CN106783230B - A kind of titanium carbide growth in situ CNTs three-dimensional composite material and preparation method thereof - Google Patents
A kind of titanium carbide growth in situ CNTs three-dimensional composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the preparation technical fields of nano-functional material, and particularly a kind of titanium carbide growth in situ CNTs three-dimensional composite material and preparation method thereof, takes titanium carbide nano-powder to be added in ultrapure water first, Co (NO is added after being uniformly dispersed3)2·6H2O carries out liquid phase reactor；Urea is added in liquid phase reactor into reaction solution after terminating, lasting stirring evaporates moisture at a constant temperature, 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 material.The present invention using titanium carbide as carrier, prepare three-dimensional composite material as catalyst, urea as carbon source, using simple pyrolysismethod, can be improved Ti by cobalt3C2Chemical property.
Description
【Technical field】
The invention belongs to the preparation 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 technique】
Recently, the discovery of a kind of material for being referred to as MXene extends the group of two-dimensional material, i.e. transition metal carbide
Or carbonitride, structure are similar with graphene.MXene material can remove the A layer element in MAX phase by corrosion, and keep
MX structure originally is constant and obtains, such as Ti3C2、Ti2C etc..MXene is with its high conductivity, bigger serface, multilayered structure, good
Good chemical stability and environment friendly, has very in fields such as lithium ion battery, supercapacitor, photocatalysis and sensors
Big application potential.In adsorbing domain, Peng etc. research shows that alkali metal intercalation Ti3C2To toxic heavy metal Pb2+Have excellent
Absorption property, can be used for effectively purifying drinking water.Ti3C2Absorption property and its surface activated hydroxyl groups abundant and greatly
The characteristics of specific surface area is closely related, has large amount of adsorption, and the rate of adsorption is fast, high sensitivity and reversible adsorption.Ti3C2To Pb2 +Adsorption capacity not will receive other high concentration ions (such as Ca in solution2+、Mg2+Deng) influence.Ti3C2With its unique layer
Shape structure be expected to administer harmful ion, heavy metal and in terms of play huge effect.As novel storage
Energy material in recent years also has much the research of MXenes on lithium ion battery and supercapacitor.Naguib etc. will
Ti2CTxApplied on LIBs electrode, under the multiplying power of C/25, specific capacity 225mAhg-1；80 cycle charge discharges are carried out with 1C
After electricity, filling specific capacity is 110mAhg-1；After carrying out 120 cycle charge-discharges with 3C, specific capacity 80mAhg-1；With 10C
After carrying out 200 cycle charge-discharges, charging capacity 70mAhg-1.The good electric conductivity of MXene nano material itself and two dimension
Layer structure is the source of its electrochemical performance.However 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 capacitor also needs further to be probed into.
Carbon nanotube is typical One-dimensional Quantum material, has good conduction, mechanics, thermal property and very high
Environmental stability (resistance to strong acid, alkali corrosion) and structural stability, make its lithium ion battery, supercapacitor, sensor and
The fields such as wave are inhaled to have a wide range of applications.Since carbon nanotube has superior electricity and mechanical property, it is considered to be composite wood
The ideal addition phase of material.Carbon nanotube has huge application latent as strengthening phase and conductive phase, in field of nanocomposite materials
Power.
Zhao etc. prepares flexible sandwich-like MXene/CNT extrusion coating paper by alternately filtering MXene and CNT dispersion system
Electrode, compares the MXene/CNT paper that pure MXene and CNT arbitrary proportion are mixed to get, and the chemical property of the electrode significantly mentions
It is high.Yan etc. is by Ti3C2It is immersed in dimethyl sulfoxide and obtains Ti through a series of processes such as magnetic agitation, interval ultrasonic treatments3C2
Commercial CNTs is obtained stablizing suspension, then by Ti by thin slice by ultrasonic treatment3C2Thin slice and CNTs are by being ultrasonically treated with not
Homogenous quantities ratio is sufficiently mixed, and is then filtered mixed liquor, is dried to obtain Ti3C2/ CNT composite material；But the price of commercialization CNTs
It is relatively high.
