CN111326347A - Zn-Cu-Se composite material and preparation method and application thereof - Google Patents
Zn-Cu-Se composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a Zn-Cu-Se composite material and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) dissolving soluble zinc salt, soluble copper salt, urea and ammonium fluoride in water, uniformly stirring, carrying out a hydrothermal reaction, centrifuging, washing and drying to obtain a Zn-Cu precursor; (2) dissolving the prepared Zn-Cu precursor and sodium selenite in water, stirring and dispersing, adding ammonia water to form uniform suspension, performing a second hydrothermal reaction, centrifuging, washing and drying to obtain the Zn-Cu-Se composite material. Compared with the prior art, the Zn-Cu-Se composite material is synthesized by two hydrothermal steps, the composite material has good electrochemical performance, the preparation method of the composite material is simple, the environment is friendly, and the synthesis time is greatly shortened.
Description
Technical Field
The invention belongs to the technical field of electrochemistry and nano materials, and relates to a Zn-Cu-Se composite material and a preparation method and application thereof.
Background
Various types of batteries, such as supercapacitors, lithium ion batteries, lithium batteries, metal air batteries, and fuel cells, are considered to be the most efficient advanced energy storage systems. Compared with a battery, the super capacitor has the advantages of strong charge-discharge capacity, high power density, strong capacity sustainability and the like, and has wider application prospect. However, conventional Electric Double Layer Capacitors (EDLCs) are limited by their low energy, and this problem can be effectively solved by replacing conventional carbon electrode materials with pseudocapacitive materials, which can store and discharge more charge by redox reactions. In addition, pseudocapacitive materials can be used to construct aqueous asymmetric supercapacitors, increasing the operating potential of aqueous EDLCs from about 1.0V to about 1.6V. Therefore, there have been many studies on transition metal oxides, hydroxides, sulfides, and selenides to achieve high energy density and high power density. The behavior of the pseudocapacitive material is determined by charge transport, since it depends on the redox reaction at or near the surface; therefore, their theoretically predicted high capacitance is rarely obtained in practical experiments.
As a constituent of the supercapacitor, an electrode material having a specific structure determines the performance of the supercapacitor. In summary, for the last decade, transition metals, especially nickel, cobalt, copper and zinc elements, have been widely used in research and development of energy storage electrode materials due to their excellent electrochemical properties and abundant natural resources. Copper zinc selenide compounds have attracted more and more attention in recent years as a novel multifunctional material because of the low toxicity of elemental selenium and the better conductivity of copper zinc selenide compounds over other chalcogen compounds. However, the electrochemical performance of the conventional zinc copper selenide compound is not particularly ideal, and the synthesis efficiency is low.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a Zn-Cu-Se composite material and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a preparation method of a Zn-Cu-Se composite material, which comprises the following steps:
(1) dissolving soluble zinc salt, soluble copper salt, urea and ammonium fluoride in water, uniformly stirring, carrying out a hydrothermal reaction, centrifuging, washing and drying to obtain a Zn-Cu precursor;
(2) dissolving the prepared Zn-Cu precursor and sodium selenite in water, stirring and dispersing, adding ammonia water to form uniform suspension, performing a second hydrothermal reaction, centrifuging, washing and drying to obtain the Zn-Cu-Se composite material.
Further, the soluble copper salt is copper acetate, and the soluble zinc salt is zinc nitrate.
Furthermore, the mol ratio of the soluble zinc salt, the soluble copper salt, the ammonium fluoride and the urea is 1 (0.5-2) to (5-8) to (4-6).
Furthermore, in the process of the primary hydrothermal reaction, the temperature is 150-.
Further, in the step (2), the concentration of the ammonia water is 13.38mol/L, and the adding amount ratio of the soluble zinc salt, the sodium selenite and the ammonia water is 1 mmol: (30-60) mg: (2-5) mL.
Further, in the step (2), the temperature is 120-160 ℃ and the time is 5-10h in the second hydrothermal reaction process.
Further, in the step (1) and the step (2), the drying mode is vacuum drying, and in the drying process, the temperature is 55-65 ℃ and the time is 10-14 h.
