CN111689531B - Low heat conductivity metallic material and preparation method thereof - Google Patents
Low heat conductivity metallic material and preparation method thereof Download PDFInfo
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- CN111689531B CN111689531B CN202010494124.5A CN202010494124A CN111689531B CN 111689531 B CN111689531 B CN 111689531B CN 202010494124 A CN202010494124 A CN 202010494124A CN 111689531 B CN111689531 B CN 111689531B
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Abstract
The present invention providesA low thermal conductivity metallic material having the formula: bi3Ir3O11. The present invention also provides a method for preparing the low thermal conductivity metallic material of the present invention, which comprises the steps of: (1) adding Bi2O3Ir powder and KClO4Mixing the raw materials in a molar ratio of 1:2:2.5 in a protective gas environment, and fully grinding to obtain a raw material mixture; (2) sealing and wrapping the raw material mixture, and synthesizing; (3) and fully grinding the synthesized sample block, cleaning, removing impurities, and air-drying to obtain the low-heat-conductivity metallic material. At 300K, Bi3Ir3O11Has a thermal conductivity of 0.6Wm‑1K‑1Resistivity of 11.42X 10‑5Omega m. The low-heat-conductivity metallic material provided by the invention has potential application prospects in the fields of battery electrodes, supercapacitors, electrocatalysis, shielding coatings and the like.
Description
Technical Field
The invention belongs to the field of material science. In particular, the invention relates to a low thermal conductivity metallic material and a preparation method thereof.
Background
Thermal conductivity (κ) is a measure of the thermal conductivity of a reactive species, i.e., the amount of heat transferred per unit interface of a body per unit temperature gradient per unit time. Metallic versus insulating, macroscopically reflecting the material's ability to conduct electricity.
In principle, the thermal conductivity of most metallic materials is attributed to the contribution of electrons in metallic compounds based on the Wiedemann-franz (wf) law. Metallic materials generally have a relatively high thermal conductivity due to the high density of heat-carrying electrons. Therefore, intrinsic low thermal conductivity and metallic properties are difficult to coexist in the material.
The traditional metallic low-heat-conductivity material is concentrated on some porous and combined composite materials, and has wide application prospects in the fields of battery electrodes, supercapacitors, electrocatalysis, shielding coatings and the like. In recent decades, researchers developed a series of thermoelectric materials with the characteristics of electronic crystal and phonon glass, and they also focused on finding a material system with the same low thermal conductivity as glass and the same good electrical property as crystal, and opened up a new idea for reducing the intrinsic thermal conductivity and electrical resistivity of the material.
However, the material systems in the prior art are relatively limited and mostly belong to semiconductor alloy systems and solid solutions thereof. Therefore, the search for metallic materials with low thermal conductivity remains a practical challenge.
Disclosure of Invention
In view of the above, the present invention is directed to a new low thermal conductivity metallic material.
The above object of the present invention is achieved by the following means.
In one aspect, the present invention provides a low thermal conductivity metallic material having the following chemical formula: bi3Ir3O11。
Preferably, in the metallic material with low thermal conductivity of the present invention, the space group of the metallic material with low thermal conductivity is Pn-3, and the lattice constant is Pn-3
Preferably, in the low thermal conductivity metallic material according to the present invention, the lattice spacing d value and the crystal plane corresponding to the characteristic peak of XRD of the low thermal conductivity metallic material have the following correspondence:
(111) of noodles
(200) Of noodles
(221) Of noodles
(310) Of noodles
(311) Of noodles
(321) Of noodles
(431) Of noodles
Preferably, in the low thermal conductivity metallic material according to the present invention, the lattice spacing d value and the crystal plane corresponding to the characteristic peak of XRD of the low thermal conductivity metallic material have the following correspondence:
(110) of noodles
(211) Of noodles
(600) Of noodles
(750) Of noodles
Preferably, in the low thermal conductive metallic material of the present invention, the thermal conductivity of the low thermal conductive metallic material is 0.6Wm at 300K-1K-1。
Preferably, in the low thermal conductivity metallic material according to the present invention, the electrical resistivity of the low thermal conductivity metallic material is 11.42 × 10 at 300K-5Ωm。
In another aspect, the present invention provides a method for preparing the low thermal conductivity metallic material of the present invention, which comprises the steps of:
(1) adding Bi2O3Ir powder and KClO4Mixing the raw materials in a molar ratio of 1:2:2.5 in a protective gas environment, and fully grinding to obtain a raw material mixture;
(2) sealing and wrapping the raw material mixture, and synthesizing;
(3) and fully grinding the synthesized sample block, cleaning, removing impurities, and air-drying to obtain the low-heat-conductivity metallic material.
