JP2017175690A - Charger, and case for electronic apparatus having the same and electronic apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a charger capable of generating sufficient electric power, for example, even at an ambient temperature or a body temperature, without using a temperature gradient or sunlight and capable of charging a secondary cell mounted on an electronic apparatus by generated electric power.SOLUTION: The charger, used for charging a secondary cell mounted on an electronic apparatus, includes: a power generation part for converting molecular oscillatory energy into electrical energy; a power supply part for supplying electric power generated by the power generation part to an electronic apparatus.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a charging device including a power generation element that converts vibration energy of molecules into electric energy, and an electronic device case and electronic device including the charging device.

  In recent years, multifunctional mobile phones (for example, smart phones), portable electronic devices such as tablet terminals, notebook computers, portable music players, and portable game machines have become more multifunctional and have higher performance.

  However, such multi-functionality and high performance improve the performance of a portable electronic device, while increasing the amount of power used, and a secondary battery (hereinafter also referred to as a battery) built in the portable electronic device. ) Was caused to shorten the driving time. In particular, portable terminals such as multi-function mobile phones and tablet terminals are frequently used in daily life, so a short battery driving time is a major problem.

  In order to solve the above problems, for example, a technique for securing a battery driving time by applying a program that reduces the amount of power used to a portable electronic device or attaching a portable charging device is examined. Has been. In particular, the portable charging device is highly useful because it recovers the electromotive force of a battery provided in the portable electronic device.

  As such a portable charging device, for example, a device (for example, Patent Document 1) in which a spare battery is built in a protective case of a portable terminal device and charging is performed using the spare battery has been proposed.

  In addition, a thermoelectric power generation element that generates electric power due to a temperature difference is disposed close to the inner surface of the casing of the mobile phone, and the electric power generated by the thermoelectric power generation element is supplied to the built-in battery of the mobile phone for charging (for example, Patent Document 2) and an apparatus (for example, Patent Document 3) that charges by supplying electric power generated by a solar cell to a built-in battery of a portable device have been proposed.

Utility model registration No. 3135487 JP 2011-66965 A JP 2011-19316 A

  However, since the charging device described in Patent Document 1 does not have a power generation capability, there is a problem that if the power stored in the spare battery is exhausted, further charging cannot be performed.

  Since the charging devices described in Patent Literature 2 and Patent Literature 3 have a power generation capability, the above problems do not occur. However, the thermoelectric power generation element used in Patent Document 2 utilizes a so-called Seebeck effect in which two types of different metals or semiconductors are joined and power is generated by a temperature gradient generated at both ends thereof. If the temperature difference between the inside and the surface of the telephone is about, it was difficult to generate enough power. Moreover, since the solar cell used in Patent Document 3 uses the photovoltaic effect to convert light energy such as sunlight into electric power, the amount of solar radiation such as a cloudy day is reduced. There is a problem that the power generation efficiency is lowered below and power generation cannot be performed at night, in a building, in a subway, or in a bag.

  The present invention has been made in view of the above problems. That is, an object of the present invention is to generate sufficient electric power, for example, even at a temperature of about room temperature or body temperature without using a temperature gradient or sunlight. It is an object of the present invention to provide a charging device capable of charging a secondary battery provided.

  The gist of the present invention is as follows.

  [1] A charging device used for charging a secondary battery provided in an electronic device, a power generation unit that converts vibration energy of molecules into electric energy, and a power supply that supplies power generated by the power generation unit to the electronic device And a charging device.

  [2] The charging device according to [1], further including a secondary battery that stores electric power generated in the power generation unit.

  [3] Furthermore, the detection means for detecting the charge state of the secondary battery provided in the electronic device, and the power supply from the power supply unit to the electronic device according to the charge state of the secondary battery provided in the electronic device. The charging device according to [1] or [2], further including a control unit that controls a supply amount.

  [4] The power generation unit includes a power generation element having a power generation layer. The power generation layer includes a power generation auxiliary material, a semiconductor material (α), and an energy level at the upper end of the valence band between the positive electrode and the negative electrode. A semiconductor material (β which is higher than the energy level at the upper end of the valence band of the semiconductor material (α) and whose energy level at the lower end of the conduction band is higher than the energy level at the lower end of the conduction band of the semiconductor material (α). The charging device according to any one of the above [1] to [3].

  [5] A case for electronic equipment, comprising the charging device according to any one of [1] to [4].

  [6] An electronic device comprising the charging device according to any one of [1] to [4].

  The charging device of the present invention includes a power generation unit that converts molecular vibrational energy (hereinafter, also referred to as thermal energy) into electrical energy, so that, for example, a temperature of about room temperature or body temperature can be used without using a temperature gradient or sunlight. Since sufficient electric power can be generated even at a temperature, it is possible to stably supply electric power to the secondary battery provided in the electronic device. In particular, since a portable terminal such as a smartphone is often worn in a chest pocket of a jacket or a pocket of a trouser, the charging device of the present invention capable of generating sufficient power depending on the body temperature of the user Can be suitably used as a charging device for a portable terminal such as a smartphone.

It is a typical block diagram which shows an example of the charging device of this invention. It is a typical block diagram which shows an example of the case for electronic devices of this invention. It is a typical block diagram which shows an example of the electric power generating element in the charging device of this invention. It is a schematic block diagram of the testing apparatus which measures the output voltage and output current of the electric power generating element in a charging device based on embodiment of this invention.

