CN113115580B - Method for preparing LDH/carbon composite material with assistance of atomic layer deposition, obtained product and application - Google Patents
Method for preparing LDH/carbon composite material with assistance of atomic layer deposition, obtained product and application Download PDFInfo
- Publication number
- CN113115580B CN113115580B CN202110348202.5A CN202110348202A CN113115580B CN 113115580 B CN113115580 B CN 113115580B CN 202110348202 A CN202110348202 A CN 202110348202A CN 113115580 B CN113115580 B CN 113115580B
- Authority
- CN
- China
- Prior art keywords
- composite material
- ldh
- carbon
- graphene
- atomic layer
- Prior art date
- Legal status (The legal status 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 status listed.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/403—Oxides of aluminium, magnesium or beryllium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Electromagnetism (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for preparing LDH/carbon composite material with the assistance of atomic layer deposition, an obtained product and application, wherein the preparation method comprises the following steps: preparation of Al of different thicknesses2O3A carbon material composite; preparing the LDH composite material. The invention combines the atomic layer deposition and the hydrothermal technology to prepare the LDH nano composite material. The method has simple process, can accurately control the thickness of the LDH and effectively solve the agglomeration defect of the LDH, and has wide application value in the fields of energy storage, electromagnetic shielding, corrosion prevention and the like.
Description
Technical Field
The invention relates to a method for preparing LDH (layered double hydroxide)/carbon composite material with the assistance of atomic layer deposition, an obtained product and application, belonging to the technical field of nano material preparation and structure regulation.
Background
Layered Double Hydroxides (LDHs) are metal hydroxides composed of two or more metal elements, and have a structure formed by overlapping main layers and interlayer anions and water molecules. The composite material has the advantages of easy modulation of the components (the type and proportion of metal ions on the laminate, the type of anions and the like), easy cutting of the structure (the number of layers, the interlayer spacing and the like), easy realization of functionalization by compounding with other materials and the like, so the composite material has wide application prospect in the fields of catalytic Oxygen Evolution (OER), energy storage, electromagnetic wave absorption, pollutant adsorption and the like.
In recent years, a series of synthetic preparation techniques have been established based on LDH materials. These techniques address the issue of regulating the ratio of different metal atoms, anion exchange, solution pH, etc., and address the shortcomings of different LDHs that can be prepared. However, when the LDH is compounded with other materials, the problems of difficulty in controlling the compounding amount, uneven dispersion, agglomeration, instability, long preparation period and the like exist, and the problems are not solved effectively in the prior art, so that the development of a technology which is simple and convenient and can accurately control and prepare the similar array structure has important significance.
Disclosure of Invention
The invention aims to provide a method for preparing an LDH/carbon composite material by atomic layer deposition assistance and an obtained product.
According to the preparation method, carbon materials such as graphene, carbon nanotubes and carbon fibers are used as substrates, and the LDH/carbon composite material is prepared by combining the atomic layer deposition and the hydrothermal technology, wherein in the prepared LDH/carbon composite material, flaky LDH is vertically longer than the carbon materials, and no agglomeration exists. The specific technical scheme is as follows:
a method for preparing an LDH/carbon composite material with the assistance of atomic layer deposition, comprising the steps of:
(1) depositing an aluminum oxide layer on the surface of the carbon material by an atomic layer deposition method to obtain an aluminum oxide/carbon composite material;
(2) and dispersing the alumina/carbon composite material into an aqueous solution containing metal salt and alkaline salt, and carrying out hydrothermal reaction to obtain the LDH/carbon composite material.
Further, in the step (1), the carbon material dispersion liquid is dropped on the carrier, and after drying, the carrier is placed in an atomic layer deposition device for alumina deposition, so as to obtain an alumina-coated carbon composite material, namely an alumina/carbon composite material. The carbon material dispersion liquid is ethanol dispersion liquid of the carbon material, the carbon material is uniformly dispersed in absolute ethanol, and in order to ensure the uniformity of dispersion, the carbon material dispersion liquid can be dispersed in an ultrasonic mode. The carbon material is present in the dispersion at a concentration of 1-2 mg/ml.
Further, in the step (1), the carbon material is graphene, carbon nanotubes or carbon fibers.
Further, in the step (1), the carrier is a quartz plate.
