CN108808176B - Oxygen dissolving type metal air battery with sub-cabin circulation and spraying - Google Patents

Abstract

A subdivision circulation and spray dissolved oxygen type metal air battery belongs to the field of metal fuel batteries and structurally comprises anode metal, an anode cabin, a cathode cabin, a buffer cabin, a cabin cover, a cabin middle sleeve, a current collecting net, an electrolyte transmission pipe, a circulating pump, a ventilation fan, a control circuit and a starting battery pack; the ventilating fan leads the air to flow through the air channel to form the direct contact reduction reaction of the air, the electrolyte and the surface of the current collecting net with the catalytic function, the cabin cover and the cabin chamber are sleeved to form an anode cabin, and the buffer cabin and the cabin chamber are sleeved to form a cathode cabin; the anode cabin and the cathode cabin are isolated by a cabin middle sleeve with holes, and wall holes are formed on an isolation cabin plate; the current collecting net is arranged in the cathode cabin and isolates the cathode cabin from an air channel for spraying the electrolyte, and the electrolyte sprayed by the wall holes flows into the current collecting net and then enters the buffer cabin; each group of the anode cabin and the cathode cabin form a battery unit, the current collecting net is the anode of the battery unit, the anode metal is the cathode of the battery unit, and a plurality of battery units form a battery stack which can be connected in series or in parallel for output.

Description

Oxygen dissolving type metal air battery with sub-cabin circulation and spraying

[ technical field ]:

the invention belongs to the field of metal air batteries, and relates to an aluminum air fuel cell system, in particular to an aluminum air fuel cell which circulates electrolyte in a sub-cabin manner and is provided with a temperature control system, a hydrogen discharge system and a filtering system.

[ background art ]:

the working principle of the metal-air battery is as follows: also known as metal fuel cells (fuel cells) are electrochemical devices that continuously convert chemical energy from a continuous supply of metal and oxidant into electrical energy. Since oxygen is stored as an active material outside the cell, power can be generated as long as fuel is continuously supplied, and the capacity is infinite. The method is mainly characterized in that the reaction process does not involve combustion, the energy conversion is carried out isothermally, and the efficiency is far higher than that of a common internal combustion engine. The metal-air battery uses oxygen in the air as a positive electrode active material, uses metal zinc, magnesium or aluminum as a negative electrode active material, and the oxygen reaches a gas-solid-liquid three-phase interface through a gas diffusion electrode to react with metal to release electric energy. Zinc air batteries, magnesium air batteries, aluminum air batteries, etc. currently in use are common examples. Wherein the aluminum and magnesium metal air battery has excellent performance theoretically,

the electrolyte is particularly suitable for directly using salt water or seawater as a neutral electrolyte, has excellent environmental harmony, and has a plurality of natural advantages of no toxicity, no harmful gas, no environmental pollution, long service life, high reliability, safe use and the like. The active development of aluminum/magnesium air batteries is an effective way to solve the problems of low energy-weight ratio, high price-energy ratio, environmental pollution and the like of the existing chemical power supply. The most representative of metals is an aluminum-air battery: as a backup power source, the instant charging device has been used in europe and america for outdoor power sources such as communication websites and the like. As an underwater power source, there have been used energy sources for ships, monitors, remote torpedoes, and diving facilities. Being a driving energy source of electric vehicles is also a main interest point for developing such batteries. The aluminum-air battery can be used on land and in deep sea, and can be used as a power source and a signal power source with long service life and high specific energy. The application range of the alkaline aluminum air battery is wide, and the alkaline aluminum air battery can be applied to emergency power supplies, portable batteries, power supplies of electric vehicles and underwater vehicles. As a propulsion power of an electric vehicle, aluminum contains energy approximately half of that of gasoline in terms of unit weight and 3 times that of gasoline in terms of unit volume. Another application of alkaline aluminum air cells is as power supplies for underwater vehicles, such as unmanned vehicles for submarines and mine surveillance, remote torpedoes, floating vehicles, and submarine-assisted power. In these applications the oxygen may be carried in a high pressure or cryogenic vessel or obtained from decomposition of hydrogen peroxide. The alkaline aluminum air battery has high energy density and can be used as a driving power source for motor vehicles and underwater devices in addition to a backup power source.

The aluminum-air battery is continuously consumed by aluminum during battery discharge to generate Al (OH)3, the valence of the aluminum is trivalent, which is equivalent to 2.98Ah/g of electrochemical equivalent, the aluminum has low enough negative bias voltage, the specific energy is larger than that of a standard hydrogen electrode, which is-1.66V, the specific energy reaches 8.140kW/kg, and the aluminum-air battery can be stored for a long time without special packaging. From the viewpoint of chargeability, the battery can be classified into a primary battery and a mechanically chargeable secondary battery (i.e., replacement of an aluminum anode). The oxidant used in the anode can be different according to different working environments of the battery, the battery uses air when working on land, and can use liquid oxygen, compressed oxygen, hydrogen peroxide or dissolved oxygen in seawater when working underwater.

