CN106784706A - A kind of carbon microspheres are used as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials and preparation method thereof - Google Patents
A kind of carbon microspheres are used as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials 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 materials and preparation method thereof, by Ti3C2Nano-powder is scattered in ultra-pure water, and glucose is added after being uniformly dispersed, and stirs the laggard water-filling thermal responses of 5~30min, obtains Ti3C2@C composites；By Ti3C2@C composites are added in ultra-pure water, and Co (NO are added after being uniformly dispersed3)2·6H2O, 2~6h of stirring reaction；Reaction adds urea after terminating, and lasting stirring at a constant temperature evaporates moisture, obtains precursor powder；Precursor powder is heat-treated, carbon microspheres is obtained as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials.Three-dimensional composite material of the present invention is in Ti3C2Superficial growth goes out CNT, and electron propagation ducts are provided using CNT, improves the conductance of material.
Description
【Technical field】
The invention belongs to the preparing technical field of nano-functional material, particularly a kind of carbon microspheres are used as transition zone carbon
Change titanium growth in situ CNTs three-dimensional composite materials 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 225mAh/g；80 cycle charge discharges are carried out with 1C
After electricity, it fills specific capacity for 110mAh/g；After carrying out 120 cycle charge-discharges with 3C, its specific capacity is 80mAh/g；Entered with 10C
After 200 cycle charge-discharges of row, its charging capacity is 70mAh/g.The good electric conductivity of MXene nano materials itself and two-dimensional layer
Shape structure is the source of its electrochemical performance.But Ti3C2Nano material self-conductive and specific capacity are relatively low, cause it
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 carbon microspheres are carbonized as transition zone
Titanium growth in situ CNTs three-dimensional composite materials and preparation method thereof, using glucose as carbon source, obtained three-dimensional composite material
Chemical property is good.
In order to achieve the above object, the present invention is adopted the following technical scheme that：
Comprise the following steps：
(1) by Ti3C2Nano-powder is scattered in ultra-pure water, glucose is added after being uniformly dispersed, after 5~30min of stirring
Hydro-thermal reaction is carried out, Ti is obtained3C2@C composites；Wherein Ti3C2The mass ratio of nano-powder and glucose is (0.05~0.2)：
(0.1~0.4)；
(2) by Ti3C2@C composites are added in ultra-pure water, and Co (NO are added after being uniformly dispersed3)2·6H2O, stirring
2~6h of reaction；Reaction adds urea after terminating, and lasting stirring at a constant temperature evaporates moisture, obtains precursor powder,
Wherein Ti3C2@C composites, 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, carbon microspheres is obtained as transition zone titanium carbide growth in situ CNTs three-dimensional composite woods
Material.
Further, Ti in step (1)3C2The ratio between nano-powder and ultra-pure water are (50~200) mg：(10~60) mL.
Further, Ti in step (1)3C2Ultrasonic disperse 30min adds glucose during nano-powder adds ultra-pure water.
Further, hydro-thermal reaction is to react 8~24h at 160~200 DEG C in step (1).
Further, every 200~500mg Ti in step (2)3C2@C composites are added to 100~400mL ultra-pure waters
In.
Further, the steady temperature in step (2) is between 60~100 DEG C.
Further, the heat treatment in step (2) is carried 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 by the use of carbon microspheres obtained in preparation method as described above as transition zone titanium carbide growth in situ CNTs tri-
Dimension composite.
