Lithium-Titanium Composite Oxide Doping for Capacity and Phase Stability

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Solution Overview

Problem

Lithium-titanium composite oxides, particularly spinel-type, face limitations in high capacity due to theoretical capacity constraints and phase separation issues during manufacturing, leading to deteriorated effective capacity and reaction speed.

Innovation Solution

A manufacturing method involving solid-phase mixing of lithium, titanium, sodium, and zirconium compounds, followed by wet-pulverization, spray-drying, and firing to control particle sizes and suppress anatase and rutile-type titanium dioxide formation, resulting in a lithium-titanium composite oxide with improved initial capacity and rate capability.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If spinel-type lithium titanate is used as electrode material, then long cycle-life and excellent reversibility are achieved, but theoretical capacity is limited to 175 mAh/g

Engineering Contradiction:
Improvecycle-lifeVSAvoidtheoretical capacity
Core Design Contradiction:
ReliabilityVSQuantity of substance

Solution Approach 1:

The patent changes the compositional parameters by introducing doping elements (magnesium, aluminum, sodium, zirconium) at controlled concentrations (0.01-0.10 mol ratio relative to Li) to modify the spinel structure, thereby increasing theoretical capacity while maintaining cycle-life through structural stabilization

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates composite doped spinel structures by incorporating multiple metal elements (Mg, Al, Na, Zr) into the Li4Ti5O12 matrix, forming a composite material system that combines the structural stability of spinel with enhanced capacity from dopant elements

Inventive Principle:
Principle #40Composite materials

2Ease of manufacture

If lithium-titanium composite oxide is manufactured conventionally, then production is simplified, but phase separation into rutile-type TiO2 occurs during manufacturing

Engineering Contradiction:
Improvemanufacturing processVSAvoidphase composition
Core Design Contradiction:
Ease of manufactureVSStability of the object's composition

Solution Approach 1:

The patent applies preliminary doping action before final sintering by incorporating dopant compounds into the raw mixture, which pre-establishes structural stability that prevents phase separation during the subsequent manufacturing process

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The patent modifies the chemical composition parameters by adding specific dopants that lower the free energy of the spinel phase, making it thermodynamically more stable and resistant to phase separation at manufacturing temperatures

Inventive Principle:
Principle #35Parameter changes

3Shape

If rutile-type TiO2 is formed in lithium-titanium composite oxide, then rock salt structure is achieved, but effective capacity deteriorates due to low reaction speed and small capacity

Engineering Contradiction:
Improvecrystal structureVSAvoideffective capacity
Core Design Contradiction:
ShapeVSQuantity of substance

Solution Approach 1:

The patent converts the potentially harmful phase separation into a beneficial outcome by using controlled doping to stabilize the desired spinel structure, preventing the formation of low-capacity rutile phase while maintaining structural integrity

Inventive Principle:
Principle #22Blessing in disguise (Convert harm into benefit)

Solution Approach 2:

The patent changes the compositional parameters by introducing dopants that preferentially stabilize the spinel phase through lattice substitution and defect formation, thereby suppressing the thermodynamic driving force for rutile phase formation

Inventive Principle:
Principle #35Parameter changes

4Quantity of substance

If doping with multiple metals is performed, then initial capacity and rate capability are improved, but manufacturing complexity increases

Engineering Contradiction:
Improveinitial capacityVSAvoidmanufacturing process complexity
Core Design Contradiction:
Quantity of substanceVSDevice complexity

Solution Approach 1:

The patent merges multiple doping elements into a single manufacturing process by incorporating all dopant compounds (MgO, Al2O3, Na2CO3, ZrO2) into one mixed powder formulation, which is then processed through a unified sintering procedure rather than sequential doping steps

Inventive Principle:
Principle #5Merging (Combining)

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 method enhances the initial capacity and rate capability of lithium-titanium composite oxides by controlling impurity content and particle sizes, leading to improved battery performance with a spinel structure and reduced impurity peaks, thus increasing battery efficiency.

Implementation Method 1

A non-aqueous electrolyte battery charged and discharged by lithium ions moving between negative and positive electrodes

Methodology Applied
Scientific EffectLithium ion intercalation/deintercalation: Absorption (physical)

Implementation Method 2

a lithium-titanium composite oxide having a high Li intercalation/deintercalation potential has drawn attention

Methodology Applied
Scientific EffectElectrochemical reaction: Redox Reactions

Implementation Method 3

spray-drying the same to adjust contents of impurities

Methodology Applied
Scientific EffectEvaporation: Evaporation

Implementation Method 4

firing the spray-dried particles to manufacture a lithium-titanium composite oxide

Methodology Applied
Scientific EffectThermal heating: Heating

Implementation Method 5

firing the spray-dried particles to manufacture a lithium-titanium composite oxide doped with different metals

Methodology Applied
Scientific EffectSolid-state reaction: Chemical Bonding

Data Source

PatentEP3000787B1Manufacturing method of lithium-titanium composite oxide doped with sodium and zirconium, and lithium-titanium composite oxide manufactured thereby
Publication Date: 2020.02.12 POHANG IRON & STEEL CO LTD
  • EP3000787B1 patent drawingFigure 1
  • EP3000787B1 patent drawingFigure 2
  • EP3000787B1 patent drawingFigure 3

AI summary

The present invention relates to a manufacturing method of a lithium-titanium composite oxide doped with two kinds of different metals and a lithium-titanium composite oxide doped with two kinds of different metals. More particularly, the present invention relates to a manufacturing method of a lithium-titanium composite oxide doped with different metals, solid-phase mixing after adjusting a mixing ratio of two kinds of different metals and pulverizing the same, and spray drying the same to adjust contents of impurities, and a lithium-titanium composite oxide doped with different metals manufactured therefrom. By doping two kinds of different metals on the surface of the lithium-titanium composite oxide of the present invention after adjusting the ratio of the two different metals to be a desirable ratio, the present invention reduces the contents of rutile-type titanium dioxide, anatase-type titanium dioxide and Li2TiO3 which have been included as impurities in the prior arts, thereby manufacturing titanium dioxide having excellent capacity characteristics and structural characteristics, and a battery including the titanium dioxide having excellent battery characteristics of high initial charge and discharge efficiency and rate capability.