CN111118564B - Nickel-nickel oxide ultrathin nanosheet material and electrodeposition preparation method and application thereof - Google Patents

Nickel-nickel oxide ultrathin nanosheet material and electrodeposition preparation method and application thereof Download PDF

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CN111118564B
CN111118564B CN201910990239.0A CN201910990239A CN111118564B CN 111118564 B CN111118564 B CN 111118564B CN 201910990239 A CN201910990239 A CN 201910990239A CN 111118564 B CN111118564 B CN 111118564B
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nickel
carbon cloth
nickel oxide
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nanosheet material
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CN111118564A (en
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韩晓鹏
李肖鹏
王杨
胡文彬
邓意达
钟澄
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Tianjin University
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Abstract

The invention relates to a nickel-nickel oxide ultrathin nanosheet material, and an electrodeposition preparation method and application thereof, wherein the surface of a carbon cloth is activated to obtain a pretreated carbon cloth; placing the carbon cloth with the activated surface as a working electrode and a carbon rod as a counter electrode in a prepared nickel salt electrolyte solution, and depositing at constant pressure by using a working station; and washing the obtained product with absolute ethyl alcohol after deposition, and drying the product in an oven to obtain the nickel-nickel oxide ultrathin nanosheet. The nickel-nickel oxide ultrathin nanosheet material is composed of nickel oxide and elemental nickel, and the nickel-nickel oxide nanosheets are uniformly distributed on the carbon cloth. The preparation method provided by the invention has the advantages of simple required equipment, convenient operation, controllable conditions, high repeatability and low preparation cost, and is suitable for industrial large-scale production.

Description

Nickel-nickel oxide ultrathin nanosheet material and electrodeposition preparation method and application thereof
Technical Field
The invention belongs to the technical field of new materials and chemical synthesis, particularly relates to a preparation method for preparing a nickel-nickel oxide ultrathin nanosheet material through electrodeposition, and provides a preparation method which is clean, simple in process and low in cost.
Background
Currently, coal, petroleum and natural gas are gradually exhausted as main energy sources at present, a large amount of pollutants are generated, environmental pollution and energy shortage become outstanding problems which plague further development of social economy, and development of clean and recyclable hydrogen energy is one of approaches for solving the problems. The hydrogen production technology comprises chemical raw material hydrogen production, photochemical hydrogen production, thermochemical hydrogen production, water electrolysis hydrogen production and the like, wherein the water electrolysis hydrogen production is considered to be the hydrogen production technology with highest efficiency and easy scale production. However, the overpotential caused by slow kinetics leads to electric energy waste, so that the wide application of hydrogen production by water electrolysis is restricted, and reduction of the overpotential of water electrolysis is the current main research direction. Platinum-based noble metal materials are currently the most commonly used commercial catalysts for hydrogen evolution, but their high cost and low reserves limit large-scale applications. The development of a non-noble metal hydrogen production catalyst with high efficiency, low price and stable performance has extremely important scientific significance and practical value.
Transition metal oxides including nickel oxide (NiO), cobalt oxide (CoO), manganese oxide (MnO), and the like are materials that have been widely studied in recent years, and among them, nickel oxide is being applied to the fields of supercapacitors, rechargeable batteries, electrolytic water, and the like, because of the characteristics of low price, large storage capacity, environmental friendliness, good stability, and the like, which are receiving increasing attention. However, poor conductivity and inadequate intermediate product adsorption can lead to poor catalytic performance. The construction of nickel-nickel oxide heterostructures is an effective strategy to improve their conductivity and catalytic performance because the binding energy of metallic nickel and hydrogen atoms is close to that of platinum metal, which can improve the conductivity of nickel oxide, regulate the interface electronic structure and act synergistically. The electrodeposition method has simple equipment, easy operation, low production cost and normal pressure, and is usually carried out at normal temperature and normal pressure; a good growth layer can be obtained on a substrate with large area and complex shape; the deposition speed is high, and the preparation time can be obviously shortened. Therefore, the preparation of the nano catalyst by adopting the electro-deposition chemical method is a technology which is easy to popularize and apply in a large scale. At present, most of the methods for synthesizing nickel-nickel oxide are two-step reduction methods, the steps are complex, and energy is wasted.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a nickel-nickel oxide ultrathin nanosheet material prepared by electrodeposition and a preparation method thereof, and has the advantages of simple preparation process, convenient operation and high repeatability; growing a nickel-nickel oxide nanosheet in situ on the carbon cloth; can be directly used as an electrode for application, does not need to additionally add a binder and a conductive agent, and has excellent energy catalysis application prospect.
