CN112670478B - Carbon sphere packaged amorphous vanadium-oxygen cluster composite material, preparation method thereof and sodium storage application - Google Patents
Carbon sphere packaged amorphous vanadium-oxygen cluster composite material, preparation method thereof and sodium storage application Download PDFInfo
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Abstract
The invention provides a carbon sphere packaged amorphous vanadium-oxygen cluster composite material, a preparation method thereof and sodium storage application, and relates to the technical field of sodium ion battery materials. The composite material provided by the invention comprises amorphous vanadium-oxygen clusters and amorphous nitrogen-doped carbon nanospheres; the amorphous nitrogen-doped carbon nanospheres have an open yolk-shell structure in which the amorphous vanadium-oxygen clusters are uniformly encapsulated; the diameter of the amorphous nitrogen-doped carbon nanosphere is 160 to 240nm, and the size of the amorphous vanadium-oxygen cluster is less than 3nm. The carbon sphere packaged amorphous vanadium-oxygen cluster composite material provided by the invention has excellent sodium ion battery negative electrode performance, such as high specific capacity, stable charge and discharge performance, high multiplying power and excellent long-cycle stability, can be effectively applied as a sodium ion battery negative electrode material, and has wide application prospects in the field of new energy.
Description
Technical Field
The invention relates to the technical field of sodium ion battery materials, in particular to a carbon sphere packaged amorphous vanadium-oxygen cluster composite material, a preparation method thereof and sodium storage application.
Background
Lithium ion batteries have a high energy density and a mature process, have been widely used in portable devices and electric vehicles, and play an important role in the field of large-scale energy storage. However, due to the shortage and uneven distribution of lithium resources in the crust, it is urgently necessary to find new energy storage devices as supplements and substitutes for lithium ion batteries. Sodium in the crust is abundant and uniformly distributed, the electrochemical properties of sodium and lithium are similar, and the working principles of corresponding batteries are the same, which means that some mature technologies in lithium ion batteries can be transferred to sodium ion batteries, so that the sodium ion batteries are considered as potential substitutes of the lithium ion batteries. Currently, many researchers have conducted serial research on electrode materials of sodium ion batteries, but still cannot meet the requirements of negative electrode materials in terms of low price, high capacity and long cycle.
The vanadium-based electrode material has multiple valence states and rich physical and chemical properties, has high theoretical capacity, and is an ideal candidate material for electrochemical energy storage devices, particularly for sodium ion battery cathodes. However, in the actual sodium storage performance test, the existing vanadium-based electrode material generally has the defects of low intrinsic conductivity, large volume expansion rate in the charging and discharging process, and poor rate and cycle stability.
Disclosure of Invention
In view of the above, the present invention aims to provide a carbon sphere encapsulated amorphous vanadium-oxygen cluster composite material, a preparation method thereof, and a sodium storage application thereof. The carbon sphere packaging amorphous vanadium-oxygen cluster composite material provided by the invention has high specific capacity, stable charge and discharge performance, high multiplying power and excellent long-cycle stability.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a carbon ball packaging amorphous vanadium-oxygen cluster composite material, which comprises amorphous vanadium-oxygen clusters and amorphous nitrogen-doped carbon nanospheres; the amorphous nitrogen-doped carbon nanospheres have an open yolk-shell structure, and the amorphous vanadium-oxygen clusters are encapsulated in the yolk-shell structure; the diameter of the amorphous nitrogen-doped carbon nanosphere is 160 to 240nm, and the size of the amorphous vanadium-oxygen cluster is less than 3nm.
The invention provides a preparation method of the carbon sphere packaged amorphous vanadium-oxygen cluster composite material, which comprises the following steps:
(1) Mixing ammonium metavanadate, water, dopamine hydrochloride and ethanol to obtain a mixed solution;
(2) Adding ammonia water into the mixed solution for self-polymerization reaction to obtain vanadium-dopamine self-polymerization yolk-core structure nanospheres;
(3) Carrying out high-temperature phase transformation on the vanadium-dopamine self-polymerization yolk-core structure nanospheres in a protective atmosphere to obtain the carbon sphere packaging amorphous vanadium-oxygen cluster composite material; the temperature of the high-temperature phase transformation is 500 to 800 ℃.
Preferably, the specific method for mixing in step (1) is as follows:
dissolving ammonium metavanadate in water, and carrying out first stirring and mixing to obtain an ammonium metavanadate aqueous solution;
adding dopamine hydrochloride into the ammonium metavanadate aqueous solution, and carrying out second stirring and mixing to obtain a mixed aqueous solution of ammonium metavanadate and dopamine hydrochloride;
and adding ethanol into the mixed aqueous solution of ammonium metavanadate and dopamine hydrochloride, and carrying out third stirring and mixing to obtain the mixed solution.
Preferably, the temperature of the first stirring mixing, the second stirring mixing and the third stirring mixing is independently 5 to 15 ℃.
Preferably, the mass ratio of the ammonium metavanadate to the dopamine hydrochloride in the step (1) is 1; the mass volume ratio of the ammonium metavanadate to the water is 0.1-2.0 g:100mL; the volume ratio of the water to the ethanol is 1.5 to 5.
