CN107445621B - Cu-Te nanocrystalline/Cu2SnSe3Thermoelectric composite material and preparation method thereof - Google Patents
Cu-Te nanocrystalline/Cu2SnSe3Thermoelectric composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of thermoelectric materials, and particularly relates to Cu-Te nanocrystalline/Cu2SnSe3The volume ratio of Cu-Te nano-crystal in the composite material is 0.2-1.2%. The Cu-Te nanocrystalline/Cu prepared by the invention2SnSe3The thermoelectric composite material shows better thermoelectric performance, and greatly improves Cu2SnSe3ZT value of the matrix; the preparation process is simple to operate, controllable in parameters and suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of thermoelectric materials, and particularly relates to Cu-Te nanocrystalline/Cu2SnSe3Thermoelectric composite materials and methods of making the same.
Background
The thermoelectric material is an energy functional material capable of realizing direct conversion of heat energy and electric energy, has a wide development prospect, and particularly is a choice of times due to the fact that the thermoelectric material is in short supply of energy resources at present. The related application field can be aerospace application power generation, and can also be a watch generating power by body temperature. In practical terms, the thermoelectric material can be applied to the recycling of industrial waste heat, and in addition, the thermoelectric material can be used for preparing environment-friendly refrigeration equipment such as refrigerators and air conditioners from the thermoelectric refrigeration perspective. The advantages of environmental protection, high precision, no noise and the like make the device have great development potential.
Thermoelectric figure of merit ZT is a fundamental parameter affecting the conversion efficiency of thermoelectric materials, and is formulated as ZT = σ S2T/k, wherein S, sigma, k and T are Seebeck coefficient, electric conductivity, thermal conductivity and absolute temperature respectively. In the field of application at present, materials such as bismuth telluride type alloys and filled skutterudite compounds are widely used. However, as further explored, various different types of thermoelectric materials were discovered and modified, although conventional thermoelectric materials have good propertiesBut the problem of expensive manufacturing cost has been a driving force for the development of new thermoelectric materials.
Cu2SnSe3The compound is a compound with a diamond-like structure, Cu-Se bonds in the compound are favorable for transporting electrons, and phonons can be effectively scattered by a complex lattice structure with a large amount of distortion, so that the thermal conductivity of the material is reduced, and the ZT value of the material is improved. Thus Cu2SnSe3The compound has great development potential in the aspect of improving thermoelectric performance. The literature (Acta Materialia, 2013, 61: 4297-.
Binary copper-based compound Cu2X (X = S, Se or Te) is a compound having a complex crystal structure. However, the binary system of Cu-Te has not been widely developed, and there is no reference to the composition as a second phase. The method prepares Cu-Te nanocrystalline by melt spinning and throwing, and prepares Cu-Te nanocrystalline/Cu by taking the Cu-Te nanocrystalline as a second phase2SnSe3The thermoelectric composite material greatly improves the Cu content of the matrix2SnSe3The thermoelectric figure of merit, the preparation method is novel, and has good application prospect.
Disclosure of Invention
The invention aims to provide Cu-Te nano crystal/Cu2SnSe3Thermoelectric composite material capable of remarkably improving Cu matrix2SnSe3Thermoelectric performance.
The invention also provides Cu-Te nano crystal/Cu2SnSe3The preparation method of the thermoelectric composite material has simple and easily controlled process and relatively low price, and is suitable for the Cu matrix2SnSe3The improvement of thermoelectric performance is particularly obvious.
The invention is realized by the following technical scheme:
the invention provides a Cu-Tenanocrystalline/Cu2SnSe3The Cu-Te nano-crystal is 0.2-1.2% of the volume ratio of the composite material.
Furthermore, the second phase of the Cu-Te nano-crystalline is mainly composed of Cu2-xTe、Cu2Te、Cu3-xTe2Phase composition.
