CN105347340B - The preparation method of graphene oxide - Google Patents
The preparation method of graphene oxide Download PDFInfo
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- CN105347340B CN105347340B CN201510924233.5A CN201510924233A CN105347340B CN 105347340 B CN105347340 B CN 105347340B CN 201510924233 A CN201510924233 A CN 201510924233A CN 105347340 B CN105347340 B CN 105347340B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
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- 239000010439 graphite Substances 0.000 claims abstract description 44
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- 238000000926 separation method Methods 0.000 claims abstract description 17
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- 239000012467 final product Substances 0.000 claims abstract description 8
- 239000007790 solid phase Substances 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 90
- 239000003513 alkali Substances 0.000 claims description 31
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
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- 239000006185 dispersion Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010289 potassium nitrite Nutrition 0.000 claims description 2
- 239000004304 potassium nitrite Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 208000011580 syndromic disease Diseases 0.000 claims description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 238000011084 recovery Methods 0.000 claims 1
- 235000010288 sodium nitrite Nutrition 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 17
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 13
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 13
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
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- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
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- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
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- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a kind of preparation method of graphene oxide, it is to add aqueous slkali to be placed in hermetic container graphite raw material, pro-oxidant, wherein, 1 ~ 50g graphite raw materials and 1 ~ 30g pro-oxidants are added in per 100ml aqueous slkalis, with replacement of oxygen gas in container and be filled with oxygen to pressure be 1 ~ 20Mpa, in temperature, 101 DEG C～650 DEG C are reacted, reaction takes out product solid-liquid separation after terminating, gained solid phase is washed and is dried, graphene oxide solid product is obtained final product, liquid phase reclaims Jing and processes Posterior circle use.The reaction can avoid the use of substantial amounts of strong acid and strong oxidizer, reduce spent acid waste liquid, the extent of reaction can be by reaction temperature and oxygenate pressure control, the graphene oxide structural failure disappearance prepared under strong acidic condition is effectively prevent, and processed with acid is simplified for the loaded down with trivial details separating, washing process of graphite oxide.Caustic solution circulation is used, and effectively reduces production cost, and process is simple, flow process are short, low cost.
Description
Technical field
The present invention relates to a kind of method for preparing graphene oxide.
Background technology
Graphene oxide（GO）, it is important intermediate that oxidation-reduction method prepares Graphene.Manchester, England in 2004
College Physics scholar An Deliegaimu and Constantine's Nuo Woxiao loves, successfully isolate single-layer graphene from graphite,
Confirm it integer quantum Hall effect and normal temperature condition can be found that with individualism and respectively under quantum hall effect, two people
Common acquisition has ignited the research to Graphene after Nobel Prize in physics in 2010.The fracture strength of Graphene is steel
200 times, while having elasticity well, stretch range can reach the 20% of own dimensions.There are Graphene great potentiality to become
The succedaneum of silicon, manufactures ultra micro transistor npn npn, and for producing the supercomputer in future, the speed of service of computer processor will
Hundreds times can be lifted.The structure of the high light transmittance of Graphene and densification causes it to be highly suitable as the original of transparent electron product
Material, such as transparent touch display screen, luminous plaque and solar panel.The surface texture for also having which unique has good resisting
Application of the bacterium effect in medical treatment and space material has great prospect.As most thin, the most hard, conductive and heat-conductive that have now been found that
The most strong a kind of novel nano-material of performance, as unique physicochemical property of Graphene has ten on the materials application of hard-core technology
Divide consequence.
The common method of Graphene is prepared at present for mechanical stripping method, oxidation-reduction method, SiC epitaxial growth methods and chemical gas
Phase sedimentation（CVD）.But four kinds of methods all have obvious disadvantage, mechanical stripping method production capacity is low, and oxidation-reduction method is using strong
Sour strong oxidizer is aoxidized, and pollution is larger but yield is high, and the common fault of SiC epitaxial growth methods and chemical vapour deposition technique is right
The having high demands of equipment, high cost and production capacity is low.
