CN108455570A - Preparation method, functionalization short carbon nanometer tube and its application of functionalization short carbon nanometer tube - Google Patents
Preparation method, functionalization short carbon nanometer tube and its application of functionalization short carbon nanometer tube Download PDFInfo
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- CN108455570A CN108455570A CN201810177610.7A CN201810177610A CN108455570A CN 108455570 A CN108455570 A CN 108455570A CN 201810177610 A CN201810177610 A CN 201810177610A CN 108455570 A CN108455570 A CN 108455570A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/02—Single-walled nanotubes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/30—Purity
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/34—Length
Abstract
The invention belongs to technical field of nano material, are related to preparation method, functionalization short carbon nanometer tube and its application of functionalization short carbon nanometer tube.Carbon nanotube, oxidisability salt and optional auxiliary agent are mixed, obtain carbon mano-tube composite by the preparation method of functionalization short carbon nanometer tube provided by the invention；Carbon mano-tube composite is handled by the way of mechanical force and chemical, obtains the carbon nanotube of functionalization/truncation；The carbon nanotube of functionalization/truncation is washed and dried to get functionalization short carbon nanometer tube.The present invention is on the basis of mechanical force and chemical, avoid the expensive and environment such as traditional strong acid, strong oxidizer harsh conditions and organic solvent it is unfriendly under the conditions of prepare functionalization shortwall carbon nanotube processing route, reduce cost, the time is shortened, the use and discharge of poisonous and harmful substance are controlled.Due to as agent and functional modification agent is truncated, also having the characteristics that yield is high, environmentally protective using oxidisability salt.
Description
Technical field
The invention belongs to technical field of nano material, are related to carbon nanotube, and in particular to the system of functionalization short carbon nanometer tube
Preparation Method, functionalization short carbon nanometer tube and its application.
Background technology
The nanometer new material that carbon nanotube is found as last century, it is great just to cause scientists at the beginning of its discovery
Study enthusiasm.Carbon nanotube is a kind of carbon material with tube-like condition, a diameter of nanoscale, has high intensity, tough
Property and elasticity modulus, draw ratio is big, specific surface area is high, and electrical and thermal conductivity performance is excellent, is receiving for great application potential
Rice material.But carbon nanotube the problem of existing in application process, always affects its practical application：1) how economical and efficient
Prepare carbon nanotube；2) simple and effective carbon nanotube dispersion technology.In addition, carbon nanotube due to caused by its own structure not
Dissolubility and it is easy to the practical problems such as surface functional group of reuniting and lack, also limits its application.
In order to improve the compatibility performance and processability of carbon nanotube and other materials, carbon nanotube is expanded in electronics
Application in the fields such as device, composite material, biological medicine, since 1998, about the correlation for improving carbon nanotube performance
Research is gradually unfolded, and including the dispersion performance for improving carbon nanotube, changes the draw ratio etc. of carbon nanotube.Improve carbon nanometer
There are mainly two types of the methods of pipe dispersion performance：1) water soluble polymer or Small molecular surfactant are added in non-covalent modification
Dispersion stabilization of the carbon nanotube in system can be improved；2) covalent modified, typically pass through strong acid, highly basic, strong oxidizer
Use, to carbon nanotube realize truncate be modified.However, whether covalent or non-covalent modification has some disadvantages：
First, the introducing of impurity has a great impact to carbon nanotube performance；Second, harsh reaction condition can cause carbon nanotube not
Recoverable fault of construction.
The major diameter of short carbon nanometer tube is smaller, and generally below 100, it is easier to it is evenly dispersed in solid phase or liquid phase medium,
Thus it is expected to be applied in more areas.Currently, the method for usually prescinding functionalized carbon nano-tube is using strong acid, by force
Alkali, strong oxidizer or organic solvent etc. (such as document J.AM.CHEM.SOC.2002,124,12418-12419 and
It is had been reported that in CARBON 46 (2008) 833-840 etc.).Some corrosivity are strong, environment is not friendly in addition to being directed to for such methods
Good, hazardous chemical application, and carbon nanotube concentration can not be too high in reaction process, and time-consuming for processing procedure, efficiency
Relatively low, reaction process is relative complex.
Mechanical force and chemical is a branch of chemistry, it studies emphatically condensed state matter and occurs when by mechanical force
Chemically or physically chemical transformation.The characteristics of by means of mechanical force and chemical, is introduced into carbon nano-tube modification field, for truncating
Or modified carbon nano-tube, the prepare with scale and application for truncating or being modified for carbon nanotube provide opportunity.Document
(ActaPhys. Chim.Sin., 2010,26 (3)：Mechanical force is introduced into the system of modified carbon nano-tube in 669-674),
With use ethanol as grinding aid, it is about the short of 200nm that the multi-walled carbon nanotube of 5-15 μm of length, which is prescinded into length, by ball milling
Then wall carbon nano tube utilizes H2O2Mix HNO3Oxidative modification is carried out to it, prescinds the carbon nanotube after being modified in solvent
Dispersibility in system is obviously improved, and surface-active site increases.However, this method needs to utilize two kinds of different technologies pair
Sample is handled, and still needs to use with dangerous, the disagreeableness chemicals of environment, cost is higher, and process is relatively cumbersome, is not inconsistent
Close industrial requirement.
