CN101173117A - Method for producing manganese dioxide coating carbon nano-tube core-shell type composite material - Google Patents
Method for producing manganese dioxide coating carbon nano-tube core-shell type composite material Download PDFInfo
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- CN101173117A CN101173117A CNA2007101561554A CN200710156155A CN101173117A CN 101173117 A CN101173117 A CN 101173117A CN A2007101561554 A CNA2007101561554 A CN A2007101561554A CN 200710156155 A CN200710156155 A CN 200710156155A CN 101173117 A CN101173117 A CN 101173117A
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Abstract
The invention discloses a preparation method of core-shell type composite materials of a manganese dioxide coated carbon nm tube. The method comprises the steps as follows: the carbon nanometer tube is put in mixed acid containing thick sulphuric acid and thick nitric acid for supersonic treatment, thereby enabling the surface of the carbon tube to contact with hydrophilic group; the carbon nanometer tube with surfactant is mixed to form suspending liquid; permanganate salts is added to react with the surfactant so as to produce the manganese dioxide which nucleates on the surface of the carbon tube; the manganese dioxide grows and forms even coating. The invention with simple technique and low production cost realizes the coating on the surface of the carbon nm tube and reduces the damages to the structure of the carbon tube. The nanometer crystals of the manganese dioxide array along the tube diameter of the carbon tube to enlarge the surface area of the coating. The composite powder has good dispersivity and high porosity. And the composite powder exhibits wide applicable prospect in the industrial fields of the chemical catalyst, the high performance battery and the super capacitor.
Description
Technical field
The present invention relates to a kind of Manganse Dioxide enveloped carbon nanometer tube core---the preparation method of shell type composite material.
Background technology
Carbon nanotube is a kind of one-dimensional material with unique texture, is curled into seamless tubular structure by the graphite carbon atomic plane, and the pipe diameter is generally several nanometers to tens nanometers, and length can reach several microns.Count difference according to the graphite surface layer, carbon nanotube can be divided into single-walled pipe, twin wall emitter lateral and multi-walled pipes.Because the performance of carbon nanotube is very peculiar, thereby it has boundless application prospect.In recent years, countries such as the U.S., Japan, Germany and China have set up nano materials research mechanism in succession, the progress of carbon nanotube is accelerated, and obtained some breakthroughs in preparation and application facet.
The macromole that carbon nanotube is made up of the carbon atom that is in the fragrant indefinite domain system has the laminate structure of similar graphite, is dissolved in any solvent hardly, and assembles bunchy easily in solution, has limited carbon nanotube application in all fields greatly.Although the theoretical specific surface area of carbon nanotube can reach 8000m
2/ g, but owing to often there is the end cap sealing at carbon pipe two ends, and carbon nanotube makes actual specific surface area of testing much smaller than theoretical prediction because intermolecular forces inevitably will be assembled bunchy.Therefore, carbon nanotube modified with functionalization even carry out the surface coat, carbon pipe end cap is opened, improve its dispersiveness, make up and have the nanostructure of unique function and application, become a research focus of carbon nanotube Application Areas.But carbon nanotube is carried out finishing and coat often will destroying its structure, make the degradation of its some aspect, therefore, when realizing modifying and coating, reduce extremely important as far as possible the destruction of carbon tubular construction.
Manganse Dioxide is a kind of intermediate oxide, generally is black or brown, and is highly stable at normal temperatures, is used for steel-making in a large number, and be used to make glass, pottery, enamel, drying battery and be used as catalyzer etc.Manganse Dioxide is subjected to increasing the attention owing to have characteristics such as cheap, environmentally friendly, that preparation is easy as energy storage material in recent years, and Manganse Dioxide is regarded as a kind of very potential electrode material for super capacitor and anode material for lithium-ion batteries.But the electroconductibility of Manganse Dioxide is relatively poor, often will add materials such as the better carbon black of conductivity, carbon nanotube in actual applications.In recent years, in the research of ultracapacitor, researcher is for metal oxide and carbon nano-tube combination electrode material, especially the core of oxide-coated carbon nanotube---the shell mould material has been carried out many research work, combines in the hope of fake capacitance that metal oxide is higher and narrower pore distribution, the good electrical conductivity of carbon nanotube.
Summary of the invention
The purpose of this invention is to provide a kind of core---the preparation method of shell type composite material with the Manganse Dioxide enveloped carbon nanometer tube.
