CN106783230A - A kind of titanium carbide growth in situ CNTs three-dimensional composite materials and preparation method thereof - Google Patents
A kind of titanium carbide growth in situ CNTs three-dimensional composite materials and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the preparing technical field of nano-functional material, particularly a kind of titanium carbide growth in situ CNTs three-dimensional composite materials and preparation method thereof, take titanium carbide nano-powder and are added in ultra-pure water first, and Co (NO are added after being uniformly dispersed3)2·6H2O, carries out liquid phase reactor；Liquid phase reactor terminates to add urea in backward reaction solution, and lasting stirring at a constant temperature evaporates moisture, obtains precursor powder；Wherein, titanium carbide nano-powder, Co (NO3)2·6H2The mass ratio of O and urea is (0.2~1.0)：(0.1~0.4)：(3.0~30.0)；By precursor powder it is levigate after be heat-treated, obtain titanium carbide growth in situ CNTs three-dimensional composite materials.Using titanium carbide as carrier, cobalt prepares three-dimensional composite material, it is possible to increase Ti to the present invention as carbon source as catalyst, urea using simple pyrolysismethod3C2Chemical property.
Description
【Technical field】
The invention belongs to the preparing technical field of nano-functional material, a kind of particularly titanium carbide growth in situ CNTs
Three-dimensional composite material and preparation method thereof.
【Background technology】
Recently, a class is referred to as the discovery of the material of MXene and extends the group of two-dimensional material, i.e. transition metal carbide
Or carbonitride, its structure is similar with Graphene.MXene materials by corroding the A layers of element removed in MAX phases, and can keep
MX structures originally are constant and obtain, such as Ti3C2、Ti2C etc..MXene is with its high conductivity, bigger serface, sandwich construction, good
Good chemical stability and environment friendly, have very in fields such as lithium ion battery, ultracapacitor, photocatalysis and sensors
Big application potential.In adsorbing domain, the research such as Peng shows the Ti of alkali metal intercalation3C2To toxic heavy metal Pb2+Have excellent
Absorption property, can be used for effectively purifying drinking water.Ti3C2The activated hydroxyl groups that enrich of absorption property and its surface and big
Specific surface area is closely related, big with adsorbance, and the rate of adsorption is fast, and sensitivity is high and the characteristics of reversible adsorption.Ti3C2To Pb2 +Adsorption capacity will not be subject to solution in other high concentration ions (such as Ca2+、Mg2+Deng) influence.Ti3C2With the layer of its uniqueness
Shape structure is expected to give play to huge effect at aspects such as improvement harmful ion, heavy metal and organic pollutions.As new storage
Energy material, on lithium ion battery and ultracapacitor, the research for MXenes in recent years also has a lot.Naguib etc. will
Ti2CTxIt is applied on LIBs electrodes, under the multiplying power of C/25, its specific capacity is 225mAhg-1；80 cycle charge discharges are carried out with 1C
After electricity, it fills specific capacity for 110mAhg-1；After carrying out 120 cycle charge-discharges with 3C, its specific capacity is 80mAhg-1；With 10C
After carrying out 200 cycle charge-discharges, its charging capacity is 70mAhg-1.MXene nano materials itself good electric conductivity and two dimension
Layer structure is the source of its electrochemical performance.But Ti3C2Nano material self-conductive and specific capacity are relatively low, cause
Its chemical property is not good enough, and the application of MXene based electrochemical capacitors also needs further to be probed into.
CNT is typical One-dimensional Quantum material, with good conduction, mechanics, thermal property and very high
Environmental stability (resistance to strong acid, alkali corrosion) and structural stability, make its lithium ion battery, ultracapacitor, sensor and
The fields such as ripple are inhaled to have a wide range of applications.Because CNT has superior electricity and mechanical property, it is considered to be composite wood
The preferable addition phase of material.CNT has huge application to dive as strengthening phase and conductive phase in field of nanocomposite materials
Power.
