CN107689414B - Preparation method of multiphase composite calcium manganate-based oxide thermoelectric material with uniformly distributed conductive metal phases - Google Patents

Preparation method of multiphase composite calcium manganate-based oxide thermoelectric material with uniformly distributed conductive metal phases Download PDF

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CN107689414B
CN107689414B CN201710682077.5A CN201710682077A CN107689414B CN 107689414 B CN107689414 B CN 107689414B CN 201710682077 A CN201710682077 A CN 201710682077A CN 107689414 B CN107689414 B CN 107689414B
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张久兴
张静文
张飞鹏
杨新宇
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Hefei University of Technology
Henan University of Urban Construction
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Abstract

The invention discloses a preparation method of a multiphase composite calcium manganate-based oxide thermoelectric material with uniformly distributed conductive metal phases, which comprises the steps of firstly, uniformly mixing nitrates of Ag, Mn and Ca by adopting a citric acid sol-gel method to prepare the multiphase composite CaMnO with the pure and fine conductive metal phases uniformly distributed3The precursor powder of the oxide thermoelectric material is then sintered in air atmosphere and normal pressure to prepare the target product. The material obtained by the invention is the same pure phase CaMnO3Compared with the high electric conductivity and low heat conductivity, the thermoelectric performance is improved; meanwhile, the preparation method has the advantages of simple and convenient process, short synthesis and forming time and the like.

