CN101523627A - Thermoelectric material, method for producing the same, and thermoelectric converter - Google Patents
Thermoelectric material, method for producing the same, and thermoelectric converter Download PDFInfo
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- CN101523627A CN101523627A CNA2007800383416A CN200780038341A CN101523627A CN 101523627 A CN101523627 A CN 101523627A CN A2007800383416 A CNA2007800383416 A CN A2007800383416A CN 200780038341 A CN200780038341 A CN 200780038341A CN 101523627 A CN101523627 A CN 101523627A
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- 239000000463 material Substances 0.000 title claims abstract description 100
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 3
- 238000005245 sintering Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 239000002994 raw material Substances 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000007493 shaping process Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 description 28
- 239000000203 mixture Substances 0.000 description 23
- 239000010955 niobium Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 15
- 230000000977 initiatory effect Effects 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 229910000484 niobium oxide Inorganic materials 0.000 description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002109 crystal growth method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000002706 hydrostatic effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000007115 recruitment Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 description 2
- 230000005619 thermoelectricity Effects 0.000 description 2
- 241000353097 Molva molva Species 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- 229910010271 silicon carbide Inorganic materials 0.000 description 1
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- -1 sintered body Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical group [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Abstract
The present invention provides a thermoelectric material useful for a thermoelectric converter having excellent energy conversion efficiency, and a method for producing the thermoelectric material. The thermoelectric material comprising an oxide containing Ti, M, and 0 and the oxide is represented by Formula (1). Ti 1-x M x O y (1) M represents at least one selected from the group consisting of V,Nb, and Ta, x is not less than 0.05 and not more than 0.5, and y is not less than 1.90 and not more than 2.02.
Description
Technical field
The present invention relates to thermo-electric converting material, its manufacture method and thermoelectric conversion element.
Background technology
So-called thermoelectric conversion power generation is meant, utilizes the phenomenon that produces voltage (thermo-electromotive force) when giving temperature difference on thermo-electric converting material (, Seebeck effect), is the generating that electric energy carries out with thermal power transfer.In thermoelectric conversion power generation, the various waste heats such as heat that can utilize underground heat or incinerator are as thermal source, but are therefore expected by people as the generating of the environment amity of practicability.
The energy conversion efficiency of thermo-electric converting material depends on the performance index (Z) of thermo-electric converting material.Performance index (Z) is to use Seebeck coefficient (α), conductivity (σ) and the thermal conductivity (κ) of this material, the value of utilizing following formula (1) to obtain, and the thermo-electric converting material that performance index is big more then can become the thermoelectric conversion element of energy conversion efficiency excellence more.
Z＝α
2×σ/K (1)
Especially, the α in the formula (1)
2* σ is called as the output factor, and this exports the big more thermo-electric converting material of the factor, then can become the thermoelectric conversion element of the output excellence of per unit temperature more.
In thermo-electric converting material, have Seebeck coefficient be on the occasion of p type thermo-electric converting material and the Seebeck coefficient n type thermo-electric converting material that is negative value.Usually, in thermoelectric conversion power generation, use the thermoelectric conversion element that p type thermo-electric converting material and n type thermo-electric converting material electricity are connected in series.Therefore, the energy conversion efficiency of thermoelectric conversion element depends on the performance index of p type thermo-electric converting material and n type thermo-electric converting material.In order to obtain the thermoelectric conversion element of energy conversion efficiency excellence, need high p type thermo-electric converting material of performance index and n type thermo-electric converting material.
As n type thermo-electric converting material, known titanium oxide and tantalum oxide (perhaps titanium oxide and niobium oxide) mixed, be shaped, and in air sintering and the thermo-electric converting material (TOHKEMY 2005-276959 communique) that obtains.
But, the output factor deficiency of the n type thermo-electric converting material of communique record.
Summary of the invention
The object of the present invention is to provide performance index and high n type thermo-electric converting material, its manufacture method and the thermoelectric conversion element of the output factor.
The inventor has carried out various researchs, and the result has finished the present invention.
That is, the invention provides following＜1 〉～＜8.
＜1〉thermo-electric converting material, this material contains: contain the oxide of Ti, M and O, wherein, oxide is by formula (1) expression,
Ti
1-xM
xO
y (1)
M is selected from least a among V, Nb and the Ta;
X is more than 0.05 below 0.5;
Y is more than 1.90 below 2.02.
