WO2020067617A1 - Procédé de récupération de propriétés électriques et d'amélioration de la stabilité d'oxydation dans un matériau bidimensionnel - Google Patents

Procédé de récupération de propriétés électriques et d'amélioration de la stabilité d'oxydation dans un matériau bidimensionnel Download PDF

Info

Publication number
WO2020067617A1
WO2020067617A1 PCT/KR2019/003787 KR2019003787W WO2020067617A1 WO 2020067617 A1 WO2020067617 A1 WO 2020067617A1 KR 2019003787 W KR2019003787 W KR 2019003787W WO 2020067617 A1 WO2020067617 A1 WO 2020067617A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
maxine
electrical properties
maxine film
annealing
Prior art date
Application number
PCT/KR2019/003787
Other languages
English (en)
Korean (ko)
Inventor
이용희
안치원
김선준
채윤정
이병주
Original Assignee
한국과학기술원
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 한국과학기술원 filed Critical 한국과학기술원
Publication of WO2020067617A1 publication Critical patent/WO2020067617A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B35/5611—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 based on titanium carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/0072—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics

Definitions

  • the present invention relates to a method for recovering electrical properties and improving oxidation stability of a two-dimensional material, and more particularly, by annealing an oxidized maxine film at a high temperature, recovering electrical properties and recovering electrical properties of a two-dimensional material that improves oxidation stability. And a method for improving oxidation stability.
  • the MAX phase (MAX phase, where M is a transition metal, A is a group 13 or 14 element, X is carbon and / or nitrogen) is a quasi-ceramic property MX, and a metal element A different from M is
  • MX transition metal
  • A is a group 13 or 14 element
  • X is carbon and / or nitrogen
  • MX is a quasi-ceramic property
  • a metal element A different from M is The combined crystals are excellent in physical properties such as electrical conductivity, oxidation resistance, and machinability.
  • more than 60 types of MAX phases are known to be synthesized.
  • the MAX phase is a two-dimensional material, but unlike graphite or metal dichalcogenide materials, the transition metal carbides are stacked with weak chemical bonds between element A and transition metal M between layers of each other. Therefore, it is difficult to transform into a two-dimensional structure using a general mechanical peeling method or a chemical peeling method.
  • MXene has similar electrical conductivity and strength as graphene, and can be applied to various application technologies ranging from energy storage devices to biomedical applications and complexes.
  • Technical problem to be achieved by the present invention is a two-dimensional material that improves the oxidation stability and recovery of the electrical properties of the maxine film by exposing the maxine film, which has been oxidized at room temperature and deteriorated in electrical properties, to hydrogen gas in a vacuum device to anneal at a high temperature. It is to provide a method of restoring electrical properties and improving oxidation stability.
  • a method for recovering electrical properties and improving oxidation stability of a two-dimensional material comprises: (a) preparing a maxine solution composed of a two-dimensional transition metal carbide and a transition metal carbonitride, (b ) Forming the prepared maxine solution into a maxine film composed of a composite material in the form of a film, (c) storing the formed maxine film at room temperature, and (d) using the oxidized maxine film through storage at room temperature. Placing in the vacuum equipment, (e) injecting hydrogen gas into the vacuum equipment in which the maxine film is placed, and (f) recovering electrical properties of the maxine film exposed to the injected hydrogen gas to a level before oxidation. To provide an annealing process for the maxin film.
  • the maxinic solution is Ti 2 C, Ti 3 C 2 , V 2 C, Nb 2 C, (Ti 0.5 , Nb 0.5 ) 2 CT x , Ti 3 CN, (V 0.5 , Cr 0.5 ) 3 C 2 , Ta 4 C 3 And any of Nb 4 C 3 may also be used. .
  • the maxinic solution may be formed of the formula M n + 1 X n .
  • M in the formula of M n + 1 X n may be a front transition metal.
  • X in the formula of M n + 1 X n may also include at least one of carbon and nitrogen.
  • the maxinic solution in step (b), may be manufactured in a film form through spin coating, drop casting, and vacuum filtration.
  • the maxin film in the step (f), may be annealed for 20 minutes to 40 minutes at a temperature of 800 ° C to 1000 ° C.
  • the ratio of the sheet resistance value of the maxine film annealed through step (f) and the sheet resistance value formed through step (b) may have a ratio of 0.9 to 1.2.
  • the functional group bound to the surface of the maxine film may be one in which the proportion of fluorine is reduced through oxidation and reduction.
  • the maxine film may be formed by forming a solid network on the surface through annealing to prevent oxidation under the infiltration of oxygen and moisture.
  • the maxin film may be annealed at a temperature of 900 ° C. for 30 minutes to maintain a sheet resistance value of 3.1 times or less compared to an initial value.
  • the vacuum equipment includes a body part formed in a hollow cylindrical shape, a quartz tube provided so that the maxine film is disposed on top of the body part, and a maxine film disposed on the top of the quartz tube.
  • a gas supply unit provided to supply the hydrogen gas at one lower end of the body portion so as to be exposed to the hydrogen gas, and the hydrogen gas supplied from the gas supply unit flows inside the body portion and contacts the maxine film and then discharges to the outside
