CN110729501B - Recycling metal fuel cell system and reaction product separation method thereof - Google Patents

Recycling metal fuel cell system and reaction product separation method thereof Download PDF

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CN110729501B
CN110729501B CN201911022224.1A CN201911022224A CN110729501B CN 110729501 B CN110729501 B CN 110729501B CN 201911022224 A CN201911022224 A CN 201911022224A CN 110729501 B CN110729501 B CN 110729501B
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electrolyte
reaction product
rotating cylinder
self
separator
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CN110729501A (en
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马泽
李跃华
黄浩
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Beijing Machinery Equipment Research Institute
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Beijing Machinery Equipment Research Institute
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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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04276—Arrangements for managing the electrolyte stream, e.g. heat exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04186—Arrangements for control of reactant parameters, e.g. pressure or concentration of liquid-charged or electrolyte-charged reactants
    • 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
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • 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
    • H01M8/04223—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
    • H01M8/04231—Purging of the reactants
    • 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

Abstract

The invention relates to a recycling metal fuel cell system and a reaction product separation method thereof, belongs to the technical field of metal fuel cells, and solves the problems of high electrolyte consumption, quick cell performance attenuation, reduced performance of auxiliary equipment and the like caused by difficult separation of reaction products in the existing metal fuel cell. The recirculating metal fuel cell system includes a metal fuel cell and an electrolyte recirculating loop; the electrolyte recirculation loop is provided with a reaction product separation device, and the reaction product separation device is used for adsorbing and separating reaction products in the electrolyte; the metal fuel cell stack includes an anode reactant inlet, an anode reactant outlet, a cathode reactant inlet, and a cathode reactant outlet. The method can continuously and efficiently separate reaction products, ensures that the electrolyte entering the battery is unsaturated electrolyte, avoids the formation of precipitated particles, and greatly improves the performance of the metal fuel battery.

Description

Recycling metal fuel cell system and reaction product separation method thereof
Technical Field
The invention relates to the technical field of metal fuel cells, in particular to a recycling metal fuel cell system and a reaction product separation method thereof.
Background
With the progress of science and technology and the improvement of living standard of people, the demand of human activities on energy is increasing day by day, and especially the rapid development of electric automobiles provides huge demand and challenge on batteries. Lithium ion batteries and proton exchange membrane fuel cells are used as two major routes for the development of current electric automobiles, but lithium ion batteries and proton exchange membrane fuel cells have the defects of short endurance mileage, long charging time, difficulty in hydrogen storage and carrying, lack of hydrogen stations and the like, and the popularization and application of the lithium ion batteries and the proton exchange membrane fuel cells also face great technical problems.
In recent years, metal fuel cells have attracted much attention, which utilize electrochemical reaction of active metal such as aluminum, magnesium, zinc, etc. and oxygen in the cell to directly convert chemical energy into electric energy for output. Because active metals such as aluminum, magnesium, zinc and the like have high energy density and are convenient and safe to store and carry, the metal fuel cell can be used in various occasions such as individual soldier power supplies, standby power supplies, electric vehicles and the like.
However, the precipitation of metal oxides on the micro-nanometer scale currently has multiple adverse effects on the performance of metal fuel cells: (1) the precipitated particles are gathered on the surface of the metal anode, so that the electrochemical reaction rate of the metal anode is influenced; (2) the precipitated particles are gathered on the surface of the cathode and block the pores of the cathode, so that the electrochemical reaction rate of the cathode is influenced; (3) the precipitated particles block the electrolyte flow channel, so that the flow resistance of the electrolyte is increased, and even the flow of the electrolyte is interrupted; (4) after the electrolyte is dissolved and saturated, the conductivity of the electrolyte is greatly reduced, so that the internal resistance of the battery is increased and the performance is reduced; (5) scaling in the electrolyte radiator results in reduced heat dissipation performance.
Disclosure of Invention
In view of the foregoing analysis, embodiments of the present invention are directed to a separation apparatus and a separation method for a reaction product of a metal fuel cell, so as to solve the technical problems of low chemical reaction rate of a cathode and an anode, poor fluidity of an electrolyte, and poor thermal conductivity in the existing metal fuel cell.
The purpose of the invention is mainly realized by the following technical scheme:
in one aspect, a recirculating metal fuel cell system is disclosed, the system comprising a metal fuel cell stack and an electrolyte recirculation loop; the electrolyte recirculation loop is provided with a reaction product separation device, and the reaction product separation device is used for adsorbing and separating reaction products in the electrolyte; the metal fuel cell stack includes an anode reactant inlet, an anode reactant outlet, a cathode reactant inlet, and a cathode reactant outlet.
In one possible design, the reaction product separation device comprises a first reaction product separator and a second reaction product separator, wherein the first reaction product separator comprises a first separator shell, a first self-rotating cylinder, a first electrolyte inlet and a first electrolyte outlet which are arranged at two ends of the first separator shell; the cylindrical surface of the first self-rotating cylinder is made of a nano-adsorption material; the first self-rotating cylinder is arranged inside the first separator shell, and a first mud scraping strip is arranged on the inner wall of the first separator shell; the first self-rotating cylinder is a hollow cylinder shell structure with a first rotating impeller arranged inside; a first electrolyte channel is formed between the first separator shell and the first self-rotating cylinder; a second electrolyte channel is formed inside the first self-rotating cylinder.
