Graphene Modification via Supercritical CO2 Exfoliation

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Solution Overview

Problem

Current methods for modifying graphene, such as chemical reduction, involve hazardous reducing agents and result in impurities and difficulty in controlling crystallite size, making it challenging to achieve desired properties and functions economically and safely.

Innovation Solution

A method using carbon dioxide at specific temperature and pressure ranges to exfoliate graphene nanoplatelets, with repeated cycles and recovery in a deionized water bath, allowing for the reuse of carbon dioxide and avoiding toxic chemicals.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If chemical reduction method is used to prepare graphene, then mass production and economic feasibility are achieved, but hazardous reducing agents are required and impurities are introduced

Engineering Contradiction:
Improvemass production capabilityVSAvoidhazardous reducing agents
Core Design Contradiction:
ProductivityVSObject-affected harmful factors

Solution Approach 1:

The invention changes the chemical parameters of the reduction process by replacing traditional hazardous reducing agents (hydrazine, sodium borohydride) with green alternatives such as sodium citrate, ascorbic acid, and ethanol. This parameter substitution maintains the mass production capability while eliminating the harmful factors associated with toxic and explosive reducing agents.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention employs inexpensive, readily available reducing agents like sodium citrate and ascorbic acid that can be easily disposed of without special handling requirements. These substitutes replace expensive and dangerous reducing agents, achieving both economic feasibility and safety by using materials that are non-toxic and environmentally friendly.

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

2Adaptability or versatility

If chemical reduction method is used to prepare graphene, then various functional groups may be easily introduced, but impurities are included and electric conductivity is decreased

Engineering Contradiction:
Improvefunctional group introductionVSAvoidpurity and conductivity control
Core Design Contradiction:
Adaptability or versatilityVSManufacturing precision

Solution Approach 1:

The invention optimizes the reduction parameters by using mild reducing agents that selectively reduce oxygen-containing functional groups without introducing new impurities. The controlled reduction process maintains high purity levels and preserves electric conductivity while still allowing functional group introduction when needed for specific applications.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention replaces harsh chemical reduction mechanisms with milder alternative mechanisms that achieve deoxygenation without the side effects of impurity formation. The use of green reducing agents provides a cleaner chemical pathway that maintains material purity and electrical properties.

Inventive Principle:
Principle #28Mechanics substitution (Replace mechanical system)

3Ease of manufacture

If traditional exfoliation methods are used, then graphene can be obtained, but crystallite size control is difficult and layers may recombine

Engineering Contradiction:
Improvegraphene productionVSAvoidcrystallite size control
Core Design Contradiction:
Ease of manufactureVSManufacturing precision

Solution Approach 1:

The invention employs periodic exfoliation cycles where graphite is repeatedly subjected to sonication, chemical treatment, and centrifugation. This periodic action allows progressive separation of layers and gradual reduction of crystallite size to desired ranges while preventing recombination through continuous processing steps.

Inventive Principle:
Principle #19Periodic action

Solution Approach 2:

The invention performs preliminary oxidation of graphite to graphite oxide before exfoliation, which introduces oxygen functional groups that weaken interlayer bonding. This preliminary action facilitates easier and more controlled exfoliation, enabling precise crystallite size control in subsequent processing steps.

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

This approach enables the production of graphene with a desired crystallite size and improved dispersibility while maintaining excellent electrical conductivity, reducing environmental impact and production costs.

Implementation Method 1

modifying the graphene nanoplatelet by temperature-raising and pressure-raising the carbon dioxide to 20 to 50°C and 73 to 200 atm, respectively

Methodology Applied
Scientific EffectSupercritical fluid: Supercritical Fluid

Implementation Method 2

exfoliating the graphene nanoplatelet by temperature-raising and pressure-raising carbon dioxide to 20 to 50°C and 73 to 200 atm, respectively

Methodology Applied
Scientific EffectExfoliation:

Implementation Method 3

pressure-releasing and cooling an exfoliated graphene; and recovering the carbon dioxide discharged from the pressure-releasing and cooling of the exfoliated graphene

Methodology Applied
Scientific EffectPressure release expansion: Depressurisation

Data Source

PatentEP3037383B1Method for modifying graphene nanoplatelets and apparatus for modifying graphene
Publication Date: 2020.05.27 HANWHA CHEMICAL CORPORATION
  • EP3037383B1 patent drawingFigure 1
  • EP3037383B1 patent drawingFigure 2~3
  • EP3037383B1 patent drawingFigure 4~5

AI summary

There are a method and an apparatus for modifying a graphene, and more specifically, a method and an apparatus for modifying a graphene capable of obtaining the graphene having a desired crystallite size by repeating a process for modifying the graphene using subcritical or supercritical carbon dioxide several times. According to the method and the apparatus for modifying the graphene of the present invention, the graphene having excellent electrical conductivity and dispersibility may be obtained.