  • an annealing portion which is disposed to surround the side wall of the body portion in which the quartz tube is disposed so that the maxima film is annealed, and a gas discharge portion provided at the other end of the body portion.
  • a pulse element may be configured as an electrode material through a stored pulse film through a method of recovering electrical properties and improving oxidation stability of the two-dimensional material.
  • the annealing at a high temperature by exposing the maxine film, which has been deteriorated in electrical properties, to hydrogen gas in a vacuum equipment, thereby improving the recovery of the electrical properties of the maxine film and improving the oxidation stability.
  • FIG. 1 is a flowchart of a method for recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of a vacuum device in which a maxine film of a method for recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention is disposed.
  • FIG. 3 is a graph showing a sheet resistance ratio according to a change in temperature of a method for recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention.
  • FIG. 4 is a graph showing a sheet resistance ratio according to a change in time in a method of recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention.
  • FIG. 5 is a graph showing the recovery rate of sheet resistance according to the degree of oxidation of a method for improving electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention.
  • FIG. 6 is a graph showing a change in sheet resistance during annealing according to an oxidation degree of a method of recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention according to temperature.
  • FIG. 7 is a graph showing a sheet resistance ratio according to the number of annealing times of a method for recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention.
  • FIG. 8 is a graph showing the overall sheet resistance ratio according to the time and temperature annealing frequency of a method for recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention.
  • FIG. 9 is a table showing the bonding state of functional groups through oxidation and reduction of a method for improving electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention.
  • FIG. 10 is a graph comparing the oxidation degree of maxine film to which hydrogen annealing is applied and non-applied in a method of recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention.
  • FIG. 11 is an enlarged photograph of a maxine film to which a hydrogen annealing is applied and not applied to a method of restoring electrical properties and improving oxidation stability of a 2D material according to an embodiment of the present invention with a scanning electron microscope.
  • FIG. 12 is a graph showing the relationship between Counts / s of Titanium Dioxide and Binding Energy by high temperature annealing of a method of recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention.
  • FIG. 13 is a graph showing the relationship between temperature and time and sheet resistance ratio through annealing of an oxidized maxine film in a method of recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention.
  • FIG. 14 is a view showing the contact angle of moisture when exposing the maxine film, which has not been annealed and the annealing process, to a high humidity in a method of recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention. It is a graph showing the relationship.
  • Figure 15 shows the difference between the electrical properties and heater properties of the oxidized maxine film and the oxidized maxine film and the annealed maxine film of the method for recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention. It is a graph shown.
  • FIG. 16 is a diagram illustrating heater characteristics according to voltages of an oxidized maxine film and an oxidized maxine film and an annealed maxine film in a method for recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention. It is a graph.
  • FIG. 17 shows the relationship between the sheet resistance ratio of the non-oxidized maxine film and the oxidized maxine film and the anoxidized maxine film of the method for recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention, and a heater characteristic. It is a graph shown.
  • FIG. 18 is a graph showing a relationship between a sheet resistance ratio and a heater characteristic of a non-oxidized maxine film and an annealing performed in a method for recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention.
  • 19 is a graph showing the relationship between sheet resistance and heater characteristics of a maxine film without annealing and an annealing performed maxine film of a method for recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention .
  • 20 is a graph of sheet resistance of a maxine film according to a hydrogen atmosphere in a method of recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention.
  • the most preferred embodiment according to the present invention comprises the steps of preparing a maxine solution consisting of a transition metal carbide and a transition metal nitride of a two-dimensional structure; Forming the prepared maxine solution into a maxine film composed of a composite material in the form of a film; Storing the formed maxine film at room temperature; Placing the oxidized maxin film through the room temperature storage in a vacuum equipment; Injecting hydrogen gas into the vacuum equipment on which the maxine film is disposed; And annealing the maxine film to restore the electrical properties of the maxine film exposed to the injected hydrogen gas to a level before oxidation. It characterized in that it comprises a.
