WO2013038889A1 - Solar cell interconnector material, solar cell interconnector, and solar cell with interconnector - Google Patents

Solar cell interconnector material, solar cell interconnector, and solar cell with interconnector Download PDF

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WO2013038889A1
WO2013038889A1 PCT/JP2012/071411 JP2012071411W WO2013038889A1 WO 2013038889 A1 WO2013038889 A1 WO 2013038889A1 JP 2012071411 W JP2012071411 W JP 2012071411W WO 2013038889 A1 WO2013038889 A1 WO 2013038889A1
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Prior art keywords
solar cell
interconnector
layer
plating layer
plating
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PCT/JP2012/071411
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French (fr)
Japanese (ja)
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稔也 津田
友森　龍夫
興 吉岡
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東洋鋼鈑株式会社
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Priority to KR1020147009313A priority Critical patent/KR101968788B1/en
Priority to CN201280045102.4A priority patent/CN103814157B/en
Publication of WO2013038889A1 publication Critical patent/WO2013038889A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/12—Semiconductors
    • C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
    • C25D7/126—Semiconductors first coated with a seed layer or a conductive layer for solar cells
    • 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
    • H01L31/05—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells
    • H01L31/0504—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells specially adapted for series or parallel connection of solar cells in a module
    • H01L31/0512—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells specially adapted for series or parallel connection of solar cells in a module made of a particular material or composition of materials
    • 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 interconnector material, a solar cell interconnector, and a solar cell with an interconnector.
  • the solar cell interconnector is a wiring material that plays a role of collecting electrical energy converted mainly by the solar cells by connecting the solar cells made of crystalline Si.
  • a solder-coated rectangular copper wire obtained by coating a rectangular copper wire with solder hot dipping has been used as an interconnector material for such a solar cell.
  • solder-coated flat copper wire is used as an interconnector material for solar cells
  • Patent Document 1 proposes an interconnector material for a solar cell in which a flat aluminum substrate is subjected to copper plating and coated with solder hot dipping.
  • a flat aluminum substrate is subjected to copper plating, since copper is expensive, a cheaper interconnector material that does not use copper is required.
  • the present invention has been made in view of such a situation, and its purpose is substantially free of copper and is relatively inexpensive, and the occurrence of defects such as cracking and peeling of the film due to the thermal history of soldering.
  • An object of the present invention is to provide a solar cell interconnector material and a solar cell interconnector that are effectively prevented.
  • Another object of the present invention is to provide a solar cell with an interconnector obtained by using such an interconnector for solar cells.
  • the present inventors have found that the above problems can be solved by a solar cell interconnector material having a Ni plating layer having a thickness of 0.2 ⁇ m or more and an Sn plating layer in order from the substrate side on the Al substrate surface.
  • the present invention has been completed.
  • an interconnector material for a solar cell which has a Ni plating layer and a Sn plating layer having a thickness of 0.2 ⁇ m or more in order from the substrate side on the surface of the Al substrate. Is done.
  • the present invention it is obtained by forming a solder layer on the surface of the Sn plating layer of the interconnector material for solar cell, and the Sn—Ni alloy layer is sequentially formed on the surface of the Al substrate from the substrate side.
  • an interconnector for a solar cell characterized by having a solder layer.
  • the Sn—Ni alloy layer is formed by causing diffusion in the Ni plating layer and the Sn plating layer by heat at the time of forming the solder layer.
  • the ratio of the Ni strength of the Sn—Ni alloy layer when analyzed by high-frequency glow discharge optical emission spectrometry to the Ni strength of the Ni plating layer before thermal diffusion is “Ni strength of Sn—Ni alloy layer”. / Ni strength of Ni plating layer before thermal diffusion "is preferably 0.15 or more.
  • the Sn—Ni alloy layer is continuously formed so as to cover the surface of the Al base.
  • a solar battery cell with an interconnector wherein any one of the above solar battery interconnectors is connected to a solar battery cell.
  • the solar battery interconnector and the solar battery cell are connected by soldering.
  • the present invention it is not necessary to substantially use copper, so that it is relatively inexpensive, and the occurrence of defects such as cracking and peeling of the film due to the thermal history of soldering is effectively prevented.
  • the interconnector material for solar cells, the interconnector for solar cells, and the solar cell with an interconnector obtained using such an interconnector for solar cells can be provided.
  • FIG. 1 is a diagram showing a configuration of a solar cell interconnector material 100 according to the present embodiment.
  • FIG. 2 is a diagram showing a configuration of the solar cell interconnector 200 according to the present embodiment.
  • FIG. 3 is a diagram showing a configuration of a solar cell interconnector 200a in which the thickness of the Ni plating layer 20 before thermal diffusion is less than 0.2 ⁇ m.
  • 4A is a cross-sectional photograph of the solar cell interconnector sample of Example 2
  • FIG. 4B is a cross-sectional photograph of the solar cell interconnector sample of Comparative Example 1.
  • FIG. 1 is a diagram showing a configuration of a solar cell interconnector material 100 according to the present embodiment.
  • FIG. 2 is a diagram showing a configuration of the solar cell interconnector 200 according to the present embodiment.
  • FIG. 3 is a diagram showing a configuration of a solar cell interconnector 200a in which the thickness of the Ni plating layer 20 before thermal diffusion is less than 0.2 ⁇ m.
  • FIG. 1 is a diagram showing a configuration of a solar cell interconnector material 100 according to the present embodiment. As shown in FIG. 1, the solar cell interconnector material 100 according to this embodiment is formed by forming a Ni plating layer 20 and a Sn plating layer 30 on both surfaces of an Al base 10 in this order.
  • the aluminum plate constituting the Al base 10 is not particularly limited, and a pure aluminum plate or any JIS standard 1000 series, 2000 series, 3000 series, 5000 series, 6000 series, or 7000 series aluminum alloy sheet is used. Among them, a 1000 series O material is particularly preferable.
  • the thickness of the Al base 10 is not particularly limited, and may be a thickness that can secure sufficient conductivity as a solar cell interconnector, but is preferably 0.1 to 0.5 mm.
  • the Ni plating layer 20 is formed by performing nickel plating on the Al base material 10.
  • the method for forming the Ni plating layer 20 on the Al base 10 is not particularly limited, but it is difficult to directly provide the Ni plating layer on the Al surface, so the Zn layer is formed in advance by displacement plating. After that, a Ni plating layer is preferably formed thereon.
  • a method for forming a Zn layer as the underlayer will be described.
  • a pure aluminum plate or an aluminum alloy plate constituting the Al base 10 is subjected to a degreasing process, and then subjected to acidic etching and smut removal, followed by Zn substitution plating.
  • the substitution plating of Zn is performed through the steps of nitric acid immersion treatment, first Zn substitution treatment, zinc nitrate stripping treatment, and second Zn substitution treatment.
  • the water washing process is implemented after the process of each process.
  • the Zn layer formed by the first Zn substitution treatment and the second Zn substitution treatment is slightly dissolved when Ni plating is performed.
  • the Zn layer is desirably formed so that the coating amount in the state after Ni plating is preferably in the range of 5 to 500 mg / m 2 , more preferably in the range of 30 to 300 mg / m 2 .
  • the coating amount of the Zn layer can be adjusted by appropriately selecting the concentration of Zn ions in the treatment liquid and the time for immersion in the treatment liquid in the second Zn substitution treatment.
  • the Ni plating layer 20 is formed by performing Ni plating on the Zn layer as the base layer.
  • the Ni plating layer 20 may be formed using any plating method of electroplating or electroless plating.
  • the thickness of the Ni plating layer 20 is 0.2 ⁇ m or more, preferably 0.2 to 3.0 ⁇ m, more preferably 0.5 to 2.0 ⁇ m.
  • the Sn plating layer 30 is formed by heat generated when the solder layer is formed. And a Ni—Sn alloy layer by diffusion.
  • the Sn plating layer 30 is formed on the Ni plating layer 20 by performing Sn plating.
  • the Sn plating layer 30 may be formed using any plating method of electroplating or electroless plating.
  • the thickness of the Sn plating layer 30 is preferably 0.5 to 3.0 ⁇ m. When the thickness of the Sn plating layer 30 is too thin, solder wettability at the time of forming the solder layer on the Sn plating layer 30 is lowered, and it becomes difficult to form a good solder layer. On the other hand, if the Sn plating layer 30 is too thick, the effect of improving the solder wettability by increasing the thickness is saturated, which is disadvantageous in terms of cost.
  • FIG. 2 is a diagram showing a configuration of the solar cell interconnector 200 according to the present embodiment.
  • the solar cell interconnector 200 according to the present embodiment uses the solar cell interconnector material 100 shown in FIG. 1 and forms the solder layer 50 on the Sn plating layer 30 of the solar cell interconnector material 100. As shown in FIG. 2, an Sn—Ni alloy layer 40 and a solder layer 50 are formed in this order on both surfaces of the Al base 10.
  • the solder layer 50 can be formed by performing molten solder plating on the Sn plating layer 30 constituting the interconnector material 100 for a solar cell shown in FIG.
  • the Ni plating layer constituting the solar cell interconnector material 100 shown in FIG. 1 is formed by forming the solder layer 50 by hot-dip solder plating and by heat when the solder layer 50 is formed.
  • the Sn—Ni alloy layer 40 is formed below the solder layer 50 as shown in FIG.
  • the bath temperature of the molten solder plating when forming the solder layer 50 is preferably 140 to 300 ° C., more preferably 180 to 250 ° C. Further, the immersion time in performing the molten solder plating is preferably 3 to 15 seconds. If the bath temperature of the molten solder plating is too low, or if the immersion time when performing the molten solder plating is too short, the formation of the solder layer 50 becomes insufficient, while the bath temperature of the molten solder plating is too high. In the case where the immersion time in performing the molten solder plating is too long, the Sn component contained in the solder layer 50 diffuses to the Al base material 10, and solid solution hardening occurs between Al and Sn. May occur, and the Sn—Ni alloy layer 40 may be cracked or peeled off.
  • the thickness of the solder layer 50 is not particularly limited, but is preferably 10 to 30 ⁇ m, more preferably 15 to 30 ⁇ m.
