CN108389732A - A kind of hydro-thermal method prepares the method and its composite material of manganese dioxide/carbon titanium composite material - Google Patents
A kind of hydro-thermal method prepares the method and its composite material of manganese dioxide/carbon titanium composite material Download PDFInfo
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- 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 the method and its composite material that a kind of hydro-thermal method prepares manganese dioxide/carbon titanium composite material, 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 dispersed4, carry out hydro-thermal reaction；Natural cooling after reaction, you can obtain manganese dioxide/carbon titanium composite material.This method can form equally distributed 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, is advantageously implemented industrialization large-scale production.
Description
Technical field
The invention belongs to the preparing technical field of nano-functional material, particularly a kind of hydro-thermal method prepares titanium dioxide
The method and its composite material of manganese/carbonization titanium composite material.
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. is to Ti3C2Equal MXene
Material has carried out intercalation research, uses hydrazine, hydrazine and dimethyl formamide mixture respectively as substance, test result is inserted into and shows,
Interplanar distance increases respectively to 0.2548 and 0.268nm from 0.195nm.The discoveries such as Naguib use tetrabutylammonium hydroxide
(TBAOH) layering is made to 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, and applied in terms of electrochemical capacitor, but its specific capacity is smaller.Rakhi etc. is existed by chemical synthesis
ε-MnO are deposited on MXene lamellas2Nano whisker is to improve the specific capacity of MXene materials.This directly chemically synthesized method obtains
The MnO arrived2It tends to reunite, in Ti3C2Surface distributing inhomogeneity, to influence its chemical property.Liu et al. passes through vacuum
Filter Ti3C2With MnO2Mixed liquor obtains flexible compound paper to improve Ti3C2Fake capacitance performance, but this method cannot be to multiple
The structure of condensation material is controlled.
Invention content
It is an object of the invention to overcome problems of the prior art, provide a kind of hydro-thermal method prepare manganese dioxide/
The method and its composite material of carbonization titanium composite material, using dopamine in Ti3C2Surface coats thin poly-dopamine (PDA) layer,
Lower-cost KMnO is used again4As manganese source, manganese dioxide/carbon titanium composite material, manganese dioxide are prepared using hydro-thermal method
It is evenly distributed securely on the surfaces Ti3C2, 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 method that hydro-thermal method prepares manganese dioxide/carbon 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, carries out hydro-thermal reaction, i.e.,
Obtain 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, Ti in step 23C2@PDA nano-powders are added to the water, and after being uniformly dispersed, add KMnO4, stirring is
It is even, carry out hydro-thermal reaction.
Further, Ti in step 23C2The ratio between@PDA nano-powders and water are (10~100) mg：(10~60) mL.
Preferably, dispersion process specifically uses ultrasonic disperse in step 2.
Preferably, Ti in step 23C2@PDA nano-powders and KMnO4Mass ratio be 1：(0.5~2).
Preferably, hydro-thermal reaction is to react 6~48h at 90~150 DEG C in step 2.
Preferably, hydro-thermal reaction carries out in homogeneous reactor.
It is a kind of to utilize 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.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, it is multiple that manganese dioxide/carbon titanium is prepared by hydro-thermal method
Condensation material.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, the present invention is in Ti3C2Surface coats PDA, and clad PDA can be protected
Protect Ti3C2The integrality of structure avoids Ti therein by KMnO4It aoxidizes and structure is caused to destroy, influence chemical property.It is another
Aspect, Mn7+There is ion outer layer empty electron orbit, two phenolic hydroxyl groups of the catechol group of poly-dopamine can provide two pairs
Lone pair electrons, in neutral or alkaline environment, catechol group and Mn7+Ion can form relatively stable chelatingligand, chela
The growth for existing for poly-dopamine surface metal chemical combination object of cooperation or deposition provide site, i.e. poly-dopamine layer can be by Mn7+
It is fixed on Ti3C2Sheet surfaces, and poly-dopamine itself has week reduction, it can be by Mn7+It is reduced to Mn4+With MnO2Form point
Cloth is in Ti3C2Sheet surfaces, and the presence of catechol group makes it have very strong adhesiveness in poly-dopamine, can incite somebody to action
The manganese dioxide of generation is firmly adhered to Ti3C2Sheet surfaces are not easy to reunite, in Ti3C2Sheet surfaces can be for a long time
It is uniformly distributed.Gained composite material has superior chemical property.It is it further in ultracapacitor, lithium ion battery etc.
