WO2007019795A1 - Superconducting material and preparing method thereof - Google Patents

Superconducting material and preparing method thereof Download PDF

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Publication number
WO2007019795A1
WO2007019795A1 PCT/CN2006/002060 CN2006002060W WO2007019795A1 WO 2007019795 A1 WO2007019795 A1 WO 2007019795A1 CN 2006002060 W CN2006002060 W CN 2006002060W WO 2007019795 A1 WO2007019795 A1 WO 2007019795A1
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superconducting material
superconducting
cuh
bacl
diamagnetic
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PCT/CN2006/002060
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French (fr)
Chinese (zh)
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Wanhai Sun
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Wanhai Sun
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00—Superconducting devices
    • H10N60/80—Constructional details
    • H10N60/85—Superconducting active materials
    • H10N60/855—Ceramic superconductors

Definitions

  • the invention relates to a superconducting material and a preparation method thereof, in particular to a superconducting material having a critical temperature T e higher than a normal temperature and a preparation method thereof.
  • the material of this T e value is Hg—Ba—Ca—Cu—O copper-based oxide material, which was developed and developed by American scientist Zhu Jingwu in 1994.
  • American and Japanese scientists invented a superconducting material of MgB 2 material with a T c of 39K.
  • the hole injection method was used to increase the T c of organic superconductors to 117K.
  • Bell Labs of the United States produced a regular ⁇ 3 ⁇ organic film, and used a field effect transistor to inject charge into the film, and superconductivity appeared in the 2.35 ⁇ film.
  • the T e of the material is increased to 52K.
  • the room temperature T e superconducting material has not yet broken through.
  • the second copper-based oxide superconducting material is technically still difficult to produce due to the brittleness defects of ceramics.
  • the conventional superconducting material closest to the technical feature of the present invention is a cobalt oxide "sticky" material invented by the Japanese Institute of Materials Research.
  • Cobalt oxide does not have superconductivity in dry state Electrically, when a cobalt oxide layer is injected into water molecules at a negative temperature of 268 °C, its magnetic susceptibility and electrical resistance drop sharply, making it a superconducting substance.
  • Cobalt oxidized "sticky" materials it is clear that the polarization covalent bond H+ of water molecules is relatively low, and the normal temperature critical temperature T c cannot be achieved. Summary of the invention
  • the object of the present invention is to provide a superconducting material having a critical temperature T c higher than a normal temperature and a preparation method thereof, in view of the defects of the existing superconducting material and the preparation method thereof.
  • the present invention provides a superconducting material, the essential components of which are: Cu, K/Na, Ba, Cl, 0 and -OH.
  • A l or 0.45 or 2 or 0.9
  • the essential components are: CuH 2 /Cuo. «Pd 0 . 55 H z , KCl/NaCK BaCl 2 , SnCl 2 /ZnCl 2 ,
  • SnO/ZnO and Sn (OH) Cl/Zn (OH) Cl Or the essential component is derived from: CuH z /Cu Q . «Pd. 55 H z , KCl/NaCK BaCl 2 , Ba0/Ca0 and Ba (OH) 2 /Ca (OH) 2 .
  • the present invention provides a method for preparing the above superconducting material, comprising: a molar ratio of 1: 1: 1: 0.4: 0.25 (1.2-x): 0.25 (1.2 + x) of CuH z , KCl/NaC BaCl 2 , SnCl 2 , SnO and Sn (OH) CI, mix with powder, compact and seal the air, heat at 550 ° C - 650 ° C for 4-5 hours, then seal the air Cool down to room temperature, seal and store, and make the composition by chemical formula
  • the superconducting material shows an upper limit temperature at the time of complete diamagnetic resistance and a superconducting critical temperature of 509 K, and when the z value is 0.4-0.7, the lower limit temperature at the time of complete diamagnetic resistance is 0 K.
  • the invention further provides a method for preparing the above superconducting material, comprising:
  • the molar ratio is 1: 1: 1: 0.4: 0.25 (1.2 - x): 0.25 (1.2 + x) CuH z , KCl / NaCl , BaCl 2 , ZnCl 2 , ZnO and Zn (OH) CI
  • CuH z KCl / NaCl , BaCl 2 , ZnCl 2 , ZnO and Zn (OH)
  • the superconducting material shows an upper limit temperature at the time of complete diamagnetic resistance and a superconducting critical temperature of 573 ⁇ .
  • the lower limit temperature at the time of complete diamagnetic is 0 ⁇ .
  • the invention also provides a preparation method of the above superconducting material, comprising:
  • the molar ratio is 2: 1: 1.5: 0.25 (l + y): 0.25 (1 - y) of CuH z , KCl / NaCK BaCl 2 ,
  • the superconducting material shows an upper limit temperature at the time of complete diamagnetic resistance and a superconducting critical temperature of 529 K.
  • the lower limit temperature at the time of complete diamagnetic resistance is 0 ⁇ :.
  • the invention further provides a method for preparing the above superconducting material, comprising:
  • the molar ratio is 2: 1: 1.5: 0.25 (l + y): 0 ⁇ 25 (1 - y) of CuH z , KCl / NaCK BaCl 2 , CaO and Ca (0H) 2 , powder mixing, compaction Airtightly sealed, heated at 650 ° C - 700 ° C for 4-5 hours, then cooled to room temperature under airtight conditions, sealed and stored, to obtain the composition from the chemical formula
  • the superconducting material shows an upper limit temperature at the time of complete diamagnetic resistance and a superconducting critical temperature of 573 ⁇ .
  • the lower limit temperature at the time of complete diamagnetic is 0 ⁇ .
  • H + p with a partial positive charge +P is derived from the 0 - H polarized covalent bond of the metal compound containing -OH (where H + p is different from the free state H + ion), and H +p is in the spatial structure of the material
  • the shared ionization (H-bond ionization) generated when adjacent 0 and C1 form an H bond, and the electron and hole super-flows are derived from Cu (or CuH z ) and H +p , respectively, and the valence state imbalance relationship between them.
  • the metal oxides and metal chlorides respectively provide oxygen, chloride anions and misaligned, layered metal cations, wherein Cu and metal cations (such as K, Ba are separated)
  • the microscopic relationship of the sub-) makes the material completely diamagnetically resistant to the upper limit temperature and the superconducting critical temperature can be 13 ⁇ 4 at room temperature.
  • the above materials are red blocks with tight structure and high hardness.
  • the present invention realizes a superconducting material having a critical temperature T c higher than a normal temperature and a preparation method thereof.
  • the polarized covalent bond H+ ions of water molecules used in cobalt oxidation "sticky" materials in the prior art are similar to the H +p ion features used in the present invention.
  • a feature different from the present invention is that the present invention uses valence electrons of H +p ions and elemental Cu in Zn(OH)Cl or Sn(OH)Cl or Ba(OH) 2 or Ca(OH) 2 (or The valence electron of the alloy CuH z , as well as the metal chloride and metal oxide, thus obtaining the complete diamagnetic state at 573 K, the T c value is much higher than the cobalt oxide "sticky water, the T c value of the material ( 5K, Negative 268 ⁇ ).
  • the invention is not a pure compound superconducting material, but It is a simple substance (or hydrogen alloy)-based superconducting material that has never appeared before. In the sense of H +p , cobalt oxide "sticky" materials provide experimental support for the effectiveness of the present invention.
  • the complete diamagnetism (Meissner effect) obtained from magnetic measurements is considered to be a superconducting material.
  • Further experiments are as follows: 1 change the experimental and magnetic measurement environment, exclude external factors such as magnetic needles or materials may carry magnetic current and other factors; 2 the composition and ratio of the experiment as the basic scheme, respectively discard the KC1 or BaCl 2 reagent, experiment, the material obtained is magnetic needle-free; 3 ZnCl 2 in the experiment is analyzed with anhydrous water, or the same manufacturer contains a small amount of hygroscopic water (opening to absorb moisture), or different ZnCl 2 with a small amount of hygroscopic water, other reagent components and ratios are unchanged, the process is unchanged, the experimental results, the use of anhydrous analytically pure ZnCl 2 , the material is not completely diamagnetic (magnetic needle is not rejected), In the case where a small amount of hygroscopic water is used and an appropriate amount of ZnO component is present, the
  • the molar ratio is 1:0. 7: 1: 0. 4: 0. 3: 0.3 CuH z , NaCl, BaCl 2 , ZnCl 2 , Zn0, [Zn (0H) Cl + NaCl]
  • composition and ratio weigh the appropriate amount of each component reagent, grind the powder, put it into high temperature resistant test tube, mix Evenly, the nozzle is stoppered and heated at 550 ° C - 650 ° C for 20 minutes. The nozzle plug should be compressed throughout the preparation process. When the heating is stopped, the prepared material is placed in a hot state close to the magnetic needle for magnetic measurement. ⁇
  • Preparation instructions (1), the purpose of using a medical syringe is to ensure that the compaction and air isolation conditions during the preparation process.
  • the above reaction may have by-products, such as Zn(0H) 2 , etc., but as long as the sealing conditions are ensured, the H 2 0 and HC 1 gases which may be generated during the production process are not allowed to escape, and the by-products can be eliminated. .
  • the above product Zn(0H)Cl + NaCl has the following reversible reaction:
  • the molar ratio is 1: 0.6: 1: 0.4: 0.2: 0.4 CuH z , KC1 , BaCl 2 , ZnCl 2 , Zn0, [Zn (OH) CI + NaCl] Among them, the [Zn(0H)Cl +NaCl] reagent was taken from the [Zn(0H)C1-NaCl] reagent prepared in Example 2.
  • the preparation method and the magnetic measurement method are the same as those in the embodiment 2, wherein the heating time is:
  • the molar ratio is 1:0.7: 1: 0.4: 0.3: 0.3 CuH z , NaCl, BaCl 2 , SnCl 2 , SnO, [Sn(0H)Cl +NaCl], among which SnCl 2 , SnO, Sn (OH) CI
  • They are stannous chloride, stannous oxide, and basic stannous chloride, wherein [Sn(0H)Cl + NaCl] is obtained from [Sn(0H)Cl - NaCl] reagent, and the reagents are prepared in the same manner.
  • [Zn(0H)Cl ⁇ NaCl] in Example 2 only ZnCl 2 was replaced with SnCl 2 .
  • the test tube is directly heated on the lamp of the alcohol lamp, and a large amount of water is precipitated, and the precipitated water accumulated on the inner wall of the test tube is removed in time until the water is substantially precipitated, leaving the fire, and then in the hot state, magnetic measurement is performed. , the magnetic needle is not repelled.
  • the water in the tube no longer precipitates, the reagent black disappears, the volume shrinks, the agglomerate is copper red, away from the fire, then magnetic measurement, immediately after the magnetic needle 1
  • the temperature is 256 °C
  • the magnetic needle starts to be arranged. 0. 6-0. 8cm, rejection time 6 minutes.
  • the molar ratio is 2: 1: 1, 5 : 0. 25 : 0. 25 CuH z , NaCK BaCl 2 , Ba0, Ba (0H) 2 , wherein Ba (0H) 2 is composed of an appropriate amount of BaCl 2 and an appropriate amount of NaOH
  • the reaction was obtained, and the BaO requirement was that the seal was well produced recently.
  • composition and ratio weigh the appropriate amount of each component reagent, grind the powder, put it into the high temperature resistant test tube, mix it, add the plug, 650 °C - 700 °C, heat for 30-40 minutes, throughout During the preparation process, it should be pressed Tight pipe plug. When the heating is stopped, the magnetic measurement is performed near the magnetic needle in a hot state.
  • Example 7 The complete diamagnetic effect of the prepared material was substantially the same as that of Example 7 except that (3 ⁇ 4) of the component of Example 7 was replaced with Cu powder, and it was explained that Example 6 was replaced with Cu powder instead of CuH z .
  • the appearance of Cu is oxidized due to the presence of K0H and water (crystal water of BaCl 2 ⁇ 2H 2 0), and also indicates that H in CuH z has a function of protecting Cu from corrosion.
  • Component CuH z powder, BaCl 2 ⁇ 2 ⁇ 2 0 (chemically pure), KC1 (analytical grade) or NaCl, [Ca (OH) 2 -
  • TC 650 °C-70
  • the material obtained can make the original static magnetic needle open, the maximum repulsion is 1.0 cm, the rejection time is 20 minutes, and the temperature at the time of complete diamagnetism is 300 °C (> 30 (TC reaches about 400 °C) to Room temperature interval.
  • Resistance measurement, same as Example 7, the bottom surface of the material has a small amount of thin molten cooling layer, where R ⁇ . The material is placed in a household refrigerator and cooled to - 18 °C - 24 °C, and then magnetic Measurement, no complete diamagnetic Sex.