In consideration of it, special propose the present invention.
Invention content
The first object of the present invention is to provide a kind of preparation method of functionalization short carbon nanometer tube, in the method, with
Major diameter carbon nanotube is raw material, using oxidisability salt as truncation agent and functional modification agent so that long carbon nanometer tube material is in machine
It under the action of tool power, is on the one hand truncated by oxidisability salt, on the one hand realizes functionalization oxidation, and then the side for passing through mechanical force and chemical
Formula obtains the shortwall carbon nanotube of functionalization；It is this method novel and unique, simple and practicable, at low cost, it is easy to accomplish the short carbon of functionalization
The technique effect of nanotube industrialization continuous production, high-efficiency environment friendly.
The second object of the present invention is to provide a kind of functionalization short carbon nanometer tube, be prepared by the method for the invention
Functionalization short carbon nanometer tube, have excellent dispersion performance while can also ensure that higher conductivity, in water, part it is organic
There is excellent dispersibility and stability in solvent and macromolecule resin.
The third object of the present invention is to provide a kind of carbon nanotube composite including above-mentioned functionalization short carbon nanometer tube
Material, conductive electrode, energy conversion/memory device or biomedical devices include these productions of above-mentioned functionalization short carbon nanometer tube
Product at least have advantage identical with above-mentioned functionalization short carbon nanometer tube.
The fourth object of the present invention is to provide a kind of application of above-mentioned functionalization short carbon nanometer tube, and above-mentioned functionalization is short
Carbon nanotube is applied in composite material, conductive electrode, energy conversion/memory device or biomedical devices, it can be improved
Production efficiency reduces production cost, environmentally protective and excellent product performance.
To achieve the above object, the technical solution adopted by the present invention is：
According to an aspect of the present invention, the present invention provides a kind of preparation method of functionalization short carbon nanometer tube, this method
Carbon nanotube, oxidisability salt and optional auxiliary agent are mixed, carbon mano-tube composite is obtained；
Carbon mano-tube composite is handled by the way of mechanical force and chemical, the carbon for obtaining functionalization/truncation is received
Mitron；
The carbon nanotube of gained functionalization/truncation is washed and dried to get functionalization short carbon nanometer tube.
Mechanical force and chemical is a branch of chemistry, it studies emphatically condensed state matter and occurs when by mechanical force
Chemically or physically chemical transformation.Specifically, mechano-chemical reation is the different role mode by mechanical force, such as grind
Mill, compression, impact, friction, shearing, extend etc., the accumulation of mechanical energy is introduced, to make the physicochemical properties of stress object
It changes with structure, activated interfaces improve reactivity, to excitation and accelerate the chemical reaction generated.With generalization
It is different to learn reaction, mechano-chemical reation is not related with temperature, and mechano-chemical reation is considered mainly by powder particle
Interaction caused by, this is one of main feature of mechano-chemical reation.The powder granule part in crushing process
Decomposition reaction, redox reaction, the dissolving of mechanical force and chemical can be generated by bearing larger stress or the alternate stress zone of action
Reaction, hydration reaction, solutionizing and solid phase reaction, the polymerisation of organic compound etc., these mechano-chemical reations and one
As chemical reaction have apparent difference.
However, preparing short (wall) the carbon nanotube research of functionalization relatively about by the method for mechanical force and chemical at present
It is weak.In view of this, in the present invention, using major diameter carbon nanotube as raw material, functionalization is obtained by the method for mechanical force and chemical
Shortwall carbon nanotube, wherein oxidisability salt can either shortening carbon nano-tube can realize functional modification to it again.And then in machine
Shortening carbon nano-tube is played under the action of tool power, and functionalization, system are carried out to carbon nanotube under conditions of mechanical activation
It is standby to obtain functionalization shortwall carbon nanotube.In addition, can be to the function of carbon nanotube by regulating and controlling mechano-chemical reation condition
Change degree and truncation size realize regulation and control.
In the present invention, functionalization shortwall carbon nanotube is prepared using oxidisability salt combination mechanical force chemical process, is compared
In strong acid, highly basic, strong oxidizer and part organic solvent, oxidisability salt of the present invention more stablizes and safety, and
Such salt is widely used in water process and soil remediation process, to environmental hazard very little；The present invention can reduce or get rid of danger
The use of danger and toxic chemical improves production efficiency, it can be achieved that scale of mass production, reduces manufacturing cost, is industrialized for it
Using laying the foundation.
