CN115029709B - Cobalt-nickel metal sulfide bifunctional electrocatalyst and preparation method and application thereof - Google Patents

Cobalt-nickel metal sulfide bifunctional electrocatalyst and preparation method and application thereof Download PDF

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CN115029709B
CN115029709B CN202210562329.1A CN202210562329A CN115029709B CN 115029709 B CN115029709 B CN 115029709B CN 202210562329 A CN202210562329 A CN 202210562329A CN 115029709 B CN115029709 B CN 115029709B
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cobalt
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nickel
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CN115029709A (en
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马江权
李庆飞
李楠
吴棉棉
沈文静
朱斌
高晓新
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Changzhou University
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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
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    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
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    • C—CHEMISTRY; METALLURGY
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    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • 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
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    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Abstract

The invention belongs to the field of preparation and application of electrocatalysts, and particularly relates to a cobalt-nickel metal sulfide bifunctional electrocatalyst, and a preparation method and application thereof. Firstly, placing blank foam nickel in an organic solvent and a dilute acid solution in sequence to ultrasonically clean impurities on the surface of the foam nickel, then placing the treated foam nickel in a cobalt source aqueous solution to react, and washing and drying after the reaction is finished to obtain a Co@NF material; calcining Co@NF and a sulfur source to obtain CoNi 2 S 4 /NiS x @nf electrocatalyst. The invention obtains the double-function electrocatalyst with nanowire shape by controlling the calcination temperature and time, increases the electrochemical active surface area, and has high activity and good stability for electrocatalytic hydrogen evolution and oxygen evolution reaction. The catalyst has excellent hydrogen evolution and oxygen evolution performance in KOH.

Description

Cobalt-nickel metal sulfide bifunctional electrocatalyst and preparation method and application thereof
Technical Field
The invention belongs to the field of preparation and application of electrocatalysts, and particularly relates to a cobalt-nickel metal sulfide bifunctional electrocatalyst, and a preparation method and application thereof.
Background
The sustainable route of development of renewable energy has led to a great deal of attention in reducing the reliance on traditional fossil fuel combustion. Electrochemical energy conversion by water splitting has great potential. It is well known that both cathodic Hydrogen Evolution (HER) and anodic Oxygen Evolution (OER) are associated with water splitting, and that they both require electrocatalysts to ensure practical rates. Up to now, noble metal-based materials have been widely used as high-efficiency electrocatalysts. However, the high cost and scarcity limit their large-scale application. Therefore, it is very important to develop a non-noble metal electrocatalyst having low cost and abundant content. In the same electrolyte, most non-noble metal electrocatalysts have high activity only for HER or OER. Against this background, there is an increasing effort to develop efficient, stable and inexpensive electrocatalysts for HER and OER dual functions.
The first row transition metals (Mn, fe, co and Ni) and their oxides, phosphides, sulfides and selenides are promising alternatives to these noble metals due to their cost effectiveness and intrinsic activity. However, the electrochemical performance and structural stability of the single-component sulfides, phosphides, and selenides need to be further enhanced compared to catalysts in industrial production.
Disclosure of Invention
The invention aims to provide a cobalt-nickel metal sulfide bifunctional electrocatalyst and a preparation method thereof, and the cobalt-nickel metal sulfide bifunctional electrocatalyst is applied to prepare hydrogen and oxygen by decomposing water under alkaline conditions, and has high catalytic activity and good stability.
The technical scheme of the invention is as follows: the preparation method of the cobalt-nickel metal sulfide bifunctional electrocatalyst provided by the invention comprises the following steps: firstly, pretreating foam nickel, dispersing a cobalt source and a reducing agent in deionized water, fully stirring, placing the pretreated foam nickel in a dispersion liquid, loading the dispersion liquid into a stainless steel autoclave, reacting at a high temperature, washing a product with deionized water and ethanol, and vacuum drying to obtain a Co@NF material; respectively placing a sulfur source and Co@NF at the upstream and downstream of a tube furnace, calcining in the tube furnace, washing the product and vacuum drying to obtain CoNi 2 S 4 /NiS x @nf electrocatalyst.