The specific energy is high: theoretically reaching 2290Wh/kg, and actually reaching 300 Wh/kg and 400Wh/kg at present. The mass of the aluminum air battery with the same energy is only 12% -15% of that of the lead-acid battery. This value is much higher than the specific energy of various batteries today.

The specific power is medium: reaching 50-200W/kg, this characteristic is apparently determined by the oxygen electrode because the operating potential of the oxygen electrode is far from its thermodynamic equilibrium potential. The exchange current density is small, and the polarization of the battery is large when the battery is discharged. The reason why the specific power of the hydrogen-oxygen fuel cell is not high is also because of this.

The service life reaches 3-4 years: this also depends primarily on the working life of the oxygen electrode, since the aluminum electrode is constantly replaceable.

Safe and reliable, nontoxic, free of harmful gas, free of environmental pollution, rich in aluminum resource and low in price: the cell reaction consumes aluminum, oxygen and water to produce Al (OH)3, the latter being an excellent precipitant for wastewater treatment today.

Among metal-air batteries, zinc-air batteries, magnesium-air batteries, aluminum-air batteries, iron-air batteries, and lithium-air batteries are currently being studied, and the electrolyte system may be a neutral electrolyte, an alkaline electrolyte, or an organic electrolyte. Compared with a chloride neutral electrolyte and an organic electrolyte system, the alkaline electrolyte has higher conductivity, and a corresponding battery system can output higher power. The alkaline electrolyte is mainly sodium hydroxide or potassium hydroxide solution. However, in the alkaline electrolyte system, there are some problems to be solved, for example, in the alkaline aluminum air battery, the following reactions occur during the discharge process of the battery:

4A1 302 6H2O-4A1(OH)3

in strongly alkaline media, the electrochemical reaction product Al (OH)3 is soluble, and reacts as follows:

4Al 302 6H20 4Na0H-4A1(OH)、4Na

then gradually reaching saturation state in the solution, and precipitating Al (OH)3 solid again.

4A1(OH) 44 Na-4A1(OH)3 (solid) 4NaOH

The aluminum hydroxide formed by the reaction at this time precipitates as crystalline gibbsite, and these precipitates have the following adverse effects as the reaction proceeds: firstly, the conductivity of the electrolyte is reduced; ② blocking the electrolyte passage. Therefore, it is necessary to separate the precipitate from the electrolyte so that the electrolyte at the reaction interface of the battery remains unchanged and the reaction proceeds stably.

In addition to the above cell reactions, the metal-air cell anode also has a side reaction, for example, an aluminum anode, as follows:

2A 16H 20-2A1(OH) 33H 2 (gas)

This reaction evolves hydrogen, consuming aluminum but not producing electricity, energy is generated in the form of heat, with the result that the energy output efficiency of the battery is reduced, and the temperature of the electrolyte increases and the evaporation amount of the electrolyte increases as heat accumulates inside the battery.

In order to increase the application range of the metal-air battery, the metal-air battery is more suitable for the fields of high power and long-time operation, such as power batteries of electric vehicles, large standby power supplies and the like, the precipitate, hydrogen and heat generated in the operation process of the battery are required to be controlled, so that the temperature and the components of the electrolyte are kept in a reasonable range, and the power output of the battery is stable.

The current situation of the aluminum-air battery is as follows: the structure can be designed to be open or closed according to practical requirements, the electrolyte can be neutral or alkaline, also can be circulating or fixed, even can be directly applied to seawater, the required oxidant can be obtained from local materials in actual environment, and air, compressed oxygen, liquid oxygen, hydrogen peroxide or oxygen dissolved in seawater are adopted.

