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CN-121983382-A - CuC-based copper oxide high-temperature superconducting material and preparation method and application thereof

CN121983382ACN 121983382 ACN121983382 ACN 121983382ACN-121983382-A

Abstract

The invention relates to the technical field of high-temperature superconducting materials, and discloses a CuC-based copper oxide high-temperature superconducting material, and a preparation method and application thereof. The chemical formula of the CuC-based copper oxide is (Cu x ,M y C 1‑x‑y )Ba 2 Ca 3 Cu 4 O 11+δ ), wherein M is at least one selected from B, al, si, ge, S, se, te, x is more than or equal to 0.1 and less than or equal to 0.9, y is more than or equal to 0 and less than or equal to 1. The preparation method comprises the steps of respectively synthesizing BaCuO 2 and Ca 2 CuO 3 precursor powder, mixing the precursor powder with a compound containing M element, and performing ball milling and sintering for multiple times to finally prepare the target material for coating.

Inventors

  • LIU HUI
  • Yang Pidao
  • GAO LEI

Assignees

  • 中国科学院物理研究所

Dates

Publication Date
20260505
Application Date
20260126

Claims (10)

  1. 1. A CuC-based copper oxide high-temperature superconducting material is characterized in that the chemical formula of the CuC-based copper oxide is (Cu x ,M y C 1-x-y )Ba 2 Ca 3 Cu 4 O 11+δ , wherein M is at least one selected from B, al, si, ge, S, se, te, x is more than or equal to 0.1 and less than or equal to 0.9, and y is more than or equal to 0 and less than or equal to 1.
  2. 2. The method for preparing the CuC-based copper oxide high-temperature superconducting material according to claim 1, wherein the target material of the CuC-based copper oxide high-temperature superconducting material is prepared by any one of a solid-phase sintering method, a sol-gel method and a precipitation method.
  3. 3. A preparation method of a CuC-based copper oxide high-temperature superconducting material is characterized by comprising the following steps: s1, synthesizing a pure-phase BaCuO 2 precursor; S2, synthesizing a pure-phase Ca 2 CuO 3 precursor; S3, mixing a compound containing M element with a BaCuO 2 precursor, a Ca 2 CuO 3 precursor and CuO through ball milling according to the molar ratio of M to Ba to Ca to Cu of 2 to 3 to 4, sequentially performing high-temperature sintering and ball milling, and repeating the high-temperature sintering and ball milling for a plurality of times to obtain the CuC-based copper oxide high-temperature superconducting material; Wherein: the M element is at least one selected from B, al, si, ge, S, se, te, and 0< y is less than or equal to 1.
  4. 4. The method according to claim 3, wherein in step S3, the M-containing compound is at least one selected from the group consisting of an oxide of M, MO 2- 、MO 3 2- 、MO 3- 、MO 4 2- and a compound consisting of MO 4 4- and Ba 2+ 、Ca 2+ .
  5. 5. The method according to claim 3 or 4, wherein M is one or more selected from the group consisting of: B 2 O 3 、Al 2 O 3 、SiO 3 、GeO 3 、SO 3 、SO 3 、SeO 3 、TeO 2 、TeO、Ca 3 (BO 3 )2、Ba 3 (BO 3 )2、CaB 4 O 7 ·4H2O、BaB 4 O 7 、Ca(BO2) 3 、Ba(BO 3 ) 3 、Ca[Al(OH) 4 ] 5 、Ba[Al(OH) 4 ] 2 、CaAl 2 O 4 、BaAl 2 O 4 、CaSiO 3 、BaSiO 3 、Ca 2 SiO 4 、Ba 2 SiO 4 、Ca 2 Si 2 O 5 、Ba 2 Si 2 O 5 、CaGeO 3 、BaGeO 3 、CaSO 4 ·2H 2 O、CaSO 4 ·0.5H 2 O、BaSO 4 、CaSO 3 ·0.5H 2 O、BaSO 3 、CaS 2 O 3 、BaS 2 O 3 、CaS 2 O 8 、BaS 2 O 8 、CaSeO 4 ·2H 2 O、BaSeO 4 、CaSeO 3 、BaSeO 3 、CaTeO 4 、BaTeO 4 、CaTeO 3 、BaTeO 3 .
  6. 6. The method of claim 3, wherein in step S3, the high-temperature sintering is performed at 850-950 ℃, the sintering time is 10-50 hours, and the ball milling time is 1-100 hours.
  7. 7. The method for preparing the pure-phase BaCuO 2 precursor, as set forth in claim 3, is characterized in that in the step S1, the method for synthesizing the pure-phase BaCuO 2 precursor comprises the steps of ball milling barium carbonate powder and copper oxide powder according to a molar ratio of 1:0.9-1, sequentially performing high-temperature sintering and ball milling, and repeating the high-temperature sintering and ball milling for a plurality of times to obtain the pure-phase BaCuO 2 precursor.
  8. 8. The method for preparing the pure-phase Ca 2 CuO 3 precursor according to the preparation method of the pure-phase Ca 2 CuO 3 precursor, which is characterized in that in the step S2, the pure-phase Ca 2 CuO 3 precursor is obtained by performing ball milling treatment on calcium carbonate powder and copper oxide powder according to a molar ratio of 1:1-1.2, then sequentially performing high-temperature sintering and ball milling treatment, and repeating the high-temperature sintering and ball milling treatment for a plurality of times.
  9. 9. The CuC-based copper oxide high-temperature superconducting material according to claim 1 or the application of the CuC-based copper oxide prepared by the preparation method according to any one of claims 3-8 in preparing superconducting thin films.
  10. 10. A preparation method of a high-temperature superconducting tape is characterized by comprising the step of depositing a superconducting film on a base band by using the CuC-based copper oxide as a target material according to claim 1 or using the CuC-based copper oxide prepared by the preparation method according to any one of claims 3-8 as a target material through a pulse laser deposition technology.

