CN113130917B - Construction method of electrocatalytic oxidation ethanol fuel cell - Google Patents
Construction method of electrocatalytic oxidation ethanol fuel cell Download PDFInfo
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- CN113130917B CN113130917B CN201911410253.5A CN201911410253A CN113130917B CN 113130917 B CN113130917 B CN 113130917B CN 201911410253 A CN201911410253 A CN 201911410253A CN 113130917 B CN113130917 B CN 113130917B
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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
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
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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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8853—Electrodeposition
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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
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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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
- Y02E60/50—Fuel cells
Abstract
The invention belongs to the technical field of fuel cells, and provides a construction method of an electrocatalytic oxidation ethanol fuel cell. The invention relates to an ethanol fuel cell which is formed by assembling a three-dimensional flower-shaped gold-nickel-platinum modified nano composite electrode as an anode, a platinum electrode as a cathode and ethanol as an electrolyte solution. The method has the advantages of high theoretical energy density, low toxicity, low cost, wide sources and the like by adopting ethanol as the fuel, has the advantages of low noble metal platinum loading capacity, low cost and high catalytic activity by adopting the Au-Ni-Pt multi-metal nano electrode as the anode, can be widely applied to small and medium power supplies such as automobile power, portable power supplies and the like, and has wide market prospect.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a construction method of an electrocatalytic oxidation ethanol fuel cell.
Background
In the 21 st century, people are confronted with ever-increasing environmental pollution problems and energy crisis. In one aspect, a large amount of harmful gases released by the combustion of fossil fuels, including, NO X 、SO X And various inhalable particles cause huge damage to the environment, and cause worry about the survival condition of people. On the other hand, the development of human economy and society is hindered by energy problems such as the drastic increase of the exploitation amount of fossil fuels, the decline of reserves, the increase of the difficulty of the exploitation and the like. This has led to a schedule for efficient, clean alternative energy research. In order to reduce the dependence on fossil energy and improve the quality of life, on the one hand, efforts are made to develop and utilize renewable energy sources, such as solar energy, wind energy, hydraulic energy, geothermal energy, biological energy and the like, according to local conditions. On the other hand, the utilization efficiency of the existing energy is to be improved. The efficiency is improved, the demand for energy can be reduced under the condition of not reducing the quality of life, and the emission of pollutants is reduced. The fuel cell is used as an energy conversion device and can directly convert chemical energy of fuel into electric energy. Because the method is not limited by the Carnot efficiency, the method has higher energy efficiency and can achieve the purpose of effectively utilizing resources.
Disclosure of Invention
In order to make up for the defects of the prior art, the invention provides a construction method of an electrocatalytic oxidation ethanol fuel cell.
The invention has the following inventive concept: the constructed Au-Ni-Pt/carbon nanotube sponge anode is connected with the cathode through a lead and inserted into an ethanol solution to spontaneously react and oxidize ethanol, so that the conversion of biomass energy to electric energy is realized, electrons generated by the anode are transferred onto the cathode through the lead, oxygen is reduced into hydroxyl ions, and the storage of the electric energy is realized.
A construction method of an electrocatalytic oxidation ethanol fuel cell comprises the following steps:
(1) Cutting carbon nanotube sponge into proper size;
(2) Performing flower-like nano-gold deposition on the modified carbon nano-tube sponge electrode by adopting an electrochemical method:
taking carbon nanotube sponge as a working electrode, a Pt electrode as a counter electrode, ag/AgCl as a reference electrode, setting the voltage to be-0.2V by adopting a time-current method, depositing 400-1600 s, and taking a sodium hydroxide solution with the concentration of 0.1mol/L as an electrolyte solution to obtain an Au/carbon nanotube sponge electrode;
(3) Preparing an Au-Ni-Pt/carbon nano tube sponge electrode with a multistage nano structure by using a time-current method, and taking the Au-Ni-Pt/carbon nano tube sponge electrode as a fuel cell anode for standby:
using Au/carbon nano tube sponge electrode as a working electrode, pt electrode as a counter electrode, ag/AgCl as a reference electrode, using a mixed solution of gold, nickel and platinum as an electrolyte solution, setting the voltage to-0.2V, and depositing for 400-1600 s
(4) Adopting a platinum electrode to form a fuel cell cathode;
(5) And connecting the prepared anode and the prepared cathode through a lead, and inserting the anode and the cathode into an ethanol solution to construct the electrocatalytic oxidation ethanol fuel cell.
