CN108365301B - Chargeable and dischargeable liquid metal battery - Google Patents
Chargeable and dischargeable liquid metal battery Download PDFInfo
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- CN108365301B CN108365301B CN201810077123.3A CN201810077123A CN108365301B CN 108365301 B CN108365301 B CN 108365301B CN 201810077123 A CN201810077123 A CN 201810077123A CN 108365301 B CN108365301 B CN 108365301B
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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
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
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- 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
- Y02E60/10—Energy storage using batteries
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a chargeable and dischargeable liquid metal battery, which comprises an air electrode, a liquid metal electrode, electrolyte, a first positive electrode led out by the air electrode and a negative electrode led out by the liquid metal electrode; the liquid metal electrode is in contact with the electrolyte to generate an oxidation reaction; the air electrode is in contact with the electrolyte and provides oxygen for the electrolyte to generate a reduction reaction; a graphite shell is arranged at one end part of the negative electrode and is connected with the liquid metal electrode through the graphite shell; the battery also comprises a second anode, wherein one end of the second anode is arranged in the electrolyte and used for providing electrons to reduce metal ions in the electrolyte so as to store energy. The rechargeable liquid metal battery provided by the invention can realize multiple charging and discharging functions, has slow battery performance decay, high specific energy and long cycle life, and can prolong the service life.
Description
Technical Field
The invention relates to the technical field of battery energy storage, in particular to a chargeable and dischargeable liquid metal battery.
Background
With the advent of the smart grid era, power systems are changing from traditional to clean, efficient and intelligent, so that day and night power grid peak-valley difference and smooth load are effectively eliminated, capacity and load are simultaneously adjusted in a micro-grid mode, power equipment operation efficiency is improved, power supply cost is reduced, and the method becomes the core content for constructing smart grids in various countries. Regardless of the elimination of the instability of the renewable energy sources to realize real grid-connected power generation, or the reduction of the peak-valley difference of the power grid between day and night and the smooth load, a large-scale and low-cost energy storage technology is required to be used as a support.
People's daily life official working and industrial electricity utilization are all more than actual demand power generation, and the purpose is in order to guarantee the continuation of power supply, do not influence the normal order and the development in certain area because of the power energy problem, but the problem brought from this is the loss and the waste of electric power, nevertheless supposes under the drive of battery and its new energy technology, can use the storage electric quantity when supplying and not meeting the demand with the electric power resource storage in the carrier to us one day. This not only solves the loss and waste problem, but the grid itself will also become more stable and efficient, as the batteries allow each community and area to manage its own power supply by itself.
The rechargeable liquid metal fuel cell is a novel high specific energy cell, which is far higher than the specific energy of various batteries at present and has long service life. The structure and the used raw materials of the battery can be changed according to the practical environment and requirements, and the battery has strong adaptability. Meanwhile, the raw materials are widely distributed, and the storage amount is huge.
The appearance and the development of the rechargeable liquid metal fuel cell can relieve the restriction of the cell on the development of some industries, and effectively promote the development of the fields of new energy automobiles, aerospace, ship industry, military power supplies and the like, in particular to the field of new energy electric automobiles.
Disclosure of Invention
The invention aims to solve the problems of fast performance attenuation, short cycle life, inconvenient battery management and high production cost of an energy storage battery in the prior art, and provides a chargeable and dischargeable liquid metal battery.
The invention provides a chargeable and dischargeable liquid metal battery, which comprises an air electrode, a liquid metal electrode, electrolyte, a first positive electrode led out by the air electrode and a negative electrode led out by the liquid metal electrode; the liquid metal electrode is in contact with the electrolyte to generate an oxidation reaction; the air electrode is in contact with the electrolyte and provides oxygen for the electrolyte to generate a reduction reaction; a graphite shell is arranged at one end part of the negative electrode and is connected with the liquid metal electrode through the graphite shell; the battery also comprises a second anode, wherein one end of the second anode is arranged in the electrolyte and used for providing electrons to reduce metal ions in the electrolyte so as to store energy.
Preferably, the negative electrode is a nickel plate with the purity of more than 99 percent; the graphite shell is composed of two high-purity graphite plates which are respectively fixed on the front side and the rear side of the nickel plate.
