WO2001009959A1 - Module de cellule solaire - Google Patents

Module de cellule solaire Download PDF

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Publication number
WO2001009959A1
WO2001009959A1 PCT/JP2000/004935 JP0004935W WO0109959A1 WO 2001009959 A1 WO2001009959 A1 WO 2001009959A1 JP 0004935 W JP0004935 W JP 0004935W WO 0109959 A1 WO0109959 A1 WO 0109959A1
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WO
WIPO (PCT)
Prior art keywords
solar cell
cell module
glass fiber
heavy metal
module according
Prior art date
Application number
PCT/JP2000/004935
Other languages
English (en)
Japanese (ja)
Inventor
Junji Nakajima
Takeshi Hibino
Kuniyoshi Omura
Shigeo Kondo
Original Assignee
Matsushita Battery Industrial Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP21590999A external-priority patent/JP3535774B2/ja
Priority claimed from JP11215908A external-priority patent/JP2001044457A/ja
Application filed by Matsushita Battery Industrial Co., Ltd. filed Critical Matsushita Battery Industrial Co., Ltd.
Publication of WO2001009959A1 publication Critical patent/WO2001009959A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
    • H01L31/046—PV modules composed of a plurality of thin film solar cells deposited on the same substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a solar cell module including a solar cell element containing a heavy metal or a heavy metal compound.
  • Si Monocrystalline, polycrystalline or amorphous silicon
  • Si itself is a material that does not need to worry about environmental pollution.
  • phosphorus is used as an impurity to make Si an n-type semiconductor
  • boron is used to make it a p-type semiconductor.
  • lead solder containing heavy metals which is considered to require environmental pollution countermeasures, is often used as a conductive material in silicon solar cell elements.
  • Compound semiconductor solar cell elements use II-VI or III-V compound semiconductors or organic semiconductors.
  • n-type semiconductors include CdS, ZnS, and GaAs
  • p-type semiconductors include CdTe, CuInSe, CuInS, and GaAs. such as ln 2 0 3, S n 0 2, S b 2 ⁇ 3 as a transparent conductive film is used, respectively.
  • Cd, Te, Se, Pb, In, Cu, Ga It contains various heavy metal components such as As, Sn, and Sb.
  • these solar cell elements are incorporated into electronic device products as various optical sensors and put to practical use, and are also used as power sources by being packaged in various devices such as watches, calculators, and road markings. .
  • no special measures have been taken to prevent heavy metal contamination.
  • solar cells are power sources that can supply clean energy by using inexhaustible sunlight, so they are going to be widely used as large-scale outdoor power supply units for houses and large electric power.
  • power supply devices themselves are increasing in size.
  • solar cell modules that package solar cell elements containing heavy metal components, or solar power generation systems that combine such solar cell modules with inverters and control devices will become widespread as large outdoor power supplies.
  • the number of solar cells increases, the amount of heavy metal components contained in these solar cells increases.
  • the present invention prevents the discharge of heavy metal components to the outside when a solar cell module or a large outdoor power supply device incorporating the same is abnormally heated by a fire or is damaged by an accident.
  • the purpose is to Disclosure of the invention
  • the solar cell module of the present invention includes a solar cell element containing a heavy metal or a heavy metal compound, and the solar cell element has a material that captures the molten or vaporized heavy metal or a heavy metal element contained in the heavy metal compound. Things.
  • the material for capturing the heavy metal element is preferably at least one of a glass fiber and a chevrel compound.
  • glass fiber when glass fiber is provided as a material for capturing the heavy metal element, it is preferable to provide the glass fiber layer so as to cover most of the back surface of the solar cell element. More preferably, the glass fiber layer is bonded to the back surface of the solar cell element with a synthetic resin.
  • the solar cell module of the present invention when the solar cell module is abnormally heated due to a fire or the like, it is possible to prevent heavy metal components contained in the solar cell element from being discharged to the outside.
  • the glass fiber layer carries at least one of a sibrel compound and a glass frit. No. This makes it possible to more effectively solve the problem of abnormal heating due to a fire or the like.
  • the solar cell module of the present invention supports a solid base material. This not only solves the problem of abnormal heating more effectively, but also prevents the elution of heavy metal components into rainwater even when the solar cell module is damaged by wind and water damage and exposed to rainwater.
  • the solar cell element includes a p-type semiconductor layer made of cadmium telluride (CdTe), and a layer of a chevrel compound is provided on the p-type semiconductor layer. .
  • CdTe cadmium telluride
  • a layer of a chevrel compound is provided on the p-type semiconductor layer.
  • FIG. 1 is a schematic cross-sectional view of the solar cell element of Example 1.
  • FIG. 2 is a schematic cross-sectional view of the solar cell element of Example 3.
  • FIG. 3 is a schematic cross-sectional view of the solar cell element of Example 4.
  • Fig. 4 is a block diagram of a solar cell heating test device.