In order to improve the hydrogen production performance, the technical content related to molybdenum source deposition is omitted on the basis of the 'nickel-molybdenum oxide quantum dot loaded on the nickel oxide nanosheet prepared by an electrodeposition method' (application number 2019104927480, application date is 2019, 6 months and 6 days), and the ultrathin nickel-nickel oxide nanosheet is prepared by a one-step method directly by using an electrodeposition technology, so that the hydrogen production catalyst with excellent performance is obtained.
The purpose of the invention is realized by the following technical scheme:
a nickel-nickel oxide ultrathin nanosheet material and an electrodeposition preparation method thereof are disclosed, wherein the nickel-nickel oxide ultrathin nanosheet material is composed of nickel oxide and a simple substance nickel phase, and the nickel-nickel oxide ultrathin nanosheets are uniformly distributed on a carbon cloth and are prepared according to the following steps:
and (2) placing carbon cloth as a working electrode and a carbon rod as a counter electrode in a prepared nickel source electrolyte solution, and performing constant-pressure deposition by using a workstation to uniformly distribute a nickel oxide-nickel material on the carbon cloth, wherein the concentration of nickel ions in the nickel source electrolyte solution is 1-20 g/L, the nickel source is nickel acetate, nickel chloride, nickel nitrate or nickel sulfate, the electrodeposition voltage is-1-6V, and the deposition time is 600-14400 s, so as to obtain the nickel-nickel oxide ultrathin nanosheet material.
In the technical scheme of the invention, the concentration of nickel ions in a nickel source electrolyte (water) solution is 5-10 g/L.
In the technical scheme of the invention, the electrodeposition voltage is-3 to-6V, and the deposition time is 3600 to 12000 s.
According to the technical scheme, after deposition, absolute ethyl alcohol is used for washing, and the nickel-nickel oxide ultrathin nanosheet is dried in an oven to obtain the nickel-nickel oxide ultrathin nanosheet prepared through electrodeposition, wherein the drying temperature in the oven is 50-80 ℃, and the drying time is 6-12 hours.
In the technical scheme of the invention, the surface of the used carbon cloth is subjected to activation treatment as follows: placing the carbon cloth in acetone, alcohol and deionized water in sequence for ultrasonic cleaning, taking out the carbon cloth after ultrasonic cleaning, immersing the carbon cloth in an acid solution, pouring the carbon cloth into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in a drying oven, carrying out activation treatment on the carbon cloth, taking out the carbon cloth, placing the carbon cloth in deionized water for ultrasonic cleaning, and drying the carbon cloth for later use; the temperature of the activation reaction is set to be 60-120 ℃, the time of the activation treatment is set to be 5-24 h, wherein:
and (3) placing the carbon cloth in acetone, alcohol and deionized water in sequence for ultrasonic cleaning, wherein the cleaning time is 10-20 min.
After activation treatment, the mixture is placed in deionized water for ultrasonic cleaning for 5-10 min.
The acid solution is a mixed solution of nitric acid and water, and 65-68 wt% of concentrated nitric acid and water are adopted according to the volume ratio of 1: 3, preparation.
And drying by using a drying oven, wherein the drying temperature is set to be 60-90 ℃, and the drying time is 10-24 h.
The temperature of the activation reaction is 80-100 ℃, and the time of the activation treatment is 10-20 h.
The nickel-nickel oxide ultrathin nanosheet material obtained by the technical scheme of the invention can be grown on the surface of carbon cloth, and can be directly used as an electrode in an alkaline system without adding a conductive agent and a binder and an electrode preparation process. The nickel-nickel oxide ultrathin nanosheet material obtained by the technical scheme of the invention is applied to electrode catalysis, is used as a cathode working electrode and an anode working electrode simultaneously in the electrode catalysis, is directly used as an integrated electrode for full water electrolysis, and takes 1.0mol/L KOH or sodium hydroxide aqueous solution as electrolyte.
Compared with the prior art, the nickel-nickel oxide nanosheet prepared by the invention contains a large number of interfaces of metallic nickel and nickel oxide, and the improvement of the electrochemical performance is promoted by constructing a large number of nano heterogeneous structures to promote electron transfer, increase the conductivity and expose more active sites; the preparation method provided by the invention has the advantages of simple required equipment, convenient operation, controllable conditions, high repeatability and low preparation cost, and is suitable for industrial large-scale production; the carbon cloth is used as a substrate supported catalyst, so that on one hand, the conductivity can be improved, and no conductive agent is required to be added; on the other hand, the obtained catalyst material can be directly used as an electrode for electrochemical performance test without adding other binders additionally. Meanwhile, the binding force between the nickel-nickel oxide ultrathin nanosheet grown in situ and the substrate is firm, the contact resistance is reduced, and the technical problem that the active substance is easy to fall off in the traditional process is solved. Thanks to the advantages, the electrode shows excellent hydrogen evolution activity and stability in alkaline solution, and has wide application prospect in hydrogen evolution fuel cells and the like.