Preferably, the liquid metal electrode adopts low-melting-point metal which is liquid at normal temperature, or alloy which is formed by combining the low-melting-point metal with one or more of zinc, tin, aluminum, lead, chromium, copper, gold and silver; the low-melting-point metal is pure gallium, pure indium or pure bismuth.
Preferably, the electrolyte is a strong base electrolyte with a pH value of more than 12 or a strong acid electrolyte with a pH value of less than 4; the concentration of the electrolyte is 0.5-7 mol/L.
Preferably, the electrolyte is sodium hydroxide, potassium hydroxide or calcium hydroxide.
Preferably, the second positive electrode is a copper plate or a nickel plate.
Preferably, the air electrode, the liquid metal electrode and the electrolyte are all arranged in the shell, and the electrolyte and the liquid metal electrode are all located in a cavity formed by the air electrode and the shell.
Preferably, the liquid metal electrode is deposited at the bottom of the cavity, the electrolyte is filled in the cavity and is positioned above the liquid metal electrode, and the liquid metal electrode is in contact with the electrolyte to generate an oxidation reaction.
Preferably, the air electrode is composed of a catalyst and a gas permeable membrane, and the gas permeable membrane is used for enabling the oxygen to enter the electrolyte to carry out reduction reaction.
Preferably, the top of the shell is provided with an electrolyte injection port, and the electrolyte injection port is communicated with the cavity and used for supplementing electrolyte into the cavity.
The rechargeable liquid metal battery provided by the invention can realize multiple charging and discharging functions, has slow battery performance decay, high specific energy and long cycle life, can prolong the service life of the battery, has a simple structure and low production cost, and can be widely applied to the fields of smart grid energy storage, electric vehicles, portable electronic equipment and the like.
Drawings
Fig. 1 is a schematic view of an overall structure of a rechargeable liquid metal battery according to the present invention;
fig. 2 is a schematic front view of a rechargeable liquid metal battery according to the present invention;
fig. 3 is a left side view schematic diagram of a rechargeable liquid metal battery according to the present invention;
description of reference numerals:
1-an air electrode; 2-liquid metal electrodes; 3-an electrolyte;
4-negative electrode; 5-a first positive electrode; 6-a second positive electrode;
7-a housing; 41-graphite shell; 71-electrolyte injection port.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but 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. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
The invention provides a chargeable and dischargeable liquid metal battery, which comprises an air electrode 1, a liquid metal electrode 2, an electrolyte 3, a first positive electrode 5 led out from the air electrode 1 and a negative electrode 4 led out from the liquid metal electrode 2, wherein the air electrode 1 is connected with the liquid metal electrode 2 through a connecting wire; the liquid metal electrode 2 is in contact with the electrolyte 3 to generate an oxidation reaction; the air electrode 1 is in contact with the electrolyte 3 and provides oxygen for the electrolyte 3 to generate a reduction reaction; a graphite shell 41 is arranged at one end part of the negative electrode 4 and is connected with the liquid metal electrode 2 through the graphite shell 41; the electrolytic cell further comprises a second anode 6, wherein one end of the second anode 6 is arranged in the electrolyte 3 and used for providing electrons to reduce metal ions in the electrolyte 3 so as to store energy.
The invention provides a chargeable and dischargeable liquid metal battery, which mainly depends on the contact of liquid metal and electrolyte to generate oxidation reaction, a first positive electrode absorbs air into the electrolyte through an air electrode to generate reduction reaction, so that chemical energy is converted into electric energy to complete a discharging process, a negative electrode is communicated with a second positive electrode, and liquid metal ions in the electrolyte are reduced into the liquid metal to return to a liquid metal electrode area again through electrons, so that energy storage is realized, and a charging process is completed. The liquid metal is oxidized into metal cations in the discharging process, the metal cations are reduced into the liquid metal again in the charging process and deposited in the liquid metal electrode area, the liquid metal is basically not consumed, the charging and discharging can be carried out for many times, the battery performance is slowly attenuated, the cycle life is long, the specific energy is high, the service life is long, the structure is simple, the production cost is low, and the method can be widely applied to the fields of smart grid energy storage, electric automobiles, portable electronic equipment and the like.
