WO2008102457A1 - Method of recovering constituent member of cis type thin-film solar cell module - Google Patents

Method of recovering constituent member of cis type thin-film solar cell module Download PDF

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Publication number
WO2008102457A1
WO2008102457A1 PCT/JP2007/053848 JP2007053848W WO2008102457A1 WO 2008102457 A1 WO2008102457 A1 WO 2008102457A1 JP 2007053848 W JP2007053848 W JP 2007053848W WO 2008102457 A1 WO2008102457 A1 WO 2008102457A1
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WO
WIPO (PCT)
Prior art keywords
solar cell
film solar
type thin
cis type
cell module
Prior art date
Application number
PCT/JP2007/053848
Other languages
French (fr)
Inventor
Katsumi Kushiya
Tadashi Okazawa
Original Assignee
Showa Shell Sekiyu K. K.
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Publication date
Application filed by Showa Shell Sekiyu K. K. filed Critical Showa Shell Sekiyu K. K.
Priority to PCT/JP2007/053848 priority Critical patent/WO2008102457A1/en
Publication of WO2008102457A1 publication Critical patent/WO2008102457A1/en

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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
    • H01L31/0248—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 characterised by their semiconductor bodies
    • H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • 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
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • 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
    • Y02E10/541—CuInSe2 material PV cells
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/82—Recycling of waste of electrical or electronic equipment [WEEE]

