CN117964370A - High-purity gallium layered carbon/nitride MAX phase material and preparation method thereof - Google Patents
High-purity gallium layered carbon/nitride MAX phase material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 22
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 104
- 239000002184 metal Substances 0.000 claims abstract description 104
- 239000000843 powder Substances 0.000 claims abstract description 60
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 238000004140 cleaning Methods 0.000 claims abstract description 20
- 238000004108 freeze drying Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000012298 atmosphere Substances 0.000 claims abstract description 15
- 239000011261 inert gas Substances 0.000 claims abstract description 15
- 238000010306 acid treatment Methods 0.000 claims abstract description 10
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- 239000000203 mixture Substances 0.000 claims description 27
- 238000000498 ball milling Methods 0.000 claims description 18
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- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
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- 239000011812 mixed powder Substances 0.000 description 23
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 14
- 238000005303 weighing Methods 0.000 description 12
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 8
- 239000010936 titanium Substances 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
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- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 description 3
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
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- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- ABLLXXOPOBEPIU-UHFFFAOYSA-N niobium vanadium Chemical compound [V].[Nb] ABLLXXOPOBEPIU-UHFFFAOYSA-N 0.000 description 2
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 2
- 229910003470 tongbaite Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
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- 239000007769 metal material Substances 0.000 description 1
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
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- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- -1 tantalum molybdenum niobium vanadium titanium Chemical compound 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/5607—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
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Abstract
The invention provides a high-purity gallium layered carbon/nitride MAX phase material and a preparation method thereof; the preparation method comprises the following steps: a) Mixing metal powder M with graphite powder X/metal nitride powder MN, and performing pre-calcination treatment in an inert gas atmosphere to obtain an MX precursor; b) Soaking molten metal Ga in the MX precursor obtained in the step a), and calcining in an inert gas atmosphere to obtain MAX phase material and unreacted metal Ga; and then removing unreacted metal Ga through acid treatment, and sequentially centrifugally cleaning and freeze-drying the obtained product to obtain the high-purity gallium-based layered carbon/nitride MAX phase material. The preparation method adopts specific process steps to realize overall better interaction, so that not only the preparation purity and the size uniformity of the MAX phase material are improved, but also the structural diversity of the MAX phase material is enriched; meanwhile, the prepared high-purity MAX has important application potential in the fields of electrochemical energy storage, catalysis, protective coating or radiation protection and the like.
Description
Technical Field
The invention relates to the technical field of layered MAX ceramic materials, in particular to a high-purity gallium layered carbon/nitride MAX phase material, a preparation method and application thereof.
Background
MAX phase materials are a class of layered carbo/nitrides having a hexagonal crystal structure, collectively referred to as MAX phases. The MAX phase has a structural general formula of M n+1AXn (wherein M is generally front transition group metal, A is mainly 13-15 groups element, X is carbon or/and nitrogen, n is more than 1-3), the crystal structure is formed by alternately stacking transition metal carbonitride layers MX and A-site atomic layers, and the MAX phase has the characteristics of metal materials and ceramic materials, and has great application prospect in the application fields of electrochemical energy storage, thermoelectric materials, radiation protection, wear-resistant coatings and the like.
Typically, the MAX phase material is synthesized from a mixed powder of M, A and X calcined by a high temperature solid phase method. However, this method is relatively easy to produce impurity phases of MX or MA in the synthesis process, and cannot meet the ideal purity requirement. In addition, the MAX phase material synthesized by the method also needs subsequent grinding treatment, so that the phase structure of the MAX phase material is easy to damage, and the obtained product is extremely nonuniform in size, which brings a plurality of challenges for performance research and application.
Disclosure of Invention
In view of the above, the present invention aims to provide a high-purity gallium-based layered carbon/nitride MAX phase material and a preparation method thereof, and the preparation method provided by the present invention can realize controllable preparation of the MAX phase material, and the prepared product has extremely high phase purity and size uniformity.
The invention provides a preparation method of a high-purity gallium-based layered carbon/nitride MAX phase material, which comprises the following steps:
a) Mixing metal powder M with graphite powder X/metal nitride powder MN, and performing pre-calcination treatment in an inert gas atmosphere to obtain an MX precursor;
b) Soaking molten metal Ga in the MX precursor obtained in the step a), and calcining in an inert gas atmosphere to obtain MAX phase material and unreacted metal Ga; and then removing unreacted metal Ga through acid treatment, and sequentially centrifugally cleaning and freeze-drying the obtained product to obtain the high-purity gallium-based layered carbon/nitride MAX phase material.