  • the Sn—Ni alloy layer 40 is diffused between the Ni plating layer 20 and the Sn plating layer 30 constituting the solar cell interconnector material 100 shown in FIG. 1 when the solder layer 50 is formed.
  • the thickness of the Ni plating layer 20 before thermal diffusion that constitutes the Sn—Ni alloy layer 40 is 0.2 ⁇ m or more, preferably 0.2 to 3.0 ⁇ m, more preferably 0.5. Since the thickness is set to ⁇ 2.0 ⁇ m, the Sn—Ni alloy layer 40 after thermal diffusion can be continuously formed so as to cover the surface of the Al base 10. That is, the Sn—Ni alloy layer 40 after thermal diffusion can be formed in such a manner that there is no break.
  • An interrupted portion 41 is generated in the layer 40a.
  • the interrupted portion 41 is generated, the adhesiveness between the Al base 10 and the Sn—Ni alloy layer 40a is deteriorated starting from the interrupted portion 41, and the Sn-Ni alloy layer 40a is not cracked.
  • a corrosive substance enters through a problem that peeling is likely to occur or a crack generated during processing or the like, a potential difference due to the corrosive substance is generated in the interrupted portion 41, and the corrosion proceeds. This will cause a malfunction.
  • the thickness of the Ni plating layer 20 before thermal diffusion that constitutes the Sn—Ni alloy layer 40 is set to 0.2 ⁇ m or more, so that Sn— The Ni alloy layer 40 can be continuously formed so as to cover the surface of the Al base 10, thereby effectively solving the above problem. If the thickness of the Ni plating layer 20 before thermal diffusion is too thick, the effect of increasing the thickness is saturated, which is disadvantageous in terms of cost.
  • the Ni intensity of the Sn—Ni alloy layer 40 when analyzed by the high-frequency glow discharge optical emission spectrometry is “Sn—Ni relative to the Ni intensity of the Ni plating layer 20 before thermal diffusion.
  • the ratio of “Ni strength of alloy layer 40 / Ni strength of Ni plating layer 20 before thermal diffusion” is preferably 0.15 or more, more preferably 0.18 or more, and further preferably 0.34 or more. .
  • the upper limit of the ratio is 1 or less.
  • the ratio of “Ni strength of Sn—Ni alloy layer 40 / Ni strength of Ni plating layer 20 before thermal diffusion” is too low, that is, the Ni content in the Sn—Ni alloy layer 40 is small and Sn content is low. If the ratio is too large, the Sn component in the Sn—Ni alloy layer 40 diffuses into the Al base 10 and solid solution hardening occurs between Al and Sn, and the Sn—Ni alloy layer 40 Cracking or peeling may occur.
  • Ni strength of Sn—Ni alloy layer 40 / Ni strength of Ni plating layer 20 before thermal diffusion is determined using, for example, a high-frequency glow discharge optical emission spectrometer. 40 and the Ni plating layer 20 before thermal diffusion were measured while sputtering with Ar plasma, and in the Sn—Ni alloy layer 40 and the Ni plating layer 20 before thermal diffusion, each of the portions with the highest Ni strength was measured. The data were respectively obtained as the Ni strength of the Sn—Ni alloy layer 40 and the Ni strength of the Ni plating layer 20 before thermal diffusion, and these were used to calculate “Ni strength of the Sn—Ni alloy layer 40 / before thermal diffusion”. The “Ni strength of the Ni plating layer 20” can be calculated.
  • the method of setting the ratio of “Ni strength of Sn—Ni alloy layer 40 / Ni strength of Ni plating layer 20 before thermal diffusion” in the above range is not particularly limited.
  • the thickness of the Ni plating layer 20 before thermal diffusion is set to 0.2 ⁇ m or more, and the bath temperature of the molten solder plating when forming the solder layer 50 and the immersion time when performing the molten solder plating are within the above-described ranges. And a method of controlling them.
  • the solar cell interconnector 200 is replaced with an Al-alloy 10 instead of a structure in which the Sn—Ni alloy layer 40 is directly formed.
  • a configuration in which the Sn—Ni alloy layer 40 is formed on the substrate 10 via the Ni plating layer 20 may be employed.
  • the bath temperature of the molten solder plating when the solder layer 50 is formed, and the immersion time when performing the molten solder plating the Ni plating layer 20 is entered.
  • the Sn component does not completely diffuse. Therefore, in such a case, the Ni plating layer 20 remains between the Al base 10 and the Sn—Ni alloy layer 40.
  • the solar cell interconnector 200 of the present embodiment is formed by diffusion between the Ni plating layer having a thickness of 0.2 ⁇ m or more and the Sn plating layer 30 due to heat when the solder layer 50 is formed. Since the Sn—Ni alloy layer 40 is provided, it is possible to effectively prevent the occurrence of defects such as cracking and peeling of the Sn—Ni alloy layer 40 due to the thermal history of soldering. Moreover, the solar cell interconnector 200 of the present embodiment does not substantially contain copper, and is therefore relatively inexpensive and advantageous in terms of cost.
  • the solar cell with an interconnector obtained by connecting the solar cell interconnector 200 and the solar cell by soldering using the solar cell interconnector 200 of the present embodiment is good in quality. Moreover, it is also excellent in cost.
  • the Sn—Ni alloy layer 40 and the solder layer 50 are formed on both surfaces of a long Al plate (coil) according to the above-described method. Those formed in this order can be obtained by slitting them to the required width. In the solar cell interconnector 200 thus obtained, the Sn—Ni alloy layer 40 and the solder layer 50 are formed on the upper and lower surfaces, while the surface forming the thickness direction (slit surface) The Sn—Ni alloy layer 40 and the solder layer 50 are not formed.
  • the solar cell interconnector 200 of the present embodiment can be obtained, for example, by forming the Sn—Ni alloy layer 40 and the solder layer 50 on the entire surface of the flat Al wire according to the above-described method. it can.
  • the obtained solar cell interconnector 200 does not go through the slit process unlike the above-described method, and therefore, the interconnector described in Patent Document 1 (Japanese Patent Laid-Open No. 2006-49666) described above is used.
  • the Sn—Ni alloy layer 40 and the solder layer 50 are formed on both the upper and lower surfaces and the surface forming the thickness direction.
  • the size of the solar cell interconnector 200 according to this embodiment is not particularly limited, but the thickness is usually 0.1 to 0.7 mm, preferably 0.1 to 0.5 mm, and the width is Usually, it is 0.5 to 10 mm, preferably 1 to 6 mm, and the length may be appropriately set according to the arrangement of solar cells and the like.
  • Example 1 As a material for forming the Al base 10, an A1100-based O material was prepared (thickness 0.3 mm, width 40 mm, length 120 mm). Then, the Al base material is degreased with an alkali solution, then etched in sulfuric acid, then desmutted in nitric acid, sodium hydroxide: 150 g / L, Rochelle salt: 50 g / L, oxidized The first Zn substitution treatment was performed by dipping in a treatment solution containing zinc: 25 g / L and ferrous chloride 1.5 g / L.
  • the Al base material subjected to the first Zn substitution treatment is immersed in a 400 g / L nitric acid aqueous solution to remove the deposited Zn, and then in the same treatment liquid as the treatment liquid used in the first Zn substitution treatment.
  • a Zn layer was formed on the Al substrate with a coating amount of 100 mg / m 2 by performing the second Zn substitution treatment by dipping for 10 seconds.
  • Ni plating layer 20 having a thickness of 0.2 ⁇ m on the Zn layer.
  • Bath composition nickel sulfate 250 g / L, nickel chloride 45 g / L, boric acid 30 g / L pH: 3-5
  • the solar cell interconnector material 100 was obtained.
  • Bath composition stannous sulfate 30 g / L, sulfuric acid 70 ml / L, appropriate amount of brightener and antioxidant pH: 1 to 2
  • the obtained solar cell interconnector material 100 is immersed in a molten solder plating bath made of Sn—Pb solder whose bath temperature is adjusted to 200 ° C. for 3 seconds to form a solder layer 50 having a thickness of 20 ⁇ m.
  • the solar cell interconnector 200 shown in FIG. 2 was manufactured.
  • the solar cell interconnector 200 manufactured in this example is the one before slitting, and the size is 40 mm in width and 120 mm in length. By slitting together with the arrangement of solar cells, etc., It can be suitably used as a solar cell interconnector.
  • the ratio of “Ni strength of Sn—Ni alloy layer 40 / Ni strength of Ni plating layer 20 before thermal diffusion” was measured by the following method. That is, first, using a high-frequency glow discharge emission spectroscopic analyzer (GDS-3860, manufactured by Rigaku Corporation), Sn-Ni alloy layer 40 and thermal diffusion under the conditions of high-frequency power: 40 W and photomultiplier voltage (Ni): 370 V. The previous Ni plating layer 20 was measured while sputtering with Ar plasma. Then, from the obtained measurement data, the peak value of each Ni intensity is obtained in the Sn—Ni alloy layer 40 and in the Ni plating layer 20 before thermal diffusion, and the respective Ni intensity of the Sn—Ni alloy layer 40 is obtained. As the strength and Ni strength of the Ni plating layer 20 before thermal diffusion, “Ni strength of the Sn—Ni alloy layer 40 / Ni strength of the Ni plating layer 20 before thermal diffusion” was calculated. The results are shown in Table 1.
  • the continuity of the Sn—Ni alloy layer 40 is determined by observing the cross section of the solar cell interconnector 200 with a field emission scanning electron microscope (FE-SEM) (JSM-6330F, manufactured by JEOL Ltd.). evaluated. As a result of observation with a field emission scanning electron microscope, a discontinuous portion as shown in FIG. 3, that is, a portion where the solder layer 50 is in direct contact with the surface of the Al base 10 (Al When the Ni content ratio is substantially zero on the surface of the base material 10), it is determined that the Sn—Ni alloy layer 40 has no continuity, and such a discontinuous portion is observed. If not, it was determined that the continuity of the Sn—Ni alloy layer 40 was “present”. The results are shown in Table 1.
