CN113470883A - Non-toxic copper oxide superconductor with high critical parameter and its preparing process - Google Patents
Non-toxic copper oxide superconductor with high critical parameter and its preparing process Download PDFInfo
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 239000002887 superconductor Substances 0.000 title claims abstract description 69
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 37
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 37
- 231100000252 nontoxic Toxicity 0.000 title claims abstract description 22
- 230000003000 nontoxic effect Effects 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000008569 process Effects 0.000 title description 2
- 239000010949 copper Substances 0.000 claims abstract description 85
- 239000000463 material Substances 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 16
- 229910052796 boron Inorganic materials 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 57
- 229910052760 oxygen Inorganic materials 0.000 claims description 57
- 239000001301 oxygen Substances 0.000 claims description 57
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 54
- 229910052737 gold Inorganic materials 0.000 claims description 54
- 239000010931 gold Substances 0.000 claims description 54
- 239000002243 precursor Substances 0.000 claims description 39
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 25
- 238000003466 welding Methods 0.000 claims description 23
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 22
- 238000000227 grinding Methods 0.000 claims description 21
- 238000003825 pressing Methods 0.000 claims description 21
- 238000007789 sealing Methods 0.000 claims description 21
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Inorganic materials [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 18
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims description 12
- 238000011049 filling Methods 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910010293 ceramic material Inorganic materials 0.000 claims 2
- 231100000701 toxic element Toxicity 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- 230000002427 irreversible effect Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 8
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- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910002480 Cu-O Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 230000005415 magnetization Effects 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 229910021521 yttrium barium copper oxide Inorganic materials 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- 229910052580 B4C Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- -1 Y-system (123 Chemical compound 0.000 description 1
- BTGZYWWSOPEHMM-UHFFFAOYSA-N [O].[Cu].[Y].[Ba] Chemical compound [O].[Cu].[Y].[Ba] BTGZYWWSOPEHMM-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 238000010587 phase diagram Methods 0.000 description 1
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- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- 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
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Abstract
本发明公开了一种具有高临界参数无毒铜氧化物超导体及其制备方法。所述铜氧化物超导体的结构式为ABa2CaxCuyOz+δ；其中，x的取值为2，y的取值为3，z的取值为8，所述δ取值为：0.76‑1，所述A为Ga，Al或B；或x的取值为3，y的取值为4，z的取值为11，所述δ取值为：0‑1，所述A为Ga，Al，B中的任一种或者A为Cu与C的组合。本发明通过高温高压方法用无毒性的较轻原子替换其中的有毒元素，合成出高临界参数无毒超导材料。
The invention discloses a nontoxic copper oxide superconductor with high critical parameters and a preparation method thereof. The structural formula of the cuprate superconductor is ABa 2 Ca x Cu y O z+δ ; wherein, the value of x is 2, the value of y is 3, the value of z is 8, and the value of δ is: 0.76-1, the A is Ga, Al or B; or the value of x is 3, the value of y is 4, the value of z is 11, the value of δ is: 0-1, the value of A It is any one of Ga, Al, and B, or A is a combination of Cu and C. In the present invention, the toxic elements are replaced with non-toxic lighter atoms by the high temperature and high pressure method, and the non-toxic superconducting material with high critical parameters is synthesized.
Description
Technical Field
The present invention relates to a material synthesis technology, which is used for growing a non-toxic copper oxide superconducting material with high critical parameters, and high-temperature superconducting materials are formed by replacing atoms with heavy toxicity with high-pressure stable non-toxic light atoms.
Background
Pressure is a basic thermodynamic variable which, like temperature, is an important factor in controlling physical phenomena. The high pressure synthesis technology is a technology in which an external high pressure is applied to an object to combine different substances or to cause a substance to undergo a multi-phase transformation, thereby obtaining a new phase, a new compound or a new material. The high pressure effect can increase the coordination number of the crystal structure of the material, improve the density, reduce the internal atomic distance and enhance the interaction. Moreover, the electron cloud overlap state changes under high pressure, and the electron configuration of the bonding electrons changes from the normal pressure. Thus, it is possible to synthesize a compound which cannot be synthesized or is difficult to synthesize at normal pressure, synthesize a high-pressure phase existing in a metastable state at normal pressure, synthesize a high-pressure phase which does not exist at normal pressure, and synthesize a compound containing a volatile substance under high pressure. At present, high pressure becomes one of the important means for synthesizing new materials, and the high-temperature high-pressure synthesis technology plays an important role in synthesizing new superconductors.
For superconductor applications, critical parameters are very important indicators, including critical transition temperature, upper and lower critical fields, irreversible field, critical current, etc. On the diagram of magnetic field and temperature of superconductor, there is a boundary line marked lossless transmission current called irreversible line HirrAnd (T) dividing the magnetic field-temperature phase diagram into two regions, wherein the superconductor can only carry certain superconducting current at the temperature and the magnetic field below the irreversible line. For practical purposes, the irreversible wire determines the upper limit of the capacity of a superconductor to carry lossless current, and generally, the higher the irreversible magnetic field is, the stronger the capacity of the superconductor to carry lossless current under a strong magnetic field is, and a better application prospect is expected. Another important parameter of superconducting materials is the critical transition temperature TcOnly below the critical temperature, the superconductor can enter a superconducting state, and therefore, a superconductor with a higher critical temperature is required for superconducting applications. Liquid nitrogen has a boiling point of 77.3K, and is a refrigerant that is easy to manufacture and low in cost. Superconductors with critical temperatures above the temperature of liquid nitrogen and high irreversible magnetic fields have therefore been found to be of major importance for superconducting large-scale applications. There are many superconductors in the copper oxide superconductor familyThe critical temperature of the body exceeding that of liquid nitrogen, e.g. Y-system (123, T)c91K), Bi-system (2223, T)c110K), Tl-system (2223, T)c125K) and Hg-series (1234, T)c124K), etc.
