CN114656243A - Calcium-manganese-oxygen thermoelectric material and preparation method thereof - Google Patents
Calcium-manganese-oxygen thermoelectric material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 87
- WDYDGOPLWKQFKI-UHFFFAOYSA-N [O].[Ca].[Mn] Chemical compound [O].[Ca].[Mn] WDYDGOPLWKQFKI-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000498 ball milling Methods 0.000 claims abstract description 55
- 239000000843 powder Substances 0.000 claims abstract description 47
- 238000007731 hot pressing Methods 0.000 claims abstract description 34
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 238000005245 sintering Methods 0.000 claims abstract description 26
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011159 matrix material Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910018663 Mn O Inorganic materials 0.000 claims 1
- 229910003176 Mn-O Inorganic materials 0.000 claims 1
- 229910002969 CaMnO3 Inorganic materials 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000292 calcium oxide Substances 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000011575 calcium Substances 0.000 description 8
- 238000004321 preservation Methods 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000003321 amplification Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- SAXPPRUNTRNAIO-UHFFFAOYSA-N [O-2].[O-2].[Ca+2].[Mn+2] Chemical compound [O-2].[O-2].[Ca+2].[Mn+2] SAXPPRUNTRNAIO-UHFFFAOYSA-N 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
The invention discloses a calcium-manganese-oxygen thermoelectric material and a preparation method thereof, wherein the thermoelectric material is a cubic phase CaMnO3As a matrix phase, lamellar CaO is used as an embedded phase, and the embedded phase is dispersed in the matrix phase and arranged in an oriented way to form CaO (CaMnO3) with a tetragonal perovskite intergrowth structurem(ii) a The preparation method comprises the following steps: taking CaO and MnO2Uniformly mixing, and then sintering at high temperature; and ball-milling the mixture sintered at high temperature to form powder, wherein the mass ratio of ball milling is 10-30: 1, ball milling for 0.5-4h to make the powder diameter reach 30-1000 nm; collecting the powder under inert gasCarrying out hot pressing treatment on the powder; the invention takes calcium oxide and manganese oxide as raw materials, and forms a tetragonal perovskite symbiotic structure CaO (CaMnO3) by ball milling and hot pressingmThereby improving the Seebeck coefficient of the thermoelectric material, controlling the ball milling mass ratio and the ball milling time, reducing the thermal conductivity, optimizing the thermoelectric conversion efficiency of the thermoelectric material, reducing the cost and being beneficial to industrial production.
Description
Technical Field
The invention relates to the technical field of thermoelectric materials, in particular to a calcium-manganese-oxygen thermoelectric material and a preparation method thereof.
Background
In recent years, with the increasing severity of fossil energy crisis, awareness of environmental protection is increasing, and the demand for new energy that can be continuously utilized is increasing. Cogeneration using thermoelectric materials, which uses the Seebeck effect in a thermoelectric generator (TEG), can generate a direct current when two different semiconductor p-type and n-type form a loop and provide a temperature difference, is receiving increasing attention from scientists and enterprises.
The thermoelectric conversion efficiency of the material is determined by the magnitude of zT, which is S2σ T/κ, wherein zT is dimensionless configuration-of-unit, S is Seebeck coefficient (. mu. V K)-1) And σ is the conductivity (S cm)-1) And κ is thermal conductivity (W m)-1K-1). The larger the zT value is, the higher the thermoelectric conversion performance of the thermoelectric material is. Therefore, according to the zT formula, a good quality thermoelectric material should have a high seebeck coefficient, high electrical conductivity, and low thermal conductivity. However, these three coefficients are difficult to optimize towards the desired direction simultaneously, since all three variables are related to the carrier concentration of the material. Where σ (σ ═ ne μ, where n is the carrier concentration, μ is the carrier mobility, and e is the electron ignition) is positively correlated with the carrier concentration of the material, the greater the carrier concentration, the greater the σ of the material. Doped semiconductor S (8 pi 2kB2m T (pi/3 n)2/3/3eh2, h is planck constant, kBIs the constant maturity of Boltzmann, m*Carrier effective mass) is inversely related to the carrier concentration of the material, with the greater the carrier concentration, the smaller the S of the material. Kappa from kappae(electronic thermal conductivity) and κL(phonon thermal conductivity) composition, wherein κe＝π2n2kB2Tμ/e,κePositively correlated with the carrier concentration, the greater the carrier concentration, κeThe larger. The only carrier concentration independent variable is κL，κLCvl/3, C is phonon heat capacity per unit area, v is mean phonon velocity, l is phonon mean free path, the seebeck coefficient and the thermal conductivity of the existing thermoelectric material are high, which results in low thermoelectric conversion efficiency, and the thermal conductivity of the prior art is lowSrTi is mostly adopted as the electric material0.7Nb0.3O3The material is made of materials with high cost, and the plasma sintering (SPS) is used, so that the industrial quantitative production is difficult to realize, and the content of Nb element in the crust is 20 ppm and is rare.
