CN111769342A - Aluminum-air battery system for efficiently recycling reaction products - Google Patents

Aluminum-air battery system for efficiently recycling reaction products Download PDF

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Publication number
CN111769342A
CN111769342A CN202010682207.7A CN202010682207A CN111769342A CN 111769342 A CN111769342 A CN 111769342A CN 202010682207 A CN202010682207 A CN 202010682207A CN 111769342 A CN111769342 A CN 111769342A
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chamber
ionic membrane
aluminum
membrane electrolysis
electrolyte
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张钧
肖建军
栗晓龙
汪旺勤
雷新望
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Zhengzhou Foguang Power Generation Equipment Co Ltd
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Zhengzhou Foguang Power Generation Equipment Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/008—Disposal or recycling of fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sustainable Energy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

The invention discloses an aluminum air battery system for efficiently recovering reaction products, which comprises an ionic membrane electrolysis chamber, a swirler and a battery stack, wherein an ionic membrane is arranged in the ionic membrane electrolysis chamber, the ionic membrane divides the ionic membrane electrolysis chamber into a cathode chamber and an anode chamber, a cathode plate is arranged in the cathode chamber, an anode plate is arranged in the anode chamber, the ionic membrane electrolysis chamber is connected with an inlet of the swirler through a pipeline, a circulating pump is arranged on the pipeline between the ionic membrane electrolysis chamber and the swirler, an overflow port at the top of the swirler is connected with the battery stack through a pipeline, and the battery stack is respectively connected with the cathode chamber and the anode chamber of the ionic membrane electrolysis chamber through pipelines. The method converts the reaction product of the tetrahydroxy sodium aluminate into the water-insoluble aluminum hydroxide, and separates the aluminum hydroxide from the electrolyte of the aluminum-air battery through solid-liquid separation, so that the aluminum in the electrolyte is completely recovered, and meanwhile, the reaction products in the electrolyte are remarkably reduced, thereby maintaining the performance of the electrolyte and enabling the system to generate electricity efficiently for a long time.

Description

Aluminum-air battery system for efficiently recycling reaction products
Technical Field
The present invention relates to the field of fuel cells, and more particularly, to an aluminum air cell system for efficiently recovering reaction products.
Background
An aluminum-air fuel cell is a chemical power source for generating electricity by chemically reacting aluminum with air in the presence of an electrolyte and a catalyst, and consumes aluminum and oxygen during the electricity generation. The electrolyte of the aluminum air battery may be neutral or alkaline, wherein the alkaline electrolyte is used in a large amount. Common alkaline electrolytes include sodium hydroxide, potassium hydroxide, and the like.
In the process of generating electricity by the alkaline aluminum air battery, taking sodium hydroxide electrolyte as an example, the following reactions occur:
2Al+2NaOH+6H2O＝2Na[Al(OH)4]+3H2↑ (1)
4Al+3O2+6H2O+4OH-＝4Al(OH)4 -(2)
2Al+6H2O＝2AlOH3↓+3H2↑ (3)
the anode aluminum of the battery monomer reacts with sodium hydroxide in the electrolyte to generate sodium tetrahydroxy aluminate Na [ Al (OH)4]In the case of an aqueous aluminum-air battery, as shown in the reaction formula (1), the reaction shown in the reaction formula (3) is also present, and the anodic aluminum reacts with water in the electrolyte to produce aluminum hydroxide Al (OH)3. Sodium tetrahydroxyaluminate Na [ Al (OH)4 in aqueous solution]With Na+And Al (OH)4 -The form exists. In the above reaction, the reaction for producing sodium tetrahydroxyaluminate is the main reaction and the reaction for producing aluminum hydroxide is the side reaction, so that a large amount of sodium tetrahydroxyaluminate exists in the reaction product, the sodium tetrahydroxyaluminate is dissolved in the electrolyte, and a small amount of aluminum hydroxide Al (OH) also exists3。
Al(OH)3Is insoluble in water, so the products in the electrolyte are more and more along with the power generation of the aluminum-air battery, and for an electrolyte circulation type aluminum-air battery system, a tiny reaction product Al (OH)3The particles circulate with the electrolyte solution. ByIn Al (OH)3Is not dissolved in the electrolyte, but is solid, and when it flows through the cell, it contains small amounts of Al (OH)3The particles may adhere to the electrodes, thereby reducing the power generation efficiency of the system and reducing the output power of the system.