In one possible design, the reaction product separation device further comprises a second reaction product separator connected with the first reaction product separator in parallel, wherein the second reaction product separator comprises a second separator shell, a second self-rotating cylinder, a second electrolyte inlet and a second electrolyte outlet, and the second electrolyte inlet and the second electrolyte outlet are arranged at two ends of the second separator shell; the cylindrical surface of the second self-rotating cylinder is made of a nano-adsorption material; the second self-rotating cylinder is arranged inside the second separator shell, and a second mud scraping strip is arranged on the inner wall of the second separator shell; the second self-rotating cylinder is a hollow cylindrical shell structure with a second rotating impeller arranged inside; a third electrolyte channel is formed between the second separator shell and the second self-rotating cylinder; and a fourth electrolyte channel is formed inside the second self-rotating cylinder.
In one possible design, the first mud scraping strip is spirally distributed along the axial direction from the first rotating cylinder.
In a possible design, the second scraper bar is helically distributed along the axis from the second rotating cylinder.
In one possible embodiment, the electrolyte recirculation circuit is provided with a first electrolyte branch and a second electrolyte branch; a first electromagnetic valve is arranged on the first electrolyte branch, and a second electromagnetic valve is arranged on the second electrolyte branch; the first electrolyte branch is connected with the first electrolyte inlet, and the second electrolyte branch is connected with the second electrolyte inlet.
In one possible design, the nano adsorption material is a nano titanium dioxide material, a nano zirconium dioxide material, a nano aluminum trioxide material or TiO material2-α-Al2O3One of the materials.
In one possible design, an electrolyte pump and an electrolyte heat dissipation device are arranged on the electrolyte recirculation loop, and the electrolyte pump is used for providing power for the electrolyte recirculation loop; the electrolyte heat dissipation device is used for cooling the electrolyte.
In one possible design, the reaction product separation device further comprises a disc separator, the disc separator is arranged on the electrolyte recirculation loop and is integrally connected in series with the first reaction product separator and the second reaction product separator, the disc separator comprises an electrolyte storage tank and a first solid reaction product collecting tank, at least one cylindrical separation disc driven by a motor to rotate is arranged in the electrolyte storage tank, and the cylindrical surface of the cylindrical separation disc is made of a nano adsorption material; the cylindrical surface of the cylindrical separation disc is provided with a first mud scraper which is used for scraping reaction products adsorbed on the cylindrical surface.
In one possible design, the two end faces of the cylindrical separating disk are made of nano-adsorption material; and the disc surfaces at two ends of the cylindrical separation disc are provided with second mud scraping plates which are used for scraping reaction products adsorbed on the disc surfaces.
In one possible design, the nano adsorption material is a nano titanium dioxide material, a nano zirconium dioxide material, a nano aluminum trioxide material or TiO material2-α-Al2O3Any of the materials.
On the other hand, the invention also discloses a reaction product separation method of the recycling metal fuel cell system, and the separation method comprises the following steps:
step 1, electrolyte in the metal fuel cell stack enters a first electrolyte branch along an electrolyte recirculation loop and enters a first electrolyte channel and a second electrolyte channel through a first electrolyte inlet, and a first self-rotating cylinder automatically rotates in a first separator shell under the flowing action of the electrolyte;
step 2, in the rotating process of the first self-rotating cylinder, a first cylindrical surface on the first self-rotating cylinder continuously adsorbs a reaction product in the electrolyte; the spiral first mud scraping strip on the inner wall of the first separator shell scrapes off the reaction product adsorbed on the surface of the first self-rotating cylinder, and the reaction product is collected into a first solid reaction product collecting tank through a first reaction product outlet;
step 3, separating the electrolyte in the first electrolyte channel and returning the electrolyte in the second electrolyte channel to the fuel cell stack through the first electrolyte outlet and the electrolyte recirculation loop;
and 4, continuously operating the first electrolytic liquid separator to realize continuous separation of reaction products in the electrolyte.
Further, when the electrolyte in the metal fuel cell enters the second electrolyte branch along the electrolyte recirculation loop, the reaction product separation method further comprises the following steps:
step 1', the electrolyte enters a third electrolyte channel and a fourth electrolyte channel through a second electrolyte inlet, and a second self-rotating cylinder automatically rotates in a second separator shell under the flowing action of the electrolyte;
step 2', in the rotating process of the second self-rotating cylinder, a second cylindrical surface on the second self-rotating cylinder continuously adsorbs a reaction product in the electrolyte; the spiral second mud scraping strip on the inner wall of the second separator shell scrapes off the reaction product adsorbed on the surface of the second self-rotating cylinder, and the reaction product is collected into a second solid reaction product collecting tank through a second reaction product outlet;
step 3', separating the electrolyte in the third electrolyte channel and the electrolyte in the fourth electrolyte channel, and returning the separated electrolyte to the metal fuel cell stack;
and 4', the second electrolytic liquid separator works continuously to realize continuous separation of reaction products in the electrolyte.
In still another aspect, the present invention also discloses a reaction product separation method of a recycled metal fuel cell system, which includes the steps of, when the reaction product separation apparatus employs a disk separator:
step 1', immersing part of a disc separator below the electrolyte level, and enabling the disc separator to continuously rotate under the driving of a motor and to be in contact with the electrolyte;
step 2', the cylindrical surface of the disc separator continuously adsorbs reaction products in the electrolyte;
step 3', the reaction product adsorbed on the cylindrical surface of the disc separator is scraped off by a first scraper and is collected by a first solid reaction product collecting tank; the electrolyte separated by the reaction product returns to the fuel cell stack through an electrolyte circulation branch;
and 4', the motor drives the disc separator to continuously rotate, so that the reaction products in the electrolyte are continuously separated.