Zn (NO) during hydrothermal reaction3)2·6H2O，Cu(CH3COO)2·H2Separate decomposition of Zn from O and urea2+、Cu2+、OH-And CO3 2-And synthesizing the zinc-copper precursor. And NH4F in F-Selectively adsorb on crystal surfaces, thereby changing the crystallization kinetic behavior of each crystal surface, finally leading the crystals to generate morphological difference, and high concentration of NH4+Can promote OH-The growth rate is improved, and crystals can grow along the two-dimensional lattice direction to form the two-dimensional nanosheet. Then, hydrothermal reaction is utilized, sodium selenite is adopted for easy selenization reaction, and a proper amount of ammonia water is added to adjust the pH value of the solution.
In the process of preparing the Zn-Cu-Se composite material, the Zn-Cu-Se composite material is prepared by the direct selenization reaction of a Zn-Cu precursor under the hydrothermal condition. The optimized Zn-Cu-Se nanosheet has an interconnected nanosheet structure, and is proved to be an excellent energy storage material.
The second technical scheme of the invention provides a Zn-Cu-Se composite material which is prepared by the preparation method and is characterized in that the Zn-Cu-Se composite material is formed by connecting nano sheets with rich pore structures.
The third technical scheme of the invention provides application of a Zn-Cu-Se composite material for preparing a working electrode and applying the composite material to a super capacitor.
Further, the preparation process of the working electrode specifically comprises the following steps:
grinding the Zn-Cu-Se composite material, uniformly mixing the Zn-Cu-Se composite material with carbon black and polytetrafluoroethylene, then pressing the mixture on a foam nickel sheet, and drying the foam nickel sheet to obtain the working electrode.
Furthermore, the mass ratio of the Zn-Cu-Se composite material to the carbon black to the polytetrafluoroethylene is 8 (0.8-1.2) to 0.8-1.2.
Furthermore, the temperature is 50-70 ℃ and the time is 10-15h in the drying process.
Compared with the prior art, the invention has the following advantages:
1) according to the invention, the Zn-Cu-Se composite material is synthesized by a two-step hydrothermal method, and the material is formed by mutually connecting nano sheets with rich pore structures, so that the flow diffusion of electrolyte is promoted, and the electrochemical performance of the material is further improved.
2) The Zn-Cu-Se composite material has higher energy density and power density due to the fact that the conductivity of the zinc copper selenide compound is superior to that of other sulfur family compounds, and the prepared working electrode can be applied to a super capacitor.
Drawings
FIG. 1 is an SEM photograph at 2 μm of a Zn-Cu-Se composite material prepared in example 1;
FIG. 2 is a CV diagram of the Zn-Cu-Se composite material prepared in example 1 at different sweep rates;
FIG. 3 is a GCD graph of Zn-Cu-Se composite prepared in example 1 at different current densities.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, the starting products or processing techniques are not specifically described, but are all conventional commercial products or conventional processing techniques in the art.
Example 1:
a preparation method of a Zn-Cu-Se composite material comprises the following steps:
1mmol of Zn (NO)3)2·6H2O，1mmol Cu(CH3COO)2·H2O，6mmol NH4F, 5mmol of urea is dissolved in 40mL of water, and after being uniformly stirred by magnetic force, the urea is transferred into 50mL of polytetrafluoroethyleneThe preparation method comprises the steps of carrying out one-step hydrothermal reaction in a stainless steel lined autoclave at the hydrothermal reaction temperature of 180 ℃ for 6 hours, taking out a sample after hydrothermal reaction, cooling, centrifuging, washing, and drying in vacuum at 60 ℃ for 12 hours to obtain a Zn-Cu precursor, dissolving the prepared Zn-Cu precursor and 60mg of sodium selenite in water, magnetically stirring and dispersing, adding 2mL of ammonia water to form uniform suspension, carrying out a second hydrothermal reaction at the hydrothermal reaction temperature of 140 ℃ for 8 hours, centrifuging, washing, and drying to obtain a Zn-Cu-Se composite material, grinding the active material, uniformly mixing with carbon black and polytetrafluoroethylene in a mass ratio of 8:1:1, pressing on a foamed nickel sheet (1cm × 1cm), and drying in a 60 ℃ oven for 12 hours to obtain a Zn-Cu-Se working electrode (recorded as ZCS-1).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: the foam nickel sheet of ZCS-1 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2M KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability. At a current density of 1A/g, the specific capacitance of the composite material reaches 1059.82F/g.
