CN108147464A - A kind of rice-shaped manganese dioxide/carbon titanium composite material and preparation method thereof - Google Patents
A kind of rice-shaped manganese dioxide/carbon titanium composite material and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of rice-shaped manganese dioxide/carbon titanium composite material and preparation method thereof, by Ti3C2Nano-powder and Dopamine hydrochloride are scattered in ultra-pure water and are uniformly mixed respectively, are stirred under dark conditions；Tris buffer solutions are added, continue to stir under dark conditions；By the separation of gained mixed solution, washing and drying, Ti is obtained3C2@PDA nano-powders；By Ti3C2@PDA nano-powders are added in CTAB solution, and KMnO is added after being uniformly dispersed4Solution carries out liquid phase reactor；Natural cooling after reaction, you can obtain rice-shaped manganese dioxide/carbon titanium composite material.This method can form equally distributed rice-shaped manganese dioxide on titanium carbide surface, and obtained composite material chemical property is good, and preparation method is low for equipment requirements, easy to operate, of low cost, be advantageously implemented industrialization large-scale production.
Description
Technical field
The invention belongs to the preparing technical field of nano-functional material, a kind of particularly rice-shaped manganese dioxide/carbon
Change titanium composite material and preparation method thereof.
Background technology
In recent years, a kind of discovery of material for being referred to as MXene extends the group of two-dimensional material, i.e. transition metal is carbonized
Object or carbonitride, structure are similar with graphene.MXene materials can remove the A layers member in its presoma MAX phases by corrosion
Element, and keep original MX structures constant and obtain, such as Ti3C2、Ti2C etc..MXene is with its high conductivity, bigger serface, more
Layer structure, good chemical stability and environment friendly, in lithium ion battery, ultracapacitor, photocatalysis and sensor etc.
There is very big application potential in field.However Ti3C2Lamellar structure easily stacks, and reduces specific surface area in this way, affects ion
In the diffusion of interlayer, chemical property is reduced, therefore these lamellas are separated.Mashtalir etc.[13]To Ti3C2Deng
MXene materials have carried out intercalation research, respectively by the use of hydrazine and hydrazine and dimethyl formamide mixture as being inserted into substance, test result
It has been shown that, interplanar distance increase respectively to 0.2548 and 0.268nm from 0.195nm.Naguib etc.[20]It was found that use tetrabutyl hydrogen-oxygen
Changing ammonium (TBAOH) becomes easier to layering, is layered on a large scale so as to fulfill MXene.It can be seen that chemical substance intercalation is to change
The effective means that kind MXene nanometer sheets stack, but often technique is cumbersome and yield is relatively low for such method.Simple MXene pieces
Layer material is easily stacked and influences its chemical property, reduces lamella and stacks other than layering, another kind is effectively done
Method is exactly compound with other materials, and the research that composite material is made of MXene has also been carried out.Zhao etc. is taken out by vacuum successively
Filter Ti3C2Suspension and CNTs dispersion liquids repeatedly obtain the Ti of flexible sandwich style3C2/ CNT extrusion coating papers.Purer Ti3C2
For, electric conductivity is more excellent, volumetric capacitance higher, can be of about 350F/cm3, and volumetric capacitance is in cycle charge-discharge 10000 times
After be held essentially constant.
In the electrode material of existing ultracapacitor, the electrode material of fake capacitance can carry out continuous reversible farad
Redox reaction, this causes the energy density of the electrode material of fake capacitance to be higher than the electrode material of double layer capacitor.Cause
This, it is compound by the way that MXene is carried out with fake capacitance electrode material (transition metal oxide, conducting polymer etc.), it can improve
While MXene materials easy stack-up issue, its chemical property is made to be significantly improved.MnO2Because its is at low cost, source is wide, electricity
Chemical property is good, environmentally friendly, is widely applied in battery industry, the active electrode as electrochemical capacitor
Material also has great application prospect.The theoretical specific capacitance of pure manganese dioxide can reach 1370F/g, be a kind of very potential
Electrode material.But the cyclical stability of pure manganese dioxide is poor, the shortcomings of low electric conductivity, results in manganese dioxide practical application
Difficulty.Research shows that manganese dioxide can obtain better capacitive property by modified.
