CN108394939B - Nano material with self-supporting nano sheet and preparation method and application thereof - Google Patents
Nano material with self-supporting nano sheet and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a nano material with self-supporting nano sheets and a preparation method and application thereof, wherein the core of the material is a metal sheet core with the particle size of 0.05-20 mu m, and the surface of the metal core is a self-supporting nano structure formed by corresponding metal hydroxide and/or metal oxide nano sheets. The metal hydroxide and/or metal oxide nanosheet is formed based on self-crosslinking assembly between the lamella and the metal core and between the lamella and the lamella, has a high specific surface area and a stable three-dimensional network structure, and combines excellent physicochemical properties of the metal hydroxide and ultrathin characteristics of the nanosheet.
Description
Technical Field
The invention relates to a nano material and a preparation method thereof, in particular to a nano material with self-supporting metal hydroxide and/or metal oxide nanosheets and a preparation method and application thereof.
Background
The metal hydroxide/oxide ultrathin nanosheet structure has attracted more and more attention in the field of catalysis due to the extremely large specific surface area and low raw material cost. The excellent electrocatalytic performance of the structure leads the structure to hopefully replace noble metal to become a new generation of electrode material which is widely applied to hydrogen production and oxygen production by water electrolysis and the electrode material of fuel cells. Meanwhile, the unique lamellar pore channel structure can realize the simultaneous utilization of two energy storage mechanisms of double electric layer capacitance and Faraday quasi-capacitance, so that the electrode material of the supercapacitor shows certain superiority.
At present, the main method for preparing the metal hydroxide/oxide nanosheet is to use metal salt as a raw material and prepare the metal hydroxide/oxide nanosheet by utilizing a hydrothermal method, a chemical deposition method, an electrodeposition method, a microwave deposition method and the like. CN104291368A discloses a preparation method of a two-dimensional single-layer magnesium-aluminum layered double-metal hydroxide/oxide nanosheet, which is to dissolve magnesium salt and aluminum salt in formamide, mix with strong alkaline hydroxide, and perform hydrothermal reaction to obtain the nanosheet. CN 105016398A discloses a nano-flake assembled cobalt iron hydroxide multistage microsphere and a preparation method thereof, wherein the method takes urea and the like as an alkali source, trisodium citrate as a complexing agent, water and n-butyl alcohol as reaction solvents, and adopts a chemical solution mixed solvent to prepare the single-layer and double-layer nano-flake assembled layered double metal hydroxide CoFe-LDHs multistage microsphere through heat. The preparation methods using metal salts as raw materials all need the action of a reducing agent, so that the preparation process is complex.
In view of this, it is also considered to use metal powders for the preparation of metal hydroxides. CN101759213A discloses a method for preparing layered double hydroxides from metal powder, which is a preparation strategy of preparing a hydrothermal solution from divalent metal powder or hydroxide thereof, trivalent metal powder or hydroxide thereof, soluble salt and deionized water according to a certain proportion and carrying out hydrothermal reaction in a hydrothermal kettle. However, the method does not realize the preparation of the metal hydroxide/oxide nanosheet, and the preparation process still needs higher temperature.
Because the metal oxide has a crystal structure with few sheets, the preparation method of the nano-sheet is more difficult. Shixue Dou et al reported a generalized metal oxide nanosheet synthesis method for the first time in the nature communication journal in 2014. Organic adhesive and surfactant are utilized to synthesize a lamellar structure containing metal oxide, and then organic matter is removed to finally obtain the metal oxide nanosheet.
It can be seen that there are three main problems in the prior art: firstly, the reactants are various chemical raw materials, so that the cost is high and the environmental pollution is great; secondly, the reaction conditions are harsh, the reaction time is long, and meanwhile, the raw materials are required to be solutions with lower concentrations, which is very unfavorable for large-scale preparation; thirdly, the expansibility of the alloy system is poor, so that part of metal materials are limited, and the preparation of the metal hydroxide/oxide nano-sheet of the composite special system cannot be easily carried out.
In summary, if a simple and easy preparation method can be adopted, it is important to prepare the metal hydroxide/oxide nanosheet by using pure transition metal and alloy powder thereof as raw materials.
Disclosure of Invention
It is an object of the present invention to overcome the disadvantages of the prior art and to provide a nanomaterial comprising nanosheets of metal hydroxides and/or metal oxides having a self-supporting structure.
Another object of the present invention is to provide a method for preparing the nanomaterial of metal hydroxide and/or metal oxide nanosheet having a self-supporting structure.
