Low-Temperature Crystalline Oxidic Coating Method

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Solution Overview

Problem

Existing methods for manufacturing crystalline oxidic compounds with alkaline and valve metals, such as LiNbO3, require high temperatures, leading to diffusion issues and capacity degradation in batteries, and are complex to scale up, especially when used as coatings on substrates that cannot tolerate high temperatures.

Innovation Solution

A method involving mixing alcoholates of alkaline and valve metals in an oxygenated organic solvent with hydrogen peroxide at room temperature, followed by adding an acid and drying at elevated temperatures below 200°C to produce a crystalline oxidic compound without substrate interaction, allowing for stable and homogeneous coatings on various substrates.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If high temperature annealing (350-900°C) is used to obtain crystalline LiNbO3 coating layer, then crystalline structure and electrochemical performance are improved, but diffusion of ions occurs leading to capacity degradation

Engineering Contradiction:
Improveelectrochemical performanceVSAvoidcapacity degradation
Core Design Contradiction:
ReliabilityVSLoss of substance

Solution Approach 1:

The invention changes the temperature parameter from high (350-900°C) to low (50-150°C) and uses a specific chemical composition (alcoholates with oxygenated organic solvent and hydrogen peroxide) to achieve crystalline formation without high temperature annealing, thereby preventing ion diffusion while maintaining electrochemical performance

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention uses hydrogen peroxide as a strong oxidant in the coating solution to facilitate the formation of crystalline LiNbO3 at low temperatures, replacing the need for high temperature thermal treatment and preventing unwanted ion diffusion

Inventive Principle:
Principle #38Strong oxidants (Accelerated oxidation)

2Manufacturing precision

If high temperature deposition (235°C) and crystallization (650°C) are used in ALD process, then thin and homogeneous layers are obtained, but the process becomes complex and difficult to scale up

Engineering Contradiction:
Improvelayer homogeneityVSAvoidprocess complexity
Core Design Contradiction:
Manufacturing precisionVSDevice complexity

Solution Approach 1:

The invention reduces the temperature parameters from ALD process (235°C deposition, 650°C crystallization) to a single low temperature step (50-150°C drying), simplifying the equipment requirements and making the process easier to scale up while maintaining layer homogeneity

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention merges the deposition and crystallization steps into a single low temperature drying process, eliminating the need for separate high temperature annealing or crystallization equipment and simplifying the overall manufacturing process

Inventive Principle:
Principle #5Merging (Combining)

3Stability of the object's composition

If high temperature processing is used to manufacture crystalline oxidic compounds, then crystalline structure is achieved, but substrates cannot tolerate the high temperatures without deformation

Engineering Contradiction:
Improvecrystalline structureVSAvoidsubstrate temperature tolerance
Core Design Contradiction:
Stability of the object's compositionVSTemperature

Solution Approach 1:

The invention changes the processing temperature from high (350-900°C) to low (50-150°C), enabling the formation of crystalline oxidic compounds on substrates that cannot withstand high temperatures, thus expanding substrate compatibility

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention uses a chemically active coating solution containing alcoholates and hydrogen peroxide as an intermediary that enables crystalline formation at low temperatures, acting as a mediator between the substrate and the crystalline oxidic compound formation process

Inventive Principle:
Principle #24Intermediary (Mediator)

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 enables the production of stable and homogeneous crystalline oxidic compounds at low temperatures, preventing substrate deformation and enhancing interfacial stability in batteries and digital printing applications, with improved electrochemical performance and broader substrate compatibility.

Implementation Method 1

The chemically active coating material may, in particular, be hydrogen peroxide, in particular with a concentration of 30 molar %

Methodology Applied
Scientific EffectChemical deposition: Chemical Beam Epitaxy

Implementation Method 2

drying the solution at an elevated temperature of 50 °C to 150 °C, whereby a powder comprising the at least one crystalline oxidic compound

Methodology Applied
Scientific EffectEvaporation: Evaporation

Implementation Method 3

drying the solution at an elevated temperature of 50 °C to 150 °C, whereby a powder comprising the at least one crystalline oxidic compound

Methodology Applied
Scientific EffectCrystallization: Crystallisation

Data Source

PatentEP4186865A1A method for manufacturing a crystalline oxidic compound
Publication Date: 2023.05.31 KARLSRUHER INST FUR TECH
  • EP4186865A1 patent drawingFigure 1~2
  • EP4186865A1 patent drawingFigure 3a~3b
  • EP4186865A1 patent drawing

AI summary

The present invention relates to a method for manufacturing a crystalline oxidic compound comprising an alkaline metal and a valve metal, to a crystalline oxidic compound as obtained by the method, and to its use as a ferroelectric material; as a coating material for electrode materials in batteries, specifically in solid-state batteries; or in digital printing, especially on a polymeric substrate. Herein, the method for manufacturing a crystalline oxidic compound comprising an alkaline metal and a valve metal comprises the following steps: a) mixing an alcoholate of an alkaline metal and an alcoholate of a valve metal in a composition of an oxygenated organic solvent and hydrogen peroxide at room temperature; b) adding an acid selected from at least one of nitric acid or hydrochloric acid at room temperature, whereby a solution is obtained; c) drying the solution at an elevated temperature of 50 °C to 150 °C, whereby a powder comprising the at least one crystalline oxidic compound comprising the alkaline metal and the valve metal is obtained. This manufacturing method operates at a low ambient working temperature, especially below 200 °C, and, thus, allows a direct manufacturing of crystalline oxidic compounds without interaction with a substrate and/or on a substrate which is not capable of tolerating higher temperatures during the manufacturing of crystalline oxidic compounds without deformation and/or deterioration. A further advantage of the low ambient working temperature is that a diffusion of elements from the at least one crystalline oxidic compound as coating material into the substrate can be avoided.