CN109065894B - Three-dimensional gradient structure anode for membrane-free oxygen-free direct methanol fuel cell and preparation method thereof - Google Patents

Three-dimensional gradient structure anode for membrane-free oxygen-free direct methanol fuel cell and preparation method thereof Download PDF

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CN109065894B
CN109065894B CN201810724279.6A CN201810724279A CN109065894B CN 109065894 B CN109065894 B CN 109065894B CN 201810724279 A CN201810724279 A CN 201810724279A CN 109065894 B CN109065894 B CN 109065894B
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原鲜霞
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Shanghai Jiaotong 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
    • H01M4/8636—Inert electrodes with catalytic activity, e.g. for fuel cells with a gradient in another property than porosity
    • H01M4/8642—Gradient in 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
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Abstract

The invention relates to a three-dimensional gradient structure anode for a film-free oxygen-free direct methanol fuel cell and a preparation method thereof. Compared with the prior art, the anode of the invention ensures that the fuel just completely reacts when reaching the electrode side close to the electrolyte, thereby avoiding the adverse effect of the anode methanol fuel permeating the electrolyte and further permeating the cathode on the performance of the cell; meanwhile, the utilization rate of the methanol fuel is improved, the utilization rate of the catalyst is improved, and the dosage of the catalyst is reduced, so that the performance of the cell is improved, and the cost of the cell is reduced. The three-dimensional gradient structure anode is applied to the membrane-free oxygen-free direct methanol fuel cell, so that the cell can use high-concentration methanol fuel at the anode, the performance of the cell is improved, and the commercial popularization and application of the cell are facilitated.

Description

Three-dimensional gradient structure anode for membrane-free oxygen-free direct methanol fuel cell and preparation method thereof
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a three-dimensional gradient structure anode of a membrane-free oxygen-free direct methanol fuel cell and a preparation method thereof.
Background
Direct Methanol Fuel Cells (DMFCs) are power generation devices that convert chemical energy into electrical energy using methanol as an anode fuel and oxygen as a cathode oxidant, and have the advantages of high energy conversion efficiency, safety, portability, environmental protection, no pollution, etc., and the reaction products are carbon dioxide and water, and thus have become a research hotspot in recent years.
Expensive proton exchange membranes and slow cathodic oxygen reduction reactions are two major technical challenges that limit the commercial application of DMFCs. Although the use of Pt/C catalysts greatly accelerates the oxygen reduction reaction to greatly improve the performance of DMFCs, their expensive price and scarce resources greatly increase the production cost of DMFCs. Also, the use of proton exchange membranes not only further increases the cost of the DMFCs, but also makes the assembly and maintenance of the cells more complicated. To overcome these difficulties, researchers have proposed to construct membrane-free oxygen-free direct methanol fuel cells by replacing the expensive proton exchange membrane with a chamber carrying an electrolyte, and replacing oxygen as an oxidant with a redox couple having high electrochemical reactivity and high potential, not only improving the performance of the cell, but also reducing its cost. However, in the operation process of the membrane-free oxygen-free direct methanol fuel cell, when the anode uses high-concentration methanol fuel, part of the methanol permeates to the cathode through the electrolyte after the methanol is not reacted completely, and mixed potential is generated, which not only reduces the performance of the cell, but also wastes the methanol fuel, and increases the cost of the cell to a certain extent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a three-dimensional gradient structure anode of a membrane-free oxygen-free direct methanol fuel cell and a preparation method thereof, wherein the three-dimensional gradient structure anode can reduce the cost and improve the performance.
The purpose of the invention can be realized by the following technical scheme: the three-dimensional gradient structure anode is characterized in that the anode is a three-dimensional gradient structure obtained by gradient coating of PtRuM/C catalysts with different metal loadings on an anode diffusion layer.
The loading amount of the metal PtRuM in the PtRuM/C catalyst is 10-80%, and M represents non-platinum group metal elements.
The three-dimensional gradient structure is characterized in that the catalyst is distributed in a gradient manner along the depth direction of the fuel cell, wherein the loading capacity of the catalyst on the first layer is 1.0-10.0mg/cm2The loading amount of the catalyst in the second layer is 0.5-5.0mg/cm2The loading amount of the catalyst on the third layer is 0.2-3.0mg/cm2… …, until the nth layer (n.gtoreq.2), the catalyst loading decreases with increasing number of coating layers.
