CN1569648A - Method for making transition metal tri-antimonide with skutterudite structure - Google Patents
Method for making transition metal tri-antimonide with skutterudite structure Download PDFInfo
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- CN1569648A CN1569648A CN200410018434.0A CN200410018434A CN1569648A CN 1569648 A CN1569648 A CN 1569648A CN 200410018434 A CN200410018434 A CN 200410018434A CN 1569648 A CN1569648 A CN 1569648A
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 28
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 8
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 8
- 238000007789 sealing Methods 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 4
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims description 18
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 230000002829 reductive effect Effects 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical group [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003252 repetitive effect Effects 0.000 claims description 2
- 238000005201 scrubbing Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 2
- 229940038773 trisodium citrate Drugs 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229910052741 iridium Inorganic materials 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910018989 CoSb Inorganic materials 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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- Powder Metallurgy (AREA)
Abstract
The invention discloses a process for preparing skutterudite structure transition metal antimonide through water heating / solvent thermal method which consists of, Co, Ni, Ru, Rh, Os, Ir} and Sb or As into deionized water or organic solvent based on the proportion determined by the chemical composition of the destination product, and charging reducing agent, sealing in high-pressure reaction kettle, reacting 10-100 hours at 100-300 deg. C, cooling down and washing repeatedly, and drying.
Description
Technical field
The present invention relates to the preparation method of semi-conductor thermoelectric material tin white cobalt structural transition metal three stibnides.
Background technology
The performance thermoelectric material of thermoelectric material is that a kind of motion by current carrier (electronics or hole) realizes the semiconductor material that electric energy and heat energy are directly changed mutually.When there was the temperature difference in the thermoelectric material two ends, thermoelectric material can be converted into heat energy electric energy output; Otherwise or when passing to electric current in thermoelectric material, thermoelectric material can be converted into heat energy with electric energy, an end heat release and the other end heat absorption.Thermoelectric material has wide practical use at aspects such as refrigeration or generatings.Can be used as the power supply of deep layer space device, field work, ocean beacon, nomadic crowd use with the power generation assembly of thermoelectric material manufacturing, or be used for industrial exhaust heat, waste-heat power generation.Refrigeration plant volume with the thermoelectric material manufacturing is little, do not need chemical mediator, can be applicable to the aspect such as part cooling, portable medical Ultralow Temperature Freezer of small-sized refrigerator, computer chip and laser detector etc., potential widely Application Areas will comprise: home freezer, refrigerator, automobile-used or household air conditioning device etc.Have no mechanical moving parts, noiseless, nothing wearing and tearing, simple in structure, outstanding advantage such as the volume shape can design on demand with the device of thermoelectric material manufacturing.
" thermoelectric figure of merit " Z characterizes: Z=(α
2σ/κ).Here α is the thermoelectric force coefficient of material, and σ is a specific conductivity, and κ is a thermal conductivity.In thermoelectric material, transition metal three antimonide materials of tin white cobalt structure are subjected to attention especially because of having higher Z value.The chemical constitution formula of tin white cobalt structural transition metal three stibnides is: M
xPn
3In the formula, M is one or more among VIIIB group 4 transition metal element of Fe, Co, Ni, Ru, Rh, Os and the Ir, x represents total atom content, 0.95≤x≤1.05, Pn is one or more among As, Sb, Sn, Pb, Se and the Te, and wherein the content of As and Sb accounts for 90% of these element total contents at least.
Transition metal three thermoelectric antimonide alloy preparation methods about the tin white cobalt structure all adopt the high temperature solid-phase sintering method basically, and this method apparatus expensive, complex process, high to the starting material requirement make preparation cost improve greatly.Therefore, the new cost of exploitation is low, energy consumption is low, the cycle is short, the technology simple and convenient preparation method has become one of focus of Materials science research.
Summary of the invention
The preparation method who the purpose of this invention is to provide transition metal three stibnides of the tin white cobalt structure that a kind of technology is easy, cost is low.
