CN113130914B - Lactose fuel cell and PtNPs/CuNPs/NiNPs/carbon cloth plastic electrode for constructing same - Google Patents

Lactose fuel cell and PtNPs/CuNPs/NiNPs/carbon cloth plastic electrode for constructing same Download PDF

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CN113130914B
CN113130914B CN201911404682.1A CN201911404682A CN113130914B CN 113130914 B CN113130914 B CN 113130914B CN 201911404682 A CN201911404682 A CN 201911404682A CN 113130914 B CN113130914 B CN 113130914B
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electrode
carbon cloth
lactose
ninps
cunps
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CN113130914A (en
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孙晶
曹厚勇
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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • 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
    • 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
    • H01M4/9041—Metals or alloys
    • 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
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material 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
    • 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
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/08—Fuel cells with aqueous electrolytes
    • H01M8/083—Alkaline fuel cells
    • 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
    • H01M2004/8684—Negative 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to a lactose fuel cell and a PtNPs/CuNPs/NiNPs/carbon cloth plastic electrode for constructing the fuel cell. A PtNPs/CuNPs/NiNPs/carbon cloth electrode is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a platinum wire is used as an auxiliary electrode to form a three-electrode system, the three-electrode system is placed in a lactose solution and a supporting electrolyte, the initial potential is set to be-0.2V, the termination potential is set to be 1V, cyclic voltammetry curves of 1mmol/L, 2mmol/L, 3mmol/L, 4mmol/L and 5mmol/L of lactose are recorded, and the control process of the electrode electrocatalytic oxidation of the lactose solution is analyzed by using a standard curve method. The invention aims to provide a noble metal modified electrode which has good catalytic oxidation effect on lactose, improves the conversion rate of chemical energy and promotes the development of fuel cells.