  A charging device according to the present invention will be described with reference to the drawings. A charging device described below, and an electronic device case and electronic device equipped with the device are one of the embodiments for carrying out the present invention, and the following embodiments are provided unless they are contrary to the gist of the present invention. It is not limited to.

[Charging device]
FIG. 1 is a schematic configuration diagram of a charging device according to the present embodiment. As shown in FIG. 1, the charging device 20 according to the present embodiment includes a power generation unit 21 including a plurality of power generation elements 1, a power supply unit 22, a substrate 23, and a wiring 24.

  The power generation unit 21 has a function of generating electrical energy by including the power generation element 1 that converts thermal energy into electrical energy. FIG. 1 shows a state in which five power generation elements 1 are connected in series through the wiring 24, but the number of power generation elements 1 constituting the power generation unit 21 and the connection form thereof are not limited to this, and the power generation elements 1 It can be determined as appropriate according to the power generation capacity and the application of the charging device. The power generation unit 21 only needs to include at least one power generation element 1, and the connection form in the case of including a plurality of power generation elements 1 may be a series connection or a parallel connection. The power generating element 1 will be described in detail in a later paragraph.

  The power supply unit 22 is electrically connected to the power generation unit 21 through a wiring 24 and is connected to be electrically connected to an external electronic device (for example, a portable terminal such as a multi-function mobile phone or a tablet terminal). A terminal (not shown) is provided.

  The power supply unit 22 is electrically connected to a charging terminal of an external electronic device, thereby supplying power generated by the power generation unit 21 to the electronic device and charging a battery provided in the electronic device. The power supply unit 22 and the charging terminal of the external electronic device may be directly connected or indirectly connected via a conductive cable or the like, but the loss of power generated by the power generation unit 21 It is preferable to connect directly from the viewpoint of reducing the amount of power. Therefore, the shape of the connection terminal of the power supply unit 22 is preferably a shape that matches the shape of the charging terminal of the external electronic device.

  In addition to a connection terminal connected to a charging terminal of an external electronic device, the power supply unit 22 outputs audio information and video information output from the electronic device to another electronic device (not shown). May be provided. Generally, in a multi-function mobile phone such as a smartphone, the charging terminal and the output terminal to the external device are often the same, and in many cases external output to other electronic devices cannot be performed during charging. By adopting such a configuration, while the connection terminal of the charging device 20 and the charging terminal of the external electronic device are connected, that is, while the electronic device is being charged, the electronic device can be replaced with another electronic device. External output to is possible.

  The wiring 24 electrically connects the power generation elements 1 and the power generation unit 21 and the power supply unit 22. The material of the wiring 24 is not particularly limited, and a known material can be used. For example, Ag, Ni, Cu, or the like used for a conductive paste containing silver or a current collector of a solar cell module. It is preferable to use at least one metal selected from the group consisting of Sn, Au, V, Al, and Pt, and an alloy, a carbon material, or a transparent conductive material (such as ITO) using these metals. Since the preferable material has a low resistance value, power loss in the wiring 24 can be suppressed. In addition, you may use said preferable material individually by 1 type or in combination of 2 or more types.

  The substrate 23 supports the power generation unit 21, the power supply unit 22, and the wiring 24. In FIG. 1, the power generation unit 21, the power supply unit 22, and the wiring 24 are formed on a substrate 23 and are fixed on the substrate 23. With such a configuration, the electrical connection between the components can be made reliable and strong, and the physical strength of the charging device 20 can be improved. Further, application to an electronic device case described later is also facilitated.

  Note that, from the viewpoint of further improving the physical strength, it is preferable that the circuit configured by the power generation unit 21, the power supply unit 22, and the wiring 24 is formed so as not to be exposed to the outside. It is preferable to use a structure in which it is formed in such a manner as to be covered with an insulating protective member.

  The material of the substrate 23 is not particularly limited as long as it has insulating properties, and a known material such as a glass substrate can be used. For example, from the viewpoint of excellent lightness and flexibility, polyimide, It is preferable to use a synthetic resin such as polyamide, polyimide amide, polyethylene terephthalate (PET), or polyethylene naphthalate (PEN).

  Moreover, it is preferable that these synthetic resins further contain a filler having insulating properties and high thermal conductivity such as alumina, silicon carbide, silica, and magnesium oxide. By including these fillers, the thermal conductivity of the substrate 23 is increased, so that heat generated by an external electronic device can be efficiently transmitted to the power generation element 1, and the power generation efficiency of the power generation element 1 can be improved. it can.

  The charging device 20 of the present invention converts heat energy into electrical energy by the power generation element 1. When this is seen from another aspect, it can be said that the charging device 20 of the present invention has a power generation capability and at the same time exhibits an endothermic effect. Therefore, when the charging device 20 of the present invention is used while being in contact with an external electronic device, heat dissipation of the electronic device main body during use of the electronic device can be assisted.

  The charging device 20 preferably includes a secondary battery (not shown) that stores the power generated in the power generation unit 21 and supplies the stored power to the power supply unit 22. When the charging device 20 includes the secondary battery, the surplus power generated in the power generation unit 21 can be stored, and the surplus power can be supplied to an external electronic device as necessary. For example, when the remaining battery capacity of the external electronic device is sufficient, the power supply unit 22 and the charging terminal of the electronic device are not connected, and the power generated in the power generation unit 21 during that time is used as the secondary battery of the charging device 20. Can be stored in

  Moreover, it is preferable that the charging apparatus 20 is provided with the switch etc. which start and stop the electric power supply to an external electronic device. By adopting such a configuration, for example, even when the power supply unit 22 and the charging terminal of the external electronic device are connected, if the remaining battery level of the electronic device is sufficient, the power generation unit 21 generates the battery. The stored power can be stored in the secondary battery of the charging device 20.

