CN111916288A - Nanotube-shaped NiCo2S4@ titanium carbide composite material and preparation method and application thereof - Google Patents
Nanotube-shaped NiCo2S4@ titanium carbide composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN111916288A CN111916288A CN202010738896.9A CN202010738896A CN111916288A CN 111916288 A CN111916288 A CN 111916288A CN 202010738896 A CN202010738896 A CN 202010738896A CN 111916288 A CN111916288 A CN 111916288A
- Authority
- CN
- China
- Prior art keywords
- nico
- titanium carbide
- composite material
- carbide composite
- nanotube
- 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
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims description 28
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 40
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000002071 nanotube Substances 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims description 58
- 238000001035 drying Methods 0.000 claims description 31
- 239000000725 suspension Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 21
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 229910003266 NiCo Inorganic materials 0.000 claims description 18
- 238000009210 therapy by ultrasound Methods 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 9
- 239000012716 precipitator Substances 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- BRWIZMBXBAOCCF-UHFFFAOYSA-N thiosemicarbazide group Chemical group NNC(=S)N BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 3
- 239000000463 material Substances 0.000 abstract description 19
- 239000007772 electrode material Substances 0.000 abstract description 11
- 239000003990 capacitor Substances 0.000 abstract description 5
- 238000011160 research Methods 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract description 3
- 238000000498 ball milling Methods 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 16
- -1 polytetrafluoroethylene Polymers 0.000 description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 238000005245 sintering Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000003760 magnetic stirring Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000001272 pressureless sintering Methods 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- 229910052976 metal sulfide Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/921—Titanium carbide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a nano-tube NiCo2S4The method comprises the following steps of firstly preparing a nanotube-shaped precursor by a first hydrothermal method, compounding the two materials by the precursor, and vulcanizing the precursor by a second hydrothermal method, wherein the material is prepared by firstlySingle-layer Ti3C2With hollow tubular NiCo2S4Compounding to prepare NiCo2S4The @ titanium carbide composite material is applied to the research of electrochemical performance of a super capacitor, wherein NiCo2S4Hollow tube loaded modified Ti3C2Additional electron transport paths may be provided, thereby increasing electron transport efficiency. Experiments show that NiCo2S4Compared with a single electrode material, the @ titanium carbide composite electrode material has more excellent specific capacitance and cycle performance.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of electrode materials, and particularly relates to a nanotube NiCo2S4The @ titanium carbide composite material and the preparation method and the application thereof.
[ background of the invention ]
With scarcity of traditional fossil energy and rapid environmental deterioration around the world, advanced energy storage systems are urgently needed, and a great deal of research attention is attracted by a supercapacitor as a novel energy storage device. With the continuous and deep research of super capacitors, the requirements of electrode materials of the super capacitors are more diversified and the range is wider. The transition metal carbide nanosheet (MXene) is obtained by selectively etching the A layer in the ternary layered compound material MAX for the first time in 2011.
The two-dimensional layered MXene material has great application potential in the field of energy storage due to higher electronic conductivity, stronger charge storage capacity and the like. Wherein Ti3C2By selectively etching a ternary layered compound Ti3AlC2The obtained transition metal carbide with the graphene-like two-dimensional structure. Ti3C2By utilizing the special layered structure, the composite material has the advantages of large specific surface area, good conductivity, good electrochemical activity and the likeDots are one of the most widely used members of two-dimensional layered MXene materials.
However, the two-dimensional MXene material has larger surface energy, so that the aggregation and stacking among the sheet layers are caused, the transmission efficiency of electrolyte among the layers is reduced, and the electrochemical utilization rate of the material is limited. In order to solve the deficiency, the electrochemical energy storage can be improved by chemical modification, loading of active materials and the like. Among various functional materials, metal sulfides have received wide attention from many researchers due to their wide application in the fields of supercapacitors, photoelectrocatalysis, batteries, sensors, and the like. It is particularly noteworthy that metal sulfides, due to their low electronegativity and high electrochemical activity, can serve as potential pseudocapacitive electrical materials. And NiCo2S4As a special type of metal sulfide, the metal sulfide has been researched by many researchers due to the advantages of diversity of morphology, outstanding pseudocapacitance behavior, high theoretical specific capacity, low electronegativity, and the like. However, like all other nanoparticles, NiCo results due to structural aggregation and relatively large particle size2S4The structure expands and contracts in charge and discharge cycles, so that the cycle retention rate is generally only 50-70%, and the actual capacity is far smaller than the theoretical capacity.
[ summary of the invention ]
The object of the present invention is to overcome the above mentioned drawbacks of the prior art by providing a nanotube-like NiCo2S4The @ titanium carbide composite material and the preparation method and the application thereof; to solve NiCo2S4And titanium carbide used alone as an electrochemical material have defects, which cause the problems of poor specific capacitance and poor cycle performance.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
nanotube-shaped NiCo2S4@ titanium carbide composite material, said NiCo2S4Attached to a titanium carbide sheet, said NiCo2S4Is in a shape of a nano tube, and the titanium carbide is in a single-sheet layer.
