CN105217622A - A kind of preparation method of controlled three-dimensional grapheme microballoon - Google Patents

A kind of preparation method of controlled three-dimensional grapheme microballoon Download PDF

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Publication number
CN105217622A
CN105217622A CN201510773548.4A CN201510773548A CN105217622A CN 105217622 A CN105217622 A CN 105217622A CN 201510773548 A CN201510773548 A CN 201510773548A CN 105217622 A CN105217622 A CN 105217622A
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China
Prior art keywords
supporting media
graphene
graphene oxide
preparation
microballoon
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CN201510773548.4A
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Chinese (zh)
Inventor
曹余良
方永进
艾新平
杨汉西
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Wuhan University WHU
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Wuhan University WHU
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Priority to CN201510773548.4A priority Critical patent/CN105217622A/en
Publication of CN105217622A publication Critical patent/CN105217622A/en
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Abstract

The invention discloses a kind of preparation method of controlled three-dimensional grapheme microballoon, with graphene oxide, Supporting Media for raw material, add appropriate solvent and be modulated into slurry, graphene oxide/supporter mixture is obtained by spraying dry, then redox graphene, obtaining Graphene/supporter mixture, by dissolving supporter, obtaining controlled three-dimensional grapheme microballoon.Synthesis cycle of the present invention is short, cheaper starting materials, technique simple, be easy to control, has significant practical value and good application prospect.

