High-temperature superconducting material and preparation method and application thereof

Abstract

The invention relates to a high-temperature superconducting material and a preparation method and application thereof, and relates to the field of superconducting materials, the chemical structural formula is as follows: A10-xBx (CO3-5) yDz, and the high-temperature superconducting material belongs to a pseudoapatite structure, wherein the element A comprises one or a combination of at least two of s-region metal, p-region metal or lanthanide rare earth elements; b comprises one or a combination of at least two of elements in the d region; cO3-5 comprises an acid radical; the element D comprises one or a combination of at least two of a non-metallic element or a group VIA metal element; in terms of molar weight, x belongs to [0-10], y belongs to (0-6), z is a chemical valence trim number greater than or less than the structural formula A10-xBx (CO3-5) yDz, and z belongs to (0-5). According to the high-temperature superconducting material provided by the invention, the A10-xBx (CO3-5) yDz designed by the pseudoapatite is designed, so that the superconducting at high temperature is realized.

Description

Technical Field

[0001] The present invention relates to the field of superconducting materials, and in particular to a high-temperature superconducting material and a preparation method and application thereof. Background Art

[0002] At present, although many theoretical calculations support that apatite is a potential superconductor, it has not been proven experimentally so far. The fundamental reason is:

[0003] 1. There is a typical one-way path in apatite, and nearly 99% of its glass phase is not conductive.

[0004] 2. The synthesis using Cu3P and Pb2SO5 will lead to the formation of various semiconductors or Cu2S, and the magnetoelectric properties are unstable; at the same time, copper-doped lead apatite is a typical Mott insulator, and superconductivity, metallicity or semiconductor requires further doping.

[0005] 3. A large number of research synthetic samples are single crystal samples mixed with copper-doped lead phosphate and apatite.

[0006] 4. Although apatite has the possibility of superconductivity, the amount of copper doping is not important for the occurrence of superconductivity. The transition between insulator-semiconductor-metallic state-superconductor states depends on the doping of non-metallic elements in the apatite channel.

[0007] Based on this, the present invention proposes A on the basis of apatite 10-x B x (CO 3-5 ) y D z and A 10-x B x (CO 3-5 ) y D z @(A,B)D can be used as a high-temperature superconductor. Summary of the invention

[0008] In view of the problems existing in the prior art, the object of the present invention is to provide a high-temperature superconducting material and a preparation method and use thereof, so as to realize the preparation of apatite-like superconducting material.

[0009] To achieve this object, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides a high temperature superconducting material, the chemical structure of the high temperature superconducting material is as follows:

[0011] A 10-x B x (CO 3-5 ) y D z, belongs to pseudoapatite structure;

[0012] Wherein, element A includes one or a combination of at least two of s-block metals, p-block metals or lanthanide rare earth elements; B includes one or a combination of at least two of d-block elements; CO 3-5 Including acid radical; element D includes one or a combination of at least two of non-metallic elements or metal elements of Group VI A; in terms of molar amount, x∈[0-10], y∈(0-6], z is greater than or less than the structural formula A 10-x B x (CO 3-5 ) y D z The chemical valence balance number and z∈(0-5].

[0013] The high temperature superconducting material provided by the present invention is designed by designing pseudoapatite A 10-x B x (CO 3-5 ) y D z , achieving superconductivity at high temperatures.

[0014] As a preferred technical solution of the present invention, the element A includes: one or a combination of at least two of Ca, Mg, Ba, Pb, Y, Ce or La.

[0015] Preferably, the element B includes: one or a combination of at least two of Sc, Mn, Zn, Cu, Mo, Hg, Fe or Ni.

[0016] As a preferred technical solution of the present invention, the CO 3-5 Including metal acid radicals or non-metal acid radicals.

[0017] Preferably, the CO 3-5 The element C includes: one of Si, S, As, C or B, or a combination of at least two of them.

[0018] As a preferred technical solution of the present invention, the element D includes one or a combination of at least two of F, Cl, O, S, Se, Te or OH.

[0019] As a preferred technical solution of the present invention, the chemical structural formula of the high temperature superconducting material is as follows: 10-x B x (CO 3-5 ) y D z @(A,B)D;

[0020] Wherein, compound (A, B) D is modified A 10-x B x (CO 3-5 )y D z or with A 10-x B x (CO 3-5 ) y D z Eutectic.

[0021] Furthermore, in A 10-x B x (CO 3-5 ) y D z The modified compound (A, B) D is introduced into the apatite-like 10-x B x (CO 3-5 ) y D z During the degenerate growth process, the conductive path is transformed from one dimension to three dimensions, and the close-proximity assimilation effect is utilized to achieve zero resistance measurement, thereby improving the superconducting performance at high temperatures.

[0022] In a second aspect, the present invention provides a method for preparing the high temperature superconducting material as described in the first aspect,

[0023] The chemical structure is A 10-x B x (CO 3-5 ) y D z When, the preparation method includes: a single-stage hydrothermal method;

[0024] The chemical structure is A 10-x B x (CO 3-5 ) y D z @(A,B)D, the preparation method includes: a multi-stage hydrothermal method, a coating method or a hydrothermal-calcination method.

[0025] The single-stage hydrothermal method comprises: subjecting the mixture solution to aging treatment and hydrothermal synthesis in sequence to obtain A 10-x B x (CO 3-5 ) y D z Superconducting materials.

[0026] Preferably, the mixture solution comprises: a soluble salt and a solvent are mixed according to a molar ratio.

[0027] Preferably, the pH value of the mixture solution is 7-10.

[0028] Preferably, the molar ratio of the soluble salt is (A+B): (CO 3-5):D=10:6:(1-5), A:B=(10-x):x, x∈[1,9], and the D element ion dosage > chemical valence balance.

[0029] Preferably, the soluble salt includes: a soluble salt containing element A and / or a soluble salt containing element B, a soluble salt containing element C and a soluble salt containing element D.

[0030] Preferably, the solid-to-liquid ratio g / mL of the aging treatment is 1:(10-1000).

[0031] Preferably, the temperature of the aging treatment is 40-80°C.

[0032] Preferably, the aging treatment time is 1-48h.

[0033] Preferably, the temperature of the hydrothermal synthesis is 110-200°C.

[0034] Preferably, the hydrothermal synthesis time is 10-48h.

[0035] Preferably, the pressure of the hydrothermal synthesis is greater than 3 MPa.

[0036] As a preferred technical solution of the present invention, the multi-stage hydrothermal method comprises: subjecting the first mixture to a first aging and a first hydrothermal treatment in sequence to obtain A 10-x B x (CO 3-5 ) y D z Materials, then the obtained A 10-x B x (CO 3-5 ) y D z The material and the second mixture are subjected to a second hydrothermal treatment to obtain A 10-x B x (CO 3-5 ) y D z @(A,B)D.

[0037] Preferably, the first mixture comprises: a first soluble salt and a first solvent are mixed according to a molar ratio.

[0038] Preferably, the pH value of the first mixture is 7-10.

[0039] Preferably, the molar ratio of the first soluble salt is (A+B): (CO 3-5 ):D=10:6:(1-5), A:B=(10-x):x, x∈[1,9].

[0040] Preferably, the first soluble salt includes: a soluble salt containing element A and / or a soluble salt containing element B, a soluble salt containing element C and a soluble salt containing element D.

[0041] Preferably, the solid-to-liquid ratio g / mL of the first aging is 1:(10-1000).

[0042] Preferably, the temperature of the first aging is 40-80°C.

[0043] Preferably, the first aging time is 1-48h.

[0044] Preferably, the temperature of the first hydrothermal treatment is 110-200°C.

[0045] Preferably, the first hydrothermal time is 10-48h.

[0046] Preferably, the first hydrothermal pressure is 1-3 MPa.

[0047] Preferably, the second mixture comprises: a mixture of a soluble salt of element D and a second solvent.

[0048] Preferably, the soluble salt of element D includes: one or a combination of at least two of potassium sulfide, sodium sulfide, ammonium sulfide, sodium chloride, ammonium chloride, sodium fluoride or sodium hydroxide.

[0049] Preferably, the mass ratio of the ion mass of the element D in the second hydrothermal treatment to the mass ratio of the solid salt in the first mixture is (0.01-100):1.

[0050] Preferably, the temperature of the second hydrothermal treatment is 110-200°C.

[0051] Preferably, the second hydrothermal time is 10-48h.

[0052] Preferably, the second hydrothermal pressure is ≥1 MPa.