Description

CuC-based copper oxide high-temperature superconducting material and preparation method and application thereof Technical Field The invention relates to the technical field of high-temperature superconducting materials, in particular to a novel CuC-based compound for coating a high-temperature superconducting strip and a preparation method thereof. Background The high-temperature superconducting material has the characteristics of zero resistance, complete diamagnetism and the like in a liquid nitrogen temperature region, and has wide prospect in the fields of strong current application (such as superconducting cables and magnets) and weak current application (such as superconducting quantum interference devices). Among many high temperature superconducting materials, copper-based superconductors have the highest superconducting transition temperature (Tc). (Cu, C) Ba 2Ca3Cu4O11+δ, abbreviated as CuC1234, is a copper oxide high-temperature superconductor, which is used as a new generation copper-based high-temperature superconductor, and a high-temperature superconducting film obtained by using the copper oxide high-temperature superconductor as a target material, shows excellent performances such as high irreversible field, low anisotropy, high critical current density (Jc) and the like, and is considered as a potential strong electricity application candidate material. However, practical applications of CuC-1234 materials face significant manufacturing challenges. For CuC-1234 bulk materials, high quality single or polycrystalline samples are obtained, which typically require extreme conditions, such as ultra-high pressures up to 3.5 to 6 GPa and high temperatures of 1000 to 1200 ℃. However, the harsh synthesis conditions result in high equipment requirements, complex process and high cost, and large-scale production is difficult to realize, so that the application basic research and the industrialized development of the material are severely limited. In practical preparation, the repeated preparation effect under the above conditions is poor. Second, cuC-1234 performs poorly in more practical film and tape preparation, particularly in physical vapor deposition techniques such as pulsed laser deposition. Specifically, the superconducting performance of the thin film strongly depends on process parameters during deposition, for example, carbon dioxide (CO 2) is often used as a source of gas for providing CO 32- in the prior art published as CuC-1234 for stabilizing a crystal structure, as in patent publication No. CN118308692a, and doping is performed during deposition of the thin film, but the inventors found that minute fluctuations in gas flow rate directly cause instability of carbon oxygen content in the thin film during experiments repeated for this patent, thereby causing significant deterioration of phase purity and superconducting performance, and thus lower superconducting transition temperature. Therefore, the CO 2 gas is used for C doping during thin film deposition, and the process window is narrow. In addition, there is a weak grain boundary junction problem in the thin film, resulting in an actual critical current density well below the theoretical value. Therefore, the CuC-1234 material prepared in the prior art has the problem of low superconducting transition temperature and critical current density. Therefore, a new design idea and preparation scheme of high-performance superconducting materials are urgently needed, the process window is widened, and the stability and repeatability of the preparation process are improved so as to improve the superconducting transition temperature and the stability of the high-temperature superconducting materials. Disclosure of Invention In order to solve the problems of low superconducting transition temperature and poor stability of the high-temperature superconducting material, the invention provides a CuC-based copper oxide high-temperature superconducting material, and a preparation method and application thereof. The specific technical scheme of the invention is as follows: in one aspect, the invention provides a CuC-based copper oxide high-temperature superconducting material, wherein the chemical formula of the CuC-based copper oxide is (Cu x,MyC1-x-y)Ba2Ca3Cu4O11+δ), M is at least one selected from B, al, si, ge, S, se, te, x is more than or equal to 0.1 and less than or equal to 0.9, and y is more than or equal to 0 and less than or equal to 1. The inventor finds in experiments that the CuC-based copper oxide obtained after M element is doped in the CuC-1234 material can stabilize the structure of the CuC-based copper oxide and can greatly stabilize the process for preparing the superconductive tape, and the superconductive film prepared by taking the CuC-based copper oxide as a target material has stable superconductive transition temperature and higher superconductive transition temperature. The chemical formula of the CuC-based copper oxide