CN112251812A - Single crystal NaNbO3Cube, preparation method and application thereof - Google Patents
Single crystal NaNbO3Cube, preparation method and application thereof Download PDFInfo
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- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
- C30B29/30—Niobates; Vanadates; Tantalates
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention belongs to the technical field of nano material preparation and the field of new energy, and particularly relates to single crystal NaNbO3Cubes and a method for their preparation and use. The single crystal NaNbO3The cube of (A) is an orthorhombic crystal form, and the side length is 100 nm-10 mu m. The preparation method comprises the steps of putting multilayer niobium-based MXenes into a tetramethylammonium hydroxide solution, heating, stirring and centrifuging to obtain a small-layer niobium-based MXenes solution. And (3) taking the small-layer niobium-based MXenes solution and sodium hydroxide powder, stirring, transferring into a reaction kettle, heating, cooling, carrying out suction filtration, and drying to obtain the product. The invention adopts a simple hydrothermal method to prepare the single crystal NaNbO3The cubic structure is uniform, and the crystallization degree is extremely high. NaNbO prepared by the invention3When the cube is used as the cathode material of the lithium ion capacitor, the cube has small size and firm block structureThe lithium ion battery has a rapid charging and discharging process and excellent cycle performance.
Description
Technical Field
The invention belongs to the field of nano material technology and new energy,in particular to a single crystal NaNbO3Cubes and a method for their preparation and use.
Background
At present, mainstream energy storage devices such as lithium ion batteries and super capacitors have been widely applied in actual life, however, due to the disadvantage of low power density or energy density of each device, the requirements of rapidly developed fields such as aerospace, electric automobiles and the like on energy storage devices with high power density, high energy density and long cycle life cannot be met. The lithium ion capacitor is a novel energy storage device between a secondary battery and a super capacitor, the positive electrode of the lithium ion capacitor adopts a double electric layer capacitor porous carbon material, the negative electrode of the lithium ion capacitor adopts an embedded lithium ion battery negative electrode material, the lithium ion capacitor combines energy storage mechanisms of the secondary battery and the super capacitor, and has the characteristics of the secondary battery and the super capacitor, and high energy density and power density can be ensured under the condition of high-rate charge and discharge. However, the most serious problem is that the kinetics of the electrode material mainly used for oxidation-reduction of the negative electrode is smaller than that of the electrode material mainly used for physical adsorption-desorption of the positive electrode double-layer carbon material. Therefore, how to match the dynamics between the positive and negative electrodes is the key point of the lithium ion capacitor.
In theory, any lithium ion insertion, insertion/extraction type negative electrode material may be a negative electrode material of a lithium ion capacitor. However, the kinetics of battery-type anode materials, which are fundamentally derived from redox reactions, are much slower than capacitive cathodes relying on fast surface ion adsorption and desorption, which leads to a mismatch between the cathode and the anode. Therefore, the rapid pseudocapacitance material, such as TiO, is mainly selected in the lithium ion capacitor2，Li4Ti5O12，V2O5，Nb2O5And the like. Among these materials, niobium-based oxide anodes have a higher theoretical capacity (Nb)2O5≈200mA h g-1And TiNbxO2+2.5x388-401 mA h g of compound-1) Are drawing increasing attention. However, the inherent low conductivity and rapid capacity decay due to structural collapse at high currents has hindered their practical application. In view of these factors, exploration is soughtA novel niobium-based oxide having high conductivity and a stable crystal structure is particularly important.
Disclosure of Invention
To overcome the above disadvantages and shortcomings, the present invention provides a single crystal NaNbO derived from a few-layer niobium-based MXenes3Cube, the NaNbO3The cube is perovskite oxide, has firm lattice framework, and good homogeneity, and the crystallization degree is high.
Another object of the present invention is to provide the above single-crystal NaNbO3The preparation method of the cube adopts simple hydrothermal reaction to realize the conversion from the two-dimensional nanosheet to the three-dimensional cube structure, and the operation cost is low.
It is another object of the present invention to provide the above NaNbO3The cube is used as a lithium ion capacitor negative electrode material, and shows a faster charge-discharge process and excellent cycle performance.