[0053] As a preferred technical solution of the present invention, the coating method comprises: preparing A on a substrate 10-x B x (CO 3-5 ) y D z film layer, and then perform crystal distortion to obtain A 10-x B x (CO 3-5 ) y D z @(A,B)D high temperature superconducting materials.

[0054] Preferably, the substrate comprises: a metal substrate, a semiconductor substrate or an oxide substrate, or a combination of at least two thereof.

[0055] Preferably, the A 10-x B x (CO 3-5 ) y D z The film layer is prepared by pulsed laser deposition, electrodeposition, magnetron sputtering or sol-gel method, or a combination of at least two of them.

[0056] Preferably, the A used in the coating method 10-x B x (CO 3-5 ) y D z The preparation process of the product is as follows:

[0057] The third mixture is subjected to a second aging and a third hydrothermal treatment in sequence to obtain A 10-x B x (CO 3-5 ) y D z product.

[0058] Preferably, the third mixture comprises: a second soluble salt and a third solvent are mixed according to a molar ratio.

[0059] Preferably, the pH value of the third mixture is 7-10.

[0060] Preferably, the molar ratio of the second soluble salt is (A+B): (CO 3-5 ):D=10:6:(1-5), A:B=(10-x):x, x∈[1,9].

[0061] Preferably, the second soluble salt includes: a soluble salt containing element A and / or a soluble salt containing element B, a soluble salt containing element C and a soluble salt containing element D.

[0062] Preferably, the solid-to-liquid ratio g / mL of the second aging is 1:(10-1000).

[0063] Preferably, the second aging temperature is 40-80°C.

[0064] Preferably, the second aging time is 1-48h.

[0065] Preferably, the temperature of the third hydrothermal treatment is 110-200°C.

[0066] Preferably, the third hydrothermal treatment lasts for 10-48 hours.

[0067] Preferably, the third hydrothermal pressure is 1-3 MPa.

[0068] Preferably, the sol-gel method comprises the following:

[0069] S1, mixing a solution containing element A and element B with a solution containing element D, placing the mixture on a substrate, and drying the mixture to form an (A, B)D film on the surface;

[0070] S2, A 10-x B x (CO 3-5 ) y The D powder is uniformly dispersed in the solvent and disposed on the surface of the obtained (A, B)D film.

[0071] Preferably, the method of setting on the substrate in S1 includes spin coating and / or dipping.

[0072] Preferably, the method of setting the surface of the obtained (A, B)D film in S2 includes one or a combination of at least two of spin coating, dipping or electrodeposition.

[0073] Preferably, the electrodeposition comprises: 10-x B x (CO 3-5 ) y D powder is dispersed in a solution containing element A and / or element B, and the substrate on which the (A, B)D film is set is used as a direct current cathode. 10-x B x (CO 3-5 ) y D powder is deposited with element A and / or element B.

[0074] Preferably, the A used in the sol-gel method 10-x B x (CO 3-5 ) y D z The powder preparation process is as follows:

[0075] The fourth mixture is subjected to a third aging and a fourth hydrothermal treatment in sequence to obtain A 10-x B x (CO 3-5 ) y D z product.

[0076] Preferably, the fourth mixture comprises: a third soluble salt and a fourth solvent are mixed according to a molar ratio.

[0077] Preferably, the pH value of the fourth mixture is 7-10.

[0078] Preferably, the molar ratio of the third soluble salt is (A+B): (CO 3-5 ):D=10:6:(1-5), A:B=(10-x):x, x∈[1,9].

[0079] Preferably, the third soluble salt includes: a soluble salt containing element A and / or a soluble salt containing element B, a soluble salt containing element C and a soluble salt containing element D.

[0080] Preferably, the solid-liquid ratio g / mL of the third aging is 1:(10-1000).

[0081] Preferably, the temperature of the third aging is 40-80°C.

[0082] Preferably, the third aging time is 1-48h.

[0083] Preferably, the temperature of the fourth hydrothermal treatment is 110-200°C.

[0084] Preferably, the fourth hydrothermal treatment lasts for 10-48 hours.

[0085] Preferably, the fourth hydrothermal pressure is 1-3 MPa.

[0086] Preferably, the crystal distortion comprises liquid phase distortion and / or gas phase distortion.

[0087] Preferably, the liquid phase distortion comprises: 10-x B x (CO 3-5 ) y D z The film layer is subjected to a fifth hydrothermal treatment in a solution containing element D.

[0088] Preferably, the ion mass of element D in the fifth hydrothermal is 10-x B x (CO 3-5 ) y D z The mass ratio of the solid salt used in the film preparation process is (0.01-100):1, and the concentration of element D is greater than 0.01 mol / L.

[0089] Preferably, the fifth hydrothermal temperature is 110-200°C.

[0090] Preferably, the fifth hydrothermal treatment lasts for 10-48 hours.

[0091] Preferably, the fifth hydrothermal pressure is ≥1 MPa.

[0092] Preferably, the gas phase distortion comprises: 10-xB x (CO 3-5 ) y D z The film layer is first calcined in an atmosphere containing element D.

[0093] Preferably, the temperature of the first calcination is ≤300°C.

[0094] Preferably, the first calcination time is 1-72 hours.

[0095] As a preferred technical solution of the present invention, the hydrothermal-roasting method comprises: 10-x B x (CO 3-5 ) y D z The material undergoes a second roasting.

[0096] Preferably, the A used in the hydrothermal-roasting method 10-x B x (CO 3-5 ) y D z The material preparation process is as follows:

[0097] The fifth mixture is subjected to the fourth aging and the sixth hydrothermal treatment in sequence to obtain A 10-x B x (CO 3-5 ) y D z materials.

[0098] Preferably, the fifth mixture comprises: a fourth soluble salt and a fifth solvent are mixed according to a molar ratio.

[0099] Preferably, the pH value of the fifth mixture is 7-10.

[0100] Preferably, the molar ratio of the fourth soluble salt is (A+B): (CO 3-5 ):D=10:6:(1-5), A:B=(10-x):x, x∈[1,9].

[0101] Preferably, the fourth soluble salt includes: a soluble salt containing element A and / or a soluble salt containing element B, a soluble salt containing element C and a soluble salt containing element D.

[0102] Preferably, the solid-to-liquid ratio g / mL of the fourth aging is 1:(10-1000).

[0103] Preferably, the temperature of the fourth aging is 40-80°C.

[0104] Preferably, the fourth aging time is 1-48h.

[0105] Preferably, the sixth hydrothermal treatment has a temperature of 110-200°C.

[0106] Preferably, the sixth hydrothermal treatment lasts for 10-48 hours.

[0107] Preferably, the sixth hydrothermal pressure is 1-3 MPa.

[0108] Preferably, the atmosphere used for the second calcination comprises one or a combination of at least two of O2, H2S, SO2 or HCl.

[0109] Preferably, the temperature of the second calcination is ≤500°C.

[0110] Preferably, the second calcination time is 1-48h.

[0111] In a third aspect, the present invention provides a use of the high temperature superconducting material according to the first aspect, wherein the use comprises:

[0112] The high-temperature superconducting material is used to prepare magnetic resonance imaging products, maglev trains, power transmission materials or power equipment.

[0113] Compared with the prior art solutions, the present invention has the following beneficial effects:

[0114] The high temperature superconducting material provided by the present invention is designed by designing pseudoapatite 10-x B x (CO 3-5 ) y D z , achieving superconductivity at high temperatures. 10-x B x (CO 3-5 ) y D z The modified compound (A, B) D is introduced into the apatite-like 10-x B x (CO 3-5 ) y D z During the degenerate growth process, the conductive path is transformed from one dimension to three dimensions, and the close-proximity assimilation effect is utilized to achieve zero resistance measurement, thereby improving the superconducting performance at high temperatures. BRIEF DESCRIPTION OF THE DRAWINGS

[0115] Figure 1 is the XRD spectrum of the high temperature superconducting material obtained in Example 1 of the present invention;

[0116] Figure 2 TEM spectrum and structural schematic diagram of the high temperature superconducting material obtained in Example 1 of the present invention;

[0117] Figure 3 The Pb in the high temperature superconducting material obtained in Example 1 of the present invention 10-x Cu x (PO4)6S z Some energy band structure diagrams;

[0118] Figure 4 is the temperature-resistance curve of the high temperature superconducting material obtained in Example 1 of the present invention;

[0119] Figure 5 is the magnetic field-critical temperature relationship of the high temperature superconducting material obtained in Example 1 of the present invention;

[0120] Figure 6 This is the 120K current-voltage curve of the high temperature superconducting material obtained in Example 1 of the present invention;

