CN109659646B - Cathode protection system and method of air battery - Google Patents
Cathode protection system and method of air battery Download PDFInfo
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- CN109659646B CN109659646B CN201811575300.7A CN201811575300A CN109659646B CN 109659646 B CN109659646 B CN 109659646B CN 201811575300 A CN201811575300 A CN 201811575300A CN 109659646 B CN109659646 B CN 109659646B
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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
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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
- H01M12/02—Details
Abstract
The invention discloses a cathode protection system and a method of an air battery, wherein the system comprises: the metering pump is connected with an oil path inlet and an oil path outlet of the air battery through an oil pipeline; the outlet of the electrolyte liquid storage tank is connected with the electrolyte pump through a transfusion pipeline, and the electrolyte pump is connected with the electrolyte inlet of the air battery through a transfusion pipeline; the inlet of the electrolyte liquid storage box is connected with the electrolyte emptying valve through a transfusion pipeline, and the electrolyte emptying valve is connected with the electrolyte outlet of the air battery through a transfusion pipeline. By implementing the system and the method, the problem of serious anode corrosion of the metal-air battery in an open circuit state is solved, the real practicability and marketization of the metal-air battery system are promoted, and the large-scale application of the metal-air battery is realized.
Description
Technical Field
The invention relates to the technical field of metal-air batteries, in particular to a cathode protection system and a cathode protection method of an air battery.
Background
The metal-air battery is a battery which takes metal with more negative electrode potential, such as magnesium, aluminum, zinc, mercury, iron and the like, as a negative electrode and takes oxygen or pure oxygen in the air as a positive electrode. Metal-air batteries have been receiving attention due to their ultra-high theoretical specific energy (e.g., 8046Wh/kg for aluminum metal-air batteries), which is considered the most promising power source for off-grid power systems and power plant extension. However, since the metal activity of the anode is greater than that of hydrogen, a hydrogen evolution reaction of the metal anode in an aqueous solution occurs, a severe self-corrosion reaction exists, the self-discharge of the anode is very severe in an unloaded state, and the self-discharge rate of the battery stored for one month in an open circuit state exceeds 80%, so that the utilization rate of the anode is very low, and the metal-air battery cannot be commercialized and cannot meet the actual use requirement. Even with the most advanced corrosion inhibition means at present, researchers have proposed over decades a variety of technical approaches to address the problem of hydrogen evolution corrosion of aluminum cathodes, including:
(1) anode alloying;
(2) adding a hydrogen evolution inhibitor into the electrolyte;
(3) a gel electrolyte;
(4) an ionic liquid electrolyte;
(5) after the battery stops working, the electrolyte is emptied, and the electrode surface is cleaned with water or an acidic solution.
However, the above solutions all come at the expense of specific energy and specific power of the battery, and although alloying and hydrogen evolution inhibitors can effectively reduce the corrosion rate of the air battery in the working state, extra solution and related containers are needed in the open circuit state; the use of gel and ionic liquid electrolytes can reduce the corrosion rate of the anode by about three orders of magnitude, but at the same time, the conductivity of the electrolyte is reduced, so that the specific power of the battery is obviously reduced, and the methods make the system structure and the control system complex and difficult to realize commercialization.
Therefore, it is an urgent technical problem to improve the utilization rate of the anode of the metal-air battery under the condition of not losing or losing less specific energy and specific power of the metal-air battery as much as possible.
Disclosure of Invention
The present invention provides a cathode protection system and method for an air battery to solve at least the above technical problems in the prior art.
In one aspect, the present invention provides a cathode protection system for an air battery, including: an oil storage tank, a metering pump, an electrolyte storage tank, an electrolyte pump and an electrolyte emptying valve,
the inlet and outlet of the oil storage tank are connected with the metering pump through an oil pipeline, and the metering pump is connected with the oil circuit inlet and outlet of the air battery through an oil pipeline;
the outlet of the electrolyte liquid storage tank is connected with the electrolyte pump through a transfusion pipeline, and the electrolyte pump is connected with the electrolyte inlet of the air battery through a transfusion pipeline;
the inlet of the electrolyte liquid storage box is connected with the electrolyte emptying valve through a transfusion pipeline, and the electrolyte emptying valve is connected with the electrolyte outlet of the air battery through a transfusion pipeline.