Definitions

  • the present invention relates to a method of recovering constituent members of a CIS type thin-film solar cell module constituted of hetero-junction thin-film solar cells employing a multinary compound semiconductor thin film as a light absorption layer.
  • a used or discarded CIS type light absorption layer and a glass substrate coated with a molybdenum film are used as an anode and a cathode, respectively, and the voltage to be applied is varied.
  • the copper, indium, and selenium constituting the CIS type light absorption layer dissolve in the electrolytic solution when voltages respectively corresponding thereto are applied, and a Cu-In-Se alloy layer serving as a metallic precursor necessary for the formation of a CIS type light absorption layer can be formed on the molybdenum-coated glass substrate as the cathode.
  • a CIS type thin-film solar cell module of the substrate structure constituted of a cover glass as a sunlight incidence part, a sealing material (functioning as an adhesive) such as, e.g., an EVA resin, a window layer, a buffer layer, a CIS type light absorption layer, a metallic back electrode layer, and a glass substrate is used as a starting material.
  • the CIS type thin-film solar cell device part (the window layer, buffer layer, CIS type light absorption layer, metallic back electrode layer, and glass substrate) is first separated by amethod inwhich the structure including the cover glass disposed through the sealing material is fixed onto a heating plate (e.g., hot plate) and heated at a temperature in the range of 130-160 0 C to soften the sealing material and the cover glass is pushed in a horizontal direction to thereby mechanically separate the cover glass from the CIS type thin-film solar cell device part.
  • the cover glass is recycled as a raw glass material.
  • the window layer and buffer layer of the CIS type thin-film solar cell device part separated are dissolved in acetic acid, and the resultant solution is reused in a buffer layer formation step.
  • the CIS type light absorption layer is recovered as a metal powder from the remaining structure comprising the CIS type light absorption layer, metallic back electrode layer, and glass substrate by the mechanical scraping method.
  • the metallic back electrode layer is dissolved away with nitric acid from the residual structure comprising the metallic back electrode layer and the glass substrate, and the metal is recovered from the nitric acid solution.
  • the glass substrate remaining is reused.
  • This method disclosed is a method in which constituent members, in particular, the CIS type light absorption layer, which is regarded as most valuable, are independently recovered.
  • Non-Patent Document 1 R.E. Goozner, et al . , Proc. r 26th IEEE Photovoltaic Specialist Conference (1997), pp.1161-1163
  • Non-Patent Document 2 S. Menezes, Proc. 2nd World Conference on Photovoltaic Energy Conversion (1998) , pp.597-600
  • An object of the invention which is for eliminating the problems described above, is to use a CIS type thin-film solar cell module, as a starting material, in which use of cadmium in the buffer layer in the CIS type thin-film solar cell device part has been eliminated and the solder material used in the electrode parts does not contain lead and to easily recover constituent members of the module by simple low-cost processing techniques suitable for the materials of the constituent members to thereby contribute to the formation of an environmentally friendly community.
  • the invention provides a method of recovering constituent members of a CIS type thin-film solar cell modulei ⁇ , wherein a structure comprises: a CIS type thin-film solar cell device part comprising a glass substrate and, superposed thereon in the following order, a metallic back electrode layer, a light absorption layer, a buffer layer, and a window layer; a cover glass ' ; and a plastic resin adhesive which bonds the device part to the cover glass and is made of a crosslinked EVAresin or the like, and the structure is heated at a temperature of 500 0 C or lower to burn the plastic resin adhesive and thereby separate the CIS type thin-film solar cell device part from the cover glass.
  • the invention provides the method of recovering constituent members of a CIS type thin-film solar cell module according to the above (1), wherein the structure is heated in a closedheating ovenhaving atmosphericpressure and equipped with a discharge gas treatment apparatus at a temperature lower than the temperature at which the light absorption layer was formed or the structure is heated in the oven at a temperature not lower than the formation temperature for the light absorption layer for a short time period of up to several minutes in which the light absorption layer does not change in composition.
  • the invention provides the method of recovering constituent members of a CIS type thin-film solar cell module according to the above (I)/ wherein the structure is heated in a closed heating oven equipped with a discharge gas treatment apparatus at a temperature in the range of 400-500 0 C.
  • the invention provides the method of recovering constituent members of a CIS type thin-film solar cell module according to the above (1) , wherein the plastic resin adhesive has a thickness in the range of 200-800 ⁇ m in terms of thickness before crosslinking.
  • the invention provides the method of recovering constituent members of a CIS type thin-film solar cell module according to any one of the above (1) to (4) , wherein the burned plastic resin adhesive, window layer, buffer layer, and light absorption layer are mechanically scraped off by the scraping method from the heated structure comprising the CIS type thin-film solar cell device part and the burned plastic resin adhesive to thereby recover a metal powder containing a slight amount of combustion products and the glass substrate having the metallic back electrode layer.
  • the invention provides the method of recovering constituent members of a CIS type thin-film solar cell module according to the above (5) , wherein the glass substrate having the metallic back electrode layer is treated with a sandblaster or a belt sander to thereby remove the metallic back electrode layer and recover the glass substrate.
  • the invention provides the method of recovering constituent members of a CIS type thin-film solar cell module according to any one of the above (1) to (6), which is for recovering constituted members from the CIS type thin-film solar cell module and which comprises recovering: the cover glass; a metal powder which is derived from the window layer, buffer layer, and light absorption layer, which are recovered from the CIS type thin-film solar cell device part and which a slight amount of combustion products derived from the burned plastic resin adhesive is adhered to the surface of; a metal powder derived from the metallic back electrode layer; and the glass substrate.
  • the invention provides the method of recovering constituent members of a CIS type thin-film solar cell module accordingto anyone of the above (1) to (7) , whereinapretreatment for removing peripheral members from the CIS type thin-film solar cell module is conducted to thereby take out a structure comprising the CIS type thin-film solar cell device part, the cover glass, and the plastic resin ' adhesive which bonds the device part to the cover glass and is made of an EVA resin or the like.
  • the invention provides the method of recovering constituent members of a CIS type thin-film solar cell module according to the above (8), wherein the peripheral members comprise a frame,- a sealing material, a connecting box having a cable, and a back sheet.
  • the invention provides the method of recovering constituent members of a CIS type thin-film solar cell module according to the above (9) , wherein the back sheet, which is used for securing electrical insulation on the back side of the glass substrate, has been bonded with the same EVA resin as that used for bonding the cover glass and, in this case, the back sheet is mechanically removed with a wire brush or the like.
  • the invention provides the method of recovering constituent members of a CIS type thin-film solar cell module according to any one of the above (8) to (10) , wherein an olefin-based plastic resin having higher removability than the EVA resin is used as an adhesive for bonding- the back sheet to the back side of the glass substrate to thereby facilitate the removal of the back sheet in processing for recycling.
  • a CIS type thin-film solar cell module in which use of cadmium in the buffer layer in a CIS type thin-film solar cell device part has been eliminated and the solder material used in the electrode parts does not contain lead is used as a starting material and constituent members of the module can be easily recovered by simple low-cost processing techniques suitable for the materials of the constituent members to thereby contribute to the formation of an environmentally friendly community.
