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CN-122025867-A - Rechargeable double electrolyte zinc-air battery

CN122025867ACN 122025867 ACN122025867 ACN 122025867ACN-122025867-A

Abstract

A rechargeable dual electrolyte zinc-air battery is disclosed, comprising a zinc metal anode, an air intake cathode, an ion conducting membrane, and an acidic catholyte and an alkaline anolyte, wherein the acidic catholyte is an aqueous acidic solution comprising an acid-compatible polymer additive. Also disclosed is a method of forming the rechargeable dual electrolyte zinc-air cell comprising the steps of providing a zinc anode, providing an air intake cathode, providing an alkaline anolyte and an acidic catholyte, wherein the acidic catholyte is an aqueous acidic solution comprising an acid-compatible polymeric additive, and the alkaline anolyte and the acidic catholyte are separated via an ion-conducting membrane. An improved method of a rechargeable dual electrolyte zinc-air battery is also disclosed.

Inventors

  • LUO SHIJING
  • Pan wending
  • LIANG YAOZHANG
  • NI MENG
  • WANG YIFEI

Assignees

  • 香港大学
  • 香港理工大学
  • 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院)

Dates

Publication Date
20260512
Application Date
20241112

Claims (20)

  1. 1. A rechargeable dual electrolyte zinc-air battery comprising: A zinc metal anode, Air is sucked into the cathode, Ion conductive membrane, and An acidic catholyte and an alkaline anolyte, Wherein the acidic catholyte is an aqueous acidic solution comprising an acid-compatible polymer additive.
  2. 2. The rechargeable dual electrolyte zinc-air cell of claim 1, wherein the acid-compatible polymer additive is selected from one or more of polyethylene oxide (PEO), polyvinyl alcohol (PVA), polyacrylonitrile (PAN), polyacrylamide (PAM), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyimide (PI), polyvinylchloride (PVC), polypropylene (PP), sodium polyacrylate (PAANa), and any combination thereof.
  3. 3. A rechargeable dual electrolyte zinc-air cell according to claim 1 or 2 wherein the concentration of the acid compatible polymer additive in the acid catholyte is in the range of 0.1-20mg mL -1 .
  4. 4. A rechargeable dual electrolyte zinc-air cell according to any of claims 1 to 3 wherein the alkaline anolyte is an aqueous alkaline solution containing an alkali-compatible polymer additive.
  5. 5. The rechargeable dual electrolyte zinc-air cell of claim 4, wherein the alkali-compatible polymer additive is selected from one or more of sodium polyacrylate (PAANa), carboxymethylcellulose (CMC), cellulose fibers, epoxy, and any combination thereof.
  6. 6. The rechargeable dual electrolyte zinc-air cell of claim 4 or 5, wherein the concentration of the base compatible polymer additive in the alkaline anolyte is from 1 to 20mg mL -1 .
  7. 7. The rechargeable bi-electrolyte zinc-air cell of any of claims 1-6, wherein the ion-conducting membrane comprises a perfluorosulfonic acid ion-exchange membrane, and/or a non-fluoride ion-exchange membrane.
  8. 8. The rechargeable dual electrolyte zinc-air cell of claim 7, wherein the perfluorosulfonic acid ion exchange membrane is selected from one or more of a Nafion 117 membrane, a Nafion115 membrane, a Nafion 211 membrane, and any combination thereof.
  9. 9. The rechargeable dual electrolyte zinc-air cell of any of claims 1-8, wherein the aqueous acidic solution comprises one or more of sulfuric acid, hydrochloric acid, nitric acid, permanganic acid, perchloric acid, selenoic acid, hydrobromic acid, hydroiodic acid, chloric acid, and any combination thereof.
  10. 10. The rechargeable bi-electrolyte zinc-air cell of any of claims 1-9, wherein the aqueous acidic solution has a H + concentration of 0.1-3M. .
  11. 11. The rechargeable dual electrolyte zinc-air cell of any of claims 4-10, wherein the aqueous alkaline solution comprises one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, francium hydroxide, and any combination thereof.
  12. 12. The rechargeable bi-electrolyte zinc-air cell of any of claims 4-11, wherein the aqueous alkaline solution has an OH - concentration of 3-8M.
  13. 13. A method of forming a rechargeable bi-electrolyte zinc-air cell according to any one of claims 1 to 12, comprising the steps of: A zinc anode is provided which is a zinc anode, Air is provided to be sucked into the cathode, Providing an alkaline anolyte and an acidic catholyte, wherein the acidic catholyte is an aqueous acidic solution comprising an acid-compatible polymer additive, and The alkaline anolyte and the acidic catholyte are separated via an ion-conducting membrane.
  14. 14. The forming method of claim 13, further comprising: the cathode is connected to a cathode current collector, wherein the cathode current collector comprises a silver foil, a graphite foil and/or a titanium foil.
  15. 15. The forming method according to claim 13 or 14, further comprising: Assembling the cells into a layered structure, housing the assembly in a poly (methyl methacrylate) (PMMA) plate, and A silicone rubber sheet was inserted between every two PMMA plates.
  16. 16. The forming method of any one of claims 13-15, wherein the cathode comprises carbon paper with Pt/C deposition.
  17. 17. An improved method of a rechargeable dual electrolyte zinc-air battery comprising a zinc metal anode, an air intake cathode, an ion conducting membrane, and an acidic catholyte and an alkaline anolyte, comprising: An acid compatible polymer additive is added to the acid catholyte.
  18. 18. The improved process of claim 17, wherein said acid-compatible polymer additive is selected from one or more of polyethylene oxide (PEO), polyvinyl alcohol (PVA), polyacrylonitrile (PAN), polyacrylamide (PAM), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyimide (PI), polyvinyl chloride (PVC), polypropylene (PP), sodium polyacrylate (PAANa), and any combination thereof.
  19. 19. The improved method of claim 17 or 18, wherein the concentration of the acid-compatible polymer additive in the acid catholyte is 0.1-20mg mL -1 .
  20. 20. The improved method of any of claims 17-19, further comprising: an alkali-compatible polymer additive is added to the alkaline anolyte.

