CN110518202B - Self-supporting V2O5rGO nano array sodium ion battery material and preparation method thereof - Google Patents

Self-supporting V2O5rGO nano array sodium ion battery material and preparation method thereof Download PDF

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CN110518202B
CN110518202B CN201910718603.8A CN201910718603A CN110518202B CN 110518202 B CN110518202 B CN 110518202B CN 201910718603 A CN201910718603 A CN 201910718603A CN 110518202 B CN110518202 B CN 110518202B
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rgo
array
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supporting
nano array
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CN110518202A (en
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高林
陈思
杨学林
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China Three Gorges University CTGU
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a reduced graphene oxide (rGO) modified self-supporting V2O5A method for preparing a nano array. Particularly, after the foamed nickel is cleaned by dilute hydrochloric acid through ultrasonic, a large amount of deionized water is continuously used for washing. V2O5the/rGO nano array is uniformly distributed on the Ni substrate and has a unit area V2O5The amount of the/rGO active substance is 4-5 mg cm‑2. The V is2O5The negative plate of the/rGO nano-array sodium ion battery takes ammonium metavanadate as a raw material, dilute hydrochloric acid is added under the water bath heating condition to adjust the pH value of the solution to 2.0-4.0, then a chemical reaction is carried out under the hydrothermal condition, and V is obtained after annealing in the air2O5And (4) nano arrays. Then, coating the nano array by using GO solution, and reducing at high temperature in nitrogen atmosphere to obtain V2O5a/rGO nanoarray. The synthesis method of the sodium ion negative electrode material is simple and easy to operate. From V2O5The sodium ion half-cell assembled by the/rGO nano-array negative plate has stable cycle performance and potential application value in the sodium ion cell.

