CN113354417A - Preparation method for in-situ generated graphene doped magnesium diboride block - Google Patents
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Abstract
The invention discloses a preparation method for in-situ generation of a graphene-doped magnesium diboride bulk material, which comprises the following steps: firstly, mixing melamine or carbon nitride with magnesium powder and carrying out ball milling to obtain a mixture containing graphene and magnesium nitride; secondly, introducing argon into the ball milling tank, exhausting, and heating the mixture to obtain a graphene mixture attached with magnesium nitride; and thirdly, mixing and grinding the graphene mixture attached with the magnesium nitride with magnesium powder and boron powder, and then briquetting and sintering to obtain the graphene-doped magnesium diboride block material. According to the invention, through mixing and ball-milling melamine or carbon nitride and magnesium powder, graphene is generated in situ and magnesium nitride particles are attached to the graphene, the graphene is promoted to enter a magnesium diboride lattice to realize effective doping while magnesium diboride is generated through subsequent sintering, and active magnesium is provided through decomposition of magnesium nitride, so that low-temperature preparation is realized, the superconducting performance of the graphene-doped magnesium diboride bulk material is enhanced, and the problem of superconducting performance reduction caused by high-temperature heat treatment doping is solved.
Description
Technical Field
The invention belongs to the technical field of high-temperature superconducting materials, and particularly relates to a preparation method for in-situ generation of a graphene-doped magnesium diboride block material.
Background
MgB2The grain boundary of the high-temperature superconductor can bear higher current, the weak connection problem of the high-temperature superconductor does not exist,while MgB2The coherence length of the magnetic field is very large, so that a magnetic flux pinning center is more easily introduced, and the critical current density under a high field is improved. self-MgB2Superconductivity discovery, doping has been the focus of research, and researchers have doped a variety of materials, including elemental metals, non-metals, multi-compounds, organics, co-doping of two or more materials, and the like.
In order to improve the performance of magnesium diboride superconductors under a magnetic field, different elements are generally introduced to be used as magnetic flux pinning centers. For example, by introducing a single element of C, Si, Al, Cu, Li, Na, Zn, etc., or by introducing a carbon compound of Al4C3、SiC、TiC、ZrC、NbC、Mo2C and the like are used as dopants to improve the superconducting performance of the magnesium diboride bulk material or the wire. Recent research results show that the graphene can effectively improve MgB2Critical current density of (d); however, in the doping process, the graphene has a large specific surface area and is easy to adsorb oxygen, so that the magnesium diboride has impurities such as magnesium oxide and the like to destroy the grain connectivity, and meanwhile, the graphene is difficult to enter a magnesium diboride crystal lattice in a low-temperature reaction, so that the irreversible field and the superconducting performance of the magnesium diboride are reduced. In the traditional method, the activity of a doping source is generally low, and effective doping can be introduced only by needing higher heat treatment temperature, so that magnesium diboride grains grow and the grain connectivity is reduced.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing graphene doped magnesium diboride bulk material by in-situ generation, aiming at the defects of the prior art. According to the method, melamine or carbon nitride and magnesium powder are mixed and ball-milled, and magnesium nitride particles are attached to graphene while graphene is generated in situ, so that the graphene is promoted to enter a magnesium diboride lattice to realize effective doping while magnesium diboride is generated in a subsequent sintering reaction, and the decomposition of magnesium nitride provides active magnesium, so that low-temperature preparation is realized, the superconducting performance of the graphene-doped magnesium diboride bulk is enhanced, and the problem of superconducting performance reduction caused by high-temperature heat treatment doping is solved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a preparation method for in-situ generation of a graphene-doped magnesium diboride bulk material is characterized by comprising the following steps:
step one, mixing melamine or carbon nitride with magnesium powder, then placing the mixture in a ball milling tank, vacuumizing the ball milling tank, and carrying out ball milling treatment to obtain a mixture containing graphene and magnesium nitride; the mass ratio of the melamine or the carbon nitride to the magnesium powder is 1: 0.5-5;
step two, introducing argon into the ball milling tank subjected to ball milling treatment in the step one, exhausting until impurity gases are removed, and then heating the mixture containing graphene and magnesium nitride to obtain a graphene mixture attached with magnesium nitride;
and step three, placing the graphene mixture attached with the magnesium nitride obtained in the step two in a glove box, mixing and grinding the graphene mixture with magnesium powder and boron powder, and then sequentially briquetting and sintering to obtain the graphene-doped magnesium diboride block.