Preferably, the mass concentration of the ammonia water in the step (2) is 25%, and the mass volume ratio of the ammonium metavanadate to the ammonia water is 0.1 to 1.0g:10mL.
Preferably, the temperature of the self-polymerization reaction in the step (2) is 5 to 15 ℃ and the time is 3 to 48h.
Preferably, after the self-polymerization reaction in the step (2), sequentially filtering, washing with solid phase water and drying the obtained self-polymerization reaction liquid to obtain the vanadium-dopamine self-polymerization yolk-core structure nanosphere; the drying temperature is 80 to 120 ℃, and the drying time is 8 to 24h.
Preferably, the time for phase inversion at high temperature in the step (3) is 1 to 5 hours.
The invention provides an application of the carbon sphere packaged amorphous vanadium-oxygen cluster composite material in the technical scheme or the carbon sphere packaged amorphous vanadium-oxygen cluster composite material prepared by the preparation method in the technical scheme in a sodium ion battery cathode (namely, sodium storage application).
The invention provides a carbon ball packaging amorphous vanadium-oxygen cluster composite material, which comprises amorphous vanadium-oxygen clusters and amorphous nitrogen-doped carbon nanospheres; the amorphous nitrogen-doped carbon nanospheres have an open yolk-shell structure, and the amorphous vanadium-oxygen clusters are encapsulated in the yolk-shell structure; the diameter of the amorphous nitrogen-doped carbon nanosphere is 160 to 240nm, and the size of the amorphous vanadium-oxygen cluster is less than 3nm. In the carbon sphere packaging amorphous vanadium-oxygen cluster composite material provided by the invention, the amorphous nitrogen-doped carbon nanospheres have an open yolk-shell structure, so that on one hand, nitrogen doping can change the microstructure and electronic state of a carbon material, improve the conductivity and defect number, facilitate sodium ion storage and improve the rate capability; the carbon material can provide large contact specific surface area, good conductivity and excellent structural stability, can effectively relieve volume change, and improves the circulation stability; on the other hand, the open yolk-shell structure is beneficial to electrolyte permeation, improves charge transmission efficiency, has a large volume expansion space and excellent structural stability, can inhibit structural deformation and collapse of the electrode material in the circulation process, and improves multiplying power and circulation stability; amorphous vanadium-oxygen clusters in the carbon sphere packaging amorphous vanadium-oxygen cluster composite material are uniformly packaged in the nitrogen-doped carbon nanospheres with yolk-shell structures, the amorphous carbon material can inhibit the growth/agglomeration of the vanadium-oxygen clusters, the limited clusters are beneficial to the embedding/desorption of sodium ions, the structural stability of the composite material is improved, the mechanical stress caused by volume change is relieved, and the multiplying power and the circulation stability are further improved; in addition, the clusters in the amorphous vanadium-oxygen cluster structure have the characteristic of isotropy, the volume expansion of the electrode material along a specific direction in the sodium treatment process can be weakened, a proper space is provided for sodium ion diffusion and storage, the defect of large radius of sodium ions is effectively overcome, and the performance of the cathode of the sodium ion battery is improved. Therefore, the carbon sphere packaged amorphous vanadium-oxygen cluster composite material provided by the invention is applied to the negative electrode of the sodium ion battery, has excellent negative electrode performance (high-performance sodium storage function) of the sodium ion battery, such as high specific capacity, stable charge and discharge performance, high multiplying power and excellent long-cycle stability, and has wide application prospects in the field of new energy.
The invention provides a preparation method of the carbon sphere packaged amorphous vanadium-oxygen cluster composite material, which is simple in process, easy in condition control and beneficial to realizing large-scale production.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image and a Transmission Electron Microscope (TEM) image of the vanadium-dopamine autopolymerization yolk-core structure nanosphere prepared in example 1, wherein (a) is the scanning electron microscope image (SEM) and (b) is the transmission electron microscope image (TEM) in fig. 1;
fig. 2 is an X-ray diffraction pattern (XRD) and an X-ray photoelectron spectrum (XPS) of the carbon sphere-encapsulated amorphous vanadium-oxygen cluster composite prepared in example 1, in which (a) is the X-ray diffraction pattern (XRD) and (b) is the X-ray photoelectron spectrum (XPS);
fig. 3 is a Scanning Electron Microscope (SEM) image of the carbon sphere-encapsulated amorphous vanadium-oxygen cluster composite prepared in example 1, and (a) and (b) in fig. 3 are Scanning Electron Microscope (SEM) images at different magnifications, respectively;
fig. 4 is a Transmission Electron Microscope (TEM) image of the carbon sphere-encapsulated amorphous vanadium-oxygen cluster composite prepared in example 1, and (a) and (b) in fig. 4 are Transmission Electron Microscope (TEM) images at different magnifications, respectively;
fig. 5 is a former third cyclic voltammetry curve and a former third charge and discharge curve of the carbon sphere encapsulated amorphous vanadium-oxygen cluster composite prepared in example 1, wherein (a) is the former third cyclic voltammetry curve, and (b) is the former third charge and discharge curve in fig. 5;
FIG. 6 is a graph of rate capability of the carbon sphere encapsulated amorphous vanadium-oxygen cluster composite prepared in example 1;
fig. 7 is a graph of the cycling stability of the carbon sphere encapsulated amorphous vanadium-oxygen cluster composite prepared in example 1 at different current densities.