Further, in the step 2', the disc surfaces at the two ends of the disc separator continuously adsorb reaction products in the electrolyte; in step 3 ", the reaction product adsorbed on the disk surfaces at both ends of the disk separator is scraped off by the second scraper and collected by the first solid reaction product collecting tank.
Compared with the prior art, the invention can realize at least one of the following beneficial effects:
(1) according to the invention, the electrolyte recycling loop is arranged, the electrolyte separating device is arranged on the electrolyte recycling loop, the electrolyte separating device is made of a nano material with characteristic adsorption capacity to metal ions, and the electrolyte pump is used for continuously driving the electrolyte to circularly flow, so that the electrolyte separating device can continuously separate reaction products from the electrolyte, the electrolyte does not need to be periodically replaced, and the use convenience of the metal fuel cell is improved.
(2) The nano adsorption material adopted by the invention is a nano titanium dioxide material, a nano zirconium dioxide material, a nano aluminum trioxide material or TiO2-α-Al2O3One of the materials. By utilizing the chemical adsorption and physical adsorption effects of the nano material on metal ions, the electrolyte treated by the first reaction product separator, the second reaction product separator and the disc separator is unsaturated, the unsaturated electrolyte has stronger carrying and discharging capacity on the reaction products in the fuel metal battery, the reaction interruption caused by the fact that the reaction products in the metal fuel battery cannot be discharged in time can be avoided, the conductivity of the electrolyte in a fuel battery stack can be improved, and the reduction of the conductivity of the electrolyte in the fuel battery stack can be realizedThe resistance of the stack ultimately improves the performance of the metal cell.
(3) The reaction product separation device comprises a first reaction product separator and a second reaction product separator which have the same structure, wherein the first reaction product separator and the second reaction product separator can work simultaneously, so that the separation efficiency of the reaction products is improved; when one of them is out of order, the other can ensure that the reaction products in the electrolyte recycling loop are continuously separated.
(4) According to the first reaction product separator, the first separator shell and the first self-rotating cylinder are arranged to divide electrolyte entering the first reaction product separator into two parts, one part enters the first electrolyte channel and is separated from a reaction product in the first self-rotating cylinder through the adsorption effect of the cylindrical surface of the first self-rotating cylinder, and the reaction product adsorbed by the first self-rotating cylinder is scraped and swept down through the first mud scraping strip; the other part of electrolyte enters the first self-rotating cylinder through the second electrolyte channel and drives the first self-rotating cylinder to rotate through the first rotating impeller in the first self-rotating cylinder so as to provide power for the first reaction product separator.
In the invention, the technical schemes can be combined with each other to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
FIG. 1 is a schematic diagram of a first reaction product separator according to example 1 of the present invention;
FIG. 2 is a schematic diagram of a second reaction product separator according to example 1 of the present invention;
fig. 3 is a front view of a first self-rotating cylinder provided in embodiment 1 of the present invention;
fig. 4 is a front view of a second self-rotating cylinder provided in embodiment 1 of the present invention;
FIG. 5 is a schematic diagram of a recycled metal fuel cell system according to the present invention;
FIG. 6 is a schematic structural view of a disc separator provided with a second mud scraper according to embodiment 2 of the present invention;
FIG. 7 is a schematic structural view of a disc separator provided with a first mud scraper according to embodiment 2 of the present invention;
fig. 8 is a front view of a disk surface of a disk separator provided in embodiment 2 of the present invention.
Reference numerals:
1-a metal fuel cell stack; 2-an anode reactant inlet; 3-anode reactant outlet; 4-a heat sink; 5-a reaction product collector; 6-electrolyte circulation branch; 7-electrolyte pump; 8-a disc separator; 9-cathode reactant outlet; 10-a cathode reactant inlet; 11-an electrolyte reservoir; 12-electrolyte level; 13-cylindrical separating disks; 14-a first mud scraper; 15-a third solid reaction product holding tank; 16-a solid reaction product; 17-the cylindrical surface of a cylindrical separation disc; 18-a second scraper; 19-a first self-rotating cylinder; 20-a first electrolyte inlet; 21-a first solid reaction product outlet; 22-a first electrolyte outlet; 23-a first separator housing; 24-a first solid reaction product holding tank; 25-a first mud scraping strip; 26-a second self-rotating cylinder; 27-a second electrolyte inlet; 28-a second solid reaction product outlet; 29-a second electrolyte outlet; 30-a second separator housing; 31-a second solid reaction product holding tank; 32-second mud scraping strip.
Detailed Description
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate preferred embodiments of the invention and together with the description, serve to explain the principles of the invention and not to limit the scope of the invention.
Example 1
The present embodiment provides a recirculating metal fuel cell system, as shown in fig. 1-5, comprising a metal fuel cell and an electrolyte recirculation loop 6; a reaction product separation device is arranged on the electrolyte recirculation loop 6 and is used for adsorbing and separating reaction products in the electrolyte; the metal fuel cell stack 1 includes an anode reactant inlet 2, an anode reactant outlet 3, a cathode reactant inlet 10, and a cathode reactant outlet 9.
