Polymer-Grafted Silicon Particles for Stable Aqueous Anodes

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Solution Overview

Problem

Lithium ion batteries with silicon anode materials face challenges such as hydrogen formation, inhomogeneous electrode coatings, and reduced capacity due to silicon's reactivity with water and volume changes during charging/discharging, leading to mechanical stress and passivation layers that reduce lithium mobility.

Innovation Solution

Polymer-grafted silicon particles with average sizes of 700 nm to 10 μm, where polymers are attached via covalent bonds using radically initiated polymerization in an aqueous medium, ensuring wash-stable binding and minimizing hydrogen formation, and providing homogeneous anode coatings.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Quantity of substance

If silicon particles are used in aqueous ink formulations, then high theoretical material capacity (4200 mAh/g) is achieved, but hydrogen formation and oxidation occur due to silicon's reactivity with water

Engineering Contradiction:
Improvesilicon contentVSAvoidhydrogen formation
Core Design Contradiction:
Quantity of substanceVSObject-generated harmful factors

Solution Approach 1:

A polymer coating is introduced as an intermediary layer between the silicon particles and the aqueous environment. This polymer shell prevents direct contact between water and silicon surface, thereby eliminating hydrogen formation and oxidation while allowing lithium ion transport. The polymer acts as a protective mediator that enables silicon to function in aqueous ink formulations without suffering from its inherent reactivity issues.

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The high reactivity of silicon with water, which normally causes harmful hydrogen formation, is converted into a beneficial protective mechanism. By applying a polymer coating, the silicon's reactivity is directed toward bonding with the polymer rather than water, transforming the potentially harmful reactive surface into a controlled interface that protects the silicon core while enabling stable aqueous processing.

Inventive Principle:
Principle #22Blessing in disguise (Convert harm into benefit)

2Stability of the object's composition

If polymers are merely coated on silicon particles, then surface coverage is achieved, but wash-stable binding is not achieved during aqueous processing

Engineering Contradiction:
Improvepolymer binding stabilityVSAvoidcoating retention
Core Design Contradiction:
Stability of the object's compositionVSReliability

Solution Approach 1:

The polymer coating is applied to the silicon particles before the ink formulation and processing steps. This preliminary coating ensures that the silicon surface is protected from water contact during subsequent aqueous processing, mixing, and application steps. The pre-formed polymer shell maintains its integrity throughout processing, preventing both hydrogen formation and polymer loss.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The polymer coating serves as a stable intermediary layer that bonds to the silicon surface and provides a water-resistant barrier. This intermediary structure ensures that the coating remains firmly attached during aqueous processing while maintaining the silicon's electrochemical functionality, achieving both wash stability and coating retention.

Inventive Principle:
Principle #24Intermediary (Mediator)

3Quantity of substance

If silicon particles undergo extreme volume changes during charging/discharging, then high capacity is achieved, but mechanical stress leads to loss of electrical contact and electrode deterioration

Engineering Contradiction:
Improvelithium capacityVSAvoidelectrode structural integrity
Core Design Contradiction:
Quantity of substanceVSStrength

Solution Approach 1:

A flexible polymer coating is applied around the silicon particles, forming a compliant shell that can accommodate the extreme volume changes (up to 300%) during lithium insertion and extraction. This flexible shell acts as a buffer that absorbs mechanical stress, preventing particle fracture and maintaining electrical contact within the electrode structure, thereby preserving both capacity and structural integrity over multiple cycles.

Inventive Principle:
Principle #30Flexible shells and thin films

Solution Approach 2:

The electrode is designed as a composite material system combining silicon particles with a polymer matrix. The polymer component provides mechanical flexibility and stress distribution, while the silicon provides high capacity. This composite structure allows the electrode to withstand volume changes without deterioration, maintaining both electrical contact and structural integrity.

Inventive Principle:
Principle #40Composite materials

4Reliability

If silicon surface reacts with electrolyte constituents, then passivating protective layers (SEI) are formed, but irreversible loss of mobile lithium occurs

Engineering Contradiction:
Improvesurface protectionVSAvoidlithium loss
Core Design Contradiction:
ReliabilityVSLoss of substance

Solution Approach 1:

The polymer coating serves as an intermediary barrier between the silicon surface and the electrolyte constituents. This protective shell prevents direct reaction between silicon and electrolyte, controlling SEI formation at the polymer-electrolyte interface rather than at the silicon surface. This intermediary positioning reduces irreversible lithium consumption while maintaining necessary surface protection.

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 polymer-grafted silicon particles result in stable, homogeneous anode coatings with reduced reactivity, improved electrochemical performance, and enhanced cycle stability of lithium ion batteries, maintaining high silicon incorporation and preventing foaming in aqueous ink formulations.

Implementation Method 1

polymers are attached via covalent bonds using radically initiated polymerization in an aqueous medium

Methodology Applied
Scientific EffectRadically initiated polymerization: Photopolymerisation

Implementation Method 2

polymers are attached via covalent bonds

Methodology Applied
Scientific EffectCovalent bonding: Chemical Bonding

Implementation Method 3

the silicon surface is highly reactive to water and is oxidized on contact with water forming silicon oxides and hydrogen

Methodology Applied
Scientific EffectOxidation: Oxidation

Data Source

PatentUS11158855B2Polymer-grafted silicon particles
Publication Date: 2021.10.26 WACKER CHEMIE AG

AI summary

The invention relates to polymer-grafted silicon particles, wherein the silicon particles have an average particle size (d50) of 700 nm to 10 μm and the polymers of the polymer-grafted silicon particles are attached to the silicon particles in a wash-stable manner in an aqueous medium.