Ruthenium Cathode Catalyst Layer for Low Hydrogen Overvoltage

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Solution Overview

Problem

Current hydrogen generating cathodes for electrolysis lack sufficient low hydrogen overvoltage, resistance against reverse current, and stability of the catalyst layer, leading to high energy consumption and reduced durability.

Innovation Solution

A cathode with a catalyst layer containing ruthenium (Ru) where the ratio of specific X-ray photoelectron spectroscopic peak intensities and crystal orientations is optimized, forming ruthenium hydroxide and oxide structures that enhance catalyst activity and reverse current resistance, using a conductive substrate like nickel with additional components like rare earth elements and metals to stabilize the layer.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Loss of energy

If conventional catalyst layers (nickel, nickel oxide, platinum group metals) are used on hydrogen generating cathodes, then the cathode can perform hydrogen generation, but the hydrogen overvoltage is not sufficiently low and the catalyst layer stability is poor

Engineering Contradiction:
Improvehydrogen overvoltageVSAvoidcatalyst layer stability
Core Design Contradiction:
Loss of energyVSReliability

Solution Approach 1:

The invention uses a composite catalyst layer containing ruthenium oxide and rare earth metal oxides (such as gadolinium oxide, terbium oxide, or dysprosium oxide) in specific ratios. This composite structure combines the catalytic activity of ruthenium oxide with the stabilizing effect of rare earth metals, achieving both low hydrogen overvoltage and long-term operational stability. The rare earth metals prevent ruthenium oxide dissolution during electrolysis while maintaining catalytic function.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The invention optimizes specific parameters including the atomic ratio of rare earth metal to ruthenium (0.01-1.0, preferably 0.05-0.5), the crystal structure of ruthenium oxide (preferably RuO2 with rutile structure), and the surface area of the catalyst layer (5-50 m²/g). These parameter optimizations ensure both low overvoltage and resistance against reverse current.

Inventive Principle:
Principle #35Parameter changes

2Productivity

If the cathode operates at high current density to improve productivity, then hydrogen generation efficiency increases, but the catalyst layer becomes unstable and dissolves

Engineering Contradiction:
Improvehydrogen generation efficiencyVSAvoidcatalyst layer durability
Core Design Contradiction:
ProductivityVSReliability

Solution Approach 1:

The rare earth metal oxides are incorporated into the catalyst layer beforehand to prevent ruthenium oxide dissolution before it occurs during high-current-density operation. The rare earth metals form a protective matrix that stabilizes the ruthenium oxide structure during electrolysis, cushioning against the dissolving effect that would otherwise occur at high current densities.

Inventive Principle:
Principle #11Beforehand cushioning (Prior cushioning)

3Ease of operation

If the cathode is used after electrolysis cessation, reverse current causes catalyst dissolution and performance degradation

Engineering Contradiction:
Improveresistance against reverse currentVSAvoidcatalyst layer stability
Core Design Contradiction:
Ease of operationVSReliability

Solution Approach 1:

The invention converts the harmful reverse current effect into a beneficial stabilization mechanism. The rare earth metal oxides have appropriate electrochemical potentials that allow them to remain stable during reverse current flow, while the ruthenium oxide maintains its catalytic activity. This combination transforms the reverse current condition from a harmful dissolving effect into a manageable operational parameter.

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 cathode achieves low hydrogen overvoltage and improved resistance against reverse current, reducing energy consumption and extending the catalyst layer's lifespan, making it suitable for long-term use in electrolysis processes.

Implementation Method 1

a catalyst layer containing a ruthenium (Ru) element, at least one or more elements selected from the elements having atomic numbers of 64 to 71, and at least one or more elements selected from the elements having atomic numbers of 21 to 30

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 2

used for the electrolysis of water or an aqueous alkali metal compound solution

Methodology Applied
Scientific EffectElectrolysis: Electrolysis

Implementation Method 3

the ratio of the maximum intensity of a Ru 3d 5/2 peak appearing between 281.4 eV and 282.4 eV to the maximum intensity of a Ru 3d 5/2 peak appearing between 280.0 eV and 281.0 eV, in an X-ray photoelectron spectroscopic measurement is 0.45 or more

Methodology Applied
Scientific EffectX-ray photoelectron spectroscopy: X-Ray

Data Source

PatentEP3239361B1Electrolysis cathode and manufacturing method therefor, and electrolysis tank
Publication Date: 2020.12.16 ASAHI KASEI KOGYO KABUSHIKI KAISHA
  • EP3239361B1 patent drawingFigure 1
  • EP3239361B1 patent drawingFigure 2
  • EP3239361B1 patent drawingFigure 3

AI summary

Provided is a cathode for electrolysis comprising a conductive substrate and a Ru element-containing catalyst layer on the conductive substrate, wherein in the catalyst layer, the ratio of the maximum intensity of the Ru 3d 5/2 peak appearing between 281.4 eV and 282.4 eV to the maximum intensity of the Ru 3d 5/2 peak appearing between 280.0 eV and 281.0 eV, in an X-ray photoelectron spectroscopic measurement is 0.45 or more.