Fuel cell without CO2 emission and electro-deposition manufacturing method of electrode of fuel cell

Abstract

The invention relates to the technical field of fuel cells, and particularly discloses a fuel cell without CO2 emission and an electrodeposition manufacturing method of an electrode of the fuel cell, the fuel cell is used for directly oxidizing ethanol into acetate, the fuel cell comprises an anode electrode, a cathode electrode and an ionic membrane arranged between the anode electrode and the cathode electrode, and the anode electrode is a nickel net electrode on which Au and Pt are deposited in sequence. The fuel cell formed based on the Pt-Au / NM electrode realizes efficient and high-selectivity simultaneous production of acetate value-added chemicals and electric energy under the condition of no CO2 emission, and has good economic benefits and environmental benefits.

Description

Technical Field

[0001] The present invention relates to the technical field of fuel cells, and particularly to an electroplating manufacturing method of a fuel cell without CO 2 emission and its electrodes. Background Art

[0002] Carbon-based fuels, covering fossil fuels and biomass fuels, are key primary energy sources and raw materials. However, traditional carbon-based fuels have low efficiency in the power generation field and produce a large amount of carbon dioxide. Although hydrogen is regarded as a clean energy source, it is currently mainly produced through the reforming process of fossil fuels, which not only consumes high energy but also emits a large amount of CO 2 . In addition, compared with liquid carbon-based fuels, hydrogen has a low volumetric energy density, resulting in high storage and transportation costs and safety risks. In contrast, bioethanol is regarded as a potential clean fuel, which has the advantages of low price, liquid state, renewable, high volumetric energy density, mature production infrastructure and industry, and easy storage and transportation. Bioethanol fuel can be manufactured through the fermentation process using biomass raw materials such as wood, straw, and corn. Ethanol fuel can also be prepared in large quantities by catalytic hydrogenation, and the CO 2 and hydrogen used are derived from the electrolysis of renewable energy water, so as to maximize the utilization of energy and resources, promote the development of a low-carbon energy system, and achieve "carbon emission reduction and carbon fixation". In addition, a direct ethanol fuel cell (DEFC) can directly convert ethanol fuel into electrical energy, showing extremely high energy conversion efficiency.

[0003] Platinum (Pt)-based catalysts have long been considered an ideal choice for the anode electrode of a direct ethanol fuel cell (DEFC). However, the strong adsorption of platinum-based catalysts to the intermediate products of the ethanol oxidation reaction causes ethanol to easily undergo excessive dehydrogenation at the anode, thereby generating CO 2 this greenhouse gas. Furthermore, the strong adsorption of the CO intermediate formed during the excessive dehydrogenation process on the platinum surface may cause "poisoning" of the catalyst. Therefore, applying a platinum-based catalyst anode electrode with both high stability and no CO 2 emission in a DEFC is a quite challenging task.

[0004] On the other hand, acetate, as a key C2 industrial raw material chemical, has versatility and wide application potential and is widely used in many fields such as chemical product preparation, food additives, cosmetics, pharmaceuticals, environmental protection and agriculture. However, the current industrial production of acetate mainly relies on fossil energy and is synthesized through methanol carbonylation technology, which requires the use of organic metal catalysts and halide promoters under high temperature and high pressure. This method not only consumes a lot of energy and resources, but also has the limitations of fossil energy, low selectivity, toxicity of raw material CO, and the generated CO 2 The challenges are that byproducts such as wastewater and CO2 are generated. 2 The technology of reducing CO to multi-carbon C2+ products has opened up a promising new avenue for sustainable fuel and chemical synthesis, although it still requires a lot of energy consumption. In addition, photocatalytic systems, piezoelectric catalytic systems, photoelectrocatalytic systems, and photothermal catalytic systems have been tried for the catalysis of CO 2 The reduction generates C2 products, but they are still insufficient in synthesis efficiency. Therefore, Pt-based anode electrocatalysts are manufactured and used in DEFC to achieve CO-free 2 The stable, efficient, and highly selective synthesis of acetate and generation of electrical energy under emission conditions is a challenging task.

