CN108364802A - A kind of manganese dioxide nanowire/titanium carbide composite material and preparation method - Google Patents
A kind of manganese dioxide nanowire/titanium carbide composite material and preparation method Download PDFInfo
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H—ELECTRICITY
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H—ELECTRICITY
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
The present invention provides a kind of manganese dioxide nanowire/titanium carbide composite material and preparation method, 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 PEG solution, and KMnO is added after being uniformly dispersed4Solution carries out liquid phase reactor；Natural cooling after reaction, you can obtain manganese dioxide nanowire/carbonization titanium composite material.This method can form equally distributed manganese dioxide nanowire 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, is 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 manganese dioxide nanowire/carbon
Change titanium composite material and preparation method thereof.
Background technology
In recent years, the discovery of a kind 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 layer members 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 prodigious application potential in field.However Ti3C2Lamellar structure is easy to stack, 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, use hydrazine and hydrazine and dimethyl formamide mixture as insertion substance, test result respectively
It has been shown that, interplanar distance increase respectively to 0.2548 and 0.268nm from 0.195nm.The discoveries such as Naguib use tetrabutylammonium hydroxide
Ammonium (TBAOH) makes layering become easier to, to realize that MXene is layered on a large scale.It can be seen that chemical substance intercalation is to improve
The effective means that MXene nanometer sheets stack, but often technique is cumbersome and yield is relatively low for such method.Simple MXene lamellas
Material is easy to be stacked and influence its chemical property, reduces lamella and stacks other than layering, another effective way
It is exactly compound with other materials, the research that composite material is made of MXene has also been carried out.Zhao etc. by being filtered by vacuum successively
Ti3C2Suspension and CNTs dispersion liquids, repeatedly obtain the Ti of sandwich style flexible3C2/ CNT extrusion coating papers.Purer Ti3C2And
Speech, electric conductivity is better, volumetric capacitance higher, can be of about 350F/cm3, and volumetric capacitance is after cycle charge-discharge 10000 times
It is 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 makes the energy density of the electrode material of fake capacitance be higher than the electrode material of double layer capacitor.Cause
This, it is compound by carrying out MXene 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.Studies have shown 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 deposits ε-MnO on MXene lamellas2Nano whisker is but this straight to improve the specific capacity of MXene materials
Meet the MnO that chemically synthesized method obtains2It tends to reunite, in Ti3C2Surface distributing inhomogeneity, 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 this method to 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 manganese dioxide nanowire/carbonization is provided
Titanium composite material and preparation method thereof, using dopamine in Ti3C2Surface coats thin poly-dopamine (PDA) layer, then uses cost
Lower KMnO4As manganese source, polyethylene glycol (PEG) is used as surfactant, and it is compound to prepare manganese dioxide nanowire/titanium carbide
Material, manganese oxide nano wire is in Ti3C2Surface is evenly distributed securely, effectively increases Ti3C2The chemical property of nano material.
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 manganese dioxide nanowire/carbonization titanium composite material, includes the following steps：
Step 1, Ti is prepared3C2@PDA nano-powders；
Step 2, PEG solution is prepared；By Ti3C2@PDA nano-powders and KMnO4It is added in PEG solution, is uniformly dispersed
Afterwards, 50~90 DEG C are heated to, 1~6h is stirred to react, obtains manganese dioxide nanowire/carbonization 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, PEG solution is prepared in step 2 is specially：The PEG solution of 1~4% (w/w) is prepared, stirring keeps PEG complete
Fully dissolved is in water.
Preferably, KMnO in step 24Using KMnO4Solution.
Further, PEG 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 1~4% (w/w) of PEG solution, KMnO4A concentration of the 20 of solution~
300mmolL-1。
Preferably, first by Ti in step 23C2@PDA nano-powders are added in PEG solution, after being uniformly dispersed, are added
KMnO4。
Further, Ti in step 23C2@PDA nano-powders are added in PEG solution, and first ultrasonic disperse is stirred for, so
After add KMnO4。
Preferably, reaction carries out under water bath condition in step 2.
