KR100994508B1 - Thermoelectric Generation Module Using Hydrogen Peroxide as Heat Source and Heat Sink - Google Patents

Abstract

The present invention relates to a thermoelectric power module having a low temperature unit, a thermoelectric element, and a high temperature unit. Specifically, a thermoelectric power module using hydrogen peroxide as a heat source and a refrigerant includes a cooling unit to which hydrogen peroxide (H ₂ O ₂ ) is transferred; A reaction part in which hydrogen peroxide transferred from the cooling part is decomposed into water and oxygen by a catalyst to generate heat; And a thermoelectric element provided between the cooling unit and the reaction unit, wherein the hydrogen peroxide transferred through the cooling unit serves as a refrigerant, and the thermoelectric element decomposes hydrogen peroxide of the cooling unit and hydrogen peroxide of the reaction unit. It has a characteristic that it has a temperature gradient due to decomposition heat generated during the process.

Hydrogen peroxide, thermoelectric element, thermoelectric module, catalyst, decomposition

Description

Thermoelectric Generation Module Using Hydrogen Peroxide as Heat Source and Heat Sink

The present invention can reduce the volume of the power source by using hydrogen peroxide as the heat source and the refrigerant, the temperature gradient of the low temperature portion and the high temperature portion is high efficiency, and can be used as a small power source, to provide an environmentally friendly thermoelectric power module.

In recent years, many researches have been made to miniaturize existing devices according to the development of the precision processing process technology including the micro machining process (MEMS) technology. These small systems are being developed all over the field, from single devices such as sensors to complex systems such as micro air vehicles and small robots. Existing secondary batteries are being used as a power source for such systems.

However, research / development of alternative power sources to solve the low energy density of the secondary battery and the inconvenience of the charging method is actively conducted worldwide.

The micro heat engine, which has been studied as a miniature power source, has a disadvantage in that it is difficult to miniaturize the high speed drive unit. Thermoelectric power generation uses the Seebeck effect to produce electrical energy from thermal energy, unlike micro heat engines.

Thermoelectric power generation requires a thermoelectric element, a heat source, and a cooling device for cooling the low temperature part. The power generation performance of thermoelectric power generation is determined by the temperature difference between the high and low temperature parts of the thermoelectric element, and a large temperature difference is required to improve the performance.

The conventional thermoelectric power module using the exothermic reaction as a heat source used a method of attaching a combustor to a high temperature part of a thermoelectric element and attaching a heat sink having a plurality of flat fins to a low temperature part using a catalytic combustion reaction as a heat source. In this case, the cooling of the low temperature part is performed through natural convection using air in the air, which causes a problem that the size of the heat sink is larger than that of the reactor and the thermoelectric element or the power generation performance is degraded (JA Federici). , DG Norton, T. Brgggemann, KW Voit, ED Wetzel, DG Vlachos.Calytic microcombustors with integrated thermoelectric elements for portable power production, 2006, Vol. 161, Journal of Power Source, 1469-1478).

In addition, a catalytic convection is used as a heat source, and a forced convection method is used to cool the low temperature part by using the air required for combustion as a refrigerant of the low temperature part of the thermoelectric element (Korean Patent No. 0849504). However, there is a problem in the low performance of the air as a refrigerant, and there is a problem that carbon dioxide, carbon monoxide, which are greenhouse gases are generated by using the combustion reaction.

An object of the present invention for solving the above problems is to use the heat of decomposition rather than combustion as a heat source and to form a low temperature portion with a liquid refrigerant, it is possible to reduce the volume of the power source, excellent cooling efficiency of the low temperature portion, high temperature portion and high temperature portion The large temperature gradient provides high efficiency, small power source, and environmentally friendly thermoelectric power module.