[0005] Therefore, the prior art still needs to be improved and developed. Summary of the invention

[0006] In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide a CO 2 The electrodeposition manufacturing method of the discharged fuel cell and its electrode is aimed at solving the problem that ethanol is easily over-dehydrogenated on the anode of the existing fuel cell to generate greenhouse gases such as carbon dioxide, causing catalyst poisoning and thus leading to a decrease in battery performance.

[0007] The technical solution of the present invention is as follows:

[0008] A CO-free 2 A fuel cell for direct oxidation of ethanol to acetate, wherein the fuel cell comprises an anode electrode, a cathode electrode and an ion membrane arranged between the anode electrode and the cathode electrode, the anode electrode is a nickel mesh electrode on which Au and Pt are sequentially deposited, and the preparation of the anode electrode comprises the steps of:

[0009] The nickel mesh is pickled to remove the surface oxide layer, and then ultrasonically cleaned for later use;

[0010] Then, the cleaned nickel mesh is clamped and immersed in a gold electrodeposition solution. Au is electrodeposited on the surface of the nickel mesh using an electrochemical workstation in a three-electrode mode. After the electrodeposition is completed, the residual gold electrodeposition solution on the surface is rinsed with deionized water.

[0011] Using the same electro - deposition method, replace the gold electro - deposition solution with a platinum electro - deposition solution, and use an electrochemical workstation to deposit Pt on the Au surface. After the electro - deposition, rinse the electrode with deionized water and dry it to obtain a nickel mesh electrode with Au and Pt deposited successively, denoted as the Pt - Au / NM electrode.

[0012] The fuel cell without CO 2 emission, wherein, adopting a three - electrode mode, using an electrochemical workstation to electro - deposit Au on the nickel mesh surface, including the steps of:

[0013] Prepare a gold electro - deposition solution, which is composed of HAuCl 4 ·4H 2 O, C 6 H 5 Na 3 O 7 and water;

[0014] Adopt a saturated calomel electrode as the reference electrode, a platinum mesh electrode as the counter electrode, and a nickel mesh as the working electrode to form a three - electrode mode;

[0015] Use an electrochemical workstation to electro - deposit gold on the nickel mesh surface in a constant - current mode, wherein the current magnitude is - 100~ - 500 mA / cm -2 , and the electro - deposition time is 1000 - 3600 s.

[0016] The fuel cell without CO 2 emission, wherein, the concentrations of HAuCl 4 ·4H 2 O and C 6 H 5 Na 3 O 7 are 0.2 - 2.0 g / L and 0.15 - 1.5 g / L respectively.

[0017] The fuel cell without CO 2 emission, wherein, using an electrochemical workstation to deposit Pt on the Au surface, including the steps of:

[0018] Prepare a platinum electro - deposition solution, which is composed of H 2 PtCl 6 ·6H 2 O, C 6 H 5 Na 3 O 7 and water;

[0019] Adopt a saturated calomel electrode as the reference electrode, a platinum mesh electrode as the counter electrode, and a nickel mesh with gold deposited on its surface as the working electrode to form a three - electrode mode;

[0020] Platinum is electroplated on the gold surface using an electrochemical workstation in the constant current mode, where the current magnitude is -100 to -500 mA cm -2 , and the electrodeposition time is 1000 - 3600 s.

[0021] The fuel cell without CO 2 emissions, where the concentrations of H 2 PtCl 6 ·6H 2 O, C 6 H 5 Na 3 O 7 are 0.2 - 2.0 g / L and 0.15 - 1.5 g / L respectively.

[0022] The fuel cell without CO 2 emissions, where in the step of pickling the nickel mesh to remove the surface oxide layer and then ultrasonically cleaning it for standby, the pickling solution is hydrochloric acid, sulfuric acid or nitric acid; the concentration of the pickling solution is 1 - 2 mol / L; the time for ultrasonic cleaning is 5 - 20 min.

[0023] The fuel cell without CO 2 emissions, where the cathode electrode material is Pt / C or Pd / C.

[0024] The fuel cell without CO 2 emissions, where the ion exchange membrane is an anion exchange membrane.

[0025] The fuel cell without CO 2 emissions, where the length of the nickel mesh is 1.5 - 75 cm and the width is 1 - 50 cm.

