CN113470883B - 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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Abstract
The present invention discloses a non-toxic copper oxide superconductor with high critical parameter and its preparation method. The structural formula of the copper oxide superconductor is ABa 2 Ca x Cu y O z+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. The present invention synthesizes non-toxic superconductive material with high critical parameters through high temperature and high pressure process to replace toxic elements with non-toxic light atoms.
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 fundamental 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, a high-pressure phase which exists metastable at normal pressure, a high-pressure phase which does not exist at normal pressure, and 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 magnetic field and temperature phase diagram of superconductor, there is a boundary line called irreversible line H for marking lossless transmission current irr (T) it divides the magnetic field-temperature phase diagram into two areas, only under the temperature and magnetic field below the irreversible line, the superconductor can carry a certain superconducting current. 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 T c Only 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. Many superconductors in the copper oxide superconductor family have critical temperatures above the temperature of liquid nitrogen, e.g. Y-series (123,T) c 91K), bi-system (2223 c 110K), tl-line (2223 c 125K) and Hg-series (1234 c 124K), 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 nontoxic, it has too strong bidimensionality, so that the superconducting critical current in a magnetic field decreases rapidly and the irreversible magnetic field is very low, and thus it cannot be applied to a strong current at a liquid nitrogen temperature. Y-series superconductorYttrium barium copper oxide (YBa) 2 Cu 3 O 7-δ YBCO 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 industry is keenly looking for non-toxic superconductors with a superconducting critical temperature above the temperature of liquid nitrogen and a higher irreversible magnetic field, so as to achieve 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: the invention relates to a nontoxic copper oxide superconductor with high critical parameters, wherein the structural formula of the copper oxide superconductor is ABa 2 Ca x Cu y O z+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 invention 2 Ca x Cu y O z+δ Polycrystalline structures and single crystal structures are included.
When the copper oxide superconductor has the formula ABa 2 Ca 2 Cu 3 O 8+δ ，ABa 2 Ca 2 Cu 3 O 8+δ From a precursor BaCuO 2.13 、Ca 2 CuO 3 、A 2 O 3 And an oxygen source, said A 2 O 3 Is Ga 2 O 3 ，Al 2 O 3 Or B 2 O 3 (ii) a When the copper oxide superconductor has the formula ABa 2 Ca 3 Cu 4 O 11+δ When A is any one of Ga, al and B, ABa 2 Ca 3 Cu 4 O 11+δ Made of BaCuO 2.13 、Ca 2 CuO 3 、CuO、A 2 O 3 And an oxygen source, when A is a combination of Cu and C, ABa 2 Ca 3 Cu 4 O 11+δ Made of BaCuO 2.13 、Ca 2 CuO 3 、CuO、CaCO 3 、BaCO 3 And an oxygen source.
Specifically, when A is a light element Ga, al or B, the copper oxide superconductor has a structural formula ABa 2 Ca 2 Cu 3 O 8+δ From a precursor BaCuO 2.13 、Ca 2 CuO 3 、A 2 O 3 And Ag 2 O (or KClO) 4 ) Is prepared from A 2 O 3 Selected from Ga 2 O 3 ，Al 2 O 3 Or B 2 O 3 One of (1); precursor BaCuO 2.13 、Ca 2 CuO 3 、A 2 O 3 And Ag 2 O (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 ABa 2 Ca 3 Cu 4 O 11+δ From a precursor BaCuO 2.13 、Ca 2 CuO 3 、CuO、A 2 O 3 And Ag 2 O (or KClO) 4 ) Prepared by a precursor BaCuO 2.13 、Ca 2 CuO 3 、CuO、A 2 O 3 And 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) Ba 2 Ca 3 Cu 4 O 11+δ From a precursor BaCuO 2.13 、Ca 2 CuO 3 、CuO、CaCO 3 、BaCO 3 And Ag 2 O (or KClO) 4 ) Prepared by a precursor BaCuO 2.13 、Ca 2 CuO 3 、CuO、CaCO 3 、BaCO 3 、Ag 2 O (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 BaCuO 2.13 By BaO 2 And 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 BaO 2 And CuO in a molar ratio of 1.
