CN114203982A - Preparation method of vanadium-based Prussian blue analogue/carbon nanotube composite material and application of vanadium-based Prussian blue analogue/carbon nanotube composite material to water-based zinc ion battery anode - Google Patents
Preparation method of vanadium-based Prussian blue analogue/carbon nanotube composite material and application of vanadium-based Prussian blue analogue/carbon nanotube composite material to water-based zinc ion battery anode Download PDFInfo
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Abstract
The invention belongs to the technical field of composite materials, relates to an electrode material, and particularly relates to a vanadium-based Prussian blue analogue/carbon nano tube ((VO)3[Fe(CN)6]2The preparation method of the/CNTs) composite material comprises the following steps: firstly, preparing a carbon nano tube dispersion liquid and a vanadyl sulfate aqueous solution, and mixing the carbon nano tube dispersion liquid and the vanadyl sulfate aqueous solution; adding the prepared deionized water solution of potassium ferricyanide, stirring uniformly, standing, centrifuging, washing with deionized water, and freeze-drying to obtain the final product. The invention also aims to apply the prepared product to the anode material of the water-based zinc ion battery. The vanadium-based Prussian blue analogue has better electrochemical performance than other similar Prussian blue analogues by adopting an in-situ self-assembly method, and the carbon nano tube network can effectively improve the compoundingThe conductivity of the material. The invention has simple and feasible operation and good composite effect and is suitable for large-scale production. The prepared composite material shows excellent zinc storage performance and has potential application prospect.
Description
Technical Field
The invention belongs to the technical field of composite materials, relates to an electrode material, and particularly relates to a vanadium-based Prussian blue analogue/carbon nano tube ((VO)3[Fe(CN)6]2CNTs) composite material and its preparation method and application in positive electrode of water system zinc ion battery.
Technical Field
At present, the development of novel batteries friendly to the environment has become a global trend, and people seek high energy and high power density and simultaneously put forward higher and higher requirements on the aspects of economy, safety, environmental friendliness and the like of the batteries. In recent years, lithium ion batteries are widely used in the market of portable devices as efficient energy storage devices, however, combustible organic electrolytes in lithium ion batteries have potential safety hazards, and in addition, electrodes of the batteries need to be prepared in a water-free environment, so that the cost of the batteries is increased. Considering the large-scale grid application, the problems of low safety and high cost are not negligible, and the relatively small reserve of lithium in the earth's surface limits its development, a variety of factors compel mankind to seek another rechargeable battery to replace the lithium ion battery.
An aqueous zinc-ion battery is widely favored by researchers as a new secondary battery, and has several advantages over other batteries: 1) high energy density and high power density, 2) good safety, 3) environmental protection, and 4) abundant and low cost zinc reserves. The excellent performance of the material also shows wide application prospect in a plurality of portable electronic devices, and is expected to become a candidate for large-scale energy storage in the future. The positive electrode material has a decisive effect on the performance of the water-based zinc ion battery. The manganese oxide has low cost but short cycle life; the vanadium-based oxides have good performance, but are difficult to synthesize on an industrial scale. Therefore, research and research on novel positive electrode materials are of great significance to the development of aqueous zinc ion batteries.
The Prussian blue analogue has the advantages of higher theoretical specific capacity, simple and convenient synthesis and the like, and is a water system zinc ion battery anode material with application potential. However, vanadium-based Prussian blue analogues ((VO)3[Fe(CN)6]2) The application of the zinc ion battery anode material in the aspect of water system zinc ion battery is not reported. Carbon Nanotubes (CNTs), which are one of the members of carbon materials, have advantages such as excellent electrical conductivity, high electrochemical stability, and large specific surface area. Will (VO)3[Fe(CN)6]2Compounding with carbon nano tube to prepare vanadium-based Prussian blue analogue/carbon nano tubeThe composite electrode material can overcome the problems of structural collapse, poor conductivity and the like of the material in the charging and discharging processes, and is an effective way for designing and developing the high-performance anode material of the water system zinc ion battery.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention is directed to a vanadium-based prussian blue analog/carbon nanotube ((VO) for positive electrode of water-based zinc-ion battery3[Fe(CN)6]2CNTs) composite material.
