CN114162866B - Vanadium oxide nano-sheet and preparation method of two-dimensional composite material of vanadium oxide nano-sheet and MXene - Google Patents
Vanadium oxide nano-sheet and preparation method of two-dimensional composite material of vanadium oxide nano-sheet and MXene Download PDFInfo
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Abstract
The invention discloses a vanadium oxide nano-sheet and a preparation method of a two-dimensional composite material of the vanadium oxide nano-sheet and MXene, wherein the preparation method of the vanadium oxide nano-sheet comprises the steps of vanadium source dispersion, vanadium oxide nucleation growth and preparation of vanadium oxide (V) 5 O 12 ·nH 2 O) nanoflakes, lyophilization of the product; the preparation method of the two-dimensional composite material of the vanadium oxide nano-sheet and the MXene comprises the steps of positively-charged pretreatment of the vanadium oxide nano-sheet, self-assembled compounding of the positively-charged vanadium oxide nano-sheet and the negatively-charged MXene nano-sheet, centrifugal washing and freeze-drying. According to the preparation method of the vanadium oxide nano-sheet, a template agent is not required to be added any more, and the yield of the obtained nano-sheet can be increased to more than 75%. When the two-dimensional composite material of the vanadium oxide nano sheet and the MXene is applied to a water-based zinc ion battery, the interface effect of the composite material shows that the composite material exceeds V 5 O 12 ·nH 2 Actual capacity of O theoretical capacity.
Description
Technical Field
The invention belongs to the technical field of water-based zinc ion battery materials, and particularly relates to a vanadium oxide nano-sheet and a preparation method of a two-dimensional composite material of the vanadium oxide nano-sheet and MXene.
Background
In the field of water-based zinc ion batteries, methods for preparing vanadium oxide nano arrays and ultrathin titanium carbide nano sheets are disclosed in Chinese patent CN105271407A, a vanadium oxide nano array and a preparation method thereof, and CN109569494A, an MXene-Ti 3 C 2 The preparation process and application of nanometer sheet are disclosed separately.
The former forms vanadium oxide nano-sheets by a hydrothermal synthesis method and then self-assembles to form a vanadium oxide nano-array, however, the method can be completed under the action of a specific template agent, and the vanadium oxide nano-array has the advantages of serious self-stacking, thicker sheets and long preparation period, and is not beneficial to the exertion of the energy storage performance of materials.
The product prepared by the latter has very limited energy storage capacity when used as a positive electrode material of the water-based zinc ion battery because the pure MXene has almost no capacity when used in the water-based zinc ion battery and does not participate in Faraday redox reaction.
Document Nano Energy 39 (2017) 151-161 mentions that by introducing commercial V 2 O 5 The powder was poured into deionized water, then directly against V 2 O 5 Ultrasonic treatment of the suspension to obtain V 2 O 5 The yield of the nano-sheets obtained by the method is low and is only 20%, and the nano-sheets have serious damage and uneven morphology.
In order to excavate novel materials suitable for energy storage devices and provide an effective preparation method and nano-sheets with good performance, we propose a process technology for preparing vanadium oxide nano-sheets by in-situ liquid phase growth ultrasonic stripping; in addition, a two-dimensional composite material of vanadium oxide nano-sheets and MXene nano-sheets and a preparation method thereof are also provided.
Disclosure of Invention
The invention aims to provide a preparation method of vanadium oxide nano-sheets, which aims to solve the problems of low yield and unsatisfactory product morphology of the preparation method of the vanadium oxide nano-sheets.
The invention further aims to provide a preparation method of the two-dimensional composite material of the vanadium oxide nano-sheet and the MXene, so as to solve the problem that the energy storage capacity of the conventional composite material is limited.
In order to solve the problems, the technical scheme of the invention is as follows:
the preparation method of the vanadium oxide nano-sheet comprises the following steps:
step A, dispersing vanadium sources;
dispersing vanadium oxide as a vanadium source in deionized water at a molar concentration of 0.022-0.047mol/L, then adding hydrogen peroxide with a molar concentration of 10-40 times that of the vanadium oxide and 8-12 drops of ethylene glycol (about 0.4-0.6 mL), then transferring the mixed solution into a water bath kettle, and magnetically stirring at a constant temperature of 30-60 ℃ for 2-3.5 hours to uniformly disperse the vanadium source.
Step B, vanadium oxide nucleation growth;
taking out the magnetons, preserving the temperature of the dispersed clear yellow solution at 30-60 ℃ for 10-30 hours, and taking out the dark green suspension from the water bath kettle after the vanadium oxide is nucleated and grows.
Step C, preparation of vanadium oxide (V) 5 O 12 ·nH 2 O) nanoflakes;
transferring the dark green suspension into an ultrasonic cleaner, and performing ultrasonic treatment at constant temperature of 30-60deg.C for 1-10 hr to obtain new V 5 O 12 ·nH 2 O is peeled off.
