CN117727568A - Yolk-shell dodecahedron transition metal oxide TMO@MXene composite material and preparation method and application thereof - Google Patents
Yolk-shell dodecahedron transition metal oxide TMO@MXene composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN117727568A CN117727568A CN202311765473.6A CN202311765473A CN117727568A CN 117727568 A CN117727568 A CN 117727568A CN 202311765473 A CN202311765473 A CN 202311765473A CN 117727568 A CN117727568 A CN 117727568A
- Authority
- CN
- China
- Prior art keywords
- nico
- shell
- composite material
- metal oxide
- transition metal
- 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 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 229910000314 transition metal oxide Inorganic materials 0.000 title claims abstract description 27
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims abstract description 151
- 229910003266 NiCo Inorganic materials 0.000 claims abstract description 133
- 239000000084 colloidal system Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 239000002243 precursor Substances 0.000 claims description 27
- 239000011858 nanopowder Substances 0.000 claims description 25
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007772 electrode material Substances 0.000 claims description 15
- 229910017709 Ni Co Inorganic materials 0.000 claims description 13
- 229910003267 Ni-Co Inorganic materials 0.000 claims description 13
- 229910003262 Ni‐Co Inorganic materials 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 8
- 102000020897 Formins Human genes 0.000 claims description 3
- 108091022623 Formins Proteins 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 21
- 239000003990 capacitor Substances 0.000 abstract description 5
- 239000002114 nanocomposite Substances 0.000 abstract description 5
- 238000004146 energy storage Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 121
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 44
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 229910052759 nickel Inorganic materials 0.000 description 15
- 239000000725 suspension Substances 0.000 description 15
- 239000002033 PVDF binder Substances 0.000 description 14
- 239000006260 foam Substances 0.000 description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 14
- 238000005303 weighing Methods 0.000 description 14
- 238000000227 grinding Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 238000002484 cyclic voltammetry Methods 0.000 description 9
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 229910021607 Silver chloride Inorganic materials 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 7
- 229910052956 cinnabar Inorganic materials 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 238000000643 oven drying Methods 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 239000006230 acetylene black Substances 0.000 description 6
- 239000011149 active material Substances 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000013329 compounding Methods 0.000 description 4
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000003775 Density Functional Theory Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 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 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Classifications
-
- 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
Abstract
The invention provides a yolk-shell dodecahedron transition metal oxide TMO@MXene composite material, a preparation method and application thereof 2 O 4 @Co 3 O 4 Double-shell nano hollow polyhedron, and NiCo is added 2 O 4 @Co 3 O 4 Double shell nano hollow polyhedron and Ti 3 C 2 The colloid solution is compounded to form the nano composite material. Ti of the invention 3 C 2 @NiCo 2 O 4 @Co 3 O 4 The invention has the advantages of good electrochemical performance, simple experimental process, controllable product morphology and safetyThe method is environment-friendly, and lays a foundation for further application in the energy storage fields of lithium ion batteries, super capacitors and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of composite materials and electrochemical energy storage materials, and relates to a yolk-shell dodecahedron transition metal oxide TMO@MXene composite material, and a preparation method and application thereof.
Background
To date, the MXene family has only included Ti 3 C 2 、Ti 2 C、(Ti 0.5 、Nb 0.5 ) 2 C、(V 0.5 、Cr 0.5 ) 3 C 2 、Ti 3 CN、Ta 4 C 3 、Nb 2 C、V 2 C and Nb 4 C 3 . According to the latest studies, the physicochemical behavior of mxnes shows unique advantages, its conductivity being even comparable to that of multi-layer graphene. Furthermore, the MXene is extremely stiff and has an in-plane elastic coefficient as high as 500Gpa according to the test result of the Density Functional Theory (DFT). Khazaeie et al found that the seebeck coefficient of semiconducting mxnes reached very high levels at low temperatures. With the development of research, the unique properties of mxnes have attracted extensive academic attention and began to explore the potential applications that it may have. For example, MXnes is considered to be an ideal energy storage material, and Xie et al successfully developed a catalyst with good application prospects as a carrier material for platinum nanoparticles, which has stable properties and does not produce additional unwanted reactions. Wang et al found that mxnes has good enzyme immobilization capacity and biocompatibility for redox proteins, which is believed to be applicable to electrochemical biosensors and to yield a number of useful applications. In the future, more MXene material will be stripped from a fairly large family of largest phases. During etching, it is important that the surface groups of the MXene species typically consist of F, OH or O. Thus, these species may be referred to as M n+1 X n T x Wherein T represents a tableA face group.
The researchers generally set new MXene-titanium carbide (Ti 3 C 2 ) Is considered as a potential and excellent supercapacitor electrode material. Due to its unique two-dimensional lamellar structure, ti 3 C 2 Has good capacity stability and specific surface area, and has outstanding electrochemical energy storage performance, in addition, ti 3 C 2 And the conductivity of the alloy is good. MXene-Ti, however 3 C 2 Has smaller theoretical specific capacity and Ti 3 C 2 Easy stacking between layers, thus restricting Ti 3 C 2 Is a practical application of the above.
The cobalt-based metal oxide has stable performance, is cheap and easy to obtain, is environment-friendly, and is an ideal supercapacitor electrode material. Wherein Co is 3 O 4 The method has excellent redox performance and higher theoretical capacitance value, but the application of the method in the aspect of super capacitors is limited by poor cycle stability and lower rate performance.
Disclosure of Invention
For Ti 3 C 2 Theoretical capacitance is low and Ti 3 C 2 The invention provides a yolk-shell dodecahedron transition metal oxide TMO@MXene composite material, a preparation method and application thereof, and Ti is used for preparing the composite material 3 C 2 、NiCo 2 O 4 And Co 3 O 4 Synergistic effect of the three components improves and promotes MXene-Ti 3 C 2 T x Electrochemical properties of the base composite.