Detailed Description
The invention provides a carbon ball packaging amorphous vanadium-oxygen cluster composite material, which comprises amorphous vanadium-oxygen clusters and amorphous nitrogen-doped carbon nanospheres; the amorphous nitrogen-doped carbon nanospheres have an open yolk-shell structure, and the amorphous vanadium-oxygen clusters are uniformly encapsulated in the yolk-shell structure; the diameter of the amorphous nitrogen-doped carbon nanosphere is 160 to 240nm, and the size of the amorphous vanadium-oxygen cluster is less than 3nm.
The carbon sphere packaging amorphous vanadium-oxygen cluster composite material comprises amorphous nitrogen-doped carbon nanospheres, wherein the amorphous nitrogen-doped carbon nanospheres are of an open yolk-shell structure, the diameter (namely the outer diameter of the shell) of each amorphous nitrogen-doped carbon nanosphere is 160-240nm, and the diameter of a core is preferably 100-140 nm. In the amorphous nitrogen-doped carbon nanospheres, on one hand, nitrogen doping can change the microstructure and electronic state of the carbon material, improve the conductivity and defect number, facilitate sodium ion storage and improve the rate capability; the carbon material can provide large contact specific surface area, good conductivity and excellent structural stability, can effectively relieve volume change and improve the circulation stability; on the other hand, the open yolk-shell structure is beneficial to electrolyte permeation and improves charge transmission efficiency, and the electrode material has a large volume expansion space and excellent structural stability, can inhibit structural deformation and collapse of the electrode material in the circulation process, and improves multiplying power and circulation stability.
The carbon sphere-encapsulated amorphous vanadium-oxygen cluster composite material also comprises amorphous vanadium-oxygen clusters (mainly formed by stacking a large number of vanadium atoms and oxygen atoms in an unordered manner), the amorphous vanadium-oxygen clusters are uniformly encapsulated in the yolk-shell structure (uniformly distributed in the core and the shell), the amorphous carbon material can inhibit the growth/agglomeration of the vanadium-oxygen clusters, the limited clusters are beneficial to sodium ion embedding/separation, the structural stability of the composite material is improved, the mechanical stress caused by volume change is relieved, and the multiplying power and the cycling stability are further improved; in addition, vanadium-oxygen in the amorphous vanadium-oxygen cluster structure has the characteristic of isotropy, the volume expansion of the electrode material along a specific direction in the sodium treatment process can be weakened, a proper space is provided for sodium ion diffusion and storage, the defect of large radius of sodium ions is effectively overcome, and the performance of the cathode of the sodium ion battery is improved.
The carbon sphere packaged amorphous vanadium-oxygen cluster composite material provided by the invention has excellent sodium ion battery negative electrode performance (high-performance sodium storage function), such as high specific capacity, stable charge and discharge performance, high multiplying power and excellent long-cycle stability, can be effectively applied as a sodium ion battery negative electrode material, and has wide application prospects in the field of new energy.
The invention provides a preparation method of the carbon sphere packaged amorphous vanadium-oxygen cluster composite material, which comprises the following steps:
(1) Mixing ammonium metavanadate, water, dopamine hydrochloride and ethanol to obtain a mixed solution;
(2) Adding ammonia water into the mixed solution for self-polymerization reaction to obtain vanadium-dopamine self-polymerization yolk-core structure nanospheres;
(3) Carrying out high-temperature phase transformation on the vanadium-dopamine self-polymerization yolk-core structure nanospheres in a protective atmosphere to obtain the carbon sphere packaging amorphous vanadium-oxygen cluster composite material; the temperature of the high-temperature phase transformation is 500 to 800 ℃.
According to the invention, ammonium metavanadate, water, dopamine hydrochloride and ethanol are mixed to obtain a mixed solution. In the present invention, the water is preferably deionized water; the ethanol is preferably absolute ethanol; the mass ratio of the ammonium metavanadate to the dopamine hydrochloride is preferably 1 to 0.5, more preferably 1; the mass volume ratio of the ammonium metavanadate to the water is preferably 0.1-2.0 g:100mL, more preferably 0.2 to 1.0g:100mL; the volume ratio of the water to the ethanol is preferably 1.5 to 5, more preferably 1. In the present invention, the specific method of mixing is preferably:
dissolving ammonium metavanadate in water, and carrying out first stirring and mixing to obtain an ammonium metavanadate aqueous solution;
adding dopamine hydrochloride into the ammonium metavanadate aqueous solution, and carrying out second stirring and mixing to obtain a mixed aqueous solution of ammonium metavanadate and dopamine hydrochloride;
and adding ethanol into the mixed aqueous solution of ammonium metavanadate and dopamine hydrochloride, and carrying out third stirring and mixing to obtain the mixed solution.