Further, in the step (1), the thickness of the dispersed droplets of the carbon material on the support is about 1 to 2 mm. The thickness is not easy to be too thick, and the deposition of alumina can be influenced by too thick thickness.
Further, in the step (1), the atomic layer deposition can be performed by using the method disclosed in the prior art, so that the alumina is deposited on the surface of the carbon material. The method, conditions, and the like of the atomic layer deposition can be adjusted according to the thickness of the alumina. For example, atomic layer deposition may be performed using the following steps: putting a carbon material into an atomic layer deposition device, controlling the temperature at 140-160 ℃, taking trimethylaluminum and water as precursors, firstly carrying out a trimethylaluminum pulse adsorption reaction, then purging redundant reactants and byproducts by using inert gas, then carrying out a water pulse adsorption reaction, and then purging redundant reactants and byproducts by using inert gas. Repeating the above 10-10000 cycles with the above cycle as one cycle until an aluminum oxide layer with the required thickness is formed. Preferably, the deposition period is 50-150 cycles.
Further, in the step (2), the metal salt is nickel chloride, and the alkaline salt is ammonium nitrate or ammonium chloride.
Further, in the step (2), the concentration of the metal salt in the aqueous solution is 0.35-0.75 mol/L, and the molar ratio of the metal salt to the alkaline salt is 0.6-1.5: 1.
further, in the step (2), the concentration of the alumina/carbon composite material in the aqueous solution is 0.1-1.5 mg/ml.
Further, in the step (2), the pH value of the system is ensured to be 8-10.
Further, in the step (2), the hydrothermal reaction is carried out in a hydrothermal reactor in a closed state. The temperature of the hydrothermal reaction is 130-150 ℃, and the heat preservation time is 20-24 h.
According to the method, the surface of the carbon material is coated with the alumina by an atomic deposition method, so that the advantage of improving the surface hydrophilicity of the carbon material is achieved. And then growing LDH on the surface of the carbon material coated with the alumina by a hydrothermal method, wherein the alumina can be used as a raw material for subsequent reaction to induce the LDH to grow on the carbon material, and the LDH can be prevented from agglomerating and the thickness of the LDH can be controlled by controlling the conditions such as the deposition thickness of the alumina. LDH grows vertically and tightly on the carbon material, has no agglomeration and is in a sheet structure.
According to the invention, carbon materials such as graphene are used as a substrate in the synthesis process, and the LDH/carbon nano composite material is prepared by a method combining atomic layer deposition and a hydrothermal technology, and the composite material is in a disordered array shape, so that the problem of LDH agglomeration is well solved, and the structural stability of LDH is improved. Compared with the prior art, the invention has the advantages that:
(1) the LDH/carbon nano composite material is prepared by combining the atomic layer deposition technology and the hydrothermal technology, the preparation process is simple and easy to implement, and the LDH thickness is accurate and controllable.
(2) The LDH/carbon nano composite material with the array structure is prepared, the problem that LDH and a carbon material are easy to aggregate is solved, the specific surface area is large, and the number of active sites is large.
(3) The LDH/carbon nano composite material prepared by the invention has good conductivity and a stable structure, and experiments show that the LDH/carbon nano composite material has high capacity in the energy storage process, and the structure is kept unchanged. The combination of the transition metal and the carbon material in the LDH is greatly improved in electromagnetic shielding performance. Due to the stable LDH structure, the material has wide application in the aspect of corrosion prevention due to the adjustability of anions between layers.
Drawings
Fig. 1 is an XRD spectrum of the LDH/graphene composite material prepared in example 1 of the present invention.
FIG. 2 is a TEM image of LDH/graphene composite materials with different thicknesses prepared in example 1 of the present invention, wherein A, 50-NiAl-LDH/graphene composite material, B, 100-NiAl-LDH/graphene composite material, and C, 150-NiAl-LDH/graphene composite material.
Fig. 3 is a BET diagram of the LDH/graphene composite material prepared in example 2 of the present invention.
Fig. 4 is a TEM image of the LDH/graphene composite material prepared in example 2 of the present invention.
Fig. 5 is a performance diagram of the LDH/graphene composite material prepared in example 1 of the present invention in an electromagnetic shielding experiment.
