Mixed Hydroxide Precipitation with Coaxial Ammonia Feed Control

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Solution Overview

Problem

Existing lithium ion batteries have limitations in energy density and cycling stability due to the properties of their cathode materials, particularly the stoichiometry, morphology, and surface characteristics of the electrode materials, which affect the lithiation process and calcination temperature sensitivity.

Innovation Solution

A process for precipitating a mixed hydroxide of Ni, Co, and Mn, optionally with Al, Mg, Zr, or Ti, using a stirred vessel with coaxial inlets for introducing ammonia and transition metal salts, allowing for controlled pH and ammonia-to-metal ratios, resulting in precursors with specific particle sizes and structures that enhance volumetric energy density and cycling stability.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If conventional precipitation methods are used to prepare cathode materials, then the basic material properties are achieved, but the volumetric energy density and cycling stability are insufficient

Engineering Contradiction:
Improvecycling stabilityVSAvoidprecipitation process control
Core Design Contradiction:
ReliabilityVSEase of manufacture

Solution Approach 1:

The precipitation process is segmented into multiple stages with different pH values and ammonia-to-metal ratios. The patent applies multi-stage precipitation where each stage targets specific particle formation requirements, enabling precise control over particle size distribution and morphology while improving cycling stability and volumetric energy density

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The patent systematically changes multiple parameters including pH value, ammonia-to-metal ratio, temperature, and addition rate during precipitation. By optimizing these parameters across different stages, the process achieves superior particle properties that enhance both cycling stability and volumetric energy density

Inventive Principle:
Principle #35Parameter changes

2Volume of stationary object

If high calcination temperature is used to improve material density, then volumetric energy density increases, but electrochemical properties become more sensitive to temperature variations

Engineering Contradiction:
Improvevolumetric energy densityVSAvoidelectrochemical property stability
Core Design Contradiction:
Volume of stationary objectVSReliability

Solution Approach 1:

The patent performs preliminary optimization of particle size, morphology, and surface properties during the precipitation stage before calcination. By pre-forming particles with optimal characteristics, the subsequent calcination process requires lower temperatures and shorter times, reducing thermal sensitivity while achieving high volumetric energy density

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The patent changes the particle properties parameters (size distribution, surface area, porosity) during precipitation to compensate for reduced calcination severity. This allows achieving high density with milder thermal treatment, thereby maintaining electrochemical property stability

Inventive Principle:
Principle #35Parameter changes

3Area of moving object

If particle size is reduced to increase surface area for better lithiation, then electrochemical performance improves, but particle aggregation and handling difficulties increase

Engineering Contradiction:
Improvespecific surface areaVSAvoidparticle handling
Core Design Contradiction:
Area of moving objectVSEase of operation

Solution Approach 1:

The patent creates particles with specific local characteristics including controlled porosity, surface morphology, and internal structure. These localized quality features enable high surface area particles to maintain good flowability and handling properties by preventing aggregation while preserving electrochemical performance

Inventive Principle:
Principle #3Local quality

Solution Approach 2:

The patent produces composite particle structures with controlled internal porosity and surface characteristics. The composite nature of these particles combines high surface area benefits with improved mechanical properties that facilitate handling and prevent aggregation

Inventive Principle:
Principle #40Composite materials

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 process produces precursors that enable lithium ion batteries with improved volumetric energy density and cycling stability by optimizing particle diameter, porosity, and surface area, reducing the impact of calcination temperature on electrochemical properties.

Implementation Method 1

a process for precipitating a mixed hydroxide of TM wherein TM comprises Ni and at least one of Co and Mn and, optionally, Al, Mg, Zr or Ti from an aqueous solution of salts of such transition metals

Methodology Applied
Scientific EffectPrecipitation: Precipitation

Implementation Method 2

introducing a 1 to 40% by weight aqueous solution of ammonia and an aqueous solution of transition metal salts through at least two inlets into said stirred vessel

Methodology Applied
Scientific EffectMixing:

Data Source

PatentEP4196444B1Process for precipitating a mixed hydroxide
Publication Date: 2024.07.24 BASF SE
  • EP4196444B1 patent drawingFigure 1~2
  • EP4196444B1 patent drawingFigure 3~4
  • EP4196444B1 patent drawingFigure 5

AI summary

Process for precipitating a mixed hydroxide of TM wherein TM comprises Ni and at least one of Co and Mn and, optionally, Al, Mg, Zr or Ti from an aqueous solution of salts of such transition metals or of Al or of Mg, wherein such process is carried out in a stirred vessel and comprises the step of introducing a 10 to 40% by weight aqueous solution of ammonia and an aqueous solution of transition metal salts through at least two inlets into said stirred vessel wherein the distance of the locations of introduction of TM and of ammonia is equal or less than 12 times the hydraulic diameter of the tip of the inlet of the ammonia, and wherein an aqueous solution ofalkali metal hydroxide is added separately from the at least two inlets.