CN101429032B - CuO-carbon nano-tube composite micro-nano-sphere, preparation and uses thereof - Google Patents
CuO-carbon nano-tube composite micro-nano-sphere, preparation and uses thereof Download PDFInfo
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- CN101429032B CN101429032B CN2007101768687A CN200710176868A CN101429032B CN 101429032 B CN101429032 B CN 101429032B CN 2007101768687 A CN2007101768687 A CN 2007101768687A CN 200710176868 A CN200710176868 A CN 200710176868A CN 101429032 B CN101429032 B CN 101429032B
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Abstract
The invention discloses a CuO-carbon nano tube composite macro-nano ball, a preparation method thereof and application of the CuO-carbon nano tube composite macro-nano ball. The method for preparing the CuO-carbon nano tube composite macro-nano ball comprises the following steps: 1) a surfactant and cupric salt are dissolved to be prepared into a reactant solution A; 2) a carbon nano tube is dispersed into N, N-dimethyl formamide to obtain a reaction solution B; 3) the reaction solution B is added into the reactant solution A, and dispersed to obtain a dispersed solution C; and 4) the dispersed solution C is added with ammonia and subjected to heating reflux reaction to obtain the CuO-carbon nano tube composite macro-nano ball. The method takes the surfactant such as polyoxyethylene-polyoxypropylene-polyoxyethylene as a structure-directing agent, adopts a simple solution reflux method for one-step synthesis to obtain the CuO-carbon nano tube composite macro-nano ball. The used preparation raw materials are simple and have wide sources; and the preparation method is simple and economic, has low energy consumption and is convenient to operate, and can realize large-scale synthesis of the CuO-carbon nano tube composite macro-nano ball.
Description
Technical field
The present invention relates to a kind of CuO-carbon nano-tube composite micro-nano-sphere and preparation method thereof and application, particularly relate to its application as lithium ion battery anode material.
Background technology
Material, the energy and information are the pillars of modern society, also are the subject matter of being concerned about the new century.The exploitation of new material might become new growth engines, determines or affect the development of an industry to a great extent.
In more than ten years in the past, have fixedly that the inorganic or organic layer nano/micron structure of pattern is not only having huge potential application foreground aspect the devices such as electronics, optics, mechanics, and because its unique character and the basic research in fields such as chemistry, physics, electronics, optics, material science and bioscience is had far reaching significance.Another field, forward position of this structural material is the novel structural material that preparation has novel characteristics and function.Wherein monodispersed level micro-nano-sphere is mainly formed by nanostructure self assemblies such as nano particle, nanometer rods, nanometer sheet, because its people's attention in the physics of novelty and chemical property and huge potential using value and extremely.The main method for preparing this structure has that thermal reduction and oxidizing process, oriented growth method, self-assembly method, template assisting growth method, no template are synthetic, hydro thermal method and wet chemistry method.But controllably synthetic monodispersed micro-nano-sphere remains a kind of challenge.
Cupric oxide is as a kind of p N-type semiconductor N, at aspects such as heterocatalysis, gas sensing, an emission, superconduction and lithium ion battery electrode materials various application is arranged, thereby synthetic cupric oxide nano/micrometer structure all there is important meaning no matter be in basic research or the actual application.The nano/micron structure of the cupric oxide of different structure comprises that nano particle, nanometer spheroid, nanometer rods, nanometer spicule, nano belt, nanotube etc. all successfully are synthesized.Liu Bin etc. have synthesized the cupric oxide tiny balloon of dandelion shape by the level assembling of nanometer sheet.Xu Yanyan etc. has successfully prepared cupric oxide thorniness/stratiform microballoon.As lithium ion battery anode material, with other oxides, though the cupric oxide theoretical specific capacity is higher, but in the process of its storage lithium, there is very big change in volume, the pucker ﹠ bloat of volume causes very big stress in the charge and discharge process, make the efflorescence of material own and influence its cyclicity, and then have influence on its application in lithium ion battery.Carbon nano-tube is as another kind of nano material, because its very high chemical stability, very high draw ratio, very strong mechanical strength, very high active surface area and very high conductivity, thereby for example be widely used aspect pseudo-capacitance, fuel cell and the secondary cell at energy storage device.With the carbon mitron be integrated into other functional structure and compound in become a hot fields of research in nanotechnology.
