Zinc-Bromine Electrolyte Composition for Bromine and Dendrite Control

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Solution Overview

Problem

Zinc-halide batteries suffer from inefficiencies due to secondary reactions in aqueous electrolytes, leading to reduced performance and stability, particularly with zinc bromine cells, where elemental bromine causes hazardous pressure and zinc dendrite formation, and halogen sequestration agents reduce stability over charge cycles.

Innovation Solution

A specific electrolyte composition for zinc bromine electrochemical cells, comprising 30-40 wt% ZnBr2, 5-15 wt% KBr, 5-15 wt% KCl, and 0.5-10 wt% quaternary ammonium agents, which enhances electrochemical performance by mitigating bromine vapor pressure and zinc dendrite formation.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If traditional aqueous zinc-bromide electrolyte is used, then the battery can store electrical energy, but secondary reactions occur leading to reduced performance and stability

Engineering Contradiction:
Improvebattery performance stabilityVSAvoidenergy loss from secondary reactions
Core Design Contradiction:
ReliabilityVSLoss of energy

Solution Approach 1:

The patent introduces a quaternary ammonium salt as an intermediary substance that mediates between bromine and water. This intermediary forms a complex with bromine that prevents direct contact between bromine and water, thereby eliminating the secondary hydrolysis reaction while still allowing the electrochemical reactions to proceed normally.

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The patent converts the harmful effect of bromine's high reactivity (which causes secondary reactions) into a benefit by utilizing the quaternary ammonium salt to control and direct this reactivity. The bromine's strong affinity for the quaternary ammonium salt is harnessed to prevent unwanted reactions while maintaining electrochemical functionality.

Inventive Principle:
Principle #22Blessing in disguise (Convert harm into benefit)

2Reliability

If excess free water is present in the electrolyte, then the electrolyte can facilitate ion transport, but bromate solids form reducing available bromide/bromine

Engineering Contradiction:
Improveelectrolyte stabilityVSAvoidavailable bromide/bromine
Core Design Contradiction:
ReliabilityVSQuantity of substance

Solution Approach 1:

The quaternary ammonium salt acts as a mediator that prevents direct interaction between bromine and water. By forming a stable complex with bromine, it eliminates the pathway for bromate formation while maintaining sufficient ionic conductivity through the aqueous medium.

Inventive Principle:
Principle #24Intermediary (Mediator)

3Object-affected harmful factors

If halogen sequestration agents like quaternary ammonium salts are added, then bromine vapor pressure is reduced, but solubility and electrolyte stability are reduced

Engineering Contradiction:
Improvebromine vapor pressureVSAvoidelectrolyte stability
Core Design Contradiction:
Object-affected harmful factorsVSReliability

Solution Approach 1:

The patent optimizes the concentration parameter of the quaternary ammonium salt to a specific range (0.1-5 wt%) where it effectively complexes with bromine to reduce vapor pressure, while simultaneously maintaining sufficient solubility and electrolyte stability. This parameter optimization resolves the contradiction by finding the optimal balance point.

Inventive Principle:
Principle #35Parameter changes

4Speed

If zinc ions form complex ions and ion pairs in aqueous solution, then ion transport occurs, but zinc dendrite formation increases

Engineering Contradiction:
Improveion transport rateVSAvoiddendrite formation resistance
Core Design Contradiction:
SpeedVSReliability

Solution Approach 1:

The quaternary ammonium salt serves as an intermediary that alters the solvation structure of zinc ions. By introducing this intermediary substance, the patent modifies how zinc ions interact with water molecules, promoting more uniform zinc deposition during charging and reducing dendrite formation while maintaining ion transport capability.

Inventive Principle:
Principle #24Intermediary (Mediator)

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

The proposed electrolyte composition improves the durability and efficiency of zinc bromine cells by reducing secondary reactions and enhancing stability over multiple charge cycles, while minimizing hazardous pressure and zinc dendrite formation.

Implementation Method 1

one or more quaternary ammonium agents... which enhances electrochemical performance by mitigating bromine vapor pressure

Methodology Applied
Scientific EffectComplexation:

Implementation Method 2

which enhances electrochemical performance by mitigating... zinc dendrite formation

Methodology Applied
Scientific EffectElectrodeposition: Electrodeposition

Implementation Method 3

The process of charging and discharging electrical current in a zinc-halide battery is generally achieved through a reaction of redox couples like Zn 2+

Methodology Applied
Scientific EffectRedox reactions: Redox Reactions

Implementation Method 4

Secondary hydrolysis reactions are also problematic for these types of storage batteries when the electrolytes are formulated with excess free water

Methodology Applied
Scientific EffectHydrolysis prevention: Hydrolysis

Data Source

PatentEP3437153B1Electrolyte for rechargeable electrochemical cell
Publication Date: 2024.11.13 EOS ENERGY TECHNOLOGY HOLDINGS LLC
  • EP3437153B1 patent drawingFigure 1
  • EP3437153B1 patent drawingFigure 2A~2B
  • EP3437153B1 patent drawingFigure 3

AI summary

The present invention provides an aqueous electrolyte for use in rechargeable zinc-halide storage batteries that possesses improved stability and durability and improves zinc-halide battery performance (e.g., energy efficiency, Coulombic efficiency, and/or the like). One aspect of the present invention provides an electrolyte for use in a secondary zinc bromine electrochemical cell comprising from about 30 wt% to about 40 wt% of ZnBr2 by weight of the electrolyte; from about 5 wt% to about 15 wt% of KBr; from about 5 wt% to about 15 wt% of KCl; and one or more quaternary ammonium agents, wherein the electrolyte comprises from about 0.5 wt% to about 10 wt% of the one or more quaternary ammonium agents.