CN109665519A - A method of cellulose up-stripping graphene in alkali systems altogether - Google Patents

A method of cellulose up-stripping graphene in alkali systems altogether Download PDF

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Publication number
CN109665519A
CN109665519A CN201910071072.8A CN201910071072A CN109665519A CN 109665519 A CN109665519 A CN 109665519A CN 201910071072 A CN201910071072 A CN 201910071072A CN 109665519 A CN109665519 A CN 109665519A
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China
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cellulose
graphene
graphite
stripping
alkali systems
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CN201910071072.8A
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卢红斌
马建华
张佳佳
王鹏
潘绍学
刘沛莹
刘意成
吴天琪
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Fudan University
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Fudan University
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/182Graphene
    • C01B32/184Preparation
    • C01B32/19Preparation by exfoliation

Abstract

The present invention relates to a kind of methods of cellulose up-stripping graphene in alkali systems altogether.Using graphite as raw material, after intercalation, mechanical work is carried out in the total aqueous slkali dissolved with cellulose, realize the high yield removing and the efficient preparation of cellulose up-stripping graphene dispersing solution of graphene, (1) raw graphite is subjected to intercalation processing, expand the interlamellar spacing of graphite, while reducing the model ylid bloom action power of graphite layers;(2) resulting intercalated graphite is removed in the total alkali systems dissolved with cellulose, obtains graphene dispersing solution.The present invention has directly obtained cellulose up-stripping graphene dispersing solution, and graphene removes yield height and defect is few;Key issues of in addition, this method low in raw material price, stripping means is safely controllable, high-efficient, efficiently solves low cost, prepare with scale and the stable dispersion and storage transport of graphene.The obtained dispersion liquid of this method can be widely used in electrode material, catalysis material, the fields such as coating material and polymer composites.

