CN109133037A - Carbon nanotube and its preparation method and application - Google Patents
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Abstract
The present invention relates to field of nanometer material technology, and in particular to a kind of carbon nanotube, the carbon nanotube are dendritic crystalline multi-walled carbon nanotube.Further relate to a kind of method for preparing carbon nanotube, this method is chemical vapour deposition technique, catalyst used in the chemical vapour deposition technique contains the first metal oxide and/or the second metal oxide, and first metal is manganese, and second metal is calcium and/or barium.Further relate to the application of the carbon nanotube and the carbon nanotube of above method preparation in lithium ion battery conductive agent, conductive plastics and conductive filler.Carbon nanotube of the invention is dendritic structures, has a preferable rigidity, good dispersibility and has the preferable performances such as conductive, thermally conductive.Carbon nanotube produced by the present invention in lithium ion battery conductive agent, conductive plastics and conductive filler due to that can be widely applied with above-mentioned various excellent properties.
Description
Technical field
The present invention relates to field of nanometer material technology, and in particular to a kind of carbon nanotube and its preparation method and application.
Background technique
Carbon nanotube is one kind by carbon atom SP2Tubular material made of hydridization curling, due to the closed structure of tube wall
And huge draw ratio, so that carbon nanotube has excellent performance, research and system in terms of electric conductivity, thermal conductivity and intensity
Standby carbon nanotube has important learning value and application prospect.
Carbon nanotube was found in 1991, by development in more than 20 years, the carbon nanotube of present industrialized production
In, most using chemical vapor deposition (CVD) preparation, chemical vapour deposition technique has continuous and automatic, yield
High, the features such as consistency is good and be widely used.Its principle are as follows: porous carrier is carried on using the high nano metal of catalytic activity
On, it cracks carbon source at high temperature, carbon atom assembling is precipitated in catalyst surface by the growth mechanism of carbon nanotube (VLS is theoretical)
At carbon nanotube.
Patent application CN104986753A discloses a kind of overlength carbon nano pipe and preparation method thereof and device.The preparation side
Method includes: that the catalyst containing Fe, Mo, Co, Cu or Ni is carried on growth substrate and is placed in reactor by (1), in the reactor
It is passed through the mixed gas of inert gas and hydrogen；(2) reactor that will be passed through mixed gas adds under the protection of inert gas
Heat is reacted to 800-1200 DEG C, then by being passed into reactor by carbon-source gas with the mixed gas that carrier gas forms；Wherein,
Carrier gas is the mixed gas of at least one of hydrogen and helium, argon gas and neon composition；(3) after reaction into reactor
It is passed through the mixed gas of inert gas and hydrogen composition, and reactor is cooled to 400 DEG C hereinafter, obtaining overlength carbon nano pipe.
This method and its device realize large area overlength carbon nano pipe by specific process conditions and special structure of reactor
Direct preparation.
Patent application CN106362745A discloses the catalyst for producing multi-walled carbon nanotube, wherein the catalysis
Agent includes the transition-metal catalyst being supported on the supporter mixture containing MgO, so that multi-walled carbon nanotube can be improved
Output, while the wall number of multi-walled carbon nanotube is reduced to reduce the sheet resistance of multi-walled carbon nanotube.
But since the flexible and huge draw ratio of the carbon nanotube itself of above method synthesis makes carbon pipe and carbon
It is easy to produce winding between pipe, and is formed agglomerate shape carbon nanotube particulate, agglomerate shape carbon after carbon pipe winds quantity increase
Nanotube particles volume is larger, it is difficult to disperses, so that it is difficult to the features such as playing the excellent conduction of carbon nanotube, heating conduction,
Therefore, prepare that dispersion performance is good, the more excellent carbon nanotube of mechanical performances such as rigidity is highly desirable.
Summary of the invention
It is easy to reunite the purpose of the invention is to overcome the flexibility of carbon nanotube of the existing technology itself larger, point
Property and the poor defect of stability are dissipated, provides a kind of carbon nanotube and its preparation method and application, which is dendritic crystalline
Rigid structure, dispersibility and stability etc. are more excellent.
To achieve the goals above, one aspect of the present invention provides a kind of carbon nanotube, which is that dendritic crystalline is more
Wall carbon nano tube.
It is further preferred that the mean wall number of multi-walled carbon nanotube is 20-80, more preferably 20-50, more preferably 20-
40。
It is further preferred that the average pipe range of the carbon nanotube is 1-20 μm, more preferably 1-10 μm, more preferably 3-
4.5μm。
It is further preferred that the draw ratio of the carbon nanotube be 1:0.005-0.1, more preferably 1:0.01-0.1, more
Preferably 1:0.02-0.05.
It is further preferred that the specific surface area of the carbon nanotube is 20-90m2/ g, preferably 30-80m2/ g, more preferably
For 40-60m2/g。
It is further preferred that the bulk density of the carbon nanotube is 0.1-0.5g/cm3, preferably 0.1-0.3g/cm3,
More preferably 0.15-0.25g/cm3。
It is further preferred that the resistivity of the carbon nanotube be 15-25 Ω cm, more preferable 16.2-17.1 Ω cm,
The thermal conductivity of the carbon nanotube is 20-35W/mK, more preferably 30.2-32.9W/mK, the tension of the carbon nanotube
Intensity is 0.4-0.8GPa, more preferably 0.72-0.78GPa, and the elasticity modulus of the carbon nanotube is 250-350GPa, more excellent
It is selected as 310-330GPa.
