CN110838583B - Carbon nanotube/M-phase vanadium dioxide composite structure, preparation method thereof and application thereof in water-based zinc ion battery - Google Patents
Carbon nanotube/M-phase vanadium dioxide composite structure, preparation method thereof and application thereof in water-based zinc ion battery Download PDFInfo
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Abstract
The invention discloses a carbon nano tube/M-phase vanadium dioxide composite structure, a preparation method thereof and application thereof in a water-based zinc ion battery. The preparation method comprises the following steps: (1) adding carbon nano tubes into deionized water, and carrying out needle point ultrasonic treatment to obtain a suspension 1; (2) adding vanadium pentoxide into the suspension 1, adding a small amount of hydrogen peroxide, and stirring to obtain a suspension 2; (3) carrying out high-temperature hydrothermal reaction on the suspension 2 for several hours and then naturally cooling; (4) carrying out suction filtration, cleaning and freeze drying on the product to obtain a primary product; and reducing the obtained primary product in a high-temperature reaction furnace at high temperature under the protection of gas to obtain the carbon nano tube/M-phase vanadium dioxide composite structure. The carbon nanotube/M-phase vanadium dioxide composite structure provided by the invention shows excellent rate performance and good stability as a water system zinc ion battery anode material. The method has wide significance for the synthesis methodology of materials and the design of other battery anode materials.
Description
Technical Field
The invention relates to the technical field of nano composite materials and electrochemistry, in particular to a carbon nano tube/M-phase vanadium dioxide composite structure, a preparation method thereof and application thereof in a water-based zinc ion battery.
Background
Rechargeable ion batteries have received increased attention due to the high energy density and stability of lithium ion batteries in recent years. However, other metal ion batteries are also receiving increasing attention due to the low crust content of lithium metal, the high cost of lithium ion batteries, and the like (Liang, s., et al., ACS Energy lett.2018,3, 2480-.
In 1988, Shoji et al first reported rechargeable Zn-MnO with neutral or weakly acidic aqueous electrolyte2Zinc ion batteries originated pioneer in aqueous zinc ion batteries (Shoji, t., et al., j.appl.electrochem.). Subsequently, more and more positive electrode materials were of interest to researchers, mainly two types, manganese-and vanadium-based (Zhang, n., et al, j.am.chem.soc.2016,138, 12894-12901; Han, s. -d., et al, chem.mater.2017,29, 4874-4884; Jiang, b., et al, electrochim.acta 2017,229, 422-428; Kundu, d., et al., nat. energy 2016,1, 16119; Yan, m., et al., adv.mater.2018,30,1703725; Ding, j., et al, adv.mater.2019, 1904369). The above documents mostly do not investigate high current density (>10A · g) charge-discharge specific capacity of the positive electrode material. In view of the large polarization at high current density, the charge-discharge specific capacity of the positive electrode material is generally greatly reduced at high current density. Therefore, it is an urgent technical problem to find a novel cathode material with better rate capability and stability, especially capable of maintaining a high specific capacity under a high current density.
The present application has been made for the above reasons.
Disclosure of Invention
In view of the problems or defects of the prior art, the invention aims to provide a carbon nanotube/M-phase vanadium dioxide composite structure, a preparation method thereof and application of the carbon nanotube/M-phase vanadium dioxide composite structure as a positive electrode material in a water-based zinc ion battery.
The invention adopts the Carbon Nano Tube (CNT) as the three-dimensional frame, can promote the transmission of the electrolyte, reduce the strain effect during the ion intercalation and reduce the influence brought by the side reaction in the electrode process; and carbon nanotube and M-phase vanadium dioxide (VO)2(M)) are uniformly distributed, avoiding the aggregation of the metal during the heat treatment; the prepared carbon nano tube/M-phase vanadium dioxide composite structure as a positive electrode material shows better rate performance and outstanding cycling stability in a water system zinc ion battery test.
In order to achieve the first object of the present invention, the present invention adopts the following technical solutions:
a carbon nanotube/M-phase vanadium dioxide composite structure, the composite structure comprising carbon nanotubes, M-phase vanadium dioxide nanoparticles, wherein: the M-phase vanadium dioxide nanoparticles are uniformly distributed in the hollow cavity of the carbon nano tube and on the surface of the 3D network structure of the carbon nano tube.
