CN106784706B - A kind of carbon microspheres are as transition zone titanium carbide growth in situ CNTs three-dimensional composite material and preparation method thereof - Google Patents
A kind of carbon microspheres are as transition zone titanium carbide growth in situ CNTs three-dimensional composite material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of carbon microspheres as transition zone titanium carbide growth in situ CNTs three-dimensional composite material and preparation method thereof, by Ti3C2Nano-powder is scattered in ultrapure water, and glucose is added after being uniformly dispersed, and is carried out hydro-thermal reaction after stirring 5~30min, is obtained Ti3C2@C composite；By Ti3C2@C composite is added in ultrapure water, and Co (NO is added after being uniformly dispersed3)2·6H2O is stirred to react 2~6h；Urea is added after reaction, and lasting stirring evaporates moisture at a constant temperature, obtains precursor powder；Precursor powder is heat-treated, obtains carbon microspheres as transition zone titanium carbide growth in situ CNTs three-dimensional composite material.Three-dimensional composite material of the present invention is in Ti3C2Surface grows carbon nanotube, provides electron propagation ducts using carbon nanotube, improves the conductivity of material.
Description
[technical field]
The invention belongs to the preparation technical fields of nano-functional material, and particularly a kind of carbon microspheres are as transition zone carbon
Change titanium 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 225mAh/g；80 cycle charge discharges are carried out with 1C
After electricity, filling specific capacity is 110mAh/g；After carrying out 120 cycle charge-discharges with 3C, specific capacity 80mAh/g；With 10C into
After 200 cycle charge-discharges of row, charging capacity 70mAh/g.The good electric conductivity of MXene nano material itself and two-dimensional layer
Shape structure is the source of its electrochemical performance.However Ti3C2Nano material self-conductive and specific capacity are relatively low, lead to it
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 carbon microspheres are provided and are carbonized as transition zone
Titanium growth in situ CNTs three-dimensional composite material and preparation method thereof, using glucose as carbon source, three-dimensional composite material obtained
Chemical property is good.
In order to achieve the above object, the present invention adopts the following technical scheme:
The following steps are included:
(1) by Ti3C2Nano-powder is scattered in ultrapure water, and glucose is added after being uniformly dispersed, after stirring 5~30min
Hydro-thermal reaction is carried out, Ti is obtained3C2@C composite；Wherein Ti3C2The mass ratio of nano-powder and glucose is (0.05~0.2):
(0.1~0.4)；
(2) by Ti3C2@C composite is added in ultrapure water, and Co (NO is added after being uniformly dispersed3)2·6H2O, stirring
React 2~6h；Urea is added after reaction, lasting stirring evaporates moisture at a constant temperature, precursor powder is obtained,
Wherein Ti3C2@C composite, Co (NO3)2·6H2The mass ratio of O and urea is (0.2~0.5): (0.1~0.4): (3.0~
30.0)；Precursor powder is heat-treated, obtains carbon microspheres as transition zone titanium carbide growth in situ CNTs three-dimensional composite wood
Material.
Further, Ti in step (1)3C2The ratio between nano-powder and ultrapure water are (50~200) mg:(10~60) mL.
Further, Ti in step (1)3C2Nano-powder is added ultrasonic disperse 30min in ultrapure water and adds glucose.
Further, in step (1) hydro-thermal reaction be 160~200 DEG C react 8~for 24 hours.
Further, every 200~500mg Ti in step (2)3C2@C composite is added to 100~400mL ultrapure water
In.
Further, the steady temperature in step (2) is between 60~100 DEG C.
Further, the heat treatment in step (2) carries out under the protection of Ar.
Further, heat treatment temperature is 600~1000 DEG C, and the time is 0.5~3h.
Further, the heating rate of heat treatment is 3~5 DEG C/min.
It is a kind of using carbon microspheres made from preparation method as described above as transition zone titanium carbide growth in situ CNTs tri-
Tie up composite material.