The application in field is laid a good foundation.In addition, this simple pyrolysismethod is low for equipment requirements, easy to operate, of low cost due to its
Etc. advantages, be advantageously implemented industrialization large-scale production.
Description of the drawings
Fig. 1 is that the SEM of manganese dioxide/carbon titanium composite material prepared by embodiment 2 schemes (a) and XRD diagram (b) (abscissa
For X-ray incident angle, ordinate is intensity).
Fig. 2 is that manganese dioxide/carbon titanium composite material (a) prepared by embodiment 2 sweeps speed (0.002V/s-0.2V/ in difference
S) the CV curve graphs under (abscissa is voltage, and ordinate is current density)；(b) it is that its capacity is (horizontal with the change curve for sweeping speed
Coordinate 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 composite materials；
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 (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
Taking-up 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/carbon titanium composite material；
First, by the Ti obtained by 10~100mg steps (3)3C2@PDA nano-powders are added in 10~60mL ultra-pure waters,
Ultrasonic disperse 30min；5~200mg KMnO are added after being uniformly dispersed4, stir 1h；It is transferred in homogeneous water heating kettle, is put into
Phase reaction device carries out hydro-thermal reaction；Natural cooling is to get to manganese dioxide/carbon titanium composite material after reaction.Wherein, water
Thermal response temperature is 90~150 DEG C, and the reaction time is 6~48h.Wherein, the mass ratio of Ti3C2@PDA nano-powders and KMnO4
It is 1：(0.5~2).
Embodiment 1
First by the Ti of 30mg3C2@PDA nano-powders, are added in 30mL ultra-pure waters, ultrasonic disperse 30min；Dispersion is equal
31.6mg KMnO are added after even4, stir 1h；It is transferred in homogeneous water heating kettle, is put into 90 DEG C of reactions of homogeneous reactor for 24 hours；Instead
Natural cooling is to get to manganese dioxide/carbon titanium composite material after answering.
Embodiment 2
First by the Ti of 30mg3C2@PDA nano-powders, are added in 30mL ultra-pure waters, ultrasonic disperse 30min；Dispersion is equal
31.6mg KMnO are added after even4, stir 1h；It is transferred in homogeneous water heating kettle, is put into 100 DEG C of reactions of homogeneous reactor for 24 hours；
Natural cooling is to get to manganese dioxide/carbon titanium composite material after reaction.
Embodiment 3
First by the Ti of 30mg3C2@PDA nano-powders, are added in 30mL ultra-pure waters, ultrasonic disperse 30min；Dispersion is equal
31.6mg KMnO are added after even4, stir 1h；It is transferred in homogeneous water heating kettle, is put into 110 DEG C of reactions of homogeneous reactor for 24 hours；
Natural cooling is to get to manganese dioxide/carbon titanium composite material after reaction.
Embodiment 4
First by the Ti of 30mg3C2@PDA nano-powders, are added in 30mL ultra-pure waters, ultrasonic disperse 30min；Dispersion is equal
31.6mg KMnO are added after even4, stir 1h；It is transferred in homogeneous water heating kettle, is put into 120 DEG C of reactions of homogeneous reactor for 24 hours；
Natural cooling is to get to manganese dioxide/carbon titanium composite material after reaction.
Embodiment 5
First by the Ti of 30mg3C2@PDA nano-powders, are added in 30mL ultra-pure waters, ultrasonic disperse 30min；Dispersion is equal
31.6mg KMnO are added after even4, stir 1h；It is transferred in homogeneous water heating kettle, is put into 130 DEG C of reactions of homogeneous reactor for 24 hours；
Natural cooling is to get to manganese dioxide/carbon titanium composite material after reaction.
Embodiment 6
First by the Ti of 30mg3C2@PDA nano-powders, are added in 30mL ultra-pure waters, ultrasonic disperse 30min；Dispersion is equal
31.6mg KMnO are added after even4, stir 1h；It is transferred in homogeneous water heating kettle, is put into 140 DEG C of reactions of homogeneous reactor for 24 hours；
Natural cooling is to get to manganese dioxide/carbon titanium composite material after reaction.
