Tin Oxide Doped Protective Layer for Electrode Durability

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Solution Overview

Problem

Existing electrodes for oxygen evolution in metal electrowinning processes face challenges such as limited operational duration and noble metal leaching, particularly with iridium-containing catalytic coatings, which require a compromise between thickness for longevity and overpotential reduction, and external protective layers offer limited effectiveness with increased operating voltage.

Innovation Solution

A valve metal substrate electrode with a coating comprising a mixture of tin oxides and doping elements like bismuth, antimony, or tantalum, combined with a catalytic layer of platinum group metals like iridium and ruthenium, where the protective layer is either internal or external to prevent corrosion and noble metal release, allowing for higher thickness without detrimental effects on conductivity or potential.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Duration of action of stationary object

If the thickness of protective intermediate layers based on valve metal oxides is increased to extend operational lifetime, then the electrode durability is improved, but the electric conductivity decreases and operating voltage increases

Engineering Contradiction:
Improveoperational lifetimeVSAvoidoperating voltage
Core Design Contradiction:
Duration of action of stationary objectVSLoss of energy

Solution Approach 1:

The invention changes the compositional parameters of the protective layer by incorporating specific doping elements (bismuth, antimony, or tantalum) at controlled concentrations (0.1-5 wt%) into the tin oxide matrix. This compositional modification enables the layer to maintain high electric conductivity even at greater thicknesses (1-10 μm), thereby extending operational lifetime without proportionally increasing operating voltage

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention creates a composite protective layer combining tin oxide as the base material with doping elements (bismuth, antimony, or tantalum) that enhance electrical conductivity. This composite structure allows the layer to simultaneously provide corrosion protection and maintain low resistance, resolving the contradiction between thickness for durability and conductivity for low operating voltage

Inventive Principle:
Principle #40Composite materials

2Power

If iridium-containing catalytic coatings are applied to reduce oxygen evolution overpotential, then catalytic activity is improved, but noble metal leaching into the electrolyte increases during start-up phase

Engineering Contradiction:
Improvecatalytic activityVSAvoidnoble metal leaching
Core Design Contradiction:
PowerVSLoss of substance

Solution Approach 1:

The invention introduces a protective layer comprising tin oxide doped with bismuth, antimony, or tantalum as an intermediary barrier between the iridium-containing catalytic coating and the electrolyte. This intermediate layer prevents direct contact between the noble metal catalyst and the corrosive electrolyte, thereby reducing leaching during the start-up phase while preserving the catalytic activity of the iridium oxide

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The invention modifies the chemical and physical parameters of the protective layer through doping with specific elements (bismuth, antimony, or tantalum) at optimized concentrations. These parameter changes enhance the layer's resistance to noble metal leaching while maintaining sufficient ionic conductivity to support high catalytic activity at the electrode surface

Inventive Principle:
Principle #35Parameter changes

3Loss of substance

If external protective layers are applied to prevent noble metal release, then noble metal retention is improved, but operating voltage increases due to limited effectiveness and added resistance

Engineering Contradiction:
Improvenoble metal releaseVSAvoidoperating voltage
Core Design Contradiction:
Loss of substanceVSLoss of energy

Solution Approach 1:

The invention optimizes the parameters of the protective layer by doping tin oxide with bismuth, antimony, or tantalum at specific concentrations (0.1-5 wt%). This compositional tuning enhances both the protective effectiveness against noble metal release and the electrical conductivity, thereby reducing the operating voltage penalty compared to conventional protective layers

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 solution significantly enhances operational duration and reduces noble metal release during start-up, maintaining high catalytic activity and low anodic potential, as demonstrated by experimental results showing improved performance compared to traditional titanium-tantalum oxide protective layers.

Implementation Method 1

the protective layer as described has no appreciable catalytic activity, being instead suitable for being combined with a catalytic layer containing noble metal oxides, the latter constituting the active component deputed to decrease the overpotential of the oxygen evolution reaction

Methodology Applied
Scientific EffectCorrosion resistance:

Implementation Method 2

a catalytic layer of platinum group metals like iridium and ruthenium, where the protective layer is either internal or external to prevent corrosion and noble metal release

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 3

allowing for higher thickness without detrimental effects on conductivity or potential

Methodology Applied
Scientific EffectElectrical conduction: Conduction (electrical)

Implementation Method 4

an electrode suitable for oxygen evolution in electrolytic processes

Methodology Applied
Scientific EffectElectrochemical reaction: Electrolysis

Implementation Method 5

the latter constituting the active component deputed to decrease the overpotential of the oxygen evolution reaction

Methodology Applied
Scientific EffectCatalysis: Catalysis

Data Source

PatentUS10407784B2Electrode for electrolytic processes
Publication Date: 2019.09.10 INDUSTRIE DE NORA SPA

AI summary

An electrode on valve metal substrate suitable for the evolution of oxygen in electrolytic processes is provided with a coating having a catalytic layer containing platinum group metals and one or more protective layers based on tin oxide modified with a doping element selected from bismuth, antimony or tantalum and with a small amount of ruthenium. The electrode is useful in processes of non-ferrous metal electrowinning.