Summary of the invention
The purpose of this invention is to provide a kind of CuO-carbon nano-tube composite micro-nano-sphere and preparation method thereof.
The present invention prepares the method for CuO-carbon nano-tube composite micro-nano-sphere, comprises the steps:
1) with surfactant and soluble copper salt dissolving, prepares reactant solution A;
2) carbon nano-tube is distributed to N, obtains reaction solution B in the dinethylformamide;
3) reaction solution B is joined among the reactant solution A, obtain dispersion soln C after the dispersion;
4) add ammoniacal liquor in dispersion soln C, then, heating reflux reaction obtains the CuO-carbon nano-tube composite micro-nano-sphere.
Wherein, the described surfactant of step 1) is a polyoxyethylene-poly-oxypropylene polyoxyethylene; Described soluble copper salt is selected from copper nitrate, copper sulphate or copper chloride; The mass ratio of described surfactant and soluble copper salt is 1: 1-1: 2.Step 2) described carbon nano-tube and N, the mass ratio of dinethylformamide is 20mg/mL-50mg/mL; Carbon nano-tube comprises many walls nanotube and Single Walled Carbon Nanotube and composition thereof among the present invention, and its size range is below 40 nanometers.The volume ratio of reaction solution B and reactant solution A is 1 in the step 3): 3-1: 6.The volume ratio of dispersion soln C and ammoniacal liquor is 1 in the step 4): 2-1: 6.
The CuO-carbon nano-tube composite micro-nano-sphere that adopts said method to obtain also belongs to protection scope of the present invention.
Another object of the present invention provides the purposes of CuO-carbon nano-tube composite micro-nano-sphere of the present invention.
The inventor confirms that by experiment CuO-carbon nano-tube composite micro-nano-sphere of the present invention can through repeatedly recycling, still can keep very high discharge capacity as the application of lithium ion battery anode material, has excellent cycle performance.Therefore, the CuO-carbon nano-tube composite micro-nano-sphere also belongs to protection scope of the present invention as the application of lithium ion battery anode material.
The present invention with surfactants such as polyoxyethylene-poly-oxypropylene polyoxyethylenes as structure directing agent, adopt the simple synthetic CuO-carbon nano-tube composite micro-nano-sphere that obtains of one step of solution circumfluence method, preparation process does not need the CuO-carbon nano-tube composite micro-nano-sphere is carried out high temperature or chemical after-treatment reason process, and this has just simplified preparation process to a great extent and has been avoided the micro-nano-sphere structural damage; Preparation is finished by simple solution circumfluence method, has avoided the hydrothermal reaction condition of HTHP; Because carbon nano-tube plays the effect of three-dimensional conductive network and structure buffer at the CuO-carbon nano-tube composite micro-nano-sphere, can significantly improve the cycle performance of CuO micro-nano-sphere as lithium ion battery anode material, thereby make material have good electrochemical; Used preparation raw material is simple, wide material sources, and preparation method's simple economy, energy consumption are low, easy to operate, can realize the extensive synthetic of CuO-carbon nano-tube composite micro-nano-sphere.
Description of drawings
Fig. 1 is the electromicroscopic photograph of CuO-carbon nano-tube composite micro-nano-sphere;
Fig. 2 is CuO micro-nano-sphere and the CuO-carbon nano-tube composite micro-nano-sphere cycle performance curve as the li-ion electrode anode material.
Embodiment
The key step that the present invention prepares the CuO-carbon nano-tube composite micro-nano-sphere is as follows:
1) with surfactant and mantoquita dissolving, prepares reactant solution A;
2) carbon nano-tube is distributed to N, obtains reaction solution B in the dinethylformamide;
3) reaction solution B is joined among the reactant solution A, obtain dispersion soln C after the dispersion;
4) add ammoniacal liquor in dispersion soln C, then, heating reflux reaction promptly obtains the CuO-carbon nano-tube composite micro-nano-sphere.