The specific technical process is as follows:
(1) Foam Nickel (NF) was used as a nickel source, cleaned by sonication in dilute HCl, distilled water and acetone, and finally dried overnight.
(2) Co (NO) 3 ) 2 ·6H 2 O is used as cobalt source, NH 4 F and CH 4 N 2 O is respectively taken as a surface modifier and a precipitator to be dissolved in deionized water, and is fully stirred until the O is completely dispersed.
Co(NO 3 ) 2 ·6H 2 O、NH 4 F and CH 4 N 2 The mass ratio of O is as follows: 0.50 to 6.00:0.05 to 0.50:0.10 to 2.50.
(3) And (3) placing the dispersion liquid obtained in the step (2) into a polytetrafluoroethylene lining, adding the pretreated foam nickel into the obtained dispersion liquid, placing the obtained dispersion liquid into a stainless steel autoclave, and then placing the obtained dispersion liquid into a blast drying oven for heating.
In the blast drying box, the temperature is set to 130 ℃ and the time is set to 5-20 h.
(4) Washing the product obtained in the step (3) by deionized water and ethanol, and drying in a vacuum drying oven to obtain Co@NF.
In a vacuum drying oven, the temperature was set at 60℃and the time was set at 12 hours.
(5) Will CH 4 N 2 S is used as a sulfur source and Co@NF is respectively arranged in N 2 Calcining for a period of time at a certain temperature at the upstream and downstream of the atmosphere tube furnace.
Distance between upstream and downstream of the tube furnace: 3-5 cm.
The calcination temperature in the tube furnace is: the calcination time is 350-500 ℃, and the calcination time is as follows: and 1-4 h.
CH 4 N 2 The area ratio of S mass to foam nickel is 2:1g/cm 2 ～4:1g/cm 2 。
(6) Washing and drying the product obtained in the step (5) to obtain a final product CoNi 2 S 4 /NiS x @nf electrocatalyst.
The invention selects proper cobalt source, nickel source, surface modifier and precipitant to control Co (NO) 3 ) 2 ·6H 2 O、NH 4 F and CH 4 N 2 O mass ratio, and the temperature and time of the blast drying box synthesize Co@NF electrocatalyst; then selecting proper sulfur source, controlling CH 4 N 2 Distance between S and Co@NF, calcination temperature and time to produce CoNi 2 S 4 /NiS x @nf electrocatalyst.
The invention also provides a CoNi 2 S 4 /NiS x The @ NF electrocatalyst is used as a working electrode for preparing hydrogen or oxygen by electrolyzing water under alkaline conditions.
CoNi 2 S 4 /NiS x The @ NF electrocatalyst is applied to an electrocatalytic hydrogen evolution and oxygen evolution performance test method, a three-electrode system is used, and a working electrode is loaded with CoNi 2 S 4 /NiS x The @ NF electrode, the counter electrode is a graphite rod electrode, the reference electrode is an Hg/HgO electrode, and the electrolyte is 1mol/L KOH solution.
The invention has the technical effects that:
(1) The catalyst provided by the invention is CoNi prepared from a composite material of cobalt-nickel mixed metal sulfide supported on foam nickel 2 S 4 /NiS x the@NF electrocatalyst has the characteristics of novel synthesis method, simple condition, easiness in operation, rapidness, high efficiency, energy conservation, environmental protection, easiness in industrial production and the like;
(2) The CoNi provided by the invention 2 S 4 /NiS x The @ NF electrocatalyst has regular nanowire appearance after the calcination temperature and time are controlled, increases the electrochemical active surface area, and has high activity and good stability for electrocatalytic hydrogen evolution and oxygen evolution reaction;
(3) The CoNi provided by the invention 2 S 4 /NiS x The @ NF electrocatalyst has high catalytic hydrogen evolution activity and good stability in alkaline electrolyte, and prepares hydrogen by electrocatalytically decomposing water in KOH electrolyte with the concentration of 1mol/L to prepare CoNi 2 S 4 /NiS x The @ NF electrocatalyst is a working electrode with a current density of-10 mA/cm 2 When the overpotential is only 77mV, the catalyst has excellent catalytic performance and stability for electrolytic water hydrogen evolution reaction.