Preparation method's step is as follows:
1) with caliber is the carbon nanotube of 10～40nm, join in the mixing acid of the vitriol oil and concentrated nitric acid preparation in 3: 1 by volume, the consumption of mixing acid is 10～15 times of carbon nanotube quality, supersound process 0.5～1 hour, filter, using the distilled water repetitive scrubbing, is 6～7 until the pH value that leaches washing lotion;
2) carbon nanotube and the tensio-active agent with the step 1) gained is added to the water, supersound process, even carbon nanotube is dispersed in the water, form suspension, the sulfuric acid that adds permanganate and mass concentration 98% then, ultrasonic 0.5～1 hour, carbon nanotube, tensio-active agent, water, permanganate and vitriolic mass ratio were 1: 1.5～2.5: 500: 10～25: 10～30;
3) filter dehydration, the distilled water repetitive scrubbing is 6～7 until the pH value that leaches washing lotion, dryness in the sun or dry being lower than under 90 ℃ of temperature obtains Manganse Dioxide enveloped carbon nanometer tube composite powder.
Above-mentioned permanganate can be potassium permanganate or sodium permanganate.Toxic because of sodium permanganate, recommend to use potassium permanganate.
Above-mentioned tensio-active agent can be Sodium dodecylbenzene sulfonate (DDBS), Sodium desoxycholate (DOC) or hexadecyl trimethyl ammonium bromide (CTABr).
The present invention adopts the purpose of mixing acid (vitriol oil and concentrated nitric acid volume ratio 3: 1) supersound process carbon nanotube, is that carbon nano tube surface is carried out oxidation, make its surface grafting-COOH ,-hydrophilic functional groups such as OH, part carbon pipe end cap is opened.The mass concentration of the vitriol oil and concentrated nitric acid is respectively 98%.
The present invention uses tensio-active agent and ultransonic purpose, is to make the hydrophilic group of tensio-active agent and the hydrophilic group coupling of carbon nano tube surface, at peripheral " capsule " that forms layer of surface active agent molecule composition of carbon pipe.This has the effect of two aspects; make on the one hand carbon nanotube dispersion suspension equably in water; avoid in subsequent reactions, forming the hard aggregation of Manganse Dioxide parcel carbon tube bank; surfactant molecule is as the buffering between strong oxidizer and the carbon nanotube on the other hand; oxidized by self; carbon nanotube is effectively protected, has avoided of the havoc of the permanganate of strong oxidizing property carbon tube-surface structure.High manganese ion is reduced generation Manganse Dioxide, the surfactant molecule of carbon pipe periphery is oxidized simultaneously, long catenate organic polymer is consumed gradually, the manganese dioxide precipitate thing is at the carbon tube-surface forming core coated carbon tube-surface gradually of growing up, even permanganate is excessive, this layer oxide compound of carbon tube-surface also can stop its oxidation to carbon pipe itself.
The invention has the beneficial effects as follows:
Preparation technology is simple, and low production cost when realizing that carbon nano tube surface coats, has alleviated the destruction to the carbon tubular construction; Manganese dioxide nanocrystal to arrangement, has increased the specific surface area of coating layer along the carbon caliber; The composite powder good dispersion has higher middle porosity; This composite powder has broad application prospects at industrial circles such as chemical industry catalysis, heavy-duty battery and ultracapacitors.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the matrix material for preparing of the present invention;
Fig. 2 is the stereoscan photograph of the matrix material for preparing of the present invention.
Embodiment
Embodiment 1:
With caliber is the carbon nanotube of 40nm, joins in the mixing acid of the vitriol oil and concentrated nitric acid preparation in 3: 1 by volume, and the consumption of mixing acid is 10 times of carbon nanotube quality, supersound process 0.5 hour, filtering, use the distilled water repetitive scrubbing, is 6～7 until the pH value that leaches washing lotion;
100mg carbon nanotube and the 150mg Sodium dodecylbenzene sulfonate of getting above gained join in the 50ml water, stir the back supersound process a little 0.5 hour, and even carbon nanotube is dispersed in the water, form steady suspension;
In above suspension, add the vitriol oil of 1.5g potassium permanganate and 3ml 98%, stirred the back ultrasonic 0.5 hour a little;
Behind the filter dehydration, use the distilled water repetitive scrubbing, be about 6～7 until the pH value that leaches washing lotion;
Gains promptly obtain Manganse Dioxide enveloped carbon nanometer tube composite powder 80 ℃ of oven dry.
The BET specific surface area of gained powder is 160.99m
2/ g, transmission electron microscope photo is seen Fig. 1, stereoscan photograph is seen Fig. 2.