The second objective of the present invention is to provide a method for preparing the carbon nanotube/M-phase vanadium dioxide composite structure, which specifically comprises the following steps:
(1) dispersed carbon nanotubes
Adding carbon nanotubes into the dispersion liquid, and performing needle point ultrasound to obtain a suspension 1;
(2) dissolving vanadium pentoxide
Adding vanadium pentoxide into the suspension 1 in the step (1), then adding a small amount of aqueous hydrogen peroxide solution, and uniformly stirring to obtain a suspension 2;
(3) high temperature hydrothermal process
Sealing the suspension 2 in the step (2) into a Polytetrafluoroethylene (PTFE) lining, placing the lining into a reaction kettle, reacting for 2-24 hours at 120-240 ℃, and naturally cooling to room temperature after the reaction is finished;
(4) preparation of carbon nanotube/M-phase vanadium dioxide composite structure
Carrying out suction filtration, cleaning and freeze drying on the product in the reaction kettle in the step (3) to obtain a primary product; and then transferring the primary product to a high-temperature reaction furnace, raising the temperature of the reaction furnace to 400-800 ℃ under the condition of protective gas, and then continuously reducing for 0.1-36 h under the conditions of gas protection and constant temperature of 400-800 ℃ to obtain the carbon nano tube/M-phase vanadium dioxide composite structure.
Further, in the above technical solution, the carbon nanotube in step (1) is any commercial carbon nanotube, and the carbon nanotube may be any one of a single-walled carbon nanotube and a multi-walled carbon nanotube or any combination of a plurality of them.
Further, in the above technical solution, the dispersion liquid in step (1) includes, but is not limited to, any one or a combination of two or more of deionized water, alcohols, ethers, lipids, and alcohol ethers, and these substances are mainly used as a carrier for dispersing carbon nanotubes. More preferably, the dispersion is deionized water.
Further, according to the technical scheme, the ultrasonic time in the step (1) is 0.1-1 h.
Further, according to the technical scheme, the vanadium pentoxide in the step (2) is any commercial vanadium pentoxide.
Further, according to the technical scheme, the using amount ratio of the carbon nanotubes to the dispersion liquid in the step (1) is (10-100) parts by mass: (20-80) parts by volume, wherein: the mass part and the volume part are based on mg and mL.
Further, according to the technical scheme, the usage ratio of the carbon nano tube in the step (1) to the vanadium pentoxide in the step (2) is (10-100) mg: (1-3) mmol.
Further, in the above technical solution, in the aqueous hydrogen peroxide solution in the step (2), the mass fraction of hydrogen peroxide is 30%.
Further, according to the technical scheme, the using amount ratio of the vanadium pentoxide to the aqueous hydrogen peroxide solution in the step (2) is (1-3) molar parts: (0.1-10) parts by volume, wherein: the molar parts and the volume parts are based on mmol and mL.
Further, according to the technical scheme, the stirring time in the step (2) is 0.1-2 hours.
Further, in the above technical scheme, the cleaning reagent used in the cleaning step in the step (4) is any one of acetone, absolute ethyl alcohol or deionized water. More preferably, the temperature of the deionized water is 20-100 ℃.
Further, in the above technical scheme, the protective gas in step (4) is a mixed gas composed of any one or more of nitrogen, argon, helium, hydrogen, and ammonia in any proportion, wherein: the purity of the nitrogen, the argon, the helium, the hydrogen and the ammonia is more than or equal to 99.99 percent.
Further, according to the technical scheme, the temperature of the high-temperature reaction furnace in the step (4) is controlled by a program, the primary product is placed in the central area of the high-temperature reaction furnace, and gas is introduced for protection. After the reduction reaction is finished, air cooling or circulating water or shallow layer freezing water is adopted for cooling. The high-temperature reaction furnace can be any one of a muffle furnace, a tube furnace or a microwave furnace; the cavity material of the high-temperature reaction furnace can be any one of quartz, corundum, ceramic or insulating brick.