The three-dimensional gradient structure is characterized in that n catalyst layers are sequentially coated on the anode diffusion layer, n is more than or equal to 2, the loading capacity of the catalyst is sequentially reduced along with the increase of the number of the coating layers, and the difference of the loading capacity of the catalyst on the adjacent catalyst layers is 0.1-5mg/cm2。
A preparation method of a three-dimensional gradient structure anode for a membrane-free oxygen-free direct methanol fuel cell is characterized by comprising the following steps: the metal loading referred to below is the proportion by weight of PtRuM in the PtRuM/C catalyst to the total weight of the entire PtRuM/C catalyst.
(1) Respectively weighing PtRuM/C catalysts with different metal capacities, mixing the PtRuM/C catalysts with Nafion emulsion and deionized water, and then ultrasonically dispersing for 0.5-6h to form uniform catalyst slurry;
(2) the mass of the bare anode diffusion layer was weighed and recorded as m0；
(3) The PtRuM/C catalyst slurry with the metal loading of 50-80% is coated on an anode diffusion layer, and then the anode diffusion layer is placed in a vacuum drying oven to be dried to obtain a first catalytic layer CL1Weighing its mass m1；
(4) PtRuM/C catalyst slurry with metal loading of 30-60% is coated on CL1Drying in a vacuum drying oven to obtain a second catalytic layer CL2Is called its mass m2；
(5) PtRuM/C catalyst slurry with metal loading of 10-40% is coated on CL2Drying in a vacuum drying oven to obtain a third catalytic layer CL3Is called its mass m3；
(6) By analogy, in the catalyst layer CLn-1Coating PtRuM/C catalyst with gradually reduced metal loading on the catalyst layer to obtain the n-th catalyst layer CLn(n is more than or equal to 2), thereby preparing the anode with the three-dimensional gradient structure.
In the step (1), the mass-volume ratio of the PtRuM/C catalyst, the Nafion emulsion and the deionized water is 0.5-22mg:100 mu L: 900 μ L.
The membrane-free oxygen-free direct methanol fuel cell is characterized by comprising an anolyte flow field plate and a catholyte flow field plate, wherein an anode, an electrolyte bearing cavity and a cathode are sequentially stacked between the anolyte flow field plate and the catholyte flow field plate, the electrolyte bearing cavity contains electrolyte, the anode uses methanol as fuel, the cathode uses a solution of a redox couple with high electrochemical reaction activity and high potential as an oxidant, and the anode is of the three-dimensional gradient structure.
The fuel used by the anode is methanol solution with the concentration of 0.1-15 mol/L;
the electrolyte is HClO with the concentration of 0.1-2.5mol/L4A solution;
the cathode adopts Fe as oxidant3+/Fe2+The mixed solution of (1), wherein the high valence ion Fe3+With low valent ion Fe2+The concentration ratio of (A) to (B) is 10:1-2: 1;
the cathode is prepared from black powder, Nafion emulsion and deionized water according to the mass volume ratio of 5-20mg:100 mu L: 900 microliter of the mixed slurry is coated on two sides of the carbon paper to prepare the carbon paper;
the thickness of the electrolyte bearing cavity is 0.1-2.0 mm;
the anolyte flow field plate and the catholyte flow field plate both adopt graphite plates.
Compared with the prior art, the anode structure of the membrane-free oxygen-free direct methanol fuel cell is optimally designed, and catalysts with different loading amounts are distributed on the anode diffusion layer in a gradient manner along the depth direction of the cell according to the change of the concentration of the anode fuel methanol and the difference of the feeding speed, so that the fuel just completely reacts when reaching the electrode side close to the electrolyte, and the adverse effect of the anode methanol fuel permeating the electrolyte and further permeating the cathode on the performance of the cell is avoided; meanwhile, the utilization rate of the methanol fuel is improved, the utilization rate of the catalyst is improved, and the dosage of the catalyst is reduced, so that the performance of the cell is improved, and the cost of the cell is reduced. The three-dimensional gradient structure anode is applied to the membrane-free oxygen-free direct methanol fuel cell, so that the cell can use high-concentration methanol fuel at the anode, thereby improving the performance of the cell and being beneficial to the commercial popularization and application of the cell.