Description

Lactose fuel cell and PtNPs/CuNPs/NiNPs/carbon cloth plastic electrode for constructing same
Technical Field
The invention relates to the field of fuel cells, in particular to application of a carbon cloth-based nano nickel/nano copper/nano platinum composite electrode (PtNPs/CuNPs/NiNPs/carbon cloth plastic electrode) in the construction of a lactose fuel cell by electrocatalytic oxidation of lactose solution.
Background
With the development of society, the demand for fossil fuels is rapidly increasing, and the exhaustion of fossil fuels and the serious pollution to the environment are accelerated, thereby limiting the development of human society and seriously affecting human health. To mitigate the environmental pollution and human health impact of fossil fuels, it is important to find alternatives to fossil fuels. The technical research and development and utilization of renewable energy resources are actively and widely carried out all over the world at present. At present, main substitutes of fossil fuels include biodiesel, liquid hydrogen, solar energy, wind energy and the like, and fuel cells are also substitutes of fossil fuels. The substitute is superior to other substitutes in the aspects of source distribution, transportation and the like, and the advantages of high cleanness, high conversion rate, low emission and the like of the fuel cell are applied to solving the energy problem.
Disclosure of Invention
In order to make up for the deficiencies of the prior art, the invention provides a lactose fuel cell and an electrode for constructing the fuel cell.
The invention has the following inventive concept: and (3) taking the carbon cloth as a substrate and a conducting layer, taking the nano nickel platinum particles as an electrochemical deposition layer, depositing the nano platinum particles on the nano copper particles, depositing the nano copper particles on the nano nickel particles, and depositing the nano nickel particles on the carbon cloth to prepare the PtNPs/CuNPs/NiNPs/carbon cloth plastic electrode. On the basis, a new method is provided for the construction of the lactose fuel cell.
In order to realize the purpose, the PtNPs/CuNPs/NiNPs/carbon cloth plastic electrode of the invention is used for constructing a lactose fuel cell as follows:
PtNPs/CuNPs/NiNPs/carbon cloth are used as an anode, and a Pt electrode is used as a cathode; sodium hydroxide solution with the concentration of 1mol/L is added into the anode pool as electrolyte solution, and lactose with the concentration of 0.01mol/L is added into the anode pool as fuel. Adding 0.01mol/L lactose solution with pH 14 sodium hydroxide as solvent into the cathode pool and introducing oxygen, and connecting the two pools by an anion exchange membrane to form the electrocatalytic oxidation lactose fuel cell.
The lactose fuel cell uses a PtNPs/CuNPs/NiNPs/carbon cloth plastic electrode as a working electrode, an Ag/AgCl electrode as a reference electrode and a platinum wire as an auxiliary electrode to form a three-electrode system, the three-electrode system is placed in lactose solution and supporting electrolyte, the set potential is-0.2-1.3V, the cyclic voltammetry curve of 1 mmol/5 mmol/L lactose is recorded, and the control process of the electrode electrocatalytic oxidation lactose solution is analyzed by using a standard curve method.
Further, the supporting electrolyte is 1mol/LNaOH, and the pH is 14.
Further, the PtNPs/CuNPs/NiNPs/carbon cloth plastic electrode comprises: the carbon cloth is used as a substrate and a conducting layer, the nano nickel platinum particles are used as an electrochemical deposition layer, the nano platinum particles are deposited on the nano copper particles, the nano copper particles are deposited on the nano nickel particles, and the nano nickel particles are deposited on the carbon cloth.
The invention develops a non-enzymatic fuel cell anode, which combines the advantages of nano materials to obtain a fuel cell anode with higher catalytic activity and stability. The invention utilizes the good conductivity of the carbon cloth to prepare the electrode with high sensitivity to lactose, and the electrode has the advantages of good catalytic effect, high sensitivity, good selectivity, stable structure and the like when the lactose is used as a base solution.
Drawings
FIG. 1 is a surface topography of a carbon cloth-based nano nickel/nano platinum composite electrode.
FIG. 2 is a comparison of cyclic voltammograms of a lactose solution versus a blank solution.
Figure 3 is a cyclic voltammogram of different concentrations of lactose solution.
Figure 4 is a standard curve of lactose at different concentrations.
FIG. 5 is a graph showing the resistance to poisoning of PtNPs/CuNPs/NiNPs/carbon cloth plastic electrode.
Detailed Description
The technical solutions of the present invention are further described below with reference to the drawings and the specific embodiments, but the present invention is not limited to the embodiments in any way. In the examples, unless otherwise specified, the experimental methods are all conventional methods; unless otherwise indicated, the experimental reagents and materials were commercially available.
The following examples PtNPs/CuNPs/NiNPs/carbon cloth plastic electrode preparation method is:
and (4) washing the carbon cloth with deionized water, and drying.
The preparation method of the PtNPs/CuNPs/NiNPs/carbon cloth plastic electrode comprises the following specific steps:
(1) a three-electrode system is adopted, a carbon cloth electrode is used as a working electrode, an Ag/AgCl electrode and a platinum wire electrode are used as reference electrodes and a counter electrode, and the three-electrode system is placed in an electrolytic cell filled with nickel sulfate (1M) solution. And (3) setting electrodeposition parameters of the electrochemical workstation by adopting a Fourier transform alternating current voltammetry method: initial potential: -0.5V, end point potential: 0.1V time, number of scan segments: 20, standing for 2 s. And (4) carrying out nitrogen protection on the deposited electrode, and standing for later use for one day to obtain the NiNPs/carbon cloth plastic electrode.