In the present invention, the temperature (liquid temperature) of the first stirring and mixing, the second stirring and mixing, and the third stirring and mixing is preferably 5 to 15 ℃, and more preferably 8 to 12 ℃. In the invention, the first stirring and mixing speed is preferably 800 to 1500r/min, the time is preferably 10min to 1h, and uniform ammonium metavanadate aqueous solution is obtained through the first stirring and mixing. In the invention, the speed of the second stirring and mixing is preferably 800 to 1500r/min, and the time is preferably 10min to 2h; and performing second stirring and mixing to obtain a light yellow mixed aqueous solution of ammonium metavanadate and dopamine hydrochloride. In the invention, the third stirring and mixing speed is preferably 800 to 1500r/min, the time is preferably 10min to 2h, and the mixed solution is obtained through third stirring and mixing.
After the mixed solution is obtained, ammonia water is added into the mixed solution for self-polymerization reaction, and the vanadium-dopamine self-polymerization yolk-core structure nanosphere is obtained. In the invention, the mass concentration of the ammonia water is preferably 25%, the adding mode of the ammonia water is preferably dropwise adding, and the dropwise adding speed is preferably 0.5 to 2 drops/second; the mass volume ratio of the ammonium metavanadate to the ammonia water is preferably 0.1 to 1.0g:10mL, more preferably 0.2 to 0.5g:10mL; after addition of ammonia, the resulting mixture was black. In the invention, the temperature of the self-polymerization reaction is preferably 5 to 15 ℃, more preferably 8 to 12 ℃, and the time is preferably 3 to 48h, more preferably 8 to 24h; the time of the self-polymerization reaction is calculated by the completion of dropwise adding of ammonia water; the self-polymerization reaction is preferably carried out under stirring conditions. In the invention, ammonia water is used as an initiator, under the alkalescent condition of the ammonia water, metavanadate ions of ammonium metavanadate and dopamine hydrochloride undergo self-polymerization to form vanadium-dopamine self-polymerization yolk-shell structure nanospheres through self-assembly, and water and ethanol provide a growth environment for self-polymerization.
After the self-polymerization reaction, the self-polymerization reaction liquid is preferably subjected to filtration, solid-phase washing and drying in sequence to obtain the vanadium-dopamine self-polymerization yolk-core structure nanosphere. The method of filtration is not particularly critical in the present invention, and filtration methods known to those skilled in the art, such as suction filtration, may be used. In the invention, the drying temperature is preferably 80 to 120 ℃, more preferably 100 to 120 ℃, and the drying time is preferably 8 to 24h, more preferably 8 to 12h; and drying to obtain black powder, namely the vanadium-dopamine self-polymerization yolk-core structure nanosphere.
After the vanadium-dopamine self-polymerization yolk-core structure nanospheres are obtained, the vanadium-dopamine self-polymerization yolk-core structure nanospheres are subjected to high-temperature phase conversion under a protective atmosphere to obtain a carbon ball packaging amorphous vanadium-oxygen cluster composite material; the temperature of the high-temperature phase transformation is 500 to 800 ℃. The protective atmosphere is not particularly required by the present invention, and those known to those skilled in the art can be used, and in the present embodiment, the protective atmosphere is preferably argon with a purity of 99.99%. In the invention, the temperature of the high-temperature phase inversion is preferably 600 to 800 ℃, and the time is preferably 1 to 5h, and more preferably 2 to 3h; the high-temperature phase inversion is preferably carried out in a tube furnace protected by high-purity argon. In the invention, in the high-temperature phase transformation process, the metavanadate in the vanadium-dopamine self-polymerization yolk-shell structure nanosphere is decomposed into amorphous vanadium-oxygen clusters; and decomposing dopamine into an amorphous nitrogen-doped carbon material to obtain the carbon sphere packaging amorphous vanadium-oxygen cluster composite material.
The preparation method provided by the invention is simple in process, easy in condition control and beneficial to realizing large-scale production.
The invention provides an application of the carbon sphere packaged amorphous vanadium-oxygen cluster composite material in the technical scheme or the carbon sphere packaged amorphous vanadium-oxygen cluster composite material prepared by the preparation method in the technical scheme in a sodium ion battery cathode (namely, sodium storage application). The method for applying the sodium-ion battery negative electrode material has no special requirement, and the application method of the sodium-ion battery negative electrode material, which is well known to a person skilled in the art, can be adopted; in the embodiment of the present invention, preferably, the carbon sphere-encapsulated amorphous vanadium-oxygen cluster composite material is mixed with a conductive agent and a binder (mass ratio 8; uniformly dispersing the mixed material in N-methyl pyrrolidone to obtain coating liquid; and coating the coating liquid on the surface of the copper foil for drying, and then cutting the coated copper foil into small wafers serving as working electrodes. The invention has no special requirements on the specific structure of the sodium ion battery, and adopts the structure of the sodium ion battery which is well known to the technical personnel in the field, namelyCan be prepared; in the embodiment of the invention, the sodium ion battery takes a sodium sheet as a counter electrode and a glass fiber membrane as a diaphragm, and electrolyte of the sodium ion battery comprises electrolyte, solvent and additive; the electrolyte is NaClO 4 The solvent is a mixed solvent of ethylene carbonate and dimethyl carbonate, and the additive is fluoroethylene carbonate; the NaClO 4 The concentration in the electrolyte is 1 mol.L -1 The volume ratio of the ethylene carbonate to the dimethyl carbonate is 1:1, the volume ratio of the fluoroethylene carbonate in the electrolyte is 5.0%. The carbon sphere packaged amorphous vanadium-oxygen cluster composite material provided by the invention has excellent sodium ion battery cathode performance when being applied to a sodium ion battery cathode, and has wide application prospect in the field of new energy.