Fig. 6 is a performance diagram of the LDH/graphene composite material prepared in example 1 of the present invention in an anticorrosion experiment.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications can be made by those skilled in the art after reading the contents of the present invention, and those equivalents also fall within the scope of the invention defined by the appended claims.
Example 1
The preparation method of the LDH/graphene nanocomposite material with different thicknesses comprises the following steps:
1. graphene pretreatment
Dissolving 20mg of graphene in a transparent small bottle of 15 ml of absolute ethyl alcohol, carrying out ultrasonic treatment for 15 min until no agglomeration exists, and judging whether the graphene is uniformly dispersed by using a rubber head dropper to obtain a graphene dispersion liquid;
2. preparation of alumina/graphene composite materials with different thicknesses
Evenly dropwise add the graphene dispersion liquid on a square quartz plate with the thickness of 8 cm x 8 cm by using a rubber head dropper, wherein the thickness of the dispersion liquid is about 1 mm, after natural drying, the quartz plate is put into an atomic layer deposition device for depositing aluminum oxide, the temperature of the atomic layer deposition device is 150 ℃, and the procedure is as follows: performing pulse adsorption reaction on a trimethyl aluminum precursor with the purity of 99%; inert gas purges redundant reactants and byproducts; pulse adsorption reaction of a deionized water precursor; the inert gas purges excess reactants and byproducts. Respectively circulating for 50, 100 and 150 circles according to the program to obtain Al with different thicknesses2O3The powder on the quartz plate is scraped off and is respectively marked as 50-Al2O3Graphene composite material and 100-Al2O3Graphene compositeMaterial, 150-Al2O3A graphene composite material;
3. preparation of LDH/graphene composite materials with different thicknesses
3 g of nickel chloride hexahydrate and 0.8 g of ammonium nitrate are dissolved in 35ml of deionized water to form a solution A, and three cups of the same solution A are prepared; respectively taking 50-Al2O3Graphene composite material and 100-Al2O3Graphene composite material 150-Al2O3Respectively dissolving 20mg of/graphene composite material in three cups of solution A, adjusting the pH value to 8 by using 1.5 mol/L of sodium hydroxide, fully stirring, respectively transferring the solution into 50 ml of hydrothermal kettle liners, sealing, transferring into an oven, and keeping the temperature at 140 ℃ for 24 hours to obtain a 50-NiAl-LDH/graphene composite material, a 100-NiAl-LDH/graphene composite material and a 150-NiAl-LDH/graphene composite material.
Fig. 1 is an XRD (X-ray diffraction) pattern of the obtained NiAl-LDH/graphene composite material, and the LDH can be judged to be successfully synthesized from the XRD pattern. FIG. 2 is a TEM image of three NiAl-LDH/graphene composite materials with different thicknesses, and it can be seen from the TEM image that LDH with different thicknesses is grafted on graphene and basically has no agglomeration phenomenon; the LDH is sheet-shaped and vertically and tightly grows on the graphene in an array shape, and the thickness of the LDH sheet is about 5 nm, 10 nm and 15 nm respectively.
Example 2
The preparation method of the LDH/graphene nano composite material and the application of the LDH/graphene nano composite material in the field of energy storage comprises the following steps:
1. graphene pretreatment
Dissolving 20mg of graphene in a transparent small bottle of 15 ml of absolute ethyl alcohol, carrying out ultrasonic treatment for 15 min, and judging whether the graphene is uniformly dispersed by using a rubber-tipped dropper to obtain a graphene dispersion liquid;
2. preparation of alumina/graphene composite material
Evenly dropwise add the graphene dispersion liquid on a square quartz plate with the thickness of about 1 mm by using a rubber head dropper, after natural drying, putting the quartz plate into an atomic layer deposition device for depositing aluminum oxide, wherein the temperature of the atomic layer deposition device is 150 ℃, and the procedure is as follows: performing pulse adsorption reaction on a trimethyl aluminum precursor with the purity of 99%; inert gas purgingThe remaining reactants and by-products; pulse adsorption reaction of a deionized water precursor; the inert gas purges excess reactants and byproducts. After circulating for 100 circles in sequence, Al is obtained2O3The graphene composite material is obtained by scraping powder on a quartz plate;
3. preparation of LDH/graphene composite material
6 g of nickel chloride hexahydrate and 2 g of ammonium chloride are dissolved in 35ml of boiling water to form a solution A; dissolving 20mg of the alumina/graphene composite material in the solution A, adjusting the pH value to 9 by using 1.5 mol/L sodium hydroxide, fully stirring, transferring the mixture into a 50 ml hydrothermal kettle liner, sealing, transferring the mixture into an oven, and keeping the temperature at 140 ℃ for 24 hours to obtain a NiAl-LDH/graphene composite material;
as can be seen from fig. 3 and 4, the obtained NiAl-LDH/graphene composite material has a large specific surface area and effectively suppresses the agglomeration phenomenon.