The invention firstly mixes the melamine or carbon nitride with the magnesium powder, and then ball-milling is carried out under the vacuum condition to generate heat to enable the mixture to react, namely C3N3(NH2)3+6Mg＝2Mg3N2+3C+2NH3Or C3N4+6Mg＝2Mg3N2+3C, attaching small-sized magnesium nitride particles to a graphene sheet layer, preparing a mixture containing graphene and magnesium nitride in situ, reducing the size of graphene, improving the reaction activity of graphene, simultaneously preventing the generated graphene from adsorbing oxygen by controlling vacuum conditions, avoiding introducing impurities, and further avoiding generating magnesium oxide impurity phases to damage the connectivity of crystal grains; then introducing argon gas into the ball milling tank after ball milling treatment, exhausting gas, removing impurity gases (mainly ammonia gas generated by the reaction of melamine and magnesium powder) in the ball milling tank, further avoiding the adsorption of the graphene on the impurity gases such as oxygen, and then heating to fully remove residual impurity gases such as oxygen and ammonia gas, and avoiding introducing into the subsequent process to obtain a graphene mixture attached with magnesium nitride; then mixing and grinding the graphene mixture attached with the magnesium nitride with magnesium powder and boron powderPressing and sintering, wherein magnesium nitride attached to graphene is simultaneously used as a dopant, so that the generation of magnesium oxide is effectively inhibited, active magnesium is provided by the decomposition of the magnesium nitride in the sintering process, and the magnesium nitride and magnesium powder added later react together to generate magnesium diboride, so that the graphene attached to the dopant is promoted to simultaneously enter a magnesium diboride crystal lattice, the effective doping is realized, the doping effect is improved, the magnetic flux pinning force of the graphene doped magnesium diboride block is improved, the upper critical field of the graphene doped magnesium diboride block under a magnetic field is further improved, the superconducting performance of the graphene doped magnesium diboride block is enhanced, the low-temperature preparation is realized, and the problems of the reduction of the connectivity of magnesium diboride crystal grains and the reduction of the superconducting performance caused by the effective doping through high-temperature heat treatment are solved.
The preparation method of the graphene-doped magnesium diboride bulk material generated in situ is characterized in that the rotation speed of the ball milling treatment in the step one is 400-2000 rpm, and the time is 1-4 h. The optimized ball milling treatment process is beneficial to promoting melamine or carbon nitride to be fully mixed and reacted with magnesium powder to obtain a mixture containing graphene and magnesium nitride. More preferably, the rotation speed of the ball milling treatment is 800rpm, and the time is 4h, which is beneficial to obtaining the graphene.
The preparation method for the graphene-doped magnesium diboride bulk material generated in situ is characterized in that the heating treatment in the second step is carried out at the temperature of 100-400 ℃ for 0.5-5 h. The temperature and time of the preferred treatment promotes adequate removal of residual gases from the graphene and magnesium nitride containing mixture. More preferably, the temperature of the heat treatment is 200 ℃ and the time is 2 hours.
