Iron Electrolyte Composition for Stable All-Iron Flow Batteries

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Solution Overview

Problem

All-iron hybrid redox flow batteries face challenges such as iron salt precipitation, slow kinetics of plating and stripping, and hydrogen evolution, which affect efficiency and durability, particularly due to differences in reaction environments between the positive and negative electrodes.

Innovation Solution

A novel electrolyte composition for all-iron redox flow batteries, incorporating additives to enhance ionic conductivity, pH control, complex formation, and oxidation inhibition, ensuring stability and balanced redox reactions in both half-cells.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Quantity of substance

If iron salts are used in high concentrations to achieve high energy density, then the energy density is improved, but the ionic conductivity decreases and salt precipitation occurs

Engineering Contradiction:
Improveenergy densityVSAvoidionic conductivity
Core Design Contradiction:
Quantity of substanceVSReliability

Solution Approach 1:

The patent introduces supporting electrolytes (such as H2SO4, Na2SO4, MgSO4, Al2(SO4)3) as intermediary substances that facilitate ionic conductivity in the high-concentration iron salt electrolyte. These supporting electrolytes act as mediators that enable ion transport without directly participating in the redox reactions, thus maintaining high ionic conductivity while allowing high iron salt concentrations for high energy density.

Inventive Principle:
Principle #24Intermediary (Mediator)

2Quantity of substance

If iron salts are used in high concentrations to achieve high energy density, then the energy density is improved, but salt precipitation occurs

Engineering Contradiction:
Improveenergy densityVSAvoidelectrolyte stability
Core Design Contradiction:
Quantity of substanceVSStability of the object's composition

Solution Approach 1:

Complexing agents (such as EDTA, citric acid, tartaric acid, gluconic acid) are introduced as intermediary substances that form stable complexes with iron ions. These complexing agents prevent iron salt precipitation by maintaining iron ions in soluble complex forms, thus ensuring electrolyte stability while allowing high iron salt concentrations for high energy density.

Inventive Principle:
Principle #24Intermediary (Mediator)

3Stability of the object's composition

If the electrolyte is maintained in a reducing environment to prevent spontaneous oxidation of Fe2+, then the electrolyte stability is improved, but the complexity of controlling the environment increases

Engineering Contradiction:
Improveelectrolyte stabilityVSAvoidenvironment control complexity
Core Design Contradiction:
Stability of the object's compositionVSDevice complexity

Solution Approach 1:

The patent employs antioxidants (such as ascorbic acid, sodium sulfite, hydrazine sulfate) that automatically maintain the reducing environment through self-service mechanisms. These antioxidants spontaneously react with oxidizing agents in the electrolyte, continuously regenerating the reducing environment without requiring external control systems, thus preventing Fe2+ oxidation while avoiding increased system complexity.

Inventive Principle:
Principle #25Self-service

4Productivity

If additives are added to inhibit H2 evolution and improve plating quality, then the cell efficiency is improved, but the device complexity increases

Engineering Contradiction:
Improvecell efficiencyVSAvoidelectrolyte composition complexity
Core Design Contradiction:
ProductivityVSDevice complexity

Solution Approach 1:

The patent uses multifunctional additives that simultaneously perform multiple roles: complexing agents (EDTA, citric acid) that prevent precipitation and enhance plating quality; antioxidants (ascorbic acid, sodium sulfite) that prevent Fe2+ oxidation and improve plating; and pH buffers that maintain stable operating conditions. This multi-functionality reduces the need for separate additives for each function, thereby improving cell efficiency while minimizing the increase in electrolyte composition complexity.

Inventive Principle:
Principle #6Universality (Multi-functionality)

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 achieves high energy and power densities with improved plating/stripping kinetics, reduced hydrogen evolution, and enhanced membrane selectivity, resulting in high coulombic efficiency and stability.

Implementation Method 1

the ionic conductivity of the electrolyte be as high as possible to minimize the internal resistance of the cell, avoiding internal current losses

Methodology Applied
Scientific EffectIonic conductivity: Conduction (electrical)

Implementation Method 2

The reactions on the positive electrode take place as in a conventional redox flow battery (redox reactions are developed on the electrode/electrolyte interface)

Methodology Applied
Scientific EffectRedox reactions: Redox Reactions

Implementation Method 3

on the negative electrode, the redox reaction during the charge step leads to a plate out of Fe0

Methodology Applied
Scientific EffectElectroplating: Electroplating

Implementation Method 4

the redox reaction during the charge step leads to a plate out of Fe0

Methodology Applied
Scientific EffectReduction: Reduction

Implementation Method 5

it is necessary that the iron salts be as concentrated as possible... Ionic conductivity is achieved by dissolving the iron salts themselves

Methodology Applied
Scientific EffectDissolution: Solvation

Data Source

PatentEP4614634A1An iron electrolyte, its process of obtainment and iron redox flow battery comprising said electrolyte
Publication Date: 2025.09.10 CONSEJO SUPERIOR DE INVESTIGACIONES CIENTIFICAS (CSIC)
  • EP4614634A1 patent drawingFigure 1
  • EP4614634A1 patent drawingFigure 2~2b
  • EP4614634A1 patent drawingFigure 3

AI summary

The invention relates to a new electrolyte involving iron salts to be used as anolyte and/or catholyte in an all-iron hybrid redox flow battery. Said electrolyte, as well as iron salts in high concentration, comprises various additives that grant key properties such as stability, balanced pH, and ionic conductivity (needed to avoid salt precipitation), and also inhibit H2 evolution/generation thus enabling good quality iron platting. Therefore, the field of the invention is the iron redox flow battery industry.