CN116288700A - Ca with high density and high preferred orientation 3 Co 4 O 9 Preparation method of base polycrystalline thermoelectric material - Google Patents
Ca with high density and high preferred orientation 3 Co 4 O 9 Preparation method of base polycrystalline thermoelectric material Download PDFInfo
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- CN116288700A CN116288700A CN202310127650.1A CN202310127650A CN116288700A CN 116288700 A CN116288700 A CN 116288700A CN 202310127650 A CN202310127650 A CN 202310127650A CN 116288700 A CN116288700 A CN 116288700A
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- 239000000463 material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011575 calcium Substances 0.000 claims abstract description 42
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- OGJLPLDTKZHLLH-UHFFFAOYSA-N [Ca].[Co] Chemical compound [Ca].[Co] OGJLPLDTKZHLLH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005303 weighing Methods 0.000 claims abstract description 3
- 238000005245 sintering Methods 0.000 claims description 24
- 238000000227 grinding Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000003746 solid phase reaction Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 10
- 239000004570 mortar (masonry) Substances 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000009827 uniform distribution Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000003825 pressing Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 230000005678 Seebeck effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/02—Production of homogeneous polycrystalline material with defined structure directly from the solid state
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Abstract
The invention discloses Ca with high density and high preferred orientation 3 Co 4 O 9 A preparation method of a base polycrystalline thermoelectric material belongs to the field of calcium cobalt-based oxide thermoelectric materials. The method of the invention is characterized in that Ca 3 Co 4 O 9 Wherein Sr element is doped in the formula Ca 3‑x Sr x Co 4 O 9 Wherein x=0.05 to 0.2; the method of the invention comprises the following steps: (1) CaCO as a powder raw material 3 (99.9％)、SrCO 3 (99.9％)、Co 3 O 4 (99.9%) in a mortar after mixing in stoichiometric proportions; (2) Mixing the above mixed powderTabletting after weighing; (3) The block sample is sintered at high temperature to obtain Ca with high density and high preferred orientation 3 Co 4 O 9 A polycrystalline thermoelectric material. The invention has low cost, simple process, less environmental pollution, high density of the obtained sample, high preferred orientation, small particle size and uniform distribution.
Description
Technical Field
The invention relates to Ca with high density and high preferred orientation 3 Co 4 O 9 Method for preparing base polycrystal thermoelectric material, belonging to calcium cobalt base oxideThe field of thermoelectric materials.
Background
In recent years, with the increase of air pollution and environmental destruction, the awareness of energy utilization efficiency is improved, and the role played by thermoelectric materials is increasing. Thermoelectric materials, also called thermoelectric materials, can convert temperature gradients into electrical energy through the seebeck effect, and the interior of the thermoelectric materials realizes thermoelectric conversion through carrier movement, and the important characteristic can be used for waste heat recovery or solar thermoelectric power generation, and can also be used as heating/refrigerating equipment. The preparation method of the thermoelectric material at the present stage is mainly a sol-gel method, the raw material cost is high, nitrogen oxides exist in the product, the environment is polluted to a certain extent, and the prepared product is difficult to realize the purposes of uniform particle distribution, high density, high preferred orientation and improved thermoelectric performance. Ca (Ca) 3 Co 4 O 9 The thermoelectric conversion can be realized efficiently, the thermal stability is good, the thermoelectric conversion can work in a high-temperature environment, and the thermoelectric conversion device is nontoxic and pollution-free, so that the thermoelectric conversion device becomes a research hot spot. Conventional Ca 3 Co 4 O 9 The base polycrystalline thermoelectric material is prepared by a sol-gel method, the method is complex, and the product performance is not ideal.
Disclosure of Invention
The invention aims to provide Ca with high density and high preferred orientation 3 Co 4 O 9 Preparation method of base polycrystalline thermoelectric material, ca 3 Co 4 O 9 Wherein Sr element is doped in the formula Ca 3-x Sr x Co 4 O 9 Wherein x=0.05 to 0.2, specifically comprising the following steps:
(1) Adopting a solid phase reaction method to make CaCO which is the raw material required by the calcium cobalt-based oxide thermoelectric material 3 、SrCO 3 、Co 3 O 4 Weighing, mixing, fully grinding and tabletting according to stoichiometric ratio.
(2) Sintering the sample obtained in the step (1) in air for one time to obtain Ca 3 Co 4 O 9 A polycrystalline thermoelectric material.