The preparation method of the graphene-doped magnesium diboride bulk material generated in situ is characterized by mixing and grinding magnesium powder, boron powder and graphene mixture attached with magnesium nitride according to the atomic ratio of magnesium to boron to graphene of 1:2 (0.02-0.4), then pressing into a block, then placing the block into a heat treatment furnace, and carrying out heat treatment for 1-3 h at the temperature of 600-850 ℃ under the protection of high-purity argon atmosphere to obtain the graphene-doped magnesium diboride bulk material; the mass purity of the magnesium powder and the boron powder is 99 percent, the mass purity of the high-purity argon is 99.99 percent, and the pressing pressure is 5 MPa-50 MPa.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, through mixing and ball-milling melamine or carbon nitride and magnesium powder, the magnesium nitride particles are attached to graphene while graphene is generated in situ, so that the graphene is promoted to enter a magnesium diboride lattice to realize effective doping while magnesium diboride is generated in a subsequent sintering reaction, the reaction activity of the graphene is improved, the doping effect is improved, the decomposition of magnesium nitride provides active magnesium, the low-temperature preparation is realized, the superconducting performance of the graphene-doped magnesium diboride bulk material is enhanced, and the problem of the decrease of the superconducting performance caused by the existing high-temperature heat treatment doping is solved.
2. According to the invention, through the combination of ball milling under vacuum and ball milling, argon is introduced, and air is exhausted to remove impurity gas, the phenomenon that the crystal grain connectivity is damaged by magnesium oxide generated from impure phases is avoided, the prepared magnesium nitride attached to graphene further inhibits the generation of magnesium oxide in the sintering process, the connectivity of magnesium diboride crystal grains in the graphene-doped magnesium diboride bulk material is ensured, and the superconducting performance of the graphene-doped magnesium diboride bulk material is further enhanced.
3. The magnesium nitride attached to the graphene is simultaneously used as a fluxing agent for magnesium-boron reaction, so that the melting and flowing of reaction raw materials are promoted to be uniformly mixed, the generation of cavities in magnesium diboride is reduced, the crystal grain connectivity is improved, the superconducting performance of the graphene-doped magnesium diboride bulk material is further enhanced, the density and the hardness of the graphene-doped magnesium diboride bulk material are improved, and the mechanical property of the graphene-doped magnesium diboride bulk material is improved.
4. According to the invention, a vacuum ball milling process is adopted, the size of graphene generated in situ is effectively controlled, the graphene with the thickness less than 1nm and the sheet diameter less than 50nm is obtained, compared with a common graphene product, the graphene is smaller in size and higher in activity, and the doping effect is further improved.
5. The preparation method is simple and easy to realize industrialization.
The technical solution of the present invention is further described in detail by examples below.
Detailed Description
Example 1
The embodiment comprises the following steps:
step one, mixing melamine and magnesium powder, then placing the mixture in a ball milling tank, vacuumizing the ball milling tank, and performing ball milling treatment to obtain a mixture containing graphene and magnesium nitride and ammonia gas; the mass ratio of the melamine to the magnesium powder is 1: 0.5; the rotation speed of the ball milling treatment is 400rpm, and the time is 4 h;
step two, introducing argon into the ball milling tank subjected to ball milling treatment in the step one, vacuumizing until impurity gases are removed, and then heating the mixture containing graphene and magnesium nitride to obtain a graphene mixture attached with magnesium nitride; the temperature of the heating treatment is 100 ℃, and the time is 5 hours;
placing the graphene mixture attached with the magnesium nitride obtained in the step two in a glove box, mixing and grinding the graphene mixture with magnesium powder and boron powder according to the atomic ratio of magnesium to boron to graphene of 1:2:0.02, pressing the mixture into a block, placing the block in a heat treatment furnace, and carrying out heat treatment for 3 hours at the temperature of 600 ℃ under the protection of high-purity argon atmosphere to obtain a graphene-doped magnesium diboride block material; the mass purity of the magnesium powder and the boron powder is 99%, the mass purity of the high-purity argon is 99.99%, and the pressing pressure is 5 MPa.