Tang etc. is with Ti3C2Nano material is matrix, and MnO is prepared by liquid-phase precipitation method and heat treatment2-Ti3C2Nanometer is multiple
Condensation material, wherein MnO2It for graininess, is applied in terms of electrochemical capacitor, but its specific capacity is smaller.Rakhi etc. is logical
It crosses chemical synthesis and ε-MnO is deposited on MXene lamellas2Nano whisker is but this straight to improve the specific capacity of MXene materials
The MnO that the method for connecing chemical synthesis obtains2It tends to reunite, in Ti3C2Surface distributing inhomogeneity, so as to influence its electrochemistry
Performance.Liu et al. is by being filtered by vacuum Ti3C2With MnO2Mixed liquor obtains flexible compound paper to improve Ti3C2Fake capacitance performance, but
It is that this method cannot control the structure of composite material.
Invention content
It is an object of the invention to overcome problems of the prior art, a kind of rice-shaped manganese dioxide/carbon is provided
Titanium composite material and preparation method thereof, using dopamine in Ti3C2Surface coats thin poly-dopamine (PDA) layer, then using cost
Relatively low KMnO4As manganese source, cetyl trimethylammonium bromide (CTAB) prepares rice-shaped titanium dioxide as surfactant
Manganese/carbonization titanium composite material, rice-shaped manganese dioxide is in Ti3C2Surface is evenly distributed securely, effectively improves Ti3C2Nano material
Chemical property.
In order to achieve the above object, the present invention adopts the following technical scheme that：
The preparation method of the present invention includes the following steps：
A kind of preparation method of rice-shaped manganese dioxide/carbon titanium composite material, includes the following steps：
Step 1, Ti is prepared3C2@PDA nano-powders；
Step 2, CTAB solution is prepared；By Ti3C2@PDA nano-powders and KMnO4It is added in CTAB solution, is uniformly dispersed
Afterwards, 50~90 DEG C are heated to, is stirred to react 1~6h, obtains rice-shaped manganese dioxide/carbon titanium composite material.
Preferably, step 1 specifically includes：By Ti3C2Nano-powder and Dopamine hydrochloride are dispersed in water and are uniformly mixed,
It is stirred under dark conditions；Tris- buffer solutions are added, are stirred under dark conditions；By gained mixed solution separation, washing and
It is dry, obtain Ti3C2@PDA nano-powders.
Preferably, CTAB solution is prepared in step 2 is specially：Prepare 50~500mmolL-1CTAB solution, stirring, make
CTAB is dissolved completely in water.
Preferably, KMnO in step 24Using KMnO4Solution.
Further, CTAB solution, Ti in step 23C2@PDA nano-powders and KMnO4The ratio between solution is (5~50) mL：
(10~100) mg：(5~50) mL, wherein, a concentration of 50~500mmolL of CTAB solution-1, KMnO4A concentration of the 20 of solution
~300mmolL-1。
Preferably, Ti in step 23C2@PDA nano-powders are added in CTAB solution, and KMnO is added after being uniformly dispersed4。
Further, Ti in step 23C2@PDA nano-powders are added in CTAB solution, first ultrasonic disperse, are stirred for
It is even, then add KMnO4。
Preferably, reaction carries out under water bath condition in step (2).
It is a kind of to utilize rice-shaped manganese dioxide/carbon titanium composite material made from preparation method as described above.
