JP5207620B2 - Power generation device, power generation device using the same, sensor and heating element - Google Patents

Description

The present invention relates to a power generation device that has high power generation efficiency, is not easily affected by power generation performance depending on operating temperature conditions, and has a simple manufacturing method and low cost, and a power generation device, a sensor, and a heating element using the power generation device.

  Conventionally, a thermoelectric conversion element is known as a change system that can extract thermal energy as electric energy (see, for example, Patent Document 1). Thermoelectric conversion elements are highly expected as power generation devices that convert waste heat into electrical energy or easily obtain electricity outdoors, but have low conversion efficiency, complicated manufacturing methods, and material costs. Since it is expensive, it has not been put into practical use.

  On the other hand, in recent years, a fuel cell that generates electricity by an electrochemical reaction between hydrogen and oxygen has attracted attention as a new energy supply source. This fuel cell includes a joined body in which an ion exchange resin film as a polymer electrolyte is sandwiched between an anode electrode and a cathode electrode, a fuel supply path for supplying hydrogen gas as a fuel between each electrode of the joined body, and an oxidant It is comprised from the separator which forms the gas supply path which supplies gas (for example, refer patent document 2).

However, in this fuel cell, since water is vaporized in a high temperature region exceeding 100 ° C., it becomes difficult to maintain the water retention capability of the ion exchange resin membrane which is a polymer electrolyte. It was considered difficult to use.
Japanese Patent Laid-Open No. 11-195817 JP-A-6-251780

The present invention provides a power generation device that has high power generation efficiency, is hardly affected by power generation performance depending on operating temperature conditions, and that is simple in manufacturing method and low in cost, and a power generation device, sensor, and heating element using the power generation device. It is intended.

In order to achieve the above object, the present invention provides a power generation device comprising:
The electromotive force layer,
An electrode layer provided on the surface of the electromotive force layer;
And the electromotive force layer is a fluorine-based polymer made of polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), nylon 6, nylon 11, nylon 12, nylon 66, and polyamide-based made of aramid resin polymer, acrylic acid co beauty, methacrylic acid, acrylonitrile, acrylonitrile - butadiene - and polar polymer is either one or two or more selected from among acrylic polymers of styrene copolymer (ABS) ,
p - (p-toluenesulfonyl amido) nitrogen-containing compounds consisting of diphenylamine, 2,2'-methylenebis (4-ethyl-6-tertiary - butylphenol), 2,2'-methylenebis (4-methyl-6-tert - butylphenol ), 4,4'-thiobis (2-methyl-6-tertiary-butylphenol), 4,4'-methylenebis (2,6-ditertiary-butylphenol), 4,4'-ethylenebis (2,6-ditertiary- Butylphenol), 4,4'-propylidenebis (2-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol) and 4,4'-isopropylidenebis (2, 6-ditertiary-butylphenol) Or at least one selected from acrylic compounds consisting of benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, trimethylolpropane tri (meth) acrylate and trimethylolpropane trioxyethyl (meth) acrylate A polar small molecule contained in the matrix of the polar polymer,
Consists of
The gist of the present invention is a power generation device that generates a charge due to a temperature difference between one surface and the other surface of the electromotive force layer, and a power generation apparatus or sensor using the power generation device.

Since the power generation device of the present invention, the power generation device or sensor using the power generation device are adapted to generate electric charges due to the temperature difference between one surface and the other surface of the electromotive force layer, the power generation efficiency is high and the operating temperature condition Therefore, the power generation performance is not adversely affected, and the manufacturing method is simple and low cost. Furthermore, the heating element of the present invention, by adding a charge to the power generation device that generates charges to generate a forced temperature difference on both sides of the power generation device, which generates heat, immediate response to the addition of the charge In addition, it is possible to secure a heat generation amount corresponding to the amount of added charge.

  The power generation device of the present invention includes an electromotive force layer and an electrode layer provided on the surface of the electromotive force layer. The electromotive force layer is composed of a polar polymer and a polar small molecule contained in a matrix of the polar polymer.

