Bis(Fluorosulfonyl)Imide Salt Synthesis With Low-TOC Fluorination

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Solution Overview

Problem

Current methods for producing bis(fluorosulfonyl)imide and its salts, such as LiFSI, face challenges in achieving high purity and economic feasibility at an industrial scale due to issues like excessive solvent use, by-product management, and impurity contamination, particularly in battery electrolyte applications.

Innovation Solution

A method involving the reaction of bis(chlorosulfonyl)imide with an onium halide in the absence or minimal presence of solvent to produce onium salts of bis(chlorosulfonyl)imide, followed by reaction with onium fluoride to obtain onium salts of bis(fluorosulfonyl)imide, and subsequently with an alkali metal salt to produce alkali metal salts of bis(fluorosulfonyl)imide, reducing solvent usage and by-product waste while maintaining high purity.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If fluorination reaction is conducted in organic solvent, then reaction proceeds smoothly, but heat generated degrades the solvent and increases TOC content

Engineering Contradiction:
Improvereaction smoothnessVSAvoidTOC content
Core Design Contradiction:
ReliabilityVSManufacturing precision

Solution Approach 1:

The invention changes the physical state parameter of the reaction medium from liquid organic solvent to molten salt state. By conducting the fluorination reaction in molten HFSO3N(SO2F) at temperatures above its melting point (100-150°C), the process eliminates solvent degradation and TOC generation while maintaining reaction efficiency through the reactive medium's high temperature state.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention replaces expensive organic solvents that require purification and disposal with a reusable molten salt system. The molten HFSO3N(SO2F) acts as both reactant and reaction medium, eliminating the need for separate solvent recovery and purification steps, thereby reducing operational costs and complexity.

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

2Manufacturing precision

If significant amount of NH4F(HF)p is used for fluorination, then chlorosulfonlyimide compound is fully fluorinated, but process becomes not cost-effective

Engineering Contradiction:
Improvefluorination completenessVSAvoidcost-effectiveness
Core Design Contradiction:
Manufacturing precisionVSEase of manufacture

Solution Approach 1:

The invention changes the chemical form of the fluorinating agent from NH4F(HF)p to HFSO3N(SO2F). This parameter change in reagent identity provides superior fluorinating capability with lower stoichiometric requirements, improving both conversion efficiency and cost-effectiveness simultaneously.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention employs a composite molecular structure in HFSO3N(SO2F) that combines fluorinating functionality with sulfonimide backbone stability. This composite structure allows the reagent to act as both fluorinating agent and potential product precursor, reducing waste and improving atom economy.

Inventive Principle:
Principle #40Composite materials

3Productivity

If chlorosulfonlyimide compound is reacted with fluorinating agent to produce NH4FSI, then fluorosulfonylimide salt is obtained, but high amounts of solid halogenated salt by-products are generated

Engineering Contradiction:
ImproveNH4FSI productionVSAvoidhalogenated salt waste
Core Design Contradiction:
ProductivityVSLoss of substance

Solution Approach 1:

The invention converts the harmful halogenated by-products into beneficial reusable materials. The HCl gas generated during fluorination is captured and converted to HFSO3N(SO2F) through reaction with SO3 and additional reagents, closing the material cycle and eliminating waste disposal needs.

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

Solution Approach 2:

Instead of discarding the HCl by-product as waste, the invention implements a recovery system where HCl is captured, converted to valuable HFSO3N(SO2F) reagent, and reused in the fluorination process. This circular approach eliminates waste and reduces raw material consumption.

Inventive Principle:
Principle #34Discarding and recovering

4Manufacturing precision

If additional treatment steps are performed to remove by-products and achieve required purity, then product purity is improved, but production cost and time increase

Engineering Contradiction:
Improveproduct purityVSAvoidproduction efficiency
Core Design Contradiction:
Manufacturing precisionVSProductivity

Solution Approach 1:

The invention performs preliminary purification by conducting the fluorination reaction directly in molten HFSO3N(SO2F) without organic solvents. This preliminary action prevents solvent-related impurities and simplifies downstream processing, as the reaction medium itself is the desired product or can be easily separated.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The invention extracts the problematic organic solvent component from the reaction system entirely, replacing it with molten inorganic salt medium. This extraction of the harmful element (organic solvent) eliminates the need for complex solvent removal and purification steps while maintaining reaction effectiveness.

Inventive Principle:
Principle #2Taking out (Extraction)

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 results in high-purity onium and alkali metal salts of bis(fluorosulfonyl)imide with reduced TOC impurities, lower production costs, and the ability to recycle by-products, enhancing the process's economic and environmental sustainability.

Implementation Method 1

reacting a bis(chlorosulfonyl)imide or a salt thereof with an onium halide other than an onium fluoride to produce an onium salt of bis(chlorosulfonyl)imide

Methodology Applied
Scientific EffectChemical reaction: Chemical Bonding

Implementation Method 2

reacting the onium salt of CSI with an onium fluoride to produce an onium salt of FSI

Methodology Applied
Scientific EffectChemical reaction: Chemical Bonding

Implementation Method 3

reacting the onium salt of FSI with an alkali metal salt to obtain an alkali metal salt of FSI

Methodology Applied
Scientific EffectChemical reaction: Chemical Bonding

Data Source

PatentUS20240051828A1Method for producing onium sulfonyl imide salts and alkali metal sulfonyl imide salts
Publication Date: 2024.02.15 SPECIALTY OPERATIONS FRANCE

AI summary

The invention relates to a new method for producing an onium salt of bis(fluorosulfonyl)imide and an alkali metal salt of bis(fluorosulfonyl)imide of high purities, as industrial scale, and with a reasonable cost when compared to the other available methods. Said method comprises the steps of reacting bis(chlorosulfonyl)imide or salts thereof with an onium halide other than an onium fluoride to produce an onium salt of bis(chlorosulfonyl)imide, reacting the onium salt of bis(chlorosulfonyl)imide with an onium fluoride to produce an onium salt of bis(fluorosulfonyl)imide; the onium salt of bis(fluorosulfonyl)imide may be further reacted with an alkali metal salt to obtain an alkali metal salt of bis(fluorosulfonyl)imide.