The thermoelectric power module using hydrogen peroxide as a heat source and a refrigerant includes a cooling unit to which hydrogen peroxide (H ₂ O ₂ ) is transferred; A reaction part in which hydrogen peroxide transferred from the cooling part is decomposed into water and oxygen by a catalyst to generate heat; And a thermoelectric element provided between the cooling unit and the reaction unit, wherein the hydrogen peroxide transferred through the cooling unit serves as a refrigerant, and the thermoelectric element decomposes hydrogen peroxide of the cooling unit and hydrogen peroxide of the reaction unit. It has a characteristic that it has a temperature gradient due to decomposition heat generated during the process.

The reaction unit is a metal foam consisting of a foamed metal; And silver, at least one catalyst selected from platinum and manganese oxides.

The reaction part is characterized in that the catalyst, preferably silver, platinum, or a mixture thereof is electroplated on the metal foam surface.

The reaction unit further comprises ceramic particles selected from one or more selected from alumina, silica, and titania, and the catalyst is supported on the ceramic particles coated on the metal foam.

The reaction part includes a metal plate having a fluid inlet gap and a fluid outlet gap at both ends and an inner gap connecting the two pores, wherein the metal foam and the catalyst are provided in the inner gap of the metal plate. There is this.

The metal foam constituting the reaction portion is preferably nickel foam.

The cooling unit includes a metal plate, one end of the metal plate is provided with pores through which hydrogen peroxide is introduced, and the other end is provided with pores through which hydrogen peroxide is discharged, and a fluid movement channel connecting the two pores inside the metal plate ( one or more channels).

The channel of the cooling unit is characterized in that the pores of the rectangular column, cylinder or hexagonal column shape including a rectangle and a square, the surface of the channel is preferably formed with surface curvature.

It is preferable that the said cooling part is aluminum.

The cooling unit and the reaction unit are each preferably in the form of a plate having a thickness: width ratio of 1: 2 to 10, and the thickness is preferably 2 to 10mm.

The thermoelectric power module has a structure in which a thermoelectric element and a cooling unit are stacked on the upper and lower portions of the reaction unit with respect to the reaction unit, and the hydrogen peroxide transferred from the cooling units provided at the upper and lower portions is the single reaction unit. It is characterized by inflow and decomposition.

In this case, the thermoelectric power module is preferably a structure in which two or more units are stacked using the stacked structure as one unit.

The present invention relates to a thermoelectric power module suitable as an ultra small power source, and has an advantage of being an environmentally friendly method in which pollutants are not discharged by heat generation using the heat of decomposition generated in the catalytic decomposition reaction of hydrogen peroxide as a heat source. There is a high advantage, there is an advantage that can supply a stable heat source.

The thermoelectric power module of the present invention is formed in the microchannel shape of the transfer path of the liquid hydrogen peroxide in the low temperature portion, the hydrogen peroxide transferred through the catalyst (catalyst provided on the metal foam) is provided in the micro-pores, so that the size of the module There is an advantage that can be miniaturized to a few mm or less.

The cooling unit of the present invention uses hydrogen peroxide in a liquid state at a normal temperature and atmospheric pressure transferred before the catalytic decomposition reaction as a refrigerant for cooling the low temperature part, thereby realizing miniaturization of the low temperature part cooling device and improving the cooling efficiency.

The reaction part of the present invention has the advantage that the decomposition reaction in which hydrogen peroxide is decomposed into water and oxygen is caused by the catalyst provided in the porous metal foam, thereby minimizing the amount of the catalyst and completely decomposing within a short time.

The thermoelectric power module of the present invention has an advantage in that a module including a reaction unit, a thermoelectric element, and a cooling unit is used as a unit, and the power generation capacity can be easily adjusted by stacking the unit.

Hereinafter, the thermoelectric power module of the present invention will be described in detail with reference to the accompanying drawings. The drawings introduced below are provided by way of example so that the spirit of the invention to those skilled in the art can fully convey. Accordingly, the present invention is not limited to the drawings presented below and may be embodied in other forms. Also, like reference numerals denote like elements throughout the specification.

Hereinafter, the technical and scientific terms used herein will be understood by those skilled in the art without departing from the scope of the present invention. Descriptions of known functions and configurations that may be unnecessarily blurred are omitted.