  • the amount of industrial wastes to be generated can be reduced by easily recovering constituent members from a CIS type thin-film solar cell module product by simple low-cost processing techniques suitable for the materials of the constituent members.
  • an off-specification product yielded in the production of CIS type thin-film solar cell modules can be recovered and processed at low cost to thereby reduce the cost of industrial-waste treatments and the amount of industrial wastes to be generated and to reduce the cost of CIS type thin-film solar cell module productionbased on the reduction in the cost of industrial-waste treatments .
  • FIG. 1 is a flowchart showing processing steps in the method of the invention for recovering constituentmembers of a CIS type thin-film solar cell module.
  • FIG. 2 is a view illustrating the constitution of a CIS- type thin-film solar cell module to be processed by the method of the invention for recovering constituent members of a CIS type thin-film solar cell module.
  • Fig. 3 is a view illustrating the constitution of a structure comprising a CIS type thin-film solar cell device part and a cover glass bonded thereto with an EVA resin.
  • Fig. 4 is a view illustrating the constitution of the CIS type thin-film solar cell device part. Description of Reference Numerals and Signs
  • the invention relates to a method of recovering constituent members of a CIS type thin-film solar cell module, i.e., a method in which constituent members are recovered from a CIS type thin-film solar cell module.
  • the CIS type thin-film solar cell module 1 comprises hetero-junction thin-film solar cells shown in Fig. 2 which employ a multinary compound semiconductor thin film as a light absorption layer.
  • the module 1 is a CIS type thin-film solar cell module including a CIS type thin-film solar cell device part 2 whichhas a light absorption layermade of ap-type semiconductor such as a Cu-III-VI 2 Group chalcopyrite semiconductor, e.g., copper indium diselenide (CISe) , copper indium gallium diselenide (CIGSe) , copper indium gallium sulfide diselenide (CIGSSe) , or copper indium gallium disulfide (CIGS) , or copper indium gallium diselenide (CIGSe) having a thin layer of copper indium gallium sulfide diselenide (CIGSSe) as a surface layer and further has a pn hetero-junction.
  • ap-type semiconductor such as a Cu-III-VI 2 Group chalcopyrite semiconductor, e.g., copper indium diselenide (CISe) , copper indium gallium diselenide (CIGSe) ,
  • the CIS type thin-film solar cell module 1 has a constitution comprising: a structure ST formed by bonding a cover glass 4 to a CIS type thin-film solar cell device part 2 with a plastic resin 3, e.g., a crosslinked EVA resin, as an adhesive; a back sheet 5 and a connecting box 6 having a cable, the sheet 5 and the box 6 being disposed on the back side of the structure ST; and a frame 8 attached to the periphery of the structure ST through a sealing material 7.
  • a plastic resin 3 e.g., a crosslinked EVA resin
  • the CIS type thin-film solar cell device part 2 has a multilayer structure comprising a glass substrate 2A and, superposed thereon in the following order, a metallic back electrode layer 2B, a light absorption layer 2C made of a p-type semiconductor, a buffer layer 2D having high resistance, and a window layer 2E comprising an n-type transparent conductive film.
  • a pretreatment (P11-P15) for removing peripheral members including a frame 8, a sealing material 7, a connecting box 6 having a cable, and a back sheet 5 from a CIS type thin-film solar cellmodule 1 is conducted.
  • a structure ST comprising a CIS type thin-film solar cell device part 2 and a cover glass 4 bonded thereto with a plastic resin 3, e.g., an EVA resin, serving as an adhesive as shown in Fig. 3 is taken out.
  • the following steps are conducted in the following order; detaching the frame 8 from the CIS type thin-film solar cell module 1, PIl; removing the sealing material 7, P12; detaching the connecting box 6 having a cable, Pl3; removing the back sheet 5, P14, by, e.g. , mechanical scraping with a wire brush in the case where the adhesive used is an EVA resin or stripping in the case where the adhesive used is an olefin-based plastic resin; and stripping off a bus bar (copper ribbon), P15.
  • constituent members including the frame 8, sealing material 7, connecting box 6 having a cable, back sheet 5, and bus bar (copper ribbon) are recovered in this pretreatment.
  • the structure ST shown in Fig. 3 is heated in a heating oven at a temperature of 500 0 C or lower, desirably at a temperature in the range of 400-500 0 C, to burn the EVA resin 3.
  • This heating (by which the resin is mostly decomposed/eliminated and is deprived of its adhesive force) enables the cover glass 4 to be easily removable from the CIS type thin-film solar cell device part 2.
  • the cover glass 4 is separated from the structure ST and recovered (P2) . Since the burning of the EVA resin 3 generates a combustion gas, the heating oven to be used is a closed one equipped with a discharge gas treatment apparatus.
  • a specific technique for the heating comprises heating the structure ST at atmospheric pressure at a temperature lower than the temperature at which the light absorption layer was formed or comprises heating the structure ST at atmospheric pressure at a temperature not lower than the formation temperature for the light absorption layer for a short period of up to several minutes in which the light absorption layer does not change in composition.
  • the EVA resin 3 (plastic resin adhesive) has a thickness in the range of 200-800 ⁇ m, desirably 400-600 ⁇ m, in terms of thickness before crosslinking.
  • the burned plastic resin 3, e.g., burned EVA resin, window layer 2E, buffer layer 2D, and light absorption layer 2C are scraped off in this order from the CIS type thin-film solar cell device part 2 by the scraping method (P3) .
  • a metal powder is recovered which comprises a slight amount of combustion products (products of combustion of the plastic resin, e.g., the EVA resin 3) and the materials of the window layer 2E, buffer layer 2D, and light absorption layer 2C.
  • the metallic back electrode layer 2B is removed with a sandblaster, belt sander, or the like (P4) . s a result, the glass substrate 2A and a metal powder, derived from the metallic back electrode layer 2B are recovered (P5) .
  • peripheral members can be separated and recovered by the pretreatment from the CIS type thin-film solar cell module 1 by a simple low-cost technique .
  • the structure ST comprising the CIS " type thin-film solar cell device part 2 and the cover glass 4 bonded thereto with a plastic resin 3, e.g., a crosslinked EVA resin, is subjected to heating/burning, which is a simple low-costprocessing technique suitable for the materials thereof, whereby the cover glass 4 can be separated and recovered.
  • a plastic resin 3 e.g., a crosslinked EVA resin
  • the burned plastic resin 3, e.g., burned EVA resin, window layer 2E, buffer layer 2D, and light absorption layer 2C can be separated and recovered from the CIS type thin-film solar cell device part 2 by the scraping method, which is a simple low-cost processing technique suitable for the materials thereof.
  • the metallic back electrode layer 2B can be separated and recovered with a sandblaster, belt sander, or the like, use of which is a simple low-cost processing technique suitable for the material thereof, and the remaining glass substrate 2A can be recovered.
  • the method of the invention for recovering constituent members of a CIS type thin-film solar cell module can easily separate and recover the members constituting the CIS type thin-film solar cell module 1 by simple low-cost processing techniques suitable for the materials thereof.
  • the method of the invention is expected to attain a processing cost reduction to or below 1/5 the cost of the method of processing for recycling described is patent document 1.
  • a CIS type thin-film solar cell module in which use of cadmium in the buffer layer in a CIS type thin-film solar cell device part has been eliminated and the solder material used in the electrode parts does not contain lead is used as a starting material and constituent members of the module can be easily recovered by simple low-cost processing techniques suitable for the materials of the constituent members to thereby contribute to the formation of an environmentally friendly community.
  • the amount of industrial wastes to be generated can be reduced by easily recovering constituent members from, a CIS type thin-film solar cell module product by simple low-cost processing techniques suitable for the materials of the constituent members.
  • an off-specification product yielded in the production of CIS type thin-film solar cell modules can be recovered and processed at low cost to thereby reduce the cost of industrial-waste treatments and the amount of industrial wastes to be generated and to reduce the cost of CIS type thin-film solar cell module productionbased on the reduction in the cost of industrial-waste treatments .