Zhao etc. prepares flexible sandwich-like MXene/CNT extrusion coating papers by alternately filtering MXene and CNT dispersion system
Electrode, contrasts the MXene/CNT paper that pure MXene is mixed to get with CNT arbitrary proportions, and the chemical property of the electrode is significantly carried
It is high.Yan etc. is by Ti3C2It is immersed in dimethyl sulfoxide (DMSO) through magnetic agitation, interval be ultrasonically treated etc. that a series of processes obtain Ti3C2
Thin slice, commercial CNTs is obtained stablizing suspension by ultrasonically treated, then by Ti3C2Thin slice is with CNTs by ultrasonically treated with not
Homogenous quantities ratio is sufficiently mixed, and then filters mixed liquor, is dried to obtain Ti3C2/ CNT composites；But the price of commercialization CNTs
Compare high.
【The content of the invention】
It is an object of the invention to overcome problems of the prior art, there is provided a kind of titanium carbide growth in situ CNTs tri-
Dimension composite and preparation method thereof, using lower-cost urea as carbon source, prepares titanium carbide growth in situ CNTs three-dimensional
Composite, it is possible to increase Ti3C2The chemical property of nano material.
In order to achieve the above object, the present invention is adopted the following technical scheme that：
Preparation method of the invention is comprised the following steps：
(1) Ti is taken first3C2Nano-powder is added in ultra-pure water, and Co (NO are added after being uniformly dispersed3)2·6H2O, enters
Row liquid phase reactor；
(2) liquid phase reactor terminates to add urea in backward reaction solution, and lasting stirring at a constant temperature evaporates moisture, obtains
To precursor powder；Wherein, Ti3C2Nano-powder, Co (NO3)2·6H2The mass ratio of O and urea is (0.2~1.0)：(0.1~
0.4)：(3.0~30.0)；
(3) precursor powder is heat-treated, is obtained titanium carbide growth in situ CNTs three-dimensional composite materials.
Further, Ti in step (1)3C2Ultrasonic disperse 30min adds Co during nano-powder adds ultra-pure water
(NO3)2·6H2O。
Further, Ti in step (1)3C2The ratio between nano-powder and the ultra-pure water of addition are (200~1000) mg：(100
~400) mL.
Further, the liquid phase reactor of step (1) is that 2~6h is stirred at room temperature.
Further, the steady temperature in step (2) is between 60~100 DEG C.
Further, Ti3C2Nano-powder, Co (NO3)2·6H2The mass ratio of O and urea is (0.2~0.5)：(0.1~
0.4)：(3.0~30.0).
Further, the heat treatment in step (3) is carried out under the protection of Ar.
Further, the heat treatment temperature in step (3) is 600~1000 DEG C, and the time is 0.5~2h.
Further, the heating rate of heat treatment is 3~5 DEG C/min in step (3).
One kind is using titanium carbide growth in situ CNTs three-dimensional composite materials obtained in preparation method as described above.
Compared with prior art, the present invention has following beneficial technique effect：
, using titanium carbide as carrier, cobalt is used as catalyst, Co for the present invention2+Ion by with titanium carbide surface oxygen functional group
Ion exchange adsorb on titanium carbide surface；Then, add the urea of low cost as carbon source, urea by with titanium carbide
The Co on surface2+Ion forms complex and inserts the lamella of titanium carbide.Finally, it is pyrolyzed under argon atmosphere, with temperature
Rising, Co2+The catalyst that Co nano particles grow as CNTs is reduced to, and urea is decomposed into carbonitride, carbonitride exists
CNTs is grown under the catalysis of Co, Ti is controlled by changing the content of urea in presoma3C2The CNTs length of superficial growth and
Density.The present invention prepares Ti using simple pyrolysismethod3C2@CNTs three-dimensional composite materials, this method can low cost, it is quick,
Environmental protection, the content by changing urea in presoma of safety, so as to realize Ti3C2The controllable life of surface C NTs length and density
It is long.Intensive CNTs is evenly distributed on Ti3C2Lamella both sides, significantly improve the specific surface area of stratified material and increase lamella
Between distance, and improve Ti3C2Electric conductivity and magnetic so that Ti3C2The chemical property of@CNTs three-dimensional composite materials is more
Better than pure Ti3C2.And for its application further in fields such as lithium ion battery, photocatalysis, suction ripples is laid a good foundation.This
Outward, this simple pyrolysismethod is advantageously implemented industrialization due to its advantage such as low for equipment requirements, easy to operate, with low cost
Large-scale production.
