CN103253657A - 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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- CN103253657A CN103253657A CN2013101757866A CN201310175786A CN103253657A CN 103253657 A CN103253657 A CN 103253657A CN 2013101757866 A CN2013101757866 A CN 2013101757866A CN 201310175786 A CN201310175786 A CN 201310175786A CN 103253657 A CN103253657 A CN 103253657A
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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 the carbon material manufacturing process technology field, relate to a kind of preparation method of three-dimensional Shi Mo Xi ∕ hollow carbon balls matrix material.The matrix material of the present invention's preparation can be widely used in electrochemical field such as ultracapacitor, capacitor type 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 electrical conductivity (7200 S/m), bigger theoretical specific surface area (2600 m
2/ g), superior performance such as high mechanical stability, so caused widely and paid close attention to.But graphene film interlayer π-π effect makes that its agglomeration is inevitable, and this has just limited the application of Graphene, especially the application on the electrochemistry.At present, a large amount of research is intended to solve the irreversible agglomeration traits of Graphene, as: sandwich structures such as (1) preparation Shi Mo Xi ∕ carbon pipe, (2) prepare three-dimensional Graphene, mainly utilize chemical Vapor deposition process, template, hydrothermal method etc.
Three-dimensional Graphene has kept superior performances such as Graphene high-specific surface area, high conductivity, its face face that can also overcome Graphene to a certain extent piles up, and unique three-dimensional porous structure is conducive to its application in electrochemistry and other fields (Bong G. C. simultaneously; 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 be the three-dimensional Graphene of preparation than effective means because its cost is low, workable, to experimental installation require low, the structure retentivity is good.But still there are some defectives in three-dimensional graphene-structured, pile up still as graphene film self π-π to exist, and this three-dimensional porous structure is easy to cave in the process of removing template, solves these a series of problems and is still a difficult problem.
Summary of the invention
The present invention proposes a kind of method for preparing three-dimensional Shi Mo Xi ∕ hollow carbon balls matrix material, matrix material can form three-dimensional porous graphene-structured, can further improve piling up of Graphene by the adding of hollow carbon balls again.Simultaneously, the existence of hollow carbon balls can prevent from removing caving in of graphene three-dimensional structure in the template procedure.
The objective of the invention is to reach by following technique means and measure.
The preparation method of three-dimensional Graphene provided by the present invention/hollow carbon balls matrix material may further comprise the steps:
0.8-1.2 wt% phenol solution and 3-5 wt% polymer drops aqueous solution is even, and vulkacit H is joined in the above-mentioned mixed solution above phenol: polymer drops after brute force stirs: the mass ratio of vulkacit H is 1:(0.8-2.4): 0.7; Above-mentioned reaction solution is transferred in the tetrafluoroethylene reactor at 130-160
oC reaction 4-5 h, naturally cool to room temperature after centrifuge washing get the hollow carbon balls presoma, be mixed with 3-5 wt% hollow carbon balls precursor water solution again; Graphite oxide is joined in the hollow carbon balls precursor water solution by certain mass ratio, ultrasonic mixing, suction filtration, the oven dry, place tube furnace, high-temperature calcination under the protection of inert gas, get final product three-dimensional Shi Mo Xi ∕ hollow carbon balls matrix material.
Described polymer drops is polystyrene spheres or polymethylmethacrylate ball.
The mass ratio of described phenol, polymer drops, vulkacit H, temperature of reaction, reaction times is relevant with wall thickness, size and the homogeneity of hollow carbon balls in the matrix material, exceed above-mentioned scope and may cause the hollow carbon balls heterogeneity, thereby can't obtain the three-dimensional Shi Mo Xi ∕ hollow carbon balls matrix material that this patent is mentioned.
Above-mentioned matrix material building-up process: graphite oxide: the mass ratio of hollow carbon balls presoma is (0.1-10): 1, the gained clad structure is obvious, no independent oxidized graphite flake and the naked ball that falls exist, and oxidized graphite flake and hollow carbon balls presoma are crosslinked 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 Graphene after the calcining is not sufficiently complete yet, and pile up phenomenon and occur.