Ca 2 CuO 3 By CaCO 3 And CuO is 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 again to be ground again for full reaction to prepare the CuO-based ceramic material.
Preferably, said CaCO 3 And CuO in a molar ratio of 2.
Precursor BaCuO 2.13 、Ca 2 CuO 3 、A 2 O 3 And oxygen source proportioning, or precursor BaCuO 2.13 、Ca 2 CuO 3 、CuO、CaCO 3 、BaCO 3 And oxygen source burdening, fully grinding and uniformly mixing, then pressing into slices, then putting 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, so that the superconductor is prepared.
The oxygen source is Ag 2 O or KClO 4 。
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 condition is 4-6 hours.
The preparation process of non-toxic copper oxide superconductor with high critical parameter includes the following steps:
(1) Precursor BaCuO 2.13 The preparation of (1): by BaO 2 And 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 Ca 2 CuO 3 The preparation of (1): by CaCO 3 And 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 again to be ground again for full reaction to prepare the CuO-based ceramic material;
(3) Precursor BaCuO 2.13 、Ca 2 CuO 3 、A 2 O 3 And oxygen source proportioning or mixing the precursor BaCuO 2.13 、Ca 2 CuO 3 、CuO、CaCO 3 、BaCO 3 And oxygen source burdening, fully grinding and uniformly mixing, then pressing into slices, then putting 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 ℃, the time for maintaining the high-pressure and high-temperature condition is 1-6 hours, and the superconductor is prepared; the oxygen source is Ag 2 O or KClO 4 (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 condition is 4-6 hours.
As one aspect of the present inventionIn a preferred embodiment, when A is a light element Ga, al or B, the copper oxide superconductor has the formula ABa 2 Ca 2 Cu 3 O 8+δ And δ takes the value: 0.76-1. As a specific embodiment of the present invention, the copper oxide superconductor has a structural formula of GaBa 2 Ca 2 Cu 3 O 8+δ 。、AlBa 2 Ca 2 Cu 3 O 8+δ Or is BBa 2 Ca 2 Cu 3 O 8+δ 。
GaBa 2 Ca 2 Cu 3 O 8+δ The preparation method of the polycrystalline structure comprises the following steps: baCuO 2.13 、Ca 2 CuO 3 、Ga 2 O 3 And oxygen source (Ag) 2 O or KClO 4 ) 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.
GaBa 2 Ca 2 Cu 3 O 8+δ The method for preparing the single crystal structure of (1) is as follows: baCuO 2.13 、Ca 2 CuO 3 、Ga 2 O 3 And oxygen source (Ag) 2 O or KClO 4 ) 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.
AlBa 2 Ca 2 Cu 3 O 8+δ The preparation method of the polycrystalline structure comprises the following steps: baCuO 2.13 、Ca 2 CuO 3 、Al 2 O 3 And oxygen source (Ag) 2 O or KClO 4 ) 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 high pressure and high pressure are maintainedThe time of the warm condition is 1 to 2 hours.
AlBa 2 Ca 2 Cu 3 O 8+δ The method for preparing the single crystal structure of (1) is as follows: baCuO 2.13 、Ca 2 CuO 3 、Al 2 O 3 And oxygen source (Ag) 2 O or KClO 4 ) 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 condition is 4-6 hours.
BBa 2 Ca 2 Cu 3 O 8+δ The preparation method of the polycrystalline structure comprises the following steps: baCuO 2.13 、Ca 2 CuO 3 、B 2 O 3 And oxygen source (Ag) 2 O or KClO 4 ) 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.