Nanotube-shaped NiCo2S4Of @ titanium carbide composite materialsThe preparation method comprises the following steps:
step 1, by Ti3AlC2Powder preparation of monolithic layered Ti3C2Powder;
step 3, dispersing the precursor F into deionized water, stirring uniformly, and adding Na2S·9H2O, stirring to obtain suspension G, carrying out hydrothermal reaction on the suspension G, centrifuging a reaction product, collecting precipitate, and drying to obtain NiCo2S4@ titanium carbide composite material.
The invention is further improved in that:
preferably, in step 1, Ti3AlC2Powder preparation of monolithic layered Ti3C2The specific process of the powder is as follows:
(1) dispersing LiF in a hydrochloric acid solution to obtain LiF dispersion liquid;
(2) adding Ti to LiF dispersion3AlC2Uniformly stirring to obtain a reaction solution B, washing the reaction solution B by deionized water until the pH value is more than 6, dissolving the centrifugal precipitate in water, and performing vacuum oxygen discharge and ultrasonic treatment to obtain a suspension C;
(3) centrifuging the suspension C, and freeze-drying the supernatant to obtain lamellar Ti3C2And (3) powder.
Preferably, in step 1, Ti3AlC2And LiF in a mass ratio of 1: 1.
Preferably, in step 2, Ti3C2The proportion of the powder, the nickel source, the cobalt source and the amino precipitator is as follows: (10-60) mg: (0.2-0.5) mmol: (0.4-1.25) mmol: (1.2-4) mmol.
Preferably, in step 2, the hydrothermal reaction temperature of the mixed solution E is 120 ℃ and the hydrothermal reaction time is 4 hours.
Preferably, in step 2, the nickel source is NiCl2·6H2O or Ni (NO)3)·6H2O, the cobalt source is CoCl2·6H2O or Co (NO)3)·6H2And O, the amino precipitator is thiosemicarbazide or urea.
Preferably, in step 3, Na2S·9H2After O is added to the precursor F, Na2S·9H2The concentration of O was 0.2 mol/L.
Preferably, in step 3, the hydrothermal reaction temperature of the suspension G is 120 ℃, the hydrothermal reaction time is 8h, and the drying temperature is 60 ℃.
The nanotubular NiCo of claim 12S4Application of @ titanium carbide composite material and nanotube NiCo2S4The @ titanium carbide composite material is used in supercapacitors and lithium ion batteries.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a nanotube-shaped NiCo2S4@ titanium carbide composite material, wherein a nickel chloride hexahydrate is used as a nickel source, a cobalt chloride hexahydrate is used as a cobalt source, a two-step hydrothermal method is adopted, firstly, a precursor in a nanotube shape is prepared by a first hydrothermal method, the two materials are compounded by the precursor, then, the precursor is vulcanized by secondary hydrothermal, and the material firstly synthesizes a single-layer Ti3C2With hollow tubular NiCo2S4Compounding to prepare NiCo2S4The @ titanium carbide composite material is applied to the research of electrochemical performance of the supercapacitor, and experiments show that NiCo2S4Compared with a single electrode material, the @ titanium carbide composite electrode material has more excellent specific capacitance and cycle performance. Wherein NiCo2S4Hollow tube loaded modified Ti3C2Additional electron transport paths may be provided, thereby increasing electron transport efficiency. The titanium carbide material has excellent conductivity as a two-dimensional supporting substrate, while NiCo2S4The composite material has high theoretical specific capacitance and abundant electron pairs, and the electrochemical performance of the composite material can be further enhanced by the synergistic effect of the high theoretical specific capacitance and the abundant electron pairs. Therefore, the invention is tested in the super capacitorThe electrode material has important significance in the fields of electrode materials and the like. NiCo synthesized by adopting the strategy2S4The @ titanium carbide composite material has more excellent specific capacitance and cycle performance.
The invention also discloses a nano-tube NiCo2S4The preparation method of the @ titanium carbide composite material adopts a two-step hydrothermal method to prepare NiCo2S4The preparation method of the @ titanium carbide composite material is simple and effective, and the prepared Ti3C2The graphene-like structure has a graphene-like structure, has a high specific surface area, is not stacked layer by layer, and provides more reactive sites.
The invention also discloses a nano-tube NiCo2S4Application of @ titanium carbide composite material in super capacitor and lithium ion battery, and verification shows that composite material NiCo is found2S4Specific capacity of @ titanium carbide electrode with respect to Ti3C2The electrode is lifted up significantly.
[ description of the drawings ]
FIG. 1 is a schematic representation of a NiCo product prepared according to example 1 of the process of the present invention2S4@ SEM scanning electron micrograph of titanium carbide composite.
Wherein (a) is a monolithic layer Ti3C2SEM photograph of (a); (b) shown as a hollow tubular NiCo2S4SEM photograph of (a);
(c) is shown as NiCo2S4@ SEM photograph of titanium carbide composite; (d) is shown as NiCo2S4The TEM image of the @ titanium carbide composite.
