CN111146454A - Preparation method of carbon paper supported Co-B composite material electrode and application of carbon paper supported Co-B composite material electrode in catalyzing sodium borohydride electrooxidation reaction - Google Patents

Preparation method of carbon paper supported Co-B composite material electrode and application of carbon paper supported Co-B composite material electrode in catalyzing sodium borohydride electrooxidation reaction Download PDF

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CN111146454A
CN111146454A CN201911412309.0A CN201911412309A CN111146454A CN 111146454 A CN111146454 A CN 111146454A CN 201911412309 A CN201911412309 A CN 201911412309A CN 111146454 A CN111146454 A CN 111146454A
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electrode
carbon paper
composite material
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supported
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CN111146454B (en
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张栋铭
刘有智
崔灿
王浩宇
程宇玲
焦纬洲
祁贵生
袁志国
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North University of China
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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
    • H01M4/9075—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
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8853—Electrodeposition
    • 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 discloses a preparation method of a carbon paper supported Co-B composite material electrode and application of the carbon paper supported Co-B composite material electrode in catalyzing sodium borohydride electrooxidation reaction. The preparation method comprises the following steps: cutting carbon paper into square sheets of 10 mm × 10 mm, using the carbon paper as working electrode, platinum sheet electrode as counter electrode, silver chloride electrode as reference electrode, and performing KCl and H treatment3BO3、CoCl2·6H2In the mixed electrodeposition liquid of O and dimethylamino borane, a traditional three-electrode system is adopted, and a constant current method is used for carrying out electrodeposition process, so that the Co-B composite material electrode supported by carbon paper is obtained. The invention does not use organic binder, thus ensuring good conductivity; in addition, the active material does not fall off in the test process, and good stability is shown; due to the synergistic effect of the Co-B composite material, the Co-B composite material shows excellent catalytic activity for sodium borohydride electrooxidation.

