CN209929451U

CN209929451U - Chlorine-magnesium fuel cell

Info

Publication number: CN209929451U
Application number: CN201920271092.5U
Authority: CN
Inventors: 权高峰; 张钰雯茜; 郭阳阳; 尹颢; 张虹桃; 刘崇亮; 鲁天慧; 曾迎; 尹冬弟; 潘厚宏
Original assignee: CHENGDU TIANZHI LIGHTWEIGHT TECHNOLOGY Co Ltd
Current assignee: CHENGDU TIANZHI LIGHTWEIGHT TECHNOLOGY Co Ltd
Priority date: 2019-03-04
Filing date: 2019-03-04
Publication date: 2020-01-10
Anticipated expiration: 2029-03-04

Abstract

The utility model discloses a chlorine magnesium fuel cell, including a chlorine magnesium fuel cell, store gasification system and electrolyte circulation regeneration system including battery body, chlorine, electrolyte circulation regeneration system includes filter, extraction agitator, water purifier, stews ware and electrolyte holding vessel, the outside intercommunication of the ware of stewing has the electrolyte holding vessel, and the second power pump is installed in the outside of electrolyte holding vessel. A battery body of a chlorine-magnesium fuel battery comprises a battery shell and a chlorine channel, wherein a cathode membrane assembly is arranged inside the battery shell, a magnesium alloy anode plate is arranged inside the cathode membrane assembly, and a battery middle shaft is fixed in the middle of the inside of the battery shell. The chlorine-magnesium fuel cell takes the multielement magnesium alloy with excellent performance as the anode, the electrochemical conversion rate is high, the electrochemical reaction is uniform, and the current and voltage are stable; chlorine is used as an oxidant, so that the electrode potential is high, the cost is low, and the energy density is high.

Description

Chlorine-magnesium fuel cell

Technical Field

The utility model relates to a novel fuel cell technical field specifically is a chlorine magnesium fuel cell.

Background

Energy is an important material basis on which human society relies to survive and develop. The electric energy is used as the most main secondary energy, and along with the rapid development of economy, the human demand for the electric energy is larger and larger, so that the transformation and the upgrade of the electric energy industry are promoted. At present, lithium ion batteries are most widely applied in the market, and have the advantages of small self-discharge, high specific capacity, good cycle performance, environmental friendliness and the like, so that the development is rapid, and the technology is relatively mature. However, the earth has limited lithium resources, the lithium ion battery has high cost and low specific energy, and has safety problems, so that the requirements of pure electric vehicles cannot be met.

Magnesium is widely used as a battery material, next to lithium, as a high-energy battery anode material. Compared with a hydrogen fuel cell, the magnesium fuel cell has high specific energy, safe and convenient use, easy storage and transportation of fuel, wide usable temperature range and rich magnesium reserve, is not only one of the most abundant metal elements in the earth crust, but also the second most chemical element in seawater, greatly reduces the cell cost and has wide application prospect.

The magnesium is active in chemical property and has high activity in neutral salt electrolyte, but oxygen and hydrogen peroxide are used as oxidants and can be electrochemically catalytically reduced into hydroxide ions in the neutral salt electrolyte to generate magnesium hydroxide precipitates, so that the battery fails, the open-circuit voltage (electrode potential when no current flows) of an oxygen electrode is minus 0.4V than the thermodynamic value of the open-circuit voltage, serious polarization occurs when current flows, and when the common magnesium alloy is used as an anode, microcell reaction, namely self-corrosion reaction, is caused due to surface impurities, so that the actual open-circuit voltage of the battery is reduced, the efficiency of the anode is reduced, and the service life is shortened. In addition, there are magnesium-seawater dissolved oxygen fuel cells, but since the content of oxygen dissolved in seawater is limited, the fuel cells have low efficiency and cannot meet the requirements of large power batteries.

SUMMERY OF THE UTILITY MODEL

An object of the utility model is to provide a chlorine magnesium fuel cell to solve some battery cost on the existing market that above-mentioned background art provided and higher, the specific energy is low excessively, and there is the security problem, problem that life is short.