＜2〉above-mentioned＜1〉record thermo-electric converting material, wherein, oxide has the rutile-type crystal structure.
＜3〉above-mentioned＜2〉thermo-electric converting material of record, wherein, the lattice constant of oxide a axle is below the above 0.4730nm of 0.4590nm, the lattice constant of oxide c axle is more than the 0.2950nm below 0.3000.
＜4〉above-mentioned＜1 〉～＜3 in the thermo-electric converting material of each record, wherein, M is Nb.
＜5〉above-mentioned＜1 〉～＜4 in the thermo-electric converting material of each record, wherein, thermo-electric converting material is a sintered body, and the relative density of sintered body is more than 60%.
＜6〉above-mentioned＜5〉record thermo-electric converting material, wherein, thermo-electric converting material is coated with not oxygen permeation membrane in its surperficial at least a portion.
＜7〉thermoelectric conversion element, it has above-mentioned＜1 〉～＜6 in the thermo-electric converting material of each record.
＜8〉manufacture method of thermo-electric converting material, it contains operation (a) and (b),
(a) preparation raw material for sintering, this raw material contains Ti, M (M be selected among V, Nb and the Ta at least a) and O, and with respect to the total amount (mole) of Ti and M, and the amount of M (mole) is more than 0.05 below 0.5; With respect to the total amount (mole) of Ti and M, the amount of O (mole) is more than 1.90 below 2.02.
(b) shaping raw material for sintering, and under the atmosphere of inert gases below 1700 ℃ more than 900 ℃, carry out sintering.
Description of drawings
Fig. 1 represents the X-ray diffractogram of sintered body 1-7.
Fig. 2 represents the lattice constant (a axle, c axle) of the thermo-electric converting material of sintered body 1-13 and the relation of mol ratio x.
Fig. 3 represents the temperature dependency of the Seebeck coefficient in the sintered body 1,3,10.
Fig. 4 represents the temperature dependency of the conductivity in the sintered body 1,3,10.
Fig. 5 represents the temperature dependency of the thermal conductivity in the sintered body 1,3,10.
Fig. 6 represents the temperature dependency of the output factor in the sintered body 1,3,10.
Fig. 7 represents the temperature dependency of the zero dimension performance index in the sintered body 1,3,10.
Embodiment
Thermo-electric converting material
Thermo-electric converting material of the present invention contains the oxide of titaniferous (Ti), M and oxygen (O).M is vanadium (V), niobium (Nb), tantalum (Ta).They can be used alone or in combination.
Oxide is represented by above-mentioned formula (1).In the formula (1), x is more than 0.05 below 0.5.Consider that from the viewpoint that increases the output factor x is preferably more than 0.05 below 0.20.If x less than 0.05, then conductivity has the trend that diminishes, and can not obtain enough output factor values.In addition, if x surpasses 0.5, then Seebeck coefficient has the trend that diminishes.
Y is more than 1.90 below 2.02.Consider that from the viewpoint that increases the output factor y is preferably more than 1.93 below 2.01.If y less than 1.90 then generates impurity crystalline phase Ti
nO
2n-1, Seebeck coefficient has the trend that diminishes, and can not obtain enough output factor values.If y surpasses 2.02, then generate the impurity crystalline phase and (for example, when M is Nb, generate TiNb
2O
5, Nb
2O
5Deng), conductivity has the trend that diminishes, and can not obtain enough output factor values.
Consider that from the viewpoint of the further raising output factor more preferably: when y is more than 1.99 2.01 when following, x is more than 0.10 below 0.15; When y is more than 1.96 and during less than 1.99, x is more than 0.15 below 0.20.
The crystal structure of oxide is rutile-type, Detitanium-ore-type, brookite type, is preferably rutile-type.If oxide is the rutile-type crystal structure,, also can provide the thermoelectric conversion element that energy conversion efficiency is good, be difficult to produce the deterioration that is caused by long-term use even when then at high temperature using.