Description

Self-supporting V2O5/rGO nano-array sodium ion battery material and preparation method thereof
Technical Field
The invention relates to a novel array type sodium ion battery cathode material, in particular to a V with a nano array shape2O5A preparation method of a/rGO sodium ion battery array material belongs to the field of sodium ion batteries.
Background
With the rapid development of economy, the importance of energy is continuously increasing. With the further consumption of traditional fossil energy sources such as coal, oil, natural gas and the like, the problem of energy shortage is urgently to be solved. As a new energy storage device, a lithium ion battery has the advantages of high specific energy, low self-discharge rate, long service life, no memory effect, environmental friendliness, etc., so that it becomes a research hotspot and is widely applied to portable electronic devices and electric vehicles at present. But instead of the other end of the tubeWith the wide application of lithium ion batteries, insufficient reserve of lithium resources becomes a fatal factor limiting the development of lithium ion batteries. The reserve of sodium element on the earth is far more than that of lithium, and the working principle of the sodium ion battery is similar to that of the lithium ion battery, so the sodium ion battery becomes an effective substitute product of the lithium ion battery. Layered transition metal oxides, in which V is a focus of research in the field of energy, have been the focus of research2O5Due to the advantages of low cost, rich resources and high safety, the material is widely applied to the positive and negative electrodes of supercapacitors and lithium ion batteries, but few reports of the material applied to the negative electrode of sodium ion batteries exist. Due to Na+Large radius, V2O5The delayed reaction kinetics caused by poor electron conductivity also leads to poor electrochemical performance, which in turn limits V2O5Further application in sodium ion batteries.
Disclosure of Invention
Aiming at the problems, the self-supporting V is synthesized by adopting a hydrothermal method2O5Nano array material of V2O5And the electrode material is combined with a three-dimensional Ni net, and further modified by rGO coating, so that the conductivity and the cycling stability of the electrode material are improved. The non-adhesive negative electrode of the sodium ion battery shows obvious charging and discharging platforms and good cycle performance, and has great potential application value.
The invention aims to prepare V by taking ammonium metavanadate as a raw material, taking a Ni net as a substrate, adjusting the pH value of a solution and utilizing a high-temperature and high-pressure environment through a hydrothermal reaction2O5The precursor of the nano array is further annealed in the air to obtain V2O5Nano array, adding GO solution, drying and adding into N2Annealing under atmosphere to obtain self-supporting V2O5a/rGO nanoarray.
The raw materials involved in the invention are ammonium metavanadate, hydrochloric acid, Ni net and GO solution. In the preparation process of the material, firstly, ammonium metavanadate is placed in a container, deionized water is added and placed in the container at 35-80 DEG CoStirring in water bath for 0.2-1 hr until the concentration of ammonium metavanadate is 0.005-0.1mol/L, and dropwise adding hydrochloric acid diluent (of hydrochloric acid diluent)The concentration is 1-4mol L-1) Adjusting the pH of the solution to 2-4. Then transferring the solution into a hydrothermal reaction kettle and adding a treated Ni net at 150-200 DEG CoC, performing hydrothermal reaction for 10-24 h, and then further performing 350-600 ℃ in airoAnnealing for 1-5h to obtain V2O5And (4) array. In order to improve the conductivity and the cycling stability of the material, V is added2O5The immersion concentration of the array is 2-10 mg mL-1Drying in GO solution for 1-5h, and adding into N2Annealing under environment to obtain the self-supporting V completely coated by rGO2O5a/rGO nanoarray.
Self-supporting V of the invention2O5the/rGO nano-array sodium ion negative electrode material and the preparation method thereof have the following characteristics:
(1) the invention has low preparation cost, simple experimental process and easy operation.
(2) V obtained by the invention2O5the/rGO nano array is uniformly covered on the substrate material and is in close contact with the substrate material.
(3) Preparation to obtain V2O5The length of the/rGO nano array is 5-20 mu m, the width of the/rGO nano array is 0.5-3.0 mu m, and the array is assembled by nano particles and has a uniform and porous appearance. And the rGO coating layer is completely covered at V2O5The array surface improves the conductivity of the array. The arrays are connected into a whole, so that a good channel is provided for electron transmission, and the structural stability of the electron transmission in the circulating process is ensured.
(4) Prepared self-supporting V2O5The active substance mass per unit area of the/rGO nano array material is 4-5 mg cm-2At such high active material loadings V2O5the/rGO electrode still has stable electrochemical cycle performance.
Description of the drawings:
fig. 1 is an XRD pattern of the sample prepared in example 1.
Fig. 2 is an SEM image of the sample prepared in example 1.
FIG. 3 is a graph showing the charge and discharge performance of the samples prepared in example 1 (a) and (b) cycle performance
Fig. 4 is an XRD pattern of the sample prepared in example 1.
Fig. 5 is an SEM image of the sample prepared in example 1.
FIG. 6 is a graph showing the charge and discharge performance of the samples prepared in example 1 (a) and (b) cycle performance
Fig. 7 is an SEM image of the sample prepared in example 2.
Fig. 8 is a graph of charge and discharge performance (a) and (b) cycle performance of the sample prepared in example 2.
Fig. 9 is an SEM image of the sample prepared in example 3.
Fig. 10 is a graph of charge and discharge performance (a) and (b) cycle performance of the sample prepared in example 3.