The thermoelectric power module according to the present invention includes a cooling unit to which hydrogen peroxide (H ₂ O ₂ ) is transferred; A reaction part in which hydrogen peroxide transferred from the cooling part is decomposed into water and oxygen by a catalyst to generate heat; And a thermoelectric element provided between the cooling unit and the reaction unit, wherein the hydrogen peroxide transferred through the cooling unit acts as a refrigerant. It has a characteristic that it has a temperature gradient due to decomposition heat generated during the process.

In the thermoelectric power module of the present invention, the thermoelectric element and the cooling unit may be configured in a concentric structure with a rod-shaped reaction unit having a circular or polygonal cross section. It may be composed of a laminated plate structure.

1 is a preferred example of the thermoelectric power module of the present invention having a laminated plate structure, in order to efficiently use the hydrogen peroxide decomposition heat generated in the reaction unit 20, the reaction unit 20, the center of the reaction unit 20 And a structure in which the thermoelectric elements 30A and 30B and the cooling units 10A and 10B are stacked below. Thermoelectric power generation module 100 of the invention is the cooling unit (10A, 10B) to which hydrogen peroxide (H ₂ O ₂ ) is transferred; A reaction part 20 in which hydrogen peroxide transferred from the cooling parts 10A and 10B is decomposed into water and oxygen by a catalyst to generate heat; And thermoelectric elements 30A and 30B provided between the cooling units 10A and 10B and the reaction unit 20. The hydrogen peroxide transferred through the cooling units 10A and 10B acts as a refrigerant. The thermoelectric elements 30A and 30B have a temperature gradient due to decomposition heat generated when hydrogen peroxide of the cooling units 10A and 10B and hydrogen peroxide of the reaction unit 20 are decomposed.

As shown in FIG. 1, the cooling units 10A and 10B which provide a cold plane to the thermoelectric elements 30A and 30B of the thermoelectric power module 100 are transported with liquid hydrogen peroxide, and simultaneously receive the hydrogen peroxide. It is characterized by cooling the thermoelectric elements 30A, 30B as a refrigerant.

Hydrogen peroxide transferred from the cooling units 10A and 10B cools the thermoelectric elements 30A and 30B and is supplied to the reaction unit 20 in a warmed state by cooling of the thermoelectric elements 30A and 30B.

The reaction unit 20 receives a heated hydrogen peroxide and performs a decomposition reaction in which hydrogen peroxide is decomposed into water and oxygen by a catalyst provided in the reaction unit 20 to generate heat of decomposition, and thermoelectric elements 30A and 30B. To provide a hot plane.

The thermoelectric elements 30A and 30B are cooled by hydrogen peroxide in the cooling units 10A and 10B and are heated by decomposition heat generated in the reaction unit 20 to generate electromotive force by thermal gradients at both ends.

As described above, the thermoelectric power module 100 of the present invention is characterized in that the refrigerant and the energy source is hydrogen peroxide, which is the same material, and in detail, the heat generated in the catalytic decomposition reaction of hydrogen peroxide as a heat source, conditions of normal temperature and pressure Hydrogen peroxide in the liquid state is characterized by using as a refrigerant for cooling the low temperature portion. As the cooling of the low temperature portion uses liquid peroxide rather than natural convection using air or air, it has excellent cooling characteristics, and has the advantage of constituting a flat type micro cooling unit away from the conventional fin-shaped heat sink.

In addition, by using hydrogen peroxide as an energy source, the fuel has the advantage of having a high energy density, it is possible to implement a micro-mini-module with the cooling unit, the hydrogen and water is discharged by using the heat of decomposition as a heat source, not combustion. It has the advantage of being an environmentally friendly power source.

Figure 2 is an example showing in more detail the cooling unit 10A or 10B of the thermoelectric power module 100 according to the present invention, as shown in Figure 2 (a) preferably the thermoelectric power module 100 of the present invention The cooling part 10 provided in the structure consists of a metal with high thermal conductivity, Preferably aluminum, Preferably it is a shape of a metal plate.