The carbon sphere encapsulated amorphous vanadium-oxygen cluster composite material, the preparation method and the application of sodium storage provided by the invention are described in detail with reference to the following examples, but the invention is not to be construed as being limited by the scope of the invention.
Example 1
A carbon sphere packaging amorphous vanadium-oxygen cluster composite material is prepared by the following steps:
(1) Weighing 0.25 g of ammonium metavanadate, stirring and dispersing in 60 mL of deionized water at 12.0 ℃ to form a uniform ammonium metavanadate aqueous solution;
(2) Weighing 0.6 g of dopamine hydrochloride, adding the dopamine hydrochloride into the ammonium metavanadate aqueous solution obtained in the step (1), and continuously stirring the solution at the temperature of 12.0 ℃ for 30min to fully dissolve the dopamine hydrochloride to obtain a light yellow mixed aqueous solution of the ammonium metavanadate and the dopamine hydrochloride;
(3) Adding 120 mL of absolute ethyl alcohol into the mixed aqueous solution of ammonium metavanadate and dopamine hydrochloride obtained in the step (2) under magnetic stirring, and continuously stirring for 50min at 12.0 ℃ to obtain a mixed solution;
(4) Adding 10mL of ammonia water with the mass concentration of 25% dropwise (1 drop/second) into the mixed solution obtained in the step (3) under magnetic stirring to obtain a black aqueous solution, and continuously stirring at 12.0 ℃ for 12 hours to carry out self-polymerization reaction; carrying out suction filtration and separation on the obtained self-polymerization reaction liquid, repeatedly washing soluble ions remained on the surface of a solid phase by deionized water, and then drying for 8 hours at the temperature of 120 ℃ to obtain black powder which is marked as a vanadium-dopamine self-polymerization precursor, namely vanadium-dopamine self-polymerization yolk-core structure nanosphere;
(5) And (3) under the protection of argon with the purity of 99.99%, carrying out heat treatment on the vanadium-dopamine self-polymerization yolk-core structure nanospheres obtained in the step (4) at 700 ℃ for 2 hours to obtain solid powder, namely the carbon sphere packaging amorphous vanadium-oxygen cluster composite material.
Fig. 1 is a Scanning Electron Microscope (SEM) image and a Transmission Electron Microscope (TEM) image of the vanadium-dopamine autopolymerization precursor obtained in step (4) of example 1, wherein (a) is the Scanning Electron Microscope (SEM) image and (b) is the Transmission Electron Microscope (TEM) image in fig. 1. As can be seen from FIG. 1 (a), the vanadium-dopamine autopolymerization precursor has a spherical structure and an open structure, and the size of the autopolymerization nanosphere ranges from 180 nm to 260 nm. As can be seen in fig. 1 (b), the vanadium-dopamine autopolymerization precursor exhibits an egg yolk-core structure. Therefore, the prepared vanadium-dopamine self-polymerization precursor is definitely a vanadium-dopamine self-polymerization yolk-core structure nanosphere.
Fig. 2 is an X-ray diffraction pattern (XRD) and an X-ray photoelectron spectrum (XPS) of the carbon sphere-encapsulated amorphous vanadium-oxygen cluster composite prepared in example 1, in which (a) is the X-ray diffraction pattern (XRD) and (b) is the X-ray photoelectron spectrum (XPS). As can be seen from fig. 2, the XRD pattern has no distinct diffraction peak, which is characteristic of a typical amorphous cluster, and in addition, has a distinct amorphous carbon peak at 25.5 degrees, which indicates that the composite material prepared in example 1 is composed of amorphous vanadium-oxygen cluster and amorphous carbon; the XPS spectra clearly show the elements carbon, oxygen, nitrogen and vanadium, where nitrogen and carbon are derived from the yolk-shell structure nitrogen doped carbon nanospheres and oxygen and vanadium are derived from the amorphous vanadium-oxygen clusters in the composite.
Fig. 3 is a Scanning Electron Microscope (SEM) graph of the carbon sphere-encapsulated amorphous vanadium-oxygen cluster composite prepared in example 1, and (a) and (b) in fig. 3 are electron microscope (SEM) graphs at different magnifications. As can be seen from figure 3, the diameter of the carbon sphere encapsulated amorphous vanadium-oxygen cluster composite material is 160 to 240nm, and the carbon sphere encapsulated amorphous vanadium-oxygen cluster composite material has an open yolk-shell structure.