The process that polymer drops, reduction-oxidation graphite are removed in above-mentioned temperature control calcining needs under inert atmosphere, and the temperature control calcining of two steps realizes.The first step calcining temperature is 100
oC-200
oC, resol generation Pintsch process in this temperature range; The second step calcining temperature is 400
oC-800
oC, at this temperature range polymer drops generation Pintsch process, graphite oxide also obtains reduction in calcination process 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 are 50-150 mL/min.
Preparation process of the present invention is simple, and is low to the experimental installation requirement, easy handling.The inventive method adopts template to prepare three-dimensional Shi Mo Xi ∕ hollow carbon balls matrix material, utilizes hollow carbon balls to prevent the destruction of the overlapping and three-dimensional structure of 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 the room temperature, 0.8 wt% phenol solution and 3 wt% polystyrene spheres aqueous solution is even, the polystyrene spheres particle diameter is 500 nm, and vulkacit H is joined in the above-mentioned mixed solution above phenol: polystyrene spheres under brute force stirs: the mass ratio of vulkacit H is 1:0.8:0.7; Above-mentioned reaction solution is transferred in the tetrafluoroethylene reactor 130
oC reacts 4 h, naturally cool to room temperature after centrifuge washing get the hollow carbon balls presoma, be mixed with 5 wt% hollow carbon balls precursor water solution again; Under the room temperature, 15 mg graphite oxides are joined in the 150 mg hollow carbon balls precursor water solution, ultrasonic 1 h gets mixed dispersion liquid, suction filtration, drying at room temperature; Product is placed in the tube furnace, and under the pure nitrogen gas protection, the control temperature rise rate is 0.5
oC ∕ min, gas flow rate are 50 mL ∕ min, at first are warming up to 100
oC is warming up to 800 after being incubated 1.5 h
oC is incubated naturally cooling behind 1.5 h, namely gets three-dimensional Shi Mo Xi ∕ hollow carbon balls matrix material.
Embodiment 2
Under the room temperature, 1.0 wt% phenol solutions and 5 wt% polymethylmethacrylate ball aqueous solution are even, the polymethylmethacrylate spherolite directly is 400 nm, vulkacit H is joined in the above-mentioned mixed solution above phenol under brute force stirs: the polymethylmethacrylate ball: the mass ratio of vulkacit H is 1:2.4:0.7; Above-mentioned reaction solution is transferred in the tetrafluoroethylene reactor 150
oC reacts 4 h, naturally cool to room temperature after centrifuge washing get the hollow carbon balls presoma, be mixed with 4 wt% hollow carbon balls precursor water solution again; Under the room temperature, 300 mg graphite oxides are joined in the 150 mg hollow carbon balls precursor water solution, ultrasonic 1.5 h get mixed dispersion liquid, suction filtration, drying at room temperature; Product is placed in the tube furnace, and under the pure argon protection, the control temperature rise rate is 2
oC ∕ min, gas flow rate are 90 mL ∕ min, at first are warming up to 200
oC is warming up to 400 after being incubated 1.5 h
oC is incubated naturally cooling behind 2 h, namely gets three-dimensional Shi Mo Xi ∕ hollow carbon balls matrix material.
Embodiment 3
Under the room temperature, 1.2 wt% phenol solutions and 4 wt% polystyrene spheres aqueous solution are even, the polystyrene spheres particle diameter is 200 nm, and vulkacit H is joined in the above-mentioned mixed solution above phenol: polystyrene spheres under brute force stirs: the mass ratio of vulkacit H is 1:1.6:0.7; Above-mentioned reaction solution is transferred in the tetrafluoroethylene reactor 180
oC reacts 4 h, naturally cool to room temperature after centrifuge washing get the hollow carbon balls presoma, be mixed with 3 wt% hollow carbon balls precursor water solution again; Under the room temperature, 1.5 g graphite oxides are joined in the 150 mg hollow carbon balls precursor water solution, ultrasonic 2 h get mixed dispersion liquid, suction filtration, drying at room temperature; Product is placed in the tube furnace, and under the pure nitrogen gas protection, the control temperature rise rate is 1
oC ∕ min, gas flow rate are 150 mL ∕ min, at first are warming up to 150
oC is warming up to 600 after being incubated 1.5 h
oC is incubated naturally cooling behind 3 h, namely gets three-dimensional Shi Mo Xi ∕ hollow carbon balls matrix material.
