Integrated metal fuel cell

Abstract

The invention relates to an integrated metal fuel cell, and belongs to the field of new energy batteries. The integrated metal fuel cell is composed of a metal-air cell and a hydrogen-air cell. Wherein the metal-air battery structure mainly comprises a metal negative electrode, a metal-air battery electrolyte chamber and a metal-air battery air positive electrode; the structure of the hydrogen-air battery mainly comprises a hydrogen collecting device, a hydrogen-air battery negative electrode, a hydrogen-air battery electrolyte chamber and a hydrogen-air battery air positive electrode. The hydrogen collection chamber and the electrolyte chamber are enclosed by the positive and negative pole shells and are made of insulating materials, so that short circuit can be avoided, and electrolyte and hydrogen leakage can be prevented. In a cell test, the integrated metal fuel cell shows high working voltage and high stability, and hydrogen recycling is realized. The limitation of a single battery technology is solved through byproduct valuation and resource recycling, the method has huge application potential in the aspects of electric transportation, ocean exploration and energy storage of a power grid scale, and the method conforms to the goals of global green energy and decarbonization.

Description

Technical Field

[0001] The present invention belongs to the field of batteries and electrochemistry, and in particular to the field of fuel cells. Background Art

[0002] In order to cope with the growing energy demand and environmental problems caused by the excessive use of traditional fossil energy, advanced energy conversion devices and technologies with high energy density and high safety have become an urgent need. Fuel cells are an ideal energy conversion device that can directly convert the chemical energy stored in the fuel into electrical energy. Hydrogen-oxygen fuel cells have the advantages of zero emissions, high energy density and high conversion efficiency. Since they are not limited by the Carnot cycle of the second law of thermodynamics, the conversion efficiency of fuel cells can reach 40%-60%, but there are still high costs and difficulties in the storage and transportation of hydrogen. Metal-air batteries inherit the advantages of hydrogen-oxygen fuel cells and use metals as energy carriers, which is conducive to storage and transportation. At the same time, metal-air batteries have attracted widespread attention from researchers because of their wide range of raw material sources, low manufacturing costs, environmentally friendly characteristics and excellent electrochemical performance. However, there are two problems with metal negative electrodes in practical applications that have a greater impact: ① In an environment in contact with air, the surface of the metal will spontaneously oxidize to form a dense oxide film. This passivation film hinders the dissolution of the metal negative electrode during discharge, causing the open circuit potential of the battery to shift positively and increase the polarization of the negative electrode; ② Water molecules will undergo associated corrosion reactions after contacting the metal, which will lead to a significant decrease in the utilization rate of the negative electrode during the open circuit and discharge process. Especially in alkaline electrolytes, since the passivation film on the metal surface can be quickly removed, the metal negative electrode will undergo severe self-corrosion. These problems restrict the development and practical application of metal-air batteries. In order to solve this problem, researchers have found that adding corrosion inhibitors to the electrolyte can better inhibit metal corrosion. But even so, corrosion still exists.

[0003] Since hydrogen-air fuel cells require hydrogen, and the metal negative electrode of metal-air batteries corrodes to produce hydrogen, combining hydrogen-air fuel cells and metal-air batteries to design an integrated metal fuel cell provides a new way to solve the problem of self-corrosion of the metal negative electrode. Summary of the invention

[0004] In view of this, in order to solve the corrosion problem of the metal negative electrode, the present invention provides a new way to recycle the hydrogen generated by the corrosion of the negative electrode of the metal-air battery. By designing an integrated metal fuel cell, the functions of the two batteries are complementary, the hydrogen is recycled, and the performance of the battery is improved.

[0005] As a preference of the present invention, the metal negative electrode in the metal-air battery includes one or more of an aluminum negative electrode, an iron negative electrode, a magnesium negative electrode, a nickel negative electrode, and a zinc negative electrode.

[0006] As a preference of the present invention, the catalyst used in the positive electrode of the metal-air battery and the hydrogen-air battery includes one or more of cobalt-based, iron-based, manganese-based, platinum-based and carbon-based catalysts.

[0007] As a preference of the present invention, the catalyst used in the hydrogen negative electrode of the hydrogen-air battery includes one or more of rhodium-based, palladium-based, copper-based, nickel-based, cesium-based and platinum-based catalysts.

