CN103208621A - Preparation method and application of carbon nanotube/titanium dioxide coaxial nanometer cable composite material - Google Patents
Preparation method and application of carbon nanotube/titanium dioxide coaxial nanometer cable composite material Download PDFInfo
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- CN103208621A CN103208621A CN2013101268145A CN201310126814A CN103208621A CN 103208621 A CN103208621 A CN 103208621A CN 2013101268145 A CN2013101268145 A CN 2013101268145A CN 201310126814 A CN201310126814 A CN 201310126814A CN 103208621 A CN103208621 A CN 103208621A
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Abstract
The invention provides a preparation method of a carbon nanotube/titanium dioxide coaxial nanometer cable composite material. The preparation method comprises the following steps of: carrying out sulfonation and modification on the surface of a bamboo-like polymer nanotube which is used as a template and a carbon source; and inducting titanium tetrabutoxide to hydrolyze by gel and roast in an inert atmosphere to prepare the carbon nanotube/titanium dioxide coaxial nanometer cable composite material. The carbon nanotube/titanium dioxide coaxial nanometer cable composite material is composed of a carbon nanotube core layer, which is of a hierarchical pore, and a titanium dioxide shell layer which is of a mesoporous structure. As a lithium ion battery negative electrode material, the carbon nanotube/titanium dioxide coaxial nanometer cable composite material has better specific capacity and cycling stability, and can be used for showing reversible lithium storage capacity of 231mAh/g after being circulated by 100 cycles under the current of 1000mA/g. The preparation method of the carbon nanotube/titanium dioxide coaxial nanometer cable composite material provided by the invention is simple in process and capable of easily obtaining materials; moreover, the carbon nanotube/titanium dioxide coaxial nanometer cable composite material can be produced in a large-scale manner, excellent in performances, and therefore, the composite material is a lithium ion battery negative electrode material with a favorable application prospect.
Description
Technical field
The invention belongs to the inorganic composite materials field, being specifically related to a kind of polymer nanotube is template and carbon source, and titanate esters is the titanium source, prepares the coaxial nano-cable composite material of carbon nano-tube/titanic oxide by sol-gel process and follow-up calcination processing.
Background technology
In recent years, along with the aggravation of environmental pollution and energy crisis, chargeable secondary lithium battery is considered to be the most potential energy storage device, is applied to the energy storage device of power vehicle, hybrid vehicle and wind power generation and solar power generation etc.Undoubtedly, the electrode material of preparation high-performance and safety is very important.Present carbon negative pole material commonly used, there are a lot of problem and shortage, there is potential safety hazard etc. during, high-power applications serious such as capacity attenuation first, therefore searching and preparation have height ratio capacity, long circulation life, high power and safe lithium ion battery negative material have become current research focus.
Titanium dioxide is because its excellent physicochemical properties, and environmental friendliness is nontoxic, cheapness, characteristics such as reserves are big and be widely used in aspects such as decoration field, photocatalysis, solar cell, lithium ion battery, senser element.Especially in the lithium ion battery field, comparing with material with carbon element has higher operating voltage (about 1.7 V), and these characteristics can be avoided the formation of Zhi Jingli effectively, thereby have improved fail safe.In addition, titanium dioxide is compared with tin ash with silicon dioxide, and the smaller volume expansion rate is arranged, and stronger cyclical stability (J Mater Sci, 2012,47,2519 – 2534) is arranged.But titanium dioxide is as a kind of semi-conducting material, and the ionic diffusion coefficient that it is low and low conductivity have hindered the further application of this material.How to pass through the regulation and control of microcosmic nanotopography, the ion electronics conduction velocity that the composite material that preparation is had complementary advantages improves material is emphasis and the difficult point of lithium ion battery negative material research.At present, research work mainly concentrates on two aspects: the one, and the pattern regulation and control, titania nanotube, nanofiber, nanometer rods, hollow nano-sphere and the flower-like nanometer particle etc. that prepare porous with methods such as template, high temperature hydro thermal methods, but the general treatment temperature of hydro thermal method is higher, it is more to consume energy, and gentle template is a kind of good selection.Be compound with the stronger material of conductivity on the other hand, as Ag, Au/TiO
2(J. Am. Chem. Soc., 2012,134,7,505 17512), C/TiO
2(Adv. Mater., 2011,23,3575 – 3579) etc., because noble metal is piled up densification, and cost is higher, by contrast, compound with material with carbon element is a kind of good selection.When the compound coaxial nano-cable of the carbon nano-tube of having reported and titanium dioxide is used for electrode material of lithium battery, have capability retention and cyclical stability (Chem. Mater., 2010,22,1908 – 1914) preferably.In sum, seek a kind of carbon source cheap and easy to get, can be used as simultaneously template again, assist the nano composite material of titanium dioxide formation high-specific surface area be a kind of good design.