BBa 2 Ca 2 Cu 3 O 8+δ The method for preparing the single crystal structure of (1) is as follows: baCuO 2.13 、Ca 2 CuO 3 、B 2 O 3 And oxygen source (Ag) 2 O or KClO 4 ) 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 condition 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 ABa 2 Ca 3 Cu 4 O 11+δ And δ is: 0-1. The structural formula of the copper oxide superconductor is GaBa 2 Ca 3 Cu 4 O 11+δ (Ga-Ba-Ca-Cu-O)、AlBa 2 Ca 3 Cu 4 O 11+δ (Al-Ba-Ca-Cu-O) or BBa 2 Ca 3 Cu 4 O 11+δ (B-Ba-Ca-Cu-O)。
GaBa 2 Ca 3 Cu 4 O 11+δ The preparation method of the polycrystalline structure comprises the following steps: baCuO 2.13 、Ca 2 CuO 3 、CuO、Ga 2 O 3 And oxygen source (Ag) 2 O or KClO 4 ) 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 condition is 1-2 hours.
GaBa 2 Ca 3 Cu 4 O 11+δ The method for preparing the single crystal structure of (1) is as follows: baCuO 2.13 、Ca 2 CuO 3 、CuO、Ga 2 O 3 And oxygen source (Ag) 2 O or KClO 4 ) 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.
AlBa 2 Ca 3 Cu 4 O 11+δ The preparation method of the polycrystalline structure comprises the following steps: baCuO 2.13 、Ca 2 CuO 3 、CuO、Al 2 O 3 And oxygen source (Ag) 2 O or KClO 4 ) 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 condition is 1-2 hours.
AlBa 2 Ca 3 Cu 4 O 11+δ The method for preparing the single crystal structure of (1) is as follows: baCuO 2.13 、Ca 2 CuO 3 、CuO、Al 2 O 3 And oxygen source (Ag) 2 O orKClO 4 ) 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.
BBa 2 Ca 3 Cu 4 O11 +δ The preparation method of the polycrystalline structure comprises the following steps: baCuO 2.13 、Ca 2 CuO 3 、CuO、B 2 O 3 And oxygen source (Ag) 2 O or KClO 4 ) 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 condition is 1-2 hours.
BBa 2 Ca 3 Cu 4 O 11+δ The method for preparing the single crystal structure of (1) is as follows: baCuO 2.13 、Ca 2 CuO 3 、CuO、B 2 O 3 And oxygen source (Ag) 2 O or KClO 4 ) In a molar ratio of 2:1.5:0.5:0.5:0.4-1.4, fully grinding, uniformly mixing, pressing into a sheet, then filling the sheet-shaped 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 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) Ba 2 Ca 3 Cu 4 O 11+δ And δ takes the value: 0-1.
(Cu,C)Ba 2 Ca 3 Cu 4 O 11+δ The preparation method of the polycrystalline structure comprises the following steps: precursor BaCuO 2.13 、Ca 2 CuO 3 、CuO、CaCO 3 、BaCO 3 Oxygen source (Ag) 2 O or KClO 4 ) The molar ratio of (A) to (B) is: 1.8:1.4:1.2-1.4:0.2:0.2:0.4 to 1.4, fully grinding, uniformly mixing, tabletting, and then pressingPutting the flaky 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 conditions is 1-2 hours.
(Cu,C)Ba 2 Ca 3 Cu 4 O 11+δ The preparation method of the single crystal structure comprises the following steps: precursor BaCuO 2.13 、Ca 2 CuO 3 、CuO、CaCO 3 、BaCO 3 Oxygen source (Ag) 2 O or KClO 4 ) 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 a sheet, then filling the sheet-shaped 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 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) 0.4 C 0.4 )Ba 2 Ca 3 Cu 4 O 11+δ 。
As a specific embodiment of the present invention, the copper oxide superconductor has a structural formula of (Cu) 0.6 C 0.4 )Ba 2 Ca 3 Cu 4 O 11+δ 。
Has the advantages that: (1) The invention synthesizes the superconductor containing the light element and the nontoxic copper oxide 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 can not be synthesized or is difficult to synthesize under normal pressure, a high pressure phase which exists metastable state under normal pressure, a high pressure phase which does not exist under normal pressure and 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 invention 2 Ca 3 Cu 4 O 11+δ Resistance magnetization of the polycrystalline sample;
FIG. 4 shows (Cu, C) Ba of the present invention 2 Ca 3 Cu 4 O 11+δ Photographs 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 invention 2 Ca 3 Cu 4 O 11+δ Comparison of irreversible magnetic field of superconductor with other copper oxide superconductor, sample1 (sample 1) is (Cu) 0.4 C 0.4 )Ba 2 Ca 3 Cu 4 O 11.234 Polycrystal, sample2 (sample 2) was (Cu) 0.6 C 0.4 )Ba 2 Ca 3 Cu 4 O 11.46 And (4) polycrystallization.
