CN105565304B - A kind of method that utilization starch prepares graphene - Google Patents
A kind of method that utilization starch prepares graphene Download PDFInfo
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- CN105565304B CN105565304B CN201510994738.9A CN201510994738A CN105565304B CN 105565304 B CN105565304 B CN 105565304B CN 201510994738 A CN201510994738 A CN 201510994738A CN 105565304 B CN105565304 B CN 105565304B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
Abstract
It is of the invention by starch and graphite in mass ratio 5 10 the invention discloses a kind of method that utilization starch prepares graphene:1 is mixed and made into gel, the HTHP provided by continuous screw extruder, starch-splitting, obtains the carbon atom of high-energy, and the continued growth on the basis of existing graphite synusia obtains grapheme material.The present invention provides the above method using starch as carbon source, and materials are extensive, and preparation process is simple, and impurity element is not introduced in preparation process, production cost is advantageously reduced, it is adaptable to industrial production.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, the method that more particularly to a kind of utilization starch prepares graphene.
Background technology
Grapheme material is successfully prepared within 2004, has triggered the upsurge of new ripple carbon materials research since then.Graphene
The plane carbon nanomaterial being made up of one layer of carbon atom, is to be currently known most thin two-dimensional material, and its thickness is only
0.335nm, it is made up of the lattice of hexagon.Connected between carbon atom in graphene by σ keys, impart graphene extremely excellent
Different mechanical property and structural rigidity.Moreover, in graphene, each carbon atom has the p electronics of a non-bonding, these p
Electronics can be moved freely in crystal, and movement velocity is up to the 1/300 of the light velocity, impart the good electric conductivity of graphene.
In optics aspect, graphene is almost fully transparent, only absorbs 2.3% light.Graphene have peculiar mechanics, optics and
Electrical properties, graphene possesses very vast potential for future development.
In order to allow outstanding grapheme material to realize industrialized production and application, must just develop one kind can give birth on a large scale
Production and the number of plies and the controllable preparation method of size.The preparation method of current graphene has mechanical stripping method, epitaxial growth method, oxidation
Reducing process, ultrasonic stripping method, organic synthesis method, solvent-thermal method, chemical vapour deposition technique etc..In these methods, in these sides
In method, mechanical stripping method and epitaxial growth method preparation efficiency are very low, it is difficult to meet large-scale needs.Though chemical vapour deposition technique
The continuous graphene film of large scale can so be obtained, it is adaptable to electronic device or transparent conductive film, can not but meet big rule
The demand of mould production.Oxidation-reduction method prepares the realization with low cost and easy of grapheme material powder, but can produce a large amount of
Waste liquid, severe contamination is caused to environment, the extensive industrialized development of graphene is limited.These methods are all with graphite ore
As former material, this mineral resources not recyclable regenerative is also unfavorable for the extensive development of graphene.
In recent years, high molecular polymer steps into the research range of people as new carbon source.China Patent Publication No.
104528696A provides a kind of preparation method of graphene, comprises the following steps：Utilize ion exchange resin, starch, fiber
Element and amorphous carbon first adsorb carbon source, then be prepared for graphene by heating as carbon source using metallic catalyst.This method will
Carbon source is expanded, and obtains the higher graphene product of quality.However, using metallic catalyst has been arrived in this method, not only to graphite
Alkene introduces impurity, and the graphene area of preparation is small, and it is poor to crystallize.
China Patent Publication No. 103787321A discloses a kind of self-supporting grapheme material and preparation method thereof, this method
It is to be heat-treated starch, washing, filtration drying.Dried product is mixed with alkali again, under anaerobic after sintering processes,
Washing, drying, obtains self-supporting graphene.Compare traditional preparation methods and raw materials used, this method has easy to operate, work
Skill process is easy, and cost is low, and the graphene prepared has the advantages that self supporting structure, is particularly suitable for large-scale industrial production.
However, this method is sintered using anaerobic, sintering temperature reaches 800-1200 DEG C, high to equipment requirement, and equipment prepares cost and carried
It is high.
In summary, present existing utilization starch, which is prepared in graphene method, does not also have a kind of technical process simple, no
Impurity element is introduced, and reaction temperature is relatively low, the graphene preparation method that raw material can be recycled.
