti, Zr and Hf) is partly substituted by Ln, this thermo-electric converting material has being made up of chemical combination formula (3 ') expression.
In said circumstances, when making that the ratio of components p of element of at least a C of being selected from, N and O satisfies p＞0.05, be easy to be included as C, the N of impurity and the ratio of components p of O during needn't accurately being controlled at production process, therefore can improve the productivity ratio of thermo-electric converting material.
By the existence of Ln, can obtain with chemical combination formula (2 ') in identical effect (it has reduced thermal conductivity κ by comprising all Ti, Zr and Hf).Therefore, in chemical combination formula (3 '), Ti, Zr and Hf needn't exist simultaneously.Therefore, for a2, b2 and c2,0≤a2≤1,0≤b2≤1,0≤c2≤1, and a2+b2+c2=1 sets up.
In addition, in chemical combination formula (3 '), for the phase of MgAgAs type crystal structure and obtain high Seebeck coefficient, x and y are set at 30≤x≤35,30≤y≤35 respectively with large volume fraction.
Usually, in half Heusler compound, when the sum of valence electron is approximately 18, can observe high Seebeck coefficient.For example, by Zr (5d
26s
2), Ni (3d
84s
2) and Sn (5s
25p
2) expression ZrNiSn the outer shell electronic configuration, so its valence electron add up to 18.The sum of the valence electron of TiNiSn and HfNiSn also is 18 as mentioned above.
On the other hand, when partly being substituted by rare earth element, because the rare earth element except Ce, Eu and Yb has by (5d as represented at least a in Ti, Zr and Hf of chemical combination formula (3 ')
16s
2) expression the outer shell electronic configuration and therefore be trivalent as a rule, therefore the sum of valence electron departs from 18 in some cases.
But, can suitably correct departing from of total valence population by regulating x and y.
Except that the effect identical with the thermo-electric converting material of representing by chemical combination formula (2 '), by partly substitute the M of half Heusler compound MNiSn (wherein M=Ti, Zr and Hf) with at least a element that is selected from Y and the rare earth element, compare with the thermo-electric converting material of representing by chemical combination formula (2 ') by the thermo-electric converting material of chemical combination formula (3 ') expression and can further reduce thermal conductivity κ.
In chemical combination formula (2 ') and (3 '), can be with at least a element part substitute element Ti, the Zr and the Hf that are selected from V, Nb, Ta, Cr, Mo and W.Above-mentioned element can be used singly or in combination with part and substitute Ti, Zr and Hf.
Substitute by this, can regulate the total valence population in the MgAgAs type crystalline phase, and as a result of can improve Seebeck coefficient α and/or reduce the electricalresistivity.
But preferably the amount that will be used to substitute is set at 30 atomic percents of total amount of Ti, Zr and Hf or littler.When the amount that is used to substitute during greater than 30 atomic percents, be different from obviously separating out mutually of MgAgAs type crystalline phase, the possibility of result has reduced Seebeck coefficient α in some cases.
In addition, at least a element that the element Ni in chemical combination formula (2 ') and (3 ') can be selected from Mn, Fe, Co and Cu partly substitutes, and above-mentioned element can be used singly or in combination with part and substitute Ni.
Substitute by this, for example, can regulate the sum of the valence electron in the MgAgAs type crystalline phase, as a result of can improve Seebeck coefficient α and/or reduce the electricalresistivity.
But preferably the amount that will be used to substitute is set at 50 atomic percentages of Ni amount or littler.Particularly, under the situation of using Cu to substitute, when it substitutes amount when too much, may suppress the growth of MgAgAs type crystalline phase in some cases, preferably the amount that will be used to substitute is set at 30 atomic percentages of Ni amount or littler.
In addition, can partly substitute chemical combination formula (2 ') and the Sn in (3 ') with at least a element that is selected from Si, Mg, As, Sb, Bi, Ge, Pb, Ga and In, above-mentioned element can be used singly or in combination to substitute Sn.
