WO2015034317A1 - 열전 재료 및 그 제조 방법 - Google Patents
열전 재료 및 그 제조 방법 Download PDFInfo
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- WO2015034317A1 WO2015034317A1 PCT/KR2014/008404 KR2014008404W WO2015034317A1 WO 2015034317 A1 WO2015034317 A1 WO 2015034317A1 KR 2014008404 W KR2014008404 W KR 2014008404W WO 2015034317 A1 WO2015034317 A1 WO 2015034317A1
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- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- the present invention relates to a thermoelectric conversion technology, and more particularly, to a thermoelectric conversion material having excellent thermoelectric conversion characteristics, a method of manufacturing the same, and a use thereof.
- Compound A semiconductor is a compound which acts as a semiconductor by combining two or more elements rather than a single element such as silicon or germanium.
- Various kinds of such compound semiconductors are currently developed and used in various fields.
- a compound semiconductor may be used in a thermoelectric conversion element using a Peltier effect, a light emitting element such as a light emitting diode or a laser diode using the photoelectric conversion effect, and a solar cell.
- thermoelectric conversion element may be applied to thermoelectric power generation, thermoelectric conversion cooling, or the like, and is generally configured in such a manner that an N-type thermoelectric semiconductor and a P-type thermoelectric semiconductor are electrically connected in series and thermally in parallel.
- thermoelectric conversion power generation is a form of power generation that converts thermal energy into electrical energy by using thermoelectric power generated by providing a temperature difference to a thermoelectric conversion element.
- thermoelectric conversion cooling is a form of cooling which converts electrical energy into thermal energy by taking advantage of the effect that a temperature difference occurs at both ends when a direct current flows through both ends of the thermoelectric conversion element.
- thermoelectric conversion element The energy conversion efficiency of such a thermoelectric conversion element is largely dependent on ZT which is a figure of merit of a thermoelectric conversion material.
- ZT may be determined according to Seebeck coefficient, electrical conductivity, thermal conductivity, and the like, and the higher the ZT value, the better the thermoelectric conversion material.
- thermoelectric materials have been proposed and developed so that they can be used as thermoelectric conversion elements.
- Cu x Se (x ⁇ 2) has been proposed and developed as Cu-Se based thermoelectric materials. This is considered to be because Cu x Se, whose composition is x or less, is already known.
- thermoelectric material having a low ZT value at low temperature is not preferable, in particular as a thermoelectric material for power generation. This is because even if such thermoelectric material is applied to a high temperature heat source, some of the material experiences a much lower temperature than the desired temperature due to the temperature gradient generated in the material itself. Therefore, a thermoelectric material capable of maintaining a high ZT value over a wide temperature range by having a high ZT value in a high temperature range of 600 ° C. or higher and a low temperature section below 600 ° C. such as 100 ° C. to 600 ° C. It needs to be developed.
- an object of the present invention is to provide a thermoelectric material having a high thermoelectric conversion performance in a wide temperature range, a method of manufacturing the same, and an apparatus using the same.
- thermoelectric material represented by the following Chemical Formula 1 after repeated studies on the thermoelectric material, and confirmed that the novel thermoelectric conversion material may have excellent thermoelectric conversion performance.
- the present invention was completed.
- x in Chemical Formula 1 may be x ⁇ 2.2.
- x in Chemical Formula 1 may be x ⁇ 2.15.
- x in Chemical Formula 1 may be x ⁇ 2.1.
- x in Chemical Formula 1 may be 2.01 ⁇ x.
- x in Chemical Formula 1 may be 2.025 ⁇ x.
- x in Chemical Formula 1 may be 2.04 ⁇ x.
- x in Chemical Formula 1 may be 2.05 ⁇ x.
- x in Chemical Formula 1 may be 2.075 ⁇ x.
- thermoelectric conversion element according to the present invention for achieving the above object includes the thermoelectric material according to the present invention.
- thermoelectric generator according to the present invention for achieving the above object includes the thermoelectric material according to the present invention.
- thermoelectric material excellent in thermoelectric conversion performance can be provided.
- thermoelectric material in the thermoelectric material according to an aspect of the present invention, a low thermal diffusivity and a low thermal conductivity, a high Seebeck coefficient and a high ZT value can be secured in a wide temperature range of 100 ° C to 600 ° C.
- thermoelectric material according to the present invention can be used as another material in place of or in addition to the conventional thermoelectric material.
- thermoelectric material according to the present invention can maintain a higher ZT value than the conventional thermoelectric material even at a temperature of 600 ° C. or lower, and even at a low temperature close to 100 ° C. to 200 ° C. Therefore, when the thermoelectric material according to the present invention is used in a thermoelectric device for power generation or the like, stable thermoelectric conversion performance can be ensured even when a material is exposed to a relatively low temperature.
- thermoelectric material according to the present invention may be used in solar cells, infrared windows (IR windows), infrared sensors, magnetic elements, memories, and the like.
- thermoelectric material 1 is a graph showing an XRD analysis result of a thermoelectric material according to various embodiments of the present disclosure.
- FIG. 2 is an enlarged graph of portion A of FIG. 1.
- thermoelectric materials according to an embodiment of the present invention.
- thermoelectric material 8 is a graph showing an XRD analysis result according to a temperature of a thermoelectric material according to an embodiment of the present invention.
- thermoelectric material 9 is a flowchart schematically illustrating a method of manufacturing a thermoelectric material according to an embodiment of the present invention.
- thermoelectric material 10 is a graph illustrating a comparison of thermal diffusivity measurement results according to temperatures of thermoelectric materials according to examples and comparative examples of the present disclosure.