Description

A kind of preparation method of controlled three-dimensional grapheme microballoon
Technical field
The present invention relates to a kind of preparation method of controlled three-dimensional grapheme microballoon, belong to grapheme material and technical field.
Background technology
Graphene (Graphene) is a kind of novel material of the individual layer sheet structure be made up of carbon atom, and it has the electronic mobility (15000cm of superelevation 2/ Vs), low resistivity (10 -6Ω cm), high specific surface (2630m 2/ g), high thermal conductivity (5300W/mK), high physical strength, is widely used in the fields such as biology, chemistry, physics, material.Obtaining Graphene with redox graphene is a kind of conventional method, high temperature reduction be a kind of can the method for scale operation Graphene.
Graphene, owing to there being large sheet structure, is difficult to prepare the controlled micro-sphere structure of size and aperture.The present invention is by adding Supporting Media spraying dry and high temperature reduction obtains controlled spherical graphite alkene.The controllable grapheme microballoon obtained may be used for all respects such as energy storage, absorption, wastewater treatment, has great potential application foreground.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of controlled three-dimensional grapheme microballoon.
Technical scheme of the present invention is:
With graphene oxide, Supporting Media for raw material, add appropriate solvent and be modulated into slurry, graphene oxide/Supporting Media mixture is obtained by spraying dry, then redox graphene, obtain Graphene/Supporting Media mixture, by dissolving Supporting Media, obtain the three-dimensional grapheme microballoon that size, aperture are controlled.
The inventive method flow process is short, easy to control, cost is low, reaches orientation, efficient, technique prepares controlled three-dimensional grapheme microballoon simply, be easy to the scale operation realizing controlled three-dimensional grapheme microballoon.
The key point of technical solution of the present invention is: carry out spraying dry by graphene oxide and Supporting Media, and redox graphene also removes Supporting Media, obtains the controlled three-dimensional grapheme microballoon of size and aperture.The method is simple to operate, and preparation time is short, pollution-free, and cost is low, and output is high.
Technical solution of the present invention specifically can comprise following steps:
(1) make graphene oxide ultrasonic disperse in a solvent, obtain the dispersion liquid of graphene oxide;
(2) in the dispersion liquid of graphene oxide, add Supporting Media, dispersed with stirring, dispersion liquid is carried out spraying dry, obtain graphene oxide/Supporting Media mixture;
(3) graphene oxide/Supporting Media mixture is carried out redox graphene, obtain Graphene/Supporting Media mixture;
(4) Graphene/Supporting Media mixture will obtained, by dissolving Supporting Media, obtains three-dimensional porous graphene oxide microballoon.
Further, the solvent that step (1) uses is water, ethanol, propyl alcohol, DMF, NMP equal solvent, obtain the dispersion liquid that concentration is 0.5 ~ 5mg/mL;
Further, the Supporting Media of use be simple substance (silica flour, iron powder, copper powder, zinc powder, carbon dust etc.), one or more in oxide compound (as silicon oxide, being oxidized sub-silicon, ferric oxide, cupric oxide, aluminum oxide, cobalt oxide, nickel oxide etc.), salt (phosphoric acid salt, vitriol, carbonate, nitrate, sodium-chlor, Sodium Bromide, sodium iodide etc.), polymkeric substance (polystyrene etc.);
Further, the massfraction of the Supporting Media of use is 5% ~ 60%;
Further, the temperature that spraying dry uses is 80 ~ 300 DEG C
Further, reduction can high temperature reduction, and high temperature reduction temperature is 200 ~ 1000 DEG C, uses atmosphere to be air, argon gas, nitrogen or hydrogen; Or with the reduction such as hydrazine hydrate, hydrogen iodide.
Further, the dissolving method of use, according to the feature selection acid dissolve of Supporting Media, alkali dissolution or other dissolution with solvents.
Based on foregoing invention principle, present method, by graphene oxide and Supporting Media are carried out spraying dry, after redox graphene, removes Supporting Media, and obtain the controlled three-dimensional grapheme of size and aperture, the present invention has the following advantages and beneficial effect:
1, selected graphene oxide and Supporting Media, raw materials cost is low;
2, by regulating the proportioning of graphene oxide and Supporting Media, the Graphene microballoon of different diameter, different aperture size can be obtained;
3, containing Graphene microballoon of the present invention, low price, synthesis technique is simple, easy to control, can be applied to the application etc. of the aspects such as chemistry, physics, biology, medical treatment;
4, synthesis cycle of the present invention is short, cheaper starting materials, technique simple, be easy to control, has significant practical value and good application prospect.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscopic picture of Graphene microballoon of the present invention.
Fig. 2 is the transmission electron microscope picture of Graphene microballoon of the present invention.
Fig. 3 is the scanning electron microscopic picture of Graphene of the present invention and titanium dioxide compound microballoon, and the transmission electron microscope picture of the Graphene obtained after dissolving titanium dioxide.
Embodiment
Embodiment 1
The graphene oxide water solution 70ml of configuration 2mg/ml, adds nano silicon oxide 10g wherein, stirs one hour, obtain slurry.By this slurry spraying dry, inlet temperature 250 DEG C, temperature out 100 DEG C, spraying dry, obtains the mixture of graphene oxide and silicon oxide.
This mixture be heated to 600 DEG C under argon gas condition and be incubated four hours, obtaining the mixture of Graphene and silicon oxide.Fall silicon oxide by certain density HF solubilize, obtain the Graphene microballoon of porous.Fig. 1 shows the scanning electron microscope (SEM) photograph of gained Graphene microballoon.
Embodiment 2
The graphene oxide water solution 100ml of configuration 5mg/ml, adds sodium-chlor 15g wherein, stirring and dissolving, obtains solution.This solution spray is dry, and inlet temperature 290 DEG C, temperature out 120 DEG C, spraying dry, obtains the mixture of graphene oxide and sodium-chlor.
By this mixture at Ar/H 2(H 2content be 10%) be warming up to 500 DEG C in atmosphere, constant temperature 5 hours, obtains the mixture of Graphene and sodium-chlor.By being added to the water by this mixture, heated and stirred dissolves sodium-chlor, obtains the Graphene microballoon of porous.Fig. 2 shows the transmission electron microscope picture of gained Graphene microballoon.
Embodiment 3
The graphene oxide water solution 100ml of configuration 1mg/ml, adds nano titanium oxide (P25) 20g wherein, stirs and obtains dispersion liquid.By this dispersion liquid spraying dry, inlet temperature 250 DEG C, temperature out 110 DEG C, spraying dry, obtains the mixture of graphene oxide and titanium dioxide.
This mixture is warming up to 400 DEG C in nitrogen atmosphere, and constant temperature 6 hours, obtains the mixture of Graphene and titanium dioxide.By joining in HF by this mixture, heated and stirred dissolves titanium dioxide, obtains the Graphene microballoon of porous.
Embodiment 4
The graphene oxide ethanolic soln 60ml of configuration 2mg/ml, adds polystyrene spheres 20g wherein, stirs and obtains dispersion liquid.By this dispersion liquid spraying dry, inlet temperature 200 DEG C, temperature out 100 DEG C, spraying dry, obtains the mixture of graphene oxide and polystyrene.
Be scattered in hydrazine hydrate solution by this mixture, 80 DEG C of constant temperature 3 hours, centrifugation, obtains the mixture of Graphene and polystyrene.Join in chloroform by this mixture, heated and stirred dissolves polystyrene, obtains the Graphene microballoon of porous.