  • FIG. 1 is a flowchart of a method for recovering electrical properties and improving oxidation stability of a 2D material according to an embodiment of the present invention
  • FIG. 2 is a method for recovering electrical properties and improving oxidation stability of a 2D material according to an embodiment of the present invention
  • Figure 3 is a cross-sectional view of the vacuum equipment is a maxine film is disposed
  • Figure 3 is a graph showing the sheet resistance ratio according to the change in temperature of the electrical properties recovery and oxidation stability improvement method according to an embodiment of the present invention
  • 4 is a graph showing a sheet resistance ratio according to a change in time in a method of recovering electrical properties and improving oxidation stability of a 2D material according to an embodiment of the present invention
  • FIG. 5 is a 2D material according to an embodiment of the present invention It is a graph showing the recovery rate of the sheet resistance according to the degree of oxidation of the method of improving the electrical properties and improving the oxidation stability
  • FIG. 6 is the electrical properties of the two-dimensional material according to an embodiment of the present invention
  • FIG. 7 is an annealing method of recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention 8 is a graph showing the sheet resistance ratio according to the number of times
  • FIG. 8 is a graph showing the total sheet resistance ratio according to the time and temperature annealing times of the method for improving electrical properties and improving oxidation stability of a 2D material according to an embodiment of the present invention.
  • Figure 9 is a table showing the bonding state of the functional groups through the oxidation and reduction of the electrical property recovery and oxidation stability improvement method of a two-dimensional material according to an embodiment of the present invention
  • Figure 10 is an embodiment of the present invention It is a graph comparing the oxidation degree of maxine film with and without applying hydrogen annealing in a method of restoring electrical properties and improving oxidation stability of a two-dimensional material.
  • 11 is a close-up picture of the electrical properties and film recovery of the hydrogen annealing of improved oxidative stability method is applied, and non-application of the two-dimensional Maxine material according to an embodiment of the present invention by a scanning electron microscope.
  • a method for recovering electrical properties and improving oxidative stability of a two-dimensional material includes (a) preparing a maxine solution composed of a two-dimensional transition metal carbide and a transition metal carbonitride, ( b) forming the prepared maxine solution into a maxine film composed of a composite material in the form of a film;
  • a method of restoring electrical properties and improving oxidation stability of a two-dimensional material includes preparing a maxine solution composed of a transition metal carbide and a transition metal carbonitride of a two-dimensional structure (S110).
  • the maxin solution is a two-dimensional layered structure, and a layer composed of atoms is stacked to form a multi-layer structure.
  • the two-dimensional multilayer structure, maxin solution is light and has low density, has excellent electrical conductivity, and can be easily separated from each other, and thus can be used as a radio wave absorber in various fields.
  • the prepared maxine solution is prepared in a film form through spin coating, drop cast, and vacuum filtration to prepare a maxine film, and spin coating as described above,
  • the maxin film can be effectively produced according to manufacturing conditions or conditions.
  • the maxine film formed through the maxine solution when it is not in use, it may be stored at room temperature, and the maxine film is exposed to air and moisture to cause an oxidation reaction, thereby reducing surface resistance and electrical properties.
  • step (S140) of placing in a vacuum equipment to use the oxidized oxidized film through normal temperature storage is also possible.
  • the electrical properties of the oxidized film oxidized through the storage at room temperature are reduced, it is placed in a vacuum device having a vacuum inside to restore it.
  • the oxidized maxine film is reduced by exposing the maxine film to hydrogen gas. Therefore, the oxidized maxine film can be restored to a state before oxidation of electrical properties and sheet resistance values through a reduction process.
  • the hydrogen gas is stored at room temperature, and oxygen and hydrogen gas are combined in the oxidized maxine film, and hydrogen gas is injected into the vacuum equipment to perform the reduction process of the maxine film.
  • the hydrogen gas can reduce the oxidation degree of the maxine film and restore electrical properties.
  • an annealing step (S160) of the maxine film to restore the electrical properties of the maxine film exposed to the injected hydrogen gas.
  • the maxine film is provided in the vacuum equipment to be exposed to hydrogen gas, and the vacuum equipment heats the inside to anneal the maxine film. Therefore, since the maxine film is heated to a high temperature in a state exposed to hydrogen gas, the original electrical properties can be restored through a reduction process in an oxidized state through storage at room temperature.
  • step (S160) of annealing the maxine film it is annealed for a predetermined temperature and time.
