Flash Sintering Nanocrystalline Zirconia Electrolytes

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Solution Overview

Problem

Current methods for manufacturing self-supporting, dense, and thin ceramic materials based on zirconium oxides or cerium oxide for solid oxide fuel cells face challenges in achieving the necessary mechanical strength and low thickness, as existing techniques require high-temperature sintering that can damage metal supports and result in insufficiently dense materials with inadequate mechanical stability.

Innovation Solution

The use of nanocrystalline powders with specific microstructural characteristics, combined with the flash sintering technique, allows for the production of extremely thin, dense, and mechanically strong ceramic materials by applying pressure and temperature in a controlled manner, enabling the creation of self-supporting electrolytes with reduced thickness and high surface area.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If traditional tape casting or screen printing techniques are used to deposit ceramic electrolyte on metal support, then the ceramic layer can be formed, but high temperature sintering (1600°C) is required which the metal support cannot withstand

Engineering Contradiction:
Improveceramic densityVSAvoidsintering temperature
Core Design Contradiction:
Manufacturing precisionVSTemperature

Solution Approach 1:

The patent changes the sintering temperature parameter from traditional 1600°C to a lower range of 900-1100°C, making the process compatible with metal supports. This is achieved by using nanocrystalline powder with specific characteristics (crystallite size 5-50 nm, agglomerate size 0.5-20 μm, specific surface 20-100 m²/g) that enable densification at lower temperatures through flash sintering

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent replaces traditional mechanical sintering methods with flash sintering technology, which uses electrical current to rapidly heat and densify the ceramic material in a controlled manner, achieving high density without requiring extreme temperatures that would damage the metal support

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

2Reliability

If the thickness of the ceramic electrolyte is reduced to improve electrical performance, then the electrical resistance decreases, but the mechanical strength becomes insufficient

Engineering Contradiction:
Improveelectrical performanceVSAvoidmechanical strength
Core Design Contradiction:
ReliabilityVSStrength

Solution Approach 1:

The patent uses composite nanocrystalline structures with controlled agglomeration, where nanoscale crystallites (5-50 nm) form agglomerates (0.5-20 μm) that provide both the thin thickness needed for low electrical resistance and the structural integrity for mechanical strength. The specific surface area (20-100 m²/g) ensures sufficient bonding area for mechanical stability

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The patent creates local density variations through controlled agglomeration, where dense nanocrystalline regions provide mechanical strength while maintaining overall thin thickness. The hierarchical structure allows different regions to fulfill different functions: nanocrystallites for density, agglomerates for strength, and controlled porosity for flexibility

Inventive Principle:
Principle #3Local quality

3Quantity of substance

If extremely thin ceramic materials are produced to reduce weight and cost, then the quantity of ceramic material decreases, but achieving sufficient mechanical stability becomes difficult

Engineering Contradiction:
Improveceramic material quantityVSAvoidmechanical stability
Core Design Contradiction:
Quantity of substanceVSStability of the object's composition

Solution Approach 1:

The patent changes the microstructural parameters of the ceramic material, specifically controlling crystallite size (5-50 nm), agglomerate size (0.5-20 μm), and specific surface area (20-100 m²/g), which enable the production of mechanically stable thin materials with reduced ceramic quantity

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent performs preliminary preparation of nanocrystalline powder with specific microstructural characteristics before sintering, ensuring that the material has the necessary properties for mechanical stability even at reduced thickness. The powder is pre-characterized and controlled to achieve the desired final product properties

Inventive Principle:
Principle #10Preliminary action

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 method enables the production of ceramic materials with porosity rates less than 4%, achieving mechanical stability and impermeability, suitable for use as solid electrolytes in fuel cells and high temperature electrolysis cells, while reducing manufacturing costs and enabling mass production of ceramic objects with planar configurations.

Implementation Method 1

The use of nanocrystalline powders with specific microstructural characteristics, combined with the flash sintering technique, allows for the production of extremely thin, dense, and mechanically strong ceramic materials by applying pressure and temperature in a controlled manner

Methodology Applied
Scientific EffectFlash sintering: Sintering

Implementation Method 2

The use of nanocrystalline powders with specific microstructural characteristics, combined with the flash sintering technique, allows for the production of extremely thin, dense, and mechanically strong ceramic materials by applying pressure and temperature in a controlled manner

Methodology Applied
Scientific EffectCompression: Compression

Data Source

PatentEP2443075B1Production of self-supporting ceramic materials having a reduced thickness and containing metal oxides
Publication Date: 2016.12.07 ELECTRICITE DE FRANCE
  • EP2443075B1 patent drawingFigure 1

AI summary

The invention relates to a method for producing a ceramic material containing metal oxide, including the following consecutive steps consisting in: (a) supplying a flash-sintering device with a nanocrystalline powder comprising crystallites and crystallite agglomerates of a material having formula Zr1-XMxO2, wherein M is selected from yttrium, scandium and cerium, or Ce1-XM'XO2 wherein M' is selected from gadolinium, scandium, samarium and yttrium, in which x is between 0 and 0.2, said powder having an average crystallite size of between 5 and 50 nm, an average crystallite-agglomerate size of between 0.5 and 20 μm, and a specific surface area of between 20 and 100 m2/g; and (b) flash-sintering said powder by applying a pressure of between 50 to 150 MPa at a temperature of between 850° C and 1400° C for a period of 5 to 30 minutes.