FIG. 1 is an SEM image of a Zn-Cu-Se composite material under the condition of 1 μm, and from the SEM image, we can see that the composite material is composed of nano sheets which are connected with each other, and the nano sheets which are not stacked not only effectively accelerate the oxidation-reduction reaction and enlarge the contact between an electrode and an electrolyte, but also provide a stable structure for a long-time cyclic process.
FIG. 2 is a CV diagram of the prepared Zn-Cu-Se composite material at different sweep rates, wherein the sweep rates are respectively 5mV/s, 10mV/s, 15mV/s, 20mV/s and 30 mV/s. As can be seen from FIG. 2, in the voltage range of-0.2 to 0.7V, there are a pair of symmetrical redox peaks, and as the sweep rate increases, the oxidation peak and the reduction peak move to the right and left, respectively. The phenomenon shows that the prepared Zn-Cu-Se composite material has good reversibility and stability.
FIG. 3 is a GCD curve of the prepared Zn-Cu-Se composite material under different current densities from FIG. 3, it can be seen that the GCD curve has a distinct platform, which means that pseudocapacitance behavior exists, and good symmetry of the curve confirms that the redox reaction has good reversibility.
Example 2:
a preparation method of a Zn-Cu-Se composite material comprises the following steps:
1mmol of Zn (NO)3)2·6H2O，0.5mmol Cu(CH3COO)2·H2O，6mmol NH4Dissolving 5mmol of urea in 40mL of water, magnetically stirring uniformly, transferring to a 50mL stainless steel autoclave with a polytetrafluoroethylene lining, carrying out a one-step hydrothermal reaction at 180 ℃ for 6h, taking out and cooling a hydrothermal sample, centrifuging, washing, and vacuum drying at 60 ℃ for 12h to obtain a Zn-Cu precursor, dissolving the prepared Zn-Cu precursor and 60mg of sodium selenite in water, magnetically stirring and dispersing, adding 2mL of ammonia water to form a uniform suspension, carrying out a second hydrothermal reaction at 140 ℃ for 8h, centrifuging, washing, and drying to obtain a Zn-Cu-Se composite material, grinding the active material, uniformly mixing with carbon black and polytetrafluoroethylene in a mass ratio of 8:1:1, pressing on a nickel foam sheet (1cm × 1cm), and drying in a 60 ℃ oven for 12h to obtain a Zn-Cu-Se working electrode (recorded as ZCS-2).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: the foam nickel sheet of ZCS-2 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2M KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability.
Example 3:
a preparation method of a Zn-Cu-Se composite material comprises the following steps:
1mmol of Zn (NO)3)2·6H2O，2mmol Cu(CH3COO)2·H2O，6mmol NH4F, 5mmol of urea dissolved in 40mLThe preparation method comprises the following steps of uniformly stirring in water by magnetic force, transferring the uniformly stirred mixture into a 50mL stainless steel autoclave with a polytetrafluoroethylene lining, carrying out one-step hydrothermal reaction at 180 ℃ for 6h, taking out and cooling a hydrothermal sample, centrifuging, washing and drying at 60 ℃ for 12h in vacuum to obtain a Zn-Cu precursor, dissolving the prepared Zn-Cu precursor and 60mg sodium selenite in water by magnetic force, stirring and dispersing the obtained solution in water by magnetic force, adding 2mL ammonia water to form a uniform suspension, carrying out a second hydrothermal reaction at 140 ℃ for 8h, centrifuging, washing and drying to obtain a Zn-Cu-Se composite material, grinding the obtained Zn-Cu-Se composite material, uniformly mixing the obtained active material with carbon black and polytetrafluoroethylene in a mass ratio of 8:1:1, pressing the obtained active material on a foamed nickel sheet (1cm × 1cm), and drying in a baking oven at 60 ℃ for 12h to obtain a Zn-Cu-Se working electrode (recorded as ZCS-3).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: the foam nickel sheet of ZCS-3 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2M KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability.
