The present application claims priority from Japanese Patent Application JP 2011-097196 filed on Apr. 25, 2011, the content of which is hereby incorporated by reference into this application.
The present invention relates to a technique of a wavelength conversion film, and in particular to a technique which is effective when applied to a solar cell and involves irradiating a fluorescent substance with near ultraviolet to blue light to excite the fluorescent substance, causing light emission to convert the wavelength of the light.
The quantum efficiency of a solar cell is generally lower in the region from ultraviolet to blue than in the region from green to near infrared. Therefore, among the wavelength components of the light which reach the solar cell, light with high quantum efficiency for the solar cell can be increased to improve the efficiency of the solar cell by converting the wavelength of ultraviolet to blue light into that of green to near infrared light. It has been known that the efficiency of the solar cell is improved by placing a wavelength conversion film on the path of light to a solar cell. For example, in Japanese Unexamined Patent Publication No. 2001-7377, a fluorescence coloring agent is used as a wavelength conversion material. Moreover, in Japanese Unexamined Patent Publication No. 2000-327715, a rare earth metal complex-containing ORMOSIL complex is used. In 58th Symposium of Japan Society of Coordination Chemistry, preliminary reports 1PF-011, an organic metal complex is used. However, durability is insufficient in the above-mentioned fluorescence coloring agent and organic metal complex, and it is difficult to maintain the functions as a wavelength conversion material for solar cells over a long period of time. In Japanese Unexamined Patent Publication No. 2003-218379, a wavelength conversion material for solar cells using a fluorescent substance is described while no specific value of improvement of the efficiency in Japanese Unexamined Patent Publication No. Hei 7-202243 is described, and improvement in the power generation efficiency is also insufficient in Japanese Unexamined Patent Publication No. 2005-147889. Japanese Unexamined Patent Publication No. 2005-147889 describes covering a light emission material with metal oxide to improve the light transmission coefficient, but as described in Japanese Unexamined Patent Publication No. 2005-147889, surface coating materials for fluorescent substances are generally metal oxide, and there is no description of coating its surface on inorganic compounds of fluorescent substance with polymer.
Wavelength conversion materials for solar cells have been under improvement through the use of fluorescent substances which are organic metal complexes and inorganic compounds as wavelength conversion materials for solar cells. However, in known wavelength conversion materials, light scattering caused by the light emission material is great, and therefore the amounts of components of light which are not oriented toward the solar battery cell but are reflected to the side where sunlight is incident are great. Accordingly, in known wavelength conversion materials, the photoelectric conversion efficiency of the solar cell has not been sufficiently improved, and further improvement of the photoelectric conversion efficiency has been required.
The present invention has been made in view of the above object, and an object of the same is to provide a technique which is capable of increasing the amount of light oriented toward the solar battery cell of the light which is incident on a wavelength conversion material, and improving the photoelectric conversion efficiency of a solar cell.
The above and other objects and novel features of the present invention will be apparent from the description and accompanying drawings of the present specification.
Among the inventions disclosed in the present application, a typical example can be briefly explained as follows:
That is, a solar cell module in one embodiment of the present invention has a front glass, a clear resin, a solar battery cell and a back sheet. Moreover, the front glass is semitempered glass for solar cells, and may have an antireflection coating in some cases. In the clear resin, a fluorescent substance which emits visible to near infrared light by being excited by near ultraviolet to blue light is contained. The fluorescent substance is in the form of being coated with polymer on its surface so that reflected light is reduced to increase the amount of light oriented toward the solar battery cell. That is, by using the solar cell in the wavelength conversion film as stated above, a solar cell module having high photoelectric conversion efficiency can be produced.
The effects obtained by a typical example of the inventions disclosed in the present application can be briefly explained as follows:
That is, in the present invention, reflection caused by a wavelength conversion material can be reduced, the quantity of light oriented towards the solar battery cell can be increased, and the photoelectric conversion efficiency of the solar cell can be improved.