  • the maxine film can be annealed for a predetermined temperature and time to recover the original electrical properties through a reduction process.
  • the predetermined temperature and time is not particularly limited as long as the maxine film can restore its original electrical properties, but is preferably annealed for 20 to 40 minutes at a temperature of 800 ° C to 1000 ° C.
  • the sheet resistance value of the maxine film annealed for a predetermined temperature and time and the sheet resistance value of the initial state maxine film before oxidation have a predetermined ratio.
  • the maxine film is stored at room temperature and oxidized due to oxygen and moisture to reduce electrical properties, and can be reduced through an annealing process to restore the original electrical properties. Accordingly, the maxine film is annealed at a temperature of 800 ° C to 1000 ° C for a time of 20 minutes to 40 minutes, so that the sheet resistance value of the maxine film annealed through step (f) and the sheet resistance of the maxine film formed through step (b).
  • the ratio of values has a ratio of 0.9 to 1.2.
  • the maxin solution is Ti 2 C, Ti 3 C 2 , V 2 C, Nb 2 C, (Ti 0.5 , Nb 0.5 ) 2 CT x , Ti 3 CN, (V 0.5 , Cr 0.5 ) 3 C 2 , Ta 4 C 3 And Nb 4 C 3 .
  • the maxin solution may be of the formula M n + 1 X n, in the formula of M n + 1 X n , M is an early transition metal, and X is at least one of carbon and nitrogen. And n may be an integer from 1 to 4.
  • the vacuum equipment is a hollow body portion formed in a cylindrical shape
  • the inside of the body portion is a quartz tube provided so that the maxine film is disposed on the top
  • the maxine film disposed on the top of the quartz tube is exposed to the hydrogen gas
  • a gas supply portion provided to supply the hydrogen gas
  • the other end of the body portion so that the hydrogen gas supplied from the gas supply portion flows inside the body portion and is contacted with the maxine film and then discharged to the outside.
  • It may include a gas discharge portion provided in the annealing portion is heated to a high temperature is disposed to surround the side wall of the body portion, the quartz tube is arranged to anneal the maxine film.
  • the vacuum equipment is provided with a body portion formed in a hollow cylindrical shape.
  • the body portion is formed in a cylindrical shape, and is provided with a hollow so that the maxine film is disposed inside the body portion.
  • a quartz tube is provided inside the body so that the maxin film is disposed on the top.
  • the quartz tube is a tube formed of quartz and is provided so as not to be deformed even when the body portion is heated to a high temperature, and is disposed inside the hollow body portion.
  • a gas supply unit is provided at one lower end of the body unit to supply the hydrogen gas.
  • the gas supply unit is supplied with the hydrogen gas to the lower end of one side of the body portion so that the maxine film disposed on the upper end of the quartz tube is exposed to the hydrogen gas.
  • the maxine film is in contact with the hydrogen gas supplied through the gas supply unit to perform the reduction process.
  • a gas discharge portion provided at the other end of the body portion is provided.
  • the gas discharge portion is provided at the other end of the body portion so that the hydrogen gas supplied from the gas supply portion flows inside the body portion and is discharged to the outside after contacting the maxine film.
  • the hydrogen gas supplied from the gas supply unit passes through the maxine film and is discharged to the gas discharge unit.
  • an annealing portion is provided to surround the side wall of the body portion on which the quartz tube is arranged to heat the body portion at a high temperature so that the maxine film is annealed. Therefore, the maxine film is heated through the annealing portion, and through the reduction process, the electrical properties of the maxine film are restored to a level before oxidation.
  • a pulse element may be configured as an electrode material through a stored pulse film through a method of recovering electrical properties and improving oxidation stability of the two-dimensional material.
  • a method for recovering electrical properties and improving oxidation stability of a two-dimensional material according to the present invention was annealed at a temperature of 100 ° C. to 900 ° C. for 30 minutes. 0 ) and the sheet resistance ratio (Rs) of the maxine film after oxidation increased to 3.19 after oxidation and decreased to 0.93 through annealing.
  • the recovery of the oxidized maxine film decreases as the sheet resistance ratio increases in an annealing process at a high temperature, so that the high temperature is more effective.
  • a method of recovering electrical properties and improving oxidation stability of a two-dimensional material according to the present invention was performed by annealing for 30 minutes or 60 minutes at a temperature of 500 ° C., which was annealed for 60 minutes at a temperature of 500 ° C. It is more effective to perform annealing for 30 minutes at a temperature of 500 ° C. than to perform.
  • a method of recovering electrical properties and improving oxidation stability of a two-dimensional material according to the present invention is a graph showing a recovery rate of sheet resistance according to oxidation degree according to temperature, and a large difference in recovery rate according to oxidation degree rather than temperature have.
  • a method for recovering electrical properties and improving oxidation stability of a two-dimensional material according to the present invention was annealed at temperatures of 500 ° C. and 900 ° C. for 30 minutes, and there is a difference in recovery rate according to the degree of oxidation.
