CN109167066A - A kind of preparation method of few layer titanium carbide growth in situ nitrogen-doped carbon nanometer pipe three-dimensional composite material - Google Patents
A kind of preparation method of few layer titanium carbide growth in situ nitrogen-doped carbon nanometer pipe three-dimensional composite material Download PDFInfo
- Publication number
- CN109167066A CN109167066A CN201811021250.8A CN201811021250A CN109167066A CN 109167066 A CN109167066 A CN 109167066A CN 201811021250 A CN201811021250 A CN 201811021250A CN 109167066 A CN109167066 A CN 109167066A
- Authority
- CN
- China
- Prior art keywords
- titanium carbide
- few layer
- added
- composite material
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the preparation technical field of nano-functional material, in particular to a kind of preparation method of few layer titanium carbide growth in situ nitrogen-doped carbon nanometer pipe three-dimensional composite material, by ternary layered Ti3AlC2Ceramic powder submerges in a solution of hydrofluoric acid, ultrapure water and dehydrated alcohol eccentric cleaning are used after heating stirring, then drying obtains two-dimensional layer titanium carbide nano-powder, is added into tetramethyl ammonium hydroxide solution, heating stirring is centrifuged to obtain few layer titanium carbide nanometer sheet dispersion liquid with deionized water；Cobalt salt is added in few layer of titanium carbide nanometer sheet dispersion liquid and is reacted, dicyandiamide is added, heating stirring to dicyandiamide is completely dissolved, then freezes, then obtains precursor powder by freeze-drying；By precursor powder it is levigate after be heat-treated, obtain few layer titanium carbide growth in situ nitrogen-doped carbon nanometer pipe three-dimensional composite material.The present invention using few layer of titanium carbide as carrier, prepare three-dimensional composite material as catalyst, dicyandiamide as carbon and nitrogen sources, using simple pyrolysismethod, can be improved the chemical property of few layer of titanium carbide by cobalt.
Description
Technical field
The invention belongs to the preparation technical fields of nano-functional material, particularly a kind of to lack layer titanium carbide growth in situ
The preparation method of nitrogen-doped carbon nanometer pipe three-dimensional composite material.
Background technique
Transition metal carbide or carbon/nitride MXenes are the newcomer in the two-dimensional material world, structure and graphene
It is similar.MXene is prepared by selective etch auxiliary liquid phase stripping method, removes the A layer element in MAX phase by corrosion, and
And it is constant to be able to maintain original MX structure, has excellent electricity, optics and mechanical property.Compared with conventional two-dimensional material,
For MXenes while with metalloid electric conductivity, the functional groups such as surface-F abundant ,-OH also assign its excellent chemical reaction
Activity and hydrophily, it is expected to as the ideal host material for constructing nano composite structure.
For New Two Dimensional MXene nano material, A atomic layer is being etched through liquid chemical method from MAX crystal
In the process, the two-dimentional MXenes prepared is the stacked body of multi-layer nano piece.These MX layers of stacking hinders two-dimensional material table
Area make full use of and electrolyte/coming into full contact between collector and electrode slice.But between multilayer MXene synusia
Interaction force it is very strong, simple mechanical stripping method can only obtain minimal amount of individual layer nanometer sheet, and preparation efficiency is extremely low.Pass through
Suitable lewis' acid is selected to weaken its interlaminar action power in MXene interlayer intercalation, then carrying out delamination through ultrasound or oscillation is one
The practicable method of kind.
Carbon nanotube is as monodimension nanometer material, and light-weight, hexagonal structure connection is perfect, has excellent mechanics, electricity
And chemical property.Carbon nanotube application field is very extensive, and high-intensitive characteristic makes it can be used as ultra-fine high strength fibre,
Also it can be used as the reinforcing material of other fibers, metal, ceramics etc..Carbon nanotube is considered as the ultimate shape of composite material hardening constituent
Formula, in field of nanocomposite materials, carbon nanotube has huge application potential as strengthening phase and conductive phase.
Document " Peng Yu, Yanwei Ma；Nanoscale, 2018,10:5906-5913 " report is by few layer of titanium carbide
Dispersion liquid is sufficiently mixed with CNTs dispersion liquid by ultrasonic treatment, is then filtered mixed liquor, is dried to obtain d-Ti3C2/ CNT is multiple
Close film；But the price of commercialization CNTs is relatively high, and the two mixing in conjunction with without the secured of growth in situ.
Summary of the invention
It is an object of the invention to overcome problems of the prior art, a kind of few layer titanium carbide growth in situ nitrogen is provided
Doped carbon nanometer pipe three-dimensional composite material and preparation method thereof, using lower-cost dicyandiamide as carbon source, using cobalt as urging
Agent prepares few layer titanium carbide growth in situ nitrogen-doped carbon nanometer pipe three-dimensional composite material, energy using few layer of titanium carbide as matrix
Enough chemical properties for improving few layer titanium carbide nano material.
In order to achieve the above object, the present invention adopts the following technical scheme: (claim)
A kind of preparation method of few layer titanium carbide growth in situ nitrogen-doped carbon nanometer pipe three-dimensional composite material, comprising the following steps:
(1) by ternary layered Ti3AlC2Ceramic powder submerges in a solution of hydrofluoric acid, is centrifugated after heating stirring, and precipitating is used
Dehydrated alcohol eccentric cleaning, then by gained precipitating drying to get two-dimensional layer titanium carbide nano-powder；
(2) the two-dimensional layer titanium carbide nano-powder for taking step (1) to prepare is added in tetramethyl ammonium hydroxide solution, and heating is stirred
It mixes, is centrifuged to obtain upper layer suspension to be less layer titanium carbide nanometer sheet dispersion liquid with deionized water；
(3) cobalt salt is added in few layer of titanium carbide nanometer sheet dispersion liquid and is reacted, dicyandiamide is added after reaction, heated
Stirring is completely dissolved to dicyandiamide, is then freezed, then be freeze-dried to obtain precursor powder；
(4) by precursor powder it is levigate after be heat-treated, it is three-dimensional to obtain few layer titanium carbide growth in situ nitrogen-doped carbon nanometer pipe
Composite material.
Preferably, the mass fraction of hydrofluoric acid solution described in step (1) is 40 wt.%, the ternary layered Ti3AlC2
The mass volume ratio of ceramic powder and hydrofluoric acid solution is 3 g:50 mL.