The invention is realized by the following technical scheme:
a preparation method of a yolk-shell dodecahedron transition metal oxide TMO@MXene composite material comprises the following steps:
s1, dispersing ZIF-67 in absolute ethyl alcohol, and adding Ni (NO) 3 ) 2 ·6H 2 O, stirring to form ZIF-67/Ni-Co precursor, collecting ZIF-67/Ni-Co precursor, washing, drying, calcining in air atmosphere to obtain NiCo 2 O 4 @Co 3 O 4 Double-shell nano hollow polyhedron;
S2，taking NiCo 2 O 4 @Co 3 O 4 Double-shell nano hollow polyhedron dispersed in water and Ti is added dropwise 3 C 2 Stirring the colloid solution, and then drying to obtain Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 。
Preferably, in S1, ZIF-67 is mixed with Ni (NO 3 ) 2 ·6H 2 The mass ratio of O is 1:2.
preferably, in S1, the calcination temperature is 350-450 ℃ and the time is 2-3 h.
Preferably, in S1, the calcination is carried out at 1-2 ℃ for min -1 Is heated to a rate of 350 to 450 ℃.
Preferably, in S1, the preparation method of the ZIF-67 comprises the following steps: co (NO) 3 ) 2 ·6H 2 O and 2-methylimidazole are dissolved in methanol, respectively, and then the resulting 2-methylimidazole solution is added to the resulting Co (NO) with stirring 3 ) 2 ·6H 2 And in the O solution, standing the obtained mixed solution at room temperature after stirring, collecting precipitate, washing and drying to obtain ZIF-67.
Preferably, in S2, niCo 2 O 4 @Co 3 O 4 And Ti is 3 C 2 The mass ratio of (C) is 100mg (40-100 mg).
Preferably, in S2, ti 3 C 2 The preparation method of the colloid solution comprises the following steps: ti is mixed with 3 C 2 Adding the nano powder into deionized water, and continuously diluting with deionized water to obtain Ti 3 C 2 Colloidal solution.
Preferably, in S2, the drying is vacuum freeze drying.
The yolk-shell dodecahedron transition metal oxide TMO@MXene composite material obtained by the preparation method.
The yolk-shell dodecahedron transition metal oxide TMO@MXene composite material is applied to a super capacitor as an electrode material.
Compared with the prior art, the invention has the following beneficial effects:
the invention carbonizes by high temperature pyrolysisNiCo synthesis method 2 O 4 @Co 3 O 4 Double-shell nano hollow polyhedron, and NiCo is added 2 O 4 @Co 3 O 4 Double shell nano hollow polyhedron and Ti 3 C 2 The colloid solution is compounded to form the nano composite material. NiCo 2 O 4 Is a typical spinel-type mixed-valence metal complex oxide, in which nickel ions occupy octahedral sites and cobalt ions occupy both octahedral and tetrahedral sites in its crystal structure. Solid state redox couple Co 2+ /Co 3+ And Ni 2+ /Ni 3+ The presence in the structure provides two active centers for pseudocapacitance generation. NiCo 2 O 4 @Co 3 O 4 The double-shell nano hollow polyhedron has lower activation energy for electron transfer due to various valence states and different performances of cations, has improved specific capacitance performance and conductivity, but has weaker stability; ti (Ti) 3 C 2 Has good capacity stability and is compatible with NiCo 2 O 4 @Co 3 O 4 After compounding, the obtained composite material not only has good capacity and conductivity, but also has good stability, and Ti 3 C 2 With NiCo 2 O 4 @Co 3 O 4 Composite improves Ti 3 C 2 The problem of easy stacking is very ideal supercapacitor electrode material. The invention uses Ti 3 C 2 、NiCo 2 O 4 And Co 3 O 4 The Ti with good appearance and excellent performance is prepared by the synergistic effect of the three components 3 C 2 @NiCo 2 O 4 @Co 3 O 4 A nanocomposite. The results of the electrochemical tests related to the invention show that at a scanning rate of 2mV/s, ti is prepared 3 C 2 @NiCo 2 O 4 @Co 3 O 4 The highest capacitance of the material reaches 1416.00F/g, so that a good modification effect is achieved; and the material has excellent cycling stability, and the capacity still has 87.83% of the original capacity after 1000 times of constant current charge and discharge under the condition of current density of 2A/g. Is hopeful to create a device which can realize the rapid conversion and storage of energy and meet the requirements of human production andthe energy demand of life, the use of traditional energy sources are saved, and the pollution is reduced. Ti of the invention 3 C 2 @NiCo 2 O 4 @Co 3 O 4 The invention has the advantages of good electrochemical performance, simple experimental process, controllable product morphology, safety and environmental protection, and lays a foundation for further application in the energy storage fields of lithium ion batteries, super capacitors and the like.
Further, for Ti 3 C 2 Problem of easy stacking between layers, multilayer Ti is obtained by freeze drying 3 C 2 The material is peeled off to become a layered two-dimensional material, which exhibits excellent conductivity and obtains a larger specific surface area.
Drawings
FIG. 1 shows the precursors ZIF-67 and NiCo prepared in example 1 2 O 4 @Co 3 O 4 SEM and TEM images of (a): (a) SEM images of precursor ZIF-67; (b) an enlarged SEM image of precursor ZIF-67; (c) NiCo 2 O 4 @Co 3 O 4 SEM images of (a); (d) NiCo 2 O 4 @Co 3 O 4 SEM images of (a); (e) NiCo 2 O 4 @Co 3 O 4 Is a TEM image of (1).
FIG. 2 is a NiCo prepared in example 1 2 O 4 @Co 3 O 4 Elemental surface scan photographs of (2): (a) NiCo 2 O 4 @Co 3 O 4 ；(b)Ni、Co、O；(c)Ni；(d)Co；(e)O。
FIG. 3 is a drawing of the preparation of Ti according to example 1 3 C 2 @NiCo 2 O 4 @Co 3 O 4 SEM image (a) and TEM image (b).
FIG. 4 is a NiCo prepared in example 1 2 O 4 @Co 3 O 4 Active material (a) and Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Cyclic voltammograms of electrodes of composite (b) at different scan rates under a three electrode system.
FIG. 5 is NiCo prepared in example 1 2 O 4 @Co 3 O 4 Active material (a) and Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 GCD plot of the electrodes of composite (b) at different current densities for a three electrode system.