Substitute by this, for example, can regulate the sum of the valence electron in the MgAgAs type crystalline phase, as a result of can improve Seebeck coefficient α and/or reduce the electricalresistivity.
But, consider harmfulness, toxicity and the material cost of the element that is used for substituting Sn, preferred element is Si, Sb and Bi.In addition, the amount that preferably will be used to substitute is set at 30 atomic percentages of Sn amount or littler.When the amount that is used to substitute during greater than 30 atomic percentages, the crystalline phase that is different from MgAgAs type crystalline phase is separated out, and the result may reduce Seebeck coefficient α in some cases.
Then, will method that make thermo-electric converting material according to the present invention be described.
At first, form the alloy of the element that comprises the scheduled volume as shown in chemical combination formula (2 ') and (3 '), for example, by arc-melting or high frequency fusing.When forming alloy, also can use the liquid hardening method, for example single-roller method, double roller therapy, spining disk method or gas atomization, or use solid phase reaction method such as the mechanical alloying method.
When needs, can heat-treat the alloy of formation like this.By this heat treatment, can suppress to be different from the formation of the phase of MgAgAs type crystalline phase, and/or can control the diameter of crystal grain.But, when at high temperature heat-treating, may increase the average crystal grain diameter of MgAgAs type crystalline phase, the result may reduce thermoelectricity capability in some cases.Therefore, heat treated temperature preferably sets less than 1200 ℃.Then, after alloy being pulverized, thus obtained powdery alloy is carried out global formation by pressure sintering, discharge plasma sintering process etc. by ball mill, Blang's grinding machine, stamping mill etc.
In order to prevent alloy oxidation, in comprising the inert gas atmosphere of Ar etc., carry out step usually such as fusing, liquid hardening, mechanical alloying, heat treatment, pulverizing and global formation.
In addition, among the present invention, in order to comprise the element of at least a C of being selected from, N and O forcibly in thermo-electric converting material, the concentration of C, N and O in the controlled atmospher gas makes above-mentioned element be contained in the material.
As possibility, situation as the front, in inert atmosphere, form after the alloy, can in the atmosphere of the gas that comprises C, N and O or its chemical compound gas such as nitrogen, oxygen, methane gas or ammonia, heat-treat, make C, N and O be contained in the thermo-electric converting material this alloy.
In addition, in the alloy melting step, when use utilizes the high-frequency induction melting method of crucible, can above-mentioned element be contained in the thermo-electric converting material from crucible material such as aluminium oxide, zirconia or magnesium oxide.
In addition, behind pulverising step, for N and the O that absorbs powder surface, can be in about 0.5-100 hour the heating in atmosphere of about 100-300 ℃ temperature.
Then, the formed body that machine work obtained obtains thermo-electric converting material of the present invention thus to have the size that needs.Can choose wantonly the shape and size of formed body are selected.For example, can be to have the cylindrical shape of 0.5-10mm external diameter and 1-30mm thickness or have the cuboid that 0.5-10mm takes advantage of the square and 1-30mm thickness of 0.5-10mm.
The another embodiment of the thermoelectric conversion element that uses thermoelectric material of the present invention then, is described with reference to Fig. 1 and Fig. 3.
The thermoelectric conversion element of the present embodiment has and essentially identical structure shown in Figure 1.
Promptly, thermoelectric conversion element 10 has the structure that comprises following key element: each all comprise the thermo-electric converting material of making by the p N-type semiconductor N (p type thermo-electric converting material) p type element 1, each all comprises the n type element 2 of the thermo-electric converting material of being made by the n N-type semiconductor N (n type thermo-electric converting material), alternately connect the electrode 3 of p type element 1 and n type element 2 and the dielectric substrate 4 of coated electrode 3.
Fig. 3 be pn semiconductor that thermoelectric conversion element 10 ' shown in Figure 1 is shown to one of zoomed-in view.
For example, suppose that situation is for wherein by maintaining dielectric substrate 4a and 4b under low temperature and the high temperature formation temperature gradient between dielectric substrate 4a and 4b.
