CN113097495B - Preparation method of Au-Ni-Pt alloy modified anode - Google Patents

Preparation method of Au-Ni-Pt alloy modified anode Download PDF

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CN113097495B
CN113097495B CN201911339876.8A CN201911339876A CN113097495B CN 113097495 B CN113097495 B CN 113097495B CN 201911339876 A CN201911339876 A CN 201911339876A CN 113097495 B CN113097495 B CN 113097495B
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electrode
adhesive tape
modified
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solution
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CN113097495A (en
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孙晶
孟维琛
廖思蓓
宋雪
郎明非
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Dalian University
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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
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • 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
    • 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
    • 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
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes
    • 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

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  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
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Abstract

A preparation method of an Au-Ni-Pt alloy modified anode belongs to the field of new energy. The method takes adhesive tape (10 multiplied by 20mm) as a substrate, a layer of PDMS is coated on the surface of the adhesive tape, after the adhesive tape is dried, a layer of gold-carbon nanotube is dripped on the surface of the adhesive tape for modification, and nickel and platinum metals are deposited on the surface of a self-made electrode through a one-step electrodeposition method, so that the Au-Ni-Pt nano alloy modified electrode is prepared. The electrode is modified by the nano noble metal, and the Pt-Au load is low due to the good catalytic effect of the noble metal, so that the cost of the electrode is low. And the microstructure of the electrode is a flower-shaped nano multidimensional structure, so that the electrode has strong anti-poisoning capability and stable structure. The Au-Ni-Pt alloy nano modified electrode grown on the conductive adhesive tape is prepared, and is favorable for good utilization of energy.