In order to achieve the above object, the utility model provides a following technical scheme: the utility model provides a chlorine magnesium fuel cell, stores gasification system and electrolyte circulation regeneration system including cell body, chlorine, the outside of cell body is connected with heat exchanger, and heat exchanger's the outside sets up and is connected with the chlorine storage tank, heat exchanger's the outside is connected with the filter through first power pump, the outside of filter is connected with the extraction agitator, and the outside intercommunication of extraction agitator has water purifier and the ware that stews, the outside intercommunication of the ware that stews has the electrolyte holding vessel, and the outside of electrolyte holding vessel installs the second power pump, filter, extraction agitator, water purifier, the ware that stews and electrolyte holding vessel constitute electrolyte circulation regeneration system, and extract agitator, water purifier and stew and constitute circulation loop.

Preferably, the heat exchanger and the chlorine storage tank form a chlorine storage gasification system, and chlorine in the chlorine storage tank is in a liquid state.

Preferably, the volume ratio of the standing device to the heat exchanger to the extraction stirrer is 1:1:1, and the liquid flow driving force among the heat exchanger, the extraction stirrer and the standing device is driven by pressure.

Preferably, the chlorine-free lithium ion battery further comprises a battery shell and a chlorine channel, wherein a cathode membrane assembly is arranged inside the battery shell, a magnesium alloy anode plate is arranged inside the cathode membrane assembly, a battery middle shaft is fixed in the middle of the inside of the battery shell, a partition plate is fixed on the outer side of the battery middle shaft, an electrolyte tank is arranged between the partition plate and the cathode membrane assembly, and the chlorine channel is arranged between the cathode membrane assembly and the battery shell.

Preferably, the battery shell is a cylindrical or rectangular shell with an accommodating space, the battery shell is made of stainless steel resistant to chloride ion corrosion, and the inner wall of the battery shell is coated with a layer of insulating material.

Preferably, the magnesium alloy anode plate is arranged into a porous curved surface structure.

Preferably, the battery middle shaft and the battery shell are fixedly connected, the interior of the battery middle shaft is communicated with the electrolyte tank, and the partition plates are uniformly distributed on the outer side of the battery middle shaft and can be combined and replaced at will.

Compared with the prior art, the beneficial effects of the utility model are that: the chlorine-magnesium fuel cell takes the multielement magnesium alloy with excellent performance as the anode, the electrochemical conversion rate is high, the electrochemical reaction is uniform, and the current and voltage are stable; chlorine is used as an oxidant, so that the electrode potential is high, the cost is low, and the energy density is high;

(1) the adopted magnesium alloy anode has excellent performance and can obviously improve the electrochemical conversion rate and the utilization rate of the battery anode;

(2) the fuel cell takes chlorine as an oxidant, and forms a cell reaction cathode together with a cathode membrane component, also called a chlorine electrode, and the electrode has higher potential and can increase the open-circuit voltage of the cell;

(3) the cathode film assembly consists of a waterproof breathable layer, a catalytic layer and a conductive layer, so that chlorine can penetrate through the magnesium alloy anode to generate electrochemical reaction to generate potential and electrolyte can be prevented from seeping;

(4) the provided electrolyte is neutral salt non-aqueous solution electrolyte, can effectively slow down the self-corrosion effect of magnesium, and improves the efficiency of the chlorine-magnesium fuel cell.

Drawings

FIG. 1 is a schematic view of a chlorine-magnesium fuel cell device according to the present invention;

FIG. 2 is a schematic view of a circular structure of a chlorine-magnesium fuel cell body according to the present invention;

fig. 3 is a schematic diagram of a square structure of a chlorine-magnesium fuel cell body according to the present invention.

In the figure: 1. a battery body; 2. a heat exchanger; 3. a chlorine storage tank; 4. a first power pump; 5. a filter; 6. an extraction stirrer; 7. a water purifier; 8. a standing device; 9. an electrolyte storage tank; 10. a second power pump; 11. a battery case; 12. a cathode membrane assembly; 13. a magnesium alloy anode plate; 14. a battery middle shaft; 15. a partition plate; 16. an electrolyte bath; 17. a chlorine gas channel; 18. a chlorine storage gasification system; 19. Electrolyte circulation regeneration system.

Detailed Description

The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments in the present invention, all other embodiments obtained by a person skilled in the art without creative work belong to the protection scope of the present invention.