  • the reduction in the sheet resistance ratio of the high-oxidation maxine film is higher than that of the low-oxidation maxine film.
  • a method of recovering electrical properties and improving oxidation stability of a two-dimensional material according to the present invention was annealed several times for 30 minutes at a temperature of 500 ° C or 10 minutes at a temperature of 900 ° C.
  • the initial oxidized maxine film had a reduced sheet resistance ratio, but the annealing performed several times thereafter did not decrease the sheet resistance ratio but slightly increased.
  • the maxine film has excessive annealing time and repetitive annealing, thereby reducing electrical characteristics and increasing sheet resistance ratio. Therefore, performing annealing once for 20 minutes to 40 minutes at a temperature of 800 ° C to 1000 ° C can restore the electrical properties of the maxine film and reduce the sheet resistance ratio.
  • the maxine film stored at room temperature has a number of functional groups such as -O, -OH, and -F bonded to the surface.
  • Coarse maxine film can reduce the proportion of fluorine (-F) on the surface.
  • the functional group is bound to the surface during acid treatment (LiF, HF) for exfoliation of maxine.
  • Fluorine bound to the maxine surface has a work function of about 5 eV.
  • the injection of electrons can be limited.
  • the fluorine group among the various functional groups (-O, -OH, -F, etc.) attached to the surface is released from the surface of the maxine film through a high temperature annealing method, thereby converting the maxine film to an electrode.
  • a high temperature annealing method it is possible to prevent the fluorine group from limiting electron injection.
  • FIG. 10 as a graph comparing the oxidation degree of the maxine film to which hydrogen annealing was applied and not applied, oxidation of the maxine film was performed in a 70 degree oven containing water vapor, and the hydrogen annealed maxine film (solid red line) After performing annealing at a temperature of 900 ° C for 30 minutes, oxidation is hardly generated even when exposed to an environment in which oxidation is promoted, but the maxine film (black solid line) without hydrogen annealing was oxidized.
  • maxine film forms a solid network, and even after 60 hours of sheet resistance, the change is not large compared to the initial value, which prevents the penetration of oxygen and moisture to prevent oxidation, but hydrogen annealing
  • the unapplied maxin film increased to 1126 times compared to the initial value after the sheet resistance had passed for 60 hours, which means that oxygen and moisture penetrated, and oxidation proceeded rapidly.
  • the oxidizing degree was compared by expanding the maxine film to which hydrogen annealing was applied and not applied with a scanning electron microscope (SEM).
  • the maxine film to which hydrogen annealing has been applied (top) has a solid network formed on the surface, but the maxine film without hydrogen annealing (bottom) has been changed to porosity by surface oxidation. Therefore, the maxine film to which hydrogen annealing is applied is resistant to oxidation due to the penetration of oxygen and moisture, so that oxidation can be prevented.
  • FIG. 12 is a graph showing the relationship between Counts / s of Titanium Dioxide and Binding Energy by high temperature annealing of a method of recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention.
  • the sheet resistance ratio of the oxidized maxine film is recovered.
  • the recovery of the sheet resistance ratio of the oxidized maxine film is reduced by a high temperature annealing, and the peak ratio of titanium dioxide is reduced by comparing annealing (a) and annealing (b). Through the reduction of titanium, the sheet resistance ratio of the maxine film is restored.
  • titanium dioxide is generated through the oxidation process of the maxine film, and the produced titanium dioxide is reduced through high temperature annealing with hydrogen, thereby recovering the sheet resistance ratio of the maxine film.
  • FIG. 13 is a graph showing the relationship between temperature and time and sheet resistance ratio through annealing of an oxidized maxine film in a method of recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention.
  • FIG. 14 is a view showing the contact angle of moisture when exposing the maxine film, which has not been annealed and the annealing process, to a high humidity in a method of recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention. It is a graph showing the relationship.
  • the maxin film without annealing initially has a contact angle of 44 degrees with the water droplet, and then the moisture rapidly permeates into the inside, and the contact angle with the droplet decreases by 10 degrees, and with hydrogen at 900 °C.
  • the contact angle with the water droplets is maintained at 42 degrees after 1 minute from the beginning.
  • a solid network is formed on the surface of the maxine film to change from a porous structure to a structure in which pores have disappeared before performing annealing, thereby preventing the penetration of moisture and oxygen.
  • Figure 15 shows the difference between the electrical properties and heater properties of the oxidized maxine film and the oxidized maxine film and the annealed maxine film of the method for recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention. It is a graph shown.