- thermoelectric material 11 is a graph illustrating a comparison of Seebeck coefficient measurement results according to temperatures of thermoelectric materials according to examples and comparative examples of the present disclosure.
- thermoelectric material 12 is a graph illustrating a comparison of ZT value measurement results according to temperatures of thermoelectric materials according to examples and comparative examples of the present disclosure.
- thermoelectric material 13 is a SIM image of a thermoelectric material according to one embodiment of the present invention.
- thermoelectric material 14 is a SIM image of a thermoelectric material according to a comparative example.
- FIG. 15 is a graph in which the y-axis is scaled only for the embodiments of FIG. 10.
- FIG. 16 is a graph illustrating a scale change of the y-axis only for the embodiments of FIG. 11.
- FIG. 17 is a graph illustrating a comparison of XRD analysis results of thermoelectric materials according to different exemplary embodiments of the present disclosure, manufactured by different synthesis methods.
- thermoelectric material 19 is a graph illustrating a comparison of lattice thermal conductivity measurement results according to temperatures of thermoelectric materials according to different embodiments of the present disclosure, manufactured by different synthesis methods.
- thermoelectric materials according to different embodiments of the present disclosure, manufactured by different synthesis methods.
- thermoelectric materials 21 is a graph illustrating a comparison of ZT value measurement results according to temperatures of thermoelectric materials according to different exemplary embodiments of the present disclosure, manufactured by different synthesis methods.
- thermoelectric material according to an aspect of the present invention may be represented by the following Chemical Formula 1.
- x ⁇ 2.2 may be.
- Chemical Formula 1 it may be configured to satisfy the condition of x ⁇ 2.1.
- the condition of 2.01 ⁇ x may be satisfied.
- it may be 2.01 ⁇ x.
- thermoelectric conversion performance of the thermoelectric material according to the present invention may be further improved.
- the condition of 2.05 ⁇ x may be satisfied.
- thermoelectric material represented by the formula (1) may include a part of the secondary phase, the amount may vary depending on the heat treatment conditions.
- thermoelectric material which concerns on this invention can also be called the thermoelectric material containing copper containing particle
- the Cu-containing particle means a particle containing at least Cu, and may be said to include not only particles composed of Cu but also particles containing one or more other elements in addition to Cu.
- the Cu-containing particles may include at least one of Cu particles composed only of a single Cu composition and Cu oxide particles in which Cu and O are bonded, such as Cu 2 O particles.
- thermoelectric material according to the present invention may include INDOT (Induced Nano DOT) as Cu-containing particles.
- INDOT refers to particles of nanometer size (eg, 1 nanometer to 100 nanometers in diameter) spontaneously generated during the formation of a thermoelectric material.
- the INDOT is not a particle artificially introduced into the thermoelectric material from the outside during the formation of the thermoelectric material, but may be a particle induced by the inside of the thermoelectric material.
- such nanodots may exist at grain boundaries of semiconductors.
- the INDOT may be generated at grain boundaries during the formation of the thermoelectric material, in particular, during the sintering process.
- the INDOT included in the thermoelectric material according to the present invention may be defined as an induced nano-dot on grain boundary spontaneously induced at the grain boundary of the semiconductor during the sintering process.
- the thermoelectric material according to the present invention can be said to be a thermoelectric material including a Cu-Se matrix and an INDOT.
- thermoelectric material according to the present invention may be said to contain a relatively large amount of Cu as compared to conventional Cu-Se-based thermoelectric materials.
- Cu may be present alone or in the form of other elements such as oxygen, without forming a matrix with Se.
- Cu which is present alone or in combination with other elements, may be present. It may be included in the form of nanodots. This will be described in more detail with reference to the experimental results.
- FIG. 1 is a graph illustrating an XRD analysis result of a thermoelectric material according to various embodiments of the present disclosure
- FIG. 2 is an enlarged graph of part A of FIG. 1.
- An analysis graph is shown for (x-axis units in degrees).
- XRD pattern analysis graphs of the embodiments are shown spaced apart from each other by a predetermined distance in the vertical direction.
- the graphs of the embodiments are shown to overlap each other without being spaced apart for convenience of comparison.
- Cu peaks appearing when Cu is present in a single composition are indicated by B.
- Cu present without forming a matrix with Se may exist in the form of nanodots.
- such Cu-containing nanodots may be present in the form of agglomerated with each other inside the thermoelectric material, particularly at the grain boundary of the Cu-Se matrix. That is, in the thermoelectric material according to the present invention, the Cu-Se matrix may be composed of a plurality of grains, and the Cu-containing INDOT may be located at grain boundaries of the matrix.
- thermoelectric materials according to an embodiment of the present invention.
- FIG. 3 is a SEM photograph of a portion of Cu 2.075 Se as an embodiment of the present invention
- FIGS. 4 and 5 are SEM photographs of different portions of Cu 2.1 Se as another embodiment of the present invention. It is a photograph. 6 is a graph showing EDS analysis results for the C1 part of FIG. 3, and FIG. 7 is a graph showing EDS analysis results for the C2 part of FIG.
- FIGS. 3 to 5 a plurality of grains having a size of about several micrometers to several tens of micrometers (for example, 1 ⁇ m to 100 ⁇ m) and a plurality of nanometer-sized particles having a smaller size than such grains are shown. It can be seen that there is a nano-dot.
- the nanodots may be formed along the grain boundaries of the matrix having a plurality of grains, and at least some of them may be present in the form of agglomeration with each other, such as a portion indicated by C2.