(4) The CoNi provided by the invention 2 S 4 /NiS x The @ NF electrocatalyst has high catalytic oxygen evolution activity and good stability in alkaline electrolyte, and prepares oxygen by electrocatalytically decomposing water in KOH electrolyte with the concentration of 1mol/L to prepare CoNi 2 S 4 /NiS x The @ NF electrocatalyst is a working electrode at a current density of 10mA/cm 2 When the overpotential is only 241mV, the catalyst has excellent catalytic performance and stability for the electrolytic water oxygen evolution reaction.
Drawings
FIG. 1 shows the CoNi obtained in example 1 of the present invention 2 S 4 /NiS x XRD patterns of @ NF and Co @ NF, NF obtained in comparative examples 1-2.
FIG. 2 shows the CoNi obtained in example 1 of the present invention 2 S 4 /NiS x SEM image of @ NF.
FIG. 3 is a graph showing the CoNi obtained in comparative example 3 of the present invention 2 S 4 /NiS x SEM image of @ NF.
FIG. 4 shows CoNi obtained in examples 1-4, example 10 and comparative example 3 according to the present invention 2 S 4 /NiS x Polarization profile of @ NF electrolyzed water HER in 1.0M KOH solution.
FIG. 5 shows the CoNi obtained in examples 1-4, example 10 and comparative example 3 according to the present invention 2 S 4 /NiS x Polarization profile of water of electrolysis OER in 1.0M KOH solution @ NF.
FIG. 6 shows the CoNi obtained in example 1, examples 5-9 and comparative examples 1-2 of the present invention 2 S 4 /NiS x Polarization profile of @ NF electrolyzed water HER in 1.0M KOH solution.
FIG. 7 shows the CoNi obtained in example 1, examples 5-9 and comparative examples 1-2 of the present invention 2 S 4 /NiS x Polarization profile of water of electrolysis OER in 1.0M KOH solution @ NF.
Detailed Description
The technical features of the present invention will be further described with reference to the accompanying drawings and examples, but the scope of the present invention is not limited thereto.
Example 1
Preparation of NF
Nickel Foam (NF) (3X 5 cm) was cleaned by sonication in HCl (3M), distilled water and acetone, each in turn, for 15min, and finally dried overnight at 60 ℃.
2.Co(NO 3 ) 2 ·6H 2 Preparation of O Dispersion
70ml deionized water was weighed into a beaker using a measuring cylinder and 1.7g Co (NO) 3 ) 2 ·6H 2 O、0.1g NH 4 F and 0.7g CH 4 N 2 The O was stirred well for 0.5h.
Preparation of Co@NF
Co (NO) 3 ) 2 ·6H 2 Slowly adding the O dispersion liquid into a polytetrafluoroethylene lining, then placing NF (3X 5 cm) into the polytetrafluoroethylene lining, finally placing the polytetrafluoroethylene lining into a stainless steel high-pressure kettle, placing the stainless steel high-pressure kettle into a blast drying oven, setting the temperature to 130 ℃, setting the drying time to 20h, cooling the product to room temperature after the time is over, and washing and drying the product to obtain Co@NF.
4.CoNi 2 S 4 /NiS x Preparation of an electrocatalyst @ NF
Weigh 4g CH 4 N 2 S is placed in a crucible, and the product Co@NF (1X 1 cm) is placed in another crucible, CH 4 N 2 The area ratio of S mass to foam nickel is 4:1g/cm 2 Two crucibles were placed in N respectively 2 The distance between the two crucibles is set to be 3cm at the upstream and downstream of the atmosphere tube furnace, the heating rate is controlled to be 1.4 ℃/min, the calcining temperature is 450 ℃, the calcining time is 2h, and the final product CoNi is obtained after the calcining is completed 2 S 4 /NiS x @nf electrocatalyst.