As further preferred technical solution, the carbon nanotube includes single-walled carbon nanotube, double-walled carbon nano-tube and more
At least one of wall carbon nano tube；
Preferably, the length of the carbon nanotube is 1~20 μm, preferably 5~15 μm.
As further preferred technical solution, the oxidisability salt includes persulfate, and the persulfate preferably includes
One or more mixtures in potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, potassium hydrogen persulfate and hydrogen persulfate sodium.
As further preferred technical solution, the auxiliary agent includes in water, alcohols solvent, ether solvent and ketones solvent
One or more mixtures；
Preferably, the auxiliary agent includes at least one of water and alcohols solvent.
As further preferred technical solution, the mode of action of the mechanical force and chemical include abrasive action, compression,
One or more combinations in percussion, rubbing action, shear action or progradation；
Preferably, the processing equipment of the mechanical force and chemical includes horizontal ball mill, vibrator, planetary type ball-milling
One or more combinations in machine, agitator mill, roller mill or sand mill.
As further preferred technical solution, the mass ratio of the carbon nanotube, oxidisability salt and auxiliary agent is 1：(1~
100)：(0~100).
As further preferred technical solution, mechanical force and chemical processing time is 1~100 hour, and preferably 6~24 is small
When；
Preferably, it is 1 that mechanical force and chemical processing parameter, which includes material ball ratio,：(10~40), automatic reaction rotating speed be 30~
300rpm/min。
According to another aspect of the present invention, the present invention also provides a kind of systems using above-mentioned functionalization short carbon nanometer tube
The functionalization short carbon nanometer tube that Preparation Method is prepared；
Preferably, the length of the functionalization short carbon nanometer tube of gained is 100nm~2 μm, preferably 100nm~1 μm.
According to another aspect of the present invention, the present invention also provides a kind of answering comprising above-mentioned functionalization short carbon nanometer tube
Condensation material, conductive electrode, energy conversion/memory device or biomedical devices.
According to another aspect of the present invention, the present invention also provides a kind of functionalization short carbon nanometer tubes in composite wood
Application in material, conductive electrode, energy conversion/memory device or biomedical devices.
Compared with prior art, the beneficial effects of the present invention are：
(1), the method for the invention, using oxidisability salt as agent and functional modification agent is truncated, using mechanical force
Method truncates and function oxidation, preparation functionalization short carbon nanometer tube, not only instead of conventional method in conjunction with machinery
In the hazardous chemicals such as common concentrated acid, concentrated base, strong oxidizer, and method is simple, efficient, environmental-friendly, safe and efficient,
It is easily achieved extensive, industrialized production.
(2), the present invention is used as oxidant using oxidisability salt, more stablizes and safe, and the oxidisability salt can either
Shortening carbon nano-tube again can realize it functional modification, and such salt is widely used in water process and soil remediation mistake
Journey, to environmental hazard very little, with good economic efficiency and environmental benefit.
(3), the functionalization short carbon nanometer tube made from the method for the present invention is equal in water, organic solvent, macromolecule resin etc.
With excellent dispersibility and stability；Meanwhile the functionalization short carbon nanometer tube has good electric conductivity, thus in composite wood
It is had a wide range of applications in terms of the fields such as material, electronic device, biologic medical.
By the present invention functionalization short carbon nanometer tube apply composite material, conductive electrode, energy conversion/memory device or
In biomedical devices, its production efficiency can be improved, reduces production cost, environmentally protective and excellent product performance.
Description of the drawings
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art are briefly described, it should be apparent that, in being described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, other drawings may also be obtained based on these drawings.
Fig. 1 is the figure (figure after the dispersion liquid of the functionalization short carbon nanometer tube obtained by the embodiment of the present invention 1 is stood one month
In be followed successively by water, ethyl alcohol, ethylene glycol, DMF, NMP from left to right)；
Fig. 2 is the TEM figures of the functionalization short carbon nanometer tube obtained by the embodiment of the present invention 2；
Fig. 3 is the infrared analysis figure of functionalization short carbon nanometer tube made from the embodiment of the present invention 2；
Fig. 4 is the TEM figures of functionalization short carbon nanometer tube made from the embodiment of the present invention 3；
Fig. 5 is that the XPS of functionalization short carbon nanometer tube made from the embodiment of the present invention 3 schemes (Fig. 5 a) and C1s swarmings spectrum
Scheme (Fig. 5 b).