Description

Preparation method of carbon paper supported Co-B composite material electrode and application of carbon paper supported Co-B composite material electrode in catalyzing sodium borohydride electrooxidation reaction
Technical Field
The invention relates to a preparation method of a carbon paper supported Co-B composite material electrode and application of the carbon paper supported Co-B composite material electrode in catalyzing sodium borohydride electrooxidation reaction, and belongs to the technical field of composite material preparation.
Background
In the modern society, energy consumption is increasing with the increase of population. The energy used by human mainly comprises three fossil energy sources of coal, petroleum and natural gas. However, they are non-renewable energy sources, and it is urgently needed to find a new energy source which can replace fossil energy.
A fuel cell is a new type of energy conversion device that can directly convert chemical energy stored in a fuel and an oxidant into electrical energy. In the energy conversion process, the energy conversion efficiency is high because the device is not limited by the Carnot cycle.
Direct borohydride fuel cells are fuel cells fueled by borohydride, which have a high energy density (9300 Wh kg)-1) Specific capacity (5668A. h. kg)-1) And battery voltage (in terms of O)2As an oxidant, the cell voltage reached 1.64V; with H2O2As an oxidant, cell voltages up to 2.11V), is a powerful competitor for the new generation of space power supplies, underwater power supplies, and high-energy, high-power-density portable power supplies. NaBH4The mass fraction of the medium hydrogen is as high as 10.6 wt.%, and the complete electrooxidation can release 8 electrons theoretically, so that the fuel is ideal.
NaBH4The anode electro-oxidation performance of (a) is one of the important factors determining the performance of a direct borohydride fuel cell. Currently, efficient NaBH4The electro-oxidation catalyst is a noble metal, but the noble metal is high in price and limited in storage capacity, so that the practical application of the electro-oxidation catalyst is limited. People are beginning to look for alternatives to precious metalsThe product can effectively catalyze the breakage of B-H bonds in borohydride and the electro-oxidation reaction of borohydride, and has low cost and good application prospect (see Dongming Zhang, Ke Ye, Dianxue Cao, Bin Wang, Kui Cheng, Yiju Li, GuilingWang)*, Yang Xu*. Co@MWNTs-Plastic: A novel electrode for NaBH4oxidation[J]Electrochimica Acta, 2015, 156: 102, 107, Junjun Zhang, Dongming Zhang*, CanCui, Haoyu Wang, Weizhou Jiao, Jing Gao and Youzhi Liu*. A three-dimensionalporous Co–P alloy supported on a copper foam as a new catalyst for sodiumborohydride electrooxidation[J]. Dalton Transactions, 2019, 48：13248-13259.）。
Disclosure of Invention
The invention aims to provide a preparation method for preparing a carbon paper supported Co-B composite material electrode with high activity by using a one-step electrodeposition method and application of the Co-B composite material electrode in catalyzing sodium borohydride electrooxidation reaction, so that the use of a noble metal catalyst is avoided, and the cost of the electrode is reduced.
The invention provides a preparation method of a carbon paper supported Co-B composite material electrode, which comprises the following steps:
(1) cutting the carbon paper into square pieces with the diameter of 10 mm multiplied by 10 mm to be used as an electrode support body;
(2) taking the carbon paper in the step (1) as a working electrode, a platinum sheet electrode as a counter electrode and a silver chloride electrode as a reference electrode, and controlling the concentration of the carbon paper in the solution to be 2.5 mol.L-1KCl、0.3 mol·L-1H3BO3、0.1 mol·L-1CoCl2·6H2In the mixed electrodeposition liquid of O and dimethylamino borane, a traditional three-electrode system is adopted, and a constant current method is used for carrying out electrodeposition process, so that the Co-B composite material electrode supported by carbon paper is obtained.
The above preparation method is further illustrated as follows:
in the electrodeposition liquid of the Co-B composite material electrode supported by the electrodeposition carbon paper, the concentration of the dimethylamino borane is 0.1-1.2 mol.L-1。
The constant currentThe flow deposition process is carried out, and the deposition current density is-5 to-50 mA cm-2The deposition time is 5-60 min.
The invention provides a carbon paper supported Co-B composite material electrode prepared by the method.
The invention provides application of the carbon paper supported Co-B composite material electrode in catalyzing sodium borohydride electrooxidation reaction.
The specific process of the application is as follows: taking a carbon paper supported Co-B composite material electrode as a working electrode, a platinum sheet electrode as a counter electrode, and a silver chloride electrode as a reference electrode, wherein the molar mass of the carbon paper supported Co-B composite material electrode is 1.0-5.0 mol.L-1NaOH and 0.01 to 1.00 mol. L-1NaBH of4Performing cyclic voltammetry test in the solution, wherein the scanning range is-1.20 to-0.20V, and the scanning speed is 10mV · s-1。
The essence of the invention is that the Co-B composite material supported by carbon paper prepared by one-step electrodeposition method is used as a high-performance catalyst to catalyze NaBH4And (3) electrooxidation reaction.
The invention has the beneficial effects that:
(1) the carbon paper as a support has the advantages of high conductivity, high porosity and the like;
(2) organic binders are not used in the preparation process of the electrode, so that the electrode has higher conductivity and stability;
(3) the Co-B compound loaded on the catalyst has higher catalytic NaBH than simple Co due to the synergistic effect4Electro-oxidation activity;
(4) compared with noble metals, the Co-based material has low price, and the cost of the electrode is greatly reduced.
Drawings
FIG. 1 is a cyclic voltammogram of a pure Co electrode (curve a) and a Co-B composite electrode prepared in example 1 (curve B).
FIG. 2 shows NaBH in test solution for Co-B composite electrodes prepared in examples 2 and 34The concentration is 0.30 mol.L-1(Curve a) and 0.40 mol. L-1(curve b) cyclic voltammogram.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1
Carbon paper cut into square pieces of 10 mm × 10 mm is used as a working electrode, a platinum sheet electrode is used as a counter electrode, a silver chloride electrode is used as a reference electrode, and the working electrode is at 2.5 mol · L-1KCl、0.3 mol·L-1H3BO3、0.1 mol·L-1CoCl2·6H2O and 0.4 mol. L-1In the mixed solution of dimethylamino borane, a traditional three-electrode system is adopted, and a constant current method is used for controlling the concentration of the dimethylamine borane at-15 mA cm-2And depositing for 20 min under the current density to obtain the Co-B composite material electrode supported by the carbon paper. Using the electrode as a working electrode, a platinum sheet electrode as a counter electrode and a silver chloride electrode as a reference electrode, and the concentration of the silver chloride in the solution is 1.0 mol.L-1NaOH and 0.20 mol. L-1NaBH of4Performing cyclic voltammetry test in the solution, wherein the scanning range is-1.20 to-0.20V, and the scanning speed is 10mV · s-1When the potential is-0.5V, the oxidation current density reaches 274.3 mA cm-2. The current density of the pure Co electrode prepared under the same condition is only 32.6 mA cm at the potential-2。
FIG. 1 shows the cyclic voltammetry curves of the pure Co electrode (curve a) and the Co-B composite electrode (curve B) corresponding to example 1, from which it can be seen that a higher oxidation current density is generated on the Co-B composite electrode, which illustrates that the Co-B composite electrode catalyzes NaBH4The activity of the electrooxidation is higher than that of a pure Co electrode.
Example 2
Carbon paper cut into square pieces of 10 mm × 10 mm is used as a working electrode, a platinum sheet electrode is used as a counter electrode, a silver chloride electrode is used as a reference electrode, and the working electrode is at 2.5 mol · L-1KCl、0.3 mol·L-1H3BO3、0.1 mol·L-1CoCl2·6H2O and 0.4 mol. L-1In the mixed solution of dimethylamino borane, a traditional three-electrode system is adopted, and a constant current method is used for controlling the concentration of the dimethylamine borane at-15 mA cm-2Depositing for 20 min under the current density to obtain the carbon paper supported Co-B composite materialAnd (4) a pole. Using the electrode as a working electrode, a platinum sheet electrode as a counter electrode and a silver chloride electrode as a reference electrode, and the concentration of the silver chloride in the solution is 1.0 mol.L-1NaOH and 0.30 mol. L-1NaBH of4Performing cyclic voltammetry test in the solution, wherein the scanning range is-1.20 to-0.20V, and the scanning speed is 10mV · s-1When the potential is-0.2V, the oxidation current density reaches 443.7 mA cm-2。
Example 3
Carbon paper cut into square pieces of 10 mm × 10 mm is used as a working electrode, a platinum sheet electrode is used as a counter electrode, a silver chloride electrode is used as a reference electrode, and the working electrode is at 2.5 mol · L-1KCl、0.3 mol·L-1H3BO3、0.1 mol·L-1CoCl2·6H2O and 0.4 mol. L-1In the mixed solution of dimethylamino borane, a traditional three-electrode system is adopted, and a constant current method is used for controlling the concentration of the dimethylamine borane at-15 mA cm-2And depositing for 20 min under the current density to obtain the Co-B composite material electrode supported by the carbon paper. Using the electrode as a working electrode, a platinum sheet electrode as a counter electrode and a silver chloride electrode as a reference electrode, and the concentration of the silver chloride in the solution is 1.0 mol.L-1NaOH and 0.40 mol. L-1NaBH of4Performing cyclic voltammetry test in the solution, wherein the scanning range is-1.20 to-0.20V, and the scanning speed is 10mV · s-1When the potential is-0.2V, the oxidation current density reaches 518.8 mA cm-2。
FIG. 2 shows NaBH of Co-B composite electrode in test solution4The concentration is 0.30 mol.L-1(Curve a corresponds to example 2) and 0.40 mol. L-1(Curve b corresponds to example 3). As can be seen from the figure, when NaBH is used4The concentration is 0.40 mol.L-1When the electrode produced a higher oxidation current density, indicating an increase in NaBH4The concentration improves the electrooxidation performance.

