WO2020077652A1 - Batterie unique à flux zinc-air rechargeable - Google Patents

Batterie unique à flux zinc-air rechargeable Download PDF

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Publication number
WO2020077652A1
WO2020077652A1 PCT/CN2018/111547 CN2018111547W WO2020077652A1 WO 2020077652 A1 WO2020077652 A1 WO 2020077652A1 CN 2018111547 W CN2018111547 W CN 2018111547W WO 2020077652 A1 WO2020077652 A1 WO 2020077652A1
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WO
WIPO (PCT)
Prior art keywords
air
electrolyte
zinc
single cell
battery
Prior art date
Application number
PCT/CN2018/111547
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English (en)
Chinese (zh)
Inventor
陈忠伟
Original Assignee
苏州沃泰丰能电池科技有限公司
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Application filed by 苏州沃泰丰能电池科技有限公司 filed Critical 苏州沃泰丰能电池科技有限公司
Publication of WO2020077652A1 publication Critical patent/WO2020077652A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • 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
    • 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
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

Definitions

  • the present invention relates to the field of metal-air batteries, in particular to a rechargeable zinc air-flow single cell.
  • Rechargeable zinc-air batteries are considered to be one of the most promising technologies due to many advantages.
  • zinc-air batteries use oxygen from the air in the atmosphere, which is not costly and inexhaustible, eliminating the need to store a fuel source in the battery.
  • the catalyst used in the zinc-air battery is not consumed in the actual electrochemical reaction, and theoretically may play a role in an infinite period.
  • the zinc-air battery uses metallic zinc, which is abundant in the earth's crust and widely distributed, as the active material. Therefore, the zinc-air battery is a low-cost, safe, and environmentally friendly energy storage device.
  • the first problem is the corrosion of the carbon contained in the cathode, which occurs during the charging phase of the battery.
  • the same cathode is used for charging and discharging cycles, and the cathode includes a porous carbon material that supports a desired catalyst.
  • the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR) occur.
  • side reactions occur, in which the carbon is corroded during the OER and the carbon is oxidized to CO 2 .
  • the catalyst supported on the carbon loses contact with the electrode, making the catalyst ineffective, resulting in a decline in battery performance.
  • the US patent US9590253 provides a dual-function catalyst for air batteries and fuel cells.
  • the dual-function catalyst has a catalytic activity for both oxygen reduction and oxygen precipitation reactions. Application prospects.
  • the second problem is the electrode deformation at the anode and the formation of zinc dendrites.
  • the metallic zinc of the anode is oxidized to zinc ions and moves into the electrolyte. Then, due to the poor solubility of zinc ions in the alkaline electrolyte, almost at the same time, these ions are deposited as zinc oxide particles.
  • the zinc oxide particles are transformed into zinc particles. These zinc particles can move down in a long-term cycle due to gravity, and this can cause the shape of the anode to change.
  • the zinc particles can also form zinc dendrites on the anode. Changes in the shape of the anode can cause energy decay, and zinc dendrites can cause sudden failure of the battery.
  • the zinc-air battery uses oxygen in the air from the atmosphere, which is free and inexhaustible, eliminating the need to store a fuel source in the battery.
  • the catalyst used in the zinc-air battery is not consumed during the actual charge-discharge electrochemical reaction, which makes it theoretically possible to play a role indefinitely.
  • Chinese patent CN201680000396 provides a rechargeable three-electrode single-flow zinc-air battery with high cycle life.
  • the electrode structure is composed of an anode and two cathodes (one for charging and the other for discharging), one for charging and the other for discharging. Using two cathodes with different functions can solve the problem of cathode carbon corrosion and catalyst loss. Make the battery more long-term operating life.
  • the main technical problem solved by the present invention is to provide a rechargeable zinc air-flow single cell, which solves the zinc crystal branch problem, and does not need to supplement metal fuel, can be repeatedly re-discharged, and the structure is more compact and optimized.
  • the flow structure of the battery designed by the present invention, the reaction equation of the battery becomes as follows:
  • a rechargeable zinc air-flow single cell includes a battery casing, an air intake cavity, an air cathode, a metal anode, an electrolyte layer, and a conductive current collecting plate; the air cathode is two pieces and is located outside the single cell The metal anode is located in the middle of the single cell, the cavity between the metal anode and the air cathode is suitable for the flow of electrolyte, the air intake cavity is connected to the air cathode side, and the current collectors are respectively Connected to the air cathode and metal anode.