FIG. 6 is NiCo prepared in example 1 2 O 4 @Co 3 O 4 Active material (a) and Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 EIS diagram of the electrode of composite (b) under a three electrode system.
FIG. 7 Ti prepared in example 1 3 C 2 、Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 And NiCo 2 O 4 @Co 3 O 4 Cyclic stability test patterns under a three electrode system.
Detailed Description
For a further understanding of the present invention, the present invention is described below in conjunction with the following examples, which are provided to further illustrate the features and advantages of the present invention and are not intended to limit the claims of the present invention.
The preparation method of the yolk-shell dodecahedron transition metal oxide TMO@MXene composite material comprises the following steps of:
s1, dispersing ZIF-67 in absolute ethyl alcohol, and adding Ni (NO) 3 ) 2 ·6H 2 O, stirring to form ZIF-67/Ni-Co precursor, collecting ZIF-67/Ni-Co precursor, washing, drying, calcining in air atmosphere to obtain NiCo 2 O 4 @Co 3 O 4 Double-shell nano hollow polyhedron;
s2, taking NiCo 2 O 4 @Co 3 O 4 Double-shell nano hollow polyhedron dispersed in water and Ti is added dropwise 3 C 2 Stirring the colloid solution, and then drying to obtain Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 。
In the S1 of the present invention, ZIF-67 and Ni (NO 3 ) 2 ·6H 2 The mass ratio of O is 1:2.
in the invention S1, the calcination is carried out at 1-2 ℃ for min -1 Is heated to a rate of 350 to 450 ℃,preserving heat for 2-3 h.
In the S1 of the invention, the preparation method of the ZIF-67 comprises the following steps: co (NO) 3 ) 2 ·6H 2 O and 2-methylimidazole are dissolved in methanol, respectively, and then the resulting 2-methylimidazole solution is added to the resulting Co (NO) with stirring 3 ) 2 ·6H 2 And in the O solution, standing the obtained mixed solution at room temperature after stirring, collecting precipitate, washing and drying to obtain ZIF-67.
In the invention S2, niCo 2 O 4 @Co 3 O 4 And Ti is 3 C 2 The mass ratio of (2) is 100 mg:40-100 mg.
In the invention S2, ti 3 C 2 The preparation method of the colloid solution comprises the following steps: ti is mixed with 3 C 2 Adding the nano powder into deionized water, and continuously diluting with deionized water to obtain Ti 3 C 2 The nano powder colloid suspension is used for standby.
In the invention S2, the drying is vacuum freeze drying.
Example 1
Step one, two-dimensional layered Ti 3 C 2 Preparing nano powder and a colloid suspension thereof;
preparation of two-dimensional layered Ti according to the existing method 3 C 2 Nano powder.
10ml of diluted solution containing 60mg of Ti 3 C 2 The nano powder colloid suspension is used for standby.
Step two, preparation of transition metal oxide TMO@MXene composite material (Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 )；
First, ZIF-67 was prepared: 2mmol Co (NO) 3 ) 2 ·6H 2 O and 8mmol of 2-methylimidazole were dissolved in 50mL of methanol, respectively. The 2-methylimidazole solution was then poured rapidly into Co (NO) with stirring 3 ) 2 ·6H 2 In the O solution, stirring for 3min, and standing the mixed solution at room temperature for 24h; collecting purple precipitate by centrifugation, washing with methanol for three times, and oven drying at 60deg.C for 12 hr;
second, synthesizeNiCo 2 O 4 @Co 3 O 4 Double shell nano hollow polyhedron: first, 40mg of ZIF-67 was dispersed in 25L of absolute ethanol, and 80mg of Ni (NO) 3 ) 2 ·6H 2 O, stirring for 30min, and forming a ZIF-67/Ni-Co precursor; centrifugally collecting, washing with ethanol for several times, and finally drying at 60 ℃ for 12 hours; then the precursor is put into a muffle furnace for 1 ℃ min -1 Heating to 350 ℃ at a rate of 2 hours to obtain NiCo 2 O 4 @Co 3 O 4 Double-shell nano hollow polyhedron;
finally, ti is synthesized 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Nano hollow polyhedron: firstly, 100mg of NiCo is taken 2 O 4 @Co 3 O 4 Dispersing in 30mL deionized water, slowly adding dropwise 10mL of a solution containing 60mg Ti 3 C 2 Stirring for 30min, transferring to vacuum freeze dryer, and drying at-45deg.C under 1Pa to obtain Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 。
Step three, ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Preparing an electrode;
the preparation method of the electrode slice made of the powdery material comprises the following steps:
firstly, ultrasonically cleaning foam nickel with the thickness of 2cm multiplied by 1cm by absolute ethyl alcohol for 2 hours, removing impurities on the surface, drying in a constant-temperature drying oven at the temperature of 40 ℃, and weighing for later use;
then Ti is added 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Mixing the composite material, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, grinding for 30min in an agate mortar, then dropwise adding 200 mu L N-methyl-2-pyrrolidone (NMP) liquid, and grinding for 20min to prepare an electrode material;
and finally, uniformly coating the obtained black mud-like slurry on foam nickel, wherein the coating amount is 2-3 mg, vacuum drying at 60 ℃ for 12h, and carrying out pressure maintaining on the dried electrode slice on a hydraulic press for 30s by using the atmospheric pressure of 5Pa, and weighing the actual mass of the small electrode slice for later use. Finally, adopting a three-electrode system to prepare Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 The electrode is used as a working electrode, the platinum sheet is used as a counter electrode, silver/silver chloride is used as a reference electrode, and a Shanghai cinnabar CHI660E electrochemical workstation is used for testing Ti under the condition of 6mol/L KOH electrolyte 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Electrochemical properties of the electrode, such as cyclic voltammogram, constant current charge and discharge, alternating current impedance and cyclic stability are tested.