Example 3
The preparation method of the LDH/graphene nano composite material and the application of the LDH/graphene nano composite material in the field of electromagnetic shielding comprises the following steps:
1. graphene pretreatment
Dissolving 20mg of graphene in a transparent small bottle of 15 ml of absolute ethyl alcohol, carrying out ultrasonic treatment for 15 min, and judging whether the graphene is uniformly dispersed by using a rubber-tipped dropper to obtain a graphene dispersion liquid;
2. preparation of alumina/graphene composite material
Evenly dropwise add the graphene dispersion liquid on a square quartz plate with the thickness of 8 cm x 8 cm by using a rubber head dropper, wherein the thickness is about 1 mm, after natural drying, the quartz plate is placed into an atomic layer deposition device for depositing aluminum oxide, the temperature of the atomic layer deposition device is 150 ℃, and the procedure is as follows: performing pulse adsorption reaction on a trimethyl aluminum precursor with the purity of 99%; inert gas purges redundant reactants and byproducts; pulse adsorption reaction of a deionized water precursor; the inert gas purges excess reactants and byproducts. After circulating for 100 circles in sequence, Al is obtained2O3The powder on the quartz plate is scraped off and is marked as Al2O3A graphene composite material;
3. preparation of LDH/graphene composite material
4.8 g of nickel chloride hexahydrate and 1.6 g of ammonium nitrate are dissolved in 35ml of deionized water to form a solution A; taking Al again2O3And dissolving 20mg of the graphene composite material in the solution A, adjusting the pH value to 8 by using 1.5 mol/L sodium hydroxide, fully stirring, transferring the mixture into a 50 ml hydrothermal kettle liner, sealing, transferring the mixture into an oven, and keeping the temperature at 140 ℃ for 24 hours. Taking alumina as a subsequent raw material, wherein the alumina is completely converted and disappears after hydrothermal treatment, and reacting with nickel chloride to obtain a NiAl-LDH/graphene composite material;
as can be seen from FIG. 5, the obtained NiAl-LDH/graphene composite material has a good electromagnetic shielding effect.
Example 4
The preparation method of the LDH/graphene nano composite material and the application of the LDH/graphene nano composite material in the field of corrosion prevention comprises the following steps:
1. graphene pretreatment
Dissolving 20mg of graphene in a transparent small bottle of 15 ml of absolute ethyl alcohol, carrying out ultrasonic treatment for 15 min, and judging whether the graphene is uniformly dispersed by using a rubber-tipped dropper to obtain a graphene dispersion liquid;
2. preparation of alumina/graphene composite material
Evenly dropwise add the graphene dispersion liquid on a square quartz plate with the thickness of 8 cm x 8 cm by using a rubber head dropper, wherein the thickness is about 1 mm, after natural drying, the quartz plate is placed into an atomic layer deposition device for depositing aluminum oxide, the temperature of the atomic layer deposition device is 150 ℃, and the procedure is as follows: performing pulse adsorption reaction on a trimethyl aluminum precursor with the purity of 99%; inert gas purges redundant reactants and byproducts; pulse adsorption reaction of a deionized water precursor; the inert gas purges excess reactants and byproducts. After circulating for 100 circles in sequence, Al is obtained2O3The powder on the quartz plate is scraped off and is marked as Al2O3A graphene composite material;
3. preparation of LDH/graphene composite material
3.6 g of nickel chloride hexahydrate and 1.51 g of ammonium nitrate are dissolved in 35ml of deionized water to form a solution A; taking Al again2O3Graphene complexesDissolving 20mg of the composite material in the solution A, adjusting the pH value to 10 by using 1.5 mol/L sodium hydroxide, fully stirring, transferring the mixture into a liner of a 50 ml hydrothermal kettle, sealing, transferring the mixture into an oven, and keeping the temperature at 140 ℃ for 24 hours to obtain a NiAl-LDH/graphene composite material;
as can be seen from FIG. 6, the obtained NiAl-LDH/graphene composite material can successfully absorb chloride ions through ion exchange in an anticorrosion experiment, so that an anticorrosion effect is achieved.