Example 4:
a preparation method of a Zn-Cu-Se composite material comprises the following steps:
1mmol of Zn (NO)3)2·6H2O，1mmol Cu(CH3COO)2·H2O，6mmol NH4Dissolving 5mmol of urea in 40mL of water, magnetically stirring uniformly, transferring to a 50mL stainless steel autoclave with a polytetrafluoroethylene lining, and carrying out one-step hydrothermal reaction at 150 ℃ for 5 hours; and taking out the sample after hydrothermal treatment, cooling, centrifuging, washing, and vacuum drying at 60 ℃ for 12h to obtain the Zn-Cu precursor. Dissolving the prepared Zn-Cu precursor and 60mg of sodium selenite in water, magnetically stirring and dispersing, adding 2mL of ammonia water to form uniform suspension, performing a second hydrothermal reaction at 140 ℃ for 8h, centrifuging, washing and drying to obtain the final productGrinding the active material, uniformly mixing the active material with carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1, pressing the mixture on a foam nickel sheet (1cm × 1cm), and drying the foam nickel sheet in a baking oven at the temperature of 60 ℃ for 12 hours to obtain a Zn-Cu-Se working electrode (recorded as ZCS-4).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: the foam nickel sheet of ZCS-4 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2M KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability.
Example 5:
a preparation method of a Zn-Cu-Se composite material comprises the following steps:
1mmol of Zn (NO)3)2·6H2O，1mmol Cu(CH3COO)2·H2O，6mmol NH4Dissolving 5mmol of urea in 40mL of water, magnetically stirring uniformly, transferring to a 50mL stainless steel autoclave with a polytetrafluoroethylene lining, carrying out a one-step hydrothermal reaction at 200 ℃ for 12h, taking out and cooling a hydrothermal sample, centrifuging, washing, and vacuum-drying at 60 ℃ for 12h to obtain a Zn-Cu precursor, dissolving the prepared Zn-Cu precursor and 60mg of sodium selenite in water, magnetically stirring and dispersing, adding 2mL of ammonia water to form a uniform suspension, carrying out a second hydrothermal reaction at 140 ℃ for 8h, centrifuging, washing, and drying to obtain a Zn-Cu-Se composite material, grinding the active material, uniformly mixing with carbon black and polytetrafluoroethylene in a mass ratio of 8:1:1, pressing on a nickel foam sheet (1cm × 1cm), and drying in a 60 ℃ oven for 12h to obtain a Zn-Cu-Se working electrode (recorded as ZCS-5).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: the foam nickel sheet of ZCS-5 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2M KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability.
Example 6:
a preparation method of a Zn-Cu-Se composite material comprises the following steps:
1mmol of Zn (NO)3)2·6H2O，1mmol Cu(CH3COO)2·H2O，6mmol NH4Dissolving 5mmol of urea in 40mL of water, magnetically stirring uniformly, transferring to a 50mL stainless steel autoclave with a polytetrafluoroethylene lining, carrying out a one-step hydrothermal reaction at 180 ℃ for 6h, taking out and cooling a hydrothermal sample, centrifuging, washing, and vacuum drying at 60 ℃ for 12h to obtain a Zn-Cu precursor, dissolving the prepared Zn-Cu precursor and 80mg of sodium selenite in water, magnetically stirring and dispersing, adding 2mL of ammonia water to form a uniform suspension, carrying out a second hydrothermal reaction at 140 ℃ for 8h, centrifuging, washing, and drying to obtain a Zn-Cu-Se composite material, grinding the active material, uniformly mixing with carbon black and polytetrafluoroethylene in a mass ratio of 8:1:1, pressing on a nickel foam sheet (1cm × 1cm), and drying in a 60 ℃ oven for 12h to obtain a Zn-Cu-Se working electrode (recorded as ZCS-6).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: the foam nickel sheet of ZCS-6 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2M KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability.
