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WO2017074002A1 - Élément thermoélectrique flexible et son procédé de production - Google Patents

Élément thermoélectrique flexible et son procédé de production Download PDF

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Publication number
WO2017074002A1
WO2017074002A1 PCT/KR2016/012054 KR2016012054W WO2017074002A1 WO 2017074002 A1 WO2017074002 A1 WO 2017074002A1 KR 2016012054 W KR2016012054 W KR 2016012054W WO 2017074002 A1 WO2017074002 A1 WO 2017074002A1
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WIPO (PCT)
Prior art keywords
electrode
thermoelectric
glass frit
flexible
weight
Prior art date
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PCT/KR2016/012054
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English (en)
Korean (ko)
Inventor
조병진
김선진
신지선
황혜림
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Korea Advanced Institute of Science and Technology KAIST
Tegway Co Ltd
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Korea Advanced Institute of Science and Technology KAIST
Tegway Co Ltd
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Priority claimed from KR1020160092668A external-priority patent/KR101829709B1/ko
Application filed by Korea Advanced Institute of Science and Technology KAIST, Tegway Co Ltd filed Critical Korea Advanced Institute of Science and Technology KAIST
Publication of WO2017074002A1 publication Critical patent/WO2017074002A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • H10N10/13—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the heat-exchanging means at the junction
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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

Definitions

  • the present invention relates to a flexible thermoelectric element, and in particular, a large-scale high integration of thermoelectric legs (TE legs) having a diameter (or width) of micrometer level is possible, and has excellent flexibility and high
  • the present invention relates to a flexible thermoelectric device having physical strength and having improved thermo-electric conversion efficiency.
  • thermoelectric effect is the direct conversion of thermal and electrical energy to each other by interaction, the seebeck effect found by thomas johann seebeck and the peltier effect found by jean charles peltier.
  • the device expressing such a thermoelectric effect is called a thermoelectric device.
  • the thermoelectric device includes a thermoelectric power generating device using a Seebeck effect that converts thermal energy into electrical energy, and a cooling device using a Peltier effect that converts electrical energy into thermal energy. It is the material and technology that best meets your needs. It is widely used in industrial fields such as automobiles, aerospace, aerospace, semiconductors, biotechnology, computers, power generation, and home appliances. Efforts to improve thermal efficiency are being conducted by research institutes and universities.
  • thermoelectric device forms a second electrode on a ceramic lower substrate such as alumina (Al 2 O 3 ), and forms a thermoelectric material made of N-type and P-type semiconductors on an electrode surface.
  • a ceramic lower substrate such as alumina (Al 2 O 3 )
  • thermoelectric material made of N-type and P-type semiconductors on an electrode surface.
  • the N-type thermoelectric material and the P-type thermoelectric material are manufactured to have a structure in which they are connected in series through the first electrode.
  • these thermoelectric devices are cascade type or segment type, and are difficult to change shape, and the application of the thermoelectric device using flexible ceramic substrates such as alumina (Al 2 O 3 ) or alumina nitride (AIN) does not require flexibility. It has a hard disadvantage.
  • thermoelectric material in 1 ⁇ 10 mm length in bulk form. It is manufactured by bonding as much as possible, but the heat loss by the upper and lower substrates is large.
  • thermoelectric devices In order to overcome these technical limitations, the Applicant, through the Republic of Korea Patent No. 10-1493797, the substrate is not located on the top and / or bottom of the thermoelectric element, the non-conductive flexible mesh is supported through the thermoelectric column array In order to secure mechanical stability and flexibility, thermoelectric devices have been proposed.
  • thermoelectric device has excellent power generation characteristics, flexibility and mechanical stability, but has a size smaller than the thickness (and / or width) of the flexible mesh as the non-conductive flexible mesh is supported through the inside of the thermoelectric column.
  • Arrays of thermoelectric columns are not feasible, and thus there is a limit to high integration of thermoelectric columns.
  • repeated stress concentration may occur in the thermoelectric column into which the flexible mesh is inserted, and thus the thermoelectric material may be damaged. It also exists.
  • the flexible mesh penetrating the thermoelectric material may lower the electrical conductivity, there may be a limit in improving the power generation efficiency.
  • an object of the present invention is to enable large-scale high integration of the thermoelectric column having a diameter (or width) of the micrometer level, has excellent flexibility, and at the same time high physical It is intended to provide a flexible thermoelectric device and a method for manufacturing the same, which may have phosphorus strength, can be lighter, and have improved thermo-electric conversion efficiency.
  • thermoelectric column array including one or more N-type thermoelectric material and P-type thermoelectric material, arranged spaced apart from each other; An electrode electrically connecting the thermoelectric materials of the thermoelectric material pillar array; And a filling material filling at least the empty space of the thermoelectric pillar array.
  • the electrode is related to a flexible thermoelectric device including a glass frit.
  • another aspect of the present invention is a) a first structure, a first structure, a first stacked substrate, a first contact thermal conductor layer, a first electrode, and a P-type thermoelectric material formed on a predetermined region on the first electrode sequentially stacked; And forming a second structure in which a second sacrificial substrate, a second contact thermal conductor layer, a second electrode, and an N-type thermoelectric material formed on a predetermined region on the second electrode are sequentially stacked.
  • thermoelectric column array a substrate on which a thermoelectric column array is formed
  • Flexible thermoelectric device by using an electrode containing a glass frit significantly improves the binding force between the electrode and the filling material, it is possible to implement a flexible thermoelectric device that excludes the flexible mesh.
  • thermoelectric device 1 is a view showing a cross section of a conventional commercial thermoelectric device.
  • FIG. 2 is a view showing a cross section of the flexible thermoelectric device according to an embodiment of the present invention.
  • thermoelectric device 3 is a schematic flowchart of a method of manufacturing a flexible thermoelectric device according to an embodiment of the present invention.
  • thermoelectric device 5 is a graph measuring the internal resistance of the device according to the radius of curvature of the flexible thermoelectric device according to an embodiment of the present invention.
  • thermoelectric device is applied to real life.
  • thermoelectric device 7 is a diagram illustrating another example in which the flexible thermoelectric device according to an embodiment of the present invention is applied to real life.
  • thermoelectric material 130, 140 thermoelectric material
  • thermoelectric material 230, 330: P-type thermoelectric material
  • thermoelectric material N-type thermoelectric material
  • Korean Patent No. 10-1493797 uses glass fibers as a flexible mesh, but when such glass fibers are located in the middle of the thermoelectric material, tension is caused by the glass fibers, which causes some flexibility. There was a problem of deterioration.
  • thermoelectric material paste and the N-type thermoelectric material paste are applied, respectively, and then annealed at the same time to respectively form the P-type thermoelectric material and the N.
  • the intermediate conditions not the optimum conditions of the respective thermoelectric materials, may be used. Two thermoelectric materials were inevitably formed, and thus, there was a problem in that the efficiency of the thermoelectric element was somewhat reduced.
  • thermoelectric legs (TE legs) array the Applicant pays attention to the fact that the electrode occupies the largest area among the components constituting the thermoelectric element, and thus the binding force between the electrode and the filling material filling the empty space of the thermoelectric legs (TE legs) array is shown.
  • the adhesive strength between the electrode and the filling material is 0.7 MPa or more, it was found that even if the flexible mesh is excluded, the mechanical and physical stability comparable to that of the conventional flexible mesh is secured. When added, it was found that the adhesive strength between the electrode and the filling material could be improved to 0.7 MPa or more, thus completing the present invention.
  • FIG. 5 is a graph illustrating a change in internal resistance according to a curvature radius of a flexible thermoelectric device according to an exemplary embodiment of the present invention.
  • the flexible thermoelectric device according to an embodiment of the present invention can be seen that has a very high flexibility that does not increase the internal resistance of the device even to a radius of curvature 4 mm, it is possible to operate even at high physical deformation It can be confirmed that the utilization as a flexible thermoelectric element is very high.
  • the present invention proposes a new flexible thermoelectric element that can exclude the flexible mesh in order to meet the technical requirements according to the application field, but the flexible mesh and the configuration proposed in the present invention independently of the mechanical As the stability can be improved, the present invention should not be construed as being limited to excluding the flexible mesh.
  • the configuration and the flexible mesh proposed in the present invention can be adopted at the same time.
  • the electrode containing the glass frit improves the mechanical stability of the device independently of the flexible mesh, so that the flexible thermoelectric device may further include a flexible mesh, if necessary.
  • the present invention includes all the contents of Korean Patent No. 10-1493797 and may refer to Korean Patent No. 10-1493797.
  • the flexible mesh corresponds to the mesh-type substrate of the Republic of Korea Patent No. 10-1493797,
  • a representative example of the flexible mesh may be a mesh-type substrate made of glass fibers.
  • thermoelectric column array including one or more N-type thermoelectric material and P-type thermoelectric material, arranged spaced apart from each other; An electrode electrically connecting the thermoelectric materials of the thermoelectric material pillar array; And a filling material filling at least the empty space of the thermoelectric pillar array.
  • the electrode may include a glass frit.
  • the electrode may include a glass frit, and in detail, may include a first conductive material and a glass frit.
  • the glass frit contained in the electrode significantly improves the binding force between the electrode and the filling material, thereby enabling the implementation of a flexible thermoelectric element in which the flexible mesh is excluded.
  • the electrode and the thermoelectric column array can be bonded using a conductive adhesive, whereby the electrode and the thermoelectric column array can be strongly bound to each other, with high thermal conductivity and electrical between the electrode and the thermoelectric column array Conduction may be possible.