CuO-carbon nano-tube composite micro-nano-sphere of the present invention is CuO micro-nano ball and carbon nano-tube compound finishing of a step in same liquid phase, and its particle size range is at the 1-3 micron.And this CuO-carbon nano-tube composite micro-nano-sphere has good electrochemical, and its main capacity contribution is provided by the active material cupric oxide of core, and still, the carbon mitron can constitute three-dimensional conductive network well mutually, improves the character that electrically contacts of electrode material; Carbon nano-tube can also the padded coaming stress that pucker ﹠ bloat caused in charge and discharge process in addition, can increase substantially the charge-discharge performance of material along one-tenth.Carbon nano-tube plays the effect of three-dimensional conductive network and structure buffer at the CuO-carbon nano-tube composite micro-nano-sphere, can significantly improve the cycle performance of CuO micro-nano-sphere as lithium ion battery anode material
Embodiment 1, preparation CuO-carbon nano-tube composite micro-nano-sphere
Take by weighing 20 milligrams of purified carbon nano-tube, add 5 milliliters of N, dinethylformamide, ultrasonic dispersion 5 hours.1.208 gram copper nitrates and 1 gram polyoxyethylene-poly-oxypropylene polyoxyethylene P123 ceaselessly are being dissolved in 40 ml waters under the condition of stirring, are forming blue solution.Subsequently scattered carbon nano-tube is joined in this solution, the assurance even carbon nanotube was disperseed in ultrasonic again 2 hours.Add 5 milliliters of 25wt% ammoniacal liquor, stir after 1 hour, 110 ℃ were refluxed 2 hours under strong agitation, and the mixture solution centrifugation with gained washes with water, and the precipitation that obtains is CuO-carbon nano-tube composite micro-nano-sphere of the present invention.
Embodiment 2, preparation CuO-carbon nano-tube composite micro-nano-sphere
Take by weighing 50 milligrams of purified carbon nano-tube, add 5 milliliters of N, dinethylformamide, ultrasonic dispersion 5 hours.1.95 gram copper nitrate and 1 gram polyoxyethylene-poly-oxypropylene polyoxyethylene P123 ceaselessly are being dissolved in 40 ml waters under the condition of stirring, form blue solution.Subsequently scattered carbon nano-tube is joined in this solution, the assurance even carbon nanotube was disperseed in ultrasonic again 2 hours.Add 15 milliliters of 25wt% ammoniacal liquor, stir after 1 hour, 130 ℃ were refluxed 2 hours under strong agitation, and the mixture solution centrifugation with gained washes with water, and the precipitation that obtains is CuO-carbon nano-tube composite micro-nano-sphere of the present invention.
Fig. 1 is the electromicroscopic photograph of gained CuO-carbon nano-tube composite micro-nano-sphere, and as seen from the figure, CuO and carbon nano-tube have formed uniform composite micro-nano-sphere, and diameter is the 1-2 micron.The inside that carbon nano-tube not only is inserted into the CuO micro-nano-sphere forms conductive network, and forms conductive network between the CuO micro-nano-sphere.
The electric performance test of embodiment 3, CuO-carbon nano-tube composite micro-nano-sphere
With the CuO micro-nano-sphere as a comparison, CuO micro-nano-sphere preparation process is as follows:
1.208 gram copper nitrates and 1 gram polyoxyethylene-poly-oxypropylene polyoxyethylene P123 ceaselessly are being dissolved in 40 ml waters under the condition of stirring, are forming blue solution.Add the ammoniacal liquor of 10 milliliters of 25wt% subsequently, solution is transformed into navy blue.Then, with solution under strong agitation 110 ℃ refluxed 2 hours, solution becomes black, the mixture solution centrifugation with gained washes with water, the precipitation that obtains is CuO micro-nano-sphere of the present invention.
The electrochemical Characterization of CuO micro-nano-sphere and CuO-carbon nano-tube composite micro-nano-sphere: its electrochemical Characterization be adopt button cell Li|1M LiPF6 (EC: DMC=1: 1) | the CuO/CuO-carbon nano-tube.CuO micro-nano-sphere/CuO-carbon nano-tube composite micro-nano-sphere, binding agent and carbon black are made into slurry with 8: 1: 1 mixed, are coated to then on the electric conductor Copper Foil.Use Celgard 2400 microporous polypropylene membranes as barrier film, the conduct of lithium sheet metal is to electrode.After assembling is finished, on the charge-discharge test instrument, measure.Discharging and recharging of test is interval for 0-3V, at room temperature tests with the electric current of 8 hour rates.The result as shown in Figure 2, the result shows, CuO-carbon nano-tube composite micro-nano-sphere (indicating with CuO/CNT among the figure) has good performance as the anode material of lithium ion battery, its cycle performance is better than the CuO micro-nano-sphere, specific capacity is about 500mAh/g, illustrates carbon nano-tube and the compound chemical property that improves the CuO micro-nano-sphere well of CuO.
