A REBCO superconducting coated conductor with a multi-element BaMO3 synergistic pinning structure and its preparation method
By introducing a multi-element BaMO3 nanopinning structure into the REBCO superconducting layer, the problems of limited doping concentration and lattice distortion in the single BaMO3 doping method were solved, and the performance of the REBCO superconducting coated conductor was improved under wide temperature range and high magnetic field conditions, enhancing the flux pinning performance and adaptability.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- INST OF ELECTRICAL ENG CHINESE ACAD OF SCI
- Filing Date
- 2026-04-02
- Publication Date
- 2026-06-19
AI Technical Summary
In the existing technology, the single BaMO3 doping method in REBCO superconducting coated conductors has problems such as limited doping concentration, lattice distortion, poor nucleation, and inability to take into account anisotropy and low-temperature performance, resulting in limited flux pinning performance under complex and wide operating conditions.
A multi-element BaMO3 nanopinning structure was adopted. By introducing BaMO3 nanopinning centers of different compositions into the REBCO superconducting layer, a combination of c-axis oriented nanorods and nanoparticle structures was formed. The coated conductor was prepared by PLD target predoping.
This study improves the flux pinning performance of REBCO superconducting coated conductors under wide temperature range and high magnetic field conditions, enhances anisotropy, has strong adaptability, good process flexibility, and high repeatability, and provides an experimental platform for studying the synergistic mechanism of multiple pinning centers.
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Figure CN122248965A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of high-temperature superconducting material preparation technology, specifically to a REBCO superconducting coated conductor with a multi-element BaMO3 synergistic pinning structure and its preparation method. Background Technology
[0002] REBa₂Cu₃Oy (REBCO, where RE represents rare earth elements) high-temperature superconducting coated conductors have wide applications in fields such as nuclear fusion high-field magnets, power transmission, magnetic resonance imaging, and high-field magnets due to their excellent critical current density (Jc) and high magnetic field performance. To improve the Jc performance of REBCO under high magnetic fields and different temperature conditions, researchers commonly use nanorods formed from BaMO₃ (M=Hf, Zr, Sn, Ti, etc.) compounds as pinning centers to induce c-axis oriented nanostructures to enhance flux pinning. Existing studies have shown that while single-type BaMO₃ nanorods perform well in a specific temperature range and magnetic field direction, their pinning enhancement effect is still limited under more complex and broader operating conditions.
[0003] Currently, the commonly used single BaMO3 doping methods mainly have the following problems: Although single BaMO3 doping (such as BaHfO3 / BaZrO3 / BaSnO3) can introduce pinning centers, the doping concentration is limited (<7 mol%). Excessive doping leads to REBCO phase separation. As the doping amount increases, single pinning phases are prone to lattice distortion and poor nucleation, reducing REBCO orientation and continuity. Single-type nanopinning centers (such as BHO) usually only have significant performance at a certain temperature or magnetic field direction (such as 77 K, vertical field). They cannot take into account both anisotropy and low-temperature performance: at low temperatures (such as 30 K, 4.2 K) or high magnetic field conditions, the improvement of Jc (critical current density) is limited. Summary of the Invention
[0004] To address the aforementioned technical problems, this invention provides a REBCO superconducting coated conductor with a multi-element BaMO3 synergistic pinning structure and its preparation method. This invention improves the flux pinning performance of the REBCO superconducting layer under wide temperature range and high magnetic field conditions by introducing a multi-element BaMO3 nano-pinning structure into the REBCO superconducting layer.
[0005] To achieve the above objectives, the present invention adopts the following technical solution:
[0006] A REBCO superconducting coated conductor with a multi-element BaMO3 synergistic pinning structure is disclosed, which has a multi-element BaMO3 nanopinning structure; wherein M is one or more elements selected from Hf, Zr, Sn, Ti, Ce, and Nb; the multi-element BaMO3 nanopinning structure is composed of at least two BaMO3 second phases with different compositions; the BaMO3 second phases form nanopinning structures with different morphologies in the REBCO matrix.