【Summary of the invention】
It is an object of the invention to overcome problems of the prior art, a kind of titanium carbide growth in situ CNTs tri- is provided
Composite material and preparation method is tieed up, using lower-cost urea as carbon source, it is three-dimensional to prepare titanium carbide growth in situ CNTs
Composite material can be improved Ti3C2The chemical property of nano material.
In order to achieve the above object, the present invention adopts the following technical scheme that：
Preparation method of the invention includes the following steps：
(1) Ti is taken first3C2Nano-powder is added in ultrapure water, and Co (NO is added after being uniformly dispersed3)2·6H2O, into
Row liquid phase reactor；
(2) urea is added after liquid phase reactor terminates into reaction solution, lasting stirring evaporates moisture at a constant temperature, 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, obtains titanium carbide growth in situ CNTs three-dimensional composite material.
Further, Ti in step (1)3C2Nano-powder is added ultrasonic disperse 30min in ultrapure water and adds Co
(NO3)2·6H2O。
Further, Ti in step (1)3C2The ratio between nano-powder and the ultrapure 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) carries 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 being heat-treated in step (3) is 3~5 DEG C/min.
It is a kind of to utilize titanium carbide growth in situ CNTs three-dimensional composite material made from preparation method as described above.
Compared with prior art, the invention has the following beneficial technical effects：
The present invention is using titanium carbide as carrier, and cobalt is as catalyst, Co2+Ion by with titanium carbide surface oxygen functional group
Ion exchange be adsorbed on titanium carbide surface；Then, urea at low cost is added as carbon source, urea by with titanium carbide
The Co on surface2+Ion forms complex and is inserted into the lamella of titanium carbide.Finally, being pyrolyzed under argon atmosphere, with temperature
Raising, Co2+It is reduced to the catalyst that Co nano particle is grown as CNTs, and urea is decomposed into carbonitride, carbonitride exists
It is grown to CNTs under the catalysis of Co, controls Ti by changing the content of urea in presoma3C2Surface growth CNTs length and
Density.The present invention prepares Ti using simple pyrolysismethod3C2@CNTs three-dimensional composite material, this method can low cost, it is quick,
Environmental protection, the safe content by changing urea in presoma, to realize Ti3C2The controllable life of surface C NTs length and density
It is long.Intensive CNTs is evenly distributed on Ti3C2Lamella two sides significantly improve the specific surface area of stratified material and increase lamella
Between distance, and improve Ti3C2Electric conductivity and magnetism so that Ti3C2The chemical property of@CNTs three-dimensional composite material is more
Better than pure Ti3C2.And it lays a good foundation for its application further in fields such as lithium ion battery, photocatalysis, suction waves.This
Outside, this simple pyrolysismethod is advantageously implemented industrialization due to its advantage such as low for equipment requirements, easy to operate, low in cost
Large-scale production.
Ti of the present invention3C2@CNTs three-dimensional composite material is by two-dimensional layer Ti3C2And it is grown on Ti3C2The distribution on surface is close
High multi-walled carbon nanotube composition is spent, provides electron propagation ducts using carbon nanotube, improves the conductivity of material, and Ti3C2It can
The transmittability between carbon nanotube is improved, to efficiently solve one-dimensional carbon nanotube and two dimension Ti3C2Heat with electron-transport
Conductibility outside directional dependence and lower face, makes composite material all have good electrical property in three-dimensional space.System of the present invention
Standby three-dimensional composite material is upper with important use value in electrochemical energy storage materials, absorbing material and catalyst carrier etc..
Document is searched for, it is found that not yet someone is in Ti so far3C2Surface in situ grows carbon nanotube, and realizes Ti3C2Surface carbon nanotube
Controllable growth.
【Detailed description of the invention】
Fig. 1 is Ti prepared by embodiment 23C2@CNTs6.0The SEM figure (a) and XRD diagram (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 graph under；It (b) is its capacity with the change curve for sweeping speed.