  • the molar ratio is 2: 1: 1.5: 0.25: 0.25 CuH z , NaC BaCl 2 , Ca0, Ca (OH) 2 preparation method: same as the embodiment 7, wherein the heating time: 1, 30 minutes, 4 magnetic measurement; Reheating extended the heating time to 45 minutes, 0 precipitation, magnetic measurement magnetic needle repulsion reduced; 2, heating time extended to 1 hour, magnetic measurement, the preparation material is not completely diamagnetic.
  • the heating time 1, 30 minutes, 4 magnetic measurement; Reheating extended the heating time to 45 minutes, 0 precipitation, magnetic measurement magnetic needle repulsion reduced; 2, heating time extended to 1 hour, magnetic measurement, the preparation material is not completely diamagnetic.
  • Reason Because the prepared airtight conditions are not guaranteed during the preparation process, Ca(OH) 2 dehydration loses the active ingredient.
  • the magnetic measurement results and the resistance measurement results of the above heating time of 30 minutes or 1 hour, respectively, are shown in Table 1 or 1 or 2.
  • the molar ratio is 2: 1: 1.5: 0.33: 0.17 CuH z , CK BaCl 2 , Ba0, Ca (OH) 2 preparation method: same as in the embodiment 9
  • the magnetic measurement and resistance measurement of the prepared materials are shown in Table 1.
  • Example 9 The composition of Example 9 and the composition of 01 were replaced with Cu powder, and Ca(0H) 2 was replaced with anhydrous Ba(OH) 2 to obtain a complete diamagnetic effect of the material, which was substantially the same as in Example 9.
  • the materials of the above examples were placed in a domestic refrigerator and cooled to - 18 ⁇ - - 24 ⁇ for magnetic measurement, and were not completely diamagnetic.
  • the magnetic measurement method of the material prepared by the invention is as follows:
  • Measuring instrument Suspended magnetic needle, mercury thermometer (measuring range - 4 ° C ⁇ 300 ° C), the magnetic needle of the above measuring device is placed in the relatively closed hole in the box, and requires no magnetic field except the geomagnetism within five meters Dry especially.
  • Measurement method When the material is prepared at high temperature and the heating is stopped, the prepared materials are placed close to the sides of the stationary magnetic needles in a hot state, and the relationship between the magnetic needles being rejected, the rejection of the repulsion and the repulsion and the temperature and time are measured.
  • Example 2 0.77 NaCl was used in the composition of Example 2, and the preparation method and magnetic measurement method were the same as those in Example 2.
  • the preparation material was not completely diamagnetic, and the resistance measurement was shown in Table 1.
  • the CaO in the component of Example 9 was replaced with [0. 5La 2 0 3 ], and the obtained material was not completely diamagnetic, and the obtained material was in the form of powder, and the resistance was R ⁇ oo.
  • the purpose of this experiment was to verify the effect of the cerium oxide rare earth component.
  • Component Cu powder (200 mesh ⁇ analytical grade) or CuH 2 (z is 0.1), BaCl 2 ⁇ 2H 2 0 (chemically pure), KC1 (analytical grade)
  • the three reagents were weighed at 2:2:1, BaCl 2 ⁇ 2H 2 0 was preheated for 5 minutes, and the crystal water was removed. After that, the three reagents were mixed with powder, and the tube was filled with a plug at 650 ° C. Heated at 700 °C, after heating for 4 minutes, the volume of the reagent in the tube was reduced, agglomerated, and heating was continued for 7 minutes to obtain a red bulk material with tight structure and high hardness. Magnetic measurement, the material obtained is not completely diamagnetic. Resistance measurement, same as in Example 7.
  • the KC1 reagent in the component of the comparative example 4 was discarded, and the two reagents of BaCl 2 and Cu powder were retained, and the distribution ratios of the two groups were unchanged.
  • the process was unchanged, the heating temperature was constant, and the heating was carried out for 10 to 20 minutes to obtain an off-white powder. Shape (not agglomerated and Cu powder is partially oxidized), no complete diamagnetism, resistance R ⁇ ⁇ .
  • the above examples are preparation experiments for carrying out the invention.
  • the preparation experiments solve the problem of complete diamagnetic and superconductivity at 300 ° C and provide a method for preparing such materials.
  • the time of the first complete diamagnetic is not very long; the second complete diamagnet has a lower limit temperature, that is, room temperature.
  • the reason is as follows: The content of CuHJ ⁇ H in the examples is insufficient (z is 0.1), and is decomposed into Cu and H at a high temperature; the preparation process does not achieve absolute sealing, which causes the loss of H of the active ingredient.
  • the unequal relationship of Cu (or H)-H +p valence in the prepared materials is mainly represented by the unbalanced relationship of Cu-H +p valence states.
  • the temperature is lower than the lower limit temperature, the heat of H +p and Cu approaches or the heat of adsorption of H +p and Cu will disappear gradually in a short time (Reference: 1 Temperature conditions of Cu de-H action ⁇ Organic chemistry In the experiment, 2 repeated heating, the material was prepared to restore complete diamagnetism), which would cause the Cu-H +p valence unbalanced system to be destroyed.
  • H +p becomes an independent positive electric center with respect to Cu, and loses hole conductivity, and there is no longer any interaction between electrons and holes, which causes the material to lose superconductivity and is completely diamagnetic. It disappears. Therefore, the root cause is the loss of H of the CuH z reagent.
  • embodiments may be made to improve the technical solution: a first confined sound process to ensure that the reversible decomposition reaction CuH z; a second increase in the z-z CuH reaches 0. 4-07.
  • the H-H + P valence imbalance relationship (this relationship is not affected by temperature and time-independent) is achieved, that is, the above two defects can be eliminated.
  • Cu M5 Pd can be used. 55 Hz instead of CuH z , material preparation, in which Pd (palladium) has good adsorption to hydrogen. Description 2. Sealing conditions for preparation experiments A heating time
  • Reagents Ba (OH) 2 and Ca (OH) 2 , 55 when TC begins to decompose and lose H20 (individual, open heat), and has a reversible reaction (in the case of airtightness)':
  • Zn(OH)Cl is basic chloranil. Therefore, it is necessary to ensure the sealing conditions at the time of preparation. When the heating time is extended under the condition of ensuring the sealing, the diffusion of the powder and the internal structure are more uniform, so that a better complete diamagnetic effect can be obtained.
  • the preparation of the existing copper-based oxide superconducting material of McCaw, and the main component of the material of the present invention is chloride and according to the above preparation experiment, the preparation of the material is guaranteed to be absolutely sealed and insulated under air conditions. Extended for 4-5 hours.
  • the preparation experiment of the example ensures that the above-mentioned enthalpy process conditions are extended, and during the experiment, the decomposition reaction occurs due to the decomposition reaction, t or tube; 3 ⁇ 4 crack, the active ingredient is lost, and the detected completeness is completely detected.
  • the diamagnetism disappears, so the force time of the experiment of the present invention is 2H5 minutes, and the internal component (especially Cu) i ⁇ is uneven due to the short heating time of the actual test.
  • # ⁇ 4 ⁇ 4 ⁇ 3 ⁇ 4 provides an important test ⁇
  • the magnetic measurement of the prepared material is prepared by measuring the magnetic resistance of the magnetic needle, starting the magnetic needle, starting the magnetic needle, and the magnetic needle is
  • the amount of material that is most repelled when rejected in the normal embodiment is completely resistant.
  • Example 1 300 300 1. 0 12 300'C-room temperature means zero Example 2 1 300 1. 0 10 30 (TC-room temperature means zero implementation 1 0 300 1. 5 12 300 ° C - room temperature
  • Example 4 1. 5 229 1. 2 8 229 ° C - room temperature ? ⁇ Implementation 1 1. 5 236 1. 5 10 236 ⁇ -Room
  • Example 7 2 250 1. 0 16 250 ° C - room temperature Zero reference
  • Example 8 300 1. 0 20 300.
  • C-Room Temperature Order Implementation 1 0 300 1. 2 20 30 (TC-Room
  • the present invention realizes a superconducting material having a critical temperature T e higher than a normal temperature and a preparation method thereof. It should be noted that the above embodiments are only intended to illustrate the technical solutions of the present invention and are not to be construed as limiting the embodiments of the present invention. The technical solutions of the present invention may be modified or equivalently substituted, and the modified technical solutions may not deviate from the spirit and scope of the technical solutions of the present invention.

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Abstract

A superconducting material, in which Cu, K/Na, Ba, Cl and O/OH are its essential components. Its molecular formula is CuAKBBaCClDOE(-OH)F or CuANaBBaCClDOE(-OH)F. And the preparing method thereof includes the following steps: grinding the admixture of CuHZ, KCl/NaCl, BaCl2, SnCl2, SnO and Sn(OH)Cl, or the admixture of CuHZ, KCl/NaCl, BaCl2, ZnCl2, ZnO and Zn(OH)Cl, or the admixture of CuHZ, KCl/NaCl, BaCl2, BaO and Ba(OH)2, or the admixture of CuHZ, KCl/NaCl, BaCl2, CaCl2, CaO and Ca(OH)2, and mixing them uniformly, and packing them, and heating them for 4-5 hours at 550 -650°C in vacuum condition, and then cooling them to the room temperature in airtight condition without air, at last airprooving and storing them to get the superconducting material.

Description

超导电材料及其制备方法 技术领域  Superconducting material and preparation method thereof
本发明涉及超导电材料及其制备方法， 尤其是临界温度 Te高于常温的超 导电材料及其制备方法。 背景技术 The invention relates to a superconducting material and a preparation method thereof, in particular to a superconducting material having a critical temperature T e higher than a normal temperature and a preparation method thereof. Background technique
1、 超导电材料现有的技术状况： 提高超导体的临界温度 Tc, 即研制高临 界温度 Te的超导电材料， 一直是超导材料研究的核心课题之一。 直到 1986 年 A. Muller和 J. G. Bednorz俩人的 "钡镧铜氧系统中可能的高 Tc超导电 性" 划时代的发明， 才使超导材料 Te突破了超低温壁垒， 达到 35K。 但是第 一直到目前为止， 超导材料 Tc的最高记录仍保持在 164K。 此 Te值的材料为 Hg— Ba— Ca— Cu—O铜系氧化物材料， 由美国科学家朱经武于 1994年研制 发明。 2001年 3月美国和日本科学家又发明了 MgB2材料的超导电材料， Tc 为 39K。 2001年有报道用空穴注入法将有机超导的 Tc提高到 117K。 2001年 3月美国贝尔实验室制造出结构有规则的 Ρ3ΗΤ有机薄膜，并用场效座晶体管 往薄膜注入电荷， 在 2.35Κ薄膜出现超导电性。 2000年 12月美国科学家把纯 的 C6。材料的 Te提高到 52K。 而常温 Te超导电材料至今仍没能突破。 第二铜 系氧化物超导材料由于其陶瓷类的脆性缺陷， 要制出工程上适用的长导线线 材， 技术上至今仍很困难。 1. Existing technical status of superconducting materials: Increasing the critical temperature T c of superconductors, that is, developing superconducting materials with high critical temperature T e , has always been one of the core topics in the research of superconducting materials. Until 1986, A. Muller and JG Bednorz's epoch-making invention of "high T c superconductivity in the beryllium copper oxygen system" made the superconducting material T e break through the ultra-low temperature barrier to 35K. But up to now, the highest record of superconducting material T c has remained at 164K. The material of this T e value is Hg—Ba—Ca—Cu—O copper-based oxide material, which was developed and developed by American scientist Zhu Jingwu in 1994. In March 2001, American and Japanese scientists invented a superconducting material of MgB 2 material with a T c of 39K. In 2001, the hole injection method was used to increase the T c of organic superconductors to 117K. In March 2001, Bell Labs of the United States produced a regular Ρ3ΗΤ organic film, and used a field effect transistor to inject charge into the film, and superconductivity appeared in the 2.35 Κ film. In December 2000, American scientists put pure C 6 . The T e of the material is increased to 52K. The room temperature T e superconducting material has not yet broken through. The second copper-based oxide superconducting material is technically still difficult to produce due to the brittleness defects of ceramics.
