Sulfide Solid Electrolyte Composition for Stable High Li-Ion Phases

Resolve Bottlenecks,
Find Innovative Solutions
Generate Solutions

Solution Overview

Problem

Existing methods for producing sulfide solid electrolytes face issues such as nitrogen discharge to the outside of the system, low thermal stability, and limited temperature range for high Li-ion conductivity phases, which affect the performance and stability of all-solid-state batteries.

Innovation Solution

A method involving the use of specific raw material compounds containing N, an element A, and an element M, selected based on high defect generation energy, to suppress nitrogen discharge and enhance thermal stability, including a composition preparation, reaction, and heat treatment process.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If Li3N is used as a raw material for sulfide solid electrolyte, then atmospheric stability (water resistance) is improved, but nitrogen is discharged to the outside of the system

Engineering Contradiction:
Improveatmospheric stabilityVSAvoidnitrogen discharge
Core Design Contradiction:
ReliabilityVSObject-generated harmful factors

Solution Approach 1:

The patent changes the chemical composition parameters by introducing specific elements (Al, Ta, Si, Sc, Mg, Nb, B, Hf, C, P, Zr, or Ti) to form new compounds that suppress nitrogen discharge while maintaining atmospheric stability. This modifies the raw material system from simple Li3N to composite sulfide solid electrolytes with enhanced properties.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates composite sulfide solid electrolyte materials by combining multiple elements (Li, P, S, N, and additional elements like Al, Ta, Si, etc.) to form new compound systems. These composite materials simultaneously achieve atmospheric stability and suppress nitrogen discharge through synergistic effects of the constituent elements.

Inventive Principle:
Principle #40Composite materials

2Reliability

If excessively high heat treatment temperature is used to precipitate high Li-ion conductive phase, then Li-ion conductivity is improved, but low Li-ion conductive phase is also precipitated

Engineering Contradiction:
ImproveLi-ion conductivityVSAvoidphase composition control
Core Design Contradiction:
ReliabilityVSManufacturing precision

Solution Approach 1:

The patent optimizes the heat treatment temperature parameter based on the specific composition of the sulfide solid electrolyte. By adjusting the temperature within a controlled range and using compositional modifications (adding elements like Al, Ta, Si, etc.), the patent achieves selective precipitation of high Li-ion conductive phases while suppressing the formation of low conductive phases.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates local compositional variations by introducing specific elements that preferentially stabilize certain phases. These elements create local regions with different properties, allowing high Li-ion conductive phases to form selectively while preventing the formation of low conductive phases even at elevated temperatures.

Inventive Principle:
Principle #3Local quality

3Stability of the object's composition

If Li3N is added to increase the temperature difference between high and low Li-ion conductive phase formation, then phase stability is improved, but the temperature difference is limited to approximately 30°C

Engineering Contradiction:
Improvephase stabilityVSAvoidtemperature range
Core Design Contradiction:
Stability of the object's compositionVSAdaptability or versatility

Solution Approach 1:

The patent develops composite sulfide solid electrolyte systems that combine multiple elements (Li, P, S, N with additional elements) to create new phase formation mechanisms. These composite materials achieve larger temperature differences between phase transitions, expanding the stable temperature range beyond the limited 30°C achieved with Li3N alone.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The patent modifies the compositional parameters by introducing elements that significantly alter the phase diagram and phase transition temperatures. This creates a broader temperature window for stable high Li-ion conductive phases, enhancing both phase stability and temperature range adaptability.

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 effectively suppresses nitrogen discharge, enhances thermal stability, and expands the temperature range for high Li-ion conductivity phases, improving the performance and stability of sulfide solid electrolytes and all-solid-state batteries.

Implementation Method 1

a raw material composition containing Li2S, P2S5, LiI, and LiBr is made amorphous

Methodology Applied
Scientific EffectAmorphization:

Implementation Method 2

subjected to a heat treatment to precipitate a high Li-ion conductive phase

Methodology Applied
Scientific EffectPrecipitation: Precipitation

Implementation Method 3

heating the intermediate to obtain a sulfide solid electrolyte

Methodology Applied
Scientific EffectHeat treatment: Heat Treatment

Data Source

PatentEP4099466B1Sulfide solid electrolyte abd all-solid-state battery
Publication Date: 2025.08.13 GS YUASA INT LTD
  • EP4099466B1 patent drawingFigure 1~2
  • EP4099466B1 patent drawingFigure 3
  • EP4099466B1 patent drawingFigure 4

AI summary

The present invention relates to a crystalline sulfide solid electrolyte comprising P, S, N, an element A, an element X, and an element M, and having crystallinity (A represents at least one element selected from the group consisting of Li, Na, and K; X represents at least one element selected from the group consisting of Cl, Br, and I; M represents at least one element selected from the group consisting of Al, Ta, Si, Sc, Mg, Nb, B, Hf, C, Zr, and Ti), wherein the crystalline structure has diffraction peaks at 2θ = 20.2° ± 0.5° and 23.6° ± 0.5° in X-ray diffraction measurement with a CuKα line.