Vanadium-based Prussian blue analogue/carbon nanotube ((VO)3[Fe(CN)6]2The preparation method of the/CNTs) composite material comprises the following steps:
(1) ultrasonically dispersing a carbon nano tube in deionized water to obtain a Carbon Nano Tube (CNTs) dispersion liquid which is called as a solution a, wherein the mass-volume ratio of the carbon nano tube to the deionized water is 5-20 mg: 10-40 mL, and preferably 10mg:20 mL;
(2) preparing a vanadyl sulfate aqueous solution called solution b, wherein the mass-volume ratio of vanadyl sulfate to deionized water is 81.5-326 mg: 5-20 mL, preferably 163mg:10 mL;
(3) adding the solution b into the solution a according to the volume ratio of 1:3, and stirring for 1.5 hours to obtain a mixed solution;
(4) preparing a deionized water solution of potassium ferricyanide, namely solution c, wherein the mass-volume ratio of potassium ferricyanide to deionized water is 82.3-329.2 mg: 5-20 mL, preferably 164.6mg:10 mL;
(5) adding the solution c into the mixed solution obtained in the step (3) according to the volume ratio of 1:3, stirring for 2-6 h at 50-70 ℃, standing, performing centrifugal separation on the obtained precipitate, washing with deionized water for several times, and performing freeze drying to obtain the vanadium-based Prussian blue analogue/carbon nano tube ((VO)3[Fe(CN)6]2/CNTs) composite material.
In a preferred embodiment of the present invention, the carbon nanotubes in step (1) are carboxylated multiwall carbon nanotubes or hydroxylated multiwall carbon nanotubes, preferably carboxylated multiwall carbon nanotubes.
Product made by the invention, (VO)3[Fe(CN)6]2The size of the nano particles is about 30nm and grows along the conductive framework of the carbon nano tube.
The invention also aims to apply the prepared product to the anode material of the water-based zinc ion battery.
The experimental procedure was as follows:
the prepared vanadium-based Prussian blue analogue/carbon nano tube ((VO)3[Fe(CN)6]2Mixing the/CNTs) composite material, the binder and the conductive agent together according to the mass ratio of 7:2:1, fully grinding, dispersing in N-methyl pyrrolidone, stirring for 12 hours, uniformly coating the obtained slurry on the surface of graphite paper serving as a current collector according to a certain thickness, drying in vacuum at 65 ℃, and removing the solvent; the graphite paper is then cut into electrode sheets for later use. The cell assembly was carried out in air, using a zinc plate as the counter electrode and the electrolyte was 2M ZnSO4An aqueous solution.
The invention will be of nanometer scale (VO)3[Fe(CN)6]2Preparation in combination with carbon nanotubes (VO)3[Fe(CN)6]2the/CNTs composite material has the following advantages:
(1) the vanadium-based Prussian blue analogue has more excellent electrochemical performance than other similar Prussian blue analogues;
(2) the carbon nanotube network can effectively improve the conductivity of the composite material;
(3)(VO)3[Fe(CN)6]2and CNTs can help to avoid (VO)3[Fe(CN)6]2Agglomeration and pulverization of the particles, and simultaneously, the charge transport performance is improved. The advantages enable the composite material to show excellent electrochemical performance, and show higher specific capacity (50mA g) when being used as a cathode material of a water system zinc ion battery-1The specific capacity of the first discharge reaches 97.5mAh g-1) And good cycling stability (at 3200mA g-1Capacity retention rate of 81.1% after 1000 cycles at the current density of (1).
Advantageous effects
The invention adopts an in-situ self-assembly method, and VO is firstly subjected to2+Adsorption to carbon nanotubes by electrostatic interactionOn the tube, then [ Fe (CN)6]3-Prepared by coprecipitation method (VO)3[Fe(CN)6]2The composite anode material of the nano particles and the carbon nano tubes shows excellent zinc storage performance and has potential application prospect. The method is simple and feasible, has good composite effect and is suitable for large-scale production.