Further, in the step (5), a sodium hydroxide solution with the concentration of 0.1mol/L is added into the anode pool as an electrolyte solution, ethanol with the concentration of 0.1mol/L is added into the cathode pool as a fuel, an ethanol solution with the concentration of 0.1mol/L and the pH value of 8-14 is added into the anode pool, and the two pools are connected by an anion exchange membrane, so that the electrocatalytic oxidation ethanol fuel cell is constructed and formed.
Further, the step (1) is specifically as follows: pretreatment of an electrode substrate: firstly, cutting the carbon nanotube sponge into 2 x 2cm cubes with the thickness of 0.2 mm.
Further, the step (3) is to configure the electrolyte solution: diluting the sulfuric acid solution to 0.5mol/L, dissolving a certain amount of solid potassium chloroaurate, nickel sulfate and potassium tetrachloroplatinate in the sulfuric acid solution to prepare a mixed solution of gold, nickel and platinum with the concentration of 3mg/mL, and standing for one day.
The method also comprises the step (6) of testing the performance of the ethanol fuel cell:
an Au-Ni-Pt/carbon nano tube sponge anode is taken as a working electrode, a Pt electrode is taken as a counter electrode, ag/AgCl is taken as a reference electrode, the working electrode is inserted into an ethanol solution with the concentration of 0.1mol/L, a cyclic voltammetry method is adopted, the voltage range is set to be 0V-1.2V, and the sweep rate is 50mV/s.
The function and the advantage of adopting ethanol as fuel in the invention are as follows: in the fuel cell, the alcohol fuel cell takes cheap and easily available alcohol as fuel, the fuel is liquid at normal temperature and normal pressure, compared with other fuel cells, the alcohol fuel cell has the advantages of safety, reliability, high energy density, low operation temperature, no electrolyte corrosion, and the like, and in addition, the alcohol fuel has wide sources, is cheap and easily available, and can be synthesized by fossil fuels such as petroleum, natural gas, coal and the like and also can be prepared by fermentation of biomass. Compared with other alcohols, ethanol is the simplest small organic molecule in chain alcohol in structure, can be produced in large quantities through crop fermentation, can also be prepared from biomass, has wide sources, is a renewable energy source, and is nontoxic. Therefore, the research of ethanol fuel cells has great application potential.
The gold-nickel-platinum modified nano composite electrode has a non-close-packed three-dimensional structure and a finer two-level flower-shaped nano structure on the basis of the three-dimensional structure, and the multi-level nano structure ensures that the surface of the electrode has a very high specific surface area; meanwhile, the electrode is composed of three metals, the nano golden flower is used as a basic framework, non-precious metal nickel is deposited, and finally platinum is used for replacing the nickel, so that the noble metal platinum loading capacity is low, the cost of the electrode is reduced, and the catalytic activity of nano platinum particles is improved. This electrode has = high catalytic efficiency and poisoning resistance in electrochemical catalytic oxidation of ethanol.
Compared with the prior art, the electrode with high sensitivity to ethanol is prepared, and when ethanol is used as a base liquid, the electrode has the advantages of good catalytic effect, high sensitivity, good selectivity, stable structure and the like.
Drawings
FIG. 1 is a schematic diagram of a three-dimensional structure of an electrocatalytic oxidation ethanol fuel cell;
FIG. 2 is a cyclic voltammogram of catalytic oxidation of ethanol by an Au-Ni-Pt electrode; wherein, the curve shown in the figure is a cyclic voltammogram of the Au-Ni-Pt nano composite electrode in ethanol (0.1M, 0.2M,0.3M,0.4M, 0.5M) with different concentrations at a scanning speed of 50 mV/s;
FIG. 3 is a linear plot of cyclic voltammetry of catalytic oxidation of ethanol by Au-Ni-Pt modified electrode;
FIG. 4 is a drawing of an experimental setup; wherein, the figure a is a test object figure; FIG. b is an electrochemical workstation; FIG. c is a schematic diagram of a three-electrode system;
FIG. 5 is a nano-metal deposition curve; where a is a 400s curve, b is an 800s curve, and c is a 1600s curve.