The method for preparing tin white cobalt structural transition metal three stibnides that the present invention proposes, the chemical constitution formula of said transition metal three stibnides is: M
xPn
3, in the formula, M is one or more among VIIIB group 4 transition metal element of Fe, Co, Ni, Ru, Rh, Os and the Ir, x represents total atom content, and 0.95≤x≤1.05, Pn is As or Sb, it is characterized in that the hot method of preparation employing hydrothermal/solvent, may further comprise the steps:
1) simple substance or the compound with VIIIB group 4 transition metal element and Sb or As becomes compound according to the determined ratio thorough mixing of the chemical ingredients of final product, in compound, add deionized water or organic solvent, obtain the mixed solution that concentration is 0.05～0.5mol/L;
2) in above-mentioned mixed solution places the reactor of autoclave, add alkaline conditioner and regulate pH value to 10～13, add reductive agent, the reductive agent mole number: the ratio of compound mole number is 3: 1～5: 1, add organic complexing agent, after the sealing reaction vessel is warming up to 100～300 ℃, reacts 10～100 hours postcooling to room temperature;
3) collect the interior solid reaction product of reactor,, obtain transition metal three stibnides of tin white cobalt structure through deionized water, organic solvent and/or dilute acid soln repetitive scrubbing after drying.
The size of the tin white cobalt structural transition metal three stibnide powder that the present invention makes is in 5～150 nanometer range.By regulating the addition of alkaline conditioner and complexing agent, can controls reaction speed and the particle diameter of resultant.
Above-mentioned steps 1) compound of said VIIIB group 4 transition metal element and Sb or As can be muriate, oxide compound, nitrate, vitriol or carbonate.
Above-mentioned steps 1) said organic solvent can be ethanol, acetone, N, dinethylformamide, pyridine, quadrol, benzene or toluene etc.,
Above-mentioned steps 2) said reductive agent can adopt NaBH in
4, KBH
4Or other alkali-metal hydroborate, also can adopt any pure metal such as Na, K, Ca, Sr or Zn.Said alkaline conditioner can be NaOH, KOH etc.Said complexing agent can be EDTA disodium salt, citric acid, Trisodium Citrate or ethylenediamine tetraacetic acid (EDTA).
Said organic solvent can be ethanol, acetone or tetracol phenixin in the step 3).
It is easy that transition metal three stibnides that the present invention adopts the hot legal system of hydrothermal/solvent to be equipped with the tin white cobalt structure have technology, and cost is low, and synthesis temperature is low, and the cycle is short, and energy consumption is low, and prepared product purity height, granularity are little, and diameter is 5～150 nanometers.
Embodiment
Below in conjunction with example the present invention is done further to state in detail.
Embodiment 1
1) with analytical pure SbCl
3And CoCl
26H
2O, in Sb: be mixed in the dehydrated alcohol after 3: 1 ratio of the Co atomic ratio batching, obtain the mixed solution that concentration is 0.2mol/L, add alkaline conditioner NaOH, regulate pH value to 10, add the EDTA disodium salt, addition is to add 10 grams in every liter of mixed solution.
2) will prepare the reaction vessel (compactedness 85%) that mixed solution places autoclave (WDF-0.25 type), and in solution, add reductive agent NaBH
4, NaBH
4Mole number and SbCl
3And CoCl
26H
2The ratio of O total mole number is 3: 1, then sealing immediately;
3) reaction vessel is heated to 190 ℃ and reacted 72 hours.
4) reaction naturally cools to room temperature after finishing, and collects the Powdered reaction product at the bottom of the still, clean several repeatedly with deionized water, dehydrated alcohol and acetone successively after, powder 110 ℃ of following vacuum-dryings 12 hours, is obtained the CoSb that particle diameter is 20～60 nano-scales
3Powder.