2、 直至目前， 与本发明技术特征最接近的现有的超导材料， 为日本物质 材料研究所发明的钴氧化物 "粘水" 材料。 干燥状态下钴氧化物不具备超导 电性， 在负 268 °C时将钴氧化物层注入水分子， 其磁化率和电阻急剧下降， 使 之成为超导物质。 钴氧化 "粘水" 材料， 显然使用了水分子的极化共价键 H+ 均比较低， 无法实现常温临界温度 Tc。 发明内容 2. Up to now, the conventional superconducting material closest to the technical feature of the present invention is a cobalt oxide "sticky" material invented by the Japanese Institute of Materials Research. Cobalt oxide does not have superconductivity in dry state Electrically, when a cobalt oxide layer is injected into water molecules at a negative temperature of 268 °C, its magnetic susceptibility and electrical resistance drop sharply, making it a superconducting substance. Cobalt oxidized "sticky" materials, it is clear that the polarization covalent bond H+ of water molecules is relatively low, and the normal temperature critical temperature T c cannot be achieved. Summary of the invention
本发明的目的是针对现有的超导材料及其制备方法的缺陷， 而提供临界 温度 Tc高于常温的超导电材料及其制备方法。 The object of the present invention is to provide a superconducting material having a critical temperature T c higher than a normal temperature and a preparation method thereof, in view of the defects of the existing superconducting material and the preparation method thereof.
为实现上述目的， 本发明提供了一种超导电材料， 该超导电材料的必要 成分是： Cu、 K/Na、 Ba、 Cl、 0和- 0H。  To achieve the above object, the present invention provides a superconducting material, the essential components of which are: Cu, K/Na, Ba, Cl, 0 and -OH.
上述超导电材料的必要成分的组合为： Ci BBaeClA (-OH) F 或 CuANaBBacClD0E (-0H)F, 其中 The combination of essential components of the above superconducting material is: Ci BBaeClA (-OH) F or Cu A Na B BacCl D 0 E (-0H) F , wherein
A=l或 0.45或 2或 0.9  A=l or 0.45 or 2 or 0.9
B=l  B=l
C=l或 2或 1.5  C=l or 2 or 1.5
D=4.1+0.25x或 4  D=4.1+0.25x or 4
Ε=0·25(1- x)或 0.25(l+y)  Ε=0·25(1- x) or 0.25(l+y)
F=0.25(l+x)或 0.5 (1-y)  F=0.25(l+x) or 0.5 (1-y)
0<x<0.4 , 0<y<0.32。  0<x<0.4, 0<y<0.32.
所述必要成分是来自： CuH2/Cuo.«Pd0.55Hz, KCl/NaCK BaCl2、 SnCl2/ZnCl2、The essential components are: CuH 2 /Cuo.«Pd 0 . 55 H z , KCl/NaCK BaCl 2 , SnCl 2 /ZnCl 2 ,
SnO/ZnO和 Sn (OH) Cl/Zn (OH) Cl。或者所述必要成分是来自： CuHz/CuQ.«Pd。.55Hz、 KCl/NaCK BaCl2、 Ba0/Ca0和 Ba (OH) 2/Ca (OH) 2。 为实现上述目的本发明提供了一种上述超导电材料的制备方法， 包括： 将摩尔 '比为 1: 1: 1: 0.4: 0.25 (1.2-x)： 0.25 (1.2 + x)的 CuHz、 KCl/NaC BaCl2、 SnCl2、 SnO和 Sn (OH) CI ,研粉混匀，压实密闭隔绝空气， 在 550°C - 650 °C的温度下， 加热 4-5 小时， 然后密闭隔绝空气状态下冷却至室温， 密封保 存， 制得组成由化学式 SnO/ZnO and Sn (OH) Cl/Zn (OH) Cl. Or the essential component is derived from: CuH z /Cu Q .«Pd. 55 H z , KCl/NaCK BaCl 2 , Ba0/Ca0 and Ba (OH) 2 /Ca (OH) 2 . In order to achieve the above object, the present invention provides a method for preparing the above superconducting material, comprising: a molar ratio of 1: 1: 1: 0.4: 0.25 (1.2-x): 0.25 (1.2 + x) of CuH z , KCl/NaC BaCl 2 , SnCl 2 , SnO and Sn (OH) CI, mix with powder, compact and seal the air, heat at 550 ° C - 650 ° C for 4-5 hours, then seal the air Cool down to room temperature, seal and store, and make the composition by chemical formula
KBaSnCuHo.3+0.25x+zO0.6C 14.1+0.25x或 NaBaSnCuH0.3+0.25x+zO0.6C 14.1+0.25x所示 ^超导电材 料， 其中， 0<x<0.4 , 0<z<0.7。 KBaSnCuHo. 3+0 . 25x+z O 0 . 6 C 1 4 . 1+0 . 25x or NaBaSnCuH 0 . 3+0 . 25x+z O 0 . 6 C 1 4 . 1+0 . 25x A conductive material, wherein 0 < x < 0.4 and 0 < z < 0.7.
所述超导电材料显示完全抗磁时的上限温度并超导临界温度为 509K, 当 z值为 0.4-0.7时， 显示完全抗磁时的下限温度为 0K。  The superconducting material shows an upper limit temperature at the time of complete diamagnetic resistance and a superconducting critical temperature of 509 K, and when the z value is 0.4-0.7, the lower limit temperature at the time of complete diamagnetic resistance is 0 K.
本发明又提供了一种上述的超导电材料的制备方法， 包括：  The invention further provides a method for preparing the above superconducting material, comprising:
将摩尔比为 1: 1： 1： 0.4: 0.25 (1.2 -x): 0.25 (1.2 + x)的 CuHz、 KCl/NaCl、 BaCl2、 ZnCl2、 ZnO和 Zn (OH) CI ,研粉混匀，压实密闭隔绝空气， 在 550°C- 650 °C的温度下， 加热 4-5 小时， 然后密闭隔绝空气状态下冷却至室温， 密封保 存， 制得组成由化学式 The molar ratio is 1: 1: 1: 0.4: 0.25 (1.2 - x): 0.25 (1.2 + x) CuH z , KCl / NaCl , BaCl 2 , ZnCl 2 , ZnO and Zn (OH) CI Uniform, compacted and sealed air, heated at 550 ° C - 650 ° C for 4-5 hours, then cooled to room temperature in a sealed air condition, sealed and stored, to obtain the composition from the chemical formula
KBaZnCuHo.3+0.25x+z00.6C 14.1+0.25x或 NaBaZnCuH0.3+0.25x+z00.6C 14.1+0.25x所示 ά 超导电材 料， 其中， 0<χ<0.4, ( ζ<0.7。 KBaZnCuHo. 3+0 . 25x+z 0 0 . 6 C 1 4 . 1+0 . 25x or NaBaZnCuH 0 . 3+0 . 25x+z 0 0 . 6 C 1 4 . 1+0 . 25x Conductive material, where 0 < χ < 0.4, ( ζ < 0.7.
所述超导电材料， 显示完全抗磁时的上限温度并超导临界温度为 573Κ, 当 ζ值为 0.4-0.7时， 显示完全抗磁时的下限温度为 0Κ。  The superconducting material shows an upper limit temperature at the time of complete diamagnetic resistance and a superconducting critical temperature of 573 Κ. When the ζ value is 0.4-0.7, the lower limit temperature at the time of complete diamagnetic is 0 Κ.
本发明还提供了一种上述的超导电材料的制备方法， 包括：  The invention also provides a preparation method of the above superconducting material, comprising:
将摩尔比为 2: 1: 1.5: 0.25(l+y): 0.25 (1— y)的 CuHz、 KCl/NaCK BaCl2、The molar ratio is 2: 1: 1.5: 0.25 (l + y): 0.25 (1 - y) of CuH z , KCl / NaCK BaCl 2 ,
BaO和 Ba(0H)2,研粉混匀， 压实密闭隔绝空气， 在 650°C- 700°C的温度下， 加 热 4-5 小时， 然后密闭隔绝空气状态下冷却至室温， 密封保存， 制得组成由 化学式 BaO and Ba(0H) 2 , mix the powder, compact and seal the air, at 650 ° C - 700 ° C, add Heat for 4-5 hours, then cool to room temperature in a sealed air condition, sealed and stored, and the composition is made up of chemical formula
KBa2Cu2HQ.5(1—y)+2zO。.75-。.25yCl4或 NaBa2Cu2H。.5(1-y)+2zOQ.75-Q.25yCl4所示的超导电材 料， 其中， 0<y<0.32, 0<z<0.7o KBa 2 Cu 2 H Q . 5(1 - y) + 2z O. 75 -. . 25y Cl 4 or NaBa 2 Cu 2 H. 5(1 - y)+2z O Q . 75 - Q . Superconducting material shown by 25y Cl 4 , where 0<y<0.32, 0<z<0.7 o
所述超导电材料， 显示完全抗磁时的上限温度并超导临界温度 为 529K， 当 ζ值为 0.4-0.7时， 显示完全抗磁时的下限温度为 0Κ：。  The superconducting material shows an upper limit temperature at the time of complete diamagnetic resistance and a superconducting critical temperature of 529 K. When the enthalpy value is 0.4-0.7, the lower limit temperature at the time of complete diamagnetic resistance is 0 Κ:.
本发明另提供了一种上述的超导电材料的制备方法， 包括：  The invention further provides a method for preparing the above superconducting material, comprising:
将摩尔比为 2: 1： 1.5： 0.25(l+y): 0· 25 (1— y)的 CuHz、 KCl/NaCK BaCl2、 CaO和 Ca(0H)2, 研粉混匀， 压实密闭隔绝空气， 在 650°C- 700°C的温度下， 加热 4-5 小时， 然后密闭隔绝空气状态下冷却至室温， 密封保存， 制得组成 由化学式 The molar ratio is 2: 1: 1.5: 0.25 (l + y): 0 · 25 (1 - y) of CuH z , KCl / NaCK BaCl 2 , CaO and Ca (0H) 2 , powder mixing, compaction Airtightly sealed, heated at 650 ° C - 700 ° C for 4-5 hours, then cooled to room temperature under airtight conditions, sealed and stored, to obtain the composition from the chemical formula
KBaL5Ca0.5Cu2H 0.5(1- y)+2z0o.75 - 0.25yCl4或 N B i. SC O.5CU2H0.5 (1 - y)+2ZOo.75 - 0.25yC 14 的 超导电材料， 其中， 0 y<0.32 , 0<ζ<0.7 。 KBa L5 Ca 0 . 5 Cu 2 H 0.5(1- y)+2z0o.75 - 0.25yCl4 or NB i. SC O.5CU2H0.5 (1 - y)+2 Z Oo.75 - 0.25yC 14 superconducting Material, where 0 y < 0.32, 0 < ζ < 0.7.
所述超导电材料， 显示完全抗磁时的上限温度并超导临界温度 为 573Κ, 当 ζ值为 0.4-0.7时， 显示完全抗磁时的下限温度为 0Κ。  The superconducting material shows an upper limit temperature at the time of complete diamagnetic resistance and a superconducting critical temperature of 573 Κ. When the ζ value is 0.4-0.7, the lower limit temperature at the time of complete diamagnetic is 0 Κ.
上述材料均存在 Cu (或 Η) — H+p价态不平衡关系。 带部分正电荷 +P 的 H+p来自含 -OH的金属化合物的 0 - H极化共价键 (这里的 H+p不同于自由 态 H+离子） ， 以及 H+p在材料空间结构中与相邻 0、 C1形成 H键时产生的共 有化电离 （H键电离） ， 电子和空穴超流子分别来自 Cu (或 CuHz)及 H+p、 以及二者的价态不平衡关系， 其中的金属氧化物及金属氯化物分别提供氧、 氯负离子及错位、 分层金属正离子， 其中的 Cu与金属正离子 (如 K、 Ba正离 子)的微观相互关系,才使得该材料完全抗磁的上限温度并超导临界温度能够 1¾于常温。 All of the above materials have a Cu (or Η)-H +p valence state imbalance relationship. H + p with a partial positive charge +P is derived from the 0 - H polarized covalent bond of the metal compound containing -OH (where H + p is different from the free state H + ion), and H +p is in the spatial structure of the material The shared ionization (H-bond ionization) generated when adjacent 0 and C1 form an H bond, and the electron and hole super-flows are derived from Cu (or CuH z ) and H +p , respectively, and the valence state imbalance relationship between them. The metal oxides and metal chlorides respectively provide oxygen, chloride anions and misaligned, layered metal cations, wherein Cu and metal cations (such as K, Ba are separated) The microscopic relationship of the sub-) makes the material completely diamagnetically resistant to the upper limit temperature and the superconducting critical temperature can be 13⁄4 at room temperature.
上述材料为 组织 结构 紧密 、 硬度较大的 红 色 块状 ， The above materials are red blocks with tight structure and high hardness.