  It is preferable that the charging device 20 includes a detection unit (not shown) that detects a charged state of a secondary battery provided in an external electronic device. In addition, the charging device 20 includes a control unit (not shown) that controls the amount of power supplied from the power supply unit 22 to the electronic device in accordance with the state of charge of the secondary battery provided in the external electronic device. It is preferable to provide. By including the detection unit and the control unit, the charging device 20 can automatically supply appropriate power according to the state of charge of the secondary battery provided in the external electronic device.

  Although it does not specifically limit as thickness of the charging device 20, For example, it is preferable that it is 0.5 mm or more, and it is more preferable that it is 1 mm or more. Further, the thickness of the charging device 20 is preferably 10 mm or less, and more preferably 5 mm or less. When the thickness of the charging device 20 is less than 0.5 mm, it tends to be difficult to obtain a sufficient power generation capability. When the thickness of the charging device 20 exceeds 10 mm, the function as a charging device. However, for example, the charging device 20 tends to be difficult to use between an existing multifunction telephone and an existing multifunction telephone protective case.

[Power generation element]
FIG. 3 is a schematic configuration diagram of the power generation element 1 constituting the power generation unit 21 of the charging device 20 according to the present embodiment. As shown in FIG. 3, the power generating element 1 according to the present embodiment has a structure in which a positive electrode 2, a hole transport layer 3, a power generating layer 4, and a negative electrode 5 are arranged in that order. . Hereinafter, the configuration of the power generation element 1 will be described.

(Positive electrode, negative electrode)
The positive electrode 2 and the negative electrode 5 are conductive materials, and a material whose work function of the positive electrode 2 is the same as or higher than that of the negative electrode 5 is used. The work function of the positive electrode 2 is preferably higher than that of the negative electrode 5.

  The positive electrode 2 is not particularly limited. For example, a conductive oxide material such as indium tin oxide (ITO), a carbon material, copper, a copper alloy, stainless steel such as SUS430, tin-plated copper, platinum, gold, or Tungsten or an oxide thereof can be used. The material of the positive electrode 2 can be determined in consideration of the work function, and is preferably higher than the work function of the material of the negative electrode 5. For example, when aluminum is used for the negative electrode 5, the material of the positive electrode 2 is preferably indium tin oxide, copper, or a carbon material from the viewpoint that it has a higher work function than the material of the negative electrode 5 and can be obtained at a low cost. When indium tin oxide is used for the negative electrode 5, the material of the positive electrode 2 is preferably platinum, gold, tungsten, or an oxide thereof from the viewpoint that the work function is higher than that of the material of the negative electrode 5. Moreover, you may use the material of the positive electrode 2 in the form which coated other metals.

  Although it does not specifically limit as the negative electrode 5, For example, magnesium alloys, such as aluminum, an aluminum alloy, Mg-Al, silver, or zinc can be used. The material of the negative electrode 5 can be determined in consideration of the work function, and is preferably lower than the work function of the material of the positive electrode 2. For example, when copper or a carbon material is used for the positive electrode 2, the material of the negative electrode 5 is preferably aluminum or zinc from the viewpoint that the work function is lower than that of the material of the positive electrode 2 and can be obtained at low cost. When platinum or gold is used for the positive electrode 2, the material of the negative electrode 5 is preferably indium tin oxide. Moreover, you may use the material of the negative electrode 5 in the form which coated other metals.

  The shapes of the positive electrode 2 and the negative electrode 5 are not particularly limited, and can be processed into a shape corresponding to the shape of the power generation element 1. For example, when the power generation element 1 is a planar arrangement type power generation element 1, the positive electrode 2 and the negative electrode 5 are disposed to face each other, and the hole transport layer 3 and the power generation layer 4 are disposed between the positive electrode 2 and the negative electrode 5. Provided.

  The planar arrangement type power generation element 1 is configured as a series arrangement type power generation element composite by sequentially connecting the positive electrodes 2 and the negative electrodes 5 of the plurality of power generation elements 1 in series, or a plurality of power generation elements. By sequentially connecting the positive electrode 2 and the negative electrode 5 of 1 in parallel, a parallel-arranged power generation element composite can be obtained. The number and connection method of the power generation elements 1 constituting the power generation element complex can be appropriately designed according to the power generation capacity required for the charging device.

(Hall transport layer)
The power generation element 1 preferably has a hole transport layer 3 between the positive electrode 2 and the power generation layer 4. By having the hole transport layer 3 between the positive electrode 2 and the power generation layer 4, the extraction of holes from the power generation layer 4 to the positive electrode 2 can be stabilized, the power generation efficiency can be improved, and the reverse current can be reduced. It can be prevented from occurring. The hole transport layer 3 is not particularly limited as long as hole conduction is observed. For example, poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT-PSS), poly (3,4-ethylenedioxythiophene) -poly (vinyl sulfonic acid), polyaniline, polypyrrole, polythiophene, poly (p-phenylene), polyfluorene, poly (p-phenylene vinylene), polythienylene vinylene, graphene, etc. It is preferable to use a p-type metal oxide such as MoO ₃ , CuAlO ₂ , CuGaO ₂ , or LiNiO ₂ . Among these, poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) or MoO ₃ is preferable from the viewpoint of high hole mobility and availability at low cost.