Preferably, which is characterized in that the mass fraction of tetramethyl ammonium hydroxide solution described in step (2) is 25 wt.%,
The mass volume ratio of two-dimensional layer titanium carbide nano-powder described in step (2) and tetramethyl ammonium hydroxide solution is 0.2 g:(5
~ 30) mL。
Preferably, the few layer of specific preparation method of titanium carbide nanometer sheet dispersion liquid described in step (2) is by deionization
Water is added in the sediment after being centrifuged for the first time, the suspension obtained after being centrifuged again after ultrasonic disperse is uniform, then plus deionized water
Centrifuging and taking suspension again after ultrasonic disperse is uniform, takes 5 ~ 6 times；Heating stirring described in step (2) is to stir 24 at 30 DEG C
h；Few layer titanium carbide nanometer sheet content is 1 mg/mL in step (2) few layer titanium carbide nanometer sheet dispersion liquid.
Preferably, stirring described in step (1) is in 50 DEG C of 72 h of stirring；Precipitating dehydrated alcohol is centrifuged clear
Being washed till centrifuged supernatant pH is 6；The drying is to dry in 60 DEG C of vacuum oven；Described is clear with dehydrated alcohol
Washing number is 4 ~ 6 times.
Preferably, the cobalt salt being added in step (3) can be four acetate hydrate cobalts, cobalt chloride hexahydrate, six nitric hydrates
Cobalt or Cobalt monosulfate heptahydrate.
Preferably, the condition reacted in step (3) is in 30 min of room temperature ultrasound；The temperature of heating stirring is 90 DEG C；Step
Suddenly the mass ratio of few layer of titanium carbide in (3), cobalt salt and dicyandiamide is (0.1 ~ 0.2): (0.2 ~ 0.4): (0.6 ~
1.0)；Wherein the power of the ultrasound is 240 watts.
Preferably, heat treatment described in step (4) carries out under the protection of nitrogen；Heat treatment temperature be 700 DEG C ~
900 DEG C, soaking time is the h of 0.5 h ~ 2；1 DEG C/min ~ 2 DEG C of heating rate/min of heat treatment.
Above-mentioned preparation method, specific operating procedure are as follows:
(1) first by the ternary layered Ti of 3 g3AlC2Ceramic powder is slowly immersed in 50 mL hydrofluoric acid solutions (40 wt.%),
Corrosion product is centrifuged after 72 h of magnetic agitation at 50 DEG C, is with dehydrated alcohol eccentric cleaning to supernatant pH value
6, then will gained precipitating in a vacuum drying oven at 60 DEG C drying to get arriving two-dimensional layer titanium carbide nano-powder；
(2) 0.2 g titanium carbide nano-powder is taken to be added in the mL of 5mL ~ 30 tetramethyl ammonium hydroxide solution (25 wt.%), 30
It at DEG C after 24 h of heating stirring, is then centrifuged for separating, deionized water is added in the sediment after being centrifuged for the first time, is uniformly dispersed
Take suspension after being centrifuged again afterwards, then plus deionized water be uniformly dispersed after centrifuging and taking suspension again, take 5 times ~ 6 times, merging is
Few layer titanium carbide nanometer sheet dispersion liquid；
(3) cobalt salt is added to progress 30 min of room temperature ultrasound in few layer of titanium carbide nanometer sheet dispersion liquid, be added after reaction
Dicyandiamide is stirred at 90 DEG C and is completely dissolved to dicyandiamide, 12 h is then freezed at -18 DEG C, then freeze at -80 DEG C
Dry 48 h obtain precursor powder；Wherein the mass ratio of few the layer titanium carbide, cobalt salt and dicyandiamide is (0.1 ~ 0.2):
(0.2 ~ 0.4): (0.6 ~ 1.0)；
(4) precursor powder being heat-treated under the protection of nitrogen after levigate, heat treatment temperature is 700 DEG C ~ 900 DEG C,
Soaking time is the h of 0.5 h ~ 2, obtains few layer titanium carbide growth in situ nitrogen-doped carbon nanometer pipe three-dimensional composite material；It is wherein hot
The heating rate of processing is 1 DEG C/min ~ 2 DEG C/min.
Few layer titanium carbide growth in situ nitrogen-doped carbon nanometer pipe three-dimensional composite wood made from-kind of the above-mentioned preparation method of utilization
Material.
A kind of application of above-mentioned few layer titanium carbide growth in situ nitrogen-doped carbon nanometer pipe three-dimensional composite material, it is described three-dimensional multiple
Condensation material can be applied to electrochemical energy storage materials, absorbing material or catalyst carrier.
D-Ti of the present invention3C2@N-CNTs three-dimensional composite material is to lack layer titanium carbide by two-dimensional layer and be grown on few layer of carbonization
The nitrogen-doped carbon nanometer pipe on titanium surface forms, and provides electron propagation ducts using carbon nanotube, improves the conductivity of material, and lacks
The transmittability between carbon nanotube can be improved in layer titanium carbide, to efficiently solve the heat of one-dimensional carbon nanotube and two-dimentional titanium carbide
With conductibility outside the directional dependence of electron-transport and lower face, make composite material that all there is good electrical property in three-dimensional space
Energy.Three-dimensional composite material prepared by the present invention is upper with important in electrochemical energy storage materials, absorbing material and catalyst carrier etc.
Use value.Document is searched for, not yet someone in few layer of titanium carbide surface in situ grows nitrogen-doped carbon nanometer pipe so far for discovery,
And realize the controllable growth of few layer titanium carbide surface carbon nanotube.
The utility model has the advantages that
(1) present invention prepares d-Ti using simple pyrolysismethod3C2@N-CNTs three-dimensional composite material, this method can it is low at
This, quick, environmental protection, safety by changing the content of dicyandiamide and the ratio of few layer titanium carbide and cobalt salt in presoma, from
And realize the controllable growth of few layer titanium carbide surface nitrogen-doped carbon nanometer pipe length and density.
(2) nitrogen-doped carbon nanometer pipe is evenly distributed on few layer of titanium carbide lamella two sides, significantly improves the ratio of stratified material
Surface area and the distance of piece interlayer is increased, and improve the electric conductivity and magnetism of few layer of titanium carbide, so that d-Ti3C2@N-CNTs
The chemical property of three-dimensional composite material is better than pure titanium carbide and few layer titanium carbide, and is it further in lithium-ion electric
The application in the fields such as pond, supercapacitor is laid a good foundation.
(3) the simple pyrolysismethod that uses of the present invention is due to advantages such as its low for equipment requirements, easy to operate, function admirables,
It is advantageously implemented industrialization large-scale production.
Detailed description of the invention
Fig. 1 is d-Ti prepared by embodiment 13C2The SEM figure (a) and XRD (b) of@N-CNTs three-dimensional composite material.
Fig. 2 is d-Ti prepared by embodiment 13C2@N-CNTs three-dimensional composite material is applied to lithium-sulfur cell: (a) 0.5 C electricity
Cycle performance under current density, (b) high rate performance.
Fig. 3 is d-Ti made from embodiment 1-3 difference pyrolysis temperature3C2The SEM of@N-CNTs three-dimensional composite material schemes, wherein
(a) it is 800 DEG C, (b) is 700 DEG C, (c) is 900 DEG C.