Drawings
FIG. 1 is a schematic diagram of a three-dimensional gradient structure anode of a membraneless oxygen-free direct methanol fuel cell;
wherein, the first layer is a carbon paper diffusion layer, and the second layer is a first catalytic layer CL1And (c) a second catalyst layer CL2And fourthly, a third catalytic layer CL3Fifthly, the nth catalyst layer CLnAnd sixthly, an electrolyte bearing cavity.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
The metal loading referred to herein is the proportion by weight of PtRuM in the PtRuM/C catalyst to the total weight of the entire PtRuM/C catalyst.
Example 1
As shown in fig. 1, the anode diffusion layer is cut to a suitable size and processed for use. 22mg, 12mg and 7mg of PtRuAu/C catalyst with metal loading of 80%, 60% and 40% are respectively weighed, mixed with 100 mu L of Naf ion emulsion and 900 mu L of deionized water and ultrasonically dispersed for 6 hours to form uniform catalyst slurry. Weighing the mass m of the bare anode diffusion layer (i)0The metal loading is 80 percentThe PtRuAu/C catalyst slurry is coated on an anode diffusion layer, and then the anode diffusion layer is dried in a vacuum drying oven to obtain a first catalytic layer CL1(II) weighing the mass m1Obtaining CL1The loading of the upper catalyst is 10.0mg/cm2(ii) a PtRuAu/C catalyst slurry with 60% metal loading was coated on CL1Drying in a vacuum drying oven to obtain a second catalytic layer CL2(iii) its mass m2Obtaining CL2The loading of the upper catalyst was 5.0mg/cm2(ii) a PtRuAu/C catalyst slurry with 40% metal loading was coated on CL2Drying in a vacuum drying oven to obtain a third catalytic layer CL3(iv) weighing its mass m3Obtaining CL3The loading of the upper catalyst was 3.0mg/cm2Thereby preparing the anode with the three-dimensional gradient structure.
And (3) mixing 20mg of carbon black powder, 100 mu L of Nafion emulsion and 900 mu L of deionized water to form uniform slurry, coating the uniform slurry on two sides of the carbon paper, and drying the carbon paper in a vacuum drying oven to obtain the cathode.
The membrane-free oxygen-free direct methanol fuel cell is assembled according to the stacking sequence of an anolyte flow field plate, a three-dimensional gradient structured anode, an electrolyte bearing cavity (sixth), a cathode and a catholyte flow field plate. The anode uses methanol fuel with the concentration of 15mol/L, the thickness of the electrolyte bearing cavity is 1mm, and the electrolyte is HClO with the concentration of 2.5mol/L4The solution, catholyte, was 2.2mol/L Fe (ClO)3And 0.22mol/L Fe (ClO)2The mixed solution of (1).
Example 2
And cutting the anode diffusion layer with a proper size for standby. 20mg and 10mg of PtRuAu/C catalyst with metal loading of 70% and 40% are respectively weighed, mixed with 100 mu L of Nafion emulsion and 900 mu L of deionized water and ultrasonically dispersed for 4 hours to form uniform catalyst slurry. Weighing the mass m of the bare anode diffusion layer0Coating PtRuAu/C catalyst slurry with 70% of metal loading on an anode diffusion layer, and then placing the anode diffusion layer in a vacuum drying oven for drying to obtain a first catalytic layer CL1Weighing its mass m1Obtaining CL1The loading of the upper catalyst was 9.0mg/cm2(ii) a P with a metal loading of 40%tRUAu/C catalyst slurry coated on CL1Drying in a vacuum drying oven to obtain a second catalytic layer CL2Is called its mass m2Obtaining CL2The loading of the upper catalyst was 5.0mg/cm2Thereby preparing the anode with the three-dimensional gradient structure.
And mixing 18mg of carbon black powder, 100 mu LmL of Nafion emulsion and 900 mu L of deionized water to form uniform slurry, coating the uniform slurry on two sides of the carbon paper, and drying the carbon paper in a vacuum drying oven to obtain the cathode.
