WO2020203543A1 - Structure de connexion de fils supraconducteurs, et fil supraconducteur - Google Patents

Structure de connexion de fils supraconducteurs, et fil supraconducteur Download PDF

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Publication number
WO2020203543A1
WO2020203543A1 PCT/JP2020/013308 JP2020013308W WO2020203543A1 WO 2020203543 A1 WO2020203543 A1 WO 2020203543A1 JP 2020013308 W JP2020013308 W JP 2020013308W WO 2020203543 A1 WO2020203543 A1 WO 2020203543A1
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Prior art keywords
wire
superconducting
oxide superconducting
layer
oxide
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PCT/JP2020/013308
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English (en)
Japanese (ja)
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智 羽生
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株式会社フジクラ
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B12/00—Superconductive or hyperconductive conductors, cables, or transmission lines
    • H01B12/02—Superconductive or hyperconductive conductors, cables, or transmission lines characterised by their form
    • H01B12/06—Films or wires on bases or cores
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
    • H01R4/58—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation characterised by the form or material of the contacting members
    • H01R4/68—Connections to or between superconductive connectors
    • 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
    • Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
    • Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment

Definitions

  • the present invention relates to a connecting structure of a superconducting wire and a superconducting wire.
  • the present application claims priority based on Japanese Patent Application No. 2019-065548 filed in Japan on March 29, 2019, the contents of which are incorporated herein by reference.
  • Patent Document 1 describes a superconducting wire having an oxide superconducting layer formed on an intermediate layer provided on a metal substrate and a copper electroplating film formed as a stabilizing layer around the superconducting layer. Further, in order to obtain a long superconducting wire, it is necessary to connect the ends of a plurality of superconducting wires. For example, in Patent Document 2, the oxide superconducting layers of the superconducting wire are opposed to each other to ensure electrical conduction between the oxide superconducting layers.
  • the oxide superconducting layers have a structure sandwiched between the metal substrates of each superconducting wire.
  • the heat treatment is performed in a state where oxygen is insufficient, so that oxygen may be desorbed from the oxide superconducting layer and the superconducting characteristics may be deteriorated.
  • the present invention has been made in view of the above circumstances, and provides a connection structure of a superconducting wire and a superconducting wire in which it is easy to adjust the oxygen non-stoichiometricity of the oxide superconducting layer after connection.
  • a first aspect of the present invention is a superconducting wire in which each end of a plurality of connecting target wires each having a first oxide superconducting layer is connected via a connecting wire having a second oxide superconducting layer.
  • the first in-plane orientation ⁇ of the first oxide superconducting layer in the direction perpendicular to the thickness direction of the first oxide superconducting layer of the plurality of connection target wires is 4.0.
  • the degree of orientation ⁇ in the second plane of the second oxide superconducting layer in the direction perpendicular to the thickness direction of the second oxide superconducting layer of the connecting wire is not more than ° and less than 5.5 °.
  • the degree of orientation in the first plane of the first oxide superconducting layer of the wire to be connected is 0.5 ° or more larger than that of ⁇ .
  • a second aspect of the present invention is the connection structure of the superconducting wire of the first aspect, wherein the plurality of connection target wires and the connection wire are each on the first substrate with the first oxide superconducting layer.
  • the first superconducting wire having the above, and the connecting wire is a second superconducting wire having the second oxide superconducting layer on the second substrate, and the first substrate of the connecting target wire and the connecting wire.
  • the first oxide superconducting layer of the connecting wire and the second oxide superconducting layer of the connecting wire may be arranged so as to face each other between the second substrate and the second substrate.
  • a third aspect of the present invention is the connecting structure of the superconducting wire according to the first or second aspect, wherein the first oxide superconducting layer of the connecting target wire and the second oxide of the connecting wire are used. It may be connected so as to be in direct contact with the superconducting layer.
  • a fourth aspect of the present invention is a connecting structure of the superconducting wire according to any one of the first to third aspects, wherein the second superconducting wire of the connecting wire is the first of the connecting target wires. It may be shorter than the superconducting wire.
  • a fifth aspect of the present invention is a superconducting wire rod in which two or more connection target wire rods are connected in the longitudinal direction, and at least one place between the two or more connection target wire rods is the first to fourth aspects. It is the connection structure of the superconducting wire material of any one aspect, and is the connection structure of the superconducting wire material.
