CN103213966A - Carbon nano tube freeze drying body/metal oxide compound - Google Patents
Carbon nano tube freeze drying body/metal oxide compound Download PDFInfo
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- CN103213966A CN103213966A CN2013101348629A CN201310134862A CN103213966A CN 103213966 A CN103213966 A CN 103213966A CN 2013101348629 A CN2013101348629 A CN 2013101348629A CN 201310134862 A CN201310134862 A CN 201310134862A CN 103213966 A CN103213966 A CN 103213966A
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Abstract
The invention discloses a carbon nano tube freeze drying body/metal oxide compound which is structurally characterized in that a carbon nano tube freeze drying body is used as a continuous matrix to react, and the metal oxide is compounded on the lamella or among the lamellas, and a continuous network structure is maintained macroscopically and microscopically after reaction. The metal oxide is any one of MnO2, SnO2 or TiO2. Uniform distributivity and shape of the compound can be controlled by a simple liquid phase method and simple synthetic parameter adjustment, so that the compound has the characteristics of short process flow, stable process, mild reaction condition and low cost. The carbon nano tube freeze drying body/metal oxide compound has important application prospect in the fields of supercapacitors, lithium ion batteries, solar batteries, photocatalysis and the like.
Description
Technical field
The invention relates to nano material, particularly a kind of liquid phase method prepares carbon nanotube lyophilize body/metal oxide composite and preparation method thereof.
Background technology
Carbon nano-tube material is widely used in the preparation of each field matrix material owing to the mechanics with many excellences, electricity and chemical property.The various countries investigator has done a large amount of work about preparation metal oxide/carbon nano-tube material composite at present.
Metal oxide is particularly had the transition metal oxide of fake capacitance character (as MnO
2Deng) in introduce the carbon tube material and can reach problems such as improving the low electricity of fake capacitance metal oxide is led, cycle performance difference, realize the combination of mixture high-energy, high power density and excellent cycle performance, this also is the research emphasis of super capacitance electrode material in recent years.The metal oxide semiconductor that is applied to dye sensitization solar battery is (as TiO
2, SnO
2Deng) in introduce small amount of carbon Guan Yike and play the effect that promotes transfer transport, increases photoelectric conversion efficiency.In a word, the fields such as ultracapacitor, lithium ion battery, solar cell, photochemical catalysis that are compounded in of carbon nano-tube material and metal oxide have the major application prospect.
Carbon nanotube lyophilize body is owing to have successive network sheet structure, can be used as a kind of successive macroscopic body and participate in gentle liquid phase reaction, carbon pipe lyophilize body/metal oxide compounds that reaction generates also keeps the previous macroscopical continuous structure of carbon pipe lyophilize body, avoided the required product of general solution reaction process to filter loaded down with trivial details steps such as collection, also ionic reaction product simple in the solution and complex reaction product simple separation can have been come out.
Summary of the invention
Purpose of the present invention, it is the shortcoming and defect that overcomes prior art, the contiguous network sheet structure of utilizing carbon nanotube lyophilize body to be had, make the lyophilize body take under the prerequisite that macrostructure keeps gentle solution reaction on its lamella or the sheet interlayer compound on metal oxide; A kind of carbon nanotube lyophilize body/metal oxide compounds that participates in still keeping after reaction and the reaction contiguous network structure on the both macro and micro with carbon nanotube lyophilize body as a kind of successive substrates is provided.
The present invention is achieved by following technical solution.