Summary of the invention
The objective of the invention is to adopt a kind of cheap and easy to get; the polymer nanotube that is produced on a large scale is as template and carbon source; come fast, simply to prepare the coaxial nano-cable composite material of carbon nano-tube/titanic oxide, and be applied to lithium ion battery negative material.
The preparation method of the carbon nano-tube/titanic oxide composite Nano cable material that the present invention proposes mainly may further comprise the steps:
Step 2 is sulfonation of polymer nanotube, selected polymer is placed concentrated sulfuric acid sulfonation a period of time (20 ~ 60 ℃ of following sulfonation 4 ~ 24 hours of uniform temperature, preferred 50 ℃ of following sulfonation 12 hours), the purpose of sulfonation is to make it surface-functionalized, introduce hydrophilic radicals such as sulfonic group, make polymer nanotube be easy to be scattered in the solution such as water, ethanol, simultaneously the group introduced of surface is easy to adsorb the metal ion, organic/inorganic group of oppositely charged etc., so the sulfonation of polymer surfaces is extremely important;
Step 3 is that the sulfonated polymers nanotube is scattered in the ethanol, add a certain amount of titanate esters and (comprise in metatitanic acid methyl esters, tetraethyl titanate, positive third fat of metatitanic acid, isopropyl titanate, the tetrabutyl titanate any one, preferred tetrabutyl titanate), stirring under low temperature environment (10 ~ 10 ℃, preferred 0 ℃) makes titanate esters be adsorbed on the surface of polymer pipe equably by electrostatic interaction.Because adsorption process is exothermic process, so low temperature more is conducive to success, coats equably.Simultaneously, we can regulate the thickness of coating layer effectively by the addition (mass ratio of titanate esters and polymer nanotube is 4 ~ 30:1, preferred 13.3:1) of regulation and control titanate esters, thus the mass percent of carbon and titanium dioxide in the adjusting composite material.Drip the titanate esters hydrolysis that low amounts of water is adsorbed the surface then, because the titanate esters hydrolysis is very fast, so rate of addition is unsuitable too fast, controls its hydrolysis rate and coat equably to guarantee it;
Step 4 is at nitrogen, (preferred nitrogen) in argon gas or the helium inert atmosphere, under 450 ~ 1000 ℃ of temperature 1 ~ 5 hour (preferred 2 hours) of (preferred 700 ℃) calcining, obtain the coaxial nano-cable composite material of carbon nano-tube/titanic oxide.Be applied to lithium cell negative pole material, show capability retention and cyclical stability preferably.
The method for preparing the coaxial nano-cable composite material of carbon nano-tube/titanic oxide provided by the invention, efficient, simple, be produced on a large scale, have practical application foreground.
Description of drawings
Fig. 1 is the TEM photo of sulfonation polydivinylbenezene.
Fig. 2 is the infrared spectrum of polydivinylbenezene (PDVB) and sulfonation polydivinylbenezene (SPDVB).
Fig. 3 is the TEM photo of sulfonation polydivinylbenezene @ titanium gel.
Fig. 4 is the HRTEM photo of the coaxial nano-cable composite material of carbon nano-tube/titanic oxide.
Fig. 5 is the XRD figure of the coaxial nano-cable composite material of carbon nano-tube/titanic oxide.
Fig. 6 is nitrogen adsorption desorption curve and the pore-size distribution of the coaxial nano-cable composite material of carbon nano-tube/titanic oxide.
The cycle life of battery when Fig. 7 does lithium cell negative pole material for the coaxial nano-cable composite material of carbon nano-tube/titanic oxide.
Embodiment
Embodiment one
The present invention is further detailed explanation below in conjunction with embodiment.
