Methanol solid oxide fuel cell power generation system
By modifying the surface of the anode pores of the solid oxide fuel cell with barium, the anode carbon deposition problem was solved, the methanol fuel conversion rate and battery durability were improved, and efficient power generation performance was achieved.
Patent Information
- Application Number
- CN202410426943.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-04-10
- Publication Date
- 2025-10-17
AI Technical Summary
Existing solid oxide fuel cells cannot directly use methanol fuel, which causes rapid decay of anode carbon deposits and affects battery performance and durability.
By modifying the anode pore surface with barium, especially using the wet impregnation method of barium nitrate solution, the interfacial pH of the nickel particles is changed, the water-gas reaction is promoted, carbon deposits are prevented, and the methanol conversion capacity and anti-carbon deposition ability are improved.
It improves the carbon deposition resistance and power generation performance of solid oxide fuel cells, extends the durability of the battery, and improves the methanol conversion rate and electrochemical performance.
Smart Images
Figure CN120809888A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present disclosure relates to the field of fuel cell technology, and in particular to a methanol solid oxide fuel cell power generation system. BACKGROUND
[0002] The extensive use of fossil resources has a serious impact on the environment, and energy saving and emission reduction has become the focus of current development. Solid oxide fuel cells have attracted widespread attention due to their outstanding energy conversion efficiency, wide range of fuel applicability, no pollution, and effective utilization of high-quality waste heat. Hydrogen is an ideal fuel for solid oxide fuel cells, but its volume energy density is low, and it needs to be liquefied in a high-pressure environment, so it is difficult to store and transport. In addition, hydrogen has high flammability and explosiveness, and can diffuse in metal materials, causing hydrogen embrittlement effect, so in order to avoid the risks brought by these characteristics of hydrogen, large-scale targeted infrastructure needs to be built. Therefore, it is urgent to find a widely available and green fuel to break the dilemma of solid oxide fuel cells being bound by hydrogen.
[0003] At room temperature and atmospheric pressure, methanol is in a liquid state, and its volume energy density is much higher than that of hydrogen (the volume energy density of methanol is 15.80 MJ / L, and that of hydrogen is only 8.50 MJ / L), making methanol more convenient than hydrogen in storage and transportation, and an excellent hydrogen storage medium. In addition, methanol has a quite mature production process, and industrial production generally uses the method of synthesizing methanol by pressurized catalytic hydrogenation of carbon monoxide and carbon dioxide, and can also be extracted and synthesized from plants and household waste. Therefore, the development of methanol solid oxide fuel cells is extremely promising.
[0004] The main obstacle to the commercialization of methanol solid oxide fuel cells is that the most advanced solid oxide fuel cells cannot directly use methanol or low water-carbon ratio methanol, and the anode of the cell will quickly deteriorate due to carbon deposition. The most common method is to add a large amount of water to the fuel, i.e., high water-carbon ratio, and the second is anode material modification. Adding a large amount of water can easily lead to fuel dilution, reducing the volume energy density of the fuel, increasing the energy consumption of fuel vaporization, and reducing the efficiency of the solid oxide fuel cell system, while the performance of the cell will also be weakened. Anode modification focuses on retaining the excellent electrochemical performance of nickel-based anodes, and although it improves the ability to resist carbon deposition, it also reduces the electrochemical performance of the cell, and lacks research on large active area cells that directly use methanol. It can be seen that there is still a great gap in the field of direct methanol solid oxide fuel cells. SUMMARY
[0005] The present disclosure provides a methanol solid oxide fuel cell power generation system to at least solve the above technical problems existing in the prior art.
[0006] According to a first aspect of the present disclosure, there is provided a methanol solid oxide fuel cell power generation system, comprising a gas supply unit, a heating unit, and a discharge unit;
[0007] The gas supply unit includes a methanol solution storage device for storing methanol solution;
[0008] The discharge unit includes a solid oxide fuel cell, which includes an anode and a cathode. The anode includes a fuel electrode inlet pipe for introducing methanol and water vapor; the pore surface of the anode is modified with barium; and the cathode includes an air electrode inlet pipe for introducing air or oxygen.