Second aspect of the present invention provides a kind of method for preparing carbon nanotube, and this method is chemical vapour deposition technique, institute
It states catalyst used in chemical vapour deposition technique and contains the first metal oxide and/or the second metal oxide, described first
Metal is manganese, and second metal is calcium and/or barium.
Third aspect present invention provides the carbon nanotube of above method preparation.
Fourth aspect present invention provides above-mentioned carbon nanotube in lithium ion battery conductive agent, conductive plastics and conductive filler
In application.
In the present invention, existing carbon nanotube due to the flexible and huge draw ratio of itself make carbon pipe and carbon pipe it
Between be easy to produce winding, and the agglomerate shape carbon nanotube easy to form after carbon pipe winds quantity increase, agglomerate shape carbon nanotube body
Product is larger, it is difficult to disperse, to be difficult to the features such as playing the excellent conduction of carbon nanotube, heating conduction.And lead in the present invention
The catalyst being made containing at least one of manganese, calcium and barium as auxiliary agent is crossed, and uses the catalyst preparation carbon nanotube, more
It can induce carbon pipe to grow in one direction, therefore be prepared into more straight carbon pipe, obtain dendritic crystalline multi-walled carbon nanotube；The dendrite
The length and draw ratio of shape multi-walled carbon nanotube are smaller, carbon pipe range and straight, rigidity with higher.Thus it is not easy to occur
Mutually winding, it is easier to disperse, more conducively the performances such as thermally conductive, conductive of performance carbon nanotube.
Detailed description of the invention
Fig. 1 is the scanning electron microscope SEM figure of carbon nanotube made from embodiment 1；
Fig. 2 a is the X-ray energy spectrometer EDS Surface scan figure of carbon nanotube made from embodiment 1, and Fig. 2 b is that embodiment 1 is made
Carbon nanotube X-ray energy spectrometer EDS elemental analysis figure；
Fig. 3 is the scanning electron microscope SEM figure of carbon nanotube made from comparative example 1；
Fig. 4 is the scanning electron microscope SEM figure (5000 times) of catalyst made from embodiment 1；
Fig. 5 is the scanning electron microscope SEM figure (50000 times) of catalyst made from embodiment 1；
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
One aspect of the present invention provides a kind of carbon nanotube, which is dendritic crystalline multi-walled carbon nanotube.
In the present invention, dendritic crystalline is the shape formed through dendritic growth, and dendritic growth process refers to be grown forward in crystal
While, the crystal of side can also grow out, to form dendrite.The example of more typical dendritic crystalline is the structure of snowflake.
Carbon nanotube according to the present invention, the carbon nanotube are multi-walled carbon nanotube, it is preferable that multi-walled carbon nanotube
Mean wall number be 20-80, more preferably 20-50, further preferably 20-40.Wherein, the wall number of carbon nanotube can pass through
Estimation algorithm obtains, and the theoretical specific surface area of single-walled carbon nanotube is 1315m2/ g, with single-wall carbon tube theoretical specific surface area divided by reality
The test specific surface area of border carbon pipe can estimate the wall number of carbon nanotube.
Carbon nanotube according to the present invention, the average pipe range of the carbon nanotube are 1-20 μm, more preferably 1-10 μ
M, further preferably 3-4.5 μm.Compared with existing carbon nanotube, the average length of dendritic crystalline multi-walled carbon nanotube of the invention
Degree is shorter, so as to avoid the mutual winding between single tube, and then improves the dispersibility and stability and machine of carbon nanotube
Tool performance etc..
Carbon nanotube according to the present invention, the draw ratio of the carbon nanotube are 1:0.005-0.1, more preferably 1:
0.01-0.1, further preferably 1:0.02-0.05.Compared with existing carbon nanotube, dendritic crystalline multi wall carbon of the invention is received
The major diameter of mitron is smaller, so as to avoid the mutual winding between single tube, and then improves the dispersed and steady of carbon nanotube
Qualitative and mechanical performance etc..
Carbon nanotube according to the present invention, the specific surface area of the carbon nanotube are 20-90m2/ g, more preferably
30-80m2/ g, further preferably 40-60m2/g。
Carbon nanotube according to the present invention, the bulk density of the carbon nanotube are 0.1-0.5g/cm3, more preferably
For 0.1-0.3g/cm3, further preferably 0.15-0.25g/cm3。
The resistivity of carbon nanotube of the invention can be 15-25 Ω cm, preferably 16.2-17.7 Ω cm；It is described
The thermal conductivity of carbon nanotube can be 20-35W/mK, and the tension of preferably 30.2-32.9W/mK, the carbon nanotube are strong
Degree can be 0.4-0.8GPa, and preferably 0.72-0.78GPa, the elasticity modulus of the carbon nanotube can be 250-350GPa,
Preferably 310-330GPa.Since carbon nanotube of the invention has dendritic structures, which can keep
Mechanical performance, dispersibility and stability also with higher while higher electric conductivity and thermal conductivity.
Second aspect of the present invention provides a kind of method for preparing carbon nanotube, and this method is chemical vapour deposition technique, institute
It states catalyst used in chemical vapour deposition technique and contains the first metal oxide and/or the second metal oxide, described first
Metal is manganese, and second metal is calcium and/or barium.