Furthermore, the heating rate of the high-temperature reaction furnace is preferably 0.1-50 ℃/min.
Furthermore, the flow rate of the protective gas is 5-500 mL/min.
The third purpose of the invention is to provide the application of the carbon nano tube/M-phase vanadium dioxide composite structure as a positive electrode material in an aqueous zinc ion battery.
An aqueous zinc-ion battery positive electrode material comprising a positive electrode active material and a binder, wherein: the anode active material is the carbon nano tube/M-phase vanadium dioxide composite structure.
An aqueous zinc ion battery positive electrode, the positive electrode comprises a current collector and a positive electrode material coated and/or filled on the current collector, wherein: the positive electrode material is the water-based zinc ion battery positive electrode material.
An aqueous zinc-ion battery comprising a positive electrode and a negative electrode, a separator provided between the positive electrode and the negative electrode, and an aqueous electrolyte, wherein: the positive electrode is the positive electrode of the aqueous zinc ion battery; the negative electrode is a metal zinc sheet, and the aqueous electrolyte is an aqueous solution containing a zinc salt electrolyte.
Compared with the prior art, the invention has the following beneficial effects:
(1) the carbon nano tube/M-phase vanadium dioxide composite structure prepared by the invention can be used for the anode of a water system zinc ion battery. The M-phase vanadium dioxide has dense channels which provide a good carrier for rapid intercalation/deintercalation of ions. Meanwhile, the carbon nano tube and the M-phase vanadium dioxide are uniformly dispersed to form a three-dimensional porous structure. The structure can promote the transmission of electrolyte, reduce the strain effect during ion intercalation and reduce the influence caused by side reaction in the electrode process; and the carbon source (carbon nano tube) and the M-phase vanadium dioxide are uniformly distributed, so that the agglomeration of metal in the heat treatment process is avoided. The water-based zinc ion battery anode material prepared by the method has the advantages of good rate capability, good stability, high coulombic efficiency and the like. And the raw materials are all commercial materials, the preparation conditions are safe and simple, easy to control and environment-friendly, the process condition cost is low, the preparation efficiency is high, the environment is friendly, the product quality and the yield are high, the method is suitable for low-carbon economy, and the method has good application and industrialization prospects.
(2) The carbon nano tube/M-phase vanadium dioxide composite structure prepared by the invention can be used in the fields of high-efficiency energy storage and conversion, catalytic conversion, substance adsorption and separation and the like. The synthesis process of the composite structure does not involve strong acid and strong alkali, and the synthesis technology is simple and controllable, and has good application prospect.
Drawings
FIG. 1 is a schematic diagram of a ball-and-stick model of M-phase vanadium dioxide in the carbon nanotube/M-phase vanadium dioxide composite structure prepared by the present invention.
Fig. 2 is an X-ray powder diffraction (XRD) pattern of the carbon nanotube/M-phase vanadium dioxide composite structure prepared in example 1.
FIG. 3 (a) is a Scanning Electron Microscope (SEM) image of the carbon nanotube/M-phase vanadium dioxide composite structure prepared in examples 1, 5 and 9; (b) scanning Electron Microscope (SEM) images of the carbon nanotube/M-phase vanadium dioxide composite structures prepared in examples 2,3, and 4; (c) scanning Electron Microscope (SEM) images of the carbon nanotube/M-phase vanadium dioxide composite structures prepared in examples 6, 7, and 8.
FIG. 4 is a Transmission Electron Microscope (TEM) image of the carbon nanotube/M-phase vanadium dioxide composite structure prepared in example 2.
FIG. 5 is a high resolution lens (HRTEM) image of the carbon nanotube/M-phase vanadium dioxide composite structure prepared in example 2.
Fig. 6 is a rate performance representation of the carbon nanotube/M-phase vanadium dioxide composite structure prepared in examples 1, 5, and 9 when used in a cathode material of an aqueous zinc-ion battery.
Fig. 7 shows the rate performance of the carbon nanotube/M-phase vanadium dioxide composite structure prepared in examples 2,3 and 4 when applied to the cathode material of an aqueous zinc-ion battery.
