Preparation method of graphene-supported V10O24. 12H2O nanobelt composite material with preferred orientation texture

Abstract

A preparation method of a graphene-supported V10O24. 12H2O nanobelt composite material with a preferred orientation texture comprises the following steps: by taking V2O5 powder and a graphene oxide suspension as raw materials, firstly adding the V2O5 powder into the graphene oxide suspension, carrying out water bath ultrasonic treatment for 30-120 minutes, then violently stirring for 10-60 minutes, and then carrying out hydrothermal reaction at 140-240 DEG C to obtain the graphene-supported V10O24. 12H2O nanobelt composite material with the preferred orientation texture. The reaction time is 4-24 hours, a product obtained after the hydrothermal reaction is completed is a grass green columnar sample, the product is washed with water for multiple times and then freeze-dried, the V10O24. 12H2O nanobelt and graphene composite material is obtained, and the V10O24. 12H2O nanobelt grows on a graphene nanosheet. The method is suitable for being applied to the field of chemical energy storage needing fast charge and fast discharge.

Description

TECHNICAL FIELD

[0001] The application relates to a battery material, in particular to a method for preparing a vanadium-based oxide by hydrothermal synthesis for use in a positive electrode material of a zinc ion battery, a lithium ion battery or a sodium ion battery or the like secondary chemical power source, and belongs to the technical field of chemistry. BACKGROUND

[0002] China is rich in vanadium resources, and the reserves rank first in the world, and has a unique advantage in the utilization of vanadium resources. Vanadium has multiple valence states, and vanadium-based oxides have multiple phase structures. As an electrode material of a secondary battery, the vanadium-based oxide has excellent energy storage performance for zinc, lithium and sodium, and can be applied to zinc ion, lithium ion and sodium ion batteries and other secondary batteries as an electrode material, and has good electrochemical energy storage performance. Therefore, it is of great scientific and practical significance to develop a vanadium-based oxide electrode material with high capacity and good cycle performance. The V 10 O 24 ·12H2O crystal has a large interplanar spacing, which is very beneficial to the solid diffusion of ions in the crystal, and has good large-current charge-discharge performance as an electrode material. It still has a high capacity under the condition of large-current charge-discharge, and is suitable for the field of secondary batteries with large-current charge-discharge, but its electronic conductivity is low, and the electronic transmission resistance is large, which restricts the further improvement of its rate performance. SUMMARY

[0003] The application aims to improve the energy storage performance of the vanadium-based oxide V 10 O 24 ·12H2O, and provides a preparation method of a graphene-supported V 10 O 24 ·12H2O nanobelt composite material. The V 10 O 24 ·12H2O nanobelt composite material has excellent energy storage performance and rate performance, and good charge-discharge cycle stability when used as an electrode material and a positive electrode material of a zinc ion battery.

[0004] To achieve the object of the application, the following technical scheme is adopted: a preparation method of a graphene-supported V 10 O 24 ·12H2O nanobelt composite material, wherein V2O5 powder and graphene oxide suspension are used as raw materials, the V2O5 powder is first added to the graphene oxide suspension, and then after water bath ultrasonic treatment for 30-120 minutes and subsequent vigorous stirring for 10-60 minutes, the mixture is heated to 140-240 oThe hydrothermal reaction is carried out at a temperature of C, and the reaction time is between 4-24 hours, and the product obtained after the hydrothermal reaction is completed is a grass green columnar sample, and after multiple water washing and freeze drying, V 10 O 24 The 12H2O nanobelt and graphene composite material, wherein V 10 O 24 The 12H2O nanobelt is grown on the graphene nanosheet.

[0005] Further, the V10O24·12H2O nanobelt in the V10O24·12H2O nanobelt and graphene composite material has a preferred exposure of a (002) crystal face, a thickness of 1-10 nanometers, and a width of 20-100 nanometers. 10 O 24 The 12H2O nanobelt has a preferred exposure of a (002) crystal face, a thickness of 1-10 nanometers, and a width of 20-100 nanometers.

[0006] Further, the mass ratio of the V2O5 powder to the graphene oxide is between 10:1 and 1:10.