(3) Carrying out secondary grinding and tabletting on the sample obtained in the step (2), and carrying out secondary sintering in air to prepare Ca with high density and high preferred orientation 3 Co 4 O 9 A polycrystalline thermoelectric material.
Preferably, the grinding time of the mixed raw materials in the steps (1) and (3) is about 2 hours, the tabletting process is that the uniaxial pressure is 8-12 MPa, the dwell time is 10 minutes, and the diameter of a sample is
The thickness is 3-4 mm.
Preferably, the sintering temperature of the mixed raw material in the step (1) is 750-850 ℃, the temperature is kept for 24 hours, and the heating rate is 10 ℃/min.
Preferably, the sintering temperature of the mixed raw material in the step (3) is 850-950 ℃, the temperature is kept for 24 hours, and the heating rate is 10 ℃/min.
The beneficial effects of the invention are as follows:
(1) The preparation process of the product is simple and easy to operate, the preparation temperature of the two times of sintering is low, no intermediate product exists, the requirements on the uniformity degree and the powder degree of the reaction raw materials are low, and the preparation cost is reduced.
(2) The product prepared by the invention has high preferred orientation and high density, and the mechanical property of the material is improved.
(3) The product prepared by the invention has a porous lamellar structure, can enhance phonon scattering and reduce heat conductivity, and is very beneficial to the improvement of thermoelectric performance of the material.
(4) The secondary sintering preparation process of the product can lead the raw materials to completely react, enhance the c-axis diffraction peak intensity of the product, and is favorable for improving the orientation factor and enhancing the mechanical property.
Drawings
Figure 1 is an XRD pattern of the product of the present invention.
FIG. 2 shows Ca with high density and high preferred orientation according to the present invention 3 Co 4 O 9 A density profile of the base polycrystalline thermoelectric material.
FIG. 3 shows Ca of high density and high preferred orientation according to the present invention 3 Co 4 O 9 A base polycrystalline thermoelectric material orientation factor curve.
FIG. 4 shows the high density and high density of the present inventionCa of preferential orientation 3 Co 4 O 9 SEM profile of the base polycrystalline thermoelectric material.
FIG. 5 shows Ca with high density and high preferred orientation according to the present invention 3 Co 4 O 9 EDS profile of the base polycrystalline thermoelectric material.
FIG. 6 is a graph of Ca at various sintering stages and process conditions 3 Co 4 O 9 XRD pattern of the base polycrystalline thermoelectric material.
Detailed Description
The invention will be described in further detail with reference to the drawings and examples, but the scope of the invention is not limited to the description.
Example 1
The Ca with high density and high preferred orientation described in this embodiment 3 Co 4 O 9 The base polycrystalline thermoelectric material specifically comprises the following steps:
(1) CaCO as a powder raw material 3 (99.9％)、SrCO 3 (99.9％)、Co 3 O 4 (99.9%) powder raw materials were mixed in stoichiometric proportions, wherein Ca: sr=2.93:0.05, and grinding was performed in a mortar for 2 hours.
(2) Pressing the sample obtained in the step (1) into a diameter under the conditions of uniaxial pressure of 8-12 MPa and dwell time of 10 minutes
A block material with the thickness of 3-4 mm.
(3) Sintering the sample obtained in the step (2) in the air at 800 ℃ for 24 hours.
(4) Fully grinding the sample obtained in the step (3) in a mortar for 2 hours, and then pressing the mixed raw materials into the diameter under the conditions of uniaxial pressure of 8-12 MPa and dwell time of 10 minutes
A block material with the thickness of 3-4 mm.
(5) The sample obtained in step (4) was sintered in air at 870 ℃ for 24 hours.
Example 2
(1) Mixing the powder raw materialsCaCO 3 (99.9％)、SrCO 3 (99.9％)、Co 3 O 4 (99.9%) powder raw materials were mixed in stoichiometric proportions, wherein Ca: sr=2.9:0.1, and grinding was performed in a mortar for 2 hours.
(2) Pressing the sample obtained in the step (1) into a diameter under the conditions of uniaxial pressure of 8-12 MPa and dwell time of 10 minutes
A block material with the thickness of 3-4 mm.
(3) Sintering the sample obtained in the step (2) in the air at 800 ℃ for 24 hours.
