CN103253657B - Preparation method of three-dimensional graphene/hollow carbon sphere composite material - Google Patents
Preparation method of three-dimensional graphene/hollow carbon sphere composite material Download PDFInfo
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Abstract
The invention belongs to the technical field of carbon material production technologies, and relates to a preparation method of a three-dimensional graphene/hollow carbon sphere composite material. The preparation method is characterized by comprising the following steps of: adding graphite oxide into a precursor aqueous solution of hollow carbon spheres, uniformly dispersing the graphite oxide by using ultrasonic waves, carrying out suction filtration to wrap the graphite oxide on the surfaces of hollow carbon precursors, and thus forming a three-dimensional composite structure; and calcinating under the protection of inert gases so as to obtain a three-dimensional graphene/hollow carbon sphere composite material. The graphene serves as a three-dimensional conductive network of the obtained composite material, so that the composite material is unique in three-dimensional porous structure and has excellent conduction characteristic. The preparation method is simple and easy to control, and can be widely applied to the electrochemical fields such as supercapacitors, capacitive type desalination and lithium ion batteries.
Description
Technical field
The invention belongs to carbon material manufacturing process technology field, relate to a kind of preparation method of three-dimensional graphene/hollow carbon sphere composite material.Matrix material prepared by the present invention can be widely used in the electrochemical field such as ultracapacitor, structure capacitance desalination, lithium ion battery.
Background technology
Graphene is as a kind of carbon material of novel bi-dimensional cellular shape structure, and it has good electroconductibility (7200 S/m), larger theoretical specific surface area (2600 m
2/ g), the superior performance such as high mechanical stability, therefore cause and pay close attention to widely.But graphene film interlayer π-π effect makes its agglomeration inevitable, which limits the application of Graphene, the application especially in electrochemistry.At present, large quantifier elimination is intended to the irreversible agglomeration traits solving Graphene, as: (1) prepares the sandwich structures such as stone ink alkene ∕ carbon pipe, and (2) prepare three-dimensional grapheme, mainly utilize chemical Vapor deposition process, template, hydrothermal method etc.
Three-dimensional grapheme maintains the superior performance such as Graphene high-specific surface area, high conductivity; its face, face that can also overcome Graphene is to a certain extent stacking, and simultaneously unique three-dimensional porous structure is conducive to its application (Bong G. C. at electrochemistry and other field; MinHo Y.; Won H. H.; Jang W. C.; Yun S. H.; 3D Macroporous Graphene Frameworks for Supercapacitors with High Energy and Power Densities).Wherein template prepares three-dimensional grapheme comparatively effective means, because its cost is low, workable, low to experimental installation requirement, structural retention good.But three-dimensional grapheme structure still exists some defects, as stacking in graphene film self π-π still exist, and this three-dimensional porous structure is easy to cave in the process removing template, solves this series of problems and is still a difficult problem.
Summary of the invention
The present invention proposes a kind of method preparing three-dimensional graphene/hollow carbon sphere composite material, matrix material can form three-dimensional porous graphene-structured, again by improving the stacking of Graphene further adding of hollow carbon balls.Meanwhile, the existence of hollow carbon balls can prevent from removing caving in of graphene three-dimensional structure in template procedure.
The object of the invention is to be reached by following technique means and measure.
The preparation method of three-dimensional grapheme provided by the present invention/hollow carbon balls matrix material, comprises the following steps:
0.8-1.2 wt% phenol solution and 3-5 wt% polymer drops aqueous solution is even, vulkacit H is joined in above-mentioned mixed solution after strong stirring, above phenol: polymer drops: the mass ratio of vulkacit H is 1:(0.8-2.4): 0.7; Above-mentioned reaction solution is transferred in tetrafluoroethylene reactor at 130-160
oc reacts 4-5 h, and after naturally cooling to room temperature, centrifuge washing obtains hollow carbon balls presoma, then is mixed with 3-5 wt% hollow carbon balls precursor water solution; Graphite oxide is joined in hollow carbon balls precursor water solution by certain mass ratio, ultrasonic mixing, suction filtration, dry, be placed in tube furnace, high-temperature calcination under protection of inert gas, three-dimensional graphene/hollow carbon sphere composite material.
Described polymer drops is polystyrene spheres or polymethylmethacrylate ball.
The mass ratio of described phenol, polymer drops, vulkacit H, temperature of reaction, the wall thickness of reaction times and hollow carbon balls in matrix material, size and homogeneity are relevant, exceed above-mentioned scope and may cause hollow carbon balls heterogeneity, thus the three-dimensional graphene/hollow carbon sphere composite material that this patent mentions cannot be obtained.
Above-mentioned matrix material building-up process: graphite oxide: the mass ratio of hollow carbon balls presoma is (0.1-10): 1, gained clad structure is obvious, without independent oxidized graphite flake and naked fall ball exist, oxidized graphite flake and hollow carbon balls presoma are cross-linked effectively, form three-dimensional composite structure.Along with the amount of graphite oxide increases, three dimensional composite structure will be more not obvious, and the structure of the three-dimensional grapheme after calcining is also sufficiently complete, and stacking phenomenon occurs.