Ti of the present invention3C2@CNTs three-dimensional composite materials are by two-dimensional layer Ti3C2And it is grown on Ti3C2The distribution on surface is close
Degree multi-walled carbon nano-tubes composition high, electron propagation ducts are provided using CNT, improve the conductance of material, and Ti3C2Can
The transmittability between CNT is improved, so as to efficiently solve one-dimensional CNT and two dimension Ti3C2Heat with electric transmission
Conductibility outside directional dependence and relatively low face, makes composite all have good electrical property in three dimensions.Present invention system
Standby three-dimensional composite material has important use value in electrochemical energy storage materials, absorbing material and catalyst carrier etc..
Search document, it is found that not yet someone is in Ti so far3C2Surface in situ grows CNT, and realizes Ti3C2Surface CNT
Controllable growth.
【Brief description of the drawings】
Fig. 1 is Ti prepared by embodiment 23C2@CNTs6.0SEM figures (a) and XRD (b) of three-dimensional composite material.
Fig. 2 is Ti prepared by embodiment 23C2@CNTs6.0Three-dimensional composite material (a) sweeps speed (0.002V/s-0.1V/ in difference
S) the CV curve maps under；B () is its capacity with the change curve for sweeping speed.
Fig. 3 is Ti obtained in embodiment 1-3 difference pyrolysis temperatures3C2@CNTs6.0The SEM figures of three-dimensional composite material, wherein
A () is 800 DEG C, (b) is 900 DEG C, and (c) is 1000 DEG C.
【Specific embodiment】
The present invention is described in further details with embodiment below in conjunction with the accompanying drawings.
Preparation method of the present invention is comprised the following steps：
(1) ternary layered Ti3AlC2The preparation of ceramic powder；
According to the method synthesis of ternary stratiform Ti of patent ZL201310497696.93AlC2Ceramic powder, its preparation process tool
Body includes：First, it is TiC according to mol ratio by experimental raw TiC, Ti, Al powders：Ti：Al=2.0：1.0：1.2 are mixed
Material；Secondly, by batch mixing, aluminum oxide ballstone and absolute ethyl alcohol according to 1：3：1 mass ratio in carrying out ball milling in corundum ball grinder, its
Middle absolute ethyl alcohol is abrasive media as ball-milling additive, aluminum oxide ballstone, and drum's speed of rotation is 300r/min, after wet ball grinding 4h
24h is dried in 40 DEG C of freeze-day with constant temperature baking ovens；Then, dry batch mixing is put into corundum crucible, in vacuum hotpressing carbon shirt-circuiting furnace
Vacuum non-pressure sintering is carried out with the heating rate of 8 DEG C/min, 1350 DEG C are heated to, 1h, vacuum ＜ 10 is incubated-2Pa, insulation knot
Cool to room temperature after beam with the furnace；Finally, to the powder dry method high-energy ball milling 2h after sintering, rotating speed is 400r/min, powder and ball
Stone ratio is 1：10, levigate powder is carried out into 400 mesh sievings, you can obtain Ti of the particle diameter less than 38 μm3AlC2Ceramic powder.
(2) two-dimensional layer Ti3C2The preparation of nano material；
Method according to patent 201410812056.7 prepares two-dimensional layer Ti3C2Nano material, its preparation process is specifically wrapped
Include:By Ti prepared in 5g steps (1)3AlC2Powder is slowly immersed in 100mL 40wt.% hydrofluoric acid solutions, at room temperature
Magnetic agitation 24h, rotating speed is 1200r/min, and corrosion product is centrifuged, 4500r/min ultra-pure water eccentric cleanings
It is about 6 to supernatant pH value, then with washes of absolute alcohol 5 times, the 24h drying in 40 DEG C of vacuum drying chambers by gained sediment,
Obtain two-dimensional layer Ti3C2Nano-powder.