In addition to the critical parameters mentioned above, an important aspect limiting the use of copper oxide is the presence of toxic elements. As described above, the copper oxide having a superconducting transition temperature higher than 100K mainly includes Bi-system, Tl-system, and Hg-system. The latter two contain the toxic elements thallium and mercury, and the irreversible magnetic field in the liquid nitrogen temperature zone is not high. Although the Bi-system is not toxic, it has too strong bidimensionality, the superconducting critical current in a magnetic field decreases rapidly, and the irreversible magnetic field is very low, so that it cannot be applied to strong electricity at the liquid nitrogen temperature. Y-series superconductor yttrium barium copper oxide (YBa)2Cu3O7-δYBCO for short) has a critical temperature exceeding the temperature of liquid nitrogen and a high irreversible magnetic field, so people currently expect large-scale application of a liquid nitrogen temperature zone on the YBCO; however, due to their short coherence length, the preparation of long wires is extremely difficult and has not been realized to date on a large scale. The superconducting science has urgent need to find a nontoxic superconductor with a superconducting critical temperature above the temperature of liquid nitrogen and a higher irreversible magnetic field so as to realize better application.
In addition, from the viewpoint of material growth, the phase formation of the high temperature superconducting material requires atoms with larger radius such as Tl, Hg, Bi, etc., which are beneficial to the formation of the framework of the copper-oxygen structure, but because these atoms are toxic or the corresponding superconducting material has defects, certain replacement is required. Toxic heavy elements are replaced by some lighter non-toxic elements, and the high-temperature high-pressure technology plays an important role.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defect that most of copper oxide superconducting materials with higher critical temperature contain toxic elements, the invention provides a method for synthesizing a high-critical-parameter nontoxic superconducting material by replacing the toxic elements in the copper oxide superconducting materials with nontoxic lighter atoms through a high-temperature high-pressure method.
The technical scheme is as follows: one kind of the invention is highA critical parameter nontoxic copper oxide superconductor, the structural formula of the copper oxide superconductor is ABa2CaxCuyOz+δ(ii) a Wherein x is 2, y is 3, z is 8, and δ is: 0.76-1, wherein A is Ga, Al or B; or x is 3, y is 4, z is 11, and δ is: 0-1, wherein A is any one of Ga, Al and B or A is the combination of Cu and C.
ABa of the invention2CaxCuyOz+δPolycrystalline structures and single crystal structures are included.
When the copper oxide superconductor has the formula ABa2Ca2Cu3O8+δ，ABa2Ca2Cu3O8+δFrom a precursor BaCuO2.13、Ca2CuO3、A2O3And an oxygen source, said A2O3Is Ga2O3，Al2O3Or B2O3(ii) a When the copper oxide superconductor has the formula ABa2Ca3Cu4O11+δWhen A is any one of Ga, Al and B, ABa2Ca3Cu4O11+δMade of BaCuO2.13、Ca2CuO3、CuO、A2O3And an oxygen source, when A is a combination of Cu and C, ABa2Ca3Cu4O11+δMade of BaCuO2.13、Ca2CuO3、CuO、CaCO3、BaCO3And an oxygen source.
Specifically, when A is a light element Ga, Al or B, the copper oxide superconductor has a structural formula ABa2Ca2Cu3O8+δFrom a precursor BaCuO2.13、Ca2CuO3、A2O3And Ag2O (or KClO)4) Is prepared from A2O3Selected from Ga2O3，Al2O3Or B2O3One of (1); precursor BaCuO2.13、Ca2CuO3、A2O3And Ag2O (or KClO)4) In a molar ratio of 2: 1: 0.5: 0-0.24.
When A is light Ga, Al or B, the copper oxide superconductor has a structural formula ABa2Ca3Cu4O11+δFrom a precursor BaCuO2.13、Ca2CuO3、CuO、A2O3And Ag2O (or KClO)4) Prepared by a precursor BaCuO2.13、Ca2CuO3、CuO、A2O3And the molar ratio of the oxygen source is 2:1.5:0.5:0.5: 0.4-1.4.
When A is the combination of Cu and C, the structural formula of the copper oxide superconductor is (Cu, C) Ba2Ca3Cu4O11+δFrom a precursor BaCuO2.13、Ca2CuO3、CuO、CaCO3、BaCO3And Ag2O (or KClO)4) Prepared by a precursor BaCuO2.13、Ca2CuO3、CuO、CaCO3、BaCO3、Ag2O (or KClO)4) In a molar ratio of 1.8: 1.4: 1.2-1.4: 0.2: 0.2: 0.4-1.4.
Precursor BaCuO2.13By BaO2And the CuO powder is fully ground in a glove box and then pressed into tablets, and the tablets are sintered for 40 to 60 hours at 900 to 950 ℃ in an oxygen atmosphere, and are fully and uniformly ground once every 20 hours to prepare the CuO powder.
Preferably, the BaO2And CuO in a molar ratio of 1: 1.
Ca2CuO3By CaCO3And CuO is uniformly ground and pressed into tablets in a glove box, firstly sintered for 10 to 20 hours at the temperature of 900 to 950 ℃ in the air, then taken out, fully ground and pressed into tablets again, then sintered for 20 to 40 hours at the temperature of 900 to 950 ℃ in an oxygen atmosphere, and taken out to be ground again for one time so as to be fully reacted.
Preferably, said CaCO3And CuO in a molar ratio of 2:1.