  • FIG. 5 is a schematic cross-sectional view of the solar cell element of Example 7.
  • FIG. 6 is a schematic sectional view of the solar cell element of Example 10. BEST MODE FOR CARRYING OUT THE INVENTION
  • the material for capturing a heavy metal element in the present invention does not chemically react with the heavy metal component at a normal temperature at which the solar cell element is used, and captures and injects the heated or molten or vaporized heavy metal component into the inside.
  • a material that has the property of The heavy metal referred to in the present invention has a specific gravity of 4 or more.
  • metal elements belonging to the groups IB to VIA in the periodic table for example, Ga, Ge, As, Se, Ag, Cd, I n, S b, T e, T l, P b and the like.
  • metal elements heavy metal elements that are included in solar cell elements for large power sources, or are likely to be included in the future, and for which environmental pollution countermeasures due to these elements should be considered especially, are considered.
  • a solar cell element provided with glass fibers as a material for capturing a heavy metal element is preferably provided with a glass fiber layer so as to cover most of the back surface.
  • the glass fiber layer is flexible and does not break and scatter. Therefore, the glass fiber that has been softened and melted during heating can cover most of the back surface of the solar cell element without any gap. As a result, the route through which the molten or vaporized heavy metal component is discharged to the outside of the solar cell element can be effectively closed. Glass fibers also have the effect of capturing these heavy metal components.
  • the glass fiber in the molten state has a property of dissolving the molten or vaporized heavy metal component and capturing the heavy metal component.
  • the glass fiber layer before being further softened has the property of absorbing and capturing heavy metal components that have been melted or vaporized in the fine spaces in the layer.
  • the glass fiber layer is It is adhered to the back surface with a synthetic resin and fixed at a predetermined location. As a result, even when the solar cell element is exposed to vibration or impact during handling, the glass fiber layer is accurately and firmly fixed to the predetermined location. As a result, the effect of closing the exhaust route and the effect of capturing the heavy metal component by the glass fiber layer can be further enhanced.
  • the glass fiber layer used in the present invention has a large number of fine spaces with a diameter of 0.1 ⁇ m to l mm, a fiber diameter of 2 to 30 m, and a basis weight of 40 g Z m 2 to 1 kg / m 2 is preferred.
  • various forms of glass fibers processed into sheets such as mineral paper, can be used.
  • the nonwoven fabric is made up of hundreds to tens of thousands of glass fiber filaments having a fiber diameter of 2 to 30 xm using an organic binder such as polyvinyl alcohol (PVA) or an inorganic binder such as silica. It is manufactured by focusing at a density of m 2.
  • Mineral paper is a powder made of powder such as calcium carbonate, aluminum hydroxide, talc, activated carbon, calcium silicate, or magnesium carbonate, or a mixture of fine fibers and glass fibers to make paper.
  • the softening temperature of the glass fiber layer is preferably 100 ° C. or lower. Further, it is desirable that the glass fiber layer has an appropriate softening temperature according to the melting temperature and the vaporization temperature of the main heavy metal component contained in the solar cell element.
  • the main heavy metal component is CdTe forming the p-type semiconductor layer, and the CdTe is about 600 Sublimation starts at ° C, and all sublime below 100 ° C.
  • CdS forming the n-type semiconductor layer starts sublimation at 500 ° C., and all sublimates at 800 ° C.
  • the sublimation temperatures of these CdTe and CdS vary depending on the bonding state and purity of the constituent atoms, and may vary within the above temperature range. This Taking these facts into consideration, when applying the present invention to a CdS / CdTe-based solar cell, a glass fiber layer having a softening temperature of 600 to 800 ° C is used. Is preferred. For this purpose, for example, a glass fiber layer containing soda lime glass as a main component is preferable. As a result, in the early stage of the fire, the molten or vaporized heavy metal component is absorbed in the microscopic space of the glass fiber layer before softening, and when the heating is further advanced, it softens and melts.
  • the molten or vaporized heavy metal component can be dissolved in the glass fiber.
  • a glass fiber layer with a thickness of about 0.2 mm to 10 mm can be used, and a layer with a thickness of 1 mm or more should be used to obtain a sufficient effect of capturing heavy metal components. Is preferred.
  • the glass fiber layer may be provided at any position as long as light reception of the solar cell element and electrical conduction in the solar cell element are not hindered.
  • a glass fiber layer is provided at a location where the heavy metal component existing inside the semiconductor layer or the electrode covering these can be effectively blocked when the heavy metal component is melted or vaporized. That is. It is preferable that the glass fiber layer is accurately fixed to the above-mentioned arrangement portion even when a mechanical external force is applied.
  • a glass fiber layer is provided so as to cover most of the back surface of the solar cell element, that is, the surface of the semiconductor layer or the surface of the electrode formed thereon. Have been. Further, the glass fiber layer is firmly fixed by bonding the glass fiber layer to the disposing portion with a synthetic resin.