Preferably, in step a) said M is selected from one or more of Ti, V, cr, zr, nb, mo, ta.
Preferably, the molar ratio of the metal powder M to the graphite powder X in step a) is 2: (0.5-2).
Preferably, the mixing in step a) is performed by ball milling; the rotation speed of the ball milling treatment is 300-500 rpm, and the time is 10-30 h.
Preferably, the temperature of the pre-calcination treatment in the step a) is 1200-1400 ℃, the heating rate is 1-10 ℃/min, and the time is 50-70 min.
Preferably, the impregnating process in step b) is specifically:
Adding molten metal Ga into the MX precursor, and grinding at 50-70 ℃ for 20-40 min to obtain an MX mixture completely wrapping Ga.
Preferably, the temperature of the calcination treatment in the step b) is 1300-1600 ℃, the heating rate is 1-10 ℃ per minute, and the time is 100-250 minutes.
Preferably, hydrochloric acid is used for the acid treatment in the step b), and the time is 300-420 min.
Preferably, in the step b), the centrifugal cleaning is carried out for 3 to 6 times by adopting deionized water and absolute ethyl alcohol; the temperature of the freeze-dried cold trap is-40 to-80 ℃ and the time is 5-15 hours.
The invention also provides a high-purity gallium-based layered carbon/nitride MAX phase material which is prepared by adopting the preparation method.
The invention provides a high-purity gallium layered carbon/nitride MAX phase material and a preparation method thereof; the preparation method comprises the following steps: a) Mixing metal powder M with graphite powder X/metal nitride powder MN, and performing pre-calcination treatment in an inert gas atmosphere to obtain an MX precursor; b) Soaking molten metal Ga in the MX precursor obtained in the step a), and calcining in an inert gas atmosphere to obtain MAX phase material and unreacted metal Ga; and then removing unreacted metal Ga through acid treatment, and sequentially centrifugally cleaning and freeze-drying the obtained product to obtain the high-purity gallium-based layered carbon/nitride MAX phase material. Compared with the prior art, the preparation method provided by the invention adopts specific process steps to realize overall better interaction: through the assembly strategy of MX and metal Ga at high temperature, the synthesized MAX phase material has extremely high phase purity and size uniformity, for example, the synthesized V 2 GaC MAX phase purity is 100 percent; in addition, by adjusting the type or proportion of the metal powder M, controllable preparation of various MAX phase materials, such as preparation of dual, multi-metal MAX and high entropy MAX phases, can be achieved. The invention not only improves the preparation purity and the size uniformity of the MAX phase material, but also enriches the structural diversity of the MAX phase material; meanwhile, the high-purity MAX prepared by the invention has important application potential in the fields of electrochemical energy storage, catalysis, protective coating or radiation protection and the like.
Drawings
FIG. 1 is an X-ray diffraction (XRD) and neutron diffraction pattern (NPD) of the sample obtained in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the sample obtained in example 1;
FIG. 3 is a Scanning Electron Microscope (SEM) element distribution map (Mapping) of the sample obtained in example 1;
FIG. 4 is a Scanning Electron Microscope (SEM) element distribution map (Mapping) of the sample obtained in example 2;
FIG. 5 is a Scanning Electron Microscope (SEM) element distribution map (Mapping) of the sample obtained in example 3;
FIG. 6 is a Scanning Electron Microscope (SEM) element distribution map (Mapping) of the sample obtained in example 4;
FIG. 7 is a Scanning Electron Microscope (SEM) element distribution map (Mapping) of the sample obtained in example 5;
FIG. 8 is a Scanning Electron Microscope (SEM) element distribution map (Mapping) of the sample obtained in example 6;
FIG. 9 is a Scanning Electron Microscope (SEM) element distribution map (Mapping) of the sample obtained in example 7;
FIG. 10 is a Scanning Electron Microscope (SEM) element distribution map (Mapping) of the sample obtained in example 8;
FIG. 11 is a Scanning Electron Microscope (SEM) element distribution map (Mapping) of the sample obtained in example 9;
FIG. 12 is a Scanning Electron Microscope (SEM) element distribution map (Mapping) of the sample obtained in example 10;
FIG. 13 is a Scanning Electron Microscope (SEM) element distribution map (Mapping) of the sample obtained in example 11.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of a high-purity gallium-based layered carbon/nitride MAX phase material, which comprises the following steps:
a) Mixing metal powder M with graphite powder X/metal nitride powder MN, and performing pre-calcination treatment in an inert gas atmosphere to obtain an MX precursor;
b) Soaking molten metal Ga in the MX precursor obtained in the step a), and calcining in an inert gas atmosphere to obtain MAX phase material and unreacted metal Ga; and then removing unreacted metal Ga through acid treatment, and sequentially centrifugally cleaning and freeze-drying the obtained product to obtain the high-purity gallium-based layered carbon/nitride MAX phase material.
