CN116288477A - Double-function high-entropy nano alloy electrocatalyst and preparation method thereof - Google Patents
Double-function high-entropy nano alloy electrocatalyst and preparation method thereof Download PDFInfo
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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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/089—Alloys
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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
- 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
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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
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- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
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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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
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- 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 bifunctional high-entropy nano alloy electrocatalyst and a preparation method thereof belong to the technical field of new material preparation. The bifunctional high-entropy nano alloy electrocatalyst comprises a porous foam nickel matrix and (Fe) electrodeposited and supported on the foam nickel matrix 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1‑x Li x (x=0.24-0.27) high entropy nano alloy, fe according to ion mole ratio 3+ ：Co 2+ ：Ni 2+ ：Cu 2+ ：Zn 2+ ：Li + =1: 1:1:1:1: (1.6-1.8); the preparation method comprises the following steps: 1) Preparing a precursor electrolyte according to the ion molar ratio; 2) Three-electricityPerforming constant potential electrodeposition on a porous foam nickel matrix under a polar system; 3) Washing and naturally drying. The preparation method of the bifunctional high-entropy nano alloy electrocatalyst is simple to operate, does not need subsequent treatment steps, has relatively excellent dual-function electrocatalytic activity of hydrogen evolution reaction and oxygen evolution reaction, and can be directly used for electrocatalytic reaction after preparation.
Description
Technical Field
The invention belongs to the technical field of new material preparation, and particularly relates to a bifunctional high-entropy nano alloy electrocatalyst and a preparation method thereof.
Background
Electrocatalytic water decomposition (2H) 2 O→O 2 +2H 2 ) As a clean and efficient hydrogen production method, the method consists of two half reactions, namely a cathodic hydrogen evolution reaction and an anodic oxygen evolution reaction. However, in practical applications, slow reaction kinetics and large overpotential limit the rapid progress of these two half reactions. The catalysts currently used in commerce are mainly noble metal based catalysts (Pt electrode for hydrogen evolution, irO for oxygen evolution) 2 And RuO (Ruo) 2 Electrode), however, the high cost, scarcity of noble metals has prevented further development of electrolyzed water. Therefore, the development of the non-noble metal-based electrocatalyst with high and stable performance and low cost is a key for promoting the scale application of the electrolyzed water, and is a difficult problem which is urgently needed to be overcome at present.
The high entropy alloy catalyst containing various metal components has excellent catalytic activity due to coordination, geometric effects, and the like. While nano-sized high-entropy alloy electrocatalysts are more widely used in the catalytic field, they are receiving much attention for their superior performance over single metal nanomaterials. According to the preparation methods reported at present, which can be used in the electrocatalytic field, the high-entropy nano alloy electrocatalyst comprises a chemical reduction method, a template method, a carbothermal oscillation method and the like, but the preparation method is simple, the preparation cost is low, the preparation method has double-function catalytic activity, and the preparation process is less, and is expected to be practically and widely prepared, and the development of new-component high-entropy nano alloy electrocatalyst and the preparation process flow are particularly important.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a bifunctional high-entropy nano alloy electrocatalyst and a preparation method thereofThe catalyst is a Li-containing high-entropy nano alloy electrocatalyst (Fe 1/5 Co 1/ 5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.24 to 0.27). The preparation method is simple to operate and quick in preparation time. Thus prepared (Fe 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x The (x=0.24-0.27) high-entropy nano alloy electrocatalyst has great scientific significance, is beneficial to realizing large-scale actual production and has certain economic value.
The bifunctional high-entropy nano alloy electrocatalyst comprises a porous foam nickel matrix and (Fe) electrodeposited and supported on the foam nickel matrix 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.24-0.27) high entropy nano alloy, wherein (Fe 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.24-0.27) the loading of the high-entropy nano alloy is 5-8 mg/cm 2 . In addition, the high-entropy nano alloy is in a cubic crystal system, fm-3m space groups, the nano microstructure is in a mutually staggered nano sheet shape, and the thickness of the nano sheet is 20-35 nm.