- the SEM photographs of FIGS. 4 and 5 clearly show that nanodots, such as nanodots having an average particle diameter of 1 nm to 500 nm, are widely distributed along the grain boundaries of the Cu-Se matrix.
- thermoelectric material according to an aspect of the present invention may be referred to as a thermoelectric material including Cu particles, in particular Cu-containing INDOT, together with a Cu-Se matrix composed of Cu and Se.
- Cu-containing INDOTs may be present in agglomerated form in the thermoelectric material.
- the Cu-containing INDOT may exist in the form of Cu alone, but may be present in the form of Cu oxide such as Cu 2 O in combination with O, as the O peak is slightly observed in FIG. 7.
- the thermoelectric material according to one aspect of the present invention may include Cu-containing nanodots, in particular, INDOT and Cu-Se matrices.
- the Cu-Se matrix may be represented by the chemical formula of Cu x Se, where x is a positive rational number.
- x may have a value around 2, for example, a value of 1.8 to 2.2.
- x may have a value of 2 or less, such as a value of 1.8 to 2.0.
- the thermoelectric material according to the present invention may include a Cu 2 Se matrix and a Cu-containing nanodot. Cu-containing nanodots can cause phonon scattering to reduce thermal diffusivity.
- the Cu-containing nanodots may be present between the crystal interfaces of the Cu—Se matrix as described above.
- the thermoelectric material according to the present invention may comprise copper particles of a single composition between the crystal interfaces of such matrices together with the Cu 2 Se matrix.
- some of the Cu-containing nanodots may be present inside the crystals of the Cu-Se matrix.
- thermoelectric material according to an aspect of the present invention may be referred to as a thermoelectric material containing Cu and Se and including a plurality of crystal structures at a predetermined temperature. That is, in the thermoelectric material according to the present invention, a crystal structure composed of Cu atoms and Se atoms may exist in two or more forms at a predetermined temperature.
- thermoelectric material according to the present invention may have a plurality of crystal lattice structures different from each other at a predetermined temperature in a temperature range of 100 ° C to 300 ° C.
- thermoelectric material 8 is a graph showing an XRD analysis result according to a temperature of a thermoelectric material according to an embodiment of the present invention.
- Figure 8 is an embodiment of the present invention, for Cu 2.1 Se, XRD at each temperature condition of 25 °C, 50 °C, 100 °C, 150 °C, 200 °C, 250 °C, 300 °C and 350 °C Is a graph measured.
- the monoclinic (Monoclinic_C2 / C) crystal structure is mainly used. It can be seen that only the corresponding peaks are present. Therefore, in the case of the thermoelectric material according to the present invention, it can be seen that at a temperature of 50 ° C. or less, crystals composed of Cu atoms and Se atoms exist in the form of a single phase of a monoclinic (Monoclinic_C2 / C) structure.
- thermoelectric material which concerns on this invention contains the some crystal structure which has both a monoclinic crystal structure and a cubic crystal structure simultaneously in the temperature condition of 100 degreeC.
- peaks corresponding to the cubic crystal structures peaks for two cubic crystal structures (Cubic_Fm-3m and Cubic_F-43m) having different space groups can be observed. have.
- thermoelectric material which concerns on this invention has a crystal structure containing 1 type of monoclinic crystal structure (Monoclinic_C2 / C) and 2 types of cubic crystal structures on 100 degreeC temperature conditions. Therefore, in this case, the thermoelectric material according to this aspect of the present invention may be said to have three or more crystal structures in which crystals composed of Cu atoms and Se atoms have a temperature condition of 100 ° C. In the thermoelectric material according to the present invention, when the temperature is increased from 50 ° C to 100 ° C, part of the monoclinic crystal structure may be phase transition into two kinds of cubic crystal structures.
- thermoelectric material according to the present invention at a temperature condition of 150 ° C to 250 ° C, particularly at least one of 150 ° C, 200 ° C and 250 ° C, crystals composed of Cu atoms and Se atoms have different space groups. It can be said that it is formed in the form containing two types of cubic crystal structures (Cubic_Fm-3m, Cubic_F-43m). In this case, the space groups of the two types of cubic crystal structures may be represented by Fm-3m and F-43m, respectively.
- thermoelectric material which concerns on this invention, as a temperature rises from 100 degreeC to 150 degreeC, it can be said that most of a monoclinic crystal structure changes into a cubic crystal structure.
- thermoelectric material according to the present invention as the temperature increases from 150 ° C. to 200 ° C., the ratio of the F-43m cubic crystal structure may be relatively increased.
- thermoelectric material according to the present invention as the temperature increases from 200 ° C. to 250 ° C., the ratio of the F-43m cubic crystal structure may be relatively reduced.
- thermoelectric material according to the present invention exists in the form of a single crystal structure in the form of Cubic_Fm-3m at a temperature of 300 ° C. or higher.
- thermoelectric material according to the present invention shows that as the temperature increases from 250 ° C to 300 ° C or more, the F-43m cubic crystal structure disappears and only the Fm-3m cubic crystal structure appears in the form of a single phase. Able to know.
- thermoelectric material according to the present invention a crystal structure composed of Cu atoms and Se atoms is mixed in a plurality of different forms at predetermined temperature conditions in a temperature range of 100 ° C to 300 ° C. can do.
- thermoelectric material according to an aspect of the present invention is a Cu-Se-based thermoelectric material containing Cu and Se, is a thermoelectric material having a lower thermal conductivity and a higher ZT value than conventional Cu-Se-based thermoelectric materials. .
- thermoelectric material according to the present invention may be composed of Cu and Se, in which case it may be represented by the chemical formula of Cu x Se, where x is a free number.
