Carbon dioxide electrolytic tank for acidic electrolyte

Abstract

The invention relates to the technical field of carbon dioxide electro-catalytic conversion, in particular to a carbon dioxide electrolytic tank for acidic electrolyte. The electrolytic tank comprises an epoxy resin glass fiber plate a, a cathode collector plate, a gas flow field plate, a silicone rubber gasket a, a cathode electrode, a cathode electrolyte plate, a silicone rubber gasket b, a proton exchange membrane, a silicone rubber gasket c, an anode electrolyte plate, a silicone rubber gasket d, an anode electrode, an anode collector plate and an epoxy resin glass fiber plate b which are arranged in sequence. According to the carbon dioxide electrolytic tank, the diffusion and reaction rate of carbon dioxide gas is increased through the gas flow field plate with the snake-shaped flow field, diffusion of carbon dioxide is promoted, carbonate deposition caused by local alkalinity on the electrodes is avoided, and electrolysis of carbon dioxide in high-concentration acidic electrolyte is achieved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electrocatalytic conversion of carbon dioxide, in particular, and especially relates to a carbon dioxide electrolytic cell for acid electrolyte. BACKGROUND

[0002] The carbon dioxide emission mainly from fossil fuel combustion continues to increase globally, which brings adverse effects and hazards to nature and human beings. In order to realize the clean and low-carbon development of fossil energy, it is necessary to make great efforts to break through the innovation of carbon dioxide resource utilization technology. The electrocatalytic conversion of carbon dioxide is an efficient, mild and controllable carbon dioxide resource utilization technology, which uses renewable energy as driving force and water as reactant to convert carbon dioxide into high value-added chemicals and fuels, and has wide application prospects.

[0003] At present, most of the researches on electrocatalytic conversion of carbon dioxide are mainly carried out in alkaline electrolyte. However, there is a serious problem of carbonate deposition when using alkaline electrolyte. The hydroxyl ions generated in situ during the reaction combine with carbon dioxide under alkaline conditions to form carbonate, which is deposited on the cathode to damage the electrode or shuttles to the anode to cause serious carbon loss. In order to overcome the problem of carbonate deposition in alkaline electrolyte, researchers have begun to explore the carbon dioxide electrolysis reaction in acid electrolyte. Although acid electrolyte can effectively reduce the problem of carbon loss, it has higher requirements for corrosion resistance of electrolytic device and electrode. Maintaining the concentration gradient of hydrogen ions and metal cations on the electrode surface is crucial to inhibit the hydrogen evolution side reaction and maintain the ion conductivity. SUMMARY

[0004] The purpose of the present application is to provide a carbon dioxide electrolytic cell for acid electrolyte, which can improve the acid resistance and carbonate deposition of the electrolytic cell, and realize acid carbon dioxide electrolysis under high concentration electrolyte conditions.

[0005] In order to achieve the above purpose, the technical scheme of the present application is as follows:

[0006] The present application provides a carbon dioxide electrolytic cell for acid electrolyte, which comprises epoxy glass fiber plate a, cathode current collector plate, gas flow field plate, silicon rubber gasket a, cathode electrode, cathode electrolyte plate, silicon rubber gasket b, proton exchange membrane, silicon rubber gasket c, anode electrolyte plate, silicon rubber gasket d, anode electrode, anode current collector plate, epoxy glass fiber plate b arranged in sequence.

[0007] The gas flow field plate is provided with a carbon dioxide gas inlet, so that the carbon dioxide diffuses to the cathode electrode in the gas flow field plate, and the gas diffuses from the back of the cathode electrode to the front to react with the electrolyte;

[0008] The cathode electrolyte plate has a circular cavity a in the middle, and the cathode electrode, the proton exchange membrane and the circular cavity a constitute the cathode electrolyte cavity. The anode electrolyte plate has a circular cavity b in the middle, and the anode electrode, the proton exchange membrane and the circular cavity b constitute the anode electrolyte cavity.

[0009] The cathode electrolyte plate is provided with a cathode electrolyte inlet and a cathode electrolyte outlet, both of which are connected to the circular cavity of the cathode electrolyte plate.

[0010] The anode electrolyte plate is provided with an anode electrolyte inlet and an anode electrolyte outlet, both of which are connected to the circular cavity of the anode electrolyte plate.