Precursor BaCuO2.13、Ca2CuO3、A2O3And oxygen source proportioning, or precursor BaCuO2.13、Ca2CuO3、CuO、CaCO3、BaCO3Preparing materials by using an oxygen source, fully grinding and uniformly mixing the materials, then pressing the materials into slices, then filling the samples which are pressed into slices into a prepared gold tube, and sealing the gold tube by using a spot welding machine; the applied pressure is 3.5-3.7GPa, the applied temperature is 1100-1150 ℃, and the time for maintaining the high-pressure and high-temperature conditions is 1-6 hours, thus preparing the superconductor.
The oxygen source is Ag2O or KClO4。
When the superconductor compound is in a polycrystalline structure, the preparation conditions are as follows: the applied pressure is 3.5-3.7GPa, the applied temperature is 1100-1150 ℃, and the time for maintaining the high-pressure and high-temperature condition is 1-2 hours; when the superconductor compound is of a single crystal structure: the applied pressure is 3.5-3.7GPa, the applied temperature is 1120-1150 ℃, and the time for maintaining the high-pressure and high-temperature conditions is 4-6 hours.
The preparation method of the nontoxic copper oxide superconductor with high critical parameters comprises the following steps:
(1) precursor BaCuO2.13The preparation of (1): by BaO2And CuO powder are fully ground in a glove box and then pressed into tablets, and the tablets are sintered for 40 to 60 hours at 900 to 950 ℃ in an oxygen atmosphere, and are fully and uniformly ground once every 20 hours to prepare the CuO powder;
(2) precursor Ca2CuO3The preparation of (1): by CaCO3And CuO are evenly ground and pressed into tablets in a glove box, firstly sintered for 10 to 20 hours at the temperature of 900 to 950 ℃ in the air, then taken out, fully ground and pressed into tablets again, then sintered for 20 to 40 hours at the temperature of 900 to 950 ℃ in oxygen atmosphere, and taken out to be ground again for one-time preparation so as to fully react;
(3) precursor BaCuO2.13、Ca2CuO3、A2O3And oxygen source proportioning, or precursor BaCuO2.13、Ca2CuO3、CuO、CaCO3、BaCO3And oxygen source proportioning, fully grinding and uniformly mixingThen pressing into a sheet, then putting the sheet sample into a prepared gold tube, and sealing the gold tube by using a spot welding machine; the applied pressure is 3.5-3.7GPa, the applied temperature is 1100-1150 ℃, and the time for maintaining the high-pressure and high-temperature condition is 1-6 hours, so as to prepare the superconductor; the oxygen source is Ag2O or KClO4(ii) a The A is any one of Ga, Al and B.
When the superconductor compound is in a polycrystalline structure, the preparation conditions are as follows: the applied pressure is 3.5-3.7GPa, the applied temperature is 1100-1150 ℃, and the time for maintaining the high-pressure and high-temperature condition is 1-2 hours; when the superconductor compound is of a single crystal structure: the applied pressure is 3.5-3.7GPa, the applied temperature is 1120-1150 ℃, and the time for maintaining the high-pressure and high-temperature conditions is 4-6 hours.
As a preferred embodiment of the present invention, when A is a light element Ga, Al or B, the copper oxide superconductor has the formula ABa2Ca2Cu3O8+δAnd δ is: 0.76-1. As a specific embodiment of the present invention, the copper oxide superconductor has a structural formula of GaBa2Ca2Cu3O8+δ。、AlBa2Ca2Cu3O8+δOr is BBa2Ca2Cu3O8+δ。
GaBa2Ca2Cu3O8+δThe preparation method of the polycrystalline structure comprises the following steps: BaCuO2.13、Ca2CuO3、Ga2O3And oxygen source (Ag)2O or KClO4) In a molar ratio of 2: 1: 0.5:0 to 0.24, fully grinding, uniformly mixing, pressing into slices, then filling the samples pressed into the slices into a prepared gold tube, and sealing the gold tube by using a spot welding machine; the applied pressure is 3.5-3.7GPa, the applied temperature is 1100-1150 ℃, and the time for maintaining the high-pressure and high-temperature conditions is 1-2 hours.
GaBa2Ca2Cu3O8+δThe method for preparing the single crystal structure of (1) is as follows: BaCuO2.13、Ca2CuO3、Ga2O3And oxygen source (Ag)2O or KClO4) In a molar ratio of 2: 1: 0.5:0 to 0.24, fully grindingGrinding, mixing uniformly, pressing into slices, putting the samples into prepared gold tubes, and sealing the gold tubes by a spot welding machine; the applied pressure is 3.5-3.7GPa, the applied temperature is 1120-1150 ℃, and the time for maintaining the high-pressure and high-temperature conditions is 4-6 hours.
AlBa2Ca2Cu3O8+δThe preparation method of the polycrystalline structure comprises the following steps: BaCuO2.13、Ca2CuO3、Al2O3And oxygen source (Ag)2O or KClO4) In a molar ratio of 2: 1: 0.5:0 to 0.24, fully grinding, uniformly mixing, pressing into slices, then filling the samples pressed into the slices into a prepared gold tube, and sealing the gold tube by using a spot welding machine; the applied pressure is 3.5-3.7GPa, the applied temperature is 1100-1150 ℃, and the time for maintaining the high-pressure and high-temperature conditions is 1-2 hours.
AlBa2Ca2Cu3O8+δThe method for preparing the single crystal structure of (1) is as follows: BaCuO2.13、Ca2CuO3、Al2O3And oxygen source (Ag)2O or KClO4) In a molar ratio of 2: 1: 0.5:0 to 0.24, fully grinding, uniformly mixing, pressing into slices, then filling the samples pressed into the slices into a prepared gold tube, and sealing the gold tube by using a spot welding machine; the applied pressure is 3.5-3.7GPa, the applied temperature is 1120-1150 ℃, and the time for maintaining the high-pressure and high-temperature conditions is 4-6 hours.