  • Example 2 Except that the thickness of the Ni plating layer 20 was changed to 0.5 ⁇ m (Example 2), 1 ⁇ m (Example 3), and 1.5 ⁇ m (Example 4), respectively, The battery interconnector material 100 and the solar cell interconnector 200 were obtained and evaluated in the same manner. The results are shown in Table 1.
  • Example 5 The interconnector material for solar cells was the same as in Example 1 except that the temperature of the molten solder plating tank when forming the solder layer 50 was changed from 200 ° C. to 250 ° C. and the solder layer 50 was formed with a thickness of 20 ⁇ m. 100 and solar cell interconnector 200 were obtained and evaluated in the same manner. The results are shown in Table 1.
  • Example 6 In the same manner as in Example 5, except that the thickness of the Ni plating layer 20 was changed to 0.5 ⁇ m (Example 6), 1 ⁇ m (Example 7), and 1.5 ⁇ m (Example 8), respectively.
  • the battery interconnector material 100 and the solar cell interconnector 200 were obtained and evaluated in the same manner. The results are shown in Table 1.
  • FIG. 4 (A) shows a cross-sectional photograph of the solar cell interconnector sample of Example 2
  • FIG. 4 (B) shows a cross-sectional photograph of the solar battery interconnector sample of Comparative Example 1.
  • Example 2 there is no discontinuous portion in the Sn—Ni alloy layer 40, and the Sn—Ni alloy layer 40 is continuous so as to cover the surface of the Al base material 10. Can be confirmed.
  • Comparative Example 1 it can be confirmed that there is a discontinuity in the Sn—Ni alloy layer 40 and the Sn—Ni alloy layer 40 has no continuity.

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Abstract

Provided is a solar cell interconnector material characterized by having, on an Al substrate surface, a 0.2μm or thicker Ni plating layer, and a Sn plating layer, in that order from the substrate side. By means of this invention, it is possible to provide a solar cell interconnector material and a solar cell interconnector which are comparatively cheap while containing essentially no copper, and which effectively prevent problems such as peeling and cracking of coatings due to the thermal history of soldering.

Description

太陽電池用インターコネクタ材料、太陽電池用インターコネクタ、およびインターコネクタ付き太陽電池セルInterconnector material for solar cell, interconnector for solar cell, and solar cell with interconnector
　本発明は、太陽電池用インターコネクタ材料、太陽電池用インターコネクタ、およびインターコネクタ付き太陽電池セルに関する。 The present invention relates to a solar cell interconnector material, a solar cell interconnector, and a solar cell with an interconnector.
　太陽電池用インターコネクタは、主として、結晶Ｓｉからなる太陽電池セル間を繋ぎ、太陽電池セルが変換した電気エネルギーを集電する役割を果たす配線材である。近年、このような太陽電池用のインターコネクタ材として、平角銅線を、はんだ溶融めっきで被覆してなる、はんだ被覆平角銅線が使用されている。 The solar cell interconnector is a wiring material that plays a role of collecting electrical energy converted mainly by the solar cells by connecting the solar cells made of crystalline Si. In recent years, a solder-coated rectangular copper wire obtained by coating a rectangular copper wire with solder hot dipping has been used as an interconnector material for such a solar cell.
　しかしながら、このようなはんだ被覆平角銅線を、太陽電池用のインターコネクタ材として使用した場合には、次のような問題がある。すなわち、はんだ被覆平角銅線と、太陽電池セルとをはんだ付けにより接合した際における熱履歴により、はんだに含まれるＳｎが、平角銅線を構成するＣｕ内に拡散してしまい、Ｃｕ－Ｓｎの金属間化合物が生成してしまい、このようなＣｕ－Ｓｎの金属間化合物は脆く、そのため、カーケンダルボイド（空孔）の生成やクラックの原因となり、品質的に劣るという問題がある。 However, when such a solder-coated flat copper wire is used as an interconnector material for solar cells, there are the following problems. That is, Sn contained in the solder diffuses into Cu constituting the rectangular copper wire due to the thermal history when the solder-coated rectangular copper wire and the solar battery cell are joined by soldering, and Cu—Sn An intermetallic compound is generated, and such an intermetallic compound of Cu—Sn is brittle. Therefore, there is a problem that the generation of a Kirkendall void (hole) or a crack is caused, resulting in poor quality.
　これに対し、たとえば、特許文献１では、平角アルミ基材に、銅めっきを施し、これをはんだ溶融めっきで被覆してなる太陽電池用のインターコネクタ材が提案されている。一方で、この特許文献１では、平角アルミ基材に、銅めっきを施すものであるが、銅は高価であるため、銅を使用しない、より安価なインターコネクタ材が求められている。 On the other hand, for example, Patent Document 1 proposes an interconnector material for a solar cell in which a flat aluminum substrate is subjected to copper plating and coated with solder hot dipping. On the other hand, in this patent document 1, although a flat aluminum substrate is subjected to copper plating, since copper is expensive, a cheaper interconnector material that does not use copper is required.
特開２００６－４９６６６号公報JP 2006-49666 A
　本発明は、このような実状に鑑みてなされ、その目的は、銅を実質的に含有せず比較的安価であり、かつ、はんだ付けの熱履歴による、皮膜の割れや剥離などの不具合の発生が有効に防止された太陽電池用インターコネクタ材料、および太陽電池用インターコネクタを提供することにある。また、本発明は、このような太陽電池用インターコネクタを用いて得られるインターコネクタ付き太陽電池セルを提供することも目的とする。 The present invention has been made in view of such a situation, and its purpose is substantially free of copper and is relatively inexpensive, and the occurrence of defects such as cracking and peeling of the film due to the thermal history of soldering. An object of the present invention is to provide a solar cell interconnector material and a solar cell interconnector that are effectively prevented. Another object of the present invention is to provide a solar cell with an interconnector obtained by using such an interconnector for solar cells.
　本発明者等は、Ａｌ基材表面に、基材側から順に、０．２μｍ以上の厚みのＮｉめっき層、およびＳｎめっき層を有する太陽電池用インターコネクタ材料により、上記課題を解決できることを見出し、本発明を完成させるに至った。 The present inventors have found that the above problems can be solved by a solar cell interconnector material having a Ni plating layer having a thickness of 0.2 μm or more and an Sn plating layer in order from the substrate side on the Al substrate surface. The present invention has been completed.
　すなわち、本発明によれば、Ａｌ基材表面に、基材側から順に、０．２μｍ以上の厚みのＮｉめっき層、およびＳｎめっき層を有することを特徴とする太陽電池用インターコネクタ材料が提供される。 That is, according to the present invention, there is provided an interconnector material for a solar cell, which has a Ni plating layer and a Sn plating layer having a thickness of 0.2 μm or more in order from the substrate side on the surface of the Al substrate. Is done.
　また、本発明によれば、上記の太陽電池用インターコネクタ材料のＳｎめっき層の表面にはんだ層を形成することにより得られ、Ａｌ基材表面に、基材側から順に、Ｓｎ－Ｎｉ合金層、およびはんだ層を有することを特徴とする太陽電池用インターコネクタが提供される。
　本発明の太陽電池用インターコネクタにおいて、前記Ｓｎ－Ｎｉ合金層は、前記Ｎｉめっき層および前記Ｓｎめっき層に、前記はんだ層を形成する際における熱により拡散を起こさせることにより形成されたものであり、高周波グロー放電発光分光分析法により分析した際の前記Ｓｎ－Ｎｉ合金層のＮｉ強度と、熱拡散前の前記Ｎｉめっき層のＮｉ強度との比が、「Ｓｎ－Ｎｉ合金層のＮｉ強度／熱拡散前のＮｉめっき層のＮｉ強度」で、０．１５以上であることが好ましい。
　本発明の太陽電池用インターコネクタにおいて、前記Ｓｎ－Ｎｉ合金層が、前記Ａｌ基材表面を覆うように、連続的に形成されていることが好ましい。 In addition, according to the present invention, it is obtained by forming a solder layer on the surface of the Sn plating layer of the interconnector material for solar cell, and the Sn—Ni alloy layer is sequentially formed on the surface of the Al substrate from the substrate side. And an interconnector for a solar cell, characterized by having a solder layer.
In the solar cell interconnector of the present invention, the Sn—Ni alloy layer is formed by causing diffusion in the Ni plating layer and the Sn plating layer by heat at the time of forming the solder layer. Yes, the ratio of the Ni strength of the Sn—Ni alloy layer when analyzed by high-frequency glow discharge optical emission spectrometry to the Ni strength of the Ni plating layer before thermal diffusion is “Ni strength of Sn—Ni alloy layer”. / Ni strength of Ni plating layer before thermal diffusion "is preferably 0.15 or more.
In the interconnector for a solar cell of the present invention, it is preferable that the Sn—Ni alloy layer is continuously formed so as to cover the surface of the Al base.
　さらに、本発明によれば、上記いずれかの太陽電池用インターコネクタを太陽電池セルに接続してなることを特徴とするインターコネクタ付き太陽電池セルが提供される。
　本発明のインターコネクタ付き太陽電池セルにおいて、前記太陽電池用インターコネクタと前記太陽電池セルとが、はんだ付けに接続されていることが好ましい。 Furthermore, according to the present invention, there is provided a solar battery cell with an interconnector, wherein any one of the above solar battery interconnectors is connected to a solar battery cell.
In the solar battery cell with an interconnector of the present invention, it is preferable that the solar battery interconnector and the solar battery cell are connected by soldering.
　本発明によれば、銅を実質的に使用する必要が無く、そのため、比較的安価であり、しかも、はんだ付けの熱履歴による、皮膜の割れや剥離などの不具合の発生が有効に防止された太陽電池用インターコネクタ材料、および太陽電池用インターコネクタ、ならびに、このような太陽電池用インターコネクタを用いて得られるインターコネクタ付き太陽電池セルを提供することができる。 According to the present invention, it is not necessary to substantially use copper, so that it is relatively inexpensive, and the occurrence of defects such as cracking and peeling of the film due to the thermal history of soldering is effectively prevented. The interconnector material for solar cells, the interconnector for solar cells, and the solar cell with an interconnector obtained using such an interconnector for solar cells can be provided.