[0011] In the above technical solution, a single-channel serpentine flow field is further provided in the middle of the gas flow field plate, through which carbon dioxide gas diffuses to the cathode electrode. This flow field arrangement can promote the diffusion of the reactant carbon dioxide gas.

[0012] In the above technical solution, the gas flow field plate is further made of graphite material or platinum-plated titanium material.

[0013] In the above technical solution, the cathode current collector is a gold-plated copper plate to improve charge conduction efficiency, and the anode current collector is a platinum-plated titanium plate to improve its corrosion resistance and charge conduction efficiency.

[0014] In the above technical solution, both the cathode electrolyte plate and the anode electrolyte plate are made of plexiglass, and the plexiglass material improves their acid resistance.

[0015] In the above technical solution, the thickness of the cathode electrolyte plate is 0.5 to 1.0 cm. This thickness ensures the amount of electrolyte in the liquid cavity within a certain carbon dioxide flow rate range to prevent open circuit.

[0016] In the above technical solution, the cathode electrolyte outlet is located above the cathode electrolyte inlet, and the anode electrolyte outlet is located above the anode electrolyte inlet. By increasing the height of the cathode and anode electrolyte outlets, the expulsion of bubbles during the reaction process is accelerated.

[0017] In the above technical solution, the cathode electrolyte plate is further provided with a reference electrode insertion hole. The reference electrode is inserted into the cathode electrolyte cavity through the reference electrode insertion hole. The reference electrode is inserted from above. The reduction in the distance between the front end of the reference electrode and the cathode electrode effectively reduces the internal resistance of the solution.

[0018] In the above technical solution, the cathode electrode is further described as a gas diffusion electrode with a surface-loaded cathode catalyst, such as nano-copper particles or Ni-NC. The area of ​​the gas diffusion electrode is the same as or slightly larger than the size of the gas flow field to ensure that the gas diffusion electrode covers the entire gas flow field. The perimeter is sealed with a silicone rubber gasket a, and the silicone rubber gasket a has an opening in the middle that matches the cathode electrode. The thickness of the silicone rubber gasket a is the same as the thickness of the cathode electrode.

[0019] In the above technical solution, the anode electrode is further described as follows: the anode electrode is based on porous metal Ti, and the surface is coated with an anode catalyst, such as iridium black, iridium dioxide or platinum carbon. The substrate is stable under acidic conditions. The anode electrode is sealed around the perimeter with a silicone rubber gasket d. The silicone rubber gasket d has an opening in the middle that matches the anode electrode, and the thickness is the same as the thickness of the anode electrode.

[0020] The beneficial effects of this invention are as follows:

[0021] 1. The carbon dioxide electrolysis cell of the present invention improves the diffusion and reaction rate of carbon dioxide gas through a gas flow field plate with a serpentine flow field, promotes carbon dioxide diffusion, avoids carbonate deposition caused by local alkalinity on the electrode, and realizes carbon dioxide electrolysis in acidic high-concentration electrolyte.

[0022] 2. The carbon dioxide electrolyzer of the present invention uses gas flow field plate, electrolyte plate and anode and cathode materials with strong acid resistance to improve the stability of the electrolyzer in acidic environment.

[0023] 3. By optimizing the volume of the cathode electrolyte chamber, this invention effectively reduces the solution impedance from the reference electrode to the working electrode and also avoids air bubbles interfering with the current path to a certain extent. Attached Figure Description

[0024] Figure 1 This is a schematic diagram of the structure of the carbon dioxide electrolysis cell of the present invention;

[0025] Figure 2 This is a schematic diagram of the gas flow field plate of the present invention;

[0026] Figure 3 This is a schematic diagram of the cathode electrolyte plate of the present invention;

[0027] Figure 4 This is a schematic diagram of the structure of the anode electrolyte plate of the present invention;

[0028] Figure 5 This is a schematic diagram of the carbon dioxide electrolysis device of the present invention;

[0029] Figure 6 This is a comparison chart of the total current density of carbon dioxide electroreduction using the carbon dioxide electrolysis device of the present invention and an electrolysis device without a gas flow field plate in Example 1.

[0030] Figure 7 The carbon dioxide electroreduction performance in different acidic potassium chloride electrolytes in Example 1;

[0031] Figure 8 The carbon dioxide electroreduction performance in different acidic potassium chloride electrolytes in Example 2 is shown.