Detailed Description
Example 1: (Cu) 0.4 C 0.4 )Ba 2 Ca 3 Cu 4 O 11.234 Synthesis of polycrystals
(1) Precursor BaCuO 2.13 : mixing BaO 2 And the CuO powder is fully ground in a glove box according to the molar ratio of 1.
(2) Precursor Ca 2 CuO 3 : caCO with a molar ratio of 2 3 And 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) BaCuO is mixed with 2.13 ，Ca 2 CuO 3 ，CuO，BaCO 3 ，CaCO 3 And Ag 2 O is mixed according to a molar ratio of 1.8:1.4:1.2:0.2:0.2:0.6, proportioning, fully grinding and uniformly mixing, then 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;
(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 according to the method of example 1 2.13 ，Ca 2 CuO 3 ，CuO，BaCO 3 ，CaCO 3 And Ag 2 The molar ratio of O is 1.8:1.4:1.4:0.2:0.2:0.826, preparation (Cu) 0.6 C 0.4 )Ba 2 Ca 3 Cu 4 O 11.46 And (4) polycrystallization.
Example 2: (Cu) 0.6 C 0.4 )Ba 2 Ca 3 Cu 4 O 11.684 Synthesis of single crystals
(1) Precursor BaCuO 2.13 : mixing BaO 2 And the CuO powder is fully ground in a glove box according to the molar ratio of 1.
(2) Precursor Ca 2 CuO 3 : caCO with the molar ratio of 2 3 And 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 BaCuO 2.13 ，Ca 2 CuO 3 ，CuO，BaCO 3 ，CaCO 3 And Ag 2 O is added according to a molar ratio of 1.8:1.4:1.4:0.2:0.2:1.05 mixing, fully grinding, uniformly mixing, pressing into slices, and then filling the samples pressed into the slices into prepared gold tubesSealing the gold tube by 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. The sample was assembled as described above and placed in the sample assembly area shown in fig. 2.
(Cu, C) Ba synthesized in examples 1 and 2 2 Ca 3 Cu 4 O 11+δ Both polycrystalline and single crystal have very high critical parameters and properties. FIG. 3 shows (Cu) 0.4 C 0.4 )Ba 2 Ca 3 Cu 4 O 11.234 Polycrystalline sample resistance and magnetization data, the irreversible field calculated at 1% standard for normal state resistance under different magnetic fields, is the highest of all superconductors to date. FIG. 4 shows (Cu) 0.6 C 0.4 )Ba 2 Ca 3 Cu 4 O 11.684 Photographs and magnetization data of single crystal samples, with very sharp superconducting transitions and T c Over 100K.
The copper oxide high-temperature superconductor (Cu, C) Ba prepared by the invention 2 Ca 3 Cu 4 O 11+δ The polycrystalline irreversible field is highest in known superconducting materials, 15t at 86K, 5t at 98k, 3T at 101k (fig. 6); whereas the prior art synthesized (Cu, C) Ba 2 Ca 3 Cu 4 O 11+δ The irreversible field of 77K is less than 8T, the irreversible field of 100K is less than 1T, and the irreversible field is far lower than that of a sample synthesized by us.
Example 3: gaBa 2 Ca 3 Cu 4 O 11.26 Preparation of (Ga-Ba-Ca-Cu-O) polycrystal
(1) Precursor BaCuO 2.13 Is made of BaO 2 And the CuO powder is fully ground in a glove box according to the molar ratio of 1.
(2) Precursor Ca 2 CuO 3 Is made of CaCO 3 And CuO were uniformly ground into tablets in a molar ratio of 2.