Compared with prior art, the invention has the following beneficial technical effects:
The invention firstly uses hydro-thermal methods to prepare Ti3C2@C composite, Ti3C2The C on surface can protect Ti3C2Structure
Integrality, and it mainly exists in the form of carbon microspheres, is evenly coated at Ti3C2Surface, by controlling hydrothermal temperature, time
And glucose content is, it can be achieved that Ti3C2The regulation of surface carbon microspheres pattern and chemical composition, carbon microspheres surface are contained a large amount of oxygen-containing
Functional group and hydrophily is very strong；Ti is then prepared using simple pyrolysismethod3C2@C@CNTs three-dimensional composite material, this method energy
Enough low costs, quick, environmental protection, the safe content by changing urea in presoma, to realize Ti3C2Surface C NTs length
And the controllable growth of density.Compared with directly in Ti3C2Surface grows CNTs and prepares Ti3C2The method of@CNTs, in Ti3C2Table
Bread covers regrowth CNTs after carbon microspheres layer, is easier to realize Ti3C2The controllable preparation of@CNTs three-dimensional composite material, and grow
CNTs mass is higher, thus Ti3C2The performances such as chemical property, absorbing property, the photocatalysis of@CNTs are also that it is further more preferably
Application in fields such as lithium ion battery, photocatalysis, suction waves is laid a good foundation.In addition, this simple pyrolysismethod is since it is to setting
It is standby to require the advantages such as low, easy to operate, low in cost, it is advantageously implemented industrialization large-scale production.Document is searched for, discovery is so far
Not yet someone is in Ti3C2Surface in situ grows carbon nanotube, and realizes Ti3C2The controllable growth of surface carbon nanotube.
Three-dimensional composite material of the present invention is by two-dimensional layer Ti3C2, transition zone carbon microspheres and be grown on Ti3C2Point on surface
The high multi-walled carbon nanotube composition of cloth density, in Ti3C2Surface grows carbon nanotube, provides electron-transport using carbon nanotube
Channel, improves the conductivity of material, and Ti3C2The transmittability between carbon nanotube can be improved, received to efficiently solve one-dimensional carbon
Mitron and two dimension Ti3C2Heat and conductibility outside the directional dependence of electron-transport and lower face, make composite material in three-dimensional space
Between all have good electrical property.Three-dimensional composite material prepared by the present invention is in electrochemical energy storage materials, absorbing material and catalysis
Agent carrier etc. is upper to have important use value.
[Detailed description of the invention]
Fig. 1 is Ti prepared by embodiment 13C2The SEM figure (a) and XRD diagram (b) of@C@CNTs three-dimensional composite material.
Fig. 2 is Ti prepared by embodiment 13C2@C@CNTs6.0 three-dimensional composite material (a) sweeps speed (0.002V/s- in difference
CV curve graph under 0.1V/s)；It (b) is its capacity with the change curve for sweeping speed.
Fig. 3 be respectively glucose additional amount be 0.4g and 0.1g when Ti3C2The SEM of@C@CNTs three-dimensional composite material schemes,
Wherein (a) is 0.4g, (b) is 0.1g.
[specific embodiment]
The present invention is described in further details with embodiment with reference to the accompanying drawing.
Above-described Ti3C2The preparation of@C@CNTs three-dimensional composite material includes the following steps:
Step 1, ternary layered Ti3AlC2The preparation of ceramic powder；
According to the method synthesis of ternary stratiform Ti of patent ZL201310497696.93AlC2Ceramic powder: firstly, will experiment
Raw material TiC, Ti, Al powder are that TiC:Ti:Al=2.0:1.0:1.2 carries out mixing according to molar ratio；Secondly, by mixing, oxidation
Aluminium ball stone and dehydrated alcohol are according to the mass ratio of 1:3:1 in carrying out ball milling in corundum ball grinder, wherein dehydrated alcohol is as ball milling
Auxiliary agent, aluminium oxide ballstone is abrasive media, in 40 DEG C of freeze-day with constant temperature baking ovens after drum's speed of rotation 300r/min, wet ball grinding 4h
Middle drying is for 24 hours；Then, dry mixing is put into corundum crucible, with the heating rate of 8 DEG C/min in vacuum hotpressing carbon shirt-circuiting furnace
Vacuum non-pressure sintering is carried out, is heated to 1350 DEG C, keeps the temperature 1h, vacuum degree < 10-2Pa cools to room temperature with the furnace after heat preservation；
Finally, revolving speed 400r/min, powder and ballstone ratio are 1:10 to sintered powder dry method high-energy ball milling 2h, it will be levigate
Powder carries out 400 mesh sievings, and Ti of the partial size less than 38 μm can be obtained3AlC2Ceramic powder.
