SiOx Negative Electrode Active Material for Li-Ion Batteries

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Solution Overview

Problem

Lithium ion secondary batteries using silicon as a negative electrode material face challenges in achieving high battery capacity and cycle characteristics due to particle expansion, cracking, and low water resistance, leading to degraded battery performance and instability during electrode preparation.

Innovation Solution

A production method involving a silicon compound SiOx (0.5≤x≤1.6) with lithium insertion, followed by contact with a polycyclic aromatic compound solution and a quinoid structure-containing solution to desorb active lithium, stabilizing the electrode and preventing violent reactions, thereby enhancing cycle retention and initial efficiency.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Quantity of substance

If silicon is used as the negative electrode active material to improve battery capacity, then the theoretical capacity increases significantly, but the particles expand and contract during charge/discharge causing cracking and degradation of cycle characteristics

Engineering Contradiction:
Improvebattery capacityVSAvoidcycle characteristics
Core Design Contradiction:
Quantity of substanceVSReliability

Solution Approach 1:

The patent uses a composite structure where silicon particles are embedded in a silicon oxide matrix (SiOx where 0.5 ≤ x ≤ 1.6). This composite material allows the silicon to provide high capacity while the silicon oxide matrix constrains volume expansion and prevents particle cracking during charge/discharge cycles, thereby maintaining cycle characteristics.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The silicon oxide matrix acts as a flexible constraint structure that accommodates the expansion and contraction of silicon particles during lithium insertion and extraction. This matrix structure prevents the silicon particles from cracking while allowing the necessary volume changes for electrochemical reactions.

Inventive Principle:
Principle #30Flexible shells and thin films

2Productivity

If lithium is inserted into the silicon compound to improve initial efficiency, then the initial charge/discharge efficiency increases, but the water resistance decreases leading to violent reactions with water

Engineering Contradiction:
Improveinitial efficiencyVSAvoidwater resistance
Core Design Contradiction:
ProductivityVSObject-affected harmful factors

Solution Approach 1:

The patent optimizes the oxygen content parameter in SiOx (where 0.5 ≤ x ≤ 1.6) to balance two competing requirements: sufficient lithium insertion capability for high initial efficiency and adequate water resistance to prevent violent reactions. By controlling the stoichiometry of silicon oxide, the material achieves both high productivity and safety.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates local quality differentiation where lithium is preferentially inserted into specific regions of the silicon compound while maintaining an oxygen-rich environment in other regions. This localized lithium insertion, controlled by the SiOx matrix structure, enhances initial efficiency while the oxygen-rich regions maintain water resistance and prevent violent reactions.

Inventive Principle:
Principle #3Local quality

3Reliability

If the oxygen content in silicon compound is increased to improve cycle characteristics, then the structural stability improves, but the lithium insertion capability decreases reducing initial efficiency

Engineering Contradiction:
Improvecycle characteristicsVSAvoidinitial efficiency
Core Design Contradiction:
ReliabilityVSProductivity

Solution Approach 1:

The patent identifies and optimizes the critical parameter x in SiOx (where 0.5 ≤ x ≤ 1.6) to achieve the optimal balance between cycle characteristics and initial efficiency. This parameter optimization allows sufficient oxygen content for structural stability while maintaining enough silicon character for lithium insertion capability.

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 method results in a negative electrode active material with improved high capacity, cycle characteristics, and reduced irreversible capacity, preventing degradation and ensuring stable battery performance even under low humidity conditions.

Implementation Method 1

inserting lithium into the silicon compound

Methodology Applied
Scientific EffectInsertion reaction: Absorption (physical)

Implementation Method 2

making the silicon compound into which the lithium has been inserted contact with a solution B containing a polycyclic aromatic compound or a derivative thereof or both thereof... making the silicon compound that has been contacted with the solution B contact with a solution C... containing a compound having a quinoid structure in a molecule as a solute

Methodology Applied
Scientific EffectDesorption: Desorption

Data Source

PatentEP3349278B1Method for producing negative electrode active material for nonaqueous electrolyte secondary batteries, method for manufacturing nonaqueous electrolyte secondary battery, method for producing negative electrode for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery
Publication Date: 2022.09.07 SHIN ETSU CHEMICAL CO LTD
  • EP3349278B1 patent drawingFigure 1
  • EP3349278B1 patent drawingFigure 2
  • EP3349278B1 patent drawingFigure 3

AI summary

The present invention provides a production method of a negative electrode active material containing a silicon compound (SiOx: 0.5≤x≤1.6) that contains Lithium comprising: making a silicon compound into which the lithium has been inserted contact with a solution B containing a polycyclic aromatic compound or a derivative thereof or both thereof (here, the solution B contains one or more kinds selected from an ether-based solvent, a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, and an amine-based solvent as a solvent); and making the silicon compound contact with a solution C (here, the solution C contains one or more kinds selected from an ether-based material, a ketone-based material, and an ester-based material as the solvent, and contains a compound having a quinoid structure in a molecule as a solute). Thereby, a production method of a negative electrode active material for nonaqueous electrolyte secondary batteries capable of increasing a battery capacity and improving the cycle characteristics is provided.