KBaSnCuH0. 3+0. 25X+z00.6Cl4. i+o. 25X 和 NaBaSnCuH0.3+0.25x+z00.6Cl4. i+o. 25X Λ" 及 KBaZnCuHo.3+0. 25χ+∑Οο. 14. 1+0. 25x和 NaBaZn( 0.3+0.25x+zO0.6Cl4.1+0. 25x材料具有热塑性，并 都具有冷脆性， 都具有可加工性， 能够加工成工程上使用的长线导电材料， 能够解决并实现现有技术不能达到的常温或高于常温的超导输电及磁悬浮技 术问题。 KBaSnCuH 0 . 3+0 . 2 5 X+z 0 0 . 6 Cl 4 . i + o. 25 X and NaBaSnCuH 0 . 3+0 . 25x+z 0 0 . 6 Cl 4 . i + o. 2 5 X Λ" and KBaZnCuHo.3+0. 25χ+∑Οο. 14. 1+0. 25x and NaBaZn( 0 . 3+0 . 25x+z O 0 . 6 Cl 4 .1+0. 25x material is thermoplastic, and They are both cold and brittle, have processability, and can be processed into long-term conductive materials used in engineering. They can solve and solve the problems of superconducting power transmission and magnetic levitation at normal temperature or above normal temperature that cannot be achieved by the prior art.
改进方案： 为了改善 CuHz成分的易热分解性， 可用 Cu 45PdQ.55Hz ( 0 < z < 0.7 ) 代替上述使用试剂组分中的 CuHz组分， 进行材料制备， 经制备， Cu0.45Pdo.55Hz在材料中分解扩散为 Cu、 Cu¾或 PdHz成分， 其中的 Pd成分对 H有良好的吸附性能。 010.45?(1。.55¾为铜钯氢合金， z = 0时为铜钯合金， 参见 《超导电性物理基础》 P15 , 管惟炎等著， 科学出版社， 1981。 Improvement scheme: In order to improve the thermal decomposition property of the CuH z component, Cu 4 5 PdQ. 55 H z ( 0 < z < 0.7 ) may be used instead of the CuH z component in the above reagent component for material preparation, preparation, Cu 0 . 45 Pdo. 55 H z decomposes and diffuses into Cu, Cu3⁄4 or PdH z components in the material, and the Pd component has good adsorption properties for H. 010. 45 ? (1. 55 3⁄4 is a copper palladium hydrogen alloy, copper palladium alloy when z = 0, see "Physical Foundation of Superconductivity" P15, Guan Weiyan, Science Press, 1981.
因此本发明实现了临界温度 Tc高于常温的超导电材料及其制备方法。 具体实施方式 Therefore, the present invention realizes a superconducting material having a critical temperature T c higher than a normal temperature and a preparation method thereof. detailed description
背景技术中的钴氧化 "粘水"材料中使用的水分子的极化共价键 H+离子， 与本发明使用的 H+p离子特征是相似的。本发明与之不同的特征在于，本发明 使用了 Zn(OH)Cl或 Sn(OH)Cl或 Ba(OH)2或 Ca(OH)2中的 H+p离子和单质 Cu 的价电子 (或合金 CuHz的价电子） , 以及金属氯化物和金属氧化物 , 从而获 得 573K下的完全抗磁态， 其 Tc值远高于钴氧化物 "粘水，，材料的 Tc值 ( 5K, 负 268 Ό )。 另一个重要区别在于， 本发明不属于纯粹的化合物超导材料， 而 是迄今为止从未出现的单质（或氢合金）一化合物超导材料。 从 H+p的意义上 讲， 钴氧化物 "粘水" 材料为本发明的有效性提供了实验支持。 The polarized covalent bond H+ ions of water molecules used in cobalt oxidation "sticky" materials in the prior art are similar to the H +p ion features used in the present invention. A feature different from the present invention is that the present invention uses valence electrons of H +p ions and elemental Cu in Zn(OH)Cl or Sn(OH)Cl or Ba(OH) 2 or Ca(OH) 2 (or The valence electron of the alloy CuH z , as well as the metal chloride and metal oxide, thus obtaining the complete diamagnetic state at 573 K, the T c value is much higher than the cobalt oxide "sticky water, the T c value of the material ( 5K, Negative 268 Ό). Another important difference is that the invention is not a pure compound superconducting material, but It is a simple substance (or hydrogen alloy)-based superconducting material that has never appeared before. In the sense of H +p , cobalt oxide "sticky" materials provide experimental support for the effectiveness of the present invention.
以下通过实施例进一步地说明本发明。 通过选取不同的实施例， 进一步 说明组分及配比， 配比均按摩尔比； 实施例中的 CuHz组分 z值为 0. 1 ; CuHz 为铜氢合金， z=0时为单质铜。 The invention is further illustrated by the following examples. By selecting various embodiments, further illustrate the composition and ratio, are by molar ratio ratio; embodiment CuH z z embodiment component value 0. 1; CuH z copper alloy hydrogen, z = 0 to elemental copper.
实施例 1  Example 1
组分：  Component:
Cu粉（ 200目， 分析纯） , BaCl2 · 2Η20 (化学純）， KC1 (分析纯）或 NaCl , ZnCl2 (分析纯， 含少量吸湿水） Cu powder (200 mesh, analytical grade), BaCl 2 · 2Η 2 0 (chemically pure), KC1 (analytical grade) or NaCl, ZnCl 2 (analytical grade, with a small amount of hygroscopic water)
材料制备  Material preparation
四种试剂按摩尔比 1 : 1 : 1 : 1称取适当量各试剂， ZnCl2加热 10分钟（550 。C ) , BaCl2 · 2H20加热 5分钟 ( 550°C ) , 除去 ZnCl2的吸湿水和 BaCl2 · 2H20 的结晶水，后， 四种试剂分别研粉混匀， 装管， 管口加塞， 在 550°C- 650°C下， 加热 15-20分钟， 制备。 制备过程中有 HC1气体和 0析出， 在一次性排出 HC1和 H20后， 在制备的整个加热过程中， 应压紧管口塞子。 Four reagents molar ratio 1: 1 : 1 : 1 Weigh the appropriate amount of each reagent, ZnCl 2 heating for 10 minutes (550 ° C), BaCl 2 · 2H 2 0 heating for 5 minutes (550 ° C), remove ZnCl 2 After absorbing water and water of BaCl 2 · 2H 2 0, the four reagents are separately mixed with powder, filled, and piped, and heated at 550 ° C - 650 ° C for 15-20 minutes. During the preparation process, HC1 gas and 0 are precipitated. After the HC1 and H 2 0 are discharged at one time, the nozzle plug should be pressed during the entire heating process.
制备材料性质检测  Preparation material properties test
[磁测量] 制得材料能使原静止的磁针排开， 最大斥幅 1. 0cm, 排斥时间 12 分钟， 后磁针被排斥现象消失。 出现此完全抗磁性时的温度在 300°C (有 实验达到约 400°C )到室温区间。  [Magnetic measurement] The material obtained can make the original static magnetic needle open, the maximum repulsion is 1. 0cm, the repulsion time is 12 minutes, and the magnetic needle is rejected. The temperature at which this complete diamagnetism occurs is at 300 ° C (with an experiment reaching about 400 ° C) to the room temperature range.
[电阻测量] 室温、 非完全抗磁态情况下， 用欧姆计 1R档测量， 指针指 零。 实验说明 [Resistance measurement] In the case of room temperature and incomplete anti-magnetic state, it is measured with an ohmmeter 1R file, and the pointer points to zero. Experimental description
由磁测量得到的完全抗磁性（迈斯纳效应） ， 认为， 该材料是超导电材 料。 其中进一步地实验如下， ①改变实验及磁测量环境， 排除使磁针排开的 外力因素或材料可能携磁携电流等因素； ②以此实验的组分及配比为基本方 案， 分别舍弃其中的 KC1或 BaCl2试剂， 进行实验， 制得材料则磁针无排斥现 象； ③把实验中的 ZnCl2分别用无水分析纯、 或同厂家含少量吸湿水（敞口放 置吸湿） 、 或不同的含少量吸湿水的 ZnCl2, 其它试剂组分及配比不变， 工艺 不变， 实验结果， 凡釆用无水分析纯的 ZnCl2, 制得材料则无完全抗磁性（磁 针不被排斥） , 而采用含少量吸湿水并必需有适量 ZnO成份存在的情况下， 制得材料又出现完全抗磁性（磁针被排斥） 。 通过对一系列的实验和 ZnCl2 水解时产生 ZnO和 Zn (OH) CI的实验观察及实验分析， 确定此实验制备材料出 现完全抗磁性时的必要试剂组分为： Cu , KC1 ， BaCl2 , ZnCl2 , ZnO , Zn (OH) CI 。 从而才确定了此实验制备材料的成分问题。 此后， 又用 CuHz代替 Cu粉， 磁针排斥效果明显增强， 最大斥幅增大到 1. 5cm。 The complete diamagnetism (Meissner effect) obtained from magnetic measurements is considered to be a superconducting material. Further experiments are as follows: 1 change the experimental and magnetic measurement environment, exclude external factors such as magnetic needles or materials may carry magnetic current and other factors; 2 the composition and ratio of the experiment as the basic scheme, respectively discard the KC1 or BaCl 2 reagent, experiment, the material obtained is magnetic needle-free; 3 ZnCl 2 in the experiment is analyzed with anhydrous water, or the same manufacturer contains a small amount of hygroscopic water (opening to absorb moisture), or different ZnCl 2 with a small amount of hygroscopic water, other reagent components and ratios are unchanged, the process is unchanged, the experimental results, the use of anhydrous analytically pure ZnCl 2 , the material is not completely diamagnetic (magnetic needle is not rejected), In the case where a small amount of hygroscopic water is used and an appropriate amount of ZnO component is present, the resulting material is completely diamagnetic (magnetic needle is repelled). Through a series of experiments and experimental observation and experimental analysis of ZnO and Zn(OH) CI produced by ZnCl 2 hydrolysis, it is determined that the necessary reagent components for the complete diamagnetism of this experimental material are: Cu, KC1, BaCl 2 , ZnCl 2 , ZnO , Zn (OH) CI . The problem of the composition of the materials prepared in this experiment was thus determined. Since then, substituting CuH z Cu powder, significantly enhanced the needle repulsion effect, the web is increased to the maximum repulsive 1. 5cm.
实施例 2  Example 2
组分及配比  Composition and ratio
摩尔比为 1: 0. 7: 1: 0. 4: 0. 3: 0. 3的 CuHz、 NaCl、 BaCl2、 ZnCl2、 Zn0、 [Zn (0H) Cl + NaCl] The molar ratio is 1:0. 7: 1: 0. 4: 0. 3: 0.3 CuH z , NaCl, BaCl 2 , ZnCl 2 , Zn0, [Zn (0H) Cl + NaCl]
其中的 [Zn (0H) Cl + NaCl]取自下述制取的 [Zn (0H) Cl · NaCl]试剂。  Among them, [Zn (0H) Cl + NaCl] was obtained from the [Zn (0H) Cl · NaCl] reagent prepared below.
制备方法  Preparation
按组分及配比， 称取适当量的各組分试剂， 研粉， 装入耐高温试管， 混 匀， 管口加塞， 在 550°C- 650°C的温度下， 加热 20分钟。 在整个制备过程中， 应压紧管口塞子。 停止加热时， 随即将制备材料在热状态下， 靠近磁针， 进 行磁测量。 · According to the composition and ratio, weigh the appropriate amount of each component reagent, grind the powder, put it into high temperature resistant test tube, mix Evenly, the nozzle is stoppered and heated at 550 ° C - 650 ° C for 20 minutes. The nozzle plug should be compressed throughout the preparation process. When the heating is stopped, the prepared material is placed in a hot state close to the magnetic needle for magnetic measurement. ·
制备材料的磁测量及电阻测量， 结果见表 1。 '  The magnetic measurement and resistance measurement of the prepared materials are shown in Table 1. '
[Zn (0H)C1 · NaCl]试剂的制取  Preparation of [Zn (0H)C1 · NaCl] reagent
在无水条件下， 按摩尔比 1: 1称取适量的无水 ZnCl2及无水 NaOH, 研粉， 装入医用注射器， 压实密闭隔绝空气， 300°C- 350°C下加热 45 分钟， 冷却至 室温， 制得上述试剂。 在无水条件下， 研粉， 密封备用。 反应式为： ZnC 12 + NaOH = Zn (OH) C 1 + NaC 1。 Under anhydrous conditions, weigh an appropriate amount of anhydrous ZnCl 2 and anhydrous NaOH at a molar ratio of 1:1, grind the powder, put it into a medical syringe, compact the sealed air, and heat at 300 ° C - 350 ° C for 45 minutes. The above reagent was obtained by cooling to room temperature. Under anhydrous conditions, grind the powder and seal it for later use. The reaction formula is: ZnC 1 2 + NaOH = Zn (OH) C 1 + NaC 1 .