  • the electrode and the filler can not be strongly bound to each other by using such an adhesive, the improvement of the binding force between the electrode and the filler should be preempted above all in order to exclude the flexible mesh which ensures mechanical stability and serves as a support.
  • the glass frit is added to the electrode to ensure that the adhesive strength between the electrode and the filling material is 0.7 MPa or more, thereby ensuring high binding force.
  • the three components of the thermoelectric column array-electrode-filling material are very strongly mediated through the electrode. By having a bonded structure, mechanical and physical stability can be ensured without compromising the flexibility of the device.
  • the adhesive strength between the electrode and the filling material is preferably 1 to 5 MPa.
  • the electrode containing the glass frit may satisfy the following relational formula (1).
  • G is the total weight (g) of the glass frit in the electrode
  • G S is the weight (g) of the glass frit located in the bonding portion of the electrode.
  • the adhesive portion is an adhesive surface that is in contact with the filling material From the adhesive layer reference electrode to 30% thickness.
  • the glass frit may be more than 45% by weight positioned in the bonding portion of the electrode to be bonded to the filling material to more effectively improve the adhesive force between the electrode and the filling material, more preferably 50% by weight or more of the glass frit is placed on the bonding portion of the electrode It is desirable to.
  • the filling material is a polymer containing a silanol group or an alkoxysilane group
  • the silanol group or alkoxysilane group may be chemically and firmly bonded to the electrode and the filling material by reacting with the metal oxide of the glass frit. It may be to have an adhesive strength of 1 to 5 MPa between and the filling material.
  • the binding force between the electrode and the filler material may be reduced by reducing the chemical bond between the electrode and the filler material.
  • the adhesive strength is less than 1 MPa, Physical stability may be degraded.
  • the relative content of the glass frit relative to the first conductive material may be adjusted in consideration of the improvement of the binding force and the electrical conductivity by the glass frit.
  • the electrode may contain 0.1 to 20 parts by weight of the glass frit based on 100 parts by weight of the first conductive material. It is possible to prevent the lowering of the electrical conductivity while ensuring excellent binding strength in the above range.
  • the content of the glass frit is less than 0.1 part by weight, the effect of improving the binding force between the electrode and the filling material may be insignificant, and when the content of the glass frit is more than 20 parts by weight, the electrical conductivity is reduced by the non-conductive glass frit.
  • the thermoelectric performance of the thermoelectric element may be lowered.
  • the electrode in order to improve the flexibility of the thermoelectric device, it is good to implement the electrode as thin as possible. However, the thinner the electrode, the lower the electrical conductivity caused by the glass frit may appear. Accordingly, the relative content of the glass frit relative to the first conductive material is preferably in the minimum content range in which the binding enhancement effect can be exhibited to the extent that the flexible mesh can be excluded. In this aspect, the electrode may contain 0.5 to 10 parts by weight, specifically 1 to 5 parts by weight, based on 100 parts by weight of the conductive material.
  • the electrode may be formed by application and heat treatment of the electrode paste containing the first conductive material and the glass frit. At this time, by adjusting the type, size, shape, etc. of the first conductive material and the glass frit contained in the electrode paste, it is possible to prevent the reduction in the electrical conductivity of the electrode itself while further improving the binding force between the electrode and the filling material.
  • the shape of the first conductive material is not particularly limited, and in particular, the first conductive material may include isotropic particles, anisotropic particles, or mixed particles of isotropic particles and anisotropic particles.
  • the first conductive material is isotropic particles such as spherical particles, the space filling property is good, and thus, homogeneous and stable electrical properties can be realized.
  • the excellent space-filling characteristics of the isotropic particles are not only good for the thermal conditions outside the thermoelectric element can be quickly transferred to the thermoelectric material through the electrode, but isotropic particles can be easily supplied at low prices and economical.
  • the first conductive material is anisotropic particles such as rod-shaped, fibrous, plate-shaped, or flake-like
  • one particle may contact (or bond) with a larger amount of other particles due to anisotropy.
  • the electrode contains anisotropic particles
  • a decrease in the electrical conductivity of the electrode can be prevented even when the flexible thermoelectric element is physically highly deformed.
  • the anisotropic particles have flexibility by the properties of the material itself or nano dimensions, such as carbon nanotubes, carbon nanowires, and silver nanowires, flexibility of the electrode itself may be improved, thereby resulting in high physical deformation in the flexible thermoelectric device. It can operate stably for a long time even in this repeatedly applied environment.
  • the anisotropic degree of the anisotropic particles e.g., aspect ratio in the case of rod or fiber shape, ratio of width to thickness in the case of plate or flake shape, etc.
  • the relative content of the anisotropic particles and the advantages of the isotropic particles can be effectively expressed to the extent that can be effectively expressed.
  • the anisotropic particles may be mixed in an amount of 1 to 50 parts by weight based on 100 parts by weight of the isotropic particles.
  • the average particle diameter of the particles may be 10 nm to 100 ⁇ m, preferably 100 nm to 50 ⁇ m, more preferably 0.5 to 20 It is preferable that the micrometer has excellent space filling properties so that external heat can be quickly transferred to the thermoelectric material, and a thinner electrode can be implemented to reduce the weight of the device and improve the flexibility of the electrode.
  • the first conductive material is anisotropic particles such as fibrous type
  • the contact area between the particles may be improved, and thus, efficiency may be improved in terms of electrical conductivity and thermal conductivity.
  • the aspect ratio (ratio of the major axis length to the short axis or the ratio of the width to the thickness) of the anisotropic particles may be from 2 to 1000, preferably from 10 to 500.
  • the type of the first conductive material according to an embodiment may be used without particular limitation as long as the material has a high thermal conductivity and electrical conductivity.
  • a carbon material or a carbon nanowire having excellent electrical conductivity may be used. Etc. can be used.
  • a metal material may be used that is excellent in thermal conductivity and electrical conductivity, and has excellent binding strength with a filling material to improve physical strength of the thermoelectric element.
  • the metal material may be a transition metal of Groups 3 to 12, and in one embodiment, nickel (Ni), copper (Cu), platinum (Pt), ruthenium (Ru), rhodium (Rh), gold (Au) ), Tungsten (W), cobalt (Co), palladium (Pd), titanium (Ti), tantalum (Ta), iron (Fe), molybdenum (Mo), hafnium (Hf), lanthanum (La), iridium (Ir) ) And silver (Ag) may be one or two or more, and it may be preferable to use copper (Cu) in view of high electrical conductivity, binding to the filler material, and low cost.
  • Glass frit according to an example is not particularly limited in its formation, and may have the same or different shape and size as the first conductive material. In one embodiment it may be spherical, acicular and / or indeterminate, but is not limited thereto.
  • the size of the glass frit may be adjusted in consideration of the flexibility and thickness of the electrode, and may have a size similar or relatively small to the first conductive material.
  • the glass frit has a relatively small size compared to the first conductive material, and in detail, the glass frit does not lower the electrical conductivity of the electrode by interfering with the contact between the first conductive material and does not reduce the flexibility of the electrode. It is good to have a small size.
  • the glass frit may have a size of 0.1 to 1 times based on the average diameter of the first conductive material, and as an example, the glass frit may be obtained through a sieve of 100 mesh or less, but must It is not limited.
  • the glass frit may be an amorphous material formed from a metal oxide, and may generate a stable glassy phase and maintain sufficient low viscosity.
  • the glass frit may be a lead-containing glass frit containing lead or a lead-free glass frit containing no lead, or a mixture thereof, but an environment-friendly and harmless lead-free glass frit is preferable.
  • the glass frit is preferably a bismuth oxide-boron oxide-zinc oxide-based glass frit containing bismuth oxide, boron oxide and zinc oxide, and the siloxane when the electrode contains bismuth oxide-boron oxide-zinc oxide-based glass frit. The binding with acid-based fillers can be improved significantly.
  • bismuth oxide-boron oxide-zinc oxide-based glass frit 60 to 90% by weight of Bi 2 O 3 , 10 to 20% by weight of ZnO and 5 to 15% by weight of B 2 O 3 in the total weight of the glass frit. It may contain%. In addition to this, it may further include one or two or more metal oxides selected from Al 2 O 3 , SiO 2 , CeO 2 , Li 2 O, Na 2 O and K 2 O, the content of the total weight of the glass frit, It may be added in 1 to 20% by weight.
  • bismuth oxide-boron oxide-zinc oxide-based glass frit examples include Bi 2 O 3 -ZnO-B 2 O 3 glass frit, Bi 2 O 3 -ZnO-SiO 2 -B 2 O 3 -Al 2 O 3 glass Frit, Bi 2 O 3 -ZnO-SiO 2 -B 2 O 3 -La 2 O 3 -Al 2 O 3 glass frit, Bi 2 O 3 -ZnO-SiO 2 -B 2 O 3 -TiO 2 glass frit, or Bi 2 O 3 -SiO 2 -B 2 O 3 -ZnO-SrO glass frit, but is not limited thereto.
  • the binding force between the electrode and the filling material can be significantly improved.
  • the functional group contained in the filler material is chemically bonded by reacting with the glass frit, it is possible to significantly improve the binding force between the electrode and the filler material.
  • the functional group may react with the hydroxyl group present in the glass frit, and specifically, may be an alkoxysilane or silanol group.
  • the electrode containing the glass frit may be a fine irregularity formed on the surface.
