LiNiMnCoO2 Electrode Active Material for Low-Temperature Rate Characteristics

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Solution Overview

Problem

Lithium-nickel-manganese-cobalt composite oxide electrodes used in nonaqueous electrolyte secondary batteries exhibit insufficient rate characteristics in low-temperature environments.

Innovation Solution

A lithium-nickel-manganese-cobalt composite oxide with a hexagonal, layered rock-salt type crystal structure, represented by the formula Li1−α[NixMnyCoz]O2, where α is between 0.1 and 0.3, and the molar ratio of Ni to Mn is between 0.5 and 0.9, with a peak intensity ratio of diffraction peaks within specific ranges, and optionally containing tungsten, is used to enhance stability and reduce internal resistance.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If lithium-nickel-manganese-cobalt composite oxide is used as electrode active material, then safety and cost are improved compared to cobalt composite oxides, but rate characteristics in low-temperature environment deteriorate

Engineering Contradiction:
ImprovesafetyVSAvoidrate characteristics in low-temperature environment
Core Design Contradiction:
ReliabilityVSProductivity

Solution Approach 1:

The patent applies parameter changes by precisely controlling the molar ratios of nickel, manganese, and cobalt in the composite oxide formula Li1−α[NixMnymCoz]O2, where x+y+z=1.0. Specifically, nickel content is controlled at 0.3-0.6, manganese at 0.1-0.3, and cobalt at 0.1-0.3, with additional constraints on their ratios. This optimization of compositional parameters achieves both improved safety and enhanced rate characteristics in low-temperature environments.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent employs composite materials by creating a lithium-nickel-manganese-cobalt composite oxide that combines four different metal elements in specific proportions. This multi-element composite approach leverages the beneficial properties of each element: nickel for capacity, manganese for stability and safety, and cobalt for electrochemical performance, achieving a balance between safety and low-temperature rate characteristics that single-element or simpler composite materials cannot provide.

Inventive Principle:
Principle #40Composite materials

2Ease of manufacture

If lithium-nickel-manganese-cobalt composite oxide is used as electrode active material, then cost is reduced compared to cobalt composite oxides, but rate characteristics in low-temperature environment deteriorate

Engineering Contradiction:
ImprovecostVSAvoidrate characteristics in low-temperature environment
Core Design Contradiction:
Ease of manufactureVSProductivity

Solution Approach 1:

The patent optimizes the compositional parameters of the composite oxide to achieve both cost-effectiveness and performance. By controlling nickel content at 0.3-0.6 (reducing expensive cobalt while maintaining capacity) and optimizing the ratios of all elements, the material achieves low-temperature rate characteristics comparable to or better than cobalt-rich compositions, thereby reducing cost without sacrificing productivity.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The four-element composite oxide structure allows for cost optimization by replacing a portion of expensive cobalt with more affordable nickel and manganese while maintaining electrochemical performance. The synergistic interaction between the four elements ensures that rate characteristics in low-temperature environments are preserved despite the reduced cobalt content, achieving both cost reduction and maintained productivity.

Inventive Principle:
Principle #40Composite materials

3Reliability

If nickel composite oxide is used as electrode material, then safety is improved and cost is reduced, but crystal structure stability deteriorates

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

Solution Approach 1:

The patent uses a four-element composite oxide (lithium-nickel-manganese-cobalt) where manganese plays a crucial role in stabilizing the crystal structure. The presence of manganese (0.1-0.3 in molar ratio) and cobalt (0.1-0.3) alongside nickel provides structural reinforcement through their combined effects, preventing the crystal structure degradation that occurs in pure nickel composite oxides, while maintaining the safety and cost advantages of nickel-based materials.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The patent stabilizes the crystal structure by optimizing the compositional parameters, specifically controlling the nickel content at 0.3-0.6 and the ratios between nickel, manganese, and cobalt. This parameter optimization ensures that the crystal structure remains stable during charge-discharge cycles, preventing degradation while maintaining the inherent safety and cost benefits of nickel-based composite oxides.

Inventive Principle:
Principle #35Parameter changes

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 described electrode active material improves rate characteristics in low-temperature environments by maintaining a stable crystal structure and reducing internal resistance, leading to enhanced battery performance.

Implementation Method 1

secondary batteries using lithium ions or other alkali metal ions as charged carriers, in which the electrochemical reaction accompanying the transfer of charge is utilized

Methodology Applied
Scientific EffectElectrochemical reaction: Redox Reactions

Implementation Method 2

lithium ion secondary batteries have spread widely

Methodology Applied
Scientific EffectIon transfer: Diffusion

Data Source

PatentUS8728344B2Electrode active material and nonaqueous electrolyte secondary battery having the same
Publication Date: 2014.05.20 MURATA MFG CO LTD

AI summary

An electrode active material that contains a lithium-nickel-manganese-cobalt composite oxide having a hexagonal, layered rock-salt type crystal structure that belongs to the space group R3m. The lithium-nickel-manganese-cobalt composite oxide is represented by the general formula Li1+α[NixMnyCoz]O2 (wherein α satisfies 0.1<α<0.3, and x, y, and z satisfy x+y+z=1, 0.075<z<0.250, and 0.50<x/y<0.90). In the powder X-ray diffraction analysis of a powder of the lithium-nickel-manganese-cobalt composite oxide using a CuKα ray, the peak intensity ratio (A/B) of the diffraction peak intensity (A) observed near 2θ=18.6±0.2° to the diffraction peak intensity (B) observed near 2θ=44.3±1.0° is more than 0 and less than 1.0.