  Examples of polar polymers include fluorine polymers such as polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), polyamide polymers such as nylon 6, nylon 11, nylon 12, nylon 66, and aramid resin, polychlorinated polymers. Any one selected from chlorinated polymers such as vinyl, polyvinylidene chloride, chlorinated polyethylene, and acrylic polymers such as acrylic acid, methacrylic acid, acrylonitrile, acrylonitrile-butadiene-styrene copolymer (ABS) 1 type or 2 types or more can be mentioned.

  In selecting a polar polymer, in addition to the price of the polar polymer, handling properties, compatibility with polar low molecules, the application and use state of the power generation device (thermal conductivity, weather resistance, It may be determined appropriately in consideration of heat resistance and the like.

A polar low molecule is contained in the matrix of the polar polymer. As the polar low molecule, N-oxydiethylene-2-benzothiazole sulfenamide and sulfur-containing compound consisting of Nt-butyl-2-benzothiazole sulfenamide, p- (p-toluenesulfonylamide) diphenylamine Nitrogen-containing compounds, 2,2'-methylenebis (4-ethyl-6-tertiary-butylphenol), 2,2'-methylenebis (4-methyl-6-tertiary-butylphenol), 4,4'-thiobis (2-methyl) -6-tertiary-butylphenol), 4,4'-methylenebis (2,6-ditertiary-butylphenol), 4,4'-ethylenebis (2,6-ditertiary-butylphenol), 4,4'-propylidenebis (2- Methyl-6-tertiary-butylphenol), 4,4'-butylide Phenolic compounds consisting of bis (3-methyl-6-tert-butylphenol) and 4,4'-isopropylidenebis (2,6-ditertiary-butylphenol), benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate And at least one selected from acrylic compounds consisting of trimethylolpropane tri (meth) acrylate and trimethylolpropane trioxyethyl (meth) acrylate .

(Delete)

(Delete)

(Delete)

In the electromotive force layer in the power generation device of the present invention, a polar low molecule is contained in the matrix of the polar polymer, so that charges are generated due to a temperature difference between one surface and the other surface of the electromotive force layer. Yes. The mechanism is considered as follows. That is, as shown in FIG. 1, the polar low molecule contained in the matrix of the polar polymer 2a corresponding to the charge of the polar group (for example, fluorine or chlorine) in the polar polymer 2a constituting the electromotive force layer 2 The polar group 2b is oriented and dispersed, and is in an electrically stable state.

However, if there is a temperature difference between the one surface and the other surface of the electromotive force layer 2 in the device, the low temperature side surface has little rotation or phase shift of the polar low molecule 2b and maintains an electrically stable state. However, as shown in FIG. 2, the polar low molecule 2b on the high temperature side surface is rotated in the matrix of the polar polymer 2a or out of phase, so that it is not in contact with the polar group of the polar polymer 2a. As a result, electrical fluctuations occur, and charges are generated accordingly. The electric power generation device 1 of the present invention is configured to take out the electric charge generated with the temperature change in the electromotive force layer 2 from the electrode 3A or 3B provided on the surface of the electromotive force layer 2 shown in FIG.

Since the power generation device of the present invention has the above power generation mechanism, the larger the temperature difference between the one surface and the other surface of the electromotive force layer, the larger the generated charge. As a matter of course, the larger the area of the power generation device (electromotive force layer), the larger the electromotive force. Further, the electromotive force generated by the difference in temperature and one side and the other side of the electromotive force layer is a DC voltage, when the temperature difference was electromotive force when changed from minus to plus +, the temperature difference from the positive The electromotive force when it changes to minus is-.

  The content of the polar low molecule in the polar polymer is preferably 10 to 200 parts by weight with respect to 100 parts by weight of the polar polymer. When the content of polar low molecules is less than 10 parts by weight, the above-mentioned sufficient power generation performance cannot be obtained, and when the content of polar low molecules exceeds 200 parts by weight, only the amount increased. The effect cannot be expected, making it uneconomical.

  The electromotive force layer can be obtained by blending and kneading a polar low molecule with the above polar polymer, and as a use form, it is formed into a film form, a plate form, a rod form, a granular form, or a fiber form. In order to secure a high area and improve the performance, or to improve the handleability, it is more preferable to use a film.