The purpose of the invention is realized by the following scheme:
single crystal NaNbO3Cube, the single crystal NaNbO3The cube is in an orthogonal crystal form; the single crystal NaNbO3The side length of the cube is 100 nm-10 mu m.
The single crystal NaNbO3The preparation method of the cube comprises the following steps:
(1) placing multilayer niobium-based MXenes in a tetramethylammonium hydroxide solution, heating to 25-55 ℃, and stirring for 6-24 hours;
(2) centrifuging the solution obtained in the step (1), pouring out the upper layer liquid, adding deionized water, vibrating to disperse the lower layer niobium-based MXenes, and centrifuging to obtain an upper layer solution, namely a small-layer niobium-based MXenes solution;
(3) adding sodium hydroxide into the small-layer niobium-based MXenes solution obtained in the step (2), and uniformly stirring to obtain a mixed solution;
(4) transferring the mixed solution obtained in the step (3) into a reaction kettle, and carrying out hydrothermal reaction at the temperature of 120-220 ℃ for 1-24 h;
(5) step by stepFiltering and drying the solution after the hydrothermal reaction in the step (4) to obtain the single crystal NaNbO3A cube.
Preferably, the multilayer niobium-based MXenes prepared in the step (1) is prepared by the following method:
(1) 2 g of Nb2Placing AlC in 20 mL of hydrofluoric acid and etching at normal temperature for 90 hours;
(2) centrifuging the etched mixed solution obtained in the step (1), and adding deionized water for repeated cleaning until the pH value of supernatant liquor is 6;
(3) and (3) taking the product in the step (2), pouring out the supernatant, and drying the lower precipitate to obtain the multilayer niobium-based MXenes.
Preferably, in the preparation method of the single crystal NaNbO3 cube, the ratio of the multilayer niobium-based MXenes and the aqueous solution of tetramethylammonium hydroxide in the step (1) is: 1 g of multilayer niobium-based MXenes corresponds to 10 mL of tetramethyltetramethyltetramethylammonium hydroxide aqueous solution;
preferably, the concentration of the few-layer niobium-based MXenes in the step (2) in the preparation method of the single-crystal NaNbO3 cube is 1-10 mol/L.
Preferably, the concentration of the sodium hydroxide in the step (3) in the mixed solution is 1-5 mol/L.
More preferably, the specific preparation method adopts the following steps:
(1) firstly, 2.0 g of Nb2Placing AlC in 20 ml of hydrofluoric acid with the mass fraction concentration of 50%, and etching at normal temperature for 90 hours;
(2) centrifuging the etched liquid in the step (1), and repeatedly cleaning with deionized water until the pH value of the supernatant is 6;
(3) pouring out supernatant liquor of the product obtained in the step (2), taking the lower-layer precipitate, and placing the lower-layer precipitate in a vacuum drying oven for drying to obtain multiple layers of MXenes;
(4) taking 1 g of the multilayer niobium-based MXenes prepared in the step (3), placing the multilayer niobium-based MXenes in 10 ml of 25% tetramethylammonium hydroxide aqueous solution with mass fraction concentration, and heating and stirring the mixture for 24 hours at the temperature of 35 ℃;
(5) centrifuging the solution obtained in the step (4), pouring out the upper-layer liquid obtained for the first time, adding deionized water into a centrifugal tube to disperse the lower-layer MXenes, and centrifuging to obtain an upper-layer solution, namely a few-layer MXenes solution;
(6) stirring 30 mL of the small-layer niobium-based MXenes solution prepared in the step (5) and 1.2-6.0 g of sodium hydroxide powder, and transferring the mixture into a 50 mL reaction kettle;
(7) placing the reaction kettle in the step (6) in an oven, and reacting for 1-24 hours at 120-220 ℃;
(8) naturally cooling to room temperature, taking out the solution obtained in the step (7), performing suction filtration, collecting and drying in an oven to obtain the single crystal NaNbO3A cube.
The single crystal NaNbO3Use of a cube, the single crystal NaNbO3The cube is used as the lithium ion capacitor cathode material.
