Lithium Titanium Sulfide Cathode Material with Selenium Substitution

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Solution Overview

Problem

Lithium titanium sulfide (Li2TiS3) cathodes in lithium-ion batteries exhibit unstable charge/discharge behavior due to the lack of titanium redox activity during the first charge, leading to rapid degradation and reduced reversible capacity over cycles, hindering industrialization.

Innovation Solution

A material with the formula Li a Ti b (A x S 3-x) is introduced, where A is a metalloid element like selenium, offering higher electronic conductivity and stability, with specific stoichiometric coefficients that enhance the material's structure and performance, such as Li2TiSe x S 3-x, which maintains a NaCl crystallographic structure and improved capacity retention.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Quantity of substance

If lithium titanium sulfide (Li2TiS3) is used as cathode material, then high reversible capacity (400 mAh/g) is achieved through multi-electron redox reactions, but the reversible capacity decreases rapidly with increasing charge/discharge cycles due to unstable charge/discharge behavior

Engineering Contradiction:
Improvereversible capacityVSAvoidcharge/discharge stability
Core Design Contradiction:
Quantity of substanceVSReliability

Solution Approach 1:

The patent modifies the chemical composition parameters of lithium titanium sulfide by substituting sulfur with selenium to create Li2TiSeS2, changing the electronic and structural properties to improve both capacity and stability simultaneously

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates a composite material combining lithium, titanium, selenium, and sulfur in specific ratios (Li2TiSeS2), where the synergistic effects of different elements provide both high capacity and stable cycling performance

Inventive Principle:
Principle #40Composite materials

2Stability of the object's composition

If titanium is stabilized in Li2TiS3 structure, then structural stability is maintained, but titanium cannot form redox couples during first charge to compensate for charge imbalance from lithium extraction

Engineering Contradiction:
Improvestructural stabilityVSAvoidcharge balance compensation
Core Design Contradiction:
Stability of the object's compositionVSReliability

Solution Approach 1:

The patent changes the oxidation state parameters and electronic structure by incorporating selenium, enabling titanium to participate in redox reactions while maintaining structural integrity through the modified crystal structure

Inventive Principle:
Principle #35Parameter changes

3Reliability

If sulfur redox activity occurs during first charge, then charge balance is maintained, but the structure is modified and sulfur activity is progressively lost over cycles

Engineering Contradiction:
Improvecharge balanceVSAvoidstructural stability
Core Design Contradiction:
ReliabilityVSStability of the object's composition

Solution Approach 1:

The patent changes the chemical composition by substituting sulfur with selenium, which has higher electronic conductivity and forms more stable bonds, preventing progressive degradation while maintaining redox activity

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent replaces sulfur (which degrades) with selenium (which is more stable), effectively substituting a less stable component with a more stable one to extend material lifetime

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

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 material exhibits a more stable charge/discharge behavior and reduced capacity loss over cycles, with a reversible capacity greater than 200 mAh/g, and capacity retention of over 75% after 15 cycles, significantly improving lithium-ion battery performance.

Implementation Method 1

the inventors attribute the better stability of the material according to the invention to the high electronic conductivity of the metalloid element

Methodology Applied
Scientific EffectElectronic conductivity: Conduction (electrical)

Implementation Method 2

Lithium titanium sulphide, of formula Li 2 TiS 3... exhibits high reversible capacity, reaching 400 mAh/g through multi-electron redox reactions

Methodology Applied
Scientific EffectRedox reactions: Redox Reactions

Data Source

PatentEP3626682B1Lithiated material
Publication Date: 2021.04.21 COMMISSARIAT A LENERGIE ATOMIQUE ET AUX ENERGIES ALTERNATIVES
  • EP3626682B1 patent drawingFigure 1~2
  • EP3626682B1 patent drawingFigure 3~4
  • EP3626682B1 patent drawingFigure 5~6

AI summary

Material of formula LiaTib(AxS3-x)c in which A is a metalloid element chosen from selenium, tellurium and their mixtures, and the stoichiometric coefficients a, b, c and x are such that ∘ 0 < x < 2.2 ; ∘ 0.4 ≤ a ≤ 4.5 ; ∘ 0.9 ≤ b ≤ 1.1 ; and ∘ 0.9 ≤ c ≤ 1.1.