A kind of threadiness combination electrode material and preparation method thereofTechnical field
The present invention relates to nano material manufacture field, more particularly, to a kind of threadiness combination electrode material and its preparation sideMethod.
Background technology
Fibrous energy storage device plays a significant role in flexible electronic device, intelligence wearing, field of portable electronic apparatus.Wherein, fibrous electrodes material is the critical material of fibrous energy storage device, receives the wide of academia and industrial quarters in recent yearsGeneral concern.
CNT has excellent mechanics and electric property, and carbon nano-tube fibre is by a large amount of nanoscale CNTsThe fibrous material assembling, has intensity height, good conductivity, flexibility, can weave and the advantage such as specific surface area is big, be to prepareThe ideal basic material of flexible fiber shape energy storage device electrode material.Carbon fiber material and metal-oxide, hydroxideThing, conducting polymer, rich lithium material isoreactivity material are compounded to form carbon nano tube composite fibre, in fibrous energy device fieldIt is with a wide range of applications.In terms of carbon nano-tube fibre combination electrode material preparation, Fudan University ren j et al. is with canSpinning carbon nano-pipe array is classified as raw material, obtains carbon nano-tube fibre by dry spinning technology, and is received in carbon by hydro-thermal methodMitron fiber surface loads one layer of manganese dioxide, obtains CNT/manganese dioxide carbon nano tube composite fibre, with assemblingThe energy of miniature electric chemical super capacitor and miniature lithium ion battery and power density are all greatly improved.Additionally, it is multipleDenier university Peng Huisheng professor et al., can prepare carbon nano-tube fibre mistake in dry spinning based on spinning carbon nano pipe arrayCheng Zhong, by the electrolysis bath equipped with active substance solution, the method being deposited by continuous electrochemical or being polymerized, is prepared carbon and receivesMitron fiber composite electrode material.In such scheme, there is complex technical process, system in the preparation of carbon nano-tube combination electrode materialStandby high cost, electrical conductivity is low, be difficult mass the shortcomings of prepare.
Content of the invention
It is an object of the invention to provide a kind of threadiness combination electrode material and preparation method thereof, the method has techniqueSimply, low cost, electrical conductivity of fibres high it is easy to the advantage of mass preparation.
One of for achieving the above object, the present invention provides a kind of preparation method of threadiness combination electrode material, shouldMethod comprises the following steps:
S1, prepare carbon nanotube agglomerate；
S2, carbon nanotube agglomerate processed by liquid phase medium make it shrink densification to form fibrous combination electrode material,Wherein, it is dispersed with active substance in liquid phase medium；
S3, the fibrous combination electrode material of collection.
As a further improvement on the present invention, described " preparing carbon nanotube agglomerate " step particularly as follows:
Reacting furnace temperature is risen to 1100 DEG C ~ 1600 DEG C, keeping temperature is stable, inject carrier gas in described reacting furnace；
Phase carbon source is injected reacting furnace, growth obtains carbon nanotube agglomerate.
As a further improvement on the present invention, described phase carbon source is ethanol, ferrocene, the mixed liquor of thiophene, wherein, secondAlcohol, ferrocene, the mass percent of thiophene are respectively 96-99%, 0.5-2%, 0.5-2%, and the injection rate of phase carbon source is 5-100ml/h.
As a further improvement on the present invention, described carrier gas is the gaseous mixture of hydrogen and noble gases or hydrogen and nitrogenBody, noble gases are argon or helium.
As a further improvement on the present invention, described active substance is metal-oxide or hydroxide or sulfide or leadsElectric polymer or rich lithium material.
As a further improvement on the present invention, described active substance is ruo2Or mn02Or nio or co3o4Or co (oh)2Orni(oh)2Or cos or nis or pan or ppy or or licoo or linio or li2tio3Or li4ti5o12Or lifepo4 orlimnpo4Or ternary richness lithium material.
As a further improvement on the present invention, described liquid phase medium is water or alcohol-based liquid.
As a further improvement on the present invention, it is provided with agitating device or the side using ultrasonic disperse in described liquid phase mediumMethod makes active substance can be uniformly dispersed in liquid phase medium.
As a further improvement on the present invention, described " collect fibrous combination electrode material " step particularly as follows:
Fibrous combination electrode material is collected on roller bearing with 1-10 m/min of speed, during collecting, permissibleFibrous combination electrode material is dried or twisting is processed.
Correspondingly, a kind of fibrous combination electrode material using preparation method described above preparation is it is characterised in that instituteState fibrous combination electrode material and include carbon nano-tube fibre and the work being attached on described carbon nano-tube fibre inside and surfaceProperty material, wherein, described active substance is metal-oxide or hydroxide or sulfide or conducting polymer or rich lithium material.
The invention has the beneficial effects as follows: the present invention passes through floating catalytic chemical vapour deposition technique synthesizing carbon nanotubes and assemblesBody, liquid phase medium adopts active substance solution or suspension, and carbon nanotube agglomerate passes through liquid phase medium and obtains so that after-contraction is fine and closeTo carbon nano-tube fibre, during shrinking densification, active substance is effectively compound in carbon nano-tube fibre surface and inside, obtainsTo fibrous combination electrode material.The method process is simple, low cost, electrical conductivity of fibres is high it is easy to prepared by mass, to fiberThe development of shape energy device is significant.