Detailed Description
The present invention will be described in further detail with reference to specific examples. According to the design purpose of the invention, simple substitution of the same kind of substances and change of the size and shape, such as changing the appearance of the electrode into a square shape or other shapes, simply changing the dosage of potassium chloroaurate, nickel sulfate, potassium tetrachloroplatinate, the value of the solution, the concentration of the solution or the deposition time, and the like, simply changing the application of the electrode, and the like, all belong to the test methods used in the following examples in the scope of the invention, and if no special description exists, all are materials, reagents and the like used in the conventional methods in the technical field, and if no special description exists, all are commercially available reagents and materials.
The Au-Ni-Pt/carbon nanotube sponge electrode of the embodiment is prepared by the following method:
(1) The carbon nanotube sponge conductive glass is used as a substrate, and the carbon nanotube sponge is cut into cubes with the thickness of 0.2mm at 2 x 2cm.
(2) Performing flower-shaped nano gold deposition on the carbon nano tube sponge electrode obtained in the step (1) by adopting an electrochemical method: and setting the voltage to be minus 0.2V and depositing for 400s to 1600s by taking an Au/carbon nanotube sponge electrode as a working electrode, a Pt electrode as a counter electrode, ag/AgCl as a reference electrode and a mixed solution of gold, nickel and platinum as an electrolyte solution. As shown in fig. 4.
When the gold deposition conditions are different, the shapes of the final multi-stage Au-Ni-pt alloy nanoflowers are changed due to the fact that the grain sizes of the nano golden flowers are different. The reason is that the time for depositing gold is long, the formed nano golden flowers are dense, the interatomic self-assembly effect is obvious, and the similar small aggregations can be connected with each other; on the contrary, when the deposition time is shorter, the distance between the nano golden flowers is sparser, so that the aggregates formed by self-assembly of atoms are more regularly and uniformly distributed. When the nano particle aggregates on the composite electrode are uniformly distributed, the electrochemical performance is particularly outstanding.
EXAMPLE 1 construction of an electrocatalytic Oxidation of ethanol Fuel cell
Taking an Au-Ni-Pt/carbon nano tube sponge electrode as an anode and a Pt electrode as a cathode; adding a sodium hydroxide solution with the concentration of 0.1mol/L into an anode pool as an electrolyte solution, adding ethanol with the concentration of 0.1mol/L into a cathode pool as a fuel, adding an ethanol solution with the concentration of 0.1mol/L and the pH value of 8-14 into the cathode pool, and connecting the two pools by an anion exchange membrane to construct the electrocatalytic oxidation ethanol fuel cell. As shown in the attached figure 1, the prepared anode and a platinum electrode are connected through a lead and inserted into an ethanol solution to construct an electrocatalytic oxidation ethanol fuel cell.
Example 2 electrocatalytic oxidation of ethanol Fuel cell Performance testing
Testing of the performance of the electrocatalytic oxidation ethanol fuel cell constructed in example 1: an electrochemical workstation is used, firstly, a circuit is connected, the modified anode is used as a working electrode, the cathode of the battery is used as a counter electrode, and the Ag/AgCl electrode is used as a contrast electrode. The catalytic activity of the cyclic voltammetry test electrode on ethanol is determined, and after the initial stable potential of the electrode is determined, a proper termination potential and a proper scanning rate are selected, so that the cyclic voltammetry curve of the electrode is obtained by scanning. The catalytic effect of the Au-Ni-Pt electrode in a 0.1mol/L,0.2mol/L,0.3mol/L,0.4mol/L,0.5mol/L ethanol solution was tested at a scan rate of 50mV/s. As shown in fig. 2 and fig. 3. As can be seen from the figure, with the continuous increase of the concentration of the ethanol solution, the oxidation current of the nano electrode in the ethanol solution is also continuously increased, the oxidation peak is also continuously increased, and the good linear response of catalyzing ethanol is presented. The highest can reach 27mA, and the Au-Ni-Pt electrode has good catalytic activity on ethanol. The fuel composed of the Au-Ni-Pt/carbon nano tube sponge electrode can efficiently convert the biological energy into the electric energy.