[0121] Figure 7 This is the 160K current-voltage curve of the high-temperature superconducting material obtained in Example 1 of the present invention;

[0122] Figure 8 The 200K current-voltage curve of the high temperature superconducting material obtained in Example 1 of the present invention;

[0123] Fig. 9 The 280K current-voltage curve of the high temperature superconducting material obtained in Example 1 of the present invention;

[0124] Fig.10 The ZFC-FC curve of the high temperature superconducting material obtained in Example 1 of the present invention, and the inset is the ZFC curve;

[0125] Fig.11 are the initial magnetization curves of the high temperature superconducting material obtained in Example 1 of the present invention at different temperatures;

[0126] Fig.12 is the hysteresis loop at 10K of the high temperature superconducting material obtained in Example 1 of the present invention;

[0127] Fig.13 is the hysteresis loop of the high temperature superconducting material obtained in Example 1 of the present invention at 250K;

[0128] Fig.14 is the hysteresis loop at 300K of the high temperature superconducting material obtained in Example 1 of the present invention;

[0129] Fig.15 is the temperature-resistance curve of the high temperature superconducting material obtained in Example 2 of the present invention;

[0130] Fig.16 is the ZFC-FC curve of the high temperature superconducting material obtained in Example 2 of the present invention;

[0131] Fig.17 The temperature-resistance curve of the high temperature superconducting material obtained in Example 3 of the present invention;

[0132] Fig.18 This is the current-voltage curve of the high-temperature superconducting material obtained in Example 3 of the present invention, from which the compensation voltage has been removed;

[0133] Fig.19 This is the XRD spectrum of the high temperature superconducting material obtained in Example 4 of the present invention;

[0134] Fig. 20 is the resistance-temperature curve of the high temperature superconducting material obtained in Example 4 of the present invention;

[0135] Fig.21 is the ZFC-FC curve of the high temperature superconducting material obtained in Example 4 of the present invention;

[0136] Fig. 22 This is the XRD spectrum of the high temperature superconducting material obtained in Example 5 of the present invention;

[0137] Fig.23 is the ZFC curve of the high temperature superconducting material obtained in Example 5 of the present invention;

[0138] Fig.24 The temperature-resistance curve of the high-temperature superconducting material obtained in Example 5 of the present invention;

[0139] Fig.25 This is the XRD spectrum of the material obtained in Example 6 of the present invention;

[0140] Fig.26 This is the ZFC-FC curve of the material obtained in Example 6 of the present invention;

[0141] Fig. 27 This is the 10K MH curve of the material obtained in Example 6 of the present invention;

[0142] Fig.28 This is the XRD spectrum of the material obtained in Inventive Example 7;

[0143] Fig.29 This is the resistance-temperature curve of the material obtained in Inventive Example 7.

[0144] The present invention is further described in detail below. However, the following examples are only simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims. DETAILED DESCRIPTION

[0145] To better illustrate the present invention and facilitate understanding of the technical solution of the present invention, typical but non-limiting embodiments of the present invention are as follows:

[0146] This embodiment provides a high-temperature superconducting material, and the chemical structure of the high-temperature superconducting material is as follows:

[0147] A 10-x B x (CO 3-5 ) y D z , belongs to pseudoapatite structure;

[0148] Wherein, element A includes one or a combination of at least two of s-block metals, p-block metals or lanthanide rare earth elements; B includes one or a combination of at least two of d-block elements; CO 3-5 Including acid radical; element D includes one or a combination of at least two of non-metallic elements or metal elements of Group VI A; in terms of molar amount, x∈[0-10], y∈(0-6], z is greater than or less than the structural formula A 10-x B x (CO 3-5 ) y D z The chemical valence balance number and z∈(0-5].

[0149] In the present invention, the pseudoapatite structure refers to a crystal structure that is similar to but different from natural apatite.

[0150] The element A includes one or a combination of at least two of Ca, Mg, Ba, Pb, Y, Ce or La.

[0151] Illustratively, the combinations of element A are as follows: a combination of Ca and Ba, a combination of Ba and Pb, a combination of Y and Ce, a combination of Ce and La, a combination of Ba, Pb, Y and Ce, a combination of Ca, Ba and Y, a combination of Ca, Pb, Y, Ce and La, and the like.

[0152] The element B includes one or a combination of at least two of Sc, Mn, Zn, Cu, Mo, Hg, Fe or Ni.

[0153] Illustratively, the combinations of element B are as follows: a combination of Sc and Mn, a combination of Zn and Cu, a combination of Mo and Hg, a combination of Fe and Ni, etc., a combination of Sc, Mn and Zn, a combination of Zn, Cu and Mo, a combination of Zn, Cu, Mo and Fe, a combination of Mn, Zn, Cu and Ni, etc.

[0154] Among them, the CO 3-5 Including metal acid radicals or non-metal acid radicals.

[0155] For example, CO 3-5The corresponding acid radicals include sulfate, carbonate, silicate, borate, thiosulfate or thiophosphate, etc.

[0156] Among them, the CO 3-5 The element C includes: one of Si, S, As, C or B, or a combination of at least two of them.

[0157] The element D includes one or a combination of at least two of F, Cl, O, S, Se, Te or OH.

[0158] Illustratively, the combination of element D includes: a combination of F and Cl, a combination of O and S, a combination of Se and Te, a combination of F and OH, a combination of F, Cl and O, a combination of Cl, O, S and Se, and the like.

[0159] Furthermore, in order to further improve the superconducting performance, the chemical structure of the high temperature superconducting material is as follows: 10- x B x (CO 3-5 ) y D z @(A,B)D;

[0160] Wherein, compound (A, B) D is modified A 10-x B x (CO 3-5 ) y D z or with A 10-x B x (CO 3-5 ) y D z Eutectic.

[0161] Furthermore, the present invention provides a method for preparing the above-mentioned high-temperature superconducting material, the preparation method comprising:

[0162] The chemical structure is A 10-x B x (CO 3-5 ) y D z When, the preparation method includes: a single-stage hydrothermal method;

[0163] The chemical structure is A 10-x B x (CO 3-5 ) y D z @(A,B)D, the preparation method includes: a multi-stage hydrothermal method, a coating method or a hydrothermal-calcination method.

[0164] The single-stage hydrothermal method comprises: subjecting the mixture solution to aging treatment and hydrothermal synthesis in sequence to obtain A10-x B x (CO 3-5 ) y D z Superconducting materials.

[0165] Preferably, the mixture solution comprises: a soluble salt and a solvent are mixed according to a molar ratio.

[0166] Preferably, the pH value of the mixture is 7-10, for example, 7, 7.5, 8, 8.5, 9, 9.5 or 10, etc., but is not limited to the listed values, and other values ​​not listed within the range also meet the requirements.

[0167] Preferably, the molar ratio of the soluble salt is (A+B): (CO 3-5 ):D=10:6:(1-5), A:B=(10-x):x, x∈[1,9], and the D element ion dosage > chemical valence balance.

[0168] Preferably, the soluble salt comprises: a soluble salt containing element A and / or a soluble salt containing element B, a soluble salt containing element C and a soluble salt containing element D, and the molar ratio of the soluble salt is controlled to be (A+B):(CO 3-5 ):D=10:6:(1-5), for example, it can be 10:6:1, 10:6:2, 10:6:3, 10:6:4 or 10:6:5, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0169] Preferably, the solid-to-liquid ratio g / mL of the aging treatment is 1:(10-1000), for example, it can be 1:10, 1:20, 1:40, 1:60, 1:80, 1:100, 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, 1:900 or 1:1000, etc., but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0170] Preferably, the temperature of the aging treatment is 40-80°C, for example, 40°C, 50°C, 60°C, 70°C or 80°C, etc., but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0171] Preferably, the aging time is 1-48h, for example, it can be 1h, 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 35h, 40h, 45h or 48h, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0172] Preferably, the temperature of the hydrothermal synthesis is 110-200°C, for example, it can be 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C or 200°C, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0173] Preferably, the hydrothermal synthesis time is 10-48 h, for example, it can be 10 h, 12 h, 14 h, 16 h, 18 h, 20 h, 22 h, 24 h, 26 h, 28 h, 30 h, 35 h, 40 h, 45 h or 48 h, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0174] Preferably, the pressure of the hydrothermal synthesis is greater than 3 MPa, for example, it may be 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa or 10 MPa, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0175] The multi-stage hydrothermal method comprises: subjecting the first mixture to a first aging and a first hydrothermal treatment in sequence to obtain A 10-x B x (CO 3-5 ) y D z Materials, then the obtained A 10-x B x (CO 3-5 ) y D z The material and the second mixture are subjected to a second hydrothermal treatment to obtain A 10-x B x (CO 3-5 ) y D z @(A,B)D.

