CN114634166A - Iron-based superconducting polycrystalline block and preparation method thereof - Google Patents

Iron-based superconducting polycrystalline block and preparation method thereof Download PDF

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CN114634166A
CN114634166A CN202210274495.1A CN202210274495A CN114634166A CN 114634166 A CN114634166 A CN 114634166A CN 202210274495 A CN202210274495 A CN 202210274495A CN 114634166 A CN114634166 A CN 114634166A
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iron
superconducting
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CN114634166B (en
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马衍伟
孙乔
王栋樑
张现平
徐中堂
董持衡
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Institute of Electrical Engineering of CAS
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/007—Tellurides or selenides of metals
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B28/00—Production of homogeneous polycrystalline material with defined structure
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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    • C01—INORGANIC CHEMISTRY
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    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention belongs to the technical field of superconducting polycrystalline blocks, and provides an iron-based (FeSe)xTe1‑x) A superconducting polycrystalline bulk and a method for producing the same. In the preparation method, a container with the same structure as the delta-phase crystal is used as a reaction container which is directly contacted with the raw material, the uniform nucleation leading factor in the cooling crystallization process is converted into the heterogeneous nucleation leading factor, the formation of the delta phase with a strong texture in the cooling phase formation process is induced, the beta superconducting phase with the strong texture is further formed, and the FeSe is greatly improved under the conditions of keeping the original melting method simple, low cost and short periodxTe1‑xThe superconducting properties of the superconducting polycrystalline bulk material. The data of the examples show that: the FeSe provided by the inventionxTe1‑xThe critical current density of the superconducting polycrystalline block material is 60000-104000A/cm under the conditions of 5K and 0T2。

Description

Iron-based superconducting polycrystalline block and preparation method thereof
Technical Field
The invention relates to the technical field of superconducting polycrystalline blocks, in particular to iron-based (FeSe)xTe1-x) A superconducting polycrystalline bulk and a method for producing the same.
Background
In 2008, LaFeAsO was discovered by Xiuyu Xiongrou group1-xFxHas a critical transition temperature (T) of 26Kc) The research hot tide of the iron-based superconductor is pulled. Iron-based superconductors having high TcHigh upper critical field (H)c2) And low anisotropy (gamma), and is one of the most promising new high-temperature superconductors. Among them, an iron-based superconductor FeSe belonging to 11 series (FeSe series)xTe1-xThe wire and strip material does not contain toxic elements, unstable elements and rare elements, meets the large-scale practical requirement, and is particularly suitable for the preparation of wire and strip materials. FeSe is prepared in the same way as other iron-based superconducting wire stripsxTe1-xSuperconducting wire tapes are also commonly prepared using the ex-situ powder tube-loading method. In this method, FeSe is required to be usedxTe1-xThe powder obtained after crushing the superconducting polycrystal is used as a precursor, thus FeSexTe1-xThe performance of the superconducting polycrystal is important.
Conventional preparation of FeSexTe1-xThe method for preparing the superconducting polycrystalline block is a solid-phase reaction method, the solid-phase reaction method is complex in manufacturing process and needs a preparation period of ten days or even one month, and simultaneously the obtained FeSexTe1-xSuperconducting polycrystalline bulk is substantially untextured and less dense, so this process is gradually being replaced by a fusion process. The existing melting method can solve FeSexTe1-xLow density of superconducting polycrystalline block, and the prepared FeSexTe1-xThe superconducting polycrystalline block has certain texture degree, but the texture degree is lower, which causes FeSexTe1-xThe critical current density of the superconducting polycrystalline block still stays at 30000A/cm under 5K and 0T2。
Disclosure of Invention
In view of the above, the present invention provides an iron-based superconducting polycrystalline bulk material and a method for preparing the same. FeSe obtained by the preparation method provided by the inventionxTe1-xThe superconducting polycrystalline block has high texture degree and excellent critical current density.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of an iron-based superconducting polycrystalline block material, wherein the chemical formula of the iron-based superconducting polycrystalline block material is FeSexTe1-xThe method comprises the following steps:
under the protective atmosphere, carrying out melt sintering on a preparation raw material of an iron-based superconducting polycrystalline block in a container, and cooling and crystallizing to obtain the iron-based superconducting polycrystalline block;
the material of the container is a trigonal substance or a hexagonal substance;
FeSexTe1-xin the formula, x is more than 0 and less than or equal to 1.