FIG. 2 is a schematic representation of a NiCo product prepared according to example 1 of the present invention2S4Electrochemical analysis test result of @ titanium carbide composite material, specifically Ti3C2，NiCo2S4And NiCo2S4@ titanium carbide at a scanning rate of 2mV s-1CV curve of time;
FIG. 3 is a NiCo product of example 1 of the process of the present invention2S4The electrochemical analysis test result of the @ titanium carbide composite material is NiCo2S4@ titanium carbide at different scan ratesCV curve (2-20 mV s)-1)。
[ detailed description ] embodiments
The invention is described in further detail below with reference to the following figures and specific examples:
the invention discloses a nano-tube NiCo2S4The @ titanium carbide composite material and the preparation method and the application thereof, wherein the method specifically comprises the following steps:
step 1, preparing Ti3AlC2Ceramic powder
(1) Weighing 100g of TiC powder, Ti powder and Al powder in a molar ratio of TiC to Al: ti: al ═ 2: 1: 1.2, obtaining a mixed material A;
(2) according to the mass ratio of 1: 3: 1, weighing a mixed material A, a grinding medium (zirconia ball stone) and a ball milling auxiliary agent (absolute ethyl alcohol), carrying out ball milling in a polytetrafluoroethylene ball milling tank at the rotating speed of 350r/min for 4h, and obtaining powder after ball milling;
(3) drying the obtained powder with uniform particle size at 40 deg.C for 24 h. After drying, sintering by using a vacuum pressureless sintering process, and establishing a temperature rise system: heating up at a heating rate of 8 ℃/min before 900 ℃, heating up at 6 ℃/min after 900 ℃, sintering at the maximum temperature of 1350 ℃, and keeping the temperature at the maximum temperature for 100 min. Cooling along with the furnace, ball-milling the product for 2h with high energy, sieving with a 200-mesh sieve, and finally drying at 40 ℃ for 48h to obtain Ti3AlC2And (3) powder.
(1) Slowly adding 2g of LiF into a polytetrafluoroethylene beaker containing 20mL of 9M HCl (specifically, 15mL of concentrated HCl with the mass concentration of 36% and 5mL of water), and magnetically stirring for 10min to uniformly disperse the LiF into a hydrochloric acid solution to obtain a LiF dispersion solution;
(2) 2g of Ti was added to the stirred homogeneous solution3AlC2Keeping continuous magnetic stirring for 24 hours at 35 ℃ and 300rpm/min to obtain reaction liquid B;
(3) centrifuging the reaction solution B by using deionized water for multiple times to wash until the pH value is more than 6, wherein the rotation speed of each centrifugal washing is 3500rpm/min, and the washing time is 2 min; and dissolving the centrifuged precipitate in 300mL of ultrapure water, performing vacuum oxygen discharge for 2h, and performing ultrasonic treatment for 1h to obtain a suspension C.
(4) Centrifuging the suspension C at 3500rpm/min for 1h, and freeze drying the centrifuged supernatant to obtain sheet Ti3C2And (3) powder.
Step 3, NiCo2S4Preparation of @ titanium carbide composite material
(1) 10-60mg of Ti3C2Dispersing the powder into 60-70mL of deionized water, and carrying out ultrasonic treatment for 30min to form uniformly dispersed suspension D;
(2) in the suspension D, the molar ratio of the nickel source to the cobalt source to the amino precipitator is (0.2-0.5): (0.4-1.25): (1.2-4), wherein the nickel source is NiCl2·6H2O or Ni (NO)3)·6H2O, the cobalt source is CoCl2·6H2O or Co (NO)3)·6H2And O, adding the amino precipitator which is thiosemicarbazide or urea, and stirring for 30min to fully and uniformly mix the solution to obtain a mixed solution E. Then pouring the stirred mixed solution E into 100mL of polytetrafluoroethylene lining for hydrothermal reaction under the reaction conditions of 120 ℃ for 4h, centrifuging the reaction product, and washing and drying the precipitate to obtain a precursor F; in this step, a hollow tubular NiCo has been obtained2(OH)4I.e. NiCo-precursor, hollow-tubular NiCo2(OH)4Ti grown in a monolithic layer3C2The above.
(3) Adding the precursor F into 70mL of deionized water, stirring for 30min, and adding 0.2M Na2S·9H2Pouring O into the mixture for ion exchange, continuously stirring for 30min to obtain a suspension G, and carrying out a second hydrothermal reaction on the suspension G at the reaction temperature of 120 ℃ for 8 h; by this procedure, a hollow tubular NiCo is formed2(OH)4Vulcanization is carried out.
(4) Cooling along with the furnace, centrifuging, washing the centrifuged product, collecting the precipitate, and finally drying at 60 ℃ in vacuum to obtain NiCo2S4@ titanium carbide compositeA material.