Example 5
The preparation method of the LDH/carbon fiber nanocomposite material with different thicknesses comprises the following steps:
1. carbon fiber pretreatment
Dissolving 20mg of carbon fiber in a transparent small bottle of 15 ml of absolute ethyl alcohol, carrying out ultrasonic treatment for 15 min until no agglomeration exists, and judging whether the carbon fiber is uniformly dispersed by using a rubber head dropper to obtain a carbon fiber dispersion liquid;
2. preparation of alumina/carbon fiber composite materials with different thicknesses
Evenly dropwise add carbon fiber dispersion liquid on 8 cm x 8 cm square quartz plate with rubber head burette, thickness is about 1 mm, treat after the natural drying, put into atomic layer deposition device with the quartz plate and carry out the deposit of aluminium oxide, atomic layer deposition device's temperature is 150 ℃, and the procedure is: performing pulse adsorption reaction on a trimethyl aluminum precursor with the purity of 99%; inert gas purges redundant reactants and byproducts; performing pulse adsorption reaction on a deionized water precursor; the inert gas purges excess reactants and byproducts. Respectively circulating for 50, 100 and 150 circles to obtain Al with different thicknesses2O3The carbon fiber composite material is prepared by scraping powder on a quartz plate, and respectively recording the powder as 50-Al2O3Carbon fiber composite material, 100-Al2O3Carbon fiber composite material, 150-Al2O3A carbon fiber composite material;
3. preparation of LDH/carbon fiber composite materials with different thicknesses
3 g of nickel chloride hexahydrate and 0.8 g of ammonium nitrate are dissolved in 35ml of deionized water to form a solution A, and three cups of the same solution A are prepared; respectively taking 50-Al2O3Carbon fiber composite material, 100-Al2O3Carbon fiber composite material, 150-Al2O320mg of/carbon fiber composite material are respectively dissolved in three cups of solution A, the pH value is adjusted to 8 by 1.5 mol/L of sodium hydroxide, the mixture is fully stirred and respectively transferred into an inner container of a 50 ml hydrothermal kettle, the inner container is transferred into an oven after being sealed, and the temperature is kept at 140 ℃ for 24 hours, so that 50-NiAl-LDH/carbon fiber composite material, 100-NiAl-LDH/carbon fiber composite material and 150-NiAl-LDH/carbon fiber composite material are obtained.
Example 6
The preparation method of the LDH/carbon nanotube nano composite material with different thicknesses comprises the following steps:
1. carbon nanotube pretreatment
Dissolving 20mg of carbon nano tube in a transparent small bottle of 15 ml of absolute ethyl alcohol, carrying out ultrasonic treatment for 15 min until no agglomeration exists, and judging whether the carbon nano tube is uniformly dispersed by using a rubber head dropper to obtain carbon nano tube dispersion liquid;
2. preparing alumina/carbon nano tube composite materials with different thicknesses
Uniformly dripping the carbon nanotube dispersion liquid on a square quartz plate with the thickness of about 1 mm by using a rubber head dropper, after natural drying, putting the quartz plate into an atomic layer deposition device for depositing aluminum oxide, wherein the temperature of the atomic layer deposition device is 150 ℃, and the procedure is as follows: performing pulse adsorption reaction on a trimethyl aluminum precursor with the purity of 99%; inert gas purges redundant reactants and byproducts; pulse adsorption reaction of a deionized water precursor; the inert gas purges excess reactants and byproducts. Respectively circulating for 50, 100 and 150 circles to obtain Al with different thicknesses2O3The carbon nanotube composite material is prepared by scraping powder on a quartz plate, and respectively marking as 50-Al2O3Carbon nanotube composite material, 100-Al2O3Carbon nanotube composite material, 150-Al2O3A carbon nanotube composite;
3. preparation of LDH/carbon nanotube composite materials with different thicknesses
3 g of nickel chloride hexahydrate and 0.8 g of ammonium nitrate are dissolved in 35ml of deionized water to form a solution A, and three cups of the same solution A are prepared; respectively taking 50-Al2O3Carbon nanotubeComposite Material, 100-Al2O3Carbon nanotube composite material, 150-Al2O320mg of/carbon nanotube composite material is respectively dissolved in the three-cup solution A, the pH value is adjusted to 8 by using 1.5 mol/L sodium hydroxide, the mixture is fully stirred and respectively transferred into the inner containers of a 50 ml hydrothermal kettle, the inner containers are transferred into an oven after being sealed, and the temperature is kept at 140 ℃ for 24 hours, so that the 50-NiAl-LDH/carbon nanotube composite material, the 100-NiAl-LDH/carbon nanotube composite material and the 150-NiAl-LDH/carbon nanotube composite material are obtained.
