CN109449396B - Self-supporting ammonium vanadate-copper vanadate hydrate-copper foam composite material and preparation method and application thereof - Google Patents
Self-supporting ammonium vanadate-copper vanadate hydrate-copper foam composite material and preparation method and application thereof Download PDFInfo
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- CN109449396B CN109449396B CN201811224282.8A CN201811224282A CN109449396B CN 109449396 B CN109449396 B CN 109449396B CN 201811224282 A CN201811224282 A CN 201811224282A CN 109449396 B CN109449396 B CN 109449396B
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- H01M10/05—Accumulators with non-aqueous electrolyte
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Abstract
The invention discloses a self-supporting ammonium vanadate-copper vanadate hydrate-copper foam composite material as well as a preparation method and application thereof, belonging to the technical field of nano materials and electrochemistry. The method comprises the following steps: 1) ultrasonically cleaning the foam copper for 0.5h by using acetone and deionized water in sequence, and then activating by using a dilute hydrochloric acid solution; 2) washing the activated foam copper with deionized water, and drying in an oven at 60 ℃ for 1-5 h; 3) putting the foamy copper obtained in the step 2) into NH4VO3And (3) standing the solution at room temperature for reaction, taking out the copper foam after the reaction is finished, repeatedly washing the copper foam by using deionized water, and drying to obtain the self-supporting ammonium vanadate-copper vanadate hydrate-copper foam composite material. The method is simple to operate, does not need a binder and a conductive agent, and is green and environment-friendly in process; the self-supporting ammonium vanadate-copper vanadate hydrate-copper foam composite material prepared by the method has a stable structure, is good in compatibility with an electrolyte and has good electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of nano materials and electrochemistry, and relates to a self-supporting ammonium vanadate-copper vanadate hydrate-copper foam composite material, and a preparation method and application thereof.
Background
The lithium ion battery is used as a high-energy battery system with the most obvious development prospect at present, and is widely applied to the fields of electric automobiles, aerospace, portable electronic equipment and the like due to the advantages of high energy density, high power density, long cycle life, wide use temperature range and the like. But the product upgrading puts higher requirements on the capacity of the lithium ion battery.
Vanadate is a material with a layered structure and can be subjected to multi-step reduction in the process of lithium ion intercalation/deintercalation, and is considered to be a lithium ion battery electrode material with potential application value [ Cheng F, Chen J. transition metal salts and salts for lithium ions [ J ]. Journal of Materials Chemistry,2011,21(27): 9841-.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a self-supporting ammonium vanadate-copper vanadate hydrate-copper foam composite material, and a preparation method and application thereof, wherein the method is simple to operate, does not need a binder or a conductive agent, and is environment-friendly in process; the self-supporting ammonium vanadate-copper vanadate hydrate-copper foam composite material prepared by the method has a stable structure, is good in compatibility with an electrolyte and has good electrochemical performance.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of a self-supporting ammonium vanadate-copper vanadate hydrate-copper foam composite material, which comprises the following steps:
1) ultrasonically cleaning the foam copper for 0.5h by using acetone and deionized water in sequence, and then activating by using a dilute hydrochloric acid solution;
2) washing the activated foam copper with deionized water, and drying in an oven at 60 ℃ for 1-5 h;
3) putting the foamy copper obtained in the step 2) into NH4VO3And (3) standing the solution at room temperature for reaction, taking out the copper foam after the reaction is finished, repeatedly washing the copper foam by using deionized water, and drying to obtain the self-supporting ammonium vanadate-copper vanadate hydrate-copper foam composite material.
Preferably, in step 1), the ultrasonic power is 300W.
Preferably, in the step 1), the concentration of the dilute hydrochloric acid solution is 0.1-1 mol/L.
Preferably, in step 3), NH4VO3The concentration of the solution is 0.1-1 mol/L.
Preferably, in the step 3), the standing reaction time is 0.5-5 d.
The invention also discloses the self-supporting ammonium vanadate-hydrated copper vanadate-foamed copper composite material prepared by the preparation method.
The invention also discloses an application of the self-supporting ammonium vanadate-copper vanadate hydrate-copper foam composite material as a lithium ion battery cathode material.