The membrane-free oxygen-free direct methanol fuel cell is assembled according to the stacking sequence of an anolyte flow field plate, a three-dimensional gradient structured anode, an electrolyte bearing cavity, a cathode and a catholyte flow field plate. The anode uses methanol fuel with the concentration of 12mol/L, the thickness of the electrolyte bearing cavity is 0.5mm, and the electrolyte is HClO with the concentration of 2.0mol/L4The solution, catholyte, was 2.2mol/L Fe (ClO)3And 0.22mol/L Fe (ClO)2The mixed solution of (1).
Example 3
And cutting the anode diffusion layer with a proper size for standby. Weighing 15mg, 6mg and 2mg of PtRuAu/C catalyst with metal loading of 70%, 60% and 40%, respectively, mixing with 100 mu L of Nafion emulsion and 900 mu L of deionized water, and then carrying out ultrasonic dispersion for 5 hours to form uniform catalyst slurry. Weighing the mass m of the bare anode diffusion layer0Coating PtRuAu/C catalyst slurry with 70% of metal loading on an anode diffusion layer, and then placing the anode diffusion layer in a vacuum drying oven for drying to obtain a first catalytic layer CL1Weighing its mass m1Obtaining CL1The loading of the upper catalyst was 7.0mg/cm2(ii) a PtRuAu/C catalyst slurry with 60% metal loading was coated on CL1Drying in a vacuum drying oven to obtain a second catalytic layer CL2Is called its mass m2Obtaining CL2The loading of the upper catalyst was 3.0mg/cm2(ii) a PtRuAu/C catalyst slurry with 40% metal loading was coated on CL2Drying in a vacuum drying oven to obtain a third catalytic layer CL3Is called its mass m3Obtaining CL3The loading of the upper catalyst is 1.0mg/cm2Thereby preparing the anode with the three-dimensional gradient structure.
And (3) mixing 20mg of carbon black powder, 100 mu L of Nafion emulsion and 900 mu L of deionized water to form uniform slurry, coating the uniform slurry on two sides of the carbon paper, and drying the carbon paper in a vacuum drying oven to obtain the cathode.
The membrane-free oxygen-free direct methanol fuel cell is assembled according to the stacking sequence of an anolyte flow field plate, a three-dimensional gradient structured anode, an electrolyte bearing cavity, a cathode and a catholyte flow field plate. The anode uses methanol fuel with the concentration of 13mol/L, the thickness of the electrolyte bearing cavity is 0.3mm, and the electrolyte is HClO with the concentration of 1.5mol/L4The catholyte is 2mol/L Fe (ClO)3And 0.22mol/L Fe (ClO)2The mixed solution of (1).
Example 4
And cutting the anode diffusion layer with a proper size for standby. Respectively weighing 8mg, 2mg, 1mg and 0.5mg of PtRuAu/C catalyst with metal loading capacity of 60%, 40%, 20% and 10%, mixing with 100 mu L Nafion emulsion and 900 mu L deionized water, and performing ultrasonic dispersion for 4 hours to form uniform catalyst slurry. Weighing the mass m of the bare anode diffusion layer0The PtRuAu/C catalyst slurry with the metal loading of 60 percent is coated on the anode diffusion layer and then is placed in a vacuum drying oven to be dried to prepare a first catalytic layer CL1Weighing its mass m1Obtaining CL1The loading of the upper catalyst was 3.0mg/cm2(ii) a PtRuAu/C catalyst slurry with 40% metal loading was coated on CL1Drying in a vacuum drying oven to obtain a second catalytic layer CL2Is called its mass m2Obtaining CL2The loading of the upper catalyst is 1.0mg/cm2(ii) a PtRuAu/C catalyst slurry with 20% metal loading was coated on CL2Drying in a vacuum drying oven to obtain a third catalytic layer CL3Is called its mass m3Obtaining CL3The loading of the upper catalyst is 0.5mg/cm2(ii) a PtRuAu/C catalyst slurry with 10% metal loading was coated on CL3Drying in a vacuum drying oven to obtain a fourth catalytic layer CL4Is called its mass m4Obtaining CL4The loading of the upper catalyst is 0.2mg/cm2Thereby preparing the anode with the three-dimensional gradient structure.
And mixing 15mg of carbon black powder, 100 mu L of Nafion emulsion and 900 mu L of deionized water to form uniform slurry, coating the uniform slurry on two sides of the carbon paper, and drying the carbon paper in a vacuum drying oven to obtain the cathode.
