CN102795614B - Preparation method of carbon nanospheres - Google Patents
Preparation method of carbon nanospheres Download PDFInfo
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- CN102795614B CN102795614B CN201210275257.9A CN201210275257A CN102795614B CN 102795614 B CN102795614 B CN 102795614B CN 201210275257 A CN201210275257 A CN 201210275257A CN 102795614 B CN102795614 B CN 102795614B
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Abstract
The invention provides a preparation method of carbon nanospheres, which comprises the following steps: 1) mixing citric acid and deionized water until the citric acid is completely dissolved, thereby obtaining an acidic solution; 2) adding soluble starch into the acidic solution prepared in the step 1), and heating in a water bath to form a homodispersed transparent sol; 3) putting the homodispersed transparent sol prepared in the step 2) in a reaction kettle, sealing, carrying out microwave heating, and naturally cooling; 4) carrying out centrifugal separation to obtain the product, washing the product with deionized water and anhydrous alcohol, and drying in vacuum; and 5) calcining the dried product, and naturally cooling to obtain the carbon nanospheres of which the diameters are 100-200nm.
Description
Technical field
The invention belongs to nanometer synthetic technology and lithium ion battery material field thereof, be specifically related to a kind of preparation method of nano carbon microsphere.
Background technology
In the negative active core-shell material of secondary lithium battery, the secondary lithium battery energy density using metallic lithium as negative active core-shell material is the highest.But metallic lithium there will be dendritic growth in charge and discharge process, makes internal short-circuit of battery, cause even blast of battery burning, security is very low.After this, the carbon material of the various ways such as refinery coke, carbon fiber, RESEARCH OF PYROCARBON, natural graphite, synthetic graphite is extensively elected to be the negative active core-shell material of serondary lithium battery.Conventionally, carbon ball has very high utility value on stored energy separates, and people adopt various raw materials to prepare carbon ball (as: 2001, Carbon, 39,2211-2214; 2008, Advanced Materials, 20,1160-1165).Meanwhile, carbon ball, except being applied to the negative active core-shell material of secondary lithium battery, can also be served as sorbent material, support of the catalyst, pharmaceutical carrier, hydrogen storage material etc.
The method of preparing at present nano carbon microsphere mainly adopts hydro-thermal reaction, and its defect is that the reaction times is long, causes the homogeneity of reaction product to be not easy to control.
Therefore, those skilled in the art is devoted to develop a kind of preparation method of new nano carbon microsphere.
Summary of the invention
The object of this invention is to provide a kind of preparation method of new nano carbon microsphere, with Reaction time shorten, increase the homogeneity of reaction product.
The preparation method of nano carbon microsphere provided by the present invention specifically comprises step:
1) citric acid and deionized water are mixed to completely and dissolve and obtain acidic solution;
2) Zulkovsky starch being added to the 1st) in the acidic solution of step preparation, heating in water bath, forms the vitreosol of homodisperse;
3) by the 2nd) vitreosol of the homodisperse of step preparation puts into reactor sealing, microwave heating, then naturally cooling;
4) centrifugation obtains product, deionized water and absolute ethanol washing for product, vacuum drying;
5) dry product through calcining, after this naturally cooling, obtains the nano carbon microsphere that diameter is 100～200nm.
Applicant, by adopting the mode of microwave heating, can shorten the time of reaction greatly, submits the homogeneity of product to.
Preferably, the 1st) in the described acidic solution of step, the concentration of described citric acid is 0.5～1.0mol/L.
Preferably, the 2nd) in the described vitreosol of step, starch concentration is 30～100g/L.
Preferably, the 2nd) in step, described heating in water bath refers to: warming-in-water to 80 DEG C also stirs more than 15 minutes.
Preferably, the 3rd) in step, described reactor is tetrafluoroethylene reactor.
Preferably, the 3rd) in step, described microwave heating refers to: microwave hyperthermia to 180～200 DEG C, react 20～30 minutes.
Preferably, the 4th) in step, the temperature of described vacuum drying is 80 DEG C.