[0007] The multi-element BaMO3 nanopinning structure is a c-axis oriented nanorod structure, a nanoparticle structure, or a combination of both.
[0008] The c-axis oriented nanorods have a diameter of 3 nm to 20 nm and a length of 50 nm to 500 nm.
[0009] The nanoparticles in the nanoparticle structure have a size of 3 nm to 50 nm and a volume fraction of 2% to 20%.
[0010] The preparation method of the REBCO superconducting coated conductor with the multi-element BaMO3 synergistic pinning structure described above is specifically as follows: the REBCO superconducting coated conductor with the multi-element BaMO3 synergistic pinning structure is prepared by pre-doping using a PLD target.
[0011] The preparation of the REBCO superconducting coated conductor using the PLD target pre-doping method specifically includes the following steps:
[0012] S1: Target preparation: Select appropriate BaMO3 raw materials as needed and prepare PLD targets in a certain proportion, wherein the PLD targets include at least two BaMO3 raw materials;
[0013] S2: Deposition: Deposit REBCO superconducting coating on the substrate according to the set deposition conditions to obtain REBCO superconducting coated conductor;
[0014] S3: Heat treatment: The REBCO superconducting coated conductor obtained in step S2 is subjected to in-situ oxidation treatment.
[0015] Step S1 specifically includes the following steps:
[0016] S11: A multi-component BaMO3 mixed phase with a certain molar ratio was prepared by powder synthesis method;
[0017] S12: Mix the mixed-doped BaMO3 powder with the REBCO precursor uniformly;
[0018] S13: Press and sinter to form a PLD target.
[0019] The molar ratio of different BaMO3 components in the multi-component BaMO3 powder is 1:9 to 9:1.
[0020] The deposition conditions are as follows: substrate temperature 750~900 ℃; oxygen pressure 100~500 mTorr; laser energy density 1~3 J / cm³. 2 Pulse frequency 10~300 Hz.
[0021] In step S3, the in-situ oxidation treatment is carried out at a temperature of 400-600°C for 3-24 hours.
[0022] The beneficial effects of this invention are as follows:
[0023] (1) The REBCO superconducting coating conductor of the multi-element BaMO3 synergistic pinning structure of the present invention has a wide range of enhanced conductor performance, with Jc performance improvement at high temperature (~77 K), medium temperature (40~60 K) and low temperature (4.2 K);
[0024] (2) The anisotropy of the REBCO superconducting coating conductor of the multi-element BaMO3 synergistic pinning structure of the present invention is significantly improved. Different types of nano-pinning structures work together to suppress performance fluctuations caused by changes in magnetic field angle.
[0025] (3) The REBCO superconducting coated conductor of the multi-element BaMO3 synergistic pinning structure of the present invention has strong adaptability and can freely combine pinning phases according to the target application, thus having process flexibility;
[0026] (4) The preparation method of the REBCO superconducting coated conductor with the multi-element BaMO3 synergistic pinning structure of the present invention has good repeatability. It uses PLD target predoping method to avoid complex in-situ injection process, and the process is stable and reliable.
[0027] (5) The REBCO superconducting coated conductor of the multi-element BaMO3 synergistic pinning structure of the present invention can promote the study of pinning mechanism and provide an experimental platform for studying the synergistic mechanism and magnetic flux dynamics response between multi-element pinning centers. Attached Figure Description
[0028] Figure 1 This is a TEM (transmission electron microscope) image of the ac surface of the REBCO superconducting coated conductor with a multi-element BaMO3 synergistic pinning structure prepared in Example 1 of the present invention.
[0029] Figure 2 This is a TEM image of the ab plane of the REBCO superconducting coated conductor with a multi-element BaMO3 synergistic pinning structure prepared in Example 1 of the present invention.