Disclosure of Invention
The invention aims to solve the technical problem of providing a calcium-manganese-oxygen thermoelectric material and a preparation method thereof aiming at the defects of the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows: a calcium-manganese-oxygen thermoelectric material in cubic phase CaMnO3The lamellar CaO is used as an embedded phase, the embedded phase is dispersed in the matrix phase and is directionally arranged to form a tetragonal perovskite intergrowth type structure CaO (CaMnO)3)mWherein m is 1, 2, 3 … ∞.
Further, the calcium manganese oxygen thermoelectric material is preferably a tetragonal perovskite intergrowth type structure CaO (CaMnO)3)mWherein m is 2-10, m is a natural number.
Wherein, the calcium manganese oxide thermoelectric material has a tetragonal perovskite intergrowth type structure CaO (CaMnO)3)mAdopts the components of CaO and MnO2Is prepared from CaO and MnO2The ratio of the amounts of substances is (m + 1): m, wherein m is 1, 2, 3 … ∞.
A preparation method of a calcium-manganese-oxygen thermoelectric material comprises the following steps:
s1, taking CaO and MnO2Uniformly mixed, CaO and MnO2The ratio of the amounts of substances is (m + 1): m, m is 1, 2, 3 … infinity, and then high-temperature sintering is carried out;
s2, performing ball milling on the mixture sintered at high temperature to form powder, wherein the mass ratio of the balls to the mixture is 10-30: 1, ball milling for 0.5-4h to ensure that the particle size of powder particles reaches 30-1000 nm;
and S3, collecting the powder, and performing hot pressing treatment on the powder under inert gas.
Further, in the preparation method, it is preferable that in step S1, the sintering temperature is 1200-1600 ℃.
Further, in the preparation method, it is preferable that the high-temperature sintering time is 4 to 18 hours in step S1.
Further, in the preparation method, preferably in step S2, the mass ratio of the balls to the mixture is (15-25): 1.
further, in the preparation method, it is preferable that in step S2, the particle diameter of the powder particles formed is 100-800 nm.
Further, in the preparation method, it is preferable that the ball milling time is 1 to 3 hours in step S2.
Further, in the preparation method, it is preferable that in step S3, the hot pressing pressure is 40-80MPa, and the hot pressing temperature is 600-900 ℃.
Further, in the preparation method, preferably in step S3, the temperature rise rate of hot pressing is 8-10 ℃/min, and the powder is subjected to heat preservation while being subjected to hot pressing, with the heat preservation time being 15-60 min.
The invention has the beneficial effects that: the invention provides a calcium-manganese-oxygen thermoelectric material and a preparation method thereof, wherein cubic phase CaMnO is used3Taking lamellar CaO as a matrix phase, and taking the lamellar CaO as an embedded phase, wherein the embedded phase is dispersed in the matrix phase and directionally arranged to form a tetragonal perovskite intergrowth type structure CaO (CaMnO)3)m(ii) a The invention takes calcium oxide and manganese oxide as raw materials, has low material cost, and has low mechanical property, high temperature resistance and thermal conductivity; by CaO and CaMnO3Embedding to generate a tetragonal perovskite intergrowth type structure CaO (CaMnO)3)mTo adjust the movement and scattering of the current carrier and the phonon in the material to ensure that the concentration of the current carrier reaches 10^15-10^19/cm^3So as to improve the Seebeck coefficient of the thermoelectric material, introduce synthesis processes such as ball milling, hot pressing and the like, reduce the particle size of the material by controlling the mass ratio of the ball to the sample mixture and the ball milling time, thereby reducing the melting point of the material to 800-1200 ℃, enabling the relative density of the material to reach 90% -97% of the theoretical density, improving the phonon diffraction of the material to achieve the purpose of reducing the thermal conductivity, and further optimizing the thermoelectric conversion efficiency of the thermoelectric material; and the preparation method of ball milling and hot pressing can reduce the hot pressing temperature, is safer and more environment-friendly, and is beneficial to industrial production.
