CN104118867A - Preparation method of graphite oxide - Google Patents

Abstract

The invention discloses a preparation method of graphite oxide. The preparation method comprises the steps: adding concentrated sulfuric acid in a dry beaker, cooling with ice water, adding a solid mixture of flake graphite and NaNO3 under constant stirring, and then slowly adding a potassium permanganate powder; after finishing addition of KMnO4, removing the water bath, and continuing stirring; slowly adding deionized water, stirring, then adding deionized water for dilution, carrying out a reaction under a condition of normal temperature, then adding hydrogen peroxide, reducing a residual oxidant until the solution becomes bright yellow, and then centrifuging to obtain a yellow-brown residue; respectively washing by an HCl solution and deionized water for 3 times, and centrifuging for one time after each washing until the filtrate is neutral; and finally placing the filter cake in a 60 DEG C drying box, and fully drying. The preparation method is safe and simple in operation and low in equipment requirements, can prepare graphite oxide with relatively high carbon-oxygen ratio; and moreover, the graphite oxide prepared by the method can be used for preparing graphene, and graphene is further applied in battery materials, composite materials, electronic devices, energy storage materials and other fields.

Description

A kind of preparation method of graphite oxide

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Technical field

The present invention relates to graphite field, be specifically related to a kind of preparation method of graphite oxide.

Background technology

Graphene is and carbon nanotube and the soccerballene emerging nano-carbon material that is same family.In within 2004, be found and stable existence after, become at once the study hotspot in each large field.It is two-dirnentional structure by carbon by honeycomb arrangement, and the repulsion stable existence being produced by the electronic cloud of both sides.Owing to thering is excellent machinery, electricity, calorifics and optical characteristics, at battery material, matrix material, electron device, a plurality of fields such as energy storage material are with a wide range of applications.

The preparation of Graphene is the focus that people pay close attention to always.The preparation method who has reported at present mainly contains mechanically peel method, epitaxial growth method, chemical Vapor deposition process and oxidation reduction process.Wherein first three methods is because of complicated operation, and condition harshness or productive rate are lowly difficult to be applied in scale operation.The advantages such as Comparatively speaking, oxidation reduction process is with low cost by it, and charge stripping efficiency is high, easy and simple to handle, and output is large are adopted by many research workers, and most possibly realize mass-producing preparation.

At present oxidation reduction process is prepared Graphene all needs first graphite, after oxide treatment obtains graphite oxide, to be peeled off into after individual layer or oxide thin layer graphite, then be reduced to Graphene.And the preparation method of graphite oxide mainly contains three kinds: Brodie method, Staudenmaier method and Hummers method.Because the above two need the cycle of quite growing in preparation process, people often use Hummers legal system for graphite oxide.But Hummers method also has shortcomings, as: water need to be added in vitriol oil dispersion liquid, the safety operation in this step and basic inorganic chemistry is inconsistent, has sizable danger.

Summary of the invention

The object of the invention is to overcome the problem that prior art exists, a kind of preparation method of graphite oxide is provided.

For realizing above-mentioned technical purpose, reach above-mentioned technique effect, the present invention is achieved through the following technical solutions:

A preparation method for graphite oxide, comprises the following steps:

Step 1) adds the 40-50mL vitriol oil in dry beaker, with frozen water, is cooled to below 10 ℃, under magnetic stirring bar constantly stirs, adds 2g crystalline flake graphite and 1gNaNO ₃solid mixture, more slowly add 6g powder potassium permanganate, control temperature of reaction below 20 ℃ simultaneously;

Step 2) treat KMn0 ₄after adding, remove water-bath, treat that temperature rises to 35 ℃, temperature is strict controlled in about 35 ℃ and continues to stir 30 min;

Step 3) slowly adds 92mL deionized water, continues to stir 15min;

Step 4) adds 142ml deionized water to dilute again, under normal temperature condition, reacts 12h, and then adding a certain amount of massfraction is 30% hydrogen peroxide reduction residual oxygen agent, continues several minutes, and solution becomes glassy yellow;

Step 5) is centrifugal while hot, obtains filemot residue;

Step 6) is 5%HCl solution and deionized water wash 3 times by volume fraction respectively, and every washing is once once centrifugal, and rotating speed is controlled at 4000rpm, uses PH detection paper simultaneously, until filtrate is neutral, till detecting sulfate radical-free with bariumchloride;

It is fully dry that step 7) is finally placed in filter cake the loft drier of 60 ℃, obtains graphite oxide.

Further, in described step (7), in loft drier, need dry 24 hours.

Beneficial effect of the present invention:

Adopt technical solution of the present invention, operational safety is simple, to equipment require lowly, can prepare the graphite oxide that carbon-to-oxygen ratio is higher; And the graphite oxide preparing by present method can be used for preparing Graphene, thereby be further applied to battery material, matrix material, electron device, a plurality of fields such as energy storage material.

Embodiment

Below in conjunction with embodiment, describe the present invention in detail.