[0030] Figure 3The curves showing the Jc (critical current density) versus external field at 20 K are for the REBCO superconducting coated conductor with a multi-element BaMO3 synergistic pinning structure and the REBCO superconducting coated conductor reinforced with a single BaMO3, prepared in Example 1 of this invention.
[0031] Figure 4 The curves showing the Jc (critical current density) versus external field at 50 K are for the REBCO superconducting coated conductor with a multi-element BaMO3 synergistic pinning structure and the REBCO superconducting coated conductor reinforced with a single BaMO3, prepared in Example 2 of this invention. Detailed Implementation
[0032] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. Furthermore, the technical features involved in the various embodiments of this invention described below can be combined with each other as long as they do not conflict with each other.
[0033] Example 1
[0034] S1: Preparation of target material:
[0035] S11: A multi-component BaMO3 mixed phase with a certain molar ratio was prepared by powder synthesis method; specifically, BaHfO3 and BaSnO3 powders were mixed in a molar ratio of 4.5:3.5 to obtain the multi-component BaMO3 mixed phase.
[0036] S12: Mix the doped BaMO3 powder with the REBCO precursor (EuBa 1.9 The mixture of Cu3Ox and other precursors was uniformly mixed and pressed into a PLD target; the molar ratio of BaHfO3 to REBCO precursor was 4.5:92.
[0037] S2: Deposition: A REBCO superconducting coating is deposited on the substrate according to the set deposition conditions to obtain a REBCO superconducting conductor. The specific deposition conditions are: substrate temperature 850℃, oxygen pressure 300 mTorr, laser wavelength 248 nm, pulse frequency 50 Hz, and energy density 2 J / cm³. 2 The substrate is an IBAD metal baseband.
[0038] S3: The REBCO superconducting coated conductor obtained in step S2 can be obtained by in-situ oxidation treatment to obtain the REBCO superconducting coated conductor with multi-element BaMO3 synergistic pinning structure. Specifically, the in-situ oxidation treatment is annealing at 450°C and one atmosphere of oxygen for 3 hours.
[0039] Figure 1This is a TEM image of the ac plane of the REBCO superconducting coated conductor with the multi-element BaMO3 synergistic pinning structure prepared in Example 1. From... Figure 1 As can be seen from the image, the REBCO superconducting coated conductor prepared in this embodiment exhibits both columnar and dot-shaped pinning centers. The columnar pinning centers are pinning centers of c-axis oriented nanorod structures, while the dot-shaped pinning centers are pinning centers of nanoparticle structures.
[0040] Figure 2 This is a TEM image of the ab plane of the REBCO superconducting coated conductor with the multi-element BaMO3 synergistic pinning structure prepared in Example 1. From... Figure 2 As can be seen from this, the REBCO superconducting coated conductor prepared in this embodiment introduces a large number of densely pinned centers.
[0041] Figure 3 These are the Jc (critical current density) versus external field curves at 20 K for the REBCO superconducting coated conductor with a multi-element BaMO3 synergistic pinning structure prepared in Example 1 and the REBCO superconducting coated conductor reinforced with a single BaMO3 element. Figure 3 As can be seen, multi-component BaMO3 doping exhibits higher performance than single-component BaMO3 doping.
[0042] Example 2
[0043] S1: Preparation of target material:
[0044] S11: A multi-component BaMO3 mixed phase with a certain molar ratio was prepared by powder synthesis method; specifically, BaHfO3 and BaSnO3 powders were mixed in a molar ratio of 4:3 to obtain the multi-component BaMO3 mixed phase.
[0045] S12: Mix the doped BaMO3 powder with the REBCO precursor (EuBa 1.9 The mixture of Cu3Ox was uniformly mixed and pressed into a PLD target; the molar ratio of BaHfO3 to REBCO precursor was 4:93.