Drawings
FIG. 1 is a scanning electron microscope photograph of the nickel-nickel oxide ultrathin nanosheet material prepared in the present invention.
FIG. 2 is a transmission electron microscope photograph of the nickel-nickel oxide ultrathin nanosheet material prepared in the present invention.
FIG. 3 is an XRD spectrum diagram of the nickel-nickel oxide ultrathin nanosheet material prepared in the present invention.
FIG. 4 is a graph of the HER LSV test curve of the nickel-nickel oxide ultrathin nanosheet material prepared according to the present invention in 1M KOH electrolyte.
FIG. 5 is a graph of the results of long-period HER stability tests of nickel-nickel oxide ultrathin nanosheets prepared in the presence of 1M KOH electrolyte.
Detailed Description
The present invention is described in detail below with reference to specific embodiments and accompanying drawings. The acid solution is a mixed solution of nitric acid and water, and 65-68 wt% of concentrated nitric acid and water are adopted according to the volume ratio of 1: 3, preparation.
Example 1
Respectively weighing nickel acetate to dissolve in deionized water to obtain 5.078g/L nickel acetate electrolyte solution; activating the surface of carbon cloth, placing the carbon cloth in acetone, alcohol and deionized water in sequence, ultrasonically cleaning for 10min, taking out the carbon cloth, placing the carbon cloth in an acid solution, pouring the carbon cloth into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, activating the carbon cloth, keeping the temperature at 90 ℃ for 12h, taking out the carbon cloth, placing the carbon cloth in the deionized water, ultrasonically cleaning for 5min, and drying the carbon cloth in the oven for later use; taking the carbon cloth with the activated surface as a working electrode and a carbon rod as a counter electrode, putting the carbon cloth and the carbon rod into a prepared nickel acetate electrolyte solution, and depositing for 3600s at a constant voltage of-3V by using a work station; and (3) washing the obtained product with absolute ethyl alcohol after deposition, and drying the product in an oven at 60 ℃ for 16h to obtain the nickel-nickel oxide ultrathin nanosheet.
FIG. 1 is a scanning electron microscope image of the nickel-nickel oxide ultrathin nanosheet material prepared by the present invention, showing that the nanosheet structure is uniformly supported on a carbon rod.
Fig. 2 shows that the nickel-nickel oxide ultrathin nanosheet prepared in the present invention shows that the synthesized nanosheet includes a large number of interfaces of metallic nickel and nickel oxide, and this structure constructs a large number of nano-heterostructures, which promote electron transfer, increase conductivity and expose more active sites, thereby promoting the improvement of electrochemical performance.
FIG. 3 is an XRD spectrum of the nickel-nickel oxide ultrathin nanosheet material prepared in the present invention, showing that the material contains metallic nickel in addition to the standard peak of carbon cloth, and has no nickel oxide peak in JCPDS Standard card No.04-0850, since nickel oxide is amorphous.
FIG. 4 is an LSV diagram of HER of the nickel-nickel oxide ultrathin nanosheet material prepared in the invention in 1M KOH electrolyte, wherein the hydrogen evolution overpotential can be reduced to below 152mV, thereby effectively reducing additional energy consumption.
Fig. 5 is a long-period HER stability test result of the nickel-nickel oxide ultrathin nanosheet material prepared in the present invention in 1M KOH (aqueous solution) electrolyte, and the material can maintain a low overpotential after continuously catalyzing hydrogen evolution in an alkaline environment for 10 hours, indicating that the material has good stability.
Example 2
Respectively weighing nickel nitrate and dissolving the nickel nitrate in deionized water to obtain 1g/L nickel acetate electrolyte solution; activating the surface of carbon cloth, placing the carbon cloth in acetone, alcohol and deionized water in sequence, ultrasonically cleaning for 10min, taking out the carbon cloth, placing the carbon cloth in an acid solution, pouring the carbon cloth into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, activating the carbon cloth, keeping the temperature for 24h at 60 ℃, placing the carbon cloth in the deionized water after taking out, ultrasonically cleaning for 5min, and drying in the oven for later use; placing the carbon cloth with the activated surface as a working electrode and the carbon rod as a counter electrode in a prepared nickel nitrate electrolyte solution, and depositing for 14400s under the constant voltage of-1V by using a work station; and washing the obtained product with absolute ethyl alcohol after deposition, and keeping the temperature in an oven at 50 ℃ for 12h for drying to obtain the nickel-nickel oxide ultrathin nanosheet.