It is that large-scale production technical grade Graphene is best that the operation difficulty of oxidation-reduction method is minimum and with low cost at this stage
Method.The concrete grammar of oxidation-reduction method is, with natural flake graphite or expanded graphite as raw material, Jing strong acid Strong oxdiatives
After agent oxidation（Strong acid and strong oxidizer are concentrated sulphuric acid, concentrated hydrochloric acid, perchloric acid, potassium permanganate etc.）The graphene oxide of preparation this
Stage is referred to as oxidation stage, then the reduction of Jing reducing agents（Reducing agent is hydrazine hydrate, sodium borohydride etc.）It is prepared into Graphene.But tradition
Oxidation stage can produce substantial amounts of spent acid, and need to dilute heat release in separation phase and further aoxidize so that concentrated acid is also difficult to
Reclaim, and in waste liquid, also have substantial amounts of separation of heavy metal ions intractability very big；Aoxidize under the conditions of concentrated acid, graphite is oxidized
Degree be difficult to control to, it is easy to graphite-structure destruction cause prepare Graphene it is of low quality.
The content of the invention
The technical problem to be solved in the present invention is：There is provided a kind of degree of oxidation controllable, little is destroyed to graphite-structure, and is avoided
The preparation method of the graphene oxide for using of strong acid in preparation process.
For solve above technical problem, the present invention provide a kind of graphene oxide preparation method, be by graphite raw material,
Pro-oxidant adds aqueous slkali to be placed in hermetic container, wherein, per 100ml aqueous slkalis in add 1 ~ 50g graphite raw materials and 1 ~
30g pro-oxidants, with replacement of oxygen gas in container and to be filled with oxygen to pressure be 1 ~ 20Mpa, in 101 DEG C～650 DEG C of temperature
Reacted, reaction takes out product solid-liquid separation after terminating, and gained solid phase is washed and is dried, and obtains final product graphene oxide solid
Product, liquid phase reclaim Jing and process Posterior circle use.
Graphite raw material be idea of the invention is that in aqueous slkali and the oxygen of certain pressure, and added in the presence of pro-oxidant
Thermal oxide prepares graphene oxide, so as to overcome oxidation-reduction method to prepare the defect that the oxidation stage of Graphene is present, the method
Degree of oxidation is controllable, destroys little to graphite-structure, and is a kind of environmentally friendly synthetic route, and the alkali liquor Jing process of generation can
To recycle, low cost, method are simple, the problems such as spent acid being produced in effectively prevent strong acid oxidation technology and separates difficult.
Under above reaction condition, in container, in-situ reaction pressure is in 10Mpa ~ 60Mpa.Solid-liquid separating method includes taking out
Filter, centrifugation；Described solid product is washed with 5% ~ 10% dilute hydrochloric acid；The solid product drying meanss be include drying, from
So dry, lyophilization.Liquid phase is recyclable, and processing method is：The concentration of solution alkali is adjusted according to the concentration of alkali before seal pot
Afterwards, use as caustic solution circulation.
Used as preferred technical scheme, the time reacted is 10 ~ 72 hours, and on this basis, preferred scheme is
The graphene oxide solid product for obtaining is dissolved in the water, ultrasonic disperse obtains final product graphene oxide dispersion soln.
Used as another kind of preferred technical scheme, the solute of described aqueous slkali is potassium hydroxide or sodium hydroxide.Here
On the basis of, the solvent of described aqueous slkali is the one kind in water, methanol, ethanol, ethylene glycol, propanol, glycerol and butanol.It is preferred that
Ground, the substance withdrawl syndrome of the aqueous slkali prepared with above-mentioned solute and solvent is as 5 ~ 20mol/L.
Used as another kind of preferred technical scheme, described pro-oxidant is potassium nitrate, potassium nitrite, sodium nitrate or nitrous
One kind in sour sodium.
Used as another kind of preferred technical scheme, the graphite raw material is natural flake graphite or expanded graphite.Preferably
The grain graininess of graphite raw material is 30～500 mesh.
As another kind of preferred technical scheme, be in temperature 350 DEG C～500 DEG C reacted.
The present invention proposes that alkali oxidation prepares the beneficial effect of graphene oxide method and is：（1）The reaction can be avoided greatly
The use of the strong acid and strong oxidizer of amount, reduces substantial amounts of spent acid waste liquid, reduces cost environmental protection.（2）Oxygen with help oxygen
Agent prepares graphene oxide with the use of alkali soluble liquid oxidation, and the extent of reaction can be by the control to reaction temperature and oxygenate pressure
And control, the problems such as effectively prevent the graphene oxide structural failure prepared under strong acidic condition and lack.（3）To operate letter
Single, separation is easy, simplifies processed with acid for the loaded down with trivial details separating, washing process of graphite oxide.（4）Caustic solution circulation is used, and is effectively reduced
Production cost, process is simple, flow process are short, low cost.