The invention also provides Cu-Te nano crystal/Cu2SnSe3The preparation method of the thermoelectric composite material comprises the following steps:
(1) weighing copper and tellurium block simple substances according to a proportion, uniformly mixing, putting into a quartz tube for spin-casting, adjusting a copper roller to a proper rotating speed, carrying out melt spin-casting under the protection of argon gas to obtain a strip-shaped sample containing Cu-Te nanocrystals, and then grinding into powder;
(2) weighing copper, tin and selenium powder simple substances according to a proportion, uniformly mixing, putting the mixture into a graphite crucible, putting the graphite crucible filled with a sample into a quartz tube, carrying out vacuum sealing on the graphite crucible, putting the graphite crucible into a resistance furnace, and carrying out fusion reaction to obtain Cu2SnSe3Casting ingot, and manually grinding the ingot to powder; the molar ratio of the copper powder to the tin powder to the selenium powder is 2:1: 3;
(3) weighing the powder prepared in the steps (1) and (2) in proportion, and putting the powder into a ball mill for planetary ball milling;
(4) putting the powder after ball milling into a graphite die, and then putting the graphite die into a discharge plasma sintering furnace for vacuum sintering to prepare Cu-Te nano crystal/Cu2SnSe3A thermoelectric composite material.
Further, in the step (1), the molar ratio of the copper blocks to the tellurium blocks is 1.6-1.8: 1.
In the further step (1), the melt spinning process parameters are as follows: the induced current frequency is 28-35 Hz, the air injection pressure is 0.02-0.06 MPa, and the rotating speed of the copper roller is 1500-3000 r/min.
Further, in the step (2), the melting reaction is carried out by adopting a two-step method: firstly, heating to 900-1000 ℃ at a heating rate of 5-10 ℃/min, then preserving heat for 10-12 h, cooling to 600 ℃ after heat preservation is finished, then preserving heat for 24h, and finally cooling to room temperature along with the furnace.
Further, in the step (3), the technological parameters of the planetary ball milling are as follows: the ball material ratio is 15: 1, the rotating speed is 200-300 r/min, wherein the star-shaped ball milling is stopped for 20min every 1h of forward ball milling, then the reverse ball milling is stopped for 1h of 20min, and the circulation is carried out for 2-3 times.
Further, in the step (4), the process parameters of the spark plasma sintering are as follows: selecting a graphite mold with the diameter of 10mm or 12mm, the vacuum degree of less than 4.5Pa, the sintering pressure of 50-60 MPa, the heating rate of 100 ℃/min, the sintering temperature of 450-500 ℃, and then preserving heat for 10 min.
The invention has the beneficial effects that:
(1) the Cu-Te nano-crystalline thin strips prepared by the method are uniformly distributed, and the grain size is about 500 nm;
(2) the Cu-Te nanocrystalline/Cu prepared by the invention2SnSe3The thermoelectric composite material shows better thermoelectric performance, and greatly improves Cu2SnSe3ZT value of the matrix;
(3) the preparation method has the advantages of simple operation of the required process, controllable parameters and suitability for large-scale production.
Description of the drawings:
FIG. 1: XRD pattern of Cu-Te compound powder prepared in example 1 by melt spinning (1500 r/min).
FIG. 2: example 1 Field Emission Scanning Electron Microscopy (FESEM) image of thin Cu-Te compound strip prepared by melt spinning (1500 r/min).
FIG. 3: Cu-Te nanocrystals/Cu prepared after ball milling in example 12SnSe3And (3) a powder XRD (X-ray diffraction) spectrum of the thermoelectric composite material.
FIG. 4: bulk Cu-Te nanocrystals/Cu in example 12SnSe3The seebeck coefficient of the thermoelectric composite material varies with temperature.
FIG. 5: bulk Cu-Te nanocrystals/Cu in example 12SnSe3The electrical conductivity of the thermoelectric composite material changes with temperature.
FIG. 6: bulk Cu-Te nanocrystals/Cu in example 12SnSe3The thermal conductivity of the thermoelectric composite material varies with temperature.
FIG. 7: bulk Cu-Te nanocrystals/Cu in example 12SnSe3The ZT value of the thermoelectric composite changes with temperature.
FIG. 8: bulk 0.8% Cu-Te nanocrystal/Cu in example 22SnSe3The seebeck coefficient of the thermoelectric composite material varies with temperature.
FIG. 9: bulk 0.8% Cu-Te nanocrystal/Cu in example 22SnSe3The thermal conductivity of the thermoelectric composite material varies with temperature.