  An electrode layer is provided on the surface of the electromotive force layer, and charges generated in the electromotive force layer are taken out through the electrode layer. As the electrode layer, a metal film selected from silver, aluminum, copper, platinum, and gold, or a conductive sheet selected from carbon and conductive plastic can be used. When a metal film is applied as the electrode layer, a film forming method such as vapor deposition of a metal such as silver, aluminum, copper, platinum, or gold on the surface of the electromotive force layer can be used. When a conductive sheet such as carbon or conductive plastic is used, a method of adhering to the surface of the electromotive force layer with an adhesive may be used.

  The power generation device of the present invention is formed by, for example, pasting a film-shaped device on a body of a transport device such as an automobile, a train, a ship, or an airplane (particularly, a bonnet, an engine cover, a ship bottom, a deck) and combining them. , When the body (bonnet, engine cover, ship bottom, deck) is warmed by heat transmitted from the engine room or by solar heat, or when the heat is not transmitted and cools down, the power generation system can be made. It can be replaced with a power source such as an air conditioner or stereo when the drive source is stopped.

  In addition, the power generation device of the present invention is, for example, a film-shaped one that is formed on a wall surface, glass surface, or roof surface of a building and combined to be heated, so that the wall surface, glass surface, or roof surface is heated by solar heat. It is possible to provide a power generation system that uses temperature changes when the heat is not transmitted and cools.

  Further, the power generation device of the present invention is formed by, for example, forming a film shape into a circulation system of a hot water supply system of a building and combining it, so that hot water is circulated and heated in the circulation system of the hot water supply system, or It can be set as the electric power generation system using the temperature change when those heat stops being transmitted and it cools.

  In addition, the power generation device of the present invention is formed by, for example, forming a film into a soundproof wall of a road, a sign or a guardrail, and compounding it, so that the sign or the guardrail is warmed by daytime, solar heat, or at night, It can be set as the power generation system using the temperature change when the solar heat is not transmitted and cools.

  In addition, the power generation device of the present invention is formed by, for example, forming a film into a personal computer (PC) casing or a CPU cover and combining them, thereby causing a temperature change caused by heat generated by driving the PC or CPU, Or it can be set as the electric power generation system using the temperature change which arises by stop of PC or CPU, and this can be made into the drive power supply of the cooling fan of PC inside or CPU.

  In addition, the power generation device of the present invention is, for example, a film-shaped device applied to a cell phone battery case to be compounded so that the case is warmed as the battery generates heat or the battery is cooled. It can be set as the electric power generation system using the temperature change which a case cools, and the obtained electricity can be utilized for battery charge of a battery.

  The power generation device of the present invention can also be used in combination with a building solar system. In this case, the solar system can be operated by solar heat during the daytime, and the power generation system using the power generation device of the present invention using the temperature change of the outside air can be operated at night so that power generation can be performed day and night.

  Fuel cells, nuclear power generators, and thermal power generators generate significant heat during power generation. Conventionally, this heat is cooled by a refrigerant or the like, and the heat is not used as it is. Therefore, by applying the power generation device of the present invention to these fuel cells, nuclear power generators, thermal power generator casings, partition walls, etc., the power generation devices can change temperature due to enormous heat from these power generation systems. Capturing and generating electricity, energy loss in conventional power generation systems can be greatly reduced.

  The power generation device of the present invention can also be used as a sensor. For example, it can be used as an alternative to pyroelectric sensors and infrared sensors, and as a road sensor for ITS.

The power generation device of the present invention can also be used as a heating element. For example, conventionally, a hot toilet seat of a toilet has to be energized at all times in order to keep the toilet seat warm. For this reason, energy loss is large and energy saving has been demanded. If the power generation device of the present invention is used for the toilet seat as the heating element, the power generation device, by the addition of charge, additional since the exothermic forcibly generate a temperature difference on both sides of the device, immediately by the addition of charge Since heat is generated in accordance with the amount of charge and the toilet seat is warmed, energy loss that is always energized can be eliminated.

  In addition, the power generation device of the present invention, the power generation device using the same, the sensor, and the heating element are not limited to the above-described examples. For example, a dye, an antifoaming agent, a preservative, and the like are included in the electromotive force layer. Modifications can be made freely within the scope of the claims.

