Li-Ion Cell Pre-Doping Chemistry for Alloy Anode Cycle Durability

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Solution Overview

Problem

Lithium ion secondary batteries face challenges in enhancing charge/discharge efficiency, maintaining high capacity and output, preventing positive electrode material deterioration during pre-doping, and reducing micro-short circuit rates, especially when using alloy-based active materials.

Innovation Solution

A lithium ion secondary battery design incorporating a positive electrode with a transition metal oxide capable of occluding and releasing lithium ions, containing Ni atoms, and a specific range of Ni3p peak energy difference, along with a negative electrode comprising carbon and alloy-based materials, optimized with a lithium compound and electrolyte composition to improve durability and efficiency.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If pre-doping is performed by forming a lithium metal layer on the negative electrode surface, then charge/discharge efficiency is improved, but the negative electrode deteriorates due to volume expansion and heat effects

Engineering Contradiction:
Improvecharge/discharge efficiencyVSAvoidnegative electrode durability
Core Design Contradiction:
ProductivityVSReliability

Solution Approach 1:

The patent introduces a lithium compound (such as lithium carbonate or lithium hydroxide) as an intermediary substance to perform pre-doping. This compound decomposes at moderate temperatures to release lithium ions, avoiding the direct contact and harmful effects of lithium metal while still achieving the desired pre-doping effect on the alloy-based active material.

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The patent changes the physical and chemical parameters of the pre-doping process by using a lithium compound instead of lithium metal. The decomposition temperature of the lithium compound is controlled to be between 100°C and 300°C, which is lower than the melting point of lithium metal (180°C), allowing pre-doping to proceed under milder conditions that prevent negative electrode deterioration.

Inventive Principle:
Principle #35Parameter changes

2Reliability

If pre-doping is performed using lithium carbonate to improve durability at high temperatures, then pre-doping can be carried out under mild conditions, but the positive electrode active material deteriorates due to reaction with lithium carbonate and CO2 gas causes separation and micro-short circuits

Engineering Contradiction:
Improvehigh temperature durabilityVSAvoidpositive electrode material deterioration and micro-short circuits
Core Design Contradiction:
ReliabilityVSObject-affected harmful factors

Solution Approach 1:

The patent extracts the harmful CO2 gas generation step from the pre-doping process by selecting lithium compounds that decompose without producing gas. This eliminates the cause of positive electrode material separation and micro-short circuits while retaining the beneficial pre-doping effect.

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The patent converts the potential harm of using lithium compounds (which can react with positive electrode materials) into a benefit by carefully selecting compounds with decomposition temperatures below the reaction temperature with positive electrode materials. The decomposition occurs first, releasing lithium ions for pre-doping, before any harmful reactions with the positive electrode can occur.

Inventive Principle:
Principle #22Blessing in disguise (Convert harm into benefit)

3Quantity of substance

If alloy-based active material is used to enhance energy density, then energy density increases, but durability decreases due to large volume expansion and contraction

Engineering Contradiction:
Improveenergy densityVSAvoidcharge-discharge cycle durability
Core Design Contradiction:
Quantity of substanceVSReliability

Solution Approach 1:

The patent applies pre-doping as a preliminary action before the alloy-based active material undergoes repeated volume expansion and contraction during charge-discharge cycles. By introducing lithium ions in advance, the material's structure is stabilized, reducing the mechanical stress and preventing deterioration that would otherwise occur during cycling.

Inventive Principle:
Principle #10Preliminary action

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 battery achieves enhanced charge/discharge efficiency, high capacity, and reduced micro-short circuit rates, while inhibiting positive electrode material deterioration and improving cycle characteristics.

Implementation Method 1

a transition metal oxide that is capable of occluding and releasing lithium ions

Methodology Applied
Scientific EffectIntercalation: Absorption (physical)

Implementation Method 2

an alloy-based active material, which contains atoms such as silicon or tin that form an alloy with lithium

Methodology Applied
Scientific EffectAlloying: Chemical Bonding

Implementation Method 3

a nonaqueous electrolyte containing lithium ions

Methodology Applied
Scientific EffectIonic conduction: Conduction (electrical)

Data Source

PatentUS11923541B2Lithium ion secondary battery
Publication Date: 2024.03.05 ASAHI KASEI KOGYO KABUSHIKI KAISHA

AI summary

A lithium ion secondary cell comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte that contains lithium ions, the lithium ion secondary cell being such that: the positive electrode has a positive electrode current collector and a positive electrode active material layer; the positive electrode active material layer contains a positive electrode active material and a lithium compound; the positive electrode active material includes a transition metal oxide; the concentration of the lithium compound, which is the portion other than the positive electrode active material in the positive electrode active material layer, is 0.1-10 mass %; the negative electrode has a negative electrode current collector and a negative electrode active material layer; the negative electrode active material layer contains 50-95 mass % of a carbon material and 5-50 mass % of an alloy-based active material.