Research progress on aluminum anodes: aluminum was used as a battery electrode for 1850 years, when Hulot described a battery using zinc (mercury) as the anode, aluminum as the cathode, and dilute sulfuric acid as the electrolyte. Aluminum was first used as the anode of a Buff cell in 1857. In 1893 amalgamated aluminum-zinc alloy was attempted to be used as an anode in carbon cathode cells. In 1948 the open circuit voltage of cells with amalgamated aluminum as the anode was up to 2.45V. After the 50's of the 20 th century, the aluminum anode was used for the first time in a Leclanche type dry cell with the system aluminum/aqueous NaOH + ZnO/porous film/MnO 2 (C). Al/MnO cells were further developed using tetrahydrate of manganese chloride as the electrolyte. In the 60's of the 20 th century, aluminum/ferrites were first identified by Zarmb and Trevethau et al. They found that the addition of zinc oxide or certain organic corrosion inhibitors, such as alkyl-dimethyl-benzylammonium salts, significantly reduced the corrosion of amalgamated aluminum anodes in sodium (or potassium) hydroxide electrolytes. The polarization and corrosion of the aluminum cathode are serious, and the two problems cause the aluminum air battery to fail to exert the advantages of a high-energy power supply so as to fully exert the excellent electrochemical performance of the aluminum, and domestic and foreign scholars make a great deal of research and find that the electrochemical performance of the aluminum air battery can be remarkably improved by adding a small amount of alloy elements into pure aluminum, so that a passivation film of the aluminum air battery is successfully dissolved in electrolyte and the potential of the passivation film is negatively shifted to be lower than-1.0V (vs. SHE), thereby opening up a path for the aluminum in the aspects of chemical power supply and cathode protection. In 1956, Rohman Reynolds Metals, developed an alloy containing 5% Zn, which was probably the original aluminum alloy anode material. In 1966, Keding and Newport studied the influence of alloy elements on aluminum anodes, and found that the addition of Hg, Ga, Sn, In, Bi, Mg, Zn, Ba, etc. can obtain aluminum alloys with a potential much more negative than that of pure aluminum, and the performance of the elements mixed In a certain proportion is much better than that of simple binary alloys. After 1970, with the development of aluminum air batteries as power sources for electric vehicles, aluminum anodes have been developed in a new stage. 1990, the uniter et Al patent applied for an aluminum battery whose anode was Al-Mg-Mn or Al-Ca-Mn to which 0.01% -0.1% Ga was also added, with an optimum concentration of 0.1% -2.0% Mg and a pure aluminum content of at least 99.85% in the alloy, resulting in effective corrosion resistance. Iarochenko et al In 2002 developed an eight-element aluminum alloy anode added with Ga, In, Sn, Ti, Cd, Pb and Fe, and obtained a better activation effect when the anode is discharged In an aluminum-air battery and the potential reaches-1.17V (vs. SCE)150mA/cm2 when the current density is 100mA/cm and the potential reaches-0.89V (vs. SCE), and applied for a patent.

Air cathode research progress: the reduction reaction of oxygen is realized by the gas diffusion electrode when the metal-air battery is discharged. The air electrode is the cathode of the metal-air battery, is a waterproof, breathable, conductive and catalytically active film, and mainly comprises active carbon, high-molecular polymer polytetrafluoroethylene, a catalyst and a current collector. Since 80% of energy loss in the metal-air battery is caused by the overpotential of the air electrode, it is an important factor for restricting the performance of the metal-air battery, and therefore, it is necessary to optimize the structure of the air electrode. The oxygen reduction process occurring at the cathode of the metal-air battery is a complex four-electron and two-electron composite reaction process. Ions or ion groups with intermediate valence states such as H2O2, HO2-, intermediate valence oxygen-containing adsorption particles or metal oxides and the like often appear in the reaction, and the reaction mechanism which is possible when the preparation steps are different has more than 50 schemes. The current density of the two-phase electrode is small because the dissolution and diffusion rates of oxygen in the aqueous solution are small. With the development of organic binding materials such as polytetrafluoroethylene and advanced membrane fabrication techniques, three-phase gas diffusion oxygen electrodes have been used. The three-phase gas diffusion oxygen electrode is generally a three-layer or four-layer composite structure formed by mechanical pressing,

mainly comprises a waterproof breathable layer, a gas diffusion layer, a catalyst layer and a conductive layer. The action of the catalyst in the air electrode is very important, and the catalysts adopted by the air cathode in domestic and overseas researches mainly comprise noble metal catalysts (platinum, platinum alloy and silver), perovskite type oxide catalysts, metal organic chelate catalysts, metal oxide (mainly manganese) catalysts and the like. The noble metal platinum-based catalyst shows good catalytic activity when used as an air cathode oxygen reduction catalyst, and researches on reduction of platinum loading and improvement of catalytic efficiency are conducted at home and abroad. In recent years, research on silver catalyst cathodes for metal fuel cells has been greatly advanced, but the high price of platinum and silver limits the marketability and application range of the catalyst. Perovskite catalysts are also preferred electrocatalysts, and corresponding studies have been carried out in recent years. Li N and the like adopt an improved amorphous citric acid precursor method to synthesize LiMn2-xCoxO4 series spinel type oxides, and the specific surface area of the catalyst is obviously increased.