Fig. 4 is the d-Ti clapped under 8 different amplification of embodiment3C2The SEM of@N-CNTs three-dimensional composite material schemes, wherein
(a) it is 15000x, (b) is 5000x, (c) is 2000x.
Specific embodiment
The present invention is described in further details with embodiment with reference to the accompanying drawing.
Embodiment 1
Firstly, by the ternary layered Ti of 3 g3AlC2Ceramic powder is slowly immersed in 50 in 50 mL hydrofluoric acid solutions (40 wt.%)
72 h of magnetic agitation at DEG C, revolving speed are 500 r/min, and then corrosion product is centrifuged, and 8000 r/min are with anhydrous
Ethyl alcohol eccentric cleaning to supernatant pH value is 6, by gained sediment in 60 DEG C of vacuum ovens 24 h drying to get to two
Tie up stratiform titanium carbide nano-powder.Then, take 0.2 g titanium carbide nano-powder that 10 mL tetramethyl ammonium hydroxide solutions (25 are added
Wt.% it in), is centrifugated after 24 h of heating stirring at 30 DEG C, adds deionized water and be centrifuged to obtain few layer titanium carbide and receive
Rice piece dispersion liquid, dispersion liquid concentration is about 1 mg/mL.It takes 125 mL to lack layer titanium carbide nanometer sheet dispersion liquid, 0.25 g tetra- is added
Acetate hydrate cobalt, 30 min of ultrasonic disperse, ultrasonic power are 240 watts；Secondly, 0.85 g dicyandiamide is added, by above-mentioned mixed liquor
Stirring to dicyandiamide dissolves at 90 DEG C, and 12 h, then 48 h of vacuum freeze drying at -80 DEG C are then freezed at -18 DEG C
Obtain presoma；Finally, precursor powder is transferred in nitrogen atmosphere tube furnace, it is heated to the heating rate of 2 DEG C/min
800 DEG C, 2 h are pyrolyzed, is taken out after room temperature is cooled under the protection of nitrogen, d-Ti can be obtained3C2@N-CNTs three-dimensional composite wood
Material.
D-Ti prepared by 35 mg3C2@N-CNTs three-dimensional composite material and the agate mortar grinding 10 of 65 mg sublimed sulfurs
Min is uniformly mixed, and is then charged into polytetrafluoroethyllining lining, the air in polytetrafluoroethyllining lining is replaced with hand by glove box
Argon gas in casing is simultaneously packed into reaction kettle, and 6 h are heated at 155 DEG C and obtain d-Ti3C2@N-CNTs/S composite material.Work electricity
Pole is prepared by slurry coating processes: slurry by 70% active material, 20% acetylene black and 10% polyvinylidene fluoride
(PVDF) binder is dissolved in N-Methyl pyrrolidone (NMP) and is made, and is uniformly coated in aluminum foil current collector.Finally, electric
Pole is in 60 DEG C of dryings.Use lithium foil as cathode and polypropylene (PP) film Celgard 2400 in the glove box equipped with argon gas
It is assembled as diaphragm by battery is tested.Electrolyte is that 1 mol/LLiTFSI and 0.1 mol/LLiNO is added3, volume ratio is
The 1,3- dioxolanes (DOL) of 1:1 and the mixed solvent of 1,2- dimethoxy-ethane (DME).Button cell is in voltage window
To carry out constant current charge-discharge test using button cell of the Wuhan LAND tester to assembling under 1.7-2.8 V, cycle performance
Current density be 0.5 C (mAh/g of 1 C=1675), high rate performance test current density be 0.2 C, 0.5 C, 1 C, 2 C,
3 C, 5 C, 0.2 C.
Embodiment 2
Firstly, by the ternary layered Ti of 3 g3AlC2Ceramic powder is slowly immersed in 50 mL hydrofluoric acid solutions (40 wt.%), and 50
72 h of magnetic agitation at DEG C, revolving speed are 500 r/min, and then corrosion product is centrifuged, and 8000 r/min are with ultrapure
Water eccentric cleaning to supernatant pH value is 6, then with washes of absolute alcohol 5 times, by gained sediment in 60 DEG C of vacuum ovens
24 h dry to arrive two-dimensional layer titanium carbide nano-powder.Then, take 0.2 g titanium carbide nano-powder that 10 mL tetramethyls are added
In base Ammonia (25 wt.%), be centrifugated after 24 h of heating stirring at 30 DEG C, add deionized water from
For gains in depth of comprehension to few layer titanium carbide nanometer sheet dispersion liquid, dispersion liquid concentration is about 1 mg/mL.100 mL are taken to lack layer titanium carbide nanometer sheet point
0.2 g C is added in dispersion liquid4H6CoO4·4(H2O), 30 min of ultrasonic disperse, ultrasonic power are 240 watts；Secondly, 0.85 g is added
Above-mentioned mixed liquor is stirred to dicyandiamide at 90 DEG C and is dissolved, 12 h then freezed at -18 DEG C, then -80 by dicyandiamide
48 h of vacuum freeze drying obtains presoma at DEG C；Finally, precursor powder is transferred in nitrogen atmosphere tube furnace, with 2 DEG C/
The heating rate of min is heated to 700 DEG C, is pyrolyzed 2 h, takes out after room temperature is cooled under the protection of nitrogen, can obtain d-
Ti3C2@N-CNTs three-dimensional composite material.
Embodiment 3
Firstly, by the ternary layered Ti of 3 g3AlC2 Ceramic powder is slowly immersed in 50 mL hydrofluoric acid solutions (40 wt.%), and 50
72 h of magnetic agitation at DEG C, revolving speed are 500 r/min, and then corrosion product is centrifuged, and 8000 r/min are with ultrapure
Water eccentric cleaning to supernatant pH value is 6, then with washes of absolute alcohol 5 times, by gained sediment in 60 DEG C of vacuum ovens
24 h dry to arrive two-dimensional layer titanium carbide nano-powder.Then, take 0.2 g titanium carbide nano-powder that 5 mL tetramethyls are added
In base Ammonia (25 wt.%), be centrifugated after 24 h of heating stirring at 30 DEG C, add deionized water from
For gains in depth of comprehension to few layer titanium carbide nanometer sheet dispersion liquid, dispersion liquid concentration is about 1 mg/mL.200 mL are taken to lack layer titanium carbide nanometer sheet point
Dispersion liquid, is added 0.4 g cobalt chloride hexahydrate, 30 min of ultrasonic disperse, and ultrasonic power is 240 watts；Secondly, it is bis- that 0.85 g is added
Above-mentioned mixed liquor is stirred to dicyandiamide at 90 DEG C and is dissolved, 12 h then freezed at -18 DEG C, then at -80 DEG C by cyanamide
Lower 48 h of vacuum freeze drying obtains presoma；Finally, precursor powder is transferred in nitrogen atmosphere tube furnace, with 2 DEG C/min
Heating rate be heated to 900 DEG C, be pyrolyzed 2 h, taken out after room temperature is cooled under the protection of nitrogen, d-Ti can be obtained3C2@N-
CNTs three-dimensional composite material.