On the one hand, ultrasonic waves are utilized to break Van der Waals bonds between material layers, so that the multi-layer structure is peeled into fewer layers or single layers V 5 O 12 ·nH 2 O nano-sheets; on the other hand, the oscillation effect of the ultrasonic wave can greatly prevent the grains from further growing and prevent the grains and the slices with larger sizes from being generated, thereby the frequency and the action time of the ultrasonic wave can be adjustedThe growth of crystal nucleus is controlled, so that the dimension of the nano sheet is controlled.
Centrifuging at 1000-3000r/min for 0.5-3 hr to obtain upper suspension of vanadium oxide (V) 5 O 12 ·nH 2 O) nanoflakes.
Step D: lyophilizing the product;
and C, rapidly freezing the upper suspension obtained in the step C, and then putting the upper suspension into a freeze dryer for drying for 72-120 hours to obtain fluffy yellow green flocculent vanadium oxide nano-sheets.
Further, the vanadium oxide used as the vanadium source in the step A is V 2 O 5 Or V 2 O 5 ·nH 2 O。
The preparation method of the two-dimensional composite material of the vanadium oxide nano-sheet and the MXene comprises the following steps on the basis of the preparation method of the vanadium oxide nano-sheet:
step E: positively charged pretreatment of vanadium oxide nano-flakes;
the vanadium oxide nano-sheet (HVO-NS) is treated with monoammonium phosphate (NH) 4 H 2 PO 4 ) Or poly (ethylene-co-propylene-dimethyl-ammonium chloride) (PDDA), the specific steps are as follows: namely vanadium oxide nano-sheet (HVO-NS) and ammonia dihydrogen phosphate (NH) 4 H 2 PO 4 ) Or adding the vanadium oxide nano-sheet (HVO-NS) and polyvinyl propyl dimethyl ammonium chloride (PDDA) into proper amount of deionized water according to a molar ratio of 1:1 to form suspension with the concentration of 1-3g/L, stirring for 1 hour at room temperature to enable the suspension to be positively charged, and then centrifugally washing the suspension with deionized water for 3 times, and collecting precipitate to obtain the positively charged vanadium oxide nano-sheet.
The purpose of this step is to make the vanadium oxide nanoflakes positively charged, thereby facilitating self-assembly in the next step.
Step F: self-assembled recombination of positively charged vanadium oxide nanoplatelets and negatively charged MXene nanoplatelets;
and E, adding the positively charged vanadium oxide nano-sheets and the negatively charged MXene nano-sheets prepared in the step E into a proper amount of deionized water according to the mass ratio of 1:1-20:1, providing a necessary liquid phase environment to enable the nano-sheets to be efficiently compounded to form a suspension with the concentration of 1-2g/L, and slowly stirring the suspension for 10-24 hours at the stirring rate of 100-300r/min to form a composite material suspension combined in a face-to-face mode.
Negatively charged MXene (Ti) 3 C 2 ) The nano-sheet is prepared by a preparation method in the prior art, and the details are shown in Chinese patent CN109569494A, an MXene-Ti 3 C 2 Preparation method of nano-sheet and application thereof, because of Ti 3 C 2 The self-electronegativity of the self-functional groups (-O, -F, -OH) is achieved, so that the self-assembly of the self-functional groups in water occurs due to electrostatic adsorption, and a composite material combined in a face-to-face mode is formed.
Step G: centrifugal washing and freeze-drying;
and F, centrifugally washing the composite material suspension prepared in the step F by deionized water, and freeze-drying for 48-72 hours to obtain the two-dimensional composite material (V) of the powdery vanadium oxide nano-sheets and the MXene 5 O 12 ·nH 2 O@MXene)。
The beneficial effects of the invention are as follows:
(1) According to the preparation method of the vanadium oxide nano sheet, in-situ liquid phase growth ultrasonic stripping is adopted, namely, when a sol-gel method is used for preparing a sample, an ultrasonic environment is added for treatment in a curing stage of hydrogel formation, so that the vanadium oxide nano sheet is prepared, a template agent is not required to be added in the preparation method, and the yield of the obtained nano sheet can be increased to more than 75%.