FIG. 10: bulk 0.8% Cu-Te nanocrystal/Cu in example 22SnSe3The ZT value of the thermoelectric composite changes with temperature.
FIG. 11: XRD pattern of Cu-Te compound powder prepared in example 3 by melt spinning (2500 r/min).
FIG. 12: a Field Emission Scanning Electron Microscope (FESEM) image of a thin Cu-Te compound strip prepared in example 3 by melt spinning (1500 r/min).
FIG. 13: bulk 1.2% Cu-Te nanocrystal/Cu in example 32SnSe3The ZT value of the thermoelectric composite changes with temperature.
Detailed Description
The invention is illustrated by the following specific examples.
Example 1
1.1 weighing 12g of high-purity (more than or equal to 99.9%) copper and tellurium block simple substances according to the molar ratio of the copper blocks to the tellurium blocks being 1.6:1, uniformly mixing, putting into a quartz tube for spin-casting, adjusting a copper roller to 1500r/min of rotation speed, carrying out melt spin-casting operation under the protection of argon (the air injection pressure is 0.02MPa) and the induced current frequency is 28Hz to obtain a strip-shaped sample containing Cu-Te nanocrystals, and manually grinding the strip-shaped sample into powder;
1.2 according to a molar ratio of 2:1:3 weighing 15g of high-purity (more than or equal to 99.9%) powder simple substances of copper, tin and selenium, uniformly mixing, putting the mixture into a graphite crucible, putting the graphite crucible containing the sample into a quartz tube, and carrying out vacuum sealing (the vacuum degree is less than 0.01MPa) treatment on the graphite crucible; will contain a samplePutting the quartz tube into a resistance furnace for smelting, heating the quartz tube from room temperature to 1000 ℃ at the heating rate of 5 ℃/min in the process of a melting reaction, then preserving heat for 12 hours, cooling to 600 ℃ after the heat preservation is finished, and then preserving heat for 24 hours to obtain Cu2SnSe3Casting ingot, and manually grinding the ingot to powder;
1.3 the powder prepared in the above step is mixed in a volume ratio of 0.4%: 1 (Cu-Te: Cu)2SnSe3) Weighing 10g of the composite sample, and then putting the composite sample into a ball mill for carrying out homogenization ball milling (ball-material ratio is 15: 1, the rotating speed is 300 r/min), wherein the star-shaped ball milling is stopped for 20min every time when the ball milling is carried out for 1h in the forward direction, and then the ball milling is carried out for 1h in the reverse direction and is stopped for 20 min;
1.4 putting the powder after the uniform ball milling into a graphite die with the diameter of 10mm, then putting the graphite die into a discharge plasma sintering furnace for vacuum sintering, and preparing the Cu-Te nano crystal/Cu under the sintering conditions that the vacuum degree is less than 4.5Pa, the sintering pressure is 55MPa, the heating rate is 100 ℃/min, the sintering temperature is 480 ℃, and then the temperature is kept for 10min2SnSe3A thermoelectric composite material.
The XRD pattern of the powder material of Cu-Te nano-crystal is shown in figure 1, the microstructure (FESEM) of the thin strip is shown in figure 2, and as can be seen from figures 1 and 2, Cu is mainly used2-xTe、Cu2Te、Cu3-xTe2Phase-composed Cu-Te compounds with grain sizes of several hundred nanometers. The XRD pattern of the powder after ball milling in step 1.3 is shown in FIG. 3, and it is understood from FIG. 3 that the composition phase of the Cu-Te compound cannot be found because the amount of Cu-Te added is too small compared with the matrix level. Finally prepared bulk Cu-Te nanocrystalline/Cu2SnSe3The changes of the seebeck, the electrical conductivity, the thermal conductivity and the ZT value of the thermoelectric composite material along with the temperature are respectively shown in figures 4, 5, 6 and 7, and it can be seen from the figures that the seebeck of the composite material is slightly higher than that of an un-compounded matrix, the thermal conductivity is obviously lower than that of the un-compounded matrix, and the ZT value is also higher than that of the un-compounded matrix.