Firstly, mixing metal powder M with graphite powder X, and carrying out pre-calcination treatment in an inert gas atmosphere to obtain an MX precursor.
In the present invention, the M is preferably selected from one or more of Ti, V, cr, zr, nb, mo, ta, more preferably one or more of Ti, V, cr, nb, mo or Ta.
The sources of the metal powder M and the graphite powder X are not particularly limited, and commercially available products known to those skilled in the art may be used.
In the present invention, the molar ratio of the metal powder M to the graphite powder X is preferably 2: (0.5 to 2), more preferably 2: (0.8 to 1.5).
In the invention, the mixing mode is preferably ball milling treatment; the rotation speed of the ball milling treatment is preferably 300-500 rpm, more preferably 400rpm, and the time is preferably 10-30 h, more preferably 12-15 h; a homogeneously mixed precursor powder is obtained.
In the present invention, the inert gas is preferably argon.
In the invention, the temperature of the pre-calcination treatment is preferably 1200-1400 ℃, which can be 1200 ℃,1300 ℃,1400 ℃, the heating rate is preferably 1-10 ℃ per minute, more preferably 5 ℃ per minute, and the time is preferably 50-70 min, which can be 50min,60min,70min.
After the MX precursor is obtained, the obtained MX precursor is soaked into molten metal Ga, and calcining treatment is carried out in an inert gas atmosphere to obtain MAX phase material and unreacted metal Ga; and then removing unreacted metal Ga through acid treatment, and sequentially centrifugally cleaning and freeze-drying the obtained product to obtain the high-purity gallium-based layered carbon/nitride MAX phase material.
In the present invention, the molten metal Ga may be obtained by heating and melting metal Ga to obtain a liquid by means well known to those skilled in the art.
In the present invention, the infiltration process is preferably specifically:
Adding molten metal Ga into the MX precursor, and grinding at 50-70 ℃ for 20-40 min to obtain an MX mixture completely wrapping Ga.
In the invention, the temperature of the calcination treatment is preferably 1300-1600 ℃, more preferably 1400-1500 ℃, the heating rate is preferably 1-10 ℃ per minute, more preferably 5 ℃ per minute, the time is preferably 100-250 min, and more preferably 200-240 min.
In the invention, hydrochloric acid is preferably adopted for the acid treatment, and the time is preferably 100-420 min, and can be 100min,120min,200min,300min,360min and 420min.
In the invention, deionized water and absolute ethyl alcohol are preferably adopted for centrifugal cleaning for 3-6 times, and preferably 4-5 times; the temperature of freeze drying is preferably-40 to-60 ℃, and the time is preferably 5 to 15 hours, more preferably 10 to 12 hours.
The invention provides a controllable preparation method of a high-purity gallium-based layered carbon/nitride MAX phase, which is a method for efficiently synthesizing MAX with uniform morphology and high purity; firstly, ball-milling and mixing metal powder M and graphite powder X/metal nitride powder MN according to a certain molar ratio to obtain uniformly mixed precursor powder, pre-calcining the obtained precursor powder in an argon atmosphere to obtain an MX precursor, adding pre-melted metal Ga into the MX precursor, heating and uniformly mixing to obtain a mixture of Ga completely infiltrating MX, calcining the mixture, and removing redundant metal Ga by pickling to obtain the high-purity MAX phase material. The MAX phase prepared by the invention has extremely high purity, and micron-sized particles with uniform size can be obtained without subsequent processing; meanwhile, the preparation of a plurality of different MAX phase materials can be realized by adjusting the types or the proportions of the metal powder M or the graphite X.
The invention also provides a high-purity gallium-based layered carbon/nitride MAX phase material which is prepared by adopting the preparation method.
In the invention, the general formula of the MAX phase material is preferably M n+1AXn;
Wherein n=1 to 3;
M comprises one or more of Ti, V, cr, zr, nb, mo, ta;
A is Ga;
X is C or/and N.
The MAX phase material provided by the invention has high purity, better size uniformity and rich structural diversity, and has important application potential in the fields of electrochemical energy storage, catalysis, protective coating or radiation protection and the like.