  • the metal anode includes an alkali-resistant metal mesh and / or metal foam permeable to electrolyte.
  • the metal anode is one or more of copper foam, metal copper mesh, nickel foam, and metal nickel mesh.
  • the air cathode includes a conductive, gas-permeable and water-impermeable alkali-resistant electrolyte membrane.
  • the outer surface of the air cathode is coated with a catalyst having catalytic activity for both oxygen reduction reaction and oxygen precipitation reaction.
  • the air intake cavity supplies air to the battery through an external air pump.
  • the electrolyte is pumped in from the bottom of the electrolyte layer by a pump and flows out from the upper part of the electrolyte layer.
  • the electrolyte is an alkaline electrolyte, including one of NaOH, KOH, LiOH or any mixture thereof.
  • the alkali concentration of the electrolyte is 1 mol / L-15 mol / L.
  • a zinc salt is dissolved in the electrolyte, and the zinc salt is one or more of ZnO, Zn (OH) 2 , K 2 Zn (OH) 4 , and Na 2 Zn (OH) 4 .
  • the concentration of zinc ions in the zinc salt is 0.05 mol / L-1.5 mol / L.
  • the present invention has the following advantages compared with the prior art:
  • a rechargeable zinc air-flow single cell is provided.
  • Oxygen in the air is used as the positive electrode active material, and the inert metal anode is used as the negative electrode, which avoids the consumption of metal fuel and enables metal ions to be charged and discharged during the battery Carry out cyclic oxidation and reduction;
  • If the alkaline solution is used as the electrolyte a flowing electrolyte is used to wash away the generated zinc oxide and other deposits with the flow of the electrolyte, and the zinc crystal branch problem will not occur;
  • the flow direction of the electrolyte from the bottom to the top can also prevent the insoluble matter generated from being precipitated to the bottom and be brought into the storage tank with the flow of the electrolyte, preventing deposition (4)
  • the battery structure is designed so that the air cathode can be permeable without water leakage, and the electrolyte ions can oxidize and oxygen evolve well on the surface of the catalyst, which solves the problems of carbon corrosion and
  • FIG. 1 is a schematic cross-sectional view of a rechargeable zinc air-flow single cell of the present invention.
  • Fig. 2 is a schematic front view of a rechargeable zinc air flow single cell of the present invention.
  • a rechargeable zinc air flow single cell includes: an air intake cavity 1, an air cathode 2, an electrolyte layer 3, a metal anode 4, the metal anode 4 is located in the center of the battery, and inside the electrolyte layer 3,
  • the air cathode 2 is located on both sides of the electrolyte layer 3, and the intake cavity 1 is connected to the outside of the air cathode 2.
  • the single cells are supported by the first battery holder 1-2 and the second battery holder 3-2 at the required positions.
  • the electrolyte flows in from the electrolyte inlet 3-3 and flows out from the electrolyte outlet 3-1.
  • An air inlet 1-1 is connected to the upper edge of the cavity 1, and is connected to the fan through the air pipe to supply air to the battery.
  • an oxidation reaction takes place on the surface of the air cathode 2, causing the OH- in the electrolyte to lose electrons to be oxidized to oxygen, and the hydroxide ions come into contact with the bifunctional catalyst 2-3 through the alkali-resistant electrolyte membrane 2-2 to react
  • the zinc oxide in the electrolyte gets a reduction reaction, which reduces the zinc oxide to elemental zinc and deposits on the surface of the metal anode 4.
  • the elemental zinc deposited on the surface of the metal anode 4 undergoes an oxidation reaction to produce zinc oxide, which is then dissolved by the alkaline electrolyte and circulated to the outside of the battery as the electrolyte flows.
  • the oxygen in the air cavity Through the alkali-resistant electrolyte membrane 2-2, the reduction reaction is carried out under the action of the dual-function catalyst 2-3, and it is reduced to OH - ions into the electrolyte, thus completing a charge-discharge cycle.
  • Metal anode 4 The anode consists of an alkali-permeable metal mesh and / or metal foam that is permeable to the electrolyte.
  • the metal mesh can be made of copper foam, metal copper mesh, nickel foam, or metal nickel mesh. As the material, when zinc oxidation-reduction reaction occurs, zinc can react on the metal anode network structure, so that the metal zinc is not consumed during the charge and discharge cycle, and no additional metal fuel is needed.
  • the alkaline electrolyte is one of potassium hydroxide, sodium hydroxide or lithium hydroxide, and the solubility of the zinc ion is better when the concentration of the alkali is in the range of 1-15 mol / L.
  • the electrolyte in the electrolyte layer 3 includes a saturated zinc salt, which is one or more of ZnO, Zn (OH) 2 , K 2 Zn (OH) 4 , Na 2 Zn (OH) 4 , zinc
  • the concentration of ions is 0.05-1.5mol / L.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Materials Engineering (AREA)
  • Hybrid Cells (AREA)