  • the electrical properties and heater characteristics according to the temperature and time of the oxidized maxine film (a), the oxidized maxine film (b), and the maxine film (c) subjected to annealing in a hydrogen atmosphere are maxima films.
  • oxidized (b) is reduced, in the case of maxine film (c), which has been re-annealed to a hydrogen atmosphere and 900 ° C, electrical and heater properties are restored.
  • FIG. 16 is a diagram illustrating heater characteristics according to voltages of an oxidized maxine film and an oxidized maxine film and an annealed maxine film in a method for recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention. It is a graph.
  • the oxidized maxine film and the oxidized maxine film and the annealed maxine film change heater characteristics according to voltages (10V, 15V, 20V, and 25V). In the case of oxidized maxine film, heater characteristics It is reduced than the non-oxidized maxine film.
  • FIG. 17 is a graph showing the relationship between the sheet resistance ratio of the non-oxidized maxine film and the oxidized maxine film and the anoxidized maxine film in a method for recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention. It is a graph shown.
  • the sheet resistance ratio of the non-oxidized maxine film is 65.3 ohm / sq, and when the sheet resistance ratio is increased to 95.5 ohm / sq by oxidizing it, the heater characteristic is reduced.
  • the sheet resistance ratio is reduced to 68.5 ohm / sq, and the heater characteristics are also increased.
  • the oxidized maxine film is oxidized to a high value and the sheet resistance ratio is increased to 990.1 ohm / sq and the heater characteristics are reduced, by performing annealing the oxidized maxine film in a hydrogen atmosphere, the sheet resistance ratio is reduced to a certain level and the heater Traits can also be restored.
  • the oxidized maxine film can recover sheet resistance ratio and heater characteristics by performing annealing in a hydrogen atmosphere.
  • FIG. 18 is a graph showing a relationship between a sheet resistance ratio and a heater characteristic of a non-oxidized maxine film and an annealing performed in a method for recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention.
  • the unoxidized maxine film and the annealing-executed maxine film at 900 ° C. and a hydrogen atmosphere have the same similar sheet resistance, or the annealed maxine film has a higher sheet resistance than the unoxidized maxine film
  • the maxine film, which is annealed in the atmosphere exhibits higher heater characteristics.
  • 19 is a graph showing the relationship between sheet resistance and heater characteristics of a maxine film without annealing and an annealing performed maxine film of a method for recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention .
  • the maxine film (a, b) that has not been annealed is exposed to the environment at 70 ° C. and 100% humidity for 24 hours, and the color has changed as the temperature decreases, but annealing is performed.
  • the maxine film (c, d) is not changed in color even after exposure to 70 ° C. and 100% humidity for 24 hours.
  • the sheet resistance and heater characteristics can be kept constant, and by performing annealing on the maxine film in the hydrogen atmosphere, the sheet resistance and heater characteristics can be restored to a certain level. You can.
  • 20 is a graph of sheet resistance of a maxine film according to a hydrogen atmosphere in a method of recovering electrical properties and improving oxidation stability of a two-dimensional material according to an embodiment of the present invention.
  • an oxidized maxine film and an oxidized maxine film are annealed in a hydrogen atmosphere. It shows a higher value of sheet resistance than maxin film. Therefore, when the annealing is performed in a hydrogen atmosphere when the sheet resistance is increased due to oxidation of the maxine film, the effect of restoring the sheet resistance becomes greater.
  • a predetermined oxidation resistance is generated by performing annealing, but it is possible to have a higher oxidation resistance by performing annealing in a hydrogen atmosphere.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention concerne un procédé de récupération de propriétés électriques et d'amélioration de la stabilité d'oxydation dans un matériau bidimensionnel et, plus particulièrement, un procédé comprenant les étapes consistant à : (a) préparer une solution de MXènes contenant un carbure de métal de transition et un carbonitrure de métal de transition, chacun présentant une structure bidimensionnelle; (b) former la solution de MXènes préparée en un film de MXènes contenant un matériau composite sous forme de film; (c) stocker le film de MXènes formé à température ambiante; (d) disposer le film de MXènes oxydé pendant le stockage à température ambiante dans un équipement sous vide de façon à utiliser le film de MXènes; (e) injecter de l'hydrogène gazeux dans l'équipement sous vide dans lequel a été disposé le film de MXènes; et (f) recuire le film de MXènes pour récupérer les propriétés électriques du film de MXènes exposé à l'hydrogène gazeux injecté à un niveau d'avant l'oxydation, moyennant quoi les propriétés électriques du film de MXènes, qui sont devenues médiocres en raison de l'oxydation à température ambiante, peuvent être récupérées par le recuit du film de MXènes avec l'exposition de celui-ci à l'hydrogène gazeux dans l'équipement sous vide.
PCT/KR2019/003787 2018-09-28 2019-04-01 Procédé de récupération de propriétés électriques et d'amélioration de la stabilité d'oxydation dans un matériau bidimensionnel WO2020067617A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020180116102A KR102178752B1 (ko) 2018-09-28 2018-09-28 2차원 물질의 전기적 특성 회복 및 산화 안정성 개선 방법
KR10-2018-0116102 2018-09-28