In addition, as the reaction progresses and the aluminum anode is consumed, more and more products are generated in the electrolyte, the conductivity of the electrolyte is lower and lower, and the power generation capacity of the system is lower and lower. The increase of the reaction products in the electrolyte liquid, and correspondingly the decrease of the reaction substances, the probability of the aluminum anode contacting with the reactants is smaller and smaller, and the system efficiency is lower and lower. Therefore, in order to maintain the efficiency of the system, the prior art is to replace the whole galvanic pile at intervals, discard the electrolyte after reaction, and replace the electrolyte with new electrolyte. This method is not suitable for use in many occasions, such as automobile use.
In the chemical reaction products of the aluminum air battery power generation, aluminum hydroxide is a usable substance, can be recycled, can be used as a flame retardant and a medicine, can also be heated to obtain aluminum oxide, can be further processed to obtain aluminum, and can be used for generating power again, so that the aluminum air fuel battery can be recycled.
The reaction product aluminum hydroxide in the power generation process is insoluble in water, so that the aluminum hydroxide can be obtained through solid-liquid separation, and the aluminum hydroxide in the electrolyte is reduced. However, the solid-liquid separation can not separate the main product of the reaction, namely the tetrahydroxy sodium aluminate, and the tetrahydroxy sodium aluminate is still in the electrolyte and participates in the circulation of the electrolyte. Along with the power generation, the performance of the electrolyte is gradually reduced due to the increase of the quantity of the tetrahydroxy sodium aluminate serving as a reaction product, the power generation efficiency of a system is gradually reduced, and meanwhile, a large quantity of aluminum such as Al (OH) is used4 -Is in a form that cannot be recovered.
Therefore, the recovery problem of the reaction product in the power generation process of the aluminum-air battery system, especially the recovery problem of the aluminum in the main product sodium tetrahydroxy aluminate, is solved, so that the reaction product in the electrolyte is reduced, the performance of the electrolyte is maintained, and the system can generate power efficiently for a long time, which becomes one of the important concerns and urgent problems to be solved in the field.
Disclosure of Invention
In order to solve the problems of gradual reduction of electrolyte performance, gradual reduction of system power generation efficiency and the like caused by increase of reaction products along with the progress of power generation reaction in the conventional aluminum-air battery system, the invention innovatively provides the aluminum-air battery system for efficiently recovering the reaction products, which converts sodium tetrahydroxy aluminate into water-insoluble aluminum hydroxide, and separates the aluminum hydroxide from the electrolyte of the aluminum-air battery through solid-liquid separation, so that all aluminum in the electrolyte is recovered, meanwhile, the reaction products in the electrolyte are remarkably reduced, the performance of the electrolyte is further maintained, and the system can generate power efficiently for a long time.
In order to achieve the above technical object, the present invention discloses an aluminum-air battery system for efficiently recovering reaction products, comprising: the ion membrane electrolysis chamber is internally provided with an ion membrane, the ion membrane electrolysis chamber is divided into a cathode chamber and an anode chamber by the ion membrane, a cathode plate is arranged in the cathode chamber, an anode plate is arranged in the anode chamber, the ion membrane electrolysis chamber is connected with an inlet of the cyclone through a pipeline, a circulating pump is arranged on the pipeline between the ion membrane electrolysis chamber and the cyclone, an overflow port at the top of the cyclone is connected with the cell stack through a pipeline, and the cell stack is respectively connected with the cathode chamber and the anode chamber of the ion membrane electrolysis chamber through pipelines.
Furthermore, the cathode chamber is communicated with the anode chamber through a connecting pipeline, and a first electromagnetic valve is arranged on the connecting pipeline.
Furthermore, a radiator is arranged on a pipeline between the cell stack and the ionic membrane electrolysis chamber, and a plurality of radiating fans are arranged below the radiator.
Furthermore, the pipeline between the cell stack and the ionic membrane electrolysis chamber comprises a first pipeline, a three-way pipe, a second pipeline and a third pipeline, wherein the first end of the first pipeline is connected with the cell stack, the second end of the first pipeline is connected with the three-way pipe, the other two ends of the three-way pipe are respectively connected with the second pipeline and the third pipeline, the second pipeline is connected into the anode chamber, the third pipeline is connected into the cathode chamber, and a second electromagnetic valve is arranged on the third pipeline.