[0046] S2: Deposition: A REBCO superconducting coating is deposited on the substrate according to the set deposition conditions to obtain a REBCO superconducting conductor. The specific deposition conditions are: substrate temperature 850℃, oxygen pressure 300 mTorr, laser wavelength 248 nm, pulse frequency 50 Hz, and energy density 2 J / cm³. 2 The substrate is an IBAD metal baseband.
[0047] S3: Perform in-situ oxidation treatment on the REBCO superconducting coated conductor obtained in step S2, i.e., anneal at 600°C and in an oxygen atmosphere at one atmosphere for 3 hours.
[0048] Figure 4These are the Jc (critical current density) versus external field curves at 50 K for the REBCO superconducting coated conductor with a multi-element BaMO3 synergistic pinning structure prepared in Example 2 and the REBCO superconducting coated conductor reinforced with a single BaMO3 element. Figure 4 As can be seen, multi-component BaMO3 doping exhibits higher performance than single-component BaMO3 doping.
[0049] Example 3
[0050] S1: Preparation of target material:
[0051] S11: A multi-component BaMO3 mixed phase with a certain molar ratio was prepared by powder synthesis method; specifically, BaHfO3, BaZrO3 (BZO) and BaTiO3 (BTO) powders were mixed in a molar ratio of 4:3:3 to obtain the multi-component BaMO3 mixed phase.
[0052] S12: Mix the doped BaMO3 powder with the REBCO precursor (EuBa 1.9 The mixture of Cu3Ox was uniformly mixed and pressed into a PLD target; the molar ratio of BaHfO3 to REBCO precursor was 4:90.
[0053] S2: Deposition: A REBCO superconducting coating is deposited on the substrate according to the set deposition conditions to obtain a REBCO superconducting conductor. The specific deposition conditions are: substrate temperature 750℃, oxygen pressure 500 mTorr, laser wavelength 248 nm, pulse frequency 10 Hz, and energy density 1 J / cm³. 2 The substrate is an IBAD metal baseband.
[0054] S3: Perform in-situ oxidation treatment on the REBCO superconducting coated conductor obtained in step S2, that is, anneal at 400°C and in an oxygen atmosphere at one atmosphere for 3 hours.
[0055] According to measurements, the anisotropy of the REBCO superconducting coated conductor with the multi-element BaMO3 synergistic pinning structure prepared in this embodiment is 3.5, while the anisotropy of the REBCO superconducting coated conductor reinforced with a single BaMO3 is 5.5.
[0056] Example 4
[0057] S1: Preparation of target material:
[0058] S11: A multi-component BaMO3 mixed phase with a certain molar ratio was prepared by powder synthesis method; specifically, BaHfO3 and BaZrO3 (BZO) powders were mixed in a molar ratio of 4:3 to obtain the multi-component BaMO3 mixed phase.
[0059] S12: Mix the doped BaMO3 powder with the REBCO precursor (EuBa 1.9The mixture of Cu3Ox was uniformly mixed and pressed into a PLD target; the molar ratio of BaHfO3 to REBCO precursor was 4:93.
[0060] S2: Deposition: A REBCO superconducting coating is deposited on the substrate according to the set deposition conditions to obtain a REBCO superconducting conductor. The specific deposition conditions are: substrate temperature 900℃, oxygen pressure 100 mTorr, laser wavelength 248 nm, pulse frequency 100 Hz, and energy density 3 J / cm³. 2 The substrate is an IBAD metal baseband.
[0061] S3: Perform in-situ oxidation treatment on the REBCO superconducting coated conductor obtained in step S2, i.e., anneal at 400°C and in an oxygen atmosphere at one atmosphere for 24 hours.
[0062] According to measurements, the Jc of the REBCO superconducting coated conductor with the multi-element BaMO3 synergistic pinning structure prepared in this embodiment is 30% higher than that of single pinning at 4.2K 10T.
