Ammonium Complex Metal Halide Electrolytes for Low-Temperature Synthesis

Resolve Bottlenecks,
Find Innovative Solutions
Generate Solutions

Solution Overview

Problem

Current solid electrolyte materials for solid-state lithium batteries face challenges such as high synthesis temperatures, brittleness, hygroscopicity, safety concerns, and limited ionic conductivity, making them unsuitable for mass production and posing risks due to their reactivity with moisture and heat.

Innovation Solution

Development of ammonium-containing complex metal halides with specific compositions and structures that enhance bulk ion conductivity, allowing for safer and more efficient production methods, including a range of ionic conductivities from 0.001 mS/cm to 15 mS/cm across various temperatures.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If oxide based materials are used for solid electrolyte, then chemical and electrochemical stability is improved, but synthesis temperature must be above 1000-1200 °C and ionic conductivity is limited to up to 1.0 mS/cm at room temperature

Engineering Contradiction:
Improvechemical and electrochemical stabilityVSAvoidsynthesis temperature
Core Design Contradiction:
ReliabilityVSUse of energy by stationary object

Solution Approach 1:

The patent changes the chemical composition parameters by introducing fluorine and ammonium into the solid electrolyte structure, forming compounds like (NH4)3Li3YCl9 and (NH4)3Li3YBr9. This compositional parameter change enables synthesis at lower temperatures (400-650°C) while achieving ionic conductivities exceeding 1 mS/cm at room temperature, resolving the contradiction between stability and synthesis energy requirements

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates composite electrolyte materials combining ammonium-containing complex metal halides with specific stoichiometric ratios of lithium, rare earth metals, and halogens. These composite structures achieve both the chemical stability of oxide materials and the lower synthesis temperature/higher ionic conductivity characteristics of halide materials

Inventive Principle:
Principle #40Composite materials

2Adaptability or versatility

If halide solid electrolytes are used, then deformability and plasticity are improved allowing high compatibility with active electrode materials, but they are hygroscopic and form hydrates or undergo hydrolysis upon exposure to moisture

Engineering Contradiction:
Improvecompatibility with active electrode materialsVSAvoidhygroscopicity and hydrolysis
Core Design Contradiction:
Adaptability or versatilityVSObject-affected harmful factors

Solution Approach 1:

The patent applies local quality by creating specific crystal structures where fluorine atoms are positioned to shield the hydrolytically sensitive metal-halogen bonds. The fluorine substitution at specific lattice positions creates localized regions of enhanced stability while maintaining the overall deformability and plasticity of the halide structure, resolving the contradiction between adaptability and moisture resistance

Inventive Principle:
Principle #3Local quality

3Reliability

If sulfide solid electrolytes are used, then ionic conductivity is improved (up to 25 mS/cm), but they have poor electrochemical stability and release toxic H2S gas when reacting with water and heat

Engineering Contradiction:
Improveionic conductivityVSAvoidtoxic H2S gas release
Core Design Contradiction:
ReliabilityVSObject-generated harmful factors

Solution Approach 1:

The patent converts the harmful reactivity of sulfides by replacing the sulfur component with fluorine-containing ammonium complexes. The fluorine atoms, which are highly electronegative and form strong bonds, replace the weak S-H bonds that lead to H2S release. This transformation maintains high ionic conductivity (exceeding 1 mS/cm at room temperature) while eliminating the toxic gas generation hazard, effectively converting a harmful material system into a safe one

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

4Reliability

If high energy ball milling based solid-state synthesis methods are used for halides, then room temperature ionic conductivity above 1 mS/cm is achieved, but expensive binary halide reactants and high temperature annealing are required making mass production difficult

Engineering Contradiction:
Improveroom temperature ionic conductivityVSAvoidmass production feasibility
Core Design Contradiction:
ReliabilityVSEase of manufacture

Solution Approach 1:

The patent applies preliminary action by pre-forming ammonium halide complexes with controlled stoichiometry before the final sintering step. The reactants are prepared in advance with precise compositional ratios, and the synthesis proceeds in a single low-temperature step (400-650°C) without requiring subsequent high-temperature annealing or expensive binary halide reactants, enabling straightforward mass production while achieving ionic conductivities above 1 mS/cm

Inventive Principle:
Principle #10Preliminary action

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 ammonium-containing complex metal halides provide improved ionic conductivity and safety, enabling cost-effective mass production of solid-state lithium batteries with reduced risks from moisture and heat reactivity.

Implementation Method 1

The solid electrolyte material can have improved bulk ion conductivity. In embodiments, the solid electrolyte material can have a bulk ion conductivity ranging from 0.001 mS/cm to 15 mS/cm for a temperature range from -80°C to 200°C

Methodology Applied
Scientific EffectIonic conduction: Conduction (electrical)

Data Source

PatentEP4101021B1Electrolyte material and methods of forming
Publication Date: 2025.09.03 SAINT GOBAIN CERAMICS & PLASTICS INC
  • EP4101021B1 patent drawingFigure 1
  • EP4101021B1 patent drawingFigure 2
  • EP4101021B1 patent drawing

AI summary

A solid electrolyte material can include an ammonium-containing complex metal halide, in an embodiment, the ammonium-containing complex metal halide can be represented by (NH4)nM3-z(Mek+)fXn+3-z+k*f, wherein 0<n, 0≤z<3, 2≤k<6, 0≤f≤1; M comprises at least an alkali metal element, X comprises a halogen, and Me comprises a divalent metal element, a trivalent metal element, a tetravalent metal element, a pentavalent metal element, a hexavalent metal element or any combination thereof.