Compared with prior art, the present invention has following beneficial technique effect：
The present invention prepares Ti first with hydro-thermal method3C2@C composites, Ti3C2The C on surface can protect Ti3C2Structure
Integrality, and it is main with the presence of carbon microspheres form, is evenly coated at Ti3C2Surface, by controlling hydrothermal temperature, time
And glucose content, it is capable of achieving Ti3C2The regulation and control of surface carbon microspheres pattern and chemical composition, carbon microspheres surface is 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 materials, this method energy
Enough low costs, quick, environmental protection, the content by changing urea in presoma of safety, so as to realize Ti3C2Surface C NTs length
And the controllable growth of density.Than directly in Ti3C2Superficial growth goes out CNTs and prepares Ti3C2The method of@CNTs, in Ti3C2Table
Bread covers regrowth CNTs after carbon microspheres layer, is more easy to realize Ti3C2The controllable preparation of@CNTs three-dimensional composite materials, and grow
CNTs mass is higher, so that Ti3C2The performances such as chemical property, absorbing property, the photocatalysis of@CNTs are also that its is further more preferably
Application in fields such as lithium ion battery, photocatalysis, suction ripples is laid a good foundation.Additionally, this simple pyrolysismethod is set due to its Dui
It is standby to require the advantage such as low, easy to operate, with low cost, it is advantageously implemented industrialization large-scale production.Search document, finds so far
Not yet someone is in Ti3C2Surface in situ grows CNT, and realizes Ti3C2The controllable growth of surface CNT.
Three-dimensional composite material of the present invention is by two-dimensional layer Ti3C2, transition zone carbon microspheres and be grown on Ti3C2Surface point
Cloth density multi-walled carbon nano-tubes composition high, in Ti3C2Superficial growth goes out CNT, and electric transmission is provided using CNT
Passage, the conductance of raising material, and Ti3C2The transmittability between CNT can be improved, is received so as to efficiently solve one-dimensional carbon
Mitron and two dimension Ti3C2Heat and conductibility outside the directional dependence of electric transmission and relatively low face, make composite 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.
【Brief description of the drawings】
Fig. 1 is Ti prepared by embodiment 13C2SEM figures (a) and XRD (b) of@C@CNTs three-dimensional composite materials.
Fig. 2 is Ti prepared by embodiment 13C2@[email protected] three-dimensional composite materials (a) sweeps speed (0.002V/s- in difference
CV curve maps under 0.1V/s)；B () is its capacity with the change curve for sweeping speed.
Fig. 3 is respectively Ti when glucose addition is 0.4g and 0.1g3C2The SEM figures of@C@CNTs three-dimensional composite materials,
Wherein (a) is 0.4g, and (b) is 0.1g.
【Specific embodiment】
The present invention is described in further details with embodiment below in conjunction with the accompanying drawings.
Above-described Ti3C2The preparation of@C@CNTs three-dimensional composite materials comprises the steps：
Step one, ternary layered Ti3AlC2The preparation of ceramic powder；
According to the method synthesis of ternary stratiform Ti of patent ZL201310497696.93AlC2Ceramic powder：First, will test
Raw material TiC, Ti, Al powder are TiC according to mol ratio：Ti：Al=2.0：1.0：1.2 carry out batch mixing；Secondly, by batch mixing, oxidation
Aluminium ball stone is with absolute ethyl alcohol according to 1：3：, in ball milling is carried out in corundum ball grinder, wherein absolute ethyl alcohol is used as ball milling for 1 mass ratio
Auxiliary agent, aluminum oxide ballstone is abrasive media, and drum's speed of rotation is 300r/min, in 40 DEG C of freeze-day with constant temperature baking ovens after wet ball grinding 4h
In dry 24h；Then, dry batch 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, 1350 DEG C are heated to, 1h, vacuum ＜ 10 is incubated-2Pa, insulation cools to room temperature with the furnace after terminating；
Finally, to the powder dry method high-energy ball milling 2h after sintering, rotating speed is 400r/min, and powder is 1 with ballstone ratio：10, will be levigate
Powder carries out 400 mesh sievings, you can obtain Ti of the particle diameter less than 38 μm3AlC2Ceramic powder.
