CN113097511B - Ni(OH)2/ZrO2Preparation method of heterostructure fuel cell cathode oxygen reduction catalyst - Google Patents

Ni(OH)2/ZrO2Preparation method of heterostructure fuel cell cathode oxygen reduction catalyst Download PDF

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CN113097511B
CN113097511B CN202110337446.3A CN202110337446A CN113097511B CN 113097511 B CN113097511 B CN 113097511B CN 202110337446 A CN202110337446 A CN 202110337446A CN 113097511 B CN113097511 B CN 113097511B
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fuel cell
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张蓉
李瑞敏
乔亚磊
张鼎
崔子祥
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Taiyuan University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
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    • 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
    • Y02E60/50—Fuel cells

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Abstract

The invention discloses a Ni (OH)2/ZrO2Heterostructure fuel cell cathode oxygen reduction catalystThe preparation method of the catalyst is ZrCl4With NiCl2Reacting in ethanol solution, washing the obtained mixture with absolute ethyl alcohol and distilled water, and drying to obtain Ni (OH)2/ZrO2Crude product of Ni (OH)2/ZrO2Mixing the crude product with absolute ethyl alcohol in proportion, carrying out ultrasonic reaction for a period of time, washing and drying with absolute ethyl alcohol and distilled water to obtain Ni (OH)2/ZrO2A heterostructure catalyst. The invention adopts cheap and high-efficiency non-noble metal catalyst with wide resource distribution as raw material, has simple preparation method and stable structure, and has wide prospect in the industrial application of basic laboratories and fuel cells.

Description

Ni(OH)2/ZrO2Preparation method of heterostructure fuel cell cathode oxygen reduction catalyst
Technical Field
The invention belongs to the technical field of materials, and particularly relates to Ni (OH)2/ZrO2Method for preparing heterostructure material, prepared Ni (OH)2/ZrO2The heterostructure material is applied to a fuel cell cathode oxygen reduction catalyst.
Background
With the emergence of global energy crisis and environmental deterioration, the development of scientific, efficient, green and sustainable energy becomes the key point of research work of all countries in the world. Among the new energy sources developed, solar energy and wind energy have received a great deal of attention from the industry and the scientific research community due to their clean and renewable characteristics, and the supply of these energy sources is limited by day and night and seasonally, and can be supplied only intermittently or in limited areas. In order to avoid these problems of energy supply stability, the electrochemical energy storage and conversion technology has been the focus of scientific research, wherein the fuel cell is a device for directly converting the chemical energy of the fuel into the electric energy, the energy conversion efficiency is high, the conversion process is not limited by the carnot cycle, and the conversion process has no combustion and no noise and pollutant discharge. Since the cathode Oxygen Reduction Reaction (ORR) of a fuel cell requires more energy consumption due to its slow kinetics involving multi-step electron transfer, and directly affects the reaction rate of the fuel cell, a great deal of work is now being done by researchers to study a cathode oxygen reduction catalyst to increase the efficiency of the oxygen reduction reaction.
Among ORR catalysts, the noble metal Pt catalyst has excellent ORR catalytic activity due to the characteristic that the d-electron orbit is not filled, however, the high cost of Pt (the average price of Pt in 2020 is 30.21 g/us dollar), scarcity (37 ppb of Pt in earth's crust), susceptibility to poisoning by methanol make it difficult to be applied to fuel cells on a large scale. Then, a non-noble metal catalyst which is cheap, efficient, wide in resource distribution and strong in stability and can replace a noble metal Pt enters the sight of people, and 3d metals (Fe, Co, Mn and Ni) in a plurality of non-noble metals are widely applied to research of ORR catalysts. In particular Ni (OH)2The catalyst (average price of Ni of 0.018227 g/dollar in 2020) showed strong ORR and OER performance under alkaline conditions, but pure Ni (OH)2Has limited electrocatalytic properties, and some researches find that doping metal has a remarkable effect on improving the activity of the catalyst, wherein Ni (OH) after doping Fe2The catalyst has the most excellent electrocatalytic performance, which is attributed to the doping of metal Fe and Ni (OH)2Short Fe-O active bond is generated, partial charge transfer activation is performed, and Ni is inhibited2+To Ni3+/Ni4+Oxidation of (2). Similarly, Goddard III et al (Goddard III, J. Am. chem. Soc, 2018, 140, 22, 6745-2Has an exceptionally high electrocatalytic activity due to active sites with radical character on the metal-oxo (MO) bond O, and studies on 17 other transition metals (Co, Ti, Mn, Zr, Mo, Ru, W, Ir, etc.) with the same character in the +4 oxidation state, which may be useful for improving Ni (OH)2The electrocatalytic activity of the catalyst has the same effect. Subsequently, Yan Junqing et al (Junming Yan, Nat Commun, 2019,10, 2149) found W doped in Ni (OH)2Has higher electrocatalytic activity because of the 3d metal W4+The outer empty orbitals of (a) allow both OH cleavage and O-O bond formation at the W sites. Furthermore, Nivery et al (Ni J, Applied Catalysis B: Environmental, 2019, 253, 170-17) found ZrO2As a carrier, the electronic state of the supported metal can be effectively adjusted, because ZrO can be stabilized by doping with low-valent cations (Y, Sc, Ca, Mg or Ni)2And is ZrO2A large number of oxygen vacancies can trap negative electrons at the center of the catalyst, which is beneficial to controlling the catalytic performance. This provides a theoretical reference for the design of ORR catalysts.