(3)Ti3C2The preparation of@CNTs three-dimensional composite materials；
First, by 200-500mg steps (2) gained Ti3C2Nano-powder, is added in 100~400mL ultra-pure waters, ultrasound
Dispersion 30min；Then, 0.1~0.4g Co (NO are added3)2·6H2O, is stirred at room temperature 2~6h；Or by 200~
500mgTi3C2Nano-powder is 7.8~8.2mmolL in 100~400mL concentration-1Co (NO3)2·6H2In O solution, room temperature
Stirring 2-6h；
Secondly, 3.0~30.0g urea is added, the lasting stirring evaporation under 60~100 DEG C of steady temperatures by above-mentioned mixed liquor
Fall moisture, obtain grey presoma；
Finally, by precursor powder with agate mortar it is levigate after, be transferred in Ar atmosphere tube furnaces, with the liter of 3~5 DEG C/min
Warm speed is heated to 600~1000 DEG C, is pyrolyzed 0.5~2h, is taken out after being cooled to normal temperature under the protection of Ar, you can obtain Ti3C2@
CNTs three-dimensional composite materials.
Embodiment 1
First, by the Ti of 300mg3C2Nano-powder, is added in 200mL ultra-pure waters, ultrasonic disperse 30min；Then, plus
Enter 0.29g Co (NO3)2·6H2O, is stirred at room temperature 4h, completes liquid phase reactor；Secondly, 6.0g urea is added, by above-mentioned mixed liquor
Lasting stirring evaporates moisture under 80 DEG C of steady temperatures, obtains grey presoma；Finally, by precursor powder agate mortar
After levigate, it be transferred in Ar atmosphere tube furnaces and be heat-treated, 800 DEG C are heated to the heating rate of 4 DEG C/min, is pyrolyzed 1h,
Taken out after normal temperature is cooled under the protection of Ar, you can obtain Ti3C2@CNTs three-dimensional composite materials.
By 50-200mg step 3 gained Ti3C2@CNTs nano-powders are with conductive carbon black and binding agent (PTFE) with 80:15:
5 mass ratio mixing, grinding 10-15min forms uniform purees in agate mortar.Secondly, above-mentioned purees is rolled into thin
Film, and 1cm*1cm is cut into, then it is bonded in the nickel foam of 2cm*1cm sizes, it is subsequently placed into vacuum drying chamber, 80 DEG C
Under dry 24h.Finally, by dried electrode slice under press, Ti is obtained in 20Mpa pressurizes 1min3C2@CNTs electrodes.
Embodiment 2
First, by the Ti of 300mg3C2Nano-powder, is added in 200mL ultra-pure waters, ultrasonic disperse 30min；Then, plus
Enter 0.29g Co (NO3)2·6H2O, is stirred at room temperature 4h；Secondly, 6.0g urea is added, by above-mentioned mixed liquor in 80 DEG C of steady temperatures
Lower lasting stirring evaporates moisture, obtains grey presoma；Finally, by precursor powder with agate mortar it is levigate after, be transferred to Ar
In atmosphere tube furnace, 900 DEG C are heated to the heating rate of 4 DEG C/min, are pyrolyzed 1h, taken after being cooled to normal temperature under the protection of Ar
Go out, you can obtain Ti3C2@CNTs three-dimensional composite materials.Fig. 1 is gained Ti3C2@CNTs6.0The SEM figures and XRD of three-dimensional composite material
Figure.It can be seen that intensive CNTs is evenly distributed on Ti3C2Lamella both sides, significantly improve specific surface area and the increasing of stratified material
The big distance of piece interlayer so that Ti3C2The performances such as the chemical property and suction ripple of@CNTs three-dimensional composite materials are better than pure
Ti3C2。
Ti3C2@CNTs6.0The preparation of electrode；
First, by 100mg Ti obtained as above3C2@CNTs6.0Nano-powder is with conductive carbon black and binding agent (PTFE) with 80:
15:5 mass ratio mixing, grinding 15min forms uniform purees in agate mortar.Secondly, above-mentioned purees is rolled
Into film, and 1cm*1cm is cut into, is then bonded in the nickel foam of 2cm*1cm sizes, be subsequently placed into vacuum drying chamber,
24h is dried at 80 DEG C.Finally, by dried electrode slice under press, Ti is respectively obtained in 20Mpa pressurizes 1min3C2@
CNTs6.0Electrode.