[0176] The first mixture comprises: a first soluble salt and a first solvent are mixed according to a molar ratio.

[0177] The pH value of the first mixture is 7-10, for example, 7, 7.5, 8, 8.5, 9, 9.5 or 10, but is not limited to the listed values, and other values ​​not listed within the range also meet the requirements.

[0178] Wherein, the controlled molar ratio of the first soluble salt is (A+B): (CO 3-5 ):D=10:6:(1-5), A:B=(10-x):x, x∈[1,9].

[0179] In the present invention, the molar ratio of the first soluble salt is controlled to be (A+B): (CO 3-5 ):D=10:6:(1-5), for example, it can be 10:6:1, 10:6:2, 10:6:3, 10:6:4 or 10:6:5, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0180] The first soluble salt includes: a soluble salt containing element A and / or a soluble salt containing element B, a soluble salt containing element C and a soluble salt containing element D.

[0181] Wherein, the solid-liquid ratio g / mL of the first aging is 1:(10-1000), for example, it can be 1:10, 1:20, 1:40, 1:60, 1:80, 1:100, 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, 1:900 or 1:1000, etc., but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0182] The first aging temperature is 40-80°C, for example, 40°C, 50°C, 60°C, 70°C or 80°C, but is not limited to the listed values, and other values ​​not listed within the range also meet the requirements.

[0183] Wherein, the first aging time is 1-48h, for example, it can be 1h, 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 35h, 40h, 45h or 48h, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0184] Among them, the temperature of the first hydrothermal is 110-200℃, for example, it can be 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, 190℃ or 200℃, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0185] Wherein, the first hydrothermal time is 10-48h, for example, it can be 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 35h, 40h, 45h or 48h, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0186] Among them, the first hydrothermal pressure is 1-3MPa, for example, it can be 1MPa, 1.2MPa, 1.4MPa, 1.6MPa, 1.8MPa, 1.9MPa, 2MPa, 2.2MPa, 2.4MPa, 2.6MPa, 2.8MPa or 3MPa, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0187] The second mixture comprises: a mixture of a soluble salt of element D and a second solvent.

[0188] Wherein, the soluble salt of the element D includes: one or a combination of at least two of potassium sulfide, sodium sulfide, ammonium sulfide, sodium chloride, ammonium chloride, sodium fluoride or sodium hydroxide.

[0189] Wherein, the mass ratio of the ion mass of the element D in the second hydrothermal reaction to the mass ratio of the solid salt in the first mixture is (0.01-100):1, for example, it can be 0.01:1, 0.02:1, 0.04:1, 0.06:1, 0.08:1, 0.1:1, 0.2:1, 0.4:1, 0.6:1, 0.8:1, 1:1, 2:1, 4:1, 6:1, 8:1, 10:1, 20:1, 40:1, 60:1, 80:1 or 100:1, etc., but is not limited to the listed values, and other values ​​not listed within the range also meet the requirements.

[0190] Wherein, the temperature of the second hydrothermal treatment is 110-200°C, for example, it can be 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C or 200°C, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0191] Wherein, the second hydrothermal time is 10-48h, for example, it can be 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 35h, 40h, 45h or 48h, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0192] The second hydrothermal pressure is ≥1 MPa, for example, it can be 1 MPa, 2 MPa, 4 MPa, 6 MPa, 8 MPa or 10 MPa, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0193] Wherein, after the second hydrothermal treatment, the obtained material is subjected to solid-liquid separation, drying and molding to obtain A 10-x B x (CO 3-5 ) y Dz @(A,B)D High temperature superconducting material products.

[0194] The drying is carried out in an inert atmosphere or a vacuum environment.

[0195] In the present invention, the inert atmosphere includes an atmosphere that does not react with the product, such as nitrogen, helium, neon or argon.

[0196] The drying temperature is ≤110°C, for example, it can be 110°C, 100°C, 90°C or 80°C, but is not limited to the listed values, and other values ​​not listed within the range also meet the requirements.

[0197] The pressure during molding is ≥5MPa, for example, it can be 5MPa, 6MPa, 7MPa, 8MPa, 9MPa or 10MPa, etc. During molding, a neutral solution such as deionized water and alcohol can be used as an adhesive, or no adhesive is used.

[0198] Exemplarily, the coating method comprises: preparing A on a substrate 10-x B x (CO 3-5 ) y D z film layer, and then perform crystal distortion to obtain A 10-x B x (CO 3-5 ) y D z @(A,B)D high temperature superconducting materials;

[0199] Wherein, the substrate comprises: one or a combination of at least two of a metal substrate, a semiconductor substrate or an oxide substrate.

[0200] For example, the material of the substrate includes: one or a combination of at least two of copper, stainless steel, gold, silver, silicon, LAO or SAO.

[0201] Among them, the A 10-x B x (CO 3-5 ) y D z The film layer is prepared by pulsed laser deposition, electrodeposition, magnetron sputtering or sol-gel method, or a combination of at least two of them.

[0202] The target material used in the pulsed laser deposition and / or magnetron sputtering includes A obtained by conventional preparation process in the art. 10-x B x (CO 3-5 ) y D z The target material or the A obtained by the first hydrothermal method of the present invention 10-xB x (CO 3-5 ) y D z product.

[0203] For example, the A used in the coating method 10-x B x (CO 3-5 ) y D z The preparation process of the product is as follows:

[0204] The third mixture is subjected to a second aging and a third hydrothermal treatment in sequence to obtain A 10-x B x (CO 3-5 ) y D z product.

[0205] Wherein, the third mixture comprises: a second soluble salt and a third solvent are mixed according to a molar ratio.

[0206] The pH value of the third mixture is 7-10, for example, 7, 7.5, 8, 8.5, 9, 9.5 or 10, but is not limited to the listed values, and other values ​​not listed within the range also meet the requirements.

[0207] Wherein, the molar ratio of the second soluble salt is controlled to be (A+B): (CO 3-5 ):D=10:6:(1-5), A:B=(10-x):x, x∈[1,9].

[0208] In the present invention, the molar ratio of the second soluble salt is controlled to be (A+B): (CO 3-5 ):D=10:6:(1-5), for example, it can be 10:6:1, 10:6:2, 10:6:3, 10:6:4 or 10:6:5, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0209] The second soluble salt includes: a soluble salt containing element A and / or a soluble salt containing element B, a soluble salt containing element C and a soluble salt containing element D.

[0210] Wherein, the solid-liquid ratio g / mL of the second aging is 1:(10-1000), for example, it can be 1:10, 1:20, 1:40, 1:60, 1:80, 1:100, 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, 1:900 or 1:1000, etc., but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0211] The second aging temperature is 40-80°C, for example, 40°C, 50°C, 60°C, 70°C or 80°C, but is not limited to the listed values, and other values ​​not listed within the range also meet the requirements.

[0212] Wherein, the second aging time is 1-48h, for example, it can be 1h, 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 35h, 40h, 45h or 48h, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0213] Among them, the temperature of the third hydrothermal is 110-200℃, for example, it can be 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, 190℃ or 200℃, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0214] Among them, the third hydrothermal time is 10-48h, for example, it can be 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 35h, 40h, 45h or 48h, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0215] Among them, the pressure of the third hydrothermal is 1-3MPa, for example, it can be 1MPa, 1.2MPa, 1.4MPa, 1.6MPa, 1.8MPa, 1.9MPa, 2MPa, 2.2MPa, 2.4MPa, 2.6MPa, 2.8MPa or 3MPa, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0216] The pulsed laser deposition method for preparing thin films can use conventional excimer laser light sources, such as ArF, KrF, XeCl, etc., with corresponding wavelengths of 193, 248, and 308 nm, respectively.

[0217] The process of preparing thin films by pulsed laser deposition needs to maintain a vacuum or pure inert gas atmosphere to prevent oxygen from penetrating.

[0218] Wherein, the sol-gel method includes the following:

[0219] S1, mixing a solution containing element A and element B with a solution containing element D, placing the mixture on a substrate, and drying the mixture to form an (A, B)D film on the surface;

[0220] S2, A 10-x Bx (CO 3-5 ) y The D powder is uniformly dispersed in the solvent and disposed on the surface of the obtained (A, B)D film.

[0221] Wherein, the method of setting on the substrate in S1 includes spin coating and / or dipping.

[0222] Wherein, the method of setting on the surface of the obtained (A, B)D film in S2 includes one or a combination of at least two of spin coating, dipping or electrodeposition.