Embodiment 2:
With caliber is the carbon nanotube of 20nm, joins in the mixing acid of the vitriol oil and concentrated nitric acid preparation in 3: 1 by volume, and the consumption of mixing acid is 15 times of carbon nanotube quality, supersound process 1 hour, filtering, use the distilled water repetitive scrubbing, is 6～7 until the pH value that leaches washing lotion;
100mg carbon nanotube and the 200mg Sodium desoxycholate of getting above gained join in the 50ml water, stir the back supersound process a little 1 hour, and even carbon nanotube is dispersed in the water, form steady suspension;
In above suspension, add the vitriol oil of 2.0g potassium permanganate and 2ml 98%, stirred the back ultrasonic 1 hour a little;
Behind the filter dehydration, use the distilled water repetitive scrubbing, be about 6～7 until the pH value that leaches washing lotion;
Gains dry naturally, promptly obtain Manganse Dioxide enveloped carbon nanometer tube composite powder.
Claims (3)
1. the core of Manganse Dioxide enveloped carbon nanometer tube---the preparation method of shell type composite material is characterized in that its step is as follows:
1) with caliber is the carbon nanotube of 10～40nm, join in the mixing acid of the vitriol oil and concentrated nitric acid preparation in 3: 1 by volume, the consumption of mixing acid is 10～15 times of carbon nanotube quality, supersound process 0.5～1 hour, filter, using the distilled water repetitive scrubbing, is 6～7 until the pH value that leaches washing lotion;
2) carbon nanotube and the tensio-active agent with the step 1) gained is added to the water, supersound process, even carbon nanotube is dispersed in the water, form suspension, the sulfuric acid that adds permanganate and mass concentration 98% then, ultrasonic 0.5～1 hour, carbon nanotube, tensio-active agent, water, permanganate and vitriolic mass ratio were 1: 1.5～2.5: 500: 10～25: 10～30;
3) filter dehydration, the distilled water repetitive scrubbing is 6～7 until the pH value that leaches washing lotion, dryness in the sun or dry being lower than under 90 ℃ of temperature obtains Manganse Dioxide enveloped carbon nanometer tube composite powder.
2. the preparation method of the core of Manganse Dioxide enveloped carbon nanometer tube according to claim 1---shell type composite material is characterized in that permanganate is potassium permanganate or sodium permanganate.
3. the preparation method of the core of Manganse Dioxide enveloped carbon nanometer tube according to claim 1---shell type composite material is characterized in that tensio-active agent is Sodium dodecylbenzene sulfonate, Sodium desoxycholate or hexadecyl trimethyl ammonium bromide.
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Cited By (14)
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| CN101923960A (en) * | 2010-08-18 | 2010-12-22 | 东华大学 | Preparation method of composite electrode material using flap-like manganese dioxide nanocrystal to coat carbon nanotubes |
| CN102208610A (en) * | 2011-04-18 | 2011-10-05 | 北京工业大学 | Preparation method of carbon coated MnO cathode material |
| CN102321398A (en) * | 2011-09-02 | 2012-01-18 | 广东工业大学 | A kind of preparation method of carbon black enveloped carbon nanometer tube heat conductive filler |
| CN103077834A (en) * | 2013-01-18 | 2013-05-01 | 南京理工大学 | Water system neutral electrolyte-based asymmetric supercapacitor and preparation method thereof |
| CN103071484A (en) * | 2013-01-10 | 2013-05-01 | 上海大学 | Preparation method of manganese dioxide nanosheet/CNT (carbon nano tube) denitration catalyst with core-shell structure |
| CN103633304A (en) * | 2013-12-06 | 2014-03-12 | 福州大学 | Method for preparing coaxially-composite nano material by using carbon nano tube as core |
| CN105384159A (en) * | 2015-11-05 | 2016-03-09 | 云南大学 | Usage of manganese dioxide coated carbon particle dielectric materials as electromagnetic wave absorption materials |
| CN105406053A (en) * | 2014-09-10 | 2016-03-16 | 苏州艾美得新能源材料有限公司 | Preparation method for cathode material and cell |
| CN110342493A (en) * | 2018-04-03 | 2019-10-18 | 清华大学 | Transition metal oxide/carbon nano tube compound material and preparation method thereof |