Example 7
The preparation method of the LDH/graphene nanocomposite material comprises the following steps:
1. graphene pretreatment
Dissolving 20mg of graphene in a transparent small bottle of 15 ml of absolute ethyl alcohol, carrying out ultrasonic treatment for 15 min until no agglomeration exists, and judging whether the graphene is uniformly dispersed by using a rubber head dropper to obtain a graphene dispersion liquid;
2. preparation of alumina/graphene composite material
Evenly dropwise add the graphene dispersion liquid on a square quartz plate with the thickness of 8 cm x 8 cm by using a rubber head dropper, wherein the thickness is about 1 mm, after natural drying, the quartz plate is placed into an atomic layer deposition device for depositing aluminum oxide, the temperature of the atomic layer deposition device is 150 ℃, and the procedure is as follows: performing pulse adsorption reaction on a trimethyl aluminum precursor with the purity of 99%; inert gas purges redundant reactants and byproducts; pulse adsorption reaction of a deionized water precursor; the inert gas purges excess reactants and byproducts. After circulating for 100 circles in sequence, Al is obtained2O3The powder on the quartz plate is scraped off and is marked as 100-Al2O3A graphene composite material;
3. preparation of LDH/graphene composite material
4.2 g of nickel chloride hexahydrate and 1.2 g of ammonium nitrate are dissolved in 35ml of deionized water to form a solution A; taking 100-Al2O3Dissolving 20mg of/graphene composite material in the solution A, adjusting the pH value to 8 by using 1.5 mol/L sodium hydroxide, fully stirring, transferring the solution into a 50 ml hydrothermal kettle liner, sealing, transferring the solution into an oven, and keeping the temperature at 140 ℃ for 24 hours to obtain 100-NiAl-LDH (lithium-layered double hydroxide) -based ion exchange membrane), whereinGraphene composite materials.
Comparative example 1
The LDH/graphene nanocomposite material is prepared by a one-step hydrothermal method, and the method comprises the following steps:
1. graphene pretreatment
Dissolving 20mg of graphene in a transparent small bottle of 15 ml of absolute ethyl alcohol, carrying out ultrasonic treatment for 15 min until no agglomeration exists, and judging whether the graphene is uniformly dispersed by using a rubber head dropper to obtain a graphene dispersion liquid;
2. hydro-thermal preparation of LDH/graphene composite material
3.6 g of nickel chloride hexahydrate, 1.2 g of aluminum nitrate nonahydrate and 0.8 g of ammonium nitrate are dissolved in 35ml of deionized water to form a solution A; and dissolving 15 ml of graphene dispersion liquid in the solution A, adjusting the pH value to 8 by using 1.5 mol/L sodium hydroxide, fully stirring, transferring the solution into a 100 ml hydrothermal kettle liner, sealing, transferring into an oven, and preserving heat at 140 ℃ for 24 hours to obtain the NiAl-LDH/graphene composite material.
The NiAl-LDH/graphene nanocomposite material prepared by the method has the advantages that graphene and LDH are easy to accumulate and agglomerate, and the material performance is influenced.