Furthermore, a filtration and recovery device is arranged below the cyclone, and the filtration and recovery device is arranged above the anode chamber.
Furthermore, the filtering and recycling device comprises an L-shaped filtering layer, the L-shaped filtering layer is fixed on the side wall of the ionic membrane electrolysis compartment, and the L-shaped filtering layer and the side wall of the ionic membrane electrolysis compartment form a filtering tank in a surrounding mode.
Furthermore, a reactant collecting net is detachably connected in a filter tank enclosed by the L-shaped filter layer and the side wall of the ionic membrane electrolysis chamber.
Further, the bottom and the lateral part of L type filter layer all are equipped with the filtration pore, the aperture that the filtration pore was crossed to L type filter layer bottom is the same, the aperture from the bottom up gradually-increasing of filtration pore was crossed to L type filter layer lateral part.
Furthermore, a cover plate is covered above the ionic membrane electrolysis compartment and used for fixing the cathode plate, the ionic membrane and the anode plate, and a cathode electrode lug and an anode electrode lug are arranged on the cover plate.
Furthermore, a plurality of oxygen exhaust holes and a plurality of hydrogen exhaust holes are formed in the cover plate.
The invention has the beneficial effects that:
(1) the aluminum-air battery system for efficiently recycling the reaction product converts the reaction product sodium tetrahydroxy aluminate into water-insoluble aluminum hydroxide, and separates the aluminum hydroxide from the electrolyte of the aluminum-air battery through solid-liquid separation, so that the aluminum in the electrolyte is completely recycled, the reaction product in the electrolyte is obviously reduced, the performance of the electrolyte is further maintained, and the system can efficiently generate electricity for a long time.
(2) The aluminum-air battery system for efficiently recycling the reaction products filters and recycles part of electrolyte carried in the separated aluminum hydroxide through the filtering and recycling device, continues to participate in chemical reaction, realizes cyclic utilization of the electrolyte, and further ensures that the battery system is in a high-efficiency operation state for a long time.
(3) The aluminum-air battery system for efficiently recycling the reaction products, provided by the invention, recycles part of reaction substance NaOH for power generation through ion membrane electrolysis, and is beneficial to maintaining the efficient power generation of the system for a long time.
Drawings
Fig. 1 is a schematic structural view of an aluminum-air battery system for efficiently recovering reaction products according to the present invention.
FIG. 2 shows Na+A selective electromigration schematic occurs through the ionic membrane.
FIG. 3 is a schematic diagram of the principle of ionic membrane electrolysis.
FIG. 4 is a schematic view showing the connection between the cover plate and the ion membrane electrolysis chamber.
FIG. 5 is a plan view of an ionic membrane electrolyte compartment.
Fig. 6 is a bottom view of the cover plate.
In the figure, the position of the upper end of the main shaft,
1. an ionic membrane electrolysis chamber; 2. a swirler; 3. a cell stack; 4. a heat sink; 5. a cathode chamber; 6. an anode chamber; 7. a circulation pump; 8. an L-shaped filter layer; 9. a reactant collection web; 10. a cover plate; 11. an ionic membrane; 12. a cathode plate; 13. an anode plate; 14. a first solenoid valve; 15. a first conduit; 16. a three-way pipe; 17. a second conduit; 18. a third pipeline; 19. a second solenoid valve; 41. a heat radiation fan; 101. a negative electrode tab; 102. a positive electrode tab; 103. an oxygen vent; 104. a hydrogen vent; 105. a cathode plate fixing groove; 106. an ionic membrane fixing groove; 107. an anode plate fixing groove.
Detailed Description
The aluminum air battery system for efficiently recovering reaction products according to the present invention will be explained and illustrated in detail with reference to the accompanying drawings.
As shown in fig. 1, this embodiment specifically discloses an aluminum-air battery system for efficiently recovering reaction products, which includes: the ionic membrane electrolysis chamber comprises an ionic membrane electrolysis chamber 1, a swirler 2 and a cell stack 3, wherein an ionic membrane 11 is arranged in the ionic membrane electrolysis chamber 1, the ionic membrane 11 divides the ionic membrane electrolysis chamber 1 into a cathode chamber 5 and an anode chamber 6, a cathode plate 12 is arranged in the cathode chamber 5, an anode plate 13 is arranged in the anode chamber 6, the ionic membrane electrolysis chamber 1 is connected with an inlet of the swirler 2 through a pipeline, a circulating pump 7 is arranged on the pipeline between the ionic membrane electrolysis chamber 1 and the swirler 2, a top overflow port of the swirler 2 is connected with the cell stack 3 through a pipeline, and the cell stack 3 is respectively connected with the cathode chamber 5 and the anode chamber 6 of the ionic membrane electrolysis chamber.