[0032] In the diagram: 1. Epoxy resin fiberglass board a, 2. Cathode current collector, 3. Gas flow field plate, 4. Silicone rubber gasket a, 5. Cathode electrolyte plate, 6. Silicone rubber gasket b, 7. Silicone rubber gasket c, 8. Anode electrolyte plate, 9. Silicone rubber gasket d, 10. Anode current collector, 11. Epoxy resin fiberglass board b, 12. Cathode electrode, 13. Proton exchange membrane, 14. Anode electrode, 15. Power supply, 16. Flow meter, 17. Pressure reducing valve, 18. II 19. Carbon dioxide cylinder; 20. Liquid pump a; 21. Cathode electrolyte tank; 22. Gas-liquid separator; 23. Gas chromatograph; 24. Cathode electrolyte collection tank; 25. Reference electrode; 26. Liquid pump b; 27. Anode electrolyte tank; 28. Anode electrolyte collection tank; 29. ​​Circular cavity a; 30. Circular cavity b; 31. Cathode electrolyte inlet; 32. Cathode electrolyte outlet; 33. Anode electrolyte inlet; 34. Carbon dioxide inlet. Detailed Implementation

[0033] The following non-limiting embodiments are intended to enable those skilled in the art to more fully understand the present invention, but do not limit the invention in any way.

[0034] like Figure 1 As shown, a carbon dioxide electrolyzer for acidic electrolytes includes, in sequence, an epoxy resin glass fiber plate a1, a cathode current collector 2, a gas flow field plate 3, a silicone rubber gasket a4, a cathode electrode 12, a cathode electrolyte plate 5, a silicone rubber gasket b6, a proton exchange membrane 13, a silicone rubber gasket c7, an anode electrolyte plate 8, a silicone rubber gasket d9, an anode electrode 14, an anode current collector 10, and an epoxy resin glass fiber plate b11. Each component is sealed by long screws.

[0035] A single-channel serpentine flow field is provided in the middle of the gas flow field plate 3, and a carbon dioxide inlet 34 is provided in the gas flow field plate 3;

[0036] A circular cavity a28 is provided in the middle of the cathode electrolyte plate 5. The cathode electrode 12, the proton exchange membrane 13 and the circular cavity a28 constitute the cathode electrolyte cavity. A circular cavity b29 is provided in the middle of the anode electrolyte plate. The anode electrode 14, the proton exchange membrane 13 and the circular cavity b29 constitute the anode electrolyte cavity.

[0037] The cathode electrolyte plate 5 is provided with a cathode electrolyte inlet 30, a cathode electrolyte outlet 31 and a reference electrode insertion hole. The cathode electrolyte inlet 30 and the cathode electrolyte outlet 31 are both connected to the circular cavity of the cathode electrolyte plate 5, and the cathode electrolyte outlet 31 is located above the cathode electrolyte inlet 30.

[0038] The anode electrolyte plate 8 is provided with an anode electrolyte inlet 32 ​​and an anode electrolyte outlet 33. Both the anode electrolyte inlet 32 ​​and the anode electrolyte outlet 33 are connected to the circular cavity of the anode electrolyte plate 8. The anode electrolyte outlet 33 is located above the anode electrolyte inlet 32.

[0039] The silicone rubber gasket a4 has an opening in the middle that matches the cathode electrode 12, and its thickness is the same as that of the cathode electrode 12. The silicone rubber gasket d9 has an opening in the middle that matches the anode electrode 14, and its thickness is the same as that of the anode electrode 14.

[0040] like Figure 2 As shown, a carbon dioxide electrolysis device for acidic electrolytes includes: the aforementioned electrolysis cell, power supply 15, shut-off valve, liquid pump a19, liquid pump b25, cathode electrolyte tank 20, cathode electrolyte collection tank 23, anode electrolyte tank 26, anode electrolyte collection tank 27, carbon dioxide cylinder 18, and gas-liquid separator 21.

[0041] The cathode current collector 2 and the anode current collector 10 are respectively connected to the working electrode and the counter electrode of the power supply 15 and are powered by the power supply 15.

[0042] The carbon dioxide inlet 34 of the gas flow field plate 3 is connected to the carbon dioxide cylinder 18. A pressure reducing valve 17 and a flow controller 16 are installed on the connecting pipeline to control and stabilize the gas flow rate. The carbon dioxide gas is introduced into the single-channel serpentine flow field in the gas flow field plate 3 through the inlet 34 and diffuses to the cathode electrode 12 and the cathode electrolyte chamber side under the action of pressure.