EXAMPLE 3 product detection
The method for detecting the ethanol oxidation product of the electrocatalytic ethanol oxidation fuel cell constructed in the example 1 on the Au-Ni-Pt/carbon nanotube sponge electrode comprises the following specific operation steps: the electrocatalytic oxidation ethanol fuel cell constructed in example 1 uses 0.1mol/L ethanol and reacts for two hours to obtain ethanol oxidation products. Detecting the product with ultraviolet-visible spectrophotometer, and deducing the product when the functional group is changed.
While the invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (4)
1. A construction method of an electrocatalytic oxidation ethanol fuel cell is characterized by comprising the following steps:
(1) Cutting carbon nanotube sponge into proper size;
(2) Performing flower-like nano-gold deposition on the modified carbon nano-tube sponge electrode by adopting an electrochemical method:
the method comprises the steps of taking carbon nano tube sponge as a working electrode, a Pt electrode as a counter electrode and Ag/AgCl as a reference electrode, setting the voltage to be-0.2V by adopting a time-current method, and depositing a sodium hydroxide solution with the concentration of 0.1mol/L for 400-1600 s to be used as an electrolyte solution to obtain an Au/carbon nano tube sponge electrode;
(3) Preparing an Au-Ni-Pt/carbon nano tube sponge electrode with a multi-stage nano structure by using a time-current method, and taking the Au-Ni-Pt/carbon nano tube sponge electrode as a fuel cell anode for standby:
setting the voltage to be minus 0.2V and depositing for 400s to 1600s by taking an Au/carbon nanotube sponge electrode as a working electrode, a Pt electrode as a counter electrode, ag/AgCl as a reference electrode and a mixed solution of gold, nickel and platinum as an electrolyte solution;
(4) Adopting a platinum electrode to form a fuel cell cathode;
(5) Connecting the prepared anode and the prepared cathode through a lead, inserting the anode and the cathode into an ethanol solution, and constructing an electrocatalytic oxidation ethanol fuel cell; in the step (5), a sodium hydroxide solution with the concentration of 0.1mol/L is added into an anode pool to serve as an electrolyte solution, ethanol with the concentration of 0.1mol/L is added into a cathode pool to serve as a fuel, an ethanol solution with the concentration of 0.1mol/L and the pH value of 8-14 is added into the cathode pool, and the two pools are connected through an anion exchange membrane, so that the electrocatalytic oxidation ethanol fuel cell is constructed and formed.
2. The method according to claim 1, wherein the step (1) is specifically: pretreatment of an electrode substrate: firstly, cutting the carbon nanotube sponge into 2 x 2cm cubes with the thickness of 0.2 mm.
3. The method as set forth in claim 1, wherein the step (3) of preparing the electrolyte solution comprises: diluting the sulfuric acid solution to 0.5mol/L, dissolving a certain amount of solid potassium chloroaurate, nickel sulfate and potassium tetrachloroplatinate in the sulfuric acid solution to prepare a mixed solution of gold, nickel and platinum with the concentration of 3mg/mL, and standing for one day.
4. The method of claim 1, further comprising the step (6) of testing the performance of the ethanol fuel cell:
an Au-Ni-Pt/carbon nano tube sponge anode is taken as a working electrode, a Pt electrode is taken as a counter electrode, ag/AgCl is taken as a reference electrode, the working electrode is inserted into an ethanol solution with the concentration of 0.1mol/L, a cyclic voltammetry method is adopted, the voltage range is set to be 0V-1.2V, and the sweep rate is 50mV/s.
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| CN102806093B (en) * | 2012-08-31 | 2014-07-09 | 重庆大学 | Preparation method of high-efficiency low-platinum catalyst for direct methanol fuel cell |
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