CN109252188B - Preparation method of nickel sulfide nano film - Google Patents

Preparation method of nickel sulfide nano film Download PDF

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Publication number
CN109252188B
CN109252188B CN201811156150.6A CN201811156150A CN109252188B CN 109252188 B CN109252188 B CN 109252188B CN 201811156150 A CN201811156150 A CN 201811156150A CN 109252188 B CN109252188 B CN 109252188B
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film
nano
nickel sulfide
sulfide nano
nickel
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CN109252188A (en
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郝秋艳
李士云
韩宇
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Hebei University of Technology
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Hebei University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

A method for preparing a nickel sulfide nano film. The method comprises the following steps: dissolving triethylene glycol and mercaptoethanol at a volume ratio of 10: 1 to obtain a mixed solvent, transferring the mixed solvent into a three-necked bottle, and then adding 1 × 3cm2The foamed nickel is immersed into a three-mouth bottle, then the three-mouth bottle is heated until the temperature reaches 150 ℃, the temperature is kept for 20min, then the heating device is turned off, and the three-mouth bottle is cooled to the room temperature, so that the nickel sulfide nano film is obtained. The invention adopts a mixed heating method to prepare the nickel sulfide nano film for the first time, greatly simplifies the preparation process of the nickel sulfide nano film, greatly reduces the consumption of experimental raw materials, and has the current density of 100mA/cm2Its OER overpotential is 320 mV.