Step 2, two-dimensional layer Ti3C2The preparation of nano material；
Method according to patent 201410812056.7 prepares two-dimensional layer Ti3C2Nano material:By institute in 5g steps (1)
The Ti of preparation3AlC2Powder is slowly immersed in 100mL 40wt.% hydrofluoric acid solutions, at room temperature magnetic agitation 24h, and rotating speed is
1200r/min, corrosion product is centrifuged, and 4500r/min ultra-pure waters eccentric cleaning to supernatant pH value is about 6,
Use washes of absolute alcohol 5 times again, the 24h drying in 40 DEG C of vacuum drying chambers, that is, obtain two-dimensional layer Ti by gained sediment3C2
Nano-powder.
Step 3, Ti3C2The preparation of@C composites；
First, by 50~200mg step 2 gained Ti3C2Nano-powder, is added in 10~60mL ultra-pure waters, ultrasound point
Dissipate 30min；Then, 0.1~0.4g glucose is added, 5~30min is stirred at room temperature；Or by Ti3C2Nano-powder is added to
10~60mL concentration is 0.009~0.150mmolL-1Glucose solution in be stirred 5~30min of reaction.
Secondly, it is transferred in 100mL water heating kettles, 160~200 DEG C of 8~24h of reaction, you can obtain Ti3C2@C composites.
Step 4, Ti3C2The preparation of@C@CNTs three-dimensional composite materials；
First, by 200~500mg step 3 gained Ti3C2@C nano powders, are added in 100~400mL ultra-pure waters, surpass
Sound disperses 30min；Then, 0.1~0.4g Co (NO are added3)2·6H2O, is stirred at room temperature 2~6h；Or by Ti3C2@C nanos
Powder is added to 100~400mL concentration for 7.8~8.2mmolL-1Co (NO3)2·6H2In O solution, 2~6h is stirred at room temperature.
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 heating rate of 3~5 DEG C/min is heated to 600~1000 DEG C, is pyrolyzed 0.5~3h, is taken after being cooled to normal temperature under the protection of Ar
Go out, you can obtain Ti3C2@C@CNTs three-dimensional composite materials.
Embodiment 1
(1)Ti3C2The preparation of@C composites；
First, by the Ti of 100mg3C2Nano-powder, is added in 60mL ultra-pure waters, ultrasonic disperse 30min；Then, add
0.4g glucose, is stirred at room temperature 30min；Secondly, it is transferred in 100mL water heating kettles, 180 DEG C of reaction 10h, you can obtain Ti3C2@C are combined
Material.
(2)Ti3C2The preparation of@C@CNTs three-dimensional composite materials；
First, by the Ti of 300mg3C2@C nano powders, are 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 in 80 DEG C of constant temperatures
The lower lasting stirring of degree evaporates moisture, obtains grey presoma；Finally, by precursor powder with agate mortar it is levigate after, be transferred to
In Ar atmosphere tube furnaces, 900 DEG C are heated to the heating rate of 4 DEG C/min, 1h are pyrolyzed, after being cooled to normal temperature under the protection of Ar
Take out, you can obtain Ti3C2@C@CNTs three-dimensional composite materials.Fig. 1 is gained Ti3C2@C@CNTs three-dimensional composite materials SEM figure and
XRD spectrum.It can be seen that intensive CNTs is evenly distributed on Ti3C2Lamella both sides, significantly improve the specific surface area of stratified material
And increase the distance of piece interlayer so that Ti3C2The performances such as the chemical property and suction ripple of@C@CNTs three-dimensional composite materials are more excellent
In pure Ti3C2。
Ti3C2@C@CNTs6.0The preparation of electrode；
First, respectively by 50-200mg Ti obtained as above3C2@C@CNTs6.0Nano-powder and conductive carbon black and binding agent
(PTFE) with 80:15:5 mass ratio mixing, grinding 15min forms uniform purees in agate mortar.Secondly, will
Above-mentioned purees rolls into film, and is cut into 1cm*1cm, is then bonded in the nickel foam of 2cm*1cm sizes, is subsequently placed into true
In empty drying box, 24h is dried at 80 DEG C.Finally, by dried electrode slice under press, distinguish in 20Mpa pressurizes 1min
Obtain Ti3C2@C@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@C@CNTs6.0The chemical property of electrode, such as circulation are lied prostrate
Peace 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 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 2
(1)Ti3C2The preparation of@C composites；
First, by the Ti of 100mg3C2Nano-powder, is added in 60mL ultra-pure waters, ultrasonic disperse 30min；Then, add
0.3g glucose, is stirred at room temperature 30min；Secondly, it is transferred in 100mL water heating kettles, 180 DEG C of reaction 10h, you can obtain Ti3C2@C are combined
Material.