In one embodiment, the air battery includes: the device comprises an anode cavity, an anode sheet, a cathode cavity, a cathode sheet and an isolating film;
the anode sheet is connected with the anode cavity and provided with an anode output end;
the cathode sheet is connected with the cathode cavity and is provided with a cathode output end;
the anode cavity and the cathode cavity are separated by the isolating film;
and an oil path inlet and an oil path outlet of the air battery are arranged in the anode cavity.
In one embodiment, the separation membrane is a hydrophilic oil-water separation membrane.
In a possible embodiment, the diameter of the isolation film is chosen to be in the range of [50nm, 100nm ].
In one embodiment, the oil storage tank stores alkali-resistant protective oil.
Another aspect of the present invention provides a method for protecting a cathode of an air battery, which is applied to a system for protecting a cathode of an air battery of the present invention, the method including:
when the air battery is in a no-load state, controlling the electrolyte pump to be closed, and opening the electrolyte emptying valve to empty the electrolyte in the internal cavity of the air battery;
according to the metering result of the metering pump, when the electrolyte in the internal cavity of the air battery is empty, the metering pump is controlled to inject protective oil in an oil storage tank into the anode cavity of the air battery, so that anode metal of the air battery is soaked in the protective oil.
In an embodiment, the method further comprises:
when the air battery needs to enter a load state, controlling the metering pump to pump the protective oil in the anode cavity of the air battery back to the oil storage tank;
according to the metering result of the metering pump, when all the protective oil in the anode cavity of the air battery is pumped back into the oil storage tank, the electrolyte emptying valve is controlled to be closed, the electrolyte pump is started, and the electrolyte in the electrolyte storage tank is injected into the cavity of the air battery again.
In an embodiment, the oil inlet and outlet of the air battery are located at the bottom of the anode cavity, and the electrolyte outlet of the battery cavity is located at the top of the anode cavity; the specific gravity of the protective oil is higher than that of water.
In one embodiment, the electrolyte inlet of the cell cavity is located at the bottom of the cathode cavity.
In one embodiment, the protective oil is perfluoropolyether oil (PFPE), or organic fluorine oil, or quaternary amine modified silicone oil.
By implementing the cathode protection system and the method of the air battery, the strong base resistant oil is added into the air battery system, the oil is rapidly filled in the standby state of the air battery, and the protective oil enters the anode cavity of the battery structure, so that the metal anode is soaked in the protective oil; because the specific gravity of the protective oil is heavier than that of water, the oil path inlet and outlet of the air battery are positioned at the bottom of the anode cavity, and the electrolyte outlet of the battery cavity is positioned at the top of the anode cavity, so that the protective oil is injected into the anode cavity, the residual electrolyte on the anode metal plate is extruded out in the process of rising in the anode cavity, and the electrolyte floats on the surface of the protective oil, thereby completely isolating the residual electrolyte and air, and effectively inhibiting the anode self-corrosion and self-discharge phenomena of the air battery.
In addition, the air battery does not pollute a metal anode, a metal cathode and electrolyte after being filled with oil, and has no negative influence on the performance of the battery. Compared with the prior art, the embodiment of the invention has the following advantages:
(1) system pipelines are reduced, a control system is simplified, the peak power density of a battery system is not obviously reduced, and the energy density is improved;
(2) the mass of the protective oil is lower than the total mass of the gas battery system, so that the volume density of the system is improved;
(3) the repeated starting system is simple, and the utilization rate of the anode is greatly improved.
Drawings
Fig. 1 is a schematic structural view of a cathode protection system of an air battery according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of an air battery according to an embodiment of the present invention;
FIG. 3 is a comparison of oil-free and oil-protected battery systems in accordance with an embodiment of the present invention in terms of performance;
fig. 4 is a graphical representation of the effect of oil protection on cell performance by intermittent cyclic discharge testing in an example of the invention.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in fig. 1, a cathode protection system for an air battery according to an embodiment of the present invention mainly includes: an oil storage tank 16, a metering pump 14, an electrolyte storage tank 15, an electrolyte pump 13 and an electrolyte drain valve 12, wherein,
an inlet and an outlet of the oil storage tank 16 are connected with the metering pump 14 through an oil pipeline, and the metering pump 14 is connected with an oil inlet and an oil outlet of the air battery through the oil pipeline;
the outlet of the electrolyte liquid storage box 15 is connected with an electrolyte pump 13 through a transfusion pipeline, and the electrolyte pump 13 is connected with the electrolyte inlet of the air battery through the transfusion pipeline;
the inlet of the electrolyte liquid storage box 15 is connected with an electrolyte emptying valve 12 through a transfusion pipeline, and the electrolyte emptying valve 12 is connected with the electrolyte outlet of the air battery through the transfusion pipeline.
