Pre-lithiated Silicon Anodes Using PVDF Binder

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Solution Overview

Problem

Silicon anodes in lithium-ion batteries face challenges due to large volume changes, leading to capacity loss and mechanical damage, and existing pre-lithiation methods with water-based binders result in rapid capacity fading and poor adhesion.

Innovation Solution

A pre-lithiated silicon anode is fabricated using a PVDF binder and a conductive additive, where the silicon is mixed with the binder and coated on a copper current collector, then compressed and pre-lithiated before assembly into a Li-ion cell, preserving the nanostructure and enhancing adhesion and cycle life.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Strength

If water-based binders (CMC, PAA, CMC/SBR) are used to provide rigidity and counteract volume expansion, then adhesion strength is improved, but capacity retention deteriorates due to rapid capacity fading

Engineering Contradiction:
Improveadhesion strengthVSAvoidcapacity retention
Core Design Contradiction:
StrengthVSReliability

Solution Approach 1:

The patent changes the binder material parameter from water-based (CMC, PAA) to organic-based PVDF, which fundamentally alters the binding mechanism and electrochemical stability. PVDF provides adequate adhesion while maintaining capacity retention through its electrochemical inertness and compatibility with pre-lithiated silicon anodes

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent adopts the binder system from conventional Li-ion batteries (PVDF used with graphite anodes) and adapts it for silicon anodes. This copying of a proven binder system from another application (graphite anodes) resolves the contradiction by providing both adequate adhesion and long-term capacity retention

Inventive Principle:
Principle #26Copying

2Duration of action of stationary object

If pre-lithiation is performed to compensate for irreversible Li loss, then cycle life is improved, but adhesion deteriorates when using water-based binders

Engineering Contradiction:
Improvecycle lifeVSAvoidadhesion
Core Design Contradiction:
Duration of action of stationary objectVSStrength

Solution Approach 1:

The patent changes the binder parameter to PVDF, which maintains its binding functionality even after pre-lithiation treatment. PVDF's organic-based chemistry and fluorinated structure provide stable adhesion to silicon particles throughout the pre-lithiation process and subsequent cycling, unlike water-based binders that fail to maintain adhesion

Inventive Principle:
Principle #35Parameter changes

3Quantity of substance

If silicon content is increased to achieve high capacity, then energy density is improved, but mechanical damage worsens due to large volume changes

Engineering Contradiction:
Improvesilicon contentVSAvoidmechanical integrity
Core Design Contradiction:
Quantity of substanceVSStrength

Solution Approach 1:

The patent performs pre-lithiation as a preliminary action before cell assembly, which pre-compensates for the irreversible lithium loss that occurs during initial cycling. This preliminary lithium insertion stabilizes the silicon structure and reduces subsequent volume changes, allowing high silicon content to be used without mechanical damage

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The patent copies the binder system from conventional graphite anodes (PVDF) and applies it to high-silicon anodes. This proven binder provides the mechanical integrity needed to withstand large volume changes, enabling high silicon content while maintaining structural stability

Inventive Principle:
Principle #26Copying

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

This approach provides improved capacity retention and extended cycle life, with the PVDF binder allowing for expansion and contraction, and the pre-lithiation process ensuring Li ions are inserted before cell assembly, resulting in a Li-ion cell with over 70% capacity retention beyond 1000 cycles.

Implementation Method 1

the PVDF binder allowing for expansion and contraction

Methodology Applied
Scientific EffectElasticity: Elasticity

Implementation Method 2

silicon based anode materials are capable of alloying with relatively large amounts of lithium

Methodology Applied
Scientific EffectAlloying:

Implementation Method 3

the pre-lithiation process ensuring Li ions are inserted before cell assembly

Methodology Applied
Scientific EffectIon insertion:

Data Source

PatentEP3201982B1Pre-lithiated silicon anodes with PVDF binder
Publication Date: 2020.05.27 A123 SYSTEMS LLC
  • EP3201982B1 patent drawingFigure 1A~1B
  • EP3201982B1 patent drawingFigure 2
  • EP3201982B1 patent drawingFigure 3

AI summary

A pre-lithiated silicon anode comprising a PVDF binder at 5-12 wt. % for use in a Li-ion cell is provided. In particular instances, a conductive additive may be added at less than 5 wt. %. The Si anode with PVDF binder is pre-lithiated prior to cell assembly and following Si anode fabrication. The combination of pre-lithiation and PVDF in the Si anode for use in a rechargeable Li-ion cell shows the unexpected result of extending the cycle life.