制取说明： （1) 、 用医用注射器的目的在于保证制取过程中的压实密闭 隔绝空气条件。 （2) 、 上述反应可能有副产物产生， 如 Zn(0H)2等， 但只要 保证密闭条件， 不使制取过程中有可能生成的 H20及 HC1气体逸出， 即可消除 副产物。 （3) 、 上述生成物 Zn(0H)Cl + NaCl , 具有如下可逆反应： Preparation instructions: (1), the purpose of using a medical syringe is to ensure that the compaction and air isolation conditions during the preparation process. (2) The above reaction may have by-products, such as Zn(0H) 2 , etc., but as long as the sealing conditions are ensured, the H 2 0 and HC 1 gases which may be generated during the production process are not allowed to escape, and the by-products can be eliminated. . (3) The above product Zn(0H)Cl + NaCl has the following reversible reaction:
Zn (OH) Cl + NaCl、 Δ 、 Na (ZnOCl) C1 + HC1 其中的 Na[ZnOCl]为氯锌酸钠， 成分为 ZnO · NaCl 。 由上述可逆反应， 在保证密闭条件、 无 HC1逸出时， 即可保证生成物 Zn(0H)Cl和 NaCl的生成 及相互均匀分散。 （4) 、 上述制取， ZnCl2量应微大于 NaOH量。 Zn (OH) Cl + NaCl, Δ , Na (ZnOCl) C1 + HC1 wherein Na[ZnOCl] is sodium chlorozincate and the composition is ZnO · NaCl. According to the above reversible reaction, when the sealing condition is ensured and no HC1 escapes, the formation of the product Zn(0H)Cl and NaCl and uniform dispersion of each other are ensured. (4) In the above preparation, the amount of ZnCl 2 should be slightly larger than the amount of NaOH.
实施例 3  Example 3
组分及配比  Composition and ratio
摩尔比为 1: 0.6: 1: 0.4: 0.2: 0.4的 CuHz、 KC1、 BaCl2、 ZnCl2、 Zn0、 [Zn (OH) CI + NaCl] 其中的 [Zn(0H)Cl +NaCl]试剂，取自实施例 2中制取的 [Zn (0H)C1 -NaCl] 试剂。 The molar ratio is 1: 0.6: 1: 0.4: 0.2: 0.4 CuH z , KC1 , BaCl 2 , ZnCl 2 , Zn0, [Zn (OH) CI + NaCl] Among them, the [Zn(0H)Cl +NaCl] reagent was taken from the [Zn(0H)C1-NaCl] reagent prepared in Example 2.
制备方法及制备材料的磁测量  Preparation method and magnetic measurement of prepared materials
制备方法及磁测量方法同实施例 2, 其中的加热时间分别为：  The preparation method and the magnetic measurement method are the same as those in the embodiment 2, wherein the heating time is:
①、 加热 30分钟， 加热过程中有少量 HC1气体逸出一次， 立即再压紧管 塞。 停止加热时， 随即将制备材料靠近磁针进行磁测量， 测量结果见表 1。 完 全抗磁的上限温度检测到的是 300°C, 有可能达到 350°C- 40(TC (表现为测量 时明显会高于温度计测量范围的上限） 。  1. Heat for 30 minutes. A small amount of HC1 gas will escape once during the heating process, and then immediately tighten the plug. When the heating is stopped, the prepared material is magnetically measured close to the magnetic needle, and the measurement results are shown in Table 1. The upper limit temperature of the full diamagnetic resistance is 300 °C, and it is possible to reach 350 °C - 40 (TC (the performance is obviously higher than the upper limit of the thermometer measurement range).
②、 第二次加热 40分钟， 冲塞， 有多量 HC1气体放出， 停止加热， 随即 将制备材料靠近磁针进行磁测量， 无完全抗磁性。 电阻测量见表 1。  2. The second heating for 40 minutes, the plug, a large amount of HC1 gas is released, stop heating, and then the preparation material is close to the magnetic needle for magnetic measurement, without complete diamagnetism. The resistance measurement is shown in Table 1.
实施例 4  Example 4
組分及配比：  Composition and ratio:
摩尔比为 1: 0.7： 1: 0.4: 0.3: 0.3的 CuHz、 NaCl、 BaCl2、 SnCl2、 Sn0、 [Sn(0H)Cl +NaCl], 其中的 SnCl2、 SnO、 Sn (OH) CI分别为氯化亚锡、 氧化亚 锡、 碱式氯化亚锡， 其中的 [Sn(0H)Cl + NaCl]取自于 [Sn(0H)Cl - NaCl]试剂, 其试剂的制取方法同于实施例 2 中的 [Zn(0H)Cl · NaCl]的制取方法， 只把其 中的 ZnCl2用 SnCl2代替。 The molar ratio is 1:0.7: 1: 0.4: 0.3: 0.3 CuH z , NaCl, BaCl 2 , SnCl 2 , SnO, [Sn(0H)Cl +NaCl], among which SnCl 2 , SnO, Sn (OH) CI They are stannous chloride, stannous oxide, and basic stannous chloride, wherein [Sn(0H)Cl + NaCl] is obtained from [Sn(0H)Cl - NaCl] reagent, and the reagents are prepared in the same manner. In the preparation method of [Zn(0H)Cl · NaCl] in Example 2, only ZnCl 2 was replaced with SnCl 2 .
制备方法及测量方法同于实施例 2。  The preparation method and measurement method are the same as those in Example 2.
制备材料的磁测量及电阻测量， 结果见表 1。  The magnetic measurement and resistance measurement of the prepared materials are shown in Table 1.
实施例 5  Example 5
组分及配比： 摩尔'比为 1 : 0. 6: 1 : 0. 4: 0. 2: 0. 4的 CuHz、 KC1、 BaCl2、 SnCl2、 Sn0、 [Sn (0H) Cl + NaCl] , 其中的 [Sn (OH) CI + NaCl]取自于实施例 4 中制取的 [Sn (OH) CI · NaCl]试剂。 Composition and ratio: Moore' ratio is 1: 0. 6: 1 : 0. 4: 0. 2: 0. 4 CuH z , KC1 , BaCl 2 , SnCl 2 , Sn0, [Sn (0H) Cl + NaCl], where [ Sn (OH) CI + NaCl] was taken from the [Sn (OH) CI · NaCl] reagent prepared in Example 4.
制备方法及测量方法同于实施例 3。  The preparation method and measurement method are the same as those in Example 3.
制备材料的磁测量及电阻测量， 结果见表 1。  The magnetic measurement and resistance measurement of the prepared materials are shown in Table 1.
实施例 6  Example 6
组分： CuHz粉， BaCl2 · 2H20 (化学纯）， 0H (分析纯）或 NaOH Component: CuHz powder, BaCl 2 · 2H 2 0 (chemically pure), 0H (analytical grade) or NaOH
配比： 2: 2： 1  Matching ratio: 2: 2: 1
材料制备及性质检测  Material preparation and property testing
三种试剂按摩尔比 2: 2: 1 称取适当量各试剂， 研粉混匀， 装管， 管口 加塞， 放入盛水的玻璃杯内，  Three kinds of reagents molar ratio 2: 2: 1 Weigh the appropriate amount of each reagent, mix the powder, install the tube, add the tube to the mouth, and put it into the glass of the water.
保持杯内水温 80°C- 82 °C , 水浴加热 5分钟， 管内试剂无水析出 （观察试 管内壁） ， 试剂少部分变黑， 取出试管， 随即靠近磁针， 做磁测量， 能使原 静止磁针排开 0. 6cm， 排斥时间 3分钟。 后， 继续在 80 °C- 82 °C的水中水浴加 热 10-15 分钟， 管内试剂黑色加重， 试剂有水析出， 取出， 做磁测量， 磁针 无被排斥现象。  Keep the water temperature in the cup 80 °C-82 °C, heat in the water bath for 5 minutes, the reagent in the tube is not precipitated (observe the inner wall of the test tube), the reagent part is blackened, the test tube is taken out, and then the magnetic needle is taken, the magnetic measurement is made, and the original static magnetic needle can be made. Discharged 0.6 cm, rejection time 3 minutes. After that, continue to heat in a water bath at 80 °C - 82 °C for 10-15 minutes. The reagent in the tube is blackened, the reagent is precipitated in water, taken out, and magnetically measured. The magnetic needle is not repelled.
再将试管直接放酒精灯灯焰上加热， 有多次多量水析出， 并及时除去积 在试管内壁上的析出水， 直到基本无水析出时， 离火， 随即在热状态下， 做 磁测量， 磁针无被排斥现象。 继续放灯焰上加热 7分钟（温度约 650°C ) , 管 内试剂不再有水析出， 试剂黑色消失， 体积缩小， 结块呈铜红色， 离火， 随 即做磁测量， 在靠近磁针后 1 分钟、 温度为 256 °C时， 磁针开始被排开 0. 6-0. 8cm, 排斥时间 6分钟。 Then, the test tube is directly heated on the lamp of the alcohol lamp, and a large amount of water is precipitated, and the precipitated water accumulated on the inner wall of the test tube is removed in time until the water is substantially precipitated, leaving the fire, and then in the hot state, magnetic measurement is performed. , the magnetic needle is not repelled. Continue to heat on the lamp flame for 7 minutes (temperature about 650 ° C), the water in the tube no longer precipitates, the reagent black disappears, the volume shrinks, the agglomerate is copper red, away from the fire, then magnetic measurement, immediately after the magnetic needle 1 When the temperature is 256 °C, the magnetic needle starts to be arranged. 0. 6-0. 8cm, rejection time 6 minutes.
取出管内红色结块样品， 在常温、 无完全抗磁状态下， 用欧姆计 1R档做 电阻测量， 指针指零。  Take out the red agglomerate sample in the tube. Under normal temperature and no complete diamagnetic condition, use the ohmmeter 1R file for resistance measurement. The pointer points to zero.
制备实验说明  Preparation experiment description
①通过对比观察，实验过程中试剂总析出水量明显多于等量的 BaCl2 ·2Η20 单独加热去结晶水时的总析出水量， 表明在实验过程中， 当 K0H与 BaCl2发生 反应生成 KC1和 Ba (0H) 2后， 高温加热时， 部分 Ba (0H) 2也参与了水析出， 生 成 BaO成份。 ②根据化学反应及实验观察， 确定， 此制备材料的组成由 CuHz、 KCK BaCl2、 BaO, Ba (OH) 2所示的化学成分组成。 ③用 NaOH代替上述实验中 的 K0H做此实验， 二者实验得到的完全抗磁性效果基本相同。 ④用 Cu粉代替 此实验中的 CuHz做此实验， 则实验始终无完全抗磁性显示， 其原因是， 在强 碱环境中、 同时又有水（主要为 BaCl2 · 2H20的结晶水）和氧存在的情况下， 加 热时， Cu极易被氧化造成的。 氧化后， Cu则丧失对 H+p的吸附作用。 1 By comparison, the total amount of water in the reagents during the experiment was significantly higher than that of the equivalent amount of BaCl 2 ·2Η 2 0 when the decrystallization water was heated alone, indicating that K0H reacted with BaCl 2 to form KC1 during the experiment. After Ba (0H) 2 , when Ba is heated at a high temperature, part of Ba (0H) 2 is also involved in water precipitation to form BaO components. 2 According to the chemical reaction and experimental observation, it was confirmed that the composition of the preparation material was composed of chemical components represented by CuH z , KCK BaCl 2 , BaO, Ba (OH) 2 . 3 Using NaOH instead of K0H in the above experiment to do this experiment, the complete diamagnetic effect obtained by the two experiments is basically the same. 4 Using Cu powder instead of CuH z in this experiment, the experiment has no complete diamagnetic display. The reason is that in the strong alkali environment, there is water (mainly BaCl 2 · 2H 2 0 crystal water). In the presence of oxygen, Cu is easily oxidized when heated. After oxidation, Cu loses its adsorption to H +p .
实施例 7  Example 7
组分及配比：  Composition and ratio:
摩尔比为 2: 1： 1, 5 : 0. 25 : 0. 25的 CuHz、 NaCK BaCl2、 Ba0、 Ba (0H) 2, 其中的 Ba (0H) 2由适量的 BaCl2与适量的 NaOH反应得到， BaO要求是密封完好 新近生产的。 The molar ratio is 2: 1: 1, 5 : 0. 25 : 0. 25 CuH z , NaCK BaCl 2 , Ba0, Ba (0H) 2 , wherein Ba (0H) 2 is composed of an appropriate amount of BaCl 2 and an appropriate amount of NaOH The reaction was obtained, and the BaO requirement was that the seal was well produced recently.