Example one

Referring to fig. 1-3, the present invention provides a technical solution: the utility model provides a chlorine magnesium fuel cell, including cell body 1, heat exchanger 2, store up chlorine jar 3, first power pump 4, filter 5, extraction agitator 6, water purifier 7, stew device 8, electrolyte holding vessel 9, second power pump 10, chlorine is stored gasification system 18 and electrolyte circulation regeneration system 19, cell body 1's the outside is connected with heat exchanger 2, and heat exchanger 2's the outside setting is connected with stores up chlorine jar 3, heat exchanger 2's the outside is connected with filter 5 through first power pump 4, filter 5's the outside is connected with extraction agitator 6, and the outside intercommunication of extraction agitator 6 has water purifier 7 and stew device 8, stew device 8's the outside intercommunication and have electrolyte holding vessel 9, and second power pump 10 is installed in electrolyte holding vessel 9's the outside.

The heat exchanger 2 and the chlorine storage tank 3 form a chlorine storage gasification system 18, the chlorine in the chlorine storage tank 3 is in a liquid state, the chlorine is stored in a liquid state, the size is small, the storage capacity is large, the safety is good, the use is convenient, the heat exchanger 2 utilizes heat exchange between the thermoelectric electrolyte solution and the liquid chlorine, the function of gasifying the liquid chlorine can be realized, and the leading-in amount and the leading-in speed of the chlorine are adjusted through a power controller; but also can separate out the electrode reaction product magnesium chloride dissolved in the electrolyte, thereby realizing the first-stage purification of the electrolyte.

An electrolyte circulating and regenerating system 19, which comprises a heat exchanger 2, a filter 5, an extraction stirrer 6, a water purifier 7, a standing device 8 and an electrolyte storage tank 9, wherein the volume ratio of the heat exchanger 2 to the extraction stirrer 6 to the volume ratio of the standing device 8 to the liquid chlorine is 1:1:1 respectively, the electrolyte cooled by heat exchange with the liquid chlorine enters the filter 5 to be filtered, and then is fully mixed with pure water in the extraction stirrer 6, magnesium chloride is exchanged from an organic medium into water, a mixed solution is introduced into the standing device 8, the two liquids are automatically layered, the lower layer is rich in water, and the upper layer is a regenerated electrolyte solution, so that the secondary purification of the electrolyte is realized; the regenerated electrolyte solution is pumped into the electrolyte storage tank 9 for replenishing the electrolyte required by the fuel cell, so that the electrode reaction is continuously carried out. The lower aqueous solution is discharged into the water purifier 7, purified several times to extract pure water, and the pure water required in the extraction agitator 6 can be supplied. If the regenerated electrolyte is lost after multiple cycles, new electrolyte can be injected into the electrolyte storage tank 9 from the outside, and the working stability of the whole battery system is ensured. The whole system works intermittently, a battery voltage monitoring system gives out signals to activate the first power pump 4 and the second power pump 10, and valves of a battery electrolyte discharge port and a chlorine gas discharge port are opened to discharge the electrolyte.

Example two

Referring to fig. 1-3, the present invention provides a technical solution: the utility model provides a chlorine magnesium fuel cell's cell body, including battery case 11, negative pole membrane module 12, magnesium alloy anode plate 13, battery axis 14, baffle 15, electrolyte bath 16 and chlorine passageway 17, battery case 11's inside is provided with negative pole membrane module 12, and negative pole membrane module 12's inside is provided with magnesium alloy anode plate 13, battery case 11's inside centre is fixed with battery axis 14, and battery axis 14's the outside is fixed with baffle 15, be provided with electrolyte bath 16 between baffle 15 and the negative pole membrane module 12, be provided with chlorine passageway 17 between negative pole membrane module 12 and the battery case 11.

The battery shell 11 is a cylindrical or rectangular shell with an accommodating space, the battery shell 11 is made of chloride ion corrosion resistant stainless steel, and the inner wall of the battery shell is coated with a layer of insulating material; the cathode membrane assembly 12 is an electronically conductive film composed of a carbon material (one or more of graphite, activated carbon, carbon fiber, carbon nanotube, nitrogen/boron doped graphene), a polytetrafluoroethylene high molecular polymer (polytetrafluoroethylene or polybenzimidazole), a current collector and a catalyst, and has the functions of water resistance, gas isolation, electric conduction and catalytic activity; the magnesium alloy anode plate 13 is a magnesium alloy formed by adding a small amount or trace of alloy elements such as aluminum, lead, zinc, manganese, cerium, indium, gallium, tin, mercury and the like into a magnesium substrate, and the magnesium alloy anode plate 13 is of a porous curved surface structure, so that the electrode reaction area is increased; the cell center shaft 14 and the cell shell 11 are fixedly connected, the cell center shaft 14 is internally communicated with an electrolyte cell 16, electrolyte can be quantitatively and uniformly distributed in each monomer of the fuel cell in series connection, and can also be conveyed to an electrolyte circulation regeneration system 19 through a pump, and the partition plates 15 are uniformly distributed (inserted) on the outer side of the cell center shaft 14, can be combined and replaced at will, can be conveniently taken out and put in the partition plates 15, and are convenient to regenerate or clean.