In addition to improving the performance of catalysts by doping, some researchers also adopt morphological engineering, defect engineering and heterostructure engineering to optimize the electrocatalytic performance, wherein heterostructures are firstly proposed in 2013 by A.K. Geim et al, the principle is that a two-dimensional material is superposed on another two-dimensional material, the structure of the materials is kept unchanged and is connected by covalent bonds, and the layers are combined together by weak van der Waals force, but the van der Waals heterostructure is not the simple superposition of the materials, but integrates the advantages of the materials into a whole, thereby achieving the purpose of regulating and controlling the properties of the materials. Numerous studies have demonstrated that transition metal heterostructure catalysts achieve the goal of increasing catalyst activity by modulating electron transport and active site and heterostructure synergies, such as FeOOH/Co/FeOOH, Co (OH)2/PANI，MoS2/Ni3S2，Ni2P/NiP2Are synthesized to enhance electrocatalytic activity.
Therefore, designing a reasonable transition metal doped heterostructure catalyst is of great significance to the industrialization of fuel cells.
Disclosure of Invention
The invention aims to provide a preparation method of a fuel cell cathode oxygen reduction catalyst, which adopts a cheap and easily-obtained non-noble metal catalyst to prepare Ni (OH) with higher catalytic activity by a simple one-step alcohol heating method2/ZrO2The cathode oxygen reduction catalyst of the heterostructure fuel cell is used for overcoming the defects that the heterostructure oxygen reduction catalyst has high preparation cost,the preparation method is complex.
A kind of Ni (OH)2/ZrO2The preparation method of the heterostructure fuel cell cathode oxygen reduction catalyst comprises the following specific steps:
(1) respectively reacting ZrCl4And NiCl2Adding into ethanol according to a certain proportion, stirring to dissolve;
(2) then, the two solutions are uniformly mixed and then are moved into a reaction kettle, and the solvothermal reaction is carried out at a certain temperature;
(3) centrifuging the obtained product in a centrifuge at 9000rpm for 10-20 minutes, washing with water and ethanol for 4-6 times, and drying at 60-80 ℃ for a period of time;
(4) mixing Ni (OH)2/ZrO2Dissolving the crude product and ethanol in proportion, and carrying out ultrasonic stripping treatment;
(5) and centrifuging the mixture subjected to ultrasonic stripping in a centrifuge at 9000rpm for 10-20 minutes, and washing the obtained product with water and ethanol for 4-6 times. And finally, drying for a period of time at 60-80 ℃. The obtained sample is Ni (OH)2/ZrO2A heterostructure catalyst.
In the above technical solution, further, the additional technical features are as follows:
in step (1), ZrCl4The ratio of the alcohol to the NiCl is 0.01: 1-0.1: 1(g/ml)2The ratio of the alcohol to the alcohol is 0.01: 1-0.2: 1(g/ml), and the stirring time is 10-30 min.
In the step (2), the reaction temperature is 130-210 ℃, and the reaction time is 6-18 h.
In step (4), Ni (OH)2/ZrO2The ratio of the crude product to the ethanol is 0.01: 1-0.3: 1(g/ml), and the ultrasonic time is 0-12 h.
Ni (OH) provided by the method of the invention2/ZrO2Heterostructure materials have the following advantages:
1. the invention adopts Ni (OH) prepared by a one-step alcohol heating method2/ZrO2Heterostructure catalyst, suppression of Ni2+The oxidation of (2) stabilizes O radicals and exposes more active sitesThe preparation cost is low, the preparation method is simple, the operation is easy, and the method is suitable for industrial production.
