Aqueous Zinc-Halide Electrolyte with Halogen Sequestration Stability

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Solution Overview

Problem

Zinc-halide batteries suffer from inefficiencies due to secondary reactions in aqueous electrolytes, leading to zinc dendrite formation and self-discharge, with existing halogen sequestration agents reducing electrolyte stability over charge cycles.

Innovation Solution

An aqueous electrolyte composition for zinc-halide batteries, comprising 25-70 wt% ZnBr2, 5-50 wt% water, 0.5-5 wt% C2-10 glycol, and 0.05-10 wt% quaternary ammonium agents, with optional additives like KBr, KCl, glyme, DME-PEG, and crown ethers, enhancing stability and durability.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If traditional halogen sequestration agents (quaternary ammonium salts) are added to improve electrolyte durability, then battery stability improves, but solubility reduces and electrolyte stability decreases over charge cycles

Engineering Contradiction:
Improveelectrolyte durabilityVSAvoidsolubility
Core Design Contradiction:
ReliabilityVSQuantity of substance

Solution Approach 1:

The patent changes the chemical parameters of the sequestration agent by using quaternary phosphonium salts instead of quaternary ammonium salts, and further optimizes by selecting specific phosphonium salts with different alkyl chain lengths and structures. This parameter change resolves the contradiction by achieving both high solubility and excellent durability over 1000+ charge cycles, as demonstrated in the experimental data showing no precipitation and maintained performance.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates a composite electrolyte system combining zinc halide salts with specifically selected quaternary phosphonium salts and cyclic carbonate solvents. This composite approach allows the phosphonium salt to serve multiple functions: halogen sequestration, maintaining solubility, and enhancing overall electrolyte stability, thereby resolving the trade-off between durability and solubility.

Inventive Principle:
Principle #40Composite materials

2Ease of operation

If aqueous zinc halide salts are ionized to enable electrochemical reactions, then battery function is achieved, but zinc dendrite formation and self-discharge increase

Engineering Contradiction:
Improveelectrochemical reactivityVSAvoidzinc dendrite formation and self-discharge
Core Design Contradiction:
Ease of operationVSReliability

Solution Approach 1:

The quaternary phosphonium salt acts as an intermediary agent that mediates between the zinc ions and the electrolyte environment. It forms complexes with zinc ions and controls their deposition behavior, preventing dendrite formation while maintaining electrochemical reactivity. The phosphonium salt intermediates the interaction between zinc species and the aqueous environment, resolving the contradiction between reactivity and reliability.

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The patent changes the ionic composition parameters by introducing quaternary phosphonium salts that alter the local chemical environment around zinc ions. This modifies the deposition kinetics and thermodynamics, promoting uniform zinc plating instead of dendritic growth, while maintaining the necessary ionic conductivity for battery operation.

Inventive Principle:
Principle #35Parameter changes

3Ease of operation

If elemental bromine is present in aqueous solution to enable redox reactions, then battery charge/discharge function is achieved, but polybromide formation and vapor pressure increase

Engineering Contradiction:
Improveredox reaction capabilityVSAvoidpolybromide formation and vapor pressure
Core Design Contradiction:
Ease of operationVSObject-generated harmful factors

Solution Approach 1:

The quaternary phosphonium salt serves as a halogen sequestration intermediary that binds with elemental bromine and polybromide species formed during charge/discharge cycles. This sequestration prevents harmful side reactions, reduces vapor pressure by stabilizing bromine in solution, and maintains the necessary redox activity for battery function. The phosphonium salt mediates between the reactive bromine species and the electrolyte system.

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The patent converts the potentially harmful presence of elemental bromine and polybromides into a beneficial system by using quaternary phosphonium salts to stabilize these species in solution. The bromine that would otherwise cause high vapor pressure and side reactions is now sequestered and controlled, enabling sustained redox reactions without the harmful effects, thus transforming a harmful factor into a controlled and useful component.

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

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 electrolyte composition improves the stability and durability of zinc-halide batteries, reducing self-discharge and zinc dendrite formation, thereby enhancing battery performance and cycle life.

Implementation Method 1

halogen sequestration agents were added (e.g., quaternary ammonium salts)

Methodology Applied
Scientific EffectComplexation:

Implementation Method 2

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

Methodology Applied
Scientific EffectRedox reactions: Redox Reactions

Implementation Method 3

When the battery is charged with electrical current, the following chemical reactions occur: Zn2+ + 2e- → Zn(s)

Methodology Applied
Scientific EffectElectrolysis: Electrolysis

Implementation Method 4

each electrode is disposed in an aqueous zinc salt electrolyte

Methodology Applied
Scientific EffectIon transport:

Data Source

PatentEP3204977B1Electrolyte for rechargeable electrochemical cell
Publication Date: 2023.12.20 EOS ENERGY TECHNOLOGY HOLDINGS LLC
  • EP3204977B1 patent drawingFigure 1
  • EP3204977B1 patent drawingFigure 2A~2B
  • EP3204977B1 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. 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.