図１は、本実施形態に係る太陽電池用インターコネクタ材料１００の構成を示す図である。FIG. 1 is a diagram showing a configuration of a solar cell interconnector material 100 according to the present embodiment. 図２は、本実施形態に係る太陽電池用インターコネクタ２００の構成を示す図である。FIG. 2 is a diagram showing a configuration of the solar cell interconnector 200 according to the present embodiment. 図３は、熱拡散前のＮｉめっき層２０の厚みを０．２μｍ未満とした太陽電池用インターコネクタ２００ａの構成を示す図である。FIG. 3 is a diagram showing a configuration of a solar cell interconnector 200a in which the thickness of the Ni plating layer 20 before thermal diffusion is less than 0.2 μm. 図４（Ａ）は、実施例２の太陽電池用インターコネクタ試料の断面写真、図４（Ｂ）は、比較例１の太陽電池用インターコネクタ試料の断面写真である。4A is a cross-sectional photograph of the solar cell interconnector sample of Example 2, and FIG. 4B is a cross-sectional photograph of the solar cell interconnector sample of Comparative Example 1. FIG.
　以下、図面に基づいて、本発明の実施形態について説明する。 Hereinafter, embodiments of the present invention will be described with reference to the drawings.
＜太陽電池用インターコネクタ材料＞
　図１は、本実施形態に係る太陽電池用インターコネクタ材料１００の構成を示す図である。図１に示すように、本実施形態に係る太陽電池用インターコネクタ材料１００は、Ａｌ基材１０の両面に、Ｎｉめっき層２０、およびＳｎめっき層３０を、この順に形成されてなる。 <Interconnector materials for solar cells>
FIG. 1 is a diagram showing a configuration of a solar cell interconnector material 100 according to the present embodiment. As shown in FIG. 1, the solar cell interconnector material 100 according to this embodiment is formed by forming a Ni plating layer 20 and a Sn plating layer 30 on both surfaces of an Al base 10 in this order.
　Ａｌ基材１０を構成するアルミニウム板としては、特に限定されず、純アルミニウム板や、ＪＩＳ規格の１０００系、２０００系、３０００系、５０００系、６０００系、７０００系のいずれのアルミニウム合金板も用いることができるが、なかでも、１０００系のＯ材が特に好ましい。Ａｌ基材１０の厚みは、特に限定されず、太陽電池用インターコネクタとして十分な導電性が確保できるような厚みとすればよいが、好ましくは０．１～０．５ｍｍである。 The aluminum plate constituting the Al base 10 is not particularly limited, and a pure aluminum plate or any JIS standard 1000 series, 2000 series, 3000 series, 5000 series, 6000 series, or 7000 series aluminum alloy sheet is used. Among them, a 1000 series O material is particularly preferable. The thickness of the Al base 10 is not particularly limited, and may be a thickness that can secure sufficient conductivity as a solar cell interconnector, but is preferably 0.1 to 0.5 mm.
　Ｎｉめっき層２０は、Ａｌ基材１０上に、ニッケルめっきを施すことにより形成される。Ａｌ基材１０上に、Ｎｉめっき層２０を形成する方法としては、特に限定されないが、Ａｌ表面上に、Ｎｉめっき層を直接設けることは困難であるため、あらかじめ、Ｚｎ層を置換めっきによって形成した後、その上にＮｉめっき層を形成するのが好ましい。以下、下地層としてＺｎ層を形成する方法について、説明する。 The Ni plating layer 20 is formed by performing nickel plating on the Al base material 10. The method for forming the Ni plating layer 20 on the Al base 10 is not particularly limited, but it is difficult to directly provide the Ni plating layer on the Al surface, so the Zn layer is formed in advance by displacement plating. After that, a Ni plating layer is preferably formed thereon. Hereinafter, a method for forming a Zn layer as the underlayer will be described.
　まず、Ａｌ基材１０を構成する純アルミニウム板またはアルミニウム合金板について、脱脂処理を行ない、次いで、酸性エッチングおよびスマット除去を行った後、Ｚｎの置換めっきを行なう。Ｚｎの置換めっきは、硝酸浸漬処理、第一Ｚｎ置換処理、硝酸亜鉛剥離処理、第二Ｚｎ置換処理の各工程を経ることにより行なわれる。この場合、各工程の処理後には水洗処理を実施する。なお、第一Ｚｎ置換処理および第二Ｚｎ置換処理により形成されるＺｎ層は、Ｎｉめっきを施す際にわずかに溶解する。そのため、Ｚｎ層は、Ｎｉめっき後の状態における皮膜量が、好ましくは５～５００ｍｇ／ｍ２の範囲、より好ましくは３０～３００ｍｇ／ｍ２の範囲となるように形成することが望ましい。なお、Ｚｎ層の皮膜量は、処理液中のＺｎイオンの濃度および第二Ｚｎ置換処理において処理液中に浸漬する時間を適宜選択することで調整することができる。 First, a pure aluminum plate or an aluminum alloy plate constituting the Al base 10 is subjected to a degreasing process, and then subjected to acidic etching and smut removal, followed by Zn substitution plating. The substitution plating of Zn is performed through the steps of nitric acid immersion treatment, first Zn substitution treatment, zinc nitrate stripping treatment, and second Zn substitution treatment. In this case, the water washing process is implemented after the process of each process. The Zn layer formed by the first Zn substitution treatment and the second Zn substitution treatment is slightly dissolved when Ni plating is performed. Therefore, the Zn layer is desirably formed so that the coating amount in the state after Ni plating is preferably in the range of 5 to 500 mg / m 2 , more preferably in the range of 30 to 300 mg / m 2 . The coating amount of the Zn layer can be adjusted by appropriately selecting the concentration of Zn ions in the treatment liquid and the time for immersion in the treatment liquid in the second Zn substitution treatment.
　次いで、下地層としてのＺｎ層の上に、Ｎｉめっきを施すことで、Ｎｉめっき層２０を形成する。Ｎｉめっき層２０は、電気めっき法または無電解めっき法のいずれのめっき法を用いて形成してもよい。Ｎｉめっき層２０の厚みは、０．２μｍ以上であり、好ましくは０．２～３．０μｍ、より好ましくは０．５～２．０μｍである。Ｎｉめっき層２０は、後述するように、太陽電池用インターコネクタ材料１００を構成するＳｎめっき層３０上に、はんだ層を形成した際に、はんだ層を形成する際における熱により、Ｓｎめっき層３０と拡散することで、Ｎｉ－Ｓｎ合金層を形成することとなる層である。 Next, the Ni plating layer 20 is formed by performing Ni plating on the Zn layer as the base layer. The Ni plating layer 20 may be formed using any plating method of electroplating or electroless plating. The thickness of the Ni plating layer 20 is 0.2 μm or more, preferably 0.2 to 3.0 μm, more preferably 0.5 to 2.0 μm. As will be described later, when the Ni plating layer 20 is formed on the Sn plating layer 30 constituting the interconnector material 100 for a solar cell, the Sn plating layer 30 is formed by heat generated when the solder layer is formed. And a Ni—Sn alloy layer by diffusion.
　Ｓｎめっき層３０は、Ｎｉめっき層２０上に、Ｓｎめっきを行なうことにより形成される。Ｓｎめっき層３０は、電気めっき法または無電解めっき法のいずれのめっき法を用いて形成してもよい。Ｓｎめっき層３０の厚みは、好ましくは０．５～３．０μｍである。Ｓｎめっき層３０の厚みが薄すぎると、Ｓｎめっき層３０上にはんだ層を形成する際における、はんだ濡れ性が低下し、良好なはんだ層を形成し難くなる。一方、Ｓｎめっき層３０の厚みが厚すぎると、厚みを増加させることによる、はんだ濡れ性の向上効果が飽和してしまうため、コスト的に不利となる。 The Sn plating layer 30 is formed on the Ni plating layer 20 by performing Sn plating. The Sn plating layer 30 may be formed using any plating method of electroplating or electroless plating. The thickness of the Sn plating layer 30 is preferably 0.5 to 3.0 μm. When the thickness of the Sn plating layer 30 is too thin, solder wettability at the time of forming the solder layer on the Sn plating layer 30 is lowered, and it becomes difficult to form a good solder layer. On the other hand, if the Sn plating layer 30 is too thick, the effect of improving the solder wettability by increasing the thickness is saturated, which is disadvantageous in terms of cost.
＜太陽電池用インターコネクタ＞
　図２は、本実施形態に係る太陽電池用インターコネクタ２００の構成を示す図である。本実施形態に係る太陽電池用インターコネクタ２００は、図１に示す太陽電池用インターコネクタ材料１００を用い、太陽電池用インターコネクタ材料１００のＳｎめっき層３０上に、はんだ層５０を形成することにより製造され、図２に示すように、Ａｌ基材１０の両面に、Ｓｎ－Ｎｉ合金層４０、およびはんだ層５０を、この順に形成されてなる。 <Solar cell interconnector>
FIG. 2 is a diagram showing a configuration of the solar cell interconnector 200 according to the present embodiment. The solar cell interconnector 200 according to the present embodiment uses the solar cell interconnector material 100 shown in FIG. 1 and forms the solder layer 50 on the Sn plating layer 30 of the solar cell interconnector material 100. As shown in FIG. 2, an Sn—Ni alloy layer 40 and a solder layer 50 are formed in this order on both surfaces of the Al base 10.
　はんだ層５０は、図１に示す太陽電池用インターコネクタ材料１００を構成するＳｎめっき層３０上に、溶融はんだめっきを施すことにより形成することができる。なお、本実施形態においては、溶融はんだめっきにより、はんだ層５０を形成することにより、はんだ層５０を形成した際における熱により、図１に示す太陽電池用インターコネクタ材料１００を構成するＮｉめっき層２０とＳｎめっき層３０との間で拡散が起こり、これにより、図２に示すように、はんだ層５０の下に、Ｓｎ－Ｎｉ合金層４０が形成されることとなる。 The solder layer 50 can be formed by performing molten solder plating on the Sn plating layer 30 constituting the interconnector material 100 for a solar cell shown in FIG. In the present embodiment, the Ni plating layer constituting the solar cell interconnector material 100 shown in FIG. 1 is formed by forming the solder layer 50 by hot-dip solder plating and by heat when the solder layer 50 is formed. As a result, the Sn—Ni alloy layer 40 is formed below the solder layer 50 as shown in FIG.