More preferably, (Fe) 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x＝0.25)。
The porosity of the foam nickel matrix is more than or equal to 98 percent, and the aperture is 0.1-0.5 mm.
The foam nickel matrix has the functions of loading and dispersing the high-entropy nano alloy, achieving excellent electrocatalytic performance for uniform deposition and improving the stability of the high-entropy nano alloy electrocatalyst. On the other hand, the foam nickel matrix improves the conductivity of the catalyst, the porous structure is favorable for the transmission of reactants and products, and the catalytic activity of the high-entropy nano alloy electrocatalyst is improved.
Under alkaline conditions of 1mol/L KOH, (Fe) 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.25) the initial potential of the hydrogen evolution reaction of the bifunctional high-entropy nano alloy electrocatalyst is-0.105V, and the current density is 10mA/cm 2 The overpotential at the time is 26mV, the initial potential of the oxygen evolution reaction is 1.44V, and the current density is 10mA/cm 2 The overpotential is 224mV, and the hydrogen evolution reaction and oxygen evolution reaction electrocatalytic performance is the most excellent.
The invention relates to a preparation method of a bifunctional high-entropy nano alloy electrocatalyst, which comprises the following specific steps:
step 1, precursor solution configuration:
according to the mole ratio of metal ions of Fe 3+ ：Co 2+ ：Ni 2+ ：Cu 2+ ：Zn 2+ =1: 1:1:1:1: (1.6-1.8) weighing the corresponding FeCl 3 ·6H 2 O、CoCl 2 、NiCl 2 ·6H 2 O、CuCl 2 ·6H 2 O、ZnCl 2 Mixing LiCl, dissolving in deionized water, sealing, mixing and stirring uniformly to obtain uniformly mixed electrolyte;
in the step 1, the materials are uniformly mixed and stirred, and the stirring time is preferably 3-4 hours.
(1) Regulating the pH value of the electrolyte obtained in the step 1 to 4-4.5, and heating to 40-50 ℃;
(2) A three-electrode system is adopted, porous foam nickel is used as a working electrode, a graphite rod is used as a counter electrode, and the counter electrode is clamped and placed into electrolyte;
(3) Using constant potential electrodeposition, wherein the deposition potential is-0.2+/-0.02V, and the deposition time is 850-900 s;
(4) And after the deposition is finished, repeatedly washing the foam nickel matrix deposited with the high-entropy nano alloy for a plurality of times, and naturally drying in air to obtain the dual-function high-entropy nano alloy electrocatalyst uniformly deposited on the foam nickel matrix.
The preparation method of the bifunctional high-entropy nano alloy electrocatalyst comprises the following steps:
in the step 1, feCl is preferable 3 ·6H 2 O concentration is 0.1mol/L, coCl 2 The concentration is 0.1mol/L,NiCl 2 ·6H 2 the concentration of O is 0.1mol/L, and CuCl 2 ·6H 2 O concentration is 0.1mol/L, znCl 2 The concentration was 0.1mol/L, and the LiCl concentration was 0.166mol/L.
In the step 2 (1), the method for adjusting the pH value comprises the following steps: maintaining the stirring rotation speed at 200-300 rpm, sucking ammonia water or 0.1mol/L dilute hydrochloric acid by using a liquid-transfering gun, and slowly regulating the pH value of the electrolyte to 4-4.5.
In the step 2 (2), the porous foam nickel substrate used had dimensions of 20mm×10mm×0.8mm. The porous foam nickel is subjected to ultrasonic pretreatment for 3-5 min by 0.5mol/L dilute hydrochloric acid, so as to remove an oxide layer on the surface, and is repeatedly washed for three times by deionized water and absolute ethyl alcohol, and is stood in air for drying.