Before the aluminum air cell system is started, electrolyte is stored in the ionic membrane electrolysis chamber 1, the electrolyte is uniformly distributed in the cathode chamber 5 and the anode chamber 6, and the liquid levels of the cathode chamber 5 and the anode chamber 6 are the same. When the system works, the circulating pump 7 is electrified. The electrolyte in the ionic membrane electrolysis chamber 1 is conveyed by the circulating pump 7 under the action of the circulating pump 7, the electrolyte flows into the cyclone 2 at a certain speed through the inlet of the cyclone 2, when the electrolyte flows through the cyclone 2, an outer cyclone of a downward cyclone and an inner cyclone of an upward cyclone are formed, the outer cyclone is mainly made of aluminum hydroxide with a high specific gravity, and the inner cyclone is mainly made of the electrolyte with a low specific gravity, so that the aluminum hydroxide which is a solid-phase substance in the electrolyte is separated in the cyclone 2 and discharged through the underflow outlet. The separated electrolyte without containing aluminum hydroxide or containing less aluminum hydroxide flows out through the top overflow port of the cyclone 2 and enters the cell stack 3, the electrolyte participates in power generation in the cell stack 3, a main product of tetrahydroxy sodium aluminate is continuously generated and a byproduct of aluminum hydroxide is continuously generated in the power generation process of the cell stack 3, the electrolyte is changed into a solution rich in tetrahydroxy sodium aluminate and aluminum hydroxide when flowing out of the cell stack 3, and the solution rich in tetrahydroxy sodium aluminate and aluminum hydroxide enters the ionic membrane electrolysis chamber 1 for ionic membrane electrolysis.
The invention adopts the ion membrane electrolysis technology to convert the sodium aluminum tetrahydroxy aluminate which is the main reaction product of the aluminum-air battery into the aluminum hydroxide, and adopts the solid-liquid separation technology to separate the aluminum hydroxide from the electrolyte, thereby realizing the recovery of the aluminum and maintaining the performance of the electrolyte.
The principle of ion membrane electrolysis:
preferably, the ionic membrane 11 is a Nafion membrane (Nafion is a copolymer of polytetrafluoroethylene (Teflon) and perfluoro-3, 6-diepoxy-4-methyl-7-decene-sulfuric acid), and the internal structural formula of the Nafion membrane can be represented as: R-SO3-H+(Na+) Wherein R represents a polymer structure. The active group being negatively charged-SO3-group and positively charged Na+Under the action of the electric field, the ion membrane 11 has ion selective passing capability.
Since the sulfonic acid group has hydrophilicity, the ionic membrane 11 becomes loose in structure after swelling in solution, and many fine curved channels are formed, so that Na is allowed to exist+Can pass through the membrane. and-SO in the film3Fixed position of-and-COO-, with repulsion of C1-And OH-The plasma functions (as shown in fig. 2) so that they cannot pass through the ionic membrane 11. As the electrolysis proceeds, the pH of the solution in the anode compartment decreases, corresponding to the addition of acid, while the pH in the cathode compartment increases, corresponding to the addition of base. Thus, the ionic membrane pair Na is utilized+The supersaturation degree of the sodium tetrahydroxyaluminate solution is improved through electrolysis, and the aluminum hydroxide can be separated out.
As shown in fig. 3, the anode plate is a passivated metal titanium plate, the cathode plate is a stainless steel flat plate, and the middle ionic membrane is a Nafion membrane. The solution in the cathode chamber is NaOH solution, and the solution in the anode chamber is tetrahydroxy sodium aluminate solution. During electrolysis, the anode chamber and the cathode chamber respectively react differently.