When oxide had the rutile-type crystal structure, the lattice constant of a axle was below the above 0.4730nm of 0.4590nm, was preferably below the above 0.4660nm of 0.4600nm; The lattice constant of c axle is below the above 0.3000nm of 0.2950nm, is preferably below the above 0.2990nm of 0.2960nm.When the lattice constant of a of oxide axle and c axle was in above-mentioned scope, the output factor of thermo-electric converting material became bigger.Lattice constant can be calculated by following method: in the X-ray diffractogram that utilizes X-ray diffraction to obtain, the peak that identification is produced by the rutile-type crystal structure, utilize least square method and calculate lattice constant by the value of this peak position (2 θ) (for example, with reference to " crystallization is resolved " universal program system (II) " Japanese crystallography and can be compiled: the quick hero of Sakurai (1967)).
Consider that from the viewpoint that increases the output factor M preferably contains Nb, more preferably only contains Nb.
The form of thermo-electric converting material is powder, sintered body, film for example, is preferably sintered body.When thermo-electric converting material is sintered body,, for example be plate, cylinder, disk, prism as long as it is shaped as the suitable shape as thermoelectric conversion element.
Consider the thermo-electric converting material that the thermo-electric converting material preferred orientation is high from the viewpoint that increases conductivity.The form that orientation is high for example is orientation sintered body, monocrystal etc.
Above-mentioned thermo-electric converting material is the n type, is the high thermo-electric converting material of the output factor, by making up with p type thermo-electric converting material, can provide performance index high thermoelectric conversion element.
The manufacture method of thermo-electric converting material
Thermo-electric converting material for example can be by forming raw material (this raw material forms thermo-electric converting material by sintering), and the method for carrying out sintering is made.For example, can make by containing above-mentioned operation (a) and method (b).
In the operation (a), can weighing contain the material of Ti and contain the material of M and mix, forming the composition of regulation, thereby make the raw material that is used for subsequent processing (b).(x is more than 0.05 below 0.5 at the thermo-electric converting material of the above-mentioned formula of preparation (1) expression; Y is more than 1.90, preferred more than 1.93, and be below 2.02, preferred below 2.01) time, can weighing and mix material that contains Ti and the material that contains M, make and satisfy Ti: M=0.95～0.5: 0.05～0.5.In addition, (x is more than 0.05 below 0.2 at the thermo-electric converting material of the above-mentioned formula of preparation (1) expression; Y is more than 1.90, preferred more than 1.93, and be below 2.02, preferred below 2.01) time, can weighing and mix material that contains Ti and the material that contains M, make and satisfy Ti: M=0.95～0.8: 0.05～0.2.For example, contain formula Ti in preparation
0.85Nb
0.15O
2.00During the thermo-electric converting material of oxide of expression, can weighing and mix TiO
2, Ti, Nb
2O
5, make Ti: Nb: the mol ratio of O is 0.85: 0.15: 2.00.
The material that contains Ti for example is: TiO
2, Ti
2O
3, TiO and so on titanium oxide and Ti.The material of titaniferous is generally the combination of at least two kinds of these materials, preferred TiO
2Combination with Ti.
The material that contains M for example is: Nb
2O
5And so on niobium oxide; Ta
2O
5And so on tantalum pentoxide; V
2O
5And so on barium oxide; And Nb, Ta, V.The material that contains M is generally at least a of these materials, is preferably oxide.
Can adopt any mode in dry type, the wet type to mix.Mixing for example can be used, and ball mill, V-Mixer, vibrating mill, pulverizing mill, refiner (dyno mill), electronic grinding machine (dynamic mill) etc. carry out.The mixture of gained can be shaped.
In addition, mixture can be calcined.For example, in mixture, with respect to the weight (mole) of Ti and M, the amount of O (mole) surpasses at 2.02 o'clock, mixture calcine under the reducibility gas atmosphere and is regulated mol ratio, can be used as the raw material use.On the other hand, when amount (mole) less than 1.90 of O, mixture is calcined under the oxidizing gas atmosphere and regulated mol ratio, can be used as raw material and use.In addition, the amount of O (mole) is that the mixture below 2.02 is then calcined under atmosphere of inert gases more than 1.90, can be suppressed at the distortion of sintered body in the aftermentioned sintering.When calcining under atmosphere of inert gases, calcination condition is relevant with the composition of mixture, and calcination time for example is 0.5～24 hour.Mixture after the calcining can be pulverized.Pulverizing for example can utilize, and ball mill, vibrating mill, pulverizing mill, refiner, electronic grinding machine etc. carry out.