In the step 2 (3), before the deposition process, the working electrode clamp and the reference electrode clamp are clamped on the working electrode simultaneously, and the foam nickel matrix is required to be placed 1-1.5 cm below the liquid level of the electrolyte, and meanwhile, the spacing distance between the foam nickel matrix and the graphite rod is kept 2-2.5 cm.
In the step 2 (4), after the deposition time is over, immediately taking out the sample, washing the sample with deionized water and absolute ethyl alcohol for multiple times to remove superfluous deposits on the surface, standing and drying in air, and naturally drying for more than or equal to 24 hours.
The bifunctional high-entropy nano alloy electrocatalyst is FeCl with equal molar ratio 3 ·6H 2 O、CoCl 2 、NiCl 2 ·6H 2 O、CuCl 2 ·6H 2 O、ZnCl 2 LiCl six chlorides in an ionic molar ratio of 1:1:1:1:1: (1.6-1.8) and performing constant potential electrodeposition on a foam nickel matrix to obtain the bifunctional high-entropy nano alloy electrocatalyst, wherein no other treatment is needed, and the obtained (Fe) is naturally dried 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x The (x=0.24-0.27) high entropy nano alloy electrocatalyst can be directly used as a working electrode.
Compared with the prior art, the dual-function high-entropy nano alloy electrocatalyst and the preparation method thereof have the beneficial effects that:
the invention adopts simple structureIs prepared by a constant potential electrodeposition method 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x The preparation method of the high-entropy nano alloy electrocatalyst (x=0.24-0.27) is simple to operate, and the high-entropy nano alloy electrocatalyst can be directly used for electrocatalytic reaction after being prepared without subsequent treatment steps.
The dual-function high-entropy nano alloy catalyst consists of low-cost metal elements Fe, co, ni, cu, zn, li, compared with Pt and IrO which are commercially used in the current electrocatalytic hydrogen evolution reaction and oxygen evolution reaction 2 、RuO 2 The noble metal catalyst has the advantages of cost and excellent dual-function electrocatalytic activity of hydrogen evolution reaction and oxygen evolution reaction.
In the preparation method of the bifunctional high-entropy nano alloy electrocatalyst, the uniformly dispersed and deposited high-entropy nano alloy structure provides a larger catalytic reaction contact area and more active sites. Directly taking the high-entropy nano alloy electrocatalyst as a working electrode to perform electrocatalytic performance test; (Fe of the invention) 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.25) high entropy nano alloy, the microstructure is a nano lamellar structure which is mutually staggered, the thickness of the thin sheet is 20-35 nm, and the (Fe) of the invention is measured under the alkaline condition of 1mol/L KOH 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.25) the initial potential of the hydrogen evolution reaction of the bifunctional high-entropy nano alloy electrocatalyst is-0.105V, and the current density is 10mA/cm 2 The overpotential at the time is 26mV, the initial potential of the oxygen evolution reaction is 1.44V, and the current density is 10mA/cm 2 The overpotential is 224mV, and the hydrogen evolution reaction and oxygen evolution reaction electrocatalytic performance is the most excellent.
The invention can be carried out within the scope of understanding by those skilled in the art from the description given above without being limited to the examples given above, while the invention can be carried out within the interval of various parameters of the preparation technique (high-entropy alloy system components, electrolyte concentration, pH, deposition potential, deposition time), all of which shall be deemed to fall within the scope of protection of the appended claims.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 shows the composition of the present invention (Fe 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.25) and (Fe) obtained in comparative example 1, comparative example 2, comparative example 3 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x= 0,0.16,0.35) XRD pattern of high entropy nano-alloy electrocatalyst.
FIG. 3 shows the composition of the present invention (Fe 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.25) and (Fe) obtained in comparative example 1, comparative example 2, comparative example 3 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x= 0,0.16,0.35) SEM topography of high entropy nano-alloy electrocatalyst; wherein, (a) is comparative example 1; (b) is comparative example 2; (c) is an example; (d) comparative example 3.