Embodiment 4
Firstly, by the ternary layered Ti of 3 g3AlC2Ceramic powder is slowly immersed in 50 mL hydrofluoric acid solutions (40 wt.%), and 50
72 h of magnetic agitation at DEG C, revolving speed are 500 r/min, and then corrosion product is centrifuged, and 8000 r/min are with ultrapure
Water eccentric cleaning to supernatant pH value is 6, then with washes of absolute alcohol 5 times, by gained sediment in 60 DEG C of vacuum ovens
24 h dry to arrive two-dimensional layer titanium carbide nano-powder.Then, take 0.2 g titanium carbide nano-powder that 10 mL tetra- are added
In ammonium hydroxide solution (25 wt.%), it is centrifugated after 24 h of heating stirring at 30 DEG C, adds deionized water
Centrifugation obtains few layer titanium carbide nanometer sheet dispersion liquid, and dispersion liquid concentration is about 1 mg/mL.100 mL are taken to lack layer titanium carbide nanometer sheet
Dispersion liquid, is added 0.4 g cabaltous nitrate hexahydrate, 30 min of ultrasonic disperse, and ultrasonic power is 240 watts；Secondly, it is bis- that 0.85 g is added
Above-mentioned mixed liquor is stirred to dicyandiamide at 90 DEG C and is dissolved, 12 h then freezed at -18 DEG C, then at -80 DEG C by cyanamide
Lower 48 h of vacuum freeze drying obtains presoma；Finally, precursor powder is transferred in nitrogen atmosphere tube furnace, with 1 DEG C/
The heating rate of min is heated to 900 DEG C, is pyrolyzed 0.5 h, takes out after room temperature is cooled under the protection of nitrogen, can obtain d-
Ti3C2@N-CNTs three-dimensional composite material.
Embodiment 5
Firstly, by the ternary layered Ti of 3 g3AlC2Ceramic powder is slowly immersed in 50 mL hydrofluoric acid solutions (40 wt.%), and 50
72 h of magnetic agitation at DEG C, revolving speed are 500 r/min, and then corrosion product is centrifuged, and 8000 r/min are with ultrapure
Water eccentric cleaning to supernatant pH value is 6, then with washes of absolute alcohol 5 times, by gained sediment in 60 DEG C of vacuum ovens
24 h dry to arrive two-dimensional layer titanium carbide nano-powder.Then, take 0.2 g titanium carbide nano-powder that 20 mL tetramethyls are added
In base Ammonia (25 wt.%), be centrifugated after 24 h of heating stirring at 30 DEG C, add deionized water from
For gains in depth of comprehension to few layer titanium carbide nanometer sheet dispersion liquid, dispersion liquid concentration is about 1 mg/mL.200 mL are taken to lack layer titanium carbide nanometer sheet point
Dispersion liquid, is added 0.2 g Cobalt monosulfate heptahydrate, 30 min of ultrasonic disperse, and ultrasonic power is 240 watts；Secondly, the bis- cyanogen of 0.85g are added
Above-mentioned mixed liquor is stirred to dicyandiamide at 90 DEG C and is dissolved, 12 h then freezed at -18 DEG C, then at -80 DEG C by amine
48 h of vacuum freeze drying obtains presoma；Finally, precursor powder is transferred in nitrogen atmosphere tube furnace, with 1 DEG C/min
Heating rate be heated to 800 DEG C, be pyrolyzed 1 h, taken out after room temperature is cooled under the protection of nitrogen, d-Ti can be obtained3C2@N-
CNTs three-dimensional composite material.
Embodiment 6
Firstly, by the ternary layered Ti of 3 g3AlC2Ceramic powder is slowly immersed in 50 mL hydrofluoric acid solutions (40 wt.%), and 50
72 h of magnetic agitation at DEG C, revolving speed are 500 r/min, and then corrosion product is centrifuged, and 8000 r/min are with ultrapure
Water eccentric cleaning to supernatant pH value is 6, then with washes of absolute alcohol 5 times, by gained sediment in 60 DEG C of vacuum ovens
24 h dry to arrive two-dimensional layer titanium carbide nano-powder.Then, take 0.2 g titanium carbide nano-powder that 30 mL tetramethyls are added
In base Ammonia (25 wt.%), be centrifugated after 24 h of heating stirring at 30 DEG C, add deionized water from
For gains in depth of comprehension to few layer titanium carbide nanometer sheet dispersion liquid, dispersion liquid concentration is about 1 mg/mL.150 mL are taken to lack layer titanium carbide nanometer sheet point
0.3 g C is added in dispersion liquid4H6CoO4·4(H2O), 30 min of ultrasonic disperse, ultrasonic power are 240 watts；Secondly, 0.85 g is added
Above-mentioned mixed liquor is stirred to dicyandiamide at 90 DEG C and is dissolved, 12 h then freezed at -18 DEG C, then -80 by dicyandiamide
48 h of vacuum freeze drying obtains presoma at DEG C；Finally, precursor powder is transferred in nitrogen atmosphere tube furnace, with 1 DEG C/
The heating rate of min is heated to 700 DEG C, is pyrolyzed 1.5 h, takes out after room temperature is cooled under the protection of nitrogen, can obtain d-
Ti3C2@N-CNTs three-dimensional composite material.
Embodiment 7
Controlling dicyandiamide content in presoma is respectively 0.5 g, 0.6 g ..., 1 g, and other conditions are the same as embodiment 1.As a result it demonstrate,proves
It is bright, the present invention by dicyandiamide content in control presoma, it can be achieved that few layer titanium carbide surface nitrogen-doped carbon nanometer pipe length and
The regulation of density, few layer titanium carbide surface length of carbon nanotube is in 100 ~ 500 nm.