[0008] As a preferred embodiment of the present invention, the electrolyte used in the integrated metal fuel cell includes an alkaline electrolyte, a neutral electrolyte, and an acidic electrolyte; wherein the alkaline electrolyte includes one or more of a potassium hydroxide solution, a lithium hydroxide solution, and a sodium hydroxide solution (0.01 M~12 M), the neutral electrolyte includes one or more of a disodium hydrogen phosphate solution, a sodium dihydrogen phosphate solution, a sodium sulfate solution, a magnesium sulfate solution, a potassium nitrate solution, an ammonium nitrate solution, and a sodium bicarbonate solution (0.01 M~12 M), and the acidic electrolyte includes one or more of a sulfuric acid solution, a phosphoric acid solution, a hydrochloric acid solution, a nitric acid solution, an organic acid solution, and a mixed acid solution (0.01 M~12 M).

[0009] As a preferred embodiment of the present invention, the structural component material of the integrated metal fuel cell includes one or more of polycarbonate, polymethyl methacrylate, polypropylene, polyethylene, stainless steel and glass fiber reinforced plastic.

[0010] As a preferred embodiment of the present invention, the sealing component material of the integrated metal fuel cell includes one or more of fluororubber, silicone rubber, epoxy resin, polyurethane, polytetrafluoroethylene, polyperfluoroethylene propylene, butyl rubber and EPDM rubber.

[0011] As a preferred embodiment of the present invention, the hydrogen collecting device consists of a hydrogen chamber, a hydrogen outlet device and a hydrogen collecting chamber, wherein the hydrogen collecting chamber can be one or more of a gas bottle, a gas collecting bag and an air bag.

[0012] As a preferred embodiment of the present invention, the integrated metal fuel cell utilizes the principle that hydrogen density is lower than that of air and it will automatically diffuse upward, and designs the hydrogen-air fuel cell and the metal-air battery into an upper and lower structure.

[0013] As a preferred embodiment of the present invention, the air positive electrode of the metal-air battery and the hydrogen-air battery mainly includes an oxygen reduction reaction catalyst layer, a current collector layer and a gas adsorption layer; the negative electrode of the hydrogen-air battery mainly includes a hydrogen oxidation reaction catalyst layer, a current collector layer and a gas adsorption layer.

[0014] The integrated metal fuel cell of the present invention has the following beneficial effects: 1. High resource utilization rate. The hydrogen generated by metal-air batteries is used in hydrogen-air fuel cells, which realizes the reuse of hydrogen resources and reduces the production cost of hydrogen.

[0015] 2. Reduce carbon footprint. Using the hydrogen produced by metal-air batteries to operate hydrogen-air fuel cells reduces the use of fossil fuels, reduces greenhouse gas emissions, and is beneficial to environmental protection.

[0016] 3. High energy density. The integration of the two batteries makes the integrated metal fuel cell have a higher energy density, can provide a larger output voltage, improve the overall energy efficiency of the system, and optimize the application scenarios of the battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention and should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without creative work.

[0018] Figure 1 The schematic diagram of the structure of an integrated metal fuel cell realized by the inventors, in which a metal-air battery and a hydrogen-air fuel cell work in coordination.

[0019] Icon: 1-structural shell; 2-metal negative electrode; 3-sealing plate; 4-structural shell; 5-sealing plate; 6-hydrogen collection chamber; 7-sealing plate; 8-gas diffusion layer; 9-hydrogen oxidation reaction catalyst layer; 10-structural shell; 11-sealing plate; 12-oxygen reduction reaction catalyst layer; 13-gas diffusion layer; 14-structural shell; 15-sealing plate; 16-oxygen reduction reaction catalyst layer; 17-gas diffusion layer; 18-structural shell. The electrolyte of the metal-air battery is stored in the lower volume of the battery shell 3 to 11, and the electrolyte of the hydrogen-air fuel cell is stored in the upper volume of the battery shell 10 to 16. DETAILED DESCRIPTION

[0020] The embodiments of the present invention are described in detail below with reference to the accompanying drawings.

[0021] It should be noted that the following embodiments and features in the embodiments may be combined with each other in the absence of conflict; and, based on the embodiments in the present disclosure, all other embodiments obtained by ordinary technicians in the field without making any creative work are within the scope of protection of the present disclosure.