Compared with the prior art, the invention has the following beneficial effects:
self-supporting (NH) of the invention4)2V3O8/Cu3V2O7(OH)2·2H2The method for preparing the O/copper foam composite material has the following remarkable characteristics: (1) the invention will be described in (NH)4)2V3O8And Cu3V2O7(OH)2·2H2The O compound grows on the foam copper in situ, and the two exert a synergistic energy storage effect to improve the electrochemical performance of the foam copper; (2) after the activation of hydrochloric acid, a cuprous oxide seed layer can be generated on the surface of the foam copper and used as an active site of the subsequent reaction. (3) The method has the advantages of simple process, easy control and operation, good safety and stability, and easy realization of industrial mass production. (4) Generating a seed layer on the surface of the foam copper through ultrasonic hydrochloric acid activation treatment, and growing out (NH) in situ as an active site4)2V3O8And Cu3V2O7(OH)2·2H2And (3) O composite product. Meanwhile, the foam copper is used as a matrix, so that the conductivity of the composite material is enhanced, and the circulation stability of the material is improved.
Drawings
FIG. 1 is a self-supporting (NH) catalyst prepared in example 5 of the present invention4)2V3O8/Cu3V2O7(OH)2·2H2XRD pattern of O/copper foam composite material;
FIG. 2 is a drawing showing a preparation process of example 5 of the present inventionSelf-supporting (NH)4)2V3O8/Cu3V2O7(OH)2·2H2SEM image of O/copper foam composite material;
FIG. 3 is a self-supporting (NH) catalyst prepared in example 5 of the present invention4)2V3O8/Cu3V2O7(OH)2·2H2Cycle performance diagram of O/copper foam composite.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below:
self-supporting (NH)4)2V3O8/Cu3V2O7(OH)2·2H2The preparation method of the O/copper foam composite material comprises the following steps:
1) and washing the foam copper with acetone and deionized water sequentially for 0.5h under the ultrasonic power of 300W. Then activating with 0.1-1mol/L dilute hydrochloric acid solution.
2) And (3) washing the activated foam copper with deionized water, and drying in an oven at 60 ℃ for 1-5 h.
3) Obtained in the step 2)Adding 0.1-1mol/L NH into the obtained foam copper4VO3Standing the solution at room temperature for 0.5-5 days, taking out the copper foam after the reaction is finished, repeatedly washing the copper foam with deionized water, and drying to obtain the self-supporting (NH)4)2V3O8/Cu3V2O7(OH)2·2H2O/copper foam composite material.
The present invention is described in further detail below with reference to examples:
example 1
1) And washing the foam copper with acetone and deionized water sequentially for 0.5h under the ultrasonic power of 300W. Then, activation was carried out with 0.1mol/L diluted hydrochloric acid solution.
2) And (3) washing the activated foam copper with deionized water, and drying in an oven at 60 ℃ for 1 h.
3) Adding the foam copper obtained in the step 2) into 0.1mol/L NH4VO3Standing the solution at room temperature for 5 days, taking out the foamy copper after the reaction is finished, repeatedly washing the foamy copper with deionized water, and drying to obtain the self-supporting (NH)4)2V3O8/Cu3V2O7(OH)2·2H2O/copper foam composite material.
Example 2
1) And washing the foam copper with acetone and deionized water sequentially for 0.5h under the ultrasonic power of 300W. Then, activation was carried out with 0.2mol/L diluted hydrochloric acid solution.
2) And (3) washing the activated foam copper with deionized water, and drying in an oven at 60 ℃ for 2 h.
3) Adding the foam copper obtained in the step 2) into 0.5mol/L NH4VO3Standing the solution at room temperature for reaction for 3d, taking out the foamy copper after the reaction is finished, repeatedly washing the foamy copper with deionized water, and drying to obtain the self-supporting (NH)4)2V3O8/Cu3V2O7(OH)2·2H2O/copper foam composite material.
Example 3
1) And washing the foam copper with acetone and deionized water sequentially for 0.5h under the ultrasonic power of 300W. Then, activation was carried out with 0.5mol/L diluted hydrochloric acid solution.
2) And (3) washing the activated foam copper by using deionized water, and drying in an oven at 60 ℃ for 3 h.
3) Adding 1mol/L NH into the foamy copper obtained in the step 2)4VO3Standing the solution at room temperature for 0.5d, taking out the copper foam after the reaction is finished, repeatedly washing the copper foam with deionized water, and drying to obtain the self-supporting (NH)4)2V3O8/Cu3V2O7(OH)2·2H2O/copper foam composite material.
Example 4
1) And washing the foam copper with acetone and deionized water sequentially for 0.5h under the ultrasonic power of 300W. Then, activation was carried out with 0.8mol/L diluted hydrochloric acid solution.