[0026] Beneficial effects: The present invention prepares the Pt - Au / NM electrode by a two - step electrodeposition method, which effectively avoids the strong adsorption of intermediate products during the ethanol oxidation reaction by traditional platinum - based catalysts, thereby preventing excessive dehydrogenation of ethanol on the anode to generate greenhouse gases such as CO 2 , improving the selectivity and environmental friendliness of the fuel cell; the prepared Pt - Au / NM electrode has excellent stability, can effectively inhibit the strong adsorption of intermediate products on the catalyst surface, avoid catalyst poisoning, and thus extend the service life of the fuel cell; by optimizing factors such as electrodeposition parameters and concentrations, the catalytic activity and selectivity of the prepared electrode are improved, thereby enhancing the overall performance of the fuel cell; the present invention uses a mature electrodeposition technology to prepare the electrode, the process route is simple, and the raw materials are widely available, which is conducive to reducing the manufacturing cost; the fuel cell based on the Pt - Au / NM electrode realizes operation without CO 2Under emission conditions, acetate value-added chemicals and electric energy are produced efficiently and with high selectivity simultaneously, with good economic and environmental benefits. Description of the Drawings

[0027] Figure 1 Schematic diagram of the direct ethanol fuel cell model prepared by the present invention.

[0028] Figure 2 SEM image of the Pt-Au / NM electrode fabricated in Example 1.

[0029] Figure 3 TEM image of the Pt-Au / NM electrode fabricated in Example 1.

[0030] Figure 4 Discharge power density curve of the fuel cell tested by an electrochemical workstation in Example 1.

[0031] Figure 5 Faraday efficiency of acetate, the ethanol oxidation product at the anode of the fuel cell tested by ion chromatography in Example 1.

[0032] Figure 6 Column chart of the concentration comparison of carbonate in the anode electrolyte of the fuel cell before and after potentiostatic testing tested by ion chromatography in Example 1. Detailed Description of the Invention

[0033] The present invention provides a fuel cell without CO 2 emission and an electrodeposition manufacturing method for its electrode. To make the objectives, technical solutions and effects of the present invention clearer and more definite, the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0034] During the ethanol oxidation reaction process of traditional platinum-based catalysts, due to the strong adsorption of intermediate products, ethanol is prone to excessive dehydrogenation on the anode, generating greenhouse gases such as carbon dioxide, reducing the selectivity and environmental friendliness of the fuel cell; at the same time, the strong adsorption of intermediate products on the catalyst surface may cause catalyst poisoning, reducing the stability and service life of the fuel cell.

[0035] Based on this, the present invention provides a fuel cell without CO 2An emission fuel cell, which is used to directly oxidize ethanol to acetate. The fuel cell includes an anode electrode, a cathode electrode, and an ion membrane disposed between the anode electrode and the cathode electrode. The anode electrode is a nickel mesh electrode sequentially deposited with Au and Pt. The preparation of the anode electrode includes the steps of: pickling the nickel mesh to remove the surface oxide layer, and ultrasonically cleaning it for later use; then clamping the cleaned nickel mesh and immersing it in a gold electrodeposition solution, adopting a three-electrode mode, and using an electrochemical workstation to electrodeposit Au on the nickel mesh surface. After the electrodeposition is completed, the surface residual gold electrodeposition solution is rinsed with deionized water; adopting the same electrodeposition method, replacing the gold electrodeposition solution with a platinum electrodeposition solution, and using an electrochemical workstation to plate Pt on the surface of Au. After the electrodeposition is ended, the electrode is rinsed with deionized water and dried to obtain a nickel mesh electrode sequentially deposited with Au and Pt, denoted as the Pt-Au / NM electrode.