It is a further object of the present invention to provide the use of the nanomaterial of metal hydroxide and/or metal oxide nanoplates having a self-supporting structure as described above.
The technical scheme adopted by the invention is as follows:
the nano material with the self-supporting metal hydroxide and/or metal oxide nanosheets is provided with a flaky metal core, the particle size of the flaky metal core is 0.05-10 mu m, and the surface of the flaky metal core is a self-supporting structure formed by the corresponding metal hydroxide and/or metal oxide nanosheets.
As a further improvement of the nano material, the average thickness of the nano sheet is 1nm to 50 nm.
As a further improvement of the nano material, the length of the nano sheet is 100 nm-100 μm.
As a further improvement of the nano material, the average thickness of the flaky metal core is 0.01-1 μm.
As a further improvement of the nano material, the metal is a transition metal element or an alloy formed by transition metals. Further, the metal is selected from at least one of cobalt, nickel, copper, iron, zinc, manganese, molybdenum, or an alloy of at least two metal elements.
A method of preparing a nanomaterial having a plurality of layers of self-supporting metal hydroxide and/or metal oxide nanoplates, comprising the steps of:
1) mixing metal sheets with the average particle size of 1-100 mu m with an aqueous solution, and fully reacting at the temperature of not higher than 80 ℃;
2) and filtering, washing and drying at the temperature of not higher than 100 ℃ after the reaction is finished to obtain the nano material with the self-supporting metal hydroxide and/or metal oxide nanosheet.
The thickness of the metal sheet is preferably 0.1 to 50 μm.
As a further improvement of the preparation method, the pH value of the aqueous solution is 7-14.
As a further improvement of the preparation method, the reaction process is properly stirred at the stirring speed of 50-500 rpm.
As a further improvement of the preparation method, the reaction temperature is 15-45 ℃.
As a further improvement of the above production method, the production method of the metal sheet includes: and mixing the metal particles with the average particle size of 1-50 mu m with a surfactant, and performing ball milling to obtain the metal sheet.
As a further improvement of the preparation method, the surfactant is polyethylene glycol, and the addition amount of the surfactant is 0.5-5% of the mass of the metal particles.
The application of the nano material with the self-supporting metal hydroxide and/or the metal oxide nanosheet as a catalytic, adsorption or energy storage material.
The invention has the beneficial effects that:
the metal hydroxide and/or metal oxide nanosheet prepared by the method is formed based on self-crosslinking assembly between the lamella and the metal core and between the lamella and the lamella, has a high specific surface area and a stable three-dimensional network structure, and combines excellent physicochemical properties of the metal hydroxide/oxide and ultrathin characteristics of the nanosheet.
The method of the invention utilizes the principle of metal corrosion to grow metal hydroxide and/or metal oxide nanosheets on the surface of metal powder, and then the metal hydroxide and/or metal oxide nanosheets are filtered and dried to be converted into self-supporting metal hydroxide and/or metal oxide nanosheet materials. Compared with the prior art, the technical scheme of the invention is novel, simple, green and environment-friendly, breaks through the limitation that a large amount of chemical reagents and a heating reaction kettle are needed in the existing preparation of the nano-sheets, and realizes the preparation without the chemical reagents by utilizing the characteristics of the metal powder.
The formed nano material with the self-supporting metal hydroxide and/or metal oxide nanosheets has excellent adsorption performance, photo-thermal and electrical properties, can be developed into an adsorption material, an energy storage material or an electrode material, for example, the nano material can be used as a heavy metal and anion dye adsorption material, a gas adsorption material, a super capacitor energy storage material, an electrode material for water electrolysis, a negative electrode material for a lithium ion battery and the like, has important potential application in the fields of environmental protection, energy sources and the like, and has very important significance for expanding the application of metal hydroxide materials.
Drawings
FIG. 1 is an electron micrograph of a raw material used in example 1;
FIG. 2 is an electron microscope photograph of flake cobalt powder prepared in example 1
Fig. 3 is an electron microscope picture of self-supporting cobalt hydroxide multistage nanoplates prepared in example 1;
FIG. 4 is an X-ray diffraction spectrum of self-supporting cobalt hydroxide multistage nanoplates prepared in example 1;
FIG. 5 is an electron microscope photograph of the nickel powder used in example 2;
fig. 6 is an electron microscope picture of the flaky nickel-cobalt alloy powder prepared in example 2;
fig. 7 is an electron microscope picture of self-supporting nickel cobalt hydroxide multistage nanoplates prepared in example 2;
FIG. 8 is an electron microscope photograph of the micron cobalt powder prepared in example 6;
FIG. 9 is an electron microscope photograph of self-supporting cobalt hydroxide particles prepared in example 6;
FIG. 10 is an electron microscope photograph of a cross section of self-supporting cobalt hydroxide particles prepared in example 6;
fig. 11 is a current-voltage curve for the self-supporting cobalt hydroxide multilevel nanoplate prepared in example 1.