Fig. 3 is Ti made from embodiment 1-3 difference pyrolysis temperature3C2@CNTs6.0The SEM of three-dimensional composite material schemes, wherein
(a) it is 800 DEG C, (b) is 900 DEG C, (c) is 1000 DEG C.
【Specific embodiment】
The present invention is described in further details with embodiment with reference to the accompanying drawing.
Preparation method of the present invention includes 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, preparation step tool
Body includes：Firstly, by experimental raw TiC, Ti, Al powder according to molar ratio be TiC：Ti：Al=2.0：1.0：1.2 are mixed
Material；Secondly, by mixing, aluminium oxide ballstone and dehydrated alcohol according to 1：3：1 mass ratio in carrying out ball milling in corundum ball grinder,
For middle dehydrated alcohol as ball-milling additive, aluminium oxide ballstone is abrasive media, after drum's speed of rotation 300r/min, wet ball grinding 4h
It is dried for 24 hours in 40 DEG C of freeze-day with constant temperature baking ovens；Then, dry 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, is heated to 1350 DEG C, keeps the temperature 1h, vacuum degree < 10-2Pa, heat preservation knot
Cool to room temperature after beam with the furnace；Finally, to sintered powder dry method high-energy ball milling 2h, revolving speed 400r/min, powder and ball
Stone ratio is 1：10, levigate powder is subjected to 400 mesh sievings, Ti of the partial size less than 38 μm can be obtained3AlC2Ceramic powder.
(2) two-dimensional layer Ti3C2The preparation of nano material；
Two-dimensional layer Ti is prepared according to the method for patent 201410812056.73C2Nano material, preparation step are specifically wrapped
It includes:By Ti prepared in 5g step (1)3AlC2Powder is slowly immersed in 100mL 40wt.% hydrofluoric acid solution, at room temperature
For 24 hours, corrosion product is centrifuged revolving speed 1200r/min magnetic agitation, 4500r/min ultrapure water eccentric cleaning
It is about 6 to supernatant pH value, then with washes of absolute alcohol 5 times, gained sediment is dried for 24 hours in 40 DEG C of vacuum ovens,
Obtain two-dimensional layer Ti3C2Nano-powder.
(3)Ti3C2The preparation of@CNTs three-dimensional composite material；
Firstly, by Ti obtained by 200-500mg step (2)3C2Nano-powder is added in 100~400mL ultrapure water, ultrasound
Disperse 30min；Then, 0.1~0.4g Co (NO is added3)2·6H22~6h is stirred at room temperature in O；Either by 200~
500mgTi3C2Nano-powder is 7.8~8.2mmolL in 100~400mL concentration-1Co (NO3)2·6H2In O solution, room temperature
Stir 2-6h；
Secondly, 3.0~30.0g urea is added, the persistently stirring evaporation under 60~100 DEG C of steady temperatures by above-mentioned mixed liquor
Fall moisture, obtains grey presoma；
Finally, by precursor powder agate mortar it is levigate after, be transferred in Ar atmosphere tube furnace, with the liter of 3~5 DEG C/min
Warm rate is heated to 600~1000 DEG C, is pyrolyzed 0.5~2h, takes out after room temperature is cooled under the protection of Ar, can obtain Ti3C2@
CNTs three-dimensional composite material.
Embodiment 1
Firstly, by the Ti of 300mg3C2Nano-powder is added in 200mL ultrapure water, ultrasonic disperse 30min；Then, add
Enter 0.29g Co (NO3)2·6H24h is stirred at room temperature in O, completes liquid phase reactor；Secondly, 6.0g urea is added, by above-mentioned mixed liquor
Persistently stirring evaporates moisture under 80 DEG C of steady temperatures, obtains grey presoma；Finally, by precursor powder agate mortar
It after levigate, be transferred in Ar atmosphere tube furnace and be heat-treated, be heated to 800 DEG C with the heating rate of 4 DEG C/min, be pyrolyzed 1h,
It is taken out after being cooled to room temperature under the protection of Ar, Ti can be obtained3C2@CNTs three-dimensional composite material.