(Electron transport layer)
Although not shown in FIG. 2, the power generation element 1 preferably further includes an electron transport layer between the negative electrode 5 and the power generation layer 4. By providing a thin film of an electron transport layer between the negative electrode 5 and the power generation layer 4, the efficiency of extracting electrons from the power generation layer 4 to the negative electrode 5 can be stabilized, and the power generation efficiency can be improved. Tends to be prevented from flowing to the negative electrode 5 side. Although there is no restriction | limiting in particular as a material used for an electron carrying layer, For example, an n-type semiconductor material etc. can be used. Specific examples of the material used for the electron transport layer include, for example, lithium fluoride, sodium fluoride, cesium fluoride, aluminum oxide, tin oxide, lithium oxide, magnesium oxide, or calcium oxide. Among these, from the viewpoint of being chemically stable, it is preferable to use lithium fluoride, aluminum oxide, or tin oxide.

(Power generation layer)
The power generation layer 4 is a layer including a power generation auxiliary material, a semiconductor material (α), and a semiconductor material (β). In the power generation layer 4, for example, the power generation auxiliary material emits infrared rays by absorbing vibration energy (thermal energy) of molecules, and the emitted infrared rays are used as energy levels of the semiconductor material (α) and the semiconductor material (β). It can be converted into electrical energy using the difference in position.

  The power generation auxiliary material is preferably an infrared radiation material capable of converting vibration energy into infrared rays and emitting the same. Although it does not specifically limit as an infrared radiation material, It is preferable to use a substance with large infrared absorption intensity, for example, silicon dioxide, silicone, carbon, or a ferrite. A substance having a large infrared absorption intensity has a high infrared radiation intensity, and therefore can emit a strong infrared radiation, resulting in an increase in power generation efficiency. Among the above substances, silicon dioxide is more preferably used because it has a high infrared absorption intensity and is inexpensive. In addition, you may use said infrared radiation material individually by 1 type or in combination of 2 or more types.

The infrared absorption intensity can be measured by a known method such as infrared spectroscopy, near infrared spectroscopy, or Raman spectroscopy. As a power generation auxiliary material, for example, when measured using near infrared spectroscopy, it is preferable to have a peak with an absorbance of 1 or more in the infrared region (for example, wave number 12500 to 4000 cm ⁻¹ ). When the power generation auxiliary material has a peak in which the absorbance is 1 or more in the infrared region, the infrared absorption intensity and the radiation intensity increase, so that the power generation efficiency can be improved.

  The average particle size of the power generation auxiliary material can be selected in various sizes within the range where there is no problem in availability and composition preparation, but the average particle size of the power generation auxiliary material is 4 to 100 nm. It is preferable that the thickness is 4 to 40 nm. When the average particle size of the power generation auxiliary material is less than 4 nm, the characteristics as the infrared radiation material tend not to be exhibited. When the average particle size exceeds 100 nm, the volume of the power generation auxiliary material becomes large. As a result, the absorption intensity (radiation intensity) decreases and the power generation efficiency tends to decrease. In this specification, the average particle diameter means the average particle diameter of primary particles, which can be measured by a scanning electron microscope (SEM) at the raw material stage, and after the composition is formed, the scanning electron microscope (SEM).

  The power generation layer 4 includes a semiconductor material (α) and a semiconductor material (β) in order to convert infrared rays emitted from the power generation auxiliary material into electrical energy. In the semiconductor material (β), the energy level at the upper end of the valence band is higher than the energy level at the upper end of the valence band of the semiconductor material (α), and the energy level at the lower end of the conduction band is the semiconductor material (α A semiconductor material higher than the energy level at the lower end of the conduction band is used. The energy difference between the upper end of the valence band of the semiconductor material (α) and the upper end of the valence band of the semiconductor material (β) is preferably 2.0 eV or less, and more preferably 0.9 eV or more. More preferably, it is 1.7 eV or less. The energy difference between the lower end of the conduction band of the semiconductor material (α) and the lower end of the conduction band of the semiconductor material (β) is preferably 2.0 eV or less, and more preferably 0.9 eV or more. More preferably, it is 1.7 eV or less.

  The mechanism of power generation in the power generation element 1 is not clear, but the semiconductor material (α) plays a role like an electron acceptor and the semiconductor material (β) plays a role like an electron donor. Thus, it is considered that infrared light energy is converted into electric energy. Specifically, the following phenomenon is presumed.

  When the energy difference between the conduction band and the valence band of the semiconductor material (α) and the semiconductor material (β) is, for example, 2.0 eV or less, the semiconductor material (α) or the semiconductor material (β) is irradiated with infrared rays. In this case, electrons existing in the conduction band of the semiconductor material (β) move to the conduction band of the semiconductor material (α) at the junction surface between the semiconductor material (α) and the semiconductor material (β), and the semiconductor Holes that existed in the valence band of the material (α) move to the valence band of the semiconductor material (β) to form a charge separation state. The electrons move through the conduction band of the semiconductor material (α) having a lower energy level than the semiconductor material (β) and flow to the positive electrode 2, and the holes move through the valence band of the semiconductor material (β) and move into the negative electrode 5. It seems that current flows through the external circuit.