  • the in-plane orientation ⁇ perpendicular to the thickness direction of the oxide superconducting layer of the connecting wire is relatively large, the oxygen non-stoichiometricity of the oxide superconducting layer is adjusted by oxygen diffusion. Becomes easier. Since the in-plane orientation ⁇ perpendicular to the thickness direction of the oxide superconducting layer of the wire to be connected is relatively small, the superconducting property of the wire to be connected is high, and the average superconducting property of the connected superconducting wire is lowered. It can be suppressed.
  • FIG. 1 shows a connection structure of the superconducting wire rod of the present embodiment.
  • This cross-sectional view schematically represents a cross section along the longitudinal direction of the superconducting wire.
  • the vertical direction of the cross-sectional view is the thickness direction of the superconducting wire
  • the horizontal direction of the cross-sectional view is the longitudinal direction of the superconducting wire.
  • the direction perpendicular to the paper surface is the width direction of the superconducting wire.
  • the superconducting wires 10, 20, and 30 constituting the connection structure include a long connection target wire 10, 20 and a short connection wire 30. Between the ends of the wire rods 10 and 20, the oxide superconducting layers 12 and 22 of the wire rods 10 and 20 to be connected are connected via the oxide superconducting layer 32 of the wire rod 30 for connection.
  • the oxide superconducting layers 12, 22, and 32 may be laminated on the substrates 11, 21, and 31, respectively.
  • Protective layers 13 and 23 may be provided on the oxide superconducting layers 12 and 22 of the connecting wire rods 10 and 20 that do not face the oxide superconducting layer 32 of the connecting wire 30.
  • connection structure of the present embodiment is a portion including one end of the connection target wires 10 and 20 and the connection wire 30. In the longitudinal direction of the wire rods 10 and 20 to be connected, another connection structure may be formed at an end portion on a side (not shown).
  • the oxide superconducting layers 12 and 22 of the connection target wires 10 and 20 face each other with the oxide superconducting layer 32 of the connection wire 30.
  • the superconducting wires 10, 20 and 30 can be arranged as described above, and the oxide superconducting layers 12, 22 and 32 can be superposed on each other.
  • a gap is interposed between the end faces of the wire rods 10 and 20 to be connected in the longitudinal direction, but this gap is not essential.
  • the end faces may be butted between the connecting target wires 10 and 20 facing each other in the longitudinal direction.
  • the superconductor When the oxide superconducting layers 12, 22 and 32 are directly bonded, the superconductor may be diffusely bonded by heating, for example.
  • a bonding layer such as silver, silver alloy, or solder may be provided between the oxide superconducting layers 12, 22, and 32 facing each other.
  • the superconducting wires 10, 20, and 30 may be fixed by providing joints (not shown) such as welding and metal plating between or around the substrates 11, 2, and 31 facing each other.
  • the oxide superconducting layers 12 and 22 of the connection target wires 10 and 20 and the connection wire are connected in at least a part of the region where the connection target wires 10 and 20 and the connection wire 30 face each other. It is preferable that the oxide superconducting layer 32 of 30 is connected so as to be in direct contact with it.
  • the bonding layer is provided between the oxide superconducting layers 12, 22 and 32 facing each other, it is preferable to set the material, film thickness and the like so as to enable oxygen diffusion.
  • oxygen heat treatment oxygen annealing
  • the ratio of the oxide to the metal element of the oxide superconductor can be optimized.
  • oxides in the direction (a-axis direction or b-axis direction) perpendicular to the thickness direction (c-axis direction) of the oxide superconducting layers 12 and 22 of the wire rods 10 and 20 to be connected oxides in the direction (a-axis direction or b-axis direction) perpendicular to the thickness direction (c-axis direction) of the oxide superconducting layers 12 and 22 of the wire rods 10 and 20 to be connected.
  • the degree of in-plane orientation ⁇ of the superconducting layer is preferably less than 5.5 °.
  • the degree of in-plane orientation of the oxide superconducting layers in the direction (a-axis direction or b-axis direction) perpendicular to the thickness direction (c-axis direction) of the oxide superconducting layers 12 and 22 of the wire rods 10 and 20 to be connected is ⁇ . Is preferably 4.0 ° or more.
  • the critical current Ic of the superconducting wire can be increased after the heat treatment as compared with the case before the heat treatment.
  • the in-plane orientation ⁇ of the oxide superconducting layer in the direction (a-axis direction or b-axis direction) perpendicular to the thickness direction (c-axis direction) of the oxide superconducting layer 32 of the connecting wire 30 is the connection target.
  • the degree of in-plane orientation of the oxide superconducting layers 12 and 22 in the direction (a-axis direction or b-axis direction) perpendicular to the thickness direction (c-axis direction) of the wires 10 and 20 is 0. It is preferably larger than 5 °. As a result, the superconducting characteristics of the oxide superconducting layer 32 of the connecting wire 30 can be kept good.
  • the in-plane orientation ⁇ is the value of the full width at half maximum (FWHM) of the crystal axis dispersion measured by performing X-ray analysis measurement of the oxide superconducting layer. The smaller the value of the in-plane orientation ⁇ , the better the crystal orientation.
  • the in-plane orientation ⁇ of the oxide superconducting layer in the direction perpendicular to the thickness direction of the oxide superconducting layer is hereinafter simply referred to as the in-plane orientation ⁇ .