Fig. 4 is a Transmission Electron Microscope (TEM) pattern of the carbon sphere-encapsulated amorphous vanadium-oxygen cluster composite material prepared in example 1, and (a) and (b) in fig. 4 are TEM patterns at different magnifications. The yolk-shell structure of the carbon nanoball composite can be seen from (a) of fig. 4, further confirming the structure shown in fig. 3; fig. 4 (b) is a local high-resolution transmission electron microscope (HR-TEM) map of the nanosphere composite, wherein a large number of dark-colored clusters exist, the size of the amorphous cluster is less than 3nm, the amorphous cluster is uniformly distributed and organically encapsulated in the yolk-shell structure carbon nanospheres, the clusters have no obvious crystal face structure, and the existence form of the vanadium-oxygen cluster in the composite is the amorphous cluster.
The carbon sphere-encapsulated amorphous vanadium-oxygen cluster composite material prepared in example 1 is subjected to electrochemical performance tests, including cyclic voltammetry performance, charge and discharge performance, rate capability and cyclic stability, wherein the cyclic voltammetry performance tests are performed at room temperature, the charge and discharge, rate and cyclic stability tests are performed in a 30 ℃ thermostat, and the assembling method of a sodium ion battery adopted in the tests is as follows: mixing a carbon ball packaging amorphous vanadium-oxygen cluster sodium storage material (electrode material), activated carbon (conductive agent) and PVDF (polyvinylidene fluoride, binder) (mass ratio is 8; the sodium sheet is a counter electrode; the glass fiber film is a diaphragm; naClO 4 Dissolution in ethylene carbonate + dimethyl carbonate (volume ratio of ethylene carbonate to dimethyl carbonate 1, naclo 4 Has a concentration of 1 mol. L -1 ) +5.0 Vol% fluoroethylene carbonate was used as electrolyte and assembled into a 2032 type button cell in a glove box. The electrochemical test results were as follows:
fig. 5 is a former third cyclic voltammogram and a former third charge and discharge curve of the carbon sphere encapsulated amorphous vanadium-oxygen cluster composite material prepared in example 1, wherein (a) is the former third cyclic voltammogram, and (b) is the former third cyclic voltammogram in fig. 5Charge and discharge curves. As can be seen from (a) in fig. 5, during the first cycle, a significant reduction peak (at 0.40V) was exhibited, mainly associated with sodium ion intercalation of amorphous vanadium-oxygen clusters and formation of a solid electrolyte film (SEI film); stable oxidation-reduction peaks are shown in the second and third cycles, and the voltammetry curves are basically coincident; as shown in FIG. 5 (b), the discharge capacity of the composite material was 1014mAh · g during the first charge and discharge -1 The charge capacity was 572.2 mAh · g -1 The lost capacity is mainly due to the decomposition of the electrolyte and the formation of SEI film, and the reversible capacity of the composite material is stably maintained at 557.2 mAh.g in the two subsequent cycles -1 Left and right. These results indicate that the carbon sphere-encapsulated amorphous vanadium-oxygen cluster composite material prepared in example 1 has high sodium storage capacity and stable charge and discharge properties.
FIG. 6 is a graph of rate capability of the carbon sphere encapsulated amorphous vanadium-oxygen cluster composite prepared in example 1, with a current density of 0.05A g -1 To 10.0 A.g -1 . As can be seen from FIG. 6, as the current density increases stepwise to 10.0A g -1 When the current density is reduced to 0.2 A.g, the reversible capacity is reduced stepwise -1 The reversible capacity increases stepwise with time. Under the same current density in front and back, the reversible capacity is basically maintained to be similar, such as 1.0 A.g -1 The specific capacity of the catalyst is 475 mAh g -1 Left and right, 5.0A. G -1 The capacity at time of 396 mAh g -1 Left and right, etc. After charging and discharging at different multiplying factors, the charge-discharge ratio is 2.0 A.g -1 The capacity of 1800 cycles was maintained at 442 mAh g at the current density of (1) -1 On the left and right, no capacity fade occurred. These results demonstrate that the carbon sphere-encapsulated amorphous vanadium-oxygen cluster composite material prepared in example 1 has excellent rate-cycle stability.
FIG. 7 is a graph of the cycling stability of the carbon sphere encapsulated amorphous vanadium-oxygen cluster composite prepared in example 1 at different current densities (10.0A g) -1 20000 cycles and 30.0A g -1 Next 30000 cycles). As can be seen from FIG. 7, the composite material has a capacity as the number of cycles increasesThe amount rose slowly at 10.0A g after 5000 cycles -1 The reversible capacity is stabilized at 340 mAh g at the current density of -1 Left and right; 30.0A. G -1 The reversible capacity is stabilized at 250 mAh g -1 Left and right. These results demonstrate that the carbon sphere-encapsulated amorphous vanadium-oxygen cluster composite material prepared in example 1 has outstanding ultra-long cycling stability performance, particularly ultra-long cycling stability at high current density. It is noted that the 30000 cycles of negative electrode material can be used for nearly 100 years when the current mobile phone is charged once a day.