Example 50 parts by weight of p- (p-toluenesulfonylamide) diphenylamine was mixed with 100 parts by weight of PVDF and kneaded, and then formed into a 1 mm thick sheet by a calender roll to obtain an electromotive force layer. Next, as shown in FIG. 3, silver plating was applied to both surfaces of the obtained electromotive force layer to provide an electrode layer to obtain a power generation device.

(Delete)

Comparative example
A power generation device was produced in the same manner as in Example except that 50 parts by weight of p- (p-toluenesulfonylamide) diphenylamine was not blended.

Next, as shown in FIG. 4, each sample of the obtained example and comparative example was placed on a desk, lead wires connected to a tester were connected to the electrodes on the front and back of each sample, and the voltage from each sample was measured. The ambient temperature on the surface of each sample was 25 ° C.

As a result of the measurement, the voltage of the sample according to the comparative example was 19.0 mV, whereas the voltage of the sample according to the example was 302.6 mV, and it was confirmed that the sample had excellent power generation performance.

The schematic diagram which showed the state in which the polar low molecule has arranged in the matrix of the polar polymer which comprises the electromotive force layer of the electric power generation device of this invention. The schematic diagram which shows the state of a polar low molecule in the matrix of a polar polymer when a temperature change is added to the electric power generation device of this invention. The disassembled perspective view which shows the electric power generation device of this invention. The perspective view which shows the experimental apparatus which evaluates the electric power generation performance accompanying a temperature change about the sample which concerns on an Example or a comparative example.

DESCRIPTION OF SYMBOLS 1 ... Electric power generation device 2 ... Electromotive force layer 2a ... Polar polymer 2b ... Polar low molecule 3A, 3B ... Electrode 4A, 4B ... Lead wire 5 ... Tester

Claims (9)

A power generation device,
The electromotive force layer,
An electrode layer provided on the surface of the electromotive force layer;
And the electromotive force layer is a fluorine-based polymer made of polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), nylon 6, nylon 11, nylon 12, nylon 66, and polyamide-based made of aramid resin polymer, acrylic acid co beauty, methacrylic acid, acrylonitrile, acrylonitrile - butadiene - and polar polymer is either one or two or more selected from among acrylic polymers of styrene copolymer (ABS) ,
p - (p-toluenesulfonyl amido) nitrogen-containing compounds consisting of diphenylamine, 2,2'-methylenebis (4-ethyl-6-tertiary - butylphenol), 2,2'-methylenebis (4-methyl-6-tert - butylphenol ), 4,4'-thiobis (2-methyl-6-tertiary-butylphenol), 4,4'-methylenebis (2,6-ditertiary-butylphenol), 4,4'-ethylenebis (2,6-ditertiary- Butylphenol), 4,4'-propylidenebis (2-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol) and 4,4'-isopropylidenebis (2, 6-ditertiary-butylphenol) Or at least one selected from acrylic compounds consisting of benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, trimethylolpropane tri (meth) acrylate and trimethylolpropane trioxyethyl (meth) acrylate A polar small molecule contained in the matrix of the polar polymer,
Consists of
A power generation device that generates electric charges by a temperature difference between one surface and the other surface of the electromotive force layer.   The power generation device according to claim 1, wherein the polar low molecule is contained in a proportion of 10 to 200 parts by weight with respect to 100 parts by weight of the polar polymer.   The power generation device according to claim 1, wherein the electromotive force layer has a film shape.   The power generation according to any one of claims 1 to 3, wherein the electrode layer is made of a metal film selected from silver, aluminum, copper, platinum and gold, or a conductive sheet selected from carbon and conductive plastics. device.   A power generation apparatus using the power generation device according to any one of claims 1 to 4.   6. The power generator according to claim 5, which is used in combination with a solar system.   6. The power generation apparatus according to claim 5, wherein the power generation apparatus is used in combination with a fuel cell and a power generation mechanism.   A sensor using the power generation device according to claim 1.   A heating element using the power generation device according to any one of claims 1 to 4.

Images