The membrane-free oxygen-free direct methanol fuel cell is assembled according to the stacking sequence of an anolyte flow field plate, a three-dimensional gradient structured anode, an electrolyte bearing cavity, a cathode and a catholyte flow field plate. The anode uses methanol fuel with the concentration of 10mol/L, the thickness of the electrolyte bearing cavity is 0.1mm, and the electrolyte is HClO with the concentration of 0.5mol/L4The catholyte is 2mol/L Fe (ClO)3And 0.22mol/L Fe (ClO)2The mixed solution of (1).
Example 5
And cutting the anode diffusion layer with a proper size for standby. 10mg, 6mg, 1.5mg and 0.5mg of PtRuCo/C catalyst with metal loading of 70%, 50%, 20% and 5% are respectively weighed, and the PtRuCo/C catalyst is mixed with 100 mu L of Nafion emulsion and 900 mu L of deionized water and then ultrasonically dispersed for 4 hours to form uniform catalyst slurry. Weighing the mass m of the bare anode diffusion layer0The PtRuCo/C catalyst slurry with 70 percent of metal loading is coated on the anode diffusion layer and then is placed in a vacuum drying oven to be dried to obtain a first catalytic layer CL1Weighing its mass m1Obtaining CL1The loading of the upper catalyst was 5.0mg/cm2(ii) a PtRuCo/C catalyst slurry with 50% metal loading was coated on CL1Drying in a vacuum drying oven to obtain a second catalytic layer CL2Is called its mass m2Obtaining CL2The loading of the upper catalyst was 3.0mg/cm2(ii) a PtRuCo/C catalyst slurry with 20% metal loading was coated on CL2Drying in a vacuum drying oven to obtain a third catalytic layer CL3Is called its mass m3Obtaining CL3The loading of the upper catalyst was 0.7mg/cm2(ii) a PtRuCo/C catalyst slurry with 5% metal loading was coated on CL3Drying in a vacuum drying oven to obtain a fourth catalytic layer CL4Is called its mass m4Obtaining CL4The loading of the upper catalyst is 0.1mg/cm2Thereby preparing the anode with the three-dimensional gradient structure.
And mixing 15mg of carbon black powder, 100 mu L of Nafion emulsion and 900 mu L of deionized water to form uniform slurry, coating the uniform slurry on two sides of the carbon paper diffusion layer, and drying the uniform slurry in a vacuum drying oven to obtain the cathode.
The membrane-free oxygen-free direct methanol fuel cell is assembled according to the stacking sequence of an anolyte flow field plate, a three-dimensional gradient structure anode, an electrolyte bearing cavity, a three-dimensional structure cathode and a catholyte flow field plate. The anode uses methanol fuel with the concentration of 10mol/L, the thickness of the electrolyte bearing cavity is 2.0mm, and the electrolyte is HClO with the concentration of 0.2mol/L4The catholyte is 2mol/L Fe (ClO)3And 0.22mol/L Fe (ClO)2The mixed solution of (1).
Example 6
And cutting the anode diffusion layer with a proper size for standby. Respectively weighing 7mg, 1mg and 0.5mg of PtRuCo/C catalyst with metal loading of 50%, 30% and 10%, mixing with 100 mu L of Nafion emulsion and 900 mu L of deionized water, and then carrying out ultrasonic dispersion for 2h to form uniform catalyst slurry. Weighing the mass m of the bare anode diffusion layer0Coating PtRuCo/C catalyst slurry with 50% of metal loading on an anode diffusion layer, and then placing the anode diffusion layer in a vacuum drying oven for drying to obtain a first catalytic layer CL1Weighing its mass m1Obtaining CL1The loading of the upper catalyst was 3.0mg/cm2(ii) a PtRuCo/C catalyst slurry with metal loading of 30% was coated on CL1Drying in a vacuum drying oven to obtain a second catalytic layer CL2Is called its mass m2Obtaining CL2The loading of the upper catalyst is 0.5mg/cm2(ii) a PtRuCo/C catalyst slurry with 10% metal loading was coated on CL2Drying in a vacuum drying oven to obtain a third catalytic layer CL3Is called its mass m3Obtaining CL3The loading of the upper catalyst is 0.2mg/cm2Thereby preparing the anode with the three-dimensional gradient structure.