CoNi prepared in example 1 2 S 4 /NiS x XRD pattern of @ NF is shown in figure 1, SEM pattern is shown in figure 2, and it can be seen from XRD and scanning electron microscope patterns that CoNi is prepared 2 S 4 /NiS x The XRD characteristic peak of the @ NF electrocatalyst is sharp and obvious, and has CoNi 2 S 4 、NiS、NiS 2 Is characterized in that the SEM morphology is in a regular nanowire shape.
Example 2
Compared with example 1, the difference is that: co (NO) 3 ) 2 ·6H 2 O 2 And (3) preparing a dispersion liquid. 70ml deionized water was weighed into a beaker using a measuring cylinder, and 0.9g Co (NO) 3 ) 2 ·6H 2 O、0.07g NH 4 F and 0.4. 0.4gCH 4 N 2 O, stirring thoroughly for 0.5h. Other preparation methods were the same as in example 1.
Example 3
Compared with example 1, the difference is that: co (NO) 3 ) 2 ·6H 2 And (3) preparing an O dispersion liquid. 70ml deionized water is measured by a measuring cylinder and poured into the furnaceInto the cup, 3.5g of Co (NO) 3 ) 2 ·6H 2 O、0.3g NH 4 F and 1.4g CH 4 N 2 O, stirring thoroughly for 0.5h. Other preparation methods were the same as in example 1.
Example 4
Compared with example 1, the difference is that: co (NO) 3 ) 2 ·6H 2 And (3) preparing an O dispersion liquid. 70ml deionized water was weighed into a beaker using a measuring cylinder, and 5.2g Co (NO) 3 ) 2 ·6H 2 O、0.4g NH 4 F and 2.2g CH 4 N 2 O, stirring thoroughly for 0.5h. Other preparation methods were the same as in example 1.
Example 5
Compared with example 1, the difference is that: preparation of Co@NF. The temperature in the forced air drying oven was set at 130℃and the drying time was set at 5 hours. Other preparation methods were the same as in example 1.
Example 6
Compared with example 1, the difference is that: coNi 2 S 4 /NiS x Preparation of an NF electrocatalyst. Two crucibles were placed in N respectively 2 The distance between the two crucibles was set to 5cm upstream and downstream of the atmosphere tube furnace. Other preparation methods were the same as in example 1.
Example 7
Compared with example 1, the difference is that: coNi 2 S 4 /NiS x Preparation of an NF electrocatalyst. The tube furnace set the calcination temperature at 350 ℃. Other preparation methods were the same as in example 1.
Example 8
Compared with example 1, the difference is that: coNi 2 S 4 /NiS x Preparation of an NF electrocatalyst. The tube furnace was set to a calcination temperature of 400 ℃. Other preparation methods were the same as in example 1.
Example 9
Compared with example 1, the difference is that: coNi 2 S 4 /NiS x Preparation of an NF electrocatalyst. The tube furnace was set to a calcination temperature of 500 ℃. Other preparation methods were the same as in example 1.
Example 10
And example 1Compared with the prior art, the method is characterized in that: coNi 2 S 4 /NiS x Preparation of an NF electrocatalyst. CH (CH) 4 N 2 The area ratio of S mass to foam nickel is 2:1g/cm 2 . Other preparation methods were the same as in example 1.
Comparative example 1
Compared with example 1, the difference is that: there is no step 4. Step 1-3 the preparation was the same as in example 1. As can be seen from the polarization graph, calcination is not carried out, so that the prepared Co@NF has large hydrogen evolution and oxygen evolution overpotential.
Comparative example 2
Compared with example 1, the difference is that: step 2-4 is not included, only NF pretreated in step 1. As can be seen from the polarization curve graph, the pretreated NF has large hydrogen evolution and oxygen evolution overpotential.