The content of the invention
In order to solve the deficiency and defect of the above method, the present invention develops the side that a kind of utilization starch prepares graphene
Method.This method is using starch as carbon source, and graphite is as growth templates, by graphite dispersion in starch-hydrocolloid, by by starch
Carbon and hydrone are cracked into, hydrone is evaporated.Meanwhile, the high-energy that carbon atom is provided by HTHP is aligned to graphite
Layer marginal position, grows bigger graphite flake layer, then ultrasonic Separation, centrifuges, and evaporation obtains graphene.Do not draw in this method
Enter other impurities element, the filter residue of acquisition is still recycled, economic and environment-friendly, is suitable for industrial production.
The present invention provides a kind of method that utilization starch prepares graphene, it is characterised in that methods described includes following step
Suddenly：
A. by starch and graphite powder 5-10 in mass ratio:1 mixing, mixes with deionized water, obtains mixed solution；
B. the mixed solution that heating stepses a is obtained stirs to 53-60 DEG C, obtains mixing gelatinized starch, is cooled to
Room temperature is placed 3-7 days, becomes starch gel mixture；
C. under inert gas shielding, the starch gel mixture that step b is obtained adds continuous screw extruder,
Continuous screw extruder is heated to 300-600 DEG C, extrusion pressure 20-50 MPa obtain solid product, and the solid product is
For the prefabricated clinker of graphene；
D. by the prefabricated clinker of graphene in ionized water is put into, ultrasonic Separation 30-60 minutes, centrifugation takes supernatant liquor,
The water being evaporated at 60-80 DEG C in clear liquid obtains graphene for 12-24 hours, and the turbid liquid of filtering lower floor obtains filter residue, and filter residue is at 60-80 DEG C
After lower dry 12-24 hours, the raw material as step a can be continued, recycled.
It is preferred that, the starch is green starch, tapioca, sweet potato starch, starch from sweet potato, farina, wheat class
Starch, water caltrop starch, Rhizoma Nelumbinis starch, cornstarch.
It is preferred that, the graphite powder is compact crystal shape graphite powder, crystalline graphite powder, expanded graphite powder or expansible graphite
Powder.
It is preferred that, the concentration of mixed solution described in step a is 50-300g/L.
It is preferred that, inert gas described in step c is argon gas, helium, neon.
It is preferred that, the part by weight of the prefabricated clinker of graphene described in step d and deionized water is 1-3:10.
Said one or multiple technical schemes in the embodiment of the present application, are at least imitated with following one or more technologies
Really：
1st, the present invention by starch admixed graphite using gel is made, and the high temperature provided by continuous screw extruder is high
Pressure, starch-splitting obtains the carbon atom of high-energy, and continued growth obtains graphene material on the basis of existing graphite synusia
Material.The present invention provides the above method and not only reduces graphene preparation temperature, and preparation process is simple.
2nd, the present invention is using starch as carbon source, and materials are extensive, advantageously reduce production cost, it is adaptable to industrial production.
3rd, the solvent that the present invention is used is environmentally safe for water.
Embodiment
By embodiment, the present invention is described in further detail, but this should not be interpreted as to the model of the present invention
Enclose and be only limitted to following example.In the case where not departing from above method thought of the present invention, according to ordinary skill knowledge
The various replacements or change made with customary means, should be included in the scope of the present invention.
Embodiment one
The present embodiment comprises the following steps：
Take barley starch and crystalline graphite powder in mass ratio 5:1 mixing, adds appropriate amount of deionized water, obtains concentration for 50g/
L mixed solutions, are heated to 53 DEG C by the mixed solution, stir, and obtain the mixing gelatinized starch mixture of coated graphite, cold
But to placement under room temperature condition 3 days, starch gel mixture is obtained, inert gas argon gas is passed through, will under argon gas protective condition
The starch gel mixture of acquisition is extruded by continuous screw extruder, sets continuous screw extruder temperature extremely
300 DEG C, extrusion pressure is 20 MPa, and it is the prefabricated clinker of graphene to obtain solid product, next, by the graphene of preparation
Prefabricated clinker is 1 according to part by weight：10 are invested in ionized water, after ultrasonic Separation 30 minutes, centrifuging and taking supernatant liquor,
The water being evaporated under the conditions of 60 DEG C in clear liquid obtains graphene, and the turbid liquid of filtering lower floor obtains filter residue, and it is small that filter residue dries 24 at 60 DEG C
Shi Hou, obtains graphene.After testing, the average thickness of the graphene sheet layer prepared in embodiment one is 0.69 nm, production
Rate is 2.5%.In this programme, the turbid liquid of filtering acquisition lower floor, which obtains filter residue, to be used as the original of next secondary response through kept dry
Material, recycles, advantageously reduces production cost.