The air battery is mainly composed of an anode 17 and a cathode 18, and the anode 17 and the cathode 18 are separated by a separation film 8. Oxygen or pure oxygen in the air of the air battery is taken as an anode, and metal with more negative electrode potential, such as magnesium, aluminum, zinc, mercury, iron and the like, is taken as a cathode.
The structure of a metal-air cell will be described in detail below with reference to fig. 2, and the cell mainly includes: an anode cavity 4, an anode sheet 6, a cathode cavity 9, a cathode sheet 10 and an isolating film 8; wherein the content of the first and second substances,
the anode sheet 6 is connected with the anode cavity 4, and the anode sheet 6 is provided with an anode output end 5;
the cathode sheet 10 is connected with the cathode cavity 9, the cathode sheet 10 has a cathode output end 11, as shown in fig. 2, the cathode output end 11 can also be a plate, and is fixedly connected with the cathode sheet;
the anode cavity 4 and the cathode cavity 9 are separated by an isolating membrane 8, the isolating membrane 8 can be a hydrophilic oil-water separation membrane, preferably a hydrophilic polytetrafluoroethylene membrane or a steel wire mesh membrane and the like, and the diameter of the isolating membrane 8 can be selected to be in the range of [50nm, 100nm ];
the oil path inlet and outlet 2 of the air battery is arranged in the anode cavity 4.
The oil storage tank stores strong alkali resistant protective oil with specific gravity higher than that of water, preferably perfluoropolyether oil (PFPE), organic fluorine oil, quaternary amine modified silicone oil, etc.
It should be noted that, since the isolation film 8 is a hydrophilic oil-water separation film and the electrolyte is a water system, the electrolytes in the anode cavity 4 and the cathode cavity 9 can flow through the isolation film 8; and the isolating film 8 can effectively isolate the protective oil, and the protective oil injected into the anode cavity 4 is prevented from entering the cathode cavity 9 through the isolating film 8.
The method of cathodic protection according to an embodiment of the present invention will be described in detail below with reference to the cathodic protection system shown in fig. 1 and the air battery structure shown in fig. 2. The cathodic protection method of the embodiment of the invention mainly comprises the following steps:
when the air battery is in a no-load state, controlling the electrolyte pump to be closed, and opening the electrolyte emptying valve to empty the electrolyte in the internal cavity of the air battery;
according to the metering result of the metering pump, when the electrolyte in the internal cavity of the air battery is empty, the metering pump is controlled to inject the protective oil in the oil storage tank into the anode cavity of the air battery, so that the anode metal of the air battery is soaked in the protective oil;
when the air battery needs to enter a load state, controlling the metering pump to pump the protective oil in the anode cavity of the air battery back to the oil storage tank;
according to the metering result of the metering pump, when the protective oil in the anode cavity of the air battery is completely pumped back into the oil storage tank, the electrolyte emptying valve is controlled to be closed, the electrolyte pump is started, and the electrolyte in the electrolyte storage tank is injected into the cavity of the air battery again.
Specifically, when the battery system works normally, the electrolyte evacuation valve 12 is closed, the electrolyte pump 13 works, the electrolyte circulates in the battery cavity, and the battery system outputs electric energy normally; when the battery system is in a no-load state, the electrolyte pump 13 needs to be closed, the electrolyte evacuation valve 12 is opened to evacuate the electrolyte in the battery cavity, the metering pump 14 is also started at the moment, when the metering pump 14 meters the capacity of the anode cavity, the electrolyte in the battery cavity is evacuated, and protective oil with the same capacity as the anode cavity 4 is injected to soak the anode metal of the battery in the protective oil, so that the anode metal of the battery is protected, and self-corrosion is prevented. When the output end of the battery system requires the battery system to be restarted, the metering pump 14 pumps the protection liquid in the anode cavity back into the oil storage tank 16, the metering pump 14 stops working, the electrolyte emptying valve 12 is closed at the moment, and the electrolyte pump 13 is started to refill the electrolyte in the electrolyte storage tank 15 into the battery cavity, so that the battery system is started to normally work.