A kind of carbon nanotube lyophilize body/metal oxide compounds, it is characterized in that, carbon nanotube lyophilize body participates in reaction as a kind of successive substrates, be on its lamella or the sheet interlayer compound on metal oxide, and still keep contiguous network structure on the both macro and micro after the reaction; Described metal oxide is MnO
2, TiO
2Perhaps SnO
2In any one;
This carbon nanotube lyophilize body/metal oxide compounds can be prepared from by following simple and easy liquid phase method;
(1) hydrothermal synthesis method is applicable to MnO
2, TiO
2Perhaps SnO
2Metal oxide and carbon pipe lyophilize body compound has following steps:
A, carbon nanotube lyophilize body is placed the stainless steel cauldron of tetrafluoroethylene, add required reaction solvent; Wherein, carbon nanotube lyophilize body/MnO
2Mixture preparation process solvent for use is KMnO
4Or KMnO
4With MnSO
4Mixed solvent; Carbon nanotube lyophilize body/SnO
2Mixture preparation process solvent for use is SnCl
4Mixed solution with NaOH.Carbon nanotube lyophilize body/TiO
2Mixture preparation process solvent for use is a tetrabutyl titanate; When the hydro-thermal reaction solvent adopts two kinds of mixed solvents, two kinds of solvent mol ratios are 1:10～10:1, wherein the reaction solvent volume requirement can complete submergence be got carbon nanotube lyophilize body, and metal oxide and carbon nanotube lyophilize volume recombination mass ratio can be controlled in 0:1～8:1 by the concentration of conditioned reaction solvent;
B, reactant is sealed in the stainless steel cauldron of tetrafluoroethylene, places and carry out hydro-thermal reaction in the thermostatic drying chamber, hydrothermal temperature is room temperature～180 ℃, and the hydro-thermal time is 1h～24h, the shared volumetric ratio of reactant＜80%;
C, be the metal hydroxides person, adopt further calcination to handle and make it be converted into metal oxide that 200～500 ℃ of calcination temperatures make carbon nanotube lyophilize body/metal oxide compounds for the hydro-thermal reaction product.
(2) alkoxide hydrolysis is applicable to TiO
2Metal oxide and carbon pipe lyophilize body compound has following steps:
A, carbon nanotube lyophilize body is heat-treated, remove carbon nanotube lyophilize system and be equipped with employed additive in the process;
B, carbon nanotube lyophilize body be impregnated in the metal alkoxide; Carbon nanotube lyophilize body/TiO
2The alkoxide that the mixture preparation is adopted is a tetrabutyl titanate.Hydrolysis and polycondensation take place in metal alkoxide on carbon nanotube lyophilize body matrix, between carbon nanotube lyophilize body plate shape structure or the surface produce and the corresponding precipitation of hydroxide of metallic element that constitutes alkoxide; The carbon nanotube lyophilize body that metal alkoxide solution requires the energy submergence to get, metal oxide and carbon nanotube lyophilize volume recombination mass ratio can be controlled in 0:1～8:1 by regulating metal alkoxide concentration;
C, reaction product make carbon nanotube lyophilize body/metal oxide compounds through liquid-solid separation, drying, calcining process.
(3) liquid phase reduction is applicable to MnO
2, TiO
2Perhaps SnO
2Metal oxide and carbon pipe lyophilize body compound has following steps:
A, carbon nanotube lyophilize body is heat-treated, remove carbon nanotube lyophilize system and be equipped with employed additive in the process, and with its HNO at 4mol/L～16mol/L
3Handle in the solution and carry out the activation of carbon nanotube lyophilize body;
B, preparation generates the Oxidizing and Reducing Agents solution of required metal oxide correspondence respectively, the concentration ratio of oxygenant and reductive agent is 1:10～10:1, the carbon nanotube lyophilize body that overall solution volume requires submergence fully to get, metal oxide and carbon nanotube lyophilize volume recombination mass ratio can be controlled in 0:1～8:1 by the concentration of conditioned reaction solvent;
C, carbon nanotube lyophilize body successively be impregnated in the oxygenant and reductant solution of step b, utilize to be adsorbed in the synthetic carbon pipe lyophilize body/metal oxide compounds of interionic redox reaction on the carbon nanotube dry body lamella.
Hydrothermal product is an oxyhydroxide when needing further calcination among described method (1) the step c, is to be not prerequisite by obviously destroying with the carbon pipe in the lyophilize body under the condition(s) of calcination of this oxyhydroxide.