Description

Preparation method of Au-Ni-Pt alloy modified anode
Technical Field
The invention belongs to the field of new energy, and particularly relates to a preparation method of an Au-Ni-Pt alloy modified anode.
Background
With the rapid increase of world economy, the consumption of human energy is increased, and the existing fossil energy cannot meet the requirements of human beings. And a fuel cell is a power generation device that directly converts chemical energy of a fuel and an oxidant into electrical energy through an electrochemical reaction. The fuel cell has many advantages in that it has high energy conversion efficiency compared to a conventional energy conversion system since it is not limited by the carnot cycle. It generally uses hydrogen as fuel, oxygen as oxidant and water as product, so that it has less environmental pollution. Because different types of fuel cells are applied to different occasions, the fuel cells have wide application. Based on this, currently, a large number of researchers around the world are engaged in the research of direct sugar fuel cells represented by glucose. Therefore, the preparation of the fuel cell anode with higher catalytic activity and stronger stability is the key to accelerate the realization of the industrialization of the fuel cell. At the present stage, biological enzymes are commonly used for the oxidation of glucose to produce fuel cell anodes with better oxidation activity. However, the enzyme cannot survive in a strongly acidic or strongly alkaline environment due to insufficient enzyme tolerance, and also cannot provide a stable current, and its application to fuel cells is limited due to the lack of an anode having high stability and high catalytic activity.
Disclosure of Invention
In view of the above disadvantages, the present invention provides a method for preparing an Au-Ni-Pt alloy modified anode, which has high stability and high catalytic activity.
The invention takes adhesive tape (10 multiplied by 20mm) as a substrate, a layer of PDMS is coated on the surface of the adhesive tape, after drying, a layer of modification liquid of gold-carbon nano tube is dripped on the surface of the adhesive tape, and nickel and platinum metals are deposited on the surface of a self-made electrode by a one-step electrodeposition method, thereby preparing the Au-Ni-Pt nano alloy modified electrode.
The invention relates to the following specific steps:
(1) cutting the adhesive tape into a specification of 10 multiplied by 20mm, coating a layer of PDMS mixed solution with the mass ratio of PDMS A solution to PDMS B solution being 10:1 on the surface of the adhesive tape, exhausting air bubbles, curing and then protecting with nitrogen for later use.
(2) Dissolving potassium chloroaurate and multi-walled carbon nanotubes in ultrapure water according to the mass ratio of 10: 1.
(3) And uniformly coating the mixed multi-wall carbon nanotube solution on the surface of the PDMS-modified adhesive tape according to a fixed amount, and naturally drying for later use.
(4) Preparing an Au-Ni-Pt/adhesive tape composite electrode: a three-electrode system is adopted, an adhesive tape modified by gold-multi-walled carbon nanotubes is used as a working electrode, an Ag/AgCl electrode and a platinum wire electrode are used as a reference electrode and a counter electrode, and the reference electrode and the counter electrode are placed in an electrolytic cell filled with a nickel sulfate solution. Setting electrodeposition parameters of an electrochemical workstation by adopting a constant current deposition method: voltage-1V, time 500 s. Immediately taking out the electrode, washing the electrode with deionized water for multiple times, quickly transferring the electrode into a newly-prepared potassium tetrachloroplatinate solution, adopting a cyclic voltammetry method, setting the voltage scanning range to be-0.7-0.8V, the scanning speed to be 100mV/s, and scanning for 20 circles. And (4) carrying out nitrogen protection on the modified electrode, and standing for three days for later use.
Has the advantages that:
the invention adopts the conductive adhesive tape as the electrode manufacturing material, the raw materials are cheap and easy to obtain, the gold nickel platinum ensures the high catalytic efficiency of the electrode on the maltose, and the oxidation current of the maltose is high;
the electrode is modified by the nano noble metal, and the Pt-Au load is low due to the good catalytic effect of the noble metal, so that the cost of the electrode is low. And the microstructure of the electrode is a flower-shaped nano multidimensional structure, so that the electrode has strong anti-poisoning capacity and stable structure. The Au-Ni-Pt alloy nano modified electrode grown on the conductive adhesive tape is prepared, and is favorable for good utilization of energy. The maltose is used as the base solution, and has the following advantages: increasing current response of an electrode to a detected object; promoting the reversibility of the reaction; thirdly, the detection limit of the detected object is reduced; fourthly, the sensitivity and the selectivity of the electrode are improved; separating catalyst, reactant and product; sixthly, adjusting the size and the positive and the negative of the electrode potential; and changing the direction of the electrochemical reaction. Compared with the conventional electrocatalysis, the electrochemical catalysis of the modified electrode can save more catalysts, and the surface of the electrode contains stronger active centers.
Drawings
Fig. 1 conductive surface characterization of the tape after pretreatment.
FIG. 2 representation of Au-Ni-Pt nanocomposite electrode.
Fig. 3 is the process of preparing the three-dimensional nanometer noble metal electrode.
FIG. 4 is a diagram of an experimental apparatus.
FIG. 5 is a diagram showing the catalytic results of cyclic voltammetry of Au-Ni-Pt alloy nano-modified electrodes in maltose solutions of different concentrations.
Detailed Description
The present invention will be described in further detail with reference to specific examples. For the purpose of the present invention, the shape and size of the electrode, the concentration of the base solution, the deposition time, the initial potential, etc. should be considered to fall within the scope of the present invention. Unless otherwise specified, all test methods used in the following examples are materials, reagents and the like used in conventional methods known in the art, and all reagents and materials are commercially available.
The RTV615 PDMS A and RTV615 PDMS B solutions of the examples were manufactured by Dalianmai.
Example 1: preparation of maltose fuel cell electrode
The working electrode Au-Ni-Pt alloy nano modified electrode of the embodiment is prepared by the following method.
An electrochemical workstation is utilized on the conduction of the self-assembled adhesive tape, a three-electrode system is utilized, the Au/adhesive tape with a nano structure is used as a working electrode, and an Ag/AgCl electrode and a platinum wire electrode are used as a reference electrode and a counter electrode and are placed in an electrolytic cell filled with a nickel sulfate solution. Setting electrodeposition parameters of an electrochemical workstation by adopting a chronoamperometry method: voltage-1V, time 500 s. Immediately taking out the electrode, washing the electrode with deionized water for multiple times, quickly transferring the electrode into a newly prepared 3mmol/L potassium tetrachloroplatinate solution, adopting a cyclic voltammetry method, setting the voltage scanning range to be-0.7-0.8V, the scanning speed to be 100mV/s, and scanning for 20 circles. And (4) carrying out nitrogen protection on the modified electrode, and standing for three days for later use.
The adhesive tape of the present example was obtained by the following method:
firstly, cutting the adhesive tape into a specification of 10 multiplied by 20mm, coating a layer of 10:1 PDMS mixed solution on the surface of the adhesive tape, exhausting air bubbles, curing and then protecting with nitrogen for later use. Then, potassium chloroaurate and multi-walled carbon nanotubes are dissolved in ultrapure water according to the mass ratio of 10: 1. And finally, uniformly coating the mixed multi-wall carbon nanotube solution on the surface of the PDMS-modified adhesive tape according to a fixed amount, and naturally drying for later use. As shown in fig. 3.
And (3) characterizing the electrochemical properties of the electrodes before and after self-assembly by using cyclic voltammetry. Electrodes before and after self-assembly were set at 0.05M H 2 SO 4 The cyclic voltammetry behavior of the solution was investigated. Potential: -0.6-1.2V, and the sweep rate is 100 mV/s. As shown in fig. 1 and 2. The conductivity of the adhesive tape before and after modification is obviously improved, and the electrochemical deposition is further facilitated.
Example 2: construction method of maltose fuel cell
KOH solutions with concentrations of 0.01, 0.1, 1 and 1.5mol/L are respectively prepared, and maltose solutions with concentrations of 0.01, 0.03, 0.05, 0.07 and 0.09mol/L are respectively prepared by using the KOH solutions with a series of concentration gradients as solvents.
The maltose fuel cell apparatus was selected using a three-electrode system with the Au-Ni-Pt alloy nano modified electrode prepared according to example 1 as the anode, Pt wire as the cathode, and saturated calomel electrode as the reference electrode, as shown in fig. 4. And respectively testing maltose solutions with different concentrations in the base solution, and carrying out catalytic oxidation reaction on the maltose solutions by using a cyclic voltammetry method. The cyclic voltammetry starting voltage was set at 2.3V and the scan rate was set at 120 mV/s.
Example 3: maltose fuel cell performance test
The performance test of the maltose fuel cell constructed in the example 2 comprises the following specific operation steps:
the maltose fuel cell constructed in example 2 was subjected to catalytic oxidation reaction using cyclic voltammetry. By the investigation, the cyclic voltammetry starting voltage was set to 2.3V and the scan rate was set to 120 mV/s.
Under the same cathode, the output voltage of the battery constructed by the low-potential anode is about 1.1V which is higher than that of the battery constructed by the unmodified anode by about 0.5V as seen from the output voltage graphs of different anodes with different deposited nano golden flowers at different time. As shown in fig. 5. Under the same cathode and anode, the concentration of maltose in the base solution is different, and the oxidation effect is best when the KOH concentration is 1mol/L and the maltose concentration is 0.06mol/L according to a cyclic voltammogram.
The electrochemical catalysis of the maltose fuel cell modified electrode can save catalyst, and the surface of the electrode contains stronger active centers. And experiments show that the noble metal modified electrode has good catalytic oxidation effect on maltose and the like, can improve the conversion rate of chemical energy, and promotes the development of fuel cells.
The equation for the maltose oxidation process is as follows:
C 12 H 22 O 11 ·H 2 O→2C 6 H 12 O 6
Figure BDA0002331968170000041
the above description is only for the purpose of illustrating the preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the technical scope disclosed in the present invention, and the technical solution and the inventive concept thereof should be covered by the scope of the present invention.

