Composite Cathode Materials for High-Rate Lithium-Ion Batteries

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Solution Overview

Problem

Lithium-ion batteries face limitations in energy storage capacity and high-power performance, particularly at high discharge rates, due to safety concerns with excess lithium, which can lead to thermal runaway and reduced capacity if not managed properly.

Innovation Solution

Incorporating a small amount (<10 wt%) of a lithium-rich or phosphate-rich phase in the positive electrode material, forming a composite cathode with an olivine structure, enhances energy storage capacity and high-power performance by forming a conductive secondary phase that contacts the olivine electroactive material, improving lithium conductivity and preventing sintering of olivine crystallites.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Quantity of substance

If excess lithium is added to increase energy storage capacity, then charge capacity increases, but safety deteriorates due to thermal runaway risk and lithium metal deposition

Engineering Contradiction:
Improveenergy storage capacityVSAvoidthermal runaway risk
Core Design Contradiction:
Quantity of substanceVSObject-affected harmful factors

Solution Approach 1:

A lithium phosphate-rich secondary phase is introduced as an intermediary component between the olivine electroactive material and the electrolyte. This secondary phase acts as a mediator that facilitates lithium ion transport while preventing direct contact between excess lithium and the electrolyte, thereby eliminating lithium metal deposition and thermal runaway risk while maintaining high charge capacity

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The positive electrode material is designed as a composite consisting of olivine electroactive material (e.g., LiFePO4) combined with a lithium phosphate-rich secondary phase. This composite structure allows the system to achieve high energy storage capacity through the olivine phase while the lithium phosphate phase provides safety by preventing lithium metal plating and thermal runaway

Inventive Principle:
Principle #40Composite materials

2Power

If discharge rate is increased to improve power capability, then power capability improves, but charge capacity deteriorates due to reduced capacity retention

Engineering Contradiction:
Improvepower capabilityVSAvoidcharge capacity retention
Core Design Contradiction:
PowerVSQuantity of substance

Solution Approach 1:

The lithium phosphate-rich secondary phase is distributed locally throughout the positive electrode material, creating regions with enhanced lithium ion conductivity. This local enhancement of ionic transport properties allows the electrode to maintain high lithium ion flux even at high discharge rates, thereby preserving charge capacity retention while improving power capability

Inventive Principle:
Principle #3Local quality

3Stability of the object's composition

If olivine crystallites are sintered to improve structural stability, then structural stability improves, but lithium conductivity deteriorates due to grain boundary formation

Engineering Contradiction:
Improvestructural stabilityVSAvoidlithium conductivity
Core Design Contradiction:
Stability of the object's compositionVSReliability

Solution Approach 1:

The lithium phosphate-rich secondary phase acts as an intermediary at the grain boundaries between olivine crystallites. Rather than allowing direct grain boundary contact that would impede lithium ion transport, the lithium phosphate phase provides a conductive pathway that mediates lithium ion transport across grain boundaries, maintaining high lithium conductivity while preserving structural stability

Inventive Principle:
Principle #24Intermediary (Mediator)

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 approach results in increased charge capacity and reversible capacity retention at high discharge rates up to 50C, while maintaining safety by controlling the lithium and phosphate content to prevent excessive lithium deposition, thus enhancing lithium-ion battery performance.

Implementation Method 1

enhances energy storage capacity and high-power performance by forming a conductive secondary phase that contacts the olivine electroactive material, improving lithium conductivity

Methodology Applied
Scientific EffectLithium ion conduction: Conduction (electrical)

Implementation Method 2

preventing sintering of olivine crystallites

Methodology Applied
Scientific EffectSintering prevention: Sintering

Data Source

PatentEP2238637B1Mixed metal olivine electrode materials for lithium ion batteries
Publication Date: 2020.04.15 A123 SYSTEMS LLC
  • EP2238637B1 patent drawingFigure 1
  • EP2238637B1 patent drawingFigure 2
  • EP2238637B1 patent drawingFigure 3

AI summary

A positive electrode material is provided including an electroactive material having one or more phases comprising lithium (Li), an electroactive metal (M), and phosphate (PO4), wherein in the fully lithiated state, the overall composition has a ratio of Li:M ranging from greater than about 1.0 to about 1.3, a ratio of (PO4)IM ranging from about 1.0 to about 1.132, M is one or more metals selected from the group consisting of Cr, Mn, Fe, Co, and Ni, and at least one phase includes an olivine lithium electroactive metal phosphate. In some instances, a composite cathode material including an electroactive olivine transition metal phosphate and a lithium and phosphate rich secondary phase is disclosed for use in a lithium ion battery.