Specifically, the electrochemical reaction occurring in the recirculating metal fuel cell system is as follows (M denotes a metal element such as Al, Mg, Zn, etc., and n is a number):
negative electrode: m + nOH- → M (OH) n + ne–
And (3) positive electrode: o is2+H2O+4e–→4OH–
And (3) total reaction: 4M + nO2+2nH2O→4M(OH)n
In the working process of the metal fuel cell system, reaction products stay in electrolyte; when the concentration of reaction products in the electrolyte increases to the solubility limit, metal oxide precipitates will form.
In order to separate the reaction product in time and avoid the generation of metal oxide precipitate, the recycling metal fuel cell system of the invention comprises a metal fuel cell stack 1 and an electrolyte recycling loop 6, a reaction product separating device is arranged on the electrolyte recycling loop 6, the reaction product separation device is made of nano materials with characteristic absorption function to the reaction products, and in the working process of the metal fuel cell system, the electrolyte continuously and circularly flows through the electrolyte recirculation loop 6, the reaction product generated inside the metal fuel cell stack 1 is dissolved into the electrolyte, and enters an electrolyte recirculation loop 6 together with the electrolyte from the metal fuel cell stack 1, the electrolyte containing reaction products enters a reaction product separation device, the reaction product is continuously separated by the reaction product separating means and collected into the reaction product collector 5.
Compared with the prior art, the metal fuel cell has the advantages that the electrolyte recirculation loop 6 is arranged, the reaction product separation device is arranged on the electrolyte recirculation loop 6 and is made of the nano material with the characteristic adsorption capacity on metal ions, and when the electrolyte circularly flows in the electrolyte recirculation loop 6, the reaction product separation device can continuously separate the reaction product from the electrolyte, so that the electrolyte does not need to be replaced periodically, and the use convenience of the metal fuel cell is improved; it should be emphasized that, by utilizing the chemical adsorption and physical adsorption of the nano material to the metal ions, the concentration of the metal ions in the electrolyte processed by the reaction product separation device is lower than the saturation concentration thereof, thereby ensuring that the electrolyte circularly flowing into the metal fuel cell stack 1 is unsaturated electrolyte which has stronger carrying and discharging capability to the reaction products in the metal fuel cell, therefore, the reaction product separation device arranged on the electrolyte recirculation loop 6 can not only avoid the reaction interruption caused by the fact that the reaction products in the metal fuel cell cannot be discharged in time, but also improve the conductivity of the electrolyte in the metal fuel cell stack 1 by separating the reaction products in the metal fuel cell stack 1 in time, and finally improve the performance of the metal fuel cell.
In order to timely separate out the reaction product in the electrolyte, the reaction product separating device comprises a first reaction product separator and a second reaction product separator, wherein the first reaction product separator comprises a first separator shell 23, a first self-rotating cylinder 19, a first electrolyte inlet and a first electrolyte outlet 22 which are arranged at two ends of the first separator shell 23; the cylindrical surface of the first self-rotating cylinder 19 is made of a nano-adsorption material; the first self-rotating cylinder 19 is arranged inside the first separator shell 23, and a first mud scraping strip 25 is arranged on the inner wall of the first separator shell 23; the first self-rotating cylinder 19 is a hollow cylindrical shell structure with a first rotating impeller arranged inside; a first electrolyte channel is formed between the first separator housing 23 and the first self-rotating cylinder 19; the first self-rotating cylinder 19 forms a second electrolyte channel inside.
Specifically, the reaction product separation device comprises a first reaction product separator, the first reaction product separator comprises a first separator shell 23, two ends of the first separator shell 23 are respectively provided with a first electrolyte inlet 20 and a first electrolyte outlet 22, and the first electrolyte inlet 20 and the first electrolyte outlet 22 are both communicated with the second electrolyte channel; a second solid reactant outlet communicated with the first electrolyte channel is arranged below the outlet of the first electrolyte, and the other end of the second solid reactant outlet is connected with a second solid reaction product collecting tank 31; it should be emphasized that the inner wall of the first separator casing 23 is provided with a first sludge scraping strip 25, the first sludge scraping strip 25 is in contact with a first self-rotating cylinder arranged inside the first separator casing 23, the first self-rotating cylinder is of a hollow cylindrical shell structure, and a plurality of rotating first impellers are arranged inside the first self-rotating cylinder; when the electrolyte enters the first electrolyte channel and the second electrolyte channel through the first electrolyte inlet 20, the first self-rotating cylinder automatically rotates in the first separator shell 23 under the flowing action of the electrolyte; meanwhile, the electrolyte in the first electrolyte channel is fully contacted with the cylindrical surface of the first self-rotating cylinder, so that the reaction product in the first electrolyte channel is adsorbed, and enters the second solid-state reaction product collecting tank 31 through the first solid-state reactant outlet under the sweeping action of the first sludge scraping strip 25; the electrolyte after the reaction product separation and the electrolyte in the first electrolyte channel are merged at a first electrolyte outlet 22 and returned to the metal fuel cell stack 1 through an electrolyte recirculation loop 6; it should be noted that the electrolyte pump 7 of the present invention continuously pumps the electrolyte into the electrolyte recycling branch, and the first reaction product separator is in a continuous working state, so that the reaction products in the electrolyte can be continuously separated.
Compared with the prior art, the first reaction product separator adopted by the invention divides the electrolyte entering the first reaction product separator into two parts by arranging the first separator shell 23 and the first self-rotating cylinder 19, one part enters the first channel of the electrolyte and further separates out the reaction product in the first self-rotating cylinder through the adsorption action of the cylindrical surface of the first self-rotating cylinder, and the reaction product adsorbed by the first self-rotating cylinder is scraped off by the first mud scraping strip 25; the other part of electrolyte enters the first self-rotating cylinder through the second electrolyte channel and drives the first self-rotating cylinder to rotate through the first rotating impeller in the first self-rotating cylinder so as to provide power for the first reaction product separator.