制备方法  Preparation
按组分及配比， 称取适当量的各组分试剂， 研粉， 装入耐高温试管， 混 匀， 管口加塞， 650 °C- 700 °C下， 加热 30-40分钟， 在整个制取过程中， 应压 紧管口塞子。 停止加热时， 随即在热状态下， 靠近磁针， 进行磁测量。 According to the composition and ratio, weigh the appropriate amount of each component reagent, grind the powder, put it into the high temperature resistant test tube, mix it, add the plug, 650 °C - 700 °C, heat for 30-40 minutes, throughout During the preparation process, it should be pressed Tight pipe plug. When the heating is stopped, the magnetic measurement is performed near the magnetic needle in a hot state.
制备材料的磁测量及电阻测量， 结果见表 1。  The magnetic measurement and resistance measurement of the prepared materials are shown in Table 1.
把实施例 7组分中的（¾ 用 Cu粉代替， 进行制备实猃， 制备材料的完全 抗磁性效果与实施例 7基本相同。 由此说明， 实施例 6又用 Cu粉代替 CuHz 制备时出现的 Cu被氧化, 是由于 K0H并水（BaCl2 · 2H20的结晶水）的存在造 成的， 同时也说明 CuHz中的 H有保护 Cu不被腐蚀的作用。 The complete diamagnetic effect of the prepared material was substantially the same as that of Example 7 except that (3⁄4) of the component of Example 7 was replaced with Cu powder, and it was explained that Example 6 was replaced with Cu powder instead of CuH z . The appearance of Cu is oxidized due to the presence of K0H and water (crystal water of BaCl 2 · 2H 2 0), and also indicates that H in CuH z has a function of protecting Cu from corrosion.
实施例 8  Example 8
组分： CuHz粉， BaCl2 ·2 Η20 (化学純) , KC1 (分析纯）或 NaCl , [Ca (OH) 2 -含Component: CuH z powder, BaCl 2 ·2 Η 2 0 (chemically pure), KC1 (analytical grade) or NaCl, [Ca (OH) 2 -
CaO] CaO]
材料制备  Material preparation
[Ca (OH) 2 ·含 CaO]试剂的制取， 把 Ca (OH) 2装管放炉火内在约 600°C下, 加热 15-20分钟， 由部分 Ca (0H) 2脱水制得。 四种试剂按 4: 3: 2: 1称取适 当量各试剂， BaCl2 . 2 H20在 55CTC下加热 5分钟， 完全除去其结晶水， 后， 四种试剂分別研粉混匀， 装管， 管口加塞， 在 650 °C-70(TC下加热， 当加热到 4分钟时， 管内试剂体积逐渐缩小， 结块， 有少量水析出， 继续加热 20-25分 钟， 制得组织结构紧密， 硬度较大的红色块状物材料。 Preparation of [Ca(OH) 2 ·CaO-containing reagent, Ca(OH) 2 is placed in a furnace fire at about 600 ° C for 15-20 minutes, and is obtained by dehydration of a portion of Ca (0H) 2 . The four reagents were weighed in an appropriate amount of 4:3:2:1, and BaCl 2 . 2 H 2 0 was heated at 55 CTC for 5 minutes to completely remove the crystal water. After that, the four reagents were separately mixed and mixed. Tube, nozzle plugging, heating at 650 °C-70 (TC), when heated to 4 minutes, the volume of the reagent in the tube is gradually reduced, agglomerated, a small amount of water is precipitated, heating is continued for 20-25 minutes, resulting in tight structure , a harder red block material.
制备材料性质检测  Preparation material properties test
磁测量， 制得材料能使原静止磁针排开， 最大斥幅 1. 0cm, 排斥时间 20 分钟， 出现此完全抗磁性时的温度在 300 °C ( > 30(TC达到约 400°C )到室温 区间。 电阻测量， 同实施例 7 , 制得材料底部表面有少量薄熔融冷却层， 此处 R→∞。 把制得材料放家用冰箱冷至 - 18 °C— 24 °C , 再做磁测量， 无完全抗磁 性。 Magnetic measurement, the material obtained can make the original static magnetic needle open, the maximum repulsion is 1.0 cm, the rejection time is 20 minutes, and the temperature at the time of complete diamagnetism is 300 °C (> 30 (TC reaches about 400 °C) to Room temperature interval. Resistance measurement, same as Example 7, the bottom surface of the material has a small amount of thin molten cooling layer, where R→∞. The material is placed in a household refrigerator and cooled to - 18 °C - 24 °C, and then magnetic Measurement, no complete diamagnetic Sex.
实验说明  Experimental description
①重复实验，得到的完全抗磁性效果同上。②改变试剂配比，如改变为 2: 1: 1: 1, 进行实验， 从实验效果看， 上述实验配比效果最佳。 ③用 NaCl 代 替 KC1或用 Cu粉代替 CuHz , 进行制备实验， 制得材料均能在 300°C下获得完 全抗磁性。 1 Repeat the experiment and obtain the complete diamagnetic effect as above. 2 Change the reagent ratio, if the change is 2: 1: 1: 1, the experiment is carried out. From the experimental results, the above experiment has the best ratio. 3 Using NaCl instead of KC1 or Cu powder instead of CuH z , the preparation experiment was carried out, and the materials obtained were all able to obtain complete diamagnetism at 300 °C.
实施例 9  Example 9
组分及配比：  Composition and ratio:
摩尔比为 2: 1： 1.5: 0.25: 0.25的 CuHz、 NaC BaCl2、 Ca0、 Ca (OH) 2 制备方法： 同实施例 7, 其中的加热时间： ①、 30分钟， 4故磁测量； 再 加热把加热时间延长到 45分钟， 有 0析出， 磁测量磁针斥幅减小； ②、 加 热时间延长到 1 小时， 磁测量， 制备材料无完全抗磁性。 原因： 因为制备过 程中不能保证制备的密闭隔绝空气条件，导致 Ca (OH) 2脱水失去有效成分造成 的。 The molar ratio is 2: 1: 1.5: 0.25: 0.25 CuH z , NaC BaCl 2 , Ca0, Ca (OH) 2 preparation method: same as the embodiment 7, wherein the heating time: 1, 30 minutes, 4 magnetic measurement; Reheating extended the heating time to 45 minutes, 0 precipitation, magnetic measurement magnetic needle repulsion reduced; 2, heating time extended to 1 hour, magnetic measurement, the preparation material is not completely diamagnetic. Reason: Because the prepared airtight conditions are not guaranteed during the preparation process, Ca(OH) 2 dehydration loses the active ingredient.
制备材料的磁测量及电阻测量  Magnetic measurement and resistance measurement of prepared materials
上述加热时间分别为 30分钟或 1小时的磁测量结果及电阻测量结果见表 1中的①或②。  The magnetic measurement results and the resistance measurement results of the above heating time of 30 minutes or 1 hour, respectively, are shown in Table 1 or 1 or 2.
实施例 10  Example 10
组分及配比：  Composition and ratio:
摩尔比为 2: 1： 1.5: 0.33: 0.17的 CuHz、 CK BaCl2、 Ba0、 Ca (OH) 2 制备方法： 同实施例 9 制备材料的磁测量及电阻测量， 结果见表 1。 The molar ratio is 2: 1: 1.5: 0.33: 0.17 CuH z , CK BaCl 2 , Ba0, Ca (OH) 2 preparation method: same as in the embodiment 9 The magnetic measurement and resistance measurement of the prepared materials are shown in Table 1.
实施例 11  Example 11
把实施例 9组分及配比中的 01 用 Cu粉代替、 Ca (0H) 2用无水 Ba (OH) 2 代替， 制得材料的完全抗磁性效果， 与实施例 9基本相同。 The composition of Example 9 and the composition of 01 were replaced with Cu powder, and Ca(0H) 2 was replaced with anhydrous Ba(OH) 2 to obtain a complete diamagnetic effect of the material, which was substantially the same as in Example 9.
以上实施例材料放家用冰箱， 冷却到 - 18 Ό- - 24 Ό , 进行磁测量， 均无 完全抗磁性。  The materials of the above examples were placed in a domestic refrigerator and cooled to - 18 Ό - - 24 Ό for magnetic measurement, and were not completely diamagnetic.
本发明制备材料的磁测量方法如下：  The magnetic measurement method of the material prepared by the invention is as follows:
测量仪器： 悬置磁针、 水银温度计（测量范围 - 4°C~300°C ) , 上述测量 装置的磁针是置于相对密闭留孔的箱体内 , 并要求周围五米内除地磁外无其 它磁场的干尤。  Measuring instrument: Suspended magnetic needle, mercury thermometer (measuring range - 4 ° C ~ 300 ° C), the magnetic needle of the above measuring device is placed in the relatively closed hole in the box, and requires no magnetic field except the geomagnetism within five meters Dry especially.
测量方法： 材料经高温制备， 停止加热时， 随即在热状态下将制备材料 分别靠近静止磁针两端的侧面， 测量磁针是否被排斥、 排斥斥幅及排斥与温 度和时间的关系。 磁针的磁场强度 H=129高斯。 测量时排出了环境因素并否 定了材料携磁、 携电流等因素对磁针的作用。 由测量认定对磁针的排斥是材 料本身的完全抗磁引起的， 也即材料的超导电性引起的。  Measurement method: When the material is prepared at high temperature and the heating is stopped, the prepared materials are placed close to the sides of the stationary magnetic needles in a hot state, and the relationship between the magnetic needles being rejected, the rejection of the repulsion and the repulsion and the temperature and time are measured. The magnetic field strength of the magnetic needle is H=129 Gauss. Environmental factors were removed during the measurement and the effects of magnetic loading and current carrying on the magnetic needle were rejected. It is determined by measurement that the repulsion of the magnetic needle is caused by the complete diamagnetism of the material itself, that is, the superconductivity of the material.
^"比例 1  ^"Proportion 1
舍去实施例 2组分中的 0. 7NaCl , 制备方法及磁测量方法同于实施例 2, 制备材料无完全抗磁性， 电阻测量见表 1。  0.77 NaCl was used in the composition of Example 2, and the preparation method and magnetic measurement method were the same as those in Example 2. The preparation material was not completely diamagnetic, and the resistance measurement was shown in Table 1.
对比例 2  Comparative example 2
用 0. 7LiCl代替实施例 2组分中的 0. 7NaCl ,制备方法及磁测量方法同于 实施例 2 , 制备材料无完全抗磁性， Cu部分被氧化， 电阻测量见表 1。 对比例 3 0.7LiCl was used instead of 0.77 NaCl in the composition of Example 2, and the preparation method and magnetic measurement method were the same as those in Example 2. The preparation material was not completely diamagnetic, and the Cu portion was oxidized. The resistance measurement is shown in Table 1. Comparative example 3
把实施例 9组分中的 CaO用 [0. 5La203]代替， 制得材料无完全抗磁性， 制 得材料呈粉末状， 电阻 R→ oo。 此实验的目的是验证氧化镧稀土成分的作用。 The CaO in the component of Example 9 was replaced with [0. 5La 2 0 3 ], and the obtained material was not completely diamagnetic, and the obtained material was in the form of powder, and the resistance was R→oo. The purpose of this experiment was to verify the effect of the cerium oxide rare earth component.
对比例 4  Comparative example 4
组分： Cu粉（200 目 ·分析纯）或 CuH2 ( z为 0. 1 ) , BaCl2 · 2H20 (化学 纯） ， KC1 (分析纯) Component: Cu powder (200 mesh · analytical grade) or CuH 2 (z is 0.1), BaCl 2 · 2H 2 0 (chemically pure), KC1 (analytical grade)
制备方法及制备材料的磁测量及电阻测量  Preparation method and magnetic measurement and resistance measurement of preparation materials
三种试剂按 2: 2 : 1称取， BaCl2 · 2H20预先加热 5分钟， 除去其结晶水, 后， 三种试剂研粉混匀， 装管， 管口加塞， 在 650 °C - 700 °C下， 加热， 当加热 4分钟后， 管内试剂体积缩小， 结块， 继续加热 7分钟， 制得组织结构紧密、 硬度较大的红色块状材料。 磁测量， 制得材料无完全抗磁性。 电阻测量， 同 实施例 7。 The three reagents were weighed at 2:2:1, BaCl 2 · 2H 2 0 was preheated for 5 minutes, and the crystal water was removed. After that, the three reagents were mixed with powder, and the tube was filled with a plug at 650 ° C. Heated at 700 °C, after heating for 4 minutes, the volume of the reagent in the tube was reduced, agglomerated, and heating was continued for 7 minutes to obtain a red bulk material with tight structure and high hardness. Magnetic measurement, the material obtained is not completely diamagnetic. Resistance measurement, same as in Example 7.