Preferably, the trigonal material comprises alpha-Al2O3And/or alpha-Si3N4。
Preferably, the hexagonal substance includes AlN, α -SiC, β -Si3N4And alpha-BN.
Preferably, when the container exists on the bottom surface of the inner cavity, the filling height h of the preparation raw material of the iron-based superconducting polycrystalline block material in the container is more than or equal to 2 times of the longest distance d of the bottom surface of the inner cavity of the container; when the container is conical, the conical angle of the conical shape is less than or equal to 28 degrees.
Preferably, the longest distance d of the bottom surface of the inner cavity of the container is less than or equal to 6 cm.
Preferably, the container is provided with a container lid; the container cover is made of the same material as the container.
Preferably, in the fusion sintering, the container is sealed in a vacuum quartz tube, and the vacuum quartz tube with the container is loaded in a muffle furnace for fusion sintering.
Preferably, the temperature of the melt sintering is 800-1600 ℃, and the time is 3-5 days.
Preferably, the cooling crystallization mode is natural cooling.
The invention also provides the iron-based superconducting polycrystalline block material obtained by the preparation method in the technical scheme, and the critical current density of the iron-based superconducting polycrystalline block material is 60000-104000A/cm under the conditions of 5K and 0T2。
The invention provides a preparation method of an iron-based superconducting polycrystalline block material, wherein the chemical formula of the iron-based superconducting polycrystalline block material is FeSexTe1-xThe method comprises the following steps: under the protective atmosphere, carrying out melt sintering on a preparation raw material of an iron-based superconducting polycrystalline block in a container, and cooling and crystallizing to obtain the iron-based superconducting polycrystalline block; the material of the container is a trigonal substance or a hexagonal substance; FeSexTe1-xWherein x is more than 0 and less than or equal to 1.
According to a FeSe phase diagram, when the raw material proportion meets the chemical formula FeSexTe1-xWhen x is more than 0 and less than or equal to 1, the phase forming process of cooling crystallization after melting sintering comprises the following steps:
1) first, the liquid phase L2By isocompositional conversion to delta' phase (
Figure BDA0003555270120000021
A complete transition);
2) subsequently, the delta' phase is converted into the delta phase by the isocomponent
Figure BDA0003555270120000022
A complete transition;
3) the temperature is further reduced, and alpha Fe is separated out from the delta phase;
4) when the temperature is reduced to 457 ℃, the precipitated alpha Fe and delta are subjected to an inclusional reaction to generate a beta phase (a)
Figure BDA0003555270120000023
Incomplete transition);
5) when the temperature is reduced to 350 ℃, the residual delta phase generates eutectoid reaction to generate beta phase and gamma' phase
Figure BDA0003555270120000031
The beta phase is the desired superconducting phase (the trace gamma' phase is a non-superconducting second phase and is not solved in an effective manner at present). Wherein L is2The transition phase δ' involved in the liquid phase transition to δ phase is negligible in the following analysis, firstly because of L2The temperature interval from delta' to delta is very small and the cooling speed of the heat treatment furnace is very high at high temperature, so that L2The time required for phase to delta phase is very short. The other is because δ' can be regarded as having the same crystal structure as the δ phase or having no specific crystal structure as the liquid phase. Therefore, the process of initial liquid phase to solid phase can be considered as L2The liquid phase changes to delta phase. The subsequent beta superconducting phase formation process is closely related to the delta phase, so the delta phase crystal growth process is of great importance.