Embodiment 7
First by the Ti of 30mg3C2@PDA nano-powders, are added in 30mL ultra-pure waters, ultrasonic disperse 30min；Dispersion is equal
31.6mg KMnO are added after even4, stir 1h；It is transferred in homogeneous water heating kettle, is put into 150 DEG C of reactions of homogeneous reactor for 24 hours；
Natural cooling is to get to manganese dioxide/carbon titanium composite material after reaction.
Embodiment 8
First by the Ti of 30mg3C2@PDA nano-powders, are added in 30mL ultra-pure waters, ultrasonic disperse 30min；Dispersion is equal
31.6mg KMnO are added after even4, stir 1h；It is transferred in homogeneous water heating kettle, is put into 100 DEG C of reaction 6h of homogeneous reactor；Instead
Natural cooling is to get to manganese dioxide/carbon titanium composite material after answering.
Embodiment 9
First by the Ti of 30mg3C2@PDA nano-powders, are added in 30mL ultra-pure waters, ultrasonic disperse 30min；Dispersion is equal
31.6mg KMnO are added after even4, stir 1h；It is transferred in homogeneous water heating kettle, is put into 100 DEG C of reaction 12h of homogeneous reactor；
Natural cooling is to get to manganese dioxide/carbon titanium composite material after reaction.
Embodiment 10
First by the Ti of 30mg3C2@PDA nano-powders, are added in 30mL ultra-pure waters, ultrasonic disperse 30min；Dispersion is equal
31.6mg KMnO are added after even4, stir 1h；It is transferred in homogeneous water heating kettle, is put into 100 DEG C of reaction 36h of homogeneous reactor；
Natural cooling is to get to manganese dioxide/carbon titanium composite material after reaction.
Embodiment 11
First by the Ti of 30mg3C2@PDA nano-powders, are added in 30mL ultra-pure waters, ultrasonic disperse 30min；Dispersion is equal
31.6mg KMnO are added after even4, stir 1h；It is transferred in homogeneous water heating kettle, is put into 100 DEG C of reaction 48h of homogeneous reactor；
Natural cooling is to get to manganese dioxide/carbon titanium composite material after reaction.
Embodiment 12
First by the Ti of 10mg3C2@PDA nano-powders, are added in 10mL ultra-pure waters, ultrasonic disperse 30min；Dispersion is equal
5mg KMnO are added after even4, stir 1h；It is transferred in homogeneous water heating kettle, is put into 100 DEG C of reaction 12h of homogeneous reactor；Reaction
After natural cooling to get to manganese dioxide/carbon titanium composite material.
Embodiment 13
First by the Ti of 50mg3C2@PDA nano-powders, are added in 40mL ultra-pure waters, ultrasonic disperse 30min；Dispersion is equal
70mg KMnO are added after even4, stir 1h；It is transferred in homogeneous water heating kettle, is put into 100 DEG C of reaction 12h of homogeneous reactor；Instead
Natural cooling is to get to manganese dioxide/carbon titanium composite material after answering.
Embodiment 14
First by the Ti of 70mg3C2@PDA nano-powders, are added in 50mL ultra-pure waters, ultrasonic disperse 30min；Dispersion is equal
100mg KMnO are added after even4, stir 1h；It is transferred in homogeneous water heating kettle, is put into 100 DEG C of reaction 12h of homogeneous reactor；Instead
Natural cooling is to get to manganese dioxide/carbon titanium composite material after answering.
Embodiment 15
First by the Ti of 100mg3C2@PDA nano-powders, are added in 60mL ultra-pure waters, ultrasonic disperse 30min；Dispersion is equal
200mg KMnO are added after even4, stir 1h；It is transferred in homogeneous water heating kettle, is put into 100 DEG C of reaction 12h of homogeneous reactor；Instead
Natural cooling is to get to manganese dioxide/carbon titanium composite material after answering.