FIG. 4 shows the composition of the present invention (Fe 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.25) and (Fe) obtained in comparative example 1 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0) high-resolution spectral contrast plot of X-ray photoelectron spectroscopy of the high-entropy nano-alloy electrocatalyst; (a) is Fe 2p; (b) is Co 2p; (c) is Ni 2p; (d) is Cu 2p; (e) is Zn 2p; and (f) is Li 1s.
FIG. 5 (Fe) obtained in the example of the present invention 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.25) and (Fe) obtained in comparative example 1, comparative example 2, comparative example 3 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x= 0,0.16,0.35) high entropy nano alloy electrocatalyst performance test charts; (a) hydrogen evolution reaction performance test; (b)) And (5) testing oxygen evolution reaction performance.
FIG. 6 shows the composition of the present invention (Fe 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.25) and (Fe) obtained in comparative example 1, comparative example 2, comparative example 3 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x= 0,0.16,0.35) high-entropy nano alloy electrocatalyst with Li doping content of 10mA/cm for hydrogen evolution reaction and oxygen evolution reaction 2 The relationship of the corresponding overpotential.
Detailed Description
It should be noted that the following detailed description of the embodiments is given in connection with the accompanying drawings in order to better explain the present invention, but the present invention is not limited to the following embodiments. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
The process flow of the following example is shown in FIG. 1.
Examples
The invention provides a bifunctional high-entropy nano alloy electrocatalyst, which consists of a porous foam nickel matrix and (Fe) deposited on the matrix 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.25) high entropy nano-alloy composition. This example is a high entropy nano-alloy prepared with Li doping content x=0.25.
The preparation method of the bifunctional high-entropy nano alloy electrocatalyst comprises the following specific steps:
step 1, preparing a precursor electrolyte:
(1) In terms of ionic mole ratio Fe 3+ ：Co 2+ ：Ni 2+ ：Cu 2+ ：Zn 2+ ：Li + =1: 1:1:1:1:1.66 weighing the corresponding FeCl 3 ·6H 2 O(2.7029g)、CoCl 2 (1.298g)、NiCl 2 ·6H 2 O(2.3769g)、CuCl 2 ·6H 2 O(1.7048g)、ZnCl 2 (1.363 g) and LiCl (0.7036 g) are mixed and dissolved in 100mL of deionized water, a beaker filled with the electrolyte is covered with a sealing film and placed on a magnetic stirrer to be stirred for 3-4 hours until a uniformly mixed electrolyte is obtained;
(1) Stably clamping the electrolyte obtained in the step 1 on a constant-temperature water bath kettle, keeping the stirring rotation speed at 200-300 rpm, sucking ammonia water or 0.1mol/L dilute hydrochloric acid by using a liquid-transferring gun, slowly adjusting the pH value of the electrolyte to 4-4.5, and heating the electrolyte to 40 ℃ in a water bath;
(2) Using a Chen Hua electrochemical workstation CHI660E, adopting a three-electrode system, taking a porous foam nickel matrix as a working electrode, taking a graphite rod as a counter electrode, and clamping and putting the counter electrode into electrolyte; wherein the porous foam nickel matrix used has dimensions of 20mm by 10mm by 0.8mm. The porous foam nickel is subjected to ultrasonic pretreatment for less than or equal to 10min by 0.5mol/L dilute hydrochloric acid, so as to remove an oxide layer on the surface, and is repeatedly washed for three times by deionized water and absolute ethyl alcohol, and is subjected to standing and air drying;
(3) Before the deposition process, the working electrode clamp and the reference electrode clamp are clamped on the working electrode simultaneously, and the foam nickel matrix is required to be placed 1-1.5 cm below the liquid level of the electrolyte, and simultaneously keeps a spacing distance of 2-2.5 cm from the graphite rod, constant potential electrodeposition is used, the deposition potential is-0.2V, and the deposition time is 900s;
(4) After the deposition, repeatedly washing the substrate deposited with the high-entropy nano alloy for a plurality of times by using deionized water and absolute ethyl alcohol, and naturally drying in air to obtain the (Fe) uniformly deposited on the substrate 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.25) high entropy nano-alloy electrocatalyst.