Claims (7)

1. a preparation method for controlled three-dimensional grapheme microballoon, is characterized in that,
With graphene oxide, Supporting Media for raw material, add appropriate solvent and be modulated into slurry, graphene oxide/Supporting Media mixture is obtained by spraying dry, then redox graphene, obtain Graphene/Supporting Media mixture, by dissolving Supporting Media, obtain the three-dimensional grapheme microballoon that size, aperture are controlled.
2. preparation method according to claim 1, is characterized in that, specifically comprises following steps:
(1) make graphene oxide ultrasonic disperse in a solvent, obtain the dispersion liquid of graphene oxide;
(2) in the dispersion liquid of graphene oxide, add Supporting Media, dispersed with stirring, dispersion liquid is carried out spraying dry, obtain graphene oxide/Supporting Media mixture;
(3) graphene oxide/Supporting Media mixture reduces, and obtains Graphene/Supporting Media mixture;
(4) Graphene/Supporting Media mixture will obtained, by dissolving Supporting Media, obtains three-dimensional porous graphene oxide microballoon.
3. preparation method according to claim 2, is characterized in that, the solvent that step (1) uses is water, ethanol, propyl alcohol, DMF or NMP, obtains the dispersion liquid that concentration is 0.5 ~ 5mg/mL.
4. preparation method according to claim 2, is characterized in that, Supporting Media is one or more in simple substance, oxide compound, salt.
5. preparation method according to claim 2, is characterized in that, the massfraction of the Supporting Media of use is 5% ~ 60%.
6. preparation method according to claim 2, is characterized in that, the temperature that spraying dry uses is 80 ~ 300 DEG C.
7. preparation method according to claim 2, is characterized in that, in step (3), reduction uses high temperature reduction, and high temperature reduction temperature is 200 ~ 1000 DEG C, uses atmosphere to be air, argon gas, nitrogen or hydrogen; Or with hydrazine hydrate or hydrogen iodide reduction.
CN201510773548.4A 2015-11-13 2015-11-13 A kind of preparation method of controlled three-dimensional grapheme microballoon Pending CN105217622A (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106602063A (en) * 2016-12-30 2017-04-26 浙江大学 Preparation method for graphene spray and application of graphene spray in lithium-sulfur battery
CN106977768A (en) * 2017-05-03 2017-07-25 杭州高烯科技有限公司 A kind of method that spitball shape graphene improves the impact strength of nylon 6
CN107055521A (en) * 2017-03-21 2017-08-18 禹城贝尔新材料有限公司 The method and the graphene microballoon of prepare with scale height rule spherical graphite alkene microballoon
CN107082414A (en) * 2015-02-13 2017-08-22 大洲电子材料株式会社 Graphene with random and irregular three-D stomata and preparation method thereof
CN107230784A (en) * 2017-06-22 2017-10-03 山东大学 A kind of spherical graphite alkene/mangano-manganic oxide composite and preparation method and application
CN107651672A (en) * 2017-10-13 2018-02-02 杭州高烯科技有限公司 A kind of preparation method of Ultralight graphene microballoon for solar absorption
CN108117913A (en) * 2016-11-28 2018-06-05 中国科学院金属研究所 A kind of preparation method and purposes of spherical graphite alkene lubricating additive
CN108441282A (en) * 2018-02-07 2018-08-24 河南大学 A kind of dispersible graphene nano composite particles and its preparation method and application
CN110357078A (en) * 2019-08-14 2019-10-22 北京大学深圳研究生院 A kind of graphene microballoon and preparation method thereof
CN111847429A (en) * 2019-04-28 2020-10-30 深圳光启岗达创新科技有限公司 Preparation method and application of three-dimensional graphene wave-absorbing material
CN112225202A (en) * 2020-10-09 2021-01-15 山东大学 Preparation method of porous graphene microsphere ultra-black material
CN112736231A (en) * 2021-01-12 2021-04-30 杭州新川新材料有限公司 Preparation method of silicon monoxide negative electrode material of lithium ion battery