[0009] The heating unit includes a water vapor generator and a temperature-controlled electric furnace; one side of the water vapor generator is connected to the methanol solution storage device, and the other side is connected to the fuel electrode air inlet pipe, and is used to heat the methanol solution in the methanol solution storage device and convert it into methanol water vapor, and the methanol water vapor is introduced into the anode of the solid oxide fuel cell as fuel gas; the temperature-controlled electric furnace is used to heat the solid oxide fuel cell to provide the operating temperature of the solid oxide fuel cell, so that the methanol water vapor and the air or oxygen undergo an electrochemical reaction to output electrical energy.
[0010] In one embodiment, the solid oxide fuel cell is a flat tube solid oxide fuel cell, comprising the anode, an electrolyte layer, a barrier layer and the cathode; the anode comprises an anode support layer and an anode functional layer.
[0011] Specifically, the thickness of the anode support layer is 1 to 1.5 mm.
[0012] Specifically, the thickness of the anode functional layer is 13-15 μm.
[0013] Specifically, the thickness of the electrolyte layer is 15 to 20 μm.
[0014] Specifically, the thickness of the barrier layer is 2 to 3 μm.
[0015] Specifically, the thickness of the anode is 15-20 μm.
[0016] In one embodiment, in the methanol-water vapor, the ratio of water vapor to carbon content in methanol (S / C) is 0.7 to 0.75.
[0017] Specifically, the solid oxide fuel cell proposed in the present disclosure can directly use low water-to-carbon ratio methanol as fuel.
[0018] In an embodiment, the method of modifying the barium is by wet impregnation of the pore surface of the anode with a barium nitrate (Ba(N03)2) solution.
[0019] Specifically, the barium-modified fuel electrode surface changes the interfacial pH of the nickel particles in the anode, thereby preferentially adsorbing water on the anode surface during the reaction, promoting the water-gas reaction (water and carbon monoxide react to produce hydrogen and carbon dioxide) in the cell, and preventing the production of carbon deposition caused by excessive carbon monoxide concentration, which is the mechanism for improving the carbon deposition resistance. In addition, the conversion of methanol also has a similar mechanism, and the promotion of the water-gas reaction will further promote the conversion and decomposition of methanol, so that the barium modification can improve the conversion of methanol in the solid oxide fuel cell, thereby improving the power generation capacity and carbon deposition resistance.
[0020] Specifically, the concentration of the barium nitrate solution is 0.3-0.4 mol / L.
[0021] More specifically, the concentration of the barium nitrate solution is 0.3 mol / L.
[0022] Specifically, the temperature of the barium nitrate solution is 70-75°C.
[0023] Specifically, the method of wet impregnation of the pore surface of the anode with the barium nitrate solution includes the following steps: sealing one end of the fuel electrode pore of the solid oxide fuel cell with wax, injecting the barium nitrate solution (70-75°C) into the fuel electrode channel through a sample injector, and then sealing the other end of the fuel electrode pore of the solid oxide fuel cell with wax; placing the solid oxide fuel cell at this time in an oven, maintaining at 50-55°C for 24-25 h to ensure that the barium nitrate solution is fully impregnated into the pores of the anode; then drying at 90-95°C for 1-1.25 h to remove the wax; and finally placing the solid oxide fuel cell in an electric resistance furnace, maintaining at 900-910°C for 3-3.2 h, and then reducing to room temperature, thereby completing the surface modification of the anode pores.
[0024] In an embodiment, the methanol solid oxide fuel cell power generation system further comprises a gas compressor connected to the air electrode gas inlet pipe for compressing the air or oxygen and introducing it into the cathode of the solid oxide fuel cell.
[0025] In an embodiment, the methanol solid oxide fuel cell power generation system further comprises a first flow meter connected to one side of the gas compressor and the other side of the air electrode gas inlet pipe for monitoring the flow of the air or oxygen.
[0026] In an embodiment, the flow rate of the air or oxygen is 1.0-1.2 SLM.
[0027] In an embodiment, the discharging unit further comprises a current collecting device and a direct current power supply; the current collecting device comprises a fuel electrode current collecting column and an air electrode current collecting column, the fuel electrode current collecting column is connected with the anode of the solid oxide fuel cell for collecting the current generated by the anode, and the air electrode current collecting column is connected with the cathode of the solid oxide fuel cell for collecting the current generated by the cathode.
[0028] The direct current power supply is connected with the solid oxide fuel cell.