Specific implementation mode
Embodiment of the present invention is described in detail below in conjunction with embodiments and examples, but this field skill
Art personnel will be understood that following embodiments and embodiment are merely to illustrate the present invention, and be not construed as the model of the limitation present invention
It encloses.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.The person that is not specified actual conditions, builds according to normal condition or manufacturer
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Mechanical force and chemical is the more emerging technology of current research field, and the application prospect in many fields is (golden extensively
Belong to alloy etc.), and equally have application in functionalized carbon nano-tube field.Functionalization is prepared about by means of the method for mechanical force
Carbon nanotube is the relatively common method of the current preparation short nanotube of functionalization, and is the side for being most expected to accomplish scale production
Method.But it is very tight by the requirement for reaction condition in mechanical force and chemical functionalization or the method for shortening carbon nano-tube
It is severe, including strong acid, highly basic, active gases etc., irreversible defect can be not only caused to the structure of carbon nanotube, but also exist
Some potential safety problems.In the present invention, by means of the moment excitation that mechanical force generates, safely and effectively oxidisability salt is utilized
Truncation/functionalized reagent is served as, realizes the preparation of short (wall) carbon nanotube of functionalization, thus method is simple and efficient, is at low cost
It is honest and clean, environmentally protective, while can accomplish scale production.This application study also for functionalization shortwall carbon nanotube has provided
The technical support of power.
In a first aspect, providing a kind of preparation method of functionalization short carbon nanometer tube, this method at least one embodiment
Carbon nanotube, oxidisability salt and optional auxiliary agent are mixed, carbon mano-tube composite is obtained；
Carbon mano-tube composite is handled by the way of mechanical force and chemical, the carbon for obtaining functionalization/truncation is received
Mitron；
The carbon nanotube of gained functionalization/truncation is washed and dried to get functionalization short carbon nanometer tube.
(length) carbon nanotube and oxidisability salt and optional auxiliary agent are first uniformly mixed by the present invention, obtain carbon nanometer
Pipe compound；Then the compound is truncated using machinery by the way of action and functionization reaction is combined and prepares functionalization shortwall
Carbon nanotube.
It is understood that above-mentioned " optional auxiliary agent " expression is：It can add and help in the carbon mano-tube composite
Agent, or do not add auxiliary agent.Above-mentioned " carbon nanotube of functionalization/truncation " indicate be：Functionalized carbon nano-tube, or truncate
Carbon nano tube or functionalization and truncation carbon nano tube.
In a preferred embodiment, the carbon nanotube includes single-walled carbon nanotube, double-walled carbon nano-tube and more
At least one of wall carbon nano tube；
Preferably, the length of the carbon nanotube is 1~20 μm, preferably 5~15 μm.
In the method for the invention, used carbon nanometer tube material can be single-walled carbon nanotube, double-walled carbon nano-tube,
Multi-walled carbon nanotube or their mixture, and then overcome existing most of method of modifying and be only applicable to single-walled carbon nanotube
Or multi-walled carbon nanotube, it can not achieve the defect of the universal method by two kinds of carbon nanotubes while modification.
The present invention length of used carbon nanometer tube material is not done it is specifically limited, such as its length can be 1~
20 μm, preferably 5~15 μm, but the size is not limited within the scope of this.For carbon nanometer tube material, existing skill can be used
Known common used material, typical but non-limiting in art, and the length of the carbon nanotube is 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μ
M, 8 μm, 10 μm, 12 μm, 14 μm, 15 μm, 16 μm, 18 μm or 20 μm.
In a preferred embodiment, the oxidisability salt is that can swash with oxidisability or under mechanical action
Send out the mixture of one or more salt in the substance of oxidisability；
Preferably, the oxidisability salt includes persulfate；
Preferably, the persulfate includes potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, potassium hydrogen persulfate and persulfuric acid
One or more mixtures in hydrogen sodium.
More stablized using the oxidisability such as potassium hydrogen persulfate salt and safe, and such salt is widely used in water process and soil
Earth repair process, to environmental hazard very little；Quick, mild condition environmental-friendly, simple for process.
In a preferred embodiment, the auxiliary agent includes in water, alcohols solvent, ether solvent and ketones solvent
One or more mixtures；
Preferably, the auxiliary agent includes at least one of water and alcohols solvent；
Preferably, the alcohols solvent includes at least one of methanol, ethyl alcohol and ethylene glycol.
Auxiliary agent in the present invention contributes to carbon nanotube and the mixing of oxidisability salt equal preferably using water or ethyl alcohol
It is even, reaction effect is improved, while environmental-friendly, of low cost, production efficiency is high.
In a preferred embodiment, the mode of action of the mechanical force and chemical include abrasive action, compression,
One or more combinations in percussion, rubbing action, shear action or progradation；
Preferably, the processing equipment of the mechanical force and chemical includes horizontal ball mill, vibrator, planetary type ball-milling
One or more combinations in machine, agitator mill, roller mill or sand mill.
It is understood that the mechanical force and chemical processing equipment employed in the present invention, preferably above-mentioned several, but not
It is limited to above-mentioned several, can also is centrifugal grinding mills, basket-type grinder or colloid mill etc..Mechanical force and chemical processing is set
It is standby, any processing equipment well known in the prior art can be used, and without limitation.
In a preferred embodiment, the mass ratio of the carbon nanotube, oxidisability salt and auxiliary agent is 1：(1~
100)：(0~100).