Under the action of an electric field, Na+Selective electromigration occurs through the ionic membrane, namely:
4Na+(Anode compartment) → 4Na+(cathode chamber)
Cathodic evolution of H2Generation of OH-Na transferred from the anode chamber 6+The combination, similar to salt electrolysis, makes it possible to obtain a high concentration of NaOH solution in the cathode compartment, producing OH-The reaction of (a) is as follows:
4H2O+4e-→2H2+4OH-
the tetrahydroxy sodium aluminate solution in the anode chamber is ionized and rapidly acidified, and the following reactions occur:
4Na[Al(OH)4]→4Na++4Al(OH)4 -
4Al(OH)4 -+H2O-4e-→4AlOH3+4H2O+O2↑
the total reaction equation of the tetrahydroxy sodium aluminate solution ion membrane electrolysis is as follows: 4Na [ Al (OH)4]+2H2O＝4A1(OH)3(Anode) +4NaOH (cathode) + O2(Anode) +2H2(cathode)
In the process of the ion membrane electrolysis, the current is gradually reduced along with the progress of the electrolysis, and when a large number of micro crystal nuclei are precipitated, the current is rapidly reduced, and the electrolysis is stopped. Only the alpha of the tetrahydroxy sodium aluminate solution is changed in the electrolysis processk(caustic ratio) does not change the structure of the solution. As electrolysis continues, H is generated in the anode compartment+The supersaturation degree of the tetrahydroxy sodium aluminate solution is increased continuously, and the decomposition is accelerated. The total effect of the electrolysis is to precipitate Al (OH) in the anode chamber3Crystal nucleus and O2Concentrated NaOH and H are obtained in the cathode chamber2. In the process, the supersaturation degree of the tetrahydroxy sodium aluminate solution is continuously improved, and the aluminum hydroxide is continuously separated out. The method for converting the tetrahydroxy sodium aluminate into the aluminum hydroxide through the ion membrane electrolysis is efficient and rapid.
The electrolyte in the power generation process of the aluminum-air battery system is treated, firstly, the main reaction product, namely the sodium tetrahydroxy aluminate in the reaction solution is converted into the aluminum hydroxide through the electrolysis of the ionic membrane, and the aluminum hydroxide is separated out through the solid-liquid separation of the electrolyte containing the aluminum hydroxide, so that the property of the electrolyte is ensured, and the aluminum hydroxide is recovered.
As shown in fig. 1, the cathode chamber 5 and the anode chamber 6 are communicated with each other through a connecting pipe, and a first electromagnetic valve 14 is provided on the connecting pipe. A radiator 4 is provided on the duct between the cell stack 3 and the ion membrane electrolysis compartment 1, and a plurality of radiator fans 41 are provided below the radiator 4. The pipeline between the cell stack 3 and the ionic membrane electrolysis chamber 1 comprises a first pipeline 15, a three-way pipe 16, a second pipeline 17 and a third pipeline 18, the first end of the first pipeline 15 is connected with the cell stack 3, the second end of the first pipeline 15 is connected with the three-way pipe 16, the radiator 4 is arranged on the first pipeline 15, the other two ends of the three-way pipe 16 are respectively connected with the second pipeline 17 and the third pipeline 18, the second pipeline 17 is connected into the anode chamber 6, the third pipeline 18 is connected into the cathode chamber 5, and a second electromagnetic valve 19 is arranged on the third pipeline 18.
The solution rich in sodium tetrahydroxyaluminate and aluminium hydroxide coming out of the stack 3, after being cooled in the radiator 4 arranged on the first pipe 15, flows through the first pipe 15 into the tee 16. At the tee 16, the electrolyte can flow into the anode chamber 6 of the ion membrane electrolysis cell 1 only through the second pipe 17, thereby completing one cycle. The electrolyte can flow into the cathode chamber 5 and the anode chamber 6 of the ion membrane electrolysis chamber 1 simultaneously through the second pipeline 17 and the third pipeline 18 at the tee pipe 16.
The first solenoid valve 14 and the second solenoid valve 19 are both normally-off solenoid valves, and are conducted when powered. In the system, the first solenoid valve 14 and the second solenoid valve 19 are designed to be energized simultaneously and de-energized simultaneously. When the first solenoid valve 14 and the second solenoid valve 19 are de-energized, the cathode chamber 5 and the anode chamber 6 are not conducted, and the electrolyte from the cell stack 3 flows only into the anode chamber 6. When the first electromagnetic valve 14 and the second electromagnetic valve 19 are simultaneously electrified, the cathode chamber 5 is communicated with the anode chamber 6, at the moment, a part of electrolyte flows into the cathode chamber 5 through the three-way pipe 16, and a part of electrolyte flows into the anode chamber 6 through the three-way pipe 16. The electrolyte flowing into the cathode chamber 5 is mixed with the electrolyte formed by the electrolysis of the ionic membrane in the cathode chamber 5, and then flows into the anode chamber 6 through the connecting pipeline and the first electromagnetic valve 14. In the anode chamber 6, the electrolyte from the cathode chamber 5 is mixed with the electrolyte in the anode chamber 6, and the mixed electrolyte is driven by the circulating pump 7 to form circulation.