The specific implementation mode is as follows:
example 1
0.01 mol of ammonium metavanadate powder was placed in a beaker and 70 mL of deionized water was added and placed in 75oC continuously stirring in water bath for 30 min, and dropwise adding 2 mol L solution-1The hydrochloric acid solution adjusted the pH to 4.0. The above solution was transferred to a 100 mL hydrothermal reaction kettle and nickel foam (3X 7 cm) was added2) At 180oC, carrying out hydrothermal reaction for 24 h, wherein the foamed nickel is leaned against the hydrothermal kettle at an angle of 60 degrees and is further 500 degrees in the airoC annealing for 1h to obtain V2O5And (4) nano arrays. It was then immersed in 3 mL GO solution (5 mg mL concentration)-1) In the middle, after drying, in N2Under atmosphere 550oAnnealing for 1h under C to obtain V2O5a/rGO nanoarray. FIG. 1 shows the V prepared2O5XRD pattern of the nano-array. It can be seen that other than Ni and NiO and V3O7In addition to the characteristic peaks of (1), V appears at 15.3 °, 20.3 °, 21.7 °, 25.9 °, 30.8 °, 32.2 °, 34.1 ° and 51.4 °, respectively2O5Characteristic peak of (1), XRD pattern and V2O5(JCPDS No. 41-1426) card consistent. For V in the synthesis process, as shown in FIG. 22O5Nanoarrays and coated V2O5SEM characterization was performed for/rGO nanoarrays. It can be seen that V was produced2O5Is in the shape of nano-belt, has a width of 2-3 μm and a lengthThe degree was 10-20 μm and was uniformly distributed on the Ni mesh (FIG. 2 a). FIGS. 2b and c are V before and after the cycle, respectively2O5SEM image of/rGO nano array, the coating of rGO in V can be seen2O5The surface of the nano array is subjected to surface treatment, and the appearance is still kept intact after circulation. The sodium ion semi-cell is assembled by taking the sodium ion semi-cell as a negative electrode material and has the volume of 200 mAh g-1The charge and discharge test is carried out under the current density, and the first discharge specific capacity reaches 1010.7 mAh g-1Capacity attenuation to 200 mAh g in the first 20 cycles-1The back volume remains stable. After 200 cycles, the product still has 140 mAh g-1The specific capacity (figure 3b), the coulombic efficiency is close to 100%, and the electrochemical performance is better.
Example 2
0.01 mol of ammonium metavanadate powder was placed in a beaker and 70 mL of deionized water was added and placed in 75oC continuously stirring in water bath for 30 min, and dropwise adding 2 mol L solution-1The hydrochloric acid solution adjusted the pH to 4.0. The above solution was transferred to a 100 mL hydrothermal reaction kettle and nickel foam (3X 7 cm) was added2) At 180oC, carrying out hydrothermal reaction for 24 h, wherein the foamed nickel is leaned in the hydrothermal kettle at an angle of 60 degrees, and then further 500 hours in airoAnnealing for 1h to obtain V2O5And (4) nano arrays. FIG. 4 shows V obtained by preparation or the like2O5XRD pattern of the nano-array. It can be seen that the peaks other than the characteristic peak of Ni are associated with V2O5(JCPDS No. 41-1426) card consistent. As shown in FIG. 5, the SEM characterization of the V thus prepared can be seen2O5The nano-particles are in a nano-belt shape, have the width of 1-3 mu m and the length of 10-20 mu m, are assembled and are uniformly distributed on the Ni net. The sodium ion semi-cell is assembled by taking the sodium ion semi-cell as a negative electrode material and has the volume of 200 mAh g-1The first discharge capacity reaches 1057.2 mAh g when the charge-discharge test is carried out under the current density-1Capacity attenuation to 138 mAh g in the first 50 cycles-1The back volume remains stable. After 200 cycles, the product still has 87 mAh g-1The specific capacity (figure 6b), the coulombic efficiency is close to 100%, and the electrochemical performance is better.
Example 3
0.01 mol of ammonium metavanadate powder was placed in a beaker and 70 mL of deionized water was added and placed in 75oC continuously stirring in water bath for 30 min, and dropwise adding 2 mol L solution-1The hydrochloric acid solution adjusted the pH to 2.0. The above solution was transferred to a 100 mL hydrothermal reaction kettle and nickel foam (3X 7 cm) was added2) At 180oC, carrying out hydrothermal reaction for 24 h, wherein the foamed nickel is leaned in the hydrothermal kettle at an angle of 60 degrees, and then further 500 hours in airoC annealing for 1h to obtain V2O5And (4) nano arrays. As shown in FIG. 7, the SEM characterization of the V thus prepared can be seen2O5The nano-film is in a nano-film array shape, has the width of 2-4 mu m and the length of 2-4.5 mu m, is assembled by nano-particles and has an obvious pore structure. Half cells were assembled for testing as in example 1, and FIG. 8 shows V prepared in example 22O5Nano array at 200 mAh g-1The first discharge capacity reaches 1025.7 mAh g under the current density-1. After 200 cycles, the capacity tends to be stable and is maintained at 85 mAh g-1And the electrochemical performance is better.
Example 4
0.01 mol of ammonium metavanadate powder was placed in a beaker and 70 mL of deionized water was added and placed in 75oC continuously stirring in water bath for 30 min, and dropwise adding 2 mol L solution-1The hydrochloric acid solution adjusted the pH to 3.0. The above solution was transferred to a 100 mL hydrothermal reaction kettle and nickel foam (3X 7 cm) was added2) At 180oC, carrying out hydrothermal reaction for 24 h, wherein the foamed nickel is leaned in the hydrothermal kettle at an angle of 60 degrees, and then further 500 hours in airoAnnealing for 1h to obtain V2O5And (4) nano arrays. As shown in FIG. 9, the SEM characterization of the V thus prepared can be seen2O5The nano-array is in a nano-array shape, the width is 0.5-2 μm, and the length is 5-20 μm. Half cells were assembled for testing as in example 1, and FIG. 10 shows V prepared in example 32O5Nano array at 200 mAh g-1At a current density, first dischargeThe capacitance reaches 1374 mAh g-1. After 200 cycles, the capacity tends to be stable and is maintained at 87 mAh g-1And the electrochemical performance is better.

