Three-Chamber Electrochemical Balancing Cell for Flow Battery pH and Charge Control

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Solution Overview

Problem

Flow batteries face sub-optimal energy storage performance and limited cycle life due to parasitic reactions, which lead to state of charge imbalances and pH fluctuations in electrolyte solutions, requiring effective rebalancing strategies that are currently lacking.

Innovation Solution

The implementation of a three-chamber electrochemical balancing cell that simultaneously adjusts pH and balances state of charge in electrolyte solutions by using cation-selective membranes and oxygen-formation catalysts, allowing for the conversion of water or hydroxide ions to address parasitic reactions without external acids or bases, thereby maintaining efficient operation at lower voltages.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If conventional two-chamber electrochemical balancing cells are used to balance state of charge, then charge imbalance is corrected, but pH fluctuations are not addressed and hydrogen evolution occurs

Engineering Contradiction:
Improvestate of charge balanceVSAvoidpH fluctuations and hydrogen evolution
Core Design Contradiction:
ReliabilityVSObject-generated harmful factors

Solution Approach 1:

The balancing cell is divided into three separate chambers (first chamber with positive electrode, second chamber with negative electrode, third chamber as pH adjustment chamber) separated by ion-exchange membranes. This segmentation allows independent control of state of charge balancing in the first two chambers while pH adjustment occurs separately in the third chamber, preventing hydrogen evolution and pH fluctuations in the electrolyte solutions.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

A third chamber acts as an intermediary pH adjustment chamber between the positive and negative half-cells. This intermediary chamber receives electrolyte solutions needing pH adjustment, performs proton transfer reactions to correct pH imbalances, and returns adjusted electrolyte to the respective half-cells, thereby eliminating the need for direct pH modification in the main electrolyte chambers and preventing harmful side reactions.

Inventive Principle:
Principle #24Intermediary (Mediator)

2Reliability

If external acids or bases are added to adjust pH in conventional systems, then pH balance is restored, but additional parasitic reactions and hydrogen evolution are triggered

Engineering Contradiction:
ImprovepH balanceVSAvoidparasitic reactions and hydrogen evolution
Core Design Contradiction:
ReliabilityVSObject-generated harmful factors

Solution Approach 1:

The third chamber performs self-service pH adjustment by utilizing proton transfer reactions between water and hydroxide ions generated during electrochemical reactions in the first and second chambers. The system automatically corrects pH imbalances through internal electrochemical processes without requiring external acid or base addition, thereby avoiding additional parasitic reactions and hydrogen evolution.

Inventive Principle:
Principle #25Self-service

Solution Approach 2:

The system converts the harmful effect of hydroxide ion accumulation (which causes pH increase and potential hydrogen evolution) into a beneficial mechanism by directing these hydroxide ions to the third chamber where they participate in controlled proton transfer reactions to adjust pH without generating hydrogen gas. The potential harm is transformed into a useful pH balancing function.

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

3Device complexity

If simple two-chamber balancing cells are used, then device complexity is low, but they cannot simultaneously address both state of charge imbalance and pH fluctuations

Engineering Contradiction:
Improvecell structureVSAvoidsimultaneous pH and charge balancing capability
Core Design Contradiction:
Device complexityVSAdaptability or versatility

Solution Approach 1:

The three-chamber electrochemical balancing cell performs multiple functions within a single integrated device: (1) balancing state of charge between positive and negative electrolyte solutions through electrochemical reactions in the first and second chambers, and (2) adjusting pH of electrolyte solutions through proton transfer reactions in the third chamber. This multi-functional design eliminates the need for separate pH adjustment systems while maintaining relatively simple device structure.

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

This approach effectively mitigates the detrimental effects of parasitic reactions by concurrently reducing pH and state of charge imbalances, enhancing the operational efficiency and longevity of flow batteries while reducing energy consumption and hydrogen generation.

Implementation Method 1

a first cation-selective membrane forming a first interface between the first chamber and the third chamber

Methodology Applied
Scientific EffectIon Exchange: Ion Exchange

Implementation Method 2

converting water into oxygen and protons in the second chamber

Methodology Applied
Scientific EffectElectrolysis: Electrolysis

Implementation Method 3

converting hydroxide ions into oxygen and water in the second chamber

Methodology Applied
Scientific EffectOxidation: Oxidation

Implementation Method 4

electrochemical reactions of the active materials that occur inside the two half-cells

Methodology Applied
Scientific EffectRedox Reactions: Redox Reactions

Data Source

PatentEP3449522B1Three-chamber electrochemical balancing cells for simultaneous modification of state of charge and acidity within a flow battery
Publication Date: 2023.08.16 LOCKHEED MARTIN ADVANCED ENERGY STORAGE LLC
  • EP3449522B1 patent drawingFigure 1~2
  • EP3449522B1 patent drawingFigure 3
  • EP3449522B1 patent drawingFigure 4

AI summary

Parasitic reactions, such as evolution of hydrogen at the negative electrode, can occur under the operating conditions of flow batteries and other electrochemical systems. Such parasitic reactions can undesirably impact operating performance by altering the pH and/or state of charge of one or both electrolyte solutions in a flow battery. Electrochemical balancing cells can allow adjustment of electrolyte solutions to take place. Electrochemical balancing cells suitable for placement in fluid communication with both electrolyte solutions of a flow battery can include: a first chamber containing a first electrode, a second chamber containing a second electrode, a third chamber disposed between the first chamber and the second chamber, a cation- selective membrane forming a first interface between the first chamber and the third chamber, and a bipolar membrane, a cation-selective membrane, or a membrane electrode assembly forming a second interface between the second chamber and the third chamber.