When the aluminum air battery system works, the ion membrane electrolysis is started, and H is separated out in the cathode chamber 52Generation of OH-Na transferred from the anode chamber 6+In combination, a high concentration NaOH solution can be obtained in the cathode compartment 5. Therefore, part of reaction substance NaOH for power generation is recovered through ion membrane electrolysis, and efficient power generation of the system can be kept for a long time. In the anode compartment 6, the sodium tetrahydroxyaluminate solution is ionized and rapidly acidified and the product A1(OH) is formed3Thus, the electrolyte in the anode chamber 6 contains more aluminium hydroxide than conventional electrolyte, so that the electrolyte is circulated and enters the cyclone 2 with more aluminium hydroxide than conventional electrolyteMore solid-phase aluminum hydroxide is separated after passing through the cyclone 2.
The electrolyte in the cathode chamber 5 can be circulated all the time or intermittently, preferably intermittently, and the intermittent circulation of the electrolyte in the cathode chamber 5 can be realized by intermittently powering on or powering off the first solenoid valve 14 and the second solenoid valve 19 simultaneously. The intermittent circulation has the advantages that the sodium hydroxide in the cathode chamber 5 is enriched to a certain degree and then replaced, so that the electrolysis efficiency can be improved, and the electrolysis electric energy can be saved.
The Nafion membrane is used as the ion membrane 11 for electrolysis, and can also be used for an aluminum air battery of potassium hydroxide electrolyte, the working principle is similar to that of the aluminum air battery of sodium hydroxide electrolyte, but potassium hydroxide is obtained in the cathode chamber 5 during electrolysis, and aluminum hydroxide is still obtained in the anode chamber 6.
The aluminum-air battery system for efficiently recovering reaction products, disclosed by the invention, has the advantages that the ionic membrane electrolysis chamber 1 integrates three functions of ionic membrane electrolysis, electrolyte storage and aluminum hydroxide recovery, the structure is simple, the operation is convenient, and the space is saved.
The invention carries out ion membrane electrolysis on the circulating electrolyte of the aluminum-air battery system, and the electrolysis is started when the concentration of the tetrahydroxy sodium aluminate in the electrolyte is not high, so that the low concentration of the tetrahydroxy sodium aluminate in the electrolyte is kept all the time, thus not only maintaining the high performance of the electrolyte, but also ensuring that the electrolysis consumes little electricity.
As shown in fig. 1, a filtration and recovery device is provided below the cyclone 2, and the filtration and recovery device is provided above the anode chamber 6. The filtering and recycling device comprises an L-shaped filtering layer 8, the L-shaped filtering layer 8 is fixed on the side wall of the ionic membrane electrolysis chamber 1, and a filtering tank is defined by the L-shaped filtering layer 8 and the side wall of the ionic membrane electrolysis chamber 1. A reactant collecting net 9 is detachably connected in a filter tank enclosed by the L-shaped filter layer 8 and the side wall of the ionic membrane electrolysis chamber 1. The bottom and the lateral part of the L-shaped filter layer 8 are both provided with filter holes, the pore diameter of the filter holes at the bottom of the L-shaped filter layer 8 is the same, and the pore diameter of the filter holes at the lateral part of the L-shaped filter layer 8 is gradually increased from bottom to top, so that the liquid filtration can be increased. In particular, when the bottom has a certain amount of reaction products, the filtration capacity through the bottom decreases, and as the products accumulate, the filtration capacity becomes smaller, and the side filtration pores become dominant.