The cooling unit 10 has an advantage of having a thin thin plate shape by using hydrogen peroxide as a refrigerant and an energy source. The metal plate of the cooling unit 10 has a thickness: width (shortest perpendicular to the thickness direction) for miniaturization of power source, smooth supply of energy source (stable temperature of the hot side of the thermoelectric element), and uniform cooling of the cold side of the thermoelectric element. Length) has a length ratio of 1: 2 to 10, and the thickness is 2mm to 10mm.

As shown in FIG. 2A, the cooling unit 10 includes a metal plate 11, and one end of the metal plate 11 is provided with a cavity 12 through which hydrogen peroxide is introduced, and the other end thereof. The pores 16 through which hydrogen peroxide is discharged are provided, and at least one fluid moving channel 14 connecting the two pores 12 and 16 is provided inside the metal plate.

The fluid movement channel improves the area where the hydrogen peroxide, which is a refrigerant, contacts the metal plate 11 and smoothly supplies hydrogen peroxide to the reaction unit 20. As shown in FIG. If a channel 14 is provided, it is preferred to be connected to each other 13, 15 at each end of the channels and to the hydrogen peroxide inlet or outlet pores 12, 16.

As shown in the example of the cross-sectional view of the channel of Figure 2 (c), the channel is characterized in that the pores of the rectangular column, cylinder or hexagonal column shape including a rectangular and square, shown in Figure 2 (b) or 2 (c). As described above, each channel is preferably separated from each other (separated by a metal plate and a partition wall of the same material).

In addition, in order to improve the cooling effect, as shown in FIG. The surface curves include curves formed by physical scratches, chemical etching, mechanical processing, and the like.

Figure 3 is an example showing in more detail the reaction unit 20 of the thermoelectric power module 100 according to the present invention, as shown in Figure 3 preferably a reaction unit provided in the thermoelectric power module 100 of the present invention 20, a metal plate 21 serving as an outer housing (housing); And a metal foam 25 provided inside the metal plate and provided with a catalyst. The metal plate 21 of the reaction unit 20 is made of a high thermal conductivity metal, preferably aluminum. Similar to the cooling unit 10, the metal plate 21 of the reaction unit 20 has a thickness: width (shortest length perpendicular to the thickness direction) for miniaturization of a power source and stable temperature maintenance of the hot surface of the thermoelectric element. The length ratio is 1: 2 to 10 is a plate-like feature, the thickness is characterized in that 2mm to 10mm.

As shown in FIG. 3A, the metal plate 21 of the reaction unit 20 discharges the fluid (hydrogen peroxide transferred from the cooling unit) inlet cavity 27 and the fluid (water and oxygen generated by decomposition of hydrogen peroxide). The air gap 22 is provided at both ends and has internal pores 23, 24, and 26 connecting the two air gaps 22 and 27. It is characterized in that the metal foam 25 is provided with a catalyst.

As shown in the cross-sectional view of FIG. 3 (b), the metal foam 25 with the catalyst is provided in the inner space 24 of the metal plate 21, and has an inner space 24 similar to the shape of the metal foam 25. Is connected (23, 26) with fluid inlet or outlet voids (27, 22) at each end.

The metal foam is a foamed metal with continuous pores, provides a high thermal conductivity, serves as a catalyst carrier providing a high specific surface area between the catalyst and hydrogen peroxide, preferably nickel foam.

The catalyst is a material selected from one or more of silver, platinum and manganese oxide, it is preferable that 10 to 20 parts by weight of the catalyst based on the weight 100 of the metal foam is supported.

The metal foam 25 equipped with the catalyst is prepared by coating a metal foam with a precursor solution by supporting the metal foam in at least one precursor solution selected from a silver precursor, a platinum precursor, and a manganese precursor, and then heat-processing the metal foam, or the metal The foams are prepared by electroplating silver, platinum, or mixtures thereof.