[0007] Further, the concentration of the graphene oxide suspension is between 0.5 and 10 mg / mL. -1

[0008] The present application has the following beneficial technical effects: the present application only uses ordinary common powder V2O5 powder and graphene oxide as raw materials, avoids using expensive vanadium-containing salt compounds and other valuable chemical reagents, and has low cost; the present application only synthesizes the graphene-supported V10O24·12H2O nanobelt composite material with preferred orientation texture through a simple hydrothermal reaction, the required equipment and process are simple, the product yield is high, and is above 99%; the graphene-supported V10O24·12H2O nanobelt composite material prepared by the present application can effectively improve the specific capacity and charge-discharge stability of zinc ion batteries, especially the charge-discharge performance under medium and high current densities, and is suitable for application in the field of fast charge and discharge chemical energy storage. 10 O 24 The graphene-supported V10O24·12H2O nanobelt composite material has a preferred exposure of a (002) crystal face, a thickness of 1-10 nanometers, and a width of 20-100 nanometers. 10 O 24 The graphene-supported V10O24·12H2O nanobelt composite material as a positive electrode material of a battery can effectively improve the specific capacity and charge-discharge stability of zinc ion batteries, especially the charge-discharge performance under medium and high current densities, and is suitable for application in the field of fast charge and discharge chemical energy storage. BRIEF DESCRIPTION OF DRAWINGS

[0009] Figure 1 FIG. 1 is an XRD spectrum of the graphene-supported V10O24·12H2O nanobelt composite material. 10 O 24 FIG. 2 is another XRD spectrum of the graphene-supported V10O24·12H2O nanobelt composite material.

[0010] Figure 2 FIG. 1 is an XRD spectrum of the graphene-supported V10O24·12H2O nanobelt composite material. 10 O 24 FIG. 2 is another XRD spectrum of the graphene-supported V10O24·12H2O nanobelt composite material. ​

[0011] Figure 3 Graphene supported V 10 O 24 • SEM image of 12H2O nanoribbon composite.

[0012] Figure 4 Graphene supported V 10 O 24 • TEM image of 12H2O nanoribbon composite.

[0013] Figure 5 Graphene supported V 10 O 24 • Rate capability plot of 12H2O nanoribbon composite as a positive electrode for zinc ion batteries.

[0014] Figure 6 Graphene supported V 10 O 24 • Charge-discharge cycling plot of 12H2O nanoribbon composite as a positive electrode for zinc ion batteries.

[0015] Figure 7 Graphene supported V 10 O 24 • Rate capability plot of 12H2O nanoribbon composite as a positive electrode for zinc ion batteries.

[0016] Figure 8 Graphene supported V 10 O 24 • Charge-discharge cycling plot of 12H2O nanoribbon composite as a positive electrode for zinc ion batteries. DETAILED DESCRIPTION Example 1