BBa2Ca2Cu3O8+δThe preparation method of the polycrystalline structure comprises the following steps: BaCuO2.13、Ca2CuO3、B2O3And oxygen source (Ag)2O or KClO4) In a molar ratio of 2: 1: 0.5:0 to 0.24, fully grinding, uniformly mixing, pressing into slices, then filling the samples pressed into the slices into a prepared gold tube, and sealing the gold tube by using a spot welding machine; the applied pressure is 3.5-3.7GPa, the applied temperature is 1100-1150 ℃, and the time for maintaining the high-pressure and high-temperature conditions is 1-2 hours.
BBa2Ca2Cu3O8+δThe method for preparing the single crystal structure of (1) is as follows: BaCuO2.13、Ca2CuO3、B2O3And oxygen source (Ag)2O or KClO4) In a molar ratio of 2: 1: 0.5:0 to 0.24, fully grinding, uniformly mixing, pressing into slices, then filling the samples pressed into the slices into a prepared gold tube, and sealing the gold tube by using a spot welding machine; the applied pressure is 3.5-3.7GPa, the applied temperature is 1120-1150 ℃, and the time for maintaining the high-pressure and high-temperature conditions is 4-6 hours.
As a preferred embodiment of the present invention, when A is a light element Ga, Al or B, the copper oxide superconductor has the formula ABa2Ca3Cu4O11+δAnd δ is: 0-1. The structural formula of the copper oxide superconductor is GaBa2Ca3Cu4O11+δ(Ga-Ba-Ca-Cu-O)、AlBa2Ca3Cu4O11+δ(Al-Ba-Ca-Cu-O) or BBa2Ca3Cu4O11+δ(B-Ba-Ca-Cu-O)。
GaBa2Ca3Cu4O11+δThe preparation method of the polycrystalline structure comprises the following steps: BaCuO2.13、Ca2CuO3、CuO、Ga2O3And oxygen source (Ag)2O or KClO4) In a molar ratio of 2:1.5:0.5:0.5: 0.4-1.4, fully grinding, uniformly mixing, pressing into slices, then putting the samples pressed into slices into a prepared gold tube, and sealing the gold tube by using a spot welding machine; the applied pressure is 3.5-3.7GPa, the applied temperature is 1100-1150 ℃, and the time for maintaining the high-pressure and high-temperature conditions is 1-2 hours.
GaBa2Ca3Cu4O11+δThe method for preparing the single crystal structure of (1) is as follows: BaCuO2.13、Ca2CuO3、CuO、Ga2O3And oxygen source (Ag)2O or KClO4) In a molar ratio of 2:1.5:0.5:0.5: 0.4-1.4, fully grinding, uniformly mixing, pressing into slices, then putting the samples pressed into slices into a prepared gold tube, and sealing the gold tube by using a spot welding machine; the applied pressure is 3.5-3.7GPa, the applied temperature is 1120-1150 ℃, and the time for maintaining the high-pressure and high-temperature conditions is 4-6 hours.
AlBa2Ca3Cu4O11+δThe preparation method of the polycrystalline structure comprises the following steps: BaCuO2.13、Ca2CuO3、CuO、Al2O3And oxygen source (Ag)2O or KClO4) In a molar ratio of 2:1.5:0.5:0.5: 0.4-1.4, fully grinding, uniformly mixing, pressing into slices, then putting the samples pressed into slices into a prepared gold tube, and sealing the gold tube by using a spot welding machine; the applied pressure is 3.5-3.7GPa, the applied temperature is 1100-1150 ℃, and the time for maintaining the high-pressure and high-temperature conditions is 1-2 hours.
AlBa2Ca3Cu4O11+δThe method for preparing the single crystal structure of (1) is as follows: BaCuO2.13、Ca2CuO3、CuO、Al2O3And oxygen source (Ag)2O or KClO4) In a molar ratio of 2:1.5:0.5:0.5: 0.4-1.4, fully grinding, uniformly mixing, pressing into slices, then putting the samples pressed into slices into a prepared gold tube, and sealing the gold tube by using a spot welding machine; the applied pressure is 3.5-3.7GPa, the applied temperature is 1120-1150 ℃, and the time for maintaining the high-pressure and high-temperature conditions is 4-6 hours.
BBa2Ca3Cu4O11+δThe preparation method of the polycrystalline structure comprises the following steps: BaCuO2.13、Ca2CuO3、CuO、B2O3And oxygen source (Ag)2O or KClO4) In a molar ratio of 2:1.5:0.5:0.5: 0.4-1.4, fully grinding, uniformly mixing, pressing into slices, then putting the samples pressed into slices into a prepared gold tube, and sealing the gold tube by using a spot welding machine; the applied pressure is 3.5-3.7GPa, the applied temperature is 1100-1150 ℃, and the time for maintaining the high-pressure and high-temperature conditions is 1-2 hours.
BBa2Ca3Cu4O11+δThe method for preparing the single crystal structure of (1) is as follows: BaCuO2.13、Ca2CuO3、CuO、B2O3And oxygen source (Ag)2O or KClO4) In a molar ratio of 2:1.5:0.5:0.5: 0.4 to 1.4, fully grinding, uniformly mixing, pressing into slices, putting the samples into prepared gold tubes, and sealing the gold tubes by a spot welding machine(ii) a The applied pressure is 3.5-3.7GPa, the applied temperature is 1120-1150 ℃, and the time for maintaining the high-pressure and high-temperature conditions is 4-6 hours.