It is a kind of to utilize manganese dioxide nanowire/carbonization 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.Studies have shown that the autoxidation polymerization using dopamine may be implemented in many organic or inorganic matrix
Surface forms poly-dopamine clad, (such as with matrix：Ceramics, metal oxide, polymer etc.) binding force it is very strong, and by
Contain a large amount of nitrogen-containing group and phenolic hydroxyl group in its structure, poly-dopamine can be used as good second order reaction platform.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 are matrix, KMnO4As manganese source, polyethylene glycol passes through simple liquid as surfactant
Manganese dioxide nanowire/carbonization titanium composite material is prepared in phase reaction.On the one hand, due in KMnO4High-temperature reaction process in,
Ti3C2In Ti also have part be oxidized to form TiO2, to destroy Ti3C2Structure, cause chemical property to reduce, this hair
It is bright in Ti3C2Surface coats PDA, and clad PDA can protect Ti3C2The integrality of structure avoids Ti therein by KMnO4Oxidation and
It causes structure to destroy, influences chemical property.On the other hand, Mn7+Ion outer layer has empty electron orbit, the adjacent benzene two of PDA
Two phenolic hydroxyl groups of phenolic group group can provide two pairs of lone pair electrons, in neutral or alkaline environment, catechol group and Mn7+Ion can
To form relatively stable chelatingligand, the growth for existing for PDA surface metal chemical combination objects of chelation or deposition provide position
Point, i.e. PDA can be by Mn7+It is fixed on Ti3C2Sheet surfaces, and PDA itself has week reduction, 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 very strong adhesiveness on PDA,
The manganese dioxide nanowire of generation can be firmly adhered to Ti3C2Sheet surfaces are not easy to reunite, in Ti3C2Lamella table
Face can be uniformly distributed for a long time.In addition, polyethylene glycol is a kind of nonionic surfactant, the backbone of indention,
The manganese dioxide of generation can be along the molecular chain growth of surfactant, and then generates manganese dioxide nanowire, with poly- second two
The content of the increase of alcohol dosage, manganese dioxide nanowire increases.Gained composite material have superior chemical property, be its into
Application of one step in fields such as ultracapacitor, lithium ion batteries is laid a good foundation.In addition, this simple pyrolysismethod is right due to its
The advantages such as equipment requirement is low, easy to operate, of low cost, are advantageously implemented industrialization large-scale production.
Description of the drawings
Fig. 1 is that the SEM of manganese dioxide nanowire/carbonization 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 manganese dioxide nanowire/carbonization titanium composite material (a) prepared by embodiment 2 sweeps speed (0.002V/s in difference
~0.2V/s) under CV curve graphs (abscissa is voltage, and ordinate is current density)；(b) be its capacity with sweep speed variation
Curve (abscissa is sweep speed, and ordinate is unit capacitance).
Specific implementation mode
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；
Two-dimensional layer Ti is prepared according to the method for patent 201410812056.73C2Nano 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, above-mentioned solution is added, are stirred at room temperature under dark conditions
0.5~2h；Either by 300~500mg Ti3C2A concentration of 12.5~14.0mmolL of 40~400mL are added in nano-powder-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 (a concentration of 50mmolL-1, pH=8.5), the room temperature under dark conditions
Stir 12~48h；Gained mixed solution is centrifuged, deionized water is cleaned to supernatant and is clarified, and is transferred in freeze drier,
It is taken out after 48h and can be obtained 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 manganese dioxide nanowire/carbonization titanium composite material；
First, 5~50mL 1~3% (w/w) PEG solution is prepared, 30min is stirred at room temperature, and so that PEG is dissolved completely in ultrapure
Water；Then, by the Ti obtained by 10~100mg steps (1)3C2@PDA nano-powders are added in PEG 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 manganese dioxide nanowire/carbonization titanium composite material.
Embodiment 1
First, 10mL 2% (w/w) PEG solution is prepared, 30min, which is stirred at room temperature, makes PEG be dissolved completely in ultra-pure water；So
Afterwards, by the Ti of 30mg3C2@PDA nano-powders are added in PEG solution, and ultrasonic disperse 30min is stirred for 1h；After stirring evenly
Add the 50mmolL of 10mL-1KMnO4Solution, 70 DEG C of heating water baths, is stirred to react 3h；Natural cooling after reaction obtains
Manganese dioxide nanowire/carbonization titanium composite material.