Embodiment 8
Firstly, by the ternary layered Ti of 3 g3AlC2Ceramic powder is slowly immersed in 50 mL hydrofluoric acid solutions (40 wt.%), and 50
72 h of magnetic agitation at DEG C, revolving speed are 500 r/min, and then corrosion product is centrifuged, and 8000 r/min are with ultrapure
Water eccentric cleaning to supernatant pH value is 6, then with washes of absolute alcohol 5 times, by gained sediment in 60 DEG C of vacuum ovens
24 h dry to arrive two-dimensional layer titanium carbide nano-powder.Then, take 0.2 g titanium carbide nano-powder that 40 mL tetramethyls are added
In base Ammonia (25 wt.%), be centrifugated after 24 h of heating stirring at 30 DEG C, add deionized water from
For gains in depth of comprehension to few layer titanium carbide nanometer sheet dispersion liquid, dispersion liquid concentration is about 1 mg/mL.50 mL are taken to lack layer titanium carbide nanometer sheet point
Dispersion liquid, is added 2.5 g, tetra- acetate hydrate cobalt, 30 min of ultrasonic disperse, and ultrasonic power is 240 watts；Secondly, the bis- cyanogen of 6.7 g are added
Above-mentioned mixed liquor is stirred to dicyandiamide at 90 DEG C and is dissolved, 12 h then freezed at -18 DEG C, then at -80 DEG C by amine
48 h of vacuum freeze drying obtains presoma；Finally, precursor powder is transferred in nitrogen atmosphere tube furnace, with 4 DEG C/min
Heating rate be heated to 800 DEG C, be pyrolyzed 2 h, taken out after room temperature is cooled under the protection of nitrogen, d-Ti can be obtained3C2@N-
CNTs three-dimensional composite material.
In addition, being obtained by embodiment 1-3, with the raising of pyrolysis temperature, length of carbon nanotube, which gradually rises to, have been grown
Entirely, as shown in Fig. 3 comparison.
The present invention provides d-Ti a kind of3C2@N-CNTs three-dimensional composite material and preparation method thereof, firstly, molten in hydrofluoric acid
Selective etch falls ternary layered Ti in liquid3AlC2In Al layer, formed two-dimensional layer titanium carbide nano material.Secondly, in tetramethyl
Two-dimentional multilayer titanium carbide is removed into few layer of titanium carbide in base Ammonia；Then, it is with few layer of titanium carbide nano material
Matrix, cobalt are catalyst, Co2+Ion is adsorbed on few layer by the ion exchange with few layer of titanium carbide surface oxygen functional group
Titanium carbide surface；Dicyandiamide is added as carbon source, dicyandiamide passes through the Co with titanium carbide surface2+Ion forms complex
And it is inserted into the lamella of few layer titanium carbide.Finally, simple pyrolysismethod Means of Pyrolyzed Precursor is used under nitrogen atmosphere, with temperature
It increases, Co2+It is reduced to catalyst of the cobalt nano-particle as carbon nano tube growth, and dicyandiamide is decomposed into carbonitride, nitridation
Carbon is grown to carbon nanotube under the catalysis of cobalt.The present invention successfully prepares d-Ti by simple pyrolysismethod3C2@N-CNTs is three-dimensional
Composite material improves few layer of titanium carbide electric conductivity, the specific surface area for expanding few layer titanium carbide, improves few layer titanium carbide itself surely
It is qualitative etc., and by dicyandiamide content in control presoma, it can be achieved that few layer titanium carbide surface length of carbon nanotube and density
Regulation；This for extending few layer titanium carbide material in the application in the fields such as supercapacitor, lithium ion battery and lithium-sulfur cell,
It has important practical significance.Carbon nanotube is grown on few layer of titanium carbide surface, it is logical to provide electron-transport using carbon nanotube
Road improves the conductivity of material, and the transmittability between carbon nanotube can be improved in few layer titanium carbide, to efficiently solve one-dimensional
Carbon nanotube and the heat of the few layer titanium carbide of two dimension and conductibility outside the directional dependence of electron-transport and lower face, make composite wood
Material all has good electrical property in three-dimensional space.
Claims (10)
1. a kind of preparation method of few layer titanium carbide growth in situ nitrogen-doped carbon nanometer pipe three-dimensional composite material, which is characterized in that
The following steps are included:
(1) by ternary layered Ti3AlC2Ceramic powder submerges in a solution of hydrofluoric acid, is centrifuged after heating stirring, and what is be centrifuged is heavy
It forms sediment and uses dehydrated alcohol eccentric cleaning, then dry gained sediment to get two-dimensional layer titanium carbide nano-powder；
(2) the two-dimensional layer titanium carbide nano-powder for taking step (1) to prepare is added in tetramethyl ammonium hydroxide solution, heating stirring
After be centrifuged, the upper layer suspension that the precipitating being centrifuged is centrifuged again with deionized water is less layer titanium carbide nanometer sheet point
Dispersion liquid；
(3) cobalt salt is added in few layer of titanium carbide nanometer sheet dispersion liquid and is reacted, dicyandiamide is added after reaction, heated
Stirring is completely dissolved to dicyandiamide, is then freezed, then obtains precursor powder by freeze-drying；
(4) by precursor powder it is levigate after be heat-treated, it is three-dimensional to obtain few layer titanium carbide growth in situ nitrogen-doped carbon nanometer pipe
Composite material.
2. preparation method according to claim 1, which is characterized in that the quality of hydrofluoric acid solution described in step (1) point
Number is 40 wt.%, the ternary layered Ti3AlC2The mass volume ratio of ceramic powder and hydrofluoric acid solution is 3 g: 50 mL；Step
Suddenly stirring described in (1) is 50 DEG C of 72 h of stirring；The precipitating dehydrated alcohol eccentric cleaning to centrifuged supernatant pH be 6；
The drying is to dry in 60 DEG C of vacuum oven；Described is 4 ~ 6 times with washes of absolute alcohol number.
3. preparation method according to claim 1, which is characterized in that tetramethyl ammonium hydroxide solution described in step (2)
Mass fraction be 25 wt.%, two-dimensional layer titanium carbide nano-powder and tetramethyl ammonium hydroxide solution described in step (2)
Mass volume ratio is 0.2 g: (5 ~ 30) mL.
4. preparation method according to claim 1, which is characterized in that few layer of titanium carbide nanometer sheet described in step (2)
The specific preparation method of dispersion liquid be by deionized water be added for the first time be centrifuged after sediment in, after ultrasonic disperse is uniform again from
The suspension obtained after the heart, then plus deionized water ultrasonic disperse it is uniform after centrifuging and taking suspension again, take 5 times ~ 6 times；Step (2)
The heating stirring is that 24 h are stirred at 30 DEG C；Few layer carbonization in step (2) few layer titanium carbide nanometer sheet dispersion liquid
Titanium nanometer sheet content is 1 mg/mL.
5. preparation method according to claim 1, which is characterized in that the cobalt salt being added in step (3) is four acetate hydrates
Cobalt, cobalt chloride hexahydrate, cabaltous nitrate hexahydrate or Cobalt monosulfate heptahydrate.
6. preparation method according to claim 1, which is characterized in that the condition reacted in step (3) is in room temperature ultrasound
30 min, wherein the power of ultrasound is 240 watts；The temperature of heating stirring is 90 DEG C；Few layer of titanium carbide, cobalt salt in step (3)
Mass ratio with dicyandiamide is (0.1 ~ 0.2): (0.2 ~ 0.4): (0.6 ~ 1.0)；Freezing described in step (3) be -
12 h are freezed at 18 DEG C, the freeze-drying is in -80 DEG C of 48 h of vacuum processing.
