Sodium Layered Oxide Cathode for High Cyclability

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Solution Overview

Problem

There is a need for composite metal oxides in sodium batteries that can deliver excellent and durable electrochemical properties, particularly high cyclability, which existing materials have not adequately addressed.

Innovation Solution

A mixed oxide composition of sodium, manganese, nickel, and cobalt with a P2 crystal structure is developed, synthesized using a co-precipitation method, which maintains structural stability and high ion diffusivity, preventing phase conversion and enhancing cyclability.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If existing sodium layered oxide materials are used, then high capacity and ion diffusivity are achieved, but cyclability and structural stability deteriorate

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

Solution Approach 1:

The patent applies composite materials by combining three transition metals (Mn, Ni, Co) in a layered oxide structure with formula Na_x[MnNiCo]O2. This composite approach creates a material that leverages the complementary properties of each metal: Mn provides structural stability, Ni enhances capacity, and Co improves ion diffusivity. The resulting composite material achieves high cyclability (96% retention after 10 cycles) and maintains structural stability during charge-discharge cycles, resolving the contradiction between reliability and compositional stability.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The patent applies local quality by creating a non-uniform distribution of transition metals within the layered oxide structure. The formula Na_x[MnNiCo]O2 indicates a specific arrangement where different metals occupy different sites in the crystal lattice, with each metal contributing its unique properties to specific regions. This localized differentiation allows the material to simultaneously achieve high capacity (from Ni-rich regions), fast ion diffusivity (from Co-rich regions), and structural stability (from Mn-rich regions), thereby improving cyclability while maintaining overall structural integrity.

Inventive Principle:
Principle #3Local quality

2Use of energy by moving object

If high voltage operation is implemented, then energy density is improved, but phase conversion and performance degradation occur

Engineering Contradiction:
Improveenergy densityVSAvoidphase stability
Core Design Contradiction:
Use of energy by moving objectVSStability of the object's composition

Solution Approach 1:

The patent applies beforehand cushioning by incorporating Mn and Co into the layered oxide structure prior to battery operation. These metals act as protective elements that preemptively stabilize the crystal structure against phase conversions that would normally occur at high voltages. The Mn4+ ions in particular provide structural reinforcement that prevents Jahn-Teller distortions and phase transitions, cushioning the material against degradation before it can occur during high-voltage charge-discharge cycles. This allows the battery to operate at high voltages (4.3V) with maintained phase stability and performance.

Inventive Principle:
Principle #11Beforehand cushioning (Prior cushioning)

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 mixed oxide composition exhibits improved cyclability and structural stability, maintaining high performance even at high voltages, significantly increasing cycle retention and durability compared to materials with only one or two transition metals.

Implementation Method 1

synthesized using a co-precipitation method

Methodology Applied
Scientific EffectCo-precipitation: Coprecipitation

Data Source

PatentEP3332437B1Sodium layered oxide as cathode material for sodium ion battery
Publication Date: 2020.09.02 TOYOTA JIDOSHA KK
  • EP3332437B1 patent drawingFigure 1
  • EP3332437B1 patent drawingFigure 2
  • EP3332437B1 patent drawingFigure 3a~3b

AI summary

The present invention relates to a mixed oxide of sodium and transition metals having the formula (1) : Nax[MnaNibCOc]02+y, wherein: 0.5≤ x ≤0.9, -0.1≤ y ≤0.1, a + b + c = 1, 4a + 2b + 3c = 4 - x + 2y, 0 < c ≤ 0.5 The present invention further relates to a process for producing such a mixed oxide, a positive electrode comprising such a mixed oxide and a sodium ion secondary battery comprising such a positive electrode.