Step 2, two-dimensional layer Ti3C2The preparation of nano material；
Two-dimensional layer Ti is prepared according to the method for patent 201410812056.73C2Nano material: by institute in 5g step (1)
The Ti of preparation3AlC2Powder is slowly immersed in 100mL 40wt.% hydrofluoric acid solution, and for 24 hours, revolving speed is magnetic agitation at room temperature
Corrosion product is centrifuged 1200r/min, and 4500r/min is about 6 with ultrapure water eccentric cleaning to supernatant pH value,
It uses washes of absolute alcohol 5 times, gained sediment is dried for 24 hours in 40 DEG C of vacuum ovens to get two-dimensional layer Ti is arrived again3C2
Nano-powder.
Step 3, Ti3C2The preparation of@C composite；
Firstly, by Ti obtained by 50~200mg step 23C2Nano-powder is added in 10~60mL ultrapure water, ultrasound point
Dissipate 30min；Then, 0.1~0.4g glucose is added, 5~30min is stirred at room temperature；Either by Ti3C2Nano-powder is added to
10~60mL concentration is 0.009~0.150mmolL-1Glucose solution in be stirred to react 5~30min.
Secondly, be transferred in 100mL water heating kettle, 160~200 DEG C of reactions 8~for 24 hours, Ti can be obtained3C2@C composite.
Step 4, Ti3C2The preparation of@C@CNTs three-dimensional composite material；
Firstly, by Ti obtained by 200~500mg step 33C2@C nano powder, is added in 100~400mL ultrapure water, surpasses
Sound disperses 30min；Then, 0.1~0.4g Co (NO is added3)2·6H22~6h is stirred at room temperature in O；Either by Ti3C2@C nano
It is 7.8~8.2mmolL that powder, which is added to 100~400mL concentration,-1Co (NO3)2·6H2In O solution, 2~6h is stirred at room temperature.
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 heating rate of 3~5 DEG C/min is heated to 600~1000 DEG C, is pyrolyzed 0.5~3h, takes after room temperature is cooled under the protection of Ar
Out, Ti can be obtained3C2@C@CNTs three-dimensional composite material.
Embodiment 1
(1)Ti3C2The preparation of@C composite；
Firstly, by the Ti of 100mg3C2Nano-powder is added in 60mL ultrapure water, ultrasonic disperse 30min；Then, it is added
0.4g glucose, is stirred at room temperature 30min；Secondly, being transferred in 100mL water heating kettle, 180 DEG C of reaction 10h can obtain Ti3C2@C is compound
Material.
(2)Ti3C2The preparation of@C@CNTs three-dimensional composite material；
Firstly, by the Ti of 300mg3C2@C nano powder, is added in 200mL ultrapure water, ultrasonic disperse 30min；Then,
0.29g Co (NO is added3)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 constant temperatures
The lower lasting stirring of degree evaporates moisture, obtains grey presoma；Finally, by precursor powder agate mortar it is levigate after, be transferred to
In Ar atmosphere tube furnace, 900 DEG C are heated to the heating rate of 4 DEG C/min, 1h is pyrolyzed, after being cooled to room temperature under the protection of Ar
It takes out, Ti can be obtained3C2@C@CNTs three-dimensional composite material.Fig. 1 is gained Ti3C2@C@CNTs three-dimensional composite material SEM figure and
XRD spectrum.It can be seen that intensive CNTs is evenly distributed on Ti3C2Lamella two sides significantly improve the specific surface area of stratified material
And the distance of piece interlayer is increased, so that Ti3C2The performances such as the chemical property and suction wave of@C@CNTs three-dimensional composite material are more excellent
In pure Ti3C2。
Ti3C2@C@CNTs6.0The preparation of electrode；
Firstly, respectively by 50-200mg Ti obtained as above3C2@C@CNTs6.0Nano-powder and conductive carbon black and binder
(PTFE) it is mixed with the mass ratio of 80:15:5, grinding grinding 15min forms uniform purees in the agate mortar.Secondly, will
Above-mentioned purees rolls into film, and is cut into 1cm*1cm, is then sticked in the nickel foam of 2cm*1cm size, is subsequently placed into true
In empty drying box, dried for 24 hours at 80 DEG C.Finally, distinguishing in 20Mpa pressure maintaining 1min by dried electrode slice under press
Obtain Ti3C2@C@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@C@CNTs6.0The chemical property of electrode, such as circulation volt
Pacify characteristic curve, constant current charge-discharge, AC impedance and cycle life.Shown in Fig. 2, (a) is Ti3C2@C@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 2
(1)Ti3C2The preparation of@C composite；
Firstly, by the Ti of 100mg3C2Nano-powder is added in 60mL ultrapure water, ultrasonic disperse 30min；Then, it is added
0.3g glucose, is stirred at room temperature 30min；Secondly, being transferred in 100mL water heating kettle, 180 DEG C of reaction 10h can obtain Ti3C2@C is compound
Material.