　なお、はんだ層５０を形成する際における、溶融はんだめっきの浴温は、好ましくは１４０～３００℃であり、より好ましくは１８０～２５０℃である。また、溶融はんだめっきを行なう際にける浸漬時間は、好ましくは３～１５秒である。溶融はんだめっきの浴温が低すぎる場合や、溶融はんだめっきを行なう際にける浸漬時間が短すぎる場合には、はんだ層５０の形成が不十分となり、一方、溶融はんだめっきの浴温が高すぎる場合や、溶融はんだめっきを行なう際にける浸漬時間が長すぎる場合には、はんだ層５０に含まれるＳｎ成分が、Ａｌ基材１０まで拡散してしまい、ＡｌとＳｎとの間で固溶硬化が起こってしまい、Ｓｎ－Ｎｉ合金層４０の割れや、剥離が発生してしまう場合がある。 The bath temperature of the molten solder plating when forming the solder layer 50 is preferably 140 to 300 ° C., more preferably 180 to 250 ° C. Further, the immersion time in performing the molten solder plating is preferably 3 to 15 seconds. If the bath temperature of the molten solder plating is too low, or if the immersion time when performing the molten solder plating is too short, the formation of the solder layer 50 becomes insufficient, while the bath temperature of the molten solder plating is too high. In the case where the immersion time in performing the molten solder plating is too long, the Sn component contained in the solder layer 50 diffuses to the Al base material 10, and solid solution hardening occurs between Al and Sn. May occur, and the Sn—Ni alloy layer 40 may be cracked or peeled off.
　はんだ層５０の厚みは、特に限定されないが、好ましくは１０～３０μｍ、より好ましくは１５～３０μｍである。 The thickness of the solder layer 50 is not particularly limited, but is preferably 10 to 30 μm, more preferably 15 to 30 μm.
　Ｓｎ－Ｎｉ合金層４０は、上述したように、はんだ層５０を形成する際に、図１に示す太陽電池用インターコネクタ材料１００を構成するＮｉめっき層２０とＳｎめっき層３０との間で拡散が起こることにより形成される合金層である。本実施形態においては、Ｓｎ－Ｎｉ合金層４０を構成することとなる熱拡散前のＮｉめっき層２０の厚みを０．２μｍ以上、好ましくは０．２～３．０μｍ、より好ましくは０．５～２．０μｍとしているため、熱拡散後のＳｎ－Ｎｉ合金層４０を、Ａｌ基材１０の表面を覆うように、連続的に形成することができる。すなわち、熱拡散後のＳｎ－Ｎｉ合金層４０を途切れ部分の無いような態様で形成することができる。 As described above, the Sn—Ni alloy layer 40 is diffused between the Ni plating layer 20 and the Sn plating layer 30 constituting the solar cell interconnector material 100 shown in FIG. 1 when the solder layer 50 is formed. Is an alloy layer formed by the occurrence of In the present embodiment, the thickness of the Ni plating layer 20 before thermal diffusion that constitutes the Sn—Ni alloy layer 40 is 0.2 μm or more, preferably 0.2 to 3.0 μm, more preferably 0.5. Since the thickness is set to ˜2.0 μm, the Sn—Ni alloy layer 40 after thermal diffusion can be continuously formed so as to cover the surface of the Al base 10. That is, the Sn—Ni alloy layer 40 after thermal diffusion can be formed in such a manner that there is no break.
　一方で、熱拡散前のＮｉめっき層２０の厚みを０．２μｍ未満とした場合には、図３に示すように、はんだ層５０を形成した際に形成される熱拡散後のＳｎ－Ｎｉ合金層４０ａには、途切れ部分４１が発生してしまう。そして、途切れ部分４１が発生した場合には、この途切れ部分４１を起点として、Ａｌ基材１０とＳｎ－Ｎｉ合金層４０ａとの密着性が低下してしまい、Ｓｎ－Ｎｉ合金層４０ａの割れや剥離が生じやすくなるという不具合や、加工時等に発生したクラックを介して、腐食物が進入した場合に、この途切れ部分４１において腐食物に起因する電位差が生じてしまい、腐食が進行してしまうという不具合が生じてしまうこととなる。 On the other hand, when the thickness of the Ni plating layer 20 before thermal diffusion is less than 0.2 μm, the Sn—Ni alloy after thermal diffusion formed when the solder layer 50 is formed as shown in FIG. An interrupted portion 41 is generated in the layer 40a. When the interrupted portion 41 is generated, the adhesiveness between the Al base 10 and the Sn—Ni alloy layer 40a is deteriorated starting from the interrupted portion 41, and the Sn-Ni alloy layer 40a is not cracked. When a corrosive substance enters through a problem that peeling is likely to occur or a crack generated during processing or the like, a potential difference due to the corrosive substance is generated in the interrupted portion 41, and the corrosion proceeds. This will cause a malfunction.
　これに対して、本実施形態によれば、Ｓｎ－Ｎｉ合金層４０を構成することとなる熱拡散前のＮｉめっき層２０の厚みを０．２μｍ以上とすることにより、熱拡散後のＳｎ－Ｎｉ合金層４０を、Ａｌ基材１０の表面を覆うように、連続的に形成することができ、これにより、上記問題を有効に解決できるものである。なお、熱拡散前のＮｉめっき層２０の厚みが厚すぎると、厚みを増加させることによる効果が飽和してしまうため、コスト的に不利となる。 On the other hand, according to the present embodiment, the thickness of the Ni plating layer 20 before thermal diffusion that constitutes the Sn—Ni alloy layer 40 is set to 0.2 μm or more, so that Sn— The Ni alloy layer 40 can be continuously formed so as to cover the surface of the Al base 10, thereby effectively solving the above problem. If the thickness of the Ni plating layer 20 before thermal diffusion is too thick, the effect of increasing the thickness is saturated, which is disadvantageous in terms of cost.
　また、本実施形態においては、高周波グロー放電発光分光分析法により分析した際のＳｎ－Ｎｉ合金層４０のＮｉ強度が、熱拡散前のＮｉめっき層２０のＮｉ強度に対して、「Ｓｎ－Ｎｉ合金層４０のＮｉ強度／熱拡散前のＮｉめっき層２０のＮｉ強度」の比率で、０．１５以上であることが好ましく、より好ましくは０．１８以上、さらに好ましくは０．３４以上である。なお、該比率の上限は、１以下である。 In the present embodiment, the Ni intensity of the Sn—Ni alloy layer 40 when analyzed by the high-frequency glow discharge optical emission spectrometry is “Sn—Ni relative to the Ni intensity of the Ni plating layer 20 before thermal diffusion. The ratio of “Ni strength of alloy layer 40 / Ni strength of Ni plating layer 20 before thermal diffusion” is preferably 0.15 or more, more preferably 0.18 or more, and further preferably 0.34 or more. . The upper limit of the ratio is 1 or less.
　「Ｓｎ－Ｎｉ合金層４０のＮｉ強度／熱拡散前のＮｉめっき層２０のＮｉ強度」の比率を上記範囲とすることにより、Ｓｎ－Ｎｉ合金層４０中に含有されるＳｎ成分のＡｌ基材１０中への拡散を防止することができ、これにより、Ｓｎ成分が、Ａｌ基材１０中に拡散することにより引き起こされる不具合、すなわち、ＡｌとＳｎとの間で固溶硬化が起こってしまい、Ｓｎ－Ｎｉ合金層４０の割れや剥離が発生してしまうという不具合を有効に防止することができる。一方、「Ｓｎ－Ｎｉ合金層４０のＮｉ強度／熱拡散前のＮｉめっき層２０のＮｉ強度」の比率が低過ぎると、すなわち、Ｓｎ－Ｎｉ合金層４０中のＮｉ含有割合が少なく、Ｓｎ含有割合が多過ぎると、Ｓｎ－Ｎｉ合金層４０中のＳｎ成分が、Ａｌ基材１０中に拡散してしまい、ＡｌとＳｎとの間で固溶硬化が起こってしまい、Ｓｎ－Ｎｉ合金層４０の割れや剥離が発生してしまう場合がある。 By setting the ratio of “Ni strength of Sn—Ni alloy layer 40 / Ni strength of Ni plating layer 20 before thermal diffusion” to the above range, an Sn base material of Sn component contained in Sn—Ni alloy layer 40 Diffusion into 10 can be prevented, thereby causing a problem caused by the Sn component diffusing into the Al base material 10, that is, solid solution hardening occurs between Al and Sn, It is possible to effectively prevent a problem that the Sn—Ni alloy layer 40 is cracked or peeled off. On the other hand, if the ratio of “Ni strength of Sn—Ni alloy layer 40 / Ni strength of Ni plating layer 20 before thermal diffusion” is too low, that is, the Ni content in the Sn—Ni alloy layer 40 is small and Sn content is low. If the ratio is too large, the Sn component in the Sn—Ni alloy layer 40 diffuses into the Al base 10 and solid solution hardening occurs between Al and Sn, and the Sn—Ni alloy layer 40 Cracking or peeling may occur.
　なお、本実施形態において、「Ｓｎ－Ｎｉ合金層４０のＮｉ強度／熱拡散前のＮｉめっき層２０のＮｉ強度」は、たとえば、高周波グロー放電発光分光分析装置を用いて、Ｓｎ－Ｎｉ合金層４０および熱拡散前のＮｉめっき層２０を、Ａｒプラズマによりスパッタリングしながら測定を行い、Ｓｎ－Ｎｉ合金層４０中および熱拡散前のＮｉめっき層２０中において、それぞれ最もＮｉ強度が高かった部分のデータを、それぞれ、Ｓｎ－Ｎｉ合金層４０のＮｉ強度、および熱拡散前のＮｉめっき層２０のＮｉ強度として求め、これらを用いて、「Ｓｎ－Ｎｉ合金層４０のＮｉ強度／熱拡散前のＮｉめっき層２０のＮｉ強度」を算出することができる。 In the present embodiment, “Ni strength of Sn—Ni alloy layer 40 / Ni strength of Ni plating layer 20 before thermal diffusion” is determined using, for example, a high-frequency glow discharge optical emission spectrometer. 40 and the Ni plating layer 20 before thermal diffusion were measured while sputtering with Ar plasma, and in the Sn—Ni alloy layer 40 and the Ni plating layer 20 before thermal diffusion, each of the portions with the highest Ni strength was measured. The data were respectively obtained as the Ni strength of the Sn—Ni alloy layer 40 and the Ni strength of the Ni plating layer 20 before thermal diffusion, and these were used to calculate “Ni strength of the Sn—Ni alloy layer 40 / before thermal diffusion”. The “Ni strength of the Ni plating layer 20” can be calculated.