Preferably, in order to further improve the specific surface area of the metal foam, the reaction part 20 further comprises ceramic particles selected from one or more of alumina, silica, and titania, and the ceramic particles are coated on the metal foam. After that, the catalyst is supported on the ceramic particles. The ceramic particles are preferably 20 to 60 parts by weight based on the weight 100 of the metal foam, and the catalyst supported on the metal foam coated with the ceramic particles by a conventional sol-gel method is 5 to 5 based on the weight 100 of the metal foam. It is preferable that it is 20 weight part.

The reaction unit 20 or the cooling unit 10 is manufactured by joining using laser welding after processing the inlet, outlet, internal pores, channels, etc. in the aluminum plate.

The thermoelectric element 30 provided between the reaction part 20 and the cooling part 10 is disposed between two electrically insulated substrates 31 and 33 of FIG. 4 (by metal wiring). A plurality of p-type and n-type semiconductor devices (for example, n diodes and p diodes, 32 of FIG. 4) connected in series include a conventional thermoelectric element structure formed alternately, and thin-film p-type and n-type semiconductor devices It includes a thermoelectric element consisting of.

4 is an example of a perspective view (FIG. 4 (a)) and a partially cut perspective view (FIG. 4 (b)) of the thermoelectric power module 100 according to the present invention. Similar to FIG. 1, the upper portion of the reaction unit 20 and The lower part is provided with thermoelectric elements 30A and 30B and cooling units 10A and 10B, respectively.

As shown in FIG. 4, the thermoelectric power module 100 of the present invention includes a hydrogen peroxide inlet 12 and an outlet 16 at both ends thereof, and preferably, a metal plate having a plurality of fluid transfer channels 14 formed therein. Cooling units 10A and 10B including 11; Fluid (hydrogen peroxide transported from the cooling section) inlet pores 27 and fluid (hydrogen peroxide decomposed water and oxygen) outlet pores 22 are formed at both ends, and the metal foam with catalyst is provided at both ends. A reaction part 20 provided in the internal voids 24 connected to the reference numerals 27 and 22; And a thermoelectric element 30 provided between the cooling unit 10 and the reaction unit 20.

As described above, the cooling unit 10 and the reaction unit 20 are ultra thin / ultra fine by using a liquid hydrogen peroxide as a refrigerant and simultaneously using hydrogen peroxide as an energy source by catalytic decomposition. It has a feature of a type metal plate structure, and has a length ratio of thickness: width (shortest length perpendicular to the thickness direction) of 1: 2 to 10, and the thickness is 2mm to 10mm. Accordingly, the thermoelectric power module (structure similar to FIG. 4) of the present invention has an advantage of being a power source of ultra-fine size having a cube shape of one side of several tens of mm in length.

As shown in FIG. 4, the reaction unit 20 is provided with two pairs of fluid inlets and fluid outlets corresponding to each other on a single metal plate 11 to connect a pair of corresponding fluid inlets and fluid outlets, respectively. The metal foam provided with the catalyst may be located in each of the internal pores. At this time, it is preferable that the inner voids connecting each of the corresponding pair of fluid inlets and fluid outlets are separated from each other.

The reaction unit 20 may include a metal foam provided with a plurality of catalysts as shown in FIG. 4, and the internal pores provided with each of the plurality of metal foams are separated from each other, and the fluid inlet and It is preferable that a fluid outlet corresponding to the inlet is provided.

The thermoelectric power module according to the present invention has a stacked structure similar to that of FIG. 4 as one unit, wherein two or more units are stacked left / right or up / down, and the generation capacity is controlled by stacking the units. There is a characteristic to become.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Those skilled in the art will recognize that many modifications and variations are possible in light of the above teachings.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and all of the equivalents or equivalents of the claims as well as the claims to be described later will belong to the scope of the present invention. .

1 is a configuration diagram of a thermoelectric power module according to the present invention,

2 is a perspective view and a cross-sectional view of the cooling unit provided in the thermoelectric power module according to the present invention;

3 is a perspective view and a cross-sectional view of a reaction unit provided in the thermoelectric power module according to the present invention;

4 is a perspective view and a partial cross-sectional view of a thermoelectric power module according to the present invention.