Comparative example 2
An LDH/graphene nanocomposite was prepared as in example 7, except that: the thickness of the graphene dispersion dropped on the quartz plate was about 4 mm. The LDH/graphene nanocomposite material obtained by the method has the advantages that due to the fact that graphene on the quartz plate is too thick, alumina is deposited unevenly, and the un-deposited graphene is mixed with the alumina/graphene, the preparation of the LDH/graphene nanocomposite material in hydrothermal reaction is inhibited to a certain extent.
Claims (3)
1. A method for preparing LDH/carbon composite material with the assistance of atomic layer deposition is characterized by comprising the following steps:
(1) depositing an aluminum oxide layer on the surface of the carbon material by an atomic layer deposition method to obtain an aluminum oxide/carbon composite material;
(2) dispersing the alumina/carbon composite material into an aqueous solution containing metal salt and alkaline salt, and obtaining an LDH/carbon composite material through a hydrothermal reaction;
the carbon material is graphene;
in the step (1), the carbon material dispersion liquid is dropped on a carrier, the carrier is placed in an atomic layer deposition device for deposition of alumina after drying, an alumina/carbon composite material is obtained, the deposition temperature is 140-; the carbon material dispersion liquid is ethanol dispersion liquid of a carbon material, the concentration of the carbon material in the dispersion liquid is 1-2 mg/ml, and the thickness of the carbon material dispersion liquid on the carrier is 1-2 mm;
in the step (2), the metal salt is nickel chloride, and the alkaline salt is ammonium nitrate or ammonium chloride;
in the step (2), the concentration of the metal salt in the aqueous solution is 0.35-0.75 mol/L, and the molar ratio of the metal salt to the alkaline salt is 0.6-1.5: 1, the concentration of the alumina/carbon composite material in the water solution is 0.1-1.5 mg/ml;
in the step (2), the pH value of the hydrothermal reaction is 8-10, the temperature of the hydrothermal reaction is 130-150 ℃, and the heat preservation time is 20-24 h.
2. An LDH/carbon composite material produced by the atomic layer deposition-assisted method of preparing an LDH/carbon composite material as claimed in claim 1.
3. The use of an LDH/carbon composite material as claimed in claim 2 in the fields of energy storage, electromagnetic shielding or corrosion protection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110348202.5A CN113115580B (en) | 2021-03-31 | 2021-03-31 | Method for preparing LDH/carbon composite material with assistance of atomic layer deposition, obtained product and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110348202.5A CN113115580B (en) | 2021-03-31 | 2021-03-31 | Method for preparing LDH/carbon composite material with assistance of atomic layer deposition, obtained product and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113115580A CN113115580A (en) | 2021-07-13 |
| CN113115580B true CN113115580B (en) | 2022-05-27 |
Family
ID=76713048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110348202.5A Active CN113115580B (en) | 2021-03-31 | 2021-03-31 | Method for preparing LDH/carbon composite material with assistance of atomic layer deposition, obtained product and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113115580B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116904960A (en) * | 2023-07-11 | 2023-10-20 | 哈尔滨理工大学 | High-temperature-resistant wave-absorbing material with core-shell structure, and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701241A (en) * | 2012-05-04 | 2012-10-03 | 北京化工大学 | Cleaning preparation method of laminated composite metal hydroxide |
| CN109023299A (en) * | 2018-07-31 | 2018-12-18 | 山东科技大学 | A kind of preparation method of the hydrotalcite of magnesium/magnesium alloy-alumina composite coating |
| CN111632614A (en) * | 2020-05-11 | 2020-09-08 | 湖北臻润环境科技股份有限公司 | Three-dimensional petal-shaped NiAl-LDH/Ti3C2Composite photocatalyst and preparation method and application thereof |
-
2021
- 2021-03-31 CN CN202110348202.5A patent/CN113115580B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701241A (en) * | 2012-05-04 | 2012-10-03 | 北京化工大学 | Cleaning preparation method of laminated composite metal hydroxide |