  • the oxide superconducting layer 32 of the connecting wire 30 faces the oxide superconducting layers 12 and 22 at the ends of the connecting wire rods 10 and 20, and the oxide superconducting layers 12, 22 and 32 overlap each other, oxidation occurs. Since the in-plane orientation ⁇ of the physical superconducting layer 32 is relatively large, the oxygen diffusion rate of the oxide superconducting layer 32 becomes high. This facilitates the adjustment of the oxygen non-stoichiometric properties of the oxide superconducting layers 12, 22, and 32 by oxygen diffusion.
  • the connected superconducting wires 10 , 20, 30 can suppress the deterioration of the average superconducting characteristics.
  • the reason why the oxygen diffusion rate of the oxide superconducting layer 32 having a large in-plane orientation ⁇ is considered to be as follows, for example. As shown in FIG. 2, when the difference in crystal orientations 41, 42, 43 between adjacent local regions in the crystal is large, grain boundaries 47 are formed, and each region is a crystal grain 44 surrounded by grain boundaries 47. It becomes 45,46. Further, as shown in FIG. 3, if the difference between the crystal orientations 41 and 42 between the adjacent local regions in the crystal is small, the grain boundary is not formed and the dislocation group 48 is formed.
  • the in-plane orientation ⁇ of the crystal is large, the regions having different crystal orientations increase in the crystal, and the defect structures such as the grain boundaries 47 and the dislocation group 48 where oxygen can diffuse increase, so that oxygen diffusion occurs. It is considered to be advantageous.
  • the crystal grains 44, 45, and 46 are simply shown as hexagons, but this is not intended for the shape of the particles.
  • the oxygen heat treatment is preferably performed at least once before or after the connection target wires 10 and 20 are connected to the connection wire 30.
  • the protective layers 13 and 23 such as silver on at least the exposed oxide superconducting layers 12 and 22. It is also possible to stack two or more protective layers 13 and 23 in the thickness direction.
  • silver or a silver alloy that can permeate oxygen under high temperature conditions may be laminated before the oxygen heat treatment, and copper or the like may be laminated on the silver or the silver alloy after the oxygen heat treatment.
  • connection target wires 10 and 20 in which the protective layers 13 and 23 are formed over the entire length of the connection target wires 10 and 20 are prepared, and the protective layer is formed from the end of the connection target wires 10 and 20 before being connected to the connection wire 30.
  • a part of 13 and 23 may be removed by etching or the like.
  • the oxide superconducting layers 12, 22, and 32 are, for example, oxide superconductors containing rare earth elements.
  • the oxide superconductor include a RE-Ba-Cu-O-based oxide superconductor represented by the general formula REBa 2 Cu 3 O 7-x (RE123) and the like.
  • the rare earth element RE include one or more of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
  • the thickness of the oxide superconducting layers 12, 22, and 32 is, for example, about 0.5 to 5 ⁇ m.
  • Artificial pins made of different materials may be introduced into the oxide superconducting layers 12, 22, and 32 as artificial crystal defects.
  • dissimilar materials used for introducing artificial pins into the oxide superconducting layers 12, 22, and 32 include BaSnO 3 (BSO), BaZrO 3 (BZO), BaHfO 3 (BHO), and BaTIO 3 (BTO).
  • BSO BaSnO 3
  • BZO BaZrO 3
  • BaTIO 3 BaTIO 3
  • the in-plane orientation ⁇ of the oxide superconducting layers 12 and 22 of the wire rods 10 and 20 to be connected is not particularly limited, but is, for example, 4.0 °, 4.2 °, 4.5 °, 4.8 °, 5 Values of 0.0 °, 5.3 °, 5.4 ° or intermediate or near these can be mentioned.
  • the in-plane orientation ⁇ of the oxide superconducting layer 12 and the in-plane orientation ⁇ of the oxide superconducting layer 22 may be about the same or different.
  • the in-plane orientation ⁇ of the oxide superconducting layer 32 of the connecting wire 30 is not particularly limited, but is, for example, 4.5 °, 4.8 °, 5.0 °, 5.3 °, 5.4 °, and the like. Values of 5.5 °, 6.0 °, 6.2 °, 7.0 °, 7.5 °, 8.0 °, or intermediate or near these, and even higher can be mentioned.
  • the difference between the in-plane orientation ⁇ of the oxide superconducting layer 32 and the in-plane orientation ⁇ of the oxide superconducting layers 12 and 22 is not particularly limited, but is, for example, 0.5 °, 0.6 °, 0.8.
  • the protective layers 13 and 23 bypass the overcurrent generated at the time of an accident, suppress the chemical reaction occurring between the oxide superconducting layers 12 and 22 and the layers provided on the protective layers 13 and 23, and the like.
  • the protective layers 13 and 23 include a silver (Ag) layer or a layer containing Ag (for example, an Ag alloy layer).
  • the Ag alloy preferably contains 50% or more of silver in terms of molar ratio or weight ratio.
  • the thickness of the protective layers 13 and 23 is preferably about 1 to 30 ⁇ m, and when the protective layers 13 and 23 are thinned, the thickness may be 10 ⁇ m or less, 5 ⁇ m or less, 2 ⁇ m or less, or the like.
  • a stabilizing layer such as a copper plating layer may be provided around the superconducting wires 10, 20, and 30.
  • the widths of the superconducting wires 10, 20, and 30 are not particularly limited, and examples thereof include 1 to 20 mm.
  • the lengths of the wire rods 10 and 20 to be connected are not particularly limited, and examples thereof include 1 m or more, 10 m or more, 100 m or more, 200 m or more, 500 m or more, and 1 km or more. It is also possible to connect a plurality of superconducting wires to form a longer wire.
  • the length of the connecting wire 30 may be as short as 1 m or less, for example.
  • the ratio of the lengths of the connecting wire rods 10 and 20 to the connecting wire rod 30 may be, for example, 10 times or more, 100 times or more, or 1000 times or more.
  • the length at which the oxide superconducting layers 12, 22 and 32 overlap between the connection target wires 10 and 20 and the connection wire 30 is not particularly limited, and examples thereof include 5 mm or more, 10 mm or more, and 20 mm or more.
  • the substrates 11, 21, 31 are, for example, tape-shaped substrates having main surfaces on both sides in the thickness direction.
  • the substrates 11, 21, 31 may have, for example, a metal substrate and an intermediate layer.
  • Specific examples of the metal constituting the metal substrate include nickel alloys typified by Hastelloy (registered trademark), stainless steel, and oriented NiW alloys in which a texture is introduced into the nickel alloy.
  • the intermediate layer is formed on the main surface on the side where the oxide superconducting layer is formed on the metal substrate.
  • the oxide superconducting layers 12, 22, directly on the substrates 11,21,31 without forming an intermediate layer, 32 can be formed.
  • the thickness of the metal substrate may be appropriately adjusted according to the intended purpose, and is, for example, in the range of 10 to 1000 ⁇ m.
  • the intermediate layer may have a multi-layer structure, and may have a diffusion prevention layer, a bed layer, an orientation layer, a cap layer, and the like in the order from the metal substrate side to the oxide superconducting layer side, for example. These layers are not always provided one by one, and some layers may be omitted, or two or more layers of the same type may be repeatedly laminated.
  • the intermediate layer may be a metal oxide. By forming the oxide superconducting layer on the intermediate layer having excellent orientation, it becomes easy to obtain the oxide superconducting layer having excellent orientation.
  • the in-plane orientation ⁇ of the oxide superconducting layer or the intermediate layer can be controlled by changing the film forming conditions such as the deposition in the ion beam assisted film formation (IBAD) method: changing the etching ratio, changing the temperature, frequency, etc. It can be carried out.
  • IBAD ion beam assisted film formation
  • the crystal axis is oriented by irradiating the vapor-deposited surface with an ion beam such as argon (Ar) at a predetermined angle.
  • the in-plane orientation degree ⁇ can be controlled by, for example, changing the balance between the vapor-deposited particles and the assist ion beam.
  • the in-plane orientation ⁇ of a layer such as an intermediate layer provided under the oxide superconducting layer
  • the in-plane orientation ⁇ of the oxide superconducting layer can be controlled.
  • the film forming method for the intermediate layer and the oxide superconducting layer is not particularly limited as long as an appropriate film forming is possible according to the composition of the metal oxide.
  • the film forming method include a dry film forming method such as a sputtering method, a vapor deposition method, an ion beam assisted film forming method (IBAD method), and a wet film forming method such as a sol-gel method.
  • the vapor deposition method include an electron beam vapor deposition method, a pulse laser vapor deposition method (PLD method), and a chemical vapor deposition method (CVD method).
  • At least one of the superconducting connecting portions has a connecting structure according to the above-described embodiment.
  • the superconducting connecting portions existing apart from each other in the longitudinal direction may have the same configuration, and the superconducting connections having different configurations may be obtained.
  • the parts may be used together.
  • an insulating tape such as polyimide may be wrapped around the outer circumference of the superconducting wire, or a resin layer may be formed.
  • An insulating coating layer such as an insulating tape or a resin layer is not indispensable, and an insulating coating layer may be appropriately provided depending on the use of the superconducting wire, or a configuration without an insulating coating layer may be provided.
  • the superconducting wire is wound along the outer peripheral surface of the winding frame in the required number of layers to form a coil-shaped multi-layered coil, and then the wound superconducting wire is covered. Can be impregnated with a resin such as an epoxy resin to fix the superconducting wire.
  • each superconducting wire was heat-treated at a temperature of 300 ° C. for 30 minutes in an oxygen (O 2 ) atmosphere. Before the heat treatment and after the heat treatment, each superconducting wire was cooled to a liquid nitrogen temperature and the critical current Ic was measured. The ratio of the increase in Ic after the heat treatment as compared with the Ic before the heat treatment was determined as the Ic increase rate. That is, when Ic before the heat treatment is Ic0 and Ic after the heat treatment is Ic1, the rate of increase in Ic is the ratio of Ic1 / Ic0.
  • the in-plane orientation ⁇ of the oxide superconducting layer of the connecting target wire which is the main wire of the superconducting wire
  • the in-plane orientation ⁇ of the oxide superconducting layer of the connecting wire is 5. 3 °
  • Ic can be increased after the heat treatment as compared with before the heat treatment.
  • the conditions of the oxygen heat treatment are not limited to the examples of this example, and may be performed at a higher temperature or for a longer period of time, for example.
  • Connection target wire (superconducting wire) 11,21 ... Connection target wire substrate, 12, 22 ... Connection target wire oxide superconducting layer, 13, 23 ... Connection target wire protection layer, 30 ... Connection Wire rod (superconducting wire), 31 ... Connection wire substrate, 32 ... Oxide superconducting layer of connecting wire, 41, 42, 43 ... Crystal orientation, 44, 45, 46 ... Crystal grain, 47 ... Grain boundary, 48 ... Dislocation group.