(2)Ti3C2The preparation of@C@CNTs three-dimensional composite material；
Firstly, by the Ti of 300mg3C2@C nano powder, is added in 200mL ultrapure water, ultrasonic disperse 30min；Then,
0.29g Co (NO is added3)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 constant temperatures
The lower lasting stirring of degree evaporates moisture, obtains grey presoma；Finally, by precursor powder agate mortar it is levigate after, be transferred to
In Ar atmosphere tube furnace, 900 DEG C are heated to the heating rate of 4 DEG C/min, 1h is pyrolyzed, after being cooled to room temperature under the protection of Ar
It takes out, Ti can be obtained3C2@C@CNTs three-dimensional composite material.
Embodiment 3
(1)Ti3C2The preparation of@C composite；
Firstly, by the Ti of 100mg3C2Nano-powder is added in 60mL ultrapure water, ultrasonic disperse 30min；Then, it is added
0.2g glucose, is stirred at room temperature 30min；Secondly, being transferred in 100mL water heating kettle, 180 DEG C of reaction 10h can obtain Ti3C2@C is compound
Material.
(2)Ti3C2The preparation of@C@CNTs three-dimensional composite material；
Firstly, by the Ti of 300mg3C2@C nano powder, is added in 200mL ultrapure water, ultrasonic disperse 30min；Then,
0.29g Co (NO is added3)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 constant temperatures
The lower lasting stirring of degree evaporates moisture, obtains grey presoma；Finally, by precursor powder agate mortar it is levigate after, be transferred to
In Ar atmosphere tube furnace, 900 DEG C are heated to the heating rate of 4 DEG C/min, 1h is pyrolyzed, after being cooled to room temperature under the protection of Ar
It takes out, Ti can be obtained3C2@C@CNTs three-dimensional composite material.
Embodiment 4
(1)Ti3C2The preparation of@C composite；
Firstly, by the Ti of 100mg3C2Nano-powder is added in 60mL ultrapure water, ultrasonic disperse 30min；Then, it is added
0.1g glucose, is stirred at room temperature 30min；Secondly, being transferred in 100mL water heating kettle, 180 DEG C of reaction 10h can obtain Ti3C2@C is compound
Material.
(2)Ti3C2The preparation of@C@CNTs three-dimensional composite material；
Firstly, by the Ti of 300mg3C2@C nano powder, is added in 200mL ultrapure water, ultrasonic disperse 30min；Then,
0.29g Co (NO is added3)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 constant temperatures
The lower lasting stirring of degree evaporates moisture, obtains grey presoma；Finally, by precursor powder agate mortar it is levigate after, be transferred to
In Ar atmosphere tube furnace, 900 DEG C are heated to the heating rate of 4 DEG C/min, 1h is pyrolyzed, after being cooled to room temperature under the protection of Ar
It takes out, Ti can be obtained3C2@C@CNTs three-dimensional composite material.
Embodiment 5
(1)Ti3C2The preparation of@C composite；
Firstly, by the Ti of 50mg3C2Nano-powder is added in 10mL ultrapure water, ultrasonic disperse 30min；Then, it is added
0.2g glucose, is stirred at room temperature 5min；Secondly, being transferred in 100mL water heating kettle, 160 DEG C of reactions for 24 hours, can obtain Ti3C2@C is compound
Material.
(2)Ti3C2The preparation of@C@CNTs three-dimensional composite material；
Firstly, by the Ti of 200mg3C2@C nano powder, is added in 100mL ultrapure water, ultrasonic disperse 30min；Then,
0.1g Co (NO is added3)2·6H22h is stirred at room temperature in O；Secondly, 3.0g urea is added, by above-mentioned mixed liquor in 60 DEG C of constant temperatures
The lower lasting stirring of degree evaporates moisture, obtains grey presoma；Finally, by precursor powder agate mortar it is levigate after, be transferred to
In Ar atmosphere tube furnace, 600 DEG C are heated to the heating rate of 3 DEG C/min, 0.5h is pyrolyzed, is cooled to room temperature under the protection of Ar
After take out, Ti can be obtained3C2@C@CNTs three-dimensional composite material.
