CN108190962A - A kind of manganese dioxide nano-plates/carbonization titanium composite material and preparation method thereof - Google Patents

A kind of manganese dioxide nano-plates/carbonization titanium composite material and preparation method thereof Download PDF

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CN108190962A
CN108190962A CN201810108345.7A CN201810108345A CN108190962A CN 108190962 A CN108190962 A CN 108190962A CN 201810108345 A CN201810108345 A CN 201810108345A CN 108190962 A CN108190962 A CN 108190962A
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nano
plates
manganese dioxide
composite material
titanium composite
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朱建锋
李学林
王雷
武文玲
方园
张佩
卫丹
王芬
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract

The present invention provides a kind of manganese dioxide nano-plates/carbonization 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 ultra-pure water, and KMnO is added after being uniformly dispersed4Solution carries out liquid phase reactor；Natural cooling after reaction, you can obtain manganese dioxide nano-plates/carbonization titanium composite material.This method can form equally distributed manganese dioxide nano-plates on titanium carbide surface, and preparation method is low for equipment requirements, easy to operate, of low cost, be advantageously implemented industrialization large-scale production.

Description

A kind of manganese dioxide nano-plates/carbonization titanium composite material and preparation method thereof
Technical field
The invention belongs to the preparing technical field of nano-functional material, a kind of particularly manganese dioxide nano-plates/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] is 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.The discoveries such as Naguib use tetrabutylammonium hydroxide 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 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 easily stacked and influences 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 flexible sandwich style3C2/ CNT extrusion coating papers, purer Ti3C2And Speech, electric conductivity is more excellent, 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 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 shortcomings of cyclical stability of pure manganese dioxide is poor, 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 manganese dioxide nano-plates/carbonization 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, manganese dioxide nano-plates/carbonization titanium composite material is prepared, manganese dioxide nano-plates exist 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：
A kind of preparation method of manganese dioxide nano-plates/carbonization titanium composite material, includes the following steps：
Step 1, Ti is prepared3C2@PDA nano-powders；
Step 2, by Ti3C2@PDA nano-powders and KMnO4It is added to the water, after being uniformly dispersed, is heated to 50~90 DEG C, 1~6h is stirred to react, obtains manganese dioxide nano-plates/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, KMnO in step 24Using KMnO4Solution.
Further, Ti in step 23C2After@PDA nano-powders are added to the water ultrasonic disperse, KMnO is added4Solution.
Further, Ti in step 23C2The ratio between@PDA nano-powders and water are (10~100) mg：(5~50) mL.
Further, Ti in step 23C2@PDA nano-powders and KMnO4The ratio between solution is (10~100) mg：(5~50) ML, wherein, KMnO4A concentration of 20~300mmolL of solution-1。
Preferably, reaction carries out under water bath condition in step 2.
It is a kind of to utilize manganese dioxide nano-plates/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.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, manganese dioxide is prepared by simple liquid phase reactor and is received Rice piece/carbonization titanium composite material.On the one hand, due in KMnO4High-temperature reaction process in, Ti3C2In Ti also have part quilt Oxidation forms TiO2, so as to destroy Ti3C2Structure, chemical property is caused to reduce, the present invention in Ti3C2Surface coats PDA, packet Coating PDA can protect Ti3C2The integrality of structure avoids Ti therein by KMnO4It aoxidizes and structure is caused to destroy, influence electrification Learn performance.On the other hand, Mn7+Ion outer layer has empty electron orbit, two phenol hydroxyls of the catechol group of poly-dopamine Base can provide two pairs of lone pair electrons, in neutral or alkaline environment, catechol group and Mn7+Ion can form relatively stable chela Ligand is closed, the growth for existing for poly-dopamine surface metal chemical combination object of chelation or deposition provide site, i.e., poly- DOPA Amine layer can be by Mn7+It is fixed on Ti3C2Sheet surfaces, and poly-dopamine 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 very strong glue in poly-dopamine The manganese dioxide nano-plates of generation can be firmly adhered to Ti by attached property3C2Sheet surfaces are not easy to reunite, so as in Ti3C2 Sheet surfaces can be uniformly distributed for a long time.Gained composite material have superior chemical property, be its further super The application in the fields such as capacitor, lithium ion battery is laid a good foundation.In addition, this simple pyrolysismethod is since it is to equipment requirement The advantages such as 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 nano-plates/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 nano-plates/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) 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 In Dopamine hydrochloride solution, 0.5~2h is stirred in room temperature shading；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 obtain Ti3C2@PDA nano-powders.
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 nano-plates/carbonization titanium composite material；
First, by 10~100mg steps (3) obtained by Ti3C2@PDA nano-powders are added in 5~50mL ultra-pure waters, are surpassed Sound disperses 30min；Then, 20~300mmolL of 5~50mL is added in-1KMnO4Aqueous solution, 50~90 DEG C of heating water baths, stirring React 1~6h；Natural cooling after reaction, you can obtain manganese dioxide nano-plates/carbonization titanium composite material.
Embodiment 1
First by the Ti of 30mg3C2@PDA nano-powders, are added in 10mL ultra-pure waters, ultrasonic disperse 30min；Then, add Enter the 50mmolL of 10mL-1KMnO4Solution, 70 DEG C of heating water baths, is stirred to react 3h；Natural cooling after reaction, you can obtain two Manganese oxide nanometer sheet/carbonization titanium composite material.
Embodiment 2
First by the Ti of 30mg3C2@PDA nano-powders, are added in 10mL ultra-pure waters, ultrasonic disperse 30min；Then, add Enter the 100mmolL of 10mL-1KMnO4Solution, 70 DEG C of heating water baths, is stirred to react 3h；Natural cooling after reaction, you can Manganese dioxide nano-plates/carbonization titanium composite material.