Description

Preparation method of nickel sulfide nano film
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a preparation method of a nickel sulfide nano film.
Background
Energy and environment are two prominent problems restricting the development of human society. The energy is the basis for human survival and is the driving force for social development and civilization progress. With the continuous progress of society, people have stronger and stronger requirements on energy. In the current energy use structure, the traditional fossil fuel still accounts for the most part, including coal, oil, natural gas and the like. As a non-renewable energy source, excessive use of fossil fuels not only causes an increasing shortage of energy sources, but also brings about huge environmental destruction. The development of safe, efficient and sustainable clean energy is the key to solving energy and environmental problems. Hydrogen energy is used as a clean and pollution-free secondary energy source, has high mass energy density, and is an ideal choice for realizing an energy strategy.
At present, hydrogen production by water electrolysis is the most promising approach, but the development of hydrogen production by water electrolysis is always hindered by the problem of high water electrolysis cost in the process of hydrogen production by water electrolysis. The use of the electrocatalyst becomes a coping strategy for most effectively reducing the cost of hydrogen production by water electrolysis. However, the reserves of noble metal catalysts for optimum electrocatalytic performance are limited and their wide application is limited. Nickel sulfide is of great interest because of its low cost, good stability, high conductivity, and other advantages, and there are also many studies on nickel sulfide.
The Zhanghua topic group in 2013 uses thiourea as a sulfur source, prepares a nickel sulfide nano material by hydrothermal for 6 hours at 180 ℃, and the concentration is 100mA/cm2The over-potential of OER is 370 mV; in 2015, Xiaoxin task group was prepared by using thiourea as a sulfur source and heating at 160 ℃ for 5 hoursThe nickel sulfide nano material is at 100mA/cm2The over-potential of OER is 350 mV; the Xiexi subject group in 2017 utilizes sulfur as a sulfur source, prepares a nickel sulfide nano material by chemical vapor deposition for 4 hours at 350 ℃, and the concentration is 100mA/cm2The overpotential for OER was 390 mV. However, in the current report, the preparation method of nickel sulfide has the defects of serious energy consumption, high temperature, high pressure, poor electrocatalytic performance and the like, and can cause the increase of the overpotential of the electrode, the ohmic drop and the overpotential of the electrode, and the reduction of the electric energy efficiency, and the preparation process in the prior art needs to be improved.
Disclosure of Invention
The invention aims to provide a preparation method of a nickel sulfide film aiming at the defects of high pressure, high temperature, long time consumption and serious raw material consumption of a hydrothermal method and a chemical vapor deposition method in the prior art. The invention adopts the mixed solvent of triethylene glycol and mercaptoethanol as a liquid-phase sulfur source for the first time, prepares the nickel sulfide film by using a mixing heating method, and shows excellent electrocatalytic performance. The invention has simple process, low cost, high repetition rate and material utilization rate, and batch preparation, and is a good preparation process of the nickel sulfide nano film.
The technical scheme of the invention is as follows:
a preparation method of a nickel sulfide nano film comprises the following steps:
(1) preparation of the Mixed solvent
Dissolving triethylene glycol and mercaptoethanol into a mixed solvent according to the volume ratio of 10: 1, and then transferring the solvent into a three-mouth bottle.
(2) Preparing foam nickel loaded nickel sulfide nano film
Mixing 1 x 3cm2Soaking the foamed nickel into the mixed solvent prepared in the step (1), then heating the three-mouth bottle to 150 ℃, keeping the temperature for 20min, and then turning off the heating device to cool the three-mouth bottle to room temperature to obtain the nickel sulfide film.
The purity of the triethylene glycol and the mercaptoethanol is 99 percent.
The purity of the foamed nickel is 95 percent, and the density of the foamed nickel is 0.45g/cm3The porosity is 95%, and the thickness is 0.5-2 mm.
The invention has the beneficial effects that:
(1) the method adopts a mixing heating method to prepare the foam nickel-loaded nickel sulfide film, thereby greatly simplifying the preparation process.
(2) The electrocatalytic performance of the nickel sulfide film prepared by the method is superior to that of the nickel sulfide nano film loaded on the foamed nickel prepared by a hydrothermal method, a chemical vapor deposition method and the like, and simultaneously, the resources are saved and the cost is low.
(3) The nickel sulfide nano film prepared by the method is uniformly loaded on the foamed nickel, and is beneficial to improving the electrocatalytic performance of the foamed nickel loaded nickel sulfide.
(4) The nickel sulfide nano film prepared by the method has good catalytic performance when applied to electrocatalysis.
Drawings
FIG. 1 is an X-ray diffraction diagram of nickel sulfide nano-films obtained at different heating temperatures and with the heat preservation time of 20 min; the heating temperatures were 120 deg.C, 150 deg.C, and 180 deg.C, respectively.
FIG. 2 is SEM images of nickel sulfide films obtained at different heating temperatures and with 20min holding time; in the graphs (a), (b) and (c), the heating temperatures were 120 ℃ and 150 ℃ and 180 ℃ respectively.
FIG. 3 is a polarization curve diagram of nickel sulfide nano-films obtained at different heating temperatures and with the holding time of 20 min.
FIG. 4 is a polarization curve diagram of nickel sulfide nano-films obtained at different holding times and heating temperatures of 150 ℃.
Detailed Description
The manufacturer of the foam nickel related to the invention is Sigma company, the purity is 95 percent, and the density is 0.45g/cm3Size of 1 x 3cm2The porosity is 95%, and the thickness is 1 mm; the triethylene glycol manufacturer is a Guangdong fine chemical research institute of Tianjin, the purity is analytically pure, and the density is 1.126g/cm3(ii) a The mercaptoethanol manufacturer is a mercaptoethanol manufacturer, an Tianjin Guangfu Fine chemical research institute, the purity is 99 percent, and the density is 1.11g/cm3。
Example 1
(1) Preparing mixed solvent
Dissolving triethylene glycol and mercaptoethanol into a mixed solvent according to the volume ratio of 10: 1, and then transferring the solvent into a three-mouth bottle.
(2) Preparing foamed nickel loaded nickel sulfide film
Mixing 1 x 3cm2Soaking the foamed nickel into the mixed solvent prepared in the step (1), then heating the three-mouth bottle to 150 ℃, keeping the temperature for 20min, and then turning off the heating device to cool the three-mouth bottle to room temperature to obtain the nickel sulfide film. The (101), (110), (003), (202), (113) and (300) crystal planes in the X-ray diffraction pattern (figure 1) correspond to the JCPDS No.44-1418 standard card respectively, and the pure-phase nickel sulfide is proved to be generated, which indicates that the method can be used for preparing the pure-phase nickel sulfide (Ni)3S2). SEM scan (2b) shows nickel sulfide (Ni)3S2) The nano film is uniformly grown on the foam Nickel (NF) and the thickness of the nickel sulfide nano film is about 2 μm, and the film has good compactness and the surface pore space is about 20 nm. The polarization curve of the sample (FIG. 3) shows that the nickel sulfide nano-film is at 100mA/cm2The OER overpotential at this time was 320mV (electrocatalytic test was performed in 1M KOH electrolyte). Compared with the Zhang Hua subject group, the OER overpotential of the nickel sulfide nano material prepared by a hydrothermal method is reduced by 50mV, and compared with the Xieti subject group, the OER overpotential of the nickel sulfide nano material prepared by a chemical vapor deposition method is reduced by 70mV.
Example 2
The other steps are the same as example 1, except that the heating temperature is changed from 150 ℃ to 120 ℃ and 180 ℃, and the nickel sulfide thin film is obtained as a result, but the uniformity of the thin film prepared at 120 ℃ is not very good, a lot of nano particles are gathered on the surface of the thin film, the thickness of the thin film is about 3 μm, the pore size of the surface is about 50nm, and the specific morphology is shown in fig. 2 a; the OER overpotential of the prepared sample applied to electrocatalysis was 340 mV. Compared with the Zhanghua subject group, the OER over potential of the nickel sulfide nano material prepared by a hydrothermal method is reduced by 30 mV; compared with the Sestus issue group, the OER overpotential of the nickel sulfide nano material prepared by the chemical vapor deposition method is reduced by 50mV, and the specific polarization curve of the sample is shown in FIG. 3. In addition, the compactness of the film prepared under the condition of 180 ℃ becomes poor, a plurality of pores can be seen on the surface of the film, the thickness of the film is about 3.5 mu m, the size of the pores on the surface is about 70nm, and the specific appearance is shown in FIG. 2 c; the OER overpotential for the sample prepared, applied to electrocatalysis, was 345 mV. Compared with the Zhanghua subject group, the OER over potential of the nickel sulfide nano material prepared by a hydrothermal method is reduced by 25 mV; compared with the Sestus issue group, the OER overpotential of the nickel sulfide nano material prepared by the chemical vapor deposition method is reduced by 45mV, and the specific polarization curve of the sample is shown in FIG. 3.
Example 3
The other steps are the same as example 1, except that the holding time is changed from 20min to 10min and 30min, and the nickel sulfide thin film is obtained. The thickness of the obtained film is about 3 mu m when the heat preservation time is 10min, but the uniformity of the film is not very good, a plurality of pores are generated on the surface, the size of the pores is about 60nm, the OER overpotential of the prepared sample is 335mV when the sample is applied to electrocatalysis, and the OER overpotential of the sample is reduced by 35mV compared with that of a nickel sulfide nano material prepared by a hydrothermal method in Zhang Hua project group; compared with the Sestus issue group, the OER overpotential of the nickel sulfide nano material prepared by the chemical vapor deposition method is reduced by 55mV, and the specific polarization curve of the sample is shown in FIG. 4. The thickness of the obtained film was about 4 μm and the pore size of the surface was about 100nm when the heat retention time was 30min, and the surface of the film was relatively rough. When the prepared sample is applied to electrocatalysis, the OER over potential of the sample is 350mV, which is 20mV lower than that of a nickel sulfide nano material prepared by a hydrothermal method in Zhang Hua project group; compared with the Sestus issue group, the OER overpotential of the nickel sulfide nano material prepared by the chemical vapor deposition method is reduced by 40mV, and the specific polarization curve of the sample is shown in FIG. 4.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
The invention is not the best known technology.