The central shaft 14 of the battery body is a pipeline for fixing the partition 15 and pumping and discharging the electrolyte, so that the electrolyte is conveyed into the battery body, the effect of reversely pumping the electrolytic waste liquid in the battery can be realized, and the electrolytic waste liquid can be reused after being pumped back into the regeneration circulating device for purification treatment. The closed feeding port is formed in the middle shaft pipeline of the battery, electrolyte can be quantitatively and uniformly distributed to each monomer of the fuel battery in series connection, the electrolyte can also be collectively pumped back to a waste material tank of the electrolyte regeneration circulating device, a plurality of clamping grooves are formed in the circumference of the pipeline and used for fixing the partition plate 15, and the partition plate 15 can be conveniently taken out and put in, so that the cleaning is facilitated.

The battery is divided into 4-12 battery monomers by the partition plate 15, and the batteries are connected in series through the positive electrode and the negative electrode, so that the power generation efficiency of the battery is improved. And the number of the battery monomers connected in series can be adjusted by arranging the partition plates 15 according to the requirements, so that the maintenance is convenient, and the service life of the battery is prolonged. The reaction anode of the cell is a magnesium alloy plate and the cathode is a cathode membrane assembly 12 and is composed of chlorine gas, which can also be called a chlorine gas electrode. Chlorine enters a chlorine channel 17 between the battery shell and the cathode membrane assembly 12 through the pipeline, can uniformly permeate the cathode membrane assembly 12 into the electrolyte tank 16, and is subjected to electrochemical reaction with the magnesium alloy anode plate 13 in the electrolyte. The cathode membrane assembly 12 consists of a waterproof breathable layer, a catalytic layer and a conductive layer, and can prevent electrolyte from permeating into a chlorine bin and convey chlorine required by battery reaction.

EXAMPLE III

Referring to fig. 1-3, the present invention provides a technical solution: a chlorine-magnesium fuel cell;

(1) anode: the magnesium alloy is made of magnesium alloy plates, has the thickness of 2-20 mm, and is characterized in that the magnesium alloy is a multi-element alloy which is formed by adding aluminum, lead, zinc, manganese and the like into a main body of magnesium and adding trace alloy elements of cerium, indium, gallium, tin and mercury. The magnesium alloy comprises the following components in percentage by weight:

(2) cathode: the film capable of penetrating electrons mainly comprises a carbon material, a high polymer and a current collector, has the functions of water resistance, air permeability, electric conduction and catalytic activity, the carbon material with the thickness of 1-10 mm is formed by one or more of graphite, activated carbon, carbon fiber, carbon nano tube and nitrogen/boron doped graphene, the high polymer is polytetrafluoroethylene or polybenzimidazole, and then catalysts such as manganese dioxide and noble metals are added to be embedded into the carbon material so as to improve the reaction activity.

(3) Electrolyte solution: the solvent comprises neutral salt and an organic solvent, wherein the neutral salt is one or a mixture of NaCl and KCl, the concentration of the neutral salt is 5-10%, the organic solvent is an amide solvent represented by N, N-Dimethylformamide (DFM), a sulfone solvent represented by dimethyl sulfoxide (DMSO), and one or more of ether compounds of tetrahydrofuran, 2-methyltetrahydrofuran, methyl ethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether. No precipitate is generated during the discharging reaction of the battery, the self-corrosion problem of the magnesium anode is relieved, the potential difference between the two electrodes is improved, and the battery efficiency is improved.

(4) The utility model discloses battery discharge reaction mechanism:

anode: magnesium loses electrons and undergoes oxidation: mg → Mg²⁺+2e^-，-2.37V

Cathode: chlorine gas is reduced to obtain electrons: cl₂+2e^-→2Cl^-，1.358V

The discharge reaction potential of the chlorine-magnesium fuel cell is 3.728V, which is higher than that of common power sources such as hydrogen fuel cell, magnesium/air cell and aluminum/air cell. And the adoption of the electrolyte limits the side reaction to generate Mg (OH)₂Precipitation and MgCO₃Precipitating to improve the efficiency of the battery.