Through detection, when the graphene-doped magnesium diboride bulk material prepared by the embodiment is at 20K, the critical current density Jc reaches 1.2 multiplied by 106A/cm2。
Example 2
The embodiment comprises the following steps:
step one, mixing carbon nitride and magnesium powder, then placing the mixture in a ball milling tank, vacuumizing the ball milling tank, and carrying out ball milling treatment to obtain a mixture containing graphene and magnesium nitride; the mass ratio of the carbon nitride to the magnesium powder is 1: 2; the rotation speed of the ball milling treatment is 2000rpm, and the time is 1 h;
step two, introducing argon into the ball milling tank subjected to ball milling treatment in the step one, vacuumizing until impurity gases are removed, and then heating the mixture containing graphene and magnesium nitride to obtain a graphene mixture attached with magnesium nitride; the temperature of the heating treatment is 400 ℃, and the time is 0.5 h;
placing the graphene mixture attached with the magnesium nitride obtained in the step two in a glove box, mixing and grinding the graphene mixture with magnesium powder and boron powder according to the atomic ratio of magnesium to boron to graphene of 1:2:0.4, pressing the mixture into a block, placing the block in a heat treatment furnace, and carrying out heat treatment for 1h at the temperature of 850 ℃ under the protection of high-purity argon atmosphere to obtain a graphene-doped magnesium diboride block material; the mass purity of the magnesium powder and the boron powder is 99%, the mass purity of the high-purity argon is 99.99%, and the pressing pressure is 50 MPa.
Through detection, when the graphene-doped magnesium diboride bulk material prepared by the embodiment is at 20K, the critical current density Jc reaches 8.2 multiplied by 105A/cm2。
Example 3
The embodiment comprises the following steps:
step one, mixing melamine and magnesium powder, then placing the mixture in a ball milling tank, vacuumizing the ball milling tank, and performing ball milling treatment to obtain a mixture containing graphene and magnesium nitride and ammonia gas; the mass ratio of the melamine to the magnesium powder is 1: 2.5; the rotation speed of the ball milling treatment is 800rpm, and the time is 3 h;
step two, introducing argon into the ball milling tank subjected to ball milling treatment in the step one, vacuumizing until impurity gases are removed, and then heating the mixture containing graphene and magnesium nitride to obtain a graphene mixture attached with magnesium nitride; the temperature of the heating treatment is 200 ℃, and the time is 4 h;
placing the graphene mixture attached with the magnesium nitride obtained in the step two in a glove box, mixing and grinding the graphene mixture with magnesium powder and boron powder according to the atomic ratio of magnesium to boron to graphene of 1:2:0.2, pressing the mixture into a block, placing the block in a heat treatment furnace, and carrying out heat treatment for 2 hours at the temperature of 700 ℃ under the protection of high-purity argon atmosphere to obtain a graphene-doped magnesium diboride block material; the mass purity of the magnesium powder and the boron powder is 99%, the mass purity of the high-purity argon is 99.99%, and the pressing pressure is 20 MPa.
Through detection, when the graphene-doped magnesium diboride bulk material prepared by the embodiment is at 20K, the critical current density Jc reaches 1.0 multiplied by 106A/cm2。
Example 4
The embodiment comprises the following steps:
step one, mixing carbon nitride and magnesium powder, then placing the mixture in a ball milling tank, vacuumizing the ball milling tank, and carrying out ball milling treatment to obtain a mixture containing graphene and magnesium nitride; the mass ratio of the carbon nitride to the magnesium powder is 1: 4; the rotation speed of the ball milling treatment is 1500rpm, and the time is 2 h;
step two, introducing argon into the ball milling tank subjected to ball milling treatment in the step one, vacuumizing until impurity gases are removed, and then heating the mixture containing graphene and magnesium nitride to obtain a graphene mixture attached with magnesium nitride; the temperature of the heating treatment is 300 ℃, and the time is 1 h;
placing the graphene mixture attached with the magnesium nitride obtained in the step two in a glove box, mixing and grinding the graphene mixture with magnesium powder and boron powder according to the atomic ratio of magnesium to boron to graphene of 1:2:0.3, pressing the mixture into a block, placing the block in a heat treatment furnace, and carrying out heat treatment for 1.5 hours at the temperature of 800 ℃ under the protection of high-purity argon atmosphere to obtain a graphene-doped magnesium diboride block; the mass purity of the magnesium powder and the boron powder is 99%, the mass purity of the high-purity argon is 99.99%, and the pressing pressure is 40 MPa.