Preferably, in the method of the present invention, the protective gas is one or more of nitrogen, helium and argon.
Preferably, in the method of the present invention, the sealing wrapping is performed by a gold capsule or a platinum capsule; more preferably, the gold or platinum capsule is cylindrical;
preferably, in the method of the present invention, the cylindrical shape has an outer diameter of 2 to 10mm, a length of 2 to 10mm, and a wall thickness of 0.5 to 2 mm.
Preferably, in the method of the present invention, the temperature used for the synthesis in step (2) is 900-1200 ℃, the pressure used for the synthesis is 5-10GPa, and the synthesis is performed for 10-60 min.
Preferably, in the method of the present invention, the synthesis in the step (2) is performed in a cubic press or a type 6-8 secondary pusher press.
The invention has the following beneficial effects:
the invention provides Bi3Ir3O11Is a new low thermal conductivity metallic material with rare low thermal conductivity and good metallic conductivity. At 300K, Bi3Ir3O11Has a thermal conductivity of 0.6Wm-1K-1Resistivity of 11.42X 10-5Omega m. The low-heat-conductivity metallic material provided by the invention has potential application prospects in the fields of battery electrodes, supercapacitors, electrocatalysis, shielding coatings and the like.
Drawings
Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 shows a metallic material Bi having low thermal conductivity according to example 1 of the present invention3Ir3O11X-ray diffraction patterns of (a);
FIG. 2 shows a metallic material Bi having low thermal conductivity according to example 1 of the present invention3Ir3O11Schematic structural diagram of (a);
FIG. 3 shows a metallic material Bi having low thermal conductivity in example 1 of the present invention3Ir3O11X-ray absorption lines of (a);
FIG. 4 shows a metallic material Bi having low thermal conductivity in example 1 of the present invention3Ir3O11A resistivity/conductivity versus temperature curve of (a);
FIG. 5 shows a metallic material Bi having low thermal conductivity in example 1 of the present invention3Ir3O11Curve of thermal conductivity with temperature ofIncluding fitted electron thermal conductivity and lattice thermal conductivity;
FIG. 6 shows a metallic material Bi having low thermal conductivity in example 1 of the present invention3Ir3O11The curve of the seebeck coefficient of (a) with temperature;
FIG. 7 shows a metallic material Bi having low thermal conductivity in example 1 of the present invention3Ir3O11Curve of constant pressure specific heat capacity with temperature.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, which are given for the purpose of illustration only and are not intended to limit the scope of the invention.
Example 1:
adding Bi2O3(purity > 99.9%), Ir powder (purity > 99.9%) and KClO4Mixing according to the stoichiometric ratio of 1:2:2.5, and then fully grinding in a glove box filled with Ar gas; filling the mixture raw materials into a gold capsule and compacting, wherein the diameter of the gold capsule is 4mm, the length of the gold capsule is 5mm, and the wall thickness of the gold capsule is 2 mm; the gold capsule is placed in a cubic apparatus press, the pressure is set to be 6GPa, the temperature is set to be 1000 ℃, and the raw materials in the gold or platinum capsule are reacted for 30 minutes under high temperature and high pressure.
FIG. 1 shows a metallic material Bi having low thermal conductivity prepared in example 13Ir3O11XRD pattern of (a).
