Carbon-Coated Macro-Porous Silicon Anodes for Lithiation Swelling

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Solution Overview

Problem

Lithium-ion batteries using carbon-based anodes face limitations in charging capacity and mechanical stability due to the volume change and formation of unstable solid-electrolyte interphase layers during lithiation, making silicon anodes unsuitable for practical battery systems.

Innovation Solution

A carbon-coated macro-porous silicon material is developed using a CO2-thermic oxidation process, where silicon is reacted with metals like magnesium or calcium to form metal silicides, which are then oxidized with CO2 to create particles with carbon coatings and macro-pores, enhancing electrical conductivity and mechanical stability.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Quantity of substance

If silicon is used as anode material to increase charging capacity, then charging capacity is improved, but mechanical stability deteriorates due to volume change

Engineering Contradiction:
Improvecharging capacityVSAvoidmechanical stability
Core Design Contradiction:
Quantity of substanceVSStrength

Solution Approach 1:

The patent employs porous silicon anode material with controlled porosity (30-70% void volume) to accommodate the 300% volume expansion during lithiation. The porous structure provides internal space for volume change without mechanical failure, maintaining structural integrity while enabling high capacity silicon-based anodes.

Inventive Principle:
Principle #31Porous materials

Solution Approach 2:

The patent creates composite structures combining silicon with carbon materials (graphite, amorphous carbon) and binding agents. These composites leverage silicon's high capacity while using carbon's mechanical stability and flexibility to constrain silicon during volume changes, preventing pulverization.

Inventive Principle:
Principle #40Composite materials

2Quantity of substance

If bulk silicon is used for high capacity, then charging capacity is improved, but cyclability deteriorates due to pulverization

Engineering Contradiction:
Improvecharging capacityVSAvoidcyclability
Core Design Contradiction:
Quantity of substanceVSDuration of action of stationary object

Solution Approach 1:

The patent divides bulk silicon into nanoscale particles (50-500 nm diameter) to prevent pulverization. The segmented nanocrystalline structure maintains electrical connectivity while reducing mechanical stress during lithiation/delithiation cycles, enabling long-term cyclability.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The patent applies thin carbon coating layers (5-50 nm) on silicon surfaces to create flexible protective shells. These carbon layers accommodate volume changes through elastic deformation while protecting the silicon core from direct contact with electrolyte and preventing particle aggregation.

Inventive Principle:
Principle #30Flexible shells and thin films

3Quantity of substance

If silicon anodes are used to increase capacity, then charging capacity is improved, but reliability deteriorates due to unstable solid-electrolyte interphase formation

Engineering Contradiction:
Improvecharging capacityVSAvoidsolid-electrolyte interphase stability
Core Design Contradiction:
Quantity of substanceVSReliability

Solution Approach 1:

The patent applies preliminary carbon coating treatment to silicon surfaces before battery assembly. This pre-formed carbon layer acts as a stable interface that prevents direct silicon-electrolyte contact, eliminating unstable SEI formation and enabling reliable first-cycle efficiency.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The patent introduces carbon materials as intermediary layers between silicon and electrolyte. This intermediate carbon phase mediates the interface, providing stable SEI formation while maintaining lithium ion transport, thus improving cycle reliability.

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

The carbon-coated macro-porous silicon anodes exhibit high electrical capacity and cyclability, with improved charging/discharging performance and stability, overcoming the limitations of traditional carbon-based anodes by accommodating volume changes and preventing solid-electrolyte interphase layer formation.

Implementation Method 1

the CO 2 -thermic oxidation process includes an initial solid state reaction between silicon and a metal or metal mixture to form a metal silicide

Methodology Applied
Scientific EffectCO2-thermic oxidation: Oxidation

Implementation Method 2

the CO 2 -thermic oxidation process includes an initial solid state reaction between silicon and a metal or metal mixture to form a metal silicide

Methodology Applied
Scientific EffectSolid state reaction: Chemical Bonding

Implementation Method 3

the carbon-coated macro-porous silicon anodes exhibit high electrical capacity and cyclability, with improved charging/discharging performance and stability

Methodology Applied
Scientific EffectElectrical conduction: Conduction (electrical)

Implementation Method 4

lithiation in silicon can involve about 300% volume change. Thus, after a few charge-discharge cycles, a bulk silicon-based anode would be pulverized

Methodology Applied
Scientific EffectVolume expansion: Thermal Expansion

Data Source

PatentEP3679613B1Batteries with anodes of carbon-coated macro-porous silicon
Publication Date: 2024.02.28 WASHINGTON STATE UNIVERSITY
  • EP3679613B1 patent drawingFigure 1A~1B
  • EP3679613B1 patent drawingFigure 2~4B
  • EP3679613B1 patent drawingFigure 3A~3D

AI summary

Silicon materials suitable for use as an anode material and associated method of production are disclosed herein. In one embodiment, a silicon material includes crystalline silicon in a matrix and macro-scale pores distributed in the matrix of the crystalline silicon. The macro-scale pores can have a size greater than 100 nanometers, and surfaces of crystalline silicon in the macro-scale pores are coated with carbon.