The product prepared is V 5+ And V is equal to 4+ V of mixed valence state 5 O 12 ·nH 2 The thickness of the O nano-sheet is about 1-10nm, the transverse dimension is about 10-30 mu m, and the O nano-sheet has good dispersibility and stability in a liquid phase; due to its presence ofThe advantages of wide interlayer spacing, good morphological characteristics, stability and the like, can be applied toAn aqueous zinc ion battery positive electrode material. Meanwhile, the energy band structure of the fluorescent material is changed to a certain extent, and the photoluminescence spectrum of the fluorescent material shows that under the excitation light with the wavelength of 365nm, an obvious emission peak with higher intensity appears at 648nm, which indicates that the fluorescent material has potential of being used as a luminescent material. In addition, the product can be mixed with a conventional carbon nano tube, and a flexible film electrode with high conductivity and self-supporting function is prepared by ultrasonic spraying; the composite material can also be compounded with other layered materials to prepare a novel composite material with a sandwich structure; the vanadium oxide nano-sheet can be used as a substrate material, and other substances can be grown on the surface of the vanadium oxide nano-sheet, so that the material can be conveniently subjected to deep modification and the like.
In addition, the method has good universality and high yield, and besides vanadium oxide, the method can realize flaky stripping for other lamellar two-dimensional materials which use a sol-gel method or can be nucleated and grown in solution.
(2) In the implementation of this process, since the vanadium oxide is typically composed of VO 4 Tetrahedral, VO 5 Pyramid or VO 6 The octahedron is formed by the layered structure of the shared edges or the shared corners, and the adjacent layers are connected by weak Van der Waals bonds, and the interlayer spacing of the vanadium oxide is greatly increased after water molecules are inserted between the layers, for example, the theoretical interlayer spacing is onlyV of (2) 2 O 5 The interlayer spacing can be enlarged to +.>The secondary bond bonding force between layers is further weakened, which provides possibility for ultrasonic stripping of few-layer nano-sheets or single-layer nano-sheets through in-situ liquid phase growth. Meanwhile, according to the Ostwald ripening mechanism (Ostwald ripening), smaller grains have larger surface energy and spontaneously become "absorbed and incorporated" by larger grains above critical dimensions, and grow into larger grains or crystals to form precipitates, which is extremely disadvantageous for the preparation of nanomaterialsA kind of electronic device. Therefore, the ultrasonic wave is not only the stripping action in the method, but also the cavitation action and the acoustic flow action of the ultrasonic wave are simultaneously utilized, and the growth of crystal grains is restrained while stripping, so that the nano-sheet with small crystal size and uniform distribution is prepared.
(3) The preparation method of the two-dimensional composite material of the vanadium oxide nano-sheet and the MXene provided by the invention is initiated, and forms a novel two-dimensional composite material (V) of the vanadium oxide nano-sheet and the MXene by adopting a mode of self-assembling the vanadium oxide nano-sheet and the MXene nano-sheet which are sheet-shaped and have wide interlayer spacing by means of electrostatic adsorption 5 O 12 ·nH 2 O@MXene)。
The composite material overcomes and improves the defects of insufficient conductivity, unstable structure, poor mechanical property and the like of the vanadium oxide by the high conductivity, hydrophilicity and good structural stability and mechanical property of MXene, and improves the defects of poor conductivity and unstable structure of the conventional vanadium oxide when the conventional vanadium oxide is used as a water-based zinc ion battery (AZIBs), thereby providing an electrode material with good comprehensive performance for the AZIBs, super capacitors and the like.
The two nano sheets are spontaneously assembled in an electrostatic adsorption mode, so that the nano sheets can be prevented from being broken, an open layered structure similar to a sandwich structure can be formed, intercalation/deintercalation of intercalation ions is facilitated, and due to a heterostructure generated by introduction of MXene with excellent conductivity, the overall conductivity of the material and the active site for ion storage are greatly increased, and the comprehensive performance of AZIBs is remarkably improved.
In addition, MXene is selected to be compounded with vanadium oxide nano-sheets to remove Ti 3 C 2 In addition, can also be of a composition similar to Ti 3 C 2 Two-dimensional layered materials of similar structure, or with electronegative functional groups, e.g. Ti 2 C、V 2 C、Nb 2 C and rGO, which have good conductivity and molecular weight ratio to Ti 3 C 2 Smaller, so in Ti 3 C 2 In the case of complexing, several substances are additionally given with V 5 O 12 ·nH 2 The O nano-sheets also have good compatibilitySex, thus can be combined with V 5 O 12 ·nH 2 O constitutes the composite material by this method.
(4) The two-dimensional composite material (V) of vanadium oxide nano-sheet and MXene prepared by the method 5 O 12 ·nH 2 O@MXene) exhibits an overrun of V 5 O 12 ·nH 2 Actual capacity of O theoretical capacity. The product prepared by the method is MXene which does not have energy storage capability in an Aqueous Zinc Ion Battery (AZIBs), and the Faraday activity of the product is activated through an interface effect generated by the composite heterostructure, so that more active sites are provided for storing intercalation ions, and further capacity contribution is provided.