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  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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  • Photovoltaic Devices (AREA)

Abstract

The object of the present invention is to recover constituent members by simple low-cost processing techniques suitable for the materials thereof to thereby reduce the amount of wastes and reduce production cost. A CIS type thin-film solar cell module 1 is subjected to a pretreatment (P11-P15) for removing peripheral members therefrom to thereby take out a structure ST comprising a solar cell device part 2 and a cover glass 4 bonded thereto with an adhesive resin 3. The structure ST is heated to burn the adhesive resin 3 to separate the cover glass 4 from the structure ST (P2). A window layer 2E, a buffer layer 2D, and a light absorption layer 2C are scraped off from the device part 2 (P3). Furthermore, a metallic back electrode layer 2B is removed (P3) to take out a glass substrate 2A.

Description

DESCRIPTION
METHOD OF RECOVERING CONSTITUENT MEMBER OF CIS TYPE THIN-FILM SOLAR CELL MODULE
Technical Field
The present invention relates to a method of recovering constituent members of a CIS type thin-film solar cell module constituted of hetero-junction thin-film solar cells employing a multinary compound semiconductor thin film as a light absorption layer.
Background Art
The CIS type thin-film solar cells were regarded as practically usable extensively and have recently been commercialized in the United States and Germany. In Japan, performance enhancement and production technique developments are being promoted enthusiastically. However, investigations from the standpoint of resource recycling are very few because it is only a short time since the CIS type thin-film solar cell modules were put on themarket andbecause off-specification products and the like are generally discarded as industrial wastes. Furthermore, there also are very few investigations on a method for effectively processing and recovering, not as a waste but as a resource, the modules which will be discarded after life expiration in the future. Under these circumstances, there are an extremely small number of publications/reports on a research/development concerning a method of recovering constituent members from an off-specification product yielded in steps for producing the modules . Namely, only three reports (two of which were written by the same person) have been published so far, which relate to an investigation utilizing an electrochemical reaction (i.e., electrodeposition method). These reports each are on an investigation on a sample having a small area, and there is a statement therein to the effect that the technique can be practiced on a pilot plant scale for commercialization. However, these are not an investigation concerning the processing of a module of a practical product size .
Two of the reports on an investigation utilizing an electrochemical reaction each are one concerning dissolution with an acid and metal recovery by the electrodeposition method. It is not a technique for recycling from a CIS type thin-film solar cell module but a method of the electrochemical recovery and reuse of metals constituting the light absorption layer of a CIS type thin-film solar cell device part.
In the first investigation, all metals (copper, indium, selenium, zinc, and other metals) constituting a CIS type thin-film solar cell of the superstrate structure are dissolved in a nitric acid solution as shown in non-patent document 1. That the CIS type thin-film solar cell to be processed in this investigation is not of the general substrate structure but of the superstrate structure, on which only a limit number of investigations have been made, can be easily presumed from the facts that the procedure does not include the separation of a cover glass, that the amount of cadmium recovered is large, which indicates that the CdS buffer layer is thick, and that the glass substrate is a glass coated with a transparent conductive SnO2 film. There is a statement in this report to the effect that metals can be recovered in two stages by the electroplating method from the nitric acid solution containing constituent metals dissolved therein, using a suitably selected electrode material and a suitably selected direct current. Namely, an alloy of copper and selenium is recovered in the first stage and cadmium is recovered in the second stage each on the cathode. On the other hand, zinc and indium remain in the nitric acid solution. The copper and selenium deposited on the cathode electrode are recovered after having been converted to CuO and SeO, respectively, by an oxidation treatment . The residual solution containing zinc and indium and oxides (ZnO and InO) are expected to be sold to a nonferrous metal refining manufacturer. There also is a statement therein to the effect that the residual solution containing zinc and indium can be further treated by, e.g., solvent extraction.
The second investigation is shown in non-patent document 2. A closed-loop electrochemical approach applicable to the recycling of a CIS type thin-film solar cell module is proposed therein because of the following reasons given therein: since the amount of metals contained in thin-film solar cells constituted of glass, plastics, and metals is generally as small as 0.05 wt% or below, which is an exceedingly slight proportion in the whole module, existing heavy-metal recovery methods are impracticable; and demolition also is improper because it results only in an increased waste amount. In this investigation, the matter to be processed is not a CIS type thin-film solar cell module, and the recovery of metals from a CIS type light absorption layer and the reuse thereof are investigated. Namely, the following technique is proposed. A used or discarded CIS type light absorption layer and a glass substrate coated with a molybdenum film are used as an anode and a cathode, respectively, and the voltage to be applied is varied. As a result, the copper, indium, and selenium constituting the CIS type light absorption layer dissolve in the electrolytic solution when voltages respectively corresponding thereto are applied, and a Cu-In-Se alloy layer serving as a metallic precursor necessary for the formation of a CIS type light absorption layer can be formed on the molybdenum-coated glass substrate as the cathode. In view of the results reported, in which the range of applied voltages is wide and the composition range fluctuates widely, this technique by itself is unsuitable for the production of a CIS type light absorption layer, for which precise compositional control is necessary. That document hence proposes to regulate the composition of the electrolytic solution so as to produce a CIS type light absorption layer having a constant composition.
To realize this proposal necessitates the quantitative analysis of trace metals andmeans to obtain high-precision determination results and supply necessary metals as a solution in an acid to the electrolytic solution. It is not easy to use this method to establish a process for producing a solar cell which is required to have a low cost and be produced at a high rate.
Furthermore, there is a statement in that document to the effect that the method necessitates an annealing step for producing a CIS type light absorption layer from the Cu-In-Se alloy layer serving as a metallic precursor and recovered on the cathode.