Method according to the present invention, it is preferable that the catalyst also contains third metal oxide, the third gold
Belonging to is at least one of magnesium, iron, cobalt, nickel, yttrium, copper, platinum, palladium, vanadium, niobium, tungsten, chromium, iridium, titanium and molybdenum, more preferably iron, cobalt and
At least one of nickel and magnesium and molybdenum, further preferably nickel, magnesium and molybdenum.Wherein, when third metal is nickel, magnesium and molybdenum,
In catalyst, the molar ratio of nickel, magnesium and molybdenum element is preferably 10-20:50-100:0.1-5, thus be more conducive to auxiliary agent calcium and/
Or manganese is used cooperatively, and the catalyst haveing excellent performance is made.When third metal is iron, magnesium and molybdenum, in catalyst, iron, magnesium and molybdenum
The molar ratio of element can be 10-20:50-100:0.1-5.When third metal is cobalt, magnesium and when molybdenum, in catalyst, cobalt, magnesium and
The molar ratio of molybdenum element can be 10-20:50-100:0.1-5
In a kind of preferred embodiment of the present invention, the catalyst contains the first metal oxide, the oxidation of the second metal
Object and third metal oxide, first metal be manganese, second metal be calcium and/or barium, the third metal be nickel,
Magnesium and molybdenum, so as to which dispersibility and the more excellent dendritic crystalline multi-walled carbon nanotube of stability is made.
Method according to the present invention, with elemental metal, the first metal oxide and the second metal oxygen in catalyst
The molar ratio of compound is preferably 1:0.1-10, more preferably 1:0.5-5, further preferably 1:1-2.5, is divided so as to be made
Dissipate property and the more excellent dendritic crystalline multi-walled carbon nanotube of stability.
Method according to the present invention, with elemental metal, the first metal oxide and third metal oxygen in catalyst
The molar ratio of compound is preferably 1:1-100, more preferably 1:20-80, further preferably 1:50-80, is divided so as to be made
Dissipate property and the more excellent dendritic crystalline multi-walled carbon nanotube of stability.
Method according to the present invention, the catalyst are preferably pellet type catalyst, which can
So that the contact area of catalyst and carbon source increases, to be more advantageous to form multi-walled carbon nanotube.
Method according to the present invention, the preparation method of catalyst can be the various conventional catalyst preparations in this field
Method, preferably coprecipitation.Coprecipitation of the invention can be the various conventional coprecipitations in this field, it is preferable that altogether
The precipitation method include: the water solution A that (1) prepares the salt containing the first metal, the second metal and third metal；(2) it prepares containing altogether
The aqueous solution B of precipitating reagent；(3) coprecipitation reaction is carried out after mixing water solution A and aqueous solution B, obtains catalyst precursor；
(4) catalyst precursor that step (3) obtains is calcined.
In the step of method according to the present invention, coprecipitation (1), the first metal, the second metal and third metal
Salt can be the first metal, the various soluble-salts of the second metal and third metal, such as can be soluble nitrate,
Sulfate or the ammonium salt of solubility etc..In a kind of specific embodiment of the invention, the salt of the first metal can be nitric acid
Manganese, bimetallic salt may include: calcium nitrate and/or barium nitrate, the salt of third metal may include: magnesium nitrate, ferric nitrate,
Cobalt nitrate, nickel nitrate, yttrium nitrate, copper nitrate, platinum nitrate, palladium nitrate, nitric acid vanadium, nitric acid niobium, nitric acid tungsten, chromic nitrate, nitric acid iridium,
At least one of Titanium Nitrate and ammonium molybdate are (preferably in magnesium nitrate, ferric nitrate, cobalt nitrate, nickel nitrate and ammonium molybdate at least
It is a kind of).
In the step of method according to the present invention, coprecipitation (1), to the first metal of obtained aqueous solution A, second
There is no particular limitation for the concentration of aqueous solution of the salt of metal and third metal, as long as making the first metal oxygen in catalyst obtained
Compound and the molar ratio of the second metal oxide are 1:0.1-10 (preferably 1:0.5-5, more preferably 1:1-2.5), the first gold medal
The molar ratio for belonging to oxide and third metal oxide is 1:1-100 (preferably 1:20-80, more preferably 1:40-80),
Wherein, the molar ratio of above-mentioned metal oxide is with elemental metal.In a specific embodiment, the of obtained aqueous solution A
The concentration of aqueous solution of the salt of one metal can be 0.1-0.2M, and the concentration of aqueous solution of bimetallic salt can be 0.05-
0.55M, the concentration of aqueous solution of the salt of third metal can be 0.1-5M.
In the step of method according to the present invention, coprecipitation (2), coprecipitator can be the various routines in this field
Coprecipitator, such as can be at least one of for ammonium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, urea and ammonium fluoride.A kind of preferred
In embodiment, coprecipitator is urea and ammonium fluoride, and the molar ratio of urea and ammonium fluoride is 1:0.1-5.Another preferred
In embodiment, the coprecipitator is at least one of ammonium hydroxide, ammonium carbonate and ammonium hydrogen carbonate.
In the step of method according to the present invention, coprecipitation (3), when coprecipitator is ammonium hydroxide, ammonium carbonate and carbon
When at least one of sour hydrogen ammonium, it is preferable that the coprecipitation reaction is implemented and the pH value of solution is adjusted to 8-9.Its
In, as long as coprecipitator concentration can adjust the pH value of solution in above-mentioned preferred scope.
In the step of method according to the present invention, coprecipitation (3), when coprecipitator is urea and ammonium fluoride,
The coprecipitation reaction is implemented and solution is kept the temperature 1-6h at 100-150 DEG C.Wherein, to urea in coprecipitator and fluorine
The concentration for changing ammonium does not have special requirement, as long as the molar ratio of urea and ammonium fluoride is made to be 1:0.1-5.