Fig. 8 is a graph showing the rate performance of the carbon nanotube/M-phase vanadium dioxide composite structure prepared in examples 6, 7 and 8 when applied to a cathode material of an aqueous zinc-ion battery.
Fig. 9 is a graph showing the results of stability tests of the carbon nanotube/M-phase vanadium dioxide composite structure prepared in example 2 in an aqueous zinc ion battery.
Detailed Description
The present invention will be described in further detail below with reference to examples. The present invention is implemented on the premise of the technology of the present invention, and the detailed embodiments and specific procedures are given to illustrate the inventive aspects of the present invention, but the scope of the present invention is not limited to the following embodiments.
Various modifications to the precise description of the invention will be readily apparent to those skilled in the art from the information contained herein without departing from the spirit and scope of the appended claims. It is to be understood that the scope of the invention is not limited to the procedures, properties, or components defined, as these embodiments, as well as others described, are intended to be merely illustrative of particular aspects of the invention. Indeed, various modifications of the embodiments of the invention which are obvious to those skilled in the art or related fields are intended to be covered by the scope of the appended claims.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
VO2Has wide application in optical devices, electronic devices and optoelectronic devices. And VO in M phase2In (b), vanadium atoms pair along the chain, resulting in a multiplication of the unit cell. The V atoms having staggered cross-sectionDisplaced and oxygen octahedra distorted (R.M. wentzcovitch, et al., Physical Review Letters,1994,72, 3389-. The structure has denser ion embedding channels and higher space utilization rate, thereby being beneficial to ion migration and further being beneficial to the improvement of multiplying power performance.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The carbon nanotubes used in the following examples of the present invention were obtained from vanadium pentoxide (V) from Suzhou constant-ball graphene technology Co., Ltd2O5) Are all available from sahn chemical technology (shanghai) ltd.
Example 1
The preparation method of the carbon nanotube/M-phase vanadium dioxide composite structure comprises the following steps:
adding 60mg of carbon nano tube into 40ml of deionized water, carrying out needle point ultrasound for 8 minutes to obtain a suspension 1, sequentially adding 2mmol of vanadium pentoxide and 5ml of aqueous hydrogen peroxide solution with the mass fraction of 30% into the suspension 1, and stirring for 30 minutes to obtain a suspension 2. And then sealing the suspension 2 in a reaction kettle with a PTFE lining for reacting at a constant temperature of 180 ℃ for 8h, after the reaction is finished, carrying out suction filtration on the product, washing the product with normal-temperature deionized water for a plurality of times, and then carrying out freeze drying at-60 ℃ for 24h to obtain a primary product. Finally, placing 0.2g of the primary product in a porcelain boat, transferring the porcelain boat into a tube furnace, heating the tube furnace to 600 ℃ at the heating rate of 15 ℃/min, roasting the porcelain boat for 2 hours at the constant temperature of 600 ℃ in argon flow, and obtaining a carbon nano tube/M-phase vanadium dioxide composite structure after roasting; wherein: the purity of the argon is more than or equal to 99.99 percent; the flow rate of the argon is 250 mL/min.
Example 2
The preparation method of the carbon nanotube/M-phase vanadium dioxide composite structure comprises the following steps:
adding 90mg of carbon nano tube into 45ml of deionized water, carrying out needle point ultrasound for 12 minutes to obtain a suspension 1, sequentially adding 1mmol of vanadium pentoxide and 5ml of aqueous hydrogen peroxide solution with the mass fraction of 30% into the suspension 1, and stirring for 40 minutes to obtain a suspension 2. And then sealing the suspension 2 in a reaction kettle with a PTFE lining, reacting at a constant temperature of 200 ℃ for 12h, after the reaction is finished, performing suction filtration on the product, washing the product with normal-temperature deionized water for a plurality of times, and then performing freeze drying at-60 ℃ for 24h to obtain a primary product. Finally, placing 0.2g of the primary product in a porcelain boat, transferring the porcelain boat into a tube furnace, heating the tube furnace to 650 ℃ at the heating rate of 25 ℃/min, roasting the porcelain boat in argon flow at the constant temperature of 650 ℃ for 2 hours, and obtaining a carbon nano tube/M-phase vanadium dioxide composite structure after roasting; wherein: the purity of the argon is more than or equal to 99.99 percent; the flow rate of the argon is 100 mL/min.