Drawings
FIG. 1 (VO) prepared in example 13[Fe(CN)6]2X-ray diffraction (XRD) patterns of/CNTs nanocomposites, with diffraction angles (2 θ) on the abscissa and in degrees; the ordinate is the diffraction intensity in cps;
FIG. 2 (VO) prepared in example 13[Fe(CN)6]2Scanning Electron Microscope (SEM) picture of/CNTs nano composite material;
FIG. 3 (VO) prepared in example 13[Fe(CN)6]2/CNTs nano composite material used as anode material of water system zinc ion battery at current density of 3200mA g-1The lower cycle performance graph and the corresponding coulombic efficiency.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Example 1
A preparation method of a vanadium-based Prussian blue analogue/carbon nanotube composite material comprises the following steps:
(1) ultrasonically dispersing 10mg of carboxylated multi-walled carbon nanotubes in 20ml of deionized water, and ultrasonically treating for 30min to obtain a carbon nanotube dispersion liquid;
(2) adding 10ml VOSO4·xH2O solution (containing VOSO)4·xH2O163 mg), stirred at room temperature for 1.5h, and then 10ml of K was added3[Fe(CN)6]Solution (containing K)3[Fe(CN)6]164.6mg), stirring the obtained mixed solution at 60 ℃ for 4h, and standing for 24 h;
(3) centrifuging the obtained precipitate, washing with deionized water for several times, and freeze drying to obtain vanadium basePrussian blue analogue/carbon nanotube composite ((VO)3[Fe(CN)6]2/CNTs)。
The prepared composite material is used as the anode material of a water-system zinc ion battery and is 50mA g-1The specific discharge capacity at first time is 97.5mAh g-1。
FIG. 1 is an XRD pattern of the product prepared in this example, in which all diffraction peaks correspond to (VO)3[Fe(CN)6]2And CNTs, indicating that (VO) was successfully prepared3[Fe(CN)6]2a/CNTs composite material.
Fig. 2 is an SEM image of the product prepared in this example, and it can be seen that vanadium-based prussian blue analog nanoparticles grow along the conductive framework of the carbon nanotube, wherein the size of the nanoparticles is about 30 nm.
FIG. 3 shows that the vanadium-based Prussian blue analog/carbon nanotube nanocomposite prepared in this example is used as a cathode material of an aqueous zinc ion battery at a current density of 3200mA g-1Cyclic performance graph of time.
Example 2
A preparation method of a vanadium-based Prussian blue analogue/carbon nanotube composite material comprises the following steps:
(1) ultrasonically dispersing 10mg of hydroxylated multi-walled carbon nanotubes in 20ml of deionized water, and ultrasonically treating for 30min to obtain a carbon nanotube dispersion liquid;
(2) adding 10ml VOSO4·xH2O solution (containing VOSO)4·xH2O163 mg), stirred at room temperature for 1.5h, and then 10ml of K was added3[Fe(CN)6]Solution (containing K)3[Fe(CN)6]164.6mg), stirring the obtained mixed solution at 60 ℃ for 4h, and standing for 24 h;
(3) centrifuging the obtained precipitate, washing with deionized water for several times, and freeze drying to obtain vanadium-based Prussian blue analogue/carbon nanotube composite material ((VO)3[Fe(CN)6]2/CNTs)。
The prepared composite material is used as the anode material of a water-system zinc ion battery and is 50mA g-1The specific discharge capacity at first time is 95.2mAh g-1。
Example 3
A preparation method of a vanadium-based Prussian blue analogue/carbon nanotube composite material comprises the following steps:
(1) ultrasonically dispersing 5mg of carboxylated multi-walled carbon nanotubes in 10ml of deionized water, and ultrasonically treating for 30min to obtain a carbon nanotube dispersion liquid;
(2) adding 10ml VOSO4·xH2O solution (containing VOSO)4·xH2O163 mg), stirred at room temperature for 1.5h, and then 10ml of K was added3[Fe(CN)6]Solution (containing K)3[Fe(CN)6]164.6mg), stirring the obtained mixed solution at 60 ℃ for 4h, and standing for 24 h;
(3) centrifuging the obtained precipitate, washing with deionized water for several times, and freeze drying to obtain vanadium-based Prussian blue analogue/carbon nanotube composite material ((VO)3[Fe(CN)6]2/CNTs)。