  • the fine iron leads to an anchoring effect between the electrode and the filler material, further improving the binding force between the electrode and the filler material, thereby ensuring excellent mechanical and physical strength of the thermoelectric element even when the flexible mesh is excluded. It may be possible to implement a more flexible device. That is, even if the physical deformation of the flexible thermoelectric element is repeatedly performed, the physical stability of the device can be ensured due to a very good binding force between the electrode and the filling material, thereby improving the life and reliability of the device.
  • the fine irregularities may be formed by applying and heat treatment of the electrode paste, or may be formed by performing an unevenness forming process after forming the electrode.
  • the surface roughness Ra may be adjusted according to the shape and size of the conductive material and the glass frit.
  • any method known in the art may be used as long as it is a method for forming fine irregularities on the surface of the electrode.
  • fine irregularities may be formed on the surface of the electrode through wet etching such as chemical etching or dry etching such as plasma treatment.
  • the fine irregularities formed on the surface of the electrode are preferably formed to a depth and a size sufficient to improve the binding force with the filling material, and in one embodiment, the surface of the fine irregularities is 0.4 to 2.0 ⁇ m. It may have a surface roughness (Ra), more preferably may have a surface roughness (Ra) of 0.7 to 1 ⁇ m.
  • the anchoring effect is excellent in the above range can greatly improve the binding force between the electrode and the filler material.
  • the electrode containing the glass frit can further improve the binding force between the electrode and the filling material by containing the glass frit. Accordingly, even if the flexible mesh is excluded, the mechanical and physical stability of the thermoelectric element may be secured, and superior flexibility may be secured by removing tension that may be caused by the flexible mesh. That is, by excluding the flexible mesh, it is possible to secure more flexibility, and have an improved binding force between the electrode and the filling material, thereby enabling highly physical deformation, and even in an environment where such physical deformation is repeatedly applied. Since the thermoelectric element can be stably operated without being damaged, it is possible to improve the reliability of the thermoelectric element.
  • the electrode containing the glass frit can improve the binding force with the filling material by containing the glass frit, and further improve the binding force by the surface roughness of the electrode Can have.
  • the adhesive strength between the electrode and the filling material may be 0.7 MPa or more, specifically 0.7 to 10 MPa, and more preferably, 1 to 5 MPa.
  • the filling material is a material filling the empty space of the column array of the thermoelectric material, it is strongly bound to the electrode so that the flexible thermoelectric element can have sufficient mechanical and physical properties, in particular low thermal conductivity By having it, the thermoelectric conversion efficiency of a thermoelectric element can be improved. Accordingly, the filling material should be a material having flexibility, and in addition, due to the characteristics of the thermoelectric element, an electrode directly contacting the heat source and an electrode formed opposite thereto (for example, if the first electrode is an electrode contacting the heat source, the opposite electrode) It is preferable that the temperature gradient between the silver and the second electrode is large, and the filling material is preferably a material having low thermal conductivity. That is, the filling material is preferably a material having flexibility and low thermal conductivity, and preferably a material capable of binding to the electrode to ensure sufficient mechanical and physical strength.
  • the filling material having flexibility and low thermal conductivity may be formed from a prepolymer.
  • the prepolymer is a polymer having a relatively low degree of polymerization containing a curable functional group (curing group), and may mean a polymer before it is filled and cured in an empty space by a thermoelectric column array. Alternatively, all may be cured to form a filling material. That is, the polymer in the initial state before or filled with the thermoelectric pillar array is called a prepolymer, and the cured material is called a filler.
  • the filler is not particularly limited as long as it has flexibility and low thermal conductivity, but specifically, for example, the filler may have a thermal conductivity of 20% or less than that of the thermoelectric material. Preferably, it is preferable to use the one having a thermal conductivity of 0.1 to 10% of the thermal conductivity of the thermoelectric material to effectively block the heat transfer to secure thermal stability.
  • the flexibility and thermal conductivity of the thermoelectric element may be adjusted according to the degree of curing of the filling material.
  • the filling material is based on the curing (100% degree of curing) of all the curing machines contained in the prepolymer. May have a degree of curing (%) satisfying the following relational formula (2).
  • N 0 is the number of average curing groups contained in one molecule of the prepolymer before the curing process, and N is the number of uncured curing groups in the N 0 after the curing process.
  • N 0 may be 2 to 20.
  • the weight average molecular weight of the prepolymer may be 100 to 500,000 g / mol, more preferably 5,000 to 100,000 g / mol.
  • the degree of curing of such a prepolymer can be controlled through the amount of heat applied in case of thermal curing, the amount of light irradiated in case of photocuring, and the content of a curing agent in case of chemical curing.
  • the prepolymer is preferably a chemically curable prepolymer having a chemically curable functional group in terms of reproducibly controlling the degree of curing of the prepolymer homogeneously in a large area, and the degree of curing of the filling material is a chemically curable prepolymer and a curing agent. It is good to control the relative amount of wah.
  • the prepolymer should have flexibility and low thermal conductivity after the curing process, and it is preferable to select the type in consideration of this.
  • the prepolymer may include a functional group capable of thermosetting, photocuring or chemical curing, but may preferably contain a functional group capable of chemical curing for more uniform curing.
  • the thermosetting prepolymer since the material is a material having low thermal conductivity, the temperature of the part directly contacting the heat source and the part not directly may be different, and thus it may be difficult to homogeneously polymerize with a predetermined degree of polymerization.
  • the prepolymer In the case of a photocurable prepolymer, the prepolymer must be filled at least after the electrode is formed across the thermoelectric material and then fills the void space of the array of thermoelectric pillars, thereby reducing the Uniform irradiation may be disturbed.
  • the curing can be uniformly achieved by simply mixing the curing agent uniformly, and the degree of curing of the filling material can be controlled only by controlling the content of the curing agent, thereby controlling flexibility and thermal conductivity. May be advantageous.
  • the prepolymer may be used without particular limitation as long as it has flexibility after curing and has low thermal conductivity.
  • silicone-based prepolymer, olefin-based elastic prepolymer or urethane-based prepolymer Etc. can be used.
  • the silicone-based prepolymer, the olefin-based elastic prepolymer and the urethane-based prepolymer has a high flexibility and elasticity after curing, the physical properties of the thermoelectric element when applied to the flexible thermoelectric element is small, the physical properties change with temperature, the flexibility is maintained in a wide temperature range This is easy and does not easily damage even frequent physical deformation has the advantage of improving the life characteristics.
  • the silicon-based prepolymer and the olefin-based elastic prepolymer has a low thermal conductivity can effectively prevent the diffusion of heat to improve the thermoelectric efficiency.
  • the binding force with the electrode may be further improved, thereby improving physical stability of the thermoelectric element.
  • the silicone prepolymer is filled and cured in the empty space formed by the thermoelectric pillar array, the alkoxysilane group or silanol group contained in the silicone prepolymer may react with the metal oxide of the glass frit in the electrode described above. As a result, the binding force between the electrode and the filling material may be further improved.
  • the olefin-based elastic prepolymer or urethane-based prepolymer may also contain an alkoxysilane group or silanol group, in this case, it is possible to improve the binding force between the electrode and the filler by the same action as the silicone-based prepolymer.
  • silicone-based prepolymers can be divided into condensation type and addition type.
  • the condensation type silicone prepolymer may be cross-cured by hydrolysis and condensation reaction in the presence of water, and the addition type silicone type prepolymer may be crosslinked due to addition reaction between the unsaturated group and the crosslinking agent of the silicone type prepolymer in the presence of a catalyst. have.
  • the condensation type silicone prepolymer may be a siloxane type prepolymer containing a silanol group as an end group, and may be formed by polymerizing a rubbery polymer by a hydrolytic condensation reaction between the silanol group and the crosslinking agent and a condensation reaction with a catalyst and water. Can be formed.
  • the condensed silicone-based prepolymer is an aliphatic polysiloxane, an aromatic polysiloxane having two or more hydroxyl groups, or a polysiloxane including siloxane repeating units each containing an aliphatic group and an aromatic group in one repeat unit or independently. Can be.
  • the aliphatic polysiloxane is polydimethylsiloxane, polydiethylsiloxane, polymethylethylsiloxane, polydimethylsiloxane-co-diethylsiloxane, polydimethylsiloxane-co containing two or more hydroxy groups.
  • -Polymethyl siloxane polymethylphenylsiloxane, polyethylphenylsiloxane, poly (dimethylsiloxane-co-diphenylsiloxane) and the like, which may be selected from -ethylmethylsiloxane and the like, and aromatic polysiloxanes contain two or more hydroxy groups. Can be selected.
  • Polysiloxanes comprising a siloxane repeating unit which includes both aliphatic and aromatic groups in one repeating unit or independently of each other include all of the repeating units of aliphatic siloxanes and repeating units of aromatic siloxanes exemplified above,
  • the aromatic substituents exemplified above may mean a form bonded to each silicon element located in one repeating unit, but is not limited thereto.
  • the crosslinking agent may be a siloxane-based curing agent containing a Si-O bond or an organosilazane-based curing agent containing a Si-N bond, and the like, and, as a non-limiting example, (CH 3 ) Si (X) 3 or Si (OR) 4 .
  • X may be a methoxy, acetoxy, oxime, amine group and the like
  • R has a lower alkyl group and may be a methyl, ethyl or propyl group in one non-limiting embodiment.
  • the catalyst is not limited as long as it is commonly used in the art, and an organic tin compound, an organic titanium compound, or an amine compound may be used as a non-limiting example.
  • the addition silicone-based prepolymer may be a siloxane-based prepolymer containing an ethylenically unsaturated group, and more particularly, may be a siloxane-based prepolymer containing a vinyl group.