Embodiment 1

In dry beaker, add the 40mL vitriol oil, with frozen water, be cooled to below 10 ℃, under magnetic stirring bar constantly stirs, add 2g crystalline flake graphite and 1gNaNO ₃solid mixture, more slowly add 6g powder potassium permanganate, control temperature of reaction below 20 ℃ simultaneously; Treat KMn0 ₄after adding, remove water-bath, treat that temperature rises to 35 ℃, temperature is strict controlled in about 35 ℃ and continues to stir 30 min; Slowly add 92mL deionized water, continue to stir 15min; Add 142ml deionized water to dilute again, under normal temperature condition, react 12h, then adding a certain amount of massfraction is 30% hydrogen peroxide reduction residual oxygen agent, continues several minutes, and solution becomes glassy yellow;

Centrifugal while hot, obtain filemot residue; By volume fraction, be 5%HCl solution and deionized water wash 3 times respectively, every washing is once once centrifugal, and rotating speed is controlled at 4000rpm, uses PH detection paper simultaneously, until filtrate is neutral, till detecting sulfate radical-free with bariumchloride; The loft drier that finally filter cake is placed in to 60 ℃ is fully dried 24 hours, obtains graphite oxide.The carbon-to-oxygen ratio of prepared graphite oxide is 2.78.

Embodiment 2

In dry beaker, add the 46mL vitriol oil, with frozen water, be cooled to below 10 ℃, under magnetic stirring bar constantly stirs, add 2g crystalline flake graphite and 1gNaNO ₃solid mixture, more slowly add 6g powder potassium permanganate, control temperature of reaction below 20 ℃ simultaneously; Treat KMn0 ₄after adding, remove water-bath, treat that temperature rises to 35 ℃, temperature is strict controlled in about 35 ℃ and continues to stir 30 min; Slowly add 92mL deionized water, continue to stir 15min; Add 142ml deionized water to dilute again, under normal temperature condition, react 12h, then adding a certain amount of massfraction is 30% hydrogen peroxide reduction residual oxygen agent, continues several minutes, and solution becomes glassy yellow; Centrifugal while hot, obtain filemot residue; By volume fraction, be 5%HCl solution and deionized water wash 3 times respectively, every washing is once once centrifugal, and rotating speed is controlled at 4000rpm, uses PH detection paper simultaneously, until filtrate is neutral, till detecting sulfate radical-free with bariumchloride; The loft drier that finally filter cake is placed in to 60 ℃ is fully dried 24 hours, obtains graphite oxide.The carbon-to-oxygen ratio of prepared graphite oxide is 2.82.

Embodiment 3

In dry beaker, add the 50mL vitriol oil, with frozen water, be cooled to below 10 ℃, under magnetic stirring bar constantly stirs, add 2g crystalline flake graphite and 1gNaNO ₃solid mixture, more slowly add 6g powder potassium permanganate, control temperature of reaction below 20 ℃ simultaneously; Treat KMn0 ₄after adding, remove water-bath, treat that temperature rises to 35 ℃, temperature is strict controlled in about 35 ℃ and continues to stir 30 min; Slowly add 92mL deionized water, continue to stir 15min; Add 142ml deionized water to dilute again, under normal temperature condition, react 12h, then adding a certain amount of massfraction is 30% hydrogen peroxide reduction residual oxygen agent, continues several minutes, and solution becomes glassy yellow; Centrifugal while hot, obtain filemot residue; By volume fraction, be 5%HCl solution and deionized water wash 3 times respectively, every washing is once once centrifugal, and rotating speed is controlled at 4000rpm, uses PH detection paper simultaneously, until filtrate is neutral, till detecting sulfate radical-free with bariumchloride; The loft drier that finally filter cake is placed in to 60 ℃ is fully dried 24 hours, obtains graphite oxide.The carbon-to-oxygen ratio of prepared graphite oxide is 2.76.

The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.

Claims (2)

1. a preparation method for graphite oxide, is characterized in that, comprises the following steps:

Step 1) adds the 40-50mL vitriol oil in dry beaker, with frozen water, is cooled to below 10 ℃, under magnetic stirring bar constantly stirs, adds 2g crystalline flake graphite and 1gNaNO ₃solid mixture, more slowly add 6g powder potassium permanganate, control temperature of reaction below 20 ℃ simultaneously;

Step 2) treat KMn0 ₄after adding, remove water-bath, treat that temperature rises to 35 ℃, temperature is strict controlled in about 35 ℃ and continues to stir 30 min;

Step 3) slowly adds 92mL deionized water, continues to stir 15min;

Step 4) adds 142ml deionized water to dilute again, under normal temperature condition, reacts 12h, and then adding a certain amount of massfraction is 30% hydrogen peroxide reduction residual oxygen agent, continues several minutes, and solution becomes glassy yellow;

Step 5) is centrifugal while hot, obtains filemot residue;

Step 6) is 5%HCl solution and deionized water wash 3 times by volume fraction respectively, and every washing is once once centrifugal, and rotating speed is controlled at 4000rpm, uses PH detection paper simultaneously, until filtrate is neutral, till detecting sulfate radical-free with bariumchloride;

It is fully dry that step 7) is finally placed in filter cake the loft drier of 60 ℃, obtains graphite oxide.

2. the preparation method of graphite oxide according to claim 1, is characterized in that, needs dry 24 hours in described step (7) in loft drier.