Drawings
The invention will be further described with reference to the accompanying drawings and examples, in which:
FIG. 1 shows a tetragonal perovskite intergrowth type CaO (CaMnO) in example 1 of the present invention3)mA structural schematic diagram of (1), (2), (3), (infinity);
FIG. 2-5 shows a tetragonal perovskite intergrowth type CaO (CaMnO) in examples 2-1 to 2-4 of the present invention3)mComparing XRD results of (wherein m is 1, 2, 3 and infinity);
FIG. 6 shows a tetragonal perovskite intergrowth type CaO (CaMnO) in examples 2-1 to 2-4 of the present invention3)mResults of seebeck coefficients of (1), (2), (3), (infinity);
FIG. 7 shows CaO (CaMnO) having tetragonal perovskite intergrowth type structure in examples 2-1 to 2-4 of the present invention3)mResults of thermal conductivity of (1, 2, 3 ∞) are compared with each other.
Detailed Description
For a more clear understanding of the technical features, objects and effects of the present invention, embodiments of the present invention will now be described in detail with reference to the accompanying drawings.
Example 1A calcium manganese oxygen thermoelectric Material in cubic phase CaMnO3Taking lamellar CaO as a matrix phase, and taking the lamellar CaO as an embedded phase, wherein the embedded phase is dispersed in the matrix phase and directionally arranged to form a tetragonal perovskite intergrowth type structure CaO (CaMnO)3)mWherein m is 1, 2, 3 … infinity, the structure of the invention can adjust the movement and scattering of carriers and phonons in the thermoelectric material to make the carrier concentration reach 10^15-10^19/cm^3Thereby achieving the purpose of improving the Seebeck coefficient of the thermoelectric material, and further optimizing the thermoelectric conversion efficiency of the thermoelectric material.
Further, CaO (CaMnO) having a tetragonal perovskite intergrowth type structure is preferable3)mWherein m is 2-10, m is a natural number. In a preferred structure, clearer CaMnO can be formed3-a CaO layered structure. I.e. cubic phase CaMnO3The embedded relation with the embedded phase CaO generates a Ruddlesden-Popper structure, which can improve the structural complexity, increase phonon diffraction and reduce the thermal conductivity. In particular, the amount of the solvent to be used,in the tetragonal perovskite intergrowth structure, m layers of CaMnO are arranged3Forming cubic phase, each layer of lamellar CaO being used as an embedded phase, one layer of CaO being embedded in two m layers of CaMnO3In cubic phase, with m layers of CaMnO3And a repeated overlapping mode of one layer of CaO, namely that each CaO layer is directionally arranged in a plurality of cubic phases CaMnO3 to form the integral calcium manganese oxygen thermoelectric material.
As shown in FIG. 1, four cases where m is 1, 2, 3, and ∞ are listed. When m is 1, a layer of CaMnO3A layer of CaO is repeatedly overlapped. When m is 2, two layers of CaMnO3A layer of CaO is repeatedly overlapped. When m is 3, three layers CaMnO3A layer of CaO is repeatedly overlapped. Relative to CaMnO when m ∞3The amount of CaO is negligible, i.e. m ∞, then only CaMnO can be considered3And (5) structure. Ten-layer CaMnO for m 103One layer of CaO, due to ten layers of CaMnO3Compared with the one-layer CaO having a very large difference in volume, the simulated structure diagram is close to the m ∞, and the simulated structure diagram is not shown in this embodiment.
CaO (CaMnO) in a tetragonal perovskite intergrowth type structure of the present invention3)mThe raw materials can adopt a component CaO and a component MnO2Is prepared from CaO and MnO2The ratio of the amounts of substances is (m + 1): m, wherein m is 1, 2, 3 … ∞. The raw materials and the proportion thereof are the prerequisite condition of the tetragonal perovskite intergrowth structure, and the definite tetragonal perovskite intergrowth structure is formed by a corresponding preparation method.