In the operation (b), as mentioned above, raw material is formed and sintering.
Be shaped for example can suppress by single shaft, calm hydraulic pressure compacting (CIP ， Leng Inter hydrostatic pressing プ レ ス), mechanical compaction, hot pressing, high temperature insostatic pressing (HIP) compacting プ レ ス such as () HIP ， Hot Inter carry out.Can suitably select corresponding to the shape of thermoelectric conversion element to be shaped.Shape for example is plate, cylinder, disk, prism.Can in raw material, add adhesive, dispersant, release agent etc. in the shaping.
Under inert atmosphere, carry out sintering.The for example nitrogenous gas of inert gas, contain the gas of rare gas, preferably contain the gas of rare gas, more preferably only contain rare gas.Consider the preferred argon gas of rare gas (Ar) from the viewpoint of operability.Sintering temperature is more than 900 ℃ below 1700 ℃, is preferably more than 1200 ℃ below 1500 ℃, more preferably more than 1250 ℃ below 1450 ℃.If 900 ℃ of sintering temperature less thaies then can not fully be carried out solid phase reaction and sintering, conductivity is reduced according to composition.If sintering temperature surpasses 1700 ℃, then according to composition, because the stripping of component or volatilization and can not obtain the target oxide, the performance index of thermo-electric converting material reduces.Sintering time was generally about 0.5～24 hour.
In the operation (b), can carry out the shaping and the sintering of raw material simultaneously.At this moment, can use hot-press arrangement, high temperature insostatic pressing (HIP) compacting (HIP) device as device.
The sintered density of gained sintered body is generally more than 60%, considers from the viewpoint of the intensity that improves sintered body, is preferably more than 80%, more preferably more than 85%.The conductivity of thermo-electric converting material that contains this high-density sintered body is big.The density of sintered body can be controlled by for example raw material particle size, forming pressure, sintering temperature, sintering time.
Can pulverize sintered body as required, the pulverizing product to gained carry out sintering more under these conditions.In addition, the surface of sintered body can apply not oxygen permeation membrane.Oxygen permeation membrane does not for example comprise: aluminium oxide, titanium oxide, zirconia, silicon dioxide, carborundum so long as oxygen can't see through or the film that is difficult to see through gets final product.Coating can adopt aerosol deposition, thermal spraying, chemical vapor deposition (CVD) etc. to carry out.Contain the thermo-electric converting material of the sintered body of this coating, even under the situation about using, still can suppress surface oxidation in oxidizing atmosphere, performance is difficult for reducing.
Thermo-electric converting material, except said method, can also adopt following method manufacturing: contain the method for co-precipitation operation, moisture thermal technology's preface method, contain method, the method that contains sputtering process, the method that contains the operation of utilizing CVD, the method that contains the sol-gel operation, the method that contains FZ (floating zone method) operation that parch (drying-up) operation, contain the method for utilizing TSCG (stencil-type crystal growth method, template-type single crystal growth method) operation.
Thermoelectric conversion element
Thermoelectric conversion element of the present invention has aforesaid n type thermo-electric converting material, has n type thermo-electric converting material, p type thermo-electric converting material, n electrode and p electrode usually.P type thermo-electric converting material for example is NaCo
2O
4, Ca
3Co
4O
9(Japanese kokai publication hei 9-321346 communique, TOHKEMY 2001-64021 communique).P type thermo-electric converting material can use commercially available product.Thermoelectric conversion element can be with known method manufacturing (for example Japanese kokai publication hei 5-315657 communique).
Embodiment
Illustrate in greater detail the present invention by embodiment.Each rerum natura of thermo-electric converting material adopts following method to measure.
1. conductivity (σ)
The sintered body test portion is processed into prism-shaped,, measures by the direct current four-terminal method with the fixing platinum line of silver paste.In nitrogen current, in the scope of room temperature～500 ℃, measure while change temperature.
2. Seebeck coefficient (α)
When being processed on the two ends of the sintered body test portion of same shape with conductance measurement, with silver paste fixedly R thermoelectricity to the platinum line, measure the temperature and the thermo-electromotive force of sintered body test portion.In nitrogen current, in the scope of room temperature～500 ℃, measure while change temperature.Cool off with the single face of cooling water pipe, make low-temp. portion, to measuring the temperature at sintered body test portion two ends, measure the thermo-electromotive force (Δ V) that produces between the both ends of the surface of sintered body test portion simultaneously with R thermoelectricity to the sintered body test portion.The temperature difference at sintered body test portion two ends (Δ T) is controlled in 0.5～10 ℃ the scope, calculates Seebeck coefficient (α) by the slope of Δ T and Δ V.