Again, using three electrode test systems, electrode slice (working electrode) and platinum electrode (to electrode), the silver-colored chlorine that will be made
Change silver electrode (reference electrode) and easy ultracapacitor is assembled into electrolytic cell, wherein electrolyte is that 6mol/L KOH are molten
Liquid, Ti is tested using Shanghai Chen Hua CHI660E electrochemical workstations3C2@CNTs6.0The chemical property of electrode, such as cyclic voltammetric
Characteristic curve, constant current charge-discharge, AC impedance and cycle life.Shown in Fig. 2, (a) is Ti3C2@CNTs6.0Speed is swept in difference
CV curve maps under (0.002V/s-0.1V/s), as we can see from the figure CV curve maps represent that its is good close to the rectangle of standard
Good capacitive property, (b) is its capacity with the change curve for sweeping speed, it can be seen that when speed is swept for 0.05V/s, its capacity is purer
Ti3C2There is great lifting.
Embodiment 3
First, by 300mg Ti3C2Nano-powder, is added in 200mL ultra-pure waters, ultrasonic disperse 30min；Then, add
0.29g Co(NO3)2·6H2O, is stirred at room temperature 4h；Secondly, 6.0g urea is added, by above-mentioned mixed liquor under 80 DEG C of steady temperatures
Lasting stirring evaporates moisture, obtains grey presoma；Finally, by precursor powder with agate mortar it is levigate after, be transferred to Ar atmosphere
Enclose in tube furnace, 1000 DEG C are heated to the heating rate of 4 DEG C/min, be pyrolyzed 1h, taken after being cooled to normal temperature under the protection of Ar
Go out, you can obtain Ti3C2@CNTs three-dimensional composite materials.
Embodiment 4
First, by 300mg Ti3C2Nano-powder, is added in 200mL ultra-pure waters, ultrasonic disperse 30min；Then, add
0.29g Co(NO3)2·6H2O, is stirred at room temperature 4h；Secondly, 6.0g urea is added, by above-mentioned mixed liquor under 80 DEG C of steady temperatures
Lasting stirring evaporates moisture, obtains grey presoma；Finally, by precursor powder with agate mortar it is levigate after, be transferred to Ar atmosphere
Enclose in tube furnace, 900 DEG C are heated to the heating rate of 4 DEG C/min, be pyrolyzed 0.5h, taken after being cooled to normal temperature under the protection of Ar
Go out, you can obtain Ti3C2@CNTs three-dimensional composite materials.
Embodiment 5
First, by 300mg Ti3C2Nano-powder, is added in 200mL ultra-pure waters, ultrasonic disperse 30min；Then, add
0.29g Co(NO3)2·6H2O, is stirred at room temperature 4h；Secondly, 6.0g urea is added, by above-mentioned mixed liquor under 80 DEG C of steady temperatures
Lasting stirring evaporates moisture, obtains grey presoma；Finally, by precursor powder with agate mortar it is levigate after, be transferred to Ar atmosphere
Enclose in tube furnace, 900 DEG C are heated to the heating rate of 4 DEG C/min, be pyrolyzed 1.5h, taken after being cooled to normal temperature under the protection of Ar
Go out, you can obtain Ti3C2@CNTs three-dimensional composite materials.
Embodiment 6
First, by 300mg Ti3C2Nano-powder, is added in 200mL ultra-pure waters, ultrasonic disperse 30min；Then, add
0.29g Co(NO3)2·6H2O, is stirred at room temperature 4h；Secondly, 6.0g urea is added, by above-mentioned mixed liquor under 80 DEG C of steady temperatures
Lasting stirring evaporates moisture, obtains grey presoma；Finally, by precursor powder with agate mortar it is levigate after, be transferred to Ar atmosphere
Enclose in tube furnace, 900 DEG C are heated to the heating rate of 4 DEG C/min, be pyrolyzed 2h, taken after being cooled to normal temperature under the protection of Ar
Go out, you can obtain Ti3C2@CNTs three-dimensional composite materials.
Embodiment 7
First, by 300mg Ti3C2Nano-powder, is added in 200mL ultra-pure waters, ultrasonic disperse 30min；Then, add
0.29g Co(NO3)2·6H2O, is stirred at room temperature 4h；Secondly, 3.0g urea is added, by above-mentioned mixed liquor under 80 DEG C of steady temperatures
Lasting stirring evaporates moisture, obtains grey presoma；Finally, by precursor powder with agate mortar it is levigate after, be transferred to Ar atmosphere
Enclose in tube furnace, 900 DEG C are heated to the heating rate of 4 DEG C/min, be pyrolyzed 1h, taken after being cooled to normal temperature under the protection of Ar
Go out, you can obtain Ti3C2@CNTs three-dimensional composite materials.