[0036] Specifically, as Figure 1 shown, external components composed of a Ti metal plate, a gold-plated current collector, and a graphite flow field plate with a serpentine flow channel are respectively arranged at both ends of the fuel cell. Among them, the Ti metal plate located on the outermost side at both ends of the fuel cell plays a role in supporting and protecting the internal structure, and also helps the mechanical stability and a certain degree of electrical conductivity of the whole battery; the gold-plated current collector is responsible for collecting the current generated on the electrode, effectively conducting the electrons generated by the electrode reaction to realize the output of electric energy, and the good electrical conductivity of gold helps to reduce the resistance and improve the performance of the battery; the graphite flow field plate with a serpentine flow channel, its serpentine flow channel design can make the reaction gas or liquid evenly distributed on the electrode surface, ensuring that the electrode reaction can proceed fully, and the graphite material has good electrical conductivity and chemical stability. In the fuel cell, the anode electrode and the cathode electrode are the key parts where the electrochemical reaction occurs. Ethanol undergoes an oxidation reaction on the anode electrode, and a reduction reaction occurs on the cathode electrode. The two work together to realize the conversion of chemical energy into electrical energy; the ion membrane is located between the anode electrode and the cathode electrode. It allows specific ions to pass through, plays a role in separating reactants and conducting ions, maintains the charge balance inside the battery, and promotes the continuous progress of the electrochemical reaction. The anode electrolyte is transported by a peristaltic pump, which can precisely control the flow rate and flow of the anode electrolyte to ensure the stable progress of the anode reaction; the cathode fuel is adjusted by a flow meter, which can monitor and control the supply of the cathode fuel in real time to meet the requirements of the cathode reaction; the temperature of the whole fuel cell is precisely controlled by a PID temperature controller. The appropriate temperature is crucial for the performance and stability of the battery. The PID temperature controller can automatically adjust according to the set temperature value to make the battery work within the optimal temperature range. As an example, the flow rate of the anode peristaltic pump is 10 - 60 rpm, and the flow rate of the cathode flow meter is 50 - 200 sccm; the temperature control range of the fuel cell is: 30 - 80 °C.

[0037] The anode electrode used in the fuel cell of the present invention is a Pt-Au / NM electrode prepared by a two-step electrodeposition method. The Pt-Au / NM electrode effectively avoids the strong adsorption of intermediate products during the ethanol oxidation reaction by traditional platinum-based catalysts, thereby preventing excessive dehydrogenation of ethanol on the anode to generate CO 2 and other greenhouse gases, improving the selectivity and environmental friendliness of the fuel cell; the prepared Pt-Au / NM electrode has excellent stability, can effectively inhibit the strong adsorption of intermediate products on the catalyst surface, avoid catalyst poisoning, and thus extend the service life of the fuel cell; by optimizing factors such as electrodeposition parameters and concentrations, the catalytic activity and selectivity of the prepared electrode are improved, thereby enhancing the overall performance of the fuel cell; the present invention uses a mature electrodeposition technology to prepare the electrode, the process route is simple, and the raw materials are widely available, which is beneficial to reducing the manufacturing cost; the fuel cell based on the Pt-Au / NM electrode of the present invention realizes the efficient and highly selective simultaneous production of acetate value-added chemicals and electric energy under the condition of no CO 2 emission, with good economic and environmental benefits.

[0038] In some embodiments, during the preparation of the Pt-Au / NM electrode, the nickel mesh preferably has a length of 1.5 - 75 cm and a width of 1 - 50 cm; the pickling solution used in the pickling process is hydrochloric acid, sulfuric acid or nitric acid, and the concentration of the pickling solution is 1 - 2 mol / L; the time for ultrasonic cleaning is 5 - 20 min.

[0039] In some embodiments, a three-electrode mode is adopted, and Au is electrodeposited on the surface of the nickel mesh using an electrochemical workstation, including the steps of: preparing a gold electrodeposition solution, which is composed of HAuCl 4 ·4H 2 O, C 6 H 5 Na 3 O 7 and water. The concentrations of HAuCl 4 ·4H 2 O and C 6 H 5 Na 3 O 7 are 0.2 - 2.0 g / L and 0.15 - 1.5 g / L respectively; a saturated calomel electrode is used as the reference electrode, a platinum mesh electrode is used as the counter electrode, and a nickel mesh is used as the working electrode to form a three-electrode mode; using an electrochemical workstation in a constant current mode, gold is electrodeposited on the surface of the nickel mesh, where the current magnitude is -100~-500 mA cm -2 , and the electrodeposition time is 1000 - 3600 s.