The structure of the solar cell module of the present invention is shown in
Moreover, the sealing material 3 plays a role of a protective material, and is disposed in a manner of covering a solar battery cell 4 which converts light energy into electric energy. A potting material of silicon, polyvinyl butyral and the like can be used as the sealing material, in addition to EVA (ethylene-vinyl acetate copolymer). As the solar battery cell 4, a single crystal silicon solar cell, a polycrystal silicon solar cell, a thin-film compound semiconductor solar cell, an amorphous silicon solar cell and various other solar cell elements can be used. A single or multiple solar battery cells 4 are disposed in the solar cell module 1, and when multiple solar battery cells 4 are disposed, they are electrically connected by interconnectors.
Moreover, the back sheet 5 may include a metal layer and a plastic film layer to provide weathering resistance, high insulating properties, and strength. The wavelength conversion material 7 can be used by being mixed into the sealing material 3 as shown in
Moreover, the wavelength conversion material 7 may take any form as long as it is present while at least sunlight is incident on the solar battery cell 4, and it is present on a light receiving surface of at least the front glass 2 or between the front glass 2 and solar battery cell 4. Moreover, the wavelength conversion material 7 may take any form as long as it can absorb the light which is incident on the solar battery cell. Therefore, it may be in any position as long as the position allows the converted light to be provided to an incident portion of sunlight of at least the solar battery cell 4, and may not be uniformly present with the same area as the surface area of the solar cell module 1.
Therefore, as the structure of the solar cell module in addition to the constitution shown in
Moreover, as shown in
Moreover, as shown in
As mentioned above, methods for producing a solar cell having a structure in which a material containing the fluorescent substance is placed on the path of light to the solar cell include a method of mixing in materials of the front glass 2 and sealing material 3, a method of adding the wavelength conversion material 7 in an appropriate solvent and applying the resulting mixture to a desired portion, among others. The method may be in any form as long as it does not prevent absorption of sunlight in the solar battery cell 4 or impair the functions of the wavelength conversion material 7. Among them, the method of using the wavelength conversion material 7 by kneading the same into the sealing material 3 shown in
In the case where a fluorescent substance material is used as the wavelength conversion material, when the size of the fluorescent substance is the order of a few μm, a component of light which is not oriented toward the solar battery cell by the reflection caused by the fluorescent substance but is reflected to the side where sunlight is incident occurs. In this case, the component reflects to the side where the component of sunlight is incident by the fluorescent substance material placed as the wavelength conversion material and does not contribute to the power generation of the solar cell.
By coating the surface of the fluorescent substance with polymer, the reflection of sunlight by the fluorescent substance can be suppressed. Metal oxides are generally known as materials for coating the surface of the fluorescent substances. They are often used in surface coating as fine particles, and materials which smoothly coat the surface of the fluorescent substance are preferable to increase light use efficiency. Moreover, the surface coating is preferable in that it can be produced easily and economically.
The quantum efficiency of the solar cell generally lowers from blue to near ultraviolet, as the wavelength of incident light becomes shorter. In contrast, the fluorescent substance having a quantum efficiency of about 0.7 to 0.9 is used as the wavelength conversion material.
An increase in the generated output due to wavelength conversion is found at the excitation edge wavelength of 350 to 670 nm with quantum efficiency of 0.6 to 0.9. The increase in the generated output is greatest when the excitation edge wavelength is 430 to 500 nm. That is, if the quantum efficiency of the wavelength conversion material is 0.6 to 0.9, the generated output of the solar cell can be maximized by using a wavelength conversion material with an excitation edge wavelength ranging from 430 to 500 nm, while if the quantum efficiency is 0.7 to 0.9, the generated output of the solar cell can be maximized by using a wavelength conversion material with an excitation edge wavelength ranging from 450 to 500 nm. Moreover, when the quantum efficiency of wavelength conversion material is 0.7 or higher, even if a wavelength conversion material having an excitation edge wavelength of 410 to 600 nm is used, the generated output of the solar cell can be improved than in the case of wavelength conversion using a known organic complex (quantum efficiency: about 0.6).