  • an uncured synthetic resin or an adhesive such as a solvent type, an emulsion type, a hot melt type, or the like is applied to the glass fiber layer. It is applied to at least one of the two surfaces and the solar cell element surface on which the glass fiber layer is to be provided, or is interposed between both surfaces. Then press both surfaces together to bring them into close contact To temporarily stop. Thereafter, the synthetic resin in the uncured state is thermally cured, or a solvent or a dispersion medium in the adhesive is volatilized to cure the synthetic resin component. The glass fiber layer is bonded to a predetermined portion of the solar cell element by the synthetic resin thus cured.
  • a synthetic resin is applied to almost the entire surface of the solar cell element surface on which the glass fiber layer is to be provided, and then almost the entire glass fiber layer. Can be adopted to adhere to the solar cell element. In order to adhere the glass fiber layer more firmly to a predetermined location, a cured synthetic resin layer is formed on almost the entire surface of the solar cell element on which the glass fiber layer is to be provided, and this curing is performed. It is also possible to adopt a method of bonding the synthetic resin layer and the glass fiber layer with the synthetic resin.
  • the solar cell module according to the present invention is configured with a solar cell element including a material for capturing a heavy metal element as one of the main components.
  • a transparent conductive film is formed on the surface opposite to the light receiving surface of a light-transmitting substrate such as a glass substrate as necessary, and an n-type semiconductor film, a p-type semiconductor film, and an electrode layer are formed thereon.
  • the photoelectric conversion part made of This photoelectric conversion unit is formed on the same translucent substrate, and is connected in series by electrodes for connection between single cells.
  • a single cell group electrically connected in parallel or series-parallel has a + side electrode and a-side electrode. The attached one is a normal form.
  • the photoelectric conversion unit also includes a single cell formed on a light-transmitting substrate and having a + electrode and a one-side electrode attached thereto.
  • Other main components of the solar cell module other than the solar cell element with a material that captures heavy metal elements are the back cover made of a glass plate, a stainless steel plate, or an aluminum steel plate that also serves as a terminal plate and a sealed container. And sealing materials such as butyl rubber. Then, a sealing material is interposed between the periphery of the surface on which the photoelectric conversion unit is formed on the side opposite to the light-receiving surface of the light-transmitting substrate and the periphery of the back cover, and sealing is performed.
  • the solar cell module of the present invention is configured by airtightly packaging a solar cell element provided with a material for capturing a group element.
  • This solar cell module may be used alone or in combination of a plurality as a power supply device.
  • one or more solar cell modules are combined with an inverter or an electric control device to constitute a solar power generation system.
  • the solar cell element provided with a material for capturing a heavy metal element in the present invention may be used, for example, by being incorporated in a device such as a calculator or a clock. In these devices, the solar cell elements are packaged in an airtight state substantially as in the case of the solar cell module.
  • one surface of the glass fiber layer is bonded to the surface opposite to the light receiving surface of the solar cell element with a synthetic resin as described above, and the other surface of the glass fiber layer is provided. May be bonded to the inner surface of the back cover of the solar cell module with a synthetic resin.
  • a simple method is to cure the uncured synthetic resin or adhesive impregnated in the glass fiber layer so that one surface of the glass fiber layer is on the surface opposite to the light receiving surface and the other is The surface can be glued to the inner surface of the back cover at the same time.
  • This solar cell module can be manufactured by adjusting the thickness of the seal layer and the like so that the glass fiber layer is bonded between the photoelectric conversion unit and the back cover without any gap.
  • the glass fiber layer can be more firmly fixed at a predetermined position. Since the solar cell element is covered by the inner surface of the back cover and the glass fiber layer adhered to the back cover with a synthetic resin, the emission of heavy metal components in a fire can be more effectively prevented. In addition, it is possible to prevent rainwater or the like from entering the solar cell element when the solar cell module is damaged.
  • the synthetic resin for bonding the glass fiber layer to the solar cell element preferably has adhesiveness and elasticity.
  • Water glass was also studied as an adhesive material other than synthetic resin.However, water glass has insufficient adhesive strength, and because it is hard, the electrodes and semiconductor films to be adhered are stressed and damaged. There was a tendency to be easy.
  • the method of bonding a glass fiber layer to a solar cell element using a synthetic resin is roughly classified as follows.
  • the bonding method 3 ') is particularly effective for securing sufficient weather resistance.
  • a synthetic resin containing isobutylene resin or a derivative thereof as a main component has excellent adhesive strength, moderate elasticity and excellent weather resistance, as well as solar cell elements such as rainwater. It is a particularly preferred material because it has an effective water repellency to prevent its ingress.
  • isobutylene resin derivative refers to a product obtained by substituting a partial side chain of the isobutylene resin with a functional group such as a methyl group, a halogen atom, or a nitrogen atom.