According to the reported results, the delta phase is a hexagonal phase with a NiAs structure, when a container made of a hexagonal substance or a trigonal substance (a special hexagonal substance) is directly contacted with a raw material, a large number of preferential nucleation sites (heterogeneous nucleation) are provided for the delta 1 phase due to the fact that the crystal structure of the container is consistent with the delta phase, and the delta 3 phase grows in a direction vertical to the container wall and is oriented towards the inside, so that the delta 5 phase with a strong texture is formed. During the further cooling process, α Fe precipitates from the δ phase, during which no structural change occurs in the δ phase except for the decrease in Fe content. When the temperature is lowered to the precipitation reaction temperature (457 ℃ C.), the precipitated alpha Fe reacts with the delta phase to form a delta 0 phase. Since the δ phase that has been formed has an extremely strong texture, and the δ 2 phase is formed on the basis of the δ phase, the δ 4 phase that is formed also has the same type of texture. Similarly, at 350 ℃, the remaining δ phase undergoes eutectoid reaction to form δ 6 phase and γ' phase with the same type of texture. Finally, a δ 7 superconducting phase with a very high degree of texture was obtained. The preparation method provided by the invention enhances FeSe by replacing the material of the container directly contacted with the raw materialxTe1-xThe texture degree of the superconducting polycrystalline block greatly improves FeSe under the condition of keeping the simplicity, low cost and short period of the original methodxTe1-xSuperconductivity of superconducting polycrystalline bulk Material。
Further, when the container exists on the bottom surface of the inner cavity, the filling height h of the preparation raw material of the iron-based superconducting polycrystalline block material in the container is more than or equal to 2 times of the longest distance d of the bottom surface of the inner cavity of the container. The main growth direction of the texture is from the side wall of the container to the inside of the container, and h is more than or equal to 2d, so that the influence of the bottom of the container on the upward-grown crystals on the texture of the whole sample is reduced to be negligible. When the container is conical, the conical angle of the cone is less than or equal to 28, so that the distance of the texture formed by the container wall to the interior can be reduced, and a good texture can be formed more easily.
Further, the longest distance d of the bottom surface of the inner cavity of the container is less than or equal to 6 cm. The smaller the longest distance of the bottom surface of the inner cavity of the container is, the shorter the distance of the texture formed inside along the container wall is, and the better the texture is easily formed. In addition, when the amount of the target product is determined, the container with the longest distance d between the bottom surface of the smaller inner cavity can more easily meet h ≧ 2d, and the influence of bottom growth polycrystal is minimized.
The data of the examples show that: the invention provides iron-based (FeSe)xTe1-x) The critical current density of the superconducting polycrystalline block material is 60000-104000A/cm under the conditions of 5K and 0T2。
Drawings
FIG. 1 shows FeSe according to the present inventionxTe1-xA flow chart for preparing a superconducting polycrystalline block;
FIG. 2 shows FeTe obtained in example 20.5Se0.5XRD diffraction pattern of the superconducting polycrystalline block;
FIG. 3 shows FeTe obtained in example 20.5Se0.5MT curve of superconducting polycrystalline bulk material;
FIG. 4 shows FeTe obtained in example 20.5Se0.5MH curve of the superconducting polycrystalline block material under 5K;
FIG. 5 shows FeTe obtained in example 20.5Se0.5Critical current density J of superconducting polycrystalline block at 5K and 0TcCurve line.
Detailed Description
The invention provides a preparation method of an iron-based superconducting polycrystalline block material, and the iron-based superconducting polycrystalline block materialHas a chemical formula of FeSexTe1-xThe method comprises the following steps:
under the protective atmosphere, carrying out melt sintering on a preparation raw material of an iron-based superconducting polycrystalline block in a container, and cooling and crystallizing to obtain the iron-based superconducting polycrystalline block;
the material of the container is a trigonal substance or a hexagonal substance;
FeSexTe1-xin the formula, x is more than 0 and less than or equal to 1.
In the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
In the present invention, the protective atmosphere preferably comprises argon.
In the present invention, the FeSexTe1-xIn the above formula, 0 < x.ltoreq.1, and more preferably 0.5, 0.4, 0.6 or 0.35.
In the present invention, the iron group (FeSe)xTe1-x) The raw material for preparing the superconducting polycrystalline block preferably includes Fe powder, Se powder, and Te powder. In the present invention, the purity of the Fe powder, Se powder, and Te powder is preferably 99.9% or more, and more preferably 99.9% or more, independently.
In the present invention, the raw materials for preparing the iron-based superconducting polycrystalline block are preferably ground and mixed before being charged into a vessel and melt-sintered; the grinding and mixing is preferably carried out in a mortar. The parameters of the grinding and mixing are not particularly limited, as long as the preparation raw materials of the iron-based superconducting polycrystalline block can be fully and uniformly mixed.