The invention provides an application of a high-entropy nano alloy electrocatalyst in catalyzing hydrogen evolution reaction and oxygen evolution reaction under the alkaline condition of 1mol/L KOH:
for the above (Fe) 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.25) high entropy nano alloy electrocatalyst, cut to 10mm x 10mm workElectrode, deposition amount of high entropy nano alloy on substrate is 5-8 mg/cm 2 An Ag/AgCl electrode is used as a reference electrode, and a graphite rod is used as a counter electrode.
Electrocatalytic performance testing was performed using the Shanghai Chenhua electrochemical workstation CHI 660E. The Cycle Voltammetry (CV) was carried out 20 times and the scan rate was 50mV/s. The scanning rate of the sexually scanned voltammetry (LSV) is 5mV/s, and the ohmic compensation is 95%. The test environment was 50 ℃.
As shown by XRD results in FIG. 2, the above-mentioned (Fe 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x The XRD result of the (x=0.25) high-entropy nano alloy is consistent with that of a standard PDF card (85-1326), the XRD result is in a cubic crystal system, the space group is Fm-3m (225), and the high-entropy nano alloy electrocatalyst is in a single-phase structure. FIG. 3 (c) shows (Fe 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.25) SEM morphology of the high entropy nano alloy on the foam nickel matrix is a staggered nano sheet structure, and the thickness of the nano sheet is about 20-35 nm. FIGS. 4 (a-f) show comparative example 1 and example (Fe) 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0, 0.25) high entropy nano alloy X-ray photoelectron spectrum, as the Li doping content increases, the binding energy of Fe 2p, co 2p, cu 2p shifts to a low binding energy to some extent. In FIG. 5 (Fe 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.25) electrocatalytic hydrogen evolution reaction test and oxygen evolution reaction test of high entropy nano alloy on foam nickel matrix. The composition of this example (Fe) was measured under alkaline conditions of 1mol/L KOH 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.25) the initial potential of the hydrogen evolution reaction of the high-entropy nano alloy electrocatalyst is-0.105V, and the current density is 10mA/cm 2 The overpotential at the time is 26mV, the initial potential of the oxygen evolution reaction is 1.44V, and the current density is 10mA/cm 2 The overpotential is 224mV, and the hydrogen evolution reaction and oxygen evolution reaction electrocatalytic performance is the most excellent.
Comparative example 1
The difference from the examples is that this comparative example is a high entropy nanoalloy prepared at a Li doping content of x=0, i.e. (Fe 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0), in the preparation process, according to the ion mole ratio Fe 3+ ：Co 2+ ：Ni 2+ ：Cu 2 + ：Zn 2+ =1: 1:1:1:1 weighing the corresponding FeCl 3 ·6H 2 O(2.7029g)、CoCl 2 (1.298g)、NiCl 2 ·6H 2 O(2.3769g)、CuCl 2 ·6H 2 O(1.7048g)、ZnCl 2 (1.363 g) and controlling the pH value of the electrolyte to be 4.5, and heating to 42 ℃; the deposition potential range was-0.25V and the deposition time was 850s.