  • the synthetic resin used in the above method 3) is a monomer oligomer or a mixture thereof, and is a state before curing. Apply to the surface to be adhered. It is preferable that the synthetic resin before curing has good coatability, does not lose the shape of the applied synthetic resin, and has characteristics that can temporarily temporarily fix the glass fiber layer at a predetermined position. Also, if the resin is forcibly applied using a hard resin, the solar cell element may be stressed and damaged, and the characteristics of the solar cell may be adversely affected. Is preferred.
  • the properties of such a synthetic resin before curing have a strong correlation with its specific gravity, and when the specific gravity is less than 0.85, the viscosity is insufficient and the fixing effect is insufficient, and exceeds 0.95. If too hard. Accordingly, the specific gravity of the synthetic resin before curing is preferably in the range of 0.85 to 0.95. This specific gravity can be adjusted by changing the degree of polymerization and the connected state of the monomers in the oligomer or the mixing ratio with the monomers. In the case of an isobutylene resin or a synthetic resin containing a derivative thereof as a main component among various kinds of synthetic resins, it is possible to relatively easily obtain a synthetic resin before curing in a preferable specific gravity range by the above adjustment method. it can.
  • the cured resin preferably has an ASKER C hardness of 10 to 50.
  • Asker C hardness is a value measured by a spring hardness tester ASKER hardness tester.
  • the cured synthetic resin must have an appropriate degree of flexibility, and a synthetic resin having an A-C hardness of less than 10 is too flexible, so the effect of fixing the glass fiber layer is insufficient.
  • a synthetic resin having an Asker C hardness of more than 50 is too hard, so that stress on the solar cell element may occur and the solar cell characteristics may be degraded.
  • the glass fiber layer supports at least one of a chevrel compound and a glass frit.
  • a chevrel compound supports at least one of a chevrel compound and a glass frit.
  • the glass frit softens with the glass fiber layer into a molten state, closing the space in the lattice of the glass fiber more densely, and further densely melting the glass surface of the solar cell element surface to the smallest detail. Can be covered with.
  • the molten glass frit has a function of dissolving and capturing the vaporized or molten heavy metal component, similarly to the above-mentioned glass fiber layer in the molten state. Therefore, the heavy metal component in the solar cell element when the solar cell is abnormally heated is also captured in the molten glass frit.
  • the glass frit is preferably a soda-lime glass having a softening temperature of 500 ° C. or less and a relatively low melting point.
  • the molten or vaporized heavy metal component reacts with the chevrel compound to form a heavy metal element. Can be trapped in the chevrel compound.
  • the class of Mo 6 X 8 (where X is at least one chalcogen element selected from the group consisting of S, Se, and Te) forms a three-dimensional lattice, and this class It has a structure in which cations such as Cu and Ag occupy the ion site between them. Cations can diffuse between the three-dimensional networks formed by this Mo 6 X 8 .
  • Chevrel compounds are metal compounds having high electron conductivity and acting as mixed electron-ion conductors. Such chevrel compounds are brought into contact with heavy metals such as Pb and Cd and heavy metal compounds such as CdS and CdTe. When heated, these heavy metal components are melted or vaporized and react with the chevrel compound, and the heavy metal elements forming these heavy metal components are trapped in the chevrel compound.
  • the Chevrel compound M Z M o 6 X 8 _ y ( however, X is S, S e, and T at least selected Ri by the group consisting of e 1 kind of chalcogen elemental, z is 0 ⁇ z ⁇ 4, y is the amount of chalcogen element deficiency, and M is the metal element.
  • a compound having excellent cation diffusivity is preferable.
  • the M element is an element that can be a + 1-valent cation. As a result, a chevrel compound that can easily capture heavy metal elements such as Pb and Cd can be obtained.
  • a chevrel compound containing at least one of Cu and Ag, which can be + 1-valent cations, as an M element is particularly preferable.
  • a chevrel compound having at least one M element selected from the group consisting of Cd, Sb, Te and In may also be preferably used as a material for trapping heavy metal elements according to the above. it can.
  • some M elements are required, and usually the most heavy metals when using a Chevrel compound of 0.05 ⁇ z ⁇ 0.2 Element can be captured.
  • the above-mentioned glass fiber layer carries a solid basic material in addition to at least one of the siblell compound and the glass frit. This effectively prevents the heavy metal components from being discharged to the outside when the solar cell is abnormally heated, and protects the water when the solar cell module is damaged and exposed to rainwater or fire water. Heavy money to Elution of genus components can be effectively prevented.
  • solid base material As the solid base material, widely used are solid materials in which an aqueous solution or an aqueous solution of a product obtained by reaction with water has alkalinity, such as a metal, a metal oxide, a metal hydroxide, and a metal carbonate. it can. These solid base materials are preferably relatively weak alkaline materials that do not diffuse into the semiconductor in the solar cell element and do not adversely affect the properties of the semiconductor. Alkaline earth metals and oxides, hydroxides and carbonates of alkaline earth metals can be used as the preferred solid base material. In addition to the above, solid bases such as Al, A1 alloy, and oxides, hydroxides, carbonates, and boraxes of metals such as Fe, Cu, V, Cr, and Mo are also preferable.