[0040] In some embodiments, platinum is electroplated on the Au surface using an electrochemical workstation, including the steps of: preparing a platinum electrodeposition solution, which consists of H 2 PtCl 6 ·6H 2 O, C 6 H 5 Na 3 O 7 and water. The concentrations of H 2 PtCl 6 ·6H 2 O and C 6 H 5 Na 3 O 7 are 0.2 - 2.0 g / L and 0.15 - 1.5 g / L respectively; using a saturated calomel electrode as the reference electrode, a platinum mesh electrode as the counter electrode, and a nickel mesh with gold deposited on its surface as the working electrode to form a three - electrode mode; using the electrochemical workstation to electroplate platinum on the gold surface in a constant - current mode, where the current magnitude is - 100~ - 500 mA cm -2 , and the electrodeposition time is 1000 - 3600 s.

[0041] In some embodiments, the cathode electrode material is Pt / C or Pd / C.

[0042] In some embodiments, the ion - exchange membrane is an anion - exchange membrane, and the model of the anion - exchange membrane is FAA - 3 - 50 or FAA - 3 - 20 or FAAM - 20.

[0043] In some embodiments, the electrolyte for the ethanol oxidation reaction consists of potassium hydroxide and ethanol; the concentration of potassium hydroxide is 0.5 - 8.0 mol / L, and the concentration of ethanol is 1 - 15 mol / L, but is not limited thereto.

[0044] The present invention will be further explained and illustrated through specific examples as follows:

[0045] Example 1

[0046] A CO - free 2An ethanol-emitting fuel cell for directly oxidizing ethanol to acetate, the fuel cell comprising an anode electrode, a cathode electrode, and an ion membrane disposed between the anode electrode and the cathode electrode. The anode electrode is a nickel mesh electrode sequentially deposited with Au and Pt. The cathode electrode is a carbon paper supporting Pt / C catalyst. The ion membrane is an anion exchange membrane of model FAA-3-20. The anolyte is a mixed aqueous solution of 2 mol / L potassium hydroxide and 2 mol / L ethanol, which is transported by a peristaltic pump at a flow rate of 10 rpm. The cathode fuel transports oxygen at a flow rate of 80 sccm through a flow meter; the fuel cell is temperature-controlled by a PID thermostat, and the operating temperature is controlled at 70 °C; the preparation of the anode electrode includes the steps:

[0047] Cut the nickel mesh (NM) into a size of 1×1.5 cm, and then immerse the NM in 2M hydrochloric acid and ultrasonically clean it for 10 min to remove the surface oxide of the NM. Then clamp the NM electrode and immerse it in the Au electroplating solution. The composition is shown in Table 1. A three-electrode system is composed of a saturated calomel electrode, a Pt mesh electrode, and an NM working electrode. Use an electrochemical workstation to electroplate Au on the surface of the NM in a constant current mode (-100 mA cm -2 , 1800 s), and after the electroplating is completed, rinse the surface residual electroplating solution with deionized water. Then perform the second electroplating. Using the same electroplating method, replace the Au electroplating solution with the Pt electroplating solution in Table 1. Use an electrochemical workstation to electroplate Pt on the surface of Au in a constant current mode (-100 mAcm -2 , 500 s). After the electroplating is finished, rinse the electrode with deionized water and dry it to obtain the Pt-Au / NM electrode.

[0048] Table 1 Composition of the electroplating solution in Example 1

[0049]

[0050]

[0051] Example 2

[0052] A CO-free 2An ethanol-emitting fuel cell for directly oxidizing ethanol to acetate, the fuel cell comprising an anode electrode, a cathode electrode, and an ion membrane disposed between the anode electrode and the cathode electrode, the anode electrode being a nickel mesh electrode sequentially deposited with Au and Pt, the cathode electrode being a carbon paper-supported Pt / C catalyst, and the ion membrane being an anion exchange membrane of model FAA-3-20. The anolyte is an aqueous solution of 2 mol / L potassium hydroxide and 2 mol / L ethanol, which is transported by a peristaltic pump at a flow rate of 30 rpm. The cathode fuel transports oxygen at a flow rate of 160 sccm through a flow meter. The fuel cell is temperature-controlled by a PID thermostat, and the operating temperature is controlled at 70 degrees Celsius; the preparation of the anode electrode includes the steps:

[0053] Cut the nickel mesh (NM) into a size of 2×3 cm, and then immerse the NM in 2M hydrochloric acid and ultrasonically clean it for 10 min to remove the surface oxide of the NM. Then clamp the NM electrode and immerse it in the Au electroplating solution, the composition of which is shown in Table 2, and form a three-electrode system with a saturated calomel electrode, a Pt mesh electrode, and the NM working electrode. Use an electrochemical workstation to electroplate Au on the surface of the NM in a constant current mode (-150 mA cm -2 , 2200 s). After the electroplating is completed, rinse the surface residual electroplating solution with deionized water. Then perform the second electroplating. Using the same electroplating method, replace the Au electroplating solution with the Pt electroplating solution in Table 2, and use an electrochemical workstation to electroplate Pt on the surface of Au in a constant current mode (-150 mA cm -2 , 750 s). After the electroplating is finished, rinse the electrode with deionized water and dry it to obtain the Pt-Au / NM electrode.

[0054] Table 2 Composition of the electroplating solution in Example 2

[0055]

[0056]

[0057] Example 3

[0058] A CO-free 2An ethanol-emitting fuel cell for directly oxidizing ethanol to acetate, the fuel cell comprising an anode electrode, a cathode electrode, and an ion membrane disposed between the anode electrode and the cathode electrode. The anode electrode is a nickel mesh electrode sequentially deposited with Au and Pt. The cathode electrode is a carbon paper-supported Pt / C catalyst. The ion membrane is an anion exchange membrane of model FAA-3-20. The anolyte is a mixed aqueous solution of 2 mol / L potassium hydroxide and 2 mol / L ethanol, which is transported by a peristaltic pump at a flow rate of 60 rpm. The cathode fuel transports oxygen at a flow rate of 200 sccm through a flow meter. The fuel cell is temperature-controlled by a PID temperature controller, and the operating temperature is controlled at 70 °C. The preparation of the anode electrode includes the steps:

[0059] Cut the nickel mesh (NM) into a size of 4×6 cm, and then immerse the NM in 2M hydrochloric acid and ultrasonically clean it for 10 min to remove the surface oxide of the NM. Then, clamp the NM electrode and immerse it in the Au electroplating solution. The composition is shown in Table 3. A three-electrode system is composed of a saturated calomel electrode, a Pt mesh electrode, and the NM working electrode. Use an electrochemical workstation in the constant current mode (-200 mA cm -2 , 2500 s) to electroplate Au on the surface of the NM. After the electroplating is completed, rinse the surface residual electroplating solution with deionized water. Then, perform the second electroplating. Using the same electroplating method, replace the Au electroplating solution with the Pt electroplating solution in Table 3. Use an electrochemical workstation in the constant current mode (-200 mA cm -2 , 900 s) to plate Pt on the surface of the Au. After the electroplating is completed, rinse the electrode with deionized water and dry it to obtain the Pt-Au / NM electrode.

[0060] Table 3 Composition of the electroplating solution in Example 3

[0061]

[0062]

[0063] Perform electron microscopy observation on the Pt-Au / NM electrode prepared in Example 1. The results are as Figure 2 shown. It can be seen from the figure that the electrode presents a network porous structure, and the network porous structure is beneficial to optimizing the mass transfer on the electrode surface to improve the electrocatalytic performance.

[0064] Figure 3 is the TEM image of the Pt-Au / NM electrode. From Figure 3The fringe spacing of 0.209 nm of a single Pt nanoparticle can be seen, which is in good match with the (111) crystal plane of face-centered cubic Pt. The fringe spacing of 0.221 nm of the Au nanoflower clusters is in good match with the (200) crystal plane of face-centered cubic Au. TEM shows that the Pt nanoparticles are loaded on the surface of the Au catalyst, and such a structure helps to fully expose the highly active Pt sites.

[0065] Figure 4 Figure 4 shows the fuel cell discharge power density curve in Example 1 obtained by testing with an electrochemical workstation. Figure 4 It clearly shows that the peak current density of the fuel cell reaches 73 mW / cm 2 .

[0066] Figure 5 Figure 5 presents the Faraday efficiency of the acetate product of ethanol oxidation at the anode of the fuel cell in Example 1 tested by ion chromatography, that is, the conversion rate of ethanol to acetate. The results show that the selectivity of acetate exceeds 95%.