By Ti obtained by 50-200mg step 33C2@CNTs nano-powder and conductive carbon black and binder (PTFE) are with 80:15:
5 mass ratio mixing grinds 10-15min in the agate mortar and forms uniform purees.Secondly, above-mentioned purees is rolled into thin
Film, and it is cut into 1cm*1cm, it is then sticked in the nickel foam of 2cm*1cm size, is subsequently placed into vacuum oven, 80 DEG C
Lower drying is for 24 hours.Finally, obtaining Ti in 20Mpa pressure maintaining 1min by dried electrode slice under press3C2@CNTs electrode.
Embodiment 2
Firstly, by the Ti of 300mg3C2Nano-powder is added in 200mL ultrapure water, ultrasonic disperse 30min；Then, add
Enter 0.29g Co (NO3)2·6H24h is stirred at room temperature in O；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 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, 1h is pyrolyzed, is taken after room temperature is cooled under the protection of Ar
Out, Ti can be obtained3C2@CNTs three-dimensional composite material.Fig. 1 is gained Ti3C2@CNTs6.0The SEM of three-dimensional composite material schemes and XRD
Figure.It can be seen that intensive CNTs is evenly distributed on Ti3C2Lamella two sides significantly improve the specific surface area and increasing of stratified material
The big distance of piece interlayer, so that Ti3C2The performances such as the chemical property and suction wave of@CNTs three-dimensional composite material are better than pure
Ti3C2。
Ti3C2@CNTs6.0The preparation of electrode；
Firstly, by 100mg Ti obtained as above3C2@CNTs6.0Nano-powder and conductive carbon black and binder (PTFE) are with 80:
15:5 mass ratio mixing, grinding grinding 15min forms uniform purees in the agate mortar.Secondly, above-mentioned purees is rolled
At film, and it is cut into 1cm*1cm, is then sticked in the nickel foam of 2cm*1cm size, is subsequently placed into vacuum oven,
It is dried for 24 hours at 80 DEG C.Finally, respectively obtaining Ti in 20Mpa pressure maintaining 1min by dried electrode slice under press3C2@
CNTs6.0Electrode.
Again, using three electrode test systems, by the electrode slice (working electrode) of production and platinum electrode (to electrode), silver-colored chlorine
Change silver electrode (reference electrode) and be assembled into easy supercapacitor in electrolytic cell, wherein electrolyte is that 6mol/L KOH is molten
Liquid tests Ti using Shanghai Chen Hua CHI660E electrochemical workstation3C2@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 graph under (0.002V/s-0.1V/s), CV curve graph indicates that its is good close to the rectangle of standard as we can see from the figure
Good capacitive property is (b) its capacity with the change curve for sweeping speed, it can be seen that when sweeping speed is 0.05V/s, capacity is purer
Ti3C2There is great promotion.
Embodiment 3
Firstly, by 300mg Ti3C2Nano-powder is added in 200mL ultrapure water, ultrasonic disperse 30min；Then, it is added
0.29g Co(NO3)2·6H24h is stirred at room temperature in O；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 agate mortar it is levigate after, be transferred to Ar atmosphere
It encloses in tube furnace, is heated to 1000 DEG C with the heating rate of 4 DEG C/min, is pyrolyzed 1h, is taken after room temperature is cooled under the protection of Ar
Out, Ti can be obtained3C2@CNTs three-dimensional composite material.
Embodiment 4
Firstly, by 300mg Ti3C2Nano-powder is added in 200mL ultrapure water, ultrasonic disperse 30min；Then, it is added
0.29g Co(NO3)2·6H24h is stirred at room temperature in O；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 agate mortar it is levigate after, be transferred to Ar atmosphere
It encloses in tube furnace, is heated to 900 DEG C with the heating rate of 4 DEG C/min, is pyrolyzed 0.5h, is taken after room temperature is cooled under the protection of Ar
Out, Ti can be obtained3C2@CNTs three-dimensional composite material.