Embodiment two
The present embodiment comprises the following steps：
Take starch from sweet potato and crystalline graphite powder in mass ratio 5:1 mixing, adds appropriate amount of deionized water, obtains concentration for 50g/
L mixed solutions, are heated to 53 DEG C by the mixed solution, stir, and obtain the mixing gelatinized starch mixture of coated graphite, cold
But to placement under room temperature condition 3 days, starch gel mixture is obtained, inert gas argon gas is passed through, will under argon gas protective condition
The starch gel mixture of acquisition is extruded by continuous screw extruder, sets continuous screw extruder temperature extremely
300 DEG C, extrusion pressure is 20 MPa, and it is the prefabricated clinker of graphene to obtain solid product, next, by the graphene of preparation
Prefabricated clinker is 1 according to part by weight：10 are invested in ionized water, after ultrasonic Separation 30 minutes, centrifuging and taking supernatant liquor,
The water being evaporated under the conditions of 60 DEG C in clear liquid obtains graphene, and the turbid liquid of filtering lower floor obtains filter residue, and it is small that filter residue dries 24 at 60 DEG C
Shi Hou, obtains graphene.After testing, the average thickness of the graphene sheet layer prepared in embodiment two is 0.72 nm, production
Rate is 3.7%.In this programme, the turbid liquid of filtering acquisition lower floor, which obtains filter residue, to be used as the original of next secondary response through kept dry
Material, recycles, advantageously reduces production cost.
Embodiment three
The present embodiment comprises the following steps：
Take starch from sweet potato and compact crystal shape graphite powder in mass ratio 8:1 mixing, adds appropriate amount of deionized water, obtains concentration
For 150g/L mixed solutions, the mixed solution is heated to 60 DEG C, stirred, the mixing gelatinized starch for obtaining coated graphite is mixed
Compound, is cooled under room temperature condition and places 5 days, obtain starch from sweet potato gel mixture, be passed through inert gas argon gas, protected in argon gas
Under the conditions of shield, the starch from sweet potato gel mixture of acquisition is extruded by continuous screw extruder, sets continuous screw anti-
Answer extruder temperature to 500 DEG C, extrusion pressure is 50 MPa, and it is the prefabricated clinker of graphene to obtain solid product, next,
By the prefabricated clinker of the graphene of preparation according to part by weight be 1：10 are invested in ionized water, after ultrasonic Separation 30 minutes, from
The heart takes supernatant liquor, and the water being evaporated under the conditions of 60 DEG C in clear liquid obtains graphene, and the turbid liquid of filtering lower floor obtains filter residue, and filter residue exists
After being dried 24 hours at 60 DEG C, graphene is obtained.After testing, the average thickness of the graphene sheet layer prepared in embodiment three
For 0.52 nm, yield is 6.7%.In this programme, filtering obtain lower floor turbid liquid obtain filter residue can through kept dry, as
The raw material of next secondary response, recycles, advantageously reduces production cost.
Example IV
The present embodiment comprises the following steps：
Take starch from sweet potato and compact crystal shape graphite powder in mass ratio 8:1 mixing, adds appropriate amount of deionized water, obtains concentration
For 150g/L mixed solutions, the mixed solution is heated to 60 DEG C, stirred, the mixing gelatinized starch for obtaining coated graphite is mixed
Compound, is cooled under room temperature condition and places 5 days, obtain starch from sweet potato gel mixture, be passed through inert gas argon gas, protected in argon gas
Under the conditions of shield, the starch from sweet potato gel mixture of acquisition is extruded by continuous screw extruder, sets continuous screw anti-
Answer extruder temperature to 300 DEG C, extrusion pressure is 50 MPa, and it is the prefabricated clinker of graphene to obtain solid product, next,
By the prefabricated clinker of the graphene of preparation according to part by weight be 3：10 are invested in ionized water, after ultrasonic Separation 30 minutes, from
The heart takes supernatant liquor, and the water being evaporated under the conditions of 80 DEG C in clear liquid obtains graphene, and the turbid liquid of filtering lower floor obtains filter residue, and filter residue exists
After being dried 18 hours at 80 DEG C, graphene is obtained.After testing, the average thickness of the graphene sheet layer prepared in example IV
For 0.59 nm, yield is 7.0%.In this programme, filtering obtain lower floor turbid liquid obtain filter residue can through kept dry, as
The raw material of next secondary response, recycles, advantageously reduces production cost.