  When the power generation auxiliary material absorbs thermal energy, the thermal energy is finally converted into electrical energy by the semiconductor material (α) and the semiconductor material (β). If this is seen from another side, it can also be considered that the element which has power generation auxiliary material, a semiconductor material ((alpha)), and a semiconductor material ((beta)) is performing endothermic reaction. Therefore, the element having the power generation auxiliary material, the semiconductor material (α), and the semiconductor material (β) can be used as a cooling means for electronic devices, for example.

  The semiconductor material (α) is preferably tin dioxide because of its high chemical stability and high electron mobility. The semiconductor material (β) preferably contains at least one material selected from the group consisting of titanium oxide, zirconium oxide, niobium oxide, tantalum oxide, tungsten oxide, and zinc oxide. When tin dioxide is used as the semiconductor material (α), the semiconductor material (β) has a higher energy level than the semiconductor material (α) and a work function lower than that of the material of the positive electrode 2. Titanium oxide, niobium oxide, tantalum oxide, zinc oxide, or the like is preferable. The combination of the preferred semiconductor material (α) and the preferred semiconductor material (β) described above is a condition that the energy difference between the upper ends of the valence band and the lower ends of the conduction bands is 2.0 eV or less. It satisfies the condition that it is 0.9 eV or more and 1.7 eV or less. In addition, you may use a semiconductor material ((alpha)) and a semiconductor material ((beta)) individually by 1 type or in combination of 2 or more types.

  The average particle diameters of the semiconductor material (α) and the semiconductor material (β) can be selected in various sizes within the range where there is no problem in availability and composition preparation, but the semiconductor material (α) The average particle size of is preferably 4 to 100 nm, and more preferably 4 to 10 nm. When the average particle diameter of the semiconductor material (α) is less than 4 nm, there is a tendency that the characteristics as a semiconductor do not appear. When the average particle diameter exceeds 100 nm, the volume of the semiconductor material (α) increases, The power generation efficiency tends to decrease.

  The structure of the power generation layer 4 is not particularly limited, and may be, for example, a laminated structure or a bulk heterojunction structure. From the viewpoint of improving power generation efficiency, a bulk heterojunction structure is preferable.

  The infrared irradiation intensity is inversely proportional to the square of the distance from the light source. From the viewpoint of preventing the attenuation of infrared irradiation intensity and improving the power generation efficiency, the power generation auxiliary material, the semiconductor material (α), and the semiconductor material (β) are each in the form of particles in the power generation layer 4. The power generation layer 4 is preferably arranged so as to have a close-packed structure or a structure close to the close-packed structure.

  In order to uniformly disperse the power generation auxiliary material, the semiconductor material (α), and the semiconductor material (β) in the power generation layer 4, each of the particles is dispersed in a solvent, and the dispersion liquid is a known method such as centrifugation. It is preferable to form the power generation layer 4 using a powder obtained by separating the solid content and the liquid content by using and thoroughly washing the solid content. The solvent to be dispersed is not particularly limited as long as it does not dissolve the power generation auxiliary material, the semiconductor material (α), and the semiconductor material (β), but it can be used safely and is inexpensive. It is preferable to use it.

  Further, when forming the power generation layer 4, the semiconductor material (β) is not directly added to the dispersion medium with the metal oxide particles as described above, but instead of the metal oxide by hydrolysis or the like. A metal oxide precursor that can be generated may be added. The precursor of the metal oxide is not particularly limited, and examples thereof include metal chlorides such as titanium chloride, niobium chloride, tantalum chloride, and zinc chloride, and metal alkoxides such as titanium alkoxide, niobium alkoxide, tantalum alkoxide, and zinc alkoxide. It is preferable to use it.

  The total mass of the power generation layer 4 is a sum of a power generation auxiliary material, a semiconductor material (α), and a semiconductor material (β). The content of the semiconductor material (α) is preferably 1 to 30% by mass and more preferably 10 to 25% by mass with respect to the total mass of the power generation layer 4. When the content of the semiconductor material (α) is less than 1% by mass with respect to the total mass of the power generation layer 4, infrared rays cannot be sufficiently converted to electric power, and power generation efficiency tends to decrease, and 30 masses. Even if the percentage exceeds 50%, no further improvement in power generation efficiency tends to be seen. Similarly, the content of the semiconductor material (β) is preferably 1 to 30% by mass and more preferably 5 to 30% by mass with respect to the total mass of the power generation layer 4. When the content of the semiconductor material (β) is less than 1% by mass with respect to the total mass of the power generation layer 4, infrared rays cannot be sufficiently converted to electric power, and power generation efficiency tends to be reduced, and 30 masses. Even if the percentage exceeds 50%, no further improvement in power generation efficiency tends to be seen.

  Further, the mixing ratio of the semiconductor material (α) and the semiconductor material (β) (semiconductor material (α) / semiconductor material (β)) is not particularly limited, but is in the range of 1/5 to 2/1 by mass ratio. Preferably there is. When the mixing ratio of the semiconductor material (α) and the semiconductor material (β) is in the above range, the efficiency of converting infrared rays into electric energy is improved, and power generation efficiency tends to be improved.

  The thickness of the power generation layer 4 varies depending on the method for producing the power generation element 1 and is not particularly limited, but is preferably in the range of 0.05 μm to 1000 μm, for example. If the thickness of the power generation layer 4 is less than 0.05 μm, it tends to cause a short circuit, and if the thickness of the power generation layer 4 exceeds 1000 μm, the internal resistance of the power generation layer 4 tends to increase, Conversion efficiency tends to decrease due to the ease of recombination of charge-separated electrons and holes.