2. The raw materials adopted by the invention are non-noble metal catalysts which are cheap and efficient, have wide resource distribution and strong stability, and the cost of the cathode oxygen reduction catalyst of the fuel cell is saved.
3. The heterostructure catalyst prepared by the invention improves the activity of the catalyst by adjusting the electron transfer and the active site and the synergistic effect of the heterostructure.
The invention has reasonable design, adopts cheap and high-efficiency non-noble metal catalyst with wide resource distribution as raw material, has simple preparation method and stable structure, and has wide prospect in the industrial application of basic laboratories and fuel cells.
Drawings
FIG. 1a shows the catalyst Ni (OH) prepared in the preferred embodiment of the present invention2/ZrO2-scanning electron microscopy pictures at 150 ℃ (T) -12h (T) -6h (ut).
FIG. 1b shows the catalyst Ni (OH) prepared in the preferred embodiment of the present invention2/ZrO2-high resolution transmission electron microscopy images at 150 ℃ (T) -12h (T) -6h (ut).
FIG. 2 shows Ni (OH) as a catalyst obtained in example 1 of the present invention2/ZrO2-linear scanning voltammogram of electrocatalytic oxygen reduction at T (where T =130 ℃, 150 ℃, 170 ℃, 190 ℃, 210 ℃).
FIG. 3 shows Ni (OH) as a catalyst obtained in example 1 of the present invention2/ZrO2Tafel slope plot for electrocatalytic oxygen reduction at T (where T =130 ℃, 150 ℃, 170 ℃, 190 ℃, 210 ℃).
FIG. 4 shows Ni (OH) as a catalyst obtained in example 2 of the present invention2/ZrO2-t (where t =3h, 6h, 9h, 12h, 24 h) linear scan voltammogram of electrocatalytic oxygen reduction.
FIG. 5 shows Ni (OH) as a catalyst obtained in example 2 of the present invention2/ZrO2-t (where t =3h, 6h, 9h, 12h, 24 h) tafel slope plot of electrocatalytic oxygen reduction.
FIG. 6 shows Ni (O) catalyst obtained in example 3 of the present inventionH)2/ZrO2-Ut (where Ut =0h, 3h, 6h, 9h, 12 h) linear scan voltammogram of electrocatalytic oxygen reduction.
FIG. 7 shows Ni (OH) as a catalyst obtained in example 3 of the present invention2/ZrO2-Ut (where Ut =0h, 3h, 6h, 9h, 12 h) tafel slope plot of electrocatalytic oxygen reduction.
Detailed Description
The following provides a detailed description of specific embodiments of the present invention.
Example 1
A kind of Ni (OH)2ZrO2The preparation method of the heterostructure fuel cell cathode oxygen reduction catalyst comprises the following steps:
0.75g of ZrCl4And 0.2g of NiCl2Respectively adding the mixture into 50ml of ethanol and 20ml of ethanol, stirring the mixture until the mixture is dissolved, uniformly mixing the mixture and the ethanol, transferring the mixture into a reaction kettle, and carrying out solvothermal reaction at a certain temperature T (T =130 ℃, 150 ℃, 170 ℃, 190 ℃, 210 ℃) for 12 hours. And centrifuging the reaction mixture in a centrifuge at 9000rpm for 10-20 minutes, washing the obtained product with water and ethanol for 4-6 times, and drying at 60-80 ℃ for a period of time. 0.1g of the dried crude product was added to 40ml of ethanol and the mixture was sonicated in a sonicator for 6 h. And centrifuging the mixture subjected to ultrasonic stripping in a centrifuge at 9000rpm for 10-20 minutes, and washing the obtained product with water and ethanol for 4-6 times. And finally, drying for a period of time at 60-80 ℃.
The obtained sample is Ni (OH)2/ZrO2Heterostructure catalysts, labelled Ni (OH)2/ZrO2-T, wherein T =130 ℃, 150 ℃, 170 ℃, 190 ℃, 210 ℃.