Compared with prior art, the present invention has technique effect beneficial below：
Poly-dopamine is that one kind that autoxidation polymerize in the environment of alkalescent by DOPA amine monomers is environmentally friendly
Biomacromolecule product.Research shows that the autoxidation polymerization using dopamine may be implemented in many organic or inorganic matrix
Surface forms poly-dopamine clad, with matrix (such as：Ceramics, metal oxide, polymer etc.) binding force it is very strong, and by
In its structure good second order reaction platform can be used as containing a large amount of nitrogen-containing group and phenolic hydroxyl group, poly-dopamine.The present invention
First with dopamine, autoxidation is aggregated in Ti in weakly alkaline environment3C2Surface coats very thin PDA layers and obtains Ti3C2@PDA
Composite material, then with Ti3C2@PDA be matrix, KMnO4As manganese source, cetyl trimethylammonium bromide is as surface-active
Agent prepares rice-shaped manganese dioxide/carbon titanium composite material by simple liquid phase reactor.On the one hand, due in KMnO4Height
In warm reaction process, Ti3C2In Ti also have part be oxidized to form TiO2, so as to destroy Ti3C2Structure, lead to electrochemistry
Reduced performance, the present invention is in Ti3C2Surface coats PDA, and clad PDA can protect Ti3C2The integrality of structure avoids therein
Ti is by KMnO4It aoxidizes and structure is caused to destroy, influence chemical property.On the other hand, Mn7+Ion outer layer has empty electronics rail
Road, two phenolic hydroxyl groups of the catechol group of PDA can provide two pairs of lone pair electrons, in neutral or alkaline environment, catechol
Group and Mn7+Ion can form relatively stable chelatingligand, the life for existing for PDA surface metal chemical combination objects of chelation
Long or deposition provides site, i.e. PDA can be by Mn7+It is fixed on Ti3C2Sheet surfaces, and PDA has week reduction in itself, it can be by Mn7 +It is reduced to Mn4+With MnO2Formal distribution in Ti3C2Sheet surfaces, and the presence of catechol group makes it have on PDA
The rice-shaped manganese dioxide of generation can be firmly adhered to Ti by very strong adhesiveness3C2Sheet surfaces are not easy to reunite, so as to
In Ti3C2Sheet surfaces can be uniformly distributed for a long time.In addition, after CTAB dissolvings, CTA is ionized out+, CTA+Front end be band just
The hydrophilic group of electricity, tail end is long chain hydrophobic group, can be formed when the concentration of CTAB in the solution reaches critical micelle concentration (CMC)
Micella；When being initially added potassium permanganate, CTAB can be aoxidized by the strong oxidizing property of potassium permanganate, be gradually reduced in potassium permanganate
Afterwards, remaining CTAB reaches critical micelle concentration, forms spherical micella；With the progress of reaction, MnO2After nucleation, assemble
Collect the outer layer of globular micelle, MnO2Beginning preferred orientation carries out growth and becomes rice-shaped, with the increase of CTAB dosages, the grain of rice
The content of shape manganese dioxide increases.Gained composite material have superior chemical property, be its further ultracapacitor,
The application in the fields such as lithium ion battery is laid a good foundation.In addition, this simple pyrolysismethod is since its is low for equipment requirements, operation letter
Just, the advantages such as of low cost are advantageously implemented industrialization large-scale production.
Description of the drawings
Fig. 1 is that the SEM of rice-shaped manganese dioxide/carbon titanium composite material prepared by embodiment 2 schemes (a) and XRD diagram (b)
(abscissa is X ray incident angle, and ordinate is intensity).
Fig. 2 is that rice-shaped manganese dioxide/carbon titanium composite material (a) prepared by embodiment 2 sweeps speed (0.002V/ in difference
S-0.2V/s the CV curve graphs under) (abscissa is voltage, and ordinate is current density)；(b) for its capacity with sweep speed variation
Curve (abscissa is sweep speed, and ordinate is unit capacitance).
Specific embodiment
The present invention is described in further details with embodiment below in conjunction with the accompanying drawings.
Preparation method of the present invention 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, preparation process tool
Body includes：First, it is TiC according to molar ratio by experimental raw TiC, Ti, Al powder：Ti：Al=2.0：1.0：1.2 are mixed
Material；Secondly, by batch mixing, aluminium oxide ballstone and absolute ethyl alcohol according to 1：3：1 mass ratio in carrying out ball milling in corundum ball grinder,
For middle absolute ethyl 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 batch mixing is put into corundum crucible, in vacuum hotpressing carbon shirt-circuiting furnace
Vacuum non-pressure sintering is carried out with the heating rate of 8 DEG C/min, 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, rotating speed 400r/min, powder and ball
Stone ratio is 1：10, levigate powder is subjected to 400 mesh sievings, you can obtain the Ti that grain size is 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, preparation process are specifically wrapped
It includes:By Ti prepared in 5g steps (1)3AlC2Powder is slowly immersed in 100mL 40wt.% hydrofluoric acid solutions, at room temperature
For 24 hours, corrosion product is centrifuged rotating speed 1200r/min magnetic agitation, 4500r/min ultra-pure water eccentric cleanings
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 drying chambers,
Obtain two-dimensional layer Ti3C2Nano-powder.