By regulating and controlling the ratio of oxidisability salt and the condition of mechanico-chemical reaction, carbon nanotube difference journey may be implemented
The functionalization and size of degree regulate and control.Typical but without limitation, the mass ratio of carbon nanotube, oxidisability salt and auxiliary agent can be
1：20：10、1：20：4、1： 10：0、1：20：0、1：20：5、1：30：4、1：50：5、1：60：10 or 1： 100：100.
In a preferred embodiment, mechanical force and chemical processing time is 1~100 hour, and preferably 6~24 is small
When；
Preferably, it is 1 that mechanical force and chemical processing parameter, which includes material ball ratio,：(10~40), automatic reaction rotating speed be 30~
300rpm/min。
Mechanical force and chemical processing time is a more important factor for controlling generated short carbon nanometer tube length, one
With the extension of mechanical force processing time, long carbon nanotube can be truncated to smaller size, further make in this way aspect
Carbon nanotube is broken；On the other hand, if mechanical force processing time is too short, long carbon nanotube cannot be fully crushed, processing time
It is long, it is economically non-remunerative, also reduces production efficiency.It is typical but without limitation, when the processing of mechanical force and chemical
Between can be 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20
Hour, 22 hours, 24 hours, 48 hours or 100 hours.
It should be noted that above-mentioned " material ball ratio " refers to the mass ratio of carbon mano-tube composite and steel ball.It is typical but non-
Restrictively, material ball ratio can be 1：10、1：15、1：20、 1：25、1：30、1：35 or 1：40.
Preferably, automatic reaction rotating speed is 40~300rpm/min；It is highly preferred that automatic reaction rotating speed be 60~
240rpm/min。
In a preferred embodiment, carbon nanotube, oxidisability salt and optional auxiliary agent are stirred mixing
Afterwards, it is reacted by the mode of mechanical force, reacts on and carry out under room temperature 1~24 hour, then add water and/or dilute hydrochloric acid
It washed, detached, purification process.
Before automatic reaction, first carbon nanotube is uniformly mixed with oxidisability salt and auxiliary agent so that raw material can fill
Tap is touched, and is then carried out mechanical force and chemical processing again, by the mixing of early period, truncation can be made to be carried out with functionalization more thorough
Bottom, it is also more uniform.
Further, in mechanical force and chemical processing procedure, oxidisability salt auxiliary abrading-ball gradually cuts carbon nanotube long-chain
It is short, and in the process, excite energy using the moment that mechanical force generates, play the effect of oxidisability, work(is carried out to carbon nanotube
The defects of energyization, the two complement each other, and obtained functionalized carbon nano-tube length is uniform, tube wall/top position is by oxygen-containing function
Group is modified.
In a preferred embodiment, the washing includes washing, pickling and the washing carried out successively.
Wherein, first step washing is to remove remaining oxidisability salt in reaction process and do not truncate/functionalization
Carbon nanotube, pickling be in order to remove metal impurities that may be present in reaction, last water-washing process be by remaining acid with
And impurity removal, it is high by acquired product purity after this three step.
In a preferred embodiment, by obtained product after washing after freeze-drying or drying, i.e.,
Obtain functionalization short carbon nanometer tube powder.
In a preferred embodiment, preparation method of the present invention can be following steps：
(a) compare carbon nanotube according to quality：Oxidisability salt：Auxiliary agent=1：(1~100)：The proportioning of (0~100), will be each
Raw material is uniformly mixed, and obtains carbon mano-tube composite；
(b) by the carbon mano-tube composite in such a way that machinery truncation action and functionization reaction is combined
Reason, operating parameter include：The quality of carbon mano-tube composite：Quality=1 of steel ball：(10~40) g, automatic reaction rotating speed are
40~300rpm/min, in horizontal ball mill, vibrator, planetary ball mill, agitator mill, roller mill or sand mill
At least one equipment in carry out mechanical oxidation reaction 1~24 hour, obtain the carbon nanotube of functionalization/truncation；
(c) deionized water, dilute hydrochloric acid and deionized water is used to carry out successively the carbon nanotube of gained functionalization/truncation
Washing, then carries out freeze-drying 24~60 hours to get functionalization short carbon nanometer tube powder by products therefrom；
Wherein, carbon nanometer tube material include in single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube at least
It is a kind of；The length of carbon nanotube is 1~15 μm；
Oxidisability salt includes one kind in potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, potassium hydrogen persulfate and hydrogen persulfate sodium
Or a variety of mixture；
Auxiliary agent includes at least one of water, ethyl alcohol and methanol.
Second aspect provides a kind of functionalization short carbon nanometer tube in some embodiments, which adopts
It is prepared with the preparation method of above-mentioned functionalization short carbon nanometer tube.
The length of functionalization short carbon nanometer tube made from method using the present invention is 100nm~2 μm, preferably 100nm
~1 μm.