Example 2
A carbon sphere packaging amorphous vanadium-oxygen cluster composite material is prepared by the following steps:
(1) Weighing 0.5g of ammonium metavanadate, stirring and dispersing in 100mL of deionized water at 10.0 ℃ to form a uniform ammonium metavanadate aqueous solution;
(2) Weighing 1.2 g of dopamine hydrochloride, adding the dopamine hydrochloride into the ammonium metavanadate aqueous solution obtained in the step (1), and continuously stirring the dopamine hydrochloride aqueous solution at 10.0 ℃ for 40min to fully dissolve the dopamine hydrochloride to obtain a light yellow mixed aqueous solution of the ammonium metavanadate and the dopamine hydrochloride;
(3) Adding 200 mL of absolute ethyl alcohol into the mixed aqueous solution of ammonium metavanadate and dopamine hydrochloride obtained in the step (2) under magnetic stirring, and continuously stirring for 1.5 hours at 10.0 ℃ to obtain a mixed solution;
(4) Adding 20 mL of ammonia water with the mass concentration of 25% dropwise (1 drop/second) into the mixed solution obtained in the step (3) under magnetic stirring to obtain a black aqueous solution, and continuously stirring at 10.0 ℃ for 24 hours to perform self-polymerization reaction; filtering and separating the obtained self-polymerization reaction liquid, repeatedly washing the solid-phase residual soluble ions by deionized water, and then drying at 100 ℃ for 10 hours to obtain black powder, namely the vanadium-dopamine self-polymerization yolk-core structure nanospheres;
(5) And (3) under the protection of argon with the purity of 99.99%, carrying out heat treatment on the vanadium-dopamine self-polymerization yolk-core structure nanospheres obtained in the step (4) at the temperature of 600 ℃ for 2 hours to obtain solid powder, namely the carbon sphere packaging amorphous vanadium-oxygen cluster composite material.
Example 3
A carbon sphere packaging amorphous vanadium-oxygen cluster composite material is prepared by the following steps:
(1) Weighing 0.1 g of ammonium metavanadate, stirring and dispersing in 40 mL of deionized water at 8.0 ℃ to form a uniform ammonium metavanadate aqueous solution;
(2) Weighing 0.3 g of dopamine hydrochloride, adding the dopamine hydrochloride into the ammonium metavanadate aqueous solution obtained in the step (1), and continuously stirring the solution at the temperature of 8.0 ℃ for 20min to fully dissolve the dopamine hydrochloride to obtain a light yellow mixed aqueous solution of the ammonium metavanadate and the dopamine hydrochloride;
(3) Adding 80 mL of absolute ethyl alcohol into the mixed aqueous solution of ammonium metavanadate and dopamine hydrochloride obtained in the step (2) under magnetic stirring, and continuously stirring for 30min at 8.0 ℃ to obtain a mixed solution;
(4) Dropwise adding 5 mL of ammonia water with the mass concentration of 25% (1 drop/second) into the mixed solution obtained in the step (3) under magnetic stirring to obtain a black aqueous solution, and continuously stirring at 8.0 ℃ for 8 hours to perform self-polymerization reaction; carrying out suction filtration and separation on the obtained self-polymerization reaction liquid, repeatedly washing soluble ions remained in a solid phase by deionized water, and then drying at the temperature of 80 ℃ for 12 hours to obtain black powder, namely the vanadium-dopamine self-polymerization yolk-core structure nanospheres;
(5) And (3) under the protection of argon with the purity of 99.99%, carrying out heat treatment on the vanadium-dopamine self-polymerization nanospheres obtained in the step (4) at 500 ℃ for 3 hours to obtain solid powder, namely the carbon sphere packaging amorphous vanadium-oxygen cluster composite material.
The X-ray diffraction pattern (XRD) and X-ray photoelectron energy spectrum (XPS) of the carbon sphere-encapsulated amorphous vanadium-oxygen cluster composites prepared in examples 2 and 3 are similar to those of fig. 2, and the carbon sphere-encapsulated amorphous vanadium-oxygen cluster composites prepared in examples 2 and 3 are each composed of amorphous vanadium-oxygen clusters and amorphous carbon; the XPS map shows elements such as carbon, oxygen, nitrogen and vanadium, wherein the nitrogen and the carbon are from yolk-shell structure nitrogen-doped carbon nanospheres, and the oxygen and the vanadium are from amorphous vanadium-oxygen clusters in the composite material.
Scanning Electron Microscope (SEM) spectra of the carbon sphere encapsulated amorphous vanadium-oxygen cluster composites prepared in examples 2 and 3 are similar to those in fig. 3, the diameters are 160 to 240nm, and the open yolk-shell structure is shown.
Transmission Electron Microscope (TEM) patterns of the carbon sphere-encapsulated amorphous vanadium-oxygen cluster composites prepared in examples 2 and 3 were similar to those of fig. 4, and the nanosphere composites had a yolk-shell structure in which a large number of dark-colored clusters were present, were uniformly distributed and organically mixed in the yolk-shell structured carbon nanospheres, and the clusters had no distinct crystal face structure, indicating that the vanadium-oxygen exists in the composites in the form of amorphous clusters.