Drawings
FIG. 1 is an SEM photograph of vanadium oxide nanoplatelets prepared according to the present invention at 8000 and 4000 times, respectively;
FIG. 2 is a TEM and SAED photograph of vanadium oxide nanoplatelets prepared according to the present invention;
FIG. 3 is an XRD pattern of a vanadium oxide nanosheet prepared in accordance with the present invention;
FIG. 4 is a V prepared according to the present invention 5 O 12 ·nH 2 SEM photograph of O@MXene two-dimensional composite material;
FIG. 5 is a V prepared according to the present invention 5 O 12 ·nH 2 TEM and SAED photographs of the O@MXene two-dimensional composite material;
FIG. 6 is a V prepared according to the present invention 5 O 12 ·nH 2 EDS photo of O@MXene two-dimensional composite material;
FIG. 7 shows the nano-sheets of pure vanadium oxide (HVO-NS) and V prepared by the present invention 5 O 12 ·
nH 2 And (3) comparing the rate performance of the electrode manufactured by the O@MXene two-dimensional composite material (the mass ratio is 3:1) with that of AZIBs.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention.
Accordingly, the detailed description of the embodiments of the invention provided below is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention.
Example 1
Steps a-D of this example are the process of preparing vanadium oxide nanoplatelets (HVO-NS).
Step E-step G is to prepare a two-dimensional composite material (V) of vanadium oxide nano-sheets and MXene by using the vanadium oxide nano-sheets prepared in step A-step D as raw materials 5 O 12 ·nH 2 O@MXene) was performed as a whole in the examples, since the starting material for the latter was prepared by the previous step.
The preparation method of the vanadium oxide nano-sheet comprises the following steps:
step A, dispersing vanadium sources;
2g of V as a vanadium source was weighed 2 O 5 ·H 2 O was added to 450mL of deionized water to form 0.022mol/L V 2 O 5 The suspension was further added with 45mL of 30% strength hydrogen peroxide solution and 8 drops of ethylene glycol (measured at about 0.4 mL), and the mixture was transferred to a water bath, and magnetically stirred at a constant temperature of 60 ℃ for 2 hours to uniformly disperse the vanadium source.
Step B, vanadium oxide nucleation growth;
taking out the magnetons, keeping the dispersed clear yellow solution at 60 ℃ for 10 hours, and taking out the suspension which turns to dark green from the water bath after the vanadium oxide is nucleated and grows.
Step C, preparation of vanadium oxide (V) 5 O 12 ·nH 2 O) nanoflakes;
transferring the dark green suspension obtained in the step B into an ultrasonic cleaner, and performing ultrasonic treatment at a constant temperature of 60 ℃ for 10 hoursWhen to newly form V 5 O 12 ·nH 2 O is peeled off.
And centrifuging the suspension at a rotating speed of 1000r/min for 3 hours, wherein the obtained upper suspension is the successfully peeled vanadium oxide nano sheet (HVO-NS) accounting for 75-85% of the total mass of the vanadium oxide. While the bottom sediment is multi-layer or massive vanadium oxide V which is not stripped successfully 5 O 12 ·nH 2 O accounts for about 15-25% of the total mass, and this process also proves that our in-situ liquid phase growth ultrasonic stripping is a very efficient means of stripping vanadium oxide.
Step D: lyophilizing the product;
and C, rapidly freezing the upper suspension obtained in the step C by liquid nitrogen, and then putting the upper suspension into a freeze dryer for drying for 72 hours to obtain fluffy yellow green flocculent vanadium oxide nano-sheets, wherein the vanadium oxide nano-sheets obtained in the embodiment are taken as samples 1-1.
A preparation method of a two-dimensional composite material of vanadium oxide nano-sheets and MXene uses the vanadium oxide nano-sheets prepared in the step D as a raw material of the step E.
Step E: positively charged pretreatment of vanadium oxide nano-flakes;
vanadium oxide nanoplatelets (HVO-NS) were pretreated with polyvinyl propyl dimethyl ammonium chloride (PDDA), for specific steps, see below:
45mg of the vanadium oxide nano-sheet (HVO-NS) obtained in the step D and 46.5316mg of a polyethylene propyl dimethyl ammonium chloride solution (PDDA) with the mass fraction of 35% are weighed and added into 30mL of deionized water for mixing (the concentration is about 3 g/L) in a molar ratio of 1:1, the mixture is stirred at room temperature for 1 hour to enable the mixture to be positively charged, and then the mixture is centrifugally washed for 3 times by using the deionized water, and a precipitate is collected, so that the positively charged vanadium oxide nano-sheet is obtained.
Step F: self-assembled recombination of positively charged vanadium oxide nanoplatelets and negatively charged MXene nanoplatelets;
the 45mg positively charged vanadium oxide nanoplatelets and 15mg negatively charged MXene nanoplatelets prepared in step E were added to 30mL deionized water (concentration 2 g/L) in a mass ratio of 3:1, and slowly stirred at a stirring rate of 150r/min for 10 hours to form a composite suspension combined in a face-to-face manner.