Publications (1)

Publication Number Publication Date
WO2020067617A1 true WO2020067617A1 (fr) 2020-04-02

Family

ID=69952908

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2019/003787 WO2020067617A1 (fr) 2018-09-28 2019-04-01 Procédé de récupération de propriétés électriques et d'amélioration de la stabilité d'oxydation dans un matériau bidimensionnel

Country Status (2)

Country Link
KR (1) KR102178752B1 (fr)
WO (1) WO2020067617A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112443051A (zh) * 2020-12-11 2021-03-05 广东康烯科技有限公司 多孔碳化钛MXene/还原氧化石墨烯基墙板

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114452837B (zh) * 2022-03-02 2023-01-17 重庆工商大学 一种MXene二维薄片膜缺陷修复的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150097397A (ko) * 2014-02-18 2015-08-26 도레 엔지니아린구 가부시키가이샤 투명 도전막의 형성 방법 및 박막 가열 건조 장치
KR20170036507A (ko) * 2015-09-24 2017-04-03 삼성전자주식회사 멕신(MXene) 나노시트 및 그 제조방법
CN106848226A (zh) * 2017-01-20 2017-06-13 西南交通大学 一种各向异性氮化钛陶瓷薄膜及其制备方法
KR20170102768A (ko) * 2016-03-02 2017-09-12 성균관대학교산학협력단 2차원 맥세인 박막의 제조방법, 이를 이용한 전자 소자의 제조 방법, 2차원 맥세인 박막을 포함하는 전자 소자

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6495115B1 (en) * 1995-09-12 2002-12-17 Omg Americas, Inc. Method to produce a transition metal carbide from a partially reduced transition metal compound
US9991122B2 (en) * 2016-08-31 2018-06-05 Micron Technology, Inc. Methods of forming semiconductor device structures including two-dimensional material structures
KR20180062080A (ko) * 2016-11-30 2018-06-08 영남대학교 산학협력단 맥신/탄화규소/페라이트 복합체 및 그 제조방법