Fig. 1 is the SEM figures and XRD diagram for the manganese dioxide/carbon titanium composite material that embodiment 2 obtains.It can be seen that dioxy
Change manganese and is evenly distributed on Ti3C2Lamella both sides significantly improve the specific surface area of stratified material and increase the distance of piece interlayer,
So that the chemical property of manganese dioxide/carbon titanium composite material is better than pure Ti3C2。
The manganese dioxide/carbon titanium obtained using embodiment 2 is received composite material and prepares electrode：First, by 50g titanium dioxides
Manganese/carbonization titanium composite material is with conductive carbon black and binder (PVDF) with 80:10:10 mass ratio mixing, is added appropriate N- first
Base-pyrrolidones, grinds 10min in the agate mortar.Secondly, above-mentioned suspension is taken to drop to 2cm*1cm sizes with liquid-transfering gun
Nickel foam on, active material area be 1cm*1cm.Then, in vacuum drying chamber, dry 12h at 120 DEG C.Finally, it will do
Dry good electrode slice obtains manganese dioxide/carbon Ti electrode under press in 20Mpa pressurizes 1min.
Using three electrode test systems, by the manganese dioxide/carbon Ti electrode (working electrode) of making and platinum electrode (to electricity
Pole), saturated calomel electrode (reference electrode) easy ultracapacitor is assembled into electrolytic cell, wherein electrolyte is
1.0mol/L Na2SO4Solution tests the electricity of manganese dioxide/carbon Ti electrode using Shanghai Chen Hua CHI660E electrochemical workstations
Chemical property, such as Cyclic voltamogram curve, constant current charge-discharge, AC impedance and cycle life.Shown in Fig. 2, (a) is titanium dioxide
Manganese/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 method that hydro-thermal method of the present invention prepares manganese dioxide/carbon 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, manganese dioxide/carbon titanium composite material is prepared by hydro-thermal method.It is a large amount of due to containing in PDA structures
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 and has very strong adhesiveness, can manganese dioxide nano-plates securely and be evenly distributed on Ti3C2Lamella table
Face is not easy to reunite, and gained composite material has superior chemical property.This is for extending Ti3C2Material ultracapacitor,
The application in the fields such as lithium ion battery, has important practical significance.Compared to reporting other preparation methods, needed for this method
Experiment condition it is fairly simple, it is at low cost, it is easy to operate.
Claims (9)
1. a kind of method that hydro-thermal method prepares 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, by Ti3C2@PDA nano-powders and KMnO4Be added to the water, after being uniformly dispersed, carry out hydro-thermal reaction to get to
Manganese dioxide/carbon titanium composite material.
2. the method that a kind of hydro-thermal method according to claim 1 prepares manganese dioxide/carbon titanium composite material, 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. the method that a kind of hydro-thermal method according to claim 1 prepares manganese dioxide/carbon titanium composite material, feature exist
In Ti in step 23C2@PDA nano-powders are added to the water, and after being uniformly dispersed, add KMnO4, stir evenly, it is anti-to carry out hydro-thermal
It answers.
4. the method that a kind of hydro-thermal method according to claim 3 prepares manganese dioxide/carbon titanium composite material, feature exist
In Ti in step 23C2The ratio between@PDA nano-powders and water are (10~100) mg：(10~60) mL.
5. the method that a kind of hydro-thermal method according to claim 1 prepares manganese dioxide/carbon titanium composite material, feature exist
In dispersion process specifically uses ultrasonic disperse in step 2.
6. the method that a kind of hydro-thermal method according to claim 1 prepares manganese dioxide/carbon titanium composite material, feature exist
In Ti in step 23C2@PDA nano-powders and KMnO4Mass ratio be 1：(0.5~2).
7. the method that a kind of hydro-thermal method according to claim 1 prepares manganese dioxide/carbon titanium composite material, feature exist
In hydro-thermal reaction is to react 6~48h at 90~150 DEG C in step 2.
8. the method that a kind of hydro-thermal method according to claim 1 prepares manganese dioxide/carbon titanium composite material, feature exist
In hydro-thermal reaction carries out in homogeneous reactor.
9. a kind of utilizing manganese dioxide/carbon titanium composite material made from claim 1-8 any one of them preparation methods.
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| CN111180701A (en) * | 2020-01-06 | 2020-05-19 | 深圳大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
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