The invention provides a high-purity gallium layered carbon/nitride MAX phase material and a preparation method thereof; the preparation method comprises the following steps: a) Mixing metal powder M with graphite powder X/metal nitride powder MN, and performing pre-calcination treatment in an inert gas atmosphere to obtain an MX precursor; b) Soaking molten metal Ga in the MX precursor obtained in the step a), and calcining in an inert gas atmosphere to obtain MAX phase material and unreacted metal Ga; and then removing unreacted metal Ga through acid treatment, and sequentially centrifugally cleaning and freeze-drying the obtained product to obtain the high-purity gallium-based layered carbon/nitride MAX phase material. Compared with the prior art, the preparation method provided by the invention adopts specific process steps to realize overall better interaction: through the assembly strategy of MX and metal Ga at high temperature, the synthesized MAX phase material has extremely high phase purity and size uniformity, for example, the synthesized V 2 GaC MAX phase purity is 100 percent; in addition, by adjusting the type or proportion of the metal powder M, controllable preparation of various MAX phase materials, such as preparation of dual, multi-metal MAX and high entropy MAX phases, can be achieved. The invention not only improves the preparation purity and the size uniformity of the MAX phase material, but also enriches the structural diversity of the MAX phase material; meanwhile, the high-purity MAX prepared by the invention has important application potential in the fields of electrochemical energy storage, catalysis, protective coating or radiation protection and the like.
In order to further illustrate the present invention, the following examples are provided. The reagents and materials used in the following examples of the present invention are all commercially available or self-made.
Example 1
(1) Weighing 20mmol of metal vanadium powder and 8mmol of graphite powder, and performing ball milling treatment at a rotating speed of 400rmp for 12 hours to finally obtain a thoroughly mixed powder sample;
(2) Under the protection of argon, the uniformly mixed powder sample is heated from room temperature to 1300 ℃ at a speed of 5 ℃/min, and the temperature is kept for 60min at the temperature, so that a sintered vanadium carbide powder sample is finally obtained;
(3) Adding 80mmol of metal Ga solution which is melted in advance into the obtained vanadium carbide powder, and grinding and mixing at the temperature of 60 ℃ for 30min to obtain a vanadium carbide mixture which completely wraps Ga;
(4) Under the protection of argon, the mixture doped with metal Ga is heated from room temperature to 1500 ℃ at a speed of 5 ℃/min, and is kept at the temperature for 240min, so that V 2 GaC MAX phase and unreacted metal Ga are finally obtained;
(5) Adding the sintered product into 50ml of hydrochloric acid solution, fully reacting for 120min, and centrifugally cleaning for 5 times by using deionized water and absolute ethyl alcohol; subsequently, the sample was subjected to a freeze-drying treatment at a cold trap temperature of-60 ℃ for a duration of 12 hours, to finally obtain pure V 2 GaC powder.
Example 2
(1) Weighing 20mmol of metallic titanium powder and 10mmol of graphite powder, and performing ball milling treatment at a rotating speed of 400rmp for 12 hours to finally obtain a thoroughly mixed powder sample;
(2) Under the protection of argon, the uniformly mixed powder sample is heated from room temperature to 1300 ℃ at a speed of 5 ℃/min, and the temperature is kept for 60min at the temperature, so that a sintered titanium carbide powder sample is finally obtained;
(3) Adding 80mmol of pre-melted metal Ga solution into the obtained titanium carbide powder, and grinding and mixing at 60 ℃ for 30min to obtain a titanium carbide mixture completely wrapping Ga;
(4) Under the protection of argon, the mixture doped with metal Ga is heated from room temperature to 1500 ℃ at a speed of 5 ℃/min, and is kept at the temperature for 240min, so that Ti 2 GaC MAX phase and unreacted metal Ga are finally obtained;
(5) Adding the sintered product into 50ml of hydrochloric acid solution, fully reacting for 120min, and centrifugally cleaning for 5 times by using deionized water and absolute ethyl alcohol; subsequently, the sample was subjected to a freeze-drying treatment at a cold trap temperature of-60 ℃ for a duration of 12 hours, to finally obtain pure Ti 2 GaC powder.