Example 2
2.1 weighing 12g of high-purity (more than or equal to 99.9%) copper and tellurium block simple substances according to the molar ratio of the copper blocks to the tellurium blocks being 1.7:1, uniformly mixing, putting into a quartz tube for spin-casting, adjusting a copper roller to 2000r/min of rotating speed, carrying out melt spin-casting operation under the protection of argon (the air injection pressure is 0.06MPa) and the induced current frequency is 30Hz to obtain a strip-shaped sample containing Cu-Te nanocrystals, and manually grinding the strip-shaped sample into powder;
2.2 according to a molar ratio of 2:1:3 weighing 15g of high-purity (more than or equal to 99.9%) powder simple substances of copper, tin and selenium, uniformly mixing, putting the mixture into a graphite crucible, putting the graphite crucible containing the sample into a quartz tube, and carrying out vacuum sealing (the vacuum degree is less than 0.01MPa) treatment on the graphite crucible; putting the quartz tube containing the sample which is well sealed in vacuum into a resistance furnace for smelting, heating the quartz tube from room temperature to 900 ℃ at the heating rate of 5 ℃/min in the process of the melting reaction, then preserving the heat for 12h, cooling to 600 ℃ after the heat preservation is finished, and then preserving the heat for 24h to obtain Cu2SnSe3Casting ingot, and manually grinding the ingot to powder;
2.3 the powder prepared in the above step is mixed in a volume ratio of 0.8%: 1 (Cu-Te: Cu)2SnSe3) Weighing 10g of the composite sample, and then putting the composite sample into a ball mill for carrying out homogenization ball milling (ball-material ratio is 15: 1, the rotating speed is 300 r/min), wherein the star-shaped ball milling is stopped for 20min every time when the ball milling is carried out for 1h in the forward direction, and then the ball milling is carried out for 1h in the reverse direction and is stopped for 20 min;
2.4 putting the powder after the ball milling into a graphite die with the diameter of 10mm, then putting the graphite die into a discharge plasma sintering furnace for vacuum sintering, and preparing the Cu-Te nano crystal/Cu under the sintering conditions that the vacuum degree is less than 4.5Pa, the sintering pressure is 60MPa, the heating rate is 100 ℃/min, the sintering temperature is 500 ℃, and then the temperature is kept for 10min2SnSe3A thermoelectric composite material.
Prepared bulk Cu-Te nanocrystalline/Cu2SnSe3The change relations of the seebeck, the thermal conductivity and the ZT value of the thermoelectric composite material along with the temperature are respectively shown in figures 8, 9 and 10, and it can be seen from the figures that the seebeck of the composite material is higher than that of an un-compounded matrix, the thermal conductivity is obviously lower than that of the un-compounded matrix, and the ZT value is also higher than that of the un-compounded matrix.
Example 3
3.1 weighing 12g of high-purity (more than or equal to 99.9%) copper and tellurium block simple substances according to the molar ratio of the copper blocks to the tellurium blocks being 1.8:1, uniformly mixing, putting into a quartz tube for spin-casting, adjusting a copper roller to 3000r/min, carrying out melt spin-casting operation under the protection of argon (the air injection pressure is 0.04MPa) and the induced current frequency is 35Hz to obtain a strip-shaped sample containing Cu-Te nanocrystals, and manually grinding into powder;
3.2 according to a molar ratio of 2:1:3 weighing 15g of high-purity (more than or equal to 99.9%) powder simple substances of copper, tin and selenium, uniformly mixing, putting the mixture into a graphite crucible, putting the graphite crucible containing the sample into a quartz tube, and carrying out vacuum sealing (the vacuum degree is less than 0.01MPa) treatment on the graphite crucible; putting the quartz tube containing the sample which is well sealed in vacuum into a resistance furnace for smelting, heating the quartz tube to 1000 ℃ from room temperature at the heating rate of 5 ℃/min in the process of the melting reaction, then preserving the heat for 10h, cooling the quartz tube to 600 ℃ after the heat preservation is finished, and then preserving the heat for 24h to obtain Cu2SnSe3Casting ingot, and manually grinding the ingot to powder;
3.3 mixing the powder prepared in the above step according to the volume ratio of 1.2%: 1 (Cu-Te: Cu)2SnSe3) Weighing 10g of the composite sample, and then putting the composite sample into a ball mill for carrying out homogenization ball milling (ball-material ratio is 15: 1, the rotating speed is 300 r/min), wherein the star-shaped ball milling is stopped for 20min every time when the ball milling is carried out for 1h in the forward direction, and then the ball milling is carried out for 1h in the reverse direction and is stopped for 20 min;
3.4 putting the powder after the ball milling into a graphite die with the diameter of 10mm, then putting the graphite die into a discharge plasma sintering furnace for vacuum sintering, and preparing the Cu-Te nano crystal/Cu under the sintering conditions that the vacuum degree is less than 4.5Pa, the sintering pressure is 55MPa, the heating rate is 100 ℃/min, the sintering temperature is 480 ℃, and then the temperature is kept for 10min2SnSe3A thermoelectric composite material.