Step 3, the preparation of titanium carbide@PDA nano-powders；
First, by 300~500mg Ti3C2Nano-powder ultrasonic disperse is in 30~300mL ultra-pure waters, ultrasonic 30min；
0.1~1.0g Dopamine hydrochlorides are dissolved in 10~100mL ultra-pure waters, add in above-mentioned solution, are stirred at room temperature under dark conditions
0.5~2h；Either by 300~500mg Ti3C2Nano-powder adds in a concentration of 12.5~14.0mmolL of 40~400mL-1's
0.5~2h is stirred in room temperature shading in Dopamine hydrochloride solution；Complete liquid phase reactor；
Add 10~100mL Tris- buffer solutions (50mmolL-1, pH=8.5), it is stirred at room temperature 12 under dark conditions
~48h；Gained mixed solution is centrifuged, deionized water is cleaned to supernatant and clarified, and is transferred in freeze drier, after 48h
It takes out and can obtain Ti3C2@PDA。
Specifically, by 500mg Ti3C2Nano-powder and 0.25g Dopamine hydrochlorides are scattered in ultra-pure water and mix respectively
Uniformly, 1h is stirred under dark conditions；25mL Tris- buffer solutions are added, continue stirring under dark conditions for 24 hours；By gained
Mixed solution separation, washing and drying, obtain Ti3C2@PDA nano-powders.
Step 4, the preparation of rice-shaped manganese dioxide/carbon titanium composite material；
First, 5~50mL, 50~500mmolL are prepared-1CTAB solution, 30min, which is stirred at room temperature, is dissolved completely in CTAB
Ultra-pure water；By the Ti obtained by 10~100mg steps (1)3C2@PDA nano-powders are added in CTAB solution, ultrasonic disperse
30min is stirred for 1h；20~300mmolL of 5~50mL is added after stirring evenly-1KMnO4Solution, 50~90 DEG C of water-baths add
Heat is stirred to react 1~6h；Natural cooling after reaction obtains rice-shaped manganese dioxide/carbon titanium composite material.
Embodiment 1
First, 10mL 100mmolL are prepared-1CTAB solution, 30min, which is stirred at room temperature, makes CTAB be dissolved completely in ultra-pure water；
By the Ti of 30mg3C2@PDA nano-powders are added in CTAB solution, and ultrasonic disperse 30min is stirred for 1h；After stirring evenly again
Add in the 50mmolL of 10mL-1KMnO4Solution, 70 DEG C of heating water baths, is stirred to react 3h；Natural cooling after reaction obtains rice
Particulate manganese dioxide/carbonization titanium composite material.
Embodiment 2
First, 10mL 100mmolL are prepared-1CTAB solution, 30min, which is stirred at room temperature, makes CTAB be dissolved completely in ultra-pure water；
By the Ti of 30mg3C2@PDA nano-powders are added in CTAB solution, and ultrasonic disperse 30min is stirred for 1h；After stirring evenly again
Add in the 100mmolL of 10mL-1KMnO4Solution, 70 DEG C of heating water baths, is stirred to react 3h；Natural cooling after reaction obtains
Rice-shaped manganese dioxide/carbon titanium composite material.
Embodiment 3
First, 10mL 100mmolL are prepared-1CTAB solution, 30min, which is stirred at room temperature, makes CTAB be dissolved completely in ultra-pure water；
By the Ti of 30mg3C2@PDA nano-powders are added in CTAB solution, and ultrasonic disperse 30min is stirred for 1h；After stirring evenly again
Add in the 200mmolL of 10mL-1KMnO4Solution, 70 DEG C of heating water baths, is stirred to react 3h；Natural cooling after reaction obtains
Rice-shaped manganese dioxide/carbon titanium composite material.
Embodiment 4
First, 10mL 100mmolL are prepared-1CTAB solution, 30min, which is stirred at room temperature, makes CTAB be dissolved completely in ultra-pure water；
By the Ti of 30mg3C2@PDA nano-powders are added in CTAB solution, and ultrasonic disperse 30min is stirred for 1h；After stirring evenly again
Add in the 100mmolL of 10mL-1KMnO4Solution, 70 DEG C of heating water baths, is stirred to react 1h；Natural cooling after reaction obtains
Rice-shaped manganese dioxide/carbon titanium composite material.