Preferably, the 5th) in step, described calcining is: under vacuum or Ar atmospheric condition, with the temperature rise rate of 10 DEG C/min, be warming up to 700～1400 DEG C, and constant temperature 2～5 hours.
Described nano carbon microsphere can be used as the negative active core-shell material of secondary lithium battery.
Below with reference to accompanying drawing, the technique effect of design of the present invention, concrete structure and generation is described further, to understand fully object of the present invention, feature and effect.
Brief description of the drawings
Fig. 1 is the SEM photo of the prepared nano carbon microsphere of a preferred embodiment of the present invention;
Fig. 2 is the prepared nano carbon microsphere of a preferred embodiment of the present invention as the negative material of lithium ion battery, typical charging and discharging curve with and cycle characteristics: with 0.01mA constant current charge, 0.5mA constant-current discharge;
Fig. 3 is the prepared nano carbon microsphere of a preferred embodiment of the present invention as the negative material of lithium ion battery, typical charging and discharging curve with and cycle characteristics: with 0.1mA constant current charge and 0.1mA constant-current discharge.
Embodiment
Embodiment 1
1) 4.6g citric acid is joined in 30ml deionized water, be stirred to completely and dissolve, the concentration of citric acid is 0.5mol/L.
2) citric acid solution heating in water bath to 80 DEG C is also kept, add starch, starch concentration is 30g/L, stirs more than 15 minutes, obtains transparent colloidal solution;
3) join in reactor and sealing, microwave heating to 180 DEG C, is incubated 30 minutes, centrifugal after naturally cooling, and with deionized water and absolute ethanol washing, 80 DEG C of oven dry of spending the night.
4) get product after oven dry under logical Ar gas condition, gas velocity is 30sccm, with the temperature rise rate of 10 DEG C/min, is warming up to 700 DEG C, and keeps constant temperature 4 hours, after this naturally cooling.
Fig. 1 is the SEM photo of the nano carbon microsphere prepared of the present embodiment.As can be seen from Figure 1, nano carbon microsphere presents uniform spherical, and through measuring, its diameter is 100～200nm.The synthetic of this nano carbon microsphere do not need through long pyroprocess, and synthetic yield is high, does not basically contain other impurity phases.Fig. 2 and Fig. 3 are the negative material of the nano carbon microsphere prepared of the present embodiment as lithium ion battery, typical charging and discharging curve with and cycle characteristics.Can find out from Fig. 2 and Fig. 3, the charging current (0.01mA/mg and 0.1mA/mg) of different sizes and discharging current (0.5mA/mg and 0.1mA/mg), its impact of electrochemistry capacitance on lithium is little, and the coulomb efficiency discharging and recharging is all greater than 99%, and there are good consistence and cycle characteristics.
1) citric acid is joined in 30ml deionized water, be stirred to completely and dissolve, the concentration of citric acid is 1mol/L.
2) citric acid solution heating in water bath to 80 DEG C is also kept, add starch, starch concentration is 100g/L, stirs more than 15 minutes, obtains transparent colloidal solution;
3) join in reactor and sealing, microwave heating to 200 DEG C, is incubated 20 minutes, centrifugal after naturally cooling, and with deionized water and absolute ethanol washing, 80 DEG C of oven dry of spending the night.
4) get product after oven dry under logical Ar gas condition, gas velocity is 30sccm, with the temperature rise rate of 10 DEG C/min, is warming up to 1400 DEG C, and keeps constant temperature 4 hours, after this naturally cooling.
In nano carbon microsphere prepared by the present embodiment and above embodiment 1, size and the charge-discharge performance of the nano carbon microsphere of preparation are similar.