Claims (6)

1. A preparation method of a carbon paper supported Co-B composite material electrode is characterized by comprising the following steps:
(1) cutting the carbon paper into square pieces with the diameter of 10 mm multiplied by 10 mm to be used as an electrode support body;
(2) taking the carbon paper in the step (1) as a working electrode, a platinum sheet electrode as a counter electrode, a silver chloride electrode as a reference electrode, and performing reaction on KCl and H3BO3、CoCl2·6H2In the mixed electrodeposition liquid of O and dimethylamino borane, a three-electrode system is adopted, and a constant current method is used for carrying out electrodeposition process, so that the Co-B composite material electrode supported by carbon paper is obtained.
2. The method of making a carbon paper supported Co-B composite electrode of claim 1, wherein: the mixed electrodeposition solution comprises 2.5 mol.L-1KCl、0.3 mol·L-1H3BO3、0.1 mol·L-1CoCl2·6H2O and 0.1 to 1.2 mol. L-1Dimethylamino borane.
3. The method of making a carbon paper supported Co-B composite electrode of claim 1, wherein: in the constant current deposition process, the deposition current density is-5 to-50 mA-cm-2The deposition time is 5-60 min.
4. A carbon paper supported Co-B composite electrode prepared by the method of any one of claims 1 to 3.
5. Use of the carbon paper supported Co-B composite electrode of claim 4 in catalyzing sodium borohydride electrooxidation.
6. Use according to claim 5, characterized in that: taking a carbon paper supported Co-B composite material electrode as a working electrode, a platinum sheet electrode as a counter electrode, and a silver chloride electrode as a reference electrode, wherein the molar mass of the carbon paper supported Co-B composite material electrode is 1.0-5.0 mol.L-1NaOH and 0.01 to 1.00 mol. L-1NaBH of4Performing cyclic voltammetry test in the solution, wherein the scanning range is-1.20 to-0.20V, and the scanning speed is 10mV · s-1。
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