The two documents on investigations shown above each disclose an electrochemical theory or idea concerning a method for electrochemically dissolving a CIS type light absorption layer in a solution and depositing constituent metals and the deposition of a Cu-In-Se alloy layer which serves as a metallic precursor and is on a level where the layer is not usable as the light absorption layer of a CIS type thin-film solar cell. Namely, those documents do not disclose a method of processing as a closed system beginning with the processing of a CIS type thin-film solar cell module as a starting material and ending with the recovery and reuse of useful constituent materials, but report an investigation concerning recovery only from a CIS type light absorption layer. The contents thereof are limited to discussions about the dissolution of the layer and recovery therefrom. No specific investigation is made therein on the recovery/reuse of other constituent materials, and only a theory/method is proposed therein.
An example of methods for recovering constituent materials of a CIS type thin-film solar cell module is disclosed in patent document 1, which is a document on a patent application made previously by the present applicant . The contents thereof are as follows. A CIS type thin-film solar cell module of the substrate structure constituted of a cover glass as a sunlight incidence part, a sealing material (functioning as an adhesive) such as, e.g., an EVA resin, a window layer, a buffer layer, a CIS type light absorption layer, a metallic back electrode layer, and a glass substrate is used as a starting material. After peripheral members are removed from the module, the CIS type thin-film solar cell device part (the window layer, buffer layer, CIS type light absorption layer, metallic back electrode layer, and glass substrate) is first separated by amethod inwhich the structure including the cover glass disposed through the sealing material is fixed onto a heating plate (e.g., hot plate) and heated at a temperature in the range of 130-1600C to soften the sealing material and the cover glass is pushed in a horizontal direction to thereby mechanically separate the cover glass from the CIS type thin-film solar cell device part. The cover glass is recycled as a raw glass material. Thereafter, the window layer and buffer layer of the CIS type thin-film solar cell device part separated are dissolved in acetic acid, and the resultant solution is reused in a buffer layer formation step. Furthermore, the CIS type light absorption layer is recovered as a metal powder from the remaining structure comprising the CIS type light absorption layer, metallic back electrode layer, and glass substrate by the mechanical scraping method. The metallic back electrode layer is dissolved away with nitric acid from the residual structure comprising the metallic back electrode layer and the glass substrate, and the metal is recovered from the nitric acid solution. The glass substrate remaining is reused. This method disclosed is a method in which constituent members, in particular, the CIS type light absorption layer, which is regarded as most valuable, are independently recovered. However, before and after the recovery of the light absorption layer, it is necessary to conduct, e.g., processing for removing/recovering the window layer and buffer layer and processing for removing/recovering the metallic back electrode layer. Since various chemicals are used in large amounts, the chemical cost is high and it is necessary to conduct waste-chemical treatments, etc. The method has had a drawback that it is in an exceedingly costly processing method.
In recent several years, researches and developments for the commercialization of CIS type thin-film solar cell modules have progressed and the modules are coming to be on the market although in small quantities. Furthermore, an attempt to eliminate in principle the use of constituent materials imposing a heavy burden on the environment, such as cadmium and lead, in solar cells has been positively proposed and the elimination has come to be practices. However,- the techniques for the recycling of a CIS type thin-film solar cell module which have been published so far are intended to be used for the recovery of a CIS type light absorption layer only. The discussions therein are limited to ones about electrochemical techniques concerning the dissolution of the layer and deposition. The recycling techniques proposed so far do not provide a method of constituent-part recovery in which a CIS type thin-film solar cell module itself is used as a starting material. [Non-Patent Document 1] R.E. Goozner, et al . , Proc. r 26th IEEE Photovoltaic Specialist Conference (1997), pp.1161-1163
[Non-Patent Document 2] S. Menezes, Proc. 2nd World Conference on Photovoltaic Energy Conversion (1998) , pp.597-600
[Patent Document 1] JP-A-2004-186547
Disclosure of the Invention
An object of the invention, which is for eliminating the problems described above, is to use a CIS type thin-film solar cell module, as a starting material, in which use of cadmium in the buffer layer in the CIS type thin-film solar cell device part has been eliminated and the solder material used in the electrode parts does not contain lead and to easily recover constituent members of the module by simple low-cost processing techniques suitable for the materials of the constituent members to thereby contribute to the formation of an environmentally friendly community.
Another object of the invention is to easily recover constituent members from a CIS type thin-film solar cell module product by simple low-cost processing techniques suitable for the materials of the constituent members to thereby reduce the amount of industrial wastes to be generated. Still another object of the invention is to recover and process at low cost an off-specification product yielded in the production of CIS type thin-film solar cell modules to thereby reduce the cost of industrial-waste treatments and the amount of industrial wastes to be generated and to reduce the cost of CIS type thin-film solar cell module production based on the reduction in the cost of industrial-waste treatments.
(1) The invention provides a method of recovering constituent members of a CIS type thin-film solar cell moduleiα, wherein a structure comprises: a CIS type thin-film solar cell device part comprising a glass substrate and, superposed thereon in the following order, a metallic back electrode layer, a light absorption layer, a buffer layer, and a window layer; a cover glass'; and a plastic resin adhesive which bonds the device part to the cover glass and is made of a crosslinked EVAresin or the like, and the structure is heated at a temperature of 5000C or lower to burn the plastic resin adhesive and thereby separate the CIS type thin-film solar cell device part from the cover glass.
(2) The invention provides the method of recovering constituent members of a CIS type thin-film solar cell module according to the above (1), wherein the structure is heated in a closedheating ovenhaving atmosphericpressure and equipped with a discharge gas treatment apparatus at a temperature lower than the temperature at which the light absorption layer was formed or the structure is heated in the oven at a temperature not lower than the formation temperature for the light absorption layer for a short time period of up to several minutes in which the light absorption layer does not change in composition.
