In-situ growth of oxygen-rich defects Cr on stainless steel 0.11 V2O 5.16 Nanoribbons, their preparation methods and applications

Abstract

The application discloses in-situ grown oxygen-rich defect Cr 0.11 V2O 5.16 nanobelt and a preparation method and application thereof. The in-situ grown oxygen-rich defect Cr 0.11 V2O 5.16 nanobelt on stainless steel is prepared through the following steps: (1) mixing NH4VO3 and oxalic acid aqueous solution with chromium nitrate aqueous solution, then putting stainless steel into the mixed solution, and carrying out high-temperature hydrothermal reaction to obtain in-situ grown Cr 0.11 V2O 5.16 nanobelt precursor; (2) calcining the in-situ grown Cr 0.11 V2O 5.16 nanobelt precursor in an air atmosphere to obtain in-situ grown Cr 0.11 V2O 5.16 nanobelt; (3) vacuum calcining the in-situ grown Cr 0.11 V2O 5.16 nanobelt to obtain in-situ grown oxygen-rich defect Cr 0.11 V2O 5.16 nanobelt on stainless steel. The in-situ grown oxygen-rich defect Cr 0.11 V2O 5.16 nanobelt on stainless steel introduces appropriate oxygen defects, optimizes the electronic structure, and exhibits high specific capacity, excellent rate performance and good cycle stability.

Description

Technical Field

[0001] This invention relates to the field of electrode material technology, specifically to an oxygen-rich defect Cr grown in situ on stainless steel. 0.11 V2O 5.16 Nanoribbons, their preparation methods, and applications. Background Technology

[0002] With the continuous growth in demand for electronic products, the steady development of electric vehicles, and increasingly higher requirements for the safety and environmental friendliness of energy storage devices, aqueous batteries will show great potential in the future battery market. Among the many aqueous battery systems, aqueous zinc-ion batteries (AZIBs) are considered a promising energy storage technology due to their high theoretical capacity (820 mAh / g), high safety, and low cost. However, the performance of AZIBs is strongly influenced by the cathode material. Therefore, the preparation of high-performance cathode materials is an important factor driving the further development of AZIBs. Currently, manganese-based, vanadium-based, and Prussian blue analogues have been studied as cathode materials for aqueous zinc-ion batteries. Among them, vanadium-based materials have attracted widespread attention due to their advantages such as low cost, easy synthesis, rich valence states, diverse crystal structures, and high theoretical specific capacity.

[0003] However, due to the interaction between vanadium oxide and Zn 2+ The strong electrostatic repulsion between Zn 2+ Slow diffusion and poor escape from the matrix lead to slow reaction kinetics and irreversible reactions. Researchers have found that a small number of intercalated ions are crucial for improving reaction kinetics. Therefore, ion-intercalated vanadium oxides, including Zn... 0.36 V2O5·nH2O, Mg 0.2 V2O5·nH2O, Ca 0.24 V2O5, and (Na,Mn)V8O 20 Vanadium-based compounds, such as nH₂O, exhibit larger interlayer spacing, faster reaction kinetics, and more stable structures, thus improving electrochemical performance. Although significant progress has been made in the study of vanadium-based compounds, they still cannot meet practical needs. There is an urgent need to find methods to further improve electrochemical performance. Summary of the Invention

[0004] The purpose of this invention is to provide an in-situ grown oxygen-rich defect Cr on stainless steel. 0.11 V2O 5.16 Nanoribbons, their preparation methods and applications, to enhance Cr 0.11 V2O 5.16 The electrochemical properties of nanomaterials are driving their application in cathode materials for aqueous zinc-ion batteries.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] This invention discloses an in-situ growth method for oxygen-rich defect Cr on stainless steel. 0.11 V2O 5.16 The preparation method of nanoribbons includes the following steps:

[0007] (1) NH4VO3 and oxalic acid aqueous solution are mixed with chromium nitrate aqueous solution, and then stainless steel is placed in the mixture for a high-temperature hydrothermal reaction to obtain Cr grown in situ on the stainless steel. 0.11 V2O 5.16 Precursor;

[0008] (2) The Cr grown in situ on the stainless steel obtained in step (1) 0.11 V2O 5.16 The precursor was calcined in air to obtain Cr grown in situ on stainless steel. 0.11 V2O 5.16 Nanoribbons;

[0009] (3) The Cr grown in situ on the stainless steel obtained in step (2) 0.11 V2O 5.16 Vacuum calcination of nanoribbons yields oxygen-rich defect Cr grown in situ on stainless steel. 0.11 V2O 5.16 Nanoribbons.

[0010] As a preferred technical solution, in step (1), the hydrothermal temperature is 120-200℃ and the reaction time is 5-48h.