[0223] Exemplarily, the electrodeposition comprises: 10-x B x (CO 3-5 ) y D powder is dispersed in a solution containing element A and / or element B, and the substrate on which the (A, B)D film is set is used as a direct current cathode. 10-x B x (CO 3-5 ) y D powder is deposited with element A and / or element B.

[0224] Among them, the A used in the sol-gel method 10-x B x (CO 3-5 ) y D z The powder can be prepared by conventional methods in the art or by the first hydrothermal method of the present invention. 10-x B x (CO 3-5 ) y D z powder.

[0225] For example, the A used in the sol-gel method 10-x B x (CO 3-5 ) y D z The powder preparation process is as follows:

[0226] The fourth mixture is subjected to a third aging and a fourth hydrothermal treatment in sequence to obtain A 10-x B x (CO 3-5 ) y D z powder.

[0227] The fourth mixture comprises: a third soluble salt and a fourth solvent are mixed according to a molar ratio;

[0228] The pH value of the fourth mixture is 7-10, for example, 7, 7.5, 8, 8.5, 9, 9.5 or 10, but is not limited to the listed values, and other values ​​not listed within the range also meet the requirements.

[0229] Wherein, the controlled molar ratio of the third soluble salt is (A+B): (CO 3-5 ):D=10:6:(1-5), A:B=(10-x):x, x∈[1,9].

[0230] In the present invention, the molar ratio of the third soluble salt is controlled to be (A+B): (CO 3-5 ):D=10:6:(1-5), for example, it can be 10:6:1, 10:6:2, 10:6:3, 10:6:4 or 10:6:5, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0231] The third soluble salt includes: a soluble salt containing element A and / or a soluble salt containing element B, a soluble salt containing element C and a soluble salt containing element D.

[0232] Among them, the solid-liquid ratio g / mL of the third aging is 1:(10-1000), for example, it can be 1:10, 1:20, 1:40, 1:60, 1:80, 1:100, 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, 1:900 or 1:1000, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0233] The temperature of the third aging is 40-80°C, for example, 40°C, 50°C, 60°C, 70°C or 80°C, but is not limited to the listed values, and other values ​​not listed within the range also meet the requirements.

[0234] Among them, the third aging time is 1-48h, for example, it can be 1h, 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 35h, 40h, 45h or 48h, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0235] Among them, the temperature of the fourth hydrothermal is 110-200℃, for example, it can be 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, 190℃ or 200℃, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0236] Among them, the fourth hydrothermal time is 10-48h, for example, it can be 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 35h, 40h, 45h or 48h, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0237] Among them, the pressure of the fourth hydrothermal is 1-3MPa, for example, it can be 1MPa, 1.2MPa, 1.4MPa, 1.6MPa, 1.8MPa, 1.9MPa, 2MPa, 2.2MPa, 2.4MPa, 2.6MPa, 2.8MPa or 3MPa, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0238] Wherein, the crystal distortion mode includes liquid phase distortion and / or gas phase distortion.

[0239] Wherein, the liquid phase distortion comprises: 10-x B x (CO 3-5 ) y D z The film layer is subjected to a fifth hydrothermal treatment in a solution containing element D.

[0240] Wherein, the mass ratio of the ion mass of element D in the fifth hydrothermal reaction to the mass ratio of the solid salt in the first mixture is (0.01-100):1, and the concentration of element D is >0.01 mol / L, for example, it can be 0.01:1, 0.02:1, 0.04:1, 0.06:1, 0.08:1, 0.1:1, 0.2:1, 0.4:1, 0.6:1, 0.8:1, 1:1, 2:1, 4:1, 6:1, 8:1, 10:1, 20:1, 40:1, 60:1, 80:1 or 100:1, etc., but is not limited to the listed values, and other values ​​not listed within the range also meet the requirements.

[0241] Among them, the temperature of the fifth hydrothermal is 110-200℃, for example, it can be 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, 190℃ or 200℃, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0242] Among them, the fifth hydrothermal time is 10-48h, for example, it can be 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 35h, 40h, 45h or 48h, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0243] Among them, the pressure of the fifth hydrothermal is ≥1MPa, for example, it can be 1MPa, 2MPa, 4MPa, 6MPa, 8MPa or 10MPa, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0244] Wherein, the gas phase distortion comprises: 10-x B x (CO 3-5 ) y D z The film layer is first calcined in an atmosphere containing element D.

[0245] The first calcination temperature is ≤300°C, for example, 300°C, 280°C, 260°C, 240°C, 220°C or 200°C, but is not limited to the listed values, and other values ​​not listed within the range also meet the requirements.

[0246] Wherein, the first calcination time is 1-72h, for example, it can be 1h, 2h, 4h, 6h, 8h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, 50h, 55h, 60h, 65h, 70h or 72h, but is not limited to the listed values, and other values ​​not listed within the range also meet the requirements.

[0247] Wherein, the hydrothermal-roasting method comprises: 10-x B x (CO 3-5 ) y D z The material undergoes a second roasting.

[0248] The atmosphere used for the second calcination includes one or a combination of at least two of O2, H2S, SO2 or HCl.

[0249] Illustratively, the combination of atmospheres used for the second calcination includes: a combination of O2 and H2S, a combination of SO2 and HCl, a combination of O2, H2S and SO2, and the like.

[0250] The second calcination temperature is ≤500°C, for example, it can be 500°C, 480°C, 460°C, 440°C, 420°C, 400°C, 350°C or 300°C, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0251] Wherein, the time of the second calcination is 1-48h, for example, it can be 1h, 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 35h, 40h, 45h or 48h, but is not limited to the listed values, and other values ​​not listed within the range also meet the requirements.

[0252] Wherein, the hydrothermal A 10-x B x (CO 3-5 ) y D z The preparation method of the material includes the conventional preparation process in the art or the method of using the first hydrothermal method of the present invention to obtain A 10-x B x (CO 3-5 ) y D z materials.

[0253] Wherein, the A used in the hydrothermal-roasting method 10-x B x (CO 3-5 ) y D z The material preparation process is as follows:

[0254] The fifth mixture is subjected to the fourth aging and the sixth hydrothermal treatment in sequence to obtain A 10-x B x (CO 3-5 ) y D z materials.

[0255] The fifth mixture comprises: a fourth soluble salt and a fifth solvent are mixed according to a molar ratio.

[0256] The pH value of the fifth mixture is 7-10, for example, 7, 7.5, 8, 8.5, 9, 9.5 or 10, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0257] Wherein, the molar ratio of the fourth soluble salt is controlled to be (A+B): (CO 3-5 ):D=10:6:(1-5), A:B=(10-x):x, x∈[1,9].

[0258] In the present invention, the molar ratio of the fourth soluble salt is controlled to be (A+B): (CO 3-5):D=10:6:(1-5), for example, it can be 10:6:1, 10:6:2, 10:6:3, 10:6:4 or 10:6:5, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0259] The fourth soluble salt includes: a soluble salt containing element A and / or a soluble salt containing element B, a soluble salt containing element C and a soluble salt containing element D.

[0260] Wherein, the solid-liquid ratio g / mL of the fourth aging is 1:(10-1000), for example, it can be 1:10, 1:20, 1:40, 1:60, 1:80, 1:100, 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, 1:900 or 1:1000, etc., but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0261] The temperature of the fourth aging is 40-80°C, for example, 40°C, 50°C, 60°C, 70°C or 80°C, but is not limited to the listed values, and other values ​​not listed within the range also meet the requirements.

[0262] Among them, the fourth aging time is 1-48h, for example, it can be 1h, 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 35h, 40h, 45h or 48h, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0263] Among them, the temperature of the sixth hydrothermal is 110-200℃, for example, it can be 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, 190℃ or 200℃, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0264] Among them, the sixth hydrothermal time is 10-48h, for example, it can be 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 35h, 40h, 45h or 48h, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0265] Among them, the pressure of the sixth hydrothermal is 1-3MPa, for example, it can be 1MPa, 1.2MPa, 1.4MPa, 1.6MPa, 1.8MPa, 1.9MPa, 2MPa, 2.2MPa, 2.4MPa, 2.6MPa, 2.8MPa or 3MPa, but is not limited to the listed values, and other unlisted values ​​within the range also meet the requirements.

[0266] In the present invention, the solvent used in the preparation process, the first solvent, the second solvent, the third solvent, the fourth solvent and the fifth solvent and other related solvents can be selected from water, ethanol and other commonly used solvents in the art.