3. thermal conductivity (κ)
While adopt laser flash method under vacuum, in the scope of room temperature～500 ℃, to change specific heat and the thermal diffusivity that temperature is measured the sintered body test portion.Adopt vacuum science and engineering Co., Ltd. system laser flash method measuring thermal conductivity device TC-7000 type to measure.
4. structure and composition analysis
Adopt the Rigaku of Co., Ltd. system X-ray diffraction determinator RINT2500TTR type, utilizing with CuK α is the crystal structure of radiogenic powder X-ray diffractometry analysed for powder test portion, sintered body test portion.The lattice constant of the rutile-type crystal structure of test portion (a axle, c axle) is calculated by following mode: use the X-ray diffraction figure that obtains by X-ray diffraction, identification utilizes least square method to calculate by the peak that the rutile-type crystal structure produces by the value of this peak position (2 θ).For the composition of the metallic element of test portion, use Philips corporate system fluorescent X-ray device PW1480 to measure.In addition, calculated by following mode for O amount contained in the test portion: (when using Ta in the initiation material is 1000 ℃ with the temperature of test portion in atmosphere, more than 1000 ℃ below 1200 ℃; When using Nb in the initiation material is 1200 ℃) under, implement heat treatment 48 hours, weight recruitment at this moment is all as the recruitment of O.
5. the density of sintered body
Measure the real density of sintered body test portion with Archimedes's method.The data of the lattice constant that obtains based on real density with by powder X-ray diffractometry are calculated relative density.
[preparation of raw material for sintering]
As initiation material, use titanium oxide (TiO
2, the former テ Network of stone ノ Co., Ltd. system, PT-401M (trade (brand) name)), Titanium (Ti, high-purity chemical) and niobium oxide (Nb
2O
5, high-purity chemical).As shown in table 1, these raw materials of weighing make them satisfy TiO
2: Ti: Nb
2O
5=0.9375: 0.0025: 0.0250, utilize dry ball (medium: plastics system ball) mixed 6 hours, obtain Ti: Nb: O=0.95: 0.05: 2.00 mixture.
[shaping, sintering]
By single shaft compacting (forming pressure: 200kg/cm
2) mixture is formed, with the discoid formed body of gained 99.9995%), 1000 ℃ of calcinings 3 hours down in argon gas atmosphere (Ar purity:.(medium: zirconia system ball) the calcining product to gained carry out the dry type pulverizing to utilize ball mill.By single shaft compacting (forming pressure: 200kg/cm
2), further hydrostatic pressing compacting (forming pressure: 1500kg/cm
2) the pulverizing product of gained are formed, 99.9995%), 1300 ℃ of following sintering 12 hours the discoid formed body that obtains is put into sintering furnace, in argon gas atmosphere (Ar purity:, obtain sintered body 1.
For sintered body 1 (thermo-electric converting material), the Seebeck coefficient (α) under measuring 500 ℃, conductivity (σ), thermal conductivity (κ), the output factor (α
2* σ), zero dimension performance index (ZT), its result is as shown in table 3.The zero dimension performance index is performance index (Z, a unit K
-1) multiply by the value that absolute temperature (T, unit K) obtains.
Embodiment 2～13
(embodiment 2～13 corresponds respectively to the making example of sintered body 2～13)
Initiation material and consumption thereof are as shown in table 1 in the sintered body 2～13.Except the use amount that changes initiation material, with the preparation of embodiment 1[raw material for sintering] and [shaping, sintering] carry out same operation, obtain sintered body 2～13.Sintered body 2～13 is the rutile-type crystal structure.Each rerum natura of sintered body 2～13 is shown in table 2, table 3.