As shown by XRD results in FIG. 2, in the above comparative example (Fe 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x The XRD result of the high-entropy nano alloy (x=0) is consistent with that of a standard PDF card (85-1326), the high-entropy nano alloy is in a cubic crystal system, the space group is Fm-3m (225), and the high-entropy nano alloy electrocatalyst is in a single-phase structure. FIG. 3 (a) shows (Fe 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0) SEM morphology of the high entropy nano alloy on the foam nickel matrix is a nano net-shaped sphere particle structure stacked with each other, and the diameter of the nano particles is about 150-180 nm. In FIG. 5 (Fe 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0) electrocatalytic hydrogen evolution reaction test and oxygen evolution reaction test of high entropy nano alloy on foam nickel matrix. The composition of this example (Fe) was measured under alkaline conditions of 1mol/L KOH 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0) the initial potential of the hydrogen evolution reaction of the high-entropy nano alloy electrocatalyst is-0.125V, and the current density is 10mA/cm 2 The overpotential at this time was 43mV, the initial potential of the oxygen evolution reaction was 1.461V, and the current density was 10mA/cm 2 The overpotential is 235mV, and compared with the example, the electro-catalytic performance of the hydrogen evolution reaction and the oxygen evolution reaction is providedAnd (3) lowering.
Comparative example 2
The difference from example 1 is that this comparative example is a high entropy nano alloy prepared at a Li doping content of x=0.166, i.e. (Fe 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.166), in the preparation process, according to the ionic molar ratio Fe 3+ ：Co 2 + ：Ni 2+ ：Cu 2+ ：Zn 2+ ：Li + =1: 1:1:1:1:1 weighing the corresponding FeCl 3 ·6H 2 O(2.7029g)、CoCl 2 (1.298g)、NiCl 2 ·6H 2 O(2.3769g)、CuCl 2 ·6H 2 O(1.7048g)、ZnCl 2 (1.363 g) and LiCl (0.4239 g) are mixed, the pH value of the electrolyte is controlled to be 4.5, and the electrolyte is heated to 42 ℃; the deposition potential range was-0.25V and the deposition time was 850s.
As shown by XRD results in FIG. 2, the above-mentioned (Fe 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x The XRD result of the (x=0.166) high-entropy nano alloy is consistent with that of a standard PDF card (85-1326), the XRD result is in a cubic crystal system, the space group is Fm-3m (225), and the high-entropy nano alloy electrocatalyst is in a single-phase structure. FIG. 3 (b) shows (Fe 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.166) SEM morphology of the high entropy nanoalloy on the foam nickel substrate, which is a structure of mutually staggered nano-flakes, the thickness of the nano-flakes is about 5-7 nm. In FIG. 5 (Fe 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.166) electrocatalytic hydrogen evolution reaction test and oxygen evolution reaction test of high entropy nano alloy on foam nickel matrix. The composition of this example (Fe) was measured under alkaline conditions of 1mol/L KOH 1/ 5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.166) the initial potential of the hydrogen evolution reaction of the high-entropy nano alloy electrocatalyst is-0.132V, and the current density is 10mA/cm 2 The overpotential at the time was 48mV, the initial potential of the oxygen evolution reaction was 1.463V, and the current density was 10mA/cm 2 The overpotential was 269mV, and the electrocatalytic performance of the hydrogen evolution reaction and the oxygen evolution reaction was reduced as compared with the examples.
Comparative example 3
The difference from example 1 is that this comparative example is a high entropy nano alloy prepared at a Li doping content of x=0.35, i.e. (Fe 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.35), in the preparation process, according to the ionic molar ratio Fe 3+ ：Co 2+ ：Ni 2 + ：Cu 2+ ：Zn 2+ ：Li + =1: 1:1:1:1:2.7 weighing the corresponding FeCl 3 ·6H 2 O(2.7029g)、CoCl 2 (1.298g)、NiCl 2 ·6H 2 O(2.3769g)、CuCl 2 ·6H 2 O(1.7048g)、ZnCl 2 (1.363 g) and LiCl (1.1411 g) are mixed, the pH value of the electrolyte is controlled to be 4.5, and the electrolyte is heated to 42 ℃; the deposition potential range was-0.25V and the deposition time was 850s.