Step G: centrifugal washing and freeze-drying;
c, centrifugally washing the composite material suspension prepared in the step F by using deionized water; and freeze-drying for 72 hours to obtain the two-dimensional composite material (V) of the powdery vanadium oxide nano-sheet and the MXene 5 O 12 ·nH 2 O@MXene), the two-dimensional composite material of vanadium oxide nanoplatelets and MXene obtained in this example (V 5 O 12 ·nH 2 O@MXene) was used as sample 1-2.
Example 2
The difference from example 1 is that:
the vanadium source weighed in step A was 2.133g of V 2 O 5 250mL of deionized water was added to finally form V with a molar concentration of 0.047mol/L 2 O 5 A suspension; adding hydrogen peroxide with the volume of 190mL; 12 drops of ethylene glycol (measured about 0.6 mL) were added; and (3) carrying out constant-temperature magnetic stirring for 3 hours at 50 ℃ in a water bath kettle to uniformly disperse the vanadium source.
And B, heating the water bath at 50 ℃ and preserving heat for 20 hours.
The temperature of the heat preservation in the step C is 50 ℃; the time of constant temperature ultrasonic treatment is 1 hour; the suspension centrifugation index is: the rotating speed is 3000r/min, and the time is 0.5 hour.
Similarly, the obtained upper suspension is the successfully peeled vanadium oxide nano-sheet (HVO-NS), which accounts for 75-85% of the total mass of the vanadium oxide. While the bottom sediment is multi-layer or massive vanadium oxide V which is not stripped successfully 5 O 12 nH2O, accounting for about 15-25% of the total mass.
Step D was flash frozen with liquid nitrogen and placed in a freeze dryer to dry for 84 hours to obtain vanadium oxide nanoplatelets as sample 2-1.
In step E, vanadium oxide nanosheets (HVO-NS) are treated with monoammonium phosphate (NH) 4 H 2 PO 4 ) The pretreatment is carried out, and the specific steps are as follows:
namely, 45mg of vanadium oxide nano-sheet (HVO-NS) and 11.588mg of monoammonium phosphate (NH) obtained in the step D are weighed 4 H 2 PO 4 ) Adding the mixture into 30mL of deionized water at a molar ratio of 1:1, mixing (the concentration is about 1.89 g/L), stirring for 1 hour at room temperature to enable the mixture to be positively charged, centrifugally washing the mixture for 3 times by using the deionized water, and collecting precipitate to obtain the positively charged vanadium oxide nano-sheet.
In the step F, 15mg of negatively charged MXene nano-sheets and 45mg of vanadium oxide nano-sheets obtained in the step D are weighed and dispersed in 40mL of deionized water (the concentration is about 1.5 g/L), the mass ratio is 3:1, and the stirring indexes are as follows: 100r/min,24 hours.
The lyophilization time in step G was 48 hours. Finally prepared two-dimensional composite material (V) of vanadium oxide nano-sheet and MXene 5 O 12 ·nH 2 O@MXene) was used as sample 2-2.
Example 3
The difference from example 1 is that:
the vanadium source weighed in step A was 2.133g of V 2 O 5 The added deionized water is 450mL, and finally V with the molar concentration of 0.026mol/L is formed 2 O 5 A suspension; adding hydrogen peroxide with the volume of 90mL; 9 drops of ethylene glycol (measured about 0.5 mL) were added; and (3) carrying out constant-temperature magnetic stirring for 3.5 hours at 50 ℃ in a water bath kettle to uniformly disperse the vanadium source.
And B, heating the water bath at 50 ℃ and preserving the heat for 30 hours.
The temperature of the heat preservation in the step C is 50 ℃; the time of constant temperature ultrasonic treatment is 3 hours; the suspension centrifugation index is: the rotating speed is 1500r/min, and the time is 1 hour.
Similarly, the obtained upper suspension is the successfully peeled vanadium oxide nano-sheet (HVO-NS), which accounts for 75-85% of the total mass of the vanadium oxide. While the bottom sediment is multi-layer or massive vanadium oxide V which is not stripped successfully 5 O 12 ·nH 2 O accounts for 15-25% of the total mass.
Step D, the vanadium oxide nanoplatelets obtained after quick freezing with liquid nitrogen and drying in a freeze dryer for 96 hours were used as sample 3-1.
