Si@C Core/Shell Nanomaterials for Li-Ion Anode Volume Expansion

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Solution Overview

Problem

Current lithium-ion battery anodes, particularly those using graphite, face limitations in electric conductivity and severe volume changes during charging and discharging, leading to poor cycling performance and high costs, making them unsuitable for long-distance electric vehicle applications.

Innovation Solution

A silicon core/carbon shell nanomaterial is fabricated using a hydrothermal method, where silicon nanoparticles are aggregated and encased in a carbon shell, providing increased conductivity and accommodating volume changes through internal gaps, thereby enhancing cycling stability and capacity.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Quantity of substance

If silicon nanoparticles are used as anode material to increase capacity, then the specific capacity is improved (more than 10 times graphite), but severe volume change during Li insertion/extraction occurs leading to poor cycling performance

Engineering Contradiction:
Improvespecific capacityVSAvoidcycling performance
Core Design Contradiction:
Quantity of substanceVSReliability

Solution Approach 1:

The patent encapsulates silicon nanoparticles within a carbon shell structure, creating a nested configuration where the silicon core is protected by the carbon shell. This nested structure allows the high-capacity silicon to undergo volume changes during lithium insertion/extraction while the carbon shell maintains structural integrity and prevents particle breakdown, thereby improving cycling performance while retaining high specific capacity.

Inventive Principle:
Principle #7Nested doll (Nesting)

Solution Approach 2:

The carbon shell acts as a flexible protective layer that can accommodate the volume expansion and contraction of silicon nanoparticles during charging and discharging cycles. This flexible shell structure prevents the silicon particles from breaking down while maintaining electrical conductivity and structural stability, directly addressing the poor cycling performance issue.

Inventive Principle:
Principle #30Flexible shells and thin films

2Quantity of substance

If silicon particles are used to increase capacity, then the specific capacity is improved, but low intrinsic electric conductivity results in poor electrical performance

Engineering Contradiction:
Improvespecific capacityVSAvoidelectric conductivity
Core Design Contradiction:
Quantity of substanceVSReliability

Solution Approach 1:

The patent creates a composite material structure combining silicon nanoparticles with a carbon shell. The carbon component provides high electrical conductivity while the silicon core provides high specific capacity. This composite structure synergistically combines the advantages of both materials, achieving both high capacity and good electrical conductivity simultaneously.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The carbon shell is specifically designed to surround only the silicon nanoparticles, creating a localized conductive network around each high-capacity particle. This local quality approach ensures that the conductivity enhancement is precisely where needed - at the interface between silicon and electrolyte - while maintaining the high specific capacity of the silicon core.

Inventive Principle:
Principle #3Local quality

3Reliability

If graphite anode is used to maintain structural stability, then cycling performance is improved, but specific capacity is limited to about 350 mAh/g

Engineering Contradiction:
Improvecycling performanceVSAvoidspecific capacity
Core Design Contradiction:
ReliabilityVSQuantity of substance

Solution Approach 1:

The patent employs a composite anode material consisting of silicon nanoparticles embedded in a carbon matrix. This composite structure combines the high capacity of silicon with the structural stability and conductivity of carbon, achieving both improved cycling performance and high specific capacity, thereby overcoming the limitations of pure graphite anodes.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The anode is segmented into discrete silicon nanoparticle units, each encapsulated in its own carbon shell. This segmentation allows each nanoparticle to independently accommodate volume changes during lithium insertion/extraction, preventing aggregate structural failure while maintaining overall anode stability and high capacity.

Inventive Principle:
Principle #1Segmentation

4Reliability

If conventional high temperature vacuum methods are used to synthesize silicon nanowires, then volume change problem is addressed, but manufacturing cost increases to 1150-5000 USD per gram and scale-up becomes impossible

Engineering Contradiction:
Improvevolume change accommodationVSAvoidmanufacturing cost
Core Design Contradiction:
ReliabilityVSEase of manufacture

Solution Approach 1:

The patent employs inexpensive, readily available materials and simple hydrothermal synthesis conditions to create the silicon@carbon core/shell structure. By using common chemicals and straightforward processing at moderate temperatures and pressures, the method dramatically reduces manufacturing costs compared to expensive vacuum-based nanowire synthesis, making large-scale production economically viable.

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

Solution Approach 2:

The patent changes the synthesis parameters from extreme conditions (high temperature, vacuum) to milder conditions (hydrothermal treatment at moderate temperature and pressure). This parameter change maintains the effectiveness of volume change accommodation while dramatically improving ease of manufacture and reducing costs, enabling scalable production.

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 Si@C core/shell structure achieves stable cycle performance and high capacity, maintaining structural integrity and conductivity, with the ability to accommodate volume changes, significantly improving lithium-ion battery performance while being cost-effective and scalable.

Implementation Method 1

heating the reaction mixture by a hydrothermal process to form one or more silicon cores and one or more carbon shells

Methodology Applied
Scientific EffectHydrothermal carbonization:

Implementation Method 2

hydrothermal carbonization of glucose in the presence of silicon nanoparticles

Methodology Applied
Scientific EffectHydrothermal carbonization of glucose:

Implementation Method 3

calcinating the silicon cores enclosed by the carbon shell by a calcination process for further carbonizing the carbon shells

Methodology Applied
Scientific EffectCalcination:

Implementation Method 4

calcination process for further carbonizing the carbon shells

Methodology Applied
Scientific EffectCarbonization:

Data Source

PatentEP2887431B1Silicon core/shell nanomaterials for high performance anode of lithium ion batteries
Publication Date: 2019.05.15 NANO & ADVANCED MATERIALS INST
  • EP2887431B1 patent drawingFigure 1(A)~1(B)
  • EP2887431B1 patent drawingFigure 2(A)~2(C)
  • EP2887431B1 patent drawingFigure 3

AI summary

The present invention is to tackle the volume expansion problem of the Si anode materials in the application of lithium ion batteries. In the present invention, a simple and green hydrothermal method is use to form loosely packed Si@C core/shell structure. A carbon coating layer is formed on controllably aggregated silicon nanoparticles in a one-step procedure by the hydrothermal carbonization of a carbon-rich precursor.