Description

A method of cellulose up-stripping graphene in alkali systems altogether
Technical field
The invention belongs to field of material technology, are related to a kind of method for being total to cellulose up-stripping graphene in alkali systems, Raw graphite progress intercalation is specially obtained into intercalated graphite;By gained intercalated graphite in the total alkali systems dissolved with cellulose into Row removing, obtains cellulose up-stripping graphene dispersing solution.
Background technique
Nearly ten years, with the research that deepens continuously to graphene and its derivant material, people are for high quality graphite The demand of alkene is also increasing, how to be efficiently synthetically prepared, and stablizes removing, facilitates storage and transportation to become and restricts graphene industry development Huge obstacle.Currently, the technology of preparing of graphene mainly has chemical vapor infiltration (CVD), oxidation-reduction method and liquid phase Stripping method etc., above method respectively have superiority and inferiority, such as graphene prepared by CVD method has very high quality, but its preparation cost occupies height Under not;Oxidation-reduction method can be with prepare with scale redox graphene, but graphene defect is more after restoring, in the application It is difficult to play the excellent characteristics of intrinsic graphene.Liquid phase stripping method be considered as most be expected to realize high-quality graphene it is low at Originally, the technology of large scale preparation, but due to π-π interaction strong between the highly inert and piece of graphene surface, cause i.e. Make under prolonged ultrasonic stripping conditions its dispersion concentration in a solvent also extremely limited.Therefore, realize that liquid phase removes graphite The efficient preparation of alkene, it is also necessary to be broken through in the following areas.First, subtract under the premise of guaranteeing that graphene crystal structure is complete It interacts between weak and then meets efficiently removing;Second, graphene is improved under the premise of guarantee graphene intrinsic excellent properties Interaction between solvent reaches stable dispersion;Third improves dispersion under the premise of guaranteeing graphene film stable dispersion Concentration is to realize convenient transportation;The large-scale industry for finally realizing liquid phase removing grapheme material is possible to based on these conditions Metaplasia produces.
The technology of the present invention proposes a kind of method for being total to cellulose up-stripping graphene in alkali systems.It is inserted by intercalator Layer expands the interlamellar spacing of graphite, weakens Interaction between layers power, and realize graphene in the total aqueous slkali dissolved with cellulose High efficiency, high quality removing.In the total alkali soluble agent dissolved with micro cellulose, on the one hand being stabilized for graphene film comes The electric double layer formed from the salt ion in ionizable graphene surface a small amount of functional group and alkaline solution, on the other hand comes from The hydrogen bond formed between graphene film and cellulose, it is thus achieved that stable dispersion of the graphene in total alkali soluble agent.This hair Bright process flow is short, and used reagent is commercially available cheap reagent, and prepared graphene defect is few, stable dispersion concentration Height efficiently solves the low-coat scaleization preparation of high-quality graphene, stable dispersion and storage transportation problem.
Summary of the invention
Present invention seek to address that existing grapheme material charge stripping efficiency is low, dispersion concentration is low, prepares graphene defect mostly etc. Problem, to by can dissolution in low temperature cellulose total alkali soluble agent use, obtain high-quality graphene dispersion liquid preparation.For This, the present invention provides a kind of methods that cellulose auxiliary shearing removing prepares graphene under alkali systems altogether.
In order to achieve the goal above, the present invention expands the interlamellar spacing of graphite by intercalation, weaken Interaction between layers power;? Dissolved with being removed in the total alkali systems of cellulose, stable graphene dispersing solution is obtained.In dispersion liquid, the stabilization of graphene film The electric double layer that the salt ion that there are one side in ionizable graphene surface a small amount of functional group and alkaline solution is formed, On the other hand the hydrogen bond formed between graphene film and cellulose, it is thus achieved that graphene is steady in total alkali soluble agent Fixed dispersion.
The method of cellulose up-stripping graphene in a kind of alkali systems altogether proposed by the present invention, the specific steps are as follows:
(1) raw graphite is subjected in the mixed liquor of oxidant and strong acid intercalation processing, obtains intercalated graphite;
(2) intercalated graphite that step (1) obtains is removed in the total alkali systems dissolved with cellulose, obtains cellulose auxiliary Remove graphene dispersing solution, in which: the concentration of graphene is 10-100 mg/mL, and the content of cellulose is in alkali systems altogether 0.05-2 wt%。
In the present invention, the raw graphite is natural or artificial graphite, and graphite particle is micro- having a size of 1 micron -500 Rice, 95% or more graphitic carbon content.
In the present invention, the oxidant is ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, sodium nitrate, potassium permanganate, weight chromium The mixture of one or more of sour potassium, potassium hyperchlorate or potassium nitrate, strong acid are the concentrated sulfuric acid, concentrated phosphoric acid, concentrated nitric acid or dense salt The mixture of one or more of acid.
In the present invention, mechanism technique described in step (2) includes high speed shear, Probe Ultrasonic Searching, water bath sonicator, ball A kind of or any combination between them in mill, sand milling or high pressure homogenization method.
In the present invention, the solvent group in cellulose solution described in step (2) becomes the alkali compounds of 3-10 wt%, 3- The urea or thiocarbamide of 20 wt%, remaining is water, and total weight meets 100%.
In the present invention, the solvent medium alkaline compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, One of potassium carbonate, lithium carbonate, sodium bicarbonate, saleratus, lithium bicarbonate, ammonium hydroxide or tetrabutylammonium or it Between any combination.
In view of the deficienciess of the prior art, the present inventor passes through long-term practice and research, skill of the invention is proposed Art scheme, the program can realize the high efficiency, low cost, large scale preparation of graphene, while resulting graphene defect is few, and For few layer of structure, solves the critical issue of graphene prepare with scale, to realize that reality of the graphene in every field is answered With providing a kind of effective way.In addition, this method can directly obtain graphene/cellulose composite material, and process flow letter It is single.
The present invention has the advantage that compared with prior art
Preparation process is simple, at low cost.Alkali soluble agent composition is the cheap raw material of industry, the dissolution of cellulose altogether selected by the present invention The feasibility of large-scale production is provided with the preparation method of graphene;Cellulose, as a kind of low-density, high-specific surface area, Excellent in mechanical performance, biodegradable environment-friendly material can be realized in the aqueous solution of sodium hydroxide/urea (thiocarbamide) Dissolution in low temperature, and the presence of cellulose molecular chain plays stable effect for removing graphene film in solution.Pass through intercalator Intercalation expands the interfloor distance between graphene film, and then weakens Interaction between layers power, further makes intercalated graphite molten Have and realize efficiently removing in the total aqueous slkali of cellulose, obtains high concentration graphene dispersion liquid.