Example 1
Step 1, Ti3AlC2Preparation of ceramic powder
(1) Weighing 100g of TiC powder, Ti powder and Al powder in a molar ratio of TiC to Al: ti: al ═ 2: 1: 1.2;
(2) then, according to the mass ratio of 1: 3: 1, weighing the mixed material, a grinding medium (zirconia ball stone) and a ball milling auxiliary agent (absolute ethyl alcohol) and carrying out ball milling in a polytetrafluoroethylene ball milling tank at the rotating speed of 350r/min for 4 h;
(3) finally, drying the obtained uniform powder at the drying temperature of 40 ℃ for 24 h. After drying, sintering by using a vacuum pressureless sintering process, and establishing a temperature rise system: heating up at a heating rate of 8 ℃/min before 900 ℃, heating up at 6 ℃/min after 900 ℃, sintering at the maximum temperature of 1350 ℃, and keeping the temperature at the maximum temperature for 100 min. Cooling along with the furnace, ball-milling the product for 2h with high energy, sieving with a 200-mesh sieve, and finally drying at 40 ℃ for 48h to obtain Ti3AlC2And (3) powder.
(1) Slowly adding 2g of LiF into a polytetrafluoroethylene beaker containing 20mL of 9M HCl (specifically, 15mL of concentrated HCl with the mass concentration of 36% and 5mL of water), and magnetically stirring for 10min to uniformly disperse the LiF into a hydrochloric acid solution to obtain a LiF dispersion solution;
(2) 2g of Ti was added to the stirred homogeneous solution3AlC2Keeping continuous magnetic stirring for 24 hours at 35 ℃ and 300rpm/min to obtain reaction liquid B;
(3) centrifuging the reaction solution B by using deionized water for multiple times to wash until the pH value is more than 6, wherein the rotation speed of each centrifugal washing is 3500rpm/min, and the washing time is 2 min; and dissolving the centrifuged precipitate in 300mL of ultrapure water, performing vacuum oxygen discharge for 2h, and performing ultrasonic treatment for 1h to obtain a suspension C.
(4) Centrifuging the suspension C at 3500rpm/min for 1h, and freeze drying the centrifuged supernatant to obtain sheet Ti3C2And (3) powder.
Step 3, NiCo2S4Preparation of @ titanium carbide nanoparticle composite material
(4) 60mg of Ti3C2Dissolved in 60ml of deionized water, and 0.5mmol of NiCl2·6H2O and 1mmol CoCl2·6H2O is added into the suspension and ultrasonic treatment is carried out for 1h, and then 2mmol of thiosemicarbazide is added and stirred for 30 min;
(5) the stirred mixed solution is subjected to hydrothermal treatment at 180 ℃ for 12 hours. Then centrifugally washing and drying to obtain NiCo2S4@ titanium carbide nanoparticle composites.
FIG. 1 shows the results at Ti3C2With a large lamellar surface, uniformly loaded NiCo2S4Hollow nanotubes, NiCo2S4Has good appearance, uniform size and is uniformly distributed in Ti3C2On a two-dimensional sheet, the results thus show that Ti was successfully prepared by the study of this experiment3C2@NiCo2S4A nanocomposite material. It can be seen that Ti3C2The lamella is used as a carbon material conductive matrix, and NiCo can be effectively inhibited2S4Self-assembly and stacking of2S4Can improve the matrix material Ti3C2The specific surface area of (a) makes it have additional active sites, thereby improving the performance in electrochemical terms.
FIG. 2 is Ti under-0.1-0.4V test in potential window3C2，NiCo2S4And NiCo2S4@ titanium carbide at a scanning rate of 2mV s-1CV plot of time, it is clear that the original Ti is3C2In contrast, composite NiCo2S4The curve for the @ titanium carbide electrode shows a larger integral area, Ti3C2,NiCo2S4And NiCo2S4The specific capacity of the electrode reaches 20F g respectively-1,1460F g-1And 1927F g-1. Composite NiCo2S4Specific capacity of @ titanium carbide electrode with respect to Ti3C2The electrode is lifted up significantly.
FIG. 3 shows NiCo2S4@ titanium carbide electrode at scan rates of 2, 5, 10 and 20mV s-1According to the lower CV curve, the area of the curve is increased along with the increase of the scanning speed, which shows that the composite material has good capacitance performance, and the curve has no obvious deformation, which shows that the electrode material has good rate performance, so that the electrode material can be used as a super capacitor electrode material with great potential.
Example 2
Step 1, Ti3AlC2Preparation of ceramic powder
(1) Weighing 100g of TiC powder, Ti powder and Al powder in a molar ratio of TiC to Al: ti: al ═ 2: 1: 1.2;
(2) then, according to the mass ratio of 1: 3: 1, weighing the mixed material, a grinding medium (zirconia ball stone) and a ball milling auxiliary agent (absolute ethyl alcohol) and carrying out ball milling in a polytetrafluoroethylene ball milling tank at the rotating speed of 350r/min for 4 h;
(3) finally, drying the obtained uniform powder at the drying temperature of 40 ℃ for 24 h. After drying, sintering by using a vacuum pressureless sintering process, and establishing a temperature rise system: heating up at a heating rate of 8 ℃/min before 900 ℃, heating up at 6 ℃/min after 900 ℃, sintering at the maximum temperature of 1350 ℃, and keeping the temperature at the maximum temperature for 100 min. Cooling along with the furnace, ball-milling the product for 2h with high energy, sieving with a 200-mesh sieve, and finally drying at 40 ℃ for 48h to obtain Ti3AlC2And (3) powder.