Embodiment 5
First, 10mL 100mmolL are prepared-1CTAB solution, 30min, which is stirred at room temperature, makes CTAB be dissolved completely in ultra-pure water；
By the Ti of 30mg3C2@PDA nano-powders are added in CTAB solution, and ultrasonic disperse 30min is stirred for 1h；After stirring evenly again
Add in the 100mmolL of 10mL-1KMnO4Solution, 70 DEG C of heating water baths, is stirred to react 2h；Natural cooling after reaction obtains
Rice-shaped manganese dioxide/carbon titanium composite material.
Embodiment 6
First, 10mL 100mmolL are prepared-1CTAB solution, 30min, which is stirred at room temperature, makes CTAB be dissolved completely in ultra-pure water；
By the Ti of 30mg3C2@PDA nano-powders are added in CTAB solution, and ultrasonic disperse 30min is stirred for 1h；After stirring evenly again
Add in the 100mmolL of 10mL-1KMnO4Solution, 70 DEG C of heating water baths, is stirred to react 4h；Natural cooling after reaction obtains
Rice-shaped manganese dioxide/carbon titanium composite material.
Embodiment 7
First, 10mL 100mmolL are prepared-1CTAB solution, 30min, which is stirred at room temperature, makes CTAB be dissolved completely in ultra-pure water；
By the Ti of 30mg3C2@PDA nano-powders are added in CTAB solution, and ultrasonic disperse 30min is stirred for 1h；After stirring evenly again
Add in the 100mmolL of 10mL-1KMnO4Solution, 70 DEG C of heating water baths, is stirred to react 5h；Natural cooling after reaction obtains
Rice-shaped manganese dioxide/carbon titanium composite material.
Embodiment 8
First, 10mL 100mmolL are prepared-1CTAB solution, 30min, which is stirred at room temperature, makes CTAB be dissolved completely in ultra-pure water；
By the Ti of 30mg3C2@PDA nano-powders are added in CTAB solution, and ultrasonic disperse 30min is stirred for 1h；After stirring evenly again
Add in the 100mmolL of 10mL-1KMnO4Solution, 70 DEG C of heating water baths, is stirred to react 6h；Natural cooling after reaction obtains
Rice-shaped manganese dioxide/carbon titanium composite material.
Embodiment 9
First, 10mL 100mmolL are prepared-1CTAB solution, 30min, which is stirred at room temperature, makes CTAB be dissolved completely in ultra-pure water；
By the Ti of 30mg3C2@PDA nano-powders are added in CTAB solution, and ultrasonic disperse 30min is stirred for 1h；After stirring evenly again
Add in the 100mmolL of 10mL-1KMnO4Solution, 50 DEG C of heating water baths, is stirred to react 3h；Natural cooling after reaction obtains
Rice-shaped manganese dioxide/carbon titanium composite material.
Embodiment 10
First, 10mL 100mmolL are prepared-1CTAB solution, 30min, which is stirred at room temperature, makes CTAB be dissolved completely in ultra-pure water；
By the Ti of 30mg3C2@PDA nano-powders are added in CTAB solution, and ultrasonic disperse 30min is stirred for 1h；After stirring evenly again
Add in the 100mmolL of 10mL-1KMnO4Solution, 60 DEG C of heating water baths, is stirred to react 3h；Natural cooling after reaction obtains
Rice-shaped manganese dioxide/carbon titanium composite material.
Embodiment 11
First, 10mL 100mmolL are prepared-1CTAB solution, 30min, which is stirred at room temperature, makes CTAB be dissolved completely in ultra-pure water；
By the Ti of 30mg3C2@PDA nano-powders are added in CTAB solution, and ultrasonic disperse 30min is stirred for 1h；After stirring evenly again
Add in the 100mmolL of 10mL-1KMnO4Solution, 80 DEG C of heating water baths, is stirred to react 3h；Natural cooling after reaction obtains
Rice-shaped manganese dioxide/carbon titanium composite material.
Embodiment 12
First, 10mL 100mmolL are prepared-1CTAB solution, 30min, which is stirred at room temperature, makes CTAB be dissolved completely in ultra-pure water；
By the Ti of 30mg3C2@PDA nano-powders are added in CTAB solution, and ultrasonic disperse 30min is stirred for 1h；After stirring evenly again
Add in the 100mmolL of 10mL-1KMnO4Solution, 90 DEG C of heating water baths, is stirred to react 3h；Natural cooling after reaction obtains
Rice-shaped manganese dioxide/carbon titanium composite material.