- thermoelectric material according to the present invention may have a thermal diffusivity of 0.5 mm 2 / s or less in a temperature range of 100 ° C. to 600 ° C.
- thermoelectric material according to the present invention may have a ZT value of 0.3 or more over the entire range of the temperature range of 100 ° C to 600 ° C.
- thermoelectric material according to the present invention may have a ZT value of 0.3 or more at a temperature condition of 100 ° C.
- thermoelectric material according to the present invention may have a ZT value of 0.4 or more at a temperature condition of 100 ° C.
- thermoelectric material according to the present invention may have a ZT value of 0.4 or more at a temperature condition of 200 ° C.
- the thermoelectric material according to the present invention may have a ZT value of 0.5 or more at a temperature condition of 200 ° C. More preferably, the thermoelectric material according to the present invention may have a ZT value greater than 0.6 at a temperature condition of 200 ° C.
- thermoelectric material according to the present invention may have a ZT value of 0.6 or higher at a temperature condition of 300 ° C.
- the thermoelectric material according to the present invention may have a ZT value of 0.75 or more at a temperature condition of 300 ° C. More preferably, the thermoelectric material according to the present invention may have a ZT value greater than 0.8 at a temperature condition of 300 ° C. More preferably, the thermoelectric material according to the present invention may have a ZT value greater than 0.9 at a temperature condition of 300 ° C.
- thermoelectric material according to the present invention may have a ZT value of 0.7 or higher at a temperature condition of 400 ° C.
- the thermoelectric material according to the present invention may have a ZT value of 0.8 or more at a temperature condition of 400 ° C.
- the thermoelectric material according to the present invention may have a ZT value of 1.0 or more at a temperature condition of 400 ° C.
- thermoelectric material according to the present invention may have a ZT value of 0.6 or higher at a temperature condition of 500 ° C.
- the thermoelectric material according to the present invention may have a ZT value of 0.7 or more at a temperature condition of 500 ° C.
- the thermoelectric material according to the present invention may have a ZT value of 1.1 or more at a temperature condition of 500 ° C.
- the thermoelectric material according to the present invention may have a ZT value of 1.3 or more at a temperature condition of 500 ° C.
- thermoelectric material according to the present invention may have a ZT value of 0.6 or higher at a temperature condition of 600 ° C.
- the thermoelectric material according to the present invention may have a ZT value of 0.8 or more at a temperature condition of 600 ° C.
- the thermoelectric material according to the present invention may have a ZT value of 1.4 or more at a temperature condition of 600 ° C.
- the thermoelectric material according to the present invention may have a ZT value of 1.8 or higher at a temperature condition of 600 ° C.
- thermoelectric material according to the present invention can be produced by the following thermoelectric material manufacturing method.
- thermoelectric material 9 is a flowchart schematically illustrating a method of manufacturing a thermoelectric material according to an embodiment of the present invention.
- the method of manufacturing a thermoelectric material according to the present invention represented by Chemical Formula 1 may include a mixture forming step S110 and a compound forming step S120.
- the mixture forming step (S110) is a step that can form a mixture by mixing Cu and Se as a raw material.
- the step S110 by measuring the Cu and Se to meet the formula (1), that is, Cu x Se (x is a positive rational number, in particular 2 ⁇ x ⁇ 2.6), and can form a mixture by mixing them That's a step.
- step S110 Cu and Se in powder form may be mixed.
- the mixing of Cu and Se is made better, and the synthesis of Cu x Se can be made better.
- the mixing of Cu and Se is carried out in the manner of hand milling (ball milling), ball milling (planetary ball mill), etc. using a mortar (mortar)
- the present invention is not limited by this specific mixing method.
- the composite material forming step (S120), by heat treating the mixture formed in the step S110 is a step to synthesize a material represented by Cu x Se (2 ⁇ x ⁇ 2.6) .
- a mixture of Cu and Se may be charged to a furnace and heated at a predetermined temperature for a predetermined time, thereby allowing the Cu x Se compound to be synthesized.
- the step S120 may be performed by a solid state reaction (SSR) method.
- SSR solid state reaction
- the raw materials used for the synthesis that is, the mixture does not change into the liquid state in the synthesis process, and the reaction may occur in the solid state.
- the step S120 may be performed for 1 hour to 24 hours in the temperature range of 200 °C to 650 °C. Since this temperature is in a temperature range lower than the melting point of Cu, when heated in this temperature range, Cu x Se may be synthesized in a state where Cu is not dissolved. In particular, the step S120 may be performed for 15 hours under a temperature condition of 500 °C.
- step S120 for the synthesis of Cu x Se, a mixture of Cu and Se is put into a cemented carbide mold to form pellets, and the mixture of such pellets is put into a fused silica tube and vacuumed. Can be sealed.
- the vacuum-sealed first mixture may be charged into a furnace and heat treated.
- thermoelectric material manufacturing method according to the present invention after the composite forming step (S120), may further comprise the step of sintering the composite (S130).
- step S130 may be performed by a hot press (Hot Press) method or a discharge plasma sintering (Spark Plasma Sintering) method.
- Hot Press Hot Press
- spark Plasma Sintering spark Plasma Sintering
- thermoelectric material according to the present invention when sintered by the pressure sintering method, it is easy to obtain a high sintered density and an effect of improving thermoelectric performance.
- the pressure sintering step may be performed under a pressure condition of 30MPa to 200MPa.
- the pressure sintering step may be performed under a temperature condition of 300 °C to 800 °C.
- the pressure sintering step may be performed for 1 minute to 12 hours under the pressure and temperature conditions.