[0022] It should be noted that various aspects of the embodiments within the scope of the appended claims are described below. It should be apparent that the aspects described herein may be embodied in a wide variety of forms, and any specific structure and / or function described herein is merely illustrative. Based on the present disclosure, it should be understood by those skilled in the art that an aspect described herein may be implemented independently of any other aspect, and two or more of these aspects may be combined in various ways. For example, any number of aspects described herein may be used to implement the device and / or practice the method. In addition, other structures and / or functionalities other than one or more of the aspects described herein may be used to implement this device and / or practice this method.

[0023] Based on the need to utilize hydrogen energy generated by metal corrosion, an integrated metal fuel cell is invented and implemented. Figure 1 The integrated metal fuel cell has an upper and lower structure and is designed with a channel through which excess water generated during the operation of the hydrogen-air fuel cell can be replenished into the electrolyte of the metal-air battery.

[0024] The volume of the hydrogen diffusion channel above the metal anode is 0.01 cm 3 ~10 m 3 , the electrolyte concentration is 0.01 M~12 M, and the contact area between the metal anode and the electrolyte is 0.01 cm 2 ~10 m 2 The volume of the hydrogen cavity is 0.01 cm 3 ~10m 3 .

[0025] The reaction process varies depending on the type of battery. In the example of aluminum metal and alkaline electrolyte, the battery reaction is as follows: Aluminum Metal Air Battery: negative electrode:

[0026] positive electrode:

[0027] Hydrogen Air Fuel Cell: negative electrode:

[0028] positive electrode:

[0029] Example 1 An aluminum sheet is placed on a stainless steel foil current collector on a non-porous acrylic plate, and a single-hole silicone rubber plate, a double-hole acrylic plate, a double-hole silicone rubber plate with a gas collection device, and a double-hole silicone rubber plate are stacked upward in sequence, and then a gas adsorption layer, a stainless steel foil current collector, and a hydrogen oxidation catalyst layer are placed on the upper hole, and then a double-hole acrylic plate and a double-hole silicone rubber plate are stacked upward in sequence, and an oxygen reduction catalyst layer, a stainless steel foil current collector, and a gas adsorption layer are placed at the lower hole of the silicone rubber plate, and then a double-hole acrylic plate and a double-hole silicone rubber plate are stacked upward in sequence, and an oxygen reduction catalyst layer, a stainless steel foil current collector layer, and a gas adsorption layer are placed at the upper hole of the silicone rubber plate, and finally a double-hole acrylic plate is covered on top, and 12 M KOH electrolyte is added to the aluminum-air battery and hydrogen-air fuel cell structures respectively to form an integrated metal fuel cell.

[0030] Example 2 An aluminum sheet is placed on a stainless steel foil current collector on a non-porous borosilicate glass shell, and a single-hole silicone rubber plate, a double-hole borosilicate glass shell, a double-hole silicone rubber plate with a gas collection device, and a double-hole silicone rubber plate are stacked upward in sequence, and then a gas adsorption layer, a stainless steel foil current collector, and a hydrogen oxidation catalyst layer are placed on the upper hole. Then, a double-hole borosilicate glass shell and a double-hole silicone rubber plate are stacked upward in sequence, and an oxygen reduction catalyst layer, a stainless steel foil current collector, and a gas adsorption layer are placed at the lower hole of the silicone rubber plate. Then, a double-hole borosilicate glass shell and a double-hole silicone rubber plate are stacked upward in sequence, and an oxygen reduction catalyst layer, a stainless steel foil current collector layer, and a gas adsorption layer are placed at the upper hole of the silicone rubber plate. Finally, a double-hole borosilicate glass shell is covered on top, and 10 MKOH electrolyte is added to the aluminum-air battery and hydrogen-air fuel cell structures respectively to form an integrated metal fuel cell.