7. preparation method according to claim 1, which is characterized in that guarantor of the heat treatment described in step (4) in nitrogen
Shield is lower to be carried out；Heat treatment temperature is 700 DEG C ~ 900 DEG C, and soaking time is the h of 0.5 h ~ 2；The heating rate of heat treatment is 1
℃/min ~ 2 ℃/min。
8. described in any item preparation methods described in -7 according to claim 1, which is characterized in that specific operating procedure are as follows:
(1) first by the ternary layered Ti of 3 g3AlC2 Ceramic powder is slowly immersed in 50 mL hydrofluoric acid solutions, magnetic at 50 DEG C
Corrosion product is centrifuged after stirring 72 h for power, is 6 with washes of absolute alcohol to supernatant pH value, then gained sinks
Starch in a vacuum drying oven at 60 DEG C drying to get arriving two-dimensional layer titanium carbide nano-powder；Wherein hydrofluoric acid solution is dense
Degree is 40 wt.%；
(2) 0.2 g titanium carbide nano-powder is taken to be added in 25 wt.% of 5mL ~ 30mL tetramethyl ammonium hydroxide solution, at 30 DEG C
It is centrifuged after lower 24 h of heating stirring, deionized water is added in the sediment after being centrifuged for the first time for the first time then, dispersion is equal
Take suspension after being centrifuged again after even, then plus deionized water be uniformly dispersed after centrifuging and taking suspension again, take 5 times ~ 6 times, merging is
For few layer of titanium carbide nanometer sheet dispersion liquid；
(3) cobalt salt is added to progress 30 min of room temperature ultrasound in few layer of titanium carbide nanometer sheet dispersion liquid, be added after reaction
Dicyandiamide is stirred at 90 DEG C and is completely dissolved to dicyandiamide, 12 h is then freezed at -18 DEG C, then freeze at -80 DEG C
Dry 48 h obtain precursor powder；Wherein the mass ratio of few the layer titanium carbide, cobalt salt and dicyandiamide is (0.1 ~ 0.2):
(0.2 ~ 0.4): (0.6 ~ 1.0)；
(4) precursor powder being heat-treated under the protection of nitrogen after levigate, heat treatment temperature is 700 DEG C ~ 900 DEG C,
Soaking time is the h of 0.5 h ~ 2, obtains few layer titanium carbide growth in situ nitrogen-doped carbon nanometer pipe three-dimensional composite material；It is wherein hot
The heating rate of processing is 1 DEG C/min ~ 2 DEG C/min.
9. a kind of utilize few layer titanium carbide growth in situ nitrogen-doped carbon made from the described in any item preparation methods of claim 1-8
Nanotube three-dimensional composite material.
10. a kind of application of few layer titanium carbide growth in situ nitrogen-doped carbon nanometer pipe three-dimensional composite material as claimed in claim 9,
It is characterized in that, the three-dimensional composite material can be applied to electrochemical energy storage materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811021250.8A CN109167066A (en) | 2018-09-03 | 2018-09-03 | A kind of preparation method of few layer titanium carbide growth in situ nitrogen-doped carbon nanometer pipe three-dimensional composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811021250.8A CN109167066A (en) | 2018-09-03 | 2018-09-03 | A kind of preparation method of few layer titanium carbide growth in situ nitrogen-doped carbon nanometer pipe three-dimensional composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109167066A true CN109167066A (en) | 2019-01-08 |
Family
ID=64893850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811021250.8A Pending CN109167066A (en) | 2018-09-03 | 2018-09-03 | A kind of preparation method of few layer titanium carbide growth in situ nitrogen-doped carbon nanometer pipe three-dimensional composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109167066A (en) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109701572A (en) * | 2019-01-24 | 2019-05-03 | 辽宁大学 | FeCo/MXene compound and its preparation method and application |
| CN110013869A (en) * | 2019-02-19 | 2019-07-16 | 武汉理工大学 | A kind of azotized carbon nano piece load titanium carbide quantum dot and its preparation method and application |
| CN110416537A (en) * | 2019-08-02 | 2019-11-05 | 广东东岛新能源股份有限公司 | Lithium titanate composite anode material and preparation method thereof and lithium ion battery |
| CN110589802A (en) * | 2019-10-28 | 2019-12-20 | 大连理工大学 | Three-dimensional MXene in-situ growth carbon nano tube and general synthesis method thereof |
| CN110970563A (en) * | 2019-12-16 | 2020-04-07 | 安徽大学 | Multi-dimensional heterojunction conductive mesh composite film, preparation method and perovskite solar cell |
| CN111215114A (en) * | 2020-01-21 | 2020-06-02 | 东莞理工学院 | g-C3N4MXene oxide composite photocatalyst and preparation method and application thereof |
| CN111229318A (en) * | 2020-04-02 | 2020-06-05 | 福州大学 | Super-hydrophobic copper-based in-situ composite catalyst and preparation method and application thereof |
| CN111282586A (en) * | 2020-03-24 | 2020-06-16 | 福州大学 | Preparation method and application of in-situ alumina coated titanium carbide catalyst |
| CN111952568A (en) * | 2020-08-19 | 2020-11-17 | 山东大学 | Sandwich structure composite material and preparation method and application thereof |
| CN112626630A (en) * | 2020-12-20 | 2021-04-09 | 江苏纳盾科技有限公司 | Preparation method and application of two-dimensional nano titanium carbide-based conductive paste |
| CN113174751A (en) * | 2021-04-09 | 2021-07-27 | 安徽大学 | Multi-stage heterostructure composite material, preparation method thereof and electromagnetic microwave absorption application |
| CN113173598A (en) * | 2021-05-07 | 2021-07-27 | 青岛科技大学 | Method for in-situ derivatization of sulfide by vanadium-based MXene |
| CN113201807A (en) * | 2021-04-30 | 2021-08-03 | 济南大学 | Ti3C2TxMXene one-dimensional hollow nanotube and preparation method and application thereof |
| CN113401906A (en) * | 2021-06-17 | 2021-09-17 | 北京佰耐特能源科技有限公司 | Non-bonding integrated titanium carbide material and preparation method thereof |
| CN113479887A (en) * | 2021-07-13 | 2021-10-08 | 郑州轻工业大学 | MXene material Ti with high thermal stability3C2Preparation method of (1) |
| CN113804712A (en) * | 2021-08-06 | 2021-12-17 | 云南大学 | Scanning electron microscope in-situ observation sample preparation method for lamellar carbon nitride etching process |
| CN114388760A (en) * | 2022-01-14 | 2022-04-22 | 北京化工大学 | Metal oxide nanosheet material, preparation method thereof and lithium ion battery |
| CN114606652A (en) * | 2022-02-17 | 2022-06-10 | 苏州美森无纺科技有限公司 | Photo-thermal regulation and control type efficient oil adsorption wiping cloth and preparation method thereof |
| CN115318320A (en) * | 2022-07-18 | 2022-11-11 | 西安交通大学 | Preparation method of carbon nitride nanosheet-loaded titanium carbide nanocomposite |
| CN115701463A (en) * | 2021-08-02 | 2023-02-10 | 安徽璜峪电磁技术有限公司 | Composite material constructed by multilevel structure and preparation method and application thereof |
| CN115818657A (en) * | 2022-11-18 | 2023-03-21 | 仲恺农业工程学院 | Preparation method of hybrid ion doped MBene composite material |
| CN117180980A (en) * | 2023-08-29 | 2023-12-08 | 华北电力大学（保定） | Composite nanofiltration membrane for efficiently intercepting ammonium sulfate and ammonium nitrate and simultaneously adsorbing and removing mercury ions and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012162893A1 (en) * | 2011-06-02 | 2012-12-06 | Zhang Panyi | High capacitance lithium ion battery containing metallic conducting materials |
| CN105085947A (en) * | 2015-08-03 | 2015-11-25 | 铜陵市胜达电子科技有限责任公司 | Multiwalled-carbon-nanotube-loaded polyimide high-dielectric-permittivity composite film doped with nano titanium carbide and used for capacitor and preparing method of composite film |
| CN105322189A (en) * | 2014-07-01 | 2016-02-10 | 中国科学院大连化学物理研究所 | Cathode material used for lithium sulfur battery, preparation and application thereof |
| CN106450205A (en) * | 2016-11-02 | 2017-02-22 | 南京工业大学 | Two-dimensional transition metal carbide (nitride) and nano sulfur particulate composite as well as preparation and application thereof |
| CN106783230A (en) * | 2016-12-27 | 2017-05-31 | 陕西科技大学 | A kind of titanium carbide growth in situ CNTs three-dimensional composite materials and preparation method thereof |
| CN107887588A (en) * | 2017-11-08 | 2018-04-06 | 黑龙江科技大学 | A kind of preparation method and application of nano-sulfur particles/two-dimensional layer carbonization titanium composite material |
| CN108258209A (en) * | 2017-12-27 | 2018-07-06 | 温州大学 | A kind of carbide/carbon nano tube/graphene carries sulphur composite material and preparation method and application |
-
2018
- 2018-09-03 CN CN201811021250.8A patent/CN109167066A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012162893A1 (en) * | 2011-06-02 | 2012-12-06 | Zhang Panyi | High capacitance lithium ion battery containing metallic conducting materials |
| CN105322189A (en) * | 2014-07-01 | 2016-02-10 | 中国科学院大连化学物理研究所 | Cathode material used for lithium sulfur battery, preparation and application thereof |
| CN105085947A (en) * | 2015-08-03 | 2015-11-25 | 铜陵市胜达电子科技有限责任公司 | Multiwalled-carbon-nanotube-loaded polyimide high-dielectric-permittivity composite film doped with nano titanium carbide and used for capacitor and preparing method of composite film |
| CN106450205A (en) * | 2016-11-02 | 2017-02-22 | 南京工业大学 | Two-dimensional transition metal carbide (nitride) and nano sulfur particulate composite as well as preparation and application thereof |
| CN106783230A (en) * | 2016-12-27 | 2017-05-31 | 陕西科技大学 | A kind of titanium carbide growth in situ CNTs three-dimensional composite materials and preparation method thereof |
| CN107887588A (en) * | 2017-11-08 | 2018-04-06 | 黑龙江科技大学 | A kind of preparation method and application of nano-sulfur particles/two-dimensional layer carbonization titanium composite material |
| CN108258209A (en) * | 2017-12-27 | 2018-07-06 | 温州大学 | A kind of carbide/carbon nano tube/graphene carries sulphur composite material and preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| PENG YU ET AL: "Binder-free 2D titanium carbide (MXene)/carbon nanotube composites for high-performance lithium-ion capacitors", 《NANOSCALE》 * |
| YOUKUI ZHANG ET AL: "In Situ Growth of Cobalt Nanoparticles Encapsulated Nitrogen-Doped Carbon Nanotubes among Ti3C2Tx(MXene) Matrix for Oxygen Reduction and Evolution", 《ADVANCED MATERIALS》 * |
Cited By (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109701572A (en) * | 2019-01-24 | 2019-05-03 | 辽宁大学 | FeCo/MXene compound and its preparation method and application |
| CN110013869B (en) * | 2019-02-19 | 2022-03-11 | 武汉理工大学 | Carbon nitride nanosheet loaded titanium carbide quantum dot and preparation method and application thereof |
| CN110013869A (en) * | 2019-02-19 | 2019-07-16 | 武汉理工大学 | A kind of azotized carbon nano piece load titanium carbide quantum dot and its preparation method and application |
| CN110416537A (en) * | 2019-08-02 | 2019-11-05 | 广东东岛新能源股份有限公司 | Lithium titanate composite anode material and preparation method thereof and lithium ion battery |
| CN110416537B (en) * | 2019-08-02 | 2022-05-31 | 广东东岛新能源股份有限公司 | Lithium titanate composite negative electrode material, preparation method thereof and lithium ion battery |
| CN110589802A (en) * | 2019-10-28 | 2019-12-20 | 大连理工大学 | Three-dimensional MXene in-situ growth carbon nano tube and general synthesis method thereof |
| CN110970563A (en) * | 2019-12-16 | 2020-04-07 | 安徽大学 | Multi-dimensional heterojunction conductive mesh composite film, preparation method and perovskite solar cell |
| CN110970563B (en) * | 2019-12-16 | 2022-08-30 | 安徽大学 | Multi-dimensional heterojunction conductive mesh composite film, preparation method and perovskite solar cell |
| CN111215114A (en) * | 2020-01-21 | 2020-06-02 | 东莞理工学院 | g-C3N4MXene oxide composite photocatalyst and preparation method and application thereof |
| CN111215114B (en) * | 2020-01-21 | 2023-05-16 | 东莞理工学院 | g-C 3 N 4 MXene oxide composite photocatalyst, and preparation method and application thereof |
| CN111282586A (en) * | 2020-03-24 | 2020-06-16 | 福州大学 | Preparation method and application of in-situ alumina coated titanium carbide catalyst |
| CN111282586B (en) * | 2020-03-24 | 2022-07-08 | 福州大学 | Preparation method and application of in-situ alumina coated titanium carbide catalyst |
| CN111229318B (en) * | 2020-04-02 | 2022-11-11 | 福州大学 | Super-hydrophobic copper-based in-situ composite catalyst and preparation method and application thereof |
| CN111229318A (en) * | 2020-04-02 | 2020-06-05 | 福州大学 | Super-hydrophobic copper-based in-situ composite catalyst and preparation method and application thereof |