In the step of method according to the present invention, coprecipitation (4), the condition of the calcining may include: temperature
For 500-850 DEG C (preferably 550-650 DEG C)；Time be 1-10h (preferably 5-8h), so as to be made have excellent performance urge
Agent.
The calcining of catalyst precursor can be carried out in air atmosphere in coprecipitation of the present invention.
Method according to the present invention, the chemical vapour deposition technique can be received for the synthesizing multi-wall carbon of this field routine
The chemical vapour deposition technique of mitron, it is preferable that the chemical vapour deposition technique includes:
(a) mixed gas of reducing gas and carrier gas is passed through in the reactor equipped with catalyst and carries out reduction treatment；
(b) mixed gas of carbon source and carrier gas is passed through in reactor and keeps the temperature 0.5-2h at 650-820 DEG C, branch is made
Crystalline multi-walled carbon nanotube.
In the step of method according to the present invention, chemical vapour deposition technique (a), the reducing gas can be hydrogen
Gas.The carrier gas can be inert gas, it is preferable that the carrier gas is at least one of helium, argon gas and nitrogen, further
Preferably argon gas.Reducing gas and the volume ratio of carrier gas can be the volume ratio of this field routine, such as can be 1-20:
100, preferably 5-10:100.
In the step of method according to the present invention, chemical vapour deposition technique (a), relative to 0.05g catalyst, step
(a) reducing gas and the flow of carrier gas mixed gas can be 60-250ml/min, preferably 110-200ml/min in.
In the step of method according to the present invention, chemical vapour deposition technique (a), reactor can be that can be carried out chemistry
The conventional reactor of gaseous phase deposition synthesizing carbon nanotubes, such as can be burning boat.Wherein, catalyst can equably be laid in burning
Boat bottom, progress reduction treatment in tube furnace can be packed by burning boat.
In the step of method according to the present invention, chemical vapour deposition technique (a), the temperature control program of reduction treatment
It preferably includes: being kept the temperature after being at the uniform velocity warming up to 650-820 DEG C, it is highly preferred that the rate of the heating is 5-15 DEG C/min, further
Preferably 8-12 DEG C/min, so as to which dispersibility and the more excellent dendritic crystalline multi-walled carbon nanotube of stability is made.The present invention
In, the time of the heat preservation can be 0.5-2h, preferably 1-1.5h.In the present invention heating can since room temperature, generally,
Room temperature refers to 10-35 DEG C.
In the step of method according to the present invention, chemical vapour deposition technique (b), the volume ratio of carbon source and carrier gas can be with
For the volume ratio of this field routine, the volume ratio of carbon source and carrier gas is 1-20:100, preferably 5-10:100.
In the step of method according to the present invention, chemical vapour deposition technique (b), relative to 0.05g catalyst, step
(b) flow of carbon source and carrier gas mixed gas can be 100-400ml/min, preferably 150-350ml/min in.
In the step of method according to the present invention, chemical vapour deposition technique (b), the carbon source can be each for this field
The carbon source of kind carbon nanotube synthesis, such as C can be selected from1-C5Hydrocarbon, C1-C8Pure and mild inorganic carbonaceous compound；Wherein, preferably
Ground, C1-C5Hydrocarbon be at least one of methane, ethane, ethylene, propylene and acetylene；Preferably, C1-C8Alcohol is methanol, ethyl alcohol
With at least one of propyl alcohol (more preferably ethyl alcohol)；Preferably, the inorganic carbonaceous compound is carbon monoxide.Relative to first
Alkane, above-mentioned alcohol have the characteristics that cracking temperature is lower as carbon source, are more advantageous to synthesis dendritic crystalline carbon nanotube.
Method according to the present invention, this method can also include: to continue after synthesizing dendritic crystalline multi-walled carbon nanotube
It is passed through carrier gas, is then cooled down, wherein introduction has been carried out above for the type of the carrier gas, and details are not described herein.In addition,
Above-mentioned cooling can be furnace cooling.
Method according to the present invention, this method can also include: to be divided carbon nanotube obtained and catalyst
From, wherein separation method may include: to impregnate sample obtained in the hydrochloric acid of 10-20 weight % and be ultrasonically treated 1-
Then 3h is successively filtered, washed and is dried.It filters, washing and the mode dried are various routines well known in the art
Method.
Third aspect present invention provides the carbon nanotube of above method preparation.
Carbon nanotube produced by the present invention is dendritic crystalline multi-walled carbon nanotube, stronger, the dendritic crystalline carbon nanotube of rigidity
Resistivity can be 15-25 Ω cm, preferably 16.2-17.1 Ω cm, thermal conductivity can be up to 20-35W/mK, excellent
It is selected as 30.2-32.9W/mK, tensile strength can be up to 0.4-0.8GPa, preferably 0.72-0.78GPa, and elasticity modulus can
To be up to 250-350GPa, preferably 310-330GPa.I.e. the obtained carbon nanotube of the present invention has rigidity, and with excellent point
Dissipate the performances such as property, stability, thermal conductivity and electric conductivity.
Fourth aspect present invention provides above-mentioned carbon nanotube in lithium ion battery conductive agent, conductive plastics and conductive filler
In application.
The present invention will be described in detail by way of examples below.
Embodiment 1
The present embodiment is for illustrating carbon nanotube and its preparation method and application of the invention.