Detailed description of the invention
Fig. 1 is the digital camera photo of cellulose up-stripping graphene dispersing solution.
Fig. 2 is removing gained graphene electron scanning micrograph.
Fig. 3 is removing gained graphene projection electron microscope photo.
Specific embodiment
Illustrate technical solution of the present invention below by way of specific example.It should be understood that the one or more that the present invention mentions Step do not repel before and after the combination step there is also between other method and steps or these specifically mentioned steps also Other method and steps can be inserted.It should also be understood that these examples are merely to illustrate the present invention rather than limitation is of the invention Range.Unless otherwise indicated, the number of various method steps is only the purpose of identification various method steps, rather than to limit each method Arrangement order or limit practical range of the invention, relativeness is altered or modified, in no substantial technological content alteration Under conditions of, when being also considered as the enforceable scope of the present invention.
Embodiment 1
200 milliliters of concentrated sulfuric acids (98%) are uniformly mixed with 10 grams of potassium permanganate (purity > 95%), 10 grams of crystalline graphite powders, are controlled System temperature is lower than 35 oC, after continuously stirring 1 hour, it is slowly added in 500 milliliters of ice water.Then 20 milliliters of dioxygens are added Water simultaneously stirs 5 minutes, and the compound between graphite layers of sulfuric acid intercalation are obtained after filtering.
By 1g cellulose, (molecular weight is 8 × 104) be dissolved in 200g basic solvent, solvent group becomes 8 wt % hydroxides Sodium, 12 wt% urea, is divided into water with group.Total alkali soluble agent is cooled to -12 firstoAfter C, then cooling solvent high speed stirring Quickly dissolution cellulose obtains transparency cellulose solution.
Intercalated graphite made above is placed in the total aqueous slkali dissolved with cellulose, high speed shear 2 hours, obtains fiber The graphene dispersing solution removed in the total aqueous alkali of element.Compared to graphite raw material, single layer and few layer graphene mixture in system Yield is greater than 90%.The graphene dispersing solution of the cellulose up-stripping stands 30 days at room temperature and has no significant precipitating.
Embodiment 2
By 100 milliliters of concentrated sulfuric acids (98%), 50 ml concentrated nitric acids (nitric acid content 96-98%) and 10 grams of potassium permanganate (purity > 95%), 10 grams of crystalline graphite powders uniformly mix, and control system temperature is lower than 35oAfter continuously stirring 1 hour, it is slowly added by C Enter in 500 milliliters of ice water.Then 20 milliliters of hydrogen peroxide are added and stir 5 minutes, the graphite of sulfonitric intercalation is obtained after filtering Intercalation compound.
By 1g cellulose, (molecular weight is 8 × 104) be dissolved in 200g basic solvent, solvent group becomes 3 wt% hydroxides Lithium, 8 wt% urea, is divided into water with group.Total alkali soluble agent is cooled to -10 first oCAfterwards, then at cooling solvent high speed stirring Quickly dissolution cellulose obtains transparency cellulose solution.
Intercalated graphite made above is placed in the total aqueous slkali dissolved with cellulose, 100 circulations of high-pressure homogeneous processing, It obtains cellulose and is total to the graphene dispersing solution dispersed in aqueous alkali.Compared to graphite raw material, single layer and few layer graphite in system Alkene mixture yield is greater than 90%.The graphene dispersing solution of the cellulose up-stripping stands 30 days at room temperature and has no aobvious Write precipitating.
Embodiment 3
200 milliliters of concentrated sulfuric acids (98%) are uniformly mixed with 8 grams of potassium permanganate (purity > 95%), 10 grams of crystalline graphite powders, are controlled System temperature is lower than 35oC after continuously stirring 1.5 hours, is slowly added in 1 liter of ice water.Then 25 milliliters of dioxygens are added Water simultaneously stirs 5 minutes, and the compound between graphite layers of sulfuric acid intercalation are obtained after filtering.
By 0.6g cellulose, (molecular weight is 8 × 104) be dissolved in 200g and be total in alkali soluble agent, solvent group becomes 10 wt % hydrogen Sodium oxide molybdena, 10 wt% thiocarbamides, is divided into water with group.Total alkali soluble agent is cooled to -8 first oCAfterwards, it is stirred in cooling solvent high speed Quickly dissolution cellulose is mixed, transparency cellulose solution is obtained.
Intercalated graphite made above is placed in the total aqueous slkali dissolved with cellulose, Probe Ultrasonic Searching is handled 2 hours, is obtained Cellulose is total to the graphene dispersing solution dispersed in aqueous alkali.Compared to graphite raw material, single layer and few layer graphene are mixed in system It closes produce rate and is greater than 90%.The graphene dispersing solution of the cellulose up-stripping stands 30 days at room temperature and has no significant heavy It forms sediment.
Comparative example 1
Crystalline flake graphite 0.5g is placed in the N-Methyl pyrrolidone solution of 200 ml, by Probe Ultrasonic Searching (power 500W, 95%) it handles 144 hours, only minimal amount of graphene sheet layer is stripped, and compared to raw material graphite, is removed yield and is less than 1%.The graphene dispersing solution stands 30 days at room temperature and has no significant precipitating.
Comparative example 2
Crystalline flake graphite 5g is followed directly in the sodium hydrate aqueous solution of pH=14 of 2L using processing 200 in high pressure homogenizer Ring homogenate, only minimal amount of graphene sheet layer is stripped, and compared to raw material graphite, removes yield less than 1%.The graphene Dispersion liquid stands 7 days at room temperature and there is significant precipitating.
Comparative example 3
200 milliliters of concentrated sulfuric acids (98%) are uniformly mixed with 10 grams of potassium permanganate (purity > 95%), 10 grams of crystalline graphite powders, are controlled System temperature is lower than 35 oC, after continuously stirring 1 hour, it is slowly added in 500 milliliters of ice water.Then 20 milliliters of dioxygens are added Water simultaneously stirs 5 minutes, and the compound between graphite layers of sulfuric acid intercalation are obtained after filtering.By the graphite of the sulfuric acid intercalation obtained after filtering Intercalation compound is mixed with 10 grams of sodium hydroxides and 250 milliliters of water.It is handled using Probe Ultrasonic Searching and obtains black graphite after ten minutes Alkene suspension.Obtained dark solution is centrifuged after ten minutes under conditions of 10000 revs/min, supernatant liquor is gone to obtain stone Black alkene water phase thickener.
The above graphene water phase thickener is placed in 500 ml deionized waters, at Probe Ultrasonic Searching (power 500W, 95%) Reason 20 hours, only a part of graphene sheet layer is stripped, and compared to raw material graphite, the graphene yield of stable dispersion is small In 30%.The graphene dispersing solution stands 7 days at room temperature and there is a small amount of precipitating.

