Cathode Active Material Heat Profile for Low-Cobalt Li-Ion Stability

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Solution Overview

Problem

The demand for large-sized, high-capacity, high-energy-density rechargeable lithium batteries has increased, but the supply of cobalt, a key component in existing positive electrode active materials, is limited and costly, and replacing cobalt with manganese and nickel leads to structural instability and reduced lithium ion diffusion.

Innovation Solution

A two-step heat treatment process is applied to a nickel-manganese-based composite oxide, involving a primary heat treatment at 200-350°C to reduce cation mixing and a secondary heat treatment at 800-1000°C to promote lithium ion diffusion and enhance structural stability, using a composition represented by Li a1 Ni x1 Mn y1 M 1< z1 M 2< O 2-b1 X b1 , where M 1< and M 2< are selected elements and X is F or S.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Ease of manufacture

If cobalt is replaced with nickel and manganese to reduce cost and increase supply availability, then manufacturing cost and material availability improve, but structural stability and lithium ion diffusion deteriorate

Engineering Contradiction:
Improvemanufacturing cost and material availabilityVSAvoidstructural stability and lithium ion diffusion
Core Design Contradiction:
Ease of manufactureVSReliability

Solution Approach 1:

The patent applies parameter changes by implementing a two-step heat treatment process with specific temperature ranges (first step: 200-350°C, second step: 800-1000°C) to optimize the crystal structure of cobalt-free lithium nickel-manganese oxide. This thermal parameter control reduces cation mixing and enhances structural stability, resolving the deterioration caused by cobalt replacement while maintaining the cost and availability benefits.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent uses composite materials by creating a layered structure of lithium nickel-manganese oxide with controlled stoichiometry (Li a1 Ni x1 Mn y1 M 1< z1 M 2< O 2-b1 X b1 where M 1< and M 2< are selected elements). This composite approach combines nickel and manganese in specific ratios with additional elements to achieve both cost reduction and structural stability, overcoming the limitations of simple substitution.

Inventive Principle:
Principle #40Composite materials

2Quantity of substance

If cobalt content is reduced or eliminated to address supply constraints, then material cost and supply security improve, but capacity and charging-discharging efficiency worsen

Engineering Contradiction:
Improvecobalt contentVSAvoidcapacity and charging-discharging efficiency
Core Design Contradiction:
Quantity of substanceVSProductivity

Solution Approach 1:

The patent employs parameter changes through precise control of heat treatment temperatures (200-350°C followed by 800-1000°C) and atmospheric conditions to optimize the crystal structure of cobalt-free materials. This enhances lithium ion diffusion pathways and reduces cation mixing, thereby improving capacity and charging-discharging efficiency without cobalt.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent applies local quality by introducing specific elements (M 1< and M 2< from selected groups) at controlled concentrations (0≤z1≤0.05, 0≤w1≤0.05) into specific positions within the crystal structure. This localized compositional optimization enhances lithium ion diffusion and electrochemical performance in the cobalt-free system.

Inventive Principle:
Principle #3Local quality

3Speed

If heat treatment temperature is increased to promote lithium ion diffusion, then lithium ion diffusion and capacity improve, but cation mixing and structural instability worsen

Engineering Contradiction:
Improvelithium ion diffusionVSAvoidcation mixing and structural stability
Core Design Contradiction:
SpeedVSStability of the object's composition

Solution Approach 1:

The patent applies segmentation by dividing the heat treatment process into two distinct steps with different temperature ranges and objectives. The first step (200-350°C) addresses lower-temperature transformations, while the second step (800-1000°C) promotes lithium ion diffusion. This segmented approach prevents excessive cation mixing that would occur in a single high-temperature step while still achieving enhanced lithium ion diffusion.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The patent uses preliminary action by performing the first heat treatment step (200-350°C) before the second step (800-1000°C). This preliminary treatment prepares the crystal structure for the subsequent high-temperature treatment, reducing cation mixing early in the process and creating a more stable framework that can withstand the higher temperatures needed for enhanced lithium ion diffusion.

Inventive Principle:
Principle #10Preliminary 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 process increases capacity, improves charging and discharging efficiency, and enhances high-temperature cycle-life characteristics by reducing cation mixing and voids, resulting in improved structural stability and lithium ion diffusion.

Implementation Method 1

applying a primary heat treatment at about 200 °C to about 350 °C

Methodology Applied
Scientific EffectHeat treatment: Heat Treatment

Implementation Method 2

applying a secondary heat treatment at about 800 °C to about 1000 °C

Methodology Applied
Scientific EffectHeat treatment: Heat Treatment

Implementation Method 3

promotes diffusion of lithium ions

Methodology Applied
Scientific EffectDiffusion: Diffusion

Data Source

PatentEP4574769A1Positive active materials, preparation methods thereof, positive electrodes, and rechargeable lithium batteries
Publication Date: 2025.06.25 SAMSUNG SDI CO LTD
  • EP4574769A1 patent drawingFigure 1
  • EP4574769A1 patent drawingFigure 2
  • EP4574769A1 patent drawingFigure 3

AI summary

A method of preparing a positive electrode active material, a positive electrode and a rechargeable lithium battery are provided. The method of preparing the positive electrode active material includes mixing nickel-manganese-based composite hydroxide and a lithium raw material and subjecting them to primary heat treatment at about 200 °C to about 350 °C and secondary heat treatment at about 800 °C to about 1000 °C.