LiF Surface Treatment for Lithium Manganese Oxide Cathodes

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Solution Overview

Problem

Lithium-ion batteries experience capacity loss due to the degradation of cathode materials caused by the reaction with hydrofluoric acid, which is generated when common electrolytes interact with water, leading to frequent recharging needs and reduced battery performance.

Innovation Solution

A method involving the selection of specific cathode active materials, such as Li1+xMyMn2-x-yO4 or Li[Li(1-2x)/3My(2-x)/3Ni x-y]O2, followed by dry blending or slurry processing with LiF, and subsequent heating to create a surface treatment of lithium fluoride (LiF) on the cathode material, which shields the cathode from acidic digestion without interfering with ion transport.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Quantity of substance

If a lithium-containing transition metal oxide cathode material is used, then high initial capacity is achieved, but capacity loss and degradation occur over time due to HF attack from electrolyte reactions

Engineering Contradiction:
Improveinitial capacityVSAvoidcapacity retention
Core Design Contradiction:
Quantity of substanceVSReliability

Solution Approach 1:

A coating layer comprising LiF and a metal fluoride (where the metal is selected from Group 2-16 elements) is applied to the cathode material surface. This intermediary coating shields the cathode active material from direct contact with HF generated from electrolyte decomposition, preventing degradation while allowing lithium ion transport to maintain capacity.

Inventive Principle:
Principle #24Intermediary (Mediator)

2Object-affected harmful factors

If conventional coating methods are used to protect cathode material, then degradation resistance improves, but battery performance is detrimentally reduced

Engineering Contradiction:
Improveresistance to HF attackVSAvoidbattery performance
Core Design Contradiction:
Object-affected harmful factorsVSReliability

Solution Approach 1:

The coating is applied specifically to the surface of the cathode particles, providing localized protection where HF attack occurs most intensely. The coating composition is tailored with specific metal fluorides to enhance resistance at the critical interface between cathode material and electrolyte, while the bulk cathode material retains its high-performance characteristics.

Inventive Principle:
Principle #3Local quality

Solution Approach 2:

The coating parameters including composition ratios of LiF to metal fluoride, coating thickness, and crystal structure are optimized to achieve the right balance between protection and performance. By controlling these parameters, the coating provides sufficient HF resistance while maintaining adequate lithium ion conductivity for high battery performance.

Inventive Principle:
Principle #35Parameter changes

3Stability of the object's composition

If doping metals are used to stabilize cathode structure, then capacity loss is reduced, but manufacturing complexity and cost increase

Engineering Contradiction:
Improvecathode structure stabilityVSAvoiddoping process complexity
Core Design Contradiction:
Stability of the object's compositionVSDevice complexity

Solution Approach 1:

Instead of complex multi-element doping processes to stabilize the cathode structure, a simpler coating approach using LiF and metal fluoride is employed. This coating acts as a protective intermediary that stabilizes the cathode material by preventing HF-induced degradation, achieving structure stability through a less complex manufacturing process.

Inventive Principle:
Principle #24Intermediary (Mediator)

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 LiF surface treatment effectively reduces the degradation of cathode materials, maintaining initial capacity and improving fade characteristics, allowing for reduced doping metal requirements and enhanced battery performance over multiple charge/discharge cycles.

Implementation Method 1

heating the resulting dry blend at a temperature between 700°C and 850°C for a two hours to six hours to activate the LiF

Methodology Applied
Scientific EffectHeating: Heating

Implementation Method 2

provide a final composition in the form of a cathode active material carrying a surface treatment of LiF on the cathode active material

Methodology Applied
Scientific EffectSurface treatment: Coatings

Data Source

PatentEP2951129B1Improved lithium manganese oxide compositions
Publication Date: 2021.03.31 EMD ACQUISITION LLC
  • EP2951129B1 patent drawingFigure 1a
  • EP2951129B1 patent drawingFigure 1b
  • EP2951129B1 patent drawingFigure 2

AI summary

The present disclosure relates to improved LMO composition suitable for use as cathode material in rechargeable lithium ion batteries. The LMO composition may be doped with an additional metal or undoped. The LMO composition carries a surface treatment of LiF that protects the LMO from acid degradation. Cathodes prepared from the improved LMO have improved fade characteristics.