[0031] Example 3 An aluminum sheet is placed on a stainless steel mesh current collector on a non-porous stainless steel shell, and a single-hole silicone rubber plate, a double-hole stainless steel shell, a double-hole silicone rubber plate with a gas collection device, and a double-hole silicone rubber plate are stacked upward in sequence, and then a gas adsorption layer, a stainless steel mesh current collector, and a hydrogen oxidation catalyst layer are placed on the upper hole, and then a double-hole stainless steel shell and a double-hole silicone rubber plate are stacked upward in sequence, and an oxygen reduction catalyst layer, a stainless steel mesh current collector, and a gas adsorption layer are placed at the lower hole of the silicone rubber plate, and then a double-hole stainless steel shell and a double-hole silicone rubber plate are stacked upward in sequence, and an oxygen reduction catalyst layer, a stainless steel mesh current collector layer, and a gas adsorption layer are placed at the upper hole of the silicone rubber plate, and finally a double-hole stainless steel shell is covered on top, and 8 M KOH electrolyte is added to the aluminum-air battery and hydrogen-air fuel cell structures respectively to form an integrated metal fuel cell.

[0032] Example 4 An aluminum sheet is placed on a stainless steel foil current collector on a non-porous acrylic plate, and a single-hole latex plate, a double-hole acrylic plate, a double-hole latex plate with a gas collection device, and a double-hole latex plate are stacked upward in sequence, and then a gas adsorption layer, a stainless steel foil current collector, and a hydrogen oxidation catalyst layer are placed on the upper hole, and then a double-hole acrylic plate and a double-hole latex plate are stacked upward in sequence, and an oxygen reduction catalyst layer, a stainless steel foil current collector, and a gas adsorption layer are placed at the lower hole of the latex plate, and then a double-hole acrylic plate and a double-hole latex plate are stacked upward in sequence, and an oxygen reduction catalyst layer, a stainless steel foil current collector, and a gas adsorption layer are placed at the upper hole of the latex plate, and finally a double-hole acrylic plate is covered on top, and 6 M KOH electrolyte is added to the aluminum-air battery and hydrogen-air fuel cell structures respectively to form an integrated metal fuel cell.

[0033] Example 5 An aluminum sheet is placed on a stainless steel foil current collector on a non-porous acrylic plate, and a single-hole polyurethane plate, a double-hole acrylic plate, a double-hole polyurethane plate with a gas collection device, and a double-hole polyurethane plate are stacked upward in sequence, and then a gas adsorption layer, a stainless steel foil current collector, and a hydrogen oxidation catalyst layer are placed on the upper hole. Then, a double-hole acrylic plate and a double-hole polyurethane plate are stacked upward in sequence, and an oxygen reduction catalyst layer, a stainless steel foil current collector, and a gas adsorption layer are placed at the lower hole of the polyurethane plate. Then, a double-hole acrylic plate and a double-hole polyurethane plate are stacked upward in sequence, and an oxygen reduction catalyst layer, a stainless steel foil current collector layer, and a gas adsorption layer are placed at the upper hole of the polyurethane plate. Finally, a double-hole acrylic plate is covered on top, and 4 M KOH electrolyte is added to the aluminum-air battery and hydrogen-air fuel cell structures respectively to form an integrated metal fuel cell.

[0034] Example 6 An aluminum sheet is placed on a carbon cloth current collector on a non-porous acrylic plate, and a single-hole rubber plate, a double-hole acrylic plate, a double-hole rubber plate with a gas collection device, and a double-hole rubber plate are stacked upward in sequence, and then a gas adsorption layer, a carbon cloth current collector, and a hydrogen oxidation catalyst layer are placed on the upper hole, and then a double-hole acrylic plate and a double-hole rubber plate are stacked upward in sequence, and an oxygen reduction catalyst layer, a carbon cloth current collector, and a gas adsorption layer are placed at the lower hole of the rubber plate, and then a double-hole acrylic plate and a double-hole rubber plate are stacked upward in sequence, and an oxygen reduction catalyst layer, a carbon cloth current collector, and a gas adsorption layer are placed at the upper hole of the rubber plate, and finally a double-hole acrylic plate is covered on top, and 2 M KOH electrolyte is added to the aluminum-air battery and hydrogen-air fuel cell structures respectively to form an integrated metal fuel cell.

[0035] Example 7 An aluminum sheet is placed on a nickel foam collector on a non-porous acrylic plate, and a single-hole rubber plate, a double-hole acrylic plate, a double-hole rubber plate with a gas collection device, and a double-hole rubber plate are stacked upward in sequence, and then a gas adsorption layer, a nickel foam collector, and a hydrogen oxidation catalyst layer are placed on the upper hole, and then a double-hole acrylic plate and a double-hole rubber plate are stacked upward in sequence, and an oxygen reduction catalyst layer, a nickel foam collector, and a gas adsorption layer are placed at the lower hole of the rubber plate, and then a double-hole acrylic plate and a double-hole rubber plate are stacked upward in sequence, and an oxygen reduction catalyst layer, a nickel foam collector layer, and a gas adsorption layer are placed at the upper hole of the rubber plate, and finally a double-hole acrylic plate is covered on top, and 1 M KOH electrolyte is added to the aluminum-air battery and hydrogen-air fuel cell structures respectively to form an integrated metal fuel cell.