Description

Preparation method of multiphase composite calcium manganate-based oxide thermoelectric material with uniformly distributed conductive metal phases
Technical Field
The invention provides a multiphase CaMnO with uniformly distributed conductive metal phases3A preparation technology of a base oxide thermoelectric material belongs to the field of thermoelectric ceramics.
Background
Thermoelectric materials are functional materials which convert heat energy and electric energy mutually by utilizing thermoelectric effect, are key basic materials in the field of high-technology new energy, and thermoelectric devices (CPU refrigerators, thermoelectric refrigerators, aerospace device power supplies and the like) made of the thermoelectric materials have many unique advantages and are widely applied to the aspects of national defense, automobiles, microelectronics, industrial waste heat and the like.
At present, the thermoelectric materials which are mature in technology and good in performance are mostly metal semiconductor alloys, but the thermoelectric materials are unstable at high temperature and are easy to oxidizeHigh in chemical conversion and cost, and most of them contain heavy metals harmful to human body, and thus are not ideal thermoelectric materials. In contrast, oxide thermoelectric materials have attracted attention in recent years because of their excellent characteristics such as no pollution, high efficiency, and low cost, and particularly their high temperature stability. Wherein, CaMnO3Belongs to an orthorhombic system, has a perovskite crystal structure, and is a potential n-type semiconductor material. CaMnO3Has a high Seebeck coefficient and non-negligible resistivity (350 mu VK-1 and 2 omega cm at room temperature), so that the thermoelectric performance at high temperature is not high. But the thermoelectric property of the material is closely related to the composition of the material, and the doping and the nano-compounding of the thermoelectric material are effective means for improving the thermoelectric property of the material at present.
And selecting the appropriate doping element and the appropriate amount of doping will increase the CaMnO3The key issue of thermoelectric performance. Ag is located in a transition group element region in the periodic table of elements, has a relative atomic mass of 107.9, and is often easy to lose electrons in a compound state+And (4) a valence of 1. And the physical and chemical properties of Ag are stable, and the electrical conductivity and the thermal conductivity are the highest in all metals. And transition metal Ag in CaMnO3The new scattering center is introduced due to the uniform distribution in the matrix, and the heavy atoms and the large-size characteristic of the new scattering center can enhance the scattering of current carriers and phonons, so that the thermoelectric performance of the material is influenced.
Disclosure of Invention
The invention aims to provide a multiphase composite CaMnO with uniformly distributed conductive metal phases3The preparation method of the base oxide thermoelectric material can greatly improve the mobility of carriers, increase the conductivity and keep a high Seebeck coefficient, thereby improving the power factor.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the multiphase composite calcium manganate-based oxide thermoelectric material with uniformly distributed conductive metal phases is characterized by comprising the following steps of:
(1) mixing Ca (NO)3)2·4H2O、Mn(NO3)2、AgNO3And citric acid according to (0.98-0.86): 1: (0.02-0.14): (5.88-5.16), mixing and dissolving in deionized water, adding a proper amount of ethylene glycol, and uniformly mixing to obtain a mixed solution;
(2) reacting the mixed solution on a constant-temperature magnetic stirrer at the temperature of 70-90 ℃ for 10-14 h to obtain brown wet gel;
(3) placing the brown wet gel in a drying box, and drying until the brown wet gel is completely dehydrated to obtain a dry gel precursor; crushing and grinding the dry gel precursor, and calcining the dry gel precursor in a muffle furnace at 950 ℃ for 5 hours to obtain the multiphase composite CaMnO with uniformly distributed conductive metal phases3A base oxide thermoelectric powder;
(4) repeatedly grinding the thermoelectric powder, adding a proper amount of polyvinyl alcohol with the mass concentration of 7%, uniformly mixing, and performing pre-pressing molding under the pressure of 5MPa to obtain an initial blank; sealing the primary blank, putting the sealed primary blank into a cold isostatic press, pressing for 1-6 min at the pressure of 250MPa, taking out the primary blank, putting the primary blank into a muffle furnace, preserving heat at 550 ℃ and discharging glue for 2-5 h to obtain a sample after glue discharging;
(5) placing the sample subjected to rubber removal into a high-temperature tube furnace to be sintered at high temperature under the air atmosphere, wherein the sintering temperature is 1200 ℃, the heat preservation time is 12h, the heating rate is 3 ℃/min, and then cooling along with the furnace to obtain the multiphase composite CaMnO with uniformly distributed conductive metal phases3A base oxide thermoelectric block.
Preferably, Ca is contained in the mixed solution obtained in the step (1)2+The concentration is 0.2 mol/L.
Preferably, the step (3) of drying the brown wet gel to be completely dehydrated is as follows: drying at 90 ℃ for 36h at constant temperature, heating to 120 ℃ and drying at constant temperature for 3-5 h, heating to 140 ℃ and drying at constant temperature for 4-6 h, and finally heating to 160 ℃ and drying at constant temperature for 1-3 h.
The invention has the beneficial effects that:
1. homogeneous phase CaMnO3Compared with the multiphase composite CaMnO with uniformly distributed conductive metal phase3The base oxide thermoelectric material is more compact and smoother in surface after being sintered, and is beneficial to improving the conductivity of the material; and isThe Ag has high conductivity and uniform distribution, and is more beneficial to improving the conductivity of the material.
2. The preparation method of the thermoelectric material provided by the invention has simple and convenient process and short synthesis and forming time; the obtained thermoelectric material has good oxidation resistance and high-temperature stability, can directly work in the atmosphere and at high temperature, does not contain rare earth elements, and has low cost.
3. The sol-gel method and the atmospheric sintering method in the air atmosphere used in the preparation method solve the problem of Ag composite CaMnO3The Ag phase in the base oxide thermoelectric material is distributed unevenly, is easy to agglomerate, has large grain size and the like.
Drawings
FIG. 1 shows a multiphase composite CaMnO3XRD pattern of the base oxide thermoelectric material;
FIG. 2 shows a multiphase composite CaMnO3Fracture morphology of the base oxide thermoelectric material.
Detailed Description
Example 1
This example prepares a heterogeneous composite CaMnO with uniformly distributed conductive metal phase as follows3Base oxide thermoelectric material:
(1) mixing Ca (NO)3)2·4H2O、Mn(NO3)2、AgNO3And citric acid in a ratio of 0.96: 1: 0.04: 5.76, mixing and dissolving in deionized water, adding a proper amount of ethylene glycol (1/10 accounting for the volume of the deionized water), and uniformly mixing to obtain a whitish mixed solution; wherein, Ca is contained in the mixed solution2+The concentration is 0.2 mol/L;
(2) reacting the mixed solution for 13 hours on a constant-temperature magnetic stirrer at 85 ℃ to obtain brown wet gel;
(3) and placing the brown wet gel in a drying oven, drying at the constant temperature of 90 ℃ for 36h, heating to 120 ℃ and drying at the constant temperature for 4h, heating to 140 ℃ and drying at the constant temperature for 5.5h, and finally heating to 160 ℃ and drying at the constant temperature for 2.5h to obtain a dry gel precursor.
Crushing and grinding the dry gel precursor, and calcining the dry gel precursor in a muffle furnace at 950 ℃ for 5 hours to obtain the conductive metalHeterogeneous composite CaMnO with uniformly distributed phases3A base oxide thermoelectric powder;
(4) repeatedly grinding the thermoelectric powder, adding a proper amount of polyvinyl alcohol with the mass concentration of 7%, uniformly mixing, and performing pre-pressing molding under the pressure of 5MPa to obtain an initial blank; sealing the primary blank, putting the sealed primary blank into a cold isostatic press, pressing for 1-6 min at the pressure of 250MPa, taking out the pressed primary blank, putting the pressed primary blank into a muffle furnace, preserving heat at 550 ℃ and discharging glue for 2-5 h to obtain a sample after glue discharging;
(5) placing the sample subjected to rubber removal into a high-temperature tube furnace to be sintered at high temperature under the air atmosphere, wherein the sintering temperature is 1200 ℃, the heat preservation time is 12h, the heating rate is 3 ℃/min, and then cooling along with the furnace to obtain the multiphase composite CaMnO with uniformly distributed conductive metal phases3A base oxide thermoelectric block.
Example 2
This example was carried out in the same manner as in example 1 to prepare a heterogeneous composite CaMnO3Based on oxide thermoelectric materials, differing only in that: ca (NO) in step (1)3)2·4H2O、Mn(NO3)2、AgNO3And citric acid in a 0.90: 1: 0.10: 5.40.
example 3
This example was carried out in the same manner as in example 1 to prepare a heterogeneous composite CaMnO3Based on oxide thermoelectric materials, differing only in that: ca (NO) in step (1)3)2·4H2O、Mn(NO3)2、AgNO3And citric acid in a 0.86: 1: 0.14: 5.16.
FIG. 1 shows the heterogeneous composite CaMnO prepared in the above example3XRD pattern of oxide-based thermoelectric material, wherein the (A) curve is pure phase CaMnO3The curves (B) and (C) correspond to the samples of example 1 and example 2, respectively. It can be seen that CaMnO is present in the sample3、Ca2Mn2O5And Ag. The XRD characterization results for the sample of example 3 were the same.
FIG. 2 shows the heterogeneous composite CaMnO prepared in the above example3Fracture morphology diagram of base oxide thermoelectric material, wherein (A) and (B) are dividedThe samples were respectively corresponding to example 1 and example 2. It can be seen that the thermoelectric material powder has the advantages of good consolidation, high density, small size of Ag in the matrix and uniform distribution.
TABLE 1 multiphase composite CaMnO measured at 600 ℃3Thermoelectric properties of the base oxide thermoelectric material. The test data shows that: with pure phase CaMnO3In contrast, the heterogeneous composite CaMnO prepared in example 23The resistivity of the oxide-based thermoelectric material is reduced by 55.1%, the thermal conductivity is reduced by 21.3%, the ZT value is improved by about 1.73 times, and the thermoelectric performance is greatly improved. CaMnO doped with Ag at Table 1600 deg.C3Thermoelectric properties of base thermoelectric materials
Figure BDA0001375743620000041