[0029] In an embodiment, the gas supplying unit further comprises a nitrogen storage device and a hydrogen storage device, the nitrogen storage device and the hydrogen storage device are respectively connected with the fuel electrode gas inlet pipe for respectively introducing nitrogen and hydrogen into the fuel electrode gas inlet pipe and into the anode.
[0030] Specifically, the nitrogen introduced into the fuel electrode gas inlet pipe is used for purging the pore channels of the anode to discharge foreign matters in the air and the fuel electrode gas inlet pipe; the hydrogen introduced into the fuel electrode gas inlet pipe is used for reducing the nickel oxide of the anode support layer and the anode functional layer (i.e. the fuel electrode) into metal nickel, and the open circuit voltage of the cell is detected during the reduction process until the open circuit voltage is stable.
[0031] In an embodiment, the gas supplying unit further comprises a second flow meter and a third flow meter, one side of the second flow meter is connected with the nitrogen storage device, the other side is connected with the fuel electrode gas inlet pipe for monitoring the flow rate of the nitrogen; one side of the third flow meter is connected with the hydrogen storage device, the other side is connected with the fuel electrode gas inlet pipe for monitoring the flow rate of the hydrogen.
[0032] In an embodiment, the flow rate of the nitrogen is 0.3-0.35 SLM.
[0033] In an embodiment, the flow rate of the hydrogen is 0.3-0.35 SLM.
[0034] In an embodiment, a plunger pump is further arranged between the methanol solution storage device and the water vapor generator, one side of the plunger pump is connected with the methanol solution storage device, the other side is connected with the water vapor generator for pumping the methanol solution in the methanol solution storage device into the water vapor generator.
[0035] In an embodiment, the plunger pump is a double plunger pump.
[0036] In an embodiment, the temperature of the water vapor generator is 130-140°C.
[0037] In a preferred embodiment, the temperature of the water vapor generator is 130°C.
[0038] In an embodiment, the solid oxide fuel cell is placed in the temperature-controlled electric furnace.
[0039] In an embodiment, the temperature of the temperature-controlled electric furnace is 700-800°C.
[0040] In a preferred embodiment, the temperature of the temperature-controlled electric furnace is 750°C.
[0041] In an embodiment, the methanol solid oxide fuel cell power generation system further comprises a current testing system connected to the anode of the solid oxide fuel cell, for detecting the discharge current of the methanol water vapor in the anode, so as to achieve the target required output voltage.
[0042] In an embodiment, the electric energy output by the methanol water vapor and the air or oxygen in the solid oxide fuel cell after the electrochemical reaction is used to supply an electrical appliance, so as to operate the electrical appliance.
[0043] Specifically, the electrical appliance includes but is not limited to a power supply system, an electric motor, etc.
[0044] In an embodiment, the reaction occurring in the anode of the methanol solid oxide fuel cell is that the methanol water vapor reacts at the fuel electrode triple phase interface to generate carbon monoxide, hydrogen and carbon dioxide, and the reaction equation is as follows:
[0045]
[0046]
[0047]
[0048] According to an embodiment of the present disclosure, at least the following beneficial effects are achieved:
[0049] 1. The battery of the present disclosure retains the advantages of high mechanical strength and easy sealing of the flat tube type solid oxide fuel cell, and improves the carbon deposition resistance of the battery, solves the carbon deposition problem of the nickel-based anode when applying alcohol fuel, and is of great significance to improving the durability and power generation performance of the methanol solid oxide fuel cell.
[0050] 2. Currently, there is no commercial product for solid oxide fuel cell directly using methanol as fuel, and the main technical challenge is that the active reaction sites of the nickel-based anode used in the most advanced solid oxide fuel cell are covered and wrapped by carbon deposition when directly using methanol fuel, resulting in performance degradation, and the carbon deposition further causes structural damage to the anode. The present disclosure improves the anti-carbon deposition capability when directly using methanol by modifying the pore surface of the anode with barium.
[0051] 3. Durability is an important indicator of methanol solid oxide fuel cell, and the battery prepared by the present disclosure has higher durability performance improvement than the unmodified flat tube type solid oxide fuel cell under the same working conditions using methanol as fuel.