(2)Ti3C2The preparation of@C@CNTs three-dimensional composite materials；
First, by the Ti of 300mg3C2@C nano powders, are 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 in 80 DEG C of constant temperatures
The lower lasting stirring of degree evaporates moisture, obtains grey presoma；Finally, by precursor powder with agate mortar it is levigate after, be transferred to
In Ar atmosphere tube furnaces, 900 DEG C are heated to the heating rate of 4 DEG C/min, 1h are pyrolyzed, after being cooled to normal temperature under the protection of Ar
Take out, you can obtain Ti3C2@C@CNTs three-dimensional composite materials.
Embodiment 3
(1)Ti3C2The preparation of@C composites；
First, by the Ti of 100mg3C2Nano-powder, is added in 60mL ultra-pure waters, ultrasonic disperse 30min；Then, add
0.2g glucose, is stirred at room temperature 30min；Secondly, it is transferred in 100mL water heating kettles, 180 DEG C of reaction 10h, you can obtain Ti3C2@C are combined
Material.
(2)Ti3C2The preparation of@C@CNTs three-dimensional composite materials；
First, by the Ti of 300mg3C2@C nano powders, are 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 in 80 DEG C of constant temperatures
The lower lasting stirring of degree evaporates moisture, obtains grey presoma；Finally, by precursor powder with agate mortar it is levigate after, be transferred to
In Ar atmosphere tube furnaces, 900 DEG C are heated to the heating rate of 4 DEG C/min, 1h are pyrolyzed, after being cooled to normal temperature under the protection of Ar
Take out, you can obtain Ti3C2@C@CNTs three-dimensional composite materials.
Embodiment 4
(1)Ti3C2The preparation of@C composites；
First, by the Ti of 100mg3C2Nano-powder, is added in 60mL ultra-pure waters, ultrasonic disperse 30min；Then, add
0.1g glucose, is stirred at room temperature 30min；Secondly, it is transferred in 100mL water heating kettles, 180 DEG C of reaction 10h, you can obtain Ti3C2@C are combined
Material.
(2)Ti3C2The preparation of@C@CNTs three-dimensional composite materials；
First, by the Ti of 300mg3C2@C nano powders, are 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 in 80 DEG C of constant temperatures
The lower lasting stirring of degree evaporates moisture, obtains grey presoma；Finally, by precursor powder with agate mortar it is levigate after, be transferred to
In Ar atmosphere tube furnaces, 900 DEG C are heated to the heating rate of 4 DEG C/min, 1h are pyrolyzed, after being cooled to normal temperature under the protection of Ar
Take out, you can obtain Ti3C2@C@CNTs three-dimensional composite materials.
Embodiment 5
(1)Ti3C2The preparation of@C composites；
First, by the Ti of 50mg3C2Nano-powder, is added in 10mL ultra-pure waters, ultrasonic disperse 30min；Then, add
0.2g glucose, is stirred at room temperature 5min；Secondly, it is transferred in 100mL water heating kettles, 160 DEG C of reaction 24h, you can obtain Ti3C2@C are combined
Material.
(2)Ti3C2The preparation of@C@CNTs three-dimensional composite materials；
First, by the Ti of 200mg3C2@C nano powders, are added in 100mL ultra-pure waters, ultrasonic disperse 30min；Then,
Add 0.1g Co (NO3)2·6H2O, is stirred at room temperature 2h；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 with agate mortar it is levigate after, be transferred to
In Ar atmosphere tube furnaces, 600 DEG C are heated to the heating rate of 3 DEG C/min, are pyrolyzed 0.5h, normal temperature is cooled under the protection of Ar
After take out, you can Ti3C2@C@CNTs three-dimensional composite materials.