Referring to FIG. 1, the precursors ZIF-67 and NiCo prepared in example 1 2 O 4 @Co 3 O 4 SEM and TEM images of (a). From FIG. 1 (a), a large number of more obvious rhombohedral dodecahedral shaped precursor ZIF-67 can be seen, indicating that the preparation of precursor ZIF-67 works well. Meanwhile, as can be seen in fig. 1 (b) at high magnification, the structure is complete and no other impurities exist, which indicates that the prepared precursor ZIF-67 is uniform in size and excellent in quality. As is apparent from FIGS. 1 (c), (d) and (e), niCo was produced 2 O 4 @Co 3 O 4 The material is of a dodecahedron hollow structure, and the particle size is about 500nm. Further demonstration of NiCo by SEM and TEM testing 2 O 4 With Co 3 O 4 Successful compounding to form NiCo 2 O 4 @Co 3 O 4 An oxide.
Referring to FIG. 2, niCo prepared in example 1 2 O 4 @Co 3 O 4 The elemental surface scan of the photo. As shown in FIGS. 2 (a) - (e), the EDX experiment shows that Ni, co and O are uniformly distributed in NiCo 2 O 4 @Co 3 O 4 In (C), proved by NiCo 2 O 4 @Co 3 O 4 Is a successful preparation of (a).
Referring to FIG. 3, ti was prepared in example 1 3 C 2 @NiCo 2 O 4 @Co 3 O 4 SEM image (a) and TEM image (b). As can be seen from FIG. 3 (a), a single sheet of layered Ti 3 C 2 Coating a large amount of NiCo 2 O 4 @Co 3 O 4 According to the results, through the research of the test, niCo is realized 2 O 4 @Co 3 O 4 In two dimensions Ti 3 C 2 Growth on the surface to successfully prepare Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Hollow polyhedral nano composite materials. As can be seen more clearly in FIG. 3 (b) at high magnification, polyhedral particles NiCo 2 O 4 @Co 3 O 4 Uniformly and lamellar Ti 3 C 2 Compounding, niCo 2 O 4 @Co 3 O 4 The surface of the product is smoother, and the product has uniform and monodisperse polyhedral particle morphology. The composite of the two materials can effectively inhibit Ti 3 C 2 Self-assembly and stacking of (c) and NiCo 2 O 4 @Co 3 O 4 Can improve the Ti of the matrix material 3 C 2 So that the material has additional active sites, thereby improving the electrochemical performance of the material.
Referring to FIG. 4, niCo prepared in example 1 2 O 4 @Co 3 O 4 Active material (a) and Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Cyclic voltammograms of electrodes of composite (b) at different scan rates under a three electrode system. As can be seen from FIGS. 4 (a), (b), niCo 2 O 4 @Co 3 O 4 Active material, ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 The composites each exhibited a pair of distinct redox peaks: near 0.19V and 0.39V and 0.25V and 0.45V potentials, respectively, with NiCo 2 O 4 @Co 3 O 4 Compared with the electrode, it can be found that Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 The electrodes have a larger CV surrounding area, indicating the Ti prepared in this experiment 3 C 2 @NiCo 2 O 4 @Co 3 O 4 The composite electrode has a greater specific capacity. Calculated by a formula, the composite material Ti is at a scanning rate of 2mV/s 3 C 2 @NiCo 2 O 4 @Co 3 O 4 The specific capacity of (C) was 1416.00F/g. As the scan proceeds, the current peaks of the cathode and anodeMove to the two poles. And under high scanning speed, the CV curve of the composite material has no obvious deformation, which proves that electrolyte ions and electrons can be in Ti 3 C 2 The layers move rapidly. And the current of the voltammogram is increased in proportion to the increase of the scanning rate, which shows that the material has the characteristic of rapid charge and discharge. It can also be seen from the observation that the electron transfer has a reversible process, good symmetry and good reversibility, which indicates that the nanocomposite can solve Ti to a certain extent 3 C 2 The capacitor has the advantages of lower theoretical capacitance, easy stacking between layers, ideal capacitance and high multiplying power performance, and can be used as an ideal supercapacitor application material.
Referring to FIG. 5, from FIG. 5 (a) NiCo 2 O 4 @Co 3 O 4 With FIG. 5 (b) Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 The GCD curves of the two complexes at different current densities can be seen for Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 The electrode material has obvious charge and discharge platforms under different current densities, which shows the pseudocapacitance characteristic of the electrode material, and is consistent with CV analysis results. Furthermore, the GCD curve remains symmetrical throughout with increasing current density and there is no significant deviation, which proves that Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Is excellent in electrochemical reversible property and excellent in rate performance, and according to comparison of test phenomena of two figures, niCo can be demonstrated 2 O 4 @Co 3 O 4 The electrode has better charge storage capacity and excellent capacitance performance after being compounded with titanium carbide. Ti at a current density of 1A/g, 2A/g and 5A/g by calculation of the formula 3 C 2 @NiCo 2 O 4 @Co 3 O 4 The mass specific capacities of (C) are 1471.67F/g, 1046.96F/g and 870.44F/g respectively.
Referring to FIG. 6, FIGS. 6 (a) and 6 (b) are NiCo 2 O 4 @Co 3 O 4 Active material, ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Of composite materialEIS impedance spectrum, which is composed of low frequency band and high frequency band. The semi-circle with smaller radius is displayed in the high frequency area, which is generated by the electrochemical impedance of the electrode, which shows that the electrode has smaller interfacial charge transfer resistance, the low frequency band is a straight line, and the characteristic of capacitance is shown as compared with NiCo 2 O 4 @Co 3 O 4 Compared with the electrode, ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 The electrochemical impedance of the composite electrode is smaller and the slope is larger, indicating Ti 3 C 2 With NiCo 2 O 4 、Co 3 O 4 The composite material has good compounding and synergistic effect, and the composite material has better capacitance property.
Referring to FIG. 7, FIG. 7 shows Ti 3 C 2 、Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 And NiCo 2 O 4 @Co 3 O 4 The specific capacity of the electrode after 1000 cycles at a current density of 2A/g was plotted against the number of cycles. As can be seen from the figure, ti after 1000 cycles 3 C 2 、Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 And NiCo 2 O 4 @Co 3 O 4 The capacity retention of (a) was 100%, 87.83% and 78.44%, respectively. This result shows that compared to NiCo 2 O 4 @Co 3 O 4 ，Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 The electrode material has better cycle stability. This is probably due to the fact that, in Ti 3 C 2 Can be used as conductive matrix to improve NiCo 2 O 4 @Co 3 O 4 Volume expansion and contraction during multiple cycling tests, reduced disruption and collapse of transition metal oxide structure, and by Ti 3 C 2 With NiCo 2 O 4 @Co 3 O 4 The conductivity of the composite material is improved, thereby improving the cycle stability of the composite material.