In contrast, the fluorescent substance also has a loss due to optical scattering, and its degree relates to its particle diameter and concentration of addition. The relationship between the particle diameter and light scattering intensity of the wavelength conversion material is such that, when the wavelength of sunlight is 500 nm, the light scattering intensity is the highest with a particle diameter of 250 nm, which is half the wavelength, due to the Mie scattering. The relationship between the light scattering intensity and particle diameter is shown in
The scattering intensity is controlled by the Rayleigh scattering with a particle diameter smaller than 250 nm, and the smaller the particle diameter, the lower the scattering intensity, while it is controlled by geometrical optics scattering with a particle diameter larger than 250 nm, and the larger the particle diameter, the lower the light scattering intensity. The light scattering intensity is lowered when the particle diameter is small, but the emission intensity of the fluorescent substance is lowered. Also the concentration of addition needs to be increased when the particle diameter is too large, which impairs functions of the sealing material. Therefore a particle diameter ranging from 10 nm to 50 μm is appropriate. In addition, the light emission efficiency of the fluorescent substance tends to abruptly lower at 1 μm or lower, and therefore more preferably, the particle diameter ranging from 1 μm to 50 μm is appropriate.
Next, the concentration of addition of the wavelength conversion material to the sealing material is desirably such that at least one fluorescent substance particle is present on the side where sunlight is incident and the fluorescent substance mixed into the sealing material is evenly exposed to sunlight. When the concentration of addition is too high, the optical scattering is increased, while when the concentration of addition is too low, an amount of light which passes through the material with its wavelength not converted increases. Accordingly, the concentration of addition of the fluorescent substance having an average particle diameter of 2.3 μm is 2% by weight. Moreover, the concentration of addition of the fluorescent substance having an average particle diameter of 5.8 μm is 5% by weight. Further, the concentration of addition of the fluorescent substance having an average particle diameter of 1.2 μm is 1% by weight. Therefore, the concentration of addition of the fluorescent substance having an average particle diameter of 1 to 5 μm is 1 to 5% by weight. However, this is the required amount of the fluorescent substance obtained by calculation herein, and the optimum concentration lies around this amount. Therefore, when an average particle diameter of the fluorescent substance is A (μm), an optimum concentration range B (% by weight) starts to exhibit its effects from about 1/200 times the optimum concentration 2 A/2.3, and the effects are found up to about 10 times. Therefore, the concentration of the fluorescent substance is good in the range from 0.004 A≦B≦8.7 A. Considering stopping and light scattering of light, more preferably, the effects of wavelength conversion is high in the range from about 1/100 times to about five times the optimum concentration 2 A/2.3. Therefore, it is thought that the concentration of the fluorescent substance is optimal in the range from 0.008 A≦B≦4.3 A. Moreover, the concentration of addition of the fluorescent substance can only be lowered when reflected light is great, but the reflected light can be reduced by coating its surface with polymer. Therefore, the concentration of addition of the wavelength conversion material can be higher than in conventional cases.
A preferable wavelength conversion material is capable of converting near ultraviolet to blue light at 500 nm or lower into green to near infrared light at 500 nm to 1100 nm and causing the light to be incident on the solar battery cell. In particular, a material is preferable which has an excitation band at 300 nm or higher where there is the sunlight spectrum intensity, a quantum efficiency of 0.7 or higher, and has an excitation edge wavelength at 410 to 600 nm. Especially, a material having an excitation edge wavelength at 430 to 500 nm is the most preferable. In addition, in terms of luminance lifetime and moisture resistance, inorganic fluorescent substance materials used for various kinds of displays, lamps, and white LEDs and other devices are preferable. However, they are limited to those which have their excitation bands distributed in near ultraviolet to blue light. In the present invention, the composition of the fluorescent substance material in which the excitation band exists in near ultraviolet light to blue light from such a perspective, and which has a high phototransformation efficiency is selected.
Such fluorescent substances include, among others, MMgAl10O17:Eu, Mn, wherein M is a fluorescent substance which is one or more elements selected from Ba, Sr and Ca, or a fluorescent substance whose parent material contains one of (Ba, Sr)2SiO4, (Ba, Sr, Ca)2SiO4, Ba2SiO4, Sr3SiO5, (Sr, Ca, Ba)3SiO5, (Ba, Sr, Ca)3MgSi2O8, Ca3Si2O7, Ca2ZnSi2O7, Ba3Sc2Si3O12 and Ca3Sc2Si3012, or a fluorescent substance whose parent material is represented by MAlSiN3, wherein M is one or more elements selected from Ba, Sr, Ca and Mg.