In addition, the invention takes calcium oxide and manganese oxide as raw materials, has low material cost, no toxicity and harm, and has low mechanical property, high temperature resistance and thermal conductivity. By CaO and CaMnO3Embedding to generate a tetragonal perovskite intergrowth type structure CaO (CaMnO)3)mThe movement and scattering of carriers and phonons in the thermoelectric material are adjusted, so that the Seebeck coefficient of the thermoelectric material is improved, and the thermoelectric conversion efficiency of the thermoelectric material is further optimized.
s1, gettingCaO and MnO2Uniformly mixed, CaO and MnO2The ratio of the amounts of substances is m + 1: m, m is 1, 2 and 3 … infinity, then high-temperature sintering is carried out, the sintering temperature is 1200-1600 ℃, and the high-temperature sintering time is 4-18 h;
s2, performing ball milling on the mixture sintered at high temperature to form powder, wherein the mass ratio of the balls to the mixture is 10-30: 1, ball milling for 0.5-4h to ensure that the particle size of powder particles reaches 30-1000 nm; further, the mass ratio of the balls to the mixture is preferably 15-25: 1; further, it is preferable that the particle diameter of the powder particles formed is 50 to 800 nm; further, the ball milling time is preferably 0.5 to 4 hours. In the invention, the ball milling step is the basis of reducing the hot pressing process conditions, so that the ball milling time and the proportion of balls and mixtures are required to be controlled during ball milling to control the particle size of the ball-milled material, any one of the ball milling time which is too long and too short and the proportion of balls and mixtures which is not qualified influences the particle size of the material powder, thus causing the particle size to be too large or too small, the material particle size to be too small, the thermoelectric property to be poor, the particle size to be too large, the required hot pressing temperature to be increased, and the industrial amplification to be unfavorable. Furthermore, the ball milling time and the ratio of the balls to the mixture also affect the formation of the layered structure of the final product, i.e., the ball milling step affects the uniform mixing degree of the raw materials, improper ball milling may cause too large or too small particle size, too large particle size may cause too high melting point, high density samples cannot be extruded by hot pressing, and phonon scattering is insufficient, resulting in high thermal conductivity and low thermoelectric figure of merit. Too small a particle size may result in too strong carrier scattering, too low electrical conductivity, and low thermoelectric figure of merit.
S3, collecting powder, carrying out hot pressing treatment on the powder under inert gas, wherein the hot pressing pressure is 40-80MPa, the hot pressing temperature is 600-3Taking lamellar CaO as a matrix phase, and taking the lamellar CaO as an embedded phase, wherein the embedded phase is dispersed in the matrix phase and directionally arranged to form a tetragonal perovskite intergrowth type structure CaO (CaMnO)3)mThe thermoelectric material, wherein m is 1, 2, 3 … ∞. The hot pressing process is more suitable for industrial production compared with plasmaThe sintering temperature of the method sintering (SPS) is 1250-1350 ℃, and the method greatly reduces the hot pressing temperature and reduces the process energy consumption.
The invention utilizes the preparation method of ball milling and hot pressing, the particle size of the material is reduced by controlling the mass ratio of the ball to the sample mixture and the ball milling time, the particle size of the material mixture is 30-1000nm, and the melting point of the calcium-manganese-oxygen thermoelectric material is reduced, the density of the calcium-manganese-oxygen material is increased, and the phonon diffraction of the calcium-manganese-oxygen material is improved to achieve the purpose of reducing the heat conductivity, thereby further optimizing the thermoelectric conversion efficiency of the thermoelectric material; and the material after high-temperature sintering is subjected to CaO and MnO2The mixture is subjected to ball milling, the temperature required by hot pressing can be reduced, the method is safer and more environment-friendly, linear amplification can be realized, industrial production can be carried out, and the formed calcium-manganese-oxygen thermoelectric material with the tetragonal perovskite intergrowth structure has high thermoelectric conversion efficiency.