FIG. 2 shows a metallic material Bi having low thermal conductivity according to example 1 of the present invention3Ir3O11Schematic structural diagram of (1). FIG. 2 shows Bi3Ir3O11Exhibit KSbO3A type structure belonging to Pn-3 space group and having a lattice parameter of
FIG. 3 shows a metallic material Bi having low thermal conductivity prepared in example 13Ir3O11X-ray absorption spectrum diagram of (a). The characteristic absorption peak of the X-ray absorption spectrum can reflect the valence state of an element, Cd in FIG. 32Ir2O7And Sr2ZnIrO6Are each Ir5+And Ir4+Reference of (B), and Bi3Ir3O11L of Ir of3The absorption peak position is between the two and is close to the theoretical value Ir4.33+。
FIG. 4 shows Bi prepared in example 13Ir3O11Resistivity/conductivity versus temperature curve. As shown in FIG. 4, as the temperature increases, the resistivity of the sample gradually increases and correspondingly the conductivity gradually decreases, and the resistivity at 300K is 11.42X 10-5Omega m. The fitting results in the low temperature range (2-30K) show that Bi3Ir3O11The electron transport of (a) corresponds to the fermi liquid behavior.
FIG. 5 shows Bi prepared in example 13Ir3O11Thermal conductivity versus temperature curve of (a). From 2K to 300K, total thermal conductivity κtotGradually increases to 0.6Wm-1K-1. This value is much smaller than that observed in other metallic materials. From WF law, κele＝LeffAnd T/rho, obtaining an electronic thermal conductivity curve, and obtaining a lattice thermal conductivity variation curve with temperature according to the difference between the total thermal conductivity and the electronic thermal conductivity.
FIG. 6 shows a metallic material Bi having low thermal conductivity prepared in example 13Ir3O11Curve of seebeck coefficient as a function of temperature. As shown in fig. 6, the curve exhibits a broad positive signal over 2-300K, i.e., the entire temperature region measured. Normally the thermoelectromotive force (S) of a metal decreases linearly with decreasing temperature, but Bi3Ir3O11The Seebeck coefficient of the crystal shows a peak value around 60K, and an empirical formula S can be usedmax≈Eg/2eTmaxTo estimate its bandgap EgCalculating to obtain EgIs 4.3X 10-3eV. Such a small band gap value also indicates that the electronic state of the material is a gapless metal state.
FIG. 7 shows Bi prepared in example 13Ir3O11Curve of specific heat at constant pressure with temperature. In FIG. 7, the specific heat increases monotonically with increasing temperature in the range of 2 to 300k, which means that no structure occurs in the material in this temperature rangeAnd long-range magnetic ordering transitions. Considering Bi3Ir3O11Metallic nature and non-magnetic, electron and phonon pairs Bi3Ir3O11All contribute to the specific heat of (c). According to the fitting result of Debye-Einstein model, the Debye temperature is only thetaD65.4K, lower than most transition metal oxides, indicating that some anharmonic atomic vibrational modes are present in the system, greatly reducing the thermal conductivity of the lattice.
The invention provides Bi3Ir3O11Is a low heat conductivity metallic material, and the heat conductivity is 0.6Wm at 300K-1K-1Resistivity of 11.42X 10-5Omega m, has potential application prospect in the fields of battery electrodes, super capacitors, electrocatalysis, shielding coatings and the like.
Example 2:
adding Bi2O3(purity > 99.9%), Ir powder (purity > 99.9%) and KClO4Mixing according to the stoichiometric ratio of 1:2:2.5, and then fully grinding in a glove box filled with Ar gas; filling the mixture raw materials into a platinum capsule and compacting, wherein the diameter of the platinum capsule is 8mm, the length of the platinum capsule is 2mm, and the wall thickness of the platinum capsule is 1 mm; placing the platinum capsule in a 6-8 type secondary pushing press, setting the pressure at 5GPa and the temperature at 1200 ℃, and reacting the raw materials in the platinum capsule for 60 minutes at high temperature and high pressure.
Bi prepared in this example3Ir3O11The structure and performance of (1) were the same as those of example 1.
Example 3:
adding Bi2O3(purity > 99.9%), Ir powder (purity > 99.9%) and KClO4Mixing according to the stoichiometric ratio of 1:2:2.5, and then fully grinding in a glove box filled with Ar gas; filling the mixture raw materials into a platinum capsule and compacting, wherein the diameter of the platinum capsule is 3mm, the length of the platinum capsule is 7mm, and the wall thickness of the platinum capsule is 0.5 mm; placing the platinum capsule in a 6-8 type two-stage pushing press, setting the pressure to be 8GPa and the temperature to be 900 ℃, and reacting the raw materials in the platinum capsule for 20 minutes at high temperature and high pressure.