Claims (5)
1. the preparation method of a three-dimensional stone China ink alkene ∕ hollow carbon balls matrix 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, and vulkacit H is joined in the above-mentioned mixed solution above phenol: polymer drops after brute force stirs: the mass ratio of vulkacit H is 1:0.8-2.4:0.7; Above-mentioned reaction solution is transferred in the tetrafluoroethylene reactor at 130-160
oC reaction 4-5 h, naturally cool to room temperature after centrifuge washing get the hollow carbon balls presoma, be mixed with 3-5 wt% hollow carbon balls precursor water solution again; Graphite oxide is joined in the hollow carbon balls precursor water solution by certain mass ratio, ultrasonic mixing, suction filtration, oven dry places tube furnace, and the temperature control calcining of two steps namely gets three-dimensional Shi Mo Xi ∕ hollow carbon balls matrix material under the protection of inert gas.
2. according to the preparation method of right 1 described three-dimensional Shi Mo Xi ∕ hollow carbon balls matrix material, it is characterized in that described polymer drops is polystyrene spheres or polymethylmethacrylate ball.
3. according to the preparation method of right 1 described three-dimensional Shi Mo Xi ∕ hollow carbon balls matrix material, it is characterized in that graphite oxide: the mass ratio of hollow carbon balls precursor water solution is 0.1-10:1.
4. according to the preparation method of right 1 described three-dimensional Shi Mo Xi ∕ hollow carbon balls matrix material, it is characterized in that the inert protective gas of high-temperature calcination process is pure nitrogen gas or argon gas; Calcination process needs two step temperature controls to realize that the first step calcining temperature is 100-200
oC, the 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 are 50-150
oC/min.
5. according to the preparation method of right 1 described three-dimensional Shi Mo Xi ∕ hollow carbon balls matrix material, it is characterized in that the made matrix material of this method is three-dimensional conductive network with Graphene, have three-dimensional porous structure.
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| CN103723716A (en) * | 2013-12-23 | 2014-04-16 | 北京化工大学 | Nitrogen-doped carbon-coated graphene oxide two-dimensional porous composite material and preparation method thereof |
| CN103903879A (en) * | 2014-02-19 | 2014-07-02 | 国家纳米科学中心 | Porous grapheme/ MnO2 composite film and preparation method and application thereof |
| CN104882594A (en) * | 2015-04-16 | 2015-09-02 | 中国人民解放军国防科学技术大学 | Three-dimensional graphene-hollow carbon sphere nano composite and preparation method thereof |
| CN104916828A (en) * | 2015-04-16 | 2015-09-16 | 中国人民解放军国防科学技术大学 | Three dimensional graphene/hollow carbon sphere/sulfur composite material, preparation method thereof, and application in lithium-sulfur batteries |
| CN105129787A (en) * | 2015-09-10 | 2015-12-09 | 上海大学 | Preparing method of three-dimensional hierarchical porous graphene |
| CN105161724A (en) * | 2015-07-30 | 2015-12-16 | 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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| 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 |
| CN103723716A (en) * | 2013-12-23 | 2014-04-16 | 北京化工大学 | Nitrogen-doped carbon-coated graphene oxide two-dimensional porous composite material and preparation method thereof |
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| CN104882594A (en) * | 2015-04-16 | 2015-09-02 | 中国人民解放军国防科学技术大学 | Three-dimensional graphene-hollow carbon sphere nano composite and preparation method thereof |
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| 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 |
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| CN106935411A (en) * | 2017-04-26 | 2017-07-07 | 常州大学 | A kind of preparation of Graphene/mesoporous carbon spheres/array polyaniline material |
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