  • the solar cell module can be used as a material. Even if the solar cell module is damaged due to the action of such a solid base material and acidic rainwater, fire-fighting water, or the like invades, it neutralizes these and changes to an alkaline aqueous solution. be able to. In this way, elution of the heavy metal component from the solar cell element is prevented by changing rainwater, fire extinguishing water, and the like to a neutral or alkaline aqueous solution in which the heavy metal component is difficult to dissolve.
  • the solar cell element includes a P-type semiconductor layer made of CdTe, and a chevrel compound is provided on the P-type semiconductor layer.
  • the chevrel compound is a mixed electron-ion conductor having a high electron conductivity because it can capture a heavy metal element and take it inside.
  • Chevrel compounds also serve as Chevrel compounds.
  • the Cd Te layer has the effect of making the C d Te layer p-type. That is, by bonding a copper chevrel compound to the CdTe layer and performing a heat treatment, Cu in the copper chevrel compound is diffused to the surface layer of the CdTe layer, and the CdTe layer becomes p-type. be able to. Therefore, it can be said that the contact of the chevrel compound layer on the CdTe layer effectively prevents the heavy metal component from being discharged to the outside.
  • the CdTe layer can be made p-type by a simple process of heat treatment, which is advantageous from the viewpoint of manufacturing cost.
  • the chevrel compound is a conductive substance, even if it is interposed between the CdTe layer and the electrode, it does not hinder the electrical conduction between the two.
  • An extremely small amount of Cu as a dopant required to convert the CdTe layer into a p-type is only a few ppm to a few 10 ppm. Therefore, the atomic ratio z of the M element in the chevrel compound used is required to stabilize the structure of the chevrel compound in the same manner as when it is used for capturing heavy metal elements.
  • the doping amount of the M element into the CdTe layer is sufficiently small, and therefore, elements other than the element which can be a +1 cation, such as Cu and Ag, are used. Even when the element is used as the M element, the same effect can be obtained by promoting the diffusion of dopant at a high temperature.
  • the M element is preferably at least one element selected from the group consisting of Cd, Sb, Te, and In. As described above, similar effects can be obtained when the M element is Cu and Ag and when C element is Cd, Sb, Te and In. In the former case, the dopant can be diffused more quickly, and moreover, the heavy metal element can be easily captured.
  • FIG. 1 shows a schematic cross section of the present embodiment in which the glass fiber layer is bonded to the surface opposite to the light receiving surface of the solar cell element, that is, the back surface of the solar cell element, with water glass.
  • a glass substrate 1 (820 ⁇ 71 1) on which a transparent conductive film 2 made of tin oxide (conductivity: about 10 ⁇ cm 2 , light transmittance: 98%) was formed.
  • a 4 mm, 3 mm thick borosilicate glass plate On a 4 mm, 3 mm thick borosilicate glass plate), a 800 angstrom thick CdS layer 3 was coated with a cadmium complex of rutile citrate at 350 ° C. It was formed by heat decomposition for minutes.
  • the transparent conductive film 2 and the CdS layer 3 were simultaneously patterned by a YAG laser to divide the film into cells.
  • a CdTe layer 4 having a thickness of 300 ⁇ was formed on the CdS layer 3 after patterning and on the exposed surface of the glass substrate 1 by proximity sublimation.
  • the CdTe layer 4 was patterned by the sandblast method and divided into 130 cell-unit films. ⁇
  • a conductive carbon paste was applied on each of the divided CdTe layers 4, and then heated and cured at 150 ° C. to form a carbon electrode 5.
  • a silver paste was applied to both ends of the single cell group configured as described above and a portion from the electrode 5 to the CdS layer 3 of the adjacent cell, and dried to form a silver electrode. These silver electrodes function as the + side electrode 6, the one side electrode 7 and the electrode 8 for connection between single cells, respectively. In this way, a solar cell element in which 130 single cells were connected in series was produced.
  • a glass fiber sheet 10 (Olivest Co., Ltd., Gravest SPP-150) having a thickness of 1.03 mm.
  • the sheet 10 is placed so as to cover a portion of the back surface of the above-mentioned solar cell element other than the + side electrode 6 and the one side electrode 7, and pressed to remove the glass fiber sheet 10 from the solar cell. Bonded to the device.
  • the periphery of the glass fiber layer is connected to the back of the solar cell element with synthetic resin
  • a schematic cross section of the present embodiment is described with reference to FIG.