Embodiment 3
First by the Ti of 30mg3C2@PDA nano-powders, are added in 10mL ultra-pure waters, ultrasonic disperse 30min；Then, add Enter the 200mmolL of 10mL-1KMnO4Solution, 70 DEG C of heating water baths, is stirred to react 3h；Natural cooling after reaction, you can Manganese dioxide nano-plates/carbonization titanium composite material.
Embodiment 4
First by the Ti of 30mg3C2@PDA nano-powders, are added in 10mL ultra-pure waters, ultrasonic disperse 30min；Then, add Enter the 100mmolL of 10mL-1KMnO4Solution, 70 DEG C of heating water baths, is stirred to react 1h；Natural cooling after reaction, you can Manganese dioxide nano-plates/carbonization titanium composite material.
Embodiment 5
First by the Ti of 30mg3C2@PDA nano-powders, are added in 10mL ultra-pure waters, ultrasonic disperse 30min；Then, add Enter the 100mmolL of 10mL-1KMnO4Solution, 70 DEG C of heating water baths, is stirred to react 2h；Natural cooling after reaction, you can Manganese dioxide nano-plates/carbonization titanium composite material.
Embodiment 6
First by the Ti of 30mg3C2@PDA nano-powders, are added in 10mL ultra-pure waters, ultrasonic disperse 30min；Then, add Enter the 100mmolL of 10mL-1KMnO4Solution, 70 DEG C of heating water baths, is stirred to react 4h；Natural cooling after reaction, you can Manganese dioxide nano-plates/carbonization titanium composite material.
Embodiment 7
First by the Ti of 30mg3C2@PDA nano-powders, are added in 10mL ultra-pure waters, ultrasonic disperse 30min；Then, add Enter the 100mmolL of 10mL-1KMnO4Solution, 70 DEG C of heating water baths, is stirred to react 5h；Natural cooling after reaction, you can Manganese dioxide nano-plates/carbonization titanium composite material.
Embodiment 8
First by the Ti of 30mg3C2@PDA nano-powders, are added in 10mL ultra-pure waters, ultrasonic disperse 30min；Then, add Enter the 100mmolL of 10mL-1KMnO4Solution, 70 DEG C of heating water baths, is stirred to react 6h；Natural cooling after reaction, you can Manganese dioxide nano-plates/carbonization titanium composite material.
Embodiment 9
First by the Ti of 30mg3C2@PDA nano-powders, are added in 10mL ultra-pure waters, ultrasonic disperse 30min；Then, add Enter the 100mmolL of 10mL-1KMnO4Solution, 50 DEG C of heating water baths, is stirred to react 1h；Natural cooling after reaction, you can Manganese dioxide nano-plates/carbonization titanium composite material.
Embodiment 10
First by the Ti of 30mg3C2@PDA nano-powders, are added in 10mL ultra-pure waters, ultrasonic disperse 30min；Then, add Enter the 100mmolL of 10mL-1KMnO4Solution, 60 DEG C of heating water baths, is stirred to react 1h；Natural cooling after reaction, you can Manganese dioxide nano-plates/carbonization titanium composite material.
Embodiment 11
First by the Ti of 30mg3C2@PDA nano-powders, are added in 10mL ultra-pure waters, ultrasonic disperse 30min；Then, add Enter the 100mmolL of 10mL-1KMnO4Solution, 80 DEG C of heating water baths, is stirred to react 1h；Natural cooling after reaction, you can Manganese dioxide nano-plates/carbonization titanium composite material.
Embodiment 12
First by the Ti of 30mg3C2@PDA nano-powders, are added in 10mL ultra-pure waters, ultrasonic disperse 30min；Then, add Enter the 100mmolL of 10mL-1KMnO4Solution, 90 DEG C of heating water baths, is stirred to react 1h；Natural cooling after reaction, you can Manganese dioxide nano-plates/carbonization titanium composite material.
Embodiment 13
First by the Ti of 10mg3C2@PDA nano-powders, are added in 5mL ultra-pure waters, ultrasonic disperse 30min；Then, add Enter the 20mmolL of 5mL-1KMnO4Solution, 90 DEG C of heating water baths, is stirred to react 1h；Natural cooling after reaction, you can obtain two Manganese oxide nanometer sheet/carbonization titanium composite material.
Embodiment 14
First by the Ti of 50mg3C2@PDA nano-powders, are added in 30mL ultra-pure waters, ultrasonic disperse 30min；Then, add Enter the 200mmolL of 30mL-1KMnO4Solution, 90 DEG C of heating water baths, is stirred to react 1h；Natural cooling after reaction, you can Manganese dioxide nano-plates/carbonization titanium composite material.
Embodiment 15
First by the Ti of 70mg3C2@PDA nano-powders, are added in 40mL ultra-pure waters, ultrasonic disperse 30min；Then, add Enter the 300mmolL of 30mL-1KMnO4Solution, 90 DEG C of heating water baths, is stirred to react 1h；Natural cooling after reaction, you can Manganese dioxide nano-plates/carbonization titanium composite material.
Embodiment 16
First by the Ti of 100mg3C2@PDA nano-powders, are added in 50mL ultra-pure waters, ultrasonic disperse 30min；Then, Add in the 100mmolL of 50mL-1KMnO4Solution, 90 DEG C of heating water baths, is stirred to react 1h；Natural cooling after reaction, you can Obtain manganese dioxide nano-plates/carbonization titanium composite material.
Fig. 1 is the SEM figures and XRD diagram for manganese dioxide nano-plates/carbonization titanium composite material that embodiment 2 obtains.It can see Go out manganese dioxide nano-plates and be 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 nano-plates/carbonization titanium composite material is better than pure Ti3C2。
The manganese dioxide nano-plates obtained using embodiment 2/carbonization titanium composite material prepares electrode：First by 50mg dioxies Change manganese nanometer sheet/carbonization titanium composite material 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, manganese dioxide nano-plates/titanium carbide electrode is obtained in 20Mpa pressurizes 1min.
Using three electrode test systems, by manganese dioxide nano-plates/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/LNa2SO4Solution tests manganese dioxide nano-plates/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) the CV curve graphs under fast (0.002V/s-0.2V/s) are swept in difference for manganese dioxide nano-plates/titanium carbide, (b) is 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 nano-plates 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, so as to protect Ti3C2The integrality of structure；Then with Ti3C2@PDA are matrix, KMnO4As manganese source, manganese dioxide nano-plates/carbonization titanium composite material is prepared by simple liquid phase reactor, due to PDA structures In containing a large amount of nitrogen-containing group and phenolic hydroxyl group, 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, securely and can be evenly distributed on manganese dioxide nano-plates Ti3C2Sheet surfaces are not easy to reunite, and gained composite material has superior chemical property.This is for extending Ti3C2Material exists The application in the fields such as ultracapacitor, lithium ion battery, has important practical significance.Compared to reporting other preparation methods, Experiment condition needed for this method is fairly simple, at low cost, easy to operate.