In order to ensure that the reaction product can be continuously separated and avoid the problem that the reaction product cannot be continuously separated due to the failure of the first reaction product separator, the reaction product separating device further comprises a second reaction product separator connected with the first reaction product separator in parallel, wherein the second reaction product separator comprises a second separator shell 30, a second self-rotating cylinder 26, a second electrolyte inlet and a second electrolyte outlet 29 which are arranged at two ends of the second separator shell 30; the cylindrical surface of the second self-rotating cylinder 26 is made of a nano-adsorption material; the second self-rotating cylinder 26 is arranged inside a second separator shell 30, and a second mud scraping strip 32 is arranged on the inner wall of the second separator shell 30; the second self-rotating cylinder 26 is a hollow cylindrical shell structure with a second rotating impeller arranged inside; a third electrolyte channel is formed between second separator housing 30 and second self-rotating cylinder 26; a fourth electrolyte channel is formed inside the second self-rotating cylinder 26.
Specifically, the second reaction product separator and the first reaction product separator are arranged in parallel and have the same structure, and the first reaction product separator and the second reaction product separator are respectively connected with a first electrolyte branch and a second electrolyte branch which are arranged on the electrolyte recirculation loop 6; a first electromagnetic valve is arranged on the first electrolyte branch, and a second electromagnetic valve is arranged on the second electrolyte branch; the first electromagnetic valve and the second electromagnetic valve are respectively used for controlling the electrolyte flow in the first electrolyte branch and the second electrolyte branch; the first electrolyte branch is connected with the first electrolyte inlet, and the second electrolyte branch is connected with the second electrolyte inlet.
It should be noted that the second reaction product separator includes a second separator housing 30, two ends of the second separator housing 30 are respectively a second electrolyte inlet 27 and a second electrolyte outlet 29, and both the second electrolyte inlet 27 and the second electrolyte outlet 29 are communicated with the third electrolyte channel; a second solid reaction product outlet 28 communicated with the second electrolyte channel is arranged below the outlet of the second electrolyte, and the other end of the second solid reaction product outlet is connected with a second solid reaction product collecting tank 31; it should be emphasized that the inner wall of the first separator casing 23 is provided with a second sludge scraping strip 32, the second sludge scraping strip 32 is in contact with a second self-rotating cylinder arranged inside the second separator casing 30, the second self-rotating cylinder is of a hollow cylindrical shell structure, and a plurality of rotating second impellers are arranged inside the second self-rotating cylinder; when the electrolyte enters the third electrolyte channel and the fourth electrolyte channel through the second electrolyte inlet 27, the second self-rotating cylinder automatically rotates in the second separator housing 30 under the flowing action of the electrolyte; meanwhile, the electrolyte in the second electrolyte channel is fully contacted with the cylindrical surface of the second self-rotating cylinder, so that the reaction product in the second electrolyte channel is adsorbed, and enters the second solid-state reaction product collecting tank 31 through the second solid-state reactant outlet under the sweeping action of the second mud scraping strip 32; the electrolyte after the reaction product separation and the electrolyte in the fourth electrolyte channel are merged at a second electrolyte outlet 29 and returned to the metal fuel cell stack 1 through the electrolyte recirculation loop 6; it should be noted that the electrolyte pump 7 of the present invention continuously pumps the electrolyte into the electrolyte recycling loop 6, and the second reaction product separator and the first reaction product separator may be in an alternate continuous operation state or in a simultaneous continuous operation state, so as to finally realize the continuous separation of the reaction products in the electrolyte.
Compared with the prior art, the reaction product separation device comprises the first reaction product separator and the second reaction product separator which have the same structure, and the first reaction product separator and the second reaction product separator can work simultaneously, so that the separation efficiency of the reaction products is improved; when one of the electrolyte recirculation loops is in failure, the other electrolyte recirculation loop can ensure that reaction products in the electrolyte recirculation loop 6 are continuously released and separated; taking the first reaction product separation device as an example, the first reaction product separator divides the electrolyte entering the first reaction product separator into two parts by arranging the first separator shell 23 and the first self-rotating cylinder 19, one part enters the first channel of the electrolyte and separates the reaction product in the first self-rotating cylinder by the adsorption action of the cylindrical surface of the first self-rotating cylinder, and the reaction product adsorbed by the first self-rotating cylinder is scraped by the first mud scraping strip 25; the other part of electrolyte enters the first self-rotating cylinder through the second electrolyte channel and drives the first self-rotating cylinder to rotate through the first rotating impeller in the first self-rotating cylinder so as to provide power for the first reaction product separator.
In order to timely and thoroughly scrape off reaction products adsorbed on the surfaces of the first self-rotating cylinder and the second self-rotating cylinder, the first sludge scraping strips 25 are spirally distributed along the axis direction of the first rotating cylinder, and the second sludge scraping strips 32 are spirally distributed along the axis direction of the second rotating cylinder.