(4) Fully grinding the sample obtained in the step (3) in a mortar for 2 hours, and then pressing the mixed raw materials into the diameter under the conditions of uniaxial pressure of 8-12 MPa and dwell time of 10 minutes
A block material with the thickness of 3-4 mm.
(5) The sample obtained in step (4) was sintered in air at 870 ℃ for 24 hours.
Example 3
(1) CaCO as a powder raw material 3 (99.9％)、SrCO 3 (99.9％)、Co 3 O 4 (99.9%) powder raw materials were mixed in stoichiometric proportions, wherein Ca: sr=2.8:0.2, and grinding was performed in a mortar for 2 hours.
(2) Pressing the sample obtained in the step (1) into a diameter under the conditions of uniaxial pressure of 8-12 MPa and dwell time of 10 minutes
A block material with the thickness of 3-4 mm.
(3) Sintering the sample obtained in the step (2) in the air at 800 ℃ for 24 hours.
(4) Fully grinding the sample obtained in the step (3) in a mortar for 2 hours, and then pressing the mixed raw materials into the diameter under the conditions of uniaxial pressure of 8-12 MPa and dwell time of 10 minutes
A block material with the thickness of 3-4 mm.
(5) The sample obtained in step (4) was sintered in air at 870 ℃ for 24 hours.
Comparative example 1
The Ca with high density and high preferred orientation described in this embodiment 3 Co 4 O 9 The base polycrystalline thermoelectric material specifically comprises the following steps:
(1) CaCO as a powder raw material 3 (99.9％)、Co 3 O 4 (99.9%) the powder raw materials were mixed in stoichiometric proportions and ground thoroughly in a mortar for 2 hours.
(2) Pressing the sample obtained in the step (1) into a diameter under the conditions of uniaxial pressure of 8-12 MPa and dwell time of 10 minutes
A block material with the thickness of 3-4 mm.
(3) Sintering the sample obtained in the step (2) in the air at 800 ℃ for 24 hours.
(4) Fully grinding the sample obtained in the step (3) in a mortar for 2 hours, and then pressing the mixed raw materials into the diameter under the conditions of uniaxial pressure of 8-12 MPa and dwell time of 10 minutes
A block material with the thickness of 3-4 mm.
(5) The sample obtained in step (4) was sintered in air at 870 ℃ for 24 hours.
FIG. 1 shows XRD patterns of the product of the invention, and the XRD patterns show that the sample shows strong diffraction peaks along the (00 l) direction after sintering by the experimental preparation method disclosed by the invention, and the sample has high sintering quality without impurity phase diffraction peaks.
FIG. 2 shows Ca with high density and high preferred orientation according to the present invention 3 Co 4 O 9 The density curve of the base polycrystalline thermoelectric material can be seen from the graph, the density of the sintered sample is gradually enhanced, and Ca is obtained by the experimental preparation method disclosed by the invention 3-x Sr x Co 4 O 9 (x=0.2) density ratio Ca of sample 3-x Sr x Co 4 O 9 (x=0) the density of the sintered sample is about 10% higher, the crystalline quality is enhanced and the mechanical properties of the material are improved.
FIG. 3 shows Ca of high density and high preferred orientation according to the present invention 3 Co 4 O 9 The graph shows that the orientation factor of the base polycrystalline thermoelectric material is enhanced along the (00 l) direction after the sample is sintered by the experimental preparation method disclosed by the invention, the crystal anisotropy is improved, and Ca 3-x Sr x Co 4 O 9 Orientation factor ratio Ca of (x=0.05) sample 3-x Sr x Co 4 O 9 The orientation factor of the (x=0) sintered sample was about 28% higher and the degree of orientation of the material was improved.
FIG. 4 shows Ca with high density and high preferred orientation according to the present invention 3 Co 4 O 9 The SEM graph of the base polycrystalline thermoelectric material shows that the crystal grains slightly grow up by the experimental preparation method disclosed by the invention, and the sample has a porous lamellar structure after sintering, so that phonon scattering can be enhanced and the thermal conductivity can be reduced.
FIG. 5 shows Ca with high density and high preferred orientation according to the present invention 3 Co 4 O 9 EDS spectrum of the base polycrystalline thermoelectric material, from the graph, it can be seen that K of Sr appears at 1.8keV after the sample is sintered by the experimental preparation method disclosed by the invention α Characteristic X-ray peak, ca with increasing Sr doping amount 3-x Sr x Co 4 O 9 The intensity of the (x=0.05, 0.1 and 0.2) ray peaks is continuously improved, and the doping effect is excellent.