Example 7:
a preparation method of a Zn-Cu-Se composite material comprises the following steps:
1mmol of Zn (NO)3)2·6H2O，1mmol Cu(CH3COO)2·H2O，6mmol NH4F, 5mmol of urea is dissolved in 40mL of water, and after being uniformly stirred by magnetic force, the urea is transferred to 50mL of polytetrafluoroethyleneThe preparation method comprises the steps of carrying out one-step hydrothermal reaction in a stainless steel lined autoclave at the hydrothermal reaction temperature of 180 ℃ for 6 hours, taking out a sample after hydrothermal reaction, cooling, centrifuging, washing, and drying in vacuum at 60 ℃ for 12 hours to obtain a Zn-Cu precursor, dissolving the prepared Zn-Cu precursor and 60mg of sodium selenite in water, magnetically stirring and dispersing, adding 5mL of ammonia water to form uniform suspension, carrying out a second hydrothermal reaction at the hydrothermal reaction temperature of 140 ℃ for 8 hours, centrifuging, washing, and drying to obtain a Zn-Cu-Se composite material, grinding the active material, uniformly mixing with carbon black and polytetrafluoroethylene in a mass ratio of 8:1:1, pressing the mixture on a foamed nickel sheet (1cm × 1cm), and drying in an oven at 60 ℃ for 12 hours to obtain a Zn-Cu-Se working electrode (recorded as ZCS-7).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: the foam nickel sheet of ZCS-7 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2M KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability.
Example 8:
a preparation method of a Zn-Cu-Se composite material comprises the following steps:
1mmol of Zn (NO)3)2·6H2O，1mmol Cu(CH3COO)2·H2O，6mmol NH4Dissolving 5mmol of urea in 40mL of water, magnetically stirring uniformly, transferring to a 50mL stainless steel autoclave with a polytetrafluoroethylene lining, and carrying out one-step hydrothermal reaction at 180 ℃ for 6 hours; and taking out the sample after hydrothermal treatment, cooling, centrifuging, washing, and vacuum drying at 60 ℃ for 12h to obtain the Zn-Cu precursor. Dissolving the prepared Zn-Cu precursor and 60mg of sodium selenite in water, magnetically stirring and dispersing, adding 2mL of ammonia water to form uniform suspension, performing a second hydrothermal reaction at 160 ℃ for 8 hours, and centrifuging, washing and drying to obtain a Zn-Cu-Se composite material; after the active material is ground,uniformly mixing the carbon black and polytetrafluoroethylene according to the mass ratio of 8:1:1, pressing the mixture on a foam nickel sheet (1cm × 1cm), and drying the foam nickel sheet in a drying oven at the temperature of 60 ℃ for 12 hours to obtain a Zn-Cu-Se working electrode (recorded as ZCS-8).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: the method comprises the following steps of taking a ZCS-8 foam nickel sheet as a working electrode, an Ag/AgCl electrode as a reference electrode, a Pt electrode as a counter electrode and 2M KOH as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability.
Example 9:
a preparation method of a Zn-Cu-Se composite material comprises the following steps:
1mmol of Zn (NO)3)2·6H2O，1mmol Cu(CH3COO)2·H2O，6mmol NH4Dissolving 5mmol of urea in 40mL of water, magnetically stirring uniformly, transferring to a 50mL stainless steel autoclave with a polytetrafluoroethylene lining, carrying out a one-step hydrothermal reaction at 180 ℃ for 6h, taking out and cooling a hydrothermal sample, centrifuging, washing, and vacuum drying at 60 ℃ for 12h to obtain a Zn-Cu precursor, dissolving the prepared Zn-Cu precursor and 60mg of sodium selenite in water, magnetically stirring and dispersing, adding 2mL of ammonia water to form a uniform suspension, carrying out a second hydrothermal reaction at 180 ℃ for 6h, centrifuging, washing, and drying to obtain a Zn-Cu-Se composite material, grinding the active material, uniformly mixing with carbon black and polytetrafluoroethylene in a mass ratio of 8:1:1, pressing on a nickel foam sheet (1cm × 1cm), and drying in a 60 ℃ oven for 12h to obtain a Zn-Cu-Se working electrode (recorded as ZCS-9).