Example 2
Step oneTwo-dimensional layered Ti 3 C 2 Preparing nano powder and a colloid suspension thereof;
preparation of two-dimensional layered Ti according to the existing method 3 C 2 Nano powder.
10ml of diluted solution containing 40mg of Ti is taken 3 C 2 The nano powder colloid suspension is used for standby.
Step two, preparation of transition metal oxide TMO@MXene composite material (Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 )；
First, ZIF-67 was prepared: 2mmol Co (NO) 3 ) 2 ·6H 2 O and 8mmol of 2-methylimidazole were dissolved in 50mL of methanol, respectively. The 2-methylimidazole solution was then poured rapidly into Co (NO) with stirring 3 ) 2 ·6H 2 In the O solution, stirring for 3min, and standing the mixed solution at room temperature for 24h; collecting purple precipitate by centrifugation, washing with methanol for three times, and oven drying at 60deg.C for 12 hr;
secondly, niCo is synthesized 2 O 4 @Co 3 O 4 Double shell nano hollow polyhedron: first, 40mg of ZIF-67 was dispersed in 25L of absolute ethanol, and 80mg of Ni (NO) 3 ) 2 ·6H 2 O, stirring for 30min, and forming a ZIF-67/Ni-Co precursor; centrifugally collecting, washing with ethanol for several times, and finally drying at 60 ℃ for 12 hours; then the precursor is put into a muffle furnace for 1 ℃ min -1 Heating to 350 ℃ at a rate of 2 hours to obtain NiCo 2 O 4 @Co 3 O 4 Double-shell nano hollow polyhedron;
finally, ti is synthesized 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Nano hollow polyhedron: firstly, 100mg of NiCo is taken 2 O 4 @Co 3 O 4 Dispersing in 30mL deionized water, slowly adding dropwise 10mL of solution containing 40mg Ti 3 C 2 Stirring for 30min, transferring to vacuum freeze dryer, and drying at-45deg.C under 1Pa to obtain Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 。
Step three, ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Preparing an electrode;
the preparation method of the electrode slice made of the powdery material comprises the following steps:
firstly, ultrasonically cleaning foam nickel with the thickness of 2cm multiplied by 1cm by absolute ethyl alcohol for 2 hours, removing impurities on the surface, drying in a constant-temperature drying oven at the temperature of 40 ℃, and weighing for later use;
then Ti is added 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Mixing the composite material, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, grinding for 30min in an agate mortar, then dropwise adding 200 mu L N-methyl-2-pyrrolidone (NMP) liquid, and grinding for 20min to prepare an electrode material;
and finally, uniformly coating the obtained black mud-like slurry on foam nickel, wherein the coating amount is 2-3 mg, vacuum drying at 60 ℃ for 12h, and carrying out pressure maintaining on the dried electrode slice on a hydraulic press for 30s by using the atmospheric pressure of 5Pa, and weighing the actual mass of the small electrode slice for later use. Finally, adopting a three-electrode system to prepare Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 The electrode is used as a working electrode, the platinum sheet is used as a counter electrode, silver/silver chloride is used as a reference electrode, and a Shanghai cinnabar CHI660E electrochemical workstation is used for testing Ti under the condition of 6mol/L KOH electrolyte 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Electrochemical properties of the electrode, such as cyclic voltammogram, constant current charge and discharge, alternating current impedance and cyclic stability are tested.
Example 3
Step one, two-dimensional layered Ti 3 C 2 Preparing nano powder and a colloid suspension thereof;
preparation of two-dimensional layered Ti according to the existing method 3 C 2 Nano powder.
10ml of diluted solution containing 80mg of Ti 3 C 2 The nano powder colloid suspension is used for standby.
Step two, preparation of transition metal oxide TMO@MXene composite material (Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 )；
First, ZIF-67 was prepared: 2mmol Co (NO) 3 ) 2 ·6H 2 O and 8mmol of 2-methylimidazole were dissolved in 50mL of methanol, respectively. The 2-methylimidazole solution was then poured rapidly into Co (NO) with stirring 3 ) 2 ·6H 2 In the O solution, stirring for 3min, and standing the mixed solution at room temperature for 24h; collecting purple precipitate by centrifugation, washing with methanol for three times, and oven drying at 60deg.C for 12 hr;
secondly, niCo is synthesized 2 O 4 @Co 3 O 4 Double shell nano hollow polyhedron: first, 40mg of ZIF-67 was dispersed in 25L of absolute ethanol, and 80mg of Ni (NO) 3 ) 2 ·6H 2 O, stirring for 30min, and forming a ZIF-67/Ni-Co precursor; centrifugally collecting, washing with ethanol for several times, and finally drying at 60 ℃ for 12 hours; then the precursor is put into a muffle furnace for 1 ℃ min -1 Heating to 350 ℃ at a rate of 2 hours to obtain NiCo 2 O 4 @Co 3 O 4 Double-shell nano hollow polyhedron;
finally, ti is synthesized 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Nano hollow polyhedron: firstly, 100mg of NiCo is taken 2 O 4 @Co 3 O 4 Dispersing in 30mL deionized water, slowly adding dropwise 10mL of solution containing 80mg Ti 3 C 2 Stirring for 30min, transferring to vacuum freeze dryer, and drying at-45deg.C under 1Pa to obtain Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 。
Step three, ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Preparing an electrode;
the preparation method of the electrode slice made of the powdery material comprises the following steps:
firstly, ultrasonically cleaning foam nickel with the thickness of 2cm multiplied by 1cm by absolute ethyl alcohol for 2 hours, removing impurities on the surface, drying in a constant-temperature drying oven at the temperature of 40 ℃, and weighing for later use;
then Ti is added 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Composite material and acetyleneMixing black and polyvinylidene fluoride (PVDF) according to a mass ratio of 8:1:1, grinding for 30min in an agate mortar, then dropwise adding 200 mu L N-methyl-2-pyrrolidone (NMP) liquid, and grinding for 20min to prepare an electrode material;
and finally, uniformly coating the obtained black mud-like slurry on foam nickel, wherein the coating amount is 2-3 mg, vacuum drying at 60 ℃ for 12h, and carrying out pressure maintaining on the dried electrode slice on a hydraulic press for 30s by using the atmospheric pressure of 5Pa, and weighing the actual mass of the small electrode slice for later use. Finally, adopting a three-electrode system to prepare Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 The electrode is used as a working electrode, the platinum sheet is used as a counter electrode, silver/silver chloride is used as a reference electrode, and a Shanghai cinnabar CHI660E electrochemical workstation is used for testing Ti under the condition of 6mol/L KOH electrolyte 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Electrochemical properties of the electrode, such as cyclic voltammogram, constant current charge and discharge, alternating current impedance and cyclic stability are tested.