Advantageous effects
(1) On the basis of few-layer niobium-based MXenes, the few-layer niobium-based MXenes are only needed to be used as a niobium source to carry out simple hydrothermal reaction, so that the transformation from a two-dimensional nanosheet to a three-dimensional cubic structure is realized;
(2) the single crystal NaNbO prepared by the invention3The cube is in an orthorhombic crystal form, the side length is 100 nm-10 mu m, the structure is uniform, and the crystallization degree is high;
(3) the single crystal NaNbO prepared by the invention3When the cube is used as a lithium ion capacitor cathode material, compared with a micron-sized cube, a nano-sized structure can shorten an ion diffusion path, so that a faster charge-discharge process and excellent cycle performance are shown.
Drawings
FIG. 1 is an SEM image (a) and a TEM image (b) of a less-layer niobium-based MXenes solution used in each example and comparative example;
FIG. 2 shows the single-crystal NaNbO prepared in example 13XRD image (a), SEM image (b), TEM image (c), and SAED diffraction image (d) of the cube;
FIG. 3 shows the single-crystal NaNbO prepared in example 23XRD image (a) and SEM image (b) of the cube;
FIG. 4 is prepared as in example 3Single crystal NaNbO3XRD image (a) and SEM image (b) of the cube;
FIG. 5 shows a single crystal NaNbO prepared in comparative example 13XRD image (a) and SEM image (b) of the cube;
FIG. 6 shows a single crystal NaNbO prepared in comparative example 23SEM image of the cube;
fig. 7 is a graph of cycle performance of negative half cells of lithium ion capacitors of examples and comparative examples.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings, examples and comparative examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The single crystal NaNbO provided by the embodiment3A preparation method of the cube comprises the following steps:
(1) 2 g of Nb2Placing AlC in 20 mL of hydrofluoric acid with the mass fraction concentration of 50% and etching at normal temperature for 90 hours;
(2) centrifuging the etched mixed solution obtained in the step (1), and adding deionized water for repeated cleaning until the pH value of supernatant liquor is 6;
(3) and (3) taking the product in the step (2), pouring out the supernatant, and drying the lower precipitate to obtain the multilayer niobium-based MXenes.
(4) Putting 1 g of multilayer niobium-based MXenes prepared in the step (3) into 10 mL of tetramethylammonium hydroxide solution, heating to 25 ℃, and stirring for 24 hours; the concentration of the aqueous tetramethylammonium hydroxide solution was 25 wt.%;
(5) centrifuging the solution obtained in the step (4), pouring out the upper layer liquid, adding deionized water, vibrating to disperse the lower layer niobium-based MXenes, and centrifuging to obtain an upper layer solution, namely a small-layer niobium-based MXenes solution;
(6) and (3) adding 2.4 g of sodium hydroxide into 30 mL of the small-layer niobium-based MXenes solution obtained in the step (2), and uniformly stirring to obtain a mixed solution.
(7) Transferring the mixed solution obtained in the step (6) into a 50 mL reaction kettle, and carrying out hydrothermal reaction at the temperature of 120 ℃ for 6 hours;
(8) filtering and drying the solution after the hydrothermal reaction in the step (7) to obtain the orthorhombic monocrystal NaNbO3Cubes with sides of about 500nm-2 μm.
FIG. 2 (a) shows the reduced niobium MXenes solution used in example 1 and the orthorhombic NaNbO prepared in example 13XRD pattern of the cube; FIG. 2 (b-c) is SEM and TEM images of the orthorhombic sodium niobate prepared in example 1, and it can be seen from the images that the prepared sodium niobate has a uniform structure, a small size and good dispersibility; FIG. 2 (d) shows NaNbO prepared in example 13Diffraction spots of the cube, it can be seen that NaNbO3A cube is a typical single crystal.