  • a siloxane chain can be bridge
  • the additional silicone-based prepolymer may be an aliphatic polysiloxane having two or more vinyl groups, an aromatic polysiloxane, or a polysiloxane including siloxane repeating units each containing an aliphatic group and an aromatic group or independently of each other. have.
  • 2 to 20 vinyl groups may be included in one polysiloxane chain, but are not limited thereto.
  • the vinyl groups may increase in proportion to more than 20 vinyl groups, which is preferable for low molecular weight polysiloxanes. The range may include two to four.
  • the aliphatic polysiloxane is polydimethylsiloxane, polydiethylsiloxane, polymethylethylsiloxane, polydimethylsiloxane-co-diethylsiloxane, polydimethylsiloxane-co- containing two or more vinyl groups.
  • aromatic polysiloxane may be selected from polydiphenylsiloxane, polymethylphenylsiloxane, polyethylphenylsiloxane, poly (dimethylsiloxane-co-diphenylsiloxane), and the like, containing two or more vinyl groups.
  • the aromatic polysiloxane may be selected from polydiphenylsiloxane, polymethylphenylsiloxane, polyethylphenylsiloxane, poly (dimethylsiloxane-co-diphenylsiloxane), and the like, containing two or more vinyl groups.
  • the aromatic polysiloxane may be selected from polydiphenylsiloxane, polymethylphenylsiloxane, polyethylphenylsiloxane, poly (dimethylsiloxane-co-diphenylsiloxane), and the like, containing two or more vinyl groups.
  • Polysiloxanes comprising a siloxane repeating unit which includes both aliphatic and aromatic groups in one repeating unit or independently of each other include all of the repeating units of aliphatic siloxanes and repeating units of aromatic siloxanes exemplified above,
  • the aromatic substituents exemplified above may mean a form bonded to each silicon element located in one repeating unit, but is not limited thereto.
  • the crosslinking agent may be used without particular limitation as long as it is a siloxane compound containing a Si—H bond, and in one non-limiting embodiment, may be an aliphatic or aromatic polysiloxane including a-(R a HSiO)-group.
  • R a may be an aliphatic group or an aromatic group, an aliphatic group may be a methyl group, an ethyl group, a propyl group, an aromatic group may be a phenyl group, a naphthyl group, and the substituent may be substituted with another substituent within a range that does not affect the crosslinking reaction.
  • polymethylhydrogensiloxane [(CH 3 ) 3 SiO (CH 3 HSiO) x Si (CH 3 ) 3 ]
  • polydimethylsiloxane [(CH 3 ) 2 HSiO ((CH 3 ) 2 SiO) x Si (CH 3 ) 2 H]
  • polyphenylhydrogensiloxane [(CH 3 ) 3 SiO (PhHSiO) x Si (CH 3 ) 3 ] or polydiphenylsiloxane [(CH 3 ) 2 HSiO ((Ph ) 2 SiO) x Si (CH 3 ) 2 H]
  • it is preferable to adjust the content of Si-H according to the number of vinyl groups contained in the additional silicone-based prepolymer for example x is 1 or more It may be, but may be more
  • the catalyst may be optionally added to promote the reaction, and is not limited as long as it is commonly used in the art, may use a platinum compound and the like as a non-limiting embodiment.
  • it may further include additives such as fillers and / or diluents.
  • the filler may use aerosol silica, quartz powder, calcium carbonate powder or diatomaceous earth powder.
  • fillers may be chemically bound to the siloxane-based prepolymer to improve the fracture toughness of the crosslinked siloxane polymer.
  • the filler may be introduced into the vinyl group or Si-H group through a coupling agent, it can be stably included in the cross-linked siloxane polymer network through the functional group.
  • the olefinic elastic prepolymer may be cross-linked and hardened by an olefinic elastic prepolymer and a crosslinking agent to form a polymer.
  • the olefin-based elastic prepolymer may be, but is not limited to, poly (ethylene-co-alpha-olefin), ethylene propylene diene monomer rubber (EPDM rubber), polyisoprene or polybutadiene, and the like.
  • the crosslinking agent may be a vulcanizing agent, and is not limited as long as it is commonly used in the art, but may be used as a non-limiting example, sulfur or organic peroxide.
  • the urethane-based prepolymer is a urethane-based prepolymer containing a first form and an unsaturated group, which are polymerized by addition condensation reaction of an isocyanate group (-NCO) and a hydroxyl group (-OH) in the presence of a catalyst by an addition reaction with a crosslinking agent. It can be divided into a second form to be a polymer.
  • a polymer may be formed by the reaction of a polyfunctional isocyanate compound containing two or more isocyanate groups and a polyol compound containing two or more hydroxyl groups.
  • the polyfunctional isocyanate compound is a non-limiting embodiment, 4,4'- diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), 1,4-diisocyanatobenzene (PPDI), 2 , 4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-bittolylene-4,4'-diisocyanate, 1,3-xylene diisocyanate, p-tetramethylxylene di Isocyanate (p-TMXDI), 1,6-diisocyanato-2,4,4-trimethylhexane, hexamethylene diisocyanate (HMDI) 1,4-cyclohex
  • the polyol-based compound may be divided into polyester polyols and polyether polyols.
  • the polyester polyol may be, but is not limited to, polyethylene adipate, polybutylene adipate, poly (1,6-hexaadipate), polydiethylene adipate, poly (e-caprolactone), and the like.
  • the polyether polyol may be, but is not limited to, polyethylene glycol, polydiethylene glycol, polytetramethylene glycol, polyethylenepropylene glycol, and the like in one specific embodiment.
  • the catalyst is not particularly limited as long as it is commonly used in the art, but may be an amine catalyst, and in one non-limiting embodiment, dimethylcyclohexylamine (DMCHM), tetramethylenediamine (TMHDA), pentamethylene Diethylenediamine (PMEDETA), tetraethylenediamine (TEDA), etc. can be used.
  • DCHM dimethylcyclohexylamine
  • TMHDA tetramethylenediamine
  • PMEDETA pentamethylene Diethylenediamine
  • TMA tetraethylenediamine
  • the polymer may be formed by an addition reaction between the urethane-based prepolymer containing an ethylenically unsaturated group and a crosslinking agent.
  • a urethane-based prepolymer may vary in structure depending on the type of the compound containing the isocyanate group and the polyol-based compound, but may be an ethylenically unsaturated group, more specifically, a urethane-based prepolymer containing a vinyl group.
  • 2 to 20 vinyl groups may be included in one polyurethane chain, but are not limited thereto.
  • the vinyl groups may increase in proportion to 20 or more, and the polyurethane having a low molecular weight In the case of the preferred range may include 2 to 4.
  • the crosslinking agent may be a vulcanizing agent, and is not limited as long as it is commonly used in the art, but may be used as a non-limiting example, sulfur or organic peroxide.
  • the content of the prepolymer, the crosslinking agent and the catalyst may be selected in consideration of the degree of curing of the polymer.
  • the crosslinking agent may be used in an amount of 1 to 100 parts by weight based on 100 parts by weight of the prepolymer, preferably 3 to 50 parts by weight, and more preferably 5 to 20 parts by weight.
  • the catalyst may be used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the prepolymer, and preferably 0.1 to 1 part by weight. It is possible to effectively form a polymer having excellent flexibility in the above range and low thermal conductivity, thereby realizing a device having excellent stability against frequent physical changes, and effectively preventing thermal diffusion, thereby greatly improving thermoelectric efficiency.
  • the filling material maintains flexibility in a wide temperature range in consideration of the environment in which the thermoelectric element is driven, and accordingly, it is preferable to adjust the glass transition temperature (T g ) of the filling material.
  • T g glass transition temperature
  • the glass transition temperature of the filling material may be -150 ⁇ 0 °C, and more preferably the maximum temperature that the glass transition temperature may have in the aspect of maintaining flexibility and binding with the electrode may be -20 °C or less.
  • the filler material maintains flexibility and mechanical properties even in an environment in which high physical deformation is applied. Accordingly, it is preferable to control the hardness (shore A) and tensile strength of the filler material. .
  • the hardness of the filler material may be 10 to 40, more preferably 20 to 30 is preferable in having a higher flexibility.
  • the tensile strength may be 30 ⁇ 300 kg / cm2, more preferably 40 ⁇ 90 kg / cm2.
  • the filling material may be formed by filling the prepolymer in the empty space formed by the thermoelectric column array, and then hardened.
  • the empty space may cause a capillary phenomenon due to the space having a fine size, and thus the prepolymer may be uniformly filled in the empty space by using a liquid material.
  • the prepolymer may be a liquid material, and in detail, the prepolymer may be a liquid or a solution dissolved in a solvent.
  • Such a liquid prepolymer can be effectively and uniformly filled in the empty space by the capillary effect, and after the hardening process to ensure good binding overall with the electrode and the thermoelectric material can further improve the mechanical and physical properties of the thermoelectric element.
  • the prepolymer itself is a liquid at a process temperature (for example, room temperature)
  • a process temperature for example, room temperature
  • the liquid prepolymer may have a viscosity of 10,000 cP or less, specifically, may have a viscosity of 1,000 to 10,000 cP, and more preferably, may have a viscosity of 2,000 to 5,000 cP. have.
  • the liquid prepolymer may be controlled by a conventional viscosity modifier so as to have a given viscosity.
  • the viscosity of the liquid prepolymer is a viscosity in which the liquid prepolymer can be easily filled in the empty space formed by the thermoelectric column array even when the capillary effect is reduced by the physical size or shape of the thermoelectric element.