  The power generation layer 4 is a layer formed by a mixture of a power generation auxiliary material, a semiconductor material (α), and a semiconductor material (β), but contains other inorganic substances and organic substances as long as the effects of the present invention are not impaired. Also good.

(Method for producing power generation element)
The production method of the power generating element 1 is not particularly limited, and can be produced by various known methods. For example, the hole transport layer 3 can be formed by dropping or applying a p-type conductive polymer on the positive electrode 2. Next, the power generation layer 4 is formed on the hole transport layer 3 by dropping or applying a dispersion in which the power generation auxiliary material, the semiconductor material (α), and the semiconductor material (β) are uniformly dispersed in a solvent. Can do. Finally, the negative electrode 5 can be formed on the power generation layer 4 by using a method such as vacuum deposition or sputtering.

  The power generating elements 1 thus manufactured can be connected so as to have a planar series structure or a parallel structure. When a power generation element complex is configured by connecting a plurality of power generation elements 1 in series, the positive electrode 2 and the negative electrode 5 of adjacent power generation elements may be connected by caulking, pressure welding, brazing, or the like to form a series structure. it can. When the power generating element 1 is configured by connecting the power generating elements 1 in parallel, the positive electrode 2 and the negative electrode 5 of the power generating element 1 are connected to the elongated electrode by caulking, pressure welding, brazing, or the like, respectively. Can be.

  Such a power generation element complex can be produced in a one-dimensional (series arrangement) or two-dimensional (parallel arrangement) by connecting a plurality of power generation elements 1, but is laminated in the thickness direction and is three-dimensional. A three-dimensional structure can also be obtained.

  In the power generation element 1 or the power generation element complex, it is preferable to prevent moisture from entering the power generation element 1. As a means for preventing moisture from entering, it is preferable to fill the periphery with a sealing material or cover the whole with a sealing material. By such moisture intrusion prevention means, it is possible to suppress a decrease in the generated current value of the power generating element 1.

[Electronic case]
FIG. 2 is a schematic configuration diagram of an electronic device case 25 including the charging device 20 according to the present embodiment. In FIG. 2, since each structure of the charging device 20 is the same as that of FIG. 1, the code number and description are abbreviate | omitted.

  As shown in FIG. 2, the charging device 20 is disposed on the side of the electronic device case 25 that contacts the back surface of the electronic device (inside the electronic device case), that is, the electronic device case 25 is attached to the electronic device. It is preferable that the charging device 20 and the electronic device are provided in contact with each other. With such a configuration, heat generated by the electronic device can be efficiently absorbed, and the power generation efficiency of the power generation element 1 can be improved.

  Moreover, it is preferable that the charging device 20 is arrange | positioned so that the electric power supply part 22 of the charging device 20 can be connected with the charging terminal of an electronic device, when the case 25 for electronic devices is mounted | worn with an electronic device.

  A method for fixing the charging device 20 to the electronic device case 25 is not particularly limited, and a fixing portion for fixing the charging device 20 to the electronic device case 25 or an electronic device case 25 is provided. A known method can be used, such as providing.

  In addition, since the electronic device and the charging device 20 can be combined in the charging terminal and the power supply unit 22, the charging device 20 is simply disposed in the electronic device case 25. It may be.

  As described above, the charging device 20 uses the power generation element 1 that converts thermal energy into electrical energy, and has a heat absorption effect. Therefore, the material of the electronic device case 25 is a heat dissipation problem of the electronic device. There are no particular considerations, and any known one can be employed.

  The structure and shape of the electronic device case 25 are not particularly limited, and can be appropriately determined according to the structure and shape of the electronic device to which the electronic device case 25 is attached. For example, when the electronic device case 25 is to be attached to a multi-function mobile phone, the electronic device case 25 is attached to a button, an earphone jack, a camera, or the like provided on the side or back of the multi-function mobile phone. In order to be usable as it is, an open portion (hole) or the like may be provided as appropriate.

[Electronics]
The electronic device of the present invention is such that the above-described charging device including a power generation unit that converts thermal energy into electrical energy is provided inside the electronic device.

  In the electronic device of the present invention, the power supply unit of the charging device may be designed to supply power directly to a battery built in the electronic device. As described above, the charging device generates electric power and has an endothermic effect, so that it can not only extend the battery driving time of an electronic device but also absorb heat generated from a CPU or the like. It is. Therefore, the electronic device of the present invention has a long battery driving time and a small amount of heat generated from the electronic device.

[Usage]
The charging device 20 of the present invention can be applied to various electronic devices, for example, a multi-function mobile phone (for example, a smartphone), a tablet terminal, a notebook computer, a portable music player, a portable game machine, a digital camera. It can be suitably used as a charging device for portable electronic devices such as video cameras. In particular, since portable terminals such as multi-function mobile phones and tablet terminals are often housed and used in a protective case, the charging device of the present invention that can be housed inside the protective case is very useful. In addition, since the charging device of the present invention can generate sufficient electric power at a temperature of about body temperature, it can be worn in a portable terminal such as a chest pocket or a pants pocket. It is particularly useful as a charging device for smartphones with a large amount.

  The power generation elements constituting the power generation unit of the remote control device according to the present embodiment will be described below in more detail with reference examples, but the present invention is not limited to these.