| CN111599604A (en) * | 2020-06-03 | 2020-08-28 | 邓新峰 | C-MnFe with shell-core structure2O4-CNT (carbon nanotube) supercapacitor electrode material and preparation method thereof |
| CN111825076A (en) * | 2020-06-19 | 2020-10-27 | 郑州轻工业大学 | Carbon nanotube/MnO 2 composite material of core-sheath nano cable structure and preparation method thereof |
| US11056692B2 (en) | 2018-04-03 | 2021-07-06 | Tsinghua University | Battery electrode, method for making the same and hybrid energy storage device using the same |
| CN113634248A (en) * | 2020-05-11 | 2021-11-12 | 山东大学 | Carbon-doped manganese dioxide catalyst for activating peroxymonosulfate and preparation method and application thereof |
| CN114420459A (en) * | 2022-01-06 | 2022-04-29 | 重庆文理学院 | Carbon/manganese dioxide composite material for super capacitor and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101923960A (en) * | 2010-08-18 | 2010-12-22 | 东华大学 | Preparation method of composite electrode material using flap-like manganese dioxide nanocrystal to coat carbon nanotubes |
| CN101923960B (en) * | 2010-08-18 | 2012-05-23 | 东华大学 | Preparation method of composite electrode material using flap-like manganese dioxide nanocrystal to coat carbon nanotubes |
| CN102208610A (en) * | 2011-04-18 | 2011-10-05 | 北京工业大学 | Preparation method of carbon coated MnO cathode material |
| CN102321398A (en) * | 2011-09-02 | 2012-01-18 | 广东工业大学 | A kind of preparation method of carbon black enveloped carbon nanometer tube heat conductive filler |
| CN103071484A (en) * | 2013-01-10 | 2013-05-01 | 上海大学 | Preparation method of manganese dioxide nanosheet/CNT (carbon nano tube) denitration catalyst with core-shell structure |
| CN103071484B (en) * | 2013-01-10 | 2014-10-01 | 上海大学 | Preparation method of manganese dioxide nanosheet/CNT (carbon nano tube) denitration catalyst with core-shell structure |
| CN103077834A (en) * | 2013-01-18 | 2013-05-01 | 南京理工大学 | Water system neutral electrolyte-based asymmetric supercapacitor and preparation method thereof |
| CN103633304A (en) * | 2013-12-06 | 2014-03-12 | 福州大学 | Method for preparing coaxially-composite nano material by using carbon nano tube as core |
| CN103633304B (en) * | 2013-12-06 | 2016-01-27 | 福州大学 | A kind of take carbon nano-tube as the method that core prepares coaxial composite nano materials |
| CN105406053A (en) * | 2014-09-10 | 2016-03-16 | 苏州艾美得新能源材料有限公司 | Preparation method for cathode material and cell |
| CN105384159A (en) * | 2015-11-05 | 2016-03-09 | 云南大学 | Usage of manganese dioxide coated carbon particle dielectric materials as electromagnetic wave absorption materials |
| CN110342493A (en) * | 2018-04-03 | 2019-10-18 | 清华大学 | Transition metal oxide/carbon nano tube compound material and preparation method thereof |
| TWI700248B (en) * | 2018-04-03 | 2020-08-01 | 鴻海精密工業股份有限公司 | Transition metal oxide/ carbon nanotube composite and method for making the same |
| US11056692B2 (en) | 2018-04-03 | 2021-07-06 | Tsinghua University | Battery electrode, method for making the same and hybrid energy storage device using the same |
| US11127953B2 (en) | 2018-04-03 | 2021-09-21 | Tsinghua University | Carbon nanotube-transition metal oxide composite and method for making the same |
| CN113634248A (en) * | 2020-05-11 | 2021-11-12 | 山东大学 | Carbon-doped manganese dioxide catalyst for activating peroxymonosulfate and preparation method and application thereof |
| CN113634248B (en) * | 2020-05-11 | 2022-12-30 | 山东大学 | Carbon-doped manganese dioxide catalyst for activating peroxymonosulfate and preparation method and application thereof |
| CN111599604A (en) * | 2020-06-03 | 2020-08-28 | 邓新峰 | C-MnFe with shell-core structure2O4-CNT (carbon nanotube) supercapacitor electrode material and preparation method thereof |
| CN111599604B (en) * | 2020-06-03 | 2021-12-24 | 国网黑龙江省电力有限公司电力科学研究院 | C-MnFe with shell-core structure2O4-CNT (carbon nanotube) supercapacitor electrode material and preparation method thereof |
| CN111825076A (en) * | 2020-06-19 | 2020-10-27 | 郑州轻工业大学 | Carbon nanotube/MnO 2 composite material of core-sheath nano cable structure and preparation method thereof |
| CN114420459A (en) * | 2022-01-06 | 2022-04-29 | 重庆文理学院 | Carbon/manganese dioxide composite material for super capacitor and preparation method thereof |
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