1, the preparation of polydivinylbenezene: in 250 mL single port flasks, contain 100 g normal heptanes, to wherein adding 4 g monomer divinylbenzene wiring solution-formings, again to wherein adding 150 mg (10) boron trifluoride etherate as initator, sealing back is ultrasonic in ultrasonic wave to obtain a large amount of red-brown precipitations, add the ethanol cessation reaction behind 15 min, filter and obtain the white cotton granulated substance.
2, the preparation of sulfonation polydivinylbenezene: take by weighing the polymer nanotube of 0.2 g drying in flask, add the 30 mL concentrated sulfuric acids, place 50 ℃ of isoperibol sulfonation 12 h, big water gaging dilution is filtered, and drying gets product.Fig. 1 is the TEM photo of sulfonation polydivinylbenezene, is ring shape nanotube through tem analysis, and diameter is 50 ~ 200 nanometers, and length is 500 nanometers ~ 5 millimeter.Fig. 2 is the infrared spectrum before and after the polydivinylbenezene sulfonation, and as seen from the figure, sulfonic acid group has successfully been introduced on the surface at polymer pipe after the sulfonation.
3, the preparation of sulfonation polydivinylbenezene @ titanium gel: take by weighing 0.15 g sulfonated polymers nanotube ultrasonic dispersion 90 min in 10 mL ethanol, drip 2.0 g tetrabutyl titanates then, the beaker that fills mixed liquor is placed 0 ℃ of ice bath high speed magnetic stirring and adsorbing 2 h, slowly drip 0.5 ml water and make the titanate esters hydrolysis, 4000 rpm are centrifugal after stirring 2 h, ethanol washing 2-3 time, 40 ℃ of vacuumizes.The TEM photo of sulfonation polydivinylbenezene @ titanium gel is seen Fig. 3.
4, the preparation of the coaxial nano-cable composite material of carbon nano-tube/titanic oxide: the gained presoma is placed tube furnace 700 ℃ of calcining 2 h under the nitrogen atmosphere protection, obtain the coaxial nano-cable composite material of carbon nano-tube/titanic oxide of black.By the microscopic appearance (Fig. 4) of high power transmission electron microscope (HRTEM) observation material, from figure, can clearly see the thickness of the composite Nano construction of cable and shell thereof; By the crystal formation (Fig. 5) of XRD diffractometer analysis of material, the crystal formation of analyzing titanium dioxide in the composite material as can be known is anatase; Adsorption desorption curve by nitrogen and pore-size distribution this composite material as can be known have porousness (Fig. 6).
Electrochemical property test: with prepared carbon nano-tube/titanic oxide nano cable composite material and acetylene black and PVDF(polyvinylidene fluoride), according to mass ratio m (active material): m (conductive agent acetylene black): the ratio of m (PVDF)=80:10:10 is mixed, with
N-Methyl pyrrolidone (NMP) is adjusted to homogenate for solvent with it, evenly be coated on the clean Copper Foil of preliminary treatment, be cut into the circular electrode sheet behind 110 ℃ of drying 12 h, in high-purity argon gas atmosphere glove box with EC/DMC(ethylene carbonate/methyl ethyl carbonate)=1:1LiPF
6Be electrolyte, microporous polypropylene membrane 2300 is barrier film, and lithium metal is for to be assembled into 2023 button cells to electrode.Above-mentioned battery is carried out the cycle life test, as shown in Figure 7: press the coaxial nano-cable composite material of carbon nano-tube/titanic oxide of embodiment one method and proportioning preparation, the battery of assembling 110 the discharge capacities after enclosing that circulates under 1000 mA/g current densities are 231mAh/g.
Claims (4)
1. the coaxial nano-cable of carbon nano-tube/titanic oxide is characterized in that, is made up of carbon nano-tube core layer and titanium dioxide shell, and the external diameter of the coaxial nano-cable of described carbon nano-tube/titanic oxide is the 60-500 nanometer, and length is 500 nanometers ~ 5 millimeter.
2. the preparation method of the coaxial nano-cable of the described carbon nano-tube/titanic oxide of claim 1, may further comprise the steps: the sulfonated polymer nanotube is scattered in the ethanol, add an amount of titanate esters, pass through sol gel reaction, under the certain reaction temperature, behind the absorption certain hour, in mixed liquor, drip a spot of water, the hydrolysis rate of control titanate esters, obtain white emulsus dispersion liquid, centrifugal, washing, drying, the material with gained obtains the coaxial nano-cable of described carbon nano-tube/titanic oxide behind the high-temperature calcination certain hour in inert atmosphere then.