Example 2
The single crystal NaNbO provided by the embodiment3A preparation method of the cube comprises the following steps:
(1) 2 g of Nb2Placing AlC in 20 mL of hydrofluoric acid with the mass fraction concentration of 40% and etching at normal temperature for 90 hours;
(2) centrifuging the etched mixed solution obtained in the step (1), and adding deionized water for repeated cleaning until the pH value of supernatant liquor is 6;
(3) taking the product in the step (2), pouring out the supernatant, and drying the lower-layer precipitate to obtain multilayer niobium-based MXenes;
(4) putting 1 g of multilayer niobium-based MXenes prepared in the step (3) into 10 mL of tetramethylammonium hydroxide solution, heating to 35 ℃, and stirring for 12 hours; the concentration of the aqueous tetramethylammonium hydroxide solution was 25 wt.%;
(5) centrifuging the solution obtained in the step (4), pouring out the upper layer liquid, adding deionized water, vibrating to disperse the lower layer niobium-based MXenes, and centrifuging to obtain an upper layer solution, namely a small-layer niobium-based MXenes solution;
(6) and (3) adding 1.2 g of sodium hydroxide into 30 mL of the small-layer niobium-based MXenes solution obtained in the step (5), and uniformly stirring to obtain a mixed solution.
(7) Transferring the mixed solution obtained in the step (6) into a 50 mL reaction kettle, and carrying out hydrothermal reaction at the temperature of 180 ℃ for 1 hour;
(8) filtering and drying the solution after the hydrothermal reaction in the step (7) to obtain the orthorhombic monocrystal NaNbO3A cube having sides of about 100nm to about 500 nm.
Example 3
The single crystal NaNbO provided by the embodiment3A preparation method of the cube comprises the following steps:
(1) 2 g of Nb2Placing AlC in 20 mL of hydrofluoric acid with the mass fraction concentration of 50% and etching at normal temperature for 90 hours;
(2) centrifuging the etched mixed solution obtained in the step (1), and adding deionized water for repeated cleaning until the pH value of supernatant liquor is 6;
(3) and (3) taking the product in the step (2), pouring out the supernatant, and drying the lower precipitate to obtain the multilayer niobium-based MXenes.
(4) Putting 1 g of multilayer niobium-based MXenes prepared in the step (3) into 10 mL of tetramethylammonium hydroxide solution, heating to 55 ℃, and stirring for 6 hours; the concentration of the aqueous tetramethylammonium hydroxide solution was 25 wt.%;
(5) centrifuging the solution obtained in the step (4), pouring out the upper layer liquid, adding deionized water, vibrating to disperse the lower layer niobium-based MXenes, and centrifuging to obtain an upper layer solution, namely a small-layer niobium-based MXenes solution;
(6) and (3) adding 6.0 g of sodium hydroxide into 30 mL of the small-layer niobium-based MXenes solution obtained in the step (5), and uniformly stirring to obtain a mixed solution.
(7) Transferring the mixed solution obtained in the step (6) into a reaction kettle, and carrying out hydrothermal reaction at the temperature of 220 ℃ for 24 hours;
(8) filtering and drying the solution after the hydrothermal reaction in the step (7) to obtain the orthorhombic monocrystal NaNbO3Cubes having sides of about 2 μm to about 10 μm.
Comparative example 1
The practical example provides a single crystal NaNbO3A preparation method of the cube comprises the following steps:
(1) 2 g of Nb2Placing AlC in 20 mL of hydrofluoric acid with the mass fraction concentration of 50% and etching at normal temperature for 90 hours;
(2) centrifuging the etched mixed solution obtained in the step (1), and adding deionized water for repeated cleaning until the pH value of supernatant liquor is 6;
(3) and (3) taking the product in the step (2), pouring out the supernatant, and drying the lower precipitate to obtain the multilayer niobium-based MXenes.
(4) Placing the multilayer niobium-based MXenes prepared in the step (3) in a tetramethylammonium hydroxide solution, heating to 55 ℃, and stirring for 6 hours; the concentration of the aqueous tetramethylammonium hydroxide solution was 25 wt.%;
(5) centrifuging the solution obtained in the step (4), pouring out the upper layer liquid, adding deionized water, vibrating to disperse the lower layer MXenes, and centrifuging to obtain an upper layer solution which is the few-layer MXenes solution;
(6) and (3) adding 7.2 g of sodium hydroxide into 30 mL of the small-layer niobium-based MXenes solution obtained in the step (2), and uniformly stirring to obtain a mixed solution.
