Cobalt Hydroxide Carbonate Precursor for Lithium-Ion Battery Cathodes

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Solution Overview

Problem

Current methods for producing cobalt-based cathode materials for lithium-ion batteries face challenges in achieving high energy density, electrochemical stability, and cost-effectiveness due to issues with particle size distribution, sodium impurities, and high processing temperatures, which affect the electrochemical performance and packing density of the materials.

Innovation Solution

A cobalt hydroxide carbonate compound with a malachite-rosasite mineral structure is used as a precursor, doped with elements like Al, Mn, and Mg, produced through a Na2CO3 precipitation process at elevated temperatures with CO2 evacuation, allowing for a spherical morphology and homogeneous dopant distribution, which enhances energy density and reduces sodium impurities.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Volume of moving object

If high sintering temperature is used to increase particle size and packing density, then volumetric energy density is improved, but process cost and energy consumption increase

Engineering Contradiction:
Improvevolumetric energy densityVSAvoidsintering energy consumption
Core Design Contradiction:
Volume of moving objectVSUse of energy by stationary object

Solution Approach 1:

The patent applies preliminary action by pre-forming spherical cobalt precursor particles with controlled size and morphology before the sintering process. This pre-shaping allows the final sintering to occur at lower temperatures since the particle size and packing density are already optimized in the precursor, eliminating the need for high-temperature sintering to achieve the desired particle characteristics.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The patent changes the parameters of the cobalt precursor (particle size, morphology, density) through controlled precipitation processes before sintering. By adjusting precipitation conditions such as pH, temperature, and additives, the precursor particles are formed with optimal characteristics that translate to high packing density in the final product without requiring high sintering temperatures.

Inventive Principle:
Principle #35Parameter changes

2Manufacturing precision

If high sintering temperature is used to achieve target particle size, then particle size distribution is improved, but electrochemical performance deteriorates due to high Li to Co stoichiometry

Engineering Contradiction:
Improveparticle size distributionVSAvoidelectrochemical performance
Core Design Contradiction:
Manufacturing precisionVSReliability

Solution Approach 1:

The patent uses preliminary action by forming spherical cobalt precursor particles with precise size control through precipitation processes before sintering. This pre-formed spherical morphology and controlled particle size distribution are maintained through lower-temperature sintering, preventing the formation of excessive Li2CO3 and maintaining optimal Li to Co stoichiometry for electrochemical performance.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The patent changes the sintering temperature parameter from conventional high temperatures to lower temperatures (900-1000°C), combined with optimized precursor characteristics. This parameter change allows achieving the desired particle size distribution without the harmful side effects of high-temperature sintering on stoichiometry and electrochemical performance.

Inventive Principle:
Principle #35Parameter changes

3Ease of manufacture

If non-shaped cobalt precursor is used to simplify manufacturing, then ease of manufacture is improved, but particle size distribution widens and span increases

Engineering Contradiction:
Improveprecursor processing simplicityVSAvoidparticle size distribution
Core Design Contradiction:
Ease of manufactureVSManufacturing precision

Solution Approach 1:

The patent applies preliminary action by implementing a controlled precipitation process that forms spherical cobalt precursor particles with narrow size distribution before sintering. This pre-shaping step is integrated into the manufacturing process, maintaining simplicity while achieving precise particle size control that would be difficult to obtain through post-processing of non-shaped precursors.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The patent changes the precipitation process parameters (pH, temperature, additives, mixing rate) to control the morphology and size of cobalt precursor particles. By optimizing these parameters, spherical particles with narrow size distribution are formed directly during precipitation, eliminating the need for complex post-processing while maintaining manufacturing simplicity.

Inventive Principle:
Principle #35Parameter changes

4Volume of moving object

If high Li to Co ratio is used during sintering to achieve target particle size, then particle growth is improved, but electrochemical performance deteriorates

Engineering Contradiction:
Improveparticle sizeVSAvoidelectrochemical performance
Core Design Contradiction:
Volume of moving objectVSReliability

Solution Approach 1:

The patent uses preliminary action by pre-forming spherical cobalt precursor particles with controlled size and morphology before sintering. This eliminates the need to use high Li to Co ratios for particle growth, as the particle size is already optimized in the precursor. The sintering process only needs to form the oxide structure, not grow particles, preserving the correct stoichiometry.

Inventive Principle:
Principle #10Preliminary action

5Ease of manufacture

If conventional precipitation process is used to produce cobalt precursor, then manufacturing cost is reduced, but sodium impurity content increases

Engineering Contradiction:
Improveprecipitation process costVSAvoidsodium impurity content
Core Design Contradiction:
Ease of manufactureVSManufacturing precision

Solution Approach 1:

The patent changes the precipitation process parameters, specifically using ammonium carbonate or ammonium bicarbonate instead of sodium carbonate, and optimizing pH control during precipitation. This parameter change effectively reduces sodium impurity content in the cobalt precursor while maintaining the cost-effectiveness and simplicity of the precipitation process.

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 approach results in a high-quality cathode material with improved electrochemical stability, increased energy density, and reduced processing costs by achieving a narrow particle size distribution and effective dopant distribution, while minimizing sodium impurities.

Implementation Method 1

a cobalt based hydroxide carbonate compound which is prepared by a precipitation process using sodium carbonate

Methodology Applied
Scientific EffectPrecipitation: Precipitation

Implementation Method 2

produced through a Na2CO3 precipitation process at elevated temperatures with CO2 evacuation

Methodology Applied
Scientific EffectHeating: Heating

Data Source

PatentEP3592706B1Precursors of cathode materials for a rechargeable lithium ion battery
Publication Date: 2023.06.14 UMICORE(BE)
  • EP3592706B1 patent drawingFigure 1~2
  • EP3592706B1 patent drawingFigure 3~4
  • EP3592706B1 patent drawingFigure 5a

AI summary

A method for manufacturing a cobalt based hydroxide carbonate compound having a malachite-rosasite mineral structure, comprising the steps of: - providing an first aqueous solution comprising a source of Co, - providing a second aqueous solution comprising Na2CO3, - mixing both solutions in a precipitation reactor at a temperature above 70°C, thereby precipitating a cobalt based hydroxide carbonate compound whilst evacuating from the reactor any CO2 formed by the precipitation reaction, wherein the residence time of the compound in the reactor is between 1 and 4 hours, and - recovering the cobalt based hydroxide carbonate compound. The cobalt based hydroxide carbonate compound is used as a precursor of a lithium cobalt based oxide usable as an active positive electrode material in lithium ion batteries.