  • An isobutylene resin made of a mixture of a monomer and an oligomer was applied as an adhesive 9 to the periphery of the same glass fiber sheet 10 as in Example 1. This was placed on the back surface of the solar cell element fabricated in the same manner as in Example 1 except for the + side electrode 6 and the one side electrode 7, and pressed to apply the glass fiber sheet 10 to the solar cell element. Temporarily stopped. Next, the applied adhesive 9 (isobutylene resin) was polymerized and cured by heating at 120 ° C. for 1 hour. In this way, the periphery of the glass fiber sheet 10 was adhered and fixed to the back surface of the solar cell element.
  • the isobutylene resin had a specific gravity of 0.89 before curing and an Asker C hardness of 27 after curing.
  • FIG. 2 shows a schematic cross section of this example in which a glass fiber layer was adhered to most of the back surface of the solar cell element.
  • the same isobutylene resin 11 as in Example 2 was applied to the back surface of the solar cell element manufactured in the same manner as in Example 1, except for the + side electrode 6 and the one side electrode 7.
  • the same glass fiber sheet 10 as in Example 2 was placed on the coating surface, and was temporarily fixed by pressing.
  • the applied isobutylene resin 11 was heated at 120 ° C. for 1 hour, thereby polymerizing and curing. In this way, the entire surface of the glass fiber sheet 10 was bonded and fixed to the back surface of the solar cell element.
  • FIG. 3 shows a schematic cross section of this example in which a glass fiber layer was bonded to a synthetic resin layer formed on the back surface of the solar cell element.
  • the same isobutylene resin as in Example 2 was applied to the back surface of the solar cell element fabricated in the same manner as in Example 1 except for the + side electrode 6 and the one-side electrode 7. Time During the heating, polymerization and curing were performed to form a synthetic resin layer 12.
  • the same isobutylene resin 11 as described above was applied to the periphery of the synthetic resin layer 12, and the same glass fiber sheet 10 as in Example 2 was placed on the synthetic resin layer 12 and pressed and temporarily fixed. .
  • the applied isobutylene resin 11 was heated at 120 ° C. for 1 hour to be polymerized and cured.
  • the periphery of the glass fiber sheet 10 was bonded to the synthetic resin layer formed on the back surface of the solar cell element, and the glass fiber sheet 10 was fixed to the solar cell element.
  • FIG. 4 is a block diagram of the solar cell heating device used for the heating test.
  • reference numeral 23 denotes a quartz glass furnace tube having a diameter of 80 cm and a length of 100 cm, 15 a tubular electric furnace for heating the furnace tube 23, and 16 a nitrogen gas inlet 17.
  • -Stainless steel inlet flange, 18 is a stainless steel outlet flange with a nitrogen gas outlet 19
  • 20 is a heavy metal collector to collect heavy metal components contained in the exhaust gas
  • the device, 21 is a gas outlet.
  • the sample 22 was cooled to 1000 ° C. For 2 hours.
  • the exhaust gas was naturally cooled while being discharged from the discharge side flange 18, and the heavy metal component in the exhaust gas solidified into fine powder was collected by a filter in the heavy metal collecting device 20.
  • the total amount of Cd contained in each of the five samples out of ten samples of Examples 1 to 4 and Comparative Example 1 was quantified by chemical analysis. The remaining five samples were each subjected to a heating test.
  • Example 1 The amount of Cd in heavy metal components collected from the exhaust gas during the heating test and the amount of Cd contained in the residue of the sample after the heating test were quantified by chemical analysis. As a result, assuming that the average of the total amount of Cd present in the sample before being subjected to the heating test is 10 O wt%, in Example 1, 99.82 wt% was contained in the residue of the sample. 0.18 wt% in the exhaust gas, in the case of Example 2, 99.85 wt% in the residue of the sample, 0.15 wt% in the exhaust gas, Example 3 In each case of Example 4 and Example 4, the presence of 99.94 wt% of Cd in the residue of the sample and 0.06 wt% of Cd in the exhaust gas were observed. In the case of Comparative Example 1, 8.1 wt% of Cd was observed in the sample residue, and 81.9 wt% of Cd in the exhaust gas.
  • Example 2 the same glass fiber layer arrangement as in Example 2 was used using various isobutylene resins in which the mixing ratio of the monomer and the oligomer was changed and the specific gravity before curing was changed in the range of 0.8 to 1.0.
  • the installed solar cell element was fabricated as a sample.
  • a synthetic resin with a specific gravity before curing of 0.85 or more it became clear that it is necessary to use a synthetic resin with a specific gravity before curing of 0.85 or more to obtain a sufficient effect.
  • the applied synthetic resin was thermally cured, the conversion efficiency of each sample was measured. As a result, when the specific gravity before curing was 0.95 or less, the conversion efficiency deteriorated by 3%. %, And when synthetic resin having a specific gravity before curing exceeding 0.95 was used, deterioration of 10% or more was observed.
  • isobutylene with a specific gravity before curing of 0.85 to 0.95 or an ASKER C hardness of 10 to 50 after curing is used.