Claims (9)
1. a method for preparing the CuO-carbon nano-tube composite micro-nano-sphere comprises the steps:
1) with surfactant and soluble copper salt dissolving, prepares reactant solution A; Described surfactant is a polyoxyethylene-poly-oxypropylene polyoxyethylene;
2) carbon nano-tube is distributed to N, obtains reaction solution B in the dinethylformamide;
3) reaction solution B is joined among the reactant solution A, obtain dispersion soln C after the dispersion;
4) add ammoniacal liquor in dispersion soln C, then, heating reflux reaction obtains the CuO-carbon nano-tube composite micro-nano-sphere.
2. method according to claim 1 is characterized in that: the described soluble copper salt of step 1) is selected from copper nitrate, copper sulphate or copper chloride.
3. method according to claim 1 is characterized in that: the mass ratio of described surfactant and soluble copper salt is 1: 1-1: 2.
4. according to claim 1 or 2 or 3 described methods, it is characterized in that: step 2) described carbon nano-tube and N, the mass volume ratio of dinethylformamide is 20mg/mL-50mg/mL; The size range of described carbon nano-tube is below 40 nanometers.
5. according to claim 1 or 2 or 3 described methods, it is characterized in that: the volume ratio of reaction solution B and reactant solution A is 1 in the step 3): 6-1: 9.
6. according to claim 1 or 2 or 3 described methods, it is characterized in that: the volume ratio of dispersion soln C and ammoniacal liquor is 1 in the step 4): 3-1: 9.
7. according to claim 1 or 2 or 3 described methods, it is characterized in that: the temperature of the described heating reflux reaction of step 4) is 110-150 ℃.
8. the CuO-carbon nano-tube composite micro-nano-sphere that obtains of the arbitrary described method of claim 1-7.
9. the described CuO-carbon nano-tube composite micro-nano-sphere of claim 8 is as the application of lithium ion battery anode material.
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| CN106654170A (en) * | 2011-10-18 | 2017-05-10 | 浙江大学 | High-performance negative electrode directly serving as lithium ion battery and battery using the negative electrode |
| CN108346782B (en) * | 2017-12-28 | 2020-08-04 | 杭州电子科技大学 | Porous copper oxide microsphere/multilayer graphene composite material and preparation method thereof |
| CN110577209A (en) * | 2019-09-19 | 2019-12-17 | 天津大学 | Preparation method for in-situ synthesis of carbon nano tube surface loaded copper oxide nano particles |
| CN114768806B (en) * | 2022-05-27 | 2023-09-22 | 江苏科技大学 | Calabash-string-shaped CuO/CNT composite catalyst and preparation method thereof |
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| US20060014068A1 (en) * | 2004-06-10 | 2006-01-19 | California Institute Of Technology | Processing techniques for the fabrication of solid acid fuel cell membrane electrode assemblies |
| CN1948157A (en) * | 2006-11-09 | 2007-04-18 | 上海大学 | Hollow bead shaped nano-cerium oxide and its preparation method |
| CN1974486A (en) * | 2006-11-21 | 2007-06-06 | 浙江大学 | Process of preparing carbon nanotube/nanometer zinc oxide sphere heterojunction |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20060014068A1 (en) * | 2004-06-10 | 2006-01-19 | California Institute Of Technology | Processing techniques for the fabrication of solid acid fuel cell membrane electrode assemblies |
| CN1948157A (en) * | 2006-11-09 | 2007-04-18 | 上海大学 | Hollow bead shaped nano-cerium oxide and its preparation method |
| CN1974486A (en) * | 2006-11-21 | 2007-06-06 | 浙江大学 | Process of preparing carbon nanotube/nanometer zinc oxide sphere heterojunction |
Non-Patent Citations (2)
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| Yongyan Mu et al..Controllable Pt Nanoparticle Deposition on Carbon Nanotubes as an Anode Catalyst for Direct Methanol Fuel Cells.《J. Phys. Chem. B》.2005,第109卷(第47期),第22212-22216页. * |
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