In the described method (3),,, generate carbon nanotube lyophilize body/metal oxide compounds so also can adopt the method that only adds oxygenant because carbon pipe itself can serve as reductive agent.The charge capacity of metal oxide can be controlled by the concentration of regulating oxygenant and reductive agent.
Beneficial effect of the present invention can and simple be regulated uniform distribution, the pattern that synthetic parameters be controlled mixture by simple and easy liquid phase method, has technical process weak point, process stabilizing, reaction conditions gentleness, characteristics that cost is low.Carbon nanotube lyophilize body/metal oxide compounds has the major application prospect in fields such as ultracapacitor, lithium ion battery, solar cell, photochemical catalysis.
Description of drawings
Fig. 1 is hydrothermal method synthetic carbon nanotube lyophilize body/MnO in the embodiment of the invention 1
2SEM image and partial enlarged drawing;
Fig. 2 is alkoxide hydrolysis synthetic carbon nanotube lyophilize body/TiO in the embodiment of the invention 2
2The SEM image;
Fig. 3 is liquid phase reduction synthetic carbon nanotube lyophilize body/MnO in the embodiment of the invention 3
2The SEM image;
Fig. 4 is liquid phase reduction synthetic carbon nanotube lyophilize body/SnO in the embodiment of the invention 4
2The SEM image.
Embodiment
Below by embodiment the present invention is described further.
Embodiment 1(hydrothermal synthesis method)
(a) get 1mmol KMnO
4Be dissolved in magnetic agitation 5min in the 15ml deionized water, add 1.5mmol MnSO again
4H
2O continues to stir 10min;
(b) mixed solution is changed in the autoclave of 0.0142g carbon nanotube lyophilize body of weighing in advance, carbon nanotube lyophilize body thorough impregnation carries out hydro-thermal reaction 2h under 140 ℃ in mixed solution; Reactant is taken out, and surplus solution goes, and deionized water wash 2～3 times in 60 ℃ of following dried overnight, can obtain carbon nanotube lyophilize body/MnO
2Mixture.
The carbon nanotube lyophilize body/MnO that obtains in the present embodiment
2The SEM figure of mixture and partial enlarged drawing picture thereof are respectively as shown in Figure 1.Can obviously find out MnO from Fig. 1
2Flower-shaped particle adhesion is on the lamella of carbon nanotube lyophilize body, and the network structure that carbon nanotube lyophilize body sheet interlayer is interconnected still well keeps.MnO as can be seen in Fig. 1 partial enlarged drawing
2The concrete combination of particle and carbon nanotube lyophilize body lamella is formed MnO as seen from the figure
2Flower-shaped particulate MnO
2Nanoneedle is partially embedded into carbon nanotube lyophilize body lamella inside, and inferring thus between this mixture interface has certain bonding strength.
Embodiment 2(alkoxide hydrolysis)
(a) organism polyvinylpyrrolidone (PVP) and Xylo-Mucine (CMC) are removed in the thermal treatment under 200 ℃ of-650 ℃ of argon gas atmosphere of carbon pipe lyophilize body;
(b) get the 3.82g tetrabutyl titanate, with its mixed solution that joins water (10ml) and ethanol (3ml) in, hydrolysis 3h gets 0.554g heat treated carbon pipe lyophilize body and is immersed in the white emulsion of upper strata;
(c) lyophilize precursor reactant thing is taken out, under argon gas atmosphere, 500 ℃ handle 1.5h, obtain carbon nanotube lyophilize body/TiO at last
2Composite structure.