(1) coprecipitation prepares catalyst:
By nickel nitrate solution (1M), calcium nitrate solution (0.55M), magnesium nitrate solution (3M), ammonium molybdate solution (0.15M) and
Manganese nitrate solution (0.2M) mixing, preparation obtain water solution A, wherein nickel nitrate solution, calcium nitrate solution, magnesium nitrate solution, molybdenum
The dosage of acid ammonium solution and manganese nitrate solution makes the molar ratio of Ni:Mo:Ca:Mn:Mg in the water solution A prepared be 20:1:3:
2:60；Urea liquid (2M) and ammonium fluoride solution (2M) are mixed in equal volume, preparation obtains aqueous solution B.Then, by water solution A
It pours into the port grinding bottle of 1000ml, is put into after closeing the lid in baking oven coprecipitated in 130 DEG C of heat preservation 5h progress with after aqueous solution B mixing
It forms sediment and reacts, the catalyst precursor washing and drying that reaction is obtained, then 550 DEG C of heat preservation 8h are calcined in air atmosphere,
Catalyst A1 can be obtained by obtained sample is levigate again, scanning electron microscope (SEM) photograph is as shown in Figure 4 and Figure 5.
(2) chemical vapour deposition technique synthesizing carbon nanotubes
A. catalyst A1 made from the step of taking 0.05g (1) is evenly laid out to burn boat bottom, is encased in tube furnace, to
The mixed gas (volume ratio 5:100, throughput control are 200ml/min) for leading to hydrogen and argon gas in tube furnace, by 10 DEG C/
The rate of min is warming up to 650 DEG C from room temperature and keeps the temperature 60min；
B. the throughput of the mixed gas of hydrogen and argon gas is switched to 50ml/min, temperature is warming up to 720 DEG C, then
The mixed gas (volume ratio 5:100, throughput control are 350ml/min) that dehydrated alcohol and argon gas are passed through into tube furnace is protected
Warm 45min takes out sample in 10 weight % wait be cooled to room temperature in the case where being only passed through argon gas by sample furnace cooling after heat preservation
Hydrochloric acid in impregnate and be ultrasonically treated 1h, then sample filtering and washing is dried, obtains dendritic crystalline carbon nanotube B1.
Embodiment 2
The present embodiment is for illustrating carbon nanotube and its preparation method and application of the invention.
(1) coprecipitation prepares catalyst:
By iron nitrate solution (0.5M), calcium nitrate solution (0.1M), magnesium nitrate solution (2M), ammonium molybdate solution (0.1M) and
Manganese nitrate solution (0.2M) mixing, preparation obtain water solution A, wherein iron nitrate solution, calcium nitrate solution, magnesium nitrate solution, molybdenum
The dosage of acid ammonium solution and manganese nitrate solution makes the molar ratio of Fe:Mo:Ca:Mn:Mg in the water solution A prepared be 20:1:3:
2:60；3h is stood after ammonia spirit (concentration 28wt%) to its pH=8 is slowly added dropwise into water solution A.Then, it will obtain
Presoma washing and drying is precipitated, then 650 DEG C of heat preservation 5h are calcined in air atmosphere, then can be obtained obtained sample is levigate
To catalyst A2.
(2) chemical vapour deposition technique synthesizing carbon nanotubes
A. catalyst A2 made from the step of taking 0.05g (1) is evenly laid out to burn boat bottom, is encased in tube furnace, to
The mixed gas (volume ratio 10:100, throughput control are 110ml/min) for leading to hydrogen and argon gas in tube furnace, by 10 DEG C/
The rate of min is warming up to 650 DEG C from room temperature and keeps the temperature 60min；
B. the throughput of the mixed gas of hydrogen and argon gas is switched to 30ml/min, temperature is warming up to 800 DEG C, then
Mixed gas (volume ratio 5:100, throughput control are 210ml/min) heat preservation of methane and argon gas is passed through into tube furnace
60min takes out sample 10 weight %'s wait be cooled to room temperature in the case where being only passed through argon gas by sample furnace cooling after heat preservation
1h is impregnated and be ultrasonically treated in hydrochloric acid, then dries sample filtering and washing, obtains dendritic crystalline carbon nanotube B2.
Embodiment 3
The present embodiment is for illustrating carbon nanotube and its preparation method and application of the invention.
(1) coprecipitation prepares catalyst:
By cobalt nitrate solution (0.5M), calcium nitrate solution (0.1M), magnesium nitrate solution (2M), ammonium molybdate solution (0.15M)
With manganese nitrate solution (0.2M) mix, preparation obtain water solution A, wherein cobalt nitrate solution, calcium nitrate solution, magnesium nitrate solution,
The dosage of ammonium molybdate solution and manganese nitrate solution makes the molar ratio of Co:Ca:Mg:Mo:Mn in the water solution A prepared be 20:3:
60:1:2；It prepares urea liquid (3M) and is used as aqueous solution B.Then, pour into 1000ml's after water solution A and aqueous solution B being mixed
It in port grinding bottle, is put into after closeing the lid in baking oven and carries out coprecipitation reaction in 110 DEG C of heat preservation 6h, before the catalyst that reaction is obtained
Body washing and drying is driven, then 550 DEG C of heat preservation 8h are calcined in air atmosphere, then levigate can be obtained of obtained sample is urged
Agent A3.
(2) chemical vapour deposition technique synthesizing carbon nanotubes
A. catalyst A3 made from the step of taking 0.05g (1) is evenly laid out to burn boat bottom, is encased in tube furnace, to
The mixed gas (volume ratio 5:100, throughput control are 200ml/min) for leading to hydrogen and argon gas in tube furnace, by 10 DEG C/
The rate of min is warming up to 650 DEG C from room temperature and keeps the temperature 60min；
B. the throughput of the mixed gas of hydrogen and argon gas is switched to 50ml/min, temperature is warming up to 710 DEG C, then
Mixed gas (volume ratio 10:100, throughput control are 150ml/min) heat preservation of acetylene and argon gas is passed through into tube furnace
45min takes out sample 10 weight %'s wait be cooled to room temperature in the case where being only passed through argon gas by sample furnace cooling after heat preservation
1h is impregnated and be ultrasonically treated in hydrochloric acid, then dries sample filtering and washing, obtains dendritic crystalline carbon nanotube B3.
Embodiment 4
The present embodiment is for illustrating carbon nanotube and its preparation method and application of the invention.
Catalyst A4 and carbon nanotube B4 are prepared according to the method for embodiment 1, unlike, by the nitric acid in embodiment 1
Calcium replaces with barium nitrate.
Embodiment 5
The present embodiment is for illustrating carbon nanotube and its preparation method and application of the invention.
Prepare catalyst A5 and carbon nanotube B5 according to the method for embodiment 1, unlike, by nickel nitrate solution (1M),
Calcium nitrate solution (0.55M), ammonium molybdate solution (0.15M) and manganese nitrate solution (0.2M) mixing, preparation obtain water solution A,
In, nickel nitrate solution, calcium nitrate solution, ammonium molybdate solution and manganese nitrate solution dosage make Ni in the water solution A prepared:
The molar ratio of Mo:Ca:Mn is 20:1:3:2.
Embodiment 6
The present embodiment is for illustrating carbon nanotube and its preparation method and application of the invention.
Prepare catalyst A6 and carbon nanotube B6 according to the method for embodiment 1, unlike, by nickel nitrate solution (1M),
Calcium nitrate solution (0.55M), magnesium nitrate solution (3M) and manganese nitrate solution (0.2M) mixing, preparation obtain water solution A, wherein
Nickel nitrate solution, calcium nitrate solution, magnesium nitrate solution, ammonium molybdate solution and manganese nitrate solution dosage make the aqueous solution prepared
The molar ratio of Ni:Ca:Mn:Mg is 20:3:2:60 in A.
Embodiment 7
The present embodiment is for illustrating carbon nanotube and its preparation method and application of the invention.
Catalyst A7 and carbon nanotube B7 are prepared according to the method for embodiment 1, unlike, nickel nitrate solution, calcium nitrate
Solution, magnesium nitrate solution, ammonium molybdate solution and manganese nitrate solution dosage make Ni:Mo:Ca:Mn:Mg in the water solution A prepared
Molar ratio be 20:1:6:2:60.
Embodiment 8
The present embodiment is for illustrating carbon nanotube and its preparation method and application of the invention.
Catalyst A8 and carbon nanotube B8 are prepared according to the method for embodiment 1, unlike, nickel nitrate solution, calcium nitrate
Solution, magnesium nitrate solution, ammonium molybdate solution and manganese nitrate solution dosage make Ni:Mo:Ca:Mn:Mg in the water solution A prepared
Molar ratio be 5:5:3:2:60.
Embodiment 9
The present embodiment is for illustrating carbon nanotube and its preparation method and application of the invention.
Catalyst A9 and carbon nanotube B9 are prepared according to the method for embodiment 1, unlike, in step (1), in air gas
The lower 400 DEG C of heat preservations 8h of atmosphere is calcined.
Comparative example 1
Prepare catalyst D1 and carbon nanotube DD1 according to the method for embodiment 1, unlike, by nickel nitrate solution (1M),
Magnesium nitrate solution (3M) and ammonium molybdate solution (0.15M) mixing, preparation obtain water solution A, wherein nickel nitrate solution, magnesium nitrate
The dosage of solution and ammonium molybdate solution makes the molar ratio of Ni:Mo:Mg in the water solution A prepared be 20:1:60.
Comparative example 2
Catalyst D2 and carbon nanotube DD2 are prepared according to the method for embodiment 3, unlike, by cobalt nitrate solution
(0.5M), magnesium nitrate solution (2M) and ammonium molybdate solution (0.15M) mixing, preparation obtain water solution A, wherein cobalt nitrate solution,
The dosage of magnesium nitrate solution and ammonium molybdate solution makes the molar ratio of Co:Mo:Mg in the water solution A prepared be 20:1:60.
Test case
Carbon made from embodiment 1 and comparative example 1 is observed using JY/T 010-1996 analytic type scanning electron microscope method
The exterior appearance of nanotube sample, the SEM figure of embodiment 1 are shown in that Fig. 1, the SEM figure of comparative example 1 are shown in Fig. 3.
It is formed using the element of carbon nanotube-sample made from JSM-7600F model X-ray energy spectrometer detection embodiment 1,
Measurement result is shown in Fig. 2 a and 2b.
According to the mean wall number of carbon nanotube made from evaluation method measurement embodiment 1-9 and comparative example 1-2, the estimation side
Method are as follows: use single-wall carbon tube theoretical specific surface area (1315m2/ g) divided by the test specific surface area of practical carbon pipe it can estimate carbon
The wall number of nanotube；According to being averaged for carbon nanotube made from scanning electron microscopic observation method measurement embodiment 1-9 and comparative example 1-2
Pipe range is surveyed according to the average diameter of carbon nanotube made from scanning electron microscopic observation method measurement embodiment 1-9 and comparative example 1-2
Determining result see the table below 1.