Embodiment five
The present embodiment comprises the following steps：
Take starch from sweet potato and compact crystal shape graphite powder in mass ratio 8:1 mixing, adds appropriate amount of deionized water, obtains concentration
For 300g/L mixed solutions, the mixed solution is heated to 60 DEG C, stirred, the mixing gelatinized starch for obtaining coated graphite is mixed
Compound, is cooled under room temperature condition and places 7 days, obtain starch from sweet potato gel mixture, be passed through inert gas argon gas, protected in argon gas
Under the conditions of shield, the starch from sweet potato gel mixture of acquisition is extruded by continuous screw extruder, sets continuous screw anti-
Answer extruder temperature to 300 DEG C, extrusion pressure is 50 MPa, and it is the prefabricated clinker of graphene to obtain solid product, next,
By the prefabricated clinker of the graphene of preparation according to part by weight be 3：10 are invested in ionized water, after ultrasonic Separation 60 minutes, from
The heart takes supernatant liquor, and the water being evaporated under the conditions of 80 DEG C in clear liquid obtains graphene, and the turbid liquid of filtering lower floor obtains filter residue, and filter residue exists
After being dried 18 hours at 80 DEG C, graphene is obtained.After testing, the average thickness of the graphene sheet layer prepared in embodiment five
For 0.83 nm, yield is 8.5%.In this programme, filtering obtain lower floor turbid liquid obtain filter residue can through kept dry, as
The raw material of next secondary response, recycles, advantageously reduces production cost.
, but those skilled in the art once know basic creation although preferred embodiments of the present invention have been described
Property concept, then can make other change and modification to these embodiments.So, appended claims are intended to be construed to include excellent
Select embodiment and fall into having altered and changing for the scope of the invention.
Obviously, those skilled in the art can carry out the essence of various changes and modification without departing from the present invention to the present invention
God and scope.So, if these modifications and variations of the present invention belong to the scope of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to comprising including these changes and modification.
Claims (6)
1. a kind of method that utilization starch prepares graphene, it is characterised in that the described method comprises the following steps：
A. by starch and graphite powder 5-10 in mass ratio:1 mixing, mixes with deionized water, obtains mixed solution；
B. the step a mixed solutions obtained are heated to 53-60 DEG C, stirred, obtain mixing gelatinized starch mixture, it is cold
But to placement under room temperature condition 3-7 days, starch gel mixture is obtained；
C. under inert gas shielding, the starch gel mixture that step b is obtained adds continuous screw extruder, sets
Continuous screw extruder temperature is to 300-600 DEG C, and extrusion pressure 20-50 MPa obtain solid product, and the solid product is
For the prefabricated clinker of graphene；
D. the prefabricated clinker of graphene is invested in ionized water, ultrasonic Separation 30~60 minutes, centrifuges, take supernatant liquor, 60-
The water being evaporated at 80 DEG C in clear liquid obtains graphene, and the turbid liquid of filtering lower floor obtains filter residue, and filter residue dries 12-24 at 60-80 DEG C
After hour, the raw material as step a can be continued, recycled.
2. the method that a kind of utilization starch according to claim 1 prepares graphene, it is characterised in that the starch is green
Beans starch, tapioca, sweet potato starch, starch from sweet potato, farina, wheat kind of starch, water caltrop starch, Rhizoma Nelumbinis starch, corn form sediment
At least one of powder.
3. the method that a kind of utilization starch according to claim 1 prepares graphene, it is characterised in that the graphite powder is
At least one of compact crystal shape graphite powder, crystalline graphite powder, expanded graphite powder, expansible graphite powder.
4. the method that a kind of utilization starch according to claim 1 prepares graphene, it is characterised in that mixed described in step a
The concentration for closing solution is 50-300g/L.
5. the method that a kind of utilization starch according to claim 1 prepares graphene, it is characterised in that described in step c
Inert gas is argon gas, helium, neon.
6. the method that a kind of utilization starch according to claim 1 prepares graphene, it is characterised in that described in step d
The prefabricated clinker of graphene and the part by weight of deionized water are 1-3:10.
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Inventor after: Wei Ying Inventor before: Chen Qing Inventor before: Zeng Juntang Inventor before: Ye Renhai Inventor before: Chen Bing |
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Effective date of registration: 20180112 Address after: No. 28, building No. 28, No. 1, Xinhua Street, Xincheng, Hohhot City, the Inner Mongolia Autonomous Region, No. 14 Patentee after: Wei Ying Address before: Qingyang District of Chengdu City, Sichuan province 610091 Dragon Industrial Port East Road 4 Patentee before: Chengdu Xinkeli Chemical Sci-Tech Co., Ltd. |
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