Example 4
Step one, two-dimensional layered Ti 3 C 2 Preparing nano powder and a colloid suspension thereof;
preparation of two-dimensional layered Ti according to the existing method 3 C 2 Nano powder.
10ml of diluted solution containing 100mg of Ti 3 C 2 The nano powder colloid suspension is used for standby.
Step two, preparation of transition metal oxide TMO@MXene composite material (Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 )；
First, ZIF-67 was prepared: 2mmol Co (NO) 3 ) 2 ·6H 2 O and 8mmol of 2-methylimidazole were dissolved in 50mL of methanol, respectively. The 2-methylimidazole solution was then poured rapidly into Co (NO) with stirring 3 ) 2 ·6H 2 In the O solution, stirring for 3min, and standing the mixed solution at room temperature for 24h; collecting purple precipitate by centrifugation, washing with methanol for three times, and oven drying at 60deg.C for 12 hr;
secondly, niCo is synthesized 2 O 4 @Co 3 O 4 Double shell nano hollow polyhedron: first, 40mg of ZIF-67 was dispersed in 25L of absolute ethanol, and 80mg of Ni (NO) 3 ) 2 ·6H 2 O, stirring for 30min, and forming a ZIF-67/Ni-Co precursor; centrifugally collecting, washing with ethanol for several times, and finally drying at 60 ℃ for 12 hours; then the precursor is put into a muffle furnace for 1 ℃ min -1 Heating to 350 ℃ at a rate of 2 hours to obtain NiCo 2 O 4 @Co 3 O 4 Double-shell nano hollow polyhedron;
finally, ti is synthesized 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Nano hollow polyhedron: firstly, 100mg of NiCo is taken 2 O 4 @Co 3 O 4 Dispersing in 30mL deionized water, slowly adding dropwise 10mL of solution containing 100mg Ti 3 C 2 Stirring for 30min, transferring to vacuum freeze dryer, and drying at-45deg.C under 1Pa to obtain Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 。
Step three, ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Preparing an electrode;
the preparation method of the electrode slice made of the powdery material comprises the following steps:
firstly, ultrasonically cleaning foam nickel with the thickness of 2cm multiplied by 1cm by absolute ethyl alcohol for 2 hours, removing impurities on the surface, drying in a constant-temperature drying oven at the temperature of 40 ℃, and weighing for later use;
then Ti is added 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Mixing the composite material, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, grinding for 30min in an agate mortar, then dropwise adding 200 mu L N-methyl-2-pyrrolidone (NMP) liquid, and grinding for 20min to prepare an electrode material;
and finally, uniformly coating the obtained black mud-like slurry on foam nickel, wherein the coating amount is 2-3 mg, vacuum drying at 60 ℃ for 12h, and carrying out pressure maintaining on the dried electrode slice on a hydraulic press for 30s by using the atmospheric pressure of 5Pa, and weighing the actual mass of the small electrode slice for later use. Finally, adopting a three-electrode system to prepare Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 The electrode is used as a working electrode, the platinum sheet is used as a counter electrode, silver/silver chloride is used as a reference electrode, and a Shanghai cinnabar CHI660E electrochemical workstation is used for testing Ti under the condition of 6mol/L KOH electrolyte 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Electrochemical properties of the electrode, such as cyclic voltammogram, constant current charge and discharge, alternating current impedance and cyclic stability are tested.
Example 5
Step one, two-dimensional layered Ti 3 C 2 Preparing nano powder and a colloid suspension thereof;
preparation of two-dimensional layered Ti according to the existing method 3 C 2 Nano powder.
10ml of diluted solution containing 60mg of Ti 3 C 2 The nano powder colloid suspension is used for standby.