Claims (6)

1. Self-supporting V2O5The application of the/rGO nano array on the cathode material of the sodium-ion battery is characterized in that: the V is2O5the/rGO nano array is assembled by nano particles and has a porous structure V2O5the/rGO nano array has the length of 5-20 μm, the width of 0.5-3.0 μm and the thickness of 0.1-0.3 μm, and the rGO is coated on V2O5The array surface and the preparation method comprise the following steps:
(1) weighing ammonium metavanadate, adding deionized water, placing the ammonium metavanadate into a water bath kettle, continuously stirring until the ammonium metavanadate is completely dissolved, dropwise adding hydrochloric acid diluent into the solution to adjust the pH value of the solution, then transferring the solution into a hydrothermal reaction kettle, placing a Ni net in the hydrothermal reaction kettle in an inclined manner to perform hydrothermal reaction, and preparing V2O5Precursor of nano array, then annealing in air to obtain V2O5The concentration of ammonium metavanadate aqueous solution is 0.005-0.1mol/L, and the concentration of hydrochloric acid diluent is 1-4mol L-1；
(2) Will V2O5The nano array is immersed in graphene oxide solution and then dried, and the solid content of GO solution is 2-10 mg mL-1Annealing the completely dried array material in a nitrogen atmosphere to obtain the self-supporting V2O5a/rGO nanoarray.
2. Self-supporting V according to claim 12O5The application of the/rGO nano array on the cathode material of the sodium-ion battery is characterized in that: v2O5The mass of the/rGO nano material active substance is 4-5 mg-cm-2。
3. The self-supporting V of claim 12O5The application of the/rGO nano array on the cathode material of the sodium-ion battery is characterized in that: heating temperature of water bath in step (1)Degree of 35-80oAnd C, heating in a water bath for 0.2-1.0 h.
4. The self-supporting V of claim 12O5The application of the/rGO nano array on the cathode material of the sodium-ion battery is characterized in that: the hydrothermal reaction temperature in the step (1) is 150-oAnd C, performing hydrothermal reaction for 10-24 hours.
5. The self-supporting V of claim 12O5The application of the/rGO nano array on the cathode material of the sodium-ion battery is characterized in that: the annealing in the step (1) is carried out in air at the temperature of 350-oAnd C, annealing for 1-5 h.
6. The self-supporting V of claim 12O5The application of the/rGO nano array on the cathode material of the sodium-ion battery is characterized in that: annealing is carried out at N2Medium temperature of 300-oAnd C, annealing for 1-5 h.
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CN111640921A (en) * 2020-05-22 2020-09-08 大连海事大学 Preparation method of vanadium compound electrode material and application of vanadium compound electrode material in water-based zinc ion battery
CN111785956B (en) * 2020-07-10 2022-04-22 西安交通大学 Flexible electrode material for lithium ion battery and preparation method thereof
CN111785960B (en) * 2020-09-03 2020-11-20 中南大学 Vanadium pentoxide/rGO coated nickel cobalt lithium manganate positive electrode material and preparation method thereof
CN114853065A (en) * 2022-05-26 2022-08-05 三峡大学 W-doped V 2 O 5 Preparation method of self-assembled nano-sheet ball electrode material
CN116613304B (en) * 2023-07-21 2023-10-24 帕瓦(长沙)新能源科技有限公司 Containing water V 3 O 7 Graphene anode material and preparation method and application thereof

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