Example 3
The preparation method of the carbon nanotube/M-phase vanadium dioxide composite structure comprises the following steps:
adding 90mg of carbon nano tube into 40ml of deionized water, carrying out needle point ultrasound for 8 minutes to obtain a suspension 1, sequentially adding 3mmol of vanadium pentoxide and 10ml of aqueous hydrogen peroxide solution with the mass fraction of 30% into the suspension 1, and stirring for 20 minutes to obtain a suspension 2. And (3) sealing the suspension 2 in a reaction kettle with a PTFE lining, reacting at 185 ℃ for 11h at constant temperature, filtering the product after the reaction is finished, washing the product with normal-temperature deionized water for a plurality of times, and freeze-drying the product at-60 ℃ for 24h to obtain a primary product. Finally, placing 0.2g of the primary product in a porcelain boat, transferring the porcelain boat into a tubular furnace, heating the tubular furnace to 660 ℃ at the heating rate of 20 ℃/min, roasting the porcelain boat in argon flow at the constant temperature of 660 ℃ for 2 hours, and obtaining a carbon nano tube/M-phase vanadium dioxide composite structure after roasting; wherein: the purity of the argon is more than or equal to 99.99 percent; the flow rate of the argon is 200 mL/min.
Example 4
The preparation method of the carbon nanotube/M-phase vanadium dioxide composite structure comprises the following steps:
adding 30mg of carbon nano tube into 50ml of deionized water, carrying out needle point ultrasound for 15 minutes to obtain a suspension 1, sequentially adding 2mmol of vanadium pentoxide and 10ml of aqueous hydrogen peroxide solution with the mass fraction of 30% into the suspension 1, and stirring for 90 minutes to obtain a suspension 2. And (3) sealing the suspension 2 in a reaction kettle with a PTFE lining, reacting at a constant temperature of 180 ℃ for 10h, after the reaction is finished, performing suction filtration on the product, washing the product with normal-temperature deionized water for a plurality of times, and then performing freeze drying at-60 ℃ for 24h to obtain a primary product. Finally, placing 0.2g of the primary product in a porcelain boat, moving the porcelain boat into a tube furnace, heating the tube furnace to 580 ℃ at the heating rate of 10 ℃/min, roasting the porcelain boat in argon flow at the constant temperature of 580 ℃ for 2 hours, and obtaining a carbon nano tube/M-phase vanadium dioxide composite structure after roasting; wherein: the purity of the argon is more than or equal to 99.99 percent; the flow rate of the argon is 10 mL/min.
Example 5
The preparation method of the carbon nanotube/M-phase vanadium dioxide composite structure comprises the following steps:
adding 30mg of carbon nano tube into 40ml of deionized water, carrying out needle point ultrasound for 20 minutes to obtain a suspension 1, sequentially adding 1mmol of vanadium pentoxide and 5ml of aqueous hydrogen peroxide solution with the mass fraction of 30% into the suspension 1, and stirring for 15 minutes to obtain a suspension 2. And (3) sealing the suspension 2 in a reaction kettle with a PTFE lining, reacting at a constant temperature of 160 ℃ for 15h, after the reaction is finished, performing suction filtration on the product, washing the product with normal-temperature deionized water for a plurality of times, and then performing freeze drying at-60 ℃ for 24h to obtain a primary product. Finally, placing 0.2g of the primary product in a porcelain boat, transferring the porcelain boat into a tube furnace, heating the tube furnace to 500 ℃ at the heating rate of 1 ℃/min, roasting the porcelain boat for 3 hours at the constant temperature of 500 ℃ in argon flow, and obtaining a carbon nano tube/M-phase vanadium dioxide composite structure after roasting and sintering; wherein: the purity of the argon is more than or equal to 99.99 percent; the flow rate of the argon is 500 mL/min.