[0052] It should be understood that the content described in this part is not intended to identify key or important features of the embodiments of the present disclosure, nor is it used to limit the scope of the present disclosure. Other features of the present disclosure will become apparent through the following description. BRIEF DESCRIPTION OF DRAWINGS
[0053] The above and other objects, features and advantages of the exemplary embodiments of the present disclosure will be more apparent from the following detailed description read in conjunction with the accompanying drawings, in which several embodiments of the present disclosure are shown by way of example, and in which:
[0054] In the drawings, identical or corresponding reference numerals indicate identical or corresponding parts.
[0055] Figure 1 A flowchart of modifying the pore surface of the anode of the solid oxide fuel cell with barium in Example 1 of the present disclosure is shown;
[0056] Figure 2 A structural schematic diagram of the methanol solid oxide fuel cell power generation system in Example 1 of the present disclosure is shown;
[0057] Figure 3 A schematic diagram of the assembly of the solid oxide fuel cell and the current collecting device in Example 1 of the present disclosure is shown;
[0058] Figure 4 Current-voltage characteristic curves of the solid oxide fuel cell with barium modification of the anode pore surface and the solid oxide fuel cell without modification of the anode pore surface in the test example of the present disclosure are shown; wherein (a) is the curve of the solid oxide fuel cell without modification of the anode pore surface; (b) is the curve of the solid oxide fuel cell with barium modification of the anode pore surface;
[0059] Figure 5 The component test of the exhaust gas under open circuit conditions and the methanol conversion rate results in the test example of the present disclosure are shown;
[0060] Figure 6 The figure shows the durability test results of the batteries of Example 1 and Comparative Example 1 in the test examples of the present disclosure;
[0061] Figure 7 The figure shows the Raman spectrum test results of the batteries of Example 1 and Comparative Example 1 after durability test in the test examples of the present disclosure.
[0062] Reference numerals:
[0063] 1-Injecting barium nitrate solution into the fuel electrode channel of the solid oxide fuel cell; 2-Placing the solid oxide fuel cell impregnated with barium nitrate solution in a box-type resistance furnace for heat preservation; 10-Solid oxide fuel cell; 11-Fuel electrode air inlet pipe; 12-Air electrode air inlet pipe; 13-Fuel electrode current collecting column; 14-Air electrode current collecting column; 20-Methanol solution storage device; 21-Double plunger pump; 22-Water vapor generator; 23-Nitrogen storage device; 24-Second flowmeter; 25-Hydrogen storage device; 26-Third flowmeter; 30-Air compressor; 31-First flowmeter; 32-Current testing system; 33-Electrical appliances. DETAILED DESCRIPTION
[0064] To make the purposes, features, and advantages of the present disclosure more apparent and understandable, the technical solutions in the embodiments of the present disclosure will be clearly and completely described below in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present disclosure, not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of the present disclosure without creative work shall fall within the scope of protection of the present disclosure.
[0065] Example 1
[0066] This embodiment provides a methanol solid oxide fuel cell power generation system 1, which is specifically as follows:
[0067] (1) Barium modification of the pore surface of the anode of the solid oxide fuel cell: Figure 1 Schematic diagram, weigh 15.68g of barium nitrate powder, dissolve it in 200mL of deionized water, and stir it at 70℃ for 2h to obtain a 0.3mol / L barium nitrate solution for impregnation. Use wax to seal one end of the fuel electrode channel of the solid oxide fuel cell, and inject the prepared barium nitrate solution (70℃) into the fuel electrode channel through the injector (see Figure 1of step 1) of the above-mentioned procedure, followed by sealing with wax at the other end of the fuel electrode channel of the solid oxide fuel cell; the solid oxide fuel cell at this time is put into an oven, 50°C for 24h, to ensure that the barium nitrate solution fully enters the channels of the anode; then dried at 90°C for 1h, for removal of the wax; finally, the solid oxide fuel cell is put into a box-type resistance furnace, 900°C for 3h (see Figure 1 of step 2) of the above-mentioned procedure, followed by reduction to room temperature, which completes the surface modification of the anode channels.