Comparative example 3
Compared with example 1, the difference is that: co (NO) 3 ) 2 ·6H 2 And (3) preparing an O dispersion liquid. Not adding NH 4 F and CH 4 N 2 O substance. Other preparation methods were the same as in example 1. As can be seen from the polarization graph and SEM, NH was not added 4 F and CH 4 N 2 O substance, which causes that cobalt source can not be loaded on foam nickel, thus preparing CoNi 2 S 4 /NiS x The hydrogen evolution and oxygen evolution overpotential of the @ NF are large, and the nano linear morphology is irregular.
Application example 1
1. Activation treatment of electrocatalyst
(1) The working electrode was CoNi in example 1 using a three electrode system 2 S 4 /NiS x The @ NF electrode, the counter electrode is a graphite rod electrode, the reference electrode is an Hg/HgO electrode, and the electrolyte is 1mol/L KOH.
(2) Cyclic Voltammetry (CV) activation. (1) HER, namely using an electrochemical workstation of Shanghai Chenhua DH7000, adopting a CV program, wherein the test interval is-0.5 to-1.6V vs. RHE, the sweeping speed is 50mV/s, and the electrodes are circulated for 20 circles to reach a stable state. (2) OER is that using the electrochemical workstation of Shanghai Chenhua DH7000, adopting CV program, the test interval is 0-0.8V vs. RHE, the sweep speed is 50mV/s, the cycle is 20, the electrode is in stable state.
2. Linear Sweep Voltammetry (LSV) test
(1) After HER activation, the switching program is a linear sweep voltammetry program with a test interval of-0.5 to-1.6 Vvs. RHE, a sweep rate of 5mV/s, and an electrocatalyst of-10 mA/cm in alkaline electrolyte 2 At this time, the overpotential was 77mV, as shown in FIGS. 4 and 6.
(2) OER, after activation, the switching procedure is a linear sweep voltammetry procedure, the test interval is 0-0.8 Vvs. RHE, the sweep speed is 5mV/s, and the electrocatalyst in the alkaline electrolyte is 10mA/cm 2 At this time, the overpotential was 241mV, as shown in FIGS. 5 and 7.
Application example 2
As shown in application example 1, coNi prepared in example 2 2 S 4 /NiS x The @ NF electrocatalyst is used for preparing hydrogen by the electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the current density is-10 mA/cm 2 At this time, the overpotential was 97mV for the electrocatalyst.
As shown in application example 1, coNi prepared in example 2 2 S 4 /NiS x The @ NF electrocatalyst is used for preparing oxygen by the electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the current density is 10mA/cm 2 When the overpotential was 392mV, the catalyst was used.
Application example 3
As shown in application example 1, coNi prepared in example 3 2 S 4 /NiS x The @ NF electrocatalyst is used for preparing hydrogen by the electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the current density is-10 mA/cm 2 At this time, the overpotential was 79mV for the electrocatalyst.
As shown in application example 1, coNi prepared in example 3 2 S 4 /NiS x The @ NF electrocatalyst is used for preparing oxygen by the electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the current density is 10mA/cm 2 At this time, the overpotential was 283mV of the electrocatalyst.
Application example 4
As shown in application example 1, coNi prepared in example 4 2 S 4 /NiS x At a concentration of @ NF electrocatalystPreparing hydrogen by electrocatalytic decomposition of water in KOH electrolyte of 1mol/L, and obtaining the hydrogen with current density of-10 mA/cm 2 At this time, the overpotential was 108mV for the electrocatalyst.
As shown in application example 1, coNi prepared in example 4 2 S 4 /NiS x The @ NF electrocatalyst is used for preparing oxygen by the electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the current density is 10mA/cm 2 At this time, the overpotential was 349mV of the electrocatalyst.
Application example 5
As shown in application example 1, coNi prepared in example 5 2 S 4 /NiS x The @ NF electrocatalyst is used for preparing hydrogen by the electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the current density is-10 mA/cm 2 At this time, the overpotential was 198mV for the electrocatalyst.
As shown in application example 1, coNi prepared in example 5 2 S 4 /NiS x The @ NF electrocatalyst is used for preparing oxygen by the electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the current density is 10mA/cm 2 At this time, the overpotential was 347mV for the electrocatalyst.