Claims (8)

1. the preparation method of a kind of manganese dioxide nano-plates/carbonization titanium composite material, which is characterized in that include the following steps：
Step 1, Ti is prepared3C2@PDA nano-powders；
Step 2, by Ti3C2@PDA nano-powders and KMnO4It is added to the water, after being uniformly dispersed, is heated to 50~90 DEG C, stirring 1~6h is reacted, obtains manganese dioxide nano-plates/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 nano-plates/carbonization titanium composite material according to claim 1, feature exist In KMnO in step 24Using KMnO4Solution.
4. a kind of preparation method of manganese dioxide nano-plates/carbonization titanium composite material according to claim 3, feature exist In Ti in step 23C2After@PDA nano-powders are added to the water ultrasonic disperse, KMnO is added4Solution.
5. a kind of preparation method of manganese dioxide nano-plates/carbonization titanium composite material according to claim 4, feature exist In Ti in step 23C2The ratio between@PDA nano-powders and water are (10~100) mg：(5~50) mL.
6. a kind of preparation method of manganese dioxide nano-plates/carbonization titanium composite material according to claim 3, feature exist In Ti in step 23C2@PDA nano-powders and KMnO4The ratio between solution is (10~100) mg：(5~50) mL, wherein, KMnO4It is molten A concentration of 20~300mmolL-1 of liquid.
7. a kind of preparation method of manganese dioxide nano-plates/carbonization titanium composite material according to claim 1, feature exist In, in step 2 reaction carried out under water bath condition.
It is 8. a kind of compound using manganese dioxide nano-plates/titanium carbide made from claim 1-7 any one of them preparation methods Material.
CN201810108345.7A 2018-02-02 2018-02-02 A kind of manganese dioxide nano-plates/carbonization titanium composite material and preparation method thereof Pending CN108190962A (en)

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CN112103095A (en) * 2020-09-02 2020-12-18 河海大学 Preparation method of manganese dioxide-based composite material applied to supercapacitor and electrochemical performance testing method thereof
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