In the present invention, the material of the container is a trigonal substance or a hexagonal substance. In the present invention, the trigonal substance preferably includes α -Al2O3And/or alpha-Si3N4Further preferably comprises alpha-Al2O3. In the present invention, the hexagonal substance preferably includes AlN, α -SiC, and β -Si3N4And alpha-BN.
In the present invention, the container is preferably provided with a container lid; the material of the container cover is preferably the same as that of the container, and thus, the description thereof is omitted.
In the invention, when the container exists on the bottom surface of the inner cavity, the filling height h of the preparation raw material of the iron-based superconducting polycrystalline block in the container is preferably more than or equal to 2 times of the longest distance d of the bottom surface of the inner cavity of the container, and the filling height h of the preparation raw material of the iron-based superconducting polycrystalline block in the container is preferably 2-100 times of the longest distance d of the bottom surface of the inner cavity of the container. In the present invention, the bottom surface of the inner cavity of the container is preferably circular in shape; the container is preferably a crucible, and the crucible is preferably a crucible with a circular inner cavity bottom surface. In the invention, the longest distance d of the bottom surface of the inner cavity of the container is preferably less than or equal to 6cm, more preferably 0.1-6 cm, and even more preferably 0.5-2.0 cm. In the invention, for the scheme that the bottom surface of the inner cavity of the container is circular, the longest distance of the bottom surface of the inner cavity of the container refers to the diameter of the circle; for the scheme that the bottom surface of the inner cavity of the container is rectangular, the longest distance of the bottom surface of the inner cavity of the container refers to the diagonal line of the rectangle.
In the invention, when the container is conical, the conical angle of the conical shape is less than or equal to 28 degrees.
In the present invention, in the melt-sintering, the vessel is preferably sealed in a vacuum quartz tube, and the vacuum quartz tube with the vessel is placed in a muffle furnace to be melt-sintered.
In the invention, the temperature of the melt sintering is preferably 800-1600 ℃, and the time is preferably 3-5 days.
In the present invention, the cooling crystallization is preferably performed by natural cooling.
In the preparation method, a container with the same structure as the delta-phase crystal is used as a reaction container which is directly contacted with the raw material, the uniform nucleation leading in the cooling crystallization process is converted into the heterogeneous nucleation leading, the formation of the delta phase with a strong texture is induced in the cooling phase formation process, the beta superconducting phase with the strong texture is further formed, and the superconducting performance of the polycrystalline block is greatly improved under the condition that the original melting method is simple, the cost is low and the period is short.
The invention also provides a preparation method of the technical schemeIron base (FeSe) obtained by the methodxTe1-x) A superconducting polycrystalline bulk material. In the present invention, the iron group (FeSe)xTe1-x) The critical current density of the superconducting polycrystalline block material is 60000-104000A/cm under the conditions of 5K and 0T2。
FIG. 1 shows Fe-based (FeSe) of the present inventionxTe1-x) A flow chart for preparing a superconducting polycrystalline block, iron-based (FeSe)xTe1-x) The preparation method comprises mixing raw materials for preparing superconducting polycrystalline block, loading into a container made of hexagonal system substance or trigonal system substance, sealing the container into a vacuum quartz tube, and loading the vacuum quartz tube with the container into a muffle furnace for melt sintering.
The iron-based superconducting polycrystalline bulk material and the method for producing the same according to the present invention will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
In an argon glove box, 10g of Fe powder (purity 99.9%), Se powder (purity 99.99%) and Te powder (purity 99.99%) were weighed in an atomic ratio of Fe: Se: Te ═ 1:0.5:0.5, mixed in a mortar, and charged into a cylindrical α -Al powder having an inner diameter of 1.5cm and an outer diameter of 1.7cm2O3The crucible (filling height about 4cm) was covered with a lid of the same material as the crucible. Sealing the crucible in a vacuum quartz tube, putting the quartz tube into a box-type muffle furnace, performing melt sintering at 880 ℃ for 3 days, cutting off a power supply, and naturally cooling the muffle furnace to room temperature to obtain FeTe with strong texture and excellent superconductivity0.5Se0.5A polycrystalline block.