Meanwhile the functionalization short carbon nanometer tube maintains the intrinsic conductivity of carbon nanotube to a certain extent, passes through
Conductivity after reduction treatment also has the promotion on the order of magnitude；
In addition, the functionalization short carbon nanometer tube is in water, ethyl alcohol, ethylene glycol, NMP, DMF, butyl equal solvent
In there is excellent dispersibility, and the stability of dispersion liquid is very good, and standing for several weeks is not in sedimentation.
It can be seen that the functionalization short carbon nanometer tube of the present invention has good dispersion stabilization, electric conductivity and can add
Work performance, therefore have a good application prospect in fields such as composite material, biologic medicals.
The third aspect, provide in some embodiments a kind of composite material comprising above-mentioned functionalization short carbon nanometer tube,
Conductive electrode, energy conversion/memory device or biomedical devices.
Fourth aspect provides a kind of functionalization short carbon nanometer tube in composite material, conduction in some embodiments
Application in electrode, energy conversion/memory device or biomedical devices.
By the present invention functionalization short carbon nanometer tube apply composite material, conductive electrode, energy conversion/memory device or
In biomedical devices, its production efficiency can be improved, reduces production cost, environmentally protective and excellent product performance.
With reference to specific embodiments and the drawings, the invention will be further described.
Embodiment 1
A kind of preparation method of functionalization short carbon nanometer tube, includes the following steps：
The multi-walled carbon nanotube of about 15 μm of length of 2g and 40g ammonium persulfate-sodium bisulfates and 20g deionized waters are stirred
It is uniformly mixed, regulation and control ratio of grinding media to material is 10：1, under conditions of rotational speed of ball-mill is 240rpm/min, ball milling 8 in planetary ball mill
Hour, obtain the carbon nanotube of functionalization/truncation；
The carbon nanotube of gained functionalization/truncation is washed with deionized, removes unreacted persulfate, low turn
Speed centrifugation removal is not truncated the/carbon nanotube of functionalization, then metal impurities present in the hydrochloric acid washed product with about 1%,
It finally uses deionized water centrifugal ultrafiltration to handle product to weakly acidic pH, is freeze-dried 48 hours, obtains functionalization short carbon nanometer tube powder
Body.
The water of obtained functionalization short carbon nanometer tube, ethyl alcohol, DMF, NMP, ethylene glycol dispersion liquid stand one in embodiment 1
Picture after month, (being followed successively by water, ethyl alcohol, ethylene glycol, DMF, NMP in Fig. 1 from left to right) as shown in Figure 1, dispersion liquid concentration is
0.5mg/ml。
From figure 1 it appears that gained functionalization short carbon nanometer tube is common molten in water, ethyl alcohol, NMP, DMF, ethylene glycol etc.
Dispersion stabilization in agent is very good.
The yield of functionalization short carbon nanometer tube is 85% in embodiment 1, and distribution of lengths is between 100~200nm, gained
Dispersion liquid can be stabilized under 5000rpm/min centrifugal conditions.Elemental analysis is carried out to gained functionalization short carbon nanometer tube
Test, elemental analysis test result show that the oxygen content in the functionalization short carbon nanometer tube is 17.89wt%, and phosphorus content is
78.11wt%.
Embodiment 2
A kind of preparation method of functionalization short carbon nanometer tube, includes the following steps：
About 15 μm of multi-walled carbon nanotubes of 50g are uniformly mixed with 500g potassium hydrogen persulfates, regulation and control ratio of grinding media to material is 10：
1, under conditions of rotational speed of ball-mill is 240rpm/min, stirring ball-milling 12 hours in agitator mill obtain functionalization/truncation
Carbon nanotube；
The carbon nanotube of gained functionalization/truncation is washed with deionized, removes unreacted ammonium persulfate, low turn
Speed centrifugation, which removes, does not truncate/functionalized carbon nano-tube, then metal impurities present in the hydrochloric acid washed product with 5%, finally uses
Deionized water ultrafiltration product is freeze-dried 48 hours to weakly acidic pH, obtains functionalization short carbon nanometer tube powder.
The TEM figures and infrared analysis collection of illustrative plates of functionalization short carbon nanometer tube obtained by embodiment 2, respectively such as Fig. 2 and Fig. 3 institutes
Show.
From Fig. 2 and Fig. 3 as can be seen that gained functionalization short carbon nanometer tube distribution of lengths 200nm~0.5 μm it
Between, oxygen-containing functional group is based on carboxyl, hydroxyl.
The functionalization short carbon nanometer tube of gained can be stabilized under 5000rpm/min centrifugal conditions in embodiment 2.It is right
Gained functionalization short carbon nanometer tube carries out elemental analysis test, and elemental analysis test result shows in the functionalization short carbon nanometer tube
Oxygen content be 8.6wt%, phosphorus content 87.5wt%.