(3) Finally BaCuO is added 2.13 ，Ca 2 CuO 3 ，CuO，Ga 2 O 3 And Ag 2 O (providing an oxygen source) was dosed according to a molar ratio of 2.5.
(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 GaBa 2 Ca 3 Cu 4 O 11.26 (Ga-Ba-Ca-Cu-O), ga-Ba-Ca-Cu-O superconducting temperatureReaching above 110K, see fig. 5.
Example 4: synthesis of Al-Ba-Ca-Cu-O
(1) Precursor BaCuO 2.13 Is made of BaO 2 And CuO powder is fully ground in a glove box according to the molar ratio of 1.
(2) Precursor Ca 2 CuO 3 Is made of CaCO 3 And CuO were uniformly ground into tablets in a molar ratio of 2.
(3) Finally BaCuO is added 2.13 ，Ca 2 CuO 3 ，CuO，Al 2 O 3 And Ag 2 And O (providing an oxygen source) is prepared according to the molar ratio of 2.
(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 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 AlBa 2 Ca 3 Cu 4 O 11+δ 。
Example 5: synthesis of B-Ba-Ca-Cu-O
(1) Precursor BaCuO 2.13 Is made of BaO 2 And CuO powder is fully ground in a glove box according to the molar ratio of 1.
(2) Precursor Ca 2 CuO 3 Is made of CaCO 3 And CuO in a molar ratio of 2The tablets were first sintered in air at 950 ℃ for 20 hours and then removed, ground again to a full density, and then sintered in an oxygen atmosphere at 900 ℃ for 40 hours, during which time they were removed and ground again in order to allow for a full reaction.
(3) Finally BaCuO is added 2.13 ，Ca 2 CuO 3 ，CuO，B 2 O 3 And Ag 2 And O (providing an oxygen source) is prepared according to the molar ratio of 2.
(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 BBa 2 Ca 3 Cu 4 O 11+δ 。
Claims (5)
1. A non-toxic copper oxide superconductor with high critical parameter is characterized in that the structural formula of the copper oxide superconductor is (Cu) 0.6 C 0.4 )Ba 2 Ca 3 Cu 4 O 11.684 A single crystal; the single crystal is prepared by the following method: precursor BaCuO 2.13 、Ca 2 CuO 3 、CuO、CaCO 3 、BaCO 3 And oxygen source proportioning, fully grinding and uniformly mixing, then pressing into a sheet, then putting the sheet sample into a prepared gold tube, sealing the gold tube by using a spot welding machine, applying pressure of 3.5-3.7GPa, applying temperature of 1120-1150 ℃, and maintaining the high-pressure and high-temperature condition for 4-6 hours.
2. The non-toxic copper oxide superconductor having a high critical parameter of claim 1, wherein the precursor BaCuO is 2.13 By BaO 2 And CuO powder are fully ground in a glove box and pressed into tablets in an oxygen atmosphere at 900 DEG CSintering at-950 ℃ for 40-60 hours, and taking out the powder every 20 hours to be fully and uniformly ground once to obtain the product.
3. The superconductor having high critical parameter and no toxicity of copper oxides of claim 2, wherein Ca is present in the superconductor 2 CuO 3 By CaCO 3 And 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.
4. The non-toxic copper oxide superconductor having a high critical parameter of claim 3, wherein the oxygen source is Ag 2 O or KClO 4 。
5. A method of preparing a nontoxic copper oxide superconductor having a high critical parameter according to claim 1, comprising: the method comprises the following steps:
(1) Precursor BaCuO 2.13 The preparation of (1): by BaO 2 And 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 in the middle to prepare the CuO powder;
(2) Precursor Ca 2 CuO 3 The preparation of (1): by CaCO 3 And 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 BaCuO 2.13 、Ca 2 CuO 3 、CuO、CaCO 3 、BaCO 3 Preparing 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 and the applied temperature is1120-1150 deg.c and maintaining the high pressure and high temperature condition for 4-6 hr to prepare superconductor; the oxygen source is Ag 2 O or KClO 4 。
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