Embodiment 2
1) with analytical pure SbCl
3, CoCl
26H
2O and FeSO47H
2O is in Sb: Co: be mixed in the deionized water after 3: 0.8: 0.2 ratio of the Fe atomic ratio batching, obtain the mixed solution that concentration is 0.4mol/L, add alkaline conditioner KOH, regulate pH value to 11, add the EDTA disodium salt, addition is to add 30 grams in every liter of mixed solution;
2) will prepare the reaction vessel that mixed solution places autoclave, and in solution, add reductive agent KBH
4, KBH
4Mole number and SbCl
3, CoCl
26H
2O and FeSO47H
2The ratio of O total mole number is 3.5: 1, then sealing immediately;
3) reaction vessel is heated to 220 ℃ and reacted 48 hours.
4) reaction naturally cools to room temperature after finishing, and collects the Powdered reaction product at the bottom of the still, clean several repeatedly with deionized water, dehydrated alcohol and acetone successively after, powder 110 ℃ of following vacuum-dryings 12 hours, is obtained the Co that particle diameter is 30～60 nano-scales
0.8Fe
0.2Sb
3Powder.
Embodiment 3
1) with analytical pure SbCl
3, high purity tellurium powder (＞99.99%) and CoCl
26H
2O, in Sb: Te: be mixed in the benzene after 2.9: 0.1: 1 ratio of the Co atomic ratio batching, obtain the mixed solution that concentration is 0.4mol/L, add alkaline conditioner NaOH, regulate pH value to 12, add the EDTA disodium salt, addition is to add 15 in every liter of mixed solution to restrain;
2) will prepare the reaction vessel that mixed solution places autoclave, and in solution, add reductive agent K, K mole number and SbCl
3, high purity tellurium powder and CoCl
26H
2The ratio of O total mole number is 4: 1, then sealing immediately;
3) reaction vessel is heated to 240 ℃ and reacted 24 hours.
4) reaction naturally cools to room temperature after finishing, and collects the Powdered reaction product at the bottom of the still, clean for several times repeatedly with deionized water, dehydrated alcohol and acetone successively after, 110 ℃ of following vacuum-dryings 12 hours, must particle diameter be the CoSb of 20～60 nano-scales with powder
2.8Te
0.2Powder.
(CuK ray, wavelength=0.154056nm) carry out composition analysis and structural analysis to the product of above-mentioned 3 embodiment respectively, show that the product of gained is respectively CoSb to adopt Rigaku-D/MAX-2550PC type X-ray diffractometer
3, Co
0.8Fe
0.2Sb
3And CoSb
2.9Te
0.1Adopt JEM-2010 (HR) type transmission electron microscope to observe the granular size and the microscopic appearance of above-mentioned product respectively, acceleration voltage is 200 KV of boundary.The result shows that the particle size of 3 products is all between 5～150 nanometers.
Claims (6)
1. the preparation method of transition metal three stibnides of tin white cobalt structure, the chemical constitution formula of said transition metal three stibnides is: M
xPn
3, in the formula, M is one or more among VIII B group 4 transition metal element of Fe, Co, Ni, Ru, Rh, Os and the Ir, x represents total atom content, and 0.95≤x≤1.05, Pn is As or Sb, it is characterized in that the hot method of preparation employing hydrothermal/solvent, may further comprise the steps:
1) simple substance or the compound with VIII B group 4 transition metal element and Sb or As becomes compound according to the determined ratio thorough mixing of the chemical ingredients of final product, in compound, add deionized water or organic solvent, obtain the mixed solution that concentration is 0.05～0.5mol/L;
2) in above-mentioned mixed solution places the reactor of autoclave, add alkaline conditioner and regulate pH value to 10～13, add reductive agent, the reductive agent mole number: the ratio of compound mole number is 3: 1～5: 1, add organic complexing agent, after the sealing reaction vessel is warming up to 100～300 ℃, reacts 10～100 hours postcooling to room temperature;
3) collect the interior solid reaction product of reactor,, obtain transition metal three stibnides of tin white cobalt structure through deionized water, organic solvent and/or dilute acid soln repetitive scrubbing after drying.