As a preferred embodiment of the present invention, when A is a combination of Cu and C, the copper oxide superconductor has a structural formula of (Cu, C) Ba2Ca3Cu4O11+δAnd δ is: 0-1.
(Cu,C)Ba2Ca3Cu4O11+δThe preparation method of the polycrystalline structure comprises the following steps: precursor BaCuO2.13、Ca2CuO3、CuO、CaCO3、BaCO3Oxygen source (Ag)2O or KClO4) The molar ratio of (A) to (B) is: 1.8: 1.4: 1.2-1.4: 0.2: 0.2: 0.4-1.4, fully grinding, uniformly mixing, pressing into slices, then putting the samples pressed into slices into a prepared gold tube, and sealing the gold tube by using a spot welding machine; the applied pressure is 3.5-3.7GPa, the applied temperature is 1100-1150 ℃, and the time for maintaining the high-pressure and high-temperature conditions is 1-2 hours.
(Cu,C)Ba2Ca3Cu4O11+δThe preparation method of the single crystal structure comprises the following steps: precursor BaCuO2.13、Ca2CuO3、CuO、CaCO3、BaCO3Oxygen source (Ag)2O or KClO4) The molar ratio of (A) to (B) is: 1.8: 1.4: 1.2-1.4: 0.2: 0.2: 0.4-1.4, fully grinding, uniformly mixing, pressing into slices, then putting the samples pressed into slices into a prepared gold tube, and sealing the gold tube by using a spot welding machine; the applied pressure is 3.5-3.7GPa, the applied temperature is 1120-1150 ℃, and the time for maintaining the high-pressure and high-temperature conditions is 4-6 hours.
As a specific embodiment of the present invention, the copper oxide superconductor has a structural formula of (Cu)0.4C0.4)Ba2Ca3Cu4O11+δ。
As a specific embodiment of the present invention, the copper oxide superconductor has a structural formula of (Cu)0.6C0.4)Ba2Ca3Cu4O11+δ。
Has the advantages that: (1) the synthesis of the superconductor containing the light element and the non-toxic copper oxide is synthesized by combining the normal pressure synthesis precursor with high temperature and high pressure sintering, the synthesis of the precursor can reduce the chemical potential barrier of the subsequent reaction, so that the subsequent reaction is more uniform, and the high pressure reaction can synthesize a compound which cannot be synthesized or is difficult to synthesize under normal pressure, synthesize a high pressure phase which exists in a metastable state under normal pressure, synthesize a high pressure phase which does not exist under normal pressure and synthesize a compound containing volatile substances. (2) The copper oxide superconductor prepared by the method does not need to use heavy elements, replaces toxic heavy elements such as Hg, Tl and the like with non-toxic light elements such as C, Ga, Al and the like by utilizing a high-temperature high-pressure technology, and synthesizes Ga-Ba-Ca-Cu-O, Al-Ba-Ca-Cu-O and B-Ba-Ca-Cu-O superconductors containing the light elements. (3) The high-voltage synthesis of the invention adopts a large-cavity press for production, applies the sample to the fields of strong current transmission, superconducting magnetic suspension and the like, greatly reduces energy loss, saves energy and does not pollute the environment.
Drawings
FIG. 1 is a schematic view of a sample assembly according to the present invention;
FIG. 2 is a schematic diagram of a high voltage module of the present invention;
FIG. 3 shows (Cu, C) Ba of the present invention2Ca3Cu4O11+δResistance magnetization of the polycrystalline sample;
FIG. 4 shows (Cu, C) Ba of the present invention2Ca3Cu4O11+δPhotographs and magnetization data of single crystal samples;
FIG. 5 is a Ga-Ba-Ca-Cu-O superconductor synthesized according to the invention;
FIG. 6 shows (Cu, C) Ba of the present invention2Ca3Cu4O11+δComparison of irreversible magnetic field of superconductor with other copper oxide superconductor, sample 1(sample1) is (Cu)0.4C0.4)Ba2Ca3Cu4O11.234Polycrystalline, sample 2(sample2) was (Cu)0.6C0.4)Ba2Ca3Cu4O11.46And (4) polycrystallization.
Detailed Description
Example 1: (Cu)0.4C0.4)Ba2Ca3Cu4O11.234Synthesis of polycrystals
(1) Precursor BaCuO2.13: mixing BaO2And CuO powder are fully ground in a glove box according to the molar ratio of 1:1, then are pressed into tablets, are sintered for 60 hours at 900 ℃ in an oxygen atmosphere, and are taken out every 20 hours and are fully and uniformly ground once to prepare the CuO powder.
(2) Precursor Ca2CuO3: CaCO with a molar ratio of 2:13And CuO is uniformly ground into pressed pieces in a glove box, and the pressed pieces are firstly sintered for 20 hours at 950 ℃ in the air, then taken out, fully ground into pressed pieces again, then sintered for 40 hours at 900 ℃ in an oxygen atmosphere, and taken out to be ground again for full reaction.
(3) Mixing BaCuO2.13，Ca2CuO3，CuO，BaCO3，CaCO3And Ag2O is mixed according to a molar ratio of 1.8: 1.4: 1.2: 0.2: 0.2: 0.6, mixing, fully grinding, uniformly mixing, pressing into slices, putting the samples pressed into the slices into a prepared gold tube, and sealing the gold tube by using a spot welding machine;
(4) and (3) performing high-pressure synthesis assembly on the gold tube with the sample, putting the gold tube into a pressure disc, applying 3.5GPa pressure on the sample by using an automatic control system of an instrument, and heating to 1150 ℃ for sintering for 1 hour to prepare the polycrystalline superconductor.