Abstract

L'invention concerne une batterie unique à flux zinc-air rechargeable. Une batterie à flux zinc-air à deux électrodes est conçue en adoptant un catalyseur à double fonction ; une batterie unique est constituée d'un boîtier de batterie, d'une cavité d'entrée d'air (1), d'une cathode à air (2), d'une anode métallique (4), d'une couche d'électrolyte (3), et d'une feuille collectrice de courant conductrice (2-1) ; la batterie utilise uniquement un type d'électrolyte, et la réaction de charge et de décharge de la batterie est immédiatement achevée dans une cavité d'électrolyte. En améliorant un système d'écoulement de liquide et une électrode métallique, la formation d'une branche de cristal de zinc est empêchée, et en améliorant une cathode à air, la cathode à air peut normalement participer à la réaction sans fuite de liquide, de telle sorte que la sécurité et la commercialisation de la batterie sont considérablement améliorées.
PCT/CN2018/111547 2018-10-16 2018-10-24 Batterie unique à flux zinc-air rechargeable WO2020077652A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201821674516.4 2018-10-16
CN201821674516.4U CN209515870U (zh) 2018-10-16 2018-10-16 一种可充电锌空液流单电池

Publications (1)

Publication Number Publication Date
WO2020077652A1 true WO2020077652A1 (fr) 2020-04-23

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WO (1) WO2020077652A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113851761B (zh) * 2021-09-01 2023-06-30 中国科学院青岛生物能源与过程研究所 一种高可逆锌-空气电池

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2884553Y (zh) * 2005-09-22 2007-03-28 北京长力联合能源技术有限公司 一种用于移动电话的锌－空气电池
CN102625960A (zh) * 2009-06-30 2012-08-01 雷沃尔特科技有限公司 金属-空气液流电池
WO2016138594A1 (fr) * 2015-03-04 2016-09-09 Zhongwei Chen Batterie au zinc-air à trois électrodes à électrolyte circulant
CN106463663A (zh) * 2014-04-29 2017-02-22 马勒国际有限公司 金属空气电池
CN107317069A (zh) * 2017-08-06 2017-11-03 鲁壮 一种金属空气电池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2884553Y (zh) * 2005-09-22 2007-03-28 北京长力联合能源技术有限公司 一种用于移动电话的锌－空气电池
CN102625960A (zh) * 2009-06-30 2012-08-01 雷沃尔特科技有限公司 金属-空气液流电池
CN106463663A (zh) * 2014-04-29 2017-02-22 马勒国际有限公司 金属空气电池
WO2016138594A1 (fr) * 2015-03-04 2016-09-09 Zhongwei Chen Batterie au zinc-air à trois électrodes à électrolyte circulant
CN107317069A (zh) * 2017-08-06 2017-11-03 鲁壮 一种金属空气电池

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