[0068] (2) As shown in Figure 2 , the above-mentioned power generation system includes a gas supply unit, a heating unit and a discharge unit;
[0069] a. The discharge unit includes a solid oxide fuel cell 10, a current collecting device and a direct current power supply;
[0070] The solid oxide fuel cell 10 (the solid oxide fuel cell after surface modification of the anode channels in (1)) is a flat tube type solid oxide fuel cell, which includes an anode, an electrolyte layer (8YSZ, 8 mol. % yttria stabilized zirconia, thickness 15 μm), a barrier layer (GDC, Gd 0.1 Ce 0.9 O 2-δ , thickness 3 μm) and a cathode (LSCF-GDC, La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ , thickness 15 μm); the anode includes an anode support layer (NiO-3YSZ, 3 mol. % yttria stabilized zirconia, thickness 1.5 mm) and an anode functional layer (NiO-8YSZ, 8 mol. % yttria stabilized zirconia, thickness 15 μm). The anode includes a fuel electrode gas inlet tube 11 for passing in methanol water vapor (low water vapor / carbon content in methanol (S / C) = 0.75); and the channel surface of the anode is barium-modified; the cathode includes an air electrode gas inlet tube 12 for passing in air; one side of a first flow meter 31 is connected to an air compressor 30, and the other side is connected to the air electrode gas inlet tube 12, for monitoring the flow of air (the flow of air is 1.0 SLM) (see Figure 2 and 3 ).
[0071] The current collecting device includes a fuel electrode current collecting column 13 and an air electrode current collecting column 14. The fuel electrode current collecting column 13 is connected with the anode of the solid oxide fuel cell 10 for collecting the current generated by the anode. The air electrode current collecting column 14 is connected with the cathode of the solid oxide fuel cell 10 for collecting the current generated by the cathode. The current collecting device and the solid oxide fuel cell 10 are assembled together through the above structure, and a schematic diagram is shown in Figure 3
[0072] A direct current power source is connected with the solid oxide fuel cell 10.
[0073] b. The gas supply unit includes a methanol solution storage device 20, a double plunger pump 21, a nitrogen storage device 23, a second flow meter 24, a hydrogen storage device 25, and a third flow meter 26.
[0074] The methanol solution storage device 20 is used for storing the methanol solution. One side of the double plunger pump 21 is connected with the methanol solution storage device 20, and the other side is connected with the water vapor generator 22, for pumping the methanol solution in the methanol solution storage device 20 into the water vapor generator 22.
[0075] One side of the second flow meter 24 is connected with the nitrogen storage device 23, and the other side is connected with the fuel electrode gas inlet pipe 11 of the solid oxide fuel cell 10, for monitoring the flow rate of the nitrogen gas (the flow rate of the nitrogen gas is 0.3 SLM, and the nitrogen gas is supplied for 5 min) supplied into the fuel electrode gas inlet pipe 11. The supply of the nitrogen gas into the fuel electrode gas inlet pipe 11 is used for purging the pores of the anode and discharging the foreign matters in the air and the fuel electrode gas inlet pipe 11.
[0076] One side of the third flow meter 26 is connected with the hydrogen storage device 25, and the other side is connected with the fuel electrode gas inlet pipe 11 of the solid oxide fuel cell 10, for monitoring the flow rate of the hydrogen gas (the flow rate of the hydrogen gas is 0.3 SLM) supplied into the fuel electrode gas inlet pipe 11. The supply of the hydrogen gas into the fuel electrode gas inlet pipe 11 is used for reducing the nickel oxide of the anode support layer and the anode functional layer (fuel electrode) into metallic nickel. During the reduction process, the open circuit voltage of the cell is detected until the open circuit voltage is stable.
[0077] c. The heating unit includes a water vapor generator 22 and a temperature control electric furnace.
[0078] One side of the water vapor generator 22 is connected with the double plunger pump 21, and the other side is connected with the fuel electrode gas inlet pipe 11 of the solid oxide fuel cell 10. The double plunger pump 21 pumps the methanol solution in the methanol solution storage device 20 into the water vapor generator 22 (the flow rate is 0.3 g / min). The water vapor generator 22 heats (the temperature is 130℃) the methanol solution to convert it into methanol water vapor, which is supplied as fuel gas into the anode of the solid oxide fuel cell 10.
[0079] The solid oxide fuel cell 10 is placed in a temperature-controlled electric furnace, which heats the solid oxide fuel cell 10 to provide an operating temperature (750°C, maintained constant). This allows the methanol vapor and air to undergo an electrochemical reaction, generating electrical energy that is then supplied to an electrical device 33, such as an electric motor, to operate the device 33. A current measurement system 32 is connected to the anode of the solid oxide fuel cell 10 to detect the discharge current of the methanol vapor in the anode, thereby achieving the target output voltage.