(1) Slowly adding 2g of LiF into a polytetrafluoroethylene beaker containing 20mL of 9M HCl, stirring for 10min to uniformly disperse the LiF into the hydrochloric acid solution, and slowly adding 2g of Ti3AlC2Keeping continuous magnetic stirring for 24 hours at 35 ℃ and 300rpm/min to obtain reaction liquid B;
(2) centrifugally cleaning the reaction solution B by deionized water for multiple times, centrifugally cleaning by deionized water (3500rpm/min, 2min) for multiple times until the pH value is more than 6, dissolving the centrifuged precipitate in 300mL of ultrapure water, then carrying out vacuum oxygen discharge for 2h, and carrying out ultrasonic treatment for 1h after completion. Centrifuging at 3500rpm/min for 1h, and freeze drying the centrifuged supernatant to obtain Ti sheet layer3C2And (3) powder.
Step 3, NiCo2S4@ titanium carbide sheet layered composite material
(1)Ti3C2Slowly adding 40mg of nano powder into 70mL of deionized water, and carrying out ultrasonic treatment at room temperature for 5min to form uniformly dispersed suspension;
(2) 0.5mmol of Ni (NO) was then added to the suspension3)·6H2O，1.25mmol Co(NO3)·6H2O and 3.75mmol thiosemicarbazide, and after magnetic stirring is continuously kept for 30min, hydrothermal reaction is carried out for 4h at 120 ℃. And after cooling, centrifuging and drying in vacuum to obtain the precursor.
(3) Adding the collected precursor into 70mL deionized water, performing ultrasonic treatment for 30min to form a suspension, and adding 0.2M Na into the suspension2S·7H2And O, keeping magnetic stirring for 30min, and then carrying out a second hydrothermal reaction on the mixed solution at the reaction temperature of 120 ℃ for 8 h.
(4) Washing the reacted mixed solution with deionized water and absolute ethyl alcohol for many times, collecting the precipitate, and vacuum drying at 60 ℃ for 12h to obtain NiCo2S4@ titanium carbide sheet layered composite material.
Example 3
Step 1, Ti3AlC2Preparation of ceramic powder
(1) Weighing 100g of TiC powder, Ti powder and Al powder in a molar ratio of TiC to Al: ti: al ═ 2: 1: 1.2;
(2) then, according to the mass ratio of 1: 3: 1, weighing the mixed material, a grinding medium (zirconia ball stone) and a ball milling auxiliary agent (absolute ethyl alcohol) and carrying out ball milling in a polytetrafluoroethylene ball milling tank at the rotating speed of 350r/min for 4 h;
(3) finally, drying the obtained uniform powder at the drying temperature of 40 ℃ for 24 h. After drying, sintering by using a vacuum pressureless sintering process, and establishing a temperature rise system: heating up at a heating rate of 8 deg.C/min before 900 deg.C, and heating up at 6 deg.C/min after 900 deg.CAnd (4) heating, wherein the sintering maximum temperature is 1350 ℃, and the temperature is kept at the maximum temperature for 100 min. Cooling along with the furnace, ball-milling the product for 2h with high energy, sieving with a 200-mesh sieve, and finally drying at 40 ℃ for 48h to obtain Ti3AlC2And (3) powder.
(1) Slowly adding 2g of LiF into a polytetrafluoroethylene beaker containing 20mL of 9M HCl, stirring for 10min to uniformly disperse the LiF into the hydrochloric acid solution, and slowly adding 2g of Ti3AlC2Keeping continuous magnetic stirring for 24 hours at 35 ℃ and 300 rpm/min;
(2) after the reaction is finished, the solution is centrifuged by deionized water (3500rpm/min, 2min) for multiple times until the pH value is more than 6, the centrifuged precipitate is dissolved in 300mL of ultrapure water, then vacuum oxygen discharge is carried out for 2h, and the ultrasonic treatment is carried out for 1h after the reaction is finished. And then centrifuging at the rotating speed of 3500rpm/min for 1h, and freeze-drying the centrifuged supernatant to obtain the lamellar Ti3C2 powder.
Step 3, NiCo2S4@ titanium carbide composite material
(1) Mixing 10mg of Ti3C2Dispersing the powder into 70mL of deionized water, and carrying out ultrasonic treatment for 30min to form uniformly dispersed suspension;
(2) then 0.2mmol of NiCl was added2·6H2O, 0.4mmol of CoCl2·6H2O and 1.2mmol of CN2H4And O, stirring for 30min to fully and uniformly mix the solution. Then pouring the stirred solution into a 100mL polytetrafluoroethylene lining for hydrothermal reaction at 120 ℃ for 4 h. Obtaining a precursor through centrifugal washing and drying;
(3) then adding the precursor into 70mL deionized water, stirring for 30min, and adding 0.2M Na2S·9H2Pouring O, continuously stirring for 30min, and carrying out a second hydrothermal reaction on the obtained suspension at the reaction temperature of 120 ℃ for 8 h;
(4) cooling with the furnace, centrifugally washing, collecting precipitate, and finally drying at 60 ℃ in vacuum to obtain NiCo2S4@ titanium carbide composite material.