Brief description
Fig. 1 is the apparatus structure schematic diagram preparing fibrous combination electrode material in the embodiment of the invention；
Fig. 2 is the cross-sectional view of fibrous combination electrode material in the embodiment of the invention;
Fig. 3 is to prepare fibrous combination electrode material method and step figure in the embodiment of the invention.
Specific embodiment
Describe the present invention below with reference to each embodiment shown in the drawings.But these embodiments are notLimit the present invention, structure, method or change functionally that those of ordinary skill in the art is made according to these embodimentsChange and be all contained in protection scope of the present invention.
Shown in ginseng Fig. 1-3, introduce a specific embodiment of the fibrous combination electrode material of present invention preparation.
The method preparing carbon nano tube composite fibre comprises the following steps:
S1, prepare carbon nanotube agglomerate.In the present embodiment, carbon nanometer is synthesized using floating catalytic chemical vapour deposition techniquePipe aggregation 20.Shown in ginseng Fig. 1, the device 10 preparing carbon nanotube agglomerate 20 of present invention offer is that horizontal chamber furnace (oven) precursor reactant fillsPut, main include reacting furnace 101 and be arranged on heater 102 at least part of periphery of reacting furnace 101, wherein, reactionOne end of stove 101 is provided with carbon source infusion appliance (not shown), certainly, in the other embodiment of the present invention, it would however also be possible to employ verticalFormula body of heater reaction unit, what it reached has the technical effect that identical.
Specifically, the temperature of reacting furnace 101 is risen to 1100 DEG C ~ 1600 DEG C, keeping temperature is stable, in reacting furnace 101Injection carrier gas it is preferable that carrier gas is the mixed gas of hydrogen and noble gases or hydrogen and nitrogen, noble gases be argon orHelium.
Phase carbon source is injected reacting furnace, growth obtains carbon nanotube agglomerate 20.Phase carbon source be ethanol, ferrocene,The mixed liquor of thiophene, wherein, ethanol, ferrocene, the mass percent of thiophene are respectively 96-99%, 0.5-2%, 0.5-2%, utilizePhase carbon source is injected in reacting furnace 101 by carbon source infusion appliance, and injection rate is 5-100ml/h, and phase carbon source is in reacting furnace 101High temperature under generate carbon nanotube agglomerate 20.
S2, carbon nanotube agglomerate is processed by liquid phase medium make it shrink densification to form fibrous combination electrode materialMaterial, wherein, is dispersed with active substance in liquid phase medium.The carbon nanotube agglomerate 20 generating in reacting furnace 101 enters liquid storageLiquid phase medium 1031 in groove 103.
Liquid phase medium 1031 is water or alcohol-based liquid, is provided with agitating device (not shown) or adopts in liquid phase medium 1031With the method for ultrasonic disperse, active substance 1032 be can be uniformly dispersed in liquid phase medium 1031.Carbon nanotube agglomerate 20 existsIt is retracted densification in liquid phase medium 1031 and forms carbon nano-tube fibre, be retracted densification in carbon nanotube agglomerate 20During process, active substance 1032 is not only effectively attached to the surface of carbon nano-tube fibre, receives also into carbon simultaneouslyThe inside of mitron fiber, obtains fibrous combination electrode material 30(and joins Fig. 2).
Preferably, active substance is metal-oxide (ruo2、mn02、nio、co3o4Deng), hydroxide (co (oh)2、ni(oh)2Deng), sulfide (cos, nis etc.), conducting polymer (pan, ppy etc.), rich lithium material (licoo, linio,li2tio3、li4ti5o12、lifepo4、limnpo4, ternary richness lithium material etc.).
S3, the fibrous combination electrode material of collection.The fibrous combination electrode material 30 being formed in liquid phase medium 1031It is drawn out liquid level to be collected.Preferably, fibrous combination electrode material 30 with 1-10 m/min of speed on roller bearing 104It is collected, during collecting, fibrous combination electrode material 30 can be dried or twisting is processed.
Include carbon nano-tube fibre and be attached to CNT using the fibrous combination electrode material of said method preparationActive substance on fibrous inside and surface, this material have flexibility, can weave, the advantage such as high connductivity, specific surface area are big, thereforeIt is suitable for the preparation of flexible electrode material, the preparation of particularly wearable flexible electrode material.
With can be compared with spinning carbon nano pipe array dry spinning fiber prepares fibrous combination electrode material for raw material, thisInvention has process is simple, low cost, electrical conductivity of fibres is high, be easy to the advantages such as prepare with scale.
It should be understood that although this specification is been described by according to embodiment, but not each embodiment only comprises oneIndividual independent technical scheme, only for clarity, those skilled in the art should will say this narrating mode of descriptionAs an entirety, the technical scheme in each embodiment can also be through appropriately combined, and forming those skilled in the art can for bright bookWith the other embodiment understanding.
The a series of detailed description of those listed above is only for the feasibility embodiment of the present invention specificallyBright, they simultaneously are not used to limit the scope of the invention, all equivalent implementations made without departing from skill spirit of the present inventionOr change should be included within the scope of the present invention.