* Description of the symbols for the main parts of the drawings *

100: thermoelectric generation module 10, 10A, 10B: cooling unit

20, 20A, 20B: reaction unit 30A, 30B: thermoelectric element

12: hydrogen peroxide inlet 16: hydrogen peroxide outlet

14 channel 27 fluid inlet

22: fluid outlet 24: internal pores

25: metal foam with catalyst 11, 21: metal plate

Claims (14)

A cooling unit to which hydrogen peroxide is transferred; A reaction part in which hydrogen peroxide transferred from the cooling part is decomposed into water and oxygen by a catalyst to generate heat; And a thermoelectric element provided between the cooling unit and the reaction unit. Hydrogen peroxide transferred through the cooling unit acts as a refrigerant, The thermoelectric power module using the hydrogen peroxide as a heat source and a coolant, characterized in that the thermoelectric element has a temperature gradient by the decomposition heat generated when the hydrogen peroxide of the cooling unit and the hydrogen peroxide decomposition of the reaction unit. The method of claim 1, The reaction unit is a metal foam consisting of a foamed metal; And at least one catalyst selected from silver, platinum, and manganese oxide. The thermoelectric power module using hydrogen peroxide as a heat source and a refrigerant. 3. The method of claim 2, The reaction unit is a thermoelectric power module using hydrogen peroxide as a heat source and a refrigerant, characterized in that the catalyst is electroplated on the surface of the metal foam. 3. The method of claim 2, The reaction unit further comprises ceramic particles selected from one or more selected from alumina, silica, and titania, and thermoelectric power generation using hydrogen peroxide as a heat source and a refrigerant, wherein the catalyst is supported on the ceramic particles coated on the metal foam. module. 3. The method of claim 2, The reaction part includes a metal plate having a fluid inlet gap and a fluid discharge gap at both ends and an inner gap connecting the two pores, wherein the metal foam and the catalyst are provided in the inner gap of the metal plate. A thermoelectric power module using hydrogen peroxide as a heat source and a refrigerant. The method according to any one of claims 2 to 5, The metal foam is a thermoelectric power module using hydrogen peroxide as a heat source and a refrigerant, characterized in that the nickel foam. The method of claim 1, The cooling unit includes a metal plate, one end of the metal plate is provided with pores through which hydrogen peroxide is introduced, and the other end is provided with pores through which hydrogen peroxide is discharged, and a fluid movement channel connecting the two pores inside the metal plate ( A thermoelectric power module using hydrogen peroxide as a heat source and a refrigerant, characterized in that one or more channels) are provided. The method of claim 7, wherein The channel is a thermoelectric power module using hydrogen peroxide as a heat source and a coolant, characterized in that the pores of the rectangular column, cylinder or hexagonal column shape including a rectangle and a square. The method of claim 7, wherein Thermoelectric power module using hydrogen peroxide as a heat source and a coolant, characterized in that the surface is curved on the surface of the channel. The method according to any one of claims 7 to 9, The cooling unit thermoelectric power module using hydrogen peroxide as a heat source and a refrigerant, characterized in that the aluminum. The method according to any one of claims 1 to 5 or 7 to 9, Each of the cooling unit and the reaction unit is a thermoelectric power module using hydrogen peroxide as a heat source and a coolant, characterized in that each plate has a thickness: width ratio of 1: 2 to 10. The method of claim 11, The thickness of the thermoelectric power module using hydrogen peroxide as a heat source and a refrigerant, characterized in that 2mm to 10mm. The method of claim 1, The thermoelectric power module has a structure in which a thermoelectric element and a cooling unit are stacked on the upper and lower portions of the reaction unit with respect to the reaction unit as a center, and the hydrogen peroxide transferred from the cooling units provided at the upper and lower portions is the single reaction unit. Thermoelectric power module using hydrogen peroxide as a heat source and a refrigerant, characterized in that the decomposition is introduced. The method of claim 13, The thermoelectric power module is a thermoelectric power module using hydrogen peroxide as a heat source and a refrigerant, characterized in that the laminated structure as a unit, two or more of the unit is stacked.

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