对比例 5  Comparative example 5
舍去对比例 4组分中的 KC1试剂， 保留 BaCl2 、 Cu粉两种试剂并两组分 配比不变， 工艺不变， 加热温度不变， 加热 10至 20分钟， 制得材料呈灰白 色粉末状（不结块并 Cu粉被部分氧化） , 无完全抗磁性， 电阻 R→∞。 The KC1 reagent in the component of the comparative example 4 was discarded, and the two reagents of BaCl 2 and Cu powder were retained, and the distribution ratios of the two groups were unchanged. The process was unchanged, the heating temperature was constant, and the heating was carried out for 10 to 20 minutes to obtain an off-white powder. Shape (not agglomerated and Cu powder is partially oxidized), no complete diamagnetism, resistance R → ∞.
分析, ①比较对比例 4或 5两个实验制得材料的外观结构， 分析得出， KC1成分对制得材料形成固体凝聚态起着重要作用。②对比例 4制得材料无完 全抗磁性， 而实施例 6至 11制得材料则具有完全抗磁性， 对比其组分构成， 显然， BaO, Ba (0H) 2或 CaO, Ca (OH) 2成分对制得材料的完全抗磁性， 是不可 缺少的必要组分。 ③根据实施例 1至 11的组分及配比， 参考现有的铜系氧化 物超导材料的空间结构， 分析， 本发明材料具有共同的配位、 分层空间结构。Analysis, 1 compare the appearance structure of the two experimentally prepared materials in Comparative Example 4 or 5. It is concluded that the KC1 component plays an important role in the formation of a solid condensed state of the material. 2 The materials prepared in Comparative Example 4 were not completely diamagnetic, and the materials prepared in Examples 6 to 11 were completely diamagnetic, compared with their composition, apparently, BaO, Ba (0H) 2 or CaO, Ca (OH) 2 The composition is an indispensable component for the complete diamagnetism of the resulting material. 3 According to the components and ratios of Examples 1 to 11, reference to existing copper oxidation The spatial structure of the superconducting material, analysis, the material of the invention has a common coordination and stratified space structure.
1、 制备实臉说明 1, preparation of real face description
说明一、 完全抗磁性缺陷及改进方案  Description 1. Complete diamagnetic defects and improvement schemes
以上实施例是为实施本发明做的制备实验，制备实验解决了 300 °C下的完 全抗磁并超导电问题， 并提供了制备这种材料的方法。 从表 1 所列数据看， 以上实施例中： 第一完全抗磁的时间不是非常持久； 第二完全抗磁性存在下 限温度即室温。 其原因是： 实施例中的 CuHJ々 H含量不足（z为 0. 1 ) , 在高 温下分解成 Cu和 H; 制备工艺没有实现绝对的密闭， 引起有效成分的 H损失 造成的。 这种情况下， 制备材料均存在的 Cu (或 H ) — H+p价态不平衡关系， 则主要表现为 Cu— H+p价态不平衡关系。 当温度低于下限温度时， H+p与 Cu的 热趋近或者称 H+p与 Cu的共有化热吸附在短时间内会逐渐消失（参考： ① Cu 脱 H作用的温度条件 ·有机化学实验， ②重复加热， 制备材料又恢复完全抗 磁性） ， 这将导致 Cu— H+p价态不平衡体系被破坏。 破坏后， H+p相对于 Cu则 变成独立的正电中心， 而失去空穴导电性、 并不再存在电子与空穴运动地相 互关联， 使材料失去超导电性， 同时完全抗磁性也随之消失。 因此根本原因 是 CuHz试剂的 H损失造成的。 The above examples are preparation experiments for carrying out the invention. The preparation experiments solve the problem of complete diamagnetic and superconductivity at 300 ° C and provide a method for preparing such materials. From the data listed in Table 1, in the above examples: the time of the first complete diamagnetic is not very long; the second complete diamagnet has a lower limit temperature, that is, room temperature. The reason is as follows: The content of CuHJ々H in the examples is insufficient (z is 0.1), and is decomposed into Cu and H at a high temperature; the preparation process does not achieve absolute sealing, which causes the loss of H of the active ingredient. In this case, the unequal relationship of Cu (or H)-H +p valence in the prepared materials is mainly represented by the unbalanced relationship of Cu-H +p valence states. When the temperature is lower than the lower limit temperature, the heat of H +p and Cu approaches or the heat of adsorption of H +p and Cu will disappear gradually in a short time (Reference: 1 Temperature conditions of Cu de-H action · Organic chemistry In the experiment, 2 repeated heating, the material was prepared to restore complete diamagnetism), which would cause the Cu-H +p valence unbalanced system to be destroyed. After the destruction, H +p becomes an independent positive electric center with respect to Cu, and loses hole conductivity, and there is no longer any interaction between electrons and holes, which causes the material to lose superconductivity and is completely diamagnetic. It disappears. Therefore, the root cause is the loss of H of the CuH z reagent.
因此可以对实施例中的技术方案进行改进：第一完善密闭工艺，保证 CuHz 分解反应的可逆； 第二增大 CuHz中的 z达到 0. 4-0. 7。从而实现 H— H+P价态不 平衡关系 （此关系不受温度影响也与时间无关） ， 即能消除上述的两个缺陷。 为了进一步提高制备材料中所含金属氢化物的热稳定性， 可用 CuM5Pd。.55Hz代 替 CuHz, 进行材料制备， 其中的 Pd (钯）对氢有良好的吸附性。 说明二、 制备实验的密闭条件 A加热时间 Thus embodiments may be made to improve the technical solution: a first confined sound process to ensure that the reversible decomposition reaction CuH z; a second increase in the z-z CuH reaches 0. 4-07. Thus, the H-H + P valence imbalance relationship (this relationship is not affected by temperature and time-independent) is achieved, that is, the above two defects can be eliminated. In order to further improve the thermal stability of the metal hydride contained in the preparation material, Cu M5 Pd can be used. 55 Hz instead of CuH z , material preparation, in which Pd (palladium) has good adsorption to hydrogen. Description 2. Sealing conditions for preparation experiments A heating time
由于试剂 CuHz 、 Zn (0H) Cl及 Sn (0H) Cl 的热稳定性差， 高温（400°C)易 分解,'并具有可逆反应 （密闭情况下）：  Due to the poor thermal stability of the reagents CuHz, Zn(0H)Cl and Sn(0H)Cl, the high temperature (400 °C) is easily decomposed, and has a reversible reaction (in the case of airtightness):
CuH^=±Cu + [H]  CuH^=±Cu + [H]
Zn (OH) Cl^=^ZnO + HCl  Zn (OH) Cl^=^ZnO + HCl
试剂 Ba (OH) 2及 Ca (OH) 2 , 55(TC时开始分解失 H20 (单独、 敞口加热情 况下） ， 并具有可逆反应 （密闭情况下）'：  Reagents Ba (OH) 2 and Ca (OH) 2 , 55 (when TC begins to decompose and lose H20 (individual, open heat), and has a reversible reaction (in the case of airtightness)':
Ba (OH)2 ^= BaO + H20 Ba (OH) 2 ^= BaO + H 2 0
Ca (0H)2 ^=^Ca0 + 0 Ca (0H) 2 ^=^Ca0 + 0
此处， Zn(OH)Cl为碱式氯牝锌。 因此， 必须保证制备时的密闭条件。 在 保证密闭条件下， 延长加热时间， 则能够使成粉的扩散及内部组织结构更均 匀， 从而获得更好的完全抗磁 效果。 麥考现有的铜系氧化物超导材料的制 备， 及本发明材料的主要成分是氯化物以及根据以上的制备实驗， 本 明材 料的制备在保证绝对密闭、 隔绝空气条件下， 力 时间应延长为 4-5 小时。 由于条件限制， 实施例的制备实验 ^舞保证上述妁工艺条件， 延长加 ^日 间， 实验过程中则由于出现分解反应， ； t 或管； ¾裂， 失去有效成分， 使已检测 到的完全抗磁性消失， 所以本发明 施例实验的力 时间是 2H5分钟， 由 于实-验加热时间短， 内部成份（尤其是 Cu ) i圹 不均匀  Here, Zn(OH)Cl is basic chloranil. Therefore, it is necessary to ensure the sealing conditions at the time of preparation. When the heating time is extended under the condition of ensuring the sealing, the diffusion of the powder and the internal structure are more uniform, so that a better complete diamagnetic effect can be obtained. The preparation of the existing copper-based oxide superconducting material of McCaw, and the main component of the material of the present invention is chloride and according to the above preparation experiment, the preparation of the material is guaranteed to be absolutely sealed and insulated under air conditions. Extended for 4-5 hours. Due to the limitation of the conditions, the preparation experiment of the example ensures that the above-mentioned enthalpy process conditions are extended, and during the experiment, the decomposition reaction occurs due to the decomposition reaction, t or tube; 3⁄4 crack, the active ingredient is lost, and the detected completeness is completely detected. The diamagnetism disappears, so the force time of the experiment of the present invention is 2H5 minutes, and the internal component (especially Cu) i圹 is uneven due to the short heating time of the actual test.
说明一、 说明二所述的改进方橐及工艺的密^条件' 就现有技术来 能够并较易解决的， 因此， 根 以上槔供的^法， 能眵铡出工 上使用^ f¾ 于常 ¾的超导榆电材料。  Note 1. The improved method and the process of the process described in the second description can be easily solved by the prior art. Therefore, the method of the above-mentioned method can be used to generate the ^f3⁄4 Often 3⁄4 superconducting neodymium materials.
本发明另一个重要意 于， #为¾明 寻 理问¾提供重要的 验依 ^ 制备材料的磁测量 制备材料 的电阻测 磁针开始 磁针开始 磁针端 磁针被 Another important implication of the present invention is that #为4⁄4明寻问3⁄4 provides an important test ^ The magnetic measurement of the prepared material is prepared by measuring the magnetic resistance of the magnetic needle, starting the magnetic needle, starting the magnetic needle, and the magnetic needle is
量（正常 实施例 被排斥时 被排斥时 部最大 排斥的 材料显示完全抗  The amount of material that is most repelled when rejected in the normal embodiment is completely resistant.
态）（欧姆 间 （分钟） 的 温 度 斥 幅 时间（分 磁的温度区间  State) (temperature between ohms (minutes) replies time (temperature interval of magnetic separation)
计 X 1R X 1R
(。c) (cm) 钟） (.c) (cm) clock)
档） 实施例 1 300 1. 0 12 300'C-室温 指零 实施例 2 1 300 1. 0 10 30(TC-室温 指零 实 施 ① 0 300 1. 5 12 300°C-室温  Example 1 300 1. 0 12 300'C-room temperature means zero Example 2 1 300 1. 0 10 30 (TC-room temperature means zero implementation 1 0 300 1. 5 12 300 ° C - room temperature
指零 例 3 ② X X X X 无完全抗磁性  Refers to zero Example 3 2 X X X X No complete diamagnetic
实施例 4 1. 5 229 1. 2 8 229 °C -室温 ？曰令 实 施 ① 1. 5 236 1. 5 10 236 Ό-室温 Example 4 1. 5 229 1. 2 8 229 ° C - room temperature ?曰令 Implementation 1 1. 5 236 1. 5 10 236 Ό-Room
指零 例 5 ② X X X X 无完全抗磁性  Refers to zero Example 5 2 X X X X No complete diamagnetic
实 施 ① 80 0. 6 3 Implementation 1 80 0. 6 3
指零 例 6 ② 2 256 0. 8 6 256 °C-45 °C  Refers to the zero case 6 2 2 256 0. 8 6 256 °C-45 °C
实施例 7 2 250 1. 0 16 250°C-室温 指零 实施例 8 300 1. 0 20 300。C-室温 曰令 实 施 ① 0 300 1. 2 20 30(TC-室温 Example 7 2 250 1. 0 16 250 ° C - room temperature Zero reference Example 8 300 1. 0 20 300. C-Room Temperature Order Implementation 1 0 300 1. 2 20 30 (TC-Room
指零 例 9 ② X X X X 无完全抗磁性  Refer to zero Example 9 2 X X X X No complete diamagnetic
实 施 ① 2 247 0. 8 10 247 °C -室温 Implementation 1 2 247 0. 8 10 247 °C - room temperature
指零 例 10 ② X X X X 无完全抗磁性  Refer to zero Example 10 2 X X X X No complete diamagnetic
实 施 ① 0 300 1. 0 20 300'C-室温 士 Implementation 1 0 300 1. 0 20 300'C-Room
曰令 例 11 ② X X X X 无完全抗磁性  曰令 Example 11 2 X X X X No complete diamagnetic
只于比例 1 无完全抗磁性 R > 500 对比例 2 无完全抗磁性 R→∞ 对比例 3 无完全抗磁性 -→ oo 对比例 4 无完全抗磁性 孑日令 对比例 5 无完全抗磁性 R→∞ 表 1 中 "磁针开始被排斥时间" 指： 停止加热， 随即将材料在热状态下 靠近磁针后多长时间磁针开始被排斥。 Only in proportion 1 No complete diamagnetic R > 500 Comparative 2 No complete diamagnetic R → ∞ Comparative 3 No complete diamagnetic - → oo Comparative example 4 No complete diamagnet 孑 Japanese comparative example 5 No complete diamagnetic R → ∞ In Table 1, "the magnetic needle starts to be repelled" means: Stop heating, and how long after the material is in the hot state close to the magnetic needle, the magnetic needle begins to be repelled.