Claims (6)

1. a kind of method of cellulose up-stripping graphene in alkali systems altogether, it is characterised in that specific step is as follows:
(1) raw graphite is subjected in the mixed liquor of oxidant and strong acid intercalation processing, obtains intercalated graphite;
(2) intercalated graphite that step (1) obtains is removed in the total alkali systems dissolved with cellulose, obtains cellulose auxiliary Remove graphene dispersing solution, in which: the concentration of graphene is 10-100 mg/mL, and the content of cellulose is in alkali systems altogether 0.05-2 wt%。
2. the method for cellulose up-stripping graphene in a kind of alkali systems altogether according to claim 1, it is characterised in that The raw graphite is natural or artificial graphite, and graphite particle is having a size of 1 micron -500 microns, graphitic carbon content 95% More than.
3. the method for cellulose up-stripping graphene in a kind of alkali systems altogether according to claim 1, it is characterised in that The oxidant is ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, sodium nitrate, potassium permanganate, potassium bichromate, potassium hyperchlorate or nitre The mixture of one or more of sour potassium, strong acid are one or more of the concentrated sulfuric acid, concentrated phosphoric acid, concentrated nitric acid or concentrated hydrochloric acid Mixture.
4. the method for cellulose up-stripping graphene in a kind of alkali systems altogether according to claim 1, it is characterised in that Mechanism technique described in step (2) includes high speed shear, Probe Ultrasonic Searching, water bath sonicator, ball milling, sand milling or high pressure homogenization method A kind of middle or any combination between them.
5. the method for cellulose up-stripping graphene in a kind of alkali systems altogether according to claim 1, it is characterised in that Solvent group in cellulose solution described in step (2) becomes the alkali compounds of 3-10 wt%, the urea or sulphur of 3-20 wt% Urea, remaining is water, and total weight meets 100%.
6. the method for cellulose up-stripping graphene in a kind of alkali systems altogether according to claim 5, it is characterised in that The solvent medium alkaline compound includes sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, carbon One of sour hydrogen sodium, saleratus, lithium bicarbonate, ammonium hydroxide or tetrabutylammonium or any combination between them.
CN201910071072.8A 2019-01-25 2019-01-25 A method of cellulose up-stripping graphene in alkali systems altogether Pending CN109665519A (en)

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Application publication date: 20190423