[0067] Figure 6 The concentration change of carbonate in the anode electrolyte of the fuel cell in Example 1 before and after the potentiostatic test was tested by ion chromatography. The test results show that the carbonate concentration remains stable before and after the test without significant increase. This indicates that the direct ethanol fuel cell prepared by the present invention avoids over-oxidation to generate CO 2 during the process of highly selectively oxidizing ethanol to generate acetate, 2 thus achieving the simultaneous generation of acetate electronic chemicals and electric energy under the condition of no CO

[0068] It should be understood that the application of the present invention is not limited to the above examples. For those of ordinary skill in the art, improvements or transformations can be made according to the above description, and all such improvements and transformations should fall within the protection scope of the appended claims of the present invention.

Claims

1. A fuel cell without CO2 emission, characterized in that: The fuel cell is used to directly oxidize ethanol into acetate. The fuel cell comprises an anode electrode, a cathode electrode and an ion membrane arranged between the anode electrode and the cathode electrode. The anode electrode is a nickel mesh electrode on which Au and Pt are sequentially deposited. The preparation of the anode electrode comprises the following steps: The nickel mesh is pickled to remove the surface oxide layer, and then ultrasonically cleaned for later use; Then, the cleaned nickel mesh is clamped and immersed in a gold electrodeposition solution. Au is electrodeposited on the surface of the nickel mesh using an electrochemical workstation in a three-electrode mode. After the electrodeposition is completed, the residual gold electrodeposition solution on the surface is rinsed with deionized water. The same electrodeposition method was used, but the gold electrodeposition solution was replaced with a platinum electrodeposition solution. Pt was plated on the Au surface using an electrochemical workstation. After the electrodeposition, the electrode was rinsed with deionized water. After drying, a nickel mesh electrode with Au and Pt deposited in sequence was obtained, which was recorded as a Pt-Au / NM electrode.

2. The CO2-free fuel cell according to claim 1, characterized in that: Au was electrodeposited on the nickel mesh surface using an electrochemical workstation in a three-electrode mode, including the following steps: preparing a gold electrodeposition solution, wherein the gold electrodeposition solution consists of HAuCl4·4H2O, C6H5Na3O7 and water; A saturated calomel electrode was used as the reference electrode, a platinum mesh electrode was used as the counter electrode, and a nickel mesh was used as the working electrode to form a three-electrode mode; Using an electrochemical workstation in constant current mode, gold was electrodeposited on the surface of the nickel mesh, where the current was -100 to -500 mA cm -2 , the electrodeposition time is 1000-3600s.

3. The CO2-free fuel cell according to claim 2, characterized in that: The concentrations of HAuCl4·4H2O and C6H5Na3O7 are 0.2-2.0 g / L and 0.15-1.5 g / L respectively.

4. The CO2-free fuel cell according to claim 2, characterized in that: Use an electrochemical workstation to plate Pt on the Au surface, including the following steps: preparing a platinum electrodeposition solution, wherein the platinum electrodeposition solution is composed of H2PtCl6·6H2O, C6H5Na3O7 and water; A saturated calomel electrode was used as the reference electrode, a platinum mesh electrode was used as the counter electrode, and a nickel mesh with gold deposited on the surface was used as the working electrode to form a three-electrode mode. Platinum was plated on the gold surface using an electrochemical workstation in constant current mode, where the current was -100 to -500 mA cm -2 , the electrodeposition time is 1000-3600s.

5. A fuel cell without CO2 emission according to claim 4, characterized in that: The concentrations of H2PtCl6·6H2O and C6H5Na3O7 are 0.2-2.0 g / L and 0.15-1.5 g / L respectively.

6. The CO2-free fuel cell according to claim 1, characterized in that: The nickel mesh is pickled to remove the surface oxide layer, and in the standby step after ultrasonic cleaning, the pickling solution is hydrochloric acid, sulfuric acid or nitric acid; the concentration of the pickling solution is 1-2 mol / L; and the ultrasonic cleaning time is 5-20 minutes.

7. The CO2-free fuel cell according to claim 1, characterized in that: The cathode electrode material is Pt / C or Pd / C.

8. The CO2-free fuel cell according to claim 1, characterized in that: The ion membrane is an anion exchange membrane.

9. The CO2-free fuel cell according to claim 1, characterized in that: The length of the nickel mesh is 1.5-75 cm and the width is 1-50 cm.

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