The metal electrode can accelerate the oxidation of the liquid metal to cause the adhesion of the electrode, so that the electrolytic reaction is stopped, the graphite shell is arranged at the end part of one end of the negative electrode 4, which is in contact with the liquid metal electrode, and the problem of the adhesion of oxides generated by the oxidation between the metal electrodes can be effectively solved through the contact between the graphite and the liquid metal, so that the stagnation of the charging and discharging processes of the battery is prevented.
In the above technical scheme, the negative electrode 4 is a nickel plate with a purity of more than 99%; the graphite shell 41 is composed of two high-purity graphite plates fixed on the front side and the rear side of the nickel plate respectively. The nickel plate has better conductivity, and the high-purity graphite plate has good anti-adhesion effect.
In the above technical scheme, the liquid metal electrode 2 is made of a low-melting-point metal which is liquid at normal temperature, or an alloy formed by combining the low-melting-point metal and one or more metals of zinc, tin, aluminum, lead, chromium, copper, gold and silver; the low-melting-point metal is pure gallium, pure indium or pure bismuth. Multiple primary battery reactions can be formed among all metals of the multi-element alloy, and the charge and discharge effects of the multi-element alloy are superior to those of a metal simple substance. The metal is in liquid state, so that the passivation problem of the metal electrode can be avoided.
In the technical scheme, the electrolyte is strong base electrolyte with the pH value more than 12 or strong acid electrolyte with the pH value less than 4; the concentration of the electrolyte is 0.5-7 mol/L.
The stronger the alkalinity is, the higher the ion ionization energy of the strong base electrolyte or the stronger the acidity is, the better the conductivity is; however, the alkalinity or acidity should not be too high, which would result in higher corrosivity and would be detrimental to the stability of the battery.
In the above technical solution, the electrolyte is preferably sodium hydroxide, potassium hydroxide or calcium hydroxide.
In the technical scheme, the second positive electrode 6 is a copper plate or a nickel plate, and the second positive electrode 6 is a sheet electrode, so that the contact area with electrolyte can be increased, the reduction efficiency of liquid metal oxide is improved, and the problem of hydrogen evolution during charging is avoided. The traditional columnar electrode has small contact area with electrolyte, low charging efficiency and serious hydrogen evolution.
In the technical scheme, the air electrode structure further comprises a shell 7, the air electrode 1, the liquid metal electrode 2 and the electrolyte 3 are arranged in the shell 7, and the electrolyte 3 and the liquid metal electrode 2 are located in a cavity formed by the air electrode 1 and the shell 7. The casing 7 of the battery is generally designed to be a cuboid, the air electrodes 1 are two blocks which are respectively vertically arranged in the casing 7 and close to two opposite side surfaces of the cuboid casing, and air leakage holes are formed in the casing 7 so as to conveniently maintain the air pressure balance inside and outside the cavity.
In the technical scheme, the liquid metal electrode 2 is deposited at the bottom of the cavity, the electrolyte 3 is filled in the cavity and positioned above the liquid metal electrode 2, and the liquid metal electrode 2 is in contact with the electrolyte 3 to generate an oxidation reaction. The liquid metal electrode 2 is arranged below the electrolyte, when the liquid metal in the electrolyte is reduced into a metal simple substance, the metal simple substance can be directly deposited and fall back to the area of the liquid metal electrode 2, the liquid metal is basically not consumed, the charging and discharging can be carried out for many times, the battery performance decay is slow, and the cycle life is long.
In the above technical solution, the air electrode 1 is composed of an oxidant and a gas permeable membrane, and the gas permeable membrane is used for allowing the oxygen to enter the electrolyte to perform a reduction reaction.