And mixing 10mg of carbon black powder, 100 mu L of Nafion emulsion and 900 mu L of deionized water to form uniform slurry, coating the uniform slurry on two sides of the carbon paper, and drying the carbon paper in a vacuum drying oven to obtain the cathode.
According to anolyte flow field plate and three-dimensional ladderThe anode with the structure, the electrolyte bearing cavity, the cathode and the cathode liquid flow field plate are stacked in sequence to form the membrane-free oxygen-free direct methanol fuel cell. The anode uses methanol fuel with the concentration of 7mol/L, the thickness of the electrolyte bearing cavity is 0.2mm, and the electrolyte is HClO with the concentration of 0.2mol/L4The solution, catholyte, was 1.54mol/L Fe (ClO)3And 0.22mol/L Fe (ClO)2The mixed solution of (1).
Example 7
And cutting the anode diffusion layer with a proper size for standby. 5mg, 1mg, 0.7mg and 0.5mg of PtRuCo/C catalyst with metal loading capacity of 60%, 30%, 15%, 10% and 5% are respectively weighed, and are mixed with 100 mu L Nafion emulsion and 900 mu L deionized water and then ultrasonically dispersed for 2h to form uniform catalyst slurry. Weighing the mass m of the bare anode diffusion layer0The PtRuCo/C catalyst slurry with the metal loading of 60 percent is coated on a carbon paper diffusion layer and then is placed in a vacuum drying oven to be dried to obtain a first catalytic layer CL1Weighing its mass m1Obtaining CL1The loading of the upper catalyst is 2.5mg/cm2(ii) a PtRuCo/C catalyst slurry with metal loading of 30% was coated on CL1Drying in a vacuum drying oven to obtain a second catalytic layer CL2Is called its mass m2Obtaining CL2The loading of the upper catalyst is 0.5mg/cm2(ii) a PtRuCo/C catalyst slurry with 15% metal loading was coated on CL2Drying in a vacuum drying oven to obtain a third catalytic layer CL3Is called its mass m3Obtaining CL3The loading of the upper catalyst is 0.4mg/cm2(ii) a PtRuCo/C catalyst slurry with 10% metal loading was coated on CL3Drying in a vacuum drying oven to obtain a fourth catalytic layer CL4Is called its mass m4Obtaining CL4The loading of the upper catalyst is 0.3mg/cm2(ii) a PtRuCo/C catalyst slurry with 5% metal loading was coated on CL4Drying in a vacuum drying oven to obtain a fifth catalyst layer CL5Is called its mass m5Obtaining CL5The loading of the upper catalyst is 0.1mg/cm2Thereby obtaining the anode with the three-dimensional gradient structure。
5mg of carbon black powder, 100 mu L of Nafion emulsion and 900 mu L of deionized water are mixed into uniform slurry to be coated on two sides of the carbon paper, and the carbon paper is dried under a vacuum drying oven to prepare the cathode.
The membrane-free oxygen-free direct methanol fuel cell is assembled according to the stacking sequence of an anolyte flow field plate, a three-dimensional gradient structured anode, an electrolyte bearing cavity, a cathode and a catholyte flow field plate. The anode uses methanol fuel with the concentration of 5mol/L, the thickness of the electrolyte bearing cavity is 0.8mm, and the electrolyte is HClO with the concentration of 0.1mol/L4The solution, catholyte, was 1.1mol/L Fe (ClO)3And 0.22mol/L Fe (ClO)2The mixed solution of (1).
Example 8
And cutting the anode diffusion layer with a proper size for standby. 2mg, 1mg and 0.5mg of PtRuFe/C catalyst with metal loading of 50%, 40% and 10% are respectively weighed, and the PtRuFe/C catalyst is mixed with 100 mu L of Nafion emulsion and 900 mu L of deionized water and then ultrasonically dispersed for 1h to form uniform catalyst slurry. Weighing the mass m of the bare anode diffusion layer0Coating PtRuFe/C catalyst slurry with 50% of metal loading on an anode diffusion layer, and then placing the anode diffusion layer in a vacuum drying oven for drying to obtain a first catalytic layer CL1Weighing its mass m1Obtaining CL1The loading of the upper catalyst is 1.0mg/cm2(ii) a PtRuFe/C catalyst slurry with 40% metal loading was coated on CL1Drying in a vacuum drying oven to obtain a second catalytic layer CL2Is called its mass m2Obtaining CL2The loading of the upper catalyst is 0.5mg/cm2(ii) a PtRuFe/C catalyst slurry with 10% metal loading was coated on CL2Drying in a vacuum drying oven to obtain a third catalytic layer CL3Is called its mass m3Obtaining CL3The loading of the upper catalyst is 0.2mg/cm2Thereby preparing the anode with the three-dimensional gradient structure.