In this case, in p type element 1, the electrode 3a of high temperature side is shifted in the hole 5 with positive charge.Therefore, in p type element 1, the electrode 3a of high temperature side compares with the electrode 3b of low temperature side has high potential.
On the other hand, in n type element 2, the electronics 6 with negative electrical charge is shifted to the electrode 3b of low temperature side.Therefore, in n type element 2, the electrode 3b of low temperature side compares with the electrode 3c of high temperature side has high potential.
As a result, between electrode 3a and 3c, produce electrical potential difference.Electrode 3a serves as positive electrode, and electrode 3b serves as negative electrode.
Thermoelectric conversion element 10 ' can obtain the high voltage suitable with structure shown in Figure 3.Because therefore the pn semiconductor can guarantee bigger electrical power to being connected in series as shown in Figure 1.
In this thermoelectric conversion element 10 ', p type element 1 and n type element 2 any or the two be by forming according to the thermo-electric converting material with chemical combination formula (2 ') and (3 ') expression of the present invention.When use only forms p type element 1 or n type element 2 according to thermoelectric material of the present invention, use Bi-Te base or Pb-Te base thermoelectricity material to form the element of another type.
Therefore, thermoelectric conversion element 10 ' can be formed by harmless and nontoxic thermo-electric converting material, can utilize the effect of this thermo-electric converting material improvement conversion efficiency of thermoelectric by the element thermoelectric conversion element 10 ' of at least a C of being selected from, N and O, and can be with good productivity ratio production.
[embodiment]
To describe in detail according to thermo-electric converting material of the present invention with reference to embodiment.
Table 1 ' be for comparing the table that purpose demonstrates the performance of embodiment 1 and comparative example 1 to 3.
After the predetermined raw material that is selected from Er, Ta, Ti, Zr, Hf, Ni, Sn, Sb and C carries out weighing, use the magnesium crucible to carry out the high frequency fusing subsequently, form alloy by fused raw material is injected mold.Then, the alloy that uses mortar to form thus grinds to form 45 μ m or littler size, in embodiment that comprises N or O and comparative example, for absorption of N on powder surface or O, carries out 1 hour heat treatment in atmosphere under 120 ℃.Then, carry out hot pressing, obtain to have the formed body of 20mm external diameter and 3mm thickness thus.Carry out hot pressing by following steps: in vacuum atmosphere,, kept this temperature 1 hour, and reduce the temperature to room temperature then with 15 ℃/minute speed elevated temperature to 1200 ℃.The formed body that machine work is handled thus is used for the evaluation of thermoelectricity capability then to have required form.
By powder x x ray diffraction and ICP emission spectrographic analysis, the phase that the remainder of thermo-electric converting material assigns to produce after the use machine work and the evaluation of its composition.As a result, confirm that MgAgAs type monocrystalline is present in all samples mutually in a large number.By this composition that analyze to obtain as table 1 ' shown in.
In addition, measure thermal diffusivity, density and the specific heat of formed body respectively by laser scintigraphy, Archimedes's method and DSC (differential scanning calorimetry), and, obtain thermal conductivity κ according to resulting result.In addition, when formed body is cut into needle-like, measure its Seebeck coefficient α.In addition, use the formed body of this needle-like to be used to utilize the electricalresistivity's of four-end method measurement.Table 1 ' show by performance index ZT (the Z=α under the 700k of Seebeck coefficient α, electricalresistivity and thermal conductivity κ acquisition
2/ ρ κ).
