Composite Cathode Material for High-Rate Battery Stability

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Solution Overview

Problem

Nonaqueous electrolyte secondary batteries face challenges in achieving both high-rate charge-discharge cycle performance and safety when using lithium-nickel-cobalt-manganese complex oxides and spinel lithium manganese oxides as positive electrode active materials, failing to meet the requirements for modern mobile electronic devices and hybrid electric vehicles.

Innovation Solution

A nonaqueous electrolyte secondary battery is developed using a mixture of tungsten- and zirconium-modified lithium nickel-cobalt-manganese oxide and spinel lithium manganese oxide in a specific proportion as the positive electrode active material, combined with a nonaqueous electrolyte containing a particular ratio of dimethyl carbonate and cyclic carbonate, which suppresses deteriorative reactions and structural collapse, enhancing safety and cycling characteristics.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Quantity of substance

If lithium-containing nickel oxide active material is used to achieve high theoretical capacity and high charge-discharge potential, then capacity is improved, but thermal stability deteriorates

Engineering Contradiction:
Improvetheoretical capacityVSAvoidthermal stability
Core Design Contradiction:
Quantity of substanceVSStability of the object's composition

Solution Approach 1:

The patent uses a composite positive electrode active material consisting of lithium-containing nickel oxide (Li1+xNi1-yMzO2) combined with spinel lithium-containing manganese oxide (LiMn2-yM1yO4). This composite structure allows the nickel oxide component to provide high capacity while the manganese oxide component provides thermal stability, resolving the contradiction between capacity and thermal stability.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The patent introduces different metal elements (M1, M2, M3) at specific positions in the crystal structure to locally enhance properties. For example, M1 in the spinel structure and M2, M3 in the lithium-containing nickel oxide provide localized structural stability and suppress harmful reactions, allowing the bulk material to maintain high capacity characteristics.

Inventive Principle:
Principle #3Local quality

2Stability of the object's composition

If lithium-containing manganese oxide active material is used to achieve low cost and excellent thermal stability, then safety is improved, but theoretical capacity deteriorates

Engineering Contradiction:
Improvethermal stabilityVSAvoidtheoretical capacity
Core Design Contradiction:
Stability of the object's compositionVSQuantity of substance

Solution Approach 1:

The patent creates a composite where lithium-containing manganese oxide (providing thermal stability and safety) is combined with lithium-containing nickel oxide (providing high capacity). The synergistic effect allows the battery to achieve both safety and high capacity, overcoming the limitation of manganese oxide's low theoretical capacity.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The patent modifies the composition parameters of lithium-containing manganese oxide by introducing metal elements M1, M2, and M3, and adjusting their ratios according to specific formulas. This parameter optimization enhances the capacity and electrochemical performance of manganese oxide while preserving its thermal stability.

Inventive Principle:
Principle #35Parameter changes

3Reliability

If spinel lithium manganese oxide is mixed with nickel oxide active material to improve safety performance, then safety is improved, but capacity and high-temperature storage performance deteriorate

Engineering Contradiction:
Improvesafety performanceVSAvoidcapacity
Core Design Contradiction:
ReliabilityVSQuantity of substance

Solution Approach 1:

The patent precisely controls the composition parameters including the ratio of lithium-containing nickel oxide to spinel lithium-containing manganese oxide (95:5 to 50:50 by mass), the content of metal elements M1, M2, M3, and the stoichiometric ratios in the formulas. This parameter optimization ensures that safety is improved while capacity and high-temperature storage performance are maintained.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent introduces specific metal elements (M2, M3) at controlled concentrations (0 < x ≤ 0.1, 0 < y ≤ 0.1) in the lithium-containing nickel oxide structure to locally suppress manganese elution and structural collapse, thereby maintaining high capacity and cycle performance while achieving improved safety through the composite structure.

Inventive Principle:
Principle #3Local quality

4Reliability

If large amounts of lithium manganese oxide are added to improve safety, then safety is improved, but high-rate charge-discharge cycle performance deteriorates

Engineering Contradiction:
ImprovesafetyVSAvoidhigh-rate charge-discharge cycle performance
Core Design Contradiction:
ReliabilityVSDuration of action of moving object

Solution Approach 1:

The patent optimizes the content ratio of spinel lithium-containing manganese oxide to lithium-containing nickel oxide within 5:95 to 50:50 by mass, and controls the metal element contents (x, y, z) to satisfy specific inequalities. This parameter optimization ensures that sufficient manganese oxide is present to suppress manganese elution and improve safety, while maintaining enough nickel oxide to preserve high-rate charge-discharge cycle performance.

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 solution effectively improves high-rate charge-discharge cycling characteristics and safety by preventing manganese elution and structural collapse, ensuring reliable performance and safety in lithium nickel-cobalt-manganese oxide-based batteries.

Implementation Method 1

lithium transition metal complex oxides represented by LiMO2 (where M is at least one of Co, Ni, and Mn) capable of reversibly absorbing and desorbing lithium ions

Methodology Applied
Scientific EffectIntercalation: Absorption (physical)

Implementation Method 2

a nonaqueous electrolyte including a nonaqueous solvent and a solute

Methodology Applied
Scientific EffectIonic conduction: Conduction (electrical)

Data Source

PatentUS9337479B2Nonaqueous electrolyte secondary battery
Publication Date: 2016.05.10 PANASONIC ENERGY CO LTD

AI summary

[Problem] To provide a nonaqueous electrolyte secondary battery exhibiting superior stability characteristics and having charge/discharge characteristics exhibiting a high-rate discharge stroke, even when a lithium-nickel-cobalt manganate and a spinel-type lithium manganate are used as the positive electrode active material. [Solution] A mixture having a specific ratio of a tungsten- and zirconium-modified lithium-nickel-cobalt manganate and a spinel-type lithium manganate is used as the positive electrode active material. Furthermore, a nonaqueous electrolyte having a specific ratio of the content of dimethyl carbonate and the content of a cyclic carbonate is used.