BaCuO was adjusted in accordance with the method of example 12.13，Ca2CuO3，CuO，BaCO3，CaCO3And Ag2The molar ratio of O is 1.8: 1.4: 1.4: 0.2: 0.2: 0.826, preparation (Cu)0.6C0.4)Ba2Ca3Cu4O11.46And (4) polycrystallization.
Example 2: (Cu)0.6C0.4)Ba2Ca3Cu4O11.684Synthesis of single crystals
(1) Precursor BaCuO2.13: mixing BaO2And CuO powder in a molar ratio of 1:1, grinding in a glove box, tabletting, sintering at 900 deg.C in oxygen atmosphere for 60 hr, and alternately adding CuO powderThe mixture is taken out for 20 hours and is fully and uniformly ground once to prepare the nano-particles.
(2) Precursor Ca2CuO3: CaCO with a molar ratio of 2:13And CuO is uniformly ground into pressed pieces in a glove box, and the pressed pieces are firstly sintered for 20 hours at 950 ℃ in the air, then taken out, fully ground into pressed pieces again, then sintered for 40 hours at 900 ℃ in an oxygen atmosphere, and taken out to be ground again for full reaction.
(3) Mixing BaCuO2.13，Ca2CuO3，CuO，BaCO3，CaCO3And Ag2O is mixed according to a molar ratio of 1.8: 1.4: 1.4: 0.2: 0.2: 1.05, burdening, fully grinding, uniformly mixing, pressing into slices, then filling the samples pressed into slices into a prepared gold tube, and sealing the gold tube by using a spot welding machine;
(4) and (3) performing high-pressure synthesis assembly on the gold tube with the sample, putting the gold tube into a pressure disc, applying 3.7GPa pressure on the sample by using an automatic control system of an instrument, and heating to 1120 ℃ for sintering for 4 hours to prepare the single crystal superconductor.
FIG. 1 is a schematic diagram of sample assembly, in which a gold tube is placed in a boron nitride sample chamber (for encapsulating and protecting a sample), and is placed in the middle of a graphite cylinder (for heating the sample) after being encapsulated, and then magnesium oxide columns (pressure transmission medium for transmitting pressure) are placed in the upper and lower parts of the boron carbide sample chamber, taking note that the two magnesium oxide columns are respectively solid and hollow, the graphite cylinder is placed in a heat-resistant glass and talc sleeve, a stainless steel column sheathed with pyrophyllite (for insulation) is placed at one end of the hollow magnesium oxide column, and finally a thermocouple (for measuring temperature) is contacted with the boron nitride sample chamber through the stainless steel column and the hollow magnesium oxide column.
Fig. 2 is a schematic view of a high pressure module, which is mainly composed of a pressure disc and a piston. The outer cylinder is made of steel, the piston part and the inner cylinder are made of tungsten carbide hard alloy materials, the piston part mainly bears axial stress, the piston enters the pressure disc when the piston is pressurized, and the piston part in the pressure disc can be radially supported by the pressure disc. After the sample is assembled as described above, it is placed in the sample assembly area shown in FIG. 2.
(Cu, C) Ba synthesized in examples 1 and 22Ca3Cu4O11+δBoth polycrystalline and single crystal have very high critical parameters and properties. FIG. 3 shows (Cu)0.4C0.4)Ba2Ca3Cu4O11.234The resistance and magnetization data of polycrystalline samples, calculated according to the 1% standard for normal state resistance under different magnetic fields, give irreversible fields that are the highest of all superconductors to date. FIG. 4 shows (Cu)0.6C0.4)Ba2Ca3Cu4O11.684Photographs and magnetization data of single crystal samples, the superconducting transition of which is very steep, and TcOver 100K.
The copper oxide high-temperature superconductor (Cu, C) Ba prepared by the invention2Ca3Cu4O11+δThe irreversible field of the poly-crystalline is highest in known superconducting materials, 15T at 86K, 5T at 98K and 3T at 101K (as shown in FIG. 6); whereas the prior art synthesized (Cu, C) Ba2Ca3Cu4O11+δThe irreversible field of 77K is less than 8T, and the irreversible field of 100K is less than 1T, which is far lower than that of the sample synthesized by us.
Example 3: GaBa2Ca3Cu4O11.26Preparation of (Ga-Ba-Ca-Cu-O) polycrystal
(1) Precursor BaCuO2.13Is made of BaO2And CuO powder are fully ground in a glove box according to the molar ratio of 1:1, then are pressed into tablets, are sintered for 60 hours at 900 ℃ in an oxygen atmosphere, and are taken out and fully and uniformly ground once every 20 hours.
(2) Precursor Ca2CuO3Is made of CaCO3And CuO were uniformly ground into tablets in a molar ratio of 2:1 in a glove box, and the tablets were first sintered in air at 950 ℃ for 20 hours, then taken out, sufficiently ground again, then sintered in an oxygen atmosphere at 900 ℃ for 40 hours, and once again ground during which time they were taken out to enable sufficient reaction.
(3) Finally BaCuO is added2.13，Ca2CuO3，CuO，Ga2O3And Ag2O (oxygen supply) is 2:1.5:0.5:0And proportioning according to the molar ratio of 5:0.5, fully grinding and uniformly mixing, pressing into a sheet, putting the sheet-shaped sample into a prepared gold tube, and sealing the gold tube by using a spot welding machine.
(4) And (3) performing high-pressure synthesis assembly on the gold tube with the sample, applying high-temperature and high-pressure conditions to the sample, assembling the sample according to the method, placing the sample into a pressure disc, and applying the high-temperature and high-pressure conditions to the sample by using an automatic control system of the instrument. For polycrystal, the applied pressure is 3.5GPa, the applied temperature is 1150 ℃, and the time for maintaining the high-pressure and high-temperature condition is 1-2 hours; successfully synthesizes a nontoxic copper oxide superconducting system with high critical parameters to successfully synthesize a nontoxic copper oxide superconductor GaBa2Ca3Cu4O11.26(Ga-Ba-Ca-Cu-O), Ga-Ba-Ca-Cu-O superconducting temperature reaches above 110K, see FIG. 5.