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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)

Abstract

Dans cette structure de connexion de fils supraconducteurs, dans laquelle des parties d'extrémité de chaque fil d'une pluralité de fils à connecter, comprenant chacune une première couche supraconductrice d'oxyde, sont connectées les unes aux autres au moyen de fils de connexion comportant une seconde couche supraconductrice d'oxyde, un premier degré d'orientation dans le plan Δφ des premières couches supraconductrices d'oxyde dans la pluralité de fils à connecter, dans une direction perpendiculaire à la direction d'épaisseur des premières couches supraconductrices d'oxyde, est au moins égal à 4,0° et inférieur à 5,5°, et un second degré d'orientation dans le plan Δφ des secondes couches supraconductrices d'oxyde dans les fils de connexion, dans une direction perpendiculaire à la direction d'épaisseur des secondes couches supraconductrices d'oxyde, est d'au moins 0,5° supérieur au premier degré d'orientation dans le plan Δφ des premières couches supraconductrices d'oxyde dans la pluralité de fils à connecter.
PCT/JP2020/013308 2019-03-29 2020-03-25 Structure de connexion de fils supraconducteurs, et fil supraconducteur WO2020203543A1 (fr)

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JP2019-065548 2019-03-29
JP2019065548A JP6707164B1 (ja) 2019-03-29 2019-03-29 超電導線材の接続構造体及び超電導線材

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011201712A (ja) * 2010-03-24 2011-10-13 Toshiba Corp 配向酸化物膜の製造方法および配向酸化物膜、酸化物超電導体
JP2015050147A (ja) * 2013-09-04 2015-03-16 東洋鋼鈑株式会社 超電導線材用基板及びその製造方法、並びに超電導線材

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011201712A (ja) * 2010-03-24 2011-10-13 Toshiba Corp 配向酸化物膜の製造方法および配向酸化物膜、酸化物超電導体
JP2015050147A (ja) * 2013-09-04 2015-03-16 東洋鋼鈑株式会社 超電導線材用基板及びその製造方法、並びに超電導線材

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