More than describe preferred embodiment of the present invention in detail.The ordinary skill that should be appreciated that this area just can design according to the present invention be made many modifications and variations without creative work.Therefore, all technician in the art, all should be in by the determined protection domain of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (4)
1. a preparation method for nano carbon microsphere, is characterized in that, described preparation method comprises the steps:
1) citric acid and deionized water are mixed to completely and dissolve and obtain acidic solution;
2) Zulkovsky starch being added to the 1st) in the acidic solution of step preparation, heating in water bath, forms the vitreosol of homodisperse;
3) by the 2nd) vitreosol of the homodisperse of step preparation puts into reactor sealing, microwave heating, then naturally cooling;
4) centrifugation obtains product, deionized water and absolute ethanol washing for product, vacuum drying;
5) dry product through calcining, after this naturally cooling, obtains the nano carbon microsphere that diameter is 100～200nm;
The 3rd) in step, described microwave heating refers to: microwave hyperthermia to 180～200 DEG C, react 20～30 minutes; The 1st) in the described acidic solution of step, the concentration of described citric acid is 0.5～1.0mol/L; The 2nd) in the described vitreosol of step, starch concentration is 30～100g/L; The 5th) in step, described calcining is: under vacuum or Ar atmospheric condition, with the temperature rise rate of 10 DEG C/min, be warming up to 700～1400 DEG C, and constant temperature 2～5 hours.
2. preparation method as claimed in claim 1, is characterized in that, the 2nd) in step, described heating in water bath refers to: warming-in-water to 80 DEG C also stirs more than 15 minutes.
3. preparation method as claimed in claim 1, is characterized in that, the 3rd) in step, described reactor is tetrafluoroethylene reactor.
4. preparation method as claimed in claim 1, is characterized in that, the 4th) in step, the temperature of described vacuum drying is 80 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103043646B (en) * | 2012-12-21 | 2014-06-04 | 浙江大学 | Method for preparing small solid carbon ball and carbon ball prepared thereby |
| CN103864049B (en) * | 2014-02-26 | 2015-10-07 | 上海大学 | Microwave degradation biological material prepares the method for fluorescent carbon nano particle |
| CN104495787A (en) * | 2014-12-12 | 2015-04-08 | 陕西科技大学 | Preparation method of negative electrode nano carbon material of lithium ion battery |
| CN105948045B (en) * | 2016-07-18 | 2018-04-03 | 湘潭大学 | A kind of preparation method and applications of N doping starch base activated carbon microballon material |
| CN112322693A (en) * | 2020-11-24 | 2021-02-05 | 上海健康医学院 | Marking method of helicobacter pylori in macrophage |
Citations (3)
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|---|---|---|---|---|
| CN1438174A (en) * | 2003-03-27 | 2003-08-27 | 上海交通大学 | Carbon nano hollow-ball and its making method |
| CN101323446A (en) * | 2008-06-27 | 2008-12-17 | 湖北大学 | Preparation of carbon nanosphere |
| CN102544459A (en) * | 2012-01-09 | 2012-07-04 | 上海交通大学 | Method for preparing graphene-coated carbon microsphere material by coating graphene oxide on carbon microsphere |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438174A (en) * | 2003-03-27 | 2003-08-27 | 上海交通大学 | Carbon nano hollow-ball and its making method |
| CN101323446A (en) * | 2008-06-27 | 2008-12-17 | 湖北大学 | Preparation of carbon nanosphere |
| CN102544459A (en) * | 2012-01-09 | 2012-07-04 | 上海交通大学 | Method for preparing graphene-coated carbon microsphere material by coating graphene oxide on carbon microsphere |
Non-Patent Citations (4)
| Title |
|---|
| "Microwave-assisted hydrothermal carbonization of lignocellulosic materials";M. Guiotoku et al.;《Materials Letters》;20090927;第63卷;第2707－2709页 * |
| "纳米炭球及其衍生物水热法制备研究进展";李敏 等;《林产化学与工业》;20110831;第31卷(第4期);第93－101页 * |
| M. Guiotoku et al.."Microwave-assisted hydrothermal carbonization of lignocellulosic materials".《Materials Letters》.2009,第63卷第2707－2709页. |
| 李敏 等."纳米炭球及其衍生物水热法制备研究进展".《林产化学与工业》.2011,第31卷(第4期),第93－101页. |
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