WO2018090161A1

WO2018090161A1 - Rechargeable zinc ion battery employing copper metal as negative electrode current collector

Info

Publication number: WO2018090161A1
Application number: PCT/CN2016/105296
Authority: WO
Inventors: 魏春光; 徐成俊; 陈彦伊
Original assignee: 深圳市寒暑科技新能源有限公司
Priority date: 2016-11-18
Filing date: 2016-11-18
Publication date: 2018-05-24

Abstract

A rechargeable zinc ion battery employing copper metal or zinc-plated copper metal as a negative electrode current collector. The battery consists of a positive electrode, a negative electrode, a separator membrane therebetween, and an electrolyte. An active material of the negative electrode is mainly the zinc element. An active material of the positive electrode is manganese dioxide. The electrolyte is a liquid electrolyte employing a soluble zinc salt and a soluble manganese salt as a solute and water as a solvent and having ionic conductivity. The battery of the present invention has characteristics such as a high capacity, a low cost, and rechargeability, and is widely applicable in fields such as mobile phones, personal digital notebooks, cordless phones, electronic toys, game machines, personal video and audio devices, portable data terminals, palm computers, and experiment devices.

Description

Rechargeable zinc ion battery with metallic copper as negative current collector

Technical field

This patent belongs to the field of battery technology, and specifically relates to a zinc ion battery using metal copper or surface galvanized metal copper as a negative current collector.

Background technique

Compared with the current rechargeable batteries such as nickel-metal hydride and lithium-ion batteries, zinc-ion batteries are safe, environmentally friendly, and have a simple production process, which can effectively reduce production costs and are environmentally friendly.

The Chinese patent (CN 101540417A) invents a zinc ion battery which comprises manganese dioxide (MnO ₂ ) as a positive electrode, zinc as a negative electrode, and an aqueous solution containing zinc ions as an electrolyte to form a rechargeable zinc ion battery. Such zinc ion rechargeable battery of the present invention based on two acts of Zn ^2+: Zn ²⁺ rapid reversible insertion and extraction behavior of manganese dioxide material having a large tunnels, on the other hand, it may be a Zn-containing Zn ²⁺ Rapid reversible dissolution and deposition in a ²⁺ neutral electrolyte such as zinc sulfate or zinc nitrate. However, in a battery such as a square or a cylindrical type that derives a current from a polar ear, the metal zinc directly used in the negative electrode directly participates in a chemical reaction during charge and discharge, thereby causing dissolution of the metal zinc, which cannot be exerted in the late stage of charge and discharge. The current collecting effect leads to low efficiency of battery charging and discharging and can not be used continuously.

The patent uses metal copper or surface galvanized metal copper as the anode current collector, which can effectively solve the phenomenon of dissolution of the anode current collector in the rechargeable zinc ion battery, and then improve the cycle performance of the battery. When zinc is used as the anode current collector, the effective cycle is 5 cycles, and when copper is used as the anode current collector, the cycle 5 is effective, and the effective cycle is up to 60% of the maximum capacity.

Summary of the invention

The original zinc ion battery uses pure zinc foil as the anode current collector. According to the results of the cycle test of the rechargeable zinc ion battery, when the zinc foil is used as the anode current collector, the battery will be charged for a long time after a certain cycle. The discharge efficiency was gradually reduced until it could not be properly charged and discharged. After dissolving the zinc-ion battery with pure zinc foil as the anode current collector, it was found that the anode current collector zinc foil was dissolved in whole or in part, and the dissolution of the anode current collector was analyzed, resulting in the battery being negative in the late stage of the cycle. Corrosion of the current collector causes the current to fail to form a current collecting effect through the zinc foil, resulting in battery damage.

This patent proposes a rechargeable zinc ion battery with metallic copper or surface galvanized metallic copper as the negative current collector, which can effectively improve the cycle performance of the rechargeable zinc ion battery and improve the coulombic efficiency of the rechargeable zinc ion battery. The negative electrode reaction of a rechargeable zinc ion battery is the deposition and dissolution of zinc, so when using metal zinc as a current collector, It participates in the reaction, causing the current collector to lose its collecting current, causing a rapid decay of capacity. In this patent, we use metal copper or surface galvanized metal copper as the anode current collector, and a layer of zinc powder or zinc powder alloy is coated on the surface to satisfy the zinc content of the zinc ion battery. The zinc ion battery fabricated by the method can achieve an effective cycle of 12, and the surface of the current collector is not observed to be corroded after the cycle. It can be seen that the zinc ion battery using metal copper or surface galvanized metal copper as the anode current collector has the advantages of high charge and discharge efficiency, good cycle performance and the like. It is foreseeable that such zinc ion batteries can be widely used in personal digital, notebook, electric toys, cordless phones, game machines, experimental devices, portable data terminals, palm computers, personal audio video devices and the like.