The prepared composite material is used as the anode material of a water-system zinc ion battery and is 50mA g-1The specific discharge capacity at first time is 89.7mAh g-1。
Example 4
A preparation method of a vanadium-based Prussian blue analogue/carbon nanotube composite material comprises the following steps:
(1) ultrasonically dispersing 20mg of carboxylated multi-walled carbon nanotubes in 40ml of deionized water, and ultrasonically treating for 30min to obtain a carbon nanotube dispersion liquid;
(2) adding 10ml VOSO4·xH2O solution (containing VOSO)4·xH2O163 mg), stirred at room temperature for 1.5h, and then 10ml of K was added3[Fe(CN)6]Solution (containing K)3[Fe(CN)6]164.6mg), stirring the obtained mixed solution at 60 ℃ for 4h, and standing for 24 h;
(3) centrifuging the obtained precipitate, washing with deionized water for several times, and freeze drying to obtain vanadium-based Prussian blue analogue/carbon nanotube composite material ((VO)3[Fe(CN)6]2/CNTs)。
The prepared composite material is used as the anode material of a water-system zinc ion battery and is 50mA g-1The specific discharge capacity at first time is 94.2mAh g-1。
Example 5
A preparation method of a vanadium-based Prussian blue analogue/carbon nanotube composite material comprises the following steps:
(1) ultrasonically dispersing 10mg of carboxylated multi-walled carbon nanotubes in 20ml of deionized water, and ultrasonically treating for 30min to obtain a carbon nanotube dispersion liquid;
(2) adding 10ml VOSO4·xH2O solution (containing VOSO)4·xH2O163 mg), stirred at room temperature for 1.5h, and then 10ml of K was added3[Fe(CN)6]Solution (containing K)3[Fe(CN)6]164.6mg), stirring the obtained mixed solution at 50 ℃ for 4h, and standing for 24 h;
(3) centrifuging the obtained precipitate, washing with deionized water for several times, and freeze drying to obtain vanadium-based Prussian blue analogue/carbon nanotube composite material ((VO)3[Fe(CN)6]2/CNTs)。
The prepared composite material is used as the anode material of a water-system zinc ion battery and is 50mA g-1The specific discharge capacity at first time is 95.1mAh g-1。
Example 6
A preparation method of a vanadium-based Prussian blue analogue/carbon nanotube composite material comprises the following steps:
(1) ultrasonically dispersing 10mg of carboxylated multi-walled carbon nanotubes in 20ml of deionized water, and ultrasonically treating for 30min to obtain a carbon nanotube dispersion liquid;
(2) adding 10ml VOSO4·xH2O solution (containing VOSO)4·xH2O163 mg), stirred at room temperature for 1.5h, and then 10ml of K was added3[Fe(CN)6]Solution (containing K)3[Fe(CN)6]164.6mg), stirring the obtained mixed solution at 70 ℃ for 4h, and standing for 24 h;
(3) centrifuging the obtained precipitate, washing with deionized water for several times, and freeze drying to obtain vanadium-based Prussian blue analogue/carbon nanotube composite material ((VO)3[Fe(CN)6]2/CNTs)。
The prepared composite material is used as the anode material of a water-system zinc ion battery and is 50mA g-1First discharge of electricitySpecific capacity of 96.3mAh g-1。
Example 7
A preparation method of a vanadium-based Prussian blue analogue/carbon nanotube composite material comprises the following steps:
(1) ultrasonically dispersing 10mg of carboxylated multi-walled carbon nanotubes in 20ml of deionized water, and ultrasonically treating for 30min to obtain a carbon nanotube dispersion liquid;
(2) adding 10ml VOSO4·xH2O solution (containing VOSO)4·xH2O163 mg), stirred at room temperature for 1.5h, and then 10ml of K was added3[Fe(CN)6]Solution (containing K)3[Fe(CN)6]164.6mg), stirring the obtained mixed solution at 50 ℃ for 2h, and standing for 24 h;
(3) centrifuging the obtained precipitate, washing with deionized water for several times, and freeze drying to obtain vanadium-based Prussian blue analogue/carbon nanotube composite material ((VO)3[Fe(CN)6]2/CNTs)。
The prepared composite material is used as the anode material of a water-system zinc ion battery and is 50mA g-1The specific discharge capacity at first time is 94.0mAh g-1。