Specifically, taking the first sludge scraping strip 25 in the first self-rotating cylinder as an example, the first sludge scraping strip 25 is disposed on the inner wall of the first separator housing 23, and the first sludge scraping strip 25 is helical and distributed helically along the axial direction from the first self-rotating cylinder. The first mud scraping strip 25 is set to be spiral and can efficiently scrape the reaction product adsorbed on the outer surface of the first self-rotating cylinder, so that the reaction product is prevented from being blocked in a cavity between the shell 23 of the first separator and the inner wall of the first self-rotating cylinder, and the reaction product enters the second solid-state reaction product collecting tank 31 through the solid-state reactant outlet to be collected. It should be noted that the position, shape and function of the second mud scraper 32 in the second self-rotating cylinder are the same as those of the first mud scraper 25, and are not described herein.
It is emphasized that at least one electrolyte pump 7 and an electrolyte heat sink 4 are arranged on the electrolyte recirculation loop 6, and the electrolyte pump 7 is used for providing power for the electrolyte recirculation loop 6; the electrolyte heat sink 4 serves to cool the electrolyte. The electrolyte pump 7 is used for driving the electrolyte to form a circulating flow, and the electrolyte heat sink 4 is used for cooling the electrolyte in the electrolyte recirculation loop 6.
For metal fuel cells using different metals such as magnesium, aluminum, zinc, etc., the reaction product is Mg2+、Al3+、Zn2+And the metal ions are dissolved in the electrolyte, and in order to fully absorb the reaction products in the electrolyte, the material of the disc separator 88 is nano titanium dioxide, nano zirconium dioxide, nano aluminum oxide and the like.
Specifically, the first reaction product separator and the second reaction product separator are made of nano titanium dioxide and nano dioxideThe hydrophilic hydroxyl on the surface of the nano ceramic has the capability of complexing with metal ions, so that the characteristic adsorption of the metal ions or hydrated metal particles is realized, and the generation of Mg (OH) after the concentration of the metal ions in the electrolyte reaches the dissolution limit is avoided2、Al(OH)3、Zn(OH)2And precipitating.
For example: in aqueous solution, ZrO2Hydrolysis of hydroxyl groups on the surface of the nanocrystal to form ZrO2The surface of the nano ceramic is positively charged. Mg (magnesium)2+Can react with OH in the electrolyte-Formation of Mg (OH)+、Mg(OH)2、[Mg-OH-Mg]3+Positively charged Mg2+(H2O)、Mg(OH)+And Mg2(OH)3+Etc. can be electrostatically adsorbed to the negatively charged ZrO in the form of a hydrate2A nano-surface. For TiO2、Al2O3Nano-class ceramics, their characteristic adsorption principle and ZrO2The nano ceramics are the same.
It should be noted that the material of the first reaction product separator and the second reaction product separator can also be a mixture of nano titanium dioxide, nano zirconium dioxide and nano aluminum oxide, such as TiO2-α-Al2O3。
Example 2
The reaction product separation device in this embodiment further includes a disc separator 8, the disc separator 8 is disposed on the electrolyte recirculation loop, the disc separator is integrally connected in series with the first reaction product separator and the second reaction product separator, as shown in fig. 6-8, the disc separator 8 of the present invention includes an electrolyte storage tank 11 and a third solid reaction product collecting tank 15, at least one cylindrical separation disc 13 driven by a motor to rotate is disposed in the electrolyte storage tank 11, and the cylindrical surface of the cylindrical separation disc is made of a nano-adsorption material; the cylindrical surface 17 of the cylindrical separation disc 13 is provided with a first scraper 14, and the first scraper 14 is used for scraping off reaction products adsorbed on the cylindrical surface.
Specifically, the disk separator 8 includes an electrolyte tank and a third solid reaction product collecting tank 15; one or more cylindrical separating disks 13 are arranged in the electrolyte storage tank 11, and the cylindrical separating disks 13 are driven by a motor to continuously rotate so that the bottoms of the cylindrical separating disks 13 are always immersed below the electrolyte liquid level 12, thereby continuously absorbing reaction products in the electrolyte; in addition, a first scraper 14 is provided on the cylindrical separation disc 13, the first scraper 14 is fixed to a partition between the electrolyte reservoir 11 and the third solid reaction product collecting tank 15, one end of the first scraper 14 is in contact with the cylindrical separation disc 13, and the first scraper 14 guides the reaction product scraped from the cylindrical surface of the cylindrical separation disc 13 into the third solid reaction product collecting tank 15 when the cylindrical separation disc 13 rotates.
The invention can rapidly separate the reaction product in the electrolyte by arranging the cylindrical separating disk 13, and has at least the following functions: firstly, the phenomenon that the electrochemical reaction rate of the metal anode is influenced because the precipitated particles are accumulated on the surface of the metal anode is avoided; secondly, the phenomenon that the deposited particles are gathered on the surface of the cathode and block the pores of the cathode to influence the electrochemical reaction rate of the cathode is avoided; and thirdly, the phenomenon that the electrolyte flow resistance is increased and even the electrolyte flow is interrupted due to the blockage of the electrolyte flow channel by the precipitated particles is avoided.
In order to more efficiently and rapidly separate reaction products in the metal fuel cell, two end faces of the cylindrical separating disc are made of nano-adsorption materials; and second mud scraping plates 18 are arranged on the disc surfaces at the two ends of the cylindrical separating disc 13, and the second mud scraping plates 18 are used for scraping off reaction products adsorbed on the disc surfaces.
Specifically, the second scraper 18 is disposed on the circular discs at two ends of the cylindrical separation disc 13, and when the cylindrical separation disc 13 is driven by the motor to rotate continuously, the circular discs made of the nano-adsorption material continuously absorb the reaction products in the electrolyte, so as to avoid that the conductivity of the electrolyte is greatly reduced after the electrolyte is dissolved and saturated, and the internal resistance of the battery is increased and the performance is reduced.