Description of the drawings
Fig. 1 is the stereoscan photograph of sample prepared by the present invention.
Specific embodiment
Embodiment 1
This example demonstrates that being 325 mesh of natural flake graphite in graphite, alkali is KOH, and pro-oxidant is KNO3Reaction
Journey and result.
Take 325 mesh natural flake graphites of 3g, 12g KOH, 3g KNO3, insert in reactor, add 25ml deionized waters
In, stir 10min.The closed rear replacement of oxygen gas reactor of reactor three times, then fill oxygen to 5Mpa, by reactor heat temperature raising
To 450 DEG C, stirring reaction 36 hours.Reaction is cooled to room temperature after terminating, and solid product is first used by reactant Jing solid-liquid separation
5% Jing dilute hydrochloric acid is washed, then deionized water is washed till neutrality, drying graphene oxide solid 2.752g at 100 DEG C.Liquid phase
Reclaim, after being adjusted to the concentration of solution alkali according to the concentration of KOH solution before reaction, use as caustic solution circulation.
Embodiment 2
This example demonstrates that being 325 mesh of natural flake graphite in graphite, alkali is KOH, and pro-oxidant is KNO3Reaction
Journey and result.
By the alkali liquor 13mL reclaimed in embodiment 1, added according to the concentration of the KOH measured before the sealing of 1 reactor of embodiment
6.25g KOH and 17mL deionized waters are adjusted to same concentrations, take 325 mesh natural flake graphites of 3g, 3g KNO3, insert reaction
In kettle, 25ml circulation alkali liquors are added, stir 10min.The closed rear replacement of oxygen gas reactor of reactor three times, then the 3Mpa that fills oxygen
By 600 DEG C of reactor heat temperature raising, stirring reaction 36 hours.Reaction terminates to be cooled to room temperature afterwards, reactant Jing solid-liquid separation,
5% dilute hydrochloric acid of solid product Jing is washed, then deionized water is washed till neutrality, drying graphene oxide solid at 100 DEG C
2.804g.Liquid phase is reclaimed, and after being adjusted to the concentration of solution alkali according to the concentration of KOH solution before reaction, is made as caustic solution circulation
With.
Embodiment 3
This example demonstrates that being 325 mesh of natural flake graphite in graphite, alkali is NaOH, and pro-oxidant is NaNO3Reaction
Process and result.
Take 325 mesh natural flake graphites of 5g, 12g NaOH, 3g NaNO3, insert in reactor, add 25ml deionizations
In water, 10min is stirred.The closed rear replacement of oxygen gas reactor of reactor three times, then the 5Mpa that fills oxygen is by reactor heat temperature raising
450 DEG C, 36 hours stirring reaction time.Reaction is cooled to room temperature after terminating, and reactant Jing solid-liquid separation, solid Jing 10% are dilute
Salt acid elution, then deionized water is washed till neutrality, drying graphene oxide solid 4.763g at 100 DEG C.Liquid phase is reclaimed, root
After according to concentration adjustment of the concentration of NaOH solution before reaction to solution alkali, use as caustic solution circulation.
Embodiment 4
This example demonstrates that being 325 mesh of natural flake graphite in graphite, alkali is KOH, and pro-oxidant is KNO3Reaction
Journey and result.
Take 325 mesh natural flake graphites of 3g, 25g KOH, 5g KNO3, insert in reactor, add 25ml deionized waters
In, stir 10min.The closed rear replacement of oxygen gas reactor of reactor three times, then the 5Mpa that fills oxygen, by reactor heat temperature raising
450 DEG C, stirring reaction 72 hours.Reaction is cooled to room temperature, solid-liquid separation, the washing of 10% dilute hydrochloric acid of solid Jing after terminating, then uses
Deionized water is washed till neutrality, drying graphene oxide solid 2.733g at 100 DEG C.Liquid phase is reclaimed, molten according to KOH before reaction
After the concentration of liquid is to the concentration adjustment of solution alkali, use as caustic solution circulation.
Embodiment 5
This example demonstrates that being 325 mesh of natural flake graphite in graphite, alkali is KOH, and pro-oxidant is KNO2Reaction
Journey and result.