Example 3
(1) Weighing 20mmol of metal chromium powder and 10mmol of graphite powder, and performing ball milling treatment at a rotating speed of 400rmp for 12 hours to finally obtain a thoroughly mixed powder sample;
(2) Under the protection of argon, the uniformly mixed powder sample is heated from room temperature to 1300 ℃ at a speed of 5 ℃/min, and the temperature is kept for 60min at the temperature, so that a sintered chromium carbide powder sample is finally obtained;
(3) Adding 80mmol of pre-melted metal Ga solution into the obtained vanadium carbide powder, and grinding and mixing at 60 ℃ for 30min to obtain a chromium carbide mixture completely wrapping Ga;
(4) Under the protection of argon, the mixture doped with metal Ga is heated from room temperature to 1500 ℃ at a speed of 5 ℃/min, and is kept at the temperature for 240min, so that Cr 2 GaC MAX phase and unreacted metal Ga are finally obtained;
(5) Adding the sintered product into 50ml of hydrochloric acid solution, fully reacting for 120min, and centrifugally cleaning for 5 times by using deionized water and absolute ethyl alcohol; subsequently, the sample was subjected to a freeze-drying treatment at a cold trap temperature of-60℃for a period of 12 hours, to finally obtain pure Cr 2 GaC powder.
Example 4
(1) Weighing 40mmol of metal vanadium powder and 30mmol of graphite powder, and performing ball milling treatment at a rotating speed of 400rmp for 12 hours to finally obtain a thoroughly mixed powder sample;
(2) Under the protection of argon, the uniformly mixed powder sample is heated from room temperature to 1300 ℃ at a speed of 5 ℃/min, and the temperature is kept for 60min at the temperature, so that a sintered vanadium carbide powder sample is finally obtained;
(3) Adding 80mmol of pre-melted metal Ga solution into the obtained vanadium carbide powder, and grinding and mixing at 60 ℃ for 30min to obtain a vanadium carbide mixture completely wrapping Ga;
(4) Under the protection of argon, the mixture doped with metal Ga is heated from room temperature to 1500 ℃ at a speed of 5 ℃/min, and is kept at the temperature for 240min, so that V 4GaC3 MAX phase and unreacted metal Ga are finally obtained;
(5) Adding the sintered product into 50ml of hydrochloric acid solution, fully reacting for 120min, and centrifugally cleaning for 5 times by using deionized water and absolute ethyl alcohol; subsequently, the sample was subjected to a freeze-drying treatment at a cold trap temperature of-60 ℃ for a duration of 12 hours, to finally obtain pure V 4GaC3 powder.
Example 5
(1) Weighing 40mmol of niobium powder and 30mmol of graphite powder, and performing ball milling treatment at a rotating speed of 400rmp for 12 hours to finally obtain a thoroughly mixed powder sample;
(2) Under the protection of argon, the uniformly mixed powder sample is heated from room temperature to 1300 ℃ at a speed of 5 ℃/min, and the temperature is kept for 60min at the temperature, so that a sintered niobium carbide powder sample is finally obtained;
(3) Adding 80mmol of pre-melted metal Ga solution into the obtained vanadium carbide powder, and grinding and mixing at 60 ℃ for 30min to obtain a vanadium carbide mixture completely wrapping Ga;
(4) Under the protection of argon, the mixture doped with metal Ga is heated from room temperature to 1500 ℃ at a speed of 5 ℃/min, and is kept at the temperature for 240min, so that Nb 4GaC3 MAX phase and unreacted metal Ga are finally obtained;
(5) Adding the sintered product into 50ml of hydrochloric acid solution, fully reacting for 120min, and centrifugally cleaning for 5 times by using deionized water and absolute ethyl alcohol; subsequently, the sample was subjected to a freeze-drying treatment at a cold trap temperature of-60 ℃ for a duration of 12 hours, to finally obtain pure Nb 4GaC3 powder.
Example 6
(1) Weighing 10mmol of metal titanium powder, 10mmol of metal vanadium powder and 10mmol of graphite powder, and performing ball milling treatment at a rotating speed of 400rmp for 12 hours to finally obtain a thoroughly mixed powder sample;
(2) Under the protection of argon, the uniformly mixed powder sample is heated from room temperature to 1300 ℃ at a speed of 5 ℃/min, and the temperature is kept for 60min at the temperature, so that a sintered titanium vanadium carbide powder sample is finally obtained;
(3) Adding 80mmol of pre-melted metal Ga solution into the obtained vanadium carbide powder, and grinding and mixing at 60 ℃ for 30min to obtain a titanium vanadium carbide mixture completely wrapping Ga;
(4) Heating the mixture doped with metal Ga from room temperature to 1500 ℃ at a speed of 5 ℃/min under the protection of argon, and preserving heat at the temperature for 240min to finally obtain TiVGaC MAX phases and unreacted metal Ga;
(5) Adding the sintered product into 50ml of hydrochloric acid solution, fully reacting for 120min, and centrifugally cleaning for 5 times by using deionized water and absolute ethyl alcohol; subsequently, the sample was subjected to a freeze-drying treatment at a cold trap temperature of-60 ℃ for a duration of 12 hours, to finally obtain a pure TiVGaC powder.