- the step S130 may be performed while flowing a gas, such as Ar, He, N 2 , which contains a part of hydrogen or does not contain hydrogen in a vacuum state.
- a gas such as Ar, He, N 2 , which contains a part of hydrogen or does not contain hydrogen in a vacuum state.
- the step S130 may be performed by pulverizing the composite formed in the step S120 into a powder form, followed by pressure sintering. In this case, while improving convenience in the sintering and measuring process, the sintered density can be further increased.
- the Cu-containing particles may be spontaneously formed in this pressure sintering step (S130). That is, Cu-containing particles of the thermoelectric material according to the present invention may be spontaneously induced in the manufacturing process, in particular, the sintering process, rather than being forcibly input from the outside. Therefore, the Cu-containing particles according to the present invention may be INDOT (Induced Nano DOT).
- the thermoelectric material according to the present invention may be a thermoelectric material including nanodots (induced nano-dot on grain boundary) spontaneously induced at the crystal interface of the matrix during the sintering process. According to this aspect of the present invention, the Cu-containing particles can be easily formed because no high effort is required to introduce Cu-containing particles into the thermoelectric material, especially the crystal interface.
- thermoelectric conversion element according to the present invention may include the above-mentioned thermoelectric material.
- the thermoelectric material according to the present invention can effectively improve the ZT value in a wide temperature range compared to conventional thermoelectric materials, especially Cu-Se-based thermoelectric materials. Therefore, the thermoelectric material according to the present invention can be usefully used in thermoelectric conversion elements in place of conventional thermoelectric conversion materials or in addition to conventional compound semiconductors.
- thermoelectric material according to the present invention can be used in a thermoelectric power generation device that performs thermoelectric power generation using a waste heat source or the like. That is, the thermoelectric generator according to the present invention includes the thermoelectric material according to the present invention described above. In the case of the thermoelectric material according to the present invention, since it shows a high ZT value in a wide temperature range, such as a temperature range of 100 ° C. to 600 ° C., it may be more usefully applied to thermoelectric power generation.
- thermoelectric material according to the present invention may be manufactured in the form of a bulk type thermoelectric material.
- Cu 2.01 Se Cu and Se in powder form were weighed to fit this formula, then placed in alumina mortar and mixed. The mixed material was placed in a cemented carbide mold to make pellets and placed in a fused silica tube and vacuum sealed. Then, it was put into a box furnace and heated at 500 ° C. for 15 hours, and after heating, it was slowly cooled to room temperature to obtain a Cu 2.01 Se composite.
- the Cu 2.01 Se composite was filled in a cemented carbide mold for hot pressing, and then hot pressed and sintered under vacuum at 650 ° C. to obtain a sample of Example 1. At this time, the sintered density was 98% or more compared with the theoretical value.
- Example 2 To synthesize Cu 2.025 Se, Cu and Se in powder form were weighed according to the chemical formula, and then mixed and synthesized in the same manner as in Example 1 to obtain a Cu 2.025 Se composite. Then, a sample of Example 2 was obtained through a sintering process in the same manner as in Example 1 above.
- Example 3 In order to synthesize Cu 2.05 Se, Cu and Se in powder form were weighed according to the chemical formula, and then mixed and synthesized in the same manner as in Example 1 to obtain a Cu 2.05 Se composite. Then, a sample of Example 3 was obtained through a sintering process in the same manner as in Example 1.
- Example 4 In order to synthesize Cu 2.075 Se, Cu and Se in powder form were weighed according to the above formula, followed by mixing and synthesis in the same manner as in Example 1 to obtain a Cu 2.075 Se composite. Then, a sample of Example 4 was obtained through a sintering process in the same manner as in Example 1.
- Example 5 In order to synthesize Cu 2.1 Se, Cu and Se in powder form were weighed according to the above formula, followed by mixing and synthesis in the same manner as in Example 1 to obtain a Cu 2.1 Se composite. Then, a sample of Example 5 was obtained through a sintering process in the same manner as in Example 1.
- Example 6 In order to synthesize Cu 2.15 Se, Cu and Se in powder form were weighed according to the above formula, followed by mixing and synthesis in the same manner as in Example 1 to obtain a Cu 2.15 Se composite. Then, a sample of Example 6 was obtained through a sintering process in the same manner as in Example 1.
- Example 7 To synthesize Cu 2.2 Se, Cu and Se in powder form were weighed according to the above formula, and then a Cu 2.2 Se composite was obtained by mixing and synthesizing in the same manner as in Example 1. Then, a sample of Example 7 was obtained through a sintering process in the same manner as in Example 1.
- Example 1 In order to synthesize Cu 1.8 Se, Cu and Se in powder form were weighed according to the above formula, and then the Cu 1.8 Se composite was obtained by mixing and synthesizing in the same manner as in Example 1. Then, a Comparative Example 1 sample was obtained through a sintering process in the same manner as in Example 1.
- thermal diffusivity was measured at predetermined temperature intervals using LFA457 (Netzsch), and the results were compared with Examples 1-7. It shows in FIG. 10 as Examples 1-3.
- thermoelectric materials of Examples 1 to 7 in which x is greater than 2 are 100 ° C. to 700 ° C., compared to the thermoelectric materials of Comparative Examples 1 to 3 in which x is 2 or less. It can be seen that the thermal diffusivity is remarkably low over the entire temperature measurement interval of.
- the sample according to the present invention has a thermal diffusivity of 0.5 mm 2 / s or less, preferably less than 0.4 mm 2 / s, over the entire temperature range of 100 ° C to 600 ° C, compared to other comparative samples. It can be seen that it is significantly lower.