(2) A three-electrode system is adopted, a NiNPs/carbon cloth plastic electrode with a nano structure is used as a working electrode and is immersed into a mixture of 5mmol/L copper sulfate and 0.05mol/L potassium nitrate, a platinum electrode is used as an auxiliary electrode, and Ag/AgCl is used as a reference electrode. Setting electrodeposition parameters of an electrochemical workstation by adopting a constant current method: setting current: 0.65A, deposition time 500 s. And washing the deposited electrode with ultrapure water, and drying the electrode with nitrogen. Immediately putting into potassium platinochloride (0.02M) solution for 5min, taking out the electrode after 5min, washing with ultrapure water, and drying with nitrogen. Obtaining the PtNPs/CuNPs/NiNPs/carbon cloth plastic electrode.
In the PtNPs/CuNPs/NiNPs/carbon cloth plastic electrode, the particle size of the nickel nano particles is only required to be larger than 150nm and smaller than 1000 nm. The particle size of CuNPs is between 100-150nm and the particle size of PtNPs is between 2-5nm, if the size of PtNPs is larger than that of CuNPs, the platinum nanoparticles cover the copper nanoparticles, the synergetic catalysis effect cannot be realized, and once the pore size of the platinum nanoparticles is too large, fuel enters a great amount, which is not beneficial to further reaction. The product is not easy to diffuse out, and if the platinum nano particles are too small, the pore diameter is small. The fuel is difficult to diffuse to the active sites of the catalyst for activation, resulting in a decrease in current and thus in a decrease in power, and poor cell performance.
Based on the surface topography of the carbon cloth/nano nickel-copper-platinum composite electrode as shown in figure 1, the nano particles on the electrode are uniform in size and distribution, and the electrocatalysis performance is particularly outstanding.
Example 1 comparison of Cyclic voltammograms of lactose solution and blank solution
First, a three-electrode system: the method comprises the following steps of taking a PtNPs/CuNPs/NiNPs/carbon cloth plastic electrode as a working electrode, an Ag/AgCl electrode as a reference electrode, a platinum wire as an auxiliary electrode, placing the auxiliary electrode in a NaOH solution with the pH value of 14 and the concentration of 1mol/L, scanning within a potential range of-0.2-1.3V by using a cyclic voltammetry method, and recording a cyclic voltammetry curve of a blank solution; then, the three-electrode system is placed in 10mmol/L lactose solution to be detected, which contains 1mol/L NaOH solution with pH value of 14 as supporting electrolyte, and scanning is carried out in a potential range of-0.2-1.3V by using cyclic voltammetry, and the cyclic voltammetry curve of lactose is recorded. As shown in fig. 2: the catalytic effect of the PtNPs/CuNPs/NiNPs/carbon cloth plastic electrode at 10mmol/L lactose was tested at a scanning speed of 100 mV/s. From the figure, it can be seen that PtNPs/CuNPs/NiNPs/carbon cloth plastic electrode has good catalytic activity to lactose. The fuel composed of the PtNPs/CuNPs/NiNPs/carbon cloth plastic electrode can convert the biological energy into the electric energy efficiently.
Example 2 Cyclic voltammetric response of PtNPs/CuNPs/NiNPs/carbon cloth Plastic electrode to the same concentration of lactose at different sweep rates
Sequentially mixing a three-electrode system: the PtNPs/CuNPs/NiNPs/carbon cloth plastic electrode is used as a working electrode, the Ag/AgCl electrode is used as a reference electrode, the platinum wire is used as an auxiliary electrode and is placed in lactose to-be-detected solutions with different concentrations, which contain 1mol/L NaOH solution with the pH value of 14 as supporting electrolyte, and scanning is carried out within the potential range of-0.2-1.3V by utilizing a cyclic voltammetry. Cyclic voltammograms were recorded at 1mmol/L, 2mmol/L, 3mmol/L, 4mmol/L, 5mmol/L lactose. As shown in the attached figures 3 and 4: as can be seen from the figure, with the increasing concentration, the oxidation current of the nano electrode in the lactose solution is also increased, the oxidation peak is also increased, and the good linear response of catalyzing lactose is presented. The redox reaction of lactose is diffusion controlled. A good linear relation exists between the two in the range of 1-10 mmol/L, the linear regression equation of the oxidation peak current and the concentration of the lactose is I09476C +4.9353, and the correlation coefficient is 0.9769.
EXAMPLE 3 determination of the antitoxic Capacity of the electrode
Firstly, the three-electrode system is placed in 10mmol/L lactose solution to be tested containing 1mol/L NaOH solution with pH value of 14 as supporting electrolyte, and the time current curve of lactose is recorded under the potential of 0.60V by using the time current method. As shown in fig. 5, the current density drops sharply at the beginning. At the beginning of the reaction, it is a fast kinetic reaction, so the active site does not contain adsorbed lactose molecules. The adsorption of new lactose molecules then depends on the release of electrocatalytic sites by lactose oxidation, or on the occupation of electrode catalytically active sites by intermediate species such as CO, CHx, etc. formed during the first few minutes (rate determining step). Therefore, the slight decrease in current density is mainly due to the poisoning of the catalyst. Furthermore, the specific current experienced a rapid drop during the entire test period in the first 300 seconds and was still a smooth and gentle change after the end of the test, with a decay of about 14%. Therefore, the electrode has strong anti-poisoning capability and stable structure.
The above description is only for the purpose of creating a preferred embodiment of the present invention, but 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 of the present invention.