Example 2
A kind of Ni (OH)2ZrO2The preparation method of the heterostructure fuel cell cathode oxygen reduction catalyst comprises the following steps:
0.75g of ZrCl4And 0.2g of NiCl2Respectively adding into 50ml ethanol and 20ml ethanol, stirring to dissolve, mixing, transferring into reaction kettle, performing solvent thermal reaction at 150 deg.C, and maintaining t: (t =3h, 6h, 9h, 12h, 24 h). And centrifuging the reaction mixture in a centrifuge at 9000rpm for 10-20 minutes, washing the obtained product with water and ethanol for 4-6 times, and drying at 60-80 ℃ for a period of time. 0.1g of the dried crude product was added to 40ml of ethanol and the mixture was sonicated in a sonicator for 6 h. And centrifuging the mixture subjected to ultrasonic stripping in a centrifuge at 9000rpm for 10-20 minutes, and washing the obtained product with water and ethanol for 4-6 times. And finally, drying for a period of time at 60-80 ℃.
The obtained sample is Ni (OH)2/ZrO2Heterostructure catalyst, labelled ni (oh)2/ZrO2-t, where t =3h, 6h, 9h, 12h, 24 h.
Example 3
A kind of Ni (OH)2ZrO2The preparation method of the heterostructure fuel cell cathode oxygen reduction catalyst comprises the following steps:
0.75g of ZrCl4And 0.2g of NiCl2Respectively adding the mixture into 50ml of ethanol and 20ml of ethanol, stirring the mixture until the mixture is dissolved, uniformly mixing the mixture and the ethanol, transferring the mixture into a reaction kettle, and carrying out solvothermal reaction at 150 ℃ for 12 hours. And centrifuging the reaction mixture in a centrifuge at 9000rpm for 10-20 minutes, washing the obtained product with water and ethanol for 4-6 times, and drying at 60-80 ℃ for a period of time. 0.1g of the dried crude product was added to 40ml of ethanol and the mixture was sonicated in a sonicator for Ut hours (Ut =0h, 3h, 6h, 9h, 12 h). And centrifuging the mixture subjected to ultrasonic stripping in a centrifuge at 9000rpm for 10-20 minutes, and washing the obtained product with water and ethanol for 4-6 times. And finally, drying for a period of time at 60-80 ℃.
The obtained sample is Ni (OH)2/ZrO2Heterostructure catalysts, labelled Ni (OH)2/ZrO2-Ut, wherein Ut =0h, 3h, 6h, 9h, 12 h.
By Ni (OH) prepared in example 12/ZrO2-T (FIGS. 2 and 3), Ni (OH) produced in example 22/ZrO2T (FIGS. 4 and 5) and Ni (OH) produced in example 32/ZrO2Linear Sweep Voltammogram (LSV) and Tafel slope plot of Ut (FIGS. 6 and 7)(Tafel slope) shows that with the increase of reaction temperature, reaction time and ultrasonic time, the LSV curve has no obvious change rule, but in Ni (OH)2/ZrO2At 150 ℃ (T) -12h (T) -6h (Ut), it has the maximum initial potential (E)onset) 0.84V, half-wave potential (E)1/2) 0.71V, number of transferred electrons (n) 3.68 and current density 3.88mA cm-2This all shows the heterostructure Ni (OH)2/ZrO2-150 ℃ (T) -12h (T) -6h (ut) have extremely excellent ORR performance. Also, to evaluate ORR kinetics, Tafel slope was estimated by Tafel equation, Ni (OH)2/ZrO2-150 ℃ (T) -12h (T) -6h (Ut) having a minimum Tafel slope of 57mV dec compared to catalysts under other reaction conditions-1This represents Ni (OH)2/ZrO2-150 ℃ (T) -12h (T) -6h (ut) have rapid ORR kinetics. Although the reaction temperature, the reaction time and the ultrasonic time have a certain influence on the oxygen reduction catalytic activity of the catalyst, the heterostructure Ni (OH) was observed at T =150 ℃, T =12h and Ut =6h2/ZrO2The catalytic activity is the best.
FIGS. 1a and 1b show Ni (OH)2/ZrO2-scanning electron microscopy and high resolution transmission electron microscopy of-150 ℃ (T) -12h (T) -6h (ut). From FIG. 1a it is evident that Ni (OH)2/ZrO2Has a structure of nanoparticles. In the meantime, in Ni (OH)2/ZrO2On the nanoparticles of (a), the lattice distances d of 0.212nm and 0.250nm detected by high-resolution transmission electron microscopy are attributable to ZrO2The (112) and (200) planes of (A), and lattice distances d of 0.176 nm, 0.228 nm and 0.218 nm detected are directed to Ni (OH)2The (102) crystal plane (101) and the (002) crystal plane of (A). Thus, the overall results of SEM and TEM analyses confirmed Ni (OH)2/ZrO2Is a heterostructure nanoparticle.