| CN109023299A (en) * | 2018-07-31 | 2018-12-18 | 山东科技大学 | A kind of preparation method of the hydrotalcite of magnesium/magnesium alloy-alumina composite coating |
| CN111632614A (en) * | 2020-05-11 | 2020-09-08 | 湖北臻润环境科技股份有限公司 | Three-dimensional petal-shaped NiAl-LDH/Ti3C2Composite photocatalyst and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Atomic layer deposition-assisted growth of CuAl LDH on carbon fiber as a peroxidase mimic for colorimetric determination of H2O2 and glucose;Lihong Wu等;《New Journal of Chemistry》;20190314;第5826-5832页 * |
| Growth of NiAl-Layered Double Hydroxide on Graphene toward Excellent Anticorrosive Microwave Absorption Application;Xuefei Xu等;《ADVANCED SCIENCE》;20210131;第1-12页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113115580A (en) | 2021-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zou et al. | Facile preparation and photocatalytic activity of oxygen vacancy rich BiOCl with {0 0 1} exposed reactive facets | |
| EP3429749B1 (en) | High aspect ratio layered double hydroxide materials and methods for preparation thereof | |
| CN113121838B (en) | Method for preparing MOF/carbon composite material with assistance of atomic layer deposition, obtained product and application | |
| CN108246331B (en) | ZnS micron composite material modified by graphene nitrogen carbide quantum dots and preparation method and application thereof | |
| Kawashima et al. | Protonated oxide, nitrided, and reoxidized K2La2Ti3O10 crystals: Visible-light-induced photocatalytic water oxidation and fabrication of their nanosheets | |
| CN113115580B (en) | Method for preparing LDH/carbon composite material with assistance of atomic layer deposition, obtained product and application | |
| Zhao et al. | Truncated concave octahedral Cu 2 O nanocrystals with {hkk} high-index facets for enhanced activity and stability in heterogeneous catalytic azide–alkyne cycloaddition | |
| CN110642240B (en) | Method for synthesizing high-purity carbon nanocoil by using composite catalyst formed on basis of multiple small-size catalysts | |
| Juibari et al. | Metal–organic framework-derived nanocomposite metal-oxides with enhanced catalytic performance in thermal decomposition of ammonium perchlorate | |
| Gunnewiek et al. | Synthesis of spinel cobalt oxide nanoparticles using a modified polymeric precursor method | |
| Dhara et al. | Two stage chemical bath deposition of MoO 3 nanorod films | |
| Dinh et al. | A solvothermal single‐step route towards shape‐controlled titanium dioxide nanocrystals | |
| Gimeno-Fabra et al. | Continuous flow synthesis of tungsten oxide (WO3) nanoplates from tungsten (VI) ethoxide | |
| Hu et al. | Microwave plasma torch synthesis of ZnAl oxides as adsorbent and photocatalyst for organic compounds removal | |
| CN113860341B (en) | High-purity platy boehmite and preparation method thereof | |
| Li et al. | Controlled fabrication and characterization of α-FeOOH nanorods | |
| CN114349060A (en) | Preparation method of carbon-supported magnetic nanoparticle nitrogen-doped magnetic graphene | |
| Zhang et al. | Research status, opportunities, challenges of cobalt phosphate based materials as OER electrocatalysts | |
| TW201425215A (en) | Method of modifying carbon-based electrode material and carbon-based electrode material formed thereby | |
| Van Ngo et al. | Synthesis of ZnO nanoparticles with tunable size and surface hydroxylation | |
| Menon et al. | Effect of calcination temperature on the microstructure and electronic properties of TiO 2–ZnO nanocomposites and implications on photocatalytic activity | |
| JP7122503B2 (en) | Method for producing photocatalyst material | |
| Heroux et al. | Nanoparticles Prepared by Salt Vapor‐Solvent Vapor Cocondensation and Controlled Nucleation: Metal Sulfides (ZnS, CdS, CdSe, PbS), and Metal Halide (LiF). Size, Aggregates, Structures, Digestive Ripening, Superlattices, and Impregnations | |
| CN113501966B (en) | Two-dimensional zinc-cobalt bimetallic ZIF catalyst and preparation method and application thereof | |
| Matsuda et al. | Comprehensive Analysis of the Chemical and Structural Transformations of Mg–Al–CO3 Layered Double Hydroxides with Different Mg/Al Ratios at Elevated Temperatures |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Wang Guizhen Inventor after: Wan Gengping Inventor after: Zhao Guoqing Inventor before: Wan Gengping Inventor before: Wang Guizhen Inventor before: Zhao Guoqing |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |