Urea-Based Ionic Liquid Electrolytes for Aluminum-Ion Batteries

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Solution Overview

Problem

Aluminum-ion batteries face challenges such as high costs due to expensive organic cations, deposition issues from anionic species, extreme hygroscopicity of ionic liquids leading to side reactions, and corrosion of metal substrates, which affect coulombic efficiency and cycle life.

Innovation Solution

Development of improved ionic liquid electrolytes using mixtures of aluminum chloride (AlCl3) and organic compounds like urea or acetamide, along with corrosion-resistant current collectors and hydrophilic polymer binders, to facilitate cost-effective, scalable, and stable aluminum-ion batteries with enhanced energy density and cycle life.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If conventional ionic liquids with organic cations are used as electrolytes, then the battery can operate, but the cost is high

Engineering Contradiction:
Improvebattery operationVSAvoidcost
Core Design Contradiction:
ReliabilityVSEase of manufacture

Solution Approach 1:

The patent replaces expensive conventional ionic liquid cations (imidazolium, pyridinium, ammonium) with inexpensive urea molecules. Urea is a cheap, readily available compound that forms stable ionic liquids with AlCl3, dramatically reducing electrolyte cost while maintaining functional performance

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

Solution Approach 2:

The patent changes the chemical composition parameters of the ionic liquid by using specific AlCl3:urea molar ratios (1.1 to 1.7, preferably 1.2 to 1.5). This parameter optimization ensures the formation of the desired [AlCl2(urea)n]+ cations while maintaining liquid state and electrochemical performance at low cost

Inventive Principle:
Principle #35Parameter changes

2Productivity

If anionic species are used for aluminum deposition, then the battery can charge, but deposition issues occur affecting coulombic efficiency

Engineering Contradiction:
Improvecharging capabilityVSAvoidcoulombic efficiency
Core Design Contradiction:
ProductivityVSReliability

Solution Approach 1:

The patent inverts the conventional approach by using cationic [AlCl2(urea)n]+ species instead of anionic species for aluminum deposition. This inversion enables reversible aluminum plating/stripping at the anode with high coulombic efficiency (95-99%), solving the deposition issues associated with anionic mechanisms

Inventive Principle:
Principle #13The other way round (Inversion)

Solution Approach 2:

The patent optimizes the AlCl3:urea molar ratio to ensure sufficient AlCl3 content (at least 1.1:1 ratio) to form the cationic [AlCl2(urea)n]+ species. This parameter control is critical for achieving the desired cationic deposition mechanism and high coulombic efficiency

Inventive Principle:
Principle #35Parameter changes

3Ease of operation

If conventional ionic liquids are used, then the battery can operate, but extreme hygroscopicity leads to side reactions

Engineering Contradiction:
Improvebattery operationVSAvoidside reactions from moisture
Core Design Contradiction:
Ease of operationVSObject-generated harmful factors

Solution Approach 1:

The patent replaces hygroscopic conventional ionic liquids with urea-based ionic liquids that have significantly reduced moisture sensitivity. Urea's molecular structure and bonding characteristics result in lower hygroscopicity, reducing water uptake and subsequent harmful side reactions while maintaining operational functionality

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

4Ease of manufacture

If metal substrates are used as current collectors, then the battery can be manufactured, but corrosion occurs reducing cycle life

Engineering Contradiction:
ImprovemanufacturabilityVSAvoidcycle life
Core Design Contradiction:
Ease of manufactureVSDuration of action of stationary object

Solution Approach 1:

The patent employs composite current collector structures, specifically carbon-based materials (carbon fiber paper, carbon cloth, graphite fiber) or metal substrates with protective carbon coatings. These composite structures provide both electrical conductivity and corrosion resistance in the AlCl3-based ionic liquid environment, enabling long cycle life while maintaining manufacturability

Inventive Principle:
Principle #40Composite materials

5Ease of manufacture

If AlCl3 and urea are mixed to form ionic liquid, then cost is reduced, but residual water and HCl require removal

Engineering Contradiction:
ImprovecostVSAvoidpurity
Core Design Contradiction:
Ease of manufactureVSManufacturing precision

Solution Approach 1:

The patent implements preliminary purification steps during electrolyte preparation, including vacuum treatment and heating to remove residual water and HCl formed during AlCl3 and urea mixing. This preliminary action ensures high purity electrolyte before battery assembly, addressing the contamination issue while maintaining the cost benefits of urea-based formulation

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 use of urea-based ionic liquid electrolytes increases theoretical energy density, maintains high coulombic efficiency across varying charge rates, and extends battery operation temperature range, while corrosion-resistant current collectors ensure long cycle life and flexibility for wearable devices.

Implementation Method 1

AlCl3 undergoes asymmetric cleavage to form a tetrachloroaluminate anion (AlCl4-) and an aluminum chloride cation (AlCl2+) in which a ligand is datively bonded to (or associated through coordination via sharing of lone pair electrons) the AlCl2+ cation

Methodology Applied
Scientific EffectAsymmetric cleavage:

Implementation Method 2

an aluminum chloride cation (AlCl2+) in which a ligand is datively bonded to (or associated through coordination via sharing of lone pair electrons) the AlCl2+ cation

Methodology Applied
Scientific EffectDative bonding: Chemical Bonding

Implementation Method 3

associated through coordination via sharing of lone pair electrons

Methodology Applied
Scientific EffectCoordination: Chemical Bonding

Implementation Method 4

adding aluminum in the ionic liquid, and subjecting the ionic liquid to vacuum for 0.2 h to 24 h to remove residual water, hydrochloric acid or organic impurities

Methodology Applied
Scientific EffectVacuum evaporation: Evaporation

Implementation Method 5

including a cationic electroactive species for aluminum deposition during charging

Methodology Applied
Scientific EffectElectrodeposition: Electrodeposition

Implementation Method 6

Due to the high natural abundance and three electron redox properties of aluminum

Methodology Applied
Scientific EffectRedox reaction: Redox Reactions

Data Source

PatentEP3391452B1Improved electrolytes, current collectors, and binders for rechargeable metal-ion batteries
Publication Date: 2024.03.27 THE BOARD OF TRUSTEES OF THE LELAND STANFORD JUNIOR UNIV
  • EP3391452B1 patent drawingFigure 1~2B
  • EP3391452B1 patent drawingFigure 4A
  • EP3391452B1 patent drawingFigure 4B~4C

AI summary

A metal -ion battery includes: 1) an anode including a metal; 2) a cathode; and 3) an ionic liquid electrolyte disposed between the anode and the cathode, wherein the ionic liquid electrolyte corresponds to a mixture of a metal halide and an organic compound.