Porous Protonated Garnet Surface for Stable Li-Metal Interfaces

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Solution Overview

Problem

Existing methods for forming porous surface layers on garnet thin films in Li-metal batteries are non-uniform, leading to issues such as Li dendrite formation, stress on the electrode, and delamination, which affect the battery's performance and stability.

Innovation Solution

A modified acid treatment method that involves pre-treating the garnet with water to form a uniform protonated surface, followed by acid treatment to create a uniform porous layer with specific thickness and pore size ranges, thereby stabilizing the surface and improving interfacial contact.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If conventional acid treatment is used to form porous surface layer on garnet, then porous structure is formed, but the porous layer is non-uniform leading to Li dendrite formation and delamination

Engineering Contradiction:

Improveuniformity of porous layerVSAvoidstability against Li dendrite formation and delamination

Core Design Contradiction:

Manufacturing precisionVSReliability

Solution Approach 1:

The patent applies preliminary water treatment to the garnet surface before acid treatment. This pre-treatment step creates a uniform protonated surface layer that serves as a foundation for subsequent uniform porous layer formation during acid treatment, preventing the non-uniformity that leads to dendrites and delamination

Inventive Principle:

Principle #10Preliminary action

Solution Approach 2:

The patent changes the chemical state of the garnet surface by protonating it through water treatment, transforming the surface composition from Li-rich to H-rich. This parameter change in surface chemistry enables uniform acid etching and subsequent uniform porous layer formation, resolving the uniformity issue

Inventive Principle:

Principle #35Parameter changes

2Reliability

If porous interlayer is formed to increase contact surface area, then Li dendrite formation is reduced, but manufacturing complexity increases

Engineering Contradiction:

Improveresistance to Li dendrite formationVSAvoidcomplexity of porous layer formation process

Core Design Contradiction:

ReliabilityVSDevice complexity

Solution Approach 1:

The patent uses a self-service approach where the garnet surface itself undergoes controlled chemical transformations (protonation followed by acid etching) to form the porous structure. The material's own surface chemistry is harnessed to create the desired porous morphology without requiring external porous templates or complex multi-step fabrication processes

Inventive Principle:

Principle #25Self-service

Solution Approach 2:

The patent directly creates a porous surface layer on the garnet through controlled acid etching of the protonated surface. This porous structure increases the Li-garnet contact area and prevents dendrite formation while maintaining a relatively simple two-step treatment process rather than introducing complex porous interlayer materials

Inventive Principle:

Principle #31Porous materials

3Shape

If Li plating is performed at lower temperatures for smooth interface, then interface quality improves, but Li pulverization and delamination occur due to non-uniform plating

Engineering Contradiction:

Improvesmoothness of interfaceVSAvoidadhesion of Li to garnet

Core Design Contradiction:

ShapeVSStrength

Solution Approach 1:

The patent creates a porous surface layer on the garnet that provides mechanical compliance and stress distribution capabilities. This porous structure can accommodate the volume changes and stresses associated with Li plating at lower temperatures, preventing pulverization and delamination while maintaining a smooth interface morphology

Inventive Principle:

Principle #31Porous materials

Solution Approach 2:

The patent modifies the surface chemistry and topology of the garnet through protonation and acid treatment, changing the surface energy and mechanical properties. These parameter changes enable the interface to withstand the stresses of low-temperature Li plating without failure, resolving the contradiction between interface smoothness and adhesion strength

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 method achieves a uniform porous layer on garnet thin films, reducing Li dendrite formation, stress on the electrode, and delamination, thereby enhancing the stability and performance of Li-metal batteries.

Implementation Method 1

pre-treating an air sensitive lithium-containing garnet with water to form a uniform protonated garnet surface composition

Methodology Applied

Scientific EffectIon exchange: Ion Exchange

Implementation Method 2

contacting the uniform protonated garnet surface composition with an acid to form a porous uniform protonated garnet surface composition

Methodology Applied

Scientific EffectChemical etching: Ablation

Data Source

PatentUS12341148B2Method for making uniform porous surface layer on garnet thin film

Publication Date: 2025.06.24 CORNING INC

AI summary

A solid garnet composition includes a bulk composition having a lithium garnet; and a surface composition having a protonated garnet on at least a portion of the exterior surface of the lithium garnet, such that the protonated garnet is uniformly disposed over the at least a portion of the exterior surface of the lithium garnet. A method of making a solid garnet composition includes pre-treating an air sensitive lithium-containing garnet with water to form a uniform protonated garnet surface composition; and contacting the uniform protonated garnet surface composition with an acid to form a porous uniform protonated garnet surface composition.