The carbon nanotube lyophilize body/TiO that obtains in the present embodiment
2Mixture SEM figure, as shown in Figure 2, paired observation is compared not compound obviously the change before to the carbon nanotube caliber and is inferred TiO greatly thus
2Be coated on the carbon nanotube outer wall more uniformly, can observe simultaneously the also partially filled TiO that gone up in the hole of lyophilize body
2
Embodiment 3(liquid phase reduction)
(a) carbon nanotube lyophilize body is removed organism polyvinylpyrrolidone (PVP) and Xylo-Mucine (CMC) prior to thermal treatment under 200 ℃ of-650 ℃ of argon gas atmosphere, again in the HNO of 4mol/L
3Dipping pre-treatment 8h in the solution;
(b) KMnO of preparation 0.1mol/L
4Solution is as the reaction oxygenant, and carbon pipe lyophilize body itself is as reduzate;
(c) get the KMnO of 10ml0.1mol/L
4Solution takes by weighing 0.04g pre-treatment carbon pipe lyophilize body and impregnated in wherein, is incubated 1h down in 80 ℃ of bath temperatures again; Take out resultant of reaction, deionized water wash, 60 ℃ of dryings can obtain carbon nanotube lyophilize body/MnO
2Mixture.
The carbon nanotube lyophilize body/MnO that obtains in the present embodiment
2Mixture SEM figure, as shown in Figure 3, MnO as seen from the figure
2Uniform particles must be deposited on the laminated structure of carbon pipe lyophilize body.
Embodiment 4(liquid phase reduction)
(a) carbon nanotube lyophilize body is removed organism polyvinylpyrrolidone (PVP) and Xylo-Mucine (CMC) prior to thermal treatment under 200 ℃ of-650 ℃ of argon gas atmosphere, again in the HNO of 4mol/L
3Pre-treatment 8h in the solution;
(b) prepare the NaBH of 0.16mol/L respectively
4The SnCl of the aqueous solution and 0.3mol/L
4Solution;
(c) adopt pretreated carbon nanotube lyophilize body 0.04g in 20ml0.16mol/L NaBH
4Vacuum impregnation 10min in the aqueous solution impregnated in 20ml0.3mol/L SnCl again with its taking-up
410min in the solution;
(d) repeat (c) process three times, last deionized water wash, 80 ℃ are dry down, can obtain carbon nanotube lyophilize body/SnO
2Mixture.
The carbon nanotube lyophilize body/SnO that obtains in the present embodiment
2Mixture SEM figure, as shown in Figure 4, paired observation carbon nanotube caliber changes SnO as can be known
2Even must being coated on the carbon tube wall.
Above-mentioned description to embodiment is to be convenient to those skilled in the art can understand and apply the invention.The person skilled in the art easily makes various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention
Claims (3)
1. carbon nanotube lyophilize body/metal oxide compounds, it is characterized in that, carbon nanotube lyophilize body participates in reaction as a kind of successive substrates, be on its lamella or the sheet interlayer compound on metal oxide, and still keep contiguous network structure on the both macro and micro after the reaction; Described metal oxide is MnO
2, SnO
2Perhaps TiO
2In any one;
This carbon nanotube lyophilize body/metal oxide compounds can be prepared from by following simple and easy liquid phase method;
(1) hydrothermal synthesis method is applicable to MnO
2, SnO
2Perhaps TiO
2Metal oxide and carbon pipe lyophilize body compound has following steps:
A, carbon nanotube lyophilize body is placed the stainless steel cauldron of tetrafluoroethylene, add required reaction solvent; Wherein, carbon nanotube lyophilize body/MnO
2Mixture preparation process solvent for use is KMnO
4Or KMnO
4With MnSO
4Mixed solvent; Carbon nanotube lyophilize body/SnO
2Mixture preparation process solvent for use is SnCl
4Mixed solution with NaOH.Carbon nanotube lyophilize body/TiO
2Mixture preparation process solvent for use is a tetrabutyl titanate; When the hydro-thermal reaction solvent adopts two kinds of mixed solvents, two kinds of solvent mol ratios are 1:10～10:1, wherein the reaction solvent volume requirement can complete submergence be got carbon nanotube lyophilize body, and metal oxide and carbon nanotube lyophilize volume recombination mass ratio can be controlled in 0:1～8:1 by the concentration of conditioned reaction solvent;
B, reactant is sealed in the stainless steel cauldron of tetrafluoroethylene, places and carry out hydro-thermal reaction in the thermostatic drying chamber, hydrothermal temperature is room temperature～180 ℃, and the hydro-thermal time is 1h～24h, the shared volumetric ratio of reactant＜80%;
C, be the metal hydroxides person, adopt further calcination to handle and make it be converted into metal oxide that 200～500 ℃ of calcination temperatures make carbon nanotube lyophilize body/metal oxide compounds for the hydro-thermal reaction product.