The characterization results of the morphology and the structure of the nickel-nickel oxide ultrathin nanosheet material by scanning, transmission electron microscopy and XRD can be used for obtaining the nickel-nickel oxide ultrathin nanosheet material. The nickel-nickel oxide ultrathin nanosheet material prepared in the embodiment is composed of nickel oxide and elemental nickel, and the nickel-nickel oxide ultrathin nanosheets are uniformly distributed on carbon cloth to construct a large number of nano heterogeneous structures.
Example 3
Respectively weighing nickel sulfate and dissolving the nickel sulfate in deionized water to obtain 20g/L nickel sulfate electrolyte solution; activating the surface of carbon cloth, placing the carbon cloth in acetone, alcohol and deionized water in sequence, ultrasonically cleaning for 10min, taking out the carbon cloth, placing the carbon cloth in an acid solution, pouring the carbon cloth into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, activating the carbon cloth, keeping the temperature for 5h at 120 ℃, placing the carbon cloth in the deionized water after taking out, ultrasonically cleaning for 5min, and drying in the oven for later use; placing the carbon cloth with the activated surface as a working electrode and the carbon rod as a counter electrode in a prepared nickel sulfate electrolyte solution, and depositing for 600s at a constant pressure of-6V in a working station; and (3) washing the obtained product with absolute ethyl alcohol after deposition, and drying the product in an oven at 80 ℃ for 6 hours to obtain the nickel-nickel oxide ultrathin nanosheet.
The characterization results of the morphology and the structure of the nickel-nickel oxide ultrathin nanosheet material by scanning, transmission electron microscopy and XRD can be used for obtaining the nickel-nickel oxide ultrathin nanosheet material. The nickel-nickel oxide ultrathin nanosheet material prepared in the embodiment is composed of nickel oxide and elemental nickel, and the nickel-nickel oxide ultrathin nanosheets are uniformly distributed on carbon cloth to construct a large number of nano heterogeneous structures.
Example 4
Respectively weighing nickel chloride and dissolving the nickel chloride in deionized water to obtain 10g/L nickel chloride electrolyte solution; activating the surface of carbon cloth, placing the carbon cloth in acetone, alcohol and deionized water in sequence, ultrasonically cleaning for 10min, taking out the carbon cloth, placing the carbon cloth in an acid solution, pouring the carbon cloth into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, activating the carbon cloth, keeping the temperature for 5h at 120 ℃, placing the carbon cloth in the deionized water after taking out, ultrasonically cleaning for 5min, and drying in the oven for later use; taking the carbon cloth with the activated surface as a working electrode and a carbon rod as a counter electrode, placing the carbon cloth and the carbon rod into a prepared nickel chloride electrolyte solution, and depositing for 1200s at a constant voltage of-4V by using a work station; and (3) washing the obtained product with absolute ethyl alcohol after deposition, and drying the product in an oven at 80 ℃ for 6 hours to obtain the nickel-nickel oxide ultrathin nanosheet.
The characterization results of the morphology and the structure of the nickel-nickel oxide ultrathin nanosheet material by scanning, transmission electron microscopy and XRD can be used for obtaining the nickel-nickel oxide ultrathin nanosheet material. The nickel-nickel oxide ultrathin nanosheet material prepared in the embodiment is composed of nickel oxide and elemental nickel, and the nickel-nickel oxide ultrathin nanosheets are uniformly distributed on carbon cloth to construct a large number of nano heterogeneous structures.
The preparation of the nickel-nickel oxide ultrathin nanosheets can be realized by adjusting the process parameters according to the content of the invention, the performance basically consistent with the invention is shown, the hydrogen evolution overpotential can be reduced to below 152mV in 1M KOH electrolyte, and the relatively low overpotential can still be maintained after the hydrogen evolution is continuously catalyzed in an alkaline environment for 10 hours. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.