Application example 6
As shown in application example 1, coNi prepared in example 6 2 S 4 /NiS x The @ NF electrocatalyst is used for preparing hydrogen by the electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the current density is-10 mA/cm 2 At this time, the overpotential was 125mV for the electrocatalyst.
As shown in application example 1, coNi prepared in example 6 2 S 4 /NiS x The @ NF electrocatalyst is used for preparing oxygen by the electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the current density is 10mA/cm 2 At this time, the overpotential was 270mV for the electrocatalyst.
Application example 7
As shown in application example 1, coNi prepared in example 7 2 S 4 /NiS x The @ NF electrocatalyst is used for preparing hydrogen by the electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the current density is-10 mA/cm 2 At this time, the overpotential was 112mV for the electrocatalyst.
Example as shown in application example 17 CoNi prepared 2 S 4 /NiS x The @ NF electrocatalyst is used for preparing oxygen by the electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the current density is 10mA/cm 2 At this time, the overpotential was 355mV of the electrocatalyst.
Application example 8
As shown in application example 1, coNi prepared in example 8 2 S 4 /NiS x The @ NF electrocatalyst is used for preparing hydrogen by the electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the current density is-10 mA/cm 2 At this time, the overpotential was 82mV for the electrocatalyst.
As shown in application example 1, coNi prepared in example 8 2 S 4 /NiS x The @ NF electrocatalyst is used for preparing oxygen by the electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the current density is 10mA/cm 2 At this time, the overpotential was 351mV for the electrocatalyst.
Application example 9
As shown in application example 1, coNi prepared in example 9 2 S 4 /NiS x The @ NF electrocatalyst is used for preparing hydrogen by the electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the current density is-10 mA/cm 2 When the overpotential was 145mV, the catalyst was used.
As shown in application example 1, coNi prepared in example 9 2 S 4 /NiS x The @ NF electrocatalyst is used for preparing oxygen by the electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the current density is 10mA/cm 2 When the overpotential was 392mV, the catalyst was used.
Application example 10
As shown in application example 1, coNi prepared in example 10 2 S 4 /NiS x The @ NF electrocatalyst is used for preparing hydrogen by the electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the current density is-10 mA/cm 2 At this time, the overpotential was 87mV for the electrocatalyst.
As shown in application example 1, coNi prepared in example 10 2 S 4 /NiS x The @ NF electrocatalyst is used for preparing oxygen by the electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the current density is 10mA/cm 2 At an overpotential of 290mVAn electrocatalyst.
Application example 11
As shown in application example 1, the Co@NF electrocatalyst prepared in comparative example 1 prepares hydrogen by electrocatalytically decomposing water in KOH electrolyte with the concentration of 1mol/L, and the current density is-10 mA/cm 2 At this time, the overpotential was 206mV for the electrocatalyst.
As shown in application example 1, the Co@NF electrocatalyst prepared in comparative example 1 prepared oxygen by electrocatalytically decomposing water in KOH electrolyte at a concentration of 1mol/L at a current density of 10mA/cm 2 At this time, the overpotential was 438mV for the electrocatalyst.
Application example 12
As shown in application example 1, the NF electrocatalyst prepared in comparative example 2 prepared hydrogen by electrocatalytically decomposing water in KOH electrolyte with a concentration of 1mol/L at a current density of-10 mA/cm 2 At this time, the overpotential was 224mV for the electrocatalyst.
As shown in application example 1, the NF electrocatalyst prepared in comparative example 2 prepared oxygen by electrocatalytically decomposing water in KOH electrolyte with a concentration of 1mol/L at a current density of 10mA/cm 2 At this time, the overpotential was 601mV of the electrocatalyst.
Application example 13
As shown in application example 1, coNi prepared in comparative example 3 2 S 4 /NiS x The @ NF electrocatalyst is used for preparing hydrogen by the electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the current density is-10 mA/cm 2 At this time, the overpotential was 180mV for the electrocatalyst.