Embodiment 8
First, by 300mg Ti3C2Nano-powder, is added in 200mL ultra-pure waters, ultrasonic disperse 30min；Then, add
0.29g Co(NO3)2·6H2O, is stirred at room temperature 4h；Secondly, 15.0g urea is added, by above-mentioned mixed liquor in 80 DEG C of steady temperatures
Lower lasting stirring evaporates moisture, obtains grey presoma；Finally, by precursor powder with agate mortar it is levigate after, be transferred to Ar
In atmosphere tube furnace, 900 DEG C are heated to the heating rate of 4 DEG C/min, are pyrolyzed 1h, taken after being cooled to normal temperature under the protection of Ar
Go out, you can obtain Ti3C2@CNTs three-dimensional composite materials.
Embodiment 9
First, by 200mg Ti3C2Nano-powder, is added in 100mL ultra-pure waters, ultrasonic disperse 30min；Then, add
0.1g Co(NO3)2·6H2O, is stirred at room temperature 2h；Secondly, 20.0g urea is added, by above-mentioned mixed liquor under 60 DEG C of steady temperatures
Lasting stirring evaporates moisture, obtains grey presoma；Finally, by precursor powder with agate mortar it is levigate after, be transferred to Ar atmosphere
Enclose in tube furnace, 600 DEG C are heated to the heating rate of 3 DEG C/min, be pyrolyzed 0.5h, taken after being cooled to normal temperature under the protection of Ar
Go out, you can obtain Ti3C2@CNTs three-dimensional composite materials.
Embodiment 10
First, by 500mg Ti3C2Nano-powder, is added in 300mL ultra-pure waters, ultrasonic disperse 30min；Then, add
0.2g Co(NO3)2·6H2O, is stirred at room temperature 3h；Secondly, 30.0g urea is added, by above-mentioned mixed liquor in 100 DEG C of steady temperatures
Lower lasting stirring evaporates moisture, obtains grey presoma；Finally, by precursor powder with agate mortar it is levigate after, be transferred to Ar
In atmosphere tube furnace, 700 DEG C are heated to the heating rate of 5 DEG C/min, 1.5h are pyrolyzed, after being cooled to normal temperature under the protection of Ar
Take out, you can obtain Ti3C2@CNTs three-dimensional composite materials.
Embodiment 11
First, by 1000mg Ti3C2Nano-powder, is added in 400mL ultra-pure waters, ultrasonic disperse 30min；Then, plus
Enter 0.4g Co (NO3)2·6H2O, is stirred at room temperature 6h；Secondly, 10.0g urea is added, by above-mentioned mixed liquor in 90 DEG C of steady temperatures
Lower lasting stirring evaporates moisture, obtains grey presoma；Finally, by precursor powder with agate mortar it is levigate after, be transferred to Ar
In atmosphere tube furnace, 850 DEG C are heated to the heating rate of 4 DEG C/min, are pyrolyzed 1h, taken after being cooled to normal temperature under the protection of Ar
Go out, you can obtain Ti3C2@CNTs three-dimensional composite materials.
Embodiment 12
Control presoma in urea content be respectively 3.0g, 6.0g ... .30.0g, other conditions are with embodiment 1.
Result proves, the present invention is capable of achieving Ti by controlling urea content in presoma3C2Surface length of carbon nanotube and
The regulation and control of density, Ti3C2Surface length of carbon nanotube is in 100~900nm.
In addition, being obtained by embodiment 1-3, with the rising of pyrolysis temperature, length of carbon nanotube gradually rises to and has grown
Entirely, as shown in Fig. 3 contrasts.