Embodiment 2
First, 10mL 2% (w/w) PEG solution is prepared, 30min, which is stirred at room temperature, makes PEG be dissolved completely in ultra-pure water；So
Afterwards, by the Ti of 30mg3C2@PDA nano-powders are added in PEG solution, and ultrasonic disperse 30min is stirred for 1h；After stirring evenly
Add the 100mmolL of 10mL-1KMnO4Solution, 70 DEG C of heating water baths, is stirred to react 3h；Natural cooling after reaction obtains
To manganese dioxide nanowire/carbonization titanium composite material.
Embodiment 3
First, 10mL 2% (w/w) PEG solution is prepared, 30min, which is stirred at room temperature, makes PEG be dissolved completely in ultra-pure water；So
Afterwards, by the Ti of 30mg3C2@PDA nano-powders are added in PEG solution, and ultrasonic disperse 30min is stirred for 1h；After stirring evenly
Add the 200mmolL of 10mL-1KMnO4Solution, 70 DEG C of heating water baths, is stirred to react 3h；Natural cooling after reaction obtains
To manganese dioxide nanowire/carbonization titanium composite material.
Embodiment 4
First, 10mL 2% (w/w) PEG solution is prepared, 30min, which is stirred at room temperature, makes PEG be dissolved completely in ultra-pure water；So
Afterwards, by the Ti of 30mg3C2@PDA nano-powders are added in PEG solution, and ultrasonic disperse 30min is stirred for 1h；After stirring evenly
Add the 100mmolL of 10mL-1KMnO4Solution, 70 DEG C of heating water baths, is stirred to react 1h；Natural cooling after reaction obtains
To manganese dioxide nanowire/carbonization titanium composite material.
Embodiment 5
First, 10mL 2% (w/w) PEG solution is prepared, 30min, which is stirred at room temperature, makes PEG be dissolved completely in ultra-pure water；So
Afterwards, by the Ti of 30mg3C2@PDA nano-powders are added in PEG solution, and ultrasonic disperse 30min is stirred for 1h；After stirring evenly
Add the 100mmolL of 10mL-1KMnO4Solution, 70 DEG C of heating water baths, is stirred to react 2h；Natural cooling after reaction obtains
To manganese dioxide nanowire/carbonization titanium composite material.
Embodiment 6
First, 10mL 2% (w/w) PEG solution is prepared, 30min, which is stirred at room temperature, makes PEG be dissolved completely in ultra-pure water；So
Afterwards, by the Ti of 30mg3C2@PDA nano-powders are added in PEG solution, and ultrasonic disperse 30min is stirred for 1h；After stirring evenly
Add the 100mmolL of 10mL-1KMnO4Solution, 70 DEG C of heating water baths, is stirred to react 4h；Natural cooling after reaction obtains
To manganese dioxide nanowire/carbonization titanium composite material.
Embodiment 7
First, 10mL 2% (w/w) PEG solution is prepared, 30min, which is stirred at room temperature, makes PEG be dissolved completely in ultra-pure water；So
Afterwards, by the Ti of 30mg3C2@PDA nano-powders are added in PEG solution, and ultrasonic disperse 30min is stirred for 1h；After stirring evenly
Add the 100mmolL of 10mL-1KMnO4Solution, 70 DEG C of heating water baths, is stirred to react 5h；Natural cooling after reaction obtains
To manganese dioxide nanowire/carbonization titanium composite material.
Embodiment 8
First, 10mL 2% (w/w) PEG solution is prepared, 30min, which is stirred at room temperature, makes PEG be dissolved completely in ultra-pure water；So
Afterwards, by the Ti of 30mg3C2@PDA nano-powders are added in PEG solution, and ultrasonic disperse 30min is stirred for 1h；After stirring evenly
Add the 100mmolL of 10mL-1KMnO4Solution, 70 DEG C of heating water baths, is stirred to react 6h；Natural cooling after reaction obtains
To manganese dioxide nanowire/carbonization titanium composite material.