  • the liquid prepolymer may have an appropriate contact angle to fill the empty space of the thermoelectric column array by a more effective capillary effect.
  • the liquid prepolymer forming the filling material by curing may be well wetted with the electrode.
  • the contact angle between the electrode and the liquid prepolymer may be more important.
  • the liquid prepolymer should be well wetted by the thermoelectric material and the electrode, especially the electrode. May cause problems with poor filling.
  • the contact angle between the electrode and the liquid prepolymer is the interfacial tension equilibrium due to the three interfacial energies of the electrode-droplet interface, the electrode-phase interface, and the droplet-phase interface when the liquid prepolymer droplet is dropped on top of the electrode in the form of a flat plate (or film). It may be a contact angle defined by. In one embodiment, the contact angle between the liquid prepolymer and the electrode may be less than 90 °, preferably 0 to 60 °.
  • the P-type thermoelectric material and the N-type thermoelectric material of the thermoelectric column array may be formed by a conventional method, in detail, to form a polycrystal using a thermoelectric material paste or It may be formed using a single crystal.
  • the use of a single crystal as a thermoelectric material the flexible thermoelectric device according to an embodiment of the present invention can be used as it is not necessary to have a mesh through the adhesion between the electrode and the filling material is improved.
  • the P-type thermoelectric material or the N-type thermoelectric material When the P-type thermoelectric material or the N-type thermoelectric material is formed into a polycrystal using a thermoelectric material paste, the P-type thermoelectric material or the N-type thermoelectric material may be formed from the P-type thermoelectric material paste or the N-type thermoelectric material paste. This is described in detail in the preparation method of the substance.
  • the N-type thermoelectric material and the P-type thermoelectric material may be used a material having a high thermal conductivity and electrical conductivity, in detail, if the thermoelectric figure of merit (ZT, thermoelectric figure of merit) is 0.1 K -1 or more specifically limited Can be used without.
  • the second conductive material may include a second conductive material.
  • the second conductive material may include an alkali metal of Group 1, an alkaline earth metal of Group 2, a transition metal of Groups 3-12, and a Group 13-16 of the Periodic Table. Any one or two or more selected from the elements of may be used.
  • the alkali metals of Group 1 may be sodium (Na), potassium (K), and the like
  • the alkaline earth metals of Group 2 may be magnesium (Mg), calcium (Ca), strontium (Sr), and the like.
  • elements of Groups 13 to 16 are aluminum (Al), silicon (Si), germanium (Ge), selenium (Se), tin (Sn), antimony (Sb), Lead (Pb
  • the N-type thermoelectric material may include a bismuth-tellurium-based (Bi x Te 1- x ) or a bismuth-telenium-selenium-based (Bi 2 Te x Se 1-x ) compound, and a P-type thermoelectric
  • the material may comprise an antimony-tellurium-based (Sb x Te 1- x ) or bismuth-antimony-tellurium-based (Bi y Sb 2-y Te 3 ) compound.
  • x may be 0 ⁇ x ⁇ 1
  • y may be 0 ⁇ y ⁇ 2.
  • the shape of the second conductive material is not particularly limited, but particles, such as spherical, rod, fibrous, plate and flake type, may be used alone or in combination, and preferably, the use of spherical particles is homogeneous and stable. Electrical characteristics can be realized.
  • the size of the second conductive material may also be controlled to form a thin thermoelectric material.
  • the second conductive material may have an average particle diameter of 10 nm to 100 ⁇ m, preferably 0.1 It may have an average particle diameter of from 50 ⁇ m.
  • the thermoelectric material may be a fine uneven surface is formed on the surface, it is possible to improve the binding force between the filling material and the thermoelectric material by the surface fine irregularities.
  • the surface of the thermoelectric material may have a surface roughness Ra of 0.1 to 10.0 ⁇ m, and more preferably, it may have a surface roughness Ra of 1.0 to 5.0 ⁇ m.
  • the method of forming the fine irregularities on the surface of the thermoelectric material is not particularly limited, and any method known in the art may be used as long as it can satisfy the surface roughness Ra.
  • fine irregularities may be formed by applying and heat-treating the thermoelectric material forming paste, or fine unevenness may be formed on the surface of the thermoelectric material through wet etching such as chemical etching or dry etching such as plasma treatment.
  • the micro-convex formation method of the thermoelectric material may be formed through a method independent of the micro-convex formation method of the electrode surface described above.
  • the flexible thermoelectric device 200 includes one or more N-type thermoelectric materials 240 and P-type thermoelectric materials 230, spaced apart from each other, as shown in FIG. A thermoelectric column array; First and second electrodes 220 and 220 ′ electrically connecting the thermoelectric materials of the thermoelectric pillar array; And a filling material 250 filling at least the empty space of the thermoelectric pillar array.
  • the first electrode and the second electrode may include a glass frit.
  • the flexible thermoelectric device may be connected to the thermoelectric column array in thermally parallel, electrically in series and / or parallel through the electrode and the thermoelectric column array.
  • the flexible thermoelectric element 200 is electrically in parallel, electrically, through the first electrode 220, the second electrode 220 'and the thermoelectric column array as shown in FIG. Can be connected in series.
  • one end of the N-type thermoelectric material 240 may be connected to one end of one surface of the first electrode 220, and one end of the second electrode 220 ′ may be connected to the other end of the N-type thermoelectric material. This can be connected.
  • One end of the P-type thermoelectric material 230 may be continuously connected to the other end of one surface of the second electrode, and the other end of the P-type thermoelectric material 230 may be spaced apart from the first electrode 220. It may be connected to one end of the electrode 220, the flexible thermoelectric element 200 may be configured by using this as a repeating unit.
  • the size and shape of the N-type thermoelectric material and the P-type thermoelectric material may be appropriately designed in consideration of the use of the thermoelectric device, so long as the flexibility of the flexible thermoelectric device is not impaired.
  • the N-type and P-type thermoelectric materials may have the same shape and size to each other. More specifically, the N-type and P-type thermoelectric material may be independently of each other, plate or columnar shape, the cross-section in the thickness or length direction has a curved shape, such as circular, elliptical or triangular, square, pentagonal, etc. It may be an angular shape.
  • the thickness of the N-type or P-type thermoelectric material may have a thickness of several tens of nanometers to several tens of millimeters.
  • the cross-sectional area of the N-type or P-type thermoelectric column may have an area of several hundred square nanometer order to several square centimeter order.
  • an N-type or P-type thermoelectric material may have a thickness of 100 nm to 5 cm, and a cross-sectional area of the thermoelectric material pillar may be 0.1 ⁇ m 2 to 10 cm 2, but the present invention is directed to the physical shape or size of the thermoelectric material. It is not limited by.
  • thermoelectric material may be manufactured in the thickness of the nanometer order.
  • the flexible thermoelectric device according to the example of the present invention may also manufacture the device in the thickness of the nanometer order, and the miniaturization and integration of the thermoelectric device may be possible.
  • the device since the device can be manufactured so that the cross-sectional area of the thermoelectric column is up to ⁇ m 2 or less, a very large number of thermoelectric pillars can be integrated within a given total device area, which is advantageous for raising the total output voltage.
  • the glass frit improves the binding force between the electrode and the filling material, thereby enabling the implementation of a flexible thermoelectric device having no flexible mesh.
  • the thickness of the thermoelectric material When the thermoelectric column array is supported through the flexible mesh, the thickness of the thermoelectric material must be larger than the thickness of the flexible mesh, and the cross-sectional area of the thermoelectric column must be at least not to escape the thermoelectric material through the eyes of the flexible mesh. The area required to be stably supported by the lattice structure is required.
  • the thermoelectric column array can be miniaturized and nanostructured, and the thermoelectric column can be freely provided within the range that satisfies the properties required for the application and does not impair the flexibility of the filling material itself. Physical design of the array is possible.
  • Method (I) of manufacturing a flexible thermoelectric device a) P-type thermoelectric material formed in a predetermined area on the first sacrificial substrate, the first contact thermal conductor layer, the first electrode, and the first electrode A first structure sequentially stacked; And forming a second structure in which a second sacrificial substrate, a second contact thermal conductor layer, a second electrode, and an N-type thermoelectric material formed on a predetermined region on the second electrode are sequentially stacked.
  • thermoelectric column array a substrate on which a thermoelectric column array is formed
  • a method of forming a first structure includes: a-1) forming a first contact thermal conductor layer on a first sacrificial substrate; a-2) forming a first electrode on the first contact thermal conductor layer; And a-3) forming a P-type thermoelectric material in a predetermined region on the first electrode.
  • the method of forming the second structure may include forming an N-type thermoelectric material in a predetermined region on the second electrode. Except for the steps to proceed the same, repeated description will be omitted.
  • the first sacrificial substrate serves as a support to maintain its shape until the completion of the flexible thermoelectric element, the sacrificial film according to the adhesive force characteristics of the first contact thermal conductor layer It may be to include more. That is, when the first sacrificial substrate does not have good adhesive strength with the first contact thermal conductor layer, no sacrificial film is required, and when the first sacrificial substrate has good adhesion, the first sacrificial substrate may further include a sacrificial film.
  • the sacrificial film may be used without particular limitation as long as it is a metal thin film or polymer layer having poor adhesion to the first sacrificial substrate.
  • the metal thin film may be a nickel thin film
  • the polymer layer may be a polymer adhesive substrate. It may be formed by coating on, specific examples of the polymer adhesive is glue, starch, acetyl cellulose (Acetyl cellulose), poly vinyl acetate (Poly vinyl acetate), epoxy (Epoxy), urethane (Urethane), chloroprene rubber (Chloroprene rubber ), Nitrile rubber, phenol resin, silicate-based, alumina cement, urea resin, melamine resin, acrylic resin, polyester resin, vinyl / phenol resin, epoxy / phenol resin, or the like It may be a mixture or compound consisting of two or more.