The present invention provides one kind Ti3C2@CNTs three-dimensional composite materials and preparation method thereof, first, synthesis of high purity fine grain
The ternary layered Ti of grain3AlC2Powder；Selective etch falls ternary layered Ti in HF solution3AlC2In Al layers, formed two-dimensional layer
Shape Ti3C2Nano material.Secondly, with Ti3C2Nano material is matrix, Co is catalyst, Co2+Ion by with Ti3C2Surface contains
The ion exchange of oxygen functional group is adsorbed in Ti3C2Surface；Then, add urea as carbon source, urea by with Ti3C2Table
The Co in face2+Ion forms complex and inserts Ti3C2Lamella in.Finally, using simple pyrolysismethod heat under argon atmosphere
Solution, with the rising of temperature, Co2+The catalyst that Co nano particles grow as CNTs is reduced to, and urea is decomposed into nitridation
Carbon, carbonitride is grown to CNTs under the catalysis of Co.The present invention successfully prepares Ti by simple pyrolysismethod3C2@CNTs are three-dimensional multiple
Condensation material, improves Ti3C2Electric conductivity, expand Ti3C2Specific surface area, improve Ti3C2Self stability etc., and by control
Urea content in presoma, is capable of achieving Ti3C2The regulation and control of surface length of carbon nanotube and density；This is for extension Ti3C2Material exists
The application in the fields such as ultracapacitor, lithium ion battery, nano adsorber and suction ripple, has important practical significance.Compared to institute
Other preparation methods are reported, the experiment condition needed for the inventive method is fairly simple, low cost is easy to operate.In Ti3C2Give birth on surface
CNT is grown, electron propagation ducts are provided using CNT, improve the conductance of material, and Ti3C2Carbon nanometer can be improved
Transmittability between pipe, so as to efficiently solve one-dimensional CNT and two dimension Ti3C2Heat and the directional dependence of electric transmission
With conductibility outside relatively low face, make composite that all there is good electrical property in three dimensions.
Claims (10)
1. a kind of preparation method of titanium carbide growth in situ CNTs three-dimensional composite materials, it is characterised in that comprise the following steps：
(1) Ti is taken first3C2Nano-powder is added in ultra-pure water, and Co (NO are added after being uniformly dispersed3)2·6H2O, carries out liquid
Phase reaction；
(2) liquid phase reactor terminates to add urea in backward reaction solution, and lasting stirring at a constant temperature evaporates moisture, before obtaining
Drive body powder；Wherein, Ti3C2Nano-powder, Co (NO3)2·6H2The mass ratio of O and urea is (0.2~1.0)：(0.1~
0.4)：(3.0~30.0)；
(3) precursor powder is heat-treated, is obtained titanium carbide growth in situ CNTs three-dimensional composite materials.
2. a kind of preparation method of titanium carbide growth in situ CNTs three-dimensional composite materials according to claim 1, its feature
It is, Ti in step (1)3C2Ultrasonic disperse 30min adds Co (NO during nano-powder adds ultra-pure water3)2·6H2O。
3. a kind of preparation method of titanium carbide growth in situ CNTs three-dimensional composite materials according to claim 1, its feature
It is, Ti in step (1)3C2The ratio between nano-powder and ultra-pure water are (200~1000) mg：(100~400) mL.
4. a kind of preparation method of titanium carbide growth in situ CNTs three-dimensional composite materials according to claim 1, its feature
It is that the liquid phase reactor of step (1) is that 2~6h is stirred at room temperature.
5. a kind of preparation method of titanium carbide growth in situ CNTs three-dimensional composite materials according to claim 1, its feature
It is that the steady temperature in step (2) is between 60~100 DEG C.
6. a kind of preparation method of titanium carbide growth in situ CNTs three-dimensional composite materials according to claim 1, its feature
It is, Ti3C2Nano-powder, Co (NO3)2·6H2The mass ratio of O and urea is (0.2~0.5)：(0.1~0.4)：(3.0~
30.0)。
7. a kind of preparation method of titanium carbide growth in situ CNTs three-dimensional composite materials according to claim 1, its feature
It is that the heat treatment in step (3) is carried out under the protection of Ar.
8. a kind of preparation method of titanium carbide growth in situ CNTs three-dimensional composite materials according to claim 1, its feature
It is that the heat treatment temperature in step (3) is 600~1000 DEG C, the time is 0.5~2h.
9. a kind of preparation method of titanium carbide growth in situ CNTs three-dimensional composite materials according to claim 1, its feature
It is that the heating rate of heat treatment is 3~5 DEG C/min in step (3).
10. titanium carbide growth in situ CNTs three-dimensional composite materials obtained in the preparation method described in a kind of utilization claim 1.
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