(2) alkoxide hydrolysis is applicable to TiO
2Metal oxide and carbon pipe lyophilize body compound has following steps:
A, carbon nanotube lyophilize body is heat-treated, remove carbon nanotube lyophilize system and be equipped with employed additive in the process;
B, carbon nanotube lyophilize body be impregnated in the metal alkoxide; Carbon nanotube lyophilize body/TiO
2The alkoxide that the mixture preparation is adopted is a tetrabutyl titanate.Hydrolysis and polycondensation take place in metal alkoxide on carbon nanotube lyophilize body matrix, between carbon nanotube lyophilize body plate shape structure or the surface produce and the corresponding precipitation of hydroxide of metallic element that constitutes alkoxide; The carbon nanotube lyophilize body that metal alkoxide solution requires the energy submergence to get, metal oxide and carbon nanotube lyophilize volume recombination mass ratio can be controlled in 0:1～8:1 by regulating metal alkoxide concentration;
C, reaction product make carbon nanotube lyophilize body/metal oxide compounds through liquid-solid separation, drying, calcining process.
(3) liquid phase reduction is applicable to MnO
2, SnO
2Perhaps TiO
2Metal oxide and carbon pipe lyophilize body compound has following steps:
A, carbon nanotube lyophilize body is heat-treated, remove carbon nanotube lyophilize system and be equipped with employed additive in the process, and with its HNO at 4mol/L～16mol/L
3Handle in the solution and carry out the activation of carbon nanotube lyophilize body;
B, preparation generates the Oxidizing and Reducing Agents solution of required metal oxide correspondence respectively, the concentration ratio of oxygenant and reductive agent is 1:10～10:1, the carbon nanotube lyophilize body that overall solution volume requires submergence fully to get, metal oxide and carbon nanotube lyophilize volume recombination mass ratio can be controlled in 0:1～8:1 by the concentration of conditioned reaction solvent;
C, carbon nanotube lyophilize body successively be impregnated in the oxygenant and reductant solution of step b, utilize to be adsorbed in the synthetic carbon pipe lyophilize body/metal oxide compounds of interionic redox reaction on the carbon nanotube dry body lamella.
2. according to the carbon nanotube lyophilize body/metal oxide compounds of claim 1, it is characterized in that, hydrothermal product is an oxyhydroxide when needing further calcination among described method (1) the step c, is to be not prerequisite by obviously destroying with the carbon pipe in the lyophilize body under the condition(s) of calcination of this oxyhydroxide.
3. according to the preparation carbon nanotube lyophilize body/metal oxide method of claim 1, it is characterized in that, in the described method (3), because carbon pipe itself can serve as reductive agent, so also can adopt the method that only adds oxygenant, generate carbon nanotube lyophilize body/metal oxide compounds.The charge capacity of metal oxide can be controlled by the concentration of regulating oxygenant and reductive agent.