The Chenghua CHI760e electrochemical workstation adopts cyclic voltammetry and constant current charging and discharging methods, and adopts a three-electrode system: the foam nickel sheet of ZCS-9 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, and 2M KOH is used as an electrolyte solution. The specific capacitance and the cyclic stability of the composite material are detected, and cyclic voltammetry tests show that the composite material has excellent redox capability.
In the preparation process of the Zn-Cu-Se composite material, the process conditions can be adjusted randomly within the following process ranges according to requirements (namely, the middle point value or the end value is selected randomly):
the mol ratio of the soluble zinc salt, the soluble copper salt, the ammonium fluoride and the urea is 1 (0.5-2) to (5-8) to (4-6);
in the process of the primary hydrothermal reaction, the temperature is 150-;
in the step (2), the concentration of the ammonia water is 13.38mol/L, and the adding amount ratio of the soluble zinc salt, the sodium selenite and the ammonia water is 1 mmol: (30-60) mg: (2-5) mL;
in the step (2), the temperature is 120-;
in the step (1) and the step (2), the drying mode is vacuum drying, and in the drying process, the temperature is 55-65 ℃ and the time is 10-14 h.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make modifications and alterations without departing from the scope of the present invention.
Claims (10)
1. A preparation method of a Zn-Cu-Se composite material is characterized by comprising the following steps:
(1) dissolving soluble zinc salt, soluble copper salt, urea and ammonium fluoride in water, uniformly stirring, carrying out a hydrothermal reaction, centrifuging, washing and drying to obtain a Zn-Cu precursor;
(2) dissolving the prepared Zn-Cu precursor and sodium selenite in water, stirring and dispersing, adding ammonia water to form uniform suspension, performing a second hydrothermal reaction, centrifuging, washing and drying to obtain the Zn-Cu-Se composite material.
2. The method according to claim 1, wherein the soluble copper salt is copper acetate and the soluble zinc salt is zinc nitrate.
3. The method of claim 1, wherein the molar ratio of the soluble zinc salt to the soluble copper salt to the ammonium fluoride to the urea is 1 (0.5-2) to (5-8) to (4-6).
4. The method for preparing Zn-Cu-Se composite material as claimed in claim 1, wherein the temperature is 150-200 ℃ and the time is 3-8h in the course of one hydrothermal reaction.
5. The method for preparing a Zn-Cu-Se composite material according to claim 1, wherein in the step (2), the concentration of ammonia water used is 13.38mol/L, and the addition ratio of the soluble zinc salt, sodium selenite and ammonia water is 1 mmol: (30-60) mg: (2-5) mL.
6. The method for preparing a Zn-Cu-Se composite material as claimed in claim 1, wherein in the step (2), the temperature is 120-160 ℃ and the time is 5-10h in the second hydrothermal reaction process.
7. The method for preparing Zn-Cu-Se composite material according to claim 1, wherein in the step (1) and the step (2), the drying mode is vacuum drying, and the temperature in the drying process is 55-65 ℃ and the time is 10-14 h.
8. A Zn-Cu-Se composite material produced by the production method according to any one of claims 1 to 8, characterized in that it is formed by connecting nanoplatelets having a rich pore structure.
9. Use of a Zn-Cu-Se composite according to claim 8 for the preparation of working electrodes and in supercapacitors.
10. The application of the Zn-Cu-Se composite material as claimed in claim 9, wherein the working electrode is prepared by the following specific steps:
grinding the Zn-Cu-Se composite material, uniformly mixing the Zn-Cu-Se composite material with carbon black and polytetrafluoroethylene, then pressing the mixture on a foamed nickel sheet, and drying the foamed nickel sheet to obtain the working electrode, wherein the mass ratio of the Zn-Cu-Se composite material to the carbon black to the polytetrafluoroethylene is 8 (0.8-1.2) to (0.8-1.2).
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