Claims (8)

1. The nickel-nickel oxide nanosheet material is characterized by consisting of nickel oxide and an elemental nickel phase, wherein the nickel-nickel oxide nanosheets are uniformly distributed on a carbon cloth and are prepared according to the following steps:
and (2) placing carbon cloth as a working electrode and a carbon rod as a counter electrode in a prepared nickel source electrolyte solution, and performing constant-pressure deposition by using a workstation to uniformly distribute nickel oxide-nickel materials on the carbon cloth, wherein in the nickel source electrolyte solution, the concentration of nickel ions is 1-20 g/L, the nickel source is nickel acetate, nickel chloride, nickel nitrate or nickel sulfate, the electrodeposition voltage is-3.0V, and the deposition time is 1h, so as to obtain the nickel-nickel oxide nanosheet material.
2. The nickel-nickel oxide nanosheet material of claim 1, wherein the carbon cloth surface used is activated as follows: placing the carbon cloth in acetone, alcohol and deionized water in sequence for ultrasonic cleaning, taking out the carbon cloth after ultrasonic cleaning, immersing the carbon cloth in an acid solution, pouring the carbon cloth into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in a drying oven, carrying out activation treatment on the carbon cloth, taking out the carbon cloth, placing the carbon cloth in deionized water for ultrasonic cleaning, and drying the carbon cloth for later use; the temperature of the activation reaction is set to be 60-120 ℃, and the time of the activation treatment is set to be 5-24 hours.
3. The nickel-nickel oxide nanosheet material as defined in claim 2, wherein in the activation treatment of the surface of the carbon cloth, the carbon cloth is successively placed in acetone, alcohol and deionized water for ultrasonic cleaning for 10-20 min; after activation treatment, placing the mixture in deionized water for ultrasonic cleaning for 5-10 min; and drying by using a drying oven, wherein the drying temperature is set to be 60-90 ℃, and the drying time is 10-24 h.
4. The nickel-nickel oxide nanosheet material as claimed in claim 2, wherein in the activation treatment of the surface of the carbon cloth used, the acid solution is a mixed solution of nitric acid and water, and 65 to 68 wt% of concentrated nitric acid and water are used in a volume ratio of 1: 3, preparing; the temperature of the activation reaction is 80-100 ℃, and the time of the activation treatment is 10-20 h.
5. A preparation method of a nickel-nickel oxide nanosheet material is characterized in that the nickel-nickel oxide nanosheet material consists of nickel oxide and elemental nickel, the nickel-nickel oxide nanosheets are uniformly distributed on carbon cloth, and the preparation method comprises the following steps:
placing carbon cloth as a working electrode and a carbon rod as a counter electrode in a prepared nickel source electrolyte solution, and performing constant-pressure deposition by using a workstation to uniformly distribute nickel oxide-nickel materials on the carbon cloth, wherein in the nickel source electrolyte solution, the concentration of nickel ions is 1-20 g/L, the nickel source is nickel acetate, nickel chloride, nickel nitrate or nickel sulfate, the electrodeposition voltage is-3.0V, and the deposition time is 1h, so as to obtain a nickel-nickel oxide nanosheet material; the surface of the carbon cloth is activated as follows: placing the carbon cloth in acetone, alcohol and deionized water in sequence for ultrasonic cleaning, taking out the carbon cloth after ultrasonic cleaning, immersing the carbon cloth in an acid solution, pouring the carbon cloth into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in a drying oven, carrying out activation treatment on the carbon cloth, taking out the carbon cloth, placing the carbon cloth in deionized water for ultrasonic cleaning, and drying the carbon cloth for later use; the temperature of the activation reaction is set to be 60-120 ℃, and the time of the activation treatment is set to be 5-24 hours.
6. The method for preparing a nickel-nickel oxide nanosheet material according to claim 5, wherein in the activation treatment of the surface of the carbon cloth, the carbon cloth is sequentially placed in acetone, alcohol and deionized water for ultrasonic cleaning for 10-20 min; after activation treatment, placing the mixture in deionized water for ultrasonic cleaning for 5-10 min; drying by using a drying oven, wherein the drying temperature is set to be 60-90 ℃, and the drying time is 10-24 h; the acid solution is a mixed solution of nitric acid and water, and 65-68 wt% of concentrated nitric acid and water are adopted according to the volume ratio of 1: 3, preparing; the temperature of the activation reaction is 80-100 ℃, and the time of the activation treatment is 10-20 h.
7. Use of a nickel-nickel oxide nanosheet material of any one of claims 1 to 4 in electrode catalysis.
8. The application of the nickel-nickel oxide nanosheet material in electrode catalysis, according to claim 7, is characterized in that the nickel-nickel oxide nanosheet material grows on the surface of carbon cloth, is directly used as an electrode in an alkaline system, is used as a cathode in electrode catalysis, and takes 1.0mol/L KOH or 1.0mol/L aqueous solution of sodium hydroxide as an electrolyte.
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