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150097397A (ko) * 2014-02-18 2015-08-26 도레 엔지니아린구 가부시키가이샤 투명 도전막의 형성 방법 및 박막 가열 건조 장치
KR20170036507A (ko) * 2015-09-24 2017-04-03 삼성전자주식회사 멕신(MXene) 나노시트 및 그 제조방법
KR20170102768A (ko) * 2016-03-02 2017-09-12 성균관대학교산학협력단 2차원 맥세인 박막의 제조방법, 이를 이용한 전자 소자의 제조 방법, 2차원 맥세인 박막을 포함하는 전자 소자
CN106848226A (zh) * 2017-01-20 2017-06-13 西南交通大学 一种各向异性氮化钛陶瓷薄膜及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RAKHI, R. B. ET AL.: "Effect of postetch annealing gas composition on the structural and electrochemical properties of Ti2CTx MXene electrodes for supercapacitor applications", CHEMISTRY OF MATERIALS, vol. 27, no. 15, 2015, pages 5314 - 5323, XP055571666, DOI: 10.1021/acs.chemmater.5b01623 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112443051A (zh) * 2020-12-11 2021-03-05 广东康烯科技有限公司 多孔碳化钛MXene/还原氧化石墨烯基墙板

Also Published As

Publication number Publication date
KR102178752B1 (ko) 2020-11-16
KR20200037000A (ko) 2020-04-08

Similar Documents

Publication Publication Date Title
WO2020067617A1 (fr) Procédé de récupération de propriétés électriques et d'amélioration de la stabilité d'oxydation dans un matériau bidimensionnel
WO2021145557A1 (fr) Procédé d'amélioration des caractéristiques de vitesse de charge/décharge d'un dispositif de stockage d'énergie à base de mxene et de nanotubes de carbone
WO2015023125A1 (fr) Dispositif de soudure de fils supraconducteurs à haute température en rebco et procédé de soudure l'utilisant
WO2021125798A1 (fr) Fibres de mxène et leur procédé de préparation
WO2019022402A2 (fr) Procédé de fabrication d'une électrode au lithium
WO2018194366A1 (fr) Porte-substrat électrostatique scellé avec un matériau d'étanchéité et son procédé de fabrication
WO2014137180A1 (fr) Dispositif électronique à base de carbone utilisant une réduction partielle d'oxyde de graphène et procédé de fabrication de celui-ci
WO2012063991A1 (fr) Procédé pour la fabrication d'une électrode d'aluminium à l'aide d'un procédé de mouillage et électrode d'aluminium fabriquée par celui-ci
JP5241392B2 (ja) 炭素質フィルムの製造方法
WO2020009421A1 (fr) Procédé de production d'oxyde de graphite et d'oxyde de graphène de manière respectueuse de l'environnement en utilisant une réaction d'hydroxylation
WO2016182118A1 (fr) Procédé de dopage de graphène à base d'une couche formant support par injection ionique
WO2019164066A1 (fr) Structure d'électrode, son procédé de fabrication, et élément électrochimique la comprenant
Suo et al. Transport critical current densities and n factors in mono-and multifilamentary MgB/sub 2//Fe tapes and wires using fine powders
WO2015102157A1 (fr) Composition pour la préparation de graphène et procédé de préparation de graphène à l'aide de celle-ci
WO2011155659A1 (fr) Procédé pour la fabrication de fil supraconducteur de diborure de magnésium, et fil supraconducteur de diborure de magnésium fabriqué au moyen de celui-ci
WO2020256394A1 (fr) Procédé de fabrication d'un matériau composite, et matériau composite
WO2022065839A1 (fr) Procédé de fabrication de flocons de graphène secs/humides et flocons de graphène ainsi fabriqués
JP3061573B2 (ja) 積層セラミックスの製造方法
WO2021033884A1 (fr) Procédé de gravure au plasma
JPH11268976A (ja) グラファイトシートの製造方法
WO2020130658A1 (fr) Film d'oxyde de graphène dopé au tungstène, son procédé de fabrication, et émetteur d'électrons le comprenant
WO2022197145A1 (fr) Mandrin électrostatique, dispositif de chauffage de mandrin électrostatique le comprenant, et dispositif de maintien de semi-conducteurs
WO2023277559A1 (fr) Mandrin électrostatique, dispositif de chauffage de mandrin électrostatique le comprenant, et dispositif de maintien de semi-conducteurs
WO2015005570A1 (fr) Poudre de céramique pour film de protection de plaque de séparation en métal de pile à combustible à oxyde solide, méthode de fabrication de celle-ci et méthode de fabrication de film de protection de plaque de séparation en métal de pile à combustible à oxyde solide utilisant celle-ci
WO2014208768A1 (fr) Procédé d'utilisation d'un composite c/c revêtu de sic

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19866761

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19866761

Country of ref document: EP

Kind code of ref document: A1