Example 6
The preparation method of the carbon nanotube/M-phase vanadium dioxide composite structure comprises the following steps:
adding 60mg of carbon nano tube into 50ml of deionized water, carrying out needle point ultrasound for 8 minutes to obtain a suspension 1, sequentially adding 3mmol of vanadium pentoxide and 10ml of aqueous hydrogen peroxide solution with the mass fraction of 30% into the suspension 1, and stirring for 60 minutes to obtain a suspension 2. And sealing the suspension liquid 2 into a reaction kettle with a PTFE lining, reacting for 16h at a constant temperature of 190 ℃, filtering the product after the reaction is finished, washing the product for a plurality of times by using normal-temperature deionized water, and freeze-drying for 24h at the temperature of-60 ℃ to obtain a primary product. Finally, placing 0.2g of the primary product in a porcelain boat, transferring the porcelain boat into a tube furnace, heating the tube furnace to 800 ℃ at the heating rate of 50 ℃/min, roasting the porcelain boat for 1 hour at the constant temperature of 800 ℃ in argon flow, and obtaining a carbon nano tube/M-phase vanadium dioxide composite structure after roasting; wherein: the purity of the argon is more than or equal to 99.99 percent; the flow rate of the argon is 100 mL/min.
Example 7
The preparation method of the carbon nanotube/M-phase vanadium dioxide composite structure comprises the following steps:
adding 90mg of carbon nano tube into 45ml of deionized water, carrying out needle point ultrasound for 18 minutes to obtain a suspension 1, sequentially adding 2mmol of vanadium pentoxide and 10ml of aqueous hydrogen peroxide solution with the mass fraction of 30% into the suspension 1, and stirring for 120 minutes to obtain a suspension 2. And (3) sealing the suspension 2 in a reaction kettle with a PTFE lining, reacting at a constant temperature of 180 ℃ for 15h, after the reaction is finished, performing suction filtration on the product, washing the product with normal-temperature deionized water for a plurality of times, and then performing freeze drying at-60 ℃ for 24h to obtain a primary product. Finally, placing 0.2g of the primary product in a porcelain boat, transferring the porcelain boat into a tube furnace, heating the tube furnace to 700 ℃ at the heating rate of 5 ℃/min, roasting the porcelain boat for 1.5 hours at the constant temperature of 700 ℃ in argon flow, and obtaining a carbon nano tube/M-phase vanadium dioxide composite structure after roasting; wherein: the purity of the argon is more than or equal to 99.99 percent; the flow rate of the argon is 50 mL/min.
Example 8
The preparation method of the carbon nanotube/M-phase vanadium dioxide composite structure comprises the following steps:
adding 30mg of carbon nano tube into 20ml of deionized water, carrying out needle point ultrasound for 20 minutes to obtain a suspension 1, sequentially adding 1mmol of vanadium pentoxide and 5ml of aqueous hydrogen peroxide solution with the mass fraction of 30% into the suspension 1, and stirring for 50 minutes to obtain a suspension 2. And (3) sealing the suspension 2 in a reaction kettle with a PTFE lining, reacting at a constant temperature of 180 ℃ for 12h, after the reaction is finished, performing suction filtration on the product, washing the product with normal-temperature deionized water for a plurality of times, and then performing freeze drying at-60 ℃ for 24h to obtain a primary product. Finally, placing 0.2g of the primary product in a porcelain boat, transferring the porcelain boat into a tube furnace, heating the tube furnace to 550 ℃ at the heating rate of 5 ℃/min, roasting the porcelain boat for 2.5 hours at the constant temperature of 550 ℃ in argon flow, and obtaining a carbon nano tube/M-phase vanadium dioxide composite structure after roasting; wherein: the purity of the argon is more than or equal to 99.99 percent; the flow rate of the argon is 300 mL/min.