(5) The utility model discloses but battery system independent use also can be as required arbitraryCombination, size range of unit cells: 150-800 mm long, 100-450 mm wide, 100-400 mm high, and 1-80 kg of total weight. The energy density is 2100wh/kg, and the current density is 150mA/cm²Under the condition of (2), the power density can reach 49 w/kg.

(6) The fuel cell has two assembling methods, one is that the unit cell system is directly connected in series/in parallel for use, the installation is convenient and fast, and the carrying and the replacement are convenient; and secondly, the battery bodies are connected in series/parallel, the same chlorine storage device and the electrolyte regeneration circulating system are shared, the size is greatly reduced, the weight is reduced, and chlorine is supplemented and the electrolyte is replaced more efficiently. A second assembly is recommended. No matter which assembling mode is adopted, the maximum power of the fuel cell system can reach 500W, and the use requirements of electric automobiles and the like are met.

(7) The utility model discloses a fuel cell life is longer, and 1 ~ 2 years are renewed once. The parts which need to be replaced are the anode plate and the cathode film, the anode plate can be remelted to prepare other parts, and the cathode film can be reused through separation and disassembly. The electrolyte can be self-circulated and cleaned, and only the separated liquid needs to be discharged periodically. The separated magnesium chloride solution can be dried and electrolyzed to regenerate metal magnesium, and can be reused as a battery anode.

Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.

Claims

1. A chlorine-magnesium fuel cell comprises a cell body (1), a chlorine storage gasification system (18) and an electrolyte circulation regeneration system (19), and is characterized in that: the outer side of the battery body (1) is connected with a heat exchanger (2), the outer side of the heat exchanger (2) is connected with a chlorine storage tank (3), the outer side of the heat exchanger (2) is connected with a filter (5) through a first power pump (4), the outer side of the filter (5) is connected with an extraction stirrer (6), the outer side of the extraction stirrer (6) is communicated with a water purifier (7) and a standing device (8), the outer side of the static device (8) is communicated with an electrolyte storage tank (9), and a second power pump (10) is arranged on the outer side of the electrolyte storage tank (9), the filter (5), the extraction stirrer (6), the water purifier (7), the standing device (8) and the electrolyte storage tank (9) form an electrolyte circulation and regeneration system (19), and the extraction stirrer (6), the water purifier (7) and the standing device (8) form a circulation loop.

2. A magnesium chloride fuel cell according to claim 1, wherein: the heat exchanger (2) and the chlorine storage tank (3) form a chlorine storage gasification system (18), and chlorine in the chlorine storage tank (3) is in a liquid state.

3. A magnesium chloride fuel cell according to claim 1, wherein: the volume ratio of the standing device (8) to the heat exchanger (2) to the extraction stirrer (6) is 1:1:1, and liquid flowing driving forces among the heat exchanger (2), the extraction stirrer (6) and the standing device (8) are all driven by pressure.

4. A magnesium chloride fuel cell according to claim 1, wherein: the chlorine-free cathode membrane assembly is characterized by further comprising a battery shell (11) and a chlorine channel (17), a cathode membrane assembly (12) is arranged inside the battery shell (11), a magnesium alloy anode plate (13) is arranged inside the cathode membrane assembly (12), a battery middle shaft (14) is fixed in the middle of the inside of the battery shell (11), a partition plate (15) is fixed on the outer side of the battery middle shaft (14), an electrolyte pool (16) is arranged between the partition plate (15) and the cathode membrane assembly (12), and the chlorine channel (17) is arranged between the cathode membrane assembly (12) and the battery shell (11).

5. A magnesium chloride fuel cell according to claim 4, wherein: the battery shell (11) is a cylindrical or rectangular shell with an accommodating space, the battery shell (11) is made of stainless steel resistant to chloride ion corrosion, and the inner wall of the battery shell is coated with a layer of insulating material.

6. A magnesium chloride fuel cell according to claim 4, wherein: the magnesium alloy anode plate (13) is of a porous curved surface structure.

7. A magnesium chloride fuel cell according to claim 4, wherein: the battery middle shaft (14) is fixedly connected with the battery shell (11), the interior of the battery middle shaft (14) is communicated with the electrolyte tank (16), and the partition plates (15) are uniformly distributed on the outer side of the battery middle shaft (14) and can be combined and replaced at will.