Moreover, an average particle diameter of the fluorescent substance used in the present invention is 10 nm to 50 μm, and is more preferably 1 μm to 50 μm, considering the light emission efficiency. Herein, an average particle diameter of the fluorescent substance can be defined as follows: methods for determining an average particle diameter of particles (fluorescent substance particles) include, among others, a method of determining by a particle size distribution measuring device and a method of directly observing by an electronic microscope. For example, in the case of using an electronic microscope, an average particle diameter can be calculated as follows: the sections of the variables of the particle diameter of particles ( . . . , 0.8 to 1.2 μm, 1.3 to 1.7 μm, 1.8 to 2.2 μm, . . . , 6.8 to 7.2 μm, 7.3 to 7.7 μm, 7.8 to 8.2 μm, . . . ) are represented by class values ( . . . , 1.0 μm, 1.5 μm, 2.0 μm, 7.0 μm, 7.5 μm, 8.0 μm, . . . ), which are represented by xi. When the frequency of the variables observed by using the electronic microscope is indicated by fi, an average value A can be represented as follows:
A=Σ×
i
f
i
/Σf
i
−Σ×
i
f
i
/N
However, Σfi=N. The excitation band wavelength of the fluorescent substance of the present invention falls within the satisfactory range as the wavelength conversion material, and therefore can provide excellent effects as a wavelength conversion material for solar cells.
A wavelength conversion material, which is a fluorescent substance whose surface is coated with polymer, is produced according to a first embodiment. Methyl methacrylate monomer is used as a raw material of the polymer. BaMgAl10O17:Eu, Mn (particle diameter: 6 μm) is used as a fluorescent substance, and is immersed in hexamethyldisilazane to impart hydrophobicity to the surface of the fluorescent substance and dried. The fluorescent substance which is subjected to the hydrophobic treatment is added to methyl methacrylate monomer, and further a small amount of V-65 is added thereto as a reaction initiator. A surfactant is further added to the methyl methacrylate monomer containing the fluorescent substance and reaction initiator added thereto, and the mixture is dispersed by an ultrasonic cleaner. Pure water is added to the resulting methyl methacrylate monomer solution, giving a reaction solution. The reaction solution in a container is placed in a temperature control furnace with rotating blades. The temperature in the furnace is maintained at 54° C. to allow reaction under a stream of nitrogen. The reaction solution is cooled, washed with water and then dried, preparing a wavelength conversion material used for the present invention.
Moreover, BaMgAI10O17:Eu, Mn having a particle diameter of 50 μm can be used as the fluorescent substance. Methyl methacrylate monomer is used as a raw material of the polymer. BaMgAl10O17:Eu, Mn (particle diameter: 50 μm) is used as the fluorescent substance, and immersed in hexamethyldisilazane to impart hydrophobicity to the surface of the fluorescent substance and dried. The fluorescent substance which is subjected to the hydrophobic treatment is added to methyl methacrylate monomer, and further a small amount of V-65 is added thereto as a reaction initiator. A surfactant is further added to the methyl methacrylate monomer containing the fluorescent substance and reaction initiator added thereto, and the mixture is dispersed by an ultrasonic cleaner. Pure water is added to the resulting methyl methacrylate monomer solution, giving a reaction solution. The reaction solution in a container is placed in a temperature control furnace with rotating blades. The temperature in the furnace is maintained at 54° C. under a stream of nitrogen to cause a reaction. The reaction solution is cooled, washed with water and then dried, preparing a wavelength conversion material used for the present invention.
Moreover, the wavelength conversion material can also be produced after the reaction initiator is applied on the surface of the fluorescent substance. Methyl methacrylate monomer is used as a raw material of the polymer. BaMgAl10O17:Eu, Mn (particle diameter: 6 μm) is used as the fluorescent substance, and immersed in hexamethyldisilazane to impart hydrophobicity to the surface of the fluorescent substance and dried. Moreover, a reaction initiator (V-65) is dissolved in a solution. The fluorescent substance is immersed in the dissolved reaction initiator solution and dried. A surfactant is further added to the methyl methacrylate monomer containing the treated fluorescent substance added thereto, and the mixture is dispersed by an ultrasonic cleaner. Pure water is added to the resulting methyl methacrylate monomer solution, giving a reaction solution. The reaction solution in a container is placed in a temperature control furnace with rotating blades, and the temperature in the furnace is maintained at 54° C. under a stream of nitrogen to cause a reaction. The reaction solution is cooled, washed with water and then dried, preparing a wavelength conversion material used for the present invention.