  • the method of forming the sacrificial film may be any method known in the art as long as it is a method capable of forming a metal thin film on the substrate.
  • spin coating, screen printing technique, physical deposition, thermal evaporation, chemical vapor deposition, electrodeposition or spraying It may be formed through a spray coating or the like.
  • the first sacrificial substrate is not limited to the type thereof as long as the first contact thermal conductor layer or the sacrificial layer has a weak adhesive strength, and does not limit the material, shape, size, etc. of the substrate.
  • the first sacrificial substrate may use any one selected from silicon, silicon oxide, sapphire, alumina, mica, germanium, silicon carbide, gold, silver, and a polymer.
  • the first contact thermal conductor layer is a step for forming a thermal conductor layer capable of minimizing heat loss of the flexible thermoelectric element.
  • the first contact thermal conductor layer may be formed of a material having high thermal conductivity.
  • aluminum nitride (AlN), Silicon nitride (Si 3 N 4 ) or alumina (Al 2 O 3 ) may be used, but is not limited thereto.
  • the method for forming the first contact thermal conductor may be any method known in the art, as long as it is a method for forming the first contact thermal conductor thin film on a substrate.
  • spin coating, screen printing technique, physical deposition, thermal evaporation, chemical vapor deposition, electrodeposition or spraying It may be formed through a spray coating or the like.
  • Step a-2) is a step for forming the first electrode, and any method may be used as long as it is a method for forming the first electrode according to a planned pattern.
  • screen printing may be performed. It may be performed by various methods such as printing, sputtering, vaporization, evaporation, chemical vapor deposition, pattern transfer, or electroplating.
  • the method may be performed through a screen printing method, and the first electrode paste may be applied to the upper portion of the first contact thermal conductor layer in a predetermined pattern, and then heat-treated to form the first electrode.
  • the first electrode paste may be an electrode paste, and may include a first conductive material, and in detail, may include a first conductive material, a first solvent, and a first binder.
  • the first electrode paste may be adjusted in composition and content of each component in consideration of the planned electrode type, thermal conductivity, electrical conductivity and thickness.
  • the first electrode paste may include a metal material or a first conductive material such as carbon nanotubes and carbon nanowires having excellent electrical conductivity, and the first conductive material may be the same as described in the flexible thermoelectric device. can do.
  • the metal material may be a transition metal of Groups 3 to 12, and in one embodiment, nickel (Ni), copper (Cu), platinum (Pt), ruthenium (Ru), rhodium (Rh), gold (Au) ), Tungsten (W), cobalt (Co), palladium (Pd), titanium (Ti), tantalum (Ta), iron (Fe), molybdenum (Mo), hafnium (Hf), lanthanum (La), iridium (Ir) )
  • silver (Ag) may be one or two or more, and it may be preferable to use copper (Cu) in view of high electrical conductivity, binding to the filler material, and low cost.
  • the first solvent is used to control the fluidity of the first electrode paste, and may be used without particular limitation as long as it can dissolve the first binder.
  • an alcohol solvent, a ketone solvent, or the like may be used.
  • Mixed solvents can be used.
  • the first binder is for adjusting the printing resolution, and in one embodiment, a resin material may be used.
  • the first electrode paste may have a sufficient thermal conductivity and electrical conductivity, and may be preferably formulated in a content range to ensure flexibility of the electrode.
  • the first electrode paste may include 10 to 90% by weight of the first conductive material, 5 to 50% by weight of the first solvent, and 2 to 10% by weight of the first binder.
  • the first electrode paste may further include a glass frit in terms of improving the binding force between the electrode and the filling material.
  • a glass frit in terms of improving the binding force between the electrode and the filling material.
  • 0.1 to 20 parts by weight may be added based on 100 parts by weight of the first conductive material. It is possible to prevent the lowering of the electrical conductivity while ensuring excellent binding strength in the above range.
  • the content of the glass frit is less than 0.1 part by weight, the effect of improving the binding force between the electrode and the filling material may be insignificant, and when the content of the glass frit is more than 20 parts by weight, the electrical conductivity is reduced by the non-conductive glass frit.
  • the thermoelectric performance of the thermoelectric element may be lowered.
  • the electrode in order to improve the flexibility of the thermoelectric device, it is good to implement the electrode as thin as possible. However, the thinner the electrode, the lower the electrical conductivity caused by the glass frit may appear. Accordingly, the relative content of the glass frit relative to the first conductive material is preferably in the minimum content range in which the binding enhancement effect can be exhibited to the extent that the flexible mesh can be excluded. In this aspect, the electrode may contain 0.5 to 10 parts by weight, specifically 1 to 5 parts by weight, based on 100 parts by weight of the conductive material.
  • the second electrode may be manufactured in the same manner as the first electrode, duplicate description thereof will be omitted.
  • the glass frit contained in the electrode significantly improves the binding force between the electrode and the filling material, thereby enabling the implementation of a flexible thermoelectric element in which the flexible mesh is excluded.
  • the electrode and the thermoelectric column array can be bonded using a conductive adhesive, whereby the electrode and the thermoelectric column array can be strongly bound to each other, with high thermal conductivity and electrical between the electrode and the thermoelectric column array Conduction may be possible.
  • the electrode and the filler can not be strongly bound to each other by using such an adhesive, the improvement of the binding force between the electrode and the filler should be preempted above all in order to exclude the flexible mesh which ensures mechanical stability and serves as a support.
  • the glass frit is added to the electrode to ensure that the adhesive strength between the electrode and the filling material is 0.7 MPa or more, thereby ensuring high binding force.
  • the three components of the thermoelectric column array-electrode-filling material are very strongly mediated through the electrode. By having a bonded structure, mechanical and physical stability can be ensured without compromising the flexibility of the device.
  • the adhesive strength between the electrode and the filling material is preferably 1 to 5 MPa.
  • the first electrode and the second electrode may satisfy the following relations 1-1 or 1-2.
  • Equation 1-1 G 1 is the total weight (g) of the glass frit in the first electrode, G S1 is the weight (g) of the glass frit located in the bonding portion of the first electrode.
  • G 2 is the total weight (g) of the glass frit in the second electrode
  • G S2 is the weight (g) of the glass frit located in the bonding portion of the second electrode.
  • the adhesive part refers to the adhesive surface in contact with the filling material, up to 30% of the thickness of the first electrode or the second electrode based on the adhesive surface.
  • the glass frit may be more than 45% by weight positioned in the bonding portion of the electrode to be bonded to the filling material to more effectively improve the adhesive force between the electrode and the filling material, more preferably 50% by weight or more of the glass frit is placed on the bonding portion of the electrode It is desirable to.
  • the filling material is a polymer containing a silanol group or an alkoxysilane group
  • the silanol group or alkoxysilane group may be chemically and firmly bonded to the electrode and the filling material by reacting with the metal oxide of the glass frit. It may be to have an adhesive strength of 1 to 5 MPa between and the filling material.
  • the binding force between the electrode and the filler material may be reduced by reducing the chemical bond between the electrode and the filler material.
  • the adhesive strength is less than 1 MPa, Physical stability may be degraded.
  • step a-3) is a step for forming a thermoelectric material.
  • the step a-3) is for forming a P-type thermoelectric material on a predetermined region on the patterned first electrode.
  • Step a-3) may be any method as long as it can form a P-type thermoelectric material in a predetermined region on the first electrode.
  • a polycrystalline body is formed using a thermoelectric paste.
  • a single crystal can be used to form the thermoelectric material.
  • the flexible thermoelectric device according to an embodiment of the present invention can be used as it is not necessary to have a mesh through the adhesion between the electrode and the filling material is improved.
  • the P-type thermoelectric material formed on the first electrode and the N-type thermoelectric material formed on the second electrode may be spaced apart from each other, as shown in FIG. 2.
  • the P-type thermoelectric material when the P-type thermoelectric material is formed into a polycrystal using a thermoelectric paste, the P-type thermoelectric material may be formed by screen printing.
  • the thermoelectric material paste may be applied to the upper portion of the first electrode in a predetermined pattern, and then heat-treated to form a thermoelectric material.
  • the P-type thermoelectric material paste may include a second conductive material, and in detail, may include a second conductive material, a second solvent, and a second binder.
  • the P-type thermoelectric material paste may be adjusted in composition and content of each component in consideration of the type of the planned thermoelectric material, thermal conductivity, electrical conductivity and thickness.
  • the second conductive material is the case described above can be used as the same material, the paste for the P-type thermoelectric material, an antimony-telru ryumgye (Sb x Te 1 -x) or bismuth-antimony-telru nyumgye (Bi y Sb 2 - y Te 3 ) is preferably used.
  • x may be 0 ⁇ x ⁇ 1
  • y may be 0 ⁇ y ⁇ 2.
  • the second solvent is for controlling the fluidity of the P-type thermoelectric material paste, and can be used without particular limitation as long as it can dissolve the second binder, in one embodiment, an alcohol solvent, a ketone solvent or these A mixed solvent of can be used.
  • the second binder is for adjusting printing resolution, and in one embodiment, a resin material may be used.
  • the paste for P-type thermoelectric material may include 10 to 90% by weight of the second conductive material, 5 to 50% by weight of the second solvent, and 2 to 10% by weight of the second binder.
