Hydrothermal Synthesis of Redox-Active Ti(IV) Coordination Compounds

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Solution Overview

Problem

Current methods for producing redox-active Ti(IV) coordination compounds for use in flow battery systems are costly and complex due to the reactivity of precursors and the need to manage undesirable by-products and counter ions.

Innovation Solution

A hydrothermal reaction method involving the direct reaction of TiO2 or other transition metal oxides with chelating agents like catechol, pyrogallol, or ascorbic acid in an aqueous medium at controlled temperatures, producing clear solutions or crystalline solids without undesirable by-products, which can be used directly as electrolytes in flow batteries.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Ease of manufacture

If traditional precursors (TiCl4, titanium alkoxides) are used to produce Ti(IV) coordination compounds, then the production process can proceed, but the precursors are highly reactive and difficult to handle at large production scale, and counter ions and by-products need to be separated and treated which adds significant cost

Engineering Contradiction:
Improveease of handling precursorsVSAvoidcomplexity of by-product management
Core Design Contradiction:
Ease of manufactureVSDevice complexity

Solution Approach 1:

The patent extracts and eliminates the problematic by-products and counter ions from the production process by using TiO2 as a starting material that does not generate these unwanted substances. The hydrothermal reaction of TiO2 with chelating agents produces only the desired coordination compounds without chloride, alcohol, or other by-products that would require separation and treatment.

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The patent uses TiO2, a stable and inexpensive material, as the starting precursor instead of expensive and reactive precursors like TiCl4 or titanium alkoxides. TiO2 is abundant, non-reactive under normal conditions, and does not generate harmful by-products, making it an ideal disposable starting material for large-scale production.

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

2Productivity

If traditional production methods are used, then Ti(IV) coordination compounds can be produced, but the process generates counter ions and by-products that require separation and treatment, increasing production cost

Engineering Contradiction:
Improveproduction efficiencyVSAvoidloss to by-products and counter ions
Core Design Contradiction:
ProductivityVSLoss of substance

Solution Approach 1:

The patent converts the traditional approach of having to deal with and remove harmful by-products into a benefit by selecting TiO2 as the starting material. This choice transforms what would normally be a waste removal problem into a clean production process where no harmful by-products are generated in the first place, thereby improving productivity and reducing material loss.

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

3Manufacturing precision

If highly reactive precursors are used, then coordination compounds can be formed, but the precursors are difficult to handle especially at large production scale

Engineering Contradiction:
Improveprecision of coordination compound formationVSAvoidease of handling at large scale
Core Design Contradiction:
Manufacturing precisionVSEase of operation

Solution Approach 1:

The patent changes the physical and chemical parameters of the starting material from highly reactive precursors (TiCl4, titanium alkoxides) to stable TiO2. This parameter change involves using a material with different reactivity, solubility, and handling characteristics that are more suitable for large-scale production while still achieving the desired coordination compound formation through hydrothermal treatment.

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

This method provides a more economical and efficient production of redox-active coordination compounds, eliminating the need for by-product management and ensuring stable, high-solubility electrolytes for flow battery systems.

Implementation Method 1

reacting TiO2 (or the corresponding oxide of the desired transition metal) in an aqueous reaction medium directly with a chelating agent, or with a combination of chelating agents, in a hydrothermal reaction zone at a temperature in the range of from 100° C to 160° C for a period of time from 4 hours up to 48 hours

Methodology Applied
Scientific EffectHydrothermal reaction:

Implementation Method 2

a flow battery is a rechargeable fuel cell in which an electrolyte containing one or more dissolved electroactive elements flows through an electrochemical cell that reversibly converts chemical energy directly to electricity

Methodology Applied
Scientific EffectElectrochemical reaction:

Data Source

PatentEP3243238B1Hydrothermal treatment method for producing redox-active transition metal coordination compounds
Publication Date: 2018.06.06 CRISTAL INORGANIC CHEM SWITZERLAND
  • EP3243238B1 patent drawingFigure 1

AI summary

A method for producing an aqueous electrolyte comprising a redox-active coordination compound of a transition metal which comprises reacting an oxide of the corresponding transition metal in an aqueous reaction medium with a chelating agent in a hydrothermal reaction zone at a temperature in the range of from 100°C to 160°C for a period of from 4 hours to 48 hours.