Claims (2)

1. A preparation method of a multiphase composite calcium manganate-based oxide thermoelectric material with uniformly distributed conductive metal phases is characterized by comprising the following steps:
(1) mixing Ca (NO)3)2·4H2O、Mn(NO3)2、AgNO3And citric acid according to (0.98-0.86): 1: (0.02-0.14): (5.88-5.16), mixing and dissolving in deionized water, adding a proper amount of ethylene glycol, and uniformly mixing to obtain a mixed solution, wherein Ca in the mixed solution is2+The concentration is 0.2 mol/L;
(2) reacting the mixed solution on a constant-temperature magnetic stirrer at the temperature of 70-90 ℃ for 10-14 h to obtain brown wet gel;
(3) placing the brown wet gel in a drying box, and drying until the brown wet gel is completely dehydrated to obtain a dry gel precursor; crushing and grinding the dry gel precursor, and calcining the dry gel precursor in a muffle furnace at 950 ℃ for 5 hours to obtain the multiphase composite CaMnO with uniformly distributed conductive metal phases3A base oxide thermoelectric powder;
(4) repeatedly grinding the thermoelectric powder, adding a proper amount of polyvinyl alcohol with the mass concentration of 7%, uniformly mixing, and performing pre-pressing molding under the pressure of 5MPa to obtain an initial blank; sealing the primary blank, putting the sealed primary blank into a cold isostatic press, pressing for 1-6 min at the pressure of 250MPa, taking out the primary blank, putting the primary blank into a muffle furnace, preserving heat at 550 ℃ and discharging glue for 2-5 h to obtain a sample after glue discharging;
(5) placing the sample subjected to rubber removal into a high-temperature tube furnace to be sintered at high temperature under the air atmosphere, wherein the sintering temperature is 1200 ℃, the heat preservation time is 12h, the heating rate is 3 ℃/min, and then cooling along with the furnace to obtain the multiphase composite CaMnO with uniformly distributed conductive metal phases3A base oxide thermoelectric block.
2. The method for preparing the multiphase composite calcium manganate-based oxide thermoelectric material having uniformly distributed conductive metal phases as set forth in claim 1, wherein: the method for drying the brown wet gel to be completely dehydrated in the step (3) comprises the following steps: drying at 90 ℃ for 36h at constant temperature, heating to 120 ℃ and drying at constant temperature for 3-5 h, heating to 140 ℃ and drying at constant temperature for 4-6 h, and finally heating to 160 ℃ and drying at constant temperature for 1-3 h.
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