Example 4
Step 1, Ti3AlC2Preparation of ceramic powder
(1) Weighing 100g of TiC powder, Ti powder and Al powder in a molar ratio of TiC to Al: ti: al ═ 2: 1: 1.2;
(2) then, according to the mass ratio of 1: 3: 1, weighing the mixed material, a grinding medium (zirconia ball stone) and a ball milling auxiliary agent (absolute ethyl alcohol) and carrying out ball milling in a polytetrafluoroethylene ball milling tank at the rotating speed of 350r/min for 4 h;
(3) finally, drying the obtained uniform powder at the drying temperature of 40 ℃ for 24 h. After drying, sintering by using a vacuum pressureless sintering process, and establishing a temperature rise system: heating up at a heating rate of 8 ℃/min before 900 ℃, heating up at 6 ℃/min after 900 ℃, sintering at the maximum temperature of 1350 ℃, and keeping the temperature at the maximum temperature for 100 min. Cooling along with the furnace, ball-milling the product for 2h with high energy, sieving with a 200-mesh sieve, and finally drying at 40 ℃ for 48h to obtain Ti3AlC2And (3) powder.
(1) Slowly adding 2g of LiF into a polytetrafluoroethylene beaker containing 20mL of 9M HCl, stirring for 10min to uniformly disperse the LiF into the hydrochloric acid solution, and slowly adding 2g of Ti3AlC2Keeping continuous magnetic stirring for 24 hours at 35 ℃ and 300 rpm/min;
(2) after the reaction is finished, the solution is centrifuged by deionized water (3500rpm/min, 2min) for multiple times until the pH value is more than 6, the centrifuged precipitate is dissolved in 300mL of ultrapure water, then vacuum oxygen discharge is carried out for 2h, and the ultrasonic treatment is carried out for 1h after the reaction is finished. And then centrifuging at the rotating speed of 3500rpm/min for 1h, and freeze-drying the centrifuged supernatant to obtain the lamellar Ti3C2 powder.
Step 3, NiCo2S4@ titanium carbide composite material
(1) 30mg of Ti3C2Dispersing the powder into 70mL of deionized water, and carrying out ultrasonic treatment for 30min to form uniformly dispersed suspension;
(2) 0.4mmol of NiCl was added2·6H2O, 0.8mmol of CoCl2·6H2O and 4mmol CN2H4And O, stirring for 30min to fully and uniformly mix the solution. Then pouring the stirred solution into a 100mL polytetrafluoroethylene lining for hydrothermal reaction at 120 ℃ for 4 h. Obtaining a precursor through centrifugal washing and drying;
(3) then adding the precursor into 70mL deionized water, stirring for 30min, and adding 0.2M Na2S·9H2Pouring O, continuously stirring for 30min, and carrying out a second hydrothermal reaction on the obtained suspension at the reaction temperature of 120 ℃ for 8 h;
(4) cooling with the furnace, centrifugally washing, collecting precipitate, and finally drying at 60 ℃ in vacuum to obtain NiCo2S4@ titanium carbide composite material.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. Nanotube-shaped NiCo2S4@ titanium carbide composite material, characterized in that said NiCo2S4Attached to a titanium carbide sheet, said NiCo2S4Is in a shape of a nano tube, and the titanium carbide is in a single-sheet layer.
2. Nanotube-shaped NiCo2S4The preparation method of the @ titanium carbide composite material is characterized by comprising the following steps of:
step 1, by Ti3AlC2Powder preparation of monolithic layered Ti3C2Powder;
step 2, adding Ti3C2Dispersing the powder in water, performing ultrasonic treatment to obtain a suspension D, adding a nickel source, a cobalt source and an amino precipitator into the suspension D, uniformly stirring to obtain a mixed solution E, and performing hydrothermal reaction on the mixed solution E to obtain a precursor F;
step 3, dispersing the precursor F into deionized water, stirring uniformly, and adding Na2S·9H2O, stirring to obtain suspension G, carrying out hydrothermal reaction on the suspension G, centrifuging a reaction product, collecting precipitate, and drying to obtain NiCo2S4@ titanium carbide composite material.
3. The nanotube-like NiCo of claim 22S4A process for preparing a @ titanium carbide composite material, characterized in that in step 1, Ti3AlC2Powder preparation of monolithic layered Ti3C2The specific process of the powder is as follows:
(1) dispersing LiF in a hydrochloric acid solution to obtain LiF dispersion liquid;
(2) adding Ti to LiF dispersion3AlC2Uniformly stirring to obtain a reaction solution B, washing the reaction solution B by deionized water until the pH value is more than 6, dissolving the centrifugal precipitate in water, and performing vacuum oxygen discharge and ultrasonic treatment to obtain a suspension C;
(3) centrifuging the suspension C, and freeze-drying the supernatant to obtain lamellar Ti3C2And (3) powder.