Table 1 '
| The composition of analyzing (atomic percentage) | Performance index ZT (700K) | |
| Embodiment 1 | ((Er 0.05(Ti 0.34Zr 0.33Hf 0.33) 0.95) 34Ni 33(Sn 0.985Sb 0.015) 33) 0.984O 0.052 | 1.24 |
| Comparative example 1 | ((Er 0.05(Ti 0.34Zr 0.33Hf 0.33) 0.95) 34Ni 33(Sn 0.985Sb 0.015) 33) 0.984O 0.0012 | 1.55 |
| Comparative example 2 | ((Er 0.05(Ti 0.34Zr 0.33Hf 0.33) 0.95) 34Ni 33(Sn 0.985Sb 0.015) 33) 0.995O 0.005 | 1.56 |
| Comparative example 3 | ((Ta 0.01(Zr 0.70Hf 0.80) 0.99) 35Ni 34Sn 31) 0.981O 0.015N 0.004 | 1.18 |
From table 1 ' as seen, ratio of components p is subjected to accurately controlling in comparative example 1 and 2, makes p≤0.05 set up, and obtains high ZT value under 700k, and for example 1.5 or bigger.On the other hand, should be appreciated that in embodiment 1 setting ratio of components makes p＞0.5 set up (can expect this ratio of components under the improvement of productivity ratio), can obtain abundant high ZT value, for example 1.24.In addition, should be appreciated that in the comparative example 3 that in chemical combination formula (2 '), does not comprise Ti,, compare with embodiment 1 and only to obtain low ZT value although controlled N and O accurately.
Claims (14)
1, a kind of by following composition formula (Ti
A1Zr
B1Hf
C1)
xA
yB
100-x-yThe thermoelectric material of expression, wherein elements A is the element of at least a Ni of being selected from and Co, element B is the element of at least a Sn of being selected from and Sb, 0≤a1≤1,0≤b1≤1,0≤c1≤1, and a1+b1+c1=1 sets up, and 30≤x≤35 and 30≤y≤35 set up, and this thermoelectric material comprise have the MgAgAs type crystal structure as principal phase, wherein the density of this thermoelectric material is greater than 99.0% of real density.
2, a kind of by following composition formula (Ln
d(Ti
A2Zr
B2Hf
C2)
1-d)
xA
yB
100-x-yThe thermoelectric material of expression, wherein element Ln is at least a element that is selected from Y and rare earth element, and elements A is the element of at least a Ni of being selected from and Co, and element B is the element of at least a Sn of being selected from and Sb, 0≤a2≤1,0≤b2≤1,0≤c2≤1, and a2+b2+c2=1 sets up, set up 0＜d≤0.3, and 30≤x≤35 and 30≤y≤35 set up, and this thermoelectric material comprise have the MgAgAs type crystal structure as principal phase, wherein the density of this thermoelectric material is greater than 99.0% of real density.
3, a kind of by following composition formula ((Ti
A1Zr
B1Hf
C1)
xNi
ySn
100-x-y)
1-pA
pThe thermo-electric converting material of expression, wherein elements A is the element of at least a C of being selected from, N and O, 0＜a1＜1,0＜b1＜1,0＜c1＜1, and a1+b1+c1=1 sets up 30≤x≤35 and 30≤y≤35 establishments, and 0.05＜p＜0.1 sets up, and this thermo-electric converting material comprise have the MgAgAs type crystal structure as principal phase.
4, a kind of by following composition formula ((Ln
d(Ti
A2Zr
B2Hf
C2)
1-d)
xNi
ySn
100-x-y)
1-pA
pThe thermo-electric converting material of expression, wherein elements A is the element of at least a C of being selected from, N and O, element Ln is at least a element that is selected from Y and rare earth element, 0≤a2≤1,0≤b2≤1,0≤c2≤1, and a2+b2+c2=1 sets up, and set up 0＜d≤0.3, and set up 30≤x≤35 and 30≤y≤35, and 0.05＜p＜0.1 sets up, and this thermo-electric converting material comprise have the MgAgAs type crystal structure as principal phase.
5, according to each thermoelectric material of claim 1-4, wherein at least a at least a element that is selected among V, Nb, Ta, Cr, Mo and the W among Ti, Zr and the Hf partly substitutes.
6, according to each thermoelectric material of claim 1-4, wherein at least a element that is selected among Mn, Fe and the Cu of elements A partly substitutes.
7, according to each thermoelectric material of claim 1-4, wherein at least a element that is selected among Si, Mg, As, Bi, Ge, Pb, Ga and the In of element B partly substitutes.