As shown in application example 1, coNi prepared in comparative example 3 2 S 4 /NiS x The @ NF electrocatalyst is used for preparing oxygen by the electrocatalytic decomposition of water in KOH electrolyte with the concentration of 1mol/L, and the current density is 10mA/cm 2 At this time, the overpotential was 330mV for the electrocatalyst.
The foregoing detailed description of the embodiments and advantages of the invention will be appreciated that the foregoing description is merely illustrative of the presently preferred embodiments of the invention, and that no limitations are intended to the scope of the invention, except insofar as modifications, additions and equivalents may be made without departing from the spirit and scope of the invention.

Claims (3)

1. The preparation method of the cobalt-nickel metal sulfide bifunctional electrocatalyst is characterized by comprising the following specific steps of:
(1) Taking foam Nickel (NF) as a nickel source, sequentially carrying out ultrasonic treatment in HCl, distilled water and acetone for cleaning, and drying overnight;
(2) Co (NO) 3 ) 2 ·6H 2 O is used as cobalt source, NH 4 F and CH 4 N 2 O is respectively taken as a surface modifier and a precipitator to be dissolved in deionized water, and is fully stirred until the O is completely dispersed; placing the obtained dispersion liquid into a polytetrafluoroethylene lining, adding the foam nickel pretreated in the step (1) into the polytetrafluoroethylene lining, placing the foam nickel into a stainless steel autoclave, and then placing the stainless steel autoclave into a blast drying oven for heating; washing the obtained product with deionized water and ethanol, and drying in a vacuum drying oven to obtain Co@NF;
wherein Co (NO) 3 ) 2 ·6H 2 O、NH 4 F and CH 4 N 2 The mass ratio of O is as follows: 0.50 to 6.00: 0.05-0.50: 0.10-2.50;
(3) Will CH 4 N 2 S is used as a sulfur source and Co@NF is respectively arranged in N 2 Calcining at high temperature in the upstream and downstream of the atmosphere tube furnace, washing and drying the product to obtain the final product CoNi 2 S 4 / NiS x An @ NF electrocatalyst; wherein x=1 or 2;
distance between upstream and downstream of the tube furnace: 3-5 cm;
the calcination temperature in the tube furnace is: the calcination time is 350-500 ℃, and the calcination time is as follows: 1-4 hours;
CH 4 N 2 the area ratio of S mass to foam nickel is 2:1g/cm 2 ~4:1g/cm 2 。
2. The method for preparing the cobalt nickel metal sulfide bifunctional electrocatalyst according to claim 1, wherein in step (2), the heating time in the blast drying oven is: 5-20 h, and the temperature is 130 ℃.
3. The use of a cobalt nickel metal sulphide dual-function electrocatalyst prepared according to the method of claim 1, wherein the cobalt nickel metal sulphide dual-function electrocatalyst is used for electrocatalytic hydrogen evolution and electrocatalytic oxygen evolution under alkaline conditions.
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CN112863887A (en) * 2020-12-28 2021-05-28 沈阳工业大学 Preparation method of high-performance cabbage-shaped heterostructure electrode material
CN113604838A (en) * 2021-08-17 2021-11-05 江苏大学 Preparation method and application of nickel-cobalt bimetallic selenide heterostructure electrocatalyst
CN114438545A (en) * 2022-03-21 2022-05-06 河北工业大学 Bimetal doped Ni3S2Preparation method of oxygen evolution electrocatalyst

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Publication number Priority date Publication date Assignee Title
CN112863887A (en) * 2020-12-28 2021-05-28 沈阳工业大学 Preparation method of high-performance cabbage-shaped heterostructure electrode material
CN113604838A (en) * 2021-08-17 2021-11-05 江苏大学 Preparation method and application of nickel-cobalt bimetallic selenide heterostructure electrocatalyst
CN114438545A (en) * 2022-03-21 2022-05-06 河北工业大学 Bimetal doped Ni3S2Preparation method of oxygen evolution electrocatalyst

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