Sodium-Blocking Layer on Titanium Composite Oxide Electrode

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Solution Overview

Problem

Nonaqueous electrolyte secondary batteries, particularly those using titanium-based negative electrodes, face challenges with low energy density and high operating potential, leading to reduced battery voltage and increased number of batteries required in series for high-voltage applications, along with instability at high temperatures due to sodium ion elution and side reactions.

Innovation Solution

The use of a sodium-containing titanium composite oxide with a monoclinic titanium dioxide sodium ion-blocking layer, which has a crystal structure belonging to the space group Cmca or Fmmm, is introduced to stabilize lithium insertion/extraction reactions at a lower potential, suppress sodium ion elution, and enhance battery performance at high temperatures.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If oxide of titanium is used as negative electrode active material, then rapid charge-and-discharge performance and long-term reliability are improved, but energy density decreases due to higher potential and lower capacity per weight

Engineering Contradiction:
Improvelong-term reliabilityVSAvoidenergy density
Core Design Contradiction:
ReliabilityVSUse of energy by moving object

Solution Approach 1:

The patent changes the crystal structure parameter of titanium oxide from conventional phases to a specific phase with space group Cmca or Fmmm, which has lower potential vs. Li/Li+ and higher capacity per weight, thereby improving energy density while maintaining reliability

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent uses a composite material consisting of titanium-including composite oxide with specific crystal phases (Cmca or Fmmm) combined with sodium-containing titanium composite oxide, achieving both high energy density and stable rapid charge-discharge performance

Inventive Principle:
Principle #40Composite materials

2Reliability

If material with high potential relative to metallic lithium is used as negative electrode material, then voltage becomes lower than conventional batteries, but this requires more batteries in series for high-voltage applications

Engineering Contradiction:
ImprovestabilityVSAvoidnumber of batteries in series
Core Design Contradiction:
ReliabilityVSDevice complexity

Solution Approach 1:

The patent changes the electrochemical potential parameter of the negative electrode material by adopting a specific crystal phase (Cmca or Fmmm) of titanium oxide, which operates at lower potential vs. Li/Li+ (improving voltage) while maintaining stability through the unique crystal structure

Inventive Principle:
Principle #35Parameter changes

3Use of energy by moving object

If sodium-containing titanium composite oxide is used to improve energy density, then sodium ion elution occurs at high temperatures causing side reactions and instability

Engineering Contradiction:
Improveenergy densityVSAvoidstability at high temperature
Core Design Contradiction:
Use of energy by moving objectVSReliability

Solution Approach 1:

The patent introduces a sodium ion-blocking layer as an intermediary between the sodium-containing titanium composite oxide and the electrolyte, preventing sodium ion elution and side reactions at high temperatures while allowing the high-energy-density material to function

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The patent creates a composite structure combining sodium-containing titanium composite oxide (for high energy density) with sodium ion-blocking layer materials (for thermal stability), achieving both high energy density and stability at elevated temperatures

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

This configuration results in a secondary battery with improved energy density, higher voltage, and extended life performance at elevated temperatures by stabilizing lithium insertion reactions and reducing side reactions, while maintaining high-rate discharge efficiency.

Implementation Method 1

a sodium ion-blocking layer formed on a surface of the active material-containing layer... the sodium ion-blocking layer contains a material impermeable to sodium ions

Methodology Applied
Scientific EffectIon blocking: Diffusion Barrier

Implementation Method 2

stabilize lithium insertion/extraction reactions at a lower potential... the active material-containing layer contains a sodium-containing titanium composite oxide

Methodology Applied
Scientific EffectLithium insertion/extraction: Absorption (physical)

Data Source

PatentEP3379614B1Electrode construct, electrode, secondary battery, battery module, battery pack, and vehicle
Publication Date: 2020.08.19 KK TOSHIBA
  • EP3379614B1 patent drawingFigure 1~2
  • EP3379614B1 patent drawingFigure 3~4
  • EP3379614B1 patent drawingFigure 5~6

AI summary

According to one approach, there is provided an electrode construct including an active material-containing layer and a sodium ion-blocking layer (8). The active material-containing layer contains a sodium-containing titanium composite oxide having a crystal structure belonging to a space group Cmca or a space group Fmmm. The sodium ion-blocking layer (8) is disposed on a surface of the active material-containing layer. The sodium ion-blocking layer (8) contains a material impermeable to sodium ions.