(3) The invention provides the method of recovering constituent members of a CIS type thin-film solar cell module according to the above (I)/ wherein the structure is heated in a closed heating oven equipped with a discharge gas treatment apparatus at a temperature in the range of 400-5000C.
(4) The invention provides the method of recovering constituent members of a CIS type thin-film solar cell module according to the above (1) , wherein the plastic resin adhesive has a thickness in the range of 200-800 μm in terms of thickness before crosslinking.
(5) The invention provides the method of recovering constituent members of a CIS type thin-film solar cell module according to any one of the above (1) to (4) , wherein the burned plastic resin adhesive, window layer, buffer layer, and light absorption layer are mechanically scraped off by the scraping method from the heated structure comprising the CIS type thin-film solar cell device part and the burned plastic resin adhesive to thereby recover a metal powder containing a slight amount of combustion products and the glass substrate having the metallic back electrode layer.
(6) The invention provides the method of recovering constituent members of a CIS type thin-film solar cell module according to the above (5) , wherein the glass substrate having the metallic back electrode layer is treated with a sandblaster or a belt sander to thereby remove the metallic back electrode layer and recover the glass substrate.
(7) The invention provides the method of recovering constituent members of a CIS type thin-film solar cell module according to any one of the above (1) to (6), which is for recovering constituted members from the CIS type thin-film solar cell module and which comprises recovering: the cover glass; a metal powder which is derived from the window layer, buffer layer, and light absorption layer, which are recovered from the CIS type thin-film solar cell device part and which a slight amount of combustion products derived from the burned plastic resin adhesive is adhered to the surface of; a metal powder derived from the metallic back electrode layer; and the glass substrate.
(8) The invention provides the method of recovering constituent members of a CIS type thin-film solar cell module accordingto anyone of the above (1) to (7) , whereinapretreatment for removing peripheral members from the CIS type thin-film solar cell module is conducted to thereby take out a structure comprising the CIS type thin-film solar cell device part, the cover glass, and the plastic resin 'adhesive which bonds the device part to the cover glass and is made of an EVA resin or the like.
(9) The invention provides the method of recovering constituent members of a CIS type thin-film solar cell module according to the above (8), wherein the peripheral members comprise a frame,- a sealing material, a connecting box having a cable, and a back sheet.
(10) The invention provides the method of recovering constituent members of a CIS type thin-film solar cell module according to the above (9) , wherein the back sheet, which is used for securing electrical insulation on the back side of the glass substrate, has been bonded with the same EVA resin as that used for bonding the cover glass and, in this case, the back sheet is mechanically removed with a wire brush or the like.
(11) The invention provides the method of recovering constituent members of a CIS type thin-film solar cell module according to any one of the above (8) to (10) , wherein an olefin-based plastic resin having higher removability than the EVA resin is used as an adhesive for bonding- the back sheet to the back side of the glass substrate to thereby facilitate the removal of the back sheet in processing for recycling.
According to the invention, a CIS type thin-film solar cell module in which use of cadmium in the buffer layer in a CIS type thin-film solar cell device part has been eliminated and the solder material used in the electrode parts does not contain lead is used as a starting material and constituent members of the module can be easily recovered by simple low-cost processing techniques suitable for the materials of the constituent members to thereby contribute to the formation of an environmentally friendly community.
Furthermore, according to the invention, the amount of industrial wastes to be generated can be reduced by easily recovering constituent members from a CIS type thin-film solar cell module product by simple low-cost processing techniques suitable for the materials of the constituent members. Moreover, according to the invention, an off-specification product yielded in the production of CIS type thin-film solar cell modules can be recovered and processed at low cost to thereby reduce the cost of industrial-waste treatments and the amount of industrial wastes to be generated and to reduce the cost of CIS type thin-film solar cell module productionbased on the reduction in the cost of industrial-waste treatments .
Brief Description of the Drawings
[Fig. 1] Fig. 1 is a flowchart showing processing steps in the method of the invention for recovering constituentmembers of a CIS type thin-film solar cell module.
[Fig. 2] Fig. 2 is a view illustrating the constitution of a CIS- type thin-film solar cell module to be processed by the method of the invention for recovering constituent members of a CIS type thin-film solar cell module.
[Fig. 3] Fig. 3 is a view illustrating the constitution of a structure comprising a CIS type thin-film solar cell device part and a cover glass bonded thereto with an EVA resin.
[Fig. 4] Fig. 4 is a view illustrating the constitution of the CIS type thin-film solar cell device part. Description of Reference Numerals and Signs
1 CIS type thin-film solar cell module
2 CIS type thin-film solar cell device part 2A glass substrate
2B metallic back electrode layer
2C p-type light absorption layer
2D n-type buffer layer having high resistance
2E n-type window layer (transparent conductive film)
3 EVA resin (adhesive)
3A CIS type thin-film solar cell device excluding glass substrate
4 cover glass ST structure
5 back sheet
6 connecting box having cable
7 sealing material
8 frame
PIl detachment of frame 8 from CIS type thin-film solar cell module 1
P12 removal of sealing material 7
Pl3 detachment of connecting box 6 having cable
P14 removal of back sheet 5
P15 stripping of bus bar (copper ribbon)
P2 burning of EVA resin 3 in heating oven and separation of cover glass 4 P3 scraping of window layer 2E, buffer layer 2D, and light absorption layer 2C from CIS type thin-film solar cell device part 2 by scraping method
P4 removal ofmetallic back electrode layer 2B (withsandblaster, belt sander, etc.)
P5 glass substrate 2A remains
Best Mode for Carrying Out the Invention
Embodiments of the invention' will be explained below.
The invention relates to a method of recovering constituent members of a CIS type thin-film solar cell module, i.e., a method in which constituent members are recovered from a CIS type thin-film solar cell module. The CIS type thin-film solar cell module 1 comprises hetero-junction thin-film solar cells shown in Fig. 2 which employ a multinary compound semiconductor thin film as a light absorption layer. In • particular, the module 1 is a CIS type thin-film solar cell module including a CIS type thin-film solar cell device part 2 whichhas a light absorption layermade of ap-type semiconductor such as a Cu-III-VI2 Group chalcopyrite semiconductor, e.g., copper indium diselenide (CISe) , copper indium gallium diselenide (CIGSe) , copper indium gallium sulfide diselenide (CIGSSe) , or copper indium gallium disulfide (CIGS) , or copper indium gallium diselenide (CIGSe) having a thin layer of copper indium gallium sulfide diselenide (CIGSSe) as a surface layer and further has a pn hetero-junction. As shown in Fig. 2 and Fig. 3, the CIS type thin-film solar cell module 1 has a constitution comprising: a structure ST formed by bonding a cover glass 4 to a CIS type thin-film solar cell device part 2 with a plastic resin 3, e.g., a crosslinked EVA resin, as an adhesive; a back sheet 5 and a connecting box 6 having a cable, the sheet 5 and the box 6 being disposed on the back side of the structure ST; and a frame 8 attached to the periphery of the structure ST through a sealing material 7.