Example 3
The present embodiment provides a reaction product separation method of a recycled metal fuel cell system, using the recycled metal fuel cell system of embodiment 1, the separation method comprising the steps of:
step 1, the electrolyte in the metal fuel cell stack 1 enters a first electrolyte branch along an electrolyte recirculation loop 6, enters a first electrolyte channel and a second electrolyte channel through a first electrolyte inlet, and a first self-rotating cylinder 19 automatically rotates in a first separator shell 23 under the flowing action of the electrolyte;
step 2, in the rotating process of the first self-rotating cylinder 19, a first cylindrical surface on the first self-rotating cylinder 19 continuously adsorbs a reaction product in the electrolyte; the spiral first mud scraping strip 25 on the inner wall of the first separator shell 23 scrapes off the reaction product adsorbed on the surface of the first self-rotating cylinder, and the reaction product is collected into the first solid-state reaction product collecting tank 24 through the first solid-state reaction product outlet 21;
step 3, the electrolyte in the first electrolyte channel is separated from the product, and the electrolyte in the second electrolyte channel returns to the fuel cell stack through the first electrolyte outlet 22 and the electrolyte recirculation loop 6;
and 4, continuously operating the first electrolytic liquid separator to realize continuous separation of reaction products in the electrolyte.
It is emphasized that when the electrolyte in the metal fuel cell enters the second electrolyte branch along the electrolyte recirculation loop 6, the reaction product separation method further comprises the following steps:
step 1', the electrolyte enters a third electrolyte channel and a fourth electrolyte channel through a second electrolyte inlet, and a second self-rotating cylinder 26 automatically rotates in a second separator shell 30 under the flowing action of the electrolyte;
step 2', in the rotating process of the second self-rotating cylinder 26, a second cylindrical surface on the second self-rotating cylinder 26 continuously adsorbs a reaction product in the electrolyte; the spiral second mud scraping strip 32 on the inner wall of the second separator shell 30 scrapes off the reaction product adsorbed on the surface of the second self-rotating cylinder, and the reaction product is collected into a second solid reaction product collecting tank 31 through the first reaction product outlet 28;
step 3', the electrolyte in the third electrolyte channel is separated from the electrolyte in the fourth electrolyte channel and returns to the fuel cell stack through a second electrolyte outlet 29 and an electrolyte recirculation loop 6;
and 4', the second electrolytic liquid separator works continuously to realize continuous separation of reaction products in the electrolyte.
Compared with the prior art, the reaction product separation method of the recycling metal fuel cell system provided by the embodiment has multiple effects on the performance of the metal fuel cell: (1) the method can avoid the aggregation of precipitated particles on the surface of the metal anode and influence on the electrochemical reaction rate of the metal anode; (2) the problem that the electrochemical reaction rate of the cathode is influenced because the precipitated particles are accumulated on the surface of the cathode and block the pores of the cathode can be avoided; (3) the problem that the flow resistance of the electrolyte is increased and even the flow of the electrolyte is interrupted due to the blockage of the electrolyte flow channel by the precipitated particles can be avoided; (4) the problem that the conductivity of the electrolyte is greatly reduced after the electrolyte is dissolved and saturated, so that the internal resistance of the battery is increased and the performance is reduced can be avoided; (5) scaling in the electrolyte radiator can be avoided, and heat dissipation performance is reduced.
Example 4
The present invention also discloses a reaction product separation method of a recycled metal fuel cell system, in the embodiment, when the recycled metal fuel cell system provided in embodiment 2 is adopted, and the reaction product separation device adopts the disk separator 8, the separation method includes the following steps:
step 1', partially immersing the disc separator 8 below the electrolyte level, and continuously rotating the disc separator 8 under the driving of a motor and contacting with the electrolyte; step 2', the cylindrical surface of the disc separator 8 continuously adsorbs reaction products in the electrolyte;
step 3', the reaction product adsorbed on the cylindrical surface of the disc separator 8 is scraped off by the first scraper 14 and collected by the first solid reaction product collecting tank 24; the electrolyte separated by the reaction product returns to the fuel cell stack through an electrolyte circulation branch;
and 4', the motor drives the disc separator 8 to continuously rotate, so that the reaction products in the electrolyte are continuously separated.
In step 2 ″, the disc surfaces at the two ends of the disc separator 8 continuously adsorb the reaction product in the electrolyte; in step 3 ″, the reaction product adsorbed on the disk surfaces at both ends of the disk separator 8 is scraped off by the second scraper 18 and collected by the first solid reaction product collecting tank 24.
Compared with the prior art, the method for separating the reaction product of the metal fuel cell provided by the embodiment has multiple functions on the performance of the metal fuel cell: (1) the method can avoid the aggregation of precipitated particles on the surface of the metal anode and influence on the electrochemical reaction rate of the metal anode; (2) the problem that the electrochemical reaction rate of the cathode is influenced because the precipitated particles are accumulated on the surface of the cathode and block the pores of the cathode can be avoided; (3) the problem that the flow resistance of the electrolyte is increased and even the flow of the electrolyte is interrupted due to the blockage of the electrolyte flow channel by the precipitated particles can be avoided; (4) the problem that the conductivity of the electrolyte is greatly reduced after the electrolyte is dissolved and saturated, so that the internal resistance of the battery is increased and the performance is reduced can be avoided; (5) scaling in the electrolyte radiator can be avoided, and heat dissipation performance is reduced.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.