- thermoelectric materials of Examples 1 to 7 according to the present invention is measured over the entire temperature measurement section of 100 ° C. to 700 ° C., compared to the thermoelectric materials of Comparative Examples 1 to 3. It can be seen that is significantly high.
- thermoelectric materials of Examples 1 to 7 according to the present invention are significantly higher than those of the Comparative Examples 1 to 3. Can be.
- the ZT value is very low in the temperature range of less than 500 ° C., and the ZT value is 0.2 or less in the low temperature section of 100 ° C. to 300 ° C.
- thermoelectric material according to the exemplary embodiment of the present invention has a very high ZT value in the high temperature section of 500 ° C. or higher, as well as the low temperature to medium temperature section of less than 500 ° C. as compared with the comparative example.
- thermoelectric materials of Examples 1 to 6 show about two times higher ZT value performance improvement at a temperature of 600 ° C., compared to the thermoelectric materials of Comparative Examples 1 to 3.
- FIG. 1
- thermoelectric material of the comparative example shows a very low ZT value of 0.15 to 0.1 or less at a temperature of 100 ° C.
- thermoelectric material of the embodiment according to the present invention is 0.3 to 0.4 even at a temperature of 100 ° C. It is showing high performance.
- thermoelectric material of the comparative example shows a very low ZT value of 0.15 to 0.1 or less, similar to the case of 100 °C, whereas the thermoelectric material of the embodiment according to the present invention is 0.4 or more, as much as 0.5 to 0.7 Shows high ZT.
- thermoelectric material of the comparative example is present in the ZT value of about 0.1 ⁇ 0.2, while the thermoelectric materials of the embodiment according to the present invention all show a value of 0.6 or more, as much as 0.7 or 0.8 or more big difference Indicates.
- thermoelectric material of the comparative example shows a ZT value of 0.1 ⁇ 0.2, a value of about 0.35, while the thermoelectric material of the embodiment according to the present invention all show a value of 0.7 or more, most of It is 0.8 or more, and a high value of 1.0 to 1.2 is shown.
- thermoelectric material of the comparative example shows a value of about 0.5 or less
- thermoelectric material of the embodiment according to the present invention shows a very high ZT value of 1.0 to 1.4 or more.
- thermoelectric materials of Comparative Examples 1 to 3 generally showed ZT values of 0.4 to 0.9, while the thermoelectric materials of Examples 1 to 5 according to the present invention had very high ZT values of 1.4 to 1.7. It can be seen that the large difference from the thermoelectric material of the comparative example.
- thermoelectric material according to each embodiment of the present invention has a significantly low thermal diffusivity over the entire temperature range of 100 ° C to 600 ° C, compared to the conventional thermoelectric material according to the comparative example, and the ZT value. It can be seen that this is significantly larger. Therefore, the thermoelectric material according to the present invention can be said to have excellent thermoelectric conversion performance, and thus can be very usefully used as a thermoelectric conversion material.
- thermoelectric material according to the present invention may further include particles containing Cu, in particular INDOT, in addition to the Cu-Se matrix. This will be described with reference to FIGS. 13 and 14.
- FIG. 13 is a scanning ion microscope (SIM) image of the sample prepared in Example 4, and FIG. 14 is a SIM image of the sample prepared in Comparative Example 3.
- SIM scanning ion microscope
- thermoelectric material represented by Cu 2.075 Se according to Example 4 of the present invention it can be seen that nanodots exist. And, as discussed above, such a nano dot is a nano dot containing Cu. In particular, as shown in FIG. 13, the nanodots may be distributed mainly along the grain boundaries.
- FIG. 10 and FIG. 11 since it is not easy to distinguish between the embodiments, it will be described with reference to FIGS. 15 and 16 for comparison between the embodiments.
- 15 and 16 are graphs of the y-axis scaled only for the embodiments of FIGS. 10 and 11.
- thermoelectric material according to the present invention represented by Chemical Formula 1 (Cu x Se)
- the thermal diffusivity is further increased when x is x> 2.04, more specifically x ⁇ 2.05. It can be seen that the lower the Seebeck coefficient is higher.
- thermal diffusivity (TD) results of FIG. 15 it can be seen that the thermal diffusivity of Examples 3 to 7 where x is greater than 2.04 is relatively low compared to Examples 1 and 2 where x of Formula 1 is generally less than 2.04. Can be.
- the results of Examples 5 to 7, and more specifically, Examples 5 and 6 are markedly low.
- the Seebeck coefficient (S) of FIG. 16 looking at the Seebeck coefficient (S) of FIG. 16, it can be seen that the Seebeck coefficient of Examples 3 to 7 where x is greater than 2.04 is relatively higher than Examples 1 and 2 where x of Formula 1 is less than 2.04. .
- the Seebeck coefficient is markedly higher than in other embodiments.
- the Seebeck coefficients of Examples 6 and 7 are very high in the range of 100 ° C to 200 ° C and in the range of 400 ° C to 600 ° C.
- thermoelectric material according to the present invention is preferably synthesized by the solid phase reaction (SSR) method.
- SSR solid phase reaction
- Cu and Se in powder form were weighed to fit this formula, then placed in alumina mortar and mixed.
- the mixed material was placed in a cemented carbide mold to make pellets and placed in a fused silica tube and vacuum sealed. Then, it was put into a box furnace and heated at 1100 ° C. for 12 hours, but the temperature rising time was 9 hours. Then, it was heated again at 800 ° C. for 24 hours, but the temperature reduction time was 24 hours. After such heating, the mixture was slowly cooled to room temperature to obtain a Cu 2.025 Se composite.