[0267] In the present invention, the soluble salt containing element A and / or the soluble salt containing element B, the soluble salt containing element C and the soluble salt containing element D can be illustratively selected as soluble phosphates, soluble sulfates, soluble carbonates, lead carbonates, copper carbonates, soluble arsenates, soluble silicates, soluble borates, soluble lead salts, soluble copper salts and soluble sulfides, etc.

[0268] Further, in order to illustrate the superconducting effect that can be achieved by the high-temperature superconducting material provided by the present invention, the following examples are used for exemplary description, as follows:

[0269] Example 1

[0270] This embodiment provides a 10-x B x (PO4) y D z @(A,B)D preparation method, wherein A is Pb, B is Cu, and D is S; wherein x is 9, y is 6, and z is 1.5 to 2, and it is a metastable structure and is prepared by a hydrothermal method.

[0271] The preparation process is as follows:

[0272] S1. After copper nitrate is fully dissolved in water, K3PO4 is added to fully precipitate it. After magnetic stirring to fully dissolve it, lead acetate is added to the solution and fully dissolved, and K3PO4 is continued to be added to fully precipitate it; the (Pb+Cu) / PO4 ion molar ratio is controlled to be 10 / 6; wherein Pb / Cu=1 / 9; the ratio of Pb+Cu cation to solvent is 0.02 mol / L; after fully mixing, K2S is added to generate PbS precipitate; the pH value of the solution is adjusted to 8, and fully stirred at 25°C for 1 hour;

[0273] S2, stirring and aging at 60°C for 48 hours. After aging, the sample is dark gray without any blue. Then the solid-liquid mixture is placed in a hydrothermal kettle and hydrothermaled at a pressure of 2MPa and a temperature of 160°C for 48 hours. After the hydrothermal, the sample is dark gray and the supernatant is colorless.

[0274] S3. Continue to add K2S to the solid-liquid mixture, and after the accumulation of the previous addition, Pb / S is equal to 1 / 10; after the mixture is settled to a colorless supernatant, it is hydrothermaled at a pressure of 2MPa and a temperature of 160°C for 48h, and the obtained sample is pure black without any blue and any metallic luster;

[0275] Among them, the element ratio of the final product is not consistent with the addition ratio of Pb and Cu, and Cu doping has the largest ratio, which is related to the selection of D element in the present invention;

[0276] Among them, the synthesized Pb 10-x Cu x (PO4)6S z In the product, when z=1, the macroscopic conductivity of the powder is poor, and the directly measured resistance is greater than 1 or 10 3 Ω; the sample is gray, if any blue appears the synthesis fails; after the second hydrothermal treatment, the sample turns pure black.

[0277] in, Figure 1 The XRD pattern of the sample obtained in this example is shown, and it can be seen that the chemical formula is Pb 10-x Cu x (PO4)6S z @(Pb,Cu)S, XRD spectrum, Pb 10-x Cu x (PO4)6S z (distorted apatite phase) overlaps with some peaks of galena;

[0278] Furthermore, Figure 2 Pb obtained in Example 1 10-x Cu x (PO4)6S z TEM image of @(Pb,Cu)S shows that the apatite phase and galena are interconnected, which indicates that Pb 10-x Cu x (PO4)6S z (distorted apatite phase) and galena ((Pb, Cu)S) have a symbiotic relationship;

[0279] Furthermore, Figure 3 The Pb content in the samples obtained in this example is shown 10-x Cu x (PO4)6S z The energy band structure spectrum corresponding to some parts is calculated for qualitative calculation and is not used as a reference for the actual structure and the results of the embodiment; the increase of copper or sulfur doping will lead to a decrease in the energy gap, z = 2;

[0280] Furthermore, Figure 4 Pb obtained in this example 10-x Cu x (PO4)6S z @(Pb,Cu)S sample resistance-temperature curve. As can be seen from the figure, under 0T magnetic field, the sample resistance changes significantly around 270K (Tc≈268K); with the increase of magnetic field ( Figure 4 The sample is highly sensitive to current. When the current increases to 50 μA, the resistance transition temperature advances to around 150 K. Figure 5 Example Pb is shown 10-x Cu x (PO4)6S z @The relationship between the transition temperature Tc and magnetic field of (Pb,Cu)S sample;

[0281] Furthermore, Figure 6 , Figure 7 , Figure 8 and Fig. 9 Pb obtained in this example 10-x Cu x (PO4)6S z The IV curves of @(Pb,Cu)S samples at temperatures of 120K, 160K, 200K and 280K. In order to stabilize the test, the voltage compensation mode was used during the test. In the voltage-current curve during the test, the voltage starting point was not 0. As can be seen from the figure, there is an obvious nonlinear platform in the curve. After 280K, the current and voltage of the sample return to linearity. The test results are consistent with Figure 4 The results shown are close, with the critical values ​​of 160K and 200K both less than 50μA;

[0282] Further, this embodiment provides Pb 10-x Cu x (PO4)6S z The zero field cooling (ZFC)-field cooling (FC) curve of @(Pb,Cu)S sample is shown in Fig.10 As shown, the sample exhibits diamagnetism below 270K and drops sharply below 30K. The change in magnetic susceptibility near 30K is caused by A 10-x B x (CO 3～5 ) y D z @(A,B)D in (A,B)D refers to (Pb,Cu)S in Example 1, wherein the magnetic field strength is 25Oe;

[0283] Further, this embodiment provides Pb 10-x Cu x (PO4)6S zThe magnetic susceptibility curves of @(Pb,Cu)S samples at different temperatures, including the initial magnetization curve and the hysteresis loop, are shown in Figure 2. Fig.11 , Fig.12 , Fig.13 and Fig.14 As shown in the figure, the sample exhibits soft magnetism at room temperature and above, which may be due to the Cu 2+ At 250K, an obvious hysteresis loop pointing to superconductivity can be observed in the sample.

[0284] It should be noted that due to the transitional vulcanization and unstable structure of the material itself, the material may undergo a series of deteriorations such as secondary oxidation in an unsealed environment. Additional protection should be provided for the material during storage and testing.

[0285] Example 2

[0286] The embodiment of the present invention provides a 10-x B x (PO4) y D z @(A,B)D preparation method, wherein A is Pb, B is Cu, and D is S; wherein x is 9, y is 6, and z is 1.5 to 2, and is a metastable structure; and is prepared by a hydrothermal method.

[0287] The preparation process is as follows:

[0288] S1. After copper nitrate is fully dissolved in water, K3PO4 is added to fully precipitate it, and then it is fully dissolved by magnetic stirring. Lead acetate is added to the solution and fully dissolved. K3PO4 is continued to be added to fully precipitate it, and the (Pb+Cu) / PO4 ion molar ratio is controlled to be 10 / 6, wherein Pb / Cu=6 / 4, and the ratio of Pb+Cu cation to solvent is 0.02 mol / L; after fully mixing, K2S potassium sulfide is added to generate PbS precipitate; the pH value of the solvent is adjusted to 8, and it is fully stirred at 25°C for 1 hour;

[0289] S2, keep stirring and start aging at 60°C for 48 hours. After aging, the sample is black-gray without any blue. The solid-liquid mixture is placed in a hydrothermal kettle and hydroheated at a pressure of 2.5 MPa and a temperature of 160°C for 48 hours. After the hydrothermal, the sample is black-gray and the supernatant is colorless.

[0290] S3. Continue to add K2S to the solid-liquid mixture, and after the accumulation of the previous addition, Pb / S is equal to 1 / 10; continue to age the mixture until the supernatant is colorless, and then hydrothermally heat it at a pressure of 1.5 MPa and a temperature of 160°C for 48 hours. The resulting sample is pure black without any blue or metallic luster.

[0291] The resistance-temperature curves of the samples obtained in this example under different magnetic fields are as follows: Fig.15 As shown, due to the possible presence of covellite impurities in the sample, the resistance of the sample cannot stably return to 0, but the superconductivity is not destroyed. When the temperature is greater than the critical temperature, the resistance of the sample increases slightly. Because of the conductivity of covellite itself and the shunting effect brought about by the thickness of the sample, the resistance change after the temperature is greater than Tc is not obvious. At the same time, under large current, the sample returns to a metallic state. The excellent conductivity may be caused by excessive sulfide. In the synthesis, attention should be paid to the scale of the distortion process flow. At the same time, the ratio of A and B (Pb and Cu in this embodiment) in the sample should be strictly controlled. The Cu / Pb molar ratio described in this embodiment is not a recommended value.