According to the method description, the strong base resistant oil is added into the air battery system, the oil is rapidly filled in the standby state of the air battery, and the protective oil enters the anode cavity of the battery structure, so that the metal anode is soaked in the protective oil; because the specific gravity of the protective oil is heavier than that of water, the oil path inlet and outlet of the air battery are positioned at the bottom of the anode cavity, and the electrolyte outlet of the battery cavity is positioned at the top of the anode cavity, so that the protective oil is injected into the anode cavity, the residual electrolyte on the anode metal plate is extruded out in the process of rising in the anode cavity, and the electrolyte floats on the surface of the protective oil, thereby completely isolating the residual electrolyte and air, and effectively inhibiting the anode self-corrosion and self-discharge phenomena of the air battery.
In addition, the air battery does not pollute a metal anode, a metal cathode and electrolyte after being filled with oil, and has no negative influence on the performance of the battery. This can be seen from fig. 3, which shows a comparison of the performance of the oil-free and oil-protected battery systems; as can be seen from fig. 3, the performance of the battery system with oil-free protection and the battery system with oil protection are not greatly different, the oil state is always near the normal value, the battery performance is not affected, and the battery performance requirement is completely met.
In addition, referring to the schematic diagram of the influence of the oil protection on the battery performance through the intermittent cyclic discharge test shown in fig. 4, the battery system is started for multiple times, which can be repeated for more than 100 times, the battery performance is not obviously attenuated, which shows that the system is not influenced by the oil-filled battery system. Compared with the anode utilization ratio without oil protection, the anode utilization ratio without oil protection is lower than 26%, and the anode utilization ratio with oil protection is higher than 30%, so that the volume energy ratio and the mass energy ratio of the system are greatly improved.
Compared with the prior art, the embodiment of the invention has the following advantages:
(1) system pipelines are reduced, a control system is simplified, the peak power density of a battery system is not obviously reduced, and the energy density is improved;
(2) the mass of the protective oil is lower than the total mass of the gas battery system, so that the volume density of the system is improved;
(3) the repeated starting system is simple, and the utilization rate of the anode is greatly improved.
In the description herein, references to the description of the term "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 invention. 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 two or more unless specifically defined otherwise.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (9)
1. A cathodic protection system for an air battery, the system comprising: an oil storage tank, a metering pump, an electrolyte storage tank, an electrolyte pump and an electrolyte emptying valve,
the inlet and outlet of the oil storage tank are connected with the metering pump through an oil pipeline, and the metering pump is connected with the oil circuit inlet and outlet of the air battery through an oil pipeline; protective oil is stored in the oil storage tank;
the outlet of the electrolyte liquid storage tank is connected with the electrolyte pump through a transfusion pipeline, and the electrolyte pump is connected with the electrolyte inlet of the air battery through a transfusion pipeline; the electrolyte storage tank stores water system electrolyte;
the inlet of the electrolyte storage tank is connected with the electrolyte emptying valve through a transfusion pipeline, and the electrolyte emptying valve is connected with the electrolyte outlet of the air battery through a transfusion pipeline;
the air battery includes: an anode cavity, a cathode cavity and an isolating film;
the anode cavity and the cathode cavity are separated by the isolating film; an oil path inlet and an oil path outlet of the air battery are arranged at the bottom of the anode cavity;
the isolating membrane is a hydrophilic oil-water separation membrane and is used for enabling electrolyte to permeate through the isolating membrane to circulate in the anode cavity and the cathode cavity; the isolating membrane is also used for preventing the protective oil from permeating through the isolating membrane from the anode cavity to enter the cathode cavity.
2. The cathode protection system for an air battery according to claim 1, wherein the air battery further comprises: an anode sheet and a cathode sheet;
the anode sheet is connected with the anode cavity and provided with an anode output end; the cathode sheet is connected with the cathode cavity and provided with a cathode output end.
3. The cathodic protection system for an air battery as in claim 1, wherein the diameter of the separator is selected to be in the range of [50nm, 100nm ].