Example 4: synthesis of Al-Ba-Ca-Cu-O
(1) Precursor BaCuO2.13Is made of BaO2And CuO powder are fully ground in a glove box according to the molar ratio of 1:1, then are pressed into tablets, are sintered for 60 hours at 900 ℃ in an oxygen atmosphere, and are taken out and fully and uniformly ground once every 20 hours.
(2) Precursor Ca2CuO3Is made of CaCO3And CuO were uniformly ground into tablets in a molar ratio of 2:1 in a glove box, and the tablets were first sintered in air at 950 ℃ for 20 hours, then taken out, sufficiently ground again, then sintered in an oxygen atmosphere at 900 ℃ for 40 hours, and once again ground during which time they were taken out to enable sufficient reaction.
(3) Finally BaCuO is added2.13，Ca2CuO3，CuO，Al2O3And Ag2And O (providing an oxygen source) is mixed according to the molar ratio of 2:1.5:0.5:0.5 (0.4-1.4), fully ground, uniformly mixed and pressed into a sheet, then the sheet-pressed sample is placed into a prepared gold tube, and the gold tube is sealed by a spot welding machine.
(4) The gold tube with the sample is synthesized and assembled under high pressure, the sample is applied with high temperature and high pressure, the sample is assembled according to the method and is put into a pressure disc, and then an automatic control system of the instrument is utilizedThe sample was subjected to high temperature and high pressure conditions. For the polycrystal, the pressure was applied at 3.5GPa, the temperature was applied at 1150 ℃ and the time for maintaining the high-pressure and high-temperature conditions was 1 to 2 hours. Successfully synthesize the nontoxic copper oxide superconductor AlBa2Ca3Cu4O11+δ。
Example 5: synthesis of B-Ba-Ca-Cu-O
(1) Precursor BaCuO2.13Is made of BaO2And CuO powder are fully ground in a glove box according to the molar ratio of 1:1, then are pressed into tablets, are sintered for 60 hours at 900 ℃ in an oxygen atmosphere, and are taken out and fully and uniformly ground once every 20 hours.
(2) Precursor Ca2CuO3Is made of CaCO3And CuO were uniformly ground into tablets in a molar ratio of 2:1 in a glove box, and the tablets were first sintered in air at 950 ℃ for 20 hours, then taken out, sufficiently ground again, then sintered in an oxygen atmosphere at 900 ℃ for 40 hours, and once again ground during which time they were taken out to enable sufficient reaction.
(3) Finally BaCuO is added2.13，Ca2CuO3，CuO，B2O3And Ag2And O (providing an oxygen source) is mixed according to the molar ratio of 2:1.5:0.5:0.5 (0.4-1.4), fully ground, uniformly mixed and pressed into a sheet, then the sheet-pressed sample is placed into a prepared gold tube, and the gold tube is sealed by a spot welding machine.
(4) And (3) performing high-pressure synthesis assembly on the gold tube with the sample, applying high-temperature and high-pressure conditions to the sample, assembling the sample according to the method, placing the sample into a pressure disc, and applying the high-temperature and high-pressure conditions to the sample by using an automatic control system of the instrument. For polycrystal, the applied pressure is 3.5GPa, the applied temperature is 1150 ℃, and the time for maintaining the high-pressure and high-temperature condition is 1-2 hours; successfully synthesize BBa2Ca3Cu4O11+δ。
Claims (10)
1. A non-toxic copper oxide superconductor with high critical parameter is characterized in that the structural formula of the copper oxide superconductor is ABa2CaxCuyOz+δ(ii) a Wherein, x isThe value of 2, the value of y is 3, the value of z is 8, and the value of delta is: 0.76-1, wherein A is Ga, Al or B; or x is 3, y is 4, z is 11, and δ is: 0-1, wherein A is any one of Ga, Al and B or A is the combination of Cu and C.
2. The superconductor of claim 1, wherein the superconductor has a formula ABa2Ca2Cu3O8+δ，ABa2Ca2Cu3O8+δFrom a precursor BaCuO2.13、Ca2CuO3、A2O3And an oxygen source, said A2O3Is Ga2O3，Al2O3Or B2O3(ii) a When the copper oxide superconductor has the formula ABa2Ca3Cu4O11+δWhen A is any one of Ga, Al and B, ABa2Ca3Cu4O11+δMade of BaCuO2.13、Ca2CuO3、CuO、A2O3And an oxygen source, when A is a combination of Cu and C, ABa2Ca3Cu4O11+δMade of BaCuO2.13、Ca2CuO3、CuO、CaCO3、BaCO3And an oxygen source.
3. The superconductor of claim 2, wherein when A is Ga, Al or B, ABa2Ca3Cu4O11+δFrom a precursor BaCuO2.13、Ca2CuO3、CuO、A2O3And the oxygen source is mixed according to a molar ratio of 2:1.5:0.5:0.5: 0.4-1.4, ABa2Ca2Cu3O8+δFrom a precursor BaCuO2.13、Ca2CuO3、A2O3And the oxygen source is mixed according to a molar ratio of 2: 1: 0.5: 0-0.24; when A is a combination of Cu and C, ABa2Ca3Cu4O11+δFrom a precursor BaCuO2.13、Ca2CuO3、CuO、CaCO3、BaCO3And the oxygen source comprises the following components in molar ratio: 1.8: 1.4: 1.2-1.4: 0.2: 0.2: 0.4-1.4.