Detailed Description
The nano material with the self-supporting metal hydroxide and/or metal oxide nanosheets is provided with a flaky metal core, the particle size of the flaky metal core is 0.05-10 mu m, and the surface of the flaky metal core is a self-supporting structure formed by the corresponding metal hydroxide and/or metal oxide nanosheets.
The self-supporting refers to that the nano sheets are mutually supported, so that the overall nano structure is relatively stable and does not collapse. The flaky metal core has high specific surface area which can be possessed by the nano particles under the condition of keeping the micron-scale dimension. The nano-sheets grown thereon can be better dispersed and mutually supported to obtain the maximum specific surface area, which is beneficial to catalytic reaction. Because the monolithic material is in a self-supporting structure, the monolithic material can be used for catalytic reaction without being loaded on other substrates, and can be easily collected and recycled because the size of the material is kept in the micrometer range.
As a further improvement of the nano material, the average thickness of the nano sheet is 1nm to 50 nm. Its thickness and length can be controlled by controlling the reaction time and temperature.
As a further improvement of the nano material, the average thickness of the flaky metal core is 0.01-1 μm.
As a further improvement of the nano material, the length of the nano sheet is 100 nm-100 μm.
As a further improvement of the nano material, the metal is a transition metal element or an alloy formed by transition metals. Further, the metal is selected from at least one of cobalt, nickel, copper, iron, zinc, manganese, molybdenum, or an alloy of at least two metal elements.
A method of preparing a nanomaterial having a plurality of layers of self-supporting metal hydroxide and/or metal oxide nanoplates, comprising the steps of:
1) mixing metal sheets with the average particle size of 1-100 mu m with an aqueous solution, and fully reacting at the temperature of not higher than 80 ℃;
2) and filtering, washing and drying at the temperature of not higher than 100 ℃ after the reaction is finished to obtain the nano material with the self-supporting metal hydroxide and/or metal oxide nanosheet.
The thickness of the metal sheet is preferably 0.1 to 50 μm.
As a further improvement of the above preparation method, the metal is a transition metal element or an alloy formed of a transition metal. Further, the metal is selected from at least one of cobalt, nickel, copper, iron, zinc, manganese, molybdenum, or an alloy of at least two metal elements. Alloys include, but are not limited to, nickel-cobalt, nickel-iron, copper-nickel, iron-cobalt-nickel, cobalt-zinc, and the like.
The reaction time can be adjusted accordingly depending on the size of the raw material metal particles used and the reaction temperature. In general, the reaction time is at least 2 hours, preferably 5 hours or more.
As a further improvement of the above production method, the production method of the metal sheet includes: and mixing the metal particles with the average particle size of 1-50 mu m with a surfactant, and performing ball milling to obtain the metal sheet.
As a further improvement of the preparation method, the surfactant is polyethylene glycol, and the addition amount of the surfactant is 0.5-5% of the mass of the metal particles.
Polyethylene glycol is added as a surfactant in the process of preparing the metal sheet by ball milling, so that the specific surface area of the metal or the alloy can be greatly improved at low cost, a large amount of dislocation and defects are introduced, and the corrosion process of the metal or the alloy is accelerated. The thickness of the flaky metal powder can easily reach the nanometer level, so that the electrochemical potential effect generated in the corrosion process is enhanced, and the corrosion is further accelerated. In addition, transition products partially dissolved in water are generated in the metal corrosion process, so that the surface nanosheet can also have a continuous growth process, and a large number of metal hydroxide nanosheets which are staggered with each other are formed on the surface of the metal or alloy. The method is favorable for obtaining the multilayer self-supporting metal hydroxide and/or metal oxide nanosheet with more excellent performance.
The application of the multilayer self-supporting metal hydroxide and/or metal oxide nanosheet as a catalytic, adsorptive or energy storage material.