In step E, vanadium oxide nanosheets (HVO-NS) are treated with monoammonium phosphate (NH) 4 H 2 PO 4 ) The pretreatment is carried out, and the specific steps are as follows:
namely, 30mg of vanadium oxide nano-sheet (HVO-NS) obtained in the step D and 7.725mg of monoammonium phosphate (NH) are weighed 4 H 2 PO 4 ) Adding the mixture into 35mL of deionized water in a molar ratio of 1:1, mixing the mixture (the concentration is 1 g/L), stirring the mixture for 1 hour at room temperature to enable the mixture to have positive charges, centrifugally washing the mixture for 3 times by using the deionized water, and collecting a precipitate to obtain the positively charged vanadium oxide nano-sheet.
In the step F, 30mg of the negatively charged MXene nano-sheets and 30mg of the vanadium oxide nano-sheets obtained in the step D are weighed and dispersed in 30mL of deionized water (the concentration is 2 g/L), the mass ratio is 1:1, and the stirring indexes are as follows: 300r/min, 16 hours.
The lyophilization time in step G was 56 hours. Finally prepared two-dimensional composite material (V) of vanadium oxide nano-sheet and MXene 5 O 12 ·nH 2 O@MXene) was used as sample 3-2.
Example 4.
The difference from example 1 is that:
the vanadium source weighed in step A was 2.133g of V 2 O 5 The added deionized water is 350mL, and finally V with the molar concentration of 0.035mol/L is formed 2 O 5 A suspension; the volume of the added hydrogen peroxide is 35mL; adding 10 drops of ethylene glycol; and (3) carrying out constant-temperature magnetic stirring for 2.5 hours at 50 ℃ in a water bath kettle to uniformly disperse the vanadium source.
The water bath heating temperature in the step B is 50 ℃, and the temperature is kept for 30 hours; .
The temperature of the heat preservation in the step C is 50 ℃; the time of constant temperature ultrasonic treatment is 5 hours; the suspension centrifugation index is: the rotation speed is 2000r/min, and the time is 1.5 hours.
Similarly, the obtained upper suspension is the successfully peeled vanadium oxide nano-sheet (HVO-NS), which accounts for 75-85% of the total mass of the vanadium oxide. While the bottom sediment is multi-layer or massive vanadium oxide V which is not stripped successfully 5 O 12 ·nH 2 O accounts for 15-25% of the total mass.
Step D, the vanadium oxide nanoplatelets obtained after flash freezing with liquid nitrogen and drying in a freeze dryer for 110 hours were used as sample 4-1.
In step E, vanadium oxide nanosheets (HVO-NS) are treated with monoammonium phosphate (NH) 4 H 2 PO 4 ) The pretreatment is carried out, and the specific steps are as follows:
namely, 50mg of vanadium oxide nano-sheet (HVO-NS) obtained in the step D and 12.87mg of monoammonium phosphate (NH) are weighed 4 H 2 PO 4 ) Adding the mixture into 50mL of deionized water in a molar ratio of 1:1, mixing the mixture (the concentration is about 1.26 g/L), stirring the mixture for 1 hour at room temperature to enable the mixture to be positively charged, centrifugally washing the mixture for 3 times by using the deionized water, and collecting a precipitate to obtain the positively charged vanadium oxide nano-sheet.
In the step F, 10mg of negatively charged MXene nano-sheets and 50mg of vanadium oxide nano-sheets obtained in the step D are weighed and dispersed in 60mL of deionized water (the concentration is 1 g/L), the mass ratio is 5:1, and the stirring indexes are as follows: 200r/min, 19 hours.
The freeze drying time in the step G is 64 hours, and finally the two-dimensional composite material (V) of the vanadium oxide nano-sheet and the MXene 5 O 12 ·nH 2 O@MXene) was used as sample 4-2.
Example 5
The difference from example 1 is that:
the vanadium source weighed in step A was 2.133g of V 2 O 5 450mL of deionized water is added to finally form a V2O5 suspension with the molar concentration of 0.026 mol/L; the volume of the added hydrogen peroxide is 90mL; 9 drops of ethylene glycol are added; (about 0.5mL measured); and (3) carrying out constant-temperature magnetic stirring for 3.5 hours at the temperature of 30 ℃ in a water bath kettle to uniformly disperse the vanadium source.
And B, heating the water bath at the temperature of 30 ℃ for 30 hours.
The temperature of the heat preservation in the step C is 30 ℃; the time of constant temperature ultrasonic treatment is 7 hours; the suspension centrifugation index is: the rotation speed is 2500r/min, and the time is 2 hours.
Also, the obtainedThe obtained upper suspension is the successfully peeled vanadium oxide nano-sheet (HVO-NS), which accounts for 75 to 85 percent of the total mass of the vanadium oxide. While the bottom sediment is multi-layer or massive vanadium oxide V which is not stripped successfully 5 O 12 nH2O, accounting for about 15-25% of the total mass.