4. A nanotube-like NiCo of claim 32S4A process for preparing a @ titanium carbide composite material, characterized in that in step 1, Ti3AlC2And LiF in a mass ratio of 1: 1.
5. The nanotube-like NiCo of claim 22S4The preparation method of the @ titanium carbide composite material is characterized in that in the step 2, Ti3C2The proportion of the powder, the nickel source, the cobalt source and the amino precipitator is as follows: (10-60) mg: (0.2-0.5) mmol: (0.4-1.25) mmol: (1.2-4) mmol.
6. The nanotube-like NiCo of claim 22S4The preparation method of the @ titanium carbide composite material is characterized in that in the step 2, the hydrothermal reaction temperature of the mixed solution E is 120 ℃, and the hydrothermal reaction time is 4 hours.
7. The nanotube-like NiCo of claim 22S4The preparation method of the @ titanium carbide composite material is characterized in that in the step 2, the nickel source is NiCl2·6H2O or Ni (NO)3)·6H2O, the cobalt source is CoCl2·6H2O or Co (NO)3)·6H2And O, the amino precipitator is thiosemicarbazide or urea.
8. The nanotube-like NiCo of claim 22S4A process for producing a @ titanium carbide composite material, characterized in that in step 3, Na2S·9H2After O is added to the precursor F, Na2S·9H2The concentration of O was 0.2 mol/L.
9. The nanotube-like NiCo of claim 22S4The preparation method of the @ titanium carbide composite material is characterized in that in the step 3, the hydrothermal reaction temperature of the suspension G is 120 ℃, the hydrothermal reaction time is 8 hours, and the drying temperature is 60 ℃.
10. The nanotubular NiCo of claim 12S4Application of @ titanium carbide composite material, characterized in that the nanotube-shaped NiCo2S4The @ titanium carbide composite material is used in supercapacitors and lithium ion batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010738896.9A CN111916288A (en) | 2020-07-28 | 2020-07-28 | Nanotube-shaped NiCo2S4@ titanium carbide composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010738896.9A CN111916288A (en) | 2020-07-28 | 2020-07-28 | Nanotube-shaped NiCo2S4@ titanium carbide composite material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111916288A true CN111916288A (en) | 2020-11-10 |
Family
ID=73286449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010738896.9A Pending CN111916288A (en) | 2020-07-28 | 2020-07-28 | Nanotube-shaped NiCo2S4@ titanium carbide composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111916288A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112978868A (en) * | 2021-03-03 | 2021-06-18 | 同济大学 | Cobalt-iron layered double hydroxide @ titanium carbide electrode material and preparation method and application thereof |
| CN113908866A (en) * | 2021-10-18 | 2022-01-11 | 中国石油大学(北京) | Titanium carbide composite material loaded with cobalt-containing compound and preparation method and application thereof |
| CN114479320A (en) * | 2021-12-21 | 2022-05-13 | 西安理工大学 | Preparation method of cobaltosic/MXene/PVDF (polyvinylidene fluoride) layered composite material |
| CN114974916A (en) * | 2022-07-04 | 2022-08-30 | 桂林电子科技大学 | Fibrous MXene loaded NiCoS composite material and preparation method and application thereof |
| CN115094455A (en) * | 2022-05-25 | 2022-09-23 | 青岛大学 | CoTe 2 Per CoP @ Ti composite material and preparation method thereof |
| CN115282985A (en) * | 2021-12-17 | 2022-11-04 | 伊犁师范大学 | NiFe 2 S 4 Semi-coke composite material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108735522A (en) * | 2018-05-25 | 2018-11-02 | 西南大学 | A kind of CoNiO2/ MXene composite material and preparation methods and application |
| CN110970229A (en) * | 2019-12-27 | 2020-04-07 | 中国地质大学（北京） | NiCo2S4@ mesophase carbon microsphere/carbon nanotube composite material and preparation method and application thereof |
-
2020
- 2020-07-28 CN CN202010738896.9A patent/CN111916288A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108735522A (en) * | 2018-05-25 | 2018-11-02 | 西南大学 | A kind of CoNiO2/ MXene composite material and preparation methods and application |
| CN110970229A (en) * | 2019-12-27 | 2020-04-07 | 中国地质大学（北京） | NiCo2S4@ mesophase carbon microsphere/carbon nanotube composite material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| JIANJIAN FU等: "Two-dimensional titanium carbide (MXene)-wrapped sisal-Like NiCo2S4 as positive electrode for High-performance hybrid pouch-type asymmetric supercapacitor", 《CHEMICAL ENGINEERING JOURNAL》 * |
| 牛冬娟: "新型MXenes-Ti3C2纳米复合材料的合成及其电化学性能", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112978868A (en) * | 2021-03-03 | 2021-06-18 | 同济大学 | Cobalt-iron layered double hydroxide @ titanium carbide electrode material and preparation method and application thereof |