[Reference Example 1]
[Preparation of mixed powder of silicon dioxide, niobium oxide and tin dioxide]
25 parts by mass of niobium pentachloride (manufactured by Junsei Chemical Co., Ltd.) was dissolved in 200 parts by mass of ethanol. Next, 2.5 parts by mass of the niobium pentachloride / ethanol solution and 10 parts by mass of a 20% aqueous dispersion of silicon dioxide (manufactured by Nissan Chemical Industries, Ltd., “ST-O-40”, average particle size 40 nm) Then, 1.5 parts by mass of a 20% aqueous dispersion of tin dioxide (manufactured by Unitika Ltd., tin oxide sol “AS20I”, average particle size 7 nm) was mixed and stirred. In the mixed water dispersion, niobium pentachloride was hydrolyzed to niobium oxide. Next, solid content was isolate | separated from the mixed water dispersion containing the obtained silicon dioxide particle, niobium oxide particle, and tin dioxide particle. The obtained solid content was sufficiently washed and then dried at 100 ° C. to obtain a mixed powder of Reference Example 1 composed of silicon dioxide particles, niobium oxide particles, and tin dioxide particles. Table 1 shows the mixing ratio of the 20% aqueous dispersion of silicon dioxide in the mixed aqueous dispersion, the niobium pentachloride / ethanol solution, and the 20% aqueous dispersion of tin dioxide, and the content of each component in the mixed powder.

[Reference Examples 2 to 5]
A mixed powder of Reference Examples 2 to 5 was obtained using the same method as in Reference Example 1 except that the mixing ratio in the mixed water dispersion was changed as shown in Table 1. Table 1 shows the content of each component in the mixed powder.

  The power generation element was produced as follows. First, a flat copper member was prepared as the positive electrode 2. Next, a flat aluminum member was prepared as the negative electrode 5, and a double-sided tape having a thickness of 0.8 mm with a 1.8 cm × 1.5 cm window opened on the aluminum member. A mixed powder composed of the silicon dioxide particles (average particle size: 40 nm), niobium oxide particles, and tin dioxide particles (average particle size: 7 nm) obtained in Reference Example 1 was filled in the window of the double-sided tape. Formed. The thickness of the power generation layer 4 is 0.8 mm, similar to the thickness of the double-sided tape. Finally, the positive electrode 2 was laminated on a double-sided tape to obtain a power generating element. About the mixed powder obtained in Reference Examples 2-5, the electric power generation element was produced using the same method.

(Evaluation)
Using the test apparatus shown in FIG. 3, the output current and output voltage of the power generation element obtained as described above were measured. In the test apparatus shown in FIG. 3, the negative electrode 5, the resistance load 10, the switch 11, the ammeter 13, and the positive electrode 2 are connected in this order by lead wires to form a circuit. A voltmeter 12 is connected to the circuit so that the voltage across the resistance load 10 can be measured. Further, the power generating element 1 is installed on the heater 6 whose temperature can be adjusted by the temperature controller 8 so that the negative electrode 5 is on the lower side and the positive electrode 2 is on the upper side. Further, a temperature sensor 9 is installed in a portion where the power generation element 1 on the heater 6 is not installed, and the temperature of the heater 6 can be measured. The heat insulating material 7 is installed so as to face the positive electrode 2 and the heater 6 from above and below. Note that the resistance of the resistive load 10 was measured by changing the resistance to 1 kΩ, 10 kΩ, 100 kΩ, or ∞. As the ammeter 13 and the voltmeter 12, a digital multimeter 8808A manufactured by FLUKE was used. Z, Cp, L, and tan δ were measured using an LCR high tester 3532-50 manufactured by Hioki Electric Co., Ltd. The measurement was performed by changing the temperature of the heater 6 to 29 ° C. (room temperature) or 100 ° C. The measurement results are shown in Table 2.

(Reference Examples 6 to 13)
A mixed powder of Reference Examples 6 to 13 was obtained using the same method as in Reference Example 1, except that the mixing ratio in the mixed water dispersion was changed as shown in Table 3. Table 3 shows the content of each component in the mixed powder.

  The power generation element was produced as follows. First, a flat copper member was prepared as the positive electrode 2. Next, a flat aluminum member was prepared as the negative electrode 5, and a double-sided tape having a thickness of 0.8 mm with a 1 cm × 1 cm window opened on the aluminum member. A window of a double-sided tape was filled with a mixed powder composed of the silicon dioxide particles (average particle size: 40 nm), niobium oxide particles, and tin dioxide particles (average particle size: 7 nm) obtained in Reference Example 6, and the power generation layer 4 Formed. The thickness of the power generation layer 4 is 0.8 mm, similar to the thickness of the double-sided tape. Finally, the positive electrode 2 was laminated on a double-sided tape to obtain a power generating element. About the mixed powder obtained by Reference Examples 7-13, the electric power generation element was produced using the same method.

[Evaluation]
About the power generation element produced using the mixed powder obtained in Reference Examples 6 to 13, the output current and the output voltage were measured by the same method as described above. Table 4 shows the measurement results of the power generation elements obtained in Reference Examples 6 to 13.