[0036] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims

1. An integrated metal fuel cell, characterized in that The integrated metal fuel cell consists of a metal-air battery at the bottom and a hydrogen-air fuel cell at the top. The hydrogen generated by the self-corrosion of the metal negative electrode of the metal-air battery can be supplied to the hydrogen side of the hydrogen-air battery to enable the hydrogen-air battery to work normally; the water generated when the hydrogen-air battery is working can be replenished into the electrolyte of the metal-air battery to make up for the water lost when the metal-air battery is working; the metal-air battery consists of a metal negative electrode, a metal-air battery electrolyte chamber, and a metal-air battery air positive electrode; the hydrogen-air battery mainly consists of a hydrogen collection device, a hydrogen-air battery negative electrode, a hydrogen-air battery electrolyte chamber, and a hydrogen-air battery air positive electrode.

2. The integrated metal fuel cell according to claim 1, characterized in that The metal negative electrode includes one or more of aluminum metal, iron metal, magnesium metal, nickel metal, and zinc metal.

3. According to the integrated metal fuel cell of claim 1, the air positive electrode of the metal-air battery includes an oxygen reduction reaction catalyst layer, a current collector layer and a gas adsorption layer; the air positive electrode of the hydrogen-air battery includes an oxygen reduction reaction catalyst layer, a current collector layer and a gas adsorption layer; the negative electrode of the hydrogen-air battery includes a hydrogen oxidation reaction catalyst layer, a current collector layer and a gas adsorption layer.

4. The integrated metal fuel cell according to claim 1, characterized in that The hydrogen collecting device consists of a hydrogen chamber, a hydrogen outlet device and a hydrogen collecting chamber, wherein the hydrogen collecting chamber can be one or more of a gas bottle, a gas collecting bag and an air bag.

5. The integrated metal fuel cell according to claim 1, characterized in that The catalysts used in the positive electrodes of metal-air batteries and hydrogen-air batteries include one or more of cobalt-based, iron-based, manganese-based, platinum-based and carbon-based catalysts.

6. The integrated metal fuel cell according to claim 1, characterized in that The catalyst used in the negative electrode of the hydrogen-air battery includes one or more of rhodium-based, palladium-based, copper-based, nickel-based, cesium-based and platinum-based catalysts.

7. The integrated metal fuel cell according to claim 1, characterized in that The structural components of the battery are made of one or more of polycarbonate, polymethyl methacrylate, polypropylene, polyethylene, stainless steel and glass fiber reinforced plastic.

8. The integrated metal fuel cell according to claim 1, characterized in that The sealing component material of the battery includes one or more of fluororubber, silicone rubber, epoxy resin, polyurethane, polytetrafluoroethylene, polyperfluoroethylene propylene, butyl rubber and EPDM rubber.

9. The integrated metal fuel cell according to claim 1, characterized in that The electrolytes used in batteries include alkaline electrolytes, neutral electrolytes, and acidic electrolytes; The alkaline electrolyte includes one or more of potassium hydroxide solution, lithium hydroxide solution and sodium hydroxide solution (0.01 M~12 M), the neutral electrolyte includes one or more of disodium hydrogen phosphate solution, sodium dihydrogen phosphate solution, sodium sulfate solution, magnesium sulfate solution, potassium nitrate solution, ammonium nitrate solution and sodium bicarbonate solution (0.01 M~12 M), and the acidic electrolyte includes one or more of sulfuric acid solution, phosphoric acid solution, hydrochloric acid solution, nitric acid solution, organic acid solution and mixed acid solution (0.01 M~12 M).

10. The integrated metal fuel cell according to claim 1, characterized in that Using the principle that hydrogen will automatically diffuse upwards because its density is lower than that of air, hydrogen-air fuel cells and metal-air batteries are designed as an upper and lower structure.

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