Description

Rechargeable double electrolyte zinc-air battery Technical Field The invention relates to the field of batteries, in particular to a rechargeable double-electrolyte zinc-air battery. Background Unlike conventional lithium ion batteries, which face safety, cost and environmental issues due to material scarcity and toxicity, zinc is abundant and inexpensive, which helps reduce the cost of the battery. Zinc is a non-toxic and recyclable material, making zinc-air batteries a sustainable and environmentally friendly renewable energy solution. Furthermore, among the various cell types, zinc-air cells have a high theoretical high energy density, allowing them to store more energy per unit weight. In addition, zinc-air batteries are generally safe because they are less prone to overheating or explosion. Thus, rechargeable zinc-air batteries are advantageous for light and compact energy storage applications. In such zinc cells, zinc metal is used as the anode, while oxygen in the air is reduced at the cathode. The main problem with current rechargeable zinc-air batteries is dendrite formation at the zinc anode, which grows with cycling and eventually reaches the counter electrode, resulting in internal shorting and failure of the battery, shortening the life and durability of the device. High concentration alkaline solutions are typically used to ensure reversibility of the zinc anode. However, the high concentration alkaline solution inevitably causes corrosion and passivation of the zinc anode, promotes parasitic hydrogen evolution reactions during battery charging, and forms carbonates by absorbing CO 2 from the air, blocking the active sites of the air cathode. U.S. Pat. No. 9,252,616 B2 discloses a zinc-air battery having a low weight and low volume device for charging the same. U.S. patent application 2020/041825 A1 discloses a dual electrolyte electrochemical cell and system that describes a cell assembly having electrodes disposed on respective current collectors and a separator disposed therebetween. The article by Song et al entitled "A Rechargeable Zn-Air Battery with High Energy Efficiency and Long Life Enabled by a Highly Water-Retentive Gel Electrolyte with Reaction Modifier"[ a rechargeable zinc-air cell with high energy efficiency and long life achieved by a high water retention gel electrolyte with reaction modifier (DOI: 10.1002/adma.201908127) shows an alkaline gel polymer electrolyte by multiple crosslinking of poly (vinyl alcohol) (PVA), poly (acrylic acid) and graphene oxide in an alkaline electrolyte and a KI modifier. This cell showed a low charge potential of 1.69V and a discharge potential of 1.24V at 2mA cm -2, and a long cycle time of 200 h. Huang et al developed rechargeable zinc// nickel cobalt and zinc-air batteries using sodium polyacrylate hydrogel electrolytes that are solid state, have high ionic conductivity and water retention. These cells exhibit improved cycling capability. However, the voltage of these single electrolyte batteries is much lower than that of lithium batteries. A zinc-air cell with a dual electrolyte rather than a single alkaline electrolyte would be advantageous, which can significantly improve cell performance and life. Disclosure of Invention The invention provides a rechargeable double-electrolyte zinc-air battery with excellent comprehensive performance, which remarkably improves the voltage of the rechargeable zinc-air battery, inhibits dendrite formation, and avoids corrosion passivation of a zinc anode and active site blockage of an air cathode, thereby improving the service life and durability of the battery. The invention provides a rechargeable double electrolyte zinc-air battery, comprising: A zinc metal anode, Air is sucked into the cathode, Ion conductive membrane, and An acidic catholyte and an alkaline anolyte, Wherein the acidic catholyte is an aqueous acidic solution comprising an acid-compatible polymer additive. The invention also provides a method for forming the rechargeable double-electrolyte zinc-air battery, which comprises the following steps: A zinc anode is provided which is a zinc anode, Air is provided to be sucked into the cathode, Providing an alkaline anolyte and an acidic catholyte, wherein the acidic catholyte is an aqueous acidic solution comprising an acid-compatible polymer additive, and The alkaline anolyte and the acidic catholyte are separated via an ion-conducting membrane. The present invention also provides an improved method of a rechargeable dual electrolyte zinc-air battery comprising a zinc metal anode, an air intake cathode, an ion conducting membrane, and an acidic catholyte and an alkaline anolyte, comprising: An acid-compatible polymer additive is added to the acid catholyte. Drawings Fig. 1 shows a configuration of a dual electrolyte zinc-air battery. Fig. 2 shows the principle of operation of the double electrolyte zinc-air cell according to the invention in the discharged (a) and charged (b) state. FIG. 3 sh