[0063] Those skilled in the art will readily understand that the above description is merely a preferred embodiment of the present invention. The above embodiments are provided only for the purpose of describing the present invention and are not intended to limit the present invention. Parts not described in detail in this specification are well-known in the art and are not intended to limit the scope of the present invention. The scope of the present invention is defined by the appended claims. All equivalent substitutions and modifications made without departing from the spirit and principle of the present invention should be covered within the scope of the present invention.
Claims
1. A REBCO superconducting coated conductor of a multi-element BaMO3 cooperative pinning structure, characterized in that, The REBCO superconducting coated conductor has a multi-element BaMO3 nanopinned structure; wherein M is one or more elements selected from Hf, Zr, Sn, and Ti; the multi-element BaMO3 nanopinned structure is composed of at least two BaMO3 second phases with different compositions; the BaMO3 second phases form nanopinned structures with different morphologies in the REBCO matrix.
2. The REBCO superconducting coated conductor with a multi-element BaMO3 synergistic pinning structure according to claim 1, characterized in that, The multi-element BaMO3 nanopinning structure is a c-axis oriented nanorod structure, a nanoparticle structure, or a combination of both.
3. The REBCO superconducting coated conductor with a multi-element BaMO3 synergistic pinning structure according to claim 2, characterized in that, The c-axis oriented nanorods have a diameter of 3 nm to 20 nm and a length of 50 nm to 500 nm.
4. The REBCO superconducting coated conductor with a multi-element BaMO3 synergistic pinning structure according to claim 2, characterized in that, The nanoparticles in the nanoparticle structure have a size of 3 nm to 50 nm, and the volume fraction of the nanoparticle structure is 2% to 20%.
5. A method for preparing a REBCO superconducting coated conductor with a multi-element BaMO3 synergistic pinning structure as described in any one of claims 1 to 4, characterized in that, The REBCO superconducting coated conductor with the multi-element BaMO3 synergistic pinning structure was prepared using a PLD target predoping method.
6. The method for preparing the REBCO superconducting coated conductor with a multi-element BaMO3 synergistic pinning structure according to claim 5, characterized in that, The preparation of the REBCO superconducting coated conductor using the PLD target predoping method specifically includes the following steps: S1: Target preparation: Select appropriate BaMO3 raw materials as needed and prepare PLD targets in a certain proportion, wherein the PLD targets include at least two BaMO3 raw materials; S2: Deposition: Deposit REBCO superconducting coating on the substrate according to the set deposition conditions to obtain REBCO superconducting coated conductor; S3: Heat treatment: The REBCO superconducting coated conductor obtained in step S2 is subjected to in-situ oxidation treatment.
7. The method for preparing the REBCO superconducting coated conductor with a multi-element BaMO3 synergistic pinning structure according to claim 6, characterized in that, Step S1 specifically includes the following steps: S11: A multi-component BaMO3 mixed phase with a certain molar ratio was prepared by powder synthesis method; S12: Mix the mixed-doped BaMO3 powder with the REBCO precursor uniformly; S13: Press and sinter to form a PLD target.
8. The method for preparing the REBCO superconducting coated conductor with a multi-element BaMO3 synergistic pinning structure according to claim 7, characterized in that, The molar ratio of different BaMO3 components in the multi-component BaMO3 powder is 1:9 to 9:
1.
9. The method for preparing the REBCO superconducting coated conductor with a multi-element BaMO3 synergistic pinning structure according to claim 6, characterized in that, The deposition conditions are: substrate temperature 750-900 ℃; oxygen pressure 100-500 mTorr; laser energy density 1-3 J / cm 2 ; pulse frequency 10-300 Hz.
10. The method for preparing the REBCO superconducting coated conductor with a multi-element BaMO3 synergistic pinning structure according to claim 6, characterized in that, The temperature of the in-situ oxidation treatment in step S3 is 400~600℃, and the time of the in-situ oxidation treatment is 3-24 hours.