As shown in Fig. 4, the CIS type thin-film solar cell device part 2 has a multilayer structure comprising a glass substrate 2A and, superposed thereon in the following order, a metallic back electrode layer 2B, a light absorption layer 2C made of a p-type semiconductor, a buffer layer 2D having high resistance, and a window layer 2E comprising an n-type transparent conductive film.
The method of the invention for recovering constituent members of a CIS type thin-filmsolar cellmodulewill be explained below.
First, a pretreatment (P11-P15) for removing peripheral members including a frame 8, a sealing material 7, a connecting box 6 having a cable, and a back sheet 5 from a CIS type thin-film solar cellmodule 1 is conducted. Thus, a structure ST comprising a CIS type thin-film solar cell device part 2 and a cover glass 4 bonded thereto with a plastic resin 3, e.g., an EVA resin, serving as an adhesive as shown in Fig. 3 is taken out.
In the pretreatment, the following steps are conducted in the following order; detaching the frame 8 from the CIS type thin-film solar cell module 1, PIl; removing the sealing material 7, P12; detaching the connecting box 6 having a cable, Pl3; removing the back sheet 5, P14, by, e.g. , mechanical scraping with a wire brush in the case where the adhesive used is an EVA resin or stripping in the case where the adhesive used is an olefin-based plastic resin; and stripping off a bus bar (copper ribbon), P15. As a result, constituent members including the frame 8, sealing material 7, connecting box 6 having a cable, back sheet 5, and bus bar (copper ribbon) are recovered in this pretreatment.
Subsequently, the structure ST shown in Fig. 3 is heated in a heating oven at a temperature of 5000C or lower, desirably at a temperature in the range of 400-5000C, to burn the EVA resin 3. This heating (by which the resin is mostly decomposed/eliminated and is deprived of its adhesive force) enables the cover glass 4 to be easily removable from the CIS type thin-film solar cell device part 2. Thereafter, the cover glass 4 is separated from the structure ST and recovered (P2) . Since the burning of the EVA resin 3 generates a combustion gas, the heating oven to be used is a closed one equipped with a discharge gas treatment apparatus. A specific technique for the heating comprises heating the structure ST at atmospheric pressure at a temperature lower than the temperature at which the light absorption layer was formed or comprises heating the structure ST at atmospheric pressure at a temperature not lower than the formation temperature for the light absorption layer for a short period of up to several minutes in which the light absorption layer does not change in composition. The EVA resin 3 (plastic resin adhesive) has a thickness in the range of 200-800 μm, desirably 400-600 μm, in terms of thickness before crosslinking.
Thereafter, the burned plastic resin 3, e.g., burned EVA resin, window layer 2E, buffer layer 2D, and light absorption layer 2C are scraped off in this order from the CIS type thin-film solar cell device part 2 by the scraping method (P3) . As a result, a metal powder is recovered which comprises a slight amount of combustion products (products of combustion of the plastic resin, e.g., the EVA resin 3) and the materials of the window layer 2E, buffer layer 2D, and light absorption layer 2C.
Subsequently, the metallic back electrode layer 2B is removed with a sandblaster, belt sander, or the like (P4) . s a result, the glass substrate 2A and a metal powder, derived from the metallic back electrode layer 2B are recovered (P5) .
As described above, according to the method of the invention for recovering constituent members of a CIS type thin-film solar cell module, peripheral members can be separated and recovered by the pretreatment from the CIS type thin-film solar cell module 1 by a simple low-cost technique . Thereafter, the structure ST comprising the CIS "type thin-film solar cell device part 2 and the cover glass 4 bonded thereto with a plastic resin 3, e.g., a crosslinked EVA resin, is subjected to heating/burning, which is a simple low-costprocessing technique suitable for the materials thereof, whereby the cover glass 4 can be separated and recovered. Furthermore, the burned plastic resin 3, e.g., burned EVA resin, window layer 2E, buffer layer 2D, and light absorption layer 2C can be separated and recovered from the CIS type thin-film solar cell device part 2 by the scraping method, which is a simple low-cost processing technique suitable for the materials thereof. Moreover, the metallic back electrode layer 2B can be separated and recovered with a sandblaster, belt sander, or the like, use of which is a simple low-cost processing technique suitable for the material thereof, and the remaining glass substrate 2A can be recovered. As a result, the method of the invention for recovering constituent members of a CIS type thin-film solar cell module can easily separate and recover the members constituting the CIS type thin-film solar cell module 1 by simple low-cost processing techniques suitable for the materials thereof. The method of the invention is expected to attain a processing cost reduction to or below 1/5 the cost of the method of processing for recycling described is patent document 1.
While the invention has been described in detail and with reference to specific examples thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
The present application is based on Japanese Patent Application No. 2005-245918 filed on August 26, 2005, and the contents are incorporated herein by reference.
Industrial Applicability
According to the invention, a CIS type thin-film solar cell module in which use of cadmium in the buffer layer in a CIS type thin-film solar cell device part has been eliminated and the solder material used in the electrode parts does not contain lead is used as a starting material and constituent members of the module can be easily recovered by simple low-cost processing techniques suitable for the materials of the constituent members to thereby contribute to the formation of an environmentally friendly community.
Furthermore, according to the invention, the amount of industrial wastes to be generated can be reduced by easily recovering constituent members from, a CIS type thin-film solar cell module product by simple low-cost processing techniques suitable for the materials of the constituent members.
Moreover, according to the invention, an off-specification product yielded in the production of CIS type thin-film solar cell modules can be recovered and processed at low cost to thereby reduce the cost of industrial-waste treatments and the amount of industrial wastes to be generated and to reduce the cost of CIS type thin-film solar cell module productionbased on the reduction in the cost of industrial-waste treatments .