  • the P-type thermoelectric material paste may further include a glass frit in terms of improving binding force between the thermoelectric material and the filling material.
  • the glass frit may be added in an amount of 2 to 10% by weight based on the total weight of the paste for thermoelectric material.
  • the P-type thermoelectric material paste may be applied to the upper portion of the first electrode in a predetermined pattern, and then heat-treated to form the P-type thermoelectric material.
  • the heat treatment conditions may be adjusted in various ways.
  • the thermoelectric device according to an embodiment of the present invention may be manufactured by removing the flexible mesh, so that the P-type thermoelectric material paste is applied on the first electrode.
  • the P-type thermoelectric material may be formed by heat treatment under optimal conditions. In the case of using the existing flexible mesh, the P-type thermoelectric material and the N-type thermoelectric material are coated and then heat-treated at the same time, so that the annealing is performed in a medium condition, thereby reducing the efficiency of the thermoelectric device.
  • thermoelectric material paste since only the P-type or N-type thermoelectric material paste is applied to the electrodes and then heat treated, respectively, the optimum annealing conditions for forming the P-type thermoelectric material and the optimum annealing for the N-type thermoelectric material are formed.
  • Each thermoelectric material may be formed under conditions.
  • the P-type thermoelectric material and the N-type thermoelectric material may be formed under optimal annealing conditions, thereby maximizing the efficiency of the thermoelectric device.
  • the optimum annealing conditions for forming the P-type thermoelectric material may vary depending on the type of the second conductive material included in the P-type thermoelectric material, and may be annealed at, for example, 300 to 1000 ° C. .
  • the second conductive material is Bi 0 . 3 Sb 1 . 7 Te 3 , Bi 0 . 8 Sb 1 . 2 Te 3 Or Bi 0 . 5 Sb 1 .
  • bismuth-antimony-tellurium-based (Bi y Sb 2-y Te 3 , 0 ⁇ y ⁇ 2) compounds such as 5 Te 3
  • the substrate on which the P-type thermoelectric paste is coated is placed in an oven at 80 to 140 ° C.
  • the annealing may proceed at a temperature higher than the temperature of the city. At this time, the annealing temperature may be 400 to 600 °C, annealing time may be 30 minutes to 120 minutes, the most optimal annealing conditions may be 80 minutes at 500 °C.
  • the second electrode may be formed in the same manner as the first structure, and then an N-type thermoelectric material may be formed in a predetermined region on the second electrode.
  • an N-type thermoelectric material paste may be used, and the N-type thermoelectric material paste may be the same as the P-type thermoelectric material paste except that the second conductive material is different.
  • bismuth is preferred to use a - (y Se y Bi 2 Te 3) compound telru ryumgye (Bi x Te 1 -x) or bismuth-titanium selenium-based telephone.
  • x may be 0 ⁇ x ⁇ 1
  • y may be 0 ⁇ y ⁇ 2.
  • an N-type thermoelectric material paste may be coated on the second electrode in a predetermined pattern, and then heat-treated to form the N-type thermoelectric material.
  • the optimum annealing conditions for the formation of the N-type thermoelectric material may vary according to the type of the second conductive material contained in the N-type thermoelectric material.
  • the second conductive material may be bismuth-tellurium-based (Bi x Te 1).
  • the substrate coated with the N-type thermoelectric paste is placed in an oven at 80 to 140 °C to dry for 5 to 20 minutes to evaporate the solvent, than the solvent evaporation temperature
  • annealing may be performed at a temperature higher than the temperature at the time of evaporation of the binder in order to increase the thermoelectric properties of the thermoelectric material.
  • the annealing temperature may be 350 to 550 ° C
  • the annealing time may be 30 minutes to 120 minutes
  • the most optimal annealing condition may be 90 minutes at 510 ° C.
  • the second conductive material contains tellurium (Te), tellurium (Te) powder in a heat treatment oven (Oven) or a heat treatment furnace (Fe) to prevent evaporation of the tellurium (Te) during high temperature heat treatment It is preferable to insert together and proceed with heat treatment.
  • step a-3 when a single crystal is formed of a P-type thermoelectric material or an N-type thermoelectric material, a single crystal including a second conductive material is manufactured, and then the shape is planned through a process such as cutting. It can be processed and bonded to the upper portion of the first electrode.
  • the method for the adhesion is not particularly limited as long as it is a method capable of bonding the electrode and the thermoelectric material.
  • the adhesion may be performed using a conductive adhesive.
  • the conductive adhesive may be a silver paste containing silver, and in one embodiment, silver (Ag) paste, tin-silver (Sn-Ag) paste, tin-silver-copper (Sn-Ag-Cu) paste or tin Antimony (Sn-Sb) paste may be used, but is not limited thereto.
  • silver (Ag) paste, tin-silver (Sn-Ag) paste, tin-silver-copper (Sn-Ag-Cu) paste or tin Antimony (Sn-Sb) paste may be used, but is not limited thereto.
  • first structure and the second structure may be connected so that the thermoelectric materials are spaced apart from each other, and as shown in FIG. 2, the structures may be connected such that the P-type thermoelectric material and the N-type thermoelectric material are alternately positioned.
  • the connection may be performed through an adhesion process, and the method for the adhesion is not particularly limited as long as it can bond the electrode and the thermoelectric material.
  • the connection may be performed using a conductive adhesive. .
  • the conductive adhesive may be a silver paste containing silver, and in one embodiment, silver (Ag) paste, tin-silver (Sn-Ag) paste, tin-silver-copper (Sn-Ag-Cu) paste or tin Antimony (Sn-Sb) paste may be used, but is not limited thereto.
  • silver (Ag) paste, tin-silver (Sn-Ag) paste, tin-silver-copper (Sn-Ag-Cu) paste or tin Antimony (Sn-Sb) paste may be used, but is not limited thereto.
  • step c) forming the filling material in the empty space between the thermoelectric column array of the substrate may be performed. That is, through this, it is possible to physically support the thermoelectric material and to ensure mechanical properties of the thermoelectric element.
  • step c) includes filling the c-1) filling material precursor into the empty space formed by the thermoelectric column array, and c-2) processing the filling material precursor to form a filling material. Can be divided into stages. In addition, after the filling material is formed, it is preferable to remove the filling material remaining in unnecessary parts other than the empty space.
  • Step c-1) is not limited as long as the filling material precursor can be filled with a gap between the N-type thermoelectric material and the P-type thermoelectric material, for example, a prepolymer, a curing agent, and the like.
  • the liquid filler containing precursor is filled in the substrate on which the electrode and thermoelectric pillar array is formed by using capillary action, or the electrode and thermoelectric material in the tank filled with the liquid filler precursor including the prepolymer and the curing agent.
  • the substrate on which the pillar array is formed may be filled and filled.
  • step c-2 is a step of forming a filling material by processing a filling material precursor filled in an empty space formed by the thermoelectric column array, and specifically, may form a filling material through curing.
  • the filling material formed through curing may be a high molecular compound.
  • the filler precursor may include a prepolymer, and when the prepolymer itself is a liquid phase, the drying process may be omitted, but when the solution phase is dissolved in a solvent, a drying process may be performed before hardening revolution. . Drying process according to one embodiment may be carried out by drying for a predetermined time at a temperature such that the solvent is enough to fly. In one embodiment, when the prepolymer is polydimethylsiloxane, the drying temperature may be from room temperature to 150 ° C., and the drying time may be 10 minutes to 24 hours.
  • the curing process may vary depending on the type and content of the prepolymer and the curing agent.
  • the curing process may be performed by adjusting the content of the thermosetting agent, the curing temperature, and the curing time. It may be performed differently depending on the type of functional group.
  • the curing process may be performed by adjusting the content, light amount and light intensity of the photocuring agent, but this may also be performed differently according to the type of the photocurable functional group.
  • the removal step can be performed by peeling only the sacrificial substrate from the contact thermal conductor layer, the method of peeling only the sacrificial substrate from the contact thermal conductor layer If it can be used without particular limitation, for example, it can be physically or chemically peeled off in the air or water.
  • the removal step can be performed by peeling only the sacrificial substrate from the contact thermal conductor layer, the method of peeling only the sacrificial substrate from the contact thermal conductor layer If it can be used without particular limitation, for example, it can be physically or chemically peeled off in the air or water.
  • the sacrificial substrate removing step may be performed by first peeling the substrate out of the sacrificial substrate and then removing the sacrificial film.
  • the peeling of the substrate may be used without particular limitation as long as it can peel only the substrate from the sacrificial film.
  • the substrate may be peeled physically or chemically in air or water.
  • the silicon oxide substrate and the nickel thin film may be Peeling occurs at the interface.
  • the sacrificial layer may be removed by etching, and the etching method is not particularly limited, but the sacrificial layer may be removed by a wet etching method and / or a chemical physical polishing method.
  • the sacrificial layer may be removed by a wet etching method.
  • the composition of the etchant may be changed according to the metal thin film type of the sacrificial layer.
  • Method (II) of manufacturing a flexible thermoelectric device includes: A) a 1-1 structure in which a 1-1 sacrificial substrate, a 1-1 contact thermal conductor layer, and a 1-1 electrode are sequentially stacked; Forming a 2-1 structure in which a 2-1 sacrificial substrate, a 2-1 contact thermal conductor layer, and a 2-1 electrode are sequentially stacked; B) forming a P-type thermoelectric material on the 3-1 sacrificial substrate and an N-type thermoelectric material on the 4-1 sacrificial substrate; C) transferring the P-type thermoelectric material and the N-type thermoelectric material into the first-first structure, respectively; D) manufacturing a substrate on which a thermoelectric pillar array is formed by physically connecting the 1-1 structure to which the P-type thermoelectric material and the N-type thermoelectric material are transferred and the 2-1 structure; E) forming a filling material in the void space between the thermoelectric pillar arrays; And F) removing the 1
  • the manufacturing method (II) of the flexible thermoelectric device after transferring the P-type thermoelectric material and the N-type thermoelectric material to the first-first structure, and connecting with the second-first structure, all the processes other than the flexible thermoelectric device are performed. It may be the same as described in the manufacturing method (I) of.