Next, a wavelength conversion material which is a fluorescent substance whose surface is coated with polymer is produced according to a second embodiment. In the wavelength conversion material according to the second embodiment, BaMgAl10O17:Eu, Mn (particle diameter: 1 μm) is used as a fluorescent substance, and immersed in hexamethyldisilazane to impart hydrophobicity to the surface of the fluorescent substance and dried. The rest of the processing is similar to that in the first embodiment.
Next, a wavelength conversion material which is a fluorescent substance whose surface is coated with polymer according to a third embodiment is produced. The wavelength conversion material according to the third embodiment (Ba, Ca, Sr) MgAl10O17:Eu, Mn (particle diameter: 6 μm) is used as a fluorescent substance, and immersed in hexamethyldisilazane to impart hydrophobicity to the surface of the fluorescent substance and dried. The rest of the processing is similar to that in the first embodiment.
Next, a wavelength conversion material which is a fluorescent substance whose surface is coated with polymer according to a fourth embodiment is produced. The fluorescent substance used is, as mentioned above, MgAl10O17:Eu, Mn, where M is a fluorescent substance which is one or more elements selected from Ba, Sr and Ca, or a fluorescent substance whose parent material contains one of (Ba, Sr)2SiO4, (Ba, Sr, Ca)2SiO4, Ba2SiO4, Sr3SiO5, (Sr, Ca, Ba)3SiO5, (Ba, Sr, Ca) 3MgSi2O8, Ca3Si2O7, Ca2ZnSi2O7, Ba3Sc2Si3O12 and Ca3Sc2Si3O12, or a fluorescent substance whose parent material is represented by MAlSiN3, where M is a fluorescent substance which is one or more elements selected from Ba, Sr, Ca and M. The fluorescent substance having a particle diameter of 1 to 50 μm can be used to produce a wavelength conversion material which is a polymer surface-coated fluorescent substance in a manner similar to the method stated above. The rest of the process is similar to that in the first embodiment. Moreover, in addition to acrylic resins, polyethylene, vinyl chloride resins and other materials can be used as the polymer for coating the fluorescent substance.
Next, a solar cell module is produced using the wavelength conversion material. Described below is the solar cell module according to the first embodiment. Small amounts of organic peroxide, a crosslinking auxiliary agent and an adhesion improver are added to a clear resin (EVA). 1.0% by weight of a wavelength conversion material prepared by coating the surface of a fluorescent substance (Ba, Ca, Sr)MgAl10O17:Eu, Mn with an acrylic resin is mixed into the mixture. After the resulting mixture is kneaded using a roll mill heated to 80° C., it is nipped between two films of polyethylene terephthalate by using a press, and a sealing material 3 containing EVA as a main component and having a thickness of 500 μm is produced. Moreover, the fluorescent substance may be composed of a single component or a mixture of components. Next, this sealing material 3 is allowed to cool to room temperature, and the polyethylene terephthalate films are removed therefrom. The sealing material 3 is laminated with the front glass 2, solar battery cell 4 and back sheet 5 as shown in
The solar cell module according to the second embodiment is produced. In second embodiment, small amounts of organic peroxide, a crosslinking auxiliary agent and an adhesion improver are added to a clear resin (EVA). 2.0% by weight of a wavelength conversion material prepared by coating the surface of a fluorescent substance (Ba, Sr)2SiO4:Eu with an acrylic resin is mixed into the mixture. The resulting mixture is kneaded using a roll mill heated to 80° C. The rest of the processing is similar to that in the first embodiment. The amperage is increased by 7% by this embodiment compared with the case where no wavelength conversion material is used.
A solar cell module according to a third embodiment is produced. Small amounts of organic peroxide, a crosslinking auxiliary agent and an adhesion improver are added to a clear resin (EVA), and 2.0% by weight of a wavelength conversion material prepared by coating the surface of a fluorescent substance CaAlSiN3:Eu with vinyl chloride is mixed into the mixture. The resulting mixture is kneaded using a roll mill heated to 80° C. The rest of the processing is similar to that in the first embodiment. The amperage increases by 5% by this embodiment compared with the case where no wavelength conversion material is used.
Number | Date | Country | Kind |
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2011-097196 | Apr 2011 | JP | national |