(7) Transferring the mixed solution obtained in the step (3) into a reaction kettle for hydrothermal reaction, wherein the temperature of the hydrothermal reaction is 180 ℃, and the reaction time is 48 hours;
(8) filtering and drying the solution after the hydrothermal reaction in the step (4) to obtain NaNbO3And (3) sampling.
FIG. 5 is NaNbO prepared in comparative example 13XRD and SEM images of (a); it can be seen that the surface of the cubes becomes uneven after hydrothermal treatment at higher concentrations of NaOH.
Comparative example 2
The single crystal NaNbO provided by the embodiment3A preparation method of the cube comprises the following steps:
(1) 2 g of Nb2Placing AlC in 20 mL of hydrofluoric acid with the mass fraction concentration of 50% and etching at normal temperature for 90 hours;
(2) centrifuging the etched mixed solution obtained in the step (1), and adding deionized water for repeated cleaning until the pH value of supernatant liquor is 6;
(3) and (3) taking the product in the step (2), pouring out the supernatant, and drying the lower precipitate to obtain the multilayer niobium-based MXenes.
(4) Placing multilayer niobium-based MXenes in a tetramethylammonium hydroxide solution, heating to 15 ℃, and stirring for 6 hours; the concentration of the aqueous tetramethylammonium hydroxide solution was 25 wt.%;
(5) centrifuging the solution obtained in the step (1), pouring out the upper layer liquid, adding deionized water, vibrating to disperse the lower layer MXenes, and centrifuging to obtain the upper layer solution, namely the less layer MXenes solution;
(6) and (3) adding 1.2 g of sodium hydroxide into 30 mL of the small-layer niobium-based MXenes solution obtained in the step (2), and uniformly stirring to obtain a mixed solution.
(7) Transferring the mixed solution obtained in the step (3) into a reaction kettle for hydrothermal reaction, wherein the temperature of the hydrothermal reaction is 80 ℃, and the reaction time is 35 hours;
(8) filtering and drying the solution after the hydrothermal reaction in the step (4) to obtain the single crystal NaNbO3And (3) sampling.
FIG. 6 is an SEM image of the product obtained in comparative example 2; it can be seen that few layers of MXenes were not completely converted into NaNbO3 cubes, with partially disordered nanofibers.
Performance test of lithium ion capacitor cathode material
And (4) performing a performance test on the lithium ion capacitor cathode material by using a button type half cell. To prepare the working electrode, an active material, acetylene black and PVDF in a mass ratio of 7:2:1 were mixed in NMP to prepare a uniform slurry. The resulting slurry was then coated onto a copper foil and vacuum dried at 110 ℃ for 11 hours. The half cell was assembled using lithium metal as the counter electrode, followed by Ar atmosphere glove box.
NaNbO prepared in examples 1-3 and comparative examples 1-23The cubes were active material and tested for performance (see figure 7). The current density used in the test was 100 mA g-1It is clear that NaNbO prepared according to examples 1-3 of the present invention3The NaNbO3 cube prepared by the cube comparison with the comparative examples 1-2 has more stable cycle performance as the anode material of the lithium ion capacitor, which depends on proper block size and proper waterThe thermal reaction time brings about a synergistic effect of a stronger lattice structure.
The technical features of the above examples and comparative examples can be arbitrarily combined, and for the sake of brevity of description, reduction of the variables of the comparative experiment, and increase of the reliability of the results of the comparative experiment, all the possible technical features in the examples are not described, but should be considered as the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express the centralized implementation mode of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. Single crystal NaNbO3Cube, characterized in that the single-crystal NaNbO3The cube is in an orthogonal crystal form; the single crystal NaNbO3The side length of the cube is 100 nm-10 mu m.