　また、本実施形態において、「Ｓｎ－Ｎｉ合金層４０のＮｉ強度／熱拡散前のＮｉめっき層２０のＮｉ強度」の比率を上記範囲とする方法としては、特に限定されるものではないが、たとえば、熱拡散前のＮｉめっき層２０の厚みを０．２μｍ以上とし、はんだ層５０を形成する際における、溶融はんだめっきの浴温、および溶融はんだめっきを行なう際にける浸漬時間を上述した範囲に制御する方法などが挙げられる。 In the present embodiment, the method of setting the ratio of “Ni strength of Sn—Ni alloy layer 40 / Ni strength of Ni plating layer 20 before thermal diffusion” in the above range is not particularly limited. For example, the thickness of the Ni plating layer 20 before thermal diffusion is set to 0.2 μm or more, and the bath temperature of the molten solder plating when forming the solder layer 50 and the immersion time when performing the molten solder plating are within the above-described ranges. And a method of controlling them.
　なお、本実施形態に係る太陽電池用インターコネクタ２００としては、図３に示すように、Ａｌ基材１０の上に、直接、Ｓｎ－Ｎｉ合金層４０が形成されている構成に代えて、Ａｌ基材１０の上に、Ｎｉめっき層２０を介して、Ｓｎ－Ｎｉ合金層４０が形成されているような構成であってもよい。特に、熱拡散前のＮｉめっき層２０の厚みや、はんだ層５０を形成する際における、溶融はんだめっきの浴温、および溶融はんだめっきを行なう際にける浸漬時間によっては、Ｎｉめっき層２０中へのＳｎ成分の拡散が完全に進行しない場合もある。そのため、このような場合には、Ａｌ基材１０と、Ｓｎ－Ｎｉ合金層４０との間に、Ｎｉめっき層２０が残存することとなる。 As shown in FIG. 3, the solar cell interconnector 200 according to the present embodiment is replaced with an Al-alloy 10 instead of a structure in which the Sn—Ni alloy layer 40 is directly formed. A configuration in which the Sn—Ni alloy layer 40 is formed on the substrate 10 via the Ni plating layer 20 may be employed. In particular, depending on the thickness of the Ni plating layer 20 before thermal diffusion, the bath temperature of the molten solder plating when the solder layer 50 is formed, and the immersion time when performing the molten solder plating, the Ni plating layer 20 is entered. In some cases, the Sn component does not completely diffuse. Therefore, in such a case, the Ni plating layer 20 remains between the Al base 10 and the Sn—Ni alloy layer 40.
　本実施形態の太陽電池用インターコネクタ２００は、はんだ層５０を形成した際における熱により、厚み０．２μｍ以上のＮｉめっき層と、Ｓｎめっき層３０との間で拡散が起こることにより形成されるＳｎ－Ｎｉ合金層４０を備えるものであるため、はんだ付けの熱履歴による、Ｓｎ－Ｎｉ合金層４０の割れや剥離などの不具合の発生を有効に防止することができる。しかも、本実施形態の太陽電池用インターコネクタ２００は、銅を実質的に含有しないものであり、そのため、比較的安価であり、コスト的にも有利なものである。 The solar cell interconnector 200 of the present embodiment is formed by diffusion between the Ni plating layer having a thickness of 0.2 μm or more and the Sn plating layer 30 due to heat when the solder layer 50 is formed. Since the Sn—Ni alloy layer 40 is provided, it is possible to effectively prevent the occurrence of defects such as cracking and peeling of the Sn—Ni alloy layer 40 due to the thermal history of soldering. Moreover, the solar cell interconnector 200 of the present embodiment does not substantially contain copper, and is therefore relatively inexpensive and advantageous in terms of cost.
　そのため、本実施形態の太陽電池用インターコネクタ２００を用い、太陽電池用インターコネクタ２００と、太陽電池セルとをはんだ付けにより接続することにより得られるインターコネクタ付き太陽電池セルは、品質的に良好であり、しかも、コスト的にも優れたものである。 Therefore, the solar cell with an interconnector obtained by connecting the solar cell interconnector 200 and the solar cell by soldering using the solar cell interconnector 200 of the present embodiment is good in quality. Moreover, it is also excellent in cost.
　なお、このような本実施形態の太陽電池用インターコネクタ２００としては、たとえば、長尺のＡｌ板（コイル）の両面に、上述した方法にしたがい、Ｓｎ－Ｎｉ合金層４０、およびはんだ層５０を、この順に形成したものを、必要な幅にスリットすることにより得ることができる。このようにして得られる太陽電池用インターコネクタ２００は、上下面に、Ｓｎ－Ｎｉ合金層４０、およびはんだ層５０が形成されている一方で、厚み方向を形成する面（スリット面）には、これらＳｎ－Ｎｉ合金層４０、およびはんだ層５０が形成されていないこととなる。 As such a solar cell interconnector 200 of this embodiment, for example, the Sn—Ni alloy layer 40 and the solder layer 50 are formed on both surfaces of a long Al plate (coil) according to the above-described method. Those formed in this order can be obtained by slitting them to the required width. In the solar cell interconnector 200 thus obtained, the Sn—Ni alloy layer 40 and the solder layer 50 are formed on the upper and lower surfaces, while the surface forming the thickness direction (slit surface) The Sn—Ni alloy layer 40 and the solder layer 50 are not formed.
　あるいは、本実施形態の太陽電池用インターコネクタ２００としては、たとえば、平角Ａｌ線の表面全面に、上述した方法にしたがい、Ｓｎ－Ｎｉ合金層４０、およびはんだ層５０を形成することにより得ることもできる。そして、この場合には、得られる太陽電池用インターコネクタ２００は、上述した方法とは異なり、スリット工程を経ないため、上述した特許文献１（特開２００６－４９６６６号公報）に記載のインターコネクタと同様に、上下面および厚み方向を形成する面のいずれにも、Ｓｎ－Ｎｉ合金層４０、およびはんだ層５０が形成されたものとなる。 Alternatively, the solar cell interconnector 200 of the present embodiment can be obtained, for example, by forming the Sn—Ni alloy layer 40 and the solder layer 50 on the entire surface of the flat Al wire according to the above-described method. it can. In this case, the obtained solar cell interconnector 200 does not go through the slit process unlike the above-described method, and therefore, the interconnector described in Patent Document 1 (Japanese Patent Laid-Open No. 2006-49666) described above is used. Similarly, the Sn—Ni alloy layer 40 and the solder layer 50 are formed on both the upper and lower surfaces and the surface forming the thickness direction.
　なお、本実施形態に係る太陽電池用インターコネクタ２００のサイズは、特に限定されないが、厚みが、通常、０．１～０．７ｍｍ、好ましくは０．１～０．５ｍｍであり、幅が、通常、０．５～１０ｍｍ、好ましくは１～６ｍｍであり、また、長さについては、太陽電池の配列等に応じて適宜設定すればよい。 The size of the solar cell interconnector 200 according to this embodiment is not particularly limited, but the thickness is usually 0.1 to 0.7 mm, preferably 0.1 to 0.5 mm, and the width is Usually, it is 0.5 to 10 mm, preferably 1 to 6 mm, and the length may be appropriately set according to the arrangement of solar cells and the like.
　以下に、実施例を挙げて、本発明についてより具体的に説明するが、本発明は、これら実施例に限定されない。 Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
＜実施例１＞
　Ａｌ基材１０を形成するための材料として、Ａ１１００系のＯ材を準備した（厚さ０．３ｍｍ、幅４０ｍｍ、長さ１２０ｍｍ）。そして、Ａｌ基材を、アルカリ液で脱脂し、次いで硫酸中でエッチング処理を施し、次いで硝酸中で脱スマット処理を施した後、水酸化ナトリウム：１５０ｇ／Ｌ、ロッシェル塩：５０ｇ／Ｌ、酸化亜鉛：２５ｇ／Ｌ、塩化第一鉄１．５ｇ／Ｌを含む処理液中に浸漬して第一Ｚｎ置換処理を行った。次いで、第一Ｚｎ置換処理を行ったＡｌ基材を、４００ｇ／Ｌの硝酸水溶液中に浸漬して置換析出したＺｎを除去した後、第一Ｚｎ置換処理で用いた処理液と同じ処理液中に、１０秒間浸漬することで第二Ｚｎ置換処理を行うことで、１００ｍｇ／ｍ２の皮膜量で、Ａｌ基材上にＺｎ層を形成した。 <Example 1>
As a material for forming the Al base 10, an A1100-based O material was prepared (thickness 0.3 mm, width 40 mm, length 120 mm). Then, the Al base material is degreased with an alkali solution, then etched in sulfuric acid, then desmutted in nitric acid, sodium hydroxide: 150 g / L, Rochelle salt: 50 g / L, oxidized The first Zn substitution treatment was performed by dipping in a treatment solution containing zinc: 25 g / L and ferrous chloride 1.5 g / L. Next, the Al base material subjected to the first Zn substitution treatment is immersed in a 400 g / L nitric acid aqueous solution to remove the deposited Zn, and then in the same treatment liquid as the treatment liquid used in the first Zn substitution treatment. In addition, a Zn layer was formed on the Al substrate with a coating amount of 100 mg / m 2 by performing the second Zn substitution treatment by dipping for 10 seconds.