Embodiment 5
Firstly, by 300mg Ti3C2Nano-powder is added in 200mL ultrapure water, ultrasonic disperse 30min；Then, it is added
0.29g Co(NO3)2·6H24h is stirred at room temperature in O；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 agate mortar it is levigate after, be transferred to Ar atmosphere
It encloses in tube furnace, is heated to 900 DEG C with the heating rate of 4 DEG C/min, is pyrolyzed 1.5h, is taken after room temperature is cooled under the protection of Ar
Out, Ti can be obtained3C2@CNTs three-dimensional composite material.
Embodiment 6
Firstly, by 300mg Ti3C2Nano-powder is added in 200mL ultrapure water, ultrasonic disperse 30min；Then, it is added
0.29g Co(NO3)2·6H24h is stirred at room temperature in O；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 agate mortar it is levigate after, be transferred to Ar atmosphere
It encloses in tube furnace, is heated to 900 DEG C with the heating rate of 4 DEG C/min, is pyrolyzed 2h, is taken after room temperature is cooled under the protection of Ar
Out, Ti can be obtained3C2@CNTs three-dimensional composite material.
Embodiment 7
Firstly, by 300mg Ti3C2Nano-powder is added in 200mL ultrapure water, ultrasonic disperse 30min；Then, it is added
0.29g Co(NO3)2·6H24h is stirred at room temperature in O；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 agate mortar it is levigate after, be transferred to Ar atmosphere
It encloses in tube furnace, is heated to 900 DEG C with the heating rate of 4 DEG C/min, is pyrolyzed 1h, is taken after room temperature is cooled under the protection of Ar
Out, Ti can be obtained3C2@CNTs three-dimensional composite material.
Embodiment 8
Firstly, by 300mg Ti3C2Nano-powder is added in 200mL ultrapure water, ultrasonic disperse 30min；Then, it is added
0.29g Co(NO3)2·6H24h is stirred at room temperature in O；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 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, 1h is pyrolyzed, is taken after room temperature is cooled under the protection of Ar
Out, Ti can be obtained3C2@CNTs three-dimensional composite material.
Embodiment 9
Firstly, by 200mg Ti3C2Nano-powder is added in 100mL ultrapure water, ultrasonic disperse 30min；Then, it is added
0.1g Co(NO3)2·6H22h is stirred at room temperature in O；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 agate mortar it is levigate after, be transferred to Ar atmosphere
It encloses in tube furnace, is heated to 600 DEG C with the heating rate of 3 DEG C/min, is pyrolyzed 0.5h, is taken after room temperature is cooled under the protection of Ar
Out, Ti can be obtained3C2@CNTs three-dimensional composite material.
Embodiment 10
Firstly, by 500mg Ti3C2Nano-powder is added in 300mL ultrapure water, ultrasonic disperse 30min；Then, it is added
0.2g Co(NO3)2·6H23h is stirred at room temperature in O；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 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 is pyrolyzed, after being cooled to room temperature under the protection of Ar
It takes out, Ti can be obtained3C2@CNTs three-dimensional composite material.
Embodiment 11
Firstly, by 1000mg Ti3C2Nano-powder is added in 400mL ultrapure water, ultrasonic disperse 30min；Then, add
Enter 0.4g Co (NO3)2·6H26h is stirred at room temperature in O；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 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, 1h is pyrolyzed, is taken after room temperature is cooled under the protection of Ar
Out, Ti can be obtained3C2@CNTs three-dimensional composite material.
Embodiment 12
Control presoma in urea content be respectively 3.0g, 6.0g ... .30.0g, other conditions are the same as embodiment 1.
The results show that the present invention is by urea content in control presoma, it can be achieved that Ti3C2Surface length of carbon nanotube and
The regulation of density, Ti3C2Surface length of carbon nanotube is in 100~900nm.
In addition, being obtained by embodiment 1-3, with the raising of pyrolysis temperature, length of carbon nanotube, which gradually rises to, have been grown
Entirely, as shown in Fig. 3 comparison.