Step D, the vanadium oxide nanoplatelets obtained after quick freezing with liquid nitrogen and drying in a freeze dryer for 120 hours were used as sample 5-1.
In step E, vanadium oxide nanosheets (HVO-NS) are treated with monoammonium phosphate (NH) 4 H 2 PO 4 ) The pretreatment is carried out, and the specific steps are as follows:
namely, 60mg of vanadium oxide nano-sheet (HVO-NS) obtained in the step D and 15.45mg of monoamino phosphate (NH) are weighed 4 H 2 PO 4 ) Adding the mixture into 60mL of deionized water at a molar ratio of 1:1, mixing (the concentration is about 1.258 g/L), stirring for 1 hour at room temperature to enable the mixture to be positively charged, centrifugally washing the mixture for 3 times by using the deionized water, and collecting precipitate to obtain the positively charged vanadium oxide nano-sheet.
In the step F, 3mg of the negatively charged MXene nano-sheets and 60mg of the vanadium oxide nano-sheets obtained in the step D are weighed and dispersed in 45mL of deionized water (the concentration is about 1.4 g/L), the mass ratio is 20:1, and the stirring indexes are as follows: 180r/min, 21 hours.
The lyophilization time in step G was 68 hours. Finally prepared two-dimensional composite material (V) of vanadium oxide nano-sheet and MXene 5 O 12 ·nH 2 O@MXene) was used as sample 5-2.
Verification test 1
Samples 1-1, 2-1, 3-1, 4-1, 5-1 prepared in examples 1 to 5, respectively, were mixed to form a new sample 1.
Sample 1 was tested by SEM (scanning electron microscope) to give figure 1;
sample 1 was subjected to TEM (transmission electron microscope) and SAED (selected area electron diffraction) to obtain FIG. 2;
sample 1 was XRD tested to give figure 3;
XRD test analysis determined that sample 1 was V 5 O 12 ·nH 2 O, V can be obtained from the 2 theta angle of the main peak (001) crystal plane 5 O 12 ·nH 2 The interlayer spacing of O isThe transverse dimension of the nano-sheet is 10-30 μm according to TEM and SEM.
Samples 1-2, 2-2, 3-2, 4-2, 5-2 prepared in examples 1-5, respectively, were mixed to form a new sample 2.
Sample 2 was tested by SEM (scanning electron microscope) to give fig. 4;
sample 2 was subjected to TEM (transmission electron microscope) and SAED (selected area electron diffraction) to obtain FIG. 5;
sample 2 was EDS tested to give FIG. 6;
it was confirmed that the sample 2 was V 5 O 12 ·nH 2 Two-dimensional composite of O nanoplatelets and MXene (V 5 O 12 ·nH 2 O@MXene), and V 5 O 12 ·nH 2 The O nanoplatelets are composited with the MXene nanoplatelets in face-to-face fashion.
Verification test 2
V prepared in example 1 5 O 12 ·nH 2 V of the O nano-sheet and the MXene nano-sheet compounded in a mass ratio of 3:1 5 O 12 ·nH 2 The O@MXene composite material was used as an AZIBs positive electrode, the performance of which was tested to obtain FIG. 7, and the actual capacity exhibited by the composite material was calculated and verified to be higher than V 5 O 12 ·nH 2 The theoretical capacity of O proceeds as follows.
1. The calculation process comprises the following steps: (V) 5 O 12 ·nH 2 O is according to V 5 O 12 Calculation of
Due to the presence of V in the electrode material during discharge/charge 5+ →V 4+ 、V 4+ →V 3+ /V 3+ →V 4+ 、V 4+ →V 5+ Thus, without considering the volume expansion of the material and the barrier to migration caused by intercalation of the intercalation ions, it is assumed that V 5 O 12 Can be totally converted into V 2 O 3 The following steps are:
i.e. each V 5 O 12 The molecule involves the transfer of 9 electrons; and V is 5 O 12 Relative molecular mass M of (2) w 446.71 g.mol -1 According to the theoretical capacity calculation formula:
wherein F is Faraday constant 96485.34 C.mol -1 N is the charge transfer number involved in the reaction.
Thus simple V 5 O 12 The theoretical mass specific capacity of the electrode is:
however, since the pure MXene electrode has no Faraday activity in AZIBs, no capacity is provided, and V is compounded in a mass ratio of 3:1 5 O 12 ·nH 2 V in O@MXene composite electrode 5 O 12 At 75% by mass, so V 5 O 12 ·nH 2 The theoretical mass specific capacity of the O@MXene composite electrode is as follows:
C THVOM ＝75％×C THVO ＝404.98mAh·g -1 (4)
FIG. 7 shows the ratio performance of V 5 O 12 ·nH 2 O@MXene electrode at 0.2 A.g -1 Has a current density of 461.20 mAh.g -1 It is apparent that V compounded at a 3:1 mass ratio can be seen 5 O 12 ·nH 2 The actual capacity of the O@MXene composite material electrode exceeds the theoretical capacity C of the electrode THVOM 。
At the same time, it can be found that: pure HVO (V) 5 O 12 ·nH 2 O)The electrode showed only 420.40 mAh.g -1 Not only lower than the theoretical mass specific capacity C THVO (539.98mAh·g -1 ) And is lower than V 5 O 12 ·nH 2 Actual capacity of the O@MXene composite.