The use amount of table 1 initiation material
Each rerum natura of table 2 sintered body
The pyroelecthc properties of table 3 sintered body
| Sintered body | Seebeck coefficient α (μ V/K) | Conductivity (S/m) | Thermal conductivity K (W/mK) | The output factor-alpha 2σ(W/mK 2) | Zero dimension performance index ZT (-) |
| Sintered body 1 | -290 | 4.09×10 3 | 3.10 | 3.43×10 -4 | 0.086 |
| Sintered body 2 | -236 | 7.65×10 3 | 3.30 | 4.26×10 -4 | 0.097 |
| Sintered body 3 | -196 | 1.12×10 4 | 3.05 | 4.30×10 -4 | 0.109 |
| Sintered body 4 | -200 | 5.43×10 3 | 2.59 | 2.17×10 -4 | 0.065 |
| Sintered body 5 | -165 | 5.29×10 3 | 1.96 | 1.44×10 -4 | 0.057 |
| Sintered body 6 | -143 | 6.15×10 3 | 1.81 | 1.26×10 -4 | 0.054 |
| Sintered body 7 | -139 | 8.36×10 3 | 1.98 | 1.62×10 -4 | 0.063 |
| Sintered body 8 | -212 | 9.04×10 3 | 3.49 | 4.07×10- 4 | 0.090 |
| Sintered body 9 | -152 | 1.43×10 4 | 3.59 | 3.31×10 -4 | 0.071 |
| Sintered body 10 | -170 | 1.89×10 4 | 3.24 | 5.47×10 -4 | 0.131 |
| Sintered body 11 | -152 | 2.17×10 4 | 3.19 | 5.04×10 -4 | 0.122 |
| Sintered body 12 | -120 | 1.80×10 4 | 2.35 | 2.60×10 -4 | 0.085 |
| Sintered body 13 | -116 | 1.61×10 4 | 2.09 | 2.18×10 -4 | 0.081 |
Embodiment 14
As initiation material, use titanium oxide (TiO
2, the former テ Network of stone ノ Co., Ltd. system, PT-401M (trade (brand) name)), Titanium (Ti, high-purity chemical) and tantalum oxide (Ta
2O
5, high-purity chemical).As shown in table 4, these raw materials of weighing make them satisfy TiO
2: Ti: Ta
2O
5=0.9375: 0.0025: 0.025, utilize dry ball (medium: plastics system ball) mixed 6 hours, obtain Ti: Ta: O=0.95: 0.05: 2.00 mixture.
For mixture, carry out [be shaped, sintering] the same operation with embodiment 1, obtain sintered body 14.Sintered body 14 has the rutile-type crystal structure.Each rerum natura of sintered body 14 is shown in table 5, table 6.
Embodiment 15,16
(embodiment 15,16 corresponds respectively to the making example of sintered body 15,16)
Initiation material and consumption thereof are as shown in table 4 in the sintered body 15,16.Except the use amount that changes initiation material, carry out same operation with embodiment 14, obtain sintered body 15,16.Sintered body 15,16 is the rutile-type crystal structure.Each rerum natura of sintered body 15,16 is shown in table 5, table 6.
The use amount of table 4 initiation material
Each rerum natura of table 5 sintered body
The pyroelecthc properties of table 6 sintered body
| Sintered body | Seebeck coefficient α (μ V/K) | Conductivity (S/m) | Thermal conductivity K (W/mK) | The output factor-alpha 2σ(W/mK 2) | Zero dimension performance index ZT (-) |
| Sintered body 14 | -323 | 2.18×10 3 | 3.37 | 2.28×10 -4 | 0.052 |
| Sintered body 15 | -228 | 3.68×10 3 | 2.56 | 1.92×10 -4 | 0.058 |
| Sintered body 16 | -158 | 8.84×10 3 | 3.15 | 2.21×10 -4 | 0，054 |
30
Comparative example 1～3
(comparative example 1～3 corresponds respectively to the making example of sintered body 17～19)
Initiation material and consumption thereof are as shown in table 7 in the sintered body 17～19.Except the use amount that changes initiation material, carry out same operation with embodiment 1 [preparation of raw material for sintering] and [shaping, sintering], obtain sintered body 17～19.Sintered body 17～19 all has TiO
2Rutile-type crystal structure and TiNb
2O
7The two-phase of different crystal structure, the real density of sintered body is lower.Each rerum natura of sintered body 17～19 is shown in table 8, table 9.