　次いで、Ｚｎ層を形成したＡｌ基材１０について下記条件にてニッケルめっきを行い、Ｚｎ層上に、厚さ０．２μｍのＮｉめっき層２０を形成した。
　　浴組成：硫酸ニッケル２５０ｇ／Ｌ、塩化ニッケル４５ｇ／Ｌ、ほう酸３０ｇ／Ｌ
　　ｐＨ：３～５
　　浴温：６０℃
　　電流密度：１～５Ａ／ｄｍ２ Next, nickel plating was performed on the Al base material 10 on which the Zn layer was formed under the following conditions to form a Ni plating layer 20 having a thickness of 0.2 μm on the Zn layer.
Bath composition: nickel sulfate 250 g / L, nickel chloride 45 g / L, boric acid 30 g / L
pH: 3-5
Bath temperature: 60 ° C
Current density: 1 to 5 A / dm 2
　次いで、Ｎｉめっき層２０を形成したＡｌ基材１０について、下記条件にてスズめっきを行い、Ｎｉめっき層上に、厚さ０．５μｍのＳｎめっき層３０を形成することで、図１に示す太陽電池用インターコネクタ材料１００を得た。
　　浴組成：硫酸第一錫３０ｇ／Ｌ、硫酸７０ｍｌ／Ｌ、適量の光沢剤および酸化防止剤
　　ｐＨ：１～２
　　浴温：４０℃
　　電流密度：５～１０Ａ／ｄｍ２ Next, the Al base material 10 on which the Ni plating layer 20 is formed is subjected to tin plating under the following conditions, and a Sn plating layer 30 having a thickness of 0.5 μm is formed on the Ni plating layer. The solar cell interconnector material 100 was obtained.
Bath composition: stannous sulfate 30 g / L, sulfuric acid 70 ml / L, appropriate amount of brightener and antioxidant pH: 1 to 2
Bath temperature: 40 ° C
Current density: 5-10 A / dm 2
　次いで、得られた太陽電池用インターコネクタ材料１００を、浴温を２００℃に調整したＳｎ－Ｐｂはんだからなる溶融はんだめっき槽に、３秒間浸漬することで、厚み２０μｍのはんだ層５０を形成することで、図２に示す太陽電池用インターコネクタ２００を製造した。なお、本実施例で製造した太陽電池用インターコネクタ２００は、スリット前のものであり、そのサイズは、幅４０ｍｍ、長さ１２０ｍｍであり、太陽電池の配列等に併せて、スリットすることにより、太陽電池用インターコネクタとして適宜使用可能なものである。そして、得られた太陽電池用インターコネクタ材料１００および太陽電池用インターコネクタ２００を用いて、以下の方法にしたがい、「Ｓｎ－Ｎｉ合金層４０のＮｉ強度／熱拡散前のＮｉめっき層２０のＮｉ強度」の比率、およびＳｎ－Ｎｉ合金層４０の連続性の評価を行った。 Next, the obtained solar cell interconnector material 100 is immersed in a molten solder plating bath made of Sn—Pb solder whose bath temperature is adjusted to 200 ° C. for 3 seconds to form a solder layer 50 having a thickness of 20 μm. Thus, the solar cell interconnector 200 shown in FIG. 2 was manufactured. In addition, the solar cell interconnector 200 manufactured in this example is the one before slitting, and the size is 40 mm in width and 120 mm in length. By slitting together with the arrangement of solar cells, etc., It can be suitably used as a solar cell interconnector. Then, using the obtained solar cell interconnector material 100 and solar cell interconnector 200, according to the following method, "Ni strength of Sn-Ni alloy layer 40 / Ni of Ni plating layer 20 before thermal diffusion" The ratio of “strength” and the continuity of the Sn—Ni alloy layer 40 were evaluated.
　「Ｓｎ－Ｎｉ合金層４０のＮｉ強度／熱拡散前のＮｉめっき層２０のＮｉ強度」の比率は、次の方法により測定した。すなわち、まず、高周波グロー放電発光分光分析装置（ＧＤＳ－３８６０、リガク社製）を用いて、高周波電力：４０Ｗ、フォトマル電圧（Ｎｉ）：３７０Ｖの条件で、Ｓｎ－Ｎｉ合金層４０および熱拡散前のＮｉめっき層２０を、Ａｒプラズマによりスパッタリングしながら測定を行った。そして、得られた測定データから、Ｓｎ－Ｎｉ合金層４０中および熱拡散前のＮｉめっき層２０中において、それぞれのＮｉ強度のピーク値を得て、それぞれを、Ｓｎ－Ｎｉ合金層４０のＮｉ強度、および熱拡散前のＮｉめっき層２０のＮｉ強度として、「Ｓｎ－Ｎｉ合金層４０のＮｉ強度／熱拡散前のＮｉめっき層２０のＮｉ強度」を算出した。結果を表１に示す。 The ratio of “Ni strength of Sn—Ni alloy layer 40 / Ni strength of Ni plating layer 20 before thermal diffusion” was measured by the following method. That is, first, using a high-frequency glow discharge emission spectroscopic analyzer (GDS-3860, manufactured by Rigaku Corporation), Sn-Ni alloy layer 40 and thermal diffusion under the conditions of high-frequency power: 40 W and photomultiplier voltage (Ni): 370 V. The previous Ni plating layer 20 was measured while sputtering with Ar plasma. Then, from the obtained measurement data, the peak value of each Ni intensity is obtained in the Sn—Ni alloy layer 40 and in the Ni plating layer 20 before thermal diffusion, and the respective Ni intensity of the Sn—Ni alloy layer 40 is obtained. As the strength and Ni strength of the Ni plating layer 20 before thermal diffusion, “Ni strength of the Sn—Ni alloy layer 40 / Ni strength of the Ni plating layer 20 before thermal diffusion” was calculated. The results are shown in Table 1.
　また、Ｓｎ－Ｎｉ合金層４０の連続性は、太陽電池用インターコネクタ２００の断面を、電界放出形走査電子顕微鏡（ＦＥ－ＳＥＭ）（ＪＳＭ－６３３０Ｆ、日本電子社製）により観察を行なうことにより評価した。電界放出形走査電子顕微鏡による観察の結果、Ｓｎ－Ｎｉ合金層４０に、図３に示すような途切れ部分、すなわち、はんだ層５０が、直接、Ａｌ基材１０表面に接触している部分（Ａｌ基材１０表面において、Ｎｉの含有割合が実質的にゼロである部分）が観察された場合には、Ｓｎ－Ｎｉ合金層４０の連続性「無し」と判断し、そのような途切れ部分が観察されなかった場合には、Ｓｎ－Ｎｉ合金層４０の連続性「有り」と判断した。結果を表１に示す。 The continuity of the Sn—Ni alloy layer 40 is determined by observing the cross section of the solar cell interconnector 200 with a field emission scanning electron microscope (FE-SEM) (JSM-6330F, manufactured by JEOL Ltd.). evaluated. As a result of observation with a field emission scanning electron microscope, a discontinuous portion as shown in FIG. 3, that is, a portion where the solder layer 50 is in direct contact with the surface of the Al base 10 (Al When the Ni content ratio is substantially zero on the surface of the base material 10), it is determined that the Sn—Ni alloy layer 40 has no continuity, and such a discontinuous portion is observed. If not, it was determined that the continuity of the Sn—Ni alloy layer 40 was “present”. The results are shown in Table 1.
＜実施例２～４＞
　Ｎｉめっき層２０の厚みを、それぞれ、０．５μｍ（実施例２）、１μｍ（実施例３）、および１．５μｍ（実施例４）に変更した以外は、実施例１と同様にして、太陽電池用インターコネクタ材料１００および太陽電池用インターコネクタ２００を得て、同様に評価を行った。結果を表１に示す。 <Examples 2 to 4>
Except that the thickness of the Ni plating layer 20 was changed to 0.5 μm (Example 2), 1 μm (Example 3), and 1.5 μm (Example 4), respectively, The battery interconnector material 100 and the solar cell interconnector 200 were obtained and evaluated in the same manner. The results are shown in Table 1.
＜実施例５＞
　はんだ層５０を形成する際の溶融はんだめっき槽の温度を２００℃から２５０℃に変更し、はんだ層５０を厚み２０μｍで形成した以外は、実施例１と同様にして、太陽電池用インターコネクタ材料１００および太陽電池用インターコネクタ２００を得て、同様に評価を行った。結果を表１に示す。 <Example 5>
The interconnector material for solar cells was the same as in Example 1 except that the temperature of the molten solder plating tank when forming the solder layer 50 was changed from 200 ° C. to 250 ° C. and the solder layer 50 was formed with a thickness of 20 μm. 100 and solar cell interconnector 200 were obtained and evaluated in the same manner. The results are shown in Table 1.
＜実施例６～８＞
　Ｎｉめっき層２０の厚みを、それぞれ、０．５μｍ（実施例６）、１μｍ（実施例７）、および１．５μｍ（実施例８）に変更した以外は、実施例５と同様にして、太陽電池用インターコネクタ材料１００および太陽電池用インターコネクタ２００を得て、同様に評価を行った。結果を表１に示す。 <Examples 6 to 8>
In the same manner as in Example 5, except that the thickness of the Ni plating layer 20 was changed to 0.5 μm (Example 6), 1 μm (Example 7), and 1.5 μm (Example 8), respectively. The battery interconnector material 100 and the solar cell interconnector 200 were obtained and evaluated in the same manner. The results are shown in Table 1.
＜比較例１，２＞
　Ｎｉめっき層２０の厚みを、それぞれ、０．１μｍ（比較例１）、および０．１５μｍ（比較例２）に変更した以外は、実施例１と同様にして、太陽電池用インターコネクタ材料１００および太陽電池用インターコネクタ２００を得て、同様に評価を行った。結果を表１に示す。 <Comparative Examples 1 and 2>
Except for changing the thickness of the Ni plating layer 20 to 0.1 μm (Comparative Example 1) and 0.15 μm (Comparative Example 2), respectively, the solar cell interconnector material 100 and The solar cell interconnector 200 was obtained and evaluated in the same manner. The results are shown in Table 1.