The performance of the catalysts prepared in examples 1-3 above was tested by the following test methods:
the electrode preparation method was the same for all samples studied, first, Glassy Carbon (GC) electrodes were made with alpha-Al2O3Powder polishingThe mixture is cleaned by absolute ethyl alcohol and distilled water in an ultrasonic way. Then, 5mg of the catalyst, 5mg of acetylene black and 3. mu.L of Nafion solution were mixed, dispersed in 0.7mL of isopropanol and 0.3mL of deionized water, and sonicated for 1h in an ice bath to form a uniform ink. Finally, 5 μ L of the ink was dropped onto the dried GC electrode and allowed to dry naturally at room temperature.
All electrochemical tests were performed on CHI660E electrochemical workstation in Chenghua, supra, a three-electrode system at room temperature using a GC electrode (4 mm diameter) as the working electrode, an Ag | AgCl/KCl (saturated) electrode as the reference electrode, and a platinum sheet electrode (10X 0.2 mm) as the counter electrode. Calibrating all potentials to be according to the equationE RHE=E Ag/AgCl+ (0.197+0.059pH) V, calculated Reversible Hydrogen Electrode (RHE), all polarization curves were corrected using iR compensation. For Linear Sweep Voltammetry (LSV), the voltage is in the range of 0-1V, and 0.01V s-1Is measured. To maintain O2Saturation, before electrochemical testing, O2At a rate of 100ml min-1Was bubbled in 0.1M KOH electrolyte for 15 minutes at 20ml min during LSV-1The flow rate of (3) was bubbled.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the detailed description is made with reference to the embodiments of the present invention, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which shall be covered by the claims of the present invention.

Claims (7)

1. A kind of Ni (OH)2/ZrO2The preparation method of the heterostructure fuel cell cathode oxygen reduction catalyst is characterized in that: the method comprises the following steps:
(1) respectively reacting ZrCl4And NiCl2Adding into ethanol, stirring to dissolve;
(2) then, the two solutions are uniformly mixed and then are moved into a reaction kettle, and the solvothermal reaction is carried out at a certain temperature;
(3) centrifuging the obtained product, washing with water and ethanol for 4-6 times, and drying at 60-80 ℃;
(4) the Ni (OH) obtained in the step (3)2/ZrO2Dissolving the crude product and ethanol in proportion, and carrying out ultrasonic stripping treatment;
(5) centrifuging the mixture after ultrasonic stripping, and washing the obtained product with water and ethanol for 4-6 times; finally, drying at 60-80 ℃ to obtain a sample which is Ni (OH)2/ZrO2A heterostructure catalyst.
2. The Ni (OH) of claim 12/ZrO2The preparation method of the heterostructure fuel cell cathode oxygen reduction catalyst is characterized in that: in the step (1), ZrCl is added into each ml of ethanol4The mass is 0.01-0.1 g, and NiCl is added into each ml of ethanol2The mass is 0.01-0.2 g, and the stirring time is 10-30 min.
3. The Ni (OH) of claim 1 or 22/ZrO2The preparation method of the heterostructure fuel cell cathode oxygen reduction catalyst is characterized in that: in the step (2), the reaction temperature is 130-210 ℃, and the reaction time is 6-18 h.
4. The Ni (OH) of claim 32/ZrO2The preparation method of the heterostructure fuel cell cathode oxygen reduction catalyst is characterized in that: in the step (4), Ni (OH) is added into each 100ml of ethanol2/ZrO20.25g of crude product, and the ultrasonic time is 0-12 h.
5. The Ni (OH) of claim 22/ZrO2The preparation method of the heterostructure fuel cell cathode oxygen reduction catalyst is characterized in that: ZrCl is added into each 100ml of ethanol4The mass is 1.5g, NiCl is added into each 10ml of ethanol2The mass was 0.1 g.
6. According to claim 3Said Ni (OH)2/ZrO2The preparation method of the heterostructure fuel cell cathode oxygen reduction catalyst is characterized in that: in the step (2), the reaction temperature is 150 ℃, and the reaction time is 12 h.
7. The Ni (OH) of claim 42/ZrO2The preparation method of the heterostructure fuel cell cathode oxygen reduction catalyst is characterized in that: in the step (4), the ultrasonic time is 6 h.
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