The ionic membrane electrolysis chamber 1 is divided into two parts by an ionic membrane 11, one part is used as a cathode chamber 5, the other part is used as an anode chamber 6, a filtering and recycling device is arranged at the part of the anode chamber 6 and is positioned at the upper part of the anode chamber 6, a reactant collecting net 9 is arranged in a filtering tank, and aluminum hydroxide discharged through a bottom flow port of the cyclone 2 is collected in the reactant collecting net 9 so as to be conveniently taken away. When an aluminum air battery system is designed, the required electrolyte amount is determined according to the power and the time consumption of the system, the size and the specification of the ionic membrane electrolysis chamber 1 are determined according to the electrolyte amount, and the filtering and recovering device is ensured to be always positioned above the electrolyte, so that the aluminum hydroxide in the filtering and recovering device can further separate the electrolyte by virtue of gravity.
The ion membrane electrolysis chamber 1 can have various forms, can be square, can be round, and is characterized by being divided into two parts by an ion membrane 11, wherein one part is used as a cathode chamber 5, and the other part is used as an anode chamber 6.
As shown in fig. 4, a cover plate 10 is covered above the ionic membrane electrolysis compartment 1, the cover plate 10 is used for fixing a cathode plate 12, an ionic membrane 11 and an anode plate 13, a negative electrode tab 101 and a positive electrode tab 102 are arranged on the cover plate 10, and the negative electrode tab 101 and the positive electrode tab 102 are used for accessing a power supply required by electrolysis. When the cover plate 10 is covered on the ionic membrane electrolysis compartment 1, the cathode plate 12, the ionic membrane 11 and the anode plate 13 are fixed in the ionic membrane electrolysis compartment 1, the ionic membrane electrolysis compartment 1 is divided into two parts by the ionic membrane 11, the part with the cathode plate 12 is the cathode chamber 5, and the part with the anode plate 13 is the anode chamber 6.
As shown in figure 5, bosses are arranged on the inner side of the front wall and the rear wall of the ion membrane electrolysis chamber 1, two bosses and the rear wall of the ion membrane electrolysis chamber 1 form a groove, and the other two bosses and the front wall of the ion membrane electrolysis chamber 1 form a groove, and the two grooves are used for clamping the ion membrane 11.
When the cathode plate 12, the anode plate 13 and the ionic membrane 11 are fixed on the cover plate 10, the cover plate 10 is covered, the ionic membrane 11 is inserted into a groove formed by the lug boss and the front wall and the rear wall of the ionic membrane electrolysis chamber 1 for placing the ionic membrane 11, and the cathode plate 12 and the anode plate 13 are also placed in place.
As shown in fig. 6, the cover plate 10 is provided with a plurality of oxygen gas discharge holes 103 and a plurality of hydrogen gas discharge holes 104. The oxygen gas vent hole 103 and the hydrogen gas vent hole 104 are arranged on the part of the cover plate 10 far away from the ion membrane 11, so that oxygen gas and hydrogen gas generated during electrolysis can be conveniently discharged. The oxygen gas outlet hole 103 is arranged at the right side of the anode chamber 6, and the hydrogen gas outlet hole 104 and the oxygen gas outlet hole 103 are spaced at a certain distance to ensure that the high-concentration hydrogen gas and oxygen gas do not meet when the aluminum-air battery system works.
The cover plate 10 is further provided with a cathode plate fixing groove 105 for fitting the cathode plate 12, an ionic membrane fixing groove 106 for fitting the ionic membrane 11, and an anode plate fixing groove 107 for fitting the anode plate 13, and the cathode plate fixing groove 105, the ionic membrane fixing groove 106, and the anode plate fixing groove 107 may be grooves or through-hole grooves. During assembly, the cover plate 10 is covered firstly, then the anode plate 13 is inserted into the anode plate fixing groove 107, the ion membrane 11 is inserted into the ion membrane fixing groove 106, and the cathode plate 12 is membrane-inserted into the cathode membrane fixing groove, so that the replacement and maintenance are more convenient.
The system adopts the ionic membrane to electrolyze and process the reaction product of the aluminum air battery system, and part of oxygen is recycled in the electrolytic anode chamber 6, so that the dependence on external oxygen is reduced for a closed use environment, and the system is more suitable for the closed use environment.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be considered limiting of the invention.
In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the description herein, references to the description of the term "the present embodiment," "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and simplifications made in the spirit of the present invention are intended to be included in the scope of the present invention.