Through detection, when the graphene-doped magnesium diboride bulk material prepared by the embodiment is at 20K, the critical current density Jc reaches 1.3 multiplied by 106A/cm2。
Example 5
The embodiment comprises the following steps:
step one, mixing melamine and magnesium powder, then placing the mixture in a ball milling tank, vacuumizing the ball milling tank, and performing ball milling treatment to obtain a mixture containing graphene and magnesium nitride and ammonia gas; the mass ratio of the carbon nitride to the magnesium powder is 1: 5; the rotation speed of the ball milling treatment is 1000rpm, and the time is 2.5 h;
step two, introducing argon into the ball milling tank subjected to ball milling treatment in the step one, vacuumizing until impurity gases are removed, and then heating the mixture containing graphene and magnesium nitride to obtain a graphene mixture attached with magnesium nitride; the temperature of the heating treatment is 250 ℃, and the time is 3 h;
placing the graphene mixture attached with the magnesium nitride obtained in the step two in a glove box, mixing and grinding the graphene mixture with magnesium powder and boron powder according to the atomic ratio of magnesium to boron to graphene of 1:2:0.1, pressing the mixture into a block, placing the block in a heat treatment furnace, and carrying out heat treatment for 3 hours at the temperature of 650 ℃ under the protection of high-purity argon atmosphere to obtain a graphene-doped magnesium diboride block material; the mass purity of the magnesium powder and the boron powder is 99%, the mass purity of the high-purity argon is 99.99%, and the pressing pressure is 40 MPa.
Through detection, when the graphene-doped magnesium diboride bulk material prepared by the embodiment is at 20K, the critical current density Jc reaches 1.16 multiplied by 106A/cm2。
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (4)
1. A preparation method for in-situ generation of a graphene-doped magnesium diboride bulk material is characterized by comprising the following steps:
step one, mixing melamine or carbon nitride with magnesium powder, then placing the mixture in a ball milling tank, vacuumizing the ball milling tank, and carrying out ball milling treatment to obtain a mixture containing graphene and magnesium nitride; the mass ratio of the melamine or the carbon nitride to the magnesium powder is 1: 0.5-5;
step two, introducing argon into the ball milling tank subjected to ball milling treatment in the step one, exhausting until impurity gases are removed, and then heating the mixture containing graphene and magnesium nitride to obtain a graphene mixture attached with magnesium nitride;
and step three, placing the graphene mixture attached with the magnesium nitride obtained in the step two in a glove box, mixing and grinding the graphene mixture with magnesium powder and boron powder, and then sequentially briquetting and sintering to obtain the graphene-doped magnesium diboride block.
2. The preparation method of the in-situ generated graphene doped magnesium diboride bulk material according to claim 1, wherein the rotation speed of the ball milling treatment in the step one is 400rpm to 2000rpm, and the time is 1h to 4 h.
3. The preparation method of the in-situ generated graphene doped magnesium diboride bulk material according to claim 1, wherein the temperature of the heating treatment in the second step is 100-400 ℃, and the time is 0.5-5 h.
4. The preparation method of the in-situ generated graphene doped magnesium diboride block material according to claim 1, characterized in that in the third step, a mixture of magnesium powder, boron powder and graphene attached with magnesium nitride is mixed and ground according to the atomic ratio of magnesium to boron to graphene of 1:2: 0.02-0.4, then pressed into a block, and then the block is placed in a heat treatment furnace and is subjected to heat treatment for 1-3 h at the temperature of 600-850 ℃ under the protection of high-purity argon atmosphere to obtain the graphene doped magnesium diboride block material; the mass purity of the magnesium powder and the boron powder is 99 percent, the mass purity of the high-purity argon is 99.99 percent, and the pressing pressure is 5 MPa-50 MPa.
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