BRIEF DESCRIPTION OF THE DRAWINGS:

Figure 1: Coulomb efficiency comparison of two anode current collectors;

Figure 2: Cycle life of two anode current collectors at a current density of 0.02 A/g.

Specific embodiment:

Preparation of positive electrode sheet: manganese dioxide powder doped with conductive carbon nanotubes: conductive carbon black: conductive graphite: carboxymethyl cellulose: styrene-butadiene rubber = 84:5:5:3:3 ratio with water solvent The mixture was mixed at a solid content of 50%, and then the slurry was drawn through a gap of 1.2 mm using a 304 steel mesh, and dried for 3 hours in a blast drying oven at 80 ° C, and then the pole piece was pressed to a thickness of 0.30 mm by a pair of rolls.

Preparation of negative electrode sheet: 1: According to zinc powder: conductive graphite sheet: carboxymethyl cellulose: styrene-butadiene rubber = 90:5:2.5:2.5 ratio The water solvent was mixed at 70% solid content. Then, the slurry is pulled through a 0.5 mm gap with a pure copper mesh, and after drying, the pole piece is pressed to a thickness of 0.20 mm by a pair of rolls; 2: mixed with NMP as a solvent in a ratio of conductive graphite: PVDF=95:5. The material was then coated on a zinc foil through a 120 um knife edge, and after drying, the pole piece was pressed to 0.11 mm by a roll machine.

Preparation of electrolyte: An aqueous solution of 2 moles per liter of ZnSO ₄ and 1 mol/L of MnSO ₄ was used as the electrolyte.

A positive electrode sheet 1, a negative electrode sheet 1, and an aqueous solution of 2 mol/L ZnSO ₄ and 1 mol/L MnSO ₄ were used as an electrolyte solution to assemble a No. 5 battery.

A positive electrode sheet 1, a negative electrode sheet 2, and an aqueous solution of 2 mol/L ZnSO ₄ and 1 mol/L MnSO ₄ were used as an electrolyte solution to assemble a No. 5 battery.

Claims

A zinc ion battery using metal copper or surface galvanized metal copper as a negative current collector, comprising a positive electrode, a negative electrode, a separator interposed therebetween, and an electrolyte containing anion and cation and having ionic conductivity, and characterized The active material of the negative electrode is mainly zinc element; the active material of the positive electrode is manganese dioxide; and the electrolyte is a solution containing zinc ions.
The zinc ion battery according to claim 1, wherein the positive electrode comprises a current collector and a positive electrode film attached to the current collector, and the positive electrode film is composed of a positive electrode. Made of the active material, electronic conductive agent and binder.
The zinc ion battery with metal copper or surface galvanized metal copper as a negative electrode current collector according to claim 1, wherein the negative electrode comprises metal copper or surface galvanized metal copper is a current collector and a negative electrode film, The negative electrode film is made of metal zinc, a carbon material, and a binder.
The zinc ion battery according to claim 1 , wherein the negative electrode comprises metal copper or the surface galvanized metal copper is a current collector and a negative electrode film. The negative electrode film is made of the active material metal zinc.
The zinc ion battery with metal copper or surface galvanized metal copper as a negative electrode current collector according to claim 1, wherein the negative electrode comprises a metal copper or a surface galvanized metal copper as a current collector and a negative electrode film. Composition, the negative electrode film is made of zinc powder, a binder, and a corrosion inhibitor.
The zinc ion battery with metal copper or surface galvanized metal copper as a negative electrode current collector according to claim 1, wherein the negative electrode comprises metal copper or surface galvanized metal copper is a current collector and a negative electrode film, The negative electrode film is made of zinc powder, a binder, and an electronic conductive agent.
The zinc ion battery with metal copper or surface galvanized metal copper as a negative electrode current collector according to claim 1, wherein the negative electrode comprises metal copper or surface galvanized metal copper is a current collector and a negative electrode film, The negative electrode film is made of zinc powder and a binder.
The zinc ion battery with metal copper or surface galvanized metal copper as a negative electrode current collector according to claim 1, wherein the negative electrode comprises metal copper or surface galvanized metal copper is a current collector and a negative electrode film, The negative electrode film is made of zinc powder, a binder, a corrosion inhibitor and an electronic conductive agent, and the amount of the electron conductive agent added is 50% or less of the mass of the negative electrode film, and the amount of the corrosion inhibitor added is 1% or less of the mass of the negative electrode film. .