The XRD pattern of the Cu-Te nano-crystalline powder material is shown in figure 11, the microstructure (FESEM) of the thin strip is shown in figure 12, and as can be seen from figures 11 and 12, the material obtained in the step 1) is mainly Cu2-xTe、Cu2Te、Cu3-xTe2Phase-composed Cu-Te compounds with grain sizes of several hundred nanometers. Finally prepared bulk Cu-Te nanocrystalline/Cu2SnSe3The ZT value of the thermoelectric composite material varies with the temperatureIn fig. 13, it can be seen that the ZT values of the composite are significantly higher than the levels without the composite.
Comparative example 1
Cu-Te nanocrystalline powder and matrix Cu were prepared according to example 1, steps 1.1 and 1.22SnSe3The thermoelectric material is prepared by mixing the powder prepared in the step with the following raw materials in a volume ratio of 0.1%: 1 (Cu-Te: Cu)2SnSe3) Weighing 10g of composite sample, putting the composite sample into a ball mill for carrying out homogenization ball milling with the ball milling parameters being the same as those in example 1, then carrying out discharge plasma sintering on the powder after ball milling with the sintering parameters being the same as those in example 1 to prepare Cu-Te nano crystal/Cu2SnSe3A thermoelectric composite material. However, for 0.1% Cu-Te nanocrystalline/Cu2SnSe3The thermoelectric performance measurement of the thermoelectric composite material is shown in table 1, and it can be seen that the electric conductivity, the thermal conductivity and the seebeck coefficient are not obviously improved at normal temperature, the ZT value is not greatly different from the matrix at high temperature of 700K, which shows that the composition of 0.1% Cu-Te nanocrystalline does not obviously improve the matrix Cu2SnSe3The thermoelectric properties of (1).
Comparative example 2
Cu-Te nanocrystalline powder and matrix Cu were prepared according to example 2, steps 1.1 and 1.22SnSe3The thermoelectric material is prepared by mixing the powder prepared in the step with the following raw materials in a volume ratio of 1.5%: 1 (Cu-Te: Cu)2SnSe3) Weighing 10g of composite sample, putting the composite sample into a ball mill for carrying out homogenization ball milling with the ball milling parameters being the same as those in example 1, then carrying out discharge plasma sintering on the powder after ball milling with the sintering parameters being the same as those in example 1 to prepare Cu-Te nano crystal/Cu2SnSe3A thermoelectric composite material. For 1.5% Cu-Te nanocrystalline/Cu2SnSe3The thermoelectric property measurement of the thermoelectric composite material is shown in table 1, it can be seen that the seebeck coefficient and the electric conductivity are both improved at normal temperature, although a certain nano structure can effectively reduce the lattice thermal conductivity of the thermoelectric material so as to reduce the total thermal conductivity, the improvement of the thermal conductivity caused by the self thermal conductivity volume effect of the 1.5 percent Cu-Te nano crystal powder exceeds the reduction of the thermal conductivity caused by the nano structure, so the thermal conductivity of the composite material is increased, and finally the ZT value of the thermoelectric composite material is reduced rather than that of a substrate at 700K at high temperatureIt is demonstrated that the 1.5% Cu-Te nanocrystalline composition does not improve the Cu matrix2SnSe3The effect of the thermoelectric performance of (a).