3. method according to claim 2, it is characterized in that: described sulfonated polymer nanotube is by in the polydivinylbenezene of the ring shape of cationic polymerization preparation, poly-(divinylbenzene-1-chloro-4-methyl-benzene) nanotube any one, in the concentrated sulfuric acid, obtain sulfonated polymer nanotube (preferred 50 ℃ of sulfonation 12 hours) after 4 ~ 24 hours in 20 ~ 60 ℃ of following sulfonation, the diameter of described sulfonated polymer nanotube is 50 ~ 200 nanometers, and length is 500 nanometers ~ 5 millimeter; Described metatitanic acid fat refers to contain at least in its molecular structure a compounds of a Ti-O-C key, comprising: any one in metatitanic acid methyl esters, tetraethyl titanate, positive third fat of metatitanic acid, isopropyl titanate, the tetrabutyl titanate, preferred tetrabutyl titanate; The mass ratio of the addition of described titanate esters and sulfonated polymer nanotube is 4 ~ 30:1, preferred 13.3:1; Described adsorption reaction temperature is-10 ~ 10 ℃, preferred 0 ℃; Described inert atmosphere is nitrogen, argon gas or helium; The high-temperature calcination temperature is 450 ~ 1000 ℃; Calcination time is 1 ~ 5 hour; Preferably in nitrogen atmosphere, calcined 2 hours under 700 ℃.
4. the coaxial nano-cable of carbon nano-tube/titanic oxide according to claim 1 is characterized in that: can be used as lithium ion battery negative material.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104538581A (en) * | 2014-12-31 | 2015-04-22 | 江苏锋驰绿色电源有限公司 | Three-dimensional porous lithium manganate film electrode and preparing method and application thereof |
| CN106784648A (en) * | 2016-11-16 | 2017-05-31 | 江汉大学 | The preparation method of multi-walled carbon nano-tubes/titanium dioxide composite lithium ion battery cathode material |
| CN107302081A (en) * | 2016-04-15 | 2017-10-27 | 华为技术有限公司 | Negative material and preparation method thereof, battery and preparation method thereof |
| CN107331839A (en) * | 2017-06-28 | 2017-11-07 | 福建师范大学 | A kind of preparation method of carbon nanotube loaded nano titanium oxide |
| CN114180620A (en) * | 2021-11-30 | 2022-03-15 | 陕西科技大学 | Preparation method for preparing titanium dioxide/carbon cathode by taking polypyrrole as template |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102758264A (en) * | 2011-04-28 | 2012-10-31 | 中国科学院化学研究所 | Polymer nanofiber and preparation method and application of functional/hybrid material thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102758264A (en) * | 2011-04-28 | 2012-10-31 | 中国科学院化学研究所 | Polymer nanofiber and preparation method and application of functional/hybrid material thereof |
Non-Patent Citations (1)
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| FEI-FEI CAO ET AL.: "Symbiotic coaxial nanocables: facile synthesis and an efficient and elegant morphological solution to the lithium storage problem", 《CHEM. MATER.》, vol. 22, 22 January 2010 (2010-01-22) * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104538581A (en) * | 2014-12-31 | 2015-04-22 | 江苏锋驰绿色电源有限公司 | Three-dimensional porous lithium manganate film electrode and preparing method and application thereof |
| CN107302081A (en) * | 2016-04-15 | 2017-10-27 | 华为技术有限公司 | Negative material and preparation method thereof, battery and preparation method thereof |
| CN106784648A (en) * | 2016-11-16 | 2017-05-31 | 江汉大学 | The preparation method of multi-walled carbon nano-tubes/titanium dioxide composite lithium ion battery cathode material |
| CN107331839A (en) * | 2017-06-28 | 2017-11-07 | 福建师范大学 | A kind of preparation method of carbon nanotube loaded nano titanium oxide |
| CN114180620A (en) * | 2021-11-30 | 2022-03-15 | 陕西科技大学 | Preparation method for preparing titanium dioxide/carbon cathode by taking polypyrrole as template |
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Application publication date: 20130717 |