Bi prepared in this example3Ir3O11The structure and performance of (1) were the same as those of example 1.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A low thermal conductivity metallic material having the formula: bi3Ir3O11；
The space group of the low-heat-conductivity metallic material is Pn-3, and the lattice constant is
2. The low thermal conductivity metallic material according to claim 1, wherein the XRD characteristic peak of the low thermal conductivity metallic material corresponds to a lattice spacing d value and a crystal plane having the following correspondence:
(111) of noodles
(200) Of noodles
(221) Of noodles
(310) Of noodles
(311) Of noodles
(321) Of noodles
(431) Of noodles
3. The low thermal conductivity metallic material according to claim 2, wherein the XRD characteristic peak of the low thermal conductivity metallic material corresponds to a lattice spacing d value and a crystal plane having the following correspondence:
(110) of noodles
(211) Of noodles
(600) Of noodles
(750) Of noodles
4. The low thermal conductive metallic material according to claim 1, wherein the thermal conductivity of the low thermal conductive metallic material is 0.6Wm at 300K-1K-1。
5. The low thermal conductivity metallic material according to claim 1, wherein the electrical resistivity of the low thermal conductivity metallic material is 11.42 x 10 at 300K-5Ωm。
6. A method of producing the low thermal conductivity metallic material according to any one of claims 1 to 5, comprising the steps of:
(1) adding Bi2O3Ir powder and KClO4Mixing the raw materials in a molar ratio of 1:2:2.5 in a protective gas environment, and fully grinding to obtain a raw material mixture;
(2) sealing and wrapping the raw material mixture, and synthesizing;
(3) fully grinding the synthesized sample block, cleaning, removing impurities, and air-drying to obtain a low-heat-conductivity metallic material;
wherein the sealing and wrapping are performed by gold capsules or platinum capsules;
the temperature used for synthesis in the step (2) is 900-1200 ℃, the pressure used for synthesis is 5-10GPa, and the synthesis is carried out for 10-60 min.
7. The method of claim 6, wherein the protective gas is one or more of nitrogen, helium, and argon.
8. The method of claim 6, wherein the gold or platinum capsule is cylindrical.
9. The method of claim 8, wherein the cylindrical shape has an outer diameter of 2-10mm, a length of 2-10mm, and a wall thickness of 0.5-2 mm.
10. The method of claim 6, wherein the synthesizing in step (2) is performed in a cubic press or a type 6-8 secondary pusher press.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1841796A (en) * | 2005-03-30 | 2006-10-04 | 三星电机株式会社 | Group iii-nitride light emitting device |
| CN103430366A (en) * | 2010-12-16 | 2013-12-04 | 庄信万丰燃料电池有限公司 | Catalyst layer |
| CN109453771A (en) * | 2018-11-13 | 2019-03-12 | 中国科学技术大学先进技术研究院 | The preparation of a kind of pyrochlore materials and its application in electro-catalysis production oxygen |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1841796A (en) * | 2005-03-30 | 2006-10-04 | 三星电机株式会社 | Group iii-nitride light emitting device |
| CN103430366A (en) * | 2010-12-16 | 2013-12-04 | 庄信万丰燃料电池有限公司 | Catalyst layer |
| EP2652821B1 (en) * | 2010-12-16 | 2020-07-08 | Johnson Matthey Fuel Cells Limited | Catalyst layer |
| CN109453771A (en) * | 2018-11-13 | 2019-03-12 | 中国科学技术大学先进技术研究院 | The preparation of a kind of pyrochlore materials and its application in electro-catalysis production oxygen |
Non-Patent Citations (1)
| Title |
|---|
| Transport, thermal and magnetic properties of Bi3Os3O11 and Bi3Ru3O11;T.Fujita.et al;《Physica B: Condensed Matter》;20050208;第328-333卷(第二期);全文 * |
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