Claims (9)

1. A recirculating metal fuel cell system comprising a metal fuel cell stack and an electrolyte recirculating loop; the electrolyte recirculation loop is provided with a reaction product separation device, and the reaction product separation device is used for adsorbing and separating the reaction product in the electrolyte; the metal fuel cell stack comprises an anode reactant inlet, an anode reactant outlet, a cathode reactant inlet and a cathode reactant outlet;
the reaction product separation device comprises a first reaction product separator, wherein the first reaction product separator comprises a first separator shell, a first self-rotating cylinder, a first electrolyte inlet and a first electrolyte outlet, and the first electrolyte inlet and the first electrolyte outlet are arranged at two ends of the first separator shell; the cylindrical surface of the first self-rotating cylinder is made of a nano-adsorption material;
the first self-rotating cylinder is arranged inside the first separator shell, and a first mud scraping strip is arranged on the inner wall of the first separator shell; the first self-rotating cylinder is a hollow cylinder shell structure with a first rotating impeller arranged inside; a first electrolyte channel is formed between the first separator shell and the first self-rotating cylinder; a second electrolyte channel is formed inside the first self-rotating cylinder.
2. The recirculating metal fuel cell system of claim 1 wherein the reaction product separating means further comprises a second reaction product separator connected in parallel with the first reaction product separator, the second reaction product separator comprising a second separator housing, a second self-rotating cylinder, a second electrolyte inlet and a second electrolyte outlet disposed at either end of the second separator housing; the cylindrical surface of the second self-rotating cylinder is made of a nano-adsorption material;
the second self-rotating cylinder is arranged inside the second separator shell, and a second sludge scraping strip is arranged on the inner wall of the second separator shell; the second self-rotating cylinder is a hollow cylindrical shell structure with a second rotating impeller arranged inside; a third electrolyte channel is formed between the second separator shell and the second self-rotating cylinder; and a fourth electrolyte channel is formed inside the second self-rotating cylinder.
3. A recycled metal fuel cell system as in claim 2, wherein the first wiper strip is helically distributed along the axis from the first rotating cylinder.
4. A recirculating metal fuel cell system as recited in claim 3, wherein the second wiper strip is helically distributed along the axis from the second rotating cylinder.
5. A recirculating metal fuel cell system as recited in claim 4 wherein the electrolyte recirculating loop has a first electrolyte branch and a second electrolyte branch; a first electromagnetic valve is arranged on the first electrolyte branch, and a second electromagnetic valve is arranged on the second electrolyte branch; the first electrolyte branch is connected with the first electrolyte inlet, and the second electrolyte branch is connected with the second electrolyte inlet.
6. The recirculating metal fuel cell system of claim 5 wherein the nano-adsorbent material is a nano-titania material, a nano-zirconia material, a nano-alumina material, or TiO2-α-Al2O3One of the materials.
7. A recirculating metal fuel cell system as claimed in any one of claims 1 to 6, wherein the electrolyte recirculating loop is provided with an electrolyte pump for powering the electrolyte recirculating loop and an electrolyte heat sink; the electrolyte heat dissipation device is used for cooling the electrolyte.
8. A reaction product separation method of a recycled metal fuel cell system, characterized in that the recycled metal fuel cell system of any one of claims 1 to 7 is used, the separation method comprising the steps of:
step 1, electrolyte in the metal fuel cell stack enters a first electrolyte branch along an electrolyte recirculation loop and enters a first electrolyte channel and a second electrolyte channel through a first electrolyte inlet, and a first self-rotating cylinder automatically rotates in a first separator shell under the flowing action of the electrolyte;
step 2, in the rotating process of the first self-rotating cylinder, a first cylindrical surface on the first self-rotating cylinder continuously adsorbs a reaction product in the electrolyte; the spiral first mud scraping strip on the inner wall of the first separator shell scrapes off the reaction product adsorbed on the surface of the first self-rotating cylinder, and the reaction product is collected into a first solid reaction product collecting tank through a first reaction product outlet;
step 3, separating the electrolyte in the first electrolyte channel and returning the electrolyte in the second electrolyte channel to the fuel cell stack through the first electrolyte outlet and the electrolyte recirculation loop;
and 4, continuously operating the first electrolytic liquid separator to realize continuous separation of reaction products in the electrolyte.
9. The reaction product separation method of a recirculating metal fuel cell system as recited in claim 8, wherein when the electrolyte in the metal fuel cell passes along the electrolyte recirculation loop into the second electrolyte branch, the reaction product separation method further comprises:
step 1', the electrolyte enters a third electrolyte channel and a fourth electrolyte channel through a second electrolyte inlet, and a second self-rotating cylinder automatically rotates in a second separator shell under the flowing action of the electrolyte;
step 2', in the rotating process of the second self-rotating cylinder, a second cylindrical surface on the second self-rotating cylinder continuously adsorbs a reaction product in the electrolyte; the spiral second mud scraping strip on the inner wall of the second separator shell scrapes off the reaction product adsorbed on the surface of the second self-rotating cylinder, and the reaction product is collected into a second solid reaction product collecting tank through a second reaction product outlet;
step 3', separating the electrolyte in the third electrolyte channel and the electrolyte in the fourth electrolyte channel, and returning the separated electrolyte to the metal fuel cell stack;
and 4', the second electrolytic liquid separator works continuously to realize continuous separation of reaction products in the electrolyte.
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