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Cited By (9)
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|---|---|---|---|---|
| CN104466156A (en) * | 2014-12-05 | 2015-03-25 | 武汉理工大学 | Manganese alkoxide, as well as compound of manganese alkoxide and graphene, preparation method and application thereof |
| CN105118692A (en) * | 2015-09-14 | 2015-12-02 | 南京大学 | Method for preparing SnO2-MnO2-Fe3O4 ternary composite capacitive material |
| CN107661755A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | Catalyst with the effect of hydrocarbon catalysis dehydrogenation and its preparation method and application and hydrocarbon dehydrogenation reaction method |
| CN107661777A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | Catalyst with the effect of hydrocarbon catalysis dehydrogenation and its preparation method and application and hydrocarbon dehydrogenation reaction method |
| CN109346734A (en) * | 2018-05-04 | 2019-02-15 | 盐城师范学院 | A kind of preparation method of manganese bioxide/carbon nano tube complex fuel battery negative pole oxygen reduction catalyst |
| CN110038546A (en) * | 2019-04-03 | 2019-07-23 | 中国环境科学研究院 | One kind is for light-catalysed nanocomposite and the preparation method and application thereof |
| CN113248868A (en) * | 2021-04-30 | 2021-08-13 | 中国科学院苏州纳米技术与纳米仿生研究所 | Nano modified composite material, preparation method and application thereof |
| CN113769711A (en) * | 2021-10-13 | 2021-12-10 | 长治医学院 | Inorganic non-metallic material with high specific surface area and preparation method thereof |
| CN118598109A (en) * | 2024-08-08 | 2024-09-06 | 四川轻化工大学 | Modified lithium iron phosphate positive electrode material, preparation method thereof and battery |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104466156B (en) * | 2014-12-05 | 2017-01-11 | 武汉理工大学 | Manganese alkoxide, as well as compound of manganese alkoxide and graphene, preparation method and application thereof |
| CN104466156A (en) * | 2014-12-05 | 2015-03-25 | 武汉理工大学 | Manganese alkoxide, as well as compound of manganese alkoxide and graphene, preparation method and application thereof |
| CN105118692A (en) * | 2015-09-14 | 2015-12-02 | 南京大学 | Method for preparing SnO2-MnO2-Fe3O4 ternary composite capacitive material |
| CN107661777B (en) * | 2016-07-27 | 2020-09-22 | 中国石油化工股份有限公司 | Catalyst with hydrocarbon dehydrogenation catalysis, preparation method and application thereof, and hydrocarbon dehydrogenation reaction method |
| CN107661755A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | Catalyst with the effect of hydrocarbon catalysis dehydrogenation and its preparation method and application and hydrocarbon dehydrogenation reaction method |
| CN107661777A (en) * | 2016-07-27 | 2018-02-06 | 中国石油化工股份有限公司 | Catalyst with the effect of hydrocarbon catalysis dehydrogenation and its preparation method and application and hydrocarbon dehydrogenation reaction method |
| CN107661755B (en) * | 2016-07-27 | 2020-09-22 | 中国石油化工股份有限公司 | Catalyst with hydrocarbon dehydrogenation catalysis, preparation method and application thereof, and hydrocarbon dehydrogenation reaction method |
| CN109346734A (en) * | 2018-05-04 | 2019-02-15 | 盐城师范学院 | A kind of preparation method of manganese bioxide/carbon nano tube complex fuel battery negative pole oxygen reduction catalyst |
| CN110038546A (en) * | 2019-04-03 | 2019-07-23 | 中国环境科学研究院 | One kind is for light-catalysed nanocomposite and the preparation method and application thereof |
| CN113248868A (en) * | 2021-04-30 | 2021-08-13 | 中国科学院苏州纳米技术与纳米仿生研究所 | Nano modified composite material, preparation method and application thereof |
| CN113248868B (en) * | 2021-04-30 | 2023-10-17 | 中国科学院苏州纳米技术与纳米仿生研究所 | Nano modified composite material, preparation method and application thereof |
| CN113769711A (en) * | 2021-10-13 | 2021-12-10 | 长治医学院 | Inorganic non-metallic material with high specific surface area and preparation method thereof |
| CN113769711B (en) * | 2021-10-13 | 2023-10-13 | 长治医学院 | Inorganic nonmetallic material with high specific surface area and preparation method thereof |
| CN118598109A (en) * | 2024-08-08 | 2024-09-06 | 四川轻化工大学 | Modified lithium iron phosphate positive electrode material, preparation method thereof and battery |
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Application publication date: 20130724 |