The use amount of table 7 initiation material
Each rerum natura of table 8 sintered body
The pyroelecthc properties of table 9 sintered body
| Sintered body | Seebeck coefficient α (μ V/K) | Conductivity (S/m) | Thermal conductivity (W/mK) | The output factor-alpha 2σ(W/mK 2) | Zero dimension performance index ZT (-) |
| Sintered body 17 | -288 | 1.11×10 3 | 1.52 | 9.21×10 -5 | 0.047 |
| Sintered body 18 | -500 | 3.78×10 2 | 1.97 | 9.44×10 -5 | 0.037 |
| Sintered body 19 | -349 | 1.82×10 2 | 2.18 | 2.22×10 -5 | 0.008 |
Industrial usability
N-shaped thermo-electric converting material of the present invention, performance index and the output factor are high, and energy conversion efficiency is high, is applicable to the large thermoelectric conversion element of output of per unit temperature.
Claims (8)
1. thermo-electric converting material, it contains the oxide of Ti, M and O, and wherein, oxide is by formula (1) expression,
Ti
1-xM
xO
y (1)
M is selected from least a among V, Nb and the Ta;
X is more than 0.05 below 0.5;
Y is more than 1.90 below 2.02.
2. the described thermo-electric converting material of claim 1, wherein, oxide has the rutile-type crystal structure.
3. the described thermo-electric converting material of claim 2, wherein, the lattice constant of oxide a axle is below the above 0.4730nm of 0.4590nm, the lattice constant of oxide c axle is below the above 0.3000nm of 0.2950nm.
4. each described thermo-electric converting material in the claim 1～3, wherein, M is Nb.
5. each described thermo-electric converting material in the claim 1～4, wherein, thermo-electric converting material is a sintered body, and the relative density of sintered body is more than 60%.
6. the described thermo-electric converting material of claim 5, wherein, thermo-electric converting material is coated with not oxygen permeation membrane in its surperficial at least a portion.
7. thermoelectric conversion element, it has each described thermo-electric converting material in the claim 1～6.
8. the manufacture method of thermo-electric converting material, it contains operation (a) and (b),
(a) preparation raw material for sintering, this raw material contains Ti, M and O, and wherein M is selected from least a among V, Nb and the Ta, and in mole, and with respect to the total amount of Ti and M, the amount of M is more than 0.05 below 0.5; In mole, with respect to the total amount of Ti and M, the amount of O is more than 1.90 below 2.02;
(b) shaping raw material for sintering, and under the atmosphere of inert gases below 1700 ℃ more than 900 ℃, carry out sintering.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006227483 | 2006-08-24 | ||
| JP227483/2006 | 2006-08-24 | ||
| JP104644/2007 | 2007-04-12 |
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| Publication Number | Publication Date |
|---|---|
| CN101523627A true CN101523627A (en) | 2009-09-02 |
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ID=41082516
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557448A (en) * | 2010-12-24 | 2012-07-11 | 株式会社日立制作所 | Thermoelectric conversion material |
| CN110078122A (en) * | 2019-05-27 | 2019-08-02 | 九江有色金属冶炼有限公司 | A kind of preparation method of p-type high purity niobium oxide |
| CN111185602A (en) * | 2020-01-14 | 2020-05-22 | 湖北若林电器科技有限公司 | Preparation process of thermoelectric conversion material with atomization effect for 3D flame electric fireplace |
| CN111819704A (en) * | 2018-07-23 | 2020-10-23 | 松下知识产权经营株式会社 | Thermoelectric conversion material and method for obtaining electric power using thermoelectric conversion material |
-
2007
- 2007-08-13 CN CNA2007800383416A patent/CN101523627A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557448A (en) * | 2010-12-24 | 2012-07-11 | 株式会社日立制作所 | Thermoelectric conversion material |
| CN111819704A (en) * | 2018-07-23 | 2020-10-23 | 松下知识产权经营株式会社 | Thermoelectric conversion material and method for obtaining electric power using thermoelectric conversion material |
| CN110078122A (en) * | 2019-05-27 | 2019-08-02 | 九江有色金属冶炼有限公司 | A kind of preparation method of p-type high purity niobium oxide |
| CN111185602A (en) * | 2020-01-14 | 2020-05-22 | 湖北若林电器科技有限公司 | Preparation process of thermoelectric conversion material with atomization effect for 3D flame electric fireplace |
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