In the above technical solution, the top of the casing 7 is provided with an electrolyte injection port 71, and the electrolyte injection port 71 is communicated with the cavity and is used for supplementing electrolyte into the cavity. In the charging and discharging process, water in the electrolyte is consumed, and the electrolyte injection port 71 is arranged at the top of the battery, so that the consumed electrolyte can be conveniently replenished, and the battery can be maintained to be recycled.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (4)
1. A chargeable and dischargeable liquid metal battery is characterized by comprising an air electrode, a liquid metal electrode, electrolyte, a first positive electrode led out by the air electrode and a negative electrode led out by the liquid metal electrode; the liquid metal electrode is in contact with the electrolyte to generate an oxidation reaction; the air electrode is in contact with the electrolyte and provides oxygen for the electrolyte to generate a reduction reaction; a graphite shell is arranged at one end part of the negative electrode and is connected with the liquid metal electrode through the graphite shell; the electrolyte also comprises a second anode, wherein one end of the second anode is arranged in the electrolyte and used for providing electrons to reduce metal ions in the electrolyte so as to store energy; the air electrode consists of an oxidant and a breathable film, and the breathable film is used for enabling the oxygen to enter the electrolyte to carry out reduction reaction;
the negative electrode is a nickel plate with the purity of more than 99 percent; the graphite shell consists of two high-purity graphite plates which are respectively fixed on the front side and the rear side of the nickel plate;
the electrolyte is sodium hydroxide, potassium hydroxide or calcium hydroxide;
the air electrode, the liquid metal electrode and the electrolyte are all arranged in the shell, and the electrolyte and the liquid metal electrode are all positioned in a cavity formed by the air electrode and the shell; the liquid metal electrode is deposited at the bottom of the cavity, the electrolyte is filled in the cavity and is positioned above the liquid metal electrode, and the liquid metal electrode is in contact with the electrolyte to generate an oxidation reaction.
2. The rechargeable liquid metal battery according to claim 1, wherein the liquid metal electrode is a low-melting metal that is liquid at normal temperature, or an alloy of the low-melting metal and one or more metals selected from zinc, tin, aluminum, lead, chromium, copper, gold, and silver; the low-melting-point metal is pure gallium, pure indium or pure bismuth.
3. The rechargeable liquid metal battery according to claim 1, wherein the second positive electrode is a copper plate or a nickel plate.
4. The rechargeable liquid metal battery as claimed in claim 1, wherein the top of the case is provided with an electrolyte injection port communicating with the cavity for replenishing electrolyte into the cavity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810077123.3A CN108365301B (en) | 2018-01-26 | 2018-01-26 | Chargeable and dischargeable liquid metal battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810077123.3A CN108365301B (en) | 2018-01-26 | 2018-01-26 | Chargeable and dischargeable liquid metal battery |
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| CN108365301A CN108365301A (en) | 2018-08-03 |
| CN108365301B true CN108365301B (en) | 2020-03-17 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110260476A (en) * | 2019-05-29 | 2019-09-20 | 佛山市中格威电子有限公司 | A kind of no battery idle call remote controler |
| CN110911692B (en) * | 2019-12-06 | 2023-05-02 | 武汉大学 | Corrosion-resistant liquid metal battery positive electrode current collector |
| CN113193179A (en) * | 2021-03-29 | 2021-07-30 | 西安交通大学 | Liquid metal battery and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4834419B1 (en) * | 1970-01-19 | 1973-10-20 | ||
| GB1471279A (en) * | 1974-08-08 | 1977-04-21 | Lucas Batteries Ltd | Metal-air batteries |
| DE2647299A1 (en) * | 1976-10-20 | 1978-04-27 | Battelle Institut E V | Rechargeable alkali metal-halogen cell with liquid electrolyte - having separator of uniform beta:alumina crystals, avoiding high self-discharge rate |
| JP6032018B2 (en) * | 2012-01-19 | 2016-11-24 | 日産自動車株式会社 | Injection metal-air battery |
| CN105098291B (en) * | 2015-07-21 | 2018-02-27 | 清华大学深圳研究生院 | Liquid metal gas cell and preparation method thereof |
| CN105609899A (en) * | 2016-02-16 | 2016-05-25 | 云南科威液态金属谷研发有限公司 | Flexible liquid metal air battery and battery pack |
| CN107017450B (en) * | 2017-03-10 | 2019-09-24 | 云南靖创液态金属热控技术研发有限公司 | Aluminium-air cell |
| CN107452940A (en) * | 2017-06-22 | 2017-12-08 | 云南铝业股份有限公司 | A kind of electrode of liquid stream three can fill zinc and air cell |
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