[0292] Furthermore, Fig.16 This is the zero-field cooling (ZFC)-field cooling (FC) curve of the sample obtained in this example. Since the azurite in the sample has superconductivity at low temperatures, the ZFC curve is divided into two sections, which are caused by covellite and distorted apatite respectively.

[0293] Example 3

[0294] In this embodiment, a high-temperature superconducting material is prepared by a PLD method. After the hydrothermal sample S2 obtained in Example 1 is sputtered onto a Si target, it is immersed in a Na2S solution (0.01 mol / L) at 180°C for 12 hours for crystal distortion, and then tested after drying. Among them, the Pb / Cu molar ratio in the hydrothermal method is 6 / 4, and the excess copper ensures that the copper doping amount in the apatite system is saturated.

[0295] The product was measured by Agilent 34420A equipment using a resistance-temperature curve. The equipment was measured in resistance compensation mode (adding an additional compensation voltage to the voltage end in the four-wire method test). When measuring a single temperature point, the temperature was kept warm for more than 10 minutes to avoid instability caused by rapid temperature changes. The test results are as follows: Fig.17 and Fig.18 As shown, it can be found that the other test results are basically consistent with those of Example 1 and Example 2.

[0296] Example 4

[0297] For comparison, this embodiment provides a synthetic intermediate sample, which is a sample after the first hydrothermal treatment, and the process is as follows:

[0298] After copper nitrate is fully dissolved in water, K3PO4 is added to fully precipitate it. After it is fully dissolved by magnetic stirring, lead acetate is added to the solution and fully dissolved. K3PO4 is continued to be added to fully precipitate it. After fully mixing, K2S is added to generate PbS precipitation. The pH value of the solution is adjusted to 8, and it is fully stirred at 25°C for 1 hour.

[0299] Then, the mixture was stirred and aged at 60°C for 48 hours. After the aging, the sample was dark gray without any blue color. The solid-liquid mixture was then placed in a hydrothermal reactor and hydrothermaled at 160°C for 48 hours. After the hydrothermal treatment, the sample was dark gray with a colorless supernatant.

[0300] The feed ratio during sample preparation was Pb:Cu:PO4:S 6:4:6:1. Fig.19 The xrd spectrum of the sample obtained in Example 4 is shown. Fig. 20 The temperature-resistance curve of the sample obtained in Example 4 is shown. The conductivity of the sample has no obvious change and is metallic conductivity. Fig.21 The ZFC-FC curve of the sample obtained in Example 4 is shown, and the sample exhibits normal paramagnetism, corresponding to the electrical conductivity.

[0301] Example 5

[0302] For comparison, this embodiment provides a preparation process of a synthesis failure sample, which is as follows:

[0303] After copper nitrate is fully dissolved in water, K3PO4 is added to fully precipitate it. After it is fully dissolved by magnetic stirring, lead acetate is added to the solution and fully dissolved. K3PO4 is continued to be added to fully precipitate it. After fully mixing, K2S is added to generate PbS precipitation. The pH value of the solution is adjusted to 8, and it is fully stirred at 25°C for 1 hour.

[0304] Afterwards, the mixture was stirred and aged at 60°C for 48 hours. After aging, the solid-liquid mixture was placed in a hydrothermal reactor and heated at 160°C for 48 hours to obtain a stable apatite structure of Pb6Cu4(PO4)6S. The mixture was then heated at 150°C for 12 hours to prepare a sodium sulfide solution, wherein the mass ratio of sulfide ions Na2S / Pb6Cu4(PO4)6S in the solution was 1 / 1.

[0305] Fig. 22 The XRD spectrum of the sample obtained in Example 5 is shown. The sample has a second hydrothermal scale excess and the sample is completely decomposed into azurite and galena. Fig.23 The ZFC curve of the sample obtained in Example 5 shows low-temperature superconductivity, which is similar to the possible superconductivity found in azurite. Fig.24 The temperature resistance jump of the sample obtained in Example 5 is demonstrated; it can be seen that after hydrothermal treatment, Pb6Cu4(PO4)6S is completely decomposed into sulfide, which has low-temperature superconductivity, and the superconductivity of the present invention is destroyed.

[0306] Example 6

[0307] As a comparison, the difference from Example 1 is that in this example, no aging is performed, the synthesis of sulfapatite is not sufficient, and a mixed phase of phosphate and sulfide is synthesized instead, so the sample is ferromagnetic. It should be particularly noted that phosphate and apatite have similar space groups and close XRD diffraction peaks, so careful inspection is required.

[0308] Fig.25 The XRD spectrum of the sample is shown, and the sample clearly has two phases and sulfide impurities. Fig.26 , Fig. 27 The magnetization curve of the sample of Example 6 is shown, and the sample is obviously ferromagnetic. Such ferromagnetic samples are a phenomenon that is very easy to occur during the implementation of the change of the synthesis method.

[0309] Example 7

[0310] In contrast, the synthesis method of Example 7 is different from that of Example 1 in that the pH value of the solution is increased to pH=12 (25°C) after K2S is added to S1 of Example 7. After synthesis, the sample is dried at high temperature in an oven, and due to the penetration of air, S in apatite is replaced by O. The synthesized sample still maintains the main structure of apatite.

[0311] Fig.28 The xrd pattern of the sample in Example 7 is shown. Fig.29 The resistance-temperature curve of Example 7 is shown. There are many material properties in the apatite system, which need to be distinguished and treated with caution during implementation. In this example, along with the generation of semiconductors and insulators, the synthesis details and products need to be carefully judged and screened.

[0312] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0313] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0314] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A high temperature superconducting material, characterized in that: The chemical structural formula of the high temperature superconducting material is as follows: A 10-x B x (CO 3-5 ) y D z , belongs to pseudoapatite structure; Wherein, element A includes one or a combination of at least two of s-block metals, p-block metals or lanthanide rare earth elements; B includes one or a combination of at least two of d-block elements; CO 3-5 Including acid radical; element D includes one or a combination of at least two of non-metallic elements or metal elements of Group VI A; in terms of molar amount, x∈[0-10], y∈(0-6], z is greater than or less than the structural formula A 10-x B x (CO 3-5 ) y D z The chemical valence balance number and z∈(0-5].

2. The high temperature superconducting material according to claim 1, characterized in that: The element A includes: one or a combination of at least two of Ca, Mg, Ba, Pb, Y, Ce or La; Preferably, the element B includes: one or a combination of at least two of Sc, Mn, Zn, Cu, Mo, Hg, Fe or Ni.

3. The high temperature superconducting material according to claim 1 or 2, characterized in that: The CO 3-5 Including metal acid radicals or non-metal acid radicals; Preferably, the CO 3-5 The element C includes: one or a combination of at least two of Si, S, As, C or B; Preferably, the element D includes one or a combination of at least two of F, Cl, O, S, Se, Te or OH.

4. The high temperature superconducting material according to any one of claims 1 to 3, characterized in that: The chemical structural formula of the high temperature superconducting material is as follows: 10-x B x (CO 3-5 ) y D z @(A,B)D; Wherein, compound (A, B) D is modified A 10-x B x (CO 3-5 ) y D z or with A 10-x B x (CO 3-5 ) y D z Eutectic.

5. A method for preparing a high temperature superconducting material according to any one of claims 1 to 4, characterized in that: The preparation method comprises: The chemical structure is A 10-x B x (CO 3-5 ) y D z When, the preparation method includes: a single-stage hydrothermal method; The chemical structure is A 10-x B x (CO 3-5 ) y D z @(A,B)D, the preparation method includes: a multi-stage hydrothermal method, a coating method or a hydrothermal-calcination method.

6. The preparation method according to claim 5, characterized in that: The single-stage hydrothermal method comprises: The mixture solution was subjected to aging treatment and hydrothermal synthesis in sequence to obtain A 10-x B x (CO 3-5 ) y D z Superconducting materials; Preferably, the mixture solution comprises: a soluble salt and a solvent are mixed according to a molar ratio; Preferably, the pH value of the mixture solution is 7-10; Preferably, the molar ratio of the soluble salt is (A+B): (CO 3-5 ):D=10:6:(1-5), A:B=(10-x):x, x∈[1,9], and the D element ion amount>chemical valence balance amount; Preferably, the soluble salt includes: a soluble salt containing element A and / or a soluble salt containing element B, a soluble salt containing element C and a soluble salt containing element D; Preferably, the solid-liquid ratio g / mL of the aging treatment is 1:(10-1000); Preferably, the temperature of the aging treatment is 40-80°C; Preferably, the aging treatment time is 1-48h; Preferably, the temperature of the hydrothermal synthesis is 110-200°C; Preferably, the hydrothermal synthesis time is 10-48h; Preferably, the pressure of the hydrothermal synthesis is greater than 3 MPa.