The process of above-mentioned temperature control calcining removing polymer drops, reduction-oxidation graphite, need under an inert atmosphere, two step temperature control calcinings realize.The first step calcining temperature is 100
oc-200
oc, resol generation Pintsch process in this temperature range; Second step calcining temperature is 400
oc-800
oc, at this temperature range polymer drops generation Pintsch process, in calcination process, graphite oxide is also reduced simultaneously.Rare gas element is pure nitrogen gas or argon gas, and temperature rise rate is 0.5-2
oc ∕ min, the flow velocity of rare gas element is 50-150 mL/min.
Preparation process of the present invention is simple, requires low, easy handling to experimental installation.The inventive method adopts template synthesis three-dimensional graphene/hollow carbon sphere composite material, utilizes hollow carbon balls to the destruction of the overlap and three-dimensional structure that prevent Graphene.The three-dimensional composite material of gained of the present invention can be widely used for electrochemical field.
Embodiment
After now specific embodiments of the invention being described in.
embodiment 1
Under room temperature, by 0.8 wt% phenol solution and 3 wt% polystyrene spheres aqueous solution even, polystyrene spheres particle diameter is 500 nm, is joined by vulkacit H in above-mentioned mixed solution, above phenol: polystyrene spheres under strong stirring: the mass ratio of vulkacit H is 1:0.8:0.7; Above-mentioned reaction solution is transferred in tetrafluoroethylene reactor 130
oc reacts 4 h, and after naturally cooling to room temperature, centrifuge washing obtains hollow carbon balls presoma, then is mixed with 5 wt% hollow carbon balls precursor water solution; Under room temperature, joined by 15 mg graphite oxides in 150 mg hollow carbon balls precursor water solution, ultrasonic 1 h, obtains mixed dispersion liquid, suction filtration, drying at room temperature; Placed by product in tube furnace, under pure nitrogen gas protection, controlling temperature rise rate is 0.5
oc ∕ min, gas flow rate is 50 mL ∕ min, is first warming up to 100
oc, is warming up to 800 after being incubated 1.5 h
oc, is incubated naturally cooling after 1.5 h, obtains three-dimensional graphene/hollow carbon sphere composite material.
embodiment 2
Under room temperature, by 1.0 wt% phenol solutions and 5 wt% polymethylmethacrylate ball aqueous solution even, polymethylmethacrylate spherolite footpath is 400 nm, vulkacit H is joined in above-mentioned mixed solution under strong stirring, above phenol: polymethylmethacrylate ball: the mass ratio of vulkacit H is 1:2.4:0.7; Above-mentioned reaction solution is transferred in tetrafluoroethylene reactor 150
oc reacts 4 h, and after naturally cooling to room temperature, centrifuge washing obtains hollow carbon balls presoma, then is mixed with 4 wt% hollow carbon balls precursor water solution; Under room temperature, joined by 300 mg graphite oxides in 150 mg hollow carbon balls precursor water solution, ultrasonic 1.5 h, obtain mixed dispersion liquid, suction filtration, drying at room temperature; Placed by product in tube furnace, under pure argon protection, controlling temperature rise rate is 2
oc ∕ min, gas flow rate is 90 mL ∕ min, is first warming up to 200
oc, is warming up to 400 after being incubated 1.5 h
oc, is incubated naturally cooling after 2 h, obtains three-dimensional graphene/hollow carbon sphere composite material.
embodiment 3
Under room temperature, by 1.2 wt% phenol solutions and 4 wt% polystyrene spheres aqueous solution even, polystyrene spheres particle diameter is 200 nm, is joined by vulkacit H in above-mentioned mixed solution, above phenol: polystyrene spheres under strong stirring: the mass ratio of vulkacit H is 1:1.6:0.7; Above-mentioned reaction solution is transferred in tetrafluoroethylene reactor 180
oc reacts 4 h, and after naturally cooling to room temperature, centrifuge washing obtains hollow carbon balls presoma, then is mixed with 3 wt% hollow carbon balls precursor water solution; Under room temperature, joined by 1.5 g graphite oxides in 150 mg hollow carbon balls precursor water solution, ultrasonic 2 h, obtain mixed dispersion liquid, suction filtration, drying at room temperature; Placed by product in tube furnace, under pure nitrogen gas protection, controlling temperature rise rate is 1
oc ∕ min, gas flow rate is 150 mL ∕ min, is first warming up to 150
oc, is warming up to 600 after being incubated 1.5 h
oc, is incubated naturally cooling after 3 h, obtains three-dimensional graphene/hollow carbon sphere composite material.