Embodiment 13
First, 5mL 50mmolL are prepared-1CTAB solution, 30min, which is stirred at room temperature, makes CTAB be dissolved completely in ultra-pure water；It will
The Ti of 10mg3C2@PDA nano-powders are added in PEG solution, ultrasonic disperse 30min；Then, the 20mmolL of 5mL is added in- 1KMnO4Solution, 90 DEG C of heating water baths, is stirred to react 1h；Natural cooling after reaction, you can obtain manganese dioxide nano-plates/carbon
Change titanium composite material.
Embodiment 14
First, 30mL 50mmolL are prepared-1CTAB solution, 30min, which is stirred at room temperature, makes CTAB be dissolved completely in ultra-pure water；It will
The Ti of 50mg3C2@PDA nano-powders are added in PEG solution, ultrasonic disperse 30min；Then, the 200mmolL of 30mL is added in- 1KMnO4Solution, 90 DEG C of heating water baths, is stirred to react 1h；Natural cooling after reaction, you can obtain manganese dioxide nano-plates/carbon
Change titanium composite material.
Embodiment 15
First, 50mL 300mmolL are prepared-1CTAB solution, 30min, which is stirred at room temperature, makes CTAB be dissolved completely in ultra-pure water；
By the Ti of 70mg3C2@PDA nano-powders are added in PEG solution, ultrasonic disperse 30min；Then, add in 30mL's
300mmolL-1KMnO4Solution, 90 DEG C of heating water baths, is stirred to react 1h；Natural cooling after reaction, you can obtain manganese dioxide
Nanometer sheet/carbonization titanium composite material.
Embodiment 16
First, 50mL 500mmolL are prepared-1CTAB solution, 30min, which is stirred at room temperature, makes CTAB be dissolved completely in ultra-pure water；
By the Ti of 100mg3C2@PDA nano-powders are added in PEG solution, ultrasonic disperse 30min；Then, add in 50mL's
100mmolL-1KMnO4Solution, 90 DEG C of heating water baths, is stirred to react 1h；Natural cooling after reaction, you can obtain manganese dioxide
Nanometer sheet/carbonization titanium composite material.
Fig. 1 is the SEM figures and XRD diagram of 2 gained rice-shaped manganese dioxide/carbon titanium composite material of embodiment.It can be seen that
Rice-shaped manganese dioxide is evenly distributed on Ti3C2Lamella both sides significantly improve the specific surface area of stratified material and increase lamella
Between distance so that the chemical property of rice-shaped manganese dioxide/carbon titanium composite material is better than pure Ti3C2。
The rice-shaped manganese dioxide/carbon titanium composite material obtained using embodiment 2 prepares electrode：First by the 50mg grain of rices
Shape manganese dioxide/carbon titanium composite material is with conductive carbon black and binding agent (PVDF) with 80:10:10 mass ratio mixing, adds in
Appropriate N- methyl-pyrrolidons, grind 10min in agate mortar.Secondly, above-mentioned suspension is taken to drop to 2cm*1cm with liquid-transfering gun
In the nickel foam of size, active material area is 1cm*1cm.Then, in vacuum drying chamber, dry 12h at 120 DEG C.
Finally, by dried electrode slice under press, rice-shaped manganese dioxide/carbon Ti electrode is obtained in 20Mpa pressurizes 1min.
Using three electrode test systems, by the rice-shaped manganese dioxide/carbon Ti electrode (working electrode) of making and platinum electricity
Pole (to electrode), saturated calomel electrode (reference electrode) are assembled into easy ultracapacitor, wherein electrolyte in electrolytic cell
For 1.0mol/LNa2SO4Solution tests rice-shaped manganese dioxide/carbon titanium using Shanghai Chen Hua CHI660E electrochemical workstations
The chemical property of electrode, such as Cyclic voltamogram curve, constant current charge-discharge, AC impedance and cycle life.Shown in Fig. 2, (a)
Sweep the CV curve graphs under fast (0.002V/s-0.2V/s) in difference for rice-shaped manganese dioxide/carbon titanium, (b) for its capacity with
Sweep the change curve of speed, it can be seen that the purer Ti of its capacity3C2There is great promotion.