Step two, preparation of transition metal oxide TMO@MXene composite material (Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 )；
First, ZIF-67 was prepared: 2mmol Co (NO) 3 ) 2 ·6H 2 O and 8mmol of 2-methylimidazole were dissolved in 50mL of methanol, respectively. The 2-methylimidazole solution was then poured rapidly into Co (NO) with stirring 3 ) 2 ·6H 2 In the O solution, stirring for 3min, and standing the mixed solution at room temperature for 24h; collecting purple precipitate by centrifugation, washing with methanol for three times, and oven drying at 60deg.C for 12 hr;
secondly, niCo is synthesized 2 O 4 @Co 3 O 4 Double shell nano hollow polyhedron: first, 40mg of ZIF-67 was dispersed in 25L of absolute ethanol, and 80mg of Ni (NO) 3 ) 2 ·6H 2 O, stirring for 30min, and forming a ZIF-67/Ni-Co precursor; centrifugally collecting, washing with ethanol for several times, and finally drying at 60 ℃ for 12 hours; then the precursor is put into a muffle furnace for 2 ℃ min -1 Heating to 350 ℃ at a rate of 2 hours to obtain NiCo 2 O 4 @Co 3 O 4 Double-shell nano hollow polyhedron;
finally, ti is synthesized 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Nano hollow polyhedron: firstly, 100mg of NiCo is taken 2 O 4 @Co 3 O 4 Dispersing in 30mL deionized water, slowly adding dropwise 10mL of a solution containing 60mg Ti 3 C 2 Stirring for 30min, transferring to vacuum freeze dryer, and drying at-45deg.C under 1Pa to obtain Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 。
Step three, ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Preparing an electrode;
the preparation method of the electrode slice made of the powdery material comprises the following steps:
firstly, ultrasonically cleaning foam nickel with the thickness of 2cm multiplied by 1cm by absolute ethyl alcohol for 2 hours, removing impurities on the surface, drying in a constant-temperature drying oven at the temperature of 40 ℃, and weighing for later use;
then Ti is added 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Mixing the composite material, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, grinding for 30min in an agate mortar, then dropwise adding 200 mu L N-methyl-2-pyrrolidone (NMP) liquid, and grinding for 20min to prepare an electrode material;
and finally, uniformly coating the obtained black mud-like slurry on foam nickel, wherein the coating amount is 2-3 mg, vacuum drying at 60 ℃ for 12h, and carrying out pressure maintaining on the dried electrode slice on a hydraulic press for 30s by using the atmospheric pressure of 5Pa, and weighing the actual mass of the small electrode slice for later use. Finally, adopting a three-electrode system to prepare Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 The electrode is used as a working electrode, the platinum sheet is used as a counter electrode, silver/silver chloride is used as a reference electrode, and a Shanghai cinnabar CHI660E electrochemical workstation is used for testing Ti under the condition of 6mol/L KOH electrolyte 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Electrochemical properties of the electrode, such as cyclic voltammogram, constant current charge and discharge, alternating current impedance and cyclic stability are tested.
Example 6
Step one, two-dimensional layered Ti 3 C 2 Preparing nano powder and a colloid suspension thereof;
preparation of two-dimensional layered Ti according to the existing method 3 C 2 Nano powder.
10ml of diluted solution containing 60mg of Ti 3 C 2 The nano powder colloid suspension is used for standby.
Step two, preparation of transition metal oxide TMO@MXene composite material (Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 )；
First, ZIF-67 was prepared: 2mmol Co (NO) 3 ) 2 ·6H 2 O and 8mmol of 2-methylimidazole were dissolved in 50mL of methanol, respectively. The 2-methylimidazole solution was then poured rapidly into Co (NO) with stirring 3 ) 2 ·6H 2 In the O solution, stirring for 3min, and standing the mixed solution at room temperature for 24h; collecting purple precipitate by centrifugation, washing with methanol for three times, and oven drying at 60deg.C for 12 hr;
secondly, niCo is synthesized 2 O 4 @Co 3 O 4 Double shell nano hollow polyhedron: first, 40mg of ZIF-67 was dispersed in 25L of absolute ethanol, and 80mg of Ni (NO) 3 ) 2 ·6H 2 O, stirring for 30min, and forming a ZIF-67/Ni-Co precursor; centrifugally collecting, washing with ethanol for several times, and finally drying at 60 ℃ for 12 hours; then the precursor is put into a muffle furnace for 2 ℃ min -1 Heating to 450 ℃ at a rate of 2 hours to obtain NiCo 2 O 4 @Co 3 O 4 Double-shell nano hollow polyhedron;
finally, ti is synthesized 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Nano hollow polyhedron: firstly, 100mg of NiCo is taken 2 O 4 @Co 3 O 4 Dispersing in 30mL deionized water, slowly adding dropwise 10mL of a solution containing 60mg Ti 3 C 2 Stirring for 30min, transferring to vacuum freeze dryer, and drying at-45deg.C under 1Pa to obtain Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 。
Step three, ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Preparing an electrode;
the preparation method of the electrode slice made of the powdery material comprises the following steps:
firstly, ultrasonically cleaning foam nickel with the thickness of 2cm multiplied by 1cm by absolute ethyl alcohol for 2 hours, removing impurities on the surface, drying in a constant-temperature drying oven at the temperature of 40 ℃, and weighing for later use;
then Ti is added 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Mixing the composite material, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, grinding for 30min in an agate mortar, then dropwise adding 200 mu L N-methyl-2-pyrrolidone (NMP) liquid, and grinding for 20min to prepare an electrode material;
and finally, uniformly coating the obtained black mud-like slurry on foam nickel, wherein the coating amount is 2-3 mg, vacuum drying at 60 ℃ for 12h, and carrying out pressure maintaining on the dried electrode slice on a hydraulic press for 30s by using the atmospheric pressure of 5Pa, and weighing the actual mass of the small electrode slice for later use. Finally, adopting a three-electrode system to prepare Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 The electrode is used as a working electrode, the platinum sheet is used as a counter electrode, silver/silver chloride is used as a reference electrode, and a Shanghai cinnabar CHI660E electrochemical workstation is used for testing Ti under the condition of 6mol/L KOH electrolyte 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Electrochemical properties of the electrode, such as cyclic voltammogram, constant current charge and discharge, alternating current impedance and cyclic stability are tested.
Example 7
Step one, two-dimensional layered Ti 3 C 2 Preparing nano powder and a colloid suspension thereof;
preparation of two-dimensional layered Ti according to the existing method 3 C 2 Nano powder.
10ml of diluted solution containing 60mg of Ti 3 C 2 The nano powder colloid suspension is used for standby.