  • a method of forming a contact thermal conductor on a sacrificial substrate, a method of forming an electrode on a contact thermal conductor, and a method of forming a thermoelectric material (the method of forming a lower substrate is the same, and the 3-1 sacrificial substrate and the 4-1
  • the sacrificial substrate may be any one selected from the materials listed in the first sacrificial substrate, and may be the same or different.)
  • the filling material forming method and the sacrificial substrate removing method are the same as those described in the manufacturing method (I) of the flexible thermoelectric device. The same bar, detailed description thereof will be omitted.
  • Step C) may be a step of transferring the P-type thermoelectric material and the N-type thermoelectric material into the 1-1 structures, respectively.
  • the P-type thermoelectric material and the N-type thermoelectric material formed on each of the 3-1 sacrificial substrate or the 4-1 sacrificial substrate can be transferred to the 1-1 structure.
  • the transfer method can be used without particular limitation so long as it is a method commonly used in the art.
  • D) physically connecting the 1-1 structure in which the P-type thermoelectric material and the N-type thermoelectric material are transferred and the 2-1 structure may be performed to manufacture a substrate on which a thermoelectric pillar array is formed.
  • the P-type thermoelectric material and the N-type thermoelectric material may be connected to the 1-1 structure and the 2-1 structure to which the P-type thermoelectric material and the N-type thermoelectric material are transferred, and as shown in FIG. 2, the P-type thermoelectric material Each structure can be connected so that and N-type thermoelectric materials are alternately positioned.
  • the connection may be performed through an adhesion process, and the method for the adhesion is not particularly limited as long as it can bond the electrode and the thermoelectric material.
  • the connection may be performed using a conductive adhesive.
  • the conductive adhesive may be a silver paste containing silver, and in one embodiment, silver (Ag) paste, tin-silver (Sn-Ag) paste, tin-silver-copper (Sn-Ag-Cu) paste or tin Antimony (Sn-Sb) paste may be used, but is not limited thereto.
  • thermoelectric device illustrates an embodiment in which the flexible thermoelectric device according to an embodiment of the present invention is applied to real life.
  • the flexible thermoelectric device can be applied to objects having various shapes.
  • the flexible thermoelectric device according to the present invention may generate power using body heat generated in a human body.
  • thermoelectric power may be applied to an arm of a human body.
  • the flexible thermoelectric device according to an embodiment of the present invention may be applied to a portion in which heat is present or needs cooling, such as an automobile, a ship, a glass window, a smartphone, an airplane, or a power plant.
  • the flexible thermoelectric device according to the present invention since the objects have an arbitrary shape, the flexible thermoelectric device according to the present invention has an advantage of being applicable to objects having various shapes.
  • the direct contact can be made according to the shape of the application site, the heat transfer efficiency is improved, thereby maximizing the performance of the thermoelectric element to the application target.
  • the thickness is thin and can be manufactured using an insulating layer having high thermal conductivity, it is possible to achieve higher thermoelectric efficiency than using an existing alumina (Al 2 O 3 ) substrate.
  • thermoelectric device and a method for manufacturing the same according to the present invention will be described in more detail with reference to the following examples.
  • the following examples are only one reference for describing the present invention in detail, and the present invention is not limited thereto and may be implemented in various forms.
  • all technical and scientific terms have the same meanings as commonly understood by one of ordinary skill in the art to which this invention belongs.
  • the terminology used in the description herein is for the purpose of effectively describing particular embodiments only and is not intended to be limiting of the invention.
  • the singular forms used in the specification and the appended claims may be intended to include the plural forms as well, unless the context clearly indicates otherwise.
  • the unit of the additive which is not specifically described in the specification may be wt%.
  • Two silicon oxide substrates (4-inch wafers) having Si layers formed as sacrificial substrates were prepared, and aluminum nitride films were formed on the respective sacrificial substrates by a spin coating method to a thickness of several hundred micrometers.
  • the electrode paste was applied onto a substrate on which each aluminum nitride film was formed, and then heat-treated to form an electrode.
  • the electrode paste includes 75.0 wt% of copper powder, 2.3 wt% of binder (Nitrocellulose), 20.3 wt% of solvent (VDT07) and glass frit (Bi 2 O 3 , Al 2 O 3 , SiO 3 , ZnO) It was prepared by mixing 2.4% by weight, which was coated on an aluminum nitride film by screen printing and heat-treated at 700 ° C. for 20 minutes to form an electrode.
  • Electrode is referred to as a second electrode).
  • the P-type thermoelectric material was coated with a P-type thermoelectric material paste on a predetermined region of the first electrode by screen printing, followed by heat treatment to form a P-type thermoelectric material.
  • the face for the P-type thermoelectric material is Bi 0 . 3 Sb 1 .
  • the N-type thermoelectric material was coated with an N-type thermoelectric material paste by a screen printing method on a predetermined region of the second electrode, and then heat-treated to form an N-type thermoelectric material.
  • the face for N-type thermoelectric material is 84.5% by weight of Bi x Te 1- x powder, 12.8% by weight of binder + solvent (7SVB-45) and glass frit (Bi 2 O 3 , Al 2 O 3 , SiO 3 , ZnO) 2.7 wt% was prepared by mixing.
  • the solvent was removed at 100 ° C. for 10 minutes, then heat treated at 250 ° C. for 30 minutes to remove the binder, and annealed at 510 ° C. for 90 minutes.
  • thermoelectric material pillar array was formed by bonding a substrate on which a P-type thermoelectric material was formed and a substrate on which an N-type thermoelectric material was formed.
  • thermoelectric column arrays were filled with empty spaces between the thermoelectric column arrays and cured to form a fill material.
  • PDMS polydimethylsiloxane
  • the silicon thin film formed on the substrate is peeled off using a laser peeling process, and the Si / SiO 2 remaining on the outside of the flexible thermoelectric element is removed.
  • the layer was removed with a mixture of HNO 3 , H 2 O, and HF (10% by volume: 75% by volume: 15% by volume) to prepare a flexible thermoelectric device.
  • the electrode was manufactured by adding glass frit, but the copper powder did not melt under the same temperature conditions, and thus the electrode was not formed properly.
  • the copper thin film without the glass frit was etched with H 2 O and HNO 3 (3: 1) for 10 minutes to form fine roughness, and then all processes except for using the electrode were performed in the same manner as in Example 1.
  • the glass frit-free copper thin film was rubbed with sand paper to form fine irregularities, and then all processes except for using the electrode were performed in the same manner as in Example 1.
  • Adhesion strength The force at which the interface was completely peeled was measured while gradually applying a force to both ends around the adhesive interface. (Pull-off test)
  • the flexible thermoelectric device manufactured according to the present invention can be confirmed that the adhesive strength between the electrode and the filling material has an excellent adhesion of 0.7 MPa or more.
  • Example 1 in which glass frit was added at 2.7% by weight of the total weight of the paste, (G S / G) x 100 was 55%, and the surface roughness was 0.79 ⁇ m, the adhesive strength was 1.09 MPa and filled with the electrode. It can be seen that the adhesion between the materials is very excellent. This is because the glass frit added in an appropriate amount is distributed at about 55% by weight of the electrode to induce chemical bonding between the fillers, thereby greatly improving the adhesive strength, and by forming a surface roughness of 0.7 ⁇ m or more on the surface of the electrode. By maximizing the anchoring effect between the electrode and the electrode, a flexible thermoelectric device having an adhesive strength of 1 MPa or more between the electrode and the filling material could be realized.
  • Example 2 (G S / G) ⁇ 100 is 40%, the area where the filler and the glass frit can react chemically, the adhesive strength between the electrode and the filler material is Example 1 It can be seen that it falls to about 70%.
  • Example 3 the surface roughness of 0.47 ⁇ m, as the effect of anchoring the filling material to the electrode slightly decreases, it can be seen that the adhesive strength between the electrode and the filling material drops to about 84% compared to Example 1.
  • Comparative Examples 1 to 3 are prepared by the electrode without the glass frit, in the case of Comparative Example 1, even though the heat treatment was performed under the same temperature conditions as in Example 1, because the glass frit is not added to the electrode paste, Since the copper powder did not melt, the electrode was not manufactured properly, and it was confirmed that the presence or absence of addition of the glass frit was also very important in the process.

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Abstract

La présente invention concerne un élément thermoélectrique flexible et son procédé de production. L'élément thermoélectrique flexible comprend : un réseau de branches thermoélectriques contenant au moins un matériau thermoélectrique de type N et un matériau thermoélectrique de type P agencés à distance l'un de l'autre ; des électrodes permettant de raccorder électriquement les matériaux thermoélectriques du réseau de branches thermoélectriques ; et un matériau de remplissage permettant de remplir au moins un espace vide du réseau de branches thermoélectriques. Les électrodes contiennent une fritte de verre.
PCT/KR2016/012054 2015-10-27 2016-10-26 Élément thermoélectrique flexible et son procédé de production Ceased WO2017074002A1 (fr)

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