[0017] Take 10 ml of 2.0 mg mL -1 Graphene oxide suspension was placed in a 50 ml beaker, then about 0.081 grams of V2O5 powder was added, first water bath ultrasonic for 60 minutes, then the solution was mixed thoroughly by vigorous stirring for about 15 minutes, then the above mixed suspension was added to the inner container of the hydrothermal kettle, and the hydrothermal kettle was tightly sealed, and hydrothermal reaction was carried out at a temperature of 180 o C for about 6 hours. After the hydrothermal kettle was cooled, the grass green columnar product was obtained, and the grass green product was washed with deionized water until the supernatant was colorless and transparent. The vacuum filtration product was freeze-dried to obtain graphene supported V 10 O 24• 12H2O nanoribbon composite material. The XRD pattern of this material is shown below. Figure 1 As shown, the characteristic peak and V 10 O 24 The 12H2O standard spectrum (JCPDS#:25-1006) showed good matching, and the (002) characteristic peak was much stronger than other characteristic peaks, indicating that the obtained product preferentially exposed the (002) crystal plane. The scanning electron microscope morphology is as follows: Figure 3 As shown, the transmission electron microscope image is as follows: Figure 4 As shown. Using this material as the positive electrode material for zinc-ion batteries, conductive carbon black as the conductive agent and polyvinylidene fluoride as the binder, they are mixed in a mass ratio of 3:2:1, and N-methylpyrrolidone solvent is added. After thorough grinding, the mixture is coated onto a titanium sheet and heated to 80°C. o The positive electrode can be prepared by vacuum drying at temperature C for 12 hours, using a zinc sheet as the counter electrode, and containing 3 mol L... -1 The aqueous solution of Zn(CF3SO3)2 (zinc trifluoromethanesulfonate) is an electrolyte solution, exhibiting excellent rate performance, such as... Figure 5 As shown, at 0.5 A g -1 1 A g -1 2 A g -1 5A g -1 10 A g -1 and 20A g -1 At current densities of [specific values], the battery specific capacity can reach 323.4 mAh g. -1 304.5 mAhg -1 290.2 mAh g -1 268.2 mAh g -1 245.4 mAh g -1 and 215.2 mAh g -1 In 10 A g -1 After undergoing 5000 charge-discharge cycles under high current, the capacity retention rate is approximately 59%, and the discharge capacity still reaches 161.9 mAh g after 5000 cycles. -1 ,like Figure 6 As shown. Example 2

[0018] The concentration transferred was 4.67 mg / mL. -1 200 ml of graphene oxide suspension was added to a 500 ml beaker, followed by 3.7 g of V₂O₅ powder. The mixture was ultrasonicated in a water bath for 2 hours and then vigorously stirred for approximately 1 hour. The resulting suspension was then transferred to the inner liner of a 250 ml hydrothermal reactor. After sealing the reactor, it was incubated at 190°C. oThe hydrothermal reaction was carried out at temperature C for about 4 hours. After the hydrothermal reactor cooled, a grass-green columnar substance was obtained. The grass-green product was filtered with deionized water until the supernatant was colorless and transparent. The product obtained by vacuum filtration was freeze-dried to obtain V-shaped material with preferred orientation texture supported by graphene. 10 O 24 • 12H2O nanoribbon composite material. The XRD pattern of this material is shown below. Figure 2 As shown. Using this material as the positive electrode material for zinc-ion batteries, conductive carbon black as a conductive agent, and polyvinylidene fluoride as a binder, they are mixed in a 3:2:1 mass ratio, and N-methylpyrrolidone solvent is added. After thorough grinding, the mixture is coated onto a titanium sheet and heated to 80°C. o The positive electrode can be prepared by vacuum drying at temperature C for 14 hours, using a zinc sheet as the counter electrode, with a concentration of 2.5 mol L... -1 The ZnSO4 aqueous solution is an electrolyte solution and exhibits excellent rate performance, such as... Figure 7 As shown, at 0.5 A g -1 1 A g -1 2 A g -1 5 A g -1 10 A g -1 and 20A g -1 At a current density of [value missing], the battery specific capacity can reach 316.2 mAh g. -1 294 mAh g -1 268.2 mAh g -1 232.7 mAh g -1 199.8 mAh g -1 and 150.6 mAh g -1 In 10 A g -1 Under high current, after 1,000 charge-discharge cycles, the capacity retention is approximately 87%, and the discharge capacity still reaches 158.9 mAh g⁻¹ after 1,000 cycles. -1 ,like Figure 8 As shown.