Example 7
(1) Weighing 10mmol of metal niobium powder, 10mmol of metal vanadium powder and 10mmol of graphite powder, and performing ball milling treatment at a rotating speed of 400rmp for 12 hours to finally obtain a thoroughly mixed powder sample;
(2) Under the protection of argon, the uniformly mixed powder sample is heated from room temperature to 1300 ℃ at a speed of 5 ℃/min, and the temperature is kept for 60min at the temperature, so that a sintered niobium vanadium carbide powder sample is finally obtained;
(3) Adding 80mmol of pre-melted metal Ga solution into the obtained vanadium carbide powder, and grinding and mixing at 60 ℃ for 30min to obtain a niobium vanadium carbide mixture completely wrapping Ga;
(4) Heating the mixture doped with metal Ga from room temperature to 1500 ℃ at a speed of 5 ℃/min under the protection of argon, and preserving heat at the temperature for 240min to finally obtain NbVGaC MAX phases and unreacted metal Ga;
(5) Adding the sintered product into 50ml of hydrochloric acid solution, fully reacting for 120min, and centrifugally cleaning for 5 times by using deionized water and absolute ethyl alcohol; subsequently, the sample was subjected to a freeze-drying treatment at a cold trap temperature of-60 ℃ for a duration of 12 hours, to finally obtain a pure NbVGaC powder.
Example 8
(1) Weighing 20/3mmol of metal niobium powder, 20/3mmol of metal vanadium powder, 20/3mmol of metal titanium powder and 10mmol of graphite powder, and performing ball milling treatment at a rotating speed of 400rmp for 12 hours to finally obtain a thoroughly mixed powder sample;
(2) Under the protection of argon, the uniformly mixed powder sample is heated from room temperature to 1300 ℃ at a speed of 5 ℃/min, and the temperature is kept for 60min at the temperature, so that a sintered niobium vanadium titanium carbide powder sample is finally obtained;
(3) Adding 80mmol of pre-melted metal Ga solution into the obtained vanadium carbide powder, and grinding and mixing at 60 ℃ for 30min to obtain a vanadium titanium niobium carbide mixture completely wrapping Ga;
(4) Raising the temperature of the mixture doped with the metal Ga from room temperature to 1500 ℃ at a speed of 5 ℃/min under the protection of argon, and preserving the temperature for 240min at the temperature to finally obtain (NbVTi) 2 GaC MAX phase and unreacted metal Ga;
(5) Adding the sintered product into 50ml of hydrochloric acid solution, fully reacting for 120min, and centrifugally cleaning for 5 times by using deionized water and absolute ethyl alcohol; subsequently, the sample was subjected to a freeze-drying treatment at a cold trap temperature of-60 ℃ for a period of 12 hours, to finally obtain pure (NbVTi) 2 GaC powder.
Example 9
(1) Weighing 5mmol of metallic molybdenum powder, 5mmol of metallic niobium powder, 5mmol of metallic vanadium powder, 5mmol of metallic titanium powder and 10mmol of graphite powder, and performing ball milling treatment at a rotating speed of 400rmp for 12 hours to finally obtain a thoroughly mixed powder sample;
(2) Under the protection of argon, the uniformly mixed powder sample is heated from room temperature to 1300 ℃ at a speed of 5 ℃/min, and the temperature is kept for 60min at the temperature, so that a sintered molybdenum niobium vanadium titanium carbide powder sample is finally obtained;
(3) Adding 80mmol of pre-melted metal Ga solution into the obtained vanadium carbide powder, and grinding and mixing at 60 ℃ for 30min to obtain a molybdenum niobium vanadium titanium carbide mixture completely wrapping Ga;
(4) Raising the temperature of the mixture doped with the metal Ga from room temperature to 1500 ℃ at a speed of 5 ℃/min under the protection of argon, and preserving the temperature for 240min at the temperature to finally obtain (MoNbVTi) 2 GaC MAX phase and unreacted metal Ga;
(5) Adding the sintered product into 50ml of hydrochloric acid solution, fully reacting for 120min, and centrifugally cleaning for 5 times by using deionized water and absolute ethyl alcohol; subsequently, the sample was subjected to a freeze-drying treatment at a cold trap temperature of-60 ℃ for a period of 12 hours, to finally obtain pure (MoNbVTi) 2 GaC powder.