Embodiment 6
(1)Ti3C2The preparation of@C composite；
Firstly, by the Ti of 200mg3C2Nano-powder is added in 30mL ultrapure water, ultrasonic disperse 30min；Then, it is added
0.2g glucose, is stirred at room temperature 20min；Secondly, being transferred in 100mL water heating kettle, 200 DEG C of reaction 8h can obtain Ti3C2@C is compound
Material.
(2)Ti3C2The preparation of@C@CNTs three-dimensional composite material；
Firstly, by the Ti of 500mg3C2@C nano powder, is added in 400mL ultrapure water, ultrasonic disperse 30min；Then,
0.4g Co (NO is added3)2·6H26h is stirred at room temperature in O；Secondly, 30.0g urea is added, above-mentioned mixed liquor is constant at 100 DEG C
At a temperature of persistently stirring evaporate moisture, obtain grey presoma；Finally, by precursor powder agate mortar it is levigate after, turn
Enter in Ar atmosphere tube furnace, is heated to 1000 DEG C with the heating rate of 5 DEG C/min, is pyrolyzed 3h, be cooled under the protection of Ar often
It is taken out after temperature, Ti can be obtained3C2@C@CNTs three-dimensional composite material.
Embodiment 7
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, obtained by embodiment 1-4, when glucose content it is excessively high when, Ti3C2Surface coated carbon microspheres partial size point
Cloth is extremely uneven, and since the probability that the presence of a large amount of carbon microspheres generates crosslinking increases, furthermore glucose content is excessively high is difficult to
Short time decompose completely, as shown in figure 3, wherein figure (a) be glucose additional amount be 0.4g when the case where, Fig. 3 (b) is glucose
The case where when additional amount is 0.1g.
The present invention provides a kind of carbon microspheres as transition zone Ti3C2The preparation method of@C@CNTs three-dimensional composite material, packet
It includes: the ternary layered Ti of high-purity fine grain3AlC2The synthesis of powder；Ti is handled by HF solution corrosion3AlC2Selective etch falls
Selective etch falls ternary layered Ti3AlC2In Al layer two-dimensional layer Ti is prepared3C2Nano material；First with Ti3C2As
Carrier, using glucose as carbon source, hydro-thermal method prepares Ti3C2@C, in Ti3C2One layer of carbon microspheres of coated with uniform, Ti3C2
The C on surface can protect Ti3C2The integrality of structure, and it mainly exists in the form of carbon microspheres, is evenly coated at Ti3C2Surface leads to
Control hydrothermal temperature, time and glucose content are crossed, it can be achieved that Ti3C2The regulation of surface carbon microspheres pattern and chemical composition,
With Ti3C2@C is as carrier, and a large amount of oxygen-containing functional groups are contained on carbon microspheres surface and hydrophily is very strong；Cobalt is as catalyst, Co2+From
Son by with Ti3C2And the ion exchange of carbon microspheres surface oxygen functional group is adsorbed on Ti3C2Surface；Then, urea is added
As carbon source, urea by with Ti3C2The Co on surface2+Ion forms complex and is inserted into Ti3C2Lamella in.Finally,
It is pyrolyzed under argon atmosphere, as the temperature rises, Co2+It is reduced to the catalyst that Co nano particle is grown as CNTs, and urea
It is decomposed into carbonitride, carbonitride is grown to CNTs under the catalysis of Co.With Ti3C2@C is matrix, and Co is catalyst, urea is carbon
Ti is successfully prepared using simple pyrolysismethod under argon atmosphere in source3C2@C@CNTs three-dimensional composite material, this method can it is low at
Originally, quick, environmental protection, the safe content by changing urea in presoma, to realize Ti3C2Surface C NTs length and density
Controllable growth.Comparison is directly in Ti3C2Surface grows CNTs and prepares Ti3C2The method of@CNTs, in Ti3C2Surface cladding
Regrowth CNTs after carbon microspheres layer is easier to realize Ti3C2The controllable preparation of@CNTs three-dimensional composite material, and the CNTs matter grown
Amount is higher, thus Ti3C2Also more preferably, this is for extending Ti for the performances such as chemical property, absorbing property, the photocatalysis of@CNTs3C2
Material has important practical significance in supercapacitor, lithium ion battery, nano adsorber and the application for inhaling the fields such as wave.
Compared to other preparation methods are reported, experiment condition needed for this method is fairly simple, at low cost, easy to operate.