[0043] The cathode electrolyte inlet 30 of the cathode electrolyte plate 5 is connected to the cathode electrolyte tank 20 through a liquid pump a19. The electrolyte is supplied by the cathode electrolyte tank through the liquid pump a19. The cathode electrolyte outlet 31 is a common outlet for the cathode electrolyte, gaseous products and unreacted carbon dioxide. This outlet is connected to the gas-liquid separator 21. In the reaction, the product of carbon dioxide electroreduction passes through the gas-liquid separator 21 together. The separated gas is passed into the gas chromatograph 22 for detection. The separated liquid flows into the cathode electrolyte collection tank 23 for offline liquid product detection.

[0044] The reference electrode 24 is inserted into the cathode electrolyte chamber through the reference electrode insertion hole of the cathode electrolyte plate 5;

[0045] The inlet of the anode electrolyte plate 8 is connected to the anode electrolyte tank 26 via a liquid pump b25. The anode electrolyte is supplied by the anode electrolyte tank 26 through the liquid pump b25. The outlet of the anode electrolyte plate 8 is connected to the anode electrolyte collection tank 27. During the reaction, oxygen, along with the oxygen evolution reaction product, flows into the anode electrolyte collection tank 27.

[0046] Example 1

[0047] The above-mentioned device for acidic carbon dioxide electrolysis was used to test the carbon dioxide electroreduction performance of the nano-copper catalyst.

[0048] Cathode electrode 12 is a gas diffusion electrode supported on a nano-copper catalyst, with a loading of 1.0 mg / cm³. -2 The electrode area is 2cm × 2cm. The anode electrode 14 is a porous titanium metal loaded with iridium black, with a loading of 10mg / cm². -2 The electrode area is 2cm × 2cm, the thickness of the cathode electrolyte plate 5 is 0.7cm, the serpentine flow field area in the middle of the gas flow field plate 3 is 2cm × 2cm, and the proton exchange membrane 13 is... Perfluorosulfonic acid ion exchange membrane 211. Assemble the electrolytic cell;

[0049] Carbon dioxide cylinder 18 reduces outlet pressure to slightly above atmospheric pressure via pressure reducing valve 17, and adjusts flow rate to 30 mL / min via flow meter 16. -1 The carbon dioxide gas flow rate is connected to the gas inlet 34 of the gas flow field plate 3;

[0050] The cathode electrolyte tank 20 contains a room-temperature potassium chloride solution with a molar concentration of 3M. The pH is adjusted to 1.5 using dilute sulfuric acid. The cathode electrolyte tank 20 is connected to a liquid pump a19, which is set to a flow rate of 5 mL / min. -1 The solution is introduced into the inlet of the cathode electrolyte plate 5. During the reaction, the cathode electrolyte and the gas flow together into the gas-liquid separation device 21 from the outlet above. The electrolyte does not need to be recovered.

[0051] The anolyte tank 26 contains a room-temperature potassium sulfate solution with a molar concentration of 0.5M. The pH is adjusted to 2 using dilute sulfuric acid. The anolyte tank 26 is connected to a liquid pump b25, which is set to a flow rate of 5 mL / min. -1 The mixture is then introduced into the inlet of the anode electrolyte plate 8, and the mixture is directly introduced into the anode electrolyte collection tank 27 without the need for recycling.

[0052] The cathode current collector 2 and the anode current collector 10 are respectively connected to the working electrode clamp and the counter electrode clamp of the power supply 15. During the reaction, a constant negative potential of -1.9V vs. Ag / AgCl is applied.

[0053] likeFigure 6 As shown, the average total current density of the carbon dioxide electroreduction reaction is 134 mA cm⁻¹. -2 .

[0054] Example 2

[0055] The performance of the Ni-NC catalyst in the electroreduction of carbon dioxide to carbon monoxide was tested using the above-mentioned acidic carbon dioxide electrolysis device.