  • a resin was used, the same effect as in the case of Example 2 was obtained.
  • the preferable specific gravity range of the resin can be similarly applied to a monomer, an oligomer, or a synthetic resin obtained by mixing them, of an isobutylene resin derivative other than the isobutylene resin and other synthetic resins.
  • the preferable hardness range of the synthetic resin after curing can be similarly applied to a case where the synthetic resin is bonded with various synthetic resin adhesives, in addition to the heat-cured synthetic resin.
  • a solar cell element was produced using a glass fiber layer in which a layer containing a chevrel compound and glass frit was formed on a glass fiber sheet.
  • a solar cell element using each of B was produced.
  • a solar cell element was produced in the same manner as in Example 2 except for the step of producing a glass fiber layer carrying a siebel compound and glass frit.
  • the paste for forming the layer to be supported on the glass fiber layer is composed of 85 wt% of each of the above-mentioned chevrel compound powders having an average particle diameter of 10 m and glass powder having an average particle diameter of 15 m as glass frit. (Melting point: 450 ° C.) A solid content of 15 wt% was prepared by mixing with diethylene glycol monobutyl ether at a weight ratio of 3: 1. Next, this paste was applied on the same glass fiber sheet 10 as used in Example 2, dried, and supported thereon a 5 m-thick chevrel compound layer.
  • Example 2 The same method as in Example 2 was applied to the solar cell element thus manufactured.
  • the Cd amount in the heavy metal component collected from the exhaust gas and the sample after the heating test were determined by chemical analysis.
  • the amount of Cd in the residue was quantified.
  • the average amount of Cd present in the sample before the heating test is 100 wt%, and the weight percentages of (A) the amount of Cd in the sample residue and (B) the amount of Cd in the exhaust gas I asked.
  • CU c ⁇ MO eS g A g as a chevrel compound. .. 5 M o s S 8, 1 1.
  • a solar cell element was fabricated using a glass fiber layer in which a layer containing a solid base material was formed on a glass fiber sheet in addition to a chevrel compound and a glass frit.
  • Example 7 In order to investigate the influence of the solid base material on the semiconductor characteristics, the solar cell elements of Example 5 and Example 6 were stored in a thermostat at 85 ° C. for 50 days, and the change in conversion efficiency was examined. As a result, there was almost no difference between the two characteristics. As a result, none of the alkaline earth metals (Mg powder and Ca powder) used as the solid base material adversely affect the characteristics of the semiconductor (CdTeCdS) in the solar cell element. Was confirmed. ⁇ Example 7 >>
  • FIG. 1 shows a schematic sectional view.
  • a glass substrate 1 75 ⁇ 75 mm, thickness 1.2 mm
  • a transparent conductive film 2 made of tin oxide (conductivity; about 10 QZ cm 2 , light transmittance; 98%) was formed.
  • the CdS layer 3 with a thickness of 800 angstroms is heated and decomposed by heating the cadmium complex of ethyl dithiolate at 350 ° C for 1 minute on a borosilicate glass plate). Formed.
  • a CdTe layer 4 having a thickness of 3 m was formed on the CdS layer 3 by a proximity sublimation method.
  • an average particle size of 1 O A solid content consisting of 85 wt% of OeSe powder and 15 wt% of glass powder having an average particle size of 15 m (melting point: 450 ° C), and a mixture of ethylene glycol monobutyl ether and a weight of 3: 1.
  • a paste prepared by mixing at a specific ratio was applied. This was dried at 150 ° C. to form a chevrel compound layer 13 having a thickness of 5 ⁇ . This chevrel compound layer 13 is heated from 400 ° C.
  • Example 9 The method of forming the chevrel compound layer was the same as that of Example 7, except that a copper angstrom compound layer having a thickness of 100 ⁇ was formed by sputtering evaporation instead of the coating and drying methods of Example 7. Solar cell element Made. ⁇ Example 9 >>
  • Example 7 Various solar cells were prepared in the same manner as in Example 7, except that the following chevrel compound to which 35 ppm copper powder was added as a dopant material was used instead of the copper chevrel compound used in Example 7.
  • a battery element was manufactured.
  • Example ? In each of Nos. 9 to 9 and Comparative Example 2, 10 solar cell elements were manufactured for each type. The total amount of Cd contained in each of the five solar cell elements was quantified by chemical analysis. The remaining five solar cell elements were subjected to a heating test in the same manner as in Example 1, and in the same manner as in Example 1, (A) a molten glass substrate of the solar cell element after the heating test. , The weight percentage of Cd contained in the residue other than the glass substrate (B), and the weight percentage of Cd in the exhaust gas (C) were determined for each case. The results are shown in Table 1. Table 1
  • Example 7 the contents of Te and Ag as heavy metal components other than Cd measured in the above heating test were measured.