Example 2-1, CaO 22.533g and 17.4667g of MnO in the form of sheets2Uniformly mixing, and then sintering at high temperature, wherein the sintering temperature is 1200 ℃, and sintering for 4 hours; performing ball milling on the mixture subjected to high-temperature sintering to form powder, wherein the mass ratio of the balls to the mixture is 10: 1, performing ball milling on the powder at any time until the particle size of the powder particles is 30-1000nm, wherein the ball milling time is 0.5 h; collecting powder, carrying out hot pressing treatment on the powder under argon gas by using a hot pressing die at the pressure of 40MPa and the temperature of 600 ℃, the heating rate of 8 ℃/min and the heat preservation time of 15min to obtain the tetragonal perovskite intergrowth structure Ca2MnO4The thermoelectric material is subjected to quality detection, XRD calculation is performed on the material before ball milling and a finished product sample (namely the sample after ball milling), the quality detection results are shown in figures 2, 6 and 7, and the detection results show that the density of the thermoelectric material is greatly improved relative to the density before ball milling, the relative density of the material reaches 90-97% of the theoretical density, the Seebeck coefficient absolute value of the Ca2MnO4 material is relatively high, the thermal conductivity of the Ca2MnO4 material is relatively low, and the thermoelectric conversion efficiency is good.
Example 2-2, CaO 19.6702g and MnO 20.3298g were sheeted in the form of layers2Uniformly mixing, then sintering at a high temperature of 1400 ℃,sintering for 12 h; and ball-milling the mixture subjected to high-temperature sintering to form powder, wherein the mass ratio of the balls to the mixture is 20: 1, detecting the particle size of powder at any time in the ball milling process until the particle size of the powder particles is 30-1000nm, and the ball milling time is 2.5 h; collecting powder, carrying out hot pressing treatment on the powder under argon gas by using a hot pressing die at the pressure of 60MPa and the temperature of 700 ℃, the heating rate of 9 ℃/min and the heat preservation time of 35min to obtain the tetragonal perovskite intergrowth structure Ca3MnO7The thermoelectric material is subjected to quality detection, XRD calculation is carried out on a sample before ball milling and a finished product sample (namely, a sample after ball milling), the quality detection results are shown in figures 3, 6 and 7, the detection results show that the relative density of the thermoelectric material is greatly improved relative to the density before ball milling, the relative density of the material reaches 90-97% of the theoretical density, and Ca accounts for 90-97% of the theoretical density3MnO7The absolute value of the Seebeck coefficient of the material is relatively high, CaO Ca3MnO7The thermal conductivity of the material is relatively low, and the thermoelectric conversion efficiency is good.
Examples 2 to 3, CaO 18.4952g and 21.5048g of MnO in the form of sheets2Uniformly mixing, and then sintering at 1600 ℃ for 18 h; and ball-milling the mixture sintered at high temperature to form powder, wherein the mass ratio of the balls to the mixture is 30: 1, detecting the particle size of powder at any time in the ball milling process until the particle size of the powder particles is 50-800nm, wherein the ball milling time is 4 hours; collecting powder, and performing hot pressing treatment on the powder under argon gas by using a hot pressing die at the pressure of 80MPa and the temperature of 900 ℃. The heating rate is 10 ℃/min, the heat preservation time is 60min, and the tetragonal perovskite intergrowth structure Ca is obtained4MnO10The thermoelectric material is subjected to quality detection, XRD calculation is carried out on a sample before ball milling and a finished product sample (namely, a sample after ball milling), the quality detection results are shown in figures 4, 6 and 7, the detection results show that the density of the thermoelectric material is greatly improved relative to the density before ball milling, the relative density of the material reaches 90-97% of the theoretical density, and Ca is contained in the thermoelectric material4MnO10The absolute value of Seebeck coefficient of the material is relatively high, Ca4MnO10The thermal conductivity of the material is relatively low, and the thermoelectric conversion efficiency is good.