Embodiment 9
First, 10mL 2% (w/w) PEG solution is prepared, 30min, which is stirred at room temperature, makes PEG be dissolved completely in ultra-pure water；So
Afterwards, by the Ti of 30mg3C2@PDA nano-powders are added in PEG solution, and ultrasonic disperse 30min is stirred for 1h；After stirring evenly
Add the 100mmolL of 10mL-1KMnO4Solution, 50 DEG C of heating water baths, is stirred to react 3h；Natural cooling after reaction obtains
To manganese dioxide nanowire/carbonization titanium composite material.
Embodiment 10
First, 10mL 2% (w/w) PEG solution is prepared, 30min, which is stirred at room temperature, makes PEG be dissolved completely in ultra-pure water；So
Afterwards, by the Ti of 30mg3C2@PDA nano-powders are added in PEG solution, and ultrasonic disperse 30min is stirred for 1h；After stirring evenly
Add the 100mmolL of 10mL-1KMnO4Solution, 60 DEG C of heating water baths, is stirred to react 3h；Natural cooling after reaction obtains
To manganese dioxide nanowire/carbonization titanium composite material.
Embodiment 11
First, 10mL 2% (w/w) PEG solution is prepared, 30min, which is stirred at room temperature, makes PEG be dissolved completely in ultra-pure water；So
Afterwards, by the Ti of 30mg3C2@PDA nano-powders are added in PEG solution, and ultrasonic disperse 30min is stirred for 1h；After stirring evenly
Add the 100mmolL of 10mL-1KMnO4Solution, 80 DEG C of heating water baths, is stirred to react 3h；Natural cooling after reaction obtains
To manganese dioxide nanowire/carbonization titanium composite material.
Embodiment 12
First, 10mL 2% (w/w) PEG solution is prepared, 30min, which is stirred at room temperature, makes PEG be dissolved completely in ultra-pure water；So
Afterwards, by the Ti of 30mg3C2@PDA nano-powders are added in PEG solution, and ultrasonic disperse 30min is stirred for 1h；After stirring evenly
Add the 100mmolL of 10mL-1KMnO4Solution, 90 DEG C of heating water baths, is stirred to react 3h；Natural cooling after reaction obtains
To manganese dioxide nanowire/carbonization titanium composite material.
Embodiment 13
First, 5mL 2% (w/w) PEG solution is prepared, 30min, which is stirred at room temperature, makes PEG be dissolved completely in ultra-pure water；Then,
By the Ti of 10mg3C2@PDA nano-powders are added in PEG solution, ultrasonic disperse 30min；Then, the 20mmolL of 5mL is added- 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 2% (w/w) PEG solution is prepared, 30min, which is stirred at room temperature, makes PEG be dissolved completely in ultra-pure water；So
Afterwards, by the Ti of 50mg3C2@PDA nano-powders are added in PEG solution, ultrasonic disperse 30min；Then, it is added 30mL's
200mmolL-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 15
First, 50mL 2% (w/w) PEG solution is prepared, 30min, which is stirred at room temperature, makes PEG be dissolved completely in ultra-pure water；So
Afterwards, by the Ti of 70mg3C2@PDA nano-powders are added in PEG solution, ultrasonic disperse 30min；Then, it is added 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 2% (w/w) PEG solution is prepared, 30min, which is stirred at room temperature, makes PEG be dissolved completely in ultra-pure water；So
Afterwards, by the Ti of 100mg3C2@PDA nano-powders are added in PEG solution, ultrasonic disperse 30min；Then, it is added 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 for manganese dioxide nanowire/carbonization titanium composite material that embodiment 2 obtains.It can see
Go out manganese dioxide nanowire and is evenly distributed on Ti3C2Lamella both sides significantly improve the specific surface area of stratified material and increase piece
The distance of interlayer so that the chemical property of manganese dioxide nanowire/carbonization titanium composite material is better than pure Ti3C2。
The manganese dioxide nanowire obtained using embodiment 2/carbonization titanium composite material prepares electrode：First by 50mg dioxies
Change manganese nano wire/carbonization titanium composite material with conductive carbon black and binder (PVDF) with 80:10:10 mass ratio mixing, is added
Appropriate N- methyl-pyrrolidons, grind 10min in the 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, manganese dioxide nanowire/titanium carbide electrode is obtained in 20Mpa pressurizes 1min.