According to the specific surface area of carbon nanotube made from nitrogen adsorption-desorption method measurement embodiment 1-9 and comparative example 1-2, survey
Determining result see the table below 1.
The resistivity of carbon nanotube made from embodiment 1-9 and comparative example 1-2 is measured according to GB/T 6615-1986 method,
1:47.5 will be pressed by embodiment 1-9 and the resulting carbon nanotube of comparative example 1-2, LiFePO 4, binder and solvent respectively:
The weight ratio of 1.5:50 is uniformly mixed, and the film at 100 μ m-thicks is then smeared on the polyimides (PI) with a thickness of 80 μm, is dried
It is dry, then resistivity is measured using the test method in GB/T 6615-1986, wherein binder PVDF, solvent
For N- Jia base Bi Ka Wan ketone (NMP).
The thermal conductivity of carbon nanotube made from embodiment 1-9 and comparative example 1-2 is measured according to ASTM E1461 standard method,
The tensile strength that carbon nanotube made from embodiment 1-9 and comparative example 1-2 is measured according to GB/T 3362-2005 method, according to
GB/T 3362-2005 method measures the elasticity modulus of carbon nanotube made from embodiment 1-9 and comparative example 1-2, and measurement result is equal
It see the table below 2.
Table 1
Table 2
Can be seen that carbon nanotube produced by the present invention by the comparison of Fig. 1 and 3 is a kind of dendritic structures, carbon nanometer
The rigidity of pipe is stronger, and carbon nanotube-sample made from comparative example 1 shows apparent flexible tubular structure, therefore, the present invention
Carbon nanotube be different from traditional carbon nanotube structure.In addition, passing through the EDS Surface scan figure and member of carbon nanotube in Fig. 2
Plain distribution map, which can be seen that, only has two kinds of elements of C, O in the carbon nanotube of synthesis, therefore, the carbon nanotube that the present invention synthesizes is pure
It spends higher.
Can be seen that by the result of table 1 and use the mean wall number of carbon nanotube of the present invention to be 20-80, average to manage
Length can be 1-20 μm, and draw ratio can be 1:0.005-0.1, and average pipe range and draw ratio are less than the prior art, in addition, this
The specific surface area of invention carbon nanotube can be 20-90m2/ g, bulk density can be 0.1-0.5g/cm3.Therefore, with existing carbon
Nanotube is compared, and carbon nanotube of the invention has more excellent performance, especially has lesser average pipe range and draw ratio.
It can be 15-25 Ω cm, the heat of the carbon nanotube by the resistivity that the data of table 2 can be seen that the carbon nanotube
Conductance can be up to 20-35W/mK, and the tensile strength of the carbon nanotube can be up to 0.4-0.8GPa, the carbon nanotube
Elasticity modulus can be up to 250-350GPa, i.e., carbon nanotube of the invention has the preferable performances such as conductive, thermally conductive.This hair
Bright carbon nanotube obtained, can be in lithium ion battery conductive agent, conductive plastics due to above-mentioned various excellent properties
It is applied in conductive filler.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (19)
1. a kind of carbon nanotube, which is characterized in that the carbon nanotube is dendritic crystalline multi-walled carbon nanotube.
2. carbon nanotube according to claim 1, wherein the mean wall number of multi-walled carbon nanotube is 20-80, preferably
20-50, more preferably 20-40；
It is further preferred that the average pipe range of the carbon nanotube is 1-20 μm, preferably 1-10 μm, more preferably 3-4.5 μm；
It is further preferred that the draw ratio of the carbon nanotube be 1:0.005-0.1, preferably 1:0.01-0.1, more preferably
1:0.02-0.05.
3. carbon nanotube according to claim 1 or 2, wherein the specific surface area of the carbon nanotube is 20-90m2/ g, it is excellent
It is selected as 30-80m2/ g, more preferably 40-60m2/g；
It is further preferred that the bulk density of the carbon nanotube is 0.1-0.5g/cm3, preferably 0.1-0.3g/cm3, more excellent
It is selected as 0.15-0.25g/cm3。
4. carbon nanotube described in any one of -3 according to claim 1, wherein the resistivity of the carbon nanotube is 15-
25 Ω cm, preferably 16.2-17.1 Ω cm；The thermal conductivity of the carbon nanotube is 20-35W/mK, preferably 30.2-
32.9W/mK, the tensile strength of the carbon nanotube are 0.4-0.8GPa, preferably 0.72-0.78GPa, the carbon nanotube
Elasticity modulus be 250-350GPa, preferably 310-330GPa.
5. a kind of method for preparing carbon nanotube, this method are chemical vapour deposition technique, which is characterized in that the chemical vapor deposition
Catalyst used in area method contains the first metal oxide and/or the second metal oxide, and first metal is manganese, described
Second metal is calcium and/or barium.
6. according to the method described in claim 5, wherein, the catalyst also contains third metal oxide, the third gold
Belong to is at least one of magnesium, iron, cobalt, nickel, yttrium, copper, platinum, palladium, vanadium, niobium, tungsten, chromium, iridium, titanium and molybdenum, preferably iron, cobalt and nickel
At least one of and magnesium and molybdenum, further preferably nickel, magnesium and molybdenum, it is highly preferred that the molar ratio of nickel, magnesium and molybdenum is 10-
20:50-100:0.1-5。
7. method according to claim 5 or 6, wherein with elemental metal, the first metal oxide and in catalyst
The molar ratio of two metal oxides is 1:0.1-10, preferably 1:0.5-5, more preferably 1:1-2.5；
With elemental metal, the molar ratio of the first metal oxide and third metal oxide is 1:1-100 in catalyst, preferably
For 1:20-80, more preferably 1:40-80.