[0056] Cathode electrode 12 is a gas diffusion electrode supported on a Ni-NC catalyst, with a loading of 2.5 mg / cm³. -2 The electrode area is 5cm × 5cm. The anode electrode 14 is a porous titanium metal loaded with iridium black, with a loading of 10mg / cm². -2 The electrode area is 5cm × 5cm, the thickness of the cathode electrolyte plate 5 is 0.7cm, the flow field area in the middle of the gas flow field plate 3 is 5cm × 5cm, and the proton exchange membrane 13 is a DuPont perfluorosulfonic acid ion exchange membrane. 211. Assemble the electrolytic cell;

[0057] Carbon dioxide cylinder 18 reduces its outlet pressure to slightly above atmospheric pressure via pressure reducing valve 17, and adjusts the flow rate to 187 mL / min via flow controller 16. -1 The carbon dioxide gas at this flow rate is connected to the inlet of the gas flow field plate 3;

[0058] The cathode electrolyte tank 20 is connected to a liquid pump a19, and the liquid pump a19 is set to a liquid flow rate of 30 mL / min. -1 The solution is introduced into the inlet of the cathode electrolyte plate 5. During the reaction, the cathode electrolyte and the gas flow together from the upper outlet into the gas-liquid separation device 21. The gas is mainly carbon monoxide, carbon dioxide and hydrogen, which is detected by gas chromatograph 22. The liquid separated by the gas-liquid separation device 21 flows into the cathode electrolyte collection tank 23. The electrolyte does not need to be recycled.

[0059] The anolyte tank 26 contains a room-temperature potassium sulfate solution with a molar concentration of 0.5M. The pH is adjusted to 2 using dilute sulfuric acid. The anolyte tank 26 is connected to a liquid pump b25, which is set to a flow rate of 30 mL / min. -1 The electrolyte is introduced into the inlet of the anode electrolyte plate 8, and the outlet is a gas-liquid mixture of electrolyte and oxygen produced by the oxygen evolution reaction. This mixture is directly introduced into the anode electrolyte collection tank 27 without the need for recycling.

[0060] The cathode current collector 2 and the anode current collector 10 are respectively connected to the working electrode clamp and the counter electrode clamp of the power supply 15. During the reaction, a constant negative potential of -1.3V to -3.7V vs. Ag / AgCl is applied.

[0061] like Figure 7As shown, under acidic conditions of pH 1.5, the partial current density of carbon monoxide reaches 258 mA cm⁻¹. -2 Furthermore, no carbonate deposition problem occurred when the potassium chloride molar concentration was ≥3M.

[0062] Example 3

[0063] The above-mentioned performance of the nano-copper catalyst in the electroreduction of carbon dioxide to produce multi-carbon products was tested using an acidic carbon dioxide electrolysis device.

[0064] Cathode electrode 12 is a gas diffusion electrode supported on a nano-copper catalyst, with a loading of 1.0 mg / cm³. -2 The electrode area is 10cm × 10cm. The anode electrode 14 is a porous titanium metal loaded with iridium black, with a loading of 10mg / cm². -2 The electrode area is 10cm × 10cm, the thickness of the cathode electrolyte plate 5 is 0.7cm, the area of ​​the serpentine flow field in the middle of the gas flow field plate is 10cm × 10cm, and the proton exchange membrane 13 is... Perfluorosulfonic acid ion exchange membrane 211. Assemble the electrolytic cell;

[0065] The carbon dioxide gas and cathode / anolyte conditions are the same as in Example 1, except that the outlet pressure of carbon dioxide cylinder 18 is reduced to slightly above atmospheric pressure via pressure reducing valve 17, and the flow rate is adjusted to 750 mL / min via flow controller 16. -1 ;

[0066] The liquid pump a19, which supplies the cathode electrolyte plate 5, is set to a liquid flow rate of 125 mL / min. -1 The liquid pump b25, which supplies the anode electrolyte plate 8, is set to a liquid flow rate of 125 mL / min. -1 The main components of the outlet above the cathode electrolyte plate 5 are cathode electrolyte, carbon dioxide, carbon monoxide, ethylene, hydrogen, ethanol, propanol, formic acid and acetic acid. Among them, the gaseous products carbon dioxide, carbon monoxide, ethylene and hydrogen are detected by gas chromatography 22, and the liquid products ethanol, propanol, formic acid and acetic acid are detected by nuclear magnetic resonance spectroscopy by periodically taking samples of the liquid in the cathode electrolyte collection tank 23. The multicarbon products refer to ethylene, ethanol, propanol and acetic acid.

[0067] The cathode current collector 2 and the anode current collector 10 are respectively connected to the working electrode clamp and the counter electrode clamp of the power supply 15. During the reaction, a constant negative potential of -1.9V to -3.5V vs. Ag / AgCl is applied.