Example 9
The preparation method of the carbon nanotube/M-phase vanadium dioxide composite structure comprises the following steps:
adding 60mg of carbon nano tube into 20ml of deionized water, carrying out needle point ultrasound for 20 minutes to obtain a suspension 1, sequentially adding 2mmol of vanadium pentoxide and 5ml of aqueous hydrogen peroxide solution with the mass fraction of 30% into the suspension 1, and stirring for 60 minutes to obtain a suspension 2. And (3) sealing the suspension in a reaction kettle with a PTFE lining, reacting at a constant temperature of 180 ℃ for 12h, after the reaction is finished, performing suction filtration on the product, washing the product with normal-temperature deionized water for a plurality of times, and then performing freeze drying at-60 ℃ for 24h to obtain a primary product. Finally, placing 0.2g of the primary product in a porcelain boat, moving the porcelain boat into a tube furnace, heating the tube furnace to 400 ℃ at the heating rate of 10 ℃/min, roasting the porcelain boat for 4 hours at the constant temperature of 400 ℃ in argon flow, and obtaining a carbon nano tube/M-phase vanadium dioxide composite structure after roasting and sintering; wherein: the purity of the argon is more than or equal to 99.99 percent; the flow rate of the argon is 200 mL/min.
And (3) testing results:
the resulting material was characterized by an XRD pattern, and fig. 2 is an X-ray powder diffraction (XRD) pattern of the carbon nanotube/M-phase vanadium dioxide composite structure prepared in example 1 above. As can be seen from the figure, the product is VO of M phase except carbon2(PDF：82-0661)。
FIG. 3 (a) is a Scanning Electron Microscope (SEM) image of the carbon nanotube/M-phase vanadium dioxide composite structure prepared in examples 1, 5 and 9; (b) scanning Electron Microscope (SEM) images of the carbon nanotube/M-phase vanadium dioxide composite structures prepared in examples 2,3, and 4; (c) scanning Electron Microscope (SEM) images of the carbon nanotube/M-phase vanadium dioxide composite structures prepared in examples 6, 7, and 8.
FIG. 4 is a Transmission Electron Micrograph (TEM) of the carbon nanotube/M-phase vanadium dioxide composite structure prepared in example 2, the TEM photograph showing that the vanadium dioxide is irregular particles.
FIG. 5 is a high resolution lens (HRTEM) image of the carbon nanotube/M-phase vanadium dioxide composite structure prepared in example 2. The (011) and (200) crystal faces displayed by the HRTEM prove that the product is determined to be M-phase VO2。
Application example 1
The carbon nanotube/M-phase vanadium dioxide composite structure prepared by the embodiments of the invention can be used as a positive electrode material to be applied to a water-based zinc ion battery.
The water system zinc ion battery of the application embodiment consists of a positive electrode, a negative electrode, electrolyte, a glass fiber diaphragm arranged between the positive electrode and the negative electrode and a CR2032 battery case; wherein: the negative electrode is a metal zinc sheet, and the electrolyte is 2MZnSO4The positive electrode was a sample of a carbon nanotube/M-phase vanadium dioxide composite structure as an active material, a poly (tetrafluoroethylene) (PTFE) suspension (60 wt%) as a binder, and acetylene black as a conductive additive in a weight ratio of 8: 1: 1, and coating the mixture on the surface of the copper foil.
The water system zinc ion battery is prepared by assembling a positive electrode, a negative electrode, electrolyte and a diaphragm into a battery shell, and the specific capacity of the water system zinc ion battery is tested by a blue CT 2001A.
As shown in FIGS. 6, 7 and 8, the carbon nanotube/M-phase vanadium dioxide composite structure prepared in each example is used for the rate performance expression of the anode material of the water-based zinc-ion battery, and is 2 A.g-1It has a medium density of 248mAh g-1Specific capacity of (2) at a high current density of 20A g-1Still maintain 232.6mAh g-1Compared with 2 A.g-1The specific capacity retention rate is 93.8%. At 40 A.g-1It can also keep 194.9 mAh.g-1The specific capacity of the material is ultrahigh in rate capability. As shown in FIG. 9, in a further stability test, the carbon nanotube/M-phase vanadium dioxide composite structure prepared by the present invention has a high current density of 20 A.g-1After 5000 cycles of lower circulationHas 196.1mAh g-1The specific capacity (85% retention rate) of the composite material shows better stability.
In conclusion, the carbon nanotube/M-phase vanadium dioxide composite structure provided by the invention has excellent rate performance and good stability when being used as a water-based zinc ion battery cathode material.