2) And (3) washing the activated foam copper by using deionized water, and drying for 4 hours in an oven at the temperature of 60 ℃.
3) Adding the foam copper obtained in the step 2) into 0.5mol/L NH4VO3Standing the solution at room temperature for reaction for 1d, taking out the foamy copper after the reaction is finished, repeatedly washing the foamy copper with deionized water, and drying to obtain the self-supporting (NH)4)2V3O8/Cu3V2O7(OH)2·2H2O/copper foam composite material.
Example 5
1) And washing the foam copper with acetone and deionized water sequentially for 0.5h under the ultrasonic power of 300W. Then, activation was carried out with a 1mol/L diluted hydrochloric acid solution.
2) And (3) washing the activated foam copper by using deionized water, and drying for 5 hours in an oven at the temperature of 60 ℃.
3) Adding the foam copper obtained in the step 2) into 0.5mol/L NH4VO3Standing the solution at room temperature for reaction for 1d, taking out the foamy copper after the reaction is finished, repeatedly washing the foamy copper with deionized water, and drying to obtain the self-supporting (NH)4)2V3O8/Cu3V2O7(OH)2·2H2O/copper foam composite material.
As can be seen from FIG. 1, the materials prepared are very good in terms of (NH)4)2V3O8/Cu3V2O7(OH)2·2H2Standard card of O/copper foam, indicating that the product is pure phase, free of other impurities. As can be seen from FIG. 2, (NH)4)2V3O8/Cu3V2O7(OH)2·2H2The appearance of the O/foamy copper is lantern-shaped particles with the diameter of 500nm, and the particle size is uniform. From FIG. 3, it can be seen that at 100mAg-1Then, its first discharge capacity was 765mAh g-1Capacity after 100 cycles is 901mAh g-1Self-supporting (NH)4)2V3O8/Cu3V2O7(OH)2·2H2The O/copper foam composite material shows excellent electrochemical performance.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (7)
1. Self-supporting (NH)4)2V3O8-Cu3V2O7(OH)2·2H2The preparation method of the O-copper foam composite material is characterized by comprising the following steps:
1) ultrasonically cleaning the foam copper for 0.5h by using acetone and deionized water in sequence, and then activating by using a dilute hydrochloric acid solution;
2) washing the activated foam copper with deionized water, and drying in an oven at 60 ℃ for 1-5 h;
3) putting the foamy copper obtained in the step 2) into NH4VO3The solution is kept stand to react at room temperature, after the reaction is finished, the copper foam is taken out and repeatedly washed by deionized water, and the self-supporting (NH) is prepared after drying4)2V3O8-Cu3V2O7(OH)2·2H2An O-copper foam composite.
2. Self-supporting (NH) according to claim 14)2V3O8-Cu3V2O7(OH)2·2H2The preparation method of the O-copper foam composite material is characterized in that in the step 1), the ultrasonic power is 300W.
3. Self-supporting (NH) according to claim 14)2V3O8-Cu3V2O7(OH)2·2H2The preparation method of the O-foamy copper composite material is characterized in that in the step 1), the concentration of the dilute hydrochloric acid solution is 0.1-1 mol/L.
4. Self-supporting (NH) according to claim 14)2V3O8-Cu3V2O7(OH)2·2H2The preparation method of the O-foam copper composite material is characterized in that in the step 3), NH is adopted4VO3The concentration of the solution is 0.1-1 mol/L.
5. Self-supporting (NH) according to claim 14)2V3O8-Cu3V2O7(OH)2·2H2The preparation method of the O-foamy copper composite material is characterized in that in the step 3), the standing reaction time is 0.5-5 d.
6. Self-supporting (NH) produced by the production method according to any one of claims 1 to 54)2V3O8-Cu3V2O7(OH)2·2H2An O-copper foam composite.
7. Self-supporting (NH) according to claim 64)2V3O8-Cu3V2O7(OH)2·2H2The O-foamy copper composite material is applied as a negative electrode material of a lithium ion battery.
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| CN101920993B (en) * | 2010-08-03 | 2012-01-18 | 复旦大学 | Preparation method and application of copper vanadate electrode material |
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| CN105047923A (en) * | 2015-08-14 | 2015-11-11 | 东莞市迈科科技有限公司 | Lithium copper vanadate anode material for lithium ion battery and preparation method of lithium copper vanadate anode material |
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