8. according to the method described in claim 7, wherein, the catalyst is pellet type catalyst；
The preparation method of the catalyst is coprecipitation；The coprecipitation includes:
(1) water solution A of the salt containing the first metal, the second metal and third metal is prepared；
(2) the aqueous solution B containing coprecipitator is prepared；
(3) coprecipitation reaction is carried out after mixing water solution A and aqueous solution B, obtains catalyst precursor；
(4) catalyst precursor that step (3) obtains is calcined.
9. according to the method described in claim 8, wherein, in step (2), the coprecipitator is ammonium hydroxide, ammonium carbonate, bicarbonate
At least one of ammonium, urea and ammonium fluoride；
Preferably, the coprecipitator is urea and ammonium fluoride, and the molar ratio of urea and ammonium fluoride is 1:0.1-5；
Preferably, the coprecipitator is at least one of ammonium hydroxide, ammonium carbonate and ammonium hydrogen carbonate.
10. according to the method described in claim 9, wherein, in step (3), when coprecipitator is ammonium hydroxide, ammonium carbonate and bicarbonate
When at least one of ammonium, the coprecipitation reaction is implemented and the pH value of solution is adjusted to 8-9；
When coprecipitator is urea and ammonium fluoride, the coprecipitation reaction is by keeping the temperature 1-6h at 100-150 DEG C for solution
And implement.
11. the method according to any one of claim 8-10, wherein in step (4), the condition packet of the calcining
Include: temperature is 500-850 DEG C, preferably 550-650 DEG C；Time is 1-10h, preferably 5-8h.
12. the method according to any one of claim 5-11, wherein the chemical vapour deposition technique includes:
(a) mixed gas of reducing gas and carrier gas is passed through in the reactor equipped with catalyst and carries out reduction treatment；
(b) mixed gas of carbon source and carrier gas is passed through in reactor and keeps the temperature 0.5-2h at 650-820 DEG C, dendritic crystalline is made
Multi-walled carbon nanotube.
13. according to the method for claim 12, wherein in step (a), the temperature control program packet of the reduction treatment
It includes: being kept the temperature after being at the uniform velocity warming up to 650-820 DEG C；
The rate of the heating be 5-15 DEG C/min, preferably 8-12 DEG C/min；
The time of the heat preservation is 0.5-2h, preferably 1-1.5h.
14. according to the method for claim 12, wherein in step (a), the reducing gas is hydrogen；
The carrier gas is inert gas, it is preferable that the carrier gas is at least one of helium, argon gas and nitrogen, further excellent
It is selected as argon gas.
15. according to the method for claim 12, wherein in step (b), the carbon source is selected from C1-C5Hydrocarbon, C1-C8Alcohol
With inorganic carbonaceous compound；
Preferably, C1-C5Hydrocarbon is at least one of methane, ethane, ethylene, propylene and acetylene；
Preferably, C1-C8Alcohol is at least one of methanol, ethyl alcohol and propyl alcohol, more preferably ethyl alcohol；
Preferably, the inorganic carbonaceous compound is carbon monoxide.
16. according to the method for claim 12, wherein in step (a), the volume ratio of reducing gas and carrier gas is 1-20:
100, preferably 5-10:100；
Preferably, relative to 0.05g catalyst, reducing gas and the flow of carrier gas mixed gas are 60-250ml/ in step (a)
Min, preferably 110-200ml/min.
17. according to the method for claim 12, wherein in step (b), the volume ratio of carbon source and carrier gas is 1-20:100,
Preferably 5-10:100；
Preferably, relative to 0.05g catalyst, the flow of carbon source and carrier gas mixed gas is 100-400ml/ in step (b)
Min, preferably 150-350ml/min.
18. the carbon nanotube of the preparation of method described in any one of claim 5-17.
19. carbon nanotube described in any one of claim 1-4 and 18 is in lithium ion battery conductive agent, conductive plastics and leads
Application in electric filler.
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| CN110694633A (en) * | 2019-10-22 | 2020-01-17 | 北京大学 | CVD preparation method of single-walled carbon nanotube |
| CN113169302A (en) * | 2019-03-28 | 2021-07-23 | 日本瑞翁株式会社 | Conductive material paste for lithium ion secondary battery electrode, slurry composition for lithium ion secondary battery electrode, electrode for lithium ion secondary battery, and lithium ion secondary battery |
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| CN110694633A (en) * | 2019-10-22 | 2020-01-17 | 北京大学 | CVD preparation method of single-walled carbon nanotube |
| CN113398972A (en) * | 2021-06-17 | 2021-09-17 | 佛山市诺蓝环保科技有限公司 | Carbon nano tube loaded transition metal oxide catalyst and preparation method thereof |
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| CN114345369A (en) * | 2022-01-12 | 2022-04-15 | 万华化学集团股份有限公司 | Acetyl oxidation catalyst, preparation method thereof and method for preparing vinyl acetate |
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| CN116281957B (en) * | 2023-04-04 | 2023-10-20 | 重庆中润新材料股份有限公司 | Preparation method of narrow-diameter distribution semiconductor single-walled carbon nanotube |
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