The present invention provides Ti a kind of3C2@CNTs three-dimensional composite material and preparation method thereof, firstly, synthesis high-purity fine grain
The ternary layered Ti of grain3AlC2Powder；Selective etch falls ternary layered Ti in HF solution3AlC2In Al layer, 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 on Ti3C2Surface；Then, urea is added as carbon source, urea by with Ti3C2Table
The Co in face2+Ion forms complex and is inserted into Ti3C2Lamella in.Finally, using simple pyrolysismethod heat under argon atmosphere
Solution, as the temperature rises, Co2+It is reduced to the catalyst that Co nano particle is grown as CNTs, and urea is decomposed into nitridation
Carbon, carbonitride are grown to CNTs under the catalysis of Co.The present invention successfully prepares Ti by simple pyrolysismethod3C2@CNTs three-dimensional is multiple
Condensation material improves Ti3C2Electric conductivity, expand Ti3C2Specific surface area, improve Ti3C2Self stability etc., and pass through control
Urea content in presoma is, it can be achieved that Ti3C2The regulation of surface length of carbon nanotube and density；This is for extending Ti3C2Material exists
Supercapacitor, lithium ion battery, nano adsorber and the application for inhaling the fields such as wave, have important practical significance.Compared to institute
Report other preparation methods, experiment condition needed for the method for the present invention is fairly simple, and it is at low cost, it is easy to operate.In Ti3C2Surface is raw
Carbon nanotube is grown, electron propagation ducts is provided using carbon nanotube, improves the conductivity of material, and Ti3C2Carbon nanometer can be improved
Transmittability between pipe, to efficiently solve one-dimensional carbon nanotube and two dimension Ti3C2Heat and the directional dependence of electron-transport
With conductibility outside lower face, make composite material that all there is good electrical property in three-dimensional space.
Claims (9)
1. a kind of preparation method of titanium carbide growth in situ CNTs three-dimensional composite material, which is characterized in that comprise the steps of：
(1) Ti is taken first3C2Nano-powder is added in ultrapure water, and Co (NO is added after being uniformly dispersed3)2·6H2O carries out liquid
Phase reaction；
(2) urea is added after liquid phase reactor terminates into reaction solution, lasting stirring evaporates moisture at a constant temperature, 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, obtains titanium carbide growth in situ CNTs three-dimensional composite material；
Ti in step (1)3C2Nano-powder is added ultrasonic disperse 30min in ultrapure water and adds Co (NO3)2·6H2O。
2. a kind of preparation method of titanium carbide growth in situ CNTs three-dimensional composite material according to claim 1, feature
It is, Ti in step (1)3C2The ratio between nano-powder and ultrapure water are (200~1000) mg：(100~400) mL.
3. a kind of preparation method of titanium carbide growth in situ CNTs three-dimensional composite material according to claim 1, feature
It is, the liquid phase reactor of step (1) is that 2~6h is stirred at room temperature.
4. a kind of preparation method of titanium carbide growth in situ CNTs three-dimensional composite material according to claim 1, feature
It is, the steady temperature in step (2) is between 60~100 DEG C.
5. a kind of preparation method of titanium carbide growth in situ CNTs three-dimensional composite material according to claim 1, 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)。
6. a kind of preparation method of titanium carbide growth in situ CNTs three-dimensional composite material according to claim 1, feature
It is, the heat treatment in step (3) carries out under the protection of Ar.
7. a kind of preparation method of titanium carbide growth in situ CNTs three-dimensional composite material according to claim 1, feature
It is, the heat treatment temperature in step (3) is 600~1000 DEG C, and the time is 0.5~2h.
8. a kind of preparation method of titanium carbide growth in situ CNTs three-dimensional composite material according to claim 1, feature
It is, the heating rate being heat-treated in step (3) is 3~5 DEG C/min.
9. a kind of utilize titanium carbide growth in situ CNTs three-dimensional composite material made from preparation method described in claim 1.
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