  • the weight of Te in the solar cell element before the heating test was set to 100 wt%
  • Example 7 15.8 wt% was contained in the molten glass substrate after the heating test.
  • 83.6 wt% of Te was detected in the residue other than, and 0.6 wt% of Te was detected in the exhaust gas.
  • the solar cell element of Comparative Example 2 17.2 wt% was contained in the molten glass substrate after combustion, 12.4 wt% in the residue other than the glass substrate, and 72.4 wt% in the exhaust gas. 0.4 wt% of Te was detected. Further, when the Ag weight in the solar cell element before the heating test was 10 O wt%, in Example 7, 6.8 wt% in the molten glass substrate after burning, During the survey, 82.7 wt% of 8 g was detected in the exhaust gas and 0.5 wt% in the exhaust gas.
  • FIG. 6 shows a schematic cross-sectional drawing of the fabricated solar cell element.
  • 31 is a p-type Si layer
  • 32 is an n-type Si layer
  • 33 is a one-side lead electrode made of lead solder
  • 41 is a + side lead electrode made of lead solder
  • 34 Is a chevrel compound layer.
  • the chevrel compound layer 34 is made of Cu in the same manner as in Example 7. .
  • Reference numeral 35 denotes a front glass substrate made of borosilicate glass
  • 36 denotes a back glass plate made of borosilicate glass, with a glass spacer 37 interposed and a translucent EVA resin 38 inside. Filled.
  • Reference numeral 39 denotes a positive electrode terminal
  • reference numeral 40 denotes a single electrode terminal, which are connected to the positive electrode 41 and the negative electrode 33, respectively.
  • Example 3 A solar cell element was produced in the same manner as in Example 10 except that the chevrel compound layer 34 was not formed.
  • the same heating test as in Example 1 was performed, and the state of lead emission was examined by chemical analysis.
  • the Pb weight in the solar cell element before the test was 10 O wt%
  • Example 10 14.6 wt% was contained in the molten glass substrate after the heating test.
  • 85 wt% of lead was detected in the residue other than the glass substrate, and 0.4 wt% of lead was detected in the exhaust gas.
  • the solar cell module of the present invention is capable of exposing heavy metal elements contained in a solar cell element to the outside when exposed to high temperatures due to fire or the like, or when damaged and exposed to rainwater. Emission can be prevented.
  • n-type CdTe and GaAs are used as n-type semiconductors.

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Abstract

L'invention concerne un module de cellule solaire comportant des cellules solaires contenant des éléments de métaux lourds. Lesdites cellules contiennent notamment un matériau capable de capturer des éléments de métaux lourds, de préférence au moins un composé de Chevrel et des fibres de verre. Plus précisément, la couche de fibres de verre couvre pratiquement tous les côtés avant et arrière des cellules solaires. De préférence, elle est collée aux cellules solaires par du plastique. La couche de fibres de verre porte de la fritte de verre et/ou un composé de Chevrel et, de préférence, une base phase solide. Dans un autre mode de réalisation, le module de cellule solaire peut être constitué d'un composé de Chevrel posé sur une couche CdTe en tant que couche de semi-conducteur de type p.
PCT/JP2000/004935 1999-07-29 2000-07-24 Module de cellule solaire WO2001009959A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP21590999A JP3535774B2 (ja) 1999-07-29 1999-07-29 太陽電池
JP21591099 1999-07-29
JP11/215910 1999-07-29
JP11215908A JP2001044457A (ja) 1999-07-29 1999-07-29 光電変換素子および太陽電池
JP11/215909 1999-07-29
JP11/215908 1999-07-29
JP2000/93788 2000-03-30
JP2000093788 2000-03-30

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11450778B2 (en) * 2016-05-31 2022-09-20 First Solar, Inc. Ag-doped photovoltaic devices and method of making

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01315966A (ja) * 1988-06-16 1989-12-20 Matsushita Electric Ind Co Ltd 光電池
JPH09116180A (ja) * 1995-10-20 1997-05-02 Kanegafuchi Chem Ind Co Ltd 半導体装置
JPH09148595A (ja) * 1995-11-28 1997-06-06 Matsushita Electric Ind Co Ltd 光電変換素子
JPH09191116A (ja) * 1996-01-10 1997-07-22 Canon Inc 太陽電池モジュール

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01315966A (ja) * 1988-06-16 1989-12-20 Matsushita Electric Ind Co Ltd 光電池
JPH09116180A (ja) * 1995-10-20 1997-05-02 Kanegafuchi Chem Ind Co Ltd 半導体装置
JPH09148595A (ja) * 1995-11-28 1997-06-06 Matsushita Electric Ind Co Ltd 光電変換素子
JPH09191116A (ja) * 1996-01-10 1997-07-22 Canon Inc 太陽電池モジュール

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11450778B2 (en) * 2016-05-31 2022-09-20 First Solar, Inc. Ag-doped photovoltaic devices and method of making

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