Using three electrode test systems, by manganese dioxide nanowire/titanium carbide 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/L Na2SO4Solution tests manganese dioxide nanowire/titanium carbide 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.As shown in Fig. 2,
(a) it is that manganese dioxide nanowire/titanium carbide sweeps the CV curve graphs under fast (0.002V/s-0.2V/s) in difference, is (b) its capacity
With the change curve for sweeping speed, it can be seen that the purer Ti of its capacity3C2There is great promotion.
The preparation method of manganese dioxide nanowire of the present invention/carbonization titanium composite material, 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 Ti3C2Knot
Ti in structure is aoxidized during the reaction, to protect Ti3C2The integrality of structure；Then with Ti3C2@PDA are matrix,
KMnO4As manganese source, polyethylene glycol prepares manganese dioxide nanowire/carbon as surfactant, by simple liquid phase reactor
Change 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
It is fixed on its position, is reduced to manganese dioxide, and phenolic hydroxyl group makes PDA have very strong adhesiveness, it can be by titanium dioxide
Manganese nano wire is secured and is evenly distributed on Ti3C2Sheet surfaces are not easy to reunite.Using backbone polyethylene glycol as it is non-from
The manganese dioxide of sub- surfactant, generation can be along the molecular chain growth of surfactant, and then generates manganese dioxide nano
Line, gained composite material have superior chemical property.This is for extending Ti3C2Material is in ultracapacitor, lithium ion battery
The application in equal fields, has important practical significance.Compared to reporting other preparation methods, the experiment condition needed for this method
It is fairly simple, it is at low cost, it is easy to operate.
Claims (9)
1. a kind of preparation method of manganese dioxide nanowire/carbonization titanium composite material, which is characterized in that include the following steps：
Step 1, Ti is prepared3C2@PDA nano-powders；
Step 2, PEG solution is prepared；By Ti3C2@PDA nano-powders and KMnO4It is added in PEG solution, after being uniformly dispersed, adds
Heat is stirred to react 1~6h to 50~90 DEG C, obtains manganese dioxide nanowire/carbonization titanium composite material.
2. a kind of preparation method of manganese dioxide nano-plates/carbonization 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 manganese dioxide nanowire/carbonization titanium composite material according to claim 1, feature exist
In preparing PEG solution in step 2 is specially：The PEG solution of 1~4% (w/w) is prepared, stirring makes PEG be dissolved completely in water.
4. a kind of preparation method of manganese dioxide nanowire/carbonization titanium composite material according to claim 1, feature exist
In KMnO in step 24Using KMnO4Solution.
5. a kind of preparation method of manganese dioxide nanowire/carbonization titanium composite material according to claim 4, feature exist
In PEG 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 1~4% (w/w) of PEG solution, KMnO4A concentration of 20~300mmolL of solution-1。
6. a kind of preparation method of manganese dioxide nanowire/carbonization titanium composite material according to claim 1, feature exist
In first by Ti in step 23C2@PDA nano-powders are added in PEG solution, after being uniformly dispersed, add KMnO4。
7. a kind of preparation method of manganese dioxide nanowire/carbonization titanium composite material according to claim 6, feature exist
In Ti in step 23C2@PDA nano-powders are added in PEG solution, and first ultrasonic disperse is stirred for, then adds KMnO4。
8. a kind of preparation method of manganese dioxide nanowire/carbonization titanium composite material according to claim 1, feature exist
In, in step 2 reaction carried out under water bath condition.