Electrochemical performance tests are carried out on the carbon sphere packaging amorphous vanadium-oxygen cluster composite materials prepared in the example 2 and the example 3, the test results are similar to the test results of the example 1, and the carbon sphere packaging amorphous vanadium-oxygen cluster sodium storage materials prepared in the example 2 and the example 3 have high sodium storage capacity, stable charge and discharge performance, excellent rate capability and ultra-long cycle stability.
As can be seen from the above examples, the carbon sphere encapsulated amorphous vanadium-oxygen cluster composite material provided by the present invention comprises amorphous vanadium-oxygen clusters and amorphous nitrogen-doped carbon nanospheres, wherein the amorphous nitrogen-doped carbon nanospheres have an open yolk-shell structure, and the amorphous vanadium-oxygen clusters are uniformly encapsulated in the yolk-shell structure; the carbon sphere packaging amorphous vanadium-oxygen cluster composite material provided by the invention has excellent sodium ion battery negative electrode performances, such as high specific capacity, stable charge and discharge performance, high multiplying power and excellent long-cycle stability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The carbon sphere encapsulated amorphous vanadium-oxygen cluster composite material is characterized in that the composite material comprises amorphous vanadium-oxygen clusters and amorphous nitrogen-doped carbon nanospheres; the amorphous nitrogen-doped carbon nanospheres have an open yolk-shell structure, and the amorphous vanadium-oxygen clusters are encapsulated in the yolk-shell structure; the diameter of the amorphous nitrogen-doped carbon nanosphere is 160 to 240nm, and the size of the amorphous vanadium-oxygen cluster is less than 3nm;
the preparation method of the carbon sphere packaged amorphous vanadium-oxygen cluster composite material comprises the following steps:
(1) Mixing ammonium metavanadate, water, dopamine hydrochloride and ethanol to obtain a mixed solution;
(2) Adding ammonia water into the mixed solution for self-polymerization reaction to obtain vanadium-dopamine self-polymerization yolk-core structure nanospheres;
(3) Carrying out high-temperature phase transformation on the vanadium-dopamine self-polymerization yolk-core structure nanospheres in a protective atmosphere to obtain the carbon sphere packaging amorphous vanadium-oxygen cluster composite material; the temperature of the high-temperature phase transformation is 500 to 800 ℃.
2. The method for preparing the carbon sphere encapsulated amorphous vanadium-oxygen cluster composite material according to claim 1, comprising the following steps:
(1) Mixing ammonium metavanadate, water, dopamine hydrochloride and ethanol to obtain a mixed solution;
(2) Adding ammonia water into the mixed solution for self-polymerization reaction to obtain vanadium-dopamine self-polymerization yolk-core structure nanospheres;
(3) Carrying out high-temperature phase transformation on the vanadium-dopamine self-polymerization yolk-core structure nanospheres in a protective atmosphere to obtain the carbon sphere packaging amorphous vanadium-oxygen cluster composite material; the temperature of the high-temperature phase transformation is 500 to 800 ℃.
3. The preparation method according to claim 2, wherein the mixing in step (1) is carried out by:
dissolving ammonium metavanadate in water, and carrying out first stirring and mixing to obtain an ammonium metavanadate aqueous solution;
adding dopamine hydrochloride into the ammonium metavanadate aqueous solution, and carrying out second stirring and mixing to obtain a mixed aqueous solution of ammonium metavanadate and dopamine hydrochloride;
and adding ethanol into the mixed aqueous solution of ammonium metavanadate and dopamine hydrochloride, and carrying out third stirring and mixing to obtain the mixed solution.
4. The production method according to claim 3, wherein the temperature of the first stirring and mixing, the second stirring and mixing, and the third stirring and mixing is independently 5 to 15 ℃.
5. The preparation method according to any one of claims 2 to 4, wherein the mass ratio of ammonium metavanadate to dopamine hydrochloride in the step (1) is 1 to 0.5 to 5; the mass volume ratio of the ammonium metavanadate to the water is 0.1-2.0 g:100mL; the volume ratio of the water to the ethanol is 1.5 to 5.
6. The preparation method according to claim 2, wherein the mass concentration of the ammonia water is 25%, and the mass volume ratio of the ammonium metavanadate to the ammonia water is 0.1 to 1.0g:10mL.
7. The preparation method according to claim 2, wherein the temperature of the autopolymerization reaction in the step (2) is 5 to 15 ℃ and the time is 3 to 48h.
8. The preparation method according to claim 2 or 7, wherein after the self-polymerization reaction in the step (2), the method further comprises sequentially filtering, washing with solid-phase water and drying the obtained self-polymerization reaction liquid to obtain the vanadium-dopamine self-polymerizing yolk-core structure nanosphere; the drying temperature is 80 to 120 ℃, and the drying time is 8 to 24h.
9. The preparation method according to claim 2, wherein the time for the phase inversion at the high temperature in the step (3) is 1 to 5 hours.
10. The carbon sphere encapsulated amorphous vanadium-oxygen cluster composite material according to claim 1 or the carbon sphere encapsulated amorphous vanadium-oxygen cluster composite material prepared by the preparation method according to any one of claims 2 to 9 is applied to the negative electrode of a sodium ion battery.
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