[0019] Example 3 The concentration transferred was 2.0 mg / mL. -1 300 ml of graphene oxide suspension was added to a 500 ml beaker, followed by 6.0 g of V₂O₅ powder. The mixture was ultrasonicated in a water bath for 1.5 hours and then vigorously stirred for approximately 0.5 hours. The resulting suspension was then added to the inner liner of a 500 ml hydrothermal reactor. After sealing the reactor tightly, it was incubated at 180°C. oThe hydrothermal reaction was carried out at temperature C for approximately 5.5 hours. After cooling the hydrothermal reactor, a grass-green columnar substance was obtained. The grass-green product was filtered with deionized water until the supernatant became colorless and transparent. The product obtained by vacuum filtration was freeze-dried to obtain graphene-supported V-shaped structures with preferred orientation. 10 O 24 • 12H2O nanoribbon composite material. This material was used as the positive electrode material for zinc-ion batteries. Conductive carbon black was used as a conductive agent, and polyvinylidene fluoride was used as a binder. The materials were mixed in a 3:2:1 mass ratio, and N-methylpyrrolidone solvent was added. After thorough grinding, the mixture was coated onto a titanium sheet and heated to 80°C. o The positive electrode can be prepared by vacuum drying at temperature C for 12 hours, using a zinc sheet as the counter electrode, and containing 3 mol L... -1 The aqueous solution of Zn(CF3SO3)2 (zinc trifluoromethanesulfonate) is an electrolyte solution, exhibiting excellent rate performance, such as... Figure 6 As shown, at 0.5 A g -1 1 A g -1 2 A g -1 5 A g -1 and 10A g -1 At current densities of [value missing], the battery specific capacity can reach 303 mAh g. -1 279.6 mAh g -1 249.4 mAh g -1 203.3 mAh g -1 and 163.1mAh g -1 , in 10 A g -1 After undergoing 10,000 charge-discharge cycles under high current, the capacity retention is approximately 62.3%, and the discharge capacity still reaches 101.6 mAh g⁻¹ after 20,000 cycles. -1 .

[0020] This invention improves the conductivity of two-dimensional graphene nanosheets with high electronic conductivity, thereby further enhancing their specific capacity, rate performance, and charge-discharge stability. Therefore, it is possible to prepare graphene nanosheets supporting V-shaped structures with preferred orientation. 10 O 24 • 12H2O nanoparticles enhance electrochemical energy storage performance, including capacity, rate capability, and charge-discharge cycle performance. Figures 5 to 8 In the process, since the charging and discharging capacities are almost identical, the two lines almost overlap, with only slight differences.

Claims

1. A graphene supported catalyst having a preferred orientation texture V 10 O 24 • A method for preparing a 12H2O nanoribbon composite material, characterized in that: With V2O5 powder and graphene oxide suspension as raw materials, first V2O5 powder is added into graphene oxide suspension, after water bath ultrasonic for 30-120 minutes and subsequent vigorous stirring for 10-60 minutes, then hydrothermal reaction is carried out at 140-240 o C, reaction time is between 4-24 hours, the product obtained after hydrothermal reaction is grass green columnar sample, after multiple water washing and freeze drying, V 10 O 24 ·12H2O nanoribbon and graphene composite material is obtained. 10 O 24 ·12H2O nanoribbon is grown on graphene nanosheet.

2. A graphene supported catalyst having a preferred orientation texture V 10 O 24 • A method for preparing 12H2O nanoribbon composites, characterized in that: V 10 O 24 • V in 12H2O nanoribbons and graphene composites 10 O 24 • 12H2O nanoribbons preferentially expose the (002) crystal plane with a thickness between 1-10 nanometers and a width between 20-100 nanometers.

3. A graphene supported catalyst having a preferred orientation texture V as claimed in claim 1 wherein the catalyst is selected from the group consisting of platinum, palladium, rhodium, ruthenium, iridium, gold, silver, copper, nickel, cobalt, iron, zinc, tin, lead, bismuth, cadmium, mercury, gallium, indium, thallium, cesium, and mixtures thereof. 10 O 24 • A method for preparing 12H2O nanoribbon composites, characterized in that: The mass ratio of V2O5 powder to graphene oxide is between 10:1 and 1:

10.

4. A graphene supported catalyst having a preferred orientation texture V as claimed in claim 1 wherein the catalyst is selected from the group consisting of platinum, palladium, rhodium, ruthenium, iridium, gold, silver, copper, nickel, cobalt, iron, zinc, tin, lead, bismuth, cadmium, mercury, gallium, indium, thallium, cesium, and mixtures thereof. 10 O 24 • A method for preparing 12H2O nanoribbon composites, characterized in that: The concentration of the graphene oxide suspension is between 0.5 and 10 mg mL -1 between 0.5 and 10 mg mL

Images