9. a kind of compound using manganese dioxide nanowire/titanium carbide made from claim 1-8 any one of them preparation methods
Material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112143890A (en) * | 2019-06-26 | 2020-12-29 | 康荷 | Low-vacuum titanium metal smelting formula and method for smelting titanium metal |
| EP4047062A1 (en) * | 2021-02-19 | 2022-08-24 | Korea Institute of Science and Technology | 2-dimensional mxene surface-modified with catechol derivative, method for preparing the same, and mxene organic ink including the same |
| CN115073974A (en) * | 2021-03-16 | 2022-09-20 | 韩国科学技术研究院 | Methylene having surface modified with catechol derivative, method for producing the same, and meikene organic ink containing the same |
| US11866597B2 (en) | 2020-02-13 | 2024-01-09 | Korea Institute Of Science And Technology | 2-dimensional MXene surface-modified with catechol derivative, method for preparing the same, and MXene organic ink including the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105609319A (en) * | 2016-01-29 | 2016-05-25 | 西北师范大学 | Flaky titanium carbide-loaded manganese dioxide composite material for super capacitor electrode material and preparation of flaky titanium carbide-loaded manganese dioxide composite material |
| CN106206065A (en) * | 2016-09-14 | 2016-12-07 | 安徽师范大学 | A kind of electrode material for super capacitor MnO2the preparation method of@PDA nano composite material |
| CN106698430A (en) * | 2016-12-27 | 2017-05-24 | 陕西科技大学 | Titanium carbide in-situ growth CNTs three-dimensional composite with polydopamine serving as transition layer and preparation method thereof |
| CN107221428A (en) * | 2017-06-13 | 2017-09-29 | 苏州大学 | A kind of metal oxide/MXene two-dimensional nanos compound, its preparation method and application |
-
2018
- 2018-02-02 CN CN201810107197.7A patent/CN108364802A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105609319A (en) * | 2016-01-29 | 2016-05-25 | 西北师范大学 | Flaky titanium carbide-loaded manganese dioxide composite material for super capacitor electrode material and preparation of flaky titanium carbide-loaded manganese dioxide composite material |
| CN106206065A (en) * | 2016-09-14 | 2016-12-07 | 安徽师范大学 | A kind of electrode material for super capacitor MnO2the preparation method of@PDA nano composite material |
| CN106698430A (en) * | 2016-12-27 | 2017-05-24 | 陕西科技大学 | Titanium carbide in-situ growth CNTs three-dimensional composite with polydopamine serving as transition layer and preparation method thereof |
| CN107221428A (en) * | 2017-06-13 | 2017-09-29 | 苏州大学 | A kind of metal oxide/MXene two-dimensional nanos compound, its preparation method and application |
Non-Patent Citations (5)
| Title |
|---|
| DING HOU 等: "Polydopamine and MnO2 core-shell composites for high-performance supercapacitors", 《APPLIED SURFACE SCIENCE》 * |
| JIAN YAN等: "Polydopamine Spheres as Active Templates for Convenient Synthesis of Various Nanostructures", 《SMALL》 * |
| RAGHAVAN BABY RAKHI 等: "Direct Chemical Synthesis of MnO2 Nanowhiskers on Transition-Metal Carbide Surfaces for Supercapacitor Applications", 《ACS APPL. MATER. INTERFACES》 * |
| WEN SHE 等: "Tunable Microwave Absorption Frequency by Aspect Ratio of Hollow Polydopamine@α-MnO2 Microspindles Studied by Electron Holography", 《ACS APPL. MATER. INTERFACES》 * |
| 尧华 等: "纳米α-Mn02形貌调控方法初探", 《化工新型材料》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112143890A (en) * | 2019-06-26 | 2020-12-29 | 康荷 | Low-vacuum titanium metal smelting formula and method for smelting titanium metal |
| US11866597B2 (en) | 2020-02-13 | 2024-01-09 | Korea Institute Of Science And Technology | 2-dimensional MXene surface-modified with catechol derivative, method for preparing the same, and MXene organic ink including the same |
| EP4047062A1 (en) * | 2021-02-19 | 2022-08-24 | Korea Institute of Science and Technology | 2-dimensional mxene surface-modified with catechol derivative, method for preparing the same, and mxene organic ink including the same |
| CN115073974A (en) * | 2021-03-16 | 2022-09-20 | 韩国科学技术研究院 | Methylene having surface modified with catechol derivative, method for producing the same, and meikene organic ink containing the same |
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