TABLE 1
Comparative example 3
Weighing 12g of high-purity (more than or equal to 99.9%) copper and tellurium block simple substances according to the molar ratio of the copper blocks to the tellurium blocks being 1.9:1, uniformly mixing, putting into a spin-casting quartz tube for spin-casting, wherein the spin-casting parameters are as in example 3.
Comparative example 4
Weighing 12g of high-purity (more than or equal to 99.9%) copper and tellurium block simple substances according to the molar ratio of the copper block to the tellurium block of 1.8:1, uniformly mixing, putting into a quartz tube for spin-casting, adjusting a copper roller to the rotation speed of 1000r/min, and carrying out melt spin-casting operation under the protection of argon (the air injection pressure is 0.01MPa) and the induced current frequency is 25Hz, and finding in the experimental process that the Cu-Te can not reach a molten state due to the change of the induced current frequency, wherein the alloy block only presents a deep red state, and can not be used for preparing a strip of Cu-Te nanocrystal by blowing and spin-casting.
Claims (8)
1. Cu-Te nanocrystalline/Cu2SnSe3The thermoelectric composite material is characterized in that the volume ratio of the Cu-Te nano-crystals in the composite material is 0.2-1.2%.
2. The Cu-Te nanocrystal/Cu of claim 12SnSe3The thermoelectric composite material is characterized in that the second phase of the Cu-Te nano-crystalline is mainly composed of Cu2-xTe、Cu2Te、Cu3-xTe2Phase composition.
3. A process as claimed in claim 1 or 2Cu-Te nanocrystalline/Cu2SnSe3The preparation method of the thermoelectric composite material is characterized by comprising the following steps:
(1) weighing copper and tellurium block simple substances according to a proportion, uniformly mixing, putting into a quartz tube for spin-casting, adjusting a copper roller to a proper rotating speed, carrying out melt spin-casting under the protection of argon gas to obtain a strip-shaped sample containing Cu-Te nanocrystals, and then grinding into powder;
(2) weighing copper, tin and selenium powder simple substances according to a proportion, uniformly mixing, putting the mixture into a graphite crucible, putting the graphite crucible filled with a sample into a quartz tube, carrying out vacuum sealing on the graphite crucible, putting the graphite crucible into a resistance furnace, and carrying out fusion reaction to obtain Cu2SnSe3Casting ingot, and manually grinding the ingot to powder;
(3) weighing the powder prepared in the steps (1) and (2) in proportion, and putting the powder into a ball mill for planetary ball milling;
(4) putting the powder after ball milling into a graphite die, and then putting the graphite die into a discharge plasma sintering furnace for vacuum sintering to prepare Cu-Te nano crystal/Cu2SnSe3A thermoelectric composite material.
4. The preparation method according to claim 3, wherein in the step (1), the molar ratio of the copper blocks to the tellurium blocks is 1.6-1.8: 1.
5. The production method according to claim 3 or 4, characterized in that: in the step (1), the melt spinning process parameters are as follows: the induced current frequency is 28-35 Hz, the air injection pressure is 0.02-0.06 MPa, and the rotating speed of the copper roller is 1500-3000 r/min.
6. The production method according to claim 3, characterized in that: in the step (2), the melt reaction is carried out by adopting a two-step method: firstly, heating to 900-1000 ℃ at a heating rate of 5-10 ℃/min, then preserving heat for 10-12 h, cooling to 600 ℃ after heat preservation is finished, then preserving heat for 24h, and finally cooling to room temperature along with the furnace.
7. The preparation method according to claim 3, wherein in the step (3), the process parameters of the planetary ball milling are as follows: the ball material ratio is 15: 1, the rotating speed is 200-300 r/min, wherein the star-shaped ball milling is stopped for 20min every 1h of forward ball milling, then the reverse ball milling is stopped for 1h of 20min, and the circulation is carried out for 2-3 times.
8. The preparation method according to claim 3, wherein in the step (4), the process parameters of the spark plasma sintering are as follows: selecting a graphite mold with the diameter of 10mm or 12mm, the vacuum degree of less than 4.5Pa, the sintering pressure of 50-60 MPa, the heating rate of 100 ℃/min, the sintering temperature of 450-500 ℃, and then preserving heat for 10 min.
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