因此本发明实现了临界温度 Te高于常温的超导电材料及其制备方法。 最后应说明的是： 以上实施例仅用以说明本发明的技术方案而非对其进 行限制， 尽管参照较佳实施例对本发明进行了详细的说明， 本领域的普通技 术人员应当理解： 其依然可以对本发明的技术方案进行修改或者等同替换， 而这些修改或者等同替换亦不能使修改后的技术方案脱离本发明技术方案的 精神和范围。 Therefore, the present invention realizes a superconducting material having a critical temperature T e higher than a normal temperature and a preparation method thereof. It should be noted that the above embodiments are only intended to illustrate the technical solutions of the present invention and are not to be construed as limiting the embodiments of the present invention. The technical solutions of the present invention may be modified or equivalently substituted, and the modified technical solutions may not deviate from the spirit and scope of the technical solutions of the present invention.

Claims

权利 要求 Rights request
1、 一种超导电材料， 其特征在于该超导电材料的必要成分是： Cu、 K/Na、 Ba、 01、 0和-011。.  A superconducting material characterized in that the essential components of the superconducting material are: Cu, K/Na, Ba, 01, 0 and -011. .
2、 根据权利要求 1所述的超导电材料， 其特征在于该超导电材料的必要 成分的组合为： CuAKBBacClD0B(-0H)F CuANaBBacClD0B (- 0H)F, 其中 2. The superconducting material according to claim 1, wherein the combination of essential components of the superconducting material is: Cu A K B Ba c Cl D 0 B (-0H) F Cu A Na B Ba c Cl D 0 B (- 0H) F , where
A=l或 Q.45或 2或 0.9  A=l or Q.45 or 2 or 0.9
B=l  B=l
C=l或 2或 1.5  C=l or 2 or 1.5
D=4.1+0.25x或 4  D=4.1+0.25x or 4
Ε=0· 25(1- X)或 0.25(l+y)  Ε=0· 25(1- X) or 0.25(l+y)
F=0.25(l+x)或 0.5(l-y)  F=0.25(l+x) or 0.5(l-y)
0<x<0.4 , 0<y<0.320 0<x<0.4, 0<y<0.32 0
3、 根据权利要求 1或 2所述的超导电材料， 其特征在于所述必要成分是 来自 ： CuHz/Cu。.45Pd。.55Hz、 KCl/NaCl 、 BaCl2、 SnCl2/ZnCl2 、 SnO/ZnO 和 Sn(0H)Cl/Zn(0H)Cl。 3. A superconducting material according to claim 1 or 2, characterized in that the essential component is derived from: CuH z /Cu. 45 Pd. 55 H z , KCl/NaCl , BaCl 2 , SnCl 2 /ZnCl 2 , SnO/ZnO and Sn(0H)Cl/Zn(0H)Cl.
4、 根据权利要求 1或 2所述的超导电材料， 其特征在于所述必要成分是 来自： CuHz/Cu。."Pd。.55Hz、 KCl/NaCK BaCl2、 BaO/CaO和 Ba (OH) 2/Ca (OH) 2。 4. A superconducting material according to claim 1 or 2, characterized in that the essential component is derived from: CuH z /Cu. "Pd.. 55 H z , KCl/NaCK BaCl 2 , BaO/CaO and Ba (OH) 2 /Ca (OH) 2 .
5、一种权利要求 1或 1所述的超导电材料的制备方法，其特征在于包括： 将摩尔比为 1: 1： 1： 0.4: 0.25(1.2 -χ): 0.25 (1.2 + x)的 CuHz、 KCl/NaCl、 BaCl2、 SnCl2、 SnO和 Sn (OH) CI ,研粉混匀，压实密闭隔绝空气， 在 550Ό-650 °C的温度下， 加热 4-5 小时， 然后密闭隔绝空气状态下冷却至室温， 密封保 存， 制得组成由化学式 A method of producing a superconducting material according to claim 1 or 1, which comprises: a molar ratio of 1: 1: 1: 0.4: 0.25 (1.2 - χ): 0.25 (1.2 + x) CuH z , KCl/NaCl, BaCl 2 , SnCl 2 , SnO and Sn (OH) CI, mix with powder, compact and seal the air, heat at 550Ό-650 °C for 4-5 hours, then seal Cooled to room temperature under air condition, sealed Chemical composition
KBaSnCuHo.3+0.2sx+z0o. 1.1+0. is或 aBaSnCuHo.3+0.25x+z00.6C 14.1+o.25x所示的超导电材 料， 其中， 0<x<0.4 ， 0<z<0.7。 KBaSnCuHo.3+0.2sx+ z 0o. 1.1+0. is or aBaSnCuHo. 3+0 . 25x+z 0 0 . 6 C 1 4 . 1+ o. 25x superconducting material, where 0<x< 0.4, 0<z<0.7.
6、 根据权利要求 5所述的超导电材料的制备方法， 其特征在于所述超导 电材料显示完全抗磁时的上限温度并超导临界温度为 509K,当 z值为 0.4-0.7 时， 显示完全抗磁时的下限温度为 οκ。  6. The method of preparing a superconducting material according to claim 5, wherein the superconducting material exhibits an upper limit temperature at a time of complete diamagnetic resistance and a superconducting critical temperature of 509 K, and when the z value is 0.4-0.7, the display The lower limit temperature at the time of complete diamagnetic resistance is οκ.
7、一种权利要求 1或 2所述的超导电材料的制备方法，其特征在于包括： 将摩尔比为 1： 1： 1： 0.4: 0.25 (1.2 - X) : 0.25 (1.2 + χ)的 CuHz、 KCl/NaCl、A method of producing a superconducting material according to claim 1 or 2, which comprises: a molar ratio of 1: 1: 1: 0.4: 0.25 (1.2 - X): 0.25 (1.2 + χ) CuH z , KCl/NaCl,
BaCl2、 ZnCl2、 ZnO和 Zn (OH) CI ,研粉混匀， 压实密闭隔绝空气， 在 550°C- 650 °C的温度下， 加热 4-5 小时， 然后密闭隔绝空气状态下冷却至室温， 密封保 存， 制得组成由化学式BaCl 2 , ZnCl 2 , ZnO and Zn (OH) CI, mixed with powder, compacted and sealed air, heated at 550 ° C - 650 ° C for 4-5 hours, then cooled in airtight state By room temperature, sealed and preserved, the composition is made up of chemical formula
BaZnCuHo.3+。.25x+zO。.6C 14.1+0.25x或 aBaZnCuHo.3+。.25x+z0。.6C 14.1+。.25x所示的超导电材 料， 其中， 0<x 0.4， 0<z<0.7。 BaZnCuHo. 3+ . . 25x+z O. 6 C 1 4 . 1+0 . 25x or aBaZnCuHo. 3+ . . 25x+z 0. . 6 C 1 4 . 1+ . . Superconducting material shown in 25x , where 0<x 0.4, 0<z<0.7.
8、 根据权利要求 7所述的超导电材料的制备方法， 其特征在于所述超导 电材料， 显示完全抗磁时的上限温度并超导临界温度为 573K, 当 z 值为 8. The method of preparing a superconducting material according to claim 7, wherein said superconducting electrically conductive material exhibits an upper limit temperature at full diamagnetic resistance and a superconducting critical temperature of 573 K, when the z value is
0.4-0.7时， 显示完全抗磁时的下限温度为 0K。 At 0.4-0.7, the lower limit temperature at full diamagnetic is 0K.
9、一种权利要求 1或 2所述的超导电材料的制备方法，其特征在于包括： 将摩尔比为 2： 1： 1.5: 0.25(l+y): 0.25 (1— y)的 CuHz、 Cl/NaCK BaCl2、A method of producing a superconducting material according to claim 1 or 2, which comprises: CuH z having a molar ratio of 2: 1: 1.5: 0.25 (l + y): 0.25 (1 - y) , Cl/NaCK BaCl 2 ,
BaO和 Ba(0H)2,研粉混匀， 压实密闭隔绝空气， 在 650°C- 700°C的温度下， 加 热 4-5 小时， 然后密闭隔绝空气状态下冷却至室温， 密封保存， 制得组成由 化学式 Ba2CU2Ho.S(l-y)+2z00.75-0.25yCl4或 NaBa2CU2H0.5 (1 - y)+2Z00.75 - 0.25yC 14所示的超导电材 料， 其中， 0<y 0.32, 0<z< 0.7。 BaO and Ba(0H) 2 , mix the powder, compact and seal the air, heat at 650 ° C - 700 ° C for 4-5 hours, then cool to room temperature in a sealed air condition, sealed and stored. Chemical composition Ba 2 CU 2 Ho.S(ly) + 2z0 0 .75-0.25yCl4 or NaBa 2 CU 2 H 0 .5 (1 - y) + 2 Z 0 0 .75 - 0.25yC 14 superconducting material, Where 0 < y 0.32, 0 < z < 0.7.
10、 根据权利要求 9 所述的超导电材料的制备方法， 其特征在于所述超 导电材料， 显示完全抗磁时的上限温度并超导临界温度 为 529K, 当 z值为 0.4-0.7时， 显示完全抗磁时的下限温度为 0K。  10. The method of preparing a superconducting material according to claim 9, wherein the superconducting material exhibits an upper limit temperature at a time of complete diamagnetic resistance and a superconducting critical temperature of 529 K, and when the z value is 0.4 to 0.7, The lower limit temperature when the full diamagnetic is displayed is 0K.
11、 一种权利要求 1或 1所述的超导电材料的制备方法， 其特征在于包 括：  A method of producing a superconducting material according to claim 1 or 1, which is characterized by comprising:
将摩尔比为 2: 1： 1.5: 0.25(l+y): 0.25 (1— y)的 CuHz、 Cl/NaC BaCl2, CaO和 Ca(0H)2, 研粉混匀， 压实密闭隔绝空气， 在 650°C- 700°C的温度下， 加热 4-5 小时， 然后密闭隔绝空气状态下冷却至室温， 密封保存， 制得组成 由化学式The molar ratio is 2: 1: 1.5: 0.25 (l + y): 0.25 (1 - y) of CuH z , Cl / NaC BaCl 2 , CaO and Ca (0H) 2 , powder mixing, compaction and sealing Air, heated at 650 ° C - 700 ° C for 4-5 hours, then cooled to room temperature in a sealed air atmosphere, sealed and stored, the composition is made up of chemical formula
Bai.5Ca。.5Cu2H0.5 a - y)+2z00.75 - o.2syC 14或 NaBai.5Ca0.5Cu2H0. s (1 - y)+2Z0。.75 - 0.2syC 14所示的 超导电材料， 其中， 0<y<0.32 , 0<ζ<0.7 。 Bai. 5 Ca. 5 Cu 2 H 0 . 5 a - y ) +2z 0 0 .75 - o.2s y C 1 4 or NaBai. 5 Ca 0 . 5 Cu 2 H 0 . s (1 - y )+2 Z 0 . 75 - 0 . 2 s y C 1 4 is a superconducting material in which 0 < y < 0.32 and 0 < ζ < 0.7.
12、 根据权利要求 11所述的超导电材料的制备方法， 其特征在于所述超 导电材料， 显示完全抗磁时的上限温度并超导临界温度 为 573Κ, 当 ζ值为 The method for preparing a superconducting material according to claim 11, wherein the superconducting material exhibits an upper limit temperature at a time of complete diamagnetic resistance and a superconducting critical temperature of 573 Κ, when the enthalpy value is
0.4-0.7时， 显示完全抗磁时的下限温度为 0Κ。 At 0.4-0.7, the lower limit temperature at full diamagnetic is 0 Κ.
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