Example 2
In an argon glove box, 10g of Fe powder (purity 99.9%), Se powder (purity 99.99%) and Te powder (purity 99.99%) were weighed in accordance with Fe: Se: Te ═ 1:0.5:0.5, and mixed in a mortar, followed by charging into a cylindrical α -Al having an inner diameter of 1cm and an outer diameter of 1.2cm2O3The crucible was filled (about 9cm in height) with a lid of the same material as the crucible. Sealing the crucible in a vacuum quartz tube, placing the quartz tube in a box-type muffle furnace, melting and sintering at 880 deg.C for 3 days, and cutting off power supply to naturally cool the muffle furnaceCooling to room temperature to obtain FeTe with strong texture and excellent superconductivity0.5Se0.5A polycrystalline block.
FIG. 2 shows the FeTe obtained0.5Se0.5XRD diffraction pattern of the superconducting polycrystalline block; as can be seen from fig. 2: the resulting FeTe0.5Se0.5The diffraction peak of the superconducting polycrystalline bulk basically belongs to a (00l) crystal plane family, which shows that the superconducting polycrystalline bulk has an extremely strong c-axis texture.
FIG. 3 shows the FeTe obtained0.5Se0.5MT curve of the bulk superconducting material can be seen from FIG. 3: the resulting FeTe0.5Se0.5The critical transition temperature of the bulk superconductor was 14.3K, and the transition width was 2K.
FIG. 4 shows FeTe obtained0.5Se0.5The MH curve of the superconducting polycrystalline block at 5K can be seen from FIG. 4: the resulting FeTe0.5Se0.5The magnetic moment of the superconducting polycrystalline block material is obviously increased at 0T, and the loop curve has larger opening and higher symmetry, which shows that the superconducting polycrystalline block material has excellent superconducting performance.
FIG. 5 shows the FeTe obtained0.5Se0.5Critical current density J of superconducting polycrystalline block at 5K and 0TcThe curves, as can be seen from fig. 5: under the conditions of 5K and 0T, FeTe is obtained0.5Se0.5The current density of the superconducting polycrystalline block reaches 76000A/cm2。
Example 3
In an argon glove box, 10g of Fe powder (purity 99.9%), Se powder (purity 99.99%) and Te powder (purity 99.99%) were weighed in accordance with Fe: Se: Te ═ 1:0.5:0.5, and mixed in a mortar, followed by charging into a cylindrical α -Al powder having an inner diameter of 0.5cm and an outer diameter of 0.7cm2O3The crucible (filling height about 36cm) was covered with a lid of the same material as the crucible. Sealing the crucible in a vacuum quartz tube, directly putting the quartz in a box-type muffle furnace, performing melt sintering at 880 ℃ for 3 days, cutting off a power supply, and naturally cooling the muffle furnace to room temperature to obtain FeTe with strong texture and excellent superconductivity0.5Se0.5A polycrystalline block.
Example 4
The difference from example 2 is that the crucible materialIs of mass alpha-Si3N4。
Example 5
The difference from the embodiment 2 is that the crucible is made of beta-Si3N4。
Example 6
The difference from example 2 is that the crucible is made of AlN.
Example 7
The differences from example 2 are: fe, Se, Te: 0.4: 0.6.
example 8
The differences from example 2 are: se, Te, 1: 0.6: 0.4.
example 9
In an argon glove box, 10g of Fe powder (purity 99.9%), Se powder (purity 99.99%) and Te powder (purity 99.99%) were weighed in accordance with Fe: Se: Te ═ 1:0.5:0.5, and mixed in a mortar, followed by charging conical α -Al of 28 ° cone angle and 7cm height2O3The crucible (filling height about 5cm) was covered with a lid of the same material as the crucible. Sealing the crucible in a vacuum quartz tube, putting the quartz tube into a box-type muffle furnace, performing melt sintering at 880 ℃ for 3 days, cutting off a power supply, and naturally cooling the muffle furnace to room temperature to obtain FeTe with strong texture and excellent superconductivity0.5Se0.5A polycrystalline block.
Example 10
In an argon glove box, 10g of Fe powder (purity 99.9%), Se powder (purity 99.99%) and Te powder (purity 99.99%) were weighed in accordance with Fe: Se: Te ═ 1:0.5:0.5, and mixed in a mortar, followed by charging a conical α -Al having a cone angle of 20 ° and a height of 8cm2O3The crucible (filling height about 6cm) was covered with a lid of the same material as the crucible. Sealing the crucible in a vacuum quartz tube, putting the quartz tube into a box-type muffle furnace, performing melt sintering at 880 ℃ for 3 days, cutting off a power supply, and naturally cooling the muffle furnace to room temperature to obtain FeTe with strong texture and excellent superconductivity0.5Se0.5A polycrystalline block.