2. the preparation method of transition metal three stibnides of tin white cobalt structure according to claim 1 is characterized in that the compound of the VIII B group 4 transition metal element described in the step 1) is muriate, oxide compound, nitrate, vitriol or carbonate.
3. the preparation method of transition metal three stibnides of tin white cobalt structure according to claim 1 is characterized in that the organic solvent described in the step 1) is ethanol, acetone, N, dinethylformamide, pyridine, quadrol, benzene or toluene.
4. the preparation method of transition metal three stibnides of tin white cobalt structure according to claim 1 is characterized in that step 2) said reductive agent is NaBH
4, KBH
4Or the hydroborate of other alkali metal, or any pure metal of Na, K, Ca, Sr or Zn.
5. the preparation method of transition metal three stibnides of tin white cobalt structure according to claim 1 is characterized in that step 2) said alkaline conditioner is NaOH, KOH, complexing agent is EDTA disodium salt, citric acid, Trisodium Citrate or ethylenediamine tetraacetic acid (EDTA).
6. the preparation method of transition metal three stibnides of tin white cobalt structure according to claim 1 is characterized in that the said organic solvent of step 3) is ethanol, acetone or tetracol phenixin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410018434.0A CN1240620C (en) | 2004-05-13 | 2004-05-13 | Method for making transition metal tri-antimonide with skutterudite structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410018434.0A CN1240620C (en) | 2004-05-13 | 2004-05-13 | Method for making transition metal tri-antimonide with skutterudite structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1569648A true CN1569648A (en) | 2005-01-26 |
| CN1240620C CN1240620C (en) | 2006-02-08 |
Family
ID=34479498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200410018434.0A Expired - Fee Related CN1240620C (en) | 2004-05-13 | 2004-05-13 | Method for making transition metal tri-antimonide with skutterudite structure |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344546C (en) * | 2005-09-21 | 2007-10-24 | 武汉理工大学 | Skutterudite thermoelectric chemical compound nanopowder cross co-precipitation preparation method |
| CN101921928A (en) * | 2009-05-01 | 2010-12-22 | 通用汽车环球科技运作公司 | Thermoelectric material with filled skutterudite crystal structure |
| US8394284B2 (en) | 2007-06-06 | 2013-03-12 | Toyota Jidosha Kabushiki Kaisha | Thermoelectric converter and method of manufacturing same |
| US8617918B2 (en) | 2007-06-05 | 2013-12-31 | Toyota Jidosha Kabushiki Kaisha | Thermoelectric converter and method thereof |
| US8828277B2 (en) | 2009-06-18 | 2014-09-09 | Toyota Jidosha Kabushiki Kaisha | Nanocomposite thermoelectric conversion material and method of producing the same |
-
2004
- 2004-05-13 CN CN200410018434.0A patent/CN1240620C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344546C (en) * | 2005-09-21 | 2007-10-24 | 武汉理工大学 | Skutterudite thermoelectric chemical compound nanopowder cross co-precipitation preparation method |
| US8617918B2 (en) | 2007-06-05 | 2013-12-31 | Toyota Jidosha Kabushiki Kaisha | Thermoelectric converter and method thereof |
| US8394284B2 (en) | 2007-06-06 | 2013-03-12 | Toyota Jidosha Kabushiki Kaisha | Thermoelectric converter and method of manufacturing same |
| CN101921928A (en) * | 2009-05-01 | 2010-12-22 | 通用汽车环球科技运作公司 | Thermoelectric material with filled skutterudite crystal structure |
| CN101921928B (en) * | 2009-05-01 | 2014-08-13 | 通用汽车环球科技运作公司 | Thermoelectric material with filled skutterudite crystal structure |
| US8828277B2 (en) | 2009-06-18 | 2014-09-09 | Toyota Jidosha Kabushiki Kaisha | Nanocomposite thermoelectric conversion material and method of producing the same |
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| Publication number | Publication date |
|---|---|
| CN1240620C (en) | 2006-02-08 |
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