7. The preparation method according to claim 5, characterized in that: The multi-stage hydrothermal method comprises: subjecting the first mixture to a first aging and a first hydrothermal treatment in sequence to obtain A 10-x B x (CO 3-5 ) y D z Materials, then the obtained A 10-x B x (CO 3-5 ) y D z The material and the second mixture are subjected to a second hydrothermal treatment to obtain A 10-x B x (CO 3-5 ) y D z @(A,B)D; Preferably, the first mixture comprises: a first soluble salt and a first solvent are mixed according to a molar ratio; Preferably, the pH value of the first mixture is 7-10; Preferably, the molar ratio of the first soluble salt is (A+B): (CO 3-5 ):D=10:6:(1-5), A:B=(10-x):x, x∈[1,9]; Preferably, the first soluble salt includes: a soluble salt containing element A and / or a soluble salt containing element B, a soluble salt containing element C and a soluble salt containing element D; Preferably, the solid-to-liquid ratio g / mL of the first aging is 1:(10-1000); Preferably, the temperature of the first aging is 40-80°C; Preferably, the first aging time is 1-48h; Preferably, the temperature of the first hydrothermal treatment is 110-200°C; Preferably, the first hydrothermal time is 10-48h; Preferably, the first hydrothermal pressure is 1-3 MPa; Preferably, the second mixture comprises: a mixture obtained by mixing a soluble salt of element D with a second solvent; Preferably, the soluble salt of element D comprises: one or a combination of at least two of potassium sulfide, sodium sulfide, ammonium sulfide, sodium chloride, ammonium chloride, sodium fluoride or sodium hydroxide; Preferably, the mass ratio of the ion mass of the element D in the second hydrothermal treatment to the mass ratio of the solid salt in the first mixture is (0.01-100):1; Preferably, the temperature of the second hydrothermal treatment is 110-200°C; Preferably, the second hydrothermal time is 10-48h; Preferably, the second hydrothermal pressure is ≥1 MPa.

8. The preparation method according to claim 5, characterized in that: The coating method comprises: preparing A on a substrate 10-x B x (CO 3-5 ) y D z film layer, and then perform crystal distortion to obtain A 10-x B x (CO 3-5 ) y D z @(A,B)D high temperature superconducting materials; Preferably, the substrate comprises: one or a combination of at least two of a metal substrate, a semiconductor substrate or an oxide substrate; Preferably, the A 10-x B x (CO 3-5 ) y D z The film layer is prepared by pulsed laser deposition, electrodeposition, magnetron sputtering or sol-gel method, or a combination of at least two thereof; Preferably, the A used in the coating method 10-x B x (CO 3-5 ) y D z The preparation process of the product is as follows: The third mixture is subjected to a second aging and a third hydrothermal treatment in sequence to obtain A 10-x B x (CO 3-5 ) y D z product; Preferably, the third mixture comprises: a mixture obtained by mixing the second soluble salt and the third solvent according to a molar ratio; Preferably, the pH value of the third mixture is 7-10; Preferably, the molar ratio of the second soluble salt is (A+B): (CO 3-5 ):D=10:6:(1-5), A:B=(10-x):x, x∈[1,9]; Preferably, the second soluble salt includes: a soluble salt containing element A and / or a soluble salt containing element B, a soluble salt containing element C and a soluble salt containing element D; Preferably, the solid-liquid ratio g / mL of the second aging is 1:(10-1000); Preferably, the second aging temperature is 40-80°C; Preferably, the second aging time is 1-48h; Preferably, the temperature of the third hydrothermal treatment is 110-200°C; Preferably, the third hydrothermal time is 10-48h; Preferably, the third hydrothermal pressure is 1-3 MPa; Preferably, the sol-gel method comprises the following: S1, mixing a solution containing element A and element B with a solution containing element D, placing the mixture on a substrate, and drying the mixture to form an (A, B)D film on the surface; S2, A 10-x B x (CO 3-5 ) y The D powder is uniformly dispersed in the solvent and disposed on the surface of the obtained (A, B)D film; Preferably, the method of disposing on the substrate in S1 includes spin coating and / or dipping; Preferably, the method of setting on the surface of the obtained (A, B)D film in S2 includes one or a combination of at least two of spin coating, dipping or electrodeposition; Preferably, the electrodeposition method provided on the surface of the obtained (A, B)D film in S2 comprises: 10-x B x (CO 3-5 ) y D powder is dispersed in a solution containing element A and / or element B, and the substrate on which the (A, B)D film is set is used as a direct current cathode. 10-x B x (CO 3-5 ) y D powder is deposited with element A and / or element B; Preferably, the A used in the sol-gel method 10-x B x (CO 3-5 ) y D z The powder preparation process is as follows: The fourth mixture is subjected to a third aging and a fourth hydrothermal treatment in sequence to obtain A 10-x B x (CO 3-5 ) y D z powder; Preferably, the fourth mixture comprises: a third soluble salt and a fourth solvent are mixed according to a molar ratio; Preferably, the pH value of the fourth mixture is 7-10; Preferably, the molar ratio of the third soluble salt is (A+B): (CO 3-5 ):D=10:6:(1-5), A:B=(10-x):x, x∈[1,9]; Preferably, the third soluble salt includes: a soluble salt containing element A and / or a soluble salt containing element B, a soluble salt containing element C and a soluble salt containing element D; Preferably, the solid-liquid ratio g / mL of the third aging is 1:(10-1000); Preferably, the temperature of the third aging is 40-80°C; Preferably, the third aging time is 1-48h; Preferably, the temperature of the fourth hydrothermal treatment is 110-200°C; Preferably, the fourth hydrothermal time is 10-48h; Preferably, the fourth hydrothermal pressure is 1-3 MPa; Preferably, the crystal distortion comprises liquid phase distortion and / or gas phase distortion; Preferably, the liquid phase distortion comprises: 10-x B x (CO 3-5 ) y D z The film layer is subjected to a fifth hydrothermal treatment in a solution containing element D; Preferably, the ion mass of element D in the fifth hydrothermal is 10-x B x (CO 3-5 ) y D z The mass ratio of solid salt used in the film preparation process is (0.01-100):1, and the concentration of element D is greater than 0.01 mol / L; Preferably, the temperature of the fifth hydrothermal treatment is 110-200°C; Preferably, the fifth hydrothermal time is 10-48h; Preferably, the fifth hydrothermal pressure is ≥1MPa; Preferably, the gas phase distortion comprises: 10-x B x (CO 3-5 ) y D z The film layer is first calcined in an atmosphere containing element D; Preferably, the temperature of the first calcination is ≤300°C; Preferably, the first calcination time is 1-72 hours.

9. The preparation method according to claim 5, characterized in that: The hydrothermal-calcination method comprises: 10-x B x (CO 3-5 ) y D z The material undergoes a second roasting; Preferably, the A used in the hydrothermal-roasting method 10-x B x (CO 3-5 ) y D z The material preparation process is as follows: The fifth mixture is subjected to the fourth aging and the sixth hydrothermal treatment in sequence to obtain A 10-x B x (CO 3-5 ) y D z materials; Preferably, the fifth mixture comprises: a fourth soluble salt and a fifth solvent are mixed according to a molar ratio; Preferably, the pH value of the fifth mixture is 7-10; Preferably, the molar ratio of the fourth soluble salt is (A+B): (CO 3-5 ):D=10:6:(1-5), A:B=(10-x):x, x∈[1,9]; Preferably, the fourth soluble salt includes: a soluble salt containing element A and / or a soluble salt containing element B, a soluble salt containing element C and a soluble salt containing element D; Preferably, the solid-to-liquid ratio g / mL of the fourth aging is 1:(10-1000); Preferably, the temperature of the fourth aging is 40-80°C; Preferably, the fourth aging time is 1-48h; Preferably, the temperature of the sixth hydrothermal treatment is 110-200°C; Preferably, the sixth hydrothermal treatment lasts for 10-48 hours; Preferably, the sixth hydrothermal pressure is 1-3 MPa; Preferably, the atmosphere used for the second calcination comprises one or a combination of at least two of O2, H2S, SO2 or HCl; Preferably, the temperature of the second calcination is ≤500°C; Preferably, the second calcination time is 1-48h.

10. A use of the high temperature superconducting material according to any one of claims 1 to 4, characterized in that: The uses include: The high-temperature superconducting material is used to prepare magnetic resonance imaging products, maglev trains, power transmission materials or power equipment.

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