Example 10
(1) Weighing 4mmol of metal tantalum powder, 4mmol of metal molybdenum powder, 4mmol of metal niobium powder, 4mmol of metal vanadium powder, 4mmol of metal titanium powder and 10mmol of graphite powder, and performing ball milling treatment at a rotating speed of 400rmp for 12 hours to finally obtain a thoroughly mixed powder sample;
(2) Under the protection of argon, the uniformly mixed powder sample is heated from room temperature to 1300 ℃ at a speed of 5 ℃/min, and the temperature is kept for 60min at the temperature, so that a sintered tantalum carbide molybdenum niobium vanadium titanium powder sample is finally obtained;
(3) Adding 80mmol of pre-melted metal Ga solution into the obtained vanadium carbide powder, and grinding and mixing at 60 ℃ for 30min to obtain a tantalum molybdenum niobium vanadium titanium carbide mixture completely wrapping Ga;
(4) Raising the temperature of the mixture doped with the metal Ga from room temperature to 1500 ℃ at a speed of 5 ℃/min under the protection of argon, and preserving the temperature for 240min at the temperature to finally obtain (TaMoNbVTi) 2 GaC MAX phase and unreacted metal Ga;
(5) Adding the sintered product into 50ml of hydrochloric acid solution, fully reacting for 120min, and centrifugally cleaning for 5 times by using deionized water and absolute ethyl alcohol; subsequently, the sample was subjected to a freeze-drying treatment at a cold trap temperature of-60 ℃ for a period of 12 hours, to finally obtain pure (TaMoNbVTi) 2 GaC powder.
Example 11
(1) Weighing 2.0g of vanadium pentoxide, and annealing at 800 ℃ in an ammonia atmosphere for 2 hours to finally obtain a VN powder sample; weighing 20mmolVN of powder and 20mmol of metal vanadium powder, and performing ball milling treatment at a rotating speed of 400rmp for 12 hours to finally obtain a thoroughly mixed powder sample;
(2) Under the protection of argon, the uniformly mixed powder sample is heated from room temperature to 1300 ℃ at a speed of 5 ℃/min, and the temperature is kept for 60min at the temperature, so that a sintered vanadium nitride powder sample is finally obtained;
(3) Adding 80mmol of pre-melted metal Ga solution into the obtained vanadium nitride powder, and grinding and mixing at 60 ℃ for 30min to obtain a vanadium nitride mixture completely wrapping Ga;
(4) Under the protection of argon, the mixture doped with metal Ga is heated from room temperature to 1500 ℃ at a speed of 5 ℃/min, and is kept at the temperature for 240min, so that V 2 GaN MAX phase and unreacted metal Ga are finally obtained;
(5) Adding the sintered product into 50ml of hydrochloric acid solution, fully reacting for 120min, and centrifugally cleaning for 5 times by using deionized water and absolute ethyl alcohol; subsequently, the sample was subjected to a freeze-drying treatment at a cold trap temperature of-60 ℃ for a duration of 12 hours, to finally obtain pure V 2 GaN powder.
The characterization results of the above embodiments are shown in fig. 1 to 13.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of a high-purity gallium-based layered carbon/nitride MAX phase material comprises the following steps:
a) Mixing metal powder M with graphite powder X/metal nitride powder MN, and performing pre-calcination treatment in an inert gas atmosphere to obtain an MX precursor;
b) Soaking molten metal Ga in the MX precursor obtained in the step a), and calcining in an inert gas atmosphere to obtain MAX phase material and unreacted metal Ga; and then removing unreacted metal Ga through acid treatment, and sequentially centrifugally cleaning and freeze-drying the obtained product to obtain the high-purity gallium-based layered carbon/nitride MAX phase material.
2. The method of claim 1, wherein M in step a) is selected from one or more of Ti, V, cr, zr, nb, mo, ta.
3. The method according to claim 1, wherein the molar ratio of the metal powder M to the graphite powder X in step a) is 2: (0.5-2).
4. The method according to claim 1, wherein the mixing in step a) is performed by ball milling; the rotation speed of the ball milling treatment is 300-500 rpm, and the time is 10-30 h.
5. The method according to claim 1, wherein the pre-calcination treatment in step a) is performed at a temperature of 1200 ℃ to 1400 ℃, a heating rate of 1 ℃/min to 10 ℃/min, and a time of 50min to 70min.