The two-dimensional composite material V of the vanadium oxide nano-sheet and the MXene prepared by the invention is shown 5 O 12 ·nH 2 O@MXene activates Faraday activity of MXene through an interface effect generated by a composite heterostructure, so that the MXene participates in oxidation-reduction reaction, and an additional active site is provided for storing intercalation ions, so that the actual capacity exceeding the theoretical capacity is shown.
Claims (2)
1. A preparation method of a vanadium oxide nano-sheet is characterized in that: the method comprises the following steps:
step A, dispersing vanadium sources;
dispersing vanadium oxide as a vanadium source in deionized water at a molar concentration of 0.022-0.047mol/L, then adding hydrogen peroxide with a molar concentration of 10-40 times that of the vanadium oxide and ethylene glycol with a molar concentration of 0.4-0.6 and mL, then transferring the mixed solution into a water bath, and magnetically stirring at a constant temperature of 30-60 ℃ for 2-3.5 hours to uniformly disperse the vanadium source, wherein the vanadium oxide as the vanadium source is V 2 O 5 Or V 2 O 5 •nH 2 O；
Step B, vanadium oxide nucleation growth;
taking out the magnetons, preserving the temperature of the dispersed clear yellow solution at 30-60 ℃ for 10-30 hours, and taking out the dark green suspension from the water bath kettle after the vanadium oxide is nucleated and grows;
step C, preparing vanadium oxide V 5 O 12 •nH 2 O nanoflakes;
transferring the dark green suspension into an ultrasonic cleaner, and performing ultrasonic treatment at constant temperature of 30-60deg.C for 1-10 hr to obtain new vanadium oxide V 5 O 12 •nH 2 Stripping O;
centrifuging the suspension at 1000-3000r/min for 0.5-3 hrThe obtained upper suspension is the vanadium oxide V which is successfully stripped 5 O 12 •nH 2 O nanoflakes;
step D: lyophilizing the product;
c, rapidly freezing the upper suspension obtained in the step C, and then putting the upper suspension into a freeze dryer for drying for 72-120 hours to obtain fluffy yellow green flocculent vanadium oxide V 5 O 12 •nH 2 O nano-sheets.
2. A preparation method of a two-dimensional composite material of vanadium oxide nano-sheets and MXene is characterized by comprising the following steps: the method is based on the preparation method of the vanadium oxide nano-sheet of claim 1, and further comprises the following steps:
step E: positively charged pretreatment of vanadium oxide nano-sheets;
the vanadium oxide V prepared in the step D 5 O 12 •nH 2 Ammonium dihydrogen phosphate NH for O nano-sheet 4 H 2 PO 4 Or poly (ethylene-co-propylene-di-methyl-ammonium chloride) (PDDA) with reference to the following steps:
i.e. vanadium oxide V 5 O 12 •nH 2 O nano-sheet and ammonium dihydrogen phosphate NH 4 H 2 PO 4 Or vanadium oxide V 5 O 12 •nH 2 Adding O nano-sheets and polyvinyl propyl dimethyl ammonium chloride PDDA into deionized water according to a molar ratio of 1:1 to form a suspension with a concentration of 1-3g/L, stirring for 1 hour at room temperature to enable the suspension to be positively charged, centrifugally washing 3 times by using deionized water, and collecting a precipitate to obtain positively charged vanadium oxide V 5 O 12 •nH 2 O nano-sheets;
step F: self-assembled recombination of positively charged vanadium oxide nanoplates with negatively charged MXene nanoplates;
the positively charged vanadium oxide V prepared in step E 5 O 12 •nH 2 Adding O nano-sheets and negatively charged MXene nano-sheets into deionized water according to the mass ratio of 1:1-20:1 to form a suspension with the concentration of 1-2g/L, and adopting the stirring speed of 100-300r/minSlowly stirring for 10-24 hours to form a composite material suspension combined in a face-to-face mode;
step G: centrifugal washing and freeze-drying;
and F, centrifugally washing the composite material suspension prepared in the step F by deionized water, and freeze-drying for 48-72 hours to obtain powdery vanadium oxide V 5 O 12 •nH 2 Two-dimensional composite material V of O nano-sheet and MXene 5 O 12 •nH 2 O@MXene。
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