Take 325 mesh natural flake graphites of 3g, 12g KOH, 3g KNO2, insert in reactor, in adding 25ml ethanol, stir
Mix 10min.The closed rear replacement of oxygen gas reactor of reactor three times, then 450 DEG C of reactor heat temperature raising stirs by the 5Mpa that fills oxygen
Mix reaction 36 hours.Reaction is cooled to room temperature after terminating, solid-liquid separation, the washing of 10% dilute hydrochloric acid of solid Jing are dried at 100 DEG C
Obtain final product graphene oxide solid 2.767g.Liquid phase is reclaimed, and the concentration of solution alkali is adjusted according to the concentration of KOH solution before reaction
Afterwards, use as caustic solution circulation.
Embodiment 6
This example demonstrates that being 200 mesh of natural flake graphite in graphite, alkali is KOH, and pro-oxidant is KNO3Reaction
Journey and result.
Take 200 mesh natural flake graphites of 3g, 20g KOH, 6g KNO3, insert in reactor, add 25ml deionized waters
In, stir 10min.The closed rear replacement of oxygen gas reactor of reactor three times, then the 6Mpa that fills oxygen, by reactor heat temperature raising
450 DEG C, stirring reaction 50 hours.Reaction is cooled to room temperature, solid-liquid separation, the washing of 10% dilute hydrochloric acid of solid Jing after terminating, then uses
Deionized water is washed till neutrality, drying graphene oxide solid 2.624g at 100 DEG C.Liquid phase is reclaimed, molten according to KOH before reaction
After the concentration of liquid is to the concentration adjustment of solution alkali, use as caustic solution circulation.
Embodiment 7
This example demonstrates that being 325 mesh of natural flake graphite in graphite, alkali is KOH, and pro-oxidant is KNO3Reaction
Journey and result.
Take 325 mesh natural flake graphites of 3g, 12g KOH, 3g KNO3, insert in reactor, add 25ml deionized waters
In, stir 10min.The closed rear replacement of oxygen gas reactor of reactor three times, then the 7Mpa that fills oxygen is by reactor heat temperature raising 450
DEG C, stirring reaction 36 hours.Reaction is cooled to room temperature after terminating, and solid-liquid separation by 10% salt acid elutions of solid elder generation Jing, then is used
Deionized water is washed till neutrality, drying graphene oxide solid 2.749g at 100 DEG C.Liquid phase is reclaimed, molten according to KOH before reaction
After the concentration of liquid is to the concentration adjustment of solution alkali, use as caustic solution circulation.By the graphene oxide solid of gained, 0.3g is taken
It is dissolved in 50ml distilled water, 100W supersound process 20min obtains final product graphite oxide dispersion alkene solution.
Embodiment 8
This example demonstrates that being 30 mesh of expanded graphite in graphite, alkali is KOH, and pro-oxidant is KNO2Course of reaction and knot
Really.
Take 30 mesh expanded graphites of 0.25g, 12g KOH, 0.25g KNO2, insert in reactor, add 25ml glycerol
In, stir 10min.The closed rear replacement of oxygen gas reactor of reactor three times, then fill oxygen to 1Mpa, by reactor heat temperature raising
To 650 DEG C, stirring reaction 10 hours.Reaction is cooled to room temperature after terminating, and solid product is first used by reactant Jing solid-liquid separation
5% Jing dilute hydrochloric acid is washed, then deionized water is washed till neutrality, drying graphene oxide solid at 100 DEG C.Liquid phase is reclaimed, root
After according to concentration adjustment of the concentration of KOH solution before reaction to solution alkali, use as caustic solution circulation.
Embodiment 9
This example demonstrates that being 500 mesh of natural flake graphite in graphite, alkali is KOH, and pro-oxidant is KNO3Reaction
Journey and result.
Take 500 mesh natural flake graphites of 12.5g, 20g KOH, 7.5g KNO3, insert in reactor, add 25ml second two
In alcohol, 10min is stirred.The closed rear replacement of oxygen gas reactor of reactor three times, then the 20Mpa that fills oxygen, reactor heating is risen
101 DEG C of temperature, stirring reaction 72 hours.Reaction is cooled to room temperature after terminating, solid-liquid separation, 10% dilute hydrochloric acid of solid Jing are washed, then
Deionized water is washed till neutrality, drying graphene oxide solid at 100 DEG C.Liquid phase is reclaimed, according to KOH solution before reaction
After concentration is to the concentration adjustment of solution alkali, use as caustic solution circulation.
Embodiment 10
This example demonstrates that being 325 mesh of expanded graphite in graphite, alkali is KOH, and pro-oxidant is KNO2Course of reaction and
As a result.