6. The method according to claim 1, wherein the infiltration in step b) is performed by:
Adding molten metal Ga into the MX precursor, and grinding at 50-70 ℃ for 20-40 min to obtain an MX mixture completely wrapping Ga.
7. The method according to claim 1, wherein the temperature of the calcination treatment in step b) is 1300 ℃ to 1600 ℃, the heating rate is 1 ℃/min to 10 ℃/min, and the time is 100min to 250min.
8. The method according to claim 1, wherein hydrochloric acid is used for the acid treatment in step b) for 300 to 420 minutes.
9. The method according to claim 1, wherein the centrifugal washing in step b) is performed 3 to 6 times by using deionized water and absolute ethyl alcohol; the temperature of the freeze-dried cold trap is-40 to-80 ℃ and the time is 5-15 hours.
10. A high purity gallium-based layered carbon/nitride MAX phase material, characterized in that it is prepared by the preparation method according to any one of claims 1 to 9.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109369188A (en) * | 2018-12-13 | 2019-02-22 | 西南交通大学 | A kind of ultra-high purity Cr2The preparation method of GaC ceramic powder |
| CN110958995A (en) * | 2017-07-13 | 2020-04-03 | 于利奇研究中心有限公司 | Method for preparing non-oxide ceramic powder |
| CN111229272A (en) * | 2020-01-19 | 2020-06-05 | 华东师范大学 | Ternary lamellar carbide Mo2Ga2C composite flower-shaped MoS2Nanoparticle composite material and preparation method and application thereof |
| CN111732103A (en) * | 2020-06-10 | 2020-10-02 | 中国科学技术大学 | Fluorine-free Mo2CTx MXenes material, preparation method and application thereof |
| CN113121236A (en) * | 2021-03-02 | 2021-07-16 | 西安交通大学 | Micron-sized three-dimensional lamellar Ti2AlC ceramic powder and preparation method thereof |
| CN113611469A (en) * | 2021-08-19 | 2021-11-05 | 中国科学技术大学 | Ga series MAX phase magnetic material and preparation method and application thereof |
| CN114751750A (en) * | 2021-01-08 | 2022-07-15 | 北京航空航天大学 | Medium-entropy MAX phase material, medium-entropy two-dimensional material, preparation method and application thereof |
| WO2022254455A1 (en) * | 2021-06-02 | 2022-12-08 | Council Of Scientific And Industrial Research | Max phases by reactive flash sintering and a method for ultrafast synthesis thereof |
| CN117534071A (en) * | 2023-12-05 | 2024-02-09 | 中国科学院过程工程研究所 | MAX phase material and preparation method and application thereof |
-
2024
- 2024-04-01 CN CN202410384549.9A patent/CN117964370B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110958995A (en) * | 2017-07-13 | 2020-04-03 | 于利奇研究中心有限公司 | Method for preparing non-oxide ceramic powder |
| CN109369188A (en) * | 2018-12-13 | 2019-02-22 | 西南交通大学 | A kind of ultra-high purity Cr2The preparation method of GaC ceramic powder |
| CN111229272A (en) * | 2020-01-19 | 2020-06-05 | 华东师范大学 | Ternary lamellar carbide Mo2Ga2C composite flower-shaped MoS2Nanoparticle composite material and preparation method and application thereof |
| CN111732103A (en) * | 2020-06-10 | 2020-10-02 | 中国科学技术大学 | Fluorine-free Mo2CTx MXenes material, preparation method and application thereof |
| CN114751750A (en) * | 2021-01-08 | 2022-07-15 | 北京航空航天大学 | Medium-entropy MAX phase material, medium-entropy two-dimensional material, preparation method and application thereof |
| CN113121236A (en) * | 2021-03-02 | 2021-07-16 | 西安交通大学 | Micron-sized three-dimensional lamellar Ti2AlC ceramic powder and preparation method thereof |
| WO2022254455A1 (en) * | 2021-06-02 | 2022-12-08 | Council Of Scientific And Industrial Research | Max phases by reactive flash sintering and a method for ultrafast synthesis thereof |
| CN113611469A (en) * | 2021-08-19 | 2021-11-05 | 中国科学技术大学 | Ga series MAX phase magnetic material and preparation method and application thereof |
| CN117534071A (en) * | 2023-12-05 | 2024-02-09 | 中国科学院过程工程研究所 | MAX phase material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 金 森: ""三元层状陶瓷Mo2Ga2C 的热压烧结及其衍生二维材料Mo2C 的制备", 金 森, 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》，第B015-987页", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, 15 January 2022 (2022-01-15), pages 015 - 987 * |
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