When the thickness of the used metal sheet is less than 0.1 μm, the specific surface area is too large, the reaction is too violent, and the oxide or hydroxide cannot completely follow the crystal face with the lowest surface energy to grow, so that a nanosheet structure cannot be generated; when the thickness of the metal sheet exceeds 50 μm, the specific surface area is too small, the reaction speed is very slow, the nano sheet cannot grow continuously, the nano sheet is converted into other shapes in the growth process, and a plurality of layers of self-supporting metal hydroxide and/or metal oxide nano sheets cannot be formed on the surface of a core.
Under neutral or alkaline conditions, the generation and growth of metal hydroxide/oxide can be promoted, and the formation of multilayer self-supporting metal hydroxide and/or metal oxide nanosheets on the surface of the metal core is facilitated. But OH in solution-When the concentration is too high, the corrosiveness is too strong, metal can be directly etched, and even the generated nano structure can be damaged. As a further improvement of the preparation method, the pH value of the aqueous solution is 7-14.
Increasing the temperature within a certain range helps to accelerate the oxidation reaction of the metal, but temperatures above 80 ℃ can result in a reaction that is too violent in destroying the nanostructures formed. To obtain multilayer self-supporting metal hydroxide and/or metal oxide nanosheets having excellent morphology, the reaction is preferably conducted at a temperature not exceeding 80 ℃. The reaction temperature is preferably 15-45 ℃ as a further improvement of the preparation method.
In order to avoid the destruction of the metal hydroxide/oxide nanosheets during drying, the temperature of drying is further preferably not more than 80 ℃, and the destruction of the metal hydroxide/oxide nanosheets can be better avoided at 60 ℃ or lower.
Stirring can make the reaction more uniform and rapid, but high-speed stirring can generate larger shearing force, so that the generated nanosheets fall off from the metal core. As a further improvement of the preparation method, the stirring speed is 50-500 rpm.
The invention only adopts transition metal or alloy powder as raw material, aqueous solution as solvent, and uses water to corrode metal to prepare the material in large scale. The preparation method is simple and easy to operate, is green and environment-friendly, does not need any chemical reagent, utilizes the principle of metal corrosion and accelerates the corrosion process by utilizing the large specific surface area of metal particles under the microscale. Meanwhile, the high curvature of the small metal particles aggravates the stress between the corrosion product (metal hydroxide) and the original metal particles, thereby ensuring the uninterrupted separation of the metal hydroxide and/or metal oxide nanosheet and the metal surface generated by corrosion. In addition, transition products partially dissolved in water are generated in the metal corrosion process, so that the surface nanosheets can also have a continuous growth process, and a large number of metal hydroxide and/or metal oxide nanosheets which are staggered with each other are formed on the surface of the metal particles.
Example 1
1) Mixing 30g of 300-mesh reduced cobalt powder, 0.2g of polyethylene glycol and 40 stainless steel balls with the diameter of 1cm, putting the mixture into a ball mill, performing ball milling at the rotating speed of 300 revolutions per minute for half an hour, and performing ball milling at the rotating speed of 500 revolutions per minute for 5 hours to obtain flaky cobalt powder;
2) mixing flake cobalt powder with 15 ml of deionized water, and standing for 48 hours at 20-25 ℃;
3) and (3) cleaning the product, and drying at 70 ℃ for 8 hours to obtain the nano material with the self-supporting cobalt hydroxide/oxide nano sheet.
FIG. 1 is an electron micrograph of a cobalt powder raw material used in this example, and it can be seen that the powder is a spherical powder having an average size of 1 μm.
Fig. 2 is an electron microscope picture of the flake cobalt powder prepared in this example.
Fig. 3 is an electron microscope picture of the cobalt hydroxide nanosheet prepared in this embodiment, and it can be seen that the self-supporting cobalt hydroxide nanosheet has a large number of gaps between lamellae, and the overall forming is good. The average thickness of the prepared cobalt hydroxide/oxide multistage nanosheet is 1 micrometer, the size of the prepared cobalt hydroxide/oxide multistage nanosheet is 10-100 micrometers, the core thickness of the cobalt metal sheet is less than 0.1 micrometer, and the average thickness of the cobalt hydroxide/oxide nanosheet is 5 nanometers.
Fig. 4 is an X-ray diffraction spectrum of the cobalt hydroxide nanosheet prepared in this example, and it can be seen that the self-supporting cobalt hydroxide nanosheet contains a large amount of metallic cobalt, demonstrating that the core is an unetched metallic cobalt sheet.