The preparation method of rice-shaped manganese dioxide/carbon titanium composite material of the present invention, including：High-purity fine grain ternary layers
Shape Ti3AlC2The synthesis of powder；Ti is handled by HF solution corrosions3AlC2Selective etch falls ternary layered Ti3AlC2In Al
Two-dimensional layer Ti is prepared in layer3C2Nano material；With Ti3C2As carrier, first with dopamine in weakly alkaline environment from
Oxidation polymerization is in Ti3C2Surface coats very thin PDA layers and obtains Ti3C2@PDA composite materials, clad PDA can avoid Ti3C2 from tying
Ti in structure is aoxidized during the reaction, so as to protect the integrality of Ti3C2 structures；Then with Ti3C2@PDA are matrix,
KMnO4As manganese source, cetyl trimethylammonium bromide prepares rice-shaped as surfactant by simple liquid phase reactor
Manganese dioxide/carbon titanium composite material, due to containing a large amount of nitrogen-containing group and phenolic hydroxyl group in PDA structures, phenolic hydroxyl group can be with
Mn7+Ion chelating is fixed on its position, is reduced to manganese dioxide, and phenolic hydroxyl group makes PDA have very strong adhesiveness, energy
It reaches rice-shaped manganese dioxide is secured and is evenly distributed on Ti3C2Sheet surfaces are not easy to reunite.The CTAB of addition is in reaction process
The middle glomerate micella of shape, MnO2The outer layer of globular micelle is gathered after nucleation, so as to MnO2Start preferred orientation and carry out growth change
Into rice-shaped.Gained composite material has superior chemical property.This is for extending Ti3C2Material ultracapacitor, lithium from
The application in the fields such as sub- battery, has important practical significance.Compared to reporting other preparation methods, the reality needed for this method
It is fairly simple to test condition, it is at low cost, it is easy to operate.
Claims (9)
1. a kind of preparation method of rice-shaped manganese dioxide/carbon titanium composite material, which is characterized in that include the following steps：
Step 1, Ti is prepared3C2@PDA nano-powders；
Step 2, CTAB solution is prepared；By Ti3C2@PDA nano-powders and KMnO4It is added in CTAB solution, after being uniformly dispersed,
50~90 DEG C are heated to, is stirred to react 1~6h, obtains rice-shaped manganese dioxide/carbon titanium composite material.
2. a kind of preparation method of rice-shaped manganese dioxide/carbon titanium composite material according to claim 1, feature exist
In step 1 specifically includes：By Ti3C2Nano-powder and Dopamine hydrochloride are dispersed in water and are uniformly mixed, under dark conditions
Stirring；Tris- buffer solutions are added, are stirred under dark conditions；By the separation of gained mixed solution, washing and drying, obtain
Ti3C2@PDA nano-powders.
3. a kind of preparation method of rice-shaped manganese dioxide/carbon titanium composite material according to claim 1, feature exist
In CTAB solution is prepared in step 2 is specially：Prepare 50~500mmolL-1CTAB solution, stirring, be completely dissolved CTAB
Yu Shui.
4. a kind of preparation method of rice-shaped manganese dioxide/carbon titanium composite material according to claim 1, feature exist
In KMnO in step 24Using KMnO4Solution.
5. a kind of preparation method of rice-shaped manganese dioxide/carbon titanium composite material according to claim 4, feature exist
In CTAB solution, Ti in step 23C2@PDA nano-powders and KMnO4The ratio between solution is (5~50) mL：(10~100) mg：(5
~50) mL, wherein, a concentration of 50~500mmolL of CTAB solution-1, KMnO4A concentration of 20~300mmolL of solution-1。
6. a kind of preparation method of rice-shaped manganese dioxide/carbon titanium composite material according to claim 1, feature exist
In Ti in step 23C2@PDA nano-powders are added in CTAB solution, and KMnO is added after being uniformly dispersed4。
7. a kind of preparation method of rice-shaped manganese dioxide/carbon titanium composite material according to claim 6, feature exist
In Ti in step 23C2@PDA nano-powders are added in CTAB solution, first ultrasonic disperse, are stirred for uniformly, then adding
KMnO4。
8. a kind of preparation method of rice-shaped manganese dioxide/carbon titanium composite material according to claim 1, feature exist
In the middle reaction of step (2) carries out under water bath condition.
It is 9. a kind of compound using rice-shaped manganese dioxide/carbon titanium made from claim 1-8 any one of them preparation methods
Material.
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