4. The cathode protection system for an air battery according to any one of claims 1 to 3, wherein the oil storage tank stores a strong alkali resistant protective oil.
5. A method for protecting a cathode of an air battery, which is applied to the system for protecting a cathode of an air battery according to any one of claims 1 to 4, the method comprising:
when the air battery is in a no-load state, controlling an electrolyte pump to be closed, opening an electrolyte emptying valve, emptying electrolyte in an internal cavity of the air battery, wherein the electrolyte is water system electrolyte and is stored in an electrolyte storage tank;
according to the metering result of a metering pump, when the electrolyte in the internal cavity of the air battery is empty, the metering pump is controlled to inject protective oil in an oil storage tank into the anode cavity of the air battery, so that anode metal of the air battery is soaked in the protective oil;
wherein the air battery includes: an anode cavity, a cathode cavity and an isolating film;
the anode cavity and the cathode cavity are separated by the isolating film; an oil path inlet and an oil path outlet of the air battery are arranged at the bottom of the anode cavity, and the isolating membrane is a hydrophilic oil-water separation membrane; the isolating film is used for enabling electrolyte to permeate through the isolating film to circulate in the anode cavity and the cathode cavity; the isolating membrane is also used for preventing the protective oil from permeating through the isolating membrane from the anode cavity to enter the cathode cavity.
6. The method of cathodic protection of an air battery of claim 5, further comprising:
when the air battery needs to enter a load state, controlling the metering pump to pump the protective oil in the anode cavity of the air battery back to the oil storage tank;
according to the metering result of the metering pump, when all the protective oil in the anode cavity of the air battery is pumped back into the oil storage tank, the electrolyte emptying valve is controlled to be closed, the electrolyte pump is started, and the electrolyte in the electrolyte storage tank is injected into the cavity of the air battery again.
7. The method for protecting the cathode of the air battery according to claim 5 or 6, wherein the oil path inlet and outlet of the air battery are positioned at the bottom of the anode cavity, and the electrolyte outlet of the battery cavity is positioned at the top of the anode cavity; the specific gravity of the protective oil is higher than that of water.
8. The method of claim 7, wherein the electrolyte inlet of the cell cavity is located at the bottom of the cathode cavity.
9. The method for the cathodic protection of an air battery as defined in claim 5 or 6, wherein said protective oil is perfluoropolyether oil PFPE, or organofluorine oil, or quaternary amine-modified silicone oil.
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| CN112542596B (en) * | 2019-09-23 | 2023-07-11 | 易航时代(北京)科技有限公司 | Self-corrosion-resistant metal-air battery and preparation method and application thereof |
| CN112864496B (en) * | 2021-02-02 | 2022-04-29 | 绿业中试低碳科技（镇江）有限公司 | Large-scale aluminum-air battery pressurization and drying system and pressurization and drying control method thereof |
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| CN101841073B (en) * | 2010-05-21 | 2012-10-10 | 余建岳 | Carbon-free metal generator |
| FR2975534B1 (en) * | 2011-05-19 | 2013-06-28 | Electricite De France | METAL-AIR ACCUMULATOR WITH PROTECTION DEVICE FOR THE AIR ELECTRODE |
| CN103515675B (en) * | 2012-06-29 | 2015-11-11 | 中国科学院大连化学物理研究所 | A kind of electrolyte intermittent circulating type metal-air batteries system |
| CN104716293B (en) * | 2013-12-13 | 2017-03-08 | 中国科学院大连化学物理研究所 | A kind of metal-air batteries electrolyte managing device and its application |
| CN204651437U (en) * | 2015-05-11 | 2015-09-16 | 中国第一汽车股份有限公司 | A kind of zinc-air cell |
| CN105186067B (en) * | 2015-07-14 | 2019-11-12 | 北京航空航天大学 | It is a kind of based on the mutual separated structure of oxygen-metal battery electrode-electric solution liquid phase |
| CN106887648B (en) * | 2015-12-16 | 2019-07-12 | 中国科学院大连化学物理研究所 | A kind of zinc/air cell group |
| KR102360032B1 (en) * | 2017-04-12 | 2022-02-08 | 삼성전자주식회사 | Metal-air battery including cathode with air path |
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