The present invention provides a kind of carbon microspheres as transition zone Ti3C2@CNTs three-dimensional composite material and preparation method thereof, mentions
High Ti3C2Electric conductivity, expand Ti3C2Specific surface area, improve Ti3C2Self stability etc., to extend Ti3C2Material exists
Supercapacitor, lithium ion battery, nano adsorber and the application for inhaling the fields such as wave.
Claims (9)
1. a kind of preparation method of carbon microspheres as transition zone titanium carbide growth in situ CNTs three-dimensional composite material, feature exist
In, comprising the following steps:
(1) by Ti3C2Nano-powder is scattered in ultrapure water, and glucose is added after being uniformly dispersed, and is carried out after stirring 5~30min
Hydro-thermal reaction obtains Ti3C2@C composite；Wherein Ti3C2The mass ratio of nano-powder and glucose is (0.05~0.2): (0.1
~0.4)；
(2) by Ti3C2@C composite is added in ultrapure water, and Co (NO is added after being uniformly dispersed3)2·6H2O is stirred to react 2
~6h；Urea is added after reaction, lasting stirring evaporates moisture at a constant temperature, precursor powder is obtained, wherein
Ti3C2@C composite, Co (NO3)2·6H2The mass ratio of O and urea is (0.2~0.5): (0.1~0.4): (3.0~
30.0)；Precursor powder is heat-treated, obtains carbon microspheres as transition zone titanium carbide growth in situ CNTs three-dimensional composite wood
Material；
In step (1) hydro-thermal reaction be 160~200 DEG C react 8~for 24 hours.
2. a kind of carbon microspheres according to claim 1 are as transition zone titanium carbide growth in situ CNTs three-dimensional composite material
Preparation method, which is characterized in that Ti in step (1)3C2The ratio between nano-powder and ultrapure water are (50~200) mg:(10~60)
mL。
3. a kind of carbon microspheres according to claim 1 are as transition zone titanium carbide growth in situ CNTs three-dimensional composite material
Preparation method, which is characterized in that Ti in step (1)3C2Nano-powder is added ultrasonic disperse 30min in ultrapure water and adds grape
Sugar.
4. a kind of carbon microspheres according to claim 1 are as transition zone titanium carbide growth in situ CNTs three-dimensional composite material
Preparation method, which is characterized in that every 200~500mg Ti in step (2)3C2It is ultrapure that@C composite is added to 100~400mL
In water.
5. a kind of carbon microspheres according to claim 1 are as transition zone titanium carbide growth in situ CNTs three-dimensional composite material
Preparation method, which is characterized in that the steady temperature in step (2) is between 60~100 DEG C.
6. a kind of carbon microspheres according to claim 1 are as transition zone titanium carbide growth in situ CNTs three-dimensional composite material
Preparation method, which is characterized in that the heat treatment in step (2) carries out under the protection of Ar.
7. a kind of carbon microspheres according to claim 1 are as transition zone titanium carbide growth in situ CNTs three-dimensional composite material
Preparation method, which is characterized in that heat treatment temperature is 600~1000 DEG C, and the time is 0.5~3h.
8. a kind of carbon microspheres according to claim 1 are as transition zone titanium carbide growth in situ CNTs three-dimensional composite material
Preparation method, which is characterized in that the heating rate of heat treatment is 3~5 DEG C/min.
9. a kind of using carbon microspheres made from preparation method described in claim 1 as transition zone titanium carbide growth in situ CNTs
Three-dimensional composite material.
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| CN108461300B (en) * | 2018-05-11 | 2020-05-12 | 西北师范大学 | Layered titanium carbide-carbon tube composite material and preparation and application thereof |
| CN109449402A (en) * | 2018-10-29 | 2019-03-08 | 北京科技大学 | A kind of nano carbon microsphere supports preparation and its application method of MXene composite material |
| CN110735151A (en) * | 2019-06-20 | 2020-01-31 | 常州大学 | Preparation method of titanium carbide composite indium zinc sulfide photo-anode |
| CN111167498B (en) * | 2020-01-19 | 2023-08-25 | 河南师范大学 | Porous g-C 3 N 4 /Ti 3 C 2 Tx heterojunction photocatalyst and preparation method thereof |
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| CN112263974B (en) * | 2020-11-24 | 2022-04-08 | 山东大学 | Spray drying method for preparing Ti3C2Method for Tx/carbon black composite microsphere |
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