Step two, preparation of transition metal oxide TMO@MXene composite material (Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 )；
FirstPreparation of ZIF-67: 2mmol Co (NO) 3 ) 2 ·6H 2 O and 8mmol of 2-methylimidazole were dissolved in 50mL of methanol, respectively. The 2-methylimidazole solution was then poured rapidly into Co (NO) with stirring 3 ) 2 ·6H 2 In the O solution, stirring for 3min, and standing the mixed solution at room temperature for 24h; collecting purple precipitate by centrifugation, washing with methanol for three times, and oven drying at 60deg.C for 12 hr;
secondly, niCo is synthesized 2 O 4 @Co 3 O 4 Double shell nano hollow polyhedron: first, 40mg of ZIF-67 was dispersed in 25L of absolute ethanol, and 80mg of Ni (NO) 3 ) 2 ·6H 2 O, stirring for 30min, and forming a ZIF-67/Ni-Co precursor; centrifugally collecting, washing with ethanol for several times, and finally drying at 60 ℃ for 12 hours; then the precursor is put into a muffle furnace for 2 ℃ min -1 Heating to 450 ℃ at a speed of 3h to obtain NiCo 2 O 4 @Co 3 O 4 Double-shell nano hollow polyhedron;
finally, ti is synthesized 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Nano hollow polyhedron: firstly, 100mg of NiCo is taken 2 O 4 @Co 3 O 4 Dispersing in 30mL deionized water, slowly adding dropwise 10mL of a solution containing 60mg Ti 3 C 2 Stirring for 30min, transferring to vacuum freeze dryer, and drying at-45deg.C under 1Pa to obtain Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 。
Step three, ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Preparing an electrode;
the preparation method of the electrode slice made of the powdery material comprises the following steps:
firstly, ultrasonically cleaning foam nickel with the thickness of 2cm multiplied by 1cm by absolute ethyl alcohol for 2 hours, removing impurities on the surface, drying in a constant-temperature drying oven at the temperature of 40 ℃, and weighing for later use;
then Ti is added 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Composite material, acetylene black, polyvinylidene fluoride (PVDF) according to 8:1:1Grinding for 30min in an agate mortar, then dropwise adding 200 mu L N-methyl-2-pyrrolidone (NMP) liquid, and grinding for 20min to prepare an electrode material;
and finally, uniformly coating the obtained black mud-like slurry on foam nickel, wherein the coating amount is 2-3 mg, vacuum drying at 60 ℃ for 12h, and carrying out pressure maintaining on the dried electrode slice on a hydraulic press for 30s by using the atmospheric pressure of 5Pa, and weighing the actual mass of the small electrode slice for later use. Finally, adopting a three-electrode system to prepare Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 The electrode is used as a working electrode, the platinum sheet is used as a counter electrode, silver/silver chloride is used as a reference electrode, and a Shanghai cinnabar CHI660E electrochemical workstation is used for testing Ti under the condition of 6mol/L KOH electrolyte 3 C 2 @NiCo 2 O 4 @Co 3 O 4 Electrochemical properties of the electrode, such as cyclic voltammogram, constant current charge and discharge, alternating current impedance and cyclic stability are tested.
Claims (10)
1. A method for preparing a yolk-shell dodecahedron transition metal oxide tmo@mxene composite material, which is characterized by comprising the following steps:
s1, dispersing ZIF-67 in absolute ethyl alcohol, and adding Ni (NO) 3 ) 2 ·6H 2 O, stirring to form ZIF-67/Ni-Co precursor, collecting ZIF-67/Ni-Co precursor, washing, drying, calcining in air atmosphere to obtain NiCo 2 O 4 @Co 3 O 4 Double-shell nano hollow polyhedron;
s2, taking NiCo 2 O 4 @Co 3 O 4 Double-shell nano hollow polyhedron dispersed in water and Ti is added dropwise 3 C 2 Stirring the colloid solution, and then drying to obtain Ti 3 C 2 @NiCo 2 O 4 @Co 3 O 4 。
2. The method for preparing a yolk-shell dodecahedron transition metal oxide TMO@MXene composite material according to claim 1, wherein in S1, ZIF-67 and Ni (NO 3 ) 2 ·6H 2 The mass ratio of O is 1:2.
3. the method for preparing a yolk-shell dodecahedron transition metal oxide TMO@MXene composite material according to claim 1, wherein in S1, the calcination temperature is 350-450 ℃ and the time is 2-3 h.
4. The method for producing a yolk-shell dodecahedron transition metal oxide TMO@MXene composite material according to claim 1, wherein in S1, the temperature is 1-2 ℃ for min during calcination -1 Is heated to a rate of 350 to 450 ℃.
5. The method for preparing the yolk-shell dodecahedron transition metal oxide TMO@MXene composite material according to claim 1, wherein in S1, the preparation method of ZIF-67 is as follows: co (NO) 3 ) 2 ·6H 2 O and 2-methylimidazole are dissolved in methanol, respectively, and then the resulting 2-methylimidazole solution is added to the resulting Co (NO) with stirring 3 ) 2 ·6H 2 And in the O solution, standing the obtained mixed solution at room temperature after stirring, collecting precipitate, washing and drying to obtain ZIF-67.
6. The method for preparing a yolk-shell dodecahedron transition metal oxide TMO@MXene composite material according to claim 1, wherein in S2, niCo 2 O 4 @Co 3 O 4 And Ti is 3 C 2 The mass ratio of (C) is 100mg (40-100 mg).
7. The method for preparing a yolk-shell dodecahedron transition metal oxide TMO@MXene composite material according to claim 1, wherein in S2, ti 3 C 2 The preparation method of the colloid solution comprises the following steps: ti is mixed with 3 C 2 Adding the nano powder into deionized water, and continuously diluting with deionized water to obtain Ti 3 C 2 Colloidal solution.
8. The method for producing a yolk-shell dodecahedron transition metal oxide tmo@mxene composite material according to claim 1, wherein in S2, the drying is vacuum freeze drying.
9. Yolk-shell dodecahedron transition metal oxide TMO@MXene composite material obtained by adopting the preparation method as claimed in any one of claims 1-8.
10. Use of the yolk-shell dodecahedron transition metal oxide tmo@mxene composite material according to claim 9 as electrode material in a supercapacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311765473.6A CN117727568A (en) | 2023-12-20 | 2023-12-20 | Yolk-shell dodecahedron transition metal oxide TMO@MXene composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311765473.6A CN117727568A (en) | 2023-12-20 | 2023-12-20 | Yolk-shell dodecahedron transition metal oxide TMO@MXene composite material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117727568A true CN117727568A (en) | 2024-03-19 |
Family
ID=90204990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311765473.6A Pending CN117727568A (en) | 2023-12-20 | 2023-12-20 | Yolk-shell dodecahedron transition metal oxide TMO@MXene composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117727568A (en) |
-
2023
- 2023-12-20 CN CN202311765473.6A patent/CN117727568A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Rational construction of bowl-like MnO2 nanosheets with excellent electrochemical performance for supercapacitor electrodes | |
| Hong