Claims (2)

1. The lactose fuel cell is characterized in that PtNPs/CuNPs/NiNPs/carbon cloth is used as an anode, and a Pt electrode is used as a cathode; adding 1mol/L sodium hydroxide solution as electrolyte solution into an anode pool, and adding 0.01mol/L lactose as fuel; adding 0.01mol/L lactose solution with pH 14 sodium hydroxide as solvent into a cathode pool, introducing oxygen, and connecting the two pools by an anion exchange membrane to construct and form an electrocatalytic oxidation lactose fuel cell;
the PtNPs/CuNPs/NiNPs/carbon cloth is a plastic electrode, the carbon cloth is used as a substrate and a conducting layer, the nano nickel platinum particles are electrochemical deposition layers, the nano platinum particles are deposited on the nano copper particles, the nano copper particles are deposited on the nano nickel particles, the nano nickel particles are deposited on the carbon cloth, and the PtNPs/CuNPs/NiNPs/carbon cloth plastic electrode is prepared; the particle size of the nano nickel particles is more than 150nm and less than 1000 nm; the particle size of the nano copper particles is 100-150nm, and the particle size of the nano platinum particles is 2-5 nm;
the specific steps for preparing the PtNPs/CuNPs/NiNPs/carbon cloth plastic electrode are as follows:
(1) a three-electrode system is adopted, a carbon cloth electrode is used as a working electrode, Ag/AgCl is used as a reference electrode, a platinum wire is used as an auxiliary electrode, the three-electrode system is placed in an electrolytic cell filled with 1M nickel sulfate solution, and an electrochemical workstation electrodeposition parameter is set by adopting a Fourier transform alternating current voltammetry method: initial potential: -0.5V, end point potential: -0.1V, number of scan segments: standing for 2s, carrying out nitrogen protection on the electrode after deposition, and standing for one day to obtain a NiNPs/carbon cloth plastic electrode;
(2) a three-electrode system is adopted, a NiNPs/carbon cloth plastic electrode with a nano structure is used as a working electrode and is immersed into a mixture of 5mmol/L copper sulfate and 0.05mol/L potassium nitrate, a platinum electrode is used as an auxiliary electrode, and Ag/AgCl is used as a reference electrode; setting electrodeposition parameters of an electrochemical workstation by adopting a constant current method: setting current: 0.65A, deposition time 500 s; and (3) rinsing the deposited electrode with ultrapure water, drying the electrode with nitrogen, immediately putting the electrode into a 0.02M potassium chloroplatinite solution for 5min, taking out the electrode after 5min, rinsing the electrode with ultrapure water, and drying the electrode with nitrogen to obtain the PtNPs/CuNPs/NiNPs/carbon cloth plastic electrode.
2. The lactose fuel cell as claimed in claim 1, characterized in that the electrolyte is 1mol/LNaOH and pH is 14.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1475050A (en) * 1974-12-18 1977-06-01 United Technologies Corp Method for catalyzing a fuel cell electrode and an electrode so produced
CN106257729A (en) * 2015-06-17 2016-12-28 中国科学院大连化学物理研究所 Self-respiration type light helps microbial fuel cell and application thereof
CN109298046A (en) * 2018-10-23 2019-02-01 大连大学 A kind of electrode and its application for alcohol catalysis
CN109298053A (en) * 2018-10-23 2019-02-01 大连大学 A method of glucose is measured using AuNPs/AgNWs/PDMS ductile electrode

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1475050A (en) * 1974-12-18 1977-06-01 United Technologies Corp Method for catalyzing a fuel cell electrode and an electrode so produced
CN106257729A (en) * 2015-06-17 2016-12-28 中国科学院大连化学物理研究所 Self-respiration type light helps microbial fuel cell and application thereof
CN109298046A (en) * 2018-10-23 2019-02-01 大连大学 A kind of electrode and its application for alcohol catalysis
CN109298053A (en) * 2018-10-23 2019-02-01 大连大学 A method of glucose is measured using AuNPs/AgNWs/PDMS ductile electrode

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