As shown by XRD results in FIG. 2, the above-mentioned (Fe 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x The XRD result of the high-entropy nano alloy (x=0.35) is consistent with that of a standard PDF card (85-1326), the high-entropy nano alloy is in a cubic crystal system, the space group is Fm-3m (225), and the high-entropy nano alloy electrocatalyst is in a single-phase structure. FIG. 3 (d) shows (Fe 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.35) SEM morphology of the high-entropy nano alloy on the foam nickel matrix is a blocky dendrite structure, which indicates that the microstructure of the high-entropy nano alloy does not have a nano lamellar structure when the Li doping content x=0.35. In FIG. 5 (Fe 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.35) electrocatalytic hydrogen evolution reaction test and oxygen evolution reaction test of high entropy nano alloy on foam nickel matrix. The composition of this example (Fe) was measured under alkaline conditions of 1mol/L KOH 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.35) the initial potential of the hydrogen evolution reaction of the high entropy nano alloy electrocatalyst is-0.121V, current density of 10mA/cm 2 The overpotential at the time was 39mV, the initial potential of the oxygen evolution reaction was 1.467V, and the current density was 10mA/cm 2 The overpotential was 246mV, and the electrocatalytic performance of the hydrogen evolution reaction and the oxygen evolution reaction was reduced as compared with the examples.
Through the comparison, the electrochemical performance of hydrogen evolution reaction and oxygen evolution reaction is the most excellent when x=0.25 along with the increase of the Li doping molar content, the morphology is the mutually staggered nano-flake microstructure, the mutually staggered nano-flake microstructure structure is favorable for increasing the reaction contact area with electrolyte, the electrochemical activity is further improved, and the thickness of the nano-flake is 20-35 nm.
For electrocatalytic hydrogen evolution reaction and oxygen evolution reaction, the concentration of the catalyst is 10mA/cm 2 The lower the corresponding overpotential of the electrocatalyst, the better the catalytic performance of the electrocatalyst, according to fig. 6, as the Li doping molar content increases, the performance of the electrocatalyst decreases instead at x=0.166, indicating that the electrocatalytic performance is not improved under the condition of doping equimolar Li in the component system; when x=0.25, the hydrogen evolution reaction performance of the electrocatalyst is improved by nearly one time compared with that of the electrocatalyst with x=0, and the oxygen evolution reaction performance is also improved to a certain extent; at x=0.35, the hydrogen evolution reaction and oxygen evolution reaction performance of the electrocatalyst are again degraded. The addition of Li to the component system can achieve the aim of regulating and controlling the catalytic performance of the electrocatalyst, namely, when the doping content of Li is x=0.25, the electrocatalytic performance of hydrogen evolution reaction and oxygen evolution reaction can be optimal.
In addition, according to the data content and experimental rules of fig. 6, when the Li doping content fluctuates in a small range in the preferred embodiment, that is, x=0.24-0.27, it is determined that the corresponding electrocatalyst still has excellent electrocatalytic performance of hydrogen evolution reaction and oxygen evolution reaction, and the Li doping content is also within the scope of patent protection.
The above description is only of the preferred embodiments of the present invention, and there is no limiting effect on the present invention, and various modifications and variations of the present invention will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A bifunctional high-entropy nano alloy electrocatalyst is characterized by comprising a porous foam nickel matrix and (Fe) electrodeposited and supported on the foam nickel matrix 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.24-0.27) high entropy nano alloy, wherein (Fe 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.24-0.27) the loading of the high-entropy nano alloy is 5-8 mg/cm 2 。
2. The bifunctional high-entropy nano alloy electrocatalyst according to claim 1, wherein the high-entropy nano alloy is in a cubic crystal system, fm-3m space group, and the nano microstructure is in a form of nano sheets interlaced with each other, and the thickness of the nano sheets is 20-35 nm.
3. The bifunctional high-entropy nano alloy electrocatalyst according to claim 1, wherein the porous foam nickel matrix has a porosity of not less than 98% and a pore size of 0.1-0.5 mm.