And mixing 7mg of carbon black powder, 100 mu L of Nafion emulsion and 900 mu L of deionized water to form uniform slurry, coating the uniform slurry on two sides of the carbon paper, and drying the carbon paper in a vacuum drying oven to obtain the cathode.
According to anolyte flow field plate and three-dimensional gradient structureThe anode, the electrolyte bearing cavity, the cathode and the cathode liquid flow field plate are stacked in sequence to form the membrane-free oxygen-free direct methanol fuel cell. The anode uses methanol fuel with the concentration of 2mol/L, the thickness of the electrolyte bearing cavity is 0.2mm, and the electrolyte is HClO with the concentration of 0.2mol/L4The solution, catholyte, was 0.88mol/L Fe (ClO)3And 0.22mol/L Fe (ClO)2The mixed solution of (1).
Example 9
And cutting the anode diffusion layer with a proper size for standby. 2mg, 1.5mg, 1mg and 0.5mg of PtRuFe/C catalyst with metal loading of 50%, 40%, 20% and 10% are respectively weighed, and the PtRuFe/C catalyst is mixed with 100 mu L of Nafion emulsion and 900 mu L of deionized water and then ultrasonically dispersed for 0.5h to form uniform catalyst slurry. Weighing the mass m of the bare anode diffusion layer0Coating PtRuFe/C catalyst slurry with 50% of metal loading on an anode diffusion layer, and then placing the anode diffusion layer in a vacuum drying oven for drying to obtain a first catalytic layer CL1Weighing its mass m1Obtaining CL1The loading of the upper catalyst is 1.0mg/cm2(ii) a PtRuFe/C catalyst slurry with 40% metal loading was coated on CL1Drying in a vacuum drying oven to obtain a second catalytic layer CL2Is called its mass m2Obtaining CL2The loading of the upper catalyst was 0.7mg/cm2(ii) a PtRuFe/C catalyst slurry with 20% metal loading was coated on CL2Drying in a vacuum drying oven to obtain a third catalytic layer CL3Is called its mass m3Obtaining CL3The loading of the upper catalyst is 0.4mg/cm2(ii) a PtRuFe/C catalyst slurry with 10% metal loading was coated on CL3Drying in a vacuum drying oven to obtain a fourth catalytic layer CL4Is called its mass m4Obtaining CL4The loading of the upper catalyst is 0.2mg/cm2Thereby preparing the anode with the three-dimensional gradient structure.
5mg of carbon black powder, 100 mu L of Nafion emulsion and 900 mu L of deionized water are mixed into uniform slurry to be coated on two sides of the carbon paper, and the carbon paper is dried under a vacuum drying oven to prepare the cathode.
According to anolyte flow field plate and three-dimensional gradient structureThe anode, the electrolyte bearing cavity, the cathode and the cathode liquid flow field plate are stacked in sequence to form the membrane-free oxygen-free direct methanol fuel cell. The anode uses methanol fuel with the concentration of 0.1mol/L, the thickness of the electrolyte bearing cavity is 0.1mm, and the electrolyte is HClO with the concentration of 0.1mol/L4The solution, catholyte, was 0.44mol/L Fe (ClO)3And 0.22mol/L Fe (ClO)2The mixed solution of (1).
The above embodiments are merely illustrative of the technical solutions of the present invention, and not restrictive, and those skilled in the art may make changes, substitutions, modifications, and simplifications in the spirit of the present invention and equivalent changes without departing from the spirit of the present invention, and shall fall within the protection scope of the claims of the present invention.