[0080] Comparative Example 1
[0081] This comparative example provides a methanol solid oxide fuel cell power generation system 2, which differs from Example 1 in that the anode pore surface of the solid oxide fuel cell in this comparative example is not modified, and the rest is the same as Example 1.
[0082] Test example
[0083] 1. The current-voltage characteristics of the solid oxide fuel cell with barium-modified anode pore surface in Example 1 and the solid oxide fuel cell with unmodified anode pore surface in Comparative Example 1 were tested, and the tail gas generated under open circuit conditions was dried and then subjected to gas phase analysis. The current-voltage characteristic curve is shown in FIG. Figure 4 As shown, the solid oxide fuel cell ( Figure 4 (a) At 750°C and 0.8V, the power density is 326.72mWcm -2 , while the solid oxide fuel cell ( Figure 4 (b) At 750°C and 0.8V, the power density is 452.87mW cm -2 The analysis results of the exhaust gas components are as follows: Figure 5 As shown, Figure 5 Under open-circuit conditions, the tail gas consisted of hydrogen, carbon monoxide, and carbon dioxide, with no methane present. The methanol conversion rate increased from 89.4% in the unmodified cell to 92.7% in the modified cell, demonstrating that the flat-tube solid oxide fuel cell of Example 1 improved both the methanol conversion rate and the electrochemical performance under methanol conditions.
[0084] 2. Using the solid oxide fuel cell with barium modified anode pore surface in Example 1 and the solid oxide fuel cell with unmodified anode pore surface in Comparative Example 1, methanol was tested at 750°C with a flow rate of 200 mA / cm 2 The current density is constant current discharge, and the results are as follows Figure 6 shown. Figure 6 It shows that the voltage of the battery of Comparative Example 1 decays rapidly and drops to 0 within one day, while the battery of Example 1 can operate stably for more than 500 hours.
[0085] 3. Raman spectroscopy was performed on the anode channel surface of the barium modified solid oxide fuel cell after durability testing of Example 1 and on the anode channel surface of the unmodified solid oxide fuel cell of Comparative Example 1 to characterize the carbon deposition in the cells, and the results are shown in Figure 7 Figure 7 As shown, carbon deposition was formed in the inlet, middle and outlet of the fuel electrode channel of the unmodified cell of Comparative Example 1, while no carbon deposition was formed in the inlet, middle and outlet of the fuel electrode channel of the barium modified cell of Example 1. This shows that the barium modification of the anode channel surface of the solid oxide fuel cell greatly improves the carbon deposition resistance of the anode.
[0086] It should be understood that the various forms of flow shown above can be reordered, added to, or deleted from without departing from the scope of the present disclosure. For example, the steps recited in the disclosure can be executed in parallel, executed in series, or executed in different orders, as long as the desired results of the technical solutions of the disclosure are achieved, and the present disclosure is not limited herein.
[0087] In addition, the terms "first", "second", etc. are only used for descriptive purposes and should not be construed as indicating or implying relative importance or implicitly indicating the number of indicated technical features. Therefore, the features defined with "first", "second" can explicitly or implicitly include at least one of the features. In the description of the present disclosure, the meaning of "a plurality of" is two or more, unless otherwise specifically limited.
[0088] The above description is only a specific implementation of the present disclosure, but the protection scope of the present disclosure is not limited thereto, and any person skilled in the art can easily think of changes or replacements within the technical scope disclosed in the present disclosure, which should be covered within the protection scope of the present disclosure. Therefore, the protection scope of the present disclosure should be subject to the protection scope of the claims.
Claims
1. A methanol solid oxide fuel cell power generation system, characterized in that: The methanol solid oxide fuel cell power generation system includes a gas supply unit, a heating unit and a discharge unit; The gas supply unit includes a methanol solution storage device for storing methanol solution; The discharge unit includes a solid oxide fuel cell, which includes an anode and a cathode. The anode includes a fuel electrode inlet pipe for introducing methanol and water vapor; the pore surface of the anode is modified with barium; and the cathode includes an air electrode inlet pipe for introducing air or oxygen. The heating unit includes a water vapor generator and a temperature-controlled electric furnace; one side of the water vapor generator is connected to the methanol solution storage device, and the other side is connected to the fuel electrode air inlet pipe, and is used to heat the methanol solution in the methanol solution storage device and convert it into methanol water vapor, and the methanol water vapor is introduced into the anode of the solid oxide fuel cell as fuel gas; the temperature-controlled electric furnace is used to heat the solid oxide fuel cell to provide the operating temperature of the solid oxide fuel cell, so that the methanol water vapor and the air or oxygen undergo an electrochemical reaction to output electrical energy.