4. The bifunctional high-entropy nanoalloy electrocatalyst according to claim 1, wherein the high-entropy nanoalloy is (Fe 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x＝0.25)。
5. The bifunctional high-entropy nano-alloy electrocatalyst according to claim 4, wherein (Fe) under 1mol/L KOH alkaline conditions 1/5 Co 1/5 Ni 1/5 Cu 1/5 Zn 1/5 ) 1-x Li x (x=0.25) the initial potential of the hydrogen evolution reaction of the bifunctional high-entropy nano alloy electrocatalyst is-0.105V, and the current density is 10mA/cm 2 The overpotential at the time is 26mV, the initial potential of oxygen evolution reaction is 1.44V, and the current density is 10mA/cm 2 The overpotential at this time was 224mV.
6. The method for preparing the bifunctional high-entropy nano alloy electrocatalyst according to any one of claims 1 to 5, comprising the steps of:
step 1, precursor solution configuration:
according to the mole ratio of metal ions of Fe 3+ ：Co 2+ ：Ni 2+ ：Cu 2+ ：Zn 2+ =1: 1:1:1:1: (1.6-1.8) weighing the corresponding FeCl 3 ·6H 2 O、CoCl 2 、NiCl 2 ·6H 2 O、CuCl 2 ·6H 2 O、ZnCl 2 Mixing LiCl, dissolving in deionized water, sealing, mixing and stirring uniformly to obtain uniformly mixed electrolyte;
step 2, preparing a high-entropy nano alloy:
(1) Regulating the pH value of the electrolyte obtained in the step 1 to 4-4.5, and heating to 40-50 ℃;
(2) A three-electrode system is adopted, porous foam nickel is used as a working electrode, a graphite rod is used as a counter electrode, and the counter electrode is clamped and placed into electrolyte;
(3) Using constant potential electrodeposition, wherein the deposition potential is-0.2+/-0.02V, and the deposition time is 850-900 s;
(4) And after the deposition is finished, repeatedly washing the foam nickel matrix deposited with the high-entropy nano alloy for a plurality of times, and naturally drying in air to obtain the dual-function high-entropy nano alloy electrocatalyst uniformly deposited on the foam nickel matrix.
7. The method for preparing the bifunctional high-entropy nano alloy electrocatalyst according to claim 6, wherein FeCl 3 ·6H 2 O concentration is 0.1mol/L, coCl 2 The concentration is 0.1mol/L, niCl 2 ·6H 2 The concentration of O is 0.1mol/L, and CuCl 2 ·6H 2 O concentration is 0.1mol/L, znCl 2 The concentration was 0.1mol/L, and the LiCl concentration was 0.166mol/L.
8. The method for preparing the bifunctional high-entropy nano alloy electrocatalyst according to claim 6, wherein in step 2 (1), the method for adjusting pH value is: maintaining the stirring rotation speed at 200-300 rpm, sucking ammonia water or 0.1mol/L dilute hydrochloric acid by using a liquid-transfering gun, and slowly regulating the pH value of the electrolyte to 4-4.5.
9. The method for preparing a bifunctional high-entropy nano-alloy electrocatalyst according to claim 6, wherein in step 2 (2), the porous foam nickel substrate used has a size of 20mm×10mm×0.8mm; the porous foam nickel is subjected to ultrasonic pretreatment for 3-5 min by 0.5mol/L dilute hydrochloric acid, repeatedly washed three times by deionized water and absolute ethyl alcohol, and kept stand and dried in air.
10. The method for preparing a bifunctional high-entropy nano-alloy electrocatalyst according to claim 6, wherein in step 2 (3), before the deposition process, the working electrode clamp and the reference electrode clamp are simultaneously clamped to the working electrode, and the foamed nickel substrate is placed 1-1.5 cm below the electrolyte level while maintaining a separation distance of 2-2.5 cm from the graphite rod.
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