Embodiment 6
(1)Ti3C2The preparation of@C composites；
First, by the Ti of 200mg3C2Nano-powder, is added in 30mL ultra-pure waters, ultrasonic disperse 30min；Then, add
0.2g glucose, is stirred at room temperature 20min；Secondly, it is transferred in 100mL water heating kettles, 200 DEG C of reaction 8h, you can obtain Ti3C2@C are combined
Material.
(2)Ti3C2The preparation of@C@CNTs three-dimensional composite materials；
First, by the Ti of 500mg3C2@C nano powders, are added in 400mL ultra-pure waters, ultrasonic disperse 30min；Then,
Add 0.4g Co (NO3)2·6H2O, is stirred at room temperature 6h；Secondly, 30.0g urea is added, above-mentioned mixed liquor is constant at 100 DEG C
At a temperature of lasting stirring evaporate moisture, obtain grey presoma；Finally, by precursor powder with agate mortar it is levigate after, turn
Enter in Ar atmosphere tube furnaces, 1000 DEG C are heated to the heating rate of 5 DEG C/min, be pyrolyzed 3h, be cooled under the protection of Ar often
Taken out after temperature, you can obtain Ti3C2@C@CNTs three-dimensional composite materials.
Embodiment 7
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, obtained by embodiment 1-4, when glucose content it is too high when, Ti3C2Surface coated carbon microspheres particle diameter point
Cloth is extremely uneven, and the probability increase of crosslinking is produced due to the presence of a large amount of carbon microspheres, furthermore glucose content is too high is difficult to
Short time decomposes complete, as shown in figure 3, wherein figure (a) is situation when glucose addition is 0.4g, Fig. 3 (b) is glucose
Situation when addition is 0.1g.
The invention provides a kind of carbon microspheres as transition zone Ti3C2The preparation method of@C@CNTs three-dimensional composite materials, bag
Include：The ternary layered Ti of high-purity fine grain3AlC2The synthesis of powder；Ti is processed by HF solution corrosions3AlC2Selective etch falls
Selective etch falls ternary layered Ti3AlC2In Al layers prepare two-dimensional layer Ti3C2Nano 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 is main with the presence of carbon microspheres form, is evenly coated at Ti3C2Surface, leads to
Control hydrothermal temperature, time and glucose content are crossed, Ti is capable of achieving3C2The regulation and control of surface carbon microspheres pattern and chemical composition,
With Ti3C2, used as carrier, a large amount of oxygen-containing functional groups are contained on carbon microspheres surface and hydrophily is very strong for@C；Cobalt is used as catalyst, Co2+From
Son by with Ti3C2And the ion exchange of carbon microspheres surface oxygen functional group is adsorbed in Ti3C2Surface；Then, urea is added
As carbon source, urea by with Ti3C2The Co on surface2+Ion forms complex and inserts Ti3C2Lamella in.Finally, exist
It is pyrolyzed under argon atmosphere, with the rising of temperature, Co2+It is reduced to the catalyst that Co nano particles grow as CNTs, and urea
Carbonitride is decomposed into, carbonitride is grown to CNTs under the catalysis of Co.With Ti3C2@C are matrix, and Co is catalyst, urea is carbon
Source, Ti is successfully prepared under argon atmosphere using simple pyrolysismethod3C2@C@CNTs three-dimensional composite materials, this method can it is low into
Originally, quick, environmental protection, the content by changing urea in presoma of safety, so as to realize Ti3C2Surface C NTs length and density
Controllable growth.Contrast is directly in Ti3C2Superficial growth goes out CNTs and prepares Ti3C2The method of@CNTs, in Ti3C2Surface coating
Regrowth CNTs after carbon microspheres layer, is more easy to realize Ti3C2The controllable preparation of@CNTs three-dimensional composite materials, and the CNTs matter for growing
Amount is higher, so that Ti3C2Also more preferably, this is for extension Ti for the performances such as chemical property, absorbing property, the photocatalysis of@CNTs3C2
Material has important practical significance in the application in the fields such as ultracapacitor, lithium ion battery, nano adsorber and suction ripple.