Comparative example 1
FeSe0.5Te0.5A method of superconducting polycrystalline, comprising the steps of:
step a, preparing Fe powder with the purity of 99.99%, Te blocks with the purity of 99.99% and Se granules with the purity of 99.99% in air according to the atomic ratio of 1:0.5:0.5, and filling the mixture into a quartz tube (the material of the quartz tube is tetragonal cristobalite) with one end sealed;
b, sealing the other port of the quartz tube filled with the raw material powder by using an acetylene welding gun;
c, sleeving the quartz tube with the sealed two ends and filled with the raw materials into a quartz tube with a larger caliber, and sealing the two ends;
d, putting the quartz tube with the two sealed ends and larger caliber into a box furnace, sintering for 3 days at 880 ℃, and naturally cooling the box furnace to room temperature to obtain high-quality FeSe0.5Te0.5A superconducting polycrystal.
Comparative example 2
Differs from example 7 only in the cylindrical form of alpha-Al having an inner diameter of 1cm and an outer diameter of 1.2cm2O3The crucible was replaced with a quartz tube (quartz tube material is tetragonal cristobalite) of the same size and shape.
Comparative example 3
Differs from example 8 only in that the inner diameter is 1cm and the outer diameter is 1.2cm2O3The crucible was replaced with a quartz tube (the material of the quartz tube was tetragonal cristobalite) of the same size and shape.
Table 1 shows FeSe obtained in examples 1 to 8 and comparative examples 1 to 3xTe1-xAnd (5) performance test results of the superconducting polycrystalline block.
Table 1 FeSe obtained in examples and comparative examplesxTe1-xPerformance test results of superconducting polycrystalline bulk Material
Figure BDA0003555270120000091
As can be seen from table 1: the FeSexTe1-xPreparation of superconducting polycrystalline bulkThe filling height h of the ingredient in the container is preferably greater than or equal to 2 times the longest distance of the bottom surface of the cavity of the container, and the larger the filling height h value is, the better the ratio of the longest distance of the bottom surface of the cavity of the container is.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of an iron-based superconducting polycrystalline block material, wherein the chemical formula of the iron-based superconducting polycrystalline block material is FeSexTe1-xThe method is characterized by comprising the following steps:
under the protective atmosphere, carrying out melt sintering on a preparation raw material of an iron-based superconducting polycrystalline block in a container, and cooling and crystallizing to obtain the iron-based superconducting polycrystalline block;
the material of the container is a trigonal substance or a hexagonal substance;
FeSexTe1-xwherein x is more than 0 and less than or equal to 1.
2. The method of claim 1, wherein the trigonal material comprises alpha-Al2O3And/or alpha-Si3N4。
3. The production method according to claim 1, wherein the hexagonal substance includes AlN, α -SiC, β -Si3N4And alpha-BN.
4. The production method according to claim 1, wherein a filling height h of the starting material for producing the iron-based superconducting polycrystalline block in the vessel is 2 times or more as long as a longest distance d of the bottom surface of the inner cavity of the vessel when the vessel is present at the bottom surface of the inner cavity; when the container is conical, the conical angle of the conical shape is less than or equal to 28 degrees.
5. The method of claim 4, wherein the longest distance d between the bottom surfaces of the cavities of the container is less than or equal to 6 cm.
6. The method of claim 1, wherein the container is provided with a container lid; the container cover is made of the same material as the container.
7. The production method according to claim 1, wherein in the melt-sintering, the vessel is enclosed in a vacuum quartz tube, and the vacuum quartz tube with the vessel is placed in a muffle furnace to be melt-sintered.
8. The method according to claim 1 or 7, wherein the temperature of the melt sintering is 800 to 1600 ℃ for 3 to 5 days.
9. The preparation method according to claim 1, wherein the cooling crystallization mode is natural cooling.
10. The iron-based superconducting polycrystalline block obtained by the preparation method according to any one of claims 1 to 9, wherein the critical current density of the iron-based superconducting polycrystalline block is 60000 to 104000A/cm at 5K and 0T2。
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