Oxyhydroxide Precursor for Nickel-Rich Cathode Materials

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Solution Overview

Problem

Nickel-rich cathode active materials for lithium metal oxides suffer from cation mixing due to the similarity in radii of Ni2+ and Li+ ions, leading to blocked lithium diffusion pathways and reduced performance, and additional processing steps to incorporate nickel in the +3 oxidation state are costly and inefficient.

Innovation Solution

A cathode active material precursor comprising a metal-containing oxyhydroxide with at least 50 mol% nickel in the +3 oxidation state, formed by combining nickel and additional metal compounds with an oxidizing agent and solvent, then heat-treated to minimize cation mixing and enhance lithium diffusion pathways.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Ease of manufacture

If conventional hydroxide precursors (Ni yM1-y(OH)2) are used, then the material can be easily manufactured, but cation mixing occurs between Ni2+ and Li+ ions leading to blocked lithium diffusion pathways

Engineering Contradiction:
Improveease of manufactureVSAvoidlithium diffusion
Core Design Contradiction:
Ease of manufactureVSReliability

Solution Approach 1:

The patent changes the oxidation state parameter of nickel from +2 in conventional hydroxide precursors to +3 in the oxyhydroxide precursor (NiyM1-y(OOH)2). This parameter change creates electrostatic repulsion between Ni3+ and Li+ ions, preventing cation mixing and blocking of lithium diffusion pathways while maintaining ease of manufacture through a modified precipitation process.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent introduces an oxidizing agent as an intermediary substance during the precursor formation process. This oxidizing agent converts Ni2+ to Ni3+ in situ, creating the beneficial electrostatic repulsion effect without requiring separate calcination steps. The oxidizing agent acts as a mediator that transforms the precursor chemistry to achieve both ease of manufacture and improved lithium diffusion.

Inventive Principle:
Principle #24Intermediary (Mediator)

2Reliability

If additional calcination in oxygen-rich environment is performed to incorporate Ni3+, then nickel oxidation state improves, but operating cost increases and capital investment is required

Engineering Contradiction:
Improvenickel oxidation stateVSAvoidoperating cost
Core Design Contradiction:
ReliabilityVSEase of manufacture

Solution Approach 1:

The patent performs the oxidation of nickel to the +3 state during the initial precursor formation process rather than requiring a separate subsequent calcination step. By incorporating the oxidizing agent in the precipitation step, the nickel is pre-oxidized before lithiation, eliminating the need for additional capital-intensive calcination facilities and reducing operating costs while achieving the desired Ni3+ oxidation state.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The patent merges the precursor formation process with the nickel oxidation process by adding the oxidizing agent to the precipitation reaction. This combines two separate operations (precursor synthesis and nickel oxidation) into a single step, eliminating the need for separate calcination equipment and reducing both capital investment and operating costs while achieving Ni3+ incorporation.

Inventive Principle:
Principle #5Merging (Combining)

3Device complexity

If conventional hydroxide precursors are used, then the process is simple, but considerable Ni2+ ions remain blocking lithium diffusion pathways

Engineering Contradiction:
Improveprocess complexityVSAvoidlithium diffusion pathway
Core Design Contradiction:
Device complexityVSReliability

Solution Approach 1:

The patent changes the chemical composition parameter of the precursor from hydroxide (—OH) to oxyhydroxide (—OOH) form with Ni3+. This parameter change fundamentally alters the interaction between nickel and lithium ions, creating electrostatic repulsion that prevents Ni2+ from blocking lithium diffusion pathways. The process complexity increases only minimally by adding an oxidizing agent to the existing 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 oxyhydroxide form of the precursor reduces cation mixing, maintaining nickel ions in the +3 state during calcination, thereby improving the performance of the resulting lithium metal oxide by maintaining open lithium diffusion pathways and enhancing capacity utilization.

Implementation Method 1

At least 50 mol. % of the nickel of the metal-containing oxyhydroxide has an oxidation state of +3

Methodology Applied
Scientific EffectOxidation: Oxidation

Implementation Method 2

further calcination of the nickel-containing hydroxide precursors in an oxygen rich environment

Methodology Applied
Scientific EffectCalcination: Heat Treatment

Implementation Method 3

the oxyhydroxide form (—OOH) of the cathode active material precursor incorporates nickel ions in a +3 oxidation state thereby minimizing cation mixing with lithium

Methodology Applied
Scientific EffectCation mixing prevention:

Data Source

PatentUS11508962B2Battery materials scale-up and processes
Publication Date: 2022.11.22 UT BATTELLE LLC

AI summary

A cathode active material precursor for a lithium metal oxide is provided. The cathode active material precursor comprises a metal-containing oxyhydroxide. The metal-containing oxyhydroxide comprises nickel and an additional metal. At least 50 mol. % of the nickel of the metal-containing oxyhydroxide has an oxidation state of +3. A method of forming a cathode active material precursor is also provided. The method comprises combining a nickel-containing compound, an additional metal-containing compound, an oxidizing agent, and a solvent to form a solution. The method further comprises exposing the solution to heat at a temperature of from about 30° C. to about 90° C. to form a precipitate comprising the metal-containing oxyhydroxide.