Compared to other preparation methods are reported, the experiment condition needed for this method is fairly simple, and low cost is easy to operate.
The invention provides a kind of carbon microspheres as transition zone Ti3C2@CNTs three-dimensional composite materials and preparation method thereof, carry
Ti high3C2Electric conductivity, expand Ti3C2Specific surface area, improve Ti3C2Self stability etc., so as to extend Ti3C2Material exists
The application in the fields such as ultracapacitor, lithium ion battery, nano adsorber and suction ripple.
Claims (10)
1. a kind of carbon microspheres as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials preparation method, its feature exists
In comprising the following steps：
(1) by Ti3C2Nano-powder is scattered in ultra-pure water, and glucose is added after being uniformly dispersed, and is carried out after 5~30min of stirring
Hydro-thermal reaction, obtains Ti3C2@C composites；Wherein Ti3C2The mass ratio of nano-powder and glucose is (0.05~0.2)：(0.1
~0.4)；
(2) by Ti3C2@C composites are added in ultra-pure water, and Co (NO are added after being uniformly dispersed3)2·6H2O, stirring reaction 2
~6h；Reaction adds urea after terminating, and lasting stirring at a constant temperature evaporates moisture, obtains precursor powder, wherein
Ti3C2@C composites, 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, carbon microspheres is obtained as transition zone titanium carbide growth in situ CNTs three-dimensional composite woods
Material.
2. a kind of carbon microspheres according to claim 1 are used as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials
Preparation method, it is characterised in that Ti in step (1)3C2The ratio between nano-powder and ultra-pure water are (50~200) mg：(10~60)
mL。
3. a kind of carbon microspheres according to claim 1 are used as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials
Preparation method, it is characterised in that Ti in step (1)3C2Ultrasonic disperse 30min adds grape during nano-powder adds ultra-pure water
Sugar.
4. a kind of carbon microspheres according to claim 1 are used as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials
Preparation method, it is characterised in that hydro-thermal reaction is to react 8~24h at 160~200 DEG C in step (1).
5. a kind of carbon microspheres according to claim 1 are used as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials
Preparation method, it is characterised in that every 200~500mg Ti in step (2)3C2It is ultrapure that@C composites are added to 100~400mL
In water.
6. a kind of carbon microspheres according to claim 1 are used as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials
Preparation method, it is characterised in that the steady temperature in step (2) is between 60~100 DEG C.
7. a kind of carbon microspheres according to claim 1 are used as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials
Preparation method, it is characterised in that the heat treatment in step (2) is carried out under the protection of Ar.
8. a kind of carbon microspheres according to claim 1 are used as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials
Preparation method, it is characterised in that heat treatment temperature is 600~1000 DEG C, the time is 0.5~3h.
9. a kind of carbon microspheres according to claim 1 are used as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials
Preparation method, it is characterised in that the heating rate of heat treatment is 3~5 DEG C/min.
10. carbon microspheres obtained in a kind of preparation method by the use of described in claim 1 are used as transition zone titanium carbide growth in situ
CNTs three-dimensional composite materials.
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| CN108417406A (en) * | 2018-01-30 | 2018-08-17 | 哈尔滨工业大学 | A kind of Ti3C2MXene-Co composite material and preparation methods |
| CN108461300A (en) * | 2018-05-11 | 2018-08-28 | 西北师范大学 | A kind of stratiform titanium carbide-carbon pipe composite material and its preparation and application |
| 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 |
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| 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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