Example 8
A preparation method of a vanadium-based Prussian blue analogue/carbon nanotube composite material comprises the following steps:
(1) ultrasonically dispersing 10mg of carboxylated multi-walled carbon nanotubes in 20ml of deionized water, and ultrasonically treating for 30min to obtain a carbon nanotube dispersion liquid;
(2) adding 10ml VOSO4·xH2O solution (containing VOSO)4·xH2O163 mg), stirred at room temperature for 1.5h, and then 10ml of K was added3[Fe(CN)6]Solution (containing K)3[Fe(CN)6]164.6mg), stirring the obtained mixed solution at 50 ℃ for 6h, and standing for 24 h;
(3) centrifuging the obtained precipitate, washing with deionized water for several times, and freeze drying to obtain vanadium-based Prussian blue analogue/carbon nanotube composite material ((VO)3[Fe(CN)6]2/CNTs)。
The prepared composite material is used as a positive electrode material of a water-based zinc ion battery50mA g-1The specific discharge capacity at first time is 94.9mAh g-1。
Example 9
A preparation method of a vanadium-based Prussian blue analogue/carbon nanotube composite material comprises the following steps:
(1) ultrasonically dispersing 10mg of carboxylated multi-walled carbon nanotubes in 20ml of deionized water, and ultrasonically treating for 30min to obtain a carbon nanotube dispersion liquid;
(2) adding 10ml VOSO4·xH2O solution (containing VOSO)4·xH2O163 mg), stirred at room temperature for 1.5h, and then 10ml of K was added3[Fe(CN)6]Solution (containing K)3[Fe(CN)6]164.6mg), the resulting mixed solution was stirred at 70 ℃ for 2 h;
(3) standing for 24h, centrifugally separating the obtained precipitate, washing with deionized water for several times, and freeze-drying to obtain the vanadium-based Prussian blue analogue/carbon nanotube composite material ((VO)3[Fe(CN)6]2/CNTs)。
The prepared composite material is used as the anode material of a water-system zinc ion battery and is 50mA g-1The specific discharge capacity at first time is 95.5mAh g-1。
Example 10
A preparation method of a vanadium-based Prussian blue analogue/carbon nanotube composite material comprises the following steps:
(1) ultrasonically dispersing 10mg of carboxylated multi-walled carbon nanotubes in 20ml of deionized water, and ultrasonically treating for 30min to obtain a carbon nanotube dispersion liquid;
(2) adding 10ml VOSO4·xH2O solution (containing VOSO)4·xH2O163 mg), stirred at room temperature for 1.5h, and then 10ml of K was added3[Fe(CN)6]Solution (containing K)3[Fe(CN)6]164.6mg), stirring the obtained mixed solution at 70 ℃ for 6h, and standing for 24 h;
(3) centrifuging the obtained precipitate, washing with deionized water for several times, and freeze drying to obtain vanadium-based Prussian blue analogue/carbon nanotube composite material ((VO)3[Fe(CN)6]2/CNTs)。
The obtained composite material is used as waterThe zinc ion battery anode material is 50mA g-1The specific discharge capacity at first time is 96.0mAh g-1。
Example 11
A preparation method of a vanadium-based Prussian blue analogue/carbon nanotube composite material comprises the following steps:
(1) ultrasonically dispersing 10mg of hydroxylated multi-walled carbon nanotubes in 20ml of deionized water, and ultrasonically treating for 30min to obtain a carbon nanotube dispersion liquid;
(2) adding 10ml VOSO4·xH2O solution (containing VOSO)4·xH2O163 mg), stirred at room temperature for 1.5h, and then 10ml of K was added3[Fe(CN)6]Solution (containing K)3[Fe(CN)6]164.6mg), stirring the obtained mixed solution at 70 ℃ for 4h, and standing for 24 h;
(3) centrifuging the obtained precipitate, washing with deionized water for several times, and freeze drying to obtain vanadium-based Prussian blue analogue/carbon nanotube composite material ((VO)3[Fe(CN)6]2/CNTs)。
The prepared composite material is used as the anode material of a water-system zinc ion battery and is 50mA g-1The specific discharge capacity at first time is 95.9mAh g-1。
Example 12
A preparation method of a vanadium-based Prussian blue analogue/carbon nanotube composite material comprises the following steps:
(1) ultrasonically dispersing 10mg of hydroxylated multi-walled carbon nanotubes in 20ml of deionized water, and ultrasonically treating for 30min to obtain a carbon nanotube dispersion liquid;
(2) adding 10ml VOSO4·xH2O solution (containing VOSO)4·xH2O163 mg), stirred at room temperature for 1.5h, and then 10ml of K was added3[Fe(CN)6]Solution (containing K)3[Fe(CN)6]164.6mg), stirring the obtained mixed solution at 50 ℃ for 4h, and standing for 24 h;
(3) centrifuging the obtained precipitate, washing with deionized water for several times, and freeze drying to obtain vanadium-based Prussian blue analogue/carbon nanotube composite material ((VO)3[Fe(CN)6]2/CNTs)。
The prepared composite material is used as the anode material of a water-system zinc ion battery and is 50mA g-1The specific discharge capacity at first time is 94.9mAh g-1。
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (9)
1. The preparation method of the vanadium-based Prussian blue analogue/carbon nanotube composite material is characterized by comprising the following steps of:
(1) ultrasonically dispersing a carbon nano tube in deionized water to obtain a carbon nano tube dispersion liquid, namely a solution a, wherein the mass-volume ratio of the carbon nano tube to the deionized water is 5-20 mg: 10-40 mL;
(2) preparing a vanadyl sulfate aqueous solution which is called as a solution b, wherein the mass-volume ratio of vanadyl sulfate to deionized water is 81.5-326 mg: 5-20 mL;
(3) adding the solution b into the solution a according to the volume ratio of 1:3, and stirring for 1.5 hours to obtain a mixed solution;
(4) preparing a deionized water solution of potassium ferricyanide, namely a solution c, wherein the mass-volume ratio of the potassium ferricyanide to the deionized water is 82.3-329.2 mg: 5-20 mL;
(5) adding the solution c into the mixed solution obtained in the step (3) according to the volume ratio of 1:3, stirring for 2-6 h at 50-70 ℃, standing, performing centrifugal separation on the obtained precipitate, washing with deionized water for several times, and freeze-drying to obtain the vanadium-based Prussian blue analogue/carbon nano tube ((VO)3[Fe(CN)6]2/CNTs) composite material.
2. The method for preparing the vanadium-based prussian blue analogue/carbon nanotube composite material according to claim 1, wherein: the mass-to-volume ratio of the carbon nanotubes to the deionized water in the step (1) is 10mg to 20 mL.
3. The method for preparing the vanadium-based prussian blue analogue/carbon nanotube composite material according to claim 1, wherein: the carbon nano tube in the step (1) is a carboxylated multi-wall carbon nano tube or a hydroxylated multi-wall carbon nano tube.
4. The method for preparing the vanadium-based prussian blue analogue/carbon nanotube composite material according to claim 1, wherein: the carbon nano tube in the step (1) is a carboxylated multi-wall carbon nano tube.
5. The method for preparing the vanadium-based prussian blue analogue/carbon nanotube composite material according to claim 1, wherein: and (3) in the step (2), the mass-to-volume ratio of the vanadyl sulfate to the deionized water is 163mg to 10 mL.
6. The method for preparing the vanadium-based prussian blue analogue/carbon nanotube composite material according to claim 1, wherein: in the step (4), the mass-to-volume ratio of the potassium ferricyanide to the deionized water is 164.6mg to 10 mL.
7. The vanadium-based Prussian blue analogue/carbon nanotube composite material prepared according to the method of any one of claims 1 to 6.
8. The vanadium-based prussian blue analog/carbon nanotube composite material according to claim 7, wherein: (VO)3[Fe(CN)6]2The size of the nano particles is about 30nm and grows along the conductive framework of the carbon nano tube.
9. Use of the vanadium-based prussian blue analogue/carbon nanotube composite material according to claim 7 or 8, wherein: the zinc oxide is applied to the anode material of the water-based zinc ion battery.
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