[0011] As a preferred technical solution, in step (2), the calcination temperature is 300-900℃, the reaction time is 1-5h, and the heating rate during calcination is 1-10℃ / min.

[0012] As a preferred technical solution, in step (3), the calcination temperature is 200-800℃, the reaction time is 0.1-5h, and the heating rate during calcination is 1-10℃ / min.

[0013] This invention also discloses an in-situ growth method for oxygen-rich defect Cr on stainless steel. 0.11 V2O 5.16 Nanoribbons, formed by in-situ growth of oxygen-rich defect Cr on the aforementioned stainless steel. 0.11 V2O 5.16 Preparation method of nanoribbons.

[0014] This invention also discloses the in-situ growth of oxygen-rich defect Cr on the aforementioned stainless steel. 0.11 V2O 5.16 Application of nanoribbons in cathode materials for aqueous zinc-ion batteries.

[0015] This invention also discloses the in-situ growth of oxygen-rich defect Cr on the aforementioned stainless steel. 0.11 V2O 5.16 Application of nanoribbons in energy storage electrode materials.

[0016] The beneficial effects of this invention are:

[0017] 1. This invention uses stainless steel as a substrate to grow oxygen-rich defective Cr in situ. 0.11 V2O 5.16 Nanoribbons suppress the deactivation problem caused by the aggregation and shedding of active materials during electrochemical reactions;

[0018] 2. This invention employs a vacuum calcination process to introduce an appropriate amount of oxygen vacancies, and optimizes the electronic structure by controlling the calcination time, thereby enabling Cr... 0.11 V2O 5.16 Its electronic structure has a high carrier concentration and a fast ion migration rate, exhibiting high specific capacity, excellent rate performance and good cycle stability, and has broad application prospects in aqueous zinc-ion batteries and other energy storage fields. Attached Figure Description

[0019] Figure 1 Oxygen-rich defect Cr grown in situ on stainless steel prepared in Example 1 0.11 V2O 5.16 Scanning electron microscope image of nanoribbons;

[0020] Figure 2 Oxygen-rich defect Cr grown in situ on stainless steel prepared in Example 1 0.11 V2O 5.16 XPS spectra of O1s in nanoribbons;

[0021] Figure 3 Oxygen-rich defect Cr grown in situ on stainless steel prepared in Example 1 0.11 V2O 5.16 XRD pattern of nanoribbons;

[0022] Figure 4 Oxygen-rich defect Cr grown in situ on stainless steel prepared in Example 1 0.11 V2O 5.16 Nanoribbons are used as positive electrode materials in aqueous zinc-ion batteries at a current of 2A g. -1 The following is a graph showing the cyclic performance.

[0023] Figure 5 Cr grown in situ on stainless steel prepared for Comparative Example 1 0.11 V2O 5.16 Nanoribbons are used as the positive electrode in aqueous zinc-ion batteries at a current of 2A g. -1 The following is a graph showing the cyclic performance. Detailed Implementation

[0024] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described below with reference to the accompanying drawings.

[0025] Example 1

[0026] (1) First, 3 mmol NH4VO3 and 0.6 g oxalic acid were dissolved in 20 mL of deionized water. Next, 10 mL of deionized water containing 0.6 mmol Cr(NO3)3·9H2O was added. The mixture was then stirred for 10 min and transferred to a 50 mL stainless steel autoclave. Simultaneously, stainless steel (SS) was placed into the autoclave. After reacting at 180 °C for 18 h, the stainless steel sheet was removed, washed three times with deionized water and ethanol, and dried at 50 °C to obtain Cr grown in situ on the stainless steel. 0.11 V2O 5.16 Precursor.

[0027] (2) The Cr grown in situ on the stainless steel obtained in step (1) 0.11 V2O 5.16 The precursor was calcined in a tube furnace at 550°C in air atmosphere (5°C min). -1 After 3 hours, Cr was obtained by in-situ growth on stainless steel. 0.11 V2O 5.16 Nanoribbons.

[0028] (3) The Cr grown in situ on the stainless steel obtained in step (2) 0.11 V2O 5.16 Nanoribbons were calcined in a vacuum tube furnace for 0.5 h (500 °C, 5 °C min). -1 Naturally cooled to room temperature, oxygen-rich defect Cr is obtained by in-situ growth on stainless steel. 0.11 V2O 5.16 Nanoribbons.

