Metal-Air Battery Cathode Electrocatalyst with Staged Hydrothermal Synthesis

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Solution Overview

Problem

Existing processes for producing cathode electrocatalysts for metal-air batteries result in unsatisfactory service life, as they rely solely on high-temperature hydrothermal reactions which do not adequately enhance the performance and longevity of the batteries.

Innovation Solution

A process involving a low-temperature hydrothermal reaction followed by a high-temperature hydrothermal reaction, where a carbon source suspension and metal source solution are mixed, and then subjected to a heating treatment under a protective atmosphere, to form a precursor that undergoes phase transition, specifically using cobalt, manganese, iron, or nickel sources with nitrogen-doped inorganic carbon sources to create a Co4N crystal phase cathode electrocatalyst.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Duration of action of stationary object

If only high-temperature hydrothermal reaction is used to produce cathode electrocatalyst, then the production process is simple, but the service life of metal-air batteries is unsatisfactory

Engineering Contradiction:
Improveservice life of metal-air batteriesVSAvoidcomplexity of production process
Core Design Contradiction:
Duration of action of stationary objectVSDevice complexity

Solution Approach 1:

The production process is segmented into three distinct stages: low-temperature hydrothermal reaction (70-85°C for 12-24 hours) to form initial precursor, high-temperature hydrothermal reaction (180°C for 12-24 hours) to form second precursor with nitrogen-doped metal species, and heating treatment (200-900°C) to achieve phase transition to Co4N crystal phase. Each stage serves a specific function in building the catalyst structure progressively, improving battery service life through controlled formation of active sites.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The low-temperature hydrothermal reaction performs preliminary action by forming the first precursor with metal species doped on carbon source surface before the high-temperature reaction. This preliminary structuring creates a foundation that enhances the effectiveness of subsequent nitrogen doping and phase transition, ensuring optimal catalyst formation that extends battery service life.

Inventive Principle:
Principle #10Preliminary action

2Duration of action of stationary object

If low-temperature hydrothermal reaction followed by high-temperature hydrothermal reaction is used, then the service life of metal-air batteries is enhanced, but the production process becomes more complex

Engineering Contradiction:
Improveservice life of metal-air batteriesVSAvoidcomplexity of production process
Core Design Contradiction:
Duration of action of stationary objectVSDevice complexity

Solution Approach 1:

The process utilizes parameter changes by transitioning from low-temperature (70-85°C) hydrothermal reaction to high-temperature (180°C) hydrothermal reaction, and finally to heating treatment (200-900°C). Each temperature stage transforms the material structure progressively: low-temperature forms precursor, high-temperature introduces nitrogen doping and creates metal-nitrogen species, and heating treatment achieves the desired Co4N crystal phase, thereby enhancing catalyst performance and battery service life through controlled parameter evolution.

Inventive Principle:
Principle #35Parameter changes

3Reliability

If multiple hydrothermal reactions and heating treatment are performed, then the cathode electrocatalyst performance is improved, but the production time is extended

Engineering Contradiction:
Improveperformance of cathode electrocatalystVSAvoidproduction time
Core Design Contradiction:
ReliabilityVSLoss of time

Solution Approach 1:

The process maintains continuity of useful action through sequential hydrothermal reactions and heating treatment without idle periods. The low-temperature hydrothermal reaction (12-24 hours) continuously forms the first precursor, followed immediately by high-temperature hydrothermal reaction (12-24 hours) to form the second precursor with nitrogen doping, and then heating treatment (1-12 hours) to achieve phase transition. This continuous transformation ensures optimal catalyst formation with Co4N crystal phase, maximizing electrocatalyst performance and reliability while minimizing total production time.

Inventive Principle:
Principle #20Continuity of useful 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

The resulting cathode electrocatalyst enhances the service life and performance of metal-air batteries by maintaining a stable voltage during charge/discharge cycles and extending the battery's operational lifespan.

Implementation Method 1

subjecting the carbon source suspension and the metal source solution to a low-temperature hydrothermal reaction so as to form a first precursor-containing product

Methodology Applied
Scientific EffectHydrothermal reaction:

Implementation Method 2

the metal source from the metal source solution being doped on a surface of the inorganic carbon source from the carbon source suspension to form the first precursor

Methodology Applied
Scientific EffectDoping: Dopants

Implementation Method 3

subjecting the first precursor-containing product and the nitrogen source solution to a high-temperature hydrothermal reaction

Methodology Applied
Scientific EffectHydrothermal reaction:

Implementation Method 4

the nitrogen source from the nitrogen source solution is decomposed to form nitrogen atoms which are further bonded to the metal source on the first precursor

Methodology Applied
Scientific EffectDecomposition: Decomposition (biological)

Implementation Method 5

nitrogen atoms which are further bonded to the metal source on the first precursor so as to form a second precursor

Methodology Applied
Scientific EffectChemical bonding: Chemical Bonding

Implementation Method 6

subjecting the second precursor to a heating treatment under a protective atmosphere, so that the second precursor undergoes a phase transition

Methodology Applied
Scientific EffectPhase transition: Phase Change

Implementation Method 7

the heating treatment being conducted at a temperature ranging from 200°C to 900°C

Methodology Applied
Scientific EffectHeating: Heating

Implementation Method 8

heating treatment under a protective atmosphere, so that the second precursor undergoes a phase transition

Methodology Applied
Scientific EffectSintering: Sintering

Data Source

PatentEP4174992B1Cathode electrocatalyst for metal air batteries and production process thereof
Publication Date: 2023.10.25 NATIONAL KAOHSIUNG UNIVERSITY OF SCIENCE & TECHNOLOGY
  • EP4174992B1 patent drawingFigure 1
  • EP4174992B1 patent drawingFigure 2

AI summary

A process of producing a cathode electrocatalyst for metal-air batteries includes providing a carbon source suspension, a metal source solution, and a nitrogen source solution, subjecting the carbon source suspension and the metal source solution to a low-temperature hydrothermal reaction, subjecting a first precursor-containing product thus formed and the nitrogen source solution to a high-temperature hydrothermal reaction, and subjecting a second precursor thus formed to a heating treatment under a protective atmosphere. A cathode electrocatalyst produced by the process is also disclosed.