Claims (8)

1. A method for preparing a nickel sulfide nano film comprises the following steps:
(1) preparing mixed solvent
Dissolving triethylene glycol and mercaptoethanol into a mixed solvent according to the volume ratio of 10: 1, and then transferring the solvent into a three-necked bottle;
(2) preparing foam nickel loaded nickel sulfide nano film
Mixing 1 x 3cm2Soaking the foamed nickel into the mixed solvent prepared in the step (1), then heating the three-mouth bottle until the temperature is 180 ℃, preserving the heat for 10-30min, and then turning off the heating device to cool the three-mouth bottle to the room temperature to obtain the nickel sulfide nano-film.
2. The method of claim 1, wherein the nickel foam has a purity of 96% and a density of 0.46g/cm3The porosity is 95%, the thickness is 0.4-2 mm, and the foamed nickel is ultrasonically cleaned in acetone, hydrochloric acid and deionized water for 15 min.
3. The method for preparing nickel sulfide nano-film according to claim 1, wherein in the step (2), the heating temperature is 120 ℃, the holding time is 20min, and the pure-phase nickel sulfide nano-film is prepared, wherein the thickness of the nano-film is 2.6-3.1 μm, and the pore size of the nano-film is 35-52 nm.
4. The method for preparing nickel sulfide nano-film according to claim 1, wherein in the step (2), the heating temperature is 150 ℃, the holding time is 20min, and the pure-phase nickel sulfide nano-film is prepared, wherein the thickness of the nano-film is 1.4-2.2 μm, and the pore size of the nano-film is 15-23 nm.
5. The method for preparing nickel sulfide nano-film according to claim 1, wherein in the step (2), the heating temperature is 180 ℃, the holding time is 20min, and the pure-phase nickel sulfide nano-film is prepared, wherein the thickness of the nano-film is 2.9-3.7 μm, and the pore size of the nano-film is 58-74 nm.
6. The method for preparing nickel sulfide nano-film according to claim 1, wherein in the step (2), the heating temperature is 150 ℃, the holding time is 10min, and the pure-phase nickel sulfide nano-film is prepared, wherein the thickness of the nano-film is 2.7-3.5 μm, and the pore size of the nano-film is 49-64 nm.
7. The method for preparing nickel sulfide nano-film according to claim 1, wherein in the step (2), the heating temperature is 150 ℃, the holding time is 30min, and the pure-phase nickel sulfide nano-film is prepared, wherein the thickness of the nano-film is 3.6-4.2 μm, and the pore size of the nano-film is 86-102 nm.
8. Use of the method of preparation of nickel sulphide nano-films according to any of claims 1 to 7 in electrocatalysis, at a current density of 100mA/cm2When the overpotential of the nickel sulfide nano film is 320-350 mV.
CN201811156150.6A 2018-09-30 2018-09-30 Preparation method of nickel sulfide nano film Expired - Fee Related CN109252188B (en)

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CN106927499A (en) * 2017-04-22 2017-07-07 南京工程学院 A kind of preparation method of multicomponent compound metal sulfide
CN108677207A (en) * 2018-05-24 2018-10-19 华南理工大学 A kind of Ni rich in sulphur vacancy3S2Nanometer rods analyse oxygen electrocatalysis material and the preparation method and application thereof

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