| CN111952568A (en) * | 2020-08-19 | 2020-11-17 | 山东大学 | Sandwich structure composite material and preparation method and application thereof |
| CN112626630A (en) * | 2020-12-20 | 2021-04-09 | 江苏纳盾科技有限公司 | Preparation method and application of two-dimensional nano titanium carbide-based conductive paste |
| CN113174751A (en) * | 2021-04-09 | 2021-07-27 | 安徽大学 | Multi-stage heterostructure composite material, preparation method thereof and electromagnetic microwave absorption application |
| CN113201807A (en) * | 2021-04-30 | 2021-08-03 | 济南大学 | Ti3C2TxMXene one-dimensional hollow nanotube and preparation method and application thereof |
| CN113173598A (en) * | 2021-05-07 | 2021-07-27 | 青岛科技大学 | Method for in-situ derivatization of sulfide by vanadium-based MXene |
| CN113173598B (en) * | 2021-05-07 | 2022-07-29 | 青岛科技大学 | Method for in-situ derivatization of sulfide from vanadium-based MXene |
| CN113401906A (en) * | 2021-06-17 | 2021-09-17 | 北京佰耐特能源科技有限公司 | Non-bonding integrated titanium carbide material and preparation method thereof |
| CN113401906B (en) * | 2021-06-17 | 2022-11-08 | 北京佰耐特能源科技有限公司 | Non-bonding integrated titanium carbide material and preparation method thereof |
| CN113479887B (en) * | 2021-07-13 | 2023-10-03 | 郑州轻工业大学 | High-thermal-stability MXene material Ti 3 C 2 Is prepared by the preparation method of (2) |
| CN113479887A (en) * | 2021-07-13 | 2021-10-08 | 郑州轻工业大学 | MXene material Ti with high thermal stability3C2Preparation method of (1) |
| CN115701463A (en) * | 2021-08-02 | 2023-02-10 | 安徽璜峪电磁技术有限公司 | Composite material constructed by multilevel structure and preparation method and application thereof |
| CN113804712A (en) * | 2021-08-06 | 2021-12-17 | 云南大学 | Scanning electron microscope in-situ observation sample preparation method for lamellar carbon nitride etching process |
| CN114388760A (en) * | 2022-01-14 | 2022-04-22 | 北京化工大学 | Metal oxide nanosheet material, preparation method thereof and lithium ion battery |
| CN114606652A (en) * | 2022-02-17 | 2022-06-10 | 苏州美森无纺科技有限公司 | Photo-thermal regulation and control type efficient oil adsorption wiping cloth and preparation method thereof |
| CN115318320A (en) * | 2022-07-18 | 2022-11-11 | 西安交通大学 | Preparation method of carbon nitride nanosheet-loaded titanium carbide nanocomposite |
| CN115318320B (en) * | 2022-07-18 | 2024-01-19 | 西安交通大学 | Preparation method of carbon nitride nanosheet-loaded titanium carbide nanocomposite |
| CN115818657A (en) * | 2022-11-18 | 2023-03-21 | 仲恺农业工程学院 | Preparation method of hybrid ion doped MBene composite material |
| CN117180980A (en) * | 2023-08-29 | 2023-12-08 | 华北电力大学（保定） | Composite nanofiltration membrane for efficiently intercepting ammonium sulfate and ammonium nitrate and simultaneously adsorbing and removing mercury ions and preparation method thereof |
| CN117180980B (en) * | 2023-08-29 | 2024-03-08 | 华北电力大学（保定） | Composite nanofiltration membrane for efficiently intercepting ammonium sulfate and ammonium nitrate and simultaneously adsorbing and removing mercury ions and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109167066A (en) | A kind of preparation method of few layer titanium carbide growth in situ nitrogen-doped carbon nanometer pipe three-dimensional composite material | |
| CN106450205B (en) | Two-dimensional transition group metal carbon/nitride and nano sulfur particle composite material and preparation and application thereof | |
| Qiu et al. | MXenes nanocomposites for energy storage and conversion | |
| CN105826527B (en) | A kind of porous silicon-carbon composite and its preparation method and application | |
| Xu et al. | A maize-like FePO 4@ MCNT nanowire composite for sodium-ion batteries via a microemulsion technique | |
| CN107394180B (en) | Two-dimensional transition group metal carbide (nitride) -nano silicon particle composite material, preparation and application | |
| CN102376937A (en) | Nanometer lithium titanate/graphene composite negative electrode material and preparation process thereof | |
| CN106129377B (en) | A kind of preparation method of sesquioxide/graphene composite material, negative electrode of lithium ion battery, lithium ion battery | |
| CN107934965B (en) | Ti3C2-Co(OH)(CO3)0.5Process for preparing nano composite material | |
| CN106229503B (en) | A kind of preparation method of nickel oxide/graphene nanocomposite material, negative electrode of lithium ion battery, lithium ion battery | |
| CN108933237B (en) | Preparation method and application of lithium ion battery positive electrode material | |
| CN108987729B (en) | Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery | |
| CN106783230A (en) | A kind of titanium carbide growth in situ CNTs three-dimensional composite materials and preparation method thereof | |
| KR101888743B1 (en) | Composite including porous grapheme and carbonaceous material | |
| CN107331839A (en) | A kind of preparation method of carbon nanotube loaded nano titanium oxide | |
| Gou et al. | Co-based metal–organic framework and its derivatives as high-performance anode materials for lithium-ion batteries | |
| CN110707301A (en) | Vanadium trioxide/carbon composite material with nanosphere structure and preparation method and application thereof | |
| CN108417800A (en) | A kind of graphene coated graphite/metal composite granule negative material and preparation method | |
| CN108091868B (en) | Multi-dimensional composite high-performance lithium ion battery cathode material and preparation method thereof | |
| CN114854030A (en) | Preparation method of single-layer MXene nanosheet/ZIF-67 composite material | |
| CN114335458B (en) | Ti3C2Tx@g-C3N4 composite material and preparation method and application thereof | |
| CN113178571B (en) | Hierarchical porous Fe3Se4@ NC @ CNTs composite material and preparation method and application thereof | |
| Gangaraju et al. | In-situ preparation of silk-cocoon derived carbon and LiFePO4 nanocomposite as cathode material for Li-ion battery | |
| CN108923027B (en) | Organic acid modified Si/TiO2Negative electrode material of/rGO @ C lithium ion battery and preparation method and application thereof | |
| CN115064664A (en) | Confined silicon dioxide/multi-walled carbon nanotube composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190108 |
|
| RJ01 | Rejection of invention patent application after publication |