Claims (5)
1. a preparation method for three-dimensional graphene/hollow carbon sphere composite material, is characterized in that having following processing step:
0.8-1.2 wt% phenol solution and 3-5 wt% polymer drops aqueous solution is even, vulkacit H is joined in above-mentioned mixed solution after strong stirring, above phenol: polymer drops: the mass ratio of vulkacit H is 1:0.8-2.4:0.7; Above-mentioned reaction solution is transferred in tetrafluoroethylene reactor at 130-160
oc reacts 4-5 h, and after naturally cooling to room temperature, centrifuge washing obtains hollow carbon balls presoma, then is mixed with 3-5 wt% hollow carbon balls precursor water solution; Join in hollow carbon balls precursor water solution by graphite oxide by certain mass ratio, ultrasonic mixing, suction filtration, dry, be placed in tube furnace, under protection of inert gas, two step temperature control calcinings, obtain three-dimensional graphene/hollow carbon sphere composite material.
2. the preparation method of the three-dimensional graphene/hollow carbon sphere composite material according to right 1, is characterized in that described polymer drops is polystyrene spheres or polymethylmethacrylate ball.
3. the preparation method of the three-dimensional graphene/hollow carbon sphere composite material according to right 1, is characterized in that graphite oxide: the mass ratio of hollow carbon balls precursor water solution is 0.1-10:1.
4. the preparation method of the three-dimensional graphene/hollow carbon sphere composite material according to right 1, is characterized in that, the inert protective gas of high-temperature burning process is pure nitrogen gas or argon gas; Calcination process needs two step temperature controls to realize, and the first step calcining temperature is 100-200
oc, second step calcining temperature is 400-800
oc, soaking time is 1-3 h; Temperature rise rate is 0.5-2
oc ∕ min, rare gas element flow velocity is 50-150 mL/min.
5. the preparation method of the three-dimensional graphene/hollow carbon sphere composite material according to right 1, is characterized in that the made matrix material of the method is three-dimensional conductive network with Graphene, has three-dimensional porous structure.。
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| CN105129763A (en) * | 2015-09-09 | 2015-12-09 | 上海大学 | Preparation method of three-dimensional graphene/mesoporous carbon sphere composite material |
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| CN103723716B (en) * | 2013-12-23 | 2016-06-08 | 北京化工大学 | Nitrogen-doped carbon cladding graphene oxide two-dimensional is composite porous and preparation method thereof |
| CN103903879B (en) * | 2014-02-19 | 2017-02-08 | 国家纳米科学中心 | Porous grapheme/ MnO2 composite film and preparation method and application thereof |
| CN104916828B (en) * | 2015-04-16 | 2017-06-16 | 中国人民解放军国防科学技术大学 | Three-dimensional grapheme hollow carbon sphere/sulphur composite and preparation method thereof and the application in lithium-sulfur cell |
| CN104882594B (en) * | 2015-04-16 | 2017-07-07 | 中国人民解放军国防科学技术大学 | Three-dimensional grapheme hollow carbon sphere nano-complex and preparation method thereof |
| CN105161724B (en) * | 2015-07-30 | 2017-05-17 | 中国人民解放军国防科学技术大学 | Porous carbon sphere for lithium-sulfur battery and preparation method and application of porous carbon sphere |
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| CN105752966B (en) * | 2016-01-27 | 2017-12-15 | 同济大学 | A kind of preparation method of graphene/hollow Nano carbon balls |
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| CN106517090B (en) * | 2016-11-25 | 2020-06-30 | 重庆文理学院 | High-performance hydrogen storage material and preparation method thereof |
| CN108689397A (en) * | 2017-04-10 | 2018-10-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | A kind of carbon hollow ball aeroge, preparation method and application |
| CN106935411B (en) * | 2017-04-26 | 2018-06-12 | 常州大学 | A kind of preparation of graphene/mesoporous carbon spheres/array polyaniline material |
| CN108183208A (en) * | 2017-12-24 | 2018-06-19 | 林荣铨 | A kind of graphene/solid carbon ball lithium ion battery negative material preparation method and preparation method thereof |
| CN111847429B (en) * | 2019-04-28 | 2023-03-21 | 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 |
| CN110649265B (en) * | 2019-11-06 | 2021-01-12 | 桑顿新能源科技(长沙)有限公司 | Conductive agent material, battery pole piece and application |
| CN115020668A (en) * | 2022-06-27 | 2022-09-06 | 广州鹏辉能源科技股份有限公司 | Carbon-based negative electrode for sodium/potassium ion battery and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167309A (en) * | 2011-03-04 | 2011-08-31 | 北京化工大学 | Preparation method of shape-controllable hollow carbon microsphere |
| CN102509643A (en) * | 2011-11-29 | 2012-06-20 | 西北师范大学 | Graphene/carbon ball composite material, and preparation and application thereof |
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| CN102167309A (en) * | 2011-03-04 | 2011-08-31 | 北京化工大学 | Preparation method of shape-controllable hollow carbon microsphere |
| CN102509643A (en) * | 2011-11-29 | 2012-06-20 | 西北师范大学 | Graphene/carbon ball composite material, and preparation and application thereof |
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| CN105129763A (en) * | 2015-09-09 | 2015-12-09 | 上海大学 | Preparation method of three-dimensional graphene/mesoporous carbon sphere composite material |
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