Embodiment 3
A kind of preparation method of functionalization short carbon nanometer tube, includes the following steps：
About 10 μm of single-walled carbon nanotube of 5g length is uniformly mixed with 100g ammonium persulfates, 20g deionized waters, is adjusted
It is 10 to control ratio of grinding media to material：1, under conditions of rotational speed of ball-mill is 240rpm/min, ball milling 12 hours, obtain work(in planetary ball mill
The carbon nanotube of energyization/truncation；
The carbon nanotube of gained functionalization/truncation is washed with deionized, removes unreacted persulfate, low turn
Speed centrifugation removal does not truncate the/carbon nanotube of functionalization, then metal impurities present in the hydrochloric acid washed product with 5%, finally
With deionized water ultrafiltration product to weakly acidic pH, it is freeze-dried 48 hours, obtains functionalization short carbon nanometer tube powder.
The TEM figures and XPS collection of illustrative plates of obtained functionalization short carbon nanometer tube, as shown in Figure 4 and Figure 5 respectively in embodiment 3.
As can be seen that the distribution of lengths of gained functionalization short carbon nanometer tube is between 200nm~1 μm from Fig. 4 and Fig. 5.
The carbon nanotube of gained can be stabilized under 5000rpm/min centrifugal conditions in embodiment 3.
Embodiment 4
A kind of preparation method of functionalization short carbon nanometer tube, includes the following steps：
The multi-walled carbon nanotube that 200g length is 15 μm is uniformly mixed with 4000g sodium peroxydisulfates, regulates and controls ratio of grinding media to material
It is 20：1, under conditions of rotational speed of ball-mill is 32rpm/min, ball milling 48 hours in horizontal ball mill obtain functionalization/truncation
Carbon nanotube；
The carbon nanotube of gained functionalization/truncation is washed with deionized, removes unreacted persulfate, low turn
Speed centrifugation removal does not truncate the/carbon nanotube of functionalization, then metal impurities present in the hydrochloric acid washed product with 5%, finally
Product is washed with deionized to weakly acidic pH, is freeze-dried 48 hours, obtains functionalization short carbon nanometer tube.
The distribution of lengths of the functionalization short carbon nanometer tube of gained is between 100nm~5 μm in embodiment 4.
Embodiment 5
A kind of preparation method of functionalization short carbon nanometer tube, includes the following steps：
By the compound of the single-walled carbon nanotube of about 10 μm of length of 5g and 200g hydrogen persulfates sodium and potassium hydrogen persulfate and
20g ethyl alcohol is uniformly mixed, and regulation and control ratio of grinding media to material is 30：1, under conditions of rotational speed of ball-mill is 300rpm/min, in planetary ball
Ball milling 24 hours in grinding machine, obtain the carbon nanotube of functionalization/truncation；
Subsequent step obtains functionalization short carbon nanometer tube with embodiment 1.
The distribution of lengths of the functionalization short carbon nanometer tube of gained is between 100nm~300nm in embodiment 5.
Embodiment 6
A kind of preparation method of functionalization short carbon nanometer tube, includes the following steps：
The stirring of the compound of the double-walled carbon nano-tube of about 15 μm of length of 10g and 300g sodium peroxydisulfates and hydrogen persulfate sodium is mixed
It closes uniformly, regulation and control ratio of grinding media to material is 15：1, it under conditions of rotational speed of ball-mill is 120rpm/min, grinds 18 hours, obtains in roller mill central roll
To the carbon nanotube of functionalization/truncation；
Subsequent step obtains functionalization short carbon nanometer tube with embodiment 1.
The distribution of lengths of the functionalization short carbon nanometer tube of gained is between 500nm~1 μm in embodiment 6.
It can be seen from above in the preparation method of the present invention, using long carbon nanotube as raw material, a certain proportion of oxygen is added
The property changed salt and optional auxiliary agent prepare functionalization short carbon nanometer tube using the method for mechanical force and chemical.Long carbon nanometer tube material exists
It under conditions of mechanism, is on the one hand truncated by oxidisability salt particle, on the one hand realizes functionalization oxidation, obtain the short carbon of functionalization
Nanotube.Simultaneously by regulating and controlling the ratio of oxidisability salt and the condition of mechanico-chemical reaction, realize that carbon nanotube is different degrees of
Functionalization and size regulation and control.The present invention avoids traditional strong acid, strong oxidizer harshness item on the basis of mechanical force and chemical
Part and organic solvent etc. be expensive and environment it is unfriendly under the conditions of prepare the processing route of functionalization short carbon nanometer tube, drop
Low production cost, shortens the reaction time, controls the use and discharge of poisonous and harmful substance.Due to using oxidisability salt
As agent and functional modification agent is truncated, the method for the present invention also has yield high, simple and practicable, environmentally protective simultaneously, and energy
Enough the features such as realizing large-scale production.