Take 325 mesh expanded graphites of 3g, 7g KOH, 3g KNO2, insert in reactor, in adding 25ml propanol, stirring
10min.The closed rear replacement of oxygen gas reactor of reactor three times, then the 3Mpa that fills oxygen is by 350 DEG C of reactor heat temperature raising, stirring
Reaction 48 hours.Reaction is cooled to room temperature after terminating, solid-liquid separation, 10% dilute hydrochloric acid of solid Jing are washed, and drying at 100 DEG C is
Obtain graphene oxide solid.Liquid phase is reclaimed, after being adjusted to the concentration of solution alkali according to the concentration of KOH solution before reaction, as alkali
Solution is recycled.
Embodiment 11
This example demonstrates that being 325 mesh of natural flake graphite in graphite, alkali is NaOH, and pro-oxidant is NaNO3Reaction
Process and result.
Take 325 mesh natural flake graphites of 3g, 20g NaOH, 3g NaNO3, insert in reactor, in adding 25ml methanol,
Stirring 10min.The closed rear replacement of oxygen gas reactor of reactor three times, then the 10Mpa that fills oxygen is by reactor heat temperature raising 500
DEG C, stirring reaction 48 hours.Reaction is cooled to room temperature after terminating, and solid-liquid separation by 10% salt acid elutions of solid elder generation Jing, then is used
Deionized water is washed till neutrality, drying graphene oxide solid at 100 DEG C.By the graphene oxide solid of gained, 0.3g is taken
It is dissolved in 50ml distilled water, 100W supersound process 20min obtains final product graphene oxide dispersion soln.
Claims (9)
1. a kind of preparation method of graphene oxide, it is characterised in that：It is close that graphite raw material, pro-oxidant add aqueous slkali to be placed in
Close in container, wherein, 1 ~ 50g graphite raw materials and 1 ~ 30g pro-oxidants are added in every 100ml aqueous slkalis, use replacement of oxygen container
Interior gas and be filled with oxygen to pressure be 1 ~ 20MPa, in temperature, 101 DEG C～650 DEG C are reacted, reaction terminate after take out reaction
Product solid-liquid separation, gained solid phase are washed and are dried, and obtain final product graphene oxide solid product, and liquid phase reclaims Jing process Posterior circles and makes
With；Described pro-oxidant is the one kind in potassium nitrate, potassium nitrite, sodium nitrate or sodium nitrite.
2. method according to claim 1, it is characterised in that：The time reacted is 10 ~ 72 hours.
3. method according to claim 2, it is characterised in that：The graphene oxide solid product for obtaining is dissolved in the water,
Ultrasonic disperse, obtains final product graphene oxide dispersion soln.
4. the method according to claim 1,2 or 3, it is characterised in that：The solute of described aqueous slkali be potassium hydroxide or
Sodium hydroxide.
5. method according to claim 4, it is characterised in that：The solvent of described aqueous slkali is water, methanol, ethanol, second
One kind in glycol, propanol, glycerol and butanol.
6. method according to claim 5, it is characterised in that：The substance withdrawl syndrome of described aqueous slkali be 5～
20mol/L。
7. the method according to claim 1,2,3,5 or 6, it is characterised in that：The graphite raw material is natural flake graphite
Or expanded graphite.
8. method according to claim 7, it is characterised in that：The grain graininess of graphite raw material is 30～500 mesh.
9. method according to claim 1, it is characterised in that：Wherein described liquid phase recovery and treatment method is according to sealing
After before kettle, the concentration of alkali is to the concentration adjustment of solution alkali, use as caustic solution circulation.
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| CN106542529A (en) * | 2016-12-06 | 2017-03-29 | 江苏悦达新材料科技有限公司 | A kind of method that green prepares high-quality graphene |
| CN107777683B (en) * | 2017-11-20 | 2020-10-23 | 浙江海虹控股集团有限公司 | Method for producing graphene oxide |
| CN108975323A (en) * | 2018-09-05 | 2018-12-11 | 七台河宝泰隆石墨烯新材料有限公司 | graphene oxide cleaning method |
| CN113782837A (en) * | 2021-08-03 | 2021-12-10 | 东风悦达起亚汽车有限公司 | Preparation method of high-quality graphene battery |
| CN114229969A (en) * | 2021-12-30 | 2022-03-25 | 山西诺沃科技有限公司 | Electronic control ionic membrane material for separating phosphate ions in water and preparation method thereof |
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