Gradient Copper Oxide Fuel Gas Electrode for Poisoning Resistance

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Solution Overview

Problem

Fuel gas electrodes, particularly those containing nickel, suffer from redox instability and poisoning by sulfur compounds and hydrocarbons, leading to performance degradation and reduced durability in fuel cells and electrolytic cells.

Innovation Solution

A method involving the diffusion of copper oxide into nickel oxide within a fuel gas electrode, creating a gradient with higher copper content on the surface and reducing the need for multiple infiltration steps, thereby enhancing resistance to poisoning and maintaining performance across temperature ranges.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If nickel is used as the primary material in fuel gas electrodes, then good electronic conductivity and network formation with YSZ are achieved, but redox instability and poisoning by sulfur compounds and hydrocarbons occur leading to performance degradation

Engineering Contradiction:
Improveelectrode stabilityVSAvoidpoisoning by sulfur compounds and hydrocarbons
Core Design Contradiction:
ReliabilityVSObject-affected harmful factors

Solution Approach 1:

The patent applies a copper-containing layer specifically to the surface region of the nickel-based fuel gas electrode, creating a gradient structure where copper concentration is highest at the surface and decreases toward the bulk. This local modification protects the electrode surface from poisoning by sulfur compounds and hydrocarbons while preserving the bulk nickel's good electronic conductivity and network formation properties.

Inventive Principle:
Principle #3Local quality

Solution Approach 2:

The patent creates a composite electrode structure combining nickel-based material with copper-containing compounds. The copper forms a protective surface layer that reduces poisoning effects, while the nickel bulk maintains electronic conductivity. This composite approach leverages the complementary strengths of both materials to resolve the contradiction between stability and resistance to harmful factors.

Inventive Principle:
Principle #40Composite materials

2Manufacturing precision

If multiple infiltration steps are used to introduce copper into the electrode, then copper distribution is improved, but processing complexity and time increase

Engineering Contradiction:
Improvecopper distributionVSAvoidprocessing steps
Core Design Contradiction:
Manufacturing precisionVSDevice complexity

Solution Approach 1:

The patent applies a copper-containing layer to the surface of the electrode before final sintering, establishing the desired copper distribution pattern in advance. The subsequent sintering process then diffuses copper from the surface layer into the bulk material, achieving uniform distribution without requiring multiple infiltration steps. This preliminary application of copper eliminates the need for repeated processing.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The patent replaces multiple mechanical infiltration operations with a single surface application followed by thermal diffusion. Instead of repeatedly introducing copper through infiltration, the process uses thermal energy to drive copper diffusion from the pre-applied surface layer into the electrode bulk, simplifying the manufacturing process while achieving the desired copper distribution.

Inventive Principle:
Principle #28Mechanics substitution (Replace mechanical system)

3Manufacturing precision

If high-temperature sintering is used to process the electrode, then good densification and microstructure are achieved, but carbon fiber formation from methane increases causing pore filling and cell breakage

Engineering Contradiction:
ImprovedensificationVSAvoidcarbon fiber formation
Core Design Contradiction:
Manufacturing precisionVSObject-generated harmful factors

Solution Approach 1:

The patent converts the potentially harmful effect of high-temperature processing into a beneficial outcome by using the sintering heat to drive copper diffusion from the surface layer into the bulk electrode. This copper enrichment at high temperature protects against carbon fiber formation during operation, transforming the high-temperature processing step from a source of harm into a protective mechanism.

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

Solution Approach 2:

The patent modifies the chemical composition parameter of the electrode surface by introducing copper-containing compounds before sintering. This compositional change alters the electrode's behavior during high-temperature processing and operation, suppressing carbon fiber formation from methane while maintaining the densification benefits of high-temperature sintering.

Inventive Principle:
Principle #35Parameter changes

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 method significantly reduces poisoning symptoms and improves durability by ensuring copper is only present where nickel is, allowing for effective operation in both medium and high-temperature applications without the need for complex high-temperature processing or multiple infiltration steps.

Implementation Method 1

the diffusion of copper oxide into nickel oxide within a fuel gas electrode, creating a gradient with higher copper content on the surface

Methodology Applied
Scientific EffectDiffusion: Diffusion

Implementation Method 2

subject it to a heat treatment (sintering step). The copper diffuses at least partially into the nickel-containing electrode

Methodology Applied
Scientific EffectThermal diffusion: Diffusion

Data Source

PatentEP3697944B1Fuel gas electrode and method for producing a fuel gas electrode
Publication Date: 2023.07.12 FORSCHUNGSZENTRUM JULICH GMBH
  • EP3697944B1 patent drawingFigure 1~2

AI summary

The invention relates to a substrate-supported fuel gas electrode, comprising an electrode substrate and an electrode layer arranged thereon, the electrode layer comprising an ion conductor and nickel oxide. The invention is characterized in that at least the electrode layer additionally comprises copper oxide with a content of at least 2 % by weight, and in that the copper oxide is present as a gradient in the electrode layer. In the method according to the invention for producing a fuel gas electrode a copper-containing layer is applied to the nickel-comprising electrode layer arranged on the electrode carrier. The layer composite is then subjected to heat treatment at more than 900°C, wherein copper diffuses at least partially from the copper-containing layer into the nickel of the electrode layer. The copper-containing layer used may comprise elemental copper, monovalent or divalent copper oxide, and also additionally an ion conductor having a mass fraction of at most 95 % by weight, preferably between 5 and 50 % by weight.