Core-Shell Lithium Manganese Oxide Cathode Coating

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Solution Overview

Problem

Existing methods for surface coating spinel LiMn2O4 to enhance cycling stability in lithium-ion batteries result in non-uniform and discontinuous coating layers, leading to unsatisfactory performance at elevated temperatures.

Innovation Solution

A process involving heat-treatment of spinel LiMxMn2-xO4 particles with P2O5 to form a continuous and uniform lithium manganese phosphate shell layer, reducing the contact area with the electrolyte and preventing Mn dissolution.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If sol-gel method or precipitation method is used for surface coating, then the spinel surface is coated with metal oxide particles, but the coating layer is not uniform and continuous

Engineering Contradiction:
Improvecycling stabilityVSAvoidcoating uniformity
Core Design Contradiction:
ReliabilityVSManufacturing precision

Solution Approach 1:

The invention changes the chemical parameters of the coating process by using phosphoric acid treatment instead of sol-gel or precipitation methods. The phosphoric acid concentration (0.1-10 M) and treatment temperature (20-100°C) are optimized to achieve uniform and continuous coating layers, resolving the contradiction between coating uniformity and cycling stability improvement.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention utilizes phase transition during the heat treatment process (calcination at 400-900°C) where the phosphoric acid-treated surface undergoes chemical transformation to form a uniform lithium phosphate coating layer. This phase transition ensures continuous coverage that prevents Mn dissolution while maintaining structural integrity.

Inventive Principle:
Principle #36Phase transitions

2Object-affected harmful factors

If isolated nano-sized metal oxide particles are attached on spinel surface, then some coating effect is achieved, but the cycling performance improvement is not satisfactory

Engineering Contradiction:
ImproveMn dissolutionVSAvoidcycling performance
Core Design Contradiction:
Object-affected harmful factorsVSReliability

Solution Approach 1:

The invention applies local quality by creating a uniform phosphoric acid treatment layer across the entire spinel surface, ensuring consistent protection against Mn dissolution. The localized chemical reaction between phosphoric acid and spinel surface creates a continuous protective barrier rather than isolated particles, significantly improving cycling performance.

Inventive Principle:
Principle #3Local quality

Solution Approach 2:

The invention creates a composite structure by combining spinel LiMn2O4 with a uniform lithium phosphate coating layer formed through phosphoric acid treatment. This composite material structure provides both the electrochemical activity of spinel and the protective properties of the phosphate coating, effectively preventing Mn dissolution and improving cycling stability.

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 core-shell structured lithiated manganese oxide exhibits significantly improved cycling stability and capacity retention at elevated temperatures, with a capacity retention of about 82% after 200 cycles at 60°C compared to 50% for untreated samples.

Implementation Method 1

heat-treatment of spinel LiMxMn2-xO4 particles with P2O5 to form a continuous and uniform lithium manganese phosphate shell layer

Methodology Applied
Scientific EffectChemical reaction: Chemical Bonding

Implementation Method 2

heat-treatment of spinel LiMxMn2-xO4 particles with P2O5

Methodology Applied
Scientific EffectHeating: Heating

Data Source

PatentEP2804836B1Process for preparing a core-shell structured lithtated manganese oxide
Publication Date: 2022.11.23 ROBERT BOSCH GMBH
  • EP2804836B1 patent drawingFigure 1~3
  • EP2804836B1 patent drawingFigure 4

AI summary

The invention relates to a process for preparing a core-shell structured lithiated manganese oxide, comprising the steps of providing spinel LiMxMn2-xO4 particles, where M is one or more metal ions selected from the group consisting of Li, Mg, Cr, Al, Co, Ni, Zn, Cu, and La, and 0<=x<1, as core particles, and subjecting the spinel particles to a heat-treatment with a reactive chemical reagent in the form of liquid or gas to form a shell layer on the surface of the core particles, and to the prepared core-shell structured lithiated manganese oxide, and its use as a cathode material for a lithium ion battery