Example 4
This example further investigated the effect of sintering regime on material properties, and the specific method of this example was the same as example 1, except that the sintering conditions were different, as shown in table 1:
TABLE 1
Ca at different sintering stages and process conditions 3 Co 4 O 9 Heat of base polycrystalAs shown in figure 6, the XRD pattern of the electric material is shown in the figure 6, products which are not sintered for the second time only generate weak (002) and (004) diffraction peaks, the orientation factor is low, the analysis shows that the sintering temperature is low, the raw material reaction is incomplete, the product has the problem of high porosity, the theoretical density cannot be approached, and the densification and the preferred c-axis orientation of the product cannot be favorably acted. Sample 5 did not reach Ca at the primary and secondary sintering reaction temperatures 3 Co 4 O 9 The generation temperature of the base polycrystalline thermoelectric material is CaCO only 3 Decomposing to form CaO and CO 2 Sample 6 has high reaction temperature, ca 3 Co 4 O 9 Decomposing the base polycrystalline thermoelectric material to produce Ca 3 Co 2 O 6 CoO and O 2 The sintering stage and process conditions of samples 5 and 6 did not reach theoretical effects. Each (00 l) diffraction peak appears in sample 1, sample 2 and sample 3, the intensity of the diffraction peak is greatly enhanced, the peak shape is sharp, and no impurity phase is observed. The experimental preparation method disclosed by the invention ensures that the raw materials are completely reacted, and the c-axis preferred single-phase Ca is obtained 3 Co 4 O 9 The product is favorable for reducing the porosity, improving the density and the orientation factor of the product.
Claims (4)
1. Ca with high density and high preferred orientation 3 Co 4 O 9 The preparation method of the base polycrystalline thermoelectric material is characterized by comprising the following steps of: at Ca 3 Co 4 O 9 Wherein Sr element is doped in the formula Ca 3-x Sr x Co 4 O 9 Wherein x=0.05 to 0.2, specifically comprising the following steps:
(1) Adopting a solid phase reaction method to make CaCO which is the raw material required by the calcium cobalt-based oxide thermoelectric material 3 、SrCO 3 、Co 3 O 4 Weighing, mixing, fully grinding and tabletting according to stoichiometric ratio;
(2) Sintering the sample obtained in the step (1) in air for one time to obtain Ca 3 Co 4 O 9 A base polycrystalline thermoelectric material;
(3) Performing secondary grinding and tabletting on the sample obtained in the step (2), and performing air compressionIntermediate secondary sintering to prepare Ca with high density and high preferred orientation 3 Co 4 O 9 A polycrystalline thermoelectric material.
2. High density and high preferential orientation Ca according to claim 1 3 Co 4 O 9 The preparation method of the base polycrystalline thermoelectric material is characterized by comprising the following steps of: grinding the mixed raw materials in the steps (1) and (2) for 1.5-2.5 hours, wherein the tabletting process is carried out under uniaxial pressure of 8-12 MPa, the pressure maintaining time is 10 minutes, and the diameter of a sample is equal to that of the sample
The thickness is 3-4 mm.
3. High density and high preferential orientation Ca according to claim 1 3 Co 4 O 9 The preparation method of the base polycrystalline thermoelectric material is characterized by comprising the following steps of: in the step (1), the sintering temperature is 750-850 ℃, the temperature is kept for 24 hours, and the heating rate is 10 ℃/min.
4. High density and high preferential orientation Ca according to claim 1 3 Co 4 O 9 The preparation method of the base polycrystalline thermoelectric material is characterized by comprising the following steps of: in the step (2), the sintering temperature is 850-950 ℃, the temperature is kept for 24 hours, and the heating rate is 10 ℃/min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310127650.1A CN116288700A (en) | 2023-02-17 | 2023-02-17 | Ca with high density and high preferred orientation 3 Co 4 O 9 Preparation method of base polycrystalline thermoelectric material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310127650.1A CN116288700A (en) | 2023-02-17 | 2023-02-17 | Ca with high density and high preferred orientation 3 Co 4 O 9 Preparation method of base polycrystalline thermoelectric material |
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| CN116288700A true CN116288700A (en) | 2023-06-23 |
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