| CN113908866A (en) * | 2021-10-18 | 2022-01-11 | 中国石油大学(北京) | Titanium carbide composite material loaded with cobalt-containing compound and preparation method and application thereof |
| CN115282985A (en) * | 2021-12-17 | 2022-11-04 | 伊犁师范大学 | NiFe 2 S 4 Semi-coke composite material and preparation method and application thereof |
| CN114479320A (en) * | 2021-12-21 | 2022-05-13 | 西安理工大学 | Preparation method of cobaltosic/MXene/PVDF (polyvinylidene fluoride) layered composite material |
| CN114479320B (en) * | 2021-12-21 | 2023-11-03 | 西安理工大学 | Preparation method of cobalt disulfide nickel/MXene/PVDF layered composite material |
| CN115094455A (en) * | 2022-05-25 | 2022-09-23 | 青岛大学 | CoTe 2 Per CoP @ Ti composite material and preparation method thereof |
| CN115094455B (en) * | 2022-05-25 | 2023-09-26 | 青岛大学 | CoTe 2 CoP@Ti composite material and preparation method thereof |
| CN114974916A (en) * | 2022-07-04 | 2022-08-30 | 桂林电子科技大学 | Fibrous MXene loaded NiCoS composite material and preparation method and application thereof |
| CN114974916B (en) * | 2022-07-04 | 2024-01-30 | 桂林电子科技大学 | Fibrous MXene-loaded NiCoS composite material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111916288A (en) | Nanotube-shaped NiCo2S4@ titanium carbide composite material and preparation method and application thereof | |
| Zhai et al. | Construction of NiCo2S4 heterostructure based on electrochemically exfoliated graphene for high-performance hybrid supercapacitor electrode | |
| Lu et al. | Synthesis of nickel chalcogenide hollow spheres using an l-cysteine-assisted hydrothermal process for efficient supercapacitor electrodes | |
| Huang et al. | Unique FeP@ C with polyhedral structure in-situ coated with reduced graphene oxide as an anode material for lithium ion batteries | |
| Ye et al. | Application of different carbon-based transition metal oxide composite materials in lithium-ion batteries | |
| Hao et al. | Hierarchical three-dimensional Fe3O4@ porous carbon matrix/graphene anodes for high performance lithium ion batteries | |
| Xiao et al. | ZnO nanoparticles encapsulated in a 3D hierarchical carbon framework as anode for lithium ion battery | |
| Xu et al. | NiO/CNTs derived from metal-organic frameworks as superior anode material for lithium-ion batteries | |
| CN107394180B (en) | Two-dimensional transition group metal carbide (nitride) -nano silicon particle composite material, preparation and application | |
| CN109560269B (en) | Hollow tin dioxide@titanium dioxide/graphene aerogel composite material and preparation method thereof | |
| Venugopal et al. | Self-assembled hollow mesoporous Co 3 O 4 hybrid architectures: a facile synthesis and application in Li-ion batteries | |
| Yang et al. | Graphene-encapsulated SnO2 hollow spheres as high-performance anode materials for lithium ion batteries | |
| CN110364372A (en) | A kind of supercapacitor vanadic acid nickel material, preparation method and application | |
| Xi et al. | Constructing MXene hydrogels and aerogels for rechargeable supercapacitors and batteries | |
| CN111554912A (en) | Tin @ carbon @ molybdenum disulfide yolk-shell structure lithium ion battery cathode composite material and preparation method thereof | |
| US20200283306A1 (en) | Preparation method of hexagonal molybdenum oxide nanorod | |
| Sui et al. | Nickel metal-organic framework microspheres loaded with nickel-cobalt sulfides for supercapacitor electrode materials | |
| CN112186182A (en) | One-dimensional hollow carbon-coated iron selenide nanotube composite electrode material and preparation method thereof | |
| Chai et al. | In-situ growth of NiAl layered double hydroxides on Ni-based metal-organic framework derived hierarchical carbon as high performance material for Zn-ion batteries | |
| Ershadi et al. | Facile synthesis of amino-functionalized mesoporous Fe3O4/rGO 3D nanocomposite by diamine compounds as Li-ion battery anodes | |
| CN106410156A (en) | Silicon-carbon composite material, preparation method and application thereof | |
| Zhang et al. | MOF-driven ultra-small hollow Co 9 S 8 nanoparticles embedded in porous carbon for lithium-ion batteries | |
| CN112786865A (en) | MoS2Preparation method and application of quasi-quantum dot/nitrogen-sulfur co-doped biomass carbon composite nano material | |
| CN114195132B (en) | Preparation method of nano germanium/three-dimensional porous graphene composite material and application of nano germanium/three-dimensional porous graphene composite material to lithium ion battery negative electrode | |
| Jiang et al. | Advanced ferroferric oxide-based composites for lithium-ion battery: Recent developments and future perspectives |
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: 20201110 |
|
| RJ01 | Rejection of invention patent application after publication |