[0068] like Figure 8 As shown, under acidic conditions at pH 1.5, the partial current density of the multi-carbon product reaches 476 mA cm⁻¹. -2 Furthermore, no carbonate deposition problem occurred even when the potassium chloride molar concentration was ≥3M.

[0069] Comparative Example 1

[0070] The difference from Example 1 is that the electrolytic cell does not contain a gas flow field plate. In this case, the cathode electrode 12 and the silicone rubber gasket a4 are in direct contact with the cathode current collector 2. Carbon dioxide gas is connected to the inlet of the cathode electrolyte plate 5 and flows into the cathode electrolyte chamber together with the cathode electrolyte to undergo an electroreduction reaction. The rest is the same as in Example 1.

[0071] like Figure 6 As shown, the average total current density of the carbon dioxide electroreduction reaction is 84 mA cm⁻¹. -2 Compared to the electrolytic cell structure with gas flow field plate 3 in Example 1, the total current density and reaction activity decreased. This result indicates that the gas flow field plate 3 with a single-channel serpentine flow field effectively promotes carbon dioxide gas diffusion and improves reaction activity.

[0072] The above embodiments are merely preferred embodiments of the present invention and are not intended to limit the implementation. The scope of protection of the present invention should be determined by the scope defined in the claims. Other variations or modifications can be made based on the above description. Obvious variations or modifications derived therefrom are still within the scope of protection of the present invention.

Claims

1. A carbon dioxide electrolytic cell for acidic electrolytes, characterized in that, The electrolytic cell comprises, in sequence, an epoxy resin glass fiber plate a, a cathode current collector, a gas flow field plate, a silicone rubber gasket a, a cathode electrode, a cathode electrolyte plate, a silicone rubber gasket b, a proton exchange membrane, a silicone rubber gasket c, an anode electrolyte plate, a silicone rubber gasket d, an anode electrode, an anode current collector, and an epoxy resin glass fiber plate b. The gas flow field plate is equipped with a carbon dioxide inlet; The cathode electrolyte plate has a circular cavity a in the middle, and the cathode electrode, the proton exchange membrane and the circular cavity a constitute the cathode electrolyte cavity. The anode electrolyte plate has a circular cavity b in the middle, and the anode electrode, the proton exchange membrane and the circular cavity b constitute the anode electrolyte cavity. The cathode electrolyte plate is provided with a cathode electrolyte inlet and a cathode electrolyte outlet, both of which are connected to the circular cavity of the cathode electrolyte plate. The anode electrolyte plate is provided with an anode electrolyte inlet and an anode electrolyte outlet, both of which are connected to the circular cavity of the anode electrolyte plate.

2. The carbon dioxide electrolytic cell for acidic electrolytes according to claim 1, characterized in that, A single-channel serpentine flow field is provided in the middle of the gas flow field plate.

3. The carbon dioxide electrolytic cell for acidic electrolytes according to claim 1, characterized in that, The gas flow field plate is made of graphite or platinum-plated titanium.

4. The carbon dioxide electrolyzer for acidic electrolytes according to claim 1, characterized in that, The cathode current collector is a gold-plated copper plate, and the anode current collector is a platinum-plated titanium plate.

5. The carbon dioxide electrolytic cell for acidic electrolytes according to claim 1, characterized in that, Both the cathode electrolyte plate and the anode electrolyte plate are made of plexiglass.

6. The carbon dioxide electrolyzer for acidic electrolytes according to claim 1, characterized in that, The thickness of the cathode electrolyte plate is 0.5 to 1.0 cm.

7. The carbon dioxide electrolytic cell for acidic electrolytes according to claim 1, characterized in that, The cathode electrolyte outlet is located above the cathode electrolyte inlet, and the anolyte electrolyte outlet is located above the anolyte inlet.

8. The carbon dioxide electrolyzer for acidic electrolytes according to claim 1, characterized in that, The cathode electrolyte plate is also provided with a reference electrode insertion hole, through which the reference electrode is inserted into the cathode electrolyte chamber.

9. The carbon dioxide electrolytic cell for acidic electrolytes according to claim 1, characterized in that, The cathode electrode is a gas diffusion electrode with a surface-supported cathode catalyst.

10. The carbon dioxide electrolyzer for acidic electrolytes according to claim 1, characterized in that, The anode electrode is based on porous metal Ti with an anode catalyst loaded on its surface.

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