Claims

1. A method of recovering constituent members of a CIS type thin-film solar cell module, wherein a structure comprises : a CIS type thin-film solar cell device part comprising a glass substrate and, superposed thereon in the following order, a metallic back electrode layer, a light absorption layer, a buffer layer, and a window layer, a cover glass, and a plastic resin adhesive which bonds the device part to the cover glass and is made of a crosslinked EVA resin or the like, and the structure is heated at a temperature of 5000C or lower to burn the plastic resin adhesive and thereby separate the CIS type thin-film solar cell device part from the cover glass.
2. The method of recovering constituent members of a CIS type thin-film solar cell module according to claim 1, wherein the structure is heated in a closed heating oven having atmospheric pressure and equipped with a discharge gas treatment apparatus at a temperature lower than the temperature at which the light absorption layer was formed, or the structure is heated in the oven at a temperature not lower than the formation temperature for the light absorption layer for a short time period of up to several minutes in which the light absorption layer does not change in composition.
3. The method of recovering constituent members of a CIS type thin-film solar cell module according to claim 1, wherein the structure is heated in a closed heating oven equipped with a discharge gas treatment apparatus at a temperature in the range of 400-5000C.
4. The method of recovering constituent members of a CIS type thin-film solar cell module according to claim 1, wherein the plastic resin adhesive has a thickness in the range of 200-800 μm in terms of thickness before crosslinking.
5. The method of recovering constituent members of a CIS type thin-film solar cell module according to any one of claims 1 to 4, wherein the burned plastic resin adhesive, window layer, buffer layer, and light absorption layer are mechanically scraped off by the scraping method from the heated structure comprising the CIS type thin-film solar cell device part and the burned plastic resin adhesive to thereby recover a metal powder containing a slight amount of combustion products and the glass substrate having the metallic back electrode layer.
6. The method of recovering constituent members of a CIS type thin-film solar cell module according to claim 5, wherein the glass substrate having the metallic back electrode layer is treated with a sandblaster or a belt sander to thereby remove the metallic back electrode layer and recover the glass substrate.
7. The method of recovering constituent members of a CIS type thin-film solar cell module according to any one of claims 1 to 6, which is for recovering constituted members fromthe CIS type thin-filmsolar cell module and is characterized by recovering: the cover glass; a metal powder which is, derived from the window layer, buffer layer, and light absorption layer, which are recovered from the CIS type thin-film solar cell device part and which a slight amount of combustion products derived from- the burned plastic resin adhesive is adhered to the surface of;' a metal powder derived from the metallic back electrode layer; and the glass substrate.
8. The method of recovering constituent members of a CIS type thin-film solar cell module according to any one of claims 1 to 7, wherein a pretreatment for removing peripheral members from the CIS type thin-film solar cell module is conducted to thereby take out a structure comprising the CIS type thin-film solar cell device part, the cover glass, and the plastic resin adhesive which bonds the device part to the cover glass and is made of an EVA resin or the like.
9. The method of recovering constituent members of a CIS type thin-film solar cell module according to claim 8, wherein the peripheral members comprise a frame, a sealing material, a connecting box having a cable, and a back sheet.
10. The method of recovering constituent members of a CIS type thin-film solar cell module according to claim 9, characterized in that the back sheet, which is used for securing electrical insulation on the back side of the glass substrate, has been bonded with the same EVA resin as that used for bonding the cover glass and, in this case, the back sheet is mechanically removed with a wire brush or the like.
11. The method of recovering constituent members of a CIS type thin-film solar cell module according to any one of claims 8 to 10, wherein an olefin-based plastic resin having higher removability than the EVA resin is used as an adhesive for bonding the back sheet to the back side of the glass substrate to thereby facilitate the removal of the back sheet inprocessing for recycling.
PCT/JP2007/053848 2007-02-22 2007-02-22 Method of recovering constituent member of cis type thin-film solar cell module WO2008102457A1 (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013089630A1 (en) * 2011-12-15 2013-06-20 Midsummer Ab Recycling of copper indium gallium diselenide
CN104201248A (en) * 2014-09-12 2014-12-10 成都科莱斯低温设备有限公司 Recovery method of thin-film solar cells
EP2998038A1 (en) * 2014-09-16 2016-03-23 SASIL S.p.A. Method and apparatus for detaching glass form a mono- or polycrystalline silicon-based photovoltaic panel
CN108666394A (en) * 2018-07-20 2018-10-16 北京铂阳顶荣光伏科技有限公司 A kind of hull cell reworking method and hull cell processing procedure rework system
CN108831995A (en) * 2018-06-08 2018-11-16 汉能新材料科技有限公司 The separation method of organic layer in a kind of flexible unit
IT202000024277A1 (en) * 2020-10-14 2022-04-14 9 Tech S R L PLANT AND APPARATUS METHOD FOR THE RECYCLING OF PHOTOVOLTAIC PANELS

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020030035A1 (en) * 2000-09-11 2002-03-14 Manuel Dieguez Process for recycling CdTe/Cds thin film solar cell modules
JP2004186547A (en) * 2002-12-05 2004-07-02 Showa Shell Sekiyu Kk Method for recovering component of cis thin-film solar cell module
WO2006068234A1 (en) * 2004-12-22 2006-06-29 Showa Shell Sekiyu K.K. Cis based thin film solar cell module, method for producing the same, and method for separating solar cell module

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020030035A1 (en) * 2000-09-11 2002-03-14 Manuel Dieguez Process for recycling CdTe/Cds thin film solar cell modules
JP2004186547A (en) * 2002-12-05 2004-07-02 Showa Shell Sekiyu Kk Method for recovering component of cis thin-film solar cell module
WO2006068234A1 (en) * 2004-12-22 2006-06-29 Showa Shell Sekiyu K.K. Cis based thin film solar cell module, method for producing the same, and method for separating solar cell module
EP1830411A1 (en) * 2004-12-22 2007-09-05 Showa Shell Sekiyu Kabushiki Kaisha Cis based thin film solar cell module, method for producing the same, and method for separating solar cell module

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013089630A1 (en) * 2011-12-15 2013-06-20 Midsummer Ab Recycling of copper indium gallium diselenide
JP2015508375A (en) * 2011-12-15 2015-03-19 ミッドサマー・アーベー Recycling of copper indium gallium diselenide
EP2791054A4 (en) * 2011-12-15 2016-03-09 Midsummer Ab Recycling of copper indium gallium diselenide
CN104201248A (en) * 2014-09-12 2014-12-10 成都科莱斯低温设备有限公司 Recovery method of thin-film solar cells
EP2998038A1 (en) * 2014-09-16 2016-03-23 SASIL S.p.A. Method and apparatus for detaching glass form a mono- or polycrystalline silicon-based photovoltaic panel
CN108831995A (en) * 2018-06-08 2018-11-16 汉能新材料科技有限公司 The separation method of organic layer in a kind of flexible unit
CN108666394A (en) * 2018-07-20 2018-10-16 北京铂阳顶荣光伏科技有限公司 A kind of hull cell reworking method and hull cell processing procedure rework system
IT202000024277A1 (en) * 2020-10-14 2022-04-14 9 Tech S R L PLANT AND APPARATUS METHOD FOR THE RECYCLING OF PHOTOVOLTAIC PANELS
EP3989296A1 (en) * 2020-10-14 2022-04-27 9-Tech S.r.l. Method, plant and apparatus for recycling photovoltaic panels

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