[Preparation of mixed powder of silicon dioxide, titanium oxide and tin dioxide]
(Reference Example 14)
25 parts by mass of titanium tetrachloride (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 100 parts by mass of ethanol. Next, 1.98 parts by mass of the titanium tetrachloride / ethanol solution and 5 parts by mass of a 20% aqueous dispersion of silicon dioxide (manufactured by Nissan Chemical Industries, Ltd., “ST-O-40”, average particle size 40 nm) 1 part by mass of a 20% aqueous dispersion of tin dioxide (manufactured by Unitika Ltd., tin oxide sol “AS20I”, average particle size 7 nm) was mixed and stirred. In the mixed water dispersion, tantalum tetrachloride was hydrolyzed to titanium oxide. Next, solid content was isolate | separated from the mixed water dispersion containing the obtained silicon dioxide particle, a tantalum oxide particle, and a tin dioxide particle. The obtained solid content was sufficiently washed and then dried at 100 ° C. to obtain a mixed powder of Reference Example 14 composed of silicon dioxide particles, tantalum oxide particles, and tin dioxide particles. Table 5 shows the mixing ratio of the 20% aqueous dispersion of silicon dioxide in the mixed aqueous dispersion, the niobium tetrachloride / ethanol solution, and the 20% aqueous dispersion of tin dioxide, and the content of each component in the mixed powder.

(Reference Examples 15-18)
A mixed powder of Reference Examples 15 to 18 was obtained using the same method as Reference Example 14 except that the mixing ratio in the mixed water dispersion was changed as shown in Table 5. Table 5 shows the content of each component in the mixed powder.

  A power generation element was produced in the same manner as in Reference Example 6, except that the power generation layer 4 was formed using the mixed powder of Reference Example 14 instead of the mixed powder composed of silicon oxide particles, niobium oxide particles, and tin dioxide particles. Was made. For the mixed powders obtained in Reference Examples 15 to 18, power generation elements were produced in the same manner as in Reference Example 14.

[Evaluation]
About the power generation element produced using the mixed powder obtained in Reference Examples 14 to 18, the output current and the output voltage were measured by the same method as described above. Table 6 shows the measurement results.

[Preparation of mixed powder of silicon dioxide, tantalum oxide, and tin dioxide]
(Reference Example 19)
5 parts by mass of tantalum tetrachloride (Wako Pure Chemical Industries, Ltd.) was dissolved in 45 parts by mass of ethanol. Next, 1 part by mass of the tantalum tetrachloride / ethanol solution, 5 parts by mass of a 20% aqueous dispersion of silicon dioxide (manufactured by Nissan Chemical Industries, Ltd., “ST-O-40”, average particle size 40 nm), 0.75 parts by mass of a 20% aqueous dispersion of tin (manufactured by Unitika Ltd., tin oxide sol “AS20I”, average particle size: 7 nm) was mixed and stirred. In the mixed water dispersion, titanium tetrachloride was hydrolyzed to titanium oxide. Next, solid content was isolate | separated from the mixed water dispersion containing the obtained silicon dioxide particle, titanium oxide particle, and tin dioxide particle. The obtained solid content was sufficiently washed and then dried at 100 ° C. to obtain a mixed powder of Reference Example 19 composed of silicon dioxide particles, titanium oxide particles, and tin dioxide particles. Table 7 shows the mixing ratio of the 20% aqueous dispersion of silicon dioxide in the mixed aqueous dispersion, the aqueous solution of niobium tetrachloride / ethanol and the 20% aqueous dispersion of tin dioxide, and the content of each component in the mixed powder.

(Reference Examples 20-23)
A mixed powder of Reference Examples 20 to 23 was obtained using the same method as in Reference Example 19 except that the mixing ratio in the mixed water dispersion was changed as shown in Table 7. Table 7 shows the content of each component in the mixed powder.

  A power generation element was produced in the same manner as in Reference Example 6, except that the power generation layer 4 was formed using the mixed powder of Reference Example 19 instead of the mixed powder composed of silicon oxide particles, niobium oxide particles, and tin dioxide particles. Was made. For the mixed powders obtained in Reference Examples 20 to 23, power generation elements were produced in the same manner as in Reference Example 19.

[Evaluation]
About the electric power generation element produced using the mixed powder obtained in Reference Examples 19-23, the output current and the output voltage were measured by the method similar to the above. Table 8 shows the measurement results.

1 Power generation element 2 Positive electrode (positive electrode plate)
3 Hole transport layer 4 Power generation layer 5 Negative electrode (negative electrode plate)
6 Heater 7 Heat Insulating Material 8 Temperature Controller 9 Temperature Sensor 10 Resistance Load 11 Switch 12 Voltmeter 13 Ammeter 20 Charging Device 21 Power Generation Unit 22 Power Supply Unit 23 Substrate 24 Wiring 25 Case for Electronic Equipment

Claims (6)

A charging device used for charging a secondary battery provided in an electronic device,
A charging device comprising: a power generation unit that converts vibration energy of molecules into electrical energy; and a power supply unit that supplies electric power generated by the power generation unit to an electronic device. Furthermore, the charging device of Claim 1 provided with the secondary battery which accumulates the electric power generated in the electric power generation part. Furthermore, the amount of power supplied from the power supply unit to the electronic device is determined according to the detection means for detecting the state of charge of the secondary battery provided in the electronic device and the state of charge of the secondary battery provided in the electronic device. The charging device according to claim 1, further comprising a control unit that controls the charging device. The power generation unit includes a power generation element having a power generation layer,
The power generation layer is between the positive electrode and the negative electrode, the power generation auxiliary material, the semiconductor material (α), and the energy level at the upper end of the valence band is higher than the energy level at the upper end of the valence band of the semiconductor material (α). The semiconductor material (β) having a high energy level at the lower end of the conduction band and higher than the energy level at the lower end of the conduction band of the semiconductor material (α). Charging device. The case for electronic devices provided with the charging device in any one of Claims 1-4. The electronic device provided with the charging device in any one of Claims 1-4.

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