2. The methanol solid oxide fuel cell power generation system according to claim 1, characterized in that: The barium modification method comprises: wet impregnating the pore surface of the anode with a barium nitrate solution, thereby completing the modification of the pore surface of the anode; Preferably, the concentration of the barium nitrate solution is 0.3-0.4 mol / L, and the temperature is 70-75°C.
3. The methanol solid oxide fuel cell power generation system according to claim 1, characterized in that: The solid oxide fuel cell is a flat tube type solid oxide fuel cell, comprising the anode, an electrolyte layer, a barrier layer and the cathode; the anode comprises an anode support layer and an anode functional layer.
4. The methanol solid oxide fuel cell power generation system according to claim 1, characterized in that: In the methanol water vapor, the ratio of water vapor to carbon content in methanol is 0.7 to 0.
75.
5. The methanol solid oxide fuel cell power generation system according to claim 1, characterized in that: The methanol solid oxide fuel cell power generation system further includes a gas compressor, which is connected to the air electrode inlet pipe and is used to compress the air or oxygen and pass it into the air electrode inlet pipe and into the cathode of the solid oxide fuel cell; Preferably, the methanol solid oxide fuel cell power generation system further includes a first flow meter, one side of which is connected to the gas compressor, and the other side of which is connected to the air electrode inlet pipe, for monitoring the flow of the air or oxygen.
6. The methanol solid oxide fuel cell power generation system according to claim 1, characterized in that: The discharge unit further includes a current collecting device and a DC power supply; the current collecting device includes a fuel electrode current collecting column and an air electrode current collecting column, the fuel electrode current collecting column is connected to the anode of the solid oxide fuel cell, and is used to collect the current generated by the anode; the air electrode current collecting column is connected to the cathode of the solid oxide fuel cell, and is used to collect the current generated by the cathode; The DC power supply is connected to the solid oxide fuel cell.
7. The methanol solid oxide fuel cell power generation system according to claim 1, characterized in that: The gas supply unit further includes a nitrogen storage device and a hydrogen storage device, wherein the nitrogen storage device and the hydrogen storage device are respectively connected to the fuel electrode air inlet pipe, and are used to respectively pass nitrogen and hydrogen into the fuel electrode air inlet pipe and into the anode; Preferably, the gas supply unit also includes a second flowmeter and a third flowmeter, one side of the second flowmeter is connected to the nitrogen storage device, and the other side is connected to the fuel electrode air inlet pipe, for monitoring the flow rate of the nitrogen; one side of the third flowmeter is connected to the hydrogen storage device, and the other side is connected to the fuel electrode air inlet pipe, for monitoring the flow rate of the hydrogen.
8. The methanol solid oxide fuel cell power generation system according to claim 1, characterized in that: A plunger pump is further provided between the methanol solution storage device and the water vapor generator, one side of the plunger pump is connected to the methanol solution storage device, and the other side is connected to the water vapor generator, for pumping the methanol solution in the methanol solution storage device into the water vapor generator; Preferably, the temperature of the water vapor generator is 130-140°C.
9. The methanol solid oxide fuel cell power generation system according to claim 1, characterized in that: The solid oxide fuel cell is placed in the temperature-controlled electric furnace; Preferably, the temperature of the temperature-controlled electric heating furnace is 700-800°C.
10. The methanol solid oxide fuel cell power generation system according to claim 1, characterized in that: The methanol solid oxide fuel cell power generation system further includes a current testing system, which is connected to the anode of the solid oxide fuel cell and is used to detect the discharge current of the methanol water vapor in the anode, so as to achieve the target output voltage; Preferably, the electrical energy outputted after the electrochemical reaction between the methanol vapor and the air or oxygen in the solid oxide fuel cell is used to supply electrical appliances to operate the electrical appliances.