Claims (6)

1. A three-dimensional gradient structure anode for a film-free oxygen-free direct methanol fuel cell is characterized in that the anode is a three-dimensional gradient structure obtained by gradient coating of PtRuM/C catalysts with different metal loads on an anode diffusion layer;
the loading amount of metal PtRuM in the PtRuM/C catalyst is 10-80%, and M represents non-platinum group metal elements;
the three-dimensional gradient structure is characterized in that n catalyst layers are sequentially coated on the anode diffusion layer, n is more than or equal to 2, the loading capacity of the catalyst is sequentially reduced along with the increase of the number of the coating layers, and the difference of the loading capacity of the catalyst on the adjacent catalyst layers is 0.1-5mg/cm2；
The three-dimensional gradient structure is characterized in that the catalyst is distributed in a gradient manner along the depth direction of the fuel cell, wherein the loading capacity of the catalyst on the first layer is 1.0-10.0mg/cm2The loading amount of the catalyst in the second layer is 0.5-5.0mg/cm2The loading amount of the catalyst on the third layer is 0.2-3.0mg/cm2… …, until the nth layer, n is more than or equal to 2, the loading of the catalyst is reduced with the increase of the number of the coating layers.
2. A method of making a three-dimensional gradient structured anode for a membraneless oxygen-free direct methanol fuel cell according to claim 1, comprising the steps of:
(1) respectively weighing PtRuM/C catalysts with different metal capacities, mixing the PtRuM/C catalysts with Nafion emulsion and deionized water, and then ultrasonically dispersing for 0.5-6h to form uniform catalyst slurry;
(2) the mass of the bare anode diffusion layer was weighed and recorded as m0；
(3) The PtRuM/C catalyst slurry with the metal loading of 50-80% is coated on an anode diffusion layer, and then the anode diffusion layer is placed in a vacuum drying oven to be dried to obtain a first catalytic layer CL1Weighing its mass m1；
(4) PtRuM/C catalyst slurry with metal loading of 30-60% is coated on CL1Drying in a vacuum drying oven to obtain a second catalytic layer CL2Is called its mass m2；
(5) PtRuM/C catalyst slurry with metal loading of 10-40% is coated on CL2Drying in a vacuum drying oven to obtain a third catalytic layer CL3Is called its mass m3；
(6) By analogy, in the catalyst layer CLn-1Coating PtRuM/C catalyst with gradually reduced metal loading on the catalyst layer to obtain the n-th catalyst layer CLnAnd n is more than or equal to 2, thus preparing the three-dimensional gradient structure anode.
3. The method for preparing the anode with the three-dimensional gradient structure for the membrane-free oxygen-free direct methanol fuel cell according to claim 2, wherein the mass-to-volume ratio of the PtRuM/C catalyst, the Nafion emulsion and the deionized water in the step (1) is 0.5-22mg:100 μ L: 900 μ L.
4. The method for preparing the anode with the three-dimensional gradient structure for the membrane-free oxygen-free direct methanol fuel cell according to claim 2, wherein the membrane-free oxygen-free direct methanol fuel cell comprises an anolyte flow field plate and a catholyte flow field plate, an anode, an electrolyte bearing cavity and a cathode are sequentially stacked between the anolyte flow field plate and the catholyte flow field plate, the electrolyte bearing cavity contains electrolyte, the anode uses methanol as fuel, and the cathode uses a solution of a redox couple with high electrochemical reaction activity and high potential as an oxidant;
the fuel used by the anode is methanol solution with the concentration of 0.1-15 mol/L;
the electrolyte is HClO with the concentration of 0.1-2.5mol/L4A solution;
the cathode adopts Fe as oxidant3+/Fe2+The mixed solution of (1), wherein the high valence ion Fe3+With low valent ion Fe2+The concentration ratio of (A) to (B) is 10:1-2: 1;
the cathode is prepared from carbon black powder, Nafion emulsion and deionized water according to the mass volume ratio of 5-20mg:100 mu L: 900 mul of the mixture is mixed into uniform slurry and then coated on two sides of the carbon paper.
5. The method for preparing the anode with the three-dimensional gradient structure for the membrane-free oxygen-free direct methanol fuel cell as claimed in claim 4, wherein the thickness of the electrolyte bearing cavity is 0.1-2.0 mm.
6. The method for preparing the anode with the three-dimensional gradient structure for the membrane-free oxygen-free direct methanol fuel cell according to claim 4, wherein the anolyte flow field plate and the catholyte flow field plate both adopt graphite plates.
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