＜比較例３，４＞
　Ｎｉめっき層２０の厚みを、それぞれ、０．１μｍ（比較例３）、および０．１５μｍ（比較例４）に変更した以外は、実施例５と同様にして、太陽電池用インターコネクタ材料１００および太陽電池用インターコネクタ２００を得て、同様に評価を行った。結果を表１に示す。 <Comparative Examples 3 and 4>
Except for changing the thickness of the Ni plating layer 20 to 0.1 μm (Comparative Example 3) and 0.15 μm (Comparative Example 4), respectively, the solar cell interconnector material 100 and The solar cell interconnector 200 was obtained and evaluated in the same manner. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、Ｎｉめっき層２０の厚みを０．２μｍ以上とした実施例１～８においては、「Ｓｎ－Ｎｉ合金層４０のＮｉ強度／熱拡散前のＮｉめっき層２０のＮｉ強度」の比率がいずれも高く、また、いずれも、Ｓｎ－Ｎｉ合金層４０が、Ａｌ基材１０表面を覆うように連続的に形成されており、図３に示すような途切れ部分は確認されなかった。 As shown in Table 1, in Examples 1 to 8 in which the thickness of the Ni plating layer 20 was 0.2 μm or more, “Ni strength of the Sn—Ni alloy layer 40 / Ni strength of the Ni plating layer 20 before thermal diffusion” In any case, the Sn—Ni alloy layer 40 is continuously formed so as to cover the surface of the Al base 10, and no discontinuity as shown in FIG. 3 is confirmed. It was.
　一方、Ｎｉめっき層２０の厚みを０．２μｍ未満とした比較例１～４においては、「Ｓｎ－Ｎｉ合金層４０のＮｉ強度／熱拡散前のＮｉめっき層２０のＮｉ強度」の比率がいずれも低く、また、いずれも、Ｓｎ－Ｎｉ合金層４０に途切れ部分が確認され、Ｓｎ－Ｎｉ合金層４０は連続性を有しないものであった。 On the other hand, in Comparative Examples 1 to 4 in which the thickness of the Ni plating layer 20 was less than 0.2 μm, the ratio of “Ni strength of Sn—Ni alloy layer 40 / Ni strength of Ni plating layer 20 before thermal diffusion” In both cases, a discontinuous portion was confirmed in the Sn—Ni alloy layer 40, and the Sn—Ni alloy layer 40 did not have continuity.
　ここで、図４（Ａ）に、実施例２の太陽電池用インターコネクタ試料の断面写真を、図４（Ｂ）に、比較例１の太陽電池用インターコネクタ試料の断面写真を、それぞれ示す。図４（Ａ）からも確認できるように、実施例２においては、Ｓｎ－Ｎｉ合金層４０に途切れ部分が存在せず、Ｓｎ－Ｎｉ合金層４０が、Ａｌ基材１０表面を覆うように連続的に形成されていることが確認できる。その一方で、比較例１においては、Ｓｎ－Ｎｉ合金層４０に途切れ部分が存在し、Ｓｎ－Ｎｉ合金層４０は連続性を有しないものであることが確認できる。 Here, FIG. 4 (A) shows a cross-sectional photograph of the solar cell interconnector sample of Example 2, and FIG. 4 (B) shows a cross-sectional photograph of the solar battery interconnector sample of Comparative Example 1. As can be confirmed from FIG. 4A, in Example 2, there is no discontinuous portion in the Sn—Ni alloy layer 40, and the Sn—Ni alloy layer 40 is continuous so as to cover the surface of the Al base material 10. Can be confirmed. On the other hand, in Comparative Example 1, it can be confirmed that there is a discontinuity in the Sn—Ni alloy layer 40 and the Sn—Ni alloy layer 40 has no continuity.
１００…太陽電池用インターコネクタ材料
２００…太陽電池用インターコネクタ
　１０…Ａｌ基材
　２０…Ｎｉめっき層
　３０…Ｓｎめっき層
　４０…Ｓｎ－Ｎｉめっき層
　５０…はんだ層 DESCRIPTION OF SYMBOLS 100 ... Solar cell interconnector material 200 ... Solar cell interconnector 10 ... Al base material 20 ... Ni plating layer 30 ... Sn plating layer 40 ... Sn-Ni plating layer 50 ... Solder layer

Claims (6)

  1. 　Ａｌ基材表面に、基材側から順に、０．２μｍ以上の厚みのＮｉめっき層、およびＳｎめっき層を有することを特徴とする太陽電池用インターコネクタ材料。 An interconnector material for a solar cell, comprising a Ni plating layer and a Sn plating layer having a thickness of 0.2 μm or more in order from the substrate side on the Al substrate surface.
  2. 　請求項１に記載の太陽電池用インターコネクタ材料のＳｎめっき層の表面にはんだ層を形成することにより得られ、
    　Ａｌ基材表面に、基材側から順に、Ｓｎ－Ｎｉ合金層、およびはんだ層を有することを特徴とする太陽電池用インターコネクタ。     It is obtained by forming a solder layer on the surface of the Sn plating layer of the solar cell interconnector material according to claim 1,
    An interconnector for a solar cell, comprising an Sn—Ni alloy layer and a solder layer in order from the substrate side on the surface of the Al substrate.
  3. 　前記Ｓｎ－Ｎｉ合金層は、前記Ｎｉめっき層および前記Ｓｎめっき層に、前記はんだ層を形成する際における熱により拡散を起こさせることにより形成されたものであり、
    　高周波グロー放電発光分光分析法により分析した際の前記Ｓｎ－Ｎｉ合金層のＮｉ強度と、熱拡散前の前記Ｎｉめっき層のＮｉ強度との比が、「Ｓｎ－Ｎｉ合金層のＮｉ強度／熱拡散前のＮｉめっき層のＮｉ強度」で、０．１５以上であることを特徴とする請求項２に記載の太陽電池用インターコネクタ。     The Sn—Ni alloy layer is formed by causing diffusion in the Ni plating layer and the Sn plating layer by heat in forming the solder layer,
    The ratio between the Ni strength of the Sn—Ni alloy layer and the Ni strength of the Ni plating layer before thermal diffusion when analyzed by high-frequency glow discharge optical emission spectrometry is “Ni strength / heat of Sn—Ni alloy layer”. The interconnector for solar cells according to claim 2, wherein the Ni strength of the Ni plating layer before diffusion is 0.15 or more.
  4. 　前記Ｓｎ－Ｎｉ合金層は、前記Ａｌ基材表面を覆うように、連続的に形成されていることを特徴とする請求項２または３に記載の太陽電池用インターコネクタ。 The solar cell interconnector according to claim 2 or 3, wherein the Sn-Ni alloy layer is continuously formed so as to cover the surface of the Al base material.
  5. 　請求項２～４のいずれかに記載の太陽電池用インターコネクタを太陽電池セルに接続してなることを特徴とするインターコネクタ付き太陽電池セル。 A solar battery cell with an interconnector, wherein the solar battery interconnector according to any one of claims 2 to 4 is connected to a solar battery cell.
  6. 　前記太陽電池用インターコネクタと前記太陽電池セルとが、はんだ付けに接続されていることを特徴とする請求項５に記載のインターコネクタ付き太陽電池セル。 The solar cell with an interconnector according to claim 5, wherein the solar cell interconnector and the solar cell are connected by soldering.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014034300A1 (en) * 2012-08-29 2014-03-06 株式会社オートネットワーク技術研究所 Connector terminal and material for connector terminals

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013258305A (en) * 2012-06-13 2013-12-26 Toyo Kohan Co Ltd Interconnector for solar cell, and solar cell with interconnector
JP5887305B2 (en) * 2013-07-04 2016-03-16 Ｊｘ金属株式会社 Metal foil for electromagnetic shielding, electromagnetic shielding material, and shielded cable
AU2017374799B2 (en) * 2016-12-16 2023-06-22 Haldor Topsøe A/S Deposition of a coating on an interconnect for solid oxide cell stacks
CN110760803A (en) * 2019-11-29 2020-02-07 东北大学 Composite coating for stainless steel connector of solid oxide fuel cell and preparation method thereof
CN112331412A (en) * 2020-10-20 2021-02-05 南通德晋昌光电科技有限公司 Supply system of interconnection strips and processing technology thereof
CN113937177A (en) * 2021-10-15 2022-01-14 苏州元昱新能源有限公司 Manufacturing method of aluminum base material photovoltaic welding strip

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05345969A (en) * 1992-06-12 1993-12-27 Kobe Steel Ltd Al series alloy metallic material excellent in solderability and plating adhesion
JP2006219736A (en) * 2005-02-14 2006-08-24 Toyo Kohan Co Ltd Surface-treated al sheet
JP2008006206A (en) * 2006-06-30 2008-01-17 Toto Ltd Toilet seat device

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1121660A (en) * 1997-07-03 1999-01-26 Hitachi Cable Ltd Connecting wire for solar battery
JP4622375B2 (en) 2004-08-06 2011-02-02 日立電線株式会社 Flat rectangular conductor for solar cell and lead wire for solar cell
JP2006206977A (en) * 2005-01-28 2006-08-10 Toyo Kohan Co Ltd SURFACE-TREATED Al SHEET HAVING EXCELLENT SOLDERABILITY
KR101612955B1 (en) * 2009-06-17 2016-04-15 엘지전자 주식회사 Interconnector and solar cell module having the same
CN202054913U (en) * 2011-03-01 2011-11-30 无锡新大中薄板有限公司 Weldable tin plating aluminum alloy strip
CN102071446B (en) * 2011-03-01 2012-05-02 无锡新大中薄板有限公司 Continuous electroplating process for weldable aluminum coiled material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05345969A (en) * 1992-06-12 1993-12-27 Kobe Steel Ltd Al series alloy metallic material excellent in solderability and plating adhesion
JP2006219736A (en) * 2005-02-14 2006-08-24 Toyo Kohan Co Ltd Surface-treated al sheet
JP2008006206A (en) * 2006-06-30 2008-01-17 Toto Ltd Toilet seat device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014034300A1 (en) * 2012-08-29 2014-03-06 株式会社オートネットワーク技術研究所 Connector terminal and material for connector terminals

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