The cobalt hydroxide/oxide nanosheets prepared in this example were subjected to a current test to further characterize the energy storage properties of the nanosheets. The specific test method comprises the following steps: the self-supporting metal hydroxide/oxide nanoplates prepared in example 1 were mixed at 2 mmThe concentration of g/ml is dispersed in deionized water, and then 10. mu.l of the suspension is dropped uniformly onto 0.07cm2The glassy carbon electrode is used as a positive electrode and assembled into a three-electrode system, the counter electrode is a platinum wire, the reference electrode is an Hg/HgO electrode, the electrolyte is a 1 mol/L potassium hydroxide solution, an electrochemical workstation is utilized to test the OER performance of the glassy carbon electrode, the scanning speed is 5mV/s, the precision is 1mV, and the voltage window is 0.3-1V. The current-voltage curve of the self-supporting cobalt hydroxide/oxide nanosheet prepared in test example 1 is shown in fig. 11 (the voltage is the standard hydrogen electrode voltage). As can be seen, the nanosheet has good electrocatalytic performance.
Example 2:
1) mixing 15g of 300-mesh reduced cobalt powder, 15g of reduced nickel powder (shown in figure 5) with the diameter less than 5 microns and 40 stainless steel balls with the diameter of 1cm, putting the mixture into a ball mill, and carrying out ball milling for 7 hours at the rotating speed of 500 revolutions per minute;
2) adding 0.4g of polyethylene glycol into a ball milling tank, performing ball milling for half an hour at the rotating speed of 300 revolutions per minute, and then performing ball milling for 3 hours at the rotating speed of 500 revolutions per minute to obtain a cobalt-nickel alloy sheet (as shown in figure 6);
3) mixing cobalt-nickel alloy powder prepared by ball milling with 15 ml of deionized water, and standing for 24 hours at 35-45 ℃;
4) the product was washed and dried at 70 ℃ for 8 hours to give nanomaterials with self-supporting cobalt nickel hydroxide/oxide nanoplates (see figure 7).
The average thickness of the prepared cobalt hydroxide/oxide nanosheet is 200 nanometers, the size of the prepared cobalt hydroxide/oxide nanosheet is 1-10 micrometers, the core thickness of the nickel-cobalt metal sheet is less than 20 nanometers, and the average thickness of the cobalt-nickel hydroxide/oxide nanosheet is 5 nanometers.
Example 3:
1) mixing 10g of 300-mesh reduced cobalt powder, 10g of reduced nickel powder smaller than 5 microns, 10g of iron powder smaller than 300 meshes and 40 stainless steel balls with the diameter of 1cm, putting the mixture into a ball mill, and carrying out ball milling for 3 hours at the rotating speed of 500 revolutions per minute;
2) adding 0.15g of polyethylene glycol into a ball milling tank, performing ball milling for half an hour at the rotating speed of 300 revolutions per minute, and then performing ball milling for 3 hours at the rotating speed of 500 revolutions per minute to obtain a cobalt-nickel-iron alloy sheet;
3) mixing cobalt-nickel alloy powder prepared by ball milling with 15 ml of deionized water, and standing for 5 hours at 70-80 ℃;
4) and (3) cleaning the product, and drying at 70 ℃ for 8 hours to obtain the nano material with the self-supporting cobalt nickel hydroxide/oxide nanosheets.
The average thickness of the prepared cobalt nickel iron hydroxide/oxide nanosheets is 2 micrometers, the size of the prepared cobalt nickel iron hydroxide/oxide nanosheets is 5-50 micrometers, the core thickness of the cobalt nickel iron metal sheet is less than 100 nanometers, and the average thickness of the cobalt nickel hydroxide/oxide nanosheets is 20 nanometers.
Example 4:
1) mixing 15g of 300-mesh zinc powder, 15g of reduced nickel powder smaller than 5 microns and 40 stainless steel balls with the diameter of 1cm, putting the mixture into a ball mill, and carrying out ball milling for 3 hours at the rotating speed of 500 r/min;
2) adding 0.8g of polyethylene glycol into a ball milling tank, performing ball milling for half an hour at the rotating speed of 300 r/min, and performing ball milling for 3 hours at the rotating speed of 500 r/min to obtain nickel-zinc alloy sheets;
3) mixing nickel-zinc alloy powder prepared by ball milling with 15 ml of deionized water, and standing for 48 hours at 15-20 ℃;
4) and (3) cleaning the product, and drying at 70 ℃ for 8 hours to obtain the nano material with the self-supporting nickel-zinc hydroxide/oxide nanosheets.