- the Cu 2.025 Se composite was filled in a cemented carbide mold for hot pressing, and then hot pressed and sintered under vacuum at 650 ° C. to obtain a Example 8 sample. At this time, the sintered density was 98% or more compared with the theoretical value.
- Example 9 In order to synthesize Cu 2.1 Se, Cu and Se in powder form were weighed according to the above formula, followed by mixing and synthesizing in the same manner as in Example 8 to obtain a Cu 2.1 Se composite. Then, a sample of Example 9 was obtained through a sintering process in the same manner as in Example 8.
- thermoelectric material was synthesized by the SSR method in which at least a part of the raw material was not dissolved, but in the case of the samples according to Examples 8 and 9, all the raw materials were The thermoelectric material was synthesized by a melting method heated above the melting point.
- XRD analysis was performed on the samples of Example 8 and Example 9 thus obtained, and the results are shown in FIG. 17.
- XRD analysis was also performed on the samples corresponding to Example 2 and Example 5 synthesized by SSR for comparison with the results, and the results are shown in FIG. 17, and a portion thereof was enlarged in FIG. 18.
- FIG. 17 for convenience of division, the XRD pattern analysis graphs of the embodiments are shown spaced apart from each other by a predetermined distance in the vertical direction. 18, the graphs of the embodiments are shown to overlap each other without being spaced apart.
- the Cu peak which appears when Cu is present in a single composition is indicated by E.
- thermoelectric material according to the present invention when synthesized by the SSR method than when synthesized by the melting method, there is more Cu present alone.
- the thermoelectric material according to the present invention in the melting method, copper does not exist in the interior of the Cu-Se matrix or in the grain boundary in the form of a nano dot, but may exit in the form of precipitated outward. Therefore, in the case of the thermoelectric material according to the present invention, it can be said that it is preferable to be synthesized by the SSR method. Advantages of the SSR method for this melting method will be described in more detail with reference to FIGS. 19 to 21.
- the lattice thermal conductivity ⁇ L , the power factor PF, and the ZT values according to temperature are measured for the Examples 2, 5, 8, and 9 and the results are obtained. It is a graph shown in comparison.
- lattice thermal conductivity was obtained using the Wiedemann-Franz Law, and the Lorentz constant used at that time was 1.86 * 10 -8 . More specifically, the lattice thermal conductivity may be calculated using the following equation.
- ⁇ L lattice thermal conductivity
- ⁇ total thermal conductivity
- ⁇ e thermal conductivity by electrical conductivity
- T temperature (K).
- Examples 2 and 5 synthesized by the SSR method lattice thermal conductivity is relatively lower than those of Examples 8 and 9 synthesized by the melting method.
- the lattice thermal conductivity change pattern with temperature is similar, but in Example 2, in the entire temperature range of 100 °C to 600 °C compared to Example 8, It can be seen that the lattice thermal conductivity is remarkably low.
- Example 5 even when comparing Example 5 and Example 9 of the same composition, the lattice thermal conductivity of Example 5 by the SSR method in the temperature range of 200 °C to 600 °C is lower than the lattice thermal conductivity of Example 9, furthermore, The higher the difference, the greater the difference.
- the power factor PF is relatively higher than the eighth and nineth embodiments synthesized by the melting method. It can be seen.
- Example 2 by the SSR method is higher than the power factor of Example 8 by the melting method in the entire temperature measurement interval of 100 °C to 600 °C.
- Example 5 is higher than Example 9 in the entire temperature measurement interval of 100 °C to 600 °C.
- Example 2 and 5 synthesized by the SSR method ZT is relatively higher than Examples 8 and 9 synthesized by the melting method. .
- Example 2 by the SSR method is higher ZT than in Example 8 by the melting method in the temperature measurement interval of 200 °C to 600 °C.
- Example 5 is higher than Example 9 in the entire temperature measurement interval of 100 °C to 600 °C.
- thermoelectric material according to the present invention can have higher thermoelectric performance than that synthesized by the SSR method than that synthesized by the melting method.
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Abstract
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Claims (8)
- 하기 화학식 1로 표시되는 열전 재료.<화학식 1>CuxSe상기 화학식 1에서, 2<x≤2.6이다.
- 제1항에 있어서,상기 화학식 1의 x는, x≤2.2인 것을 특징으로 하는 열전 재료.
- 제1항에 있어서,상기 화학식 1의 x는, x≤2.15인 것을 특징으로 하는 열전 재료.
- 제1항에 있어서,상기 화학식 1의 x는, x≤2.1인 것을 특징으로 하는 열전 재료.
- 제1항에 있어서,상기 화학식 1의 x는, 2.01≤x인 것을 특징으로 하는 열전 재료.
- 제1항에 있어서,상기 화학식 1의 x는, 2.025≤x인 것을 특징으로 하는 열전 재료.
- 제1항 내지 제6항 중 어느 한 항에 따른 열전 재료를 포함하는 열전 변환 소자.
- 제1항 내지 제6항 중 어느 한 항에 따른 열전 재료를 포함하는 열전 발전 장치.