Claims (10)

1. An aluminum-air battery system for efficiently recovering reaction products, comprising: an ionic membrane electrolysis chamber (1), a swirler (2) and a battery stack (3), wherein an ionic membrane (11) is arranged in the ionic membrane electrolysis chamber (1), the ionic membrane (11) divides the ionic membrane electrolysis chamber (1) into a cathode chamber (5) and an anode chamber (6), a cathode plate (12) is arranged in the cathode chamber (5), an anode plate (13) is arranged in the anode chamber (6), the ionic membrane electrolysis chamber (1) is connected with the inlet of the cyclone (2) through a pipeline, a circulating pump (7) is arranged on a pipeline between the ionic membrane electrolysis chamber (1) and the cyclone (2), the top overflow port of the cyclone (2) is connected with the cell stack (3) through a pipeline, the cell stack (3) is respectively connected with the cathode chamber (5) and the anode chamber (6) of the ionic membrane electrolysis chamber (1) through pipelines.
2. The aluminum-air cell system for the efficient recovery of reaction products according to claim 1, wherein the cathode chamber (5) and the anode chamber (6) are communicated with each other through a connection pipe, and the connection pipe is provided with a first electromagnetic valve (14).
3. The aluminum-air battery system for recovering reaction products with high efficiency as recited in claim 1, wherein a heat sink (4) is provided on a pipe between the cell stack (3) and the ionic membrane electrolysis compartment (1), and a plurality of heat radiation fans (41) are provided below the heat sink (4).
4. An aluminum air cell system for high efficiency recovery of reaction products according to any of claims 1 to 3 wherein the piping between the cell stack (3) and the ion membrane electrolysis compartment (1) comprises a first piping (15), a tee (16), a second piping (17) and a third piping (18), a first end of the first piping (15) is connected to the cell stack (3), a second end of the first piping (15) is connected to the tee (16), the other two ends of the tee (16) are respectively connected to the second piping (17) and the third piping (18), the second piping (17) is connected to the anode chamber (6), the third piping (18) is connected to the cathode chamber (5), and a second electromagnetic valve (19) is provided on the third piping (18).
5. The aluminum-air battery system for efficient recovery of reaction products according to claim 1, wherein a filtration recovery device is provided below the cyclone (2), and the filtration recovery device is provided above the anode chamber (6).
6. The aluminum-air battery system for efficiently recovering reaction products according to claim 5, wherein the filtration recovery device comprises an L-shaped filter layer (8), the L-shaped filter layer (8) is fixed on the side wall of the ionic membrane electrolysis chamber (1), and the L-shaped filter layer (8) and the side wall of the ionic membrane electrolysis chamber (1) form a filter tank.
7. The aluminum-air battery system for efficiently recovering reaction products as claimed in claim 6, wherein a reactant collecting net (9) is detachably connected in a filter tank enclosed by the L-shaped filter layer (8) and the side wall of the ionic membrane electrolysis chamber (1).
8. The aluminum-air battery system for efficiently recycling reaction products according to claim 6 or 7, wherein the bottom and the side of the L-shaped filter layer (8) are provided with filter holes, the bottom filter holes of the L-shaped filter layer (8) have the same pore size, and the side filter holes of the L-shaped filter layer (8) have gradually increased pore size from bottom to top.
9. The aluminum-air battery system for efficiently recovering reaction products according to claim 1, wherein a cover plate (10) is covered above the ionic membrane electrolysis compartment (1), the cover plate (10) is used for fixing the cathode plate (12), the ionic membrane (11) and the anode plate (13), and a negative electrode tab (101) and a positive electrode tab (102) are arranged on the cover plate (10).
10. The aluminum-air battery system for efficiently recovering reaction products according to claim 9, wherein the cover plate (10) is provided with a plurality of oxygen vents (103) and a plurality of hydrogen vents (104).
CN202010682207.7A 2020-07-15 2020-07-15 Aluminum-air battery system for efficiently recycling reaction products Pending CN111769342A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113120932A (en) * 2021-04-26 2021-07-16 济南易航新材料科技有限公司 System and method for preparing high-purity nano aluminum oxide
CN114044533A (en) * 2021-12-14 2022-02-15 中国科学技术大学 Energy-saving process for producing aluminum chloride

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113120932A (en) * 2021-04-26 2021-07-16 济南易航新材料科技有限公司 System and method for preparing high-purity nano aluminum oxide
CN114044533A (en) * 2021-12-14 2022-02-15 中国科学技术大学 Energy-saving process for producing aluminum chloride

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