The method of the present invention is simple and efficient and environmentally protective, and can mass prepare with fine dispersion performance, conduction
The shortwall carbon nanotube of property and stability, this application also for carbon nanotube in fields such as composite material, electronic devices provide
New possibility.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of preparation method of functionalization short carbon nanometer tube, which is characterized in that this method by carbon nanotube, oxidisability salt and
Optional auxiliary agent is mixed, and carbon mano-tube composite is obtained；
Carbon mano-tube composite is handled by the way of mechanical force and chemical, obtains the carbon nanotube of functionalization/truncation；
The carbon nanotube of gained functionalization/truncation is washed and dried to get functionalization short carbon nanometer tube.
2. the preparation method of functionalization short carbon nanometer tube according to claim 1, which is characterized in that the carbon nanotube packet
Include at least one of single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube；
Preferably, the length of the carbon nanotube is 1~20 μm, preferably 5~15 μm.
3. the preparation method of functionalization short carbon nanometer tube according to claim 1, which is characterized in that the oxidisability salt packet
Persulfate is included, the persulfate preferably includes potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, potassium hydrogen persulfate and persulfuric acid
One or more mixtures in hydrogen sodium.
4. the preparation method of functionalization short carbon nanometer tube according to claim 1, which is characterized in that the auxiliary agent includes
One or more mixtures in water, alcohols solvent, ether solvent and ketones solvent；
Preferably, the auxiliary agent includes at least one of water and alcohols solvent.
5. according to the preparation method of Claims 1 to 4 any one of them functionalization short carbon nanometer tube, which is characterized in that described
The mode of action of mechanical force and chemical includes abrasive action, compression, percussion, rubbing action, shear action or extends work
One or more combinations in；
Preferably, the processing equipment of the mechanical force and chemical includes horizontal ball mill, vibrator, planetary ball mill, stirs
Mix one or more combinations in grinding machine, roller mill or sand mill.
6. according to the preparation method of Claims 1 to 4 any one of them functionalization short carbon nanometer tube, which is characterized in that described
The mass ratio of carbon nanotube, oxidisability salt and auxiliary agent is 1：(1~100)：(0~100).
7. according to the preparation method of Claims 1 to 4 any one of them functionalization short carbon nanometer tube, which is characterized in that machinery
Power chemical process time is 1~100 hour, preferably 6~24 hours；
Preferably, it is 1 that mechanical force and chemical processing parameter, which includes material ball ratio,：(10~40), automatic reaction rotating speed are 30~300rpm/
min。
8. the functionalization being prepared using the preparation method of claim 1~7 any one of them functionalization short carbon nanometer tube
Short carbon nanometer tube；
Preferably, the length of the functionalization short carbon nanometer tube of gained is 100nm~2 μm, preferably 100nm~1 μm.
9. composite material, conductive electrode comprising functionalization short carbon nanometer tube according to any one of claims 8, energy conversion/memory
Part or biomedical devices.
10. functionalization short carbon nanometer tube according to any one of claims 8 composite material, conductive electrode, energy conversion/memory device or
Application in biomedical devices.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110980695A (en) * | 2019-12-31 | 2020-04-10 | 厦门大学 | Controllable shearing method of carbon-based nano material |
| CN116281961A (en) * | 2023-03-10 | 2023-06-23 | 北京化工大学 | Port selective functionalized carbon nanotube and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100084007A1 (en) * | 2008-10-07 | 2010-04-08 | Seong-Mu Jo | Modified carbon nanotube grafted by living polymer, carbon nanotube electrode and dye-sensitized solar cell using the same, and each preparation method thereof |
| RU2528985C2 (en) * | 2012-07-03 | 2014-09-20 | Общество с ограниченной ответственностью "НаноТехЦентр" | Method of modifying carbon nanotubes |
| CN107541996A (en) * | 2016-06-25 | 2018-01-05 | 董晓 | A kind of preparation method of modified carbon nano-tube electromagnetic shielding paper |
-
2018
- 2018-03-02 CN CN201810177610.7A patent/CN108455570B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100084007A1 (en) * | 2008-10-07 | 2010-04-08 | Seong-Mu Jo | Modified carbon nanotube grafted by living polymer, carbon nanotube electrode and dye-sensitized solar cell using the same, and each preparation method thereof |
| RU2528985C2 (en) * | 2012-07-03 | 2014-09-20 | Общество с ограниченной ответственностью "НаноТехЦентр" | Method of modifying carbon nanotubes |
| CN107541996A (en) * | 2016-06-25 | 2018-01-05 | 董晓 | A kind of preparation method of modified carbon nano-tube electromagnetic shielding paper |
Non-Patent Citations (1)
| Title |
|---|
| PENG LIU: "Ultrasonic-assisted chemical oxidative cutting of multiwalled carbon nanotubes with ammonium persulfate in neutral media", 《APPLIED PHYSICS A》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110980695A (en) * | 2019-12-31 | 2020-04-10 | 厦门大学 | Controllable shearing method of carbon-based nano material |
| CN116281961A (en) * | 2023-03-10 | 2023-06-23 | 北京化工大学 | Port selective functionalized carbon nanotube and preparation method thereof |
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