Claims (1)

1. A preparation method of an Au-Ni-Pt alloy modified anode is characterized by comprising the following steps:
s1, cutting an adhesive tape into a specification of 10 x 20mm, coating a layer of PDMS mixed solution on the surface of the adhesive tape, exhausting bubbles, curing and then protecting with nitrogen for later use;
s2, dissolving potassium chloroaurate and multi-walled carbon nanotubes in ultrapure water according to the mass ratio of 10: 1;
s3, uniformly coating the mixed multi-wall carbon nanotube solution on the surface of the PDMS-modified adhesive tape according to a fixed amount, and naturally drying for later use;
s4, preparing an Au-Ni-Pt/adhesive tape composite electrode: adopting a three-electrode system, taking an adhesive tape modified by a gold-multi-walled carbon nanotube as a working electrode, taking an Ag/AgCl electrode and a platinum wire electrode as reference electrodes and a counter electrode, and putting the reference electrodes and the counter electrode into an electrolytic cell filled with a nickel sulfate solution; setting electrodeposition parameters of an electrochemical workstation by adopting a constant current deposition method: voltage-1V and time 500 s; immediately taking out the electrode, washing with deionized water, quickly transferring to a newly prepared potassium tetrachloroplatinate solution with the concentration of 3mmol/L, adopting a cyclic voltammetry method, setting the voltage scanning range to be-0.7-0.8V, the scanning speed to be 100mV/s, scanning for 20 circles, carrying out nitrogen protection on the modified electrode, and standing for later use after three days.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002367434A (en) * 2001-06-08 2002-12-20 Daido Steel Co Ltd Corrosion resistant metal member and metal separator for fuel cell using the member
CN104091958A (en) * 2014-07-09 2014-10-08 哈尔滨工程大学 Preparation method of graphene-attached plastic supported AuCo sodium borohydride electro-oxidation catalyst
CN109298046A (en) * 2018-10-23 2019-02-01 大连大学 A kind of electrode and its application for alcohol catalysis

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002367434A (en) * 2001-06-08 2002-12-20 Daido Steel Co Ltd Corrosion resistant metal member and metal separator for fuel cell using the member
CN104091958A (en) * 2014-07-09 2014-10-08 哈尔滨工程大学 Preparation method of graphene-attached plastic supported AuCo sodium borohydride electro-oxidation catalyst
CN109298046A (en) * 2018-10-23 2019-02-01 大连大学 A kind of electrode and its application for alcohol catalysis

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