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CN104009205A (en) * 2014-06-12 2014-08-27 上海中聚佳华电池科技有限公司 Hollow graphene ball and preparation method and application thereof
CN104591165A (en) * 2014-12-30 2015-05-06 江南石墨烯研究院 Method for preparing graphene nanospheres

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104009205A (en) * 2014-06-12 2014-08-27 上海中聚佳华电池科技有限公司 Hollow graphene ball and preparation method and application thereof
CN104591165A (en) * 2014-12-30 2015-05-06 江南石墨烯研究院 Method for preparing graphene nanospheres

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107082414A (en) * 2015-02-13 2017-08-22 大洲电子材料株式会社 Graphene with random and irregular three-D stomata and preparation method thereof
CN108117913B (en) * 2016-11-28 2021-05-18 中国科学院金属研究所 Preparation method and application of spherical graphene lubricating additive
CN108117913A (en) * 2016-11-28 2018-06-05 中国科学院金属研究所 A kind of preparation method and purposes of spherical graphite alkene lubricating additive
CN106602063A (en) * 2016-12-30 2017-04-26 浙江大学 Preparation method for graphene spray and application of graphene spray in lithium-sulfur battery
CN107055521A (en) * 2017-03-21 2017-08-18 禹城贝尔新材料有限公司 The method and the graphene microballoon of prepare with scale height rule spherical graphite alkene microballoon
CN106977768B (en) * 2017-05-03 2019-01-01 杭州高烯科技有限公司 A kind of method that spitball shape graphene improves 6 impact strength of nylon
CN106977768A (en) * 2017-05-03 2017-07-25 杭州高烯科技有限公司 A kind of method that spitball shape graphene improves the impact strength of nylon 6
CN107230784A (en) * 2017-06-22 2017-10-03 山东大学 A kind of spherical graphite alkene/mangano-manganic oxide composite and preparation method and application
CN107651672B (en) * 2017-10-13 2019-11-22 杭州高烯科技有限公司 A kind of preparation method of the Ultralight graphene microballoon for solar absorption
CN107651672A (en) * 2017-10-13 2018-02-02 杭州高烯科技有限公司 A kind of preparation method of Ultralight graphene microballoon for solar absorption
CN108441282A (en) * 2018-02-07 2018-08-24 河南大学 A kind of dispersible graphene nano composite particles and its preparation method and application
CN108441282B (en) * 2018-02-07 2021-01-22 河南大学 Dispersible graphene nano composite particles and preparation method and application thereof
CN111847429A (en) * 2019-04-28 2020-10-30 深圳光启岗达创新科技有限公司 Preparation method and application of three-dimensional graphene wave-absorbing material
CN110357078A (en) * 2019-08-14 2019-10-22 北京大学深圳研究生院 A kind of graphene microballoon and preparation method thereof
CN112225202A (en) * 2020-10-09 2021-01-15 山东大学 Preparation method of porous graphene microsphere ultra-black material
CN112736231A (en) * 2021-01-12 2021-04-30 杭州新川新材料有限公司 Preparation method of silicon monoxide negative electrode material of lithium ion battery

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Application publication date: 20160106