The carbon nano tube is used as a three-dimensional frame, so that the transmission of electrolyte is promoted, the strain effect during ion intercalation is reduced, and the influence caused by side reaction in the electrode process is reduced; the carbon source and the metal salt are uniformly distributed, so that the aggregation of metal in the heat treatment process is avoided; the prepared carbon nano tube/M-phase vanadium dioxide composite structure shows better rate performance and outstanding cycling stability in a water system zinc ion battery test. The systematic research on the method not only can provide a novel vanadium-based aqueous zinc ion cathode material, but also has wide significance on the synthesis methodology of the material and the design of other battery cathode materials.
Claims (8)
1. A carbon nano tube/M-phase vanadium dioxide composite structure is characterized in that: the composite structure comprises a carbon nano tube and M-phase vanadium dioxide nano particles, wherein: the M-phase vanadium dioxide nanoparticles are uniformly distributed in the hollow cavity of the carbon nano tube and on the surface of the 3D network structure of the carbon nano tube; the carbon nano tube/M-phase vanadium dioxide composite structure is prepared by the following method, and the method comprises the following steps:
(1) dispersed carbon nanotubes
Adding carbon nanotubes into the dispersion liquid, and performing needle point ultrasound to obtain a suspension 1;
(2) dissolving vanadium pentoxide
Adding vanadium pentoxide into the suspension 1 in the step (1), then adding a small amount of aqueous hydrogen peroxide solution, and uniformly stirring to obtain a suspension 2;
(3) high temperature hydrothermal process
Sealing the suspension 2 in the step (2) into a Polytetrafluoroethylene (PTFE) lining, placing the lining into a reaction kettle, reacting for 2-24 hours at 120-240 ℃, and naturally cooling to room temperature after the reaction is finished;
(4) preparation of carbon nanotube/M-phase vanadium dioxide composite structure
Carrying out suction filtration, cleaning and freeze drying on the product in the reaction kettle in the step (3) to obtain a primary product; then transferring the primary product into a high-temperature reaction furnace, raising the temperature of the reaction furnace to 400-800 ℃ under the condition of protective gas, and then continuously reducing for 0.1-36 h under the conditions of gas protection and constant temperature of 400-800 ℃ to obtain the carbon nano tube/M-phase vanadium dioxide composite structure;
the dosage ratio of the carbon nano tube in the step (1) to the vanadium pentoxide in the step (2) is (10-100) mg: (1-3) mmol.
2. The carbon nanotube/M-phase vanadium dioxide composite structure of claim 1, wherein: the dosage ratio of the vanadium pentoxide to the aqueous hydrogen peroxide solution in the step (2) is (1-3) molar parts: (0.1-10) parts by volume, wherein: the molar parts and the volume parts are based on mmol and mL.
3. The carbon nanotube/M-phase vanadium dioxide composite structure of claim 1, wherein: the temperature rise rate of the high-temperature reaction furnace is 0.1-50 ℃/min.
4. The carbon nanotube/M-phase vanadium dioxide composite structure of claim 1, wherein: the flow rate of the protective gas is 5-500 mL/min.
5. The use of the carbon nanotube/M-phase vanadium dioxide composite structure of any one of claims 1 to 4 as a positive electrode material in an aqueous zinc-ion battery.
6. A positive electrode material for a water-based zinc-ion battery, characterized in that: the positive electrode material includes a positive electrode active material and a binder, wherein: the positive electrode active material is the carbon nanotube/M-phase vanadium dioxide composite structure according to any one of claims 1 to 4.
7. A positive electrode for a water-based zinc ion battery, characterized in that: the positive electrode comprises a current collector and a positive electrode material coated and/or filled on the current collector, wherein: the positive electrode material is the aqueous zinc-ion battery positive electrode material according to claim 6.
8. An aqueous zinc-ion battery characterized in that: comprising a positive electrode and a negative electrode, a separator provided between the positive electrode and the negative electrode, and an aqueous electrolyte, wherein: the positive electrode is the aqueous zinc-ion battery positive electrode according to claim 7; the negative electrode is a metal zinc sheet, and the aqueous electrolyte is an aqueous solution containing a zinc salt electrolyte.
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