The average thickness of the prepared nickel-zinc hydroxide/oxide nanosheets is 1 micrometer, the size of the prepared nickel-zinc hydroxide/oxide nanosheets is 5-50 micrometers, the core thickness of the nickel-zinc metal sheet is less than 100 nanometers, and the average thickness of the cobalt-nickel hydroxide/oxide nanosheets is 10 nanometers.
Example 5:
1) mixing 15g of 300-mesh zinc powder, 15g of 300-mesh copper powder and 40 stainless steel balls with the diameter of 1cm, putting the mixture into a ball mill, and carrying out ball milling for 3 hours at the rotating speed of 500 r/min;
2) adding 1.5g of polyethylene glycol into a ball milling tank, performing ball milling for half an hour at the rotating speed of 300 revolutions per minute, and then performing ball milling for 3 hours at the rotating speed of 500 revolutions per minute to obtain a copper-zinc alloy sheet;
3) mixing copper-zinc alloy powder prepared by ball milling with 15 ml of deionized water, and standing for 24 hours at 15-20 ℃;
4) and cleaning the product, and drying at 70 ℃ for 8 hours to obtain the nano material with the self-supporting copper zinc hydroxide/oxide nanosheets.
The average thickness of the prepared copper-zinc hydroxide/oxide nanosheets is 1 micrometer, the size of the prepared copper-zinc hydroxide/oxide nanosheets is 10-100 micrometers, the core thickness of the copper-zinc metal sheet is less than 100 nanometers, and the average thickness of the copper-zinc hydroxide/oxide nanosheets is 5 nanometers.
Example 6:
1) 30g of 300-mesh reduced cobalt powder and 40 stainless steel balls with the diameter of 1cm are mixed and put into a ball mill, and 300 revolutions are carried out firstly
Ball milling is carried out for half an hour at the rotating speed of minutes, and then ball milling is carried out for 5 hours at 500 revolutions per minute to obtain micron cobalt powder;
2) mixing micron cobalt powder with 15 ml of deionized water, and standing for 48 hours at 20-25 ℃;
3) and (3) cleaning the product, and drying at 70 ℃ for 8 hours to obtain the nano material with the self-supporting cobalt hydroxide/oxide nano sheet.
Fig. 8 shows the micron cobalt powder prepared in this example.
Fig. 9 is an electron microscope picture of the cobalt hydroxide/oxide particles prepared in this example.
Fig. 10 is an electron microscope picture of a cross section of the cobalt hydroxide/oxide particle prepared in this example, and it can be seen that the self-supporting cobalt hydroxide/oxide particle has a large number of gaps between the lamellae, and the overall shape is good. But the core remains more and has a smaller specific surface area than the platelet-shaped nanosheets.
Comparative example 1:
the same as example 1, except that the ball-milled flake cobalt powder was reacted at 100 ℃ for 2 hours to prepare a nanomaterial.
The results show that nanomaterials with self-supporting metal hydroxide and/or metal oxide nanoplates cannot be prepared.
Claims (3)
1. A nanometer material with self-supporting metal hydroxide and/or metal oxide nanosheets is provided with a flaky metal core, the particle size of the flaky metal core is 0.05-10 microns, and the surface of the flaky metal core is a self-supporting structure formed by the corresponding metal hydroxide and/or metal oxide nanosheets;
the average thickness of the flaky metal core is 0.01-1 mu m; the average thickness of the nano-sheets is 1 nm-50 nm; the length of the nano sheet is 100 nm-100 mu m;
the metal is a transition metal element or an alloy formed by transition metals; the metal is selected from at least one of cobalt, nickel, copper, iron, zinc, manganese and molybdenum, or an alloy formed by at least two metal elements;
the preparation method of the nano material with the self-supporting metal hydroxide and/or metal oxide nano sheets comprises the following steps:
1) mixing metal sheets with the average particle size of 1-100 mu m with an aqueous solution, and fully reacting at the temperature of not higher than 70 ℃;
2) filtering, washing and drying at the temperature of not higher than 100 ℃ after the reaction is finished to obtain the nano material with the self-supporting metal hydroxide and/or metal oxide nano sheet;
the pH value of the water solution is 7-14.
2. The nanomaterial of claim 1, wherein: the preparation method of the metal sheet comprises the following steps: and mixing metal particles with the average particle size of 1-50 mu m with a surfactant, and performing ball milling to obtain the metal sheet.
3. The nanomaterial of claim 2, wherein: the surfactant is polyethylene glycol, and the addition amount of the surfactant is 0.5-5% of the mass of the metal particles.
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