Electrolytic Cathode Coating for Chlor-Alkali Stability

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Solution Overview

Problem

Industrial electrolytic processes face challenges with cathodic overvoltage, corrosion, and limited tolerance to current inversions in chlor-alkali electrolysis, particularly with nickel cathodes coated with ruthenium oxide or platinum, which suffer from poor adhesion and inadequate stability.

Innovation Solution

A cathode composition featuring a nickel substrate with a dual coating: a palladium-based protection zone and a platinum/ruthenium-based activation zone, where palladium acts as a reversible hydrogen sponge to mitigate current inversions and enhance adhesion, and rare earth elements like praseodymium stabilize the catalysts.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Use of energy by moving object

If nickel cathodes are coated with ruthenium oxide or platinum to reduce cathodic overvoltage, then catalytic activity for hydrogen evolution is improved, but adhesion of the coating to substrate deteriorates

Engineering Contradiction:
Improvecathodic overvoltageVSAvoidcoating adhesion
Core Design Contradiction:
Use of energy by moving objectVSReliability

Solution Approach 1:

The patent applies composite materials by creating a multi-layer coating structure consisting of a nickel substrate, an intermediate adhesion layer containing nickel oxide and ruthenium oxide, and an outer catalytic layer containing platinum or ruthenium. This composite structure resolves the adhesion problem by introducing the intermediate layer that bonds both to the nickel substrate and to the noble metal catalyst layer, while maintaining the catalytic activity of the outer layer for hydrogen evolution.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The patent uses an intermediate layer as a mediator between the nickel substrate and the noble metal catalyst. This intermediate layer, containing nickel oxide and ruthenium oxide, serves as an adhesion promoter that prevents direct contact between the nickel substrate and the catalyst layer, thereby preventing galvanic corrosion and improving coating adhesion while still allowing efficient electron transfer for catalysis.

Inventive Principle:
Principle #24Intermediary (Mediator)

2Use of energy by moving object

If nickel cathodes are coated with ruthenium oxide or platinum to reduce cathodic overvoltage, then catalytic activity for hydrogen evolution is improved, but lifetime and stability in electrolysis conditions deteriorate

Engineering Contradiction:
Improvecathodic overvoltageVSAvoidcathode lifetime
Core Design Contradiction:
Use of energy by moving objectVSDuration of action of stationary object

Solution Approach 1:

The multi-layer composite structure provides both catalytic activity and long-term stability. The outer layer of platinum or ruthenium maintains high catalytic activity for hydrogen evolution, while the intermediate layer of nickel oxide and ruthenium oxide provides structural support and protects the nickel substrate from corrosion in the harsh electrolysis environment, thereby extending cathode lifetime.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The intermediate layer acts as a protective mediator that shields the nickel substrate from direct exposure to the corrosive electrolyte and from potential damage during current inversions. This layer contains nickel oxide and ruthenium oxide which are chemically stable in alkaline conditions, thus protecting the underlying nickel and extending the overall cathode lifetime.

Inventive Principle:
Principle #24Intermediary (Mediator)

3Use of energy by moving object

If nickel cathodes are coated with ruthenium oxide or platinum to reduce cathodic overvoltage, then catalytic activity for hydrogen evolution is improved, but tolerance to current inversions deteriorates

Engineering Contradiction:
Improvecathodic overvoltageVSAvoidcurrent inversion tolerance
Core Design Contradiction:
Use of energy by moving objectVSReliability

Solution Approach 1:

The intermediate layer containing nickel oxide and ruthenium oxide serves as a protective mediator during current inversions. When current direction reverses, this intermediate layer prevents direct galvanic interaction between the nickel substrate and the noble metal catalyst, reducing the severity of damage during inversion events and improving the cathode's tolerance to such accidental conditions.

Inventive Principle:
Principle #24Intermediary (Mediator)

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 exhibits improved catalytic activity, increased durability, and higher tolerance to accidental current inversions, maintaining stable performance and extending operational life in industrial conditions.

Implementation Method 1

palladium acts as a reversible hydrogen sponge to mitigate current inversions

Methodology Applied
Scientific EffectHydrogen absorption: Absorption (physical)

Implementation Method 2

palladium, especially in conjunction with silver, forms hydrides, which are ionised in case of current inversion thereby preventing the cathode potential to be shifted to values high enough to give rise to significant dissolution phenomena of ruthenium and platinum

Methodology Applied
Scientific EffectHydride formation and ionization: Ionisation

Implementation Method 3

a second active zone comprising platinum and/or ruthenium, optionally mixed with a small amount of rhodium, having a catalytic function toward cathodic hydrogen evolution

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 4

the addition of elements like Cr or Pr can preserve the catalyst activity while contributing to the stability thereof

Methodology Applied
Scientific EffectOxidation: Oxidation

Data Source

PatentEP2084308B1Cathode for electrolytic processes
Publication Date: 2016.05.18 INDUSTRIE DE NORA SPA

AI summary

The invention relates to a cathode for electrolytic processes, particularly suitable for hydrogen evolution in chlor-alkali electrolysis, consisting of a nickel substrate provided with a coating comprising a protective zone containing palladium and a physically distinct catalytic activation containing platinum or ruthenium optionally mixed with a highly oxidising metal oxide, preferably chromium or praseodymium oxide.