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EP14841843.7A EP3026719B1 (en) | 2013-09-09 | 2014-09-05 | Thermoelectric materials and their manufacturing method |
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US20220278263A1 (en) * | 2019-08-30 | 2022-09-01 | Sumitomo Electric Industries, Ltd. | Thermoelectric conversion material, thermoelectric conversion element, thermoelectric conversion module, and optical sensor |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008515212A (ja) * | 2004-09-30 | 2008-05-08 | ビーエーエスエフ ソシエタス・ヨーロピア | 熱電材料の接合 |
KR20090106320A (ko) * | 2008-04-04 | 2009-10-08 | 삼성전자주식회사 | 디칼코게나이드 열전재료 |
KR20090110831A (ko) * | 2006-12-01 | 2009-10-22 | 메사추세츠 인스티튜트 오브 테크놀로지 | 나노 구조의 열전 재료에서의 높은 성능 지수를 위한 방법 |
KR20120124466A (ko) * | 2010-01-29 | 2012-11-13 | 캘리포니아 인스티튜트 오브 테크놀로지 | 높은 열전 성능을 가지는 나노복합체 및 방법 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7573133B2 (en) * | 2003-12-09 | 2009-08-11 | Uri Cohen | Interconnect structures and methods for their fabrication |
US7709958B2 (en) * | 2004-06-18 | 2010-05-04 | Uri Cohen | Methods and structures for interconnect passivation |
US8518287B2 (en) | 2008-04-04 | 2013-08-27 | Samsung Electronics Co., Ltd. | Dichalcogenide thermoelectric material |
CN101333645B (zh) | 2008-07-16 | 2011-09-14 | 清华大学 | 一种制备铜铟硒溅射靶材的工艺 |
JP4803282B2 (ja) | 2009-06-18 | 2011-10-26 | トヨタ自動車株式会社 | ナノコンポジット熱電変換材料およびその製造方法 |
CN101645473B (zh) * | 2009-09-09 | 2011-01-05 | 北京有色金属研究总院 | 薄膜太阳能电池吸收层用硒化物材料的制备方法 |
KR20110052225A (ko) * | 2009-11-12 | 2011-05-18 | 삼성전자주식회사 | 나노복합체형 열전재료 및 이를 포함하는 열전소자와 열전모듈 |
US8021641B2 (en) * | 2010-02-04 | 2011-09-20 | Alliance For Sustainable Energy, Llc | Methods of making copper selenium precursor compositions with a targeted copper selenide content and precursor compositions and thin films resulting therefrom |
KR101876947B1 (ko) | 2011-01-25 | 2018-07-10 | 엘지이노텍 주식회사 | 나노 구조의 벌크소재를 이용한 열전소자와 이를 포함하는 열전모듈 및 그의 제조 방법 |
JP5713743B2 (ja) * | 2011-03-22 | 2015-05-07 | Dowaエレクトロニクス株式会社 | セレン化銅粒子粉末およびその製造方法 |
JP5713756B2 (ja) * | 2011-03-30 | 2015-05-07 | Dowaエレクトロニクス株式会社 | セレン化銅粒子粉末およびその製造方法 |
CN102674270A (zh) | 2012-05-25 | 2012-09-19 | 武汉理工大学 | 一种低温固相反应制备Cu2Se热电材料的方法 |
JP6219399B2 (ja) * | 2013-03-19 | 2017-10-25 | 武漢理工大学 | 自己伝播燃焼合成の判定方法およびその新基準に基づく熱電化合物の調製方法 |
CN103909264B (zh) * | 2013-06-07 | 2016-05-11 | 武汉理工大学 | 一种具有纳米孔结构的高性能Cu2Se块体热电材料及其快速制备方法 |
CN104211024B (zh) * | 2013-06-04 | 2016-02-10 | 中国科学院上海硅酸盐研究所 | P型可逆相变高性能热电材料及其制备方法 |
US9761777B2 (en) * | 2013-09-09 | 2017-09-12 | Lg Chem, Ltd. | Thermoelectric materials |
US9761778B2 (en) * | 2013-09-09 | 2017-09-12 | Lg Chem, Ltd. | Method for manufacturing thermoelectric materials |
JP6460352B2 (ja) * | 2013-09-09 | 2019-01-30 | エルジー・ケム・リミテッド | 熱電材料 |
-
2014
- 2014-09-05 CN CN201480049267.8A patent/CN105518890B/zh active Active
- 2014-09-05 JP JP2016536048A patent/JP6216064B2/ja active Active
- 2014-09-05 US US14/905,260 patent/US10002999B2/en active Active
- 2014-09-05 EP EP14841843.7A patent/EP3026719B1/en active Active
- 2014-09-05 TW TW103130845A patent/TWI656667B/zh active
- 2014-09-05 WO PCT/KR2014/008404 patent/WO2015034317A1/ko active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008515212A (ja) * | 2004-09-30 | 2008-05-08 | ビーエーエスエフ ソシエタス・ヨーロピア | 熱電材料の接合 |
KR20090110831A (ko) * | 2006-12-01 | 2009-10-22 | 메사추세츠 인스티튜트 오브 테크놀로지 | 나노 구조의 열전 재료에서의 높은 성능 지수를 위한 방법 |
KR20090106320A (ko) * | 2008-04-04 | 2009-10-08 | 삼성전자주식회사 | 디칼코게나이드 열전재료 |
KR20120124466A (ko) * | 2010-01-29 | 2012-11-13 | 캘리포니아 인스티튜트 오브 테크놀로지 | 높은 열전 성능을 가지는 나노복합체 및 방법 |
Non-Patent Citations (4)
Title |
---|
NANO ENERGY, vol. 1, 2012, pages 472 - 478 |
NATURE MATERIALS, vol. 11, 2012, pages 422 - 425 |
See also references of EP3026719A4 |
YUNXIANG HU ET AL.: "Deposition of copper selenide thin films and nanoparticles.", JOURNAL OF CRYSTAL GROWTH, vol. 297, 13 October 2006 (2006-10-13), pages 61 - 65, XP028016785 * |
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