SiOx-Graphite Composite Negative Electrode for Battery Swelling

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Solution Overview

Problem

Non-aqueous secondary batteries using silicon oxide (SiOx) as a negative electrode material face issues with volumetric expansion and shrinkage during charge and discharge cycles, leading to battery swelling and reduced cycle characteristics due to its low conductivity and high reactivity with solvents.

Innovation Solution

A composite negative electrode material is developed, combining SiOx with carbon and graphite, where SiOx is coated with a conductive carbon material to form a conductive network, and the SiOx crystallite diameter is controlled to 50 nm or less, with a specific atom ratio of O to Si and a graphite content of 70-95 mass%, to enhance conductivity and stability.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Quantity of substance

If SiOx is used as negative electrode material to increase capacity, then charge discharge capacity is improved, but volumetric expansion and shrinkage cause battery swelling and reduced cycle characteristics

Engineering Contradiction:
Improvecharge discharge capacityVSAvoidcycle characteristics
Core Design Contradiction:
Quantity of substanceVSReliability

Solution Approach 1:

The patent embeds ultrafine Si particles (average particle diameter 0.01 to 1 μm) within a SiO2 matrix structure, creating a nested configuration where the active Si cores are protected by the more stable SiO2 shell. This nested structure allows the high-capacity Si to undergo volumetric changes while being constrained and protected by the SiO2 matrix, preventing particle crushing and maintaining structural integrity during charge-discharge cycles.

Inventive Principle:
Principle #7Nested doll (Nesting)

Solution Approach 2:

The patent employs a composite material system consisting of Si particles dispersed in a SiO2 matrix, combined with carbonaceous materials and conductive agents. This composite structure integrates the high capacity of Si with the structural stability of SiO2 and the conductivity of carbon materials, achieving both high charge-discharge capacity and good cycle characteristics while suppressing battery swelling.

Inventive Principle:
Principle #40Composite materials

2Speed

If SiOx particles are made ultrafine to improve load characteristics, then load characteristic is improved, but conductivity remains low and reactivity with solvent increases

Engineering Contradiction:
Improveload characteristicVSAvoidconductivity
Core Design Contradiction:
SpeedVSReliability

Solution Approach 1:

The patent introduces carbonaceous materials (such as graphite, amorphous carbon, or carbon nanotubes) as intermediary components that form conductive networks around and between the SiOx particles. These carbon materials act as mediators that provide electrical pathways, compensating for the low intrinsic conductivity of ultrafine SiOx particles while maintaining their high surface area and fast reaction kinetics for improved load characteristics.

Inventive Principle:
Principle #24Intermediary (Mediator)

3Reliability

If SiOx surfaces are coated with conductive material to improve conductivity, then load characteristic is improved, but manufacturing complexity increases

Engineering Contradiction:
ImproveconductivityVSAvoidmanufacturing process
Core Design Contradiction:
ReliabilityVSDevice complexity

Solution Approach 1:

The patent combines multiple functional components (Si particles, SiO2 matrix, carbonaceous materials, and conductive agents) into a single integrated composite material system that can be processed together as one unit. This merging approach eliminates the need for separate coating steps, as all components are mixed and formed simultaneously into electrode structures, simplifying the manufacturing process while achieving both high conductivity and structural stability.

Inventive Principle:
Principle #5Merging (Combining)

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 composite electrode material improves charge discharge cycle characteristics and suppresses battery swelling by maintaining conductivity and structural integrity during cycles, while maintaining a high capacity retention rate over 500 cycles.

Implementation Method 1

combining SiOx with carbon and graphite, where SiOx is coated with a conductive carbon material to form a conductive network

Methodology Applied
Scientific EffectConduction (electrical): Conduction (electrical)

Implementation Method 2

SiOx exhibits large volumetric expansion and shrinkage associated with the charge and the discharge reaction

Methodology Applied
Scientific EffectThermal Expansion: Thermal Expansion

Implementation Method 3

The material containing Si and O as constitution elements has a crystallite diameter of 50 nm or less

Methodology Applied
Scientific EffectCrystallisation: Crystallisation

Data Source

PatentUS9537139B2Negative electrode for non-aqueous secondary battery, and a non-aqueous secondary battery
Publication Date: 2017.01.03 MAXELL LTD

AI summary

[Objectives] The present invention provides a non-aqueous secondary battery in which a material containing Si and O as constituent elements is used in a negative electrode. The present invention provides a non-aqueous secondary battery having good charge discharge cycle characteristics, and suppressing the battery swelling associated with the charge and the discharge. Also, the present invention relates to a negative electrode that can provide the non-aqueous secondary battery. [Solution] The negative electrode includes a negative electrode active material, including a composite of a material containing Si and O as constitution elements (atom ratio x of O to Si is 0.5≦x≦1.5) in combination with a carbon material, and graphite. The graphite has an average particle diameter dg (μm) of 4 to 20 μm. The material containing Si and O as constitution elements has an average particle diameter ds (μm) of 1 μm or more. The ratio ds/dg (i.e., ds to dg) is 0.05 to 1. The material containing Si and O as constitution elements has a crystallite diameter of 50 nm or less, the crystallite diameter is calculated from a half width at a (220) plane of Si obtained by an X-ray diffraction method, using Scherrer Formula. In 100 mass % of the composite of the material containing Si and O as constitution elements, and the carbon material, a ratio of the material containing Si and O as constitution elements is 70 to 95 mass %.