Examples 2 to 4, CaO 15.6844g and 24.3156g of MnO in the form of sheets2Uniformly mixing, and then sintering at a high temperature of 1400 ℃ for 4 hours; and ball-milling the mixture sintered at high temperature to form powder, wherein the mass ratio of the balls to the mixture is 20: 1, detecting the particle size of powder at any time in the ball milling process until the particle size of the powder particles is 30-1000nm, wherein the ball milling time is 2 hours; collecting powder, and performing hot pressing treatment on the powder under argon gas by using a hot pressing die, wherein the pressure is 60MPa, and the temperature is 800 ℃. The heating rate is 8 ℃/min, the heat preservation time is 40min, and the tetragonal perovskite intergrowth structure CaMnO is obtained3The thermoelectric material is subjected to quality detection, XRD calculation is carried out on a material sample before ball milling and a finished product sample (namely, a sample after ball milling), the quality detection results are shown in figures 5, 6 and 7, the detection results show that the density of the thermoelectric material is greatly improved relative to the density before ball milling, the relative density of the material reaches 90-97% of the theoretical density, and CaMnO is used3The absolute value of Seebeck coefficient of the material is relatively high, and the material is CaMnO3The thermal conductivity of the material is relatively low, and the thermoelectric conversion efficiency is good.
Examples 2 to 5, CaO 16.6019g and 23.3981g of MnO in the form of sheets2Uniformly mixing, and then sintering at high temperature, wherein the sintering temperature is 1300 ℃, and sintering is carried out for 10 hours; and ball-milling the mixture sintered at high temperature to form powder, wherein the mass ratio of the balls to the mixture is 20: 1, performing ball milling on the powder particle size at any time until the particle size of the powder particle is 50-800nm, wherein the ball milling time is 2.5 h; collecting powder, carrying out hot pressing treatment on the powder under argon gas by using a hot pressing die at the pressure of 65MPa and the temperature of 750 ℃, the heating rate of 9 ℃/min and the heat preservation time of 30min to obtain the tetragonal perovskite intergrowth structure Ca6Mn5O16A thermoelectric material.
Claims (11)
1. The calcium-manganese-oxygen thermoelectric material is characterized in that cubic phase CaMnO is adopted3The lamellar CaO is used as an embedded phase, the embedded phase is dispersed in the matrix phase and is directionally arranged to form a tetragonal perovskite intergrowth type structure CaO (CaMnO)3)mWherein m is 1, 2, 3 … ∞.
2. The calcium manganese oxygen thermoelectric material according to claim 1, wherein said tetragonal perovskite intergrowth type structure CaO (CaMnO)3)mWherein m is 2-10, m is a natural number.
3. The calcium-manganese-oxygen thermoelectric material according to claim 1, wherein a tetragonal perovskite intergrowth type structure CaO (CaMnO)3)mAdopts the components of CaO and MnO2Is prepared from CaO and MnO2The ratio of the amounts of substances is (m + 1): m, wherein m is 1, 2, 3 … ∞.
4. The preparation method of the calcium-manganese-oxygen thermoelectric material is characterized by comprising the following steps of:
s1, taking CaO and MnO2Uniformly mixed, CaO and MnO2The ratio of the amounts of substances is (m + 1): m, m is 1, 2, 3 … infinity, and then high-temperature sintering is carried out;
s2, performing ball milling on the mixture sintered at high temperature to form powder, wherein the mass ratio of the balls to the mixture is (10-30): 1, ball milling for 0.5-4h to ensure that the particle size of powder particles reaches 30-1000 nm;
and S3, collecting the powder, and performing hot pressing treatment on the powder under inert gas.
5. The method as claimed in claim 4, wherein the sintering temperature is 1200-1600 ℃ in step S1.
6. The method of claim 5, wherein in step S1, the high temperature sintering time is 4-18 h.
7. The method for preparing a calcium-manganese-oxygen thermoelectric material as claimed in claim 4, wherein in step S2, the mass ratio of the balls to the mixture is (15-25): 1.
8. the method of claim 4, wherein in step S2, the particle size of the powder is 50-800 nm.
9. The method for preparing a calcium-manganese-oxygen thermoelectric material as claimed in claim 4, wherein in step S2, the ball milling time is 1-3 h.
10. The method as claimed in claim 4, wherein the hot-pressing pressure is 40-80MPa, and the hot-pressing temperature is 600-900 ℃ in step S3.
11. The method for preparing a Ca-Mn-O thermoelectric material as claimed in claim 4, wherein in step S3, the heating rate of hot pressing is 8-10 ℃/min, and the powder is held while being hot pressed for 15-60 min.
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| CN116675518A (en) * | 2023-06-01 | 2023-09-01 | 江西理工大学 | Single-layer and double-layer perovskite multiferroic multiphase material, and preparation method and application thereof |
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