8, a kind of thermoelectric conversion element comprises:
At least one comprises the p type element of p type thermoelectric material; With
At least one comprises the n type element of n type thermoelectric material, and p type element and n type element alternately are connected in series each other,
Wherein p type thermoelectric material and n type thermoelectric material is at least a by following composition formula (Ti
A1Zr
B1Hf
C1)
xA
yB
100-x-yExpression, wherein elements A is the element of at least a Ni of being selected from and Co, element B is the element of at least a Sn of being selected from and Sb, 0≤a1≤1,0≤b1≤1,0≤c1≤1, set up with a1+b1+c1=1, and 30≤x≤35 and 30≤y≤35 set up, and p type and n type thermoelectric material at least a comprise have the MgAgAs type crystal structure as principal phase, wherein the density of this thermoelectric material is greater than 99.0% of real density.
9, a kind of thermoelectric conversion element comprises:
At least one comprises the p type element of p type thermoelectric material; With
At least one comprises the n type element of n type thermoelectric material, and p type element and n type element alternately are connected in series each other,
Wherein p type thermoelectric material and n type thermoelectric material is at least a by following composition formula (Ln
d(Ti
A2Zr
B2Hf
C2)
1-d)
xA
yB
100-x-yExpression, wherein element Ln is at least a element that is selected from Y and rare earth element, elements A is the element of at least a Ni of being selected from and Co, element B is the element of at least a Sn of being selected from and Sb, 0≤a2≤1,0≤b2≤1,0≤c2≤1, set up with a2+b2+c2=1, set up 0＜d≤0.3, and 30≤x≤35 and 30≤y≤35 set up, and p type and n type thermoelectric material at least a comprise have the MgAgAs type crystal structure as principal phase, wherein the density of this thermoelectric material is greater than 99.0% of real density.
10, a kind of thermoelectric conversion element comprises:
At least one comprises the p type element of p type thermo-electric converting material; With
At least one comprises the n type element of n type thermo-electric converting material, and p type element and n type element alternately are connected in series each other,
Wherein p type thermo-electric converting material and n type thermo-electric converting material is at least a by following composition formula (Ti
A1Zr
B1Hf
C1)
xNi
ySn
100-x-yExpression, wherein elements A is the element of at least a C of being selected from, N and O, 0＜a1＜1,0＜b1＜1,0＜c1＜1 and a1+b1+c1=1 set up, and set up 30≤x≤35 and 30≤y≤35, and 0.05＜p＜0.1 sets up, and p type and n type thermoelectric material at least a comprise have the MgAgAs type crystal structure as principal phase.
11, a kind of thermoelectric conversion element comprises:
At least one comprises the p type element of p type thermo-electric converting material; With
At least one comprises the n type element of n type thermo-electric converting material, and p type element and n type element alternately are connected in series each other,
Wherein p type thermoelectric material and n type thermoelectric material is at least a by following composition formula ((Ln
d(Ti
A2Zr
B2Hf
C2)
1-d)
xNi
ySn
100-x-y)
1-pA
pExpression, wherein elements A is the element of at least a C of being selected from, N and O, element Ln is at least a element that is selected from Y and rare earth element, 0≤a2≤1,0≤b2≤1,0≤c2≤1, set up with a2+b2+c2=1, set up 0＜d≤0.3, and set up 30≤x≤35 and 30≤y≤35, and 0.05＜p＜0.1 sets up, and p type and n type thermoelectric material at least a comprise have the MgAgAs type crystal structure as principal phase.
12, according to each thermoelectric conversion element of claim 8-12, wherein at least a among Ti, Zr and the Hf partly substituted by at least a element that is selected from V, Nb, Ta, Cr, Mo and W.
13, according to each thermoelectric conversion element of claim 8-12, wherein elements A is partly substituted by at least a element that is selected from Mn, Fe and Cu.
14, according to each thermoelectric conversion element of claim 8-12, wherein element B is partly substituted by at least a element that is selected from Si, Mg, As, Bi, Ge, Pb, Ga and In.
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