ALD Ceria Diffusion Barrier for SOFC Cathode

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Solution Overview

Problem

Current methods for manufacturing cathode diffusion barrier layers in solid oxide fuel cells (SOFC) face challenges such as undesirable reactions with zirconia electrolytes, limited ion conductivity, and high production costs, particularly at lower temperatures, which affect the efficiency and longevity of SOFC.

Innovation Solution

The method involves depositing a dense ceria diffusion barrier layer using Atomic Layer Deposition (ALD) on a sintered half-cell, followed by applying a cobaltite-based cathode layer and heating between 1000-1200 °C, utilizing lanthanide diketonates as precursors and ozone or water for self-limiting growth, to form a continuous and efficient barrier.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If conventional screen printing and sintering methods are used to produce ceria diffusion barrier layers, then thick porous layers (0.5-5 micrometers) are formed with some reaction to substrate, but manufacturing cost and complexity increase

Engineering Contradiction:
Improvelayer densityVSAvoidmanufacturing cost
Core Design Contradiction:
Manufacturing precisionVSEase of manufacture

Solution Approach 1:

The patent replaces the mechanical screen printing and high-temperature sintering process with Atomic Layer Deposition, a vapor-phase deposition technique. This substitution achieves dense barrier layers at lower temperatures (400-800°C) with better control over layer thickness and density, reducing manufacturing complexity and cost while improving layer quality.

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

Solution Approach 2:

The patent changes the deposition temperature parameter from conventional sintering temperatures (1200-1400°C) to lower ALD temperatures (400-800°C), which enables formation of dense barrier layers without the need for expensive high-temperature equipment and reduces energy consumption, thereby improving ease of manufacture.

Inventive Principle:
Principle #35Parameter changes

2Reliability

If Pulsed Laser Deposition or Magnetron Sputtering are used to deposit ceria layers at lower temperatures, then columnar structure is formed avoiding electrolyte reactions, but production cost increases and scalability to large area is difficult

Engineering Contradiction:
Improvechemical stabilityVSAvoidproduction scalability
Core Design Contradiction:
ReliabilityVSProductivity

Solution Approach 1:

The patent replaces expensive Pulsed Laser Deposition or Magnetron Sputtering equipment with ALD technology, which uses simple vapor-phase precursors and can be scaled to large areas more easily. This substitution maintains chemical stability through lower temperature deposition while improving productivity and scalability.

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

Solution Approach 2:

The ALD process used in the patent is a universal deposition technique that can deposit conformal layers on complex geometries and large areas, making it more scalable than specialized techniques like PLD or sputtering. The same ALD equipment can produce both dense barrier layers and functional cathode layers, improving overall production efficiency.

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

3Reliability

If dense ceria diffusion barrier layers are formed, then better contact with electrolyte for ion transfer is achieved, but manufacturing complexity increases due to additional processing steps

Engineering Contradiction:
Improveion transfer efficiencyVSAvoidprocessing steps
Core Design Contradiction:
ReliabilityVSDevice complexity

Solution Approach 1:

The patent merges the deposition of the ceria diffusion barrier layer and the cathode layer into a single ALD process sequence, where the same equipment and methodology are used for both layers. This integration simplifies manufacturing complexity while ensuring dense, well-contacted layers for efficient ion transfer.

Inventive Principle:
Principle #5Merging (Combining)

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 results in a denser, more efficient cathode diffusion barrier with lower electrical resistivity, improved diffusion resistance, and cost-effective large-area production, enhancing the longevity and efficiency of SOFC.

Implementation Method 1

depositing a dense ceria diffusion barrier layer using Atomic Layer Deposition (ALD) on a sintered half-cell

Methodology Applied
Scientific EffectAtomic Layer Deposition: Chemical Vapour Deposition

Implementation Method 2

The ALD process deposits thin layers of solid materials using two or more different vapor phase precursors

Methodology Applied
Scientific EffectVapor phase deposition: Physical Vapour Deposition

Implementation Method 3

heating between 1000-1200 °C, utilizing lanthanide diketonates as precursors and ozone or water for self-limiting growth, to form a continuous and efficient barrier

Methodology Applied
Scientific EffectSintering: Sintering

Data Source

PatentEP3099836B1A method of producing SOFC cathode diffusion barrier layer and a sofc
Publication Date: 2022.04.20 ELCOGEN
  • EP3099836B1 patent drawingFigure 1
  • EP3099836B1 patent drawingFigure 2
  • EP3099836B1 patent drawingFigure 3

AI summary

The invention provides an improved method for producing cathode diffusion barrier layer, and a SOFC with high efficiency and longevity. It comprises depositing a pure ceria or aliovalently doped ceria layer, by ALD, on the electrolyte layer of the sintered half cell. The surface of a electrolyte onto which film is to be deposited is exposed to a dose of vapor from one or more lanthanide first precursors. Any excess of unreacted vapor from that precursor is removed. Next, a vapor dose of the second precursor is brought to the surface and allowed to react. A second purge completes the ALD cycle, which is repeated to build up thicker films. This ceria layer forms a cathode diffusion barrier layer on top of which a cobaltite based cathode layer is applied by screenprinting, and the cathode diffusion barrier layer and cathode layer are heated together to form a SOFC.