4. The non-toxic copper oxide superconductor having a high critical parameter of claim 3, wherein the precursor BaCuO is2.13By BaO2And the CuO powder is fully ground in a glove box and then pressed into tablets, and the tablets are sintered for 40 to 60 hours at 900 to 950 ℃ in an oxygen atmosphere, and are fully and uniformly ground once every 20 hours to prepare the CuO powder.
5. The nontoxic copper oxide superconductor having a high critical parameter of claim 4, wherein Ca is2CuO3By CaCO3And CuO is uniformly ground and pressed into tablets in a glove box, firstly sintered for 10 to 20 hours at the temperature of 900 to 950 ℃ in the air, then taken out, fully ground and pressed into tablets again, then sintered for 20 to 40 hours at the temperature of 900 to 950 ℃ in an oxygen atmosphere, and taken out and ground again to prepare the CuO-based ceramic material.
6. The superconductor of claim 5, wherein BaCuO is a precursor2.13、Ca2CuO3、A2O3And oxygen source proportioning, or precursor BaCuO2.13、Ca2CuO3、CuO、CaCO3、BaCO3Preparing materials by using an oxygen source, fully grinding and uniformly mixing the materials, then pressing the materials into slices, then filling the samples which are pressed into slices into a prepared gold tube, and sealing the gold tube by using a spot welding machine; the applied pressure is 3.5-3.7GPa, the applied temperature is 1100-1150 ℃, and the time for maintaining the high-pressure and high-temperature conditions is 1-6 hours, thus preparing the superconductor.
7. The superconductor of claim 6, wherein the source of oxygen is Ag2O or KClO4。
8. The superconductor of claim 7, wherein when the superconductor compound is a polycrystalline structure, the superconductor is prepared by: the applied pressure is 3.5-3.7GPa, the applied temperature is 1100-1150 ℃, and the time for maintaining the high-pressure and high-temperature condition is 1-2 hours; when the superconductor compound is of a single crystal structure: the applied pressure is 3.5-3.7GPa, the applied temperature is 1120-1150 ℃, and the time for maintaining the high-pressure and high-temperature conditions is 4-6 hours.
9. A method for preparing a nontoxic copper oxide superconductor with high critical parameters is characterized in that: the method comprises the following steps:
(1) precursor BaCuO2.13The preparation of (1): by BaO2And CuO powder are fully ground in a glove box and then pressed into tablets, and the tablets are sintered for 40 to 60 hours at 900 to 950 ℃ in an oxygen atmosphere, and are fully and uniformly ground once every 20 hours to prepare the CuO powder;
(2) precursor Ca2CuO3The preparation of (1): by CaCO3And CuO are evenly ground and pressed into tablets in a glove box, firstly sintered for 10 to 20 hours at the temperature of 900 to 950 ℃ in the air, then taken out, fully ground and pressed into tablets again, then sintered for 20 to 40 hours at the temperature of 900 to 950 ℃ in oxygen atmosphere, and taken out and ground again to prepare the CuO-based ceramic material;
(3) precursor BaCuO2.13、Ca2CuO3、A2O3And oxygen source proportioning, or precursor BaCuO2.13、Ca2CuO3、CuO、CaCO3、BaCO3Preparing materials by using an oxygen source, fully grinding and uniformly mixing the materials, then pressing the materials into slices, then filling the samples which are pressed into slices into a prepared gold tube, and sealing the gold tube by using a spot welding machine; the applied pressure is 3.5-3.7GPa, the applied temperature is 1100-1150 ℃, and the time for maintaining the high-pressure and high-temperature condition is 1-6 hours, so as to prepare the superconductor; the oxygen source is Ag2O or KClO4(ii) a The A is any one of Ga, Al and B.
10. The production method according to claim 9, wherein when the superconductor compound has a polycrystalline structure, the production conditions are as follows: the applied pressure is 3.5-3.7GPa, the applied temperature is 1100-1150 ℃, and the time for maintaining the high-pressure and high-temperature condition is 1-2 hours; when the superconductor compound is of a single crystal structure: the applied pressure is 3.5-3.7GPa, the applied temperature is 1120-1150 ℃, and the time for maintaining the high-pressure and high-temperature conditions is 4-6 hours.
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| CN117819959A (en) * | 2023-12-28 | 2024-04-05 | 中国科学院物理研究所 | Large-size Cu1234 superconducting block material and preparation method thereof |
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| YUE ZHANG等: "Unprecedented high irreversibility line in the nontoxic cuprate superconductor (Cu,C)Ba2Ca3Cu4O11+δ", 《SCIENCE ADVANCED》 * |
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| CN115340386A (en) * | 2022-08-19 | 2022-11-15 | 陕西国际商贸学院 | Preparation method of high-Tc nano-particle doped magnesium diboride |
| CN115340386B (en) * | 2022-08-19 | 2023-01-17 | 陕西国际商贸学院 | A kind of preparation method of high Tc nanoparticles doped magnesium diboride |
| CN117819959A (en) * | 2023-12-28 | 2024-04-05 | 中国科学院物理研究所 | Large-size Cu1234 superconducting block material and preparation method thereof |
| CN117819959B (en) * | 2023-12-28 | 2025-03-11 | 中国科学院物理研究所 | Large-size Cu1234 superconducting block material and preparation method thereof |
| CN118866459A (en) * | 2024-07-05 | 2024-10-29 | 中国科学院物理研究所 | A Cu1223 superconductor and preparation method thereof |
| CN118866459B (en) * | 2024-07-05 | 2024-12-27 | 中国科学院物理研究所 | Cu1223 superconductor and preparation method thereof |
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