2. The single crystal NaNbO of claim 13The preparation method of the cube is characterized by comprising the following steps of:
(1) placing multilayer niobium-based MXenes in a tetramethylammonium hydroxide solution, heating to 25-55 ℃, and stirring for 6-24 hours;
(2) centrifuging the solution obtained in the step (1), pouring out the upper layer liquid, adding deionized water, vibrating to disperse the lower layer niobium-based MXenes, and centrifuging to obtain an upper layer solution, namely a small-layer niobium-based MXenes solution;
(3) adding sodium hydroxide into the small-layer niobium-based MXenes solution obtained in the step (2), and uniformly stirring to obtain a mixed solution;
(4) carrying out hydrothermal reaction on the mixed solution obtained in the step (3), wherein the temperature of the hydrothermal reaction is 120-220 ℃, and the reaction time is 1-24 h;
(5) filtering and drying the solution after the hydrothermal reaction in the step (4) to obtain the single crystal NaNbO3A cube.
3. The single crystal NaNbO of claim 23The preparation method of the cube is characterized in that the multilayer niobium-based MXenes prepared in the step (1) is prepared by adopting the following method:
(1) 2 g of Nb2Placing AlC in 20 mL of hydrofluoric acid and etching at normal temperature for 90 hours;
(2) centrifuging the etched mixed solution obtained in the step (1), and adding deionized water for repeated cleaning until the pH value of supernatant liquor is 6;
(3) and (3) taking the product in the step (2), pouring out the supernatant, and drying the lower precipitate to obtain the multilayer niobium-based MXenes.
4. The single crystal NaNbO of claim 23The preparation method of the cube is characterized in that the ratio of the multilayer niobium-based MXenes to the tetramethylammonium hydroxide aqueous solution in the step (1) is as follows: 1 g of multilayer niobium-based MXene corresponds to 10 mL of tetramethylammonium hydroxide aqueous solution; the concentration of the aqueous tetramethylammonium hydroxide solution was 25 wt.%.
5. The single crystal NaNbO of claim 23The cube preparation method is characterized in that the concentration of the few-layer niobium-based MXenes in the step (2) is 1-10 mol/L.
6. The single crystal NaNbO of claim 23The cube preparation method is characterized in that the concentration of sodium hydroxide in the mixed solution in the step (3) is 1-5 mol/L.
7. The preparation method according to any one of claims 2 to 6, characterized in that the specific preparation method comprises the following steps:
(1) firstly, 2.0 g of Nb2Placing AlC in 20 ml of hydrofluoric acid with the mass fraction concentration of 50%, and etching at normal temperature for 90 hours;
(2) centrifuging the etched liquid in the step (1), and repeatedly cleaning with deionized water until the pH value of the supernatant is 6;
(3) pouring out supernatant liquor of the product obtained in the step (2), taking the lower-layer precipitate, and placing the lower-layer precipitate in a vacuum drying oven for drying to obtain multilayer niobium-based MXenes;
(4) taking 1 g of the multilayer niobium-based MXenes prepared in the step (3), placing the multilayer niobium-based MXenes in 10 ml of 25% tetramethylammonium hydroxide aqueous solution with mass fraction concentration, and heating and stirring the mixture for 24 hours at the temperature of 35 ℃;
(5) centrifuging the solution obtained in the step (4), pouring out the upper-layer liquid obtained for the first time, adding deionized water into a centrifugal tube to disperse the lower-layer MXenes, and centrifuging to obtain an upper-layer solution, namely the low-layer niobium-based MXenes solution;
(6) stirring 30 mL of the small-layer niobium-based MXenes solution prepared in the step (5) and 1.2-6.0 g of sodium hydroxide powder, and transferring the mixture into a 50 mL reaction kettle;
(7) placing the reaction kettle in the step (6) in an oven, and reacting for 1-24 hours at 120-220 ℃;
(8) naturally cooling to room temperature, taking out the solution obtained in the step (7), performing suction filtration, collecting and drying in an oven to obtain the single crystal NaNbO3A cube.
8. A single crystal NaNbO as claimed in claim 13Use of a cube, characterized in that the single crystal NaNbO3The cube is used as the lithium ion capacitor cathode material.
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| CN113526556B (en) * | 2021-07-12 | 2022-07-22 | 济南大学 | WNb of single crystal particle assembly sheet layer2O8And preparation method and application thereof |
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