Research progress of the electrolyte: the electrolyte adopted by the aluminum-air battery mainly has alkaline and neutral electrolytes. The development of the aluminum air battery with the alkaline electrolyte can trace the results of Zarmb, Trevethan and the like in the 60 th 20 th century, and researches prove the feasibility of the alkaline aluminum air battery technology. Most aluminum air cells thereafter use strong base electrolytes. It is common for the polarization of both air cathodes and aluminum anodes to be relatively small in alkaline electrolytes that KOH also employs NaOH. The optimum concentration range for NaOH to be used is 3-5M considering that the Al (OH) precipitate will be converted to A1(OH) in the regenerator. The electrolyte can be designed into two structural forms of electrolyte circulation and non-circulation, and the electrolyte circulation and non-circulation structure is respectively suitable for different occasions.

The current technical defects are as follows: the commercial application has the obstacles of oxygen electrode polarization, anode over-corrosion, non-uniform dissolution and the like, so that the output of the battery is unstable, and although the electrolyte circulation can be slightly improved, the power density cannot be well exerted; with regard to the weight that causes defects: oxygen electrode polarization (passivation) accounts for more than 85% of the barrier weight, which severely limits the specific energy/specific power; over-corrosion of the anode, non-uniform dissolution and the like belong to secondary obstacles, and the overall efficiency and service life are slightly limited.

[ summary of the invention ]:

the invention aims to provide a novel metal air fuel cell, which completely omits a waterproof breathable and activated carbon diffusion layer in an air cathode structure, and initiates that a catalytic collector net directly contacts an air-electrolyte interface; meanwhile, the sediment is effectively filtered/separated by means of the existing electrolyte circulation; the internal temperature of the battery is controlled by the existing cathode airflow, so that higher specific power and specific energy can be realized, metal (aluminum) is convenient to replace and precipitates are convenient to remove, and the battery can be widely applied to the field of electric automobiles or large-scale standby power supplies.

The technical scheme of the invention is as follows:

the invention relates to a metal-air battery which comprises anode metal, an anode cabin, a cathode cabin, a buffer cabin, a cabin cover, a cabin middle sleeve, a current collecting net (catalysis), an electrolyte transmission pipe, a circulating pump, a ventilation fan, a control circuit and a starting battery pack; the specific connection relationship of the structure is divided into a spraying space type at the upper part of the cathode cabin and a spraying space type at the lower part of the cathode cabin:

the structure of the spray space type at the upper part of the cathode cabin is characterized in that anode metal is arranged in the anode cabin, a small hole is processed at the upper part of the anode cabin, water is sprayed out under the liquid pressure of the anode cabin, the flow rate is increased along with the increase of the liquid pressure, the sprayed electrolyte firstly enters the spray space at the upper part of the cathode cabin (the space is just an airflow channel) to absorb oxygen molecules, and then flows into a buffer cabin below the cathode cabin after flowing through a current collecting net; each group of anode cabin and cathode cabin form a battery unit, the output anode of the battery is a current collecting net, the output cathode of the battery is anode metal, and a plurality of units form a battery stack which can be connected in series or in parallel for output; the spraying space at the upper part of the cathode cabin is the space enclosed by the cabin cover and the cathode cabin wall of the cabin middle sleeve, and the structure wall of the isolation part is provided with wall holes; especially, wall holes are required to be processed in the spraying space which is also used as an air channel, and the sprayed electrolyte is dissolved with sufficient oxygen molecules and then flows through the flow collecting net to enter the buffer cabin; under the action of the liquid pressure in the anode cabin, the electrolyte in the anode cabin is sprayed to the cathode cabin through the anode cabin wall holes, and the sprayed electrolyte continuously flows through the current collecting net to complete the cyclic reciprocation of the cathode cabin, the anode cabin, the buffer cabin and the cathode cabin;

the structure of the spraying space type at the lower part of the cathode cabin is characterized in that the spraying space is arranged in the buffer cabin, and the structural wall of the separation part of the anode cabin and the cathode cabin sleeved in the cabin is provided with a wall hole; wall holes are also processed at the bottom of the anode cabin to lead to the buffer cabin, air can forcibly flow through the spraying space through a ventilation fan, and the cabin cover and the cabin middle sleeve are in a sealed connection relationship to keep the anode cabin and the cathode cabin isolated from the external space; after being fully dissolved by the sprayed electrolyte, oxygen molecules flow through the buffer cabin and are filtered and then are pumped back to the cathode cabin by the hydraulic pump, and the circulation reciprocating of the cathode cabin, the anode cabin, the buffer cabin and the cathode cabin is completed.