[0029] Comparative Example 1

[0030] (1) First, 3 mmol NH4VO3 and 0.6 g oxalic acid were dissolved in 20 mL of deionized water. Next, 10 mL of deionized water containing 0.6 mmol Cr(NO3)3·9H2O was added. The mixture was then stirred for 10 min and transferred to a 50 mL stainless steel autoclave. Simultaneously, stainless steel (SS) was placed into the autoclave. After reacting at 180 °C for 18 h, the stainless steel sheet was removed, washed three times with deionized water and ethanol, and dried at 50 °C to obtain Cr grown in situ on the stainless steel. 0.11 V2O 5.16 Precursor.

[0031] (2) The Cr grown in situ on the stainless steel obtained in step (1) 0.11 V2O 5.16 The precursor was calcined in a tube furnace at 550°C in air atmosphere (5°C min). -1 After 3 hours, Cr was obtained by in-situ growth on stainless steel. 0.11 V2O 5.16 Nanoribbons.

[0032] Figure 1 Oxygen-rich defect Cr grown in situ on stainless steel prepared in Example 1 0.11 V2O 5.16 Scanning electron microscope image of nanoribbons, showing the morphology of the material as nanoribbons uniformly grown on stainless steel.

[0033] Figure 2 Oxygen-rich defect Cr grown in situ on stainless steel prepared in Example 1 0.11 V2O 5.16 O1s XPS spectra of nanoribbons, by Figure 2 The characteristic peak of oxygen vacancies can be clearly observed.

[0034] Figure 3 Oxygen-rich defect Cr grown in situ on stainless steel prepared in Example 1 0.11 V2O 5.16 The XRD patterns of the nanoribbons show that their characteristic peaks correspond perfectly to those on the standard card.

[0035] The Cr prepared in Example 1 and Comparative Example 1 0.11 V2O 5.16 Nanoribbons are used to assemble button batteries, and the cycling performance of the materials is tested.

[0036] The Cr prepared in Example 1 and Comparative Example 1 were respectively 0.11 V2O 5.16 A battery was assembled using nanoribbons as the positive electrode, zinc foil as the negative electrode, glass fiber as the separator, and 2M ZnSO4·7H2O as the electrolyte. The assembled battery was then subjected to electrochemical performance testing on a LAND battery testing system.

[0037] Figure 4 Oxygen-rich defect Cr grown in situ on stainless steel prepared in Example 1 0.11 V2O 5.16 Nanoribbons are used as positive electrode materials in aqueous zinc-ion batteries at a current of 2A g. -1 The following cycle performance graph shows the oxygen-enriched defects in Cr. 0.11 V2O 5.16 Nanoribbon electrode materials exhibit excellent cycle stability and high specific capacity.

[0038] Figure 5Cr grown in situ on stainless steel prepared for Comparative Example 1 0.11 V2O 5.16 Nanoribbons are used as the positive electrode in aqueous zinc-ion batteries at a current of 2A g. -1 The following cycle performance graph shows that Cr in Comparative Example 1... 0.11 V2O 5.16 The specific capacity of the nanoribbon electrode material is much lower than that of the oxygen-rich defect Cr in Example 1. 0.11 V2O 5.16 Nanoribbon electrode materials.

[0039] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. An in-situ grown oxygen-rich defect Cr on stainless steel 0.11 V2O 5.16 The application of nanoribbons in the cathode material of aqueous zinc-ion batteries is characterized by: The oxygen-rich defect Cr grown in situ on the stainless steel 0.11 V2O 5.16 The preparation method of nanoribbons includes the following steps: (1) Mix NH4VO3 and oxalic acid aqueous solution with chromium nitrate aqueous solution, then put stainless steel into the mixture and carry out a high-temperature hydrothermal reaction to obtain Cr grown in situ on stainless steel. 0.11 V2O 5.16 Precursor; (2) The Cr grown in situ on the stainless steel obtained in step (1) 0.11 V2O 5.16 The precursor was calcined in air to obtain Cr grown in situ on stainless steel. 0.11 V2O 5.16 Nanoribbons; in step (2), the calcination temperature is 300-900℃, the reaction time is 1-5 h, and the heating rate during calcination is 1-10℃ / min; (3) The Cr grown in situ on the stainless steel obtained in step (2) 0.11 V2O 5.16 Vacuum calcination of nanoribbons yields oxygen-rich defect Cr grown in situ on stainless steel. 0.11 V2O 5.16 Nanoribbons; in step (3), the calcination temperature is 200-800℃, the reaction time is 0.1-5 h, and the heating rate during calcination is 1-10℃ / min.

2. The method for in-situ growth of oxygen-rich defect Cr on stainless steel according to claim 1 0.11 V2O 5.16 The application of nanoribbons in the cathode material of aqueous zinc-ion batteries is characterized by: In step (1), the hydrothermal temperature is 120-200℃ and the reaction time is 5-48 h.

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