The operation process of the battery comprises the steps of firstly storing electrolyte in an anode cabin and a buffer cabin, then driving a circulating pump to begin to reinject the electrolyte into the anode cabin by a control circuit under the power supply of a starting battery pack or an external power supply, wherein the electrolyte in the anode cabin flows to a cathode cabin through a small hole in a cabin under the action of liquid pressure, and the flow rate is positively correlated with the pressure; because the ventilating fan enables air to flow through the air channel, oxygen molecules, the sprayed electrolyte and the surface of the current collecting net with the catalytic function are kept to be fully contacted, the electrolyte performs a reduction reaction at the cathode of the oxygen molecules on the surface of the current collecting net, the electrolyte with reaction precipitates enters the buffer cabin, and the cell stack starts to supply power; then, the filtered electrolyte is pumped back to the anode cabin by a circulating pump to circulate; the electrolyte transmission pipes are respectively communicated with the buffer cabin and the anode cabin, the electrolyte transmission pipe interface for returning the liquid is arranged on the side surface of the cabin cover or the middle sleeve of the cabin, and the electrolyte transmission pipe interface for pumping the liquid is arranged on the side surface or the bottom surface of the buffer cabin; the heat dissipation is completed by air cooling of the ventilating fan, and the heat dissipation amount and the oxygen supply amount are adjusted by the rotating speed of the ventilating fan; the temperature control system monitors the temperature of the electrolyte or the anode aluminum body or the current collecting net and feeds back the temperature to the control circuit by connecting a temperature sensor; the electrolyte filters and isolates the solid products of the reaction and passes through an electrolyte filter screen of the buffer cabin; if the external power supply of the battery system needs to be stopped, the circulating pump is stopped or liquid is pumped reversely, and the external power supply of the battery is stopped. When power is needed to be supplied, the electrolyte circulating system is started, and the battery can be stopped and restarted by controlling the switch of the electrolyte circulating system pump. In addition, the residual electrolyte and the precipitate are discharged into the buffer cabin through a normally open small hole at the bottom of a sleeve in the cabin on the anode cabin, and the diameter of the normally open small hole is limited by the circulation that the leakage does not influence the normal circulation. Firstly, placing anode metal in an anode cabin, storing electrolyte in the anode cabin and a buffer cabin to ensure that the electrolyte obtains a spraying space in a cathode cabin or the buffer cabin, then driving a circulating pump to carry out forced circulation by a control circuit under the power supply of a starting battery pack or an external power supply to start reinjection of the electrolyte into the anode cabin, and enabling a battery to enter a working state; the device is characterized in that the hatch cover and the cabin middle sleeve form an anode cabin, and the buffer cabin, the cabin middle sleeve and the buffer cabin form a cathode cabin; the circulating pump drives the electrolyte to circularly reciprocate along the anode cabin, the cathode cabin, the buffer cabin, the anode cabin or the cathode cabin, the anode cabin, the buffer cabin and the cathode cabin; the anode cabin and the cathode cabin are separated by a cabin middle sleeve or a cabin cover; a spraying space is reserved at the upper part or the lower part of the cathode chamber, namely a space communicated with the atmosphere, and air can flow through the space forcibly by a ventilation fan to form a gas-liquid mixing space of oxygen-dissolved electrolyte; the anode cabin and the cathode cabin of each group form a battery unit, the current collecting net is the anode of the battery unit, the anode metal is the cathode of the battery unit, a plurality of battery units form a battery stack, and power output is generated after parallel connection or series connection.

Electrolyte in the system flows circularly, and the circulating path of the electrolyte is an anode cabin, a cathode cabin, a buffer cabin and an anode cabin in sequence; or the power supply of the circulating pump and the ventilation fan is 2 independent motors or 1 motor in common.

The electrolysis circulating path comprises a buffer cabin and a circulating pump; the buffer cabin is positioned below the cathode cabin, the buffer cabin is a hollow liquid container with an upper opening, the upper opening is used for receiving electrolyte flowing downwards from the cathode cabin, an electrolyte outlet is formed in the lower part or the side surface and connected with an electrolyte transmission pipe, and the volume of the electrolyte transmission pipe and the connecting piece is required to be capable of containing the whole electrolyte. The pump is a corrosion-resistant one-way pump or two-way pump such as a centrifugal pump, a diaphragm pump or a plunger pump and the like which is controlled to be opened or closed by an electric signal.

The structural characteristics of the uniformity and the equal amount of electrolyte entering each monomer within a certain time are kept, so that the electrochemical uniformity of the monocells is ensured; the pipe diameter and route of an electrolyte transmission pipe distributed to the battery unit do not need to be specially arranged; when the closing treatment of the anode cabin cover is not carried out, the pipe diameter and the route of an electrolyte transmission pipe distributed to the battery unit are normalized, and special arrangement is needed.

The ventilating fan is arranged on the side surface of the battery, is communicated with the space of the cathode cabin and the buffer cabin, and is isolated by the current collecting net to form the communication of an air channel for spraying, so that the content of oxygen required by the air electrode in the discharging process is ensured, and meanwhile, the stable operation of the battery stack is ensured under the condition that the temperature is not higher than 80 ℃ in order to remove the redundant heat generated in the discharging process of the battery. The ventilation mode can be air blast or air exhaust mode. The switch of the ventilation system is controlled by an electrical signal. The air channel is used for air intake from one side or two sides of the cabin middle sleeve or the buffer cabin and air exhaust from one side of the cabin middle sleeve or the buffer cabin side, and the ventilation fan is installed at the air intake end or the air exhaust end.

The temperature measurements include temperature sensors located at various locations in the stack and in the electrolyte tank. The temperature sensor is used for detecting the temperature of the outer surface of the cell stack and the temperature of electrolyte so as to start and stop a heat dissipation system. When the temperature of the electrolyte measured by the temperature sensor is higher than the specified upper limit, the temperature is reduced through heat dissipation by the heat dissipation system through the switch of the control valve.

The electrolyte tank is made of corrosion-resistant materials such as ABS, nylon, PP, PE and the like, or a metal shell is lined with the above materials, is used for placing a filter disc, electrolyte and solid separators, and can be provided with a pipeline valve for emptying the electrolyte. The main components of the battery system are all cabins and pipelines made of alkali-resistant materials, such as ABS engineering plastics, polytetrafluoroethylene materials, nylon, stainless steel and modified materials thereof, such as PE, and the materials are required to be alkali-resistant and have slow aging speed. In order to prevent the product from blocking the fine holes of the filter screen, the filter screen is inclined, and the inclined angle is preferably 30-90 degrees. The insulating material selection area and the inclined tube filter of each cabin structure can be made of corrosion-resistant materials such as ABS, PP, nylon and the like, and the filter cloth can be made of stainless steel, nylon and the like. The battery unit and the buffer cabin are connected by adopting a pipeline made of alkali-resistant functional materials, such as polytetrafluoroethylene, ABS engineering plastics, nylon and the like. The battery units can be sealed by using a uniform hatch cover and fastening the hatch cover through a sealing gasket with silica gel and alkali-resistant fluororubber.

The electrolyte is forced to pass through a filter screen to filter sediments, and the filter screen can be selectively placed in a buffer cabin or a sediment filtering cabin with increased strength; the buffer cabin is convenient to disassemble and assemble, and sediments are removed and metal is replaced regularly. The material of the filter screen is made of alkali-resistant related materials, such as a stainless steel material containing nickel, a nylon material and the like. And each grid is provided with a sediment storage space at the lower part of the sediment filter box. The product that does not pass through the filter screen falls into the storage space at the bottom of the sedimentation filter tank due to gravity. According to the steps, the integral precipitation filter box realizes the following functions that when saturated solution passes through the precipitation filter, aluminum hydroxide precipitation is generated, newly crystallized crystals continuously grow to a certain size, the crystal grains are separated from electrolyte after being filtered and precipitated, the filtered electrolyte returns to a battery, and chemical reaction continues to occur until the battery reaction is finished.

The performance of the current collecting net of the invention requires that silver, platinum and alloy or other solid materials with cathode catalysis function are adopted, and a net-shaped metal structure is used for fixing the materials, wherein the metal anode comprises zinc, magnesium, aluminum, lithium, iron and the like, and the current collecting net is a conductive net-shaped structure formed by metal or alloy groups comprising platinum and silver or wrapped with a catalytic substance; the cathode chamber is arranged along the electrolyte water flow direction to cater to the water flow collected by spraying the electrolyte.

The invention has the beneficial characteristics that:

the air fuel cell system of aluminum/magnesium and the like overcomes the common defects of the traditional cells and has obvious advantages that the cell system is a sealing system; the battery system is added with a chemical reaction chamber separated by 2 spaces by a porous chamber middle sleeve; the collector net directly contacts with air; a waterproof breathable film and an active carbon air diffusion layer used in the traditional technology are omitted, a ventilation fan can independently control the dissolved oxygen amount, and a circulating pump can independently control the reaction amount; the combination of the two can make the reaction efficiency higher, the specific power obtain great increase, even reliable and stable.

[ description of the drawings ]

FIG. 1 is a schematic structural view of an upper spray type cabin-divided circulation and spray dissolved oxygen metal-air battery

FIG. 2 is a schematic view of a structure of a lower spray type cabin-divided circulation and spray dissolved oxygen metal-air battery

Description of reference numerals:

1 anodic metal

2 anode cabin

3 cathode chamber

4 electrolyte delivery pipe

5 cabin middle sleeve

6 flow collecting net

7 side flow hole

8 circulating pump

9 ventilating fan

10 oxygen gas flow through channel

11 shower space

12 electrolyte

13 negative electrode (Anode)

14 positive electrode (cathode)

15 cabin middle sleeve

16 spray holes

17 anode cabin spray hole

18 buffer cabin

19 cabin partition

20 spray water column

21 hatch cover

22 cathode compartment shunting electrolyte

23 ventilating fan

24 filter screen

25 start-up battery pack and control circuit

26 precipitation of

27 holes of partition board

28 liquid return port of cathode chamber

29 temperature sensor

30 anode cabin liquid return port

31 buffer electrolyte

[ examples of embodiment ]

The following description of the preferred embodiments of the present invention is provided in conjunction with the accompanying drawings, in which:

as shown in fig. 1:

the cabin cover (21) and the cabin middle sleeve (5) enclose an anode cabin (2), and the anode cabin (2) is characterized in that a closed space with higher pressure (relative to the cathode cabin) is provided with anode metal (1) inside; the structure part containing the spray holes (16) can be a part of a cabin cover (21), so that after the cabin cover is opened, anode metal is exposed and is communicated with a circulating pump (8) through an anode cabin liquid return port (30), a cabin partition plate (19) separates a cabin middle sleeve (5) into a plurality of anode cabins and cathode cabins, a secondary flow hole (7) penetrates through the cabin partition plate (19) and leaks to the cathode cabins, and a buffer cabin (18), the cabin middle sleeve (5) and the buffer cabin (2) enclose a cathode cabin (3); the circulating pump (8) drives the electrolyte (31) to circularly reciprocate along the anode cabin, the cathode cabin, the buffer cabin, the anode cabin or the cathode cabin, the anode cabin, the buffer cabin and the cathode cabin; the anode cabin (2) and the cathode cabin (3) are separated by a cabin middle sleeve (5) or a cabin cover (21); the structure is characterized in that a spraying space (11) is reserved at the upper part or the lower part of the cathode cabin (2), the spraying space (11) is a space communicated with the atmosphere, the corresponding part of the cabin middle sleeve (5) is opened, the space is opened to the air, the air can forcibly flow through the space (1 electric fan or a plurality of electric fans can be connected) by connecting a ventilation fan (23) at the opening, and a gas-liquid mixed space of oxygen-dissolved electrolyte is formed, and is just led out through the side wall of the cabin middle sleeve (5), so that the insulation and the sealing are easy; the spray holes (16); the anode cabin and the cathode cabin of each group form a battery unit, the current collecting net (6) is a positive electrode (14) of the battery unit, the anode metal (1) is a negative electrode (13) of the battery unit, the electrodes can be led out to form a battery stack through a plurality of battery units, and power output is generated after the electrodes are connected in parallel or in series; the filter screen (24) cuts off the sediment (26) in the buffer cabin (2), the buffer electrolyte (31) is clean, and the filter screen (24) is easy to take out from the buffer cabin (18); the battery pack and control circuit (25) is started to receive a signal from the temperature sensor (29), and the circulation pump (8) and the ventilation fan (9) are driven to change the cooling degree to adjust the temperature.

The three components of the cabin cover (21), the cabin middle sleeve (5) and the buffer cabin (18) can be disassembled and separated, so that the metal or the current collecting net (6) is easy to replace.

As shown in fig. 2:

compared with the figure 1, the characteristics are basically consistent, and the slight difference is summarized as that the spraying space is arranged in the buffer cabin (18), and the partition plate holes (27) are arranged on the structural wall of the separation part of the anode cabin (2) and the cathode cabin (3) of the cabin middle sleeve (15); anode metal (1) is placed in an anode cabin (2), an anode cabin spray hole (17) is also processed at the bottom of the cabin and leads to a buffer cabin (18), air can forcibly flow through a spray water column (20) of a spray space through a ventilation fan (23), a cabin cover (21) and a cabin middle sleeve (15) are in a sealed connection relation (in the figure, a certain distance is intentionally separated for clear expression), and the anode cabin (2) and a cathode cabin (3) are kept isolated from an external space; after being fully dissolved by the sprayed electrolyte, oxygen molecules flow through the buffer cabin (18) and are filtered, and then are pumped back to the cathode cabin (3) by the circulating pump (6), the circulating pump (6) is butted with the electrolyte transmission pipe (4) to reinject the electrolyte into the electrolyte return port (28) of the cathode cabin, the electrolyte rich in oxygen is injected into the electrolyte return port (28) of the cathode cabin, and as the anode cabin (2) and the cathode cabin (3) are sealed to the outside, the liquid is sprayed out through the partition plate holes (27) due to the pressure of the liquid; the anode is conveyed to the anode cabin (2) from the cathode cabin (3), and simultaneously the pressure enables an anode cabin spray hole (17) at the bottom of the anode cabin (2) to spray to the space in the buffer cabin (18); the circulation of the cathode cabin, the anode cabin, the buffer cabin and the cathode cabin is completed, the anode cabin and the cathode cabin of each group form a battery unit, the current collecting net (6) is a positive electrode (14) of the battery unit, the anode metal (1) is a negative electrode (13) of the battery unit, the electrodes can be led out to form a battery stack through a plurality of battery units, and the battery stack is connected in parallel or in series to generate power output.

Claims (5)

1. The compartment circulation and spraying dissolved oxygen type metal air battery comprises anode metal, an anode compartment, a cathode compartment, a buffer compartment, a compartment cover, a compartment middle sleeve, a current collecting net, an electrolyte transmission pipe, a circulation pump, a ventilation fan, a control circuit and a starting battery pack; firstly, placing anode metal in an anode cabin, storing electrolyte in the anode cabin and a buffer cabin to ensure that the electrolyte obtains a spraying space in a cathode cabin or the buffer cabin, then driving a circulating pump to carry out forced circulation by a control circuit under the power supply of a starting battery pack or an external power supply to start reinjection of the electrolyte into the anode cabin, and enabling a battery to enter a working state; the device is characterized in that the cabin cover and the cabin chamber are sleeved to form an anode cabin, and the buffer cabin and the cabin chamber are sleeved to form a cathode cabin; the circulating pump drives the electrolyte to circularly reciprocate along the anode cabin, the cathode cabin, the buffer cabin, the anode cabin or the cathode cabin, the anode cabin, the buffer cabin and the cathode cabin; the anode cabin and the cathode cabin are separated by a cabin middle sleeve or a cabin cover; a spraying space is reserved at the upper part or the lower part of the cathode chamber, the spraying space is a space communicated with the atmosphere, and air can flow through the space forcibly by a ventilation fan to form a gas-liquid mixing space of the dissolved oxygen electrolyte; the anode cabin and the cathode cabin of each group form a battery unit, the current collecting net is the anode of the battery unit, the anode metal is the cathode of the battery unit, a plurality of battery units form a battery stack, and power output is generated after parallel connection or series connection.

2. The compartment-circulating, spray-dissolved oxygen type metal-air battery according to claim 1, characterized in that: the spraying space at the upper part of the cathode cabin is a space enclosed by a cabin cover and a cathode cabin wall of a cabin middle sleeve, a vent hole is formed at the upper part of the cabin middle sleeve corresponding to the cathode cabin, and a wall hole is formed on the structure wall of the separation part of the anode cabin and the cathode cabin of the cabin middle sleeve; the spraying space is also used as an air channel, and oxygen molecules are fully dissolved by the sprayed electrolyte and then flow through the flow collecting net and enter the buffer cabin; under the action of the liquid pressure in the anode cabin, the electrolyte in the anode cabin is sprayed to the cathode cabin through the anode cabin wall holes, and the sprayed electrolyte continuously flows through the current collecting net to complete the cyclic reciprocation of the cathode cabin, the anode cabin, the buffer cabin and the cathode cabin; the spraying space at the lower part of the cathode cabin is the upper space of the buffer cabin, and the structural wall of the separation part of the anode cabin and the cathode cabin sleeved in the cabin is provided with a wall hole; the bottom of the anode cabin is also provided with a wall hole, and the cabin cover and the cabin middle sleeve are in a sealing connection relationship to keep the anode cabin and the cathode cabin isolated from the external space; the cabin middle sleeve can enable air to forcibly flow through the spraying space through the ventilating fan, and after the air is fully dissolved by the sprayed electrolyte, the air flows through the buffer cabin and is filtered and then is pumped back to the cathode cabin by the hydraulic pump, so that the circulation reciprocating of the cathode cabin, the anode cabin, the buffer cabin and the cathode cabin is completed.

3. The compartment-circulating, spray-dissolved oxygen type metal-air battery according to claim 1, characterized in that: the air channel is used for air intake from one side or two sides of the cabin middle sleeve or the buffer cabin and air exhaust from one side of the cabin middle sleeve or the buffer cabin side, and the ventilation fan is installed at the air intake end or the air exhaust end.

4. The compartment-circulating, spray-dissolved oxygen type metal-air battery according to claim 1, characterized in that: the current collecting net is a conductive net structure formed by platinum, silver or alloy thereof or wrapped with a catalytic substance; the cathode chamber is arranged along the electrolyte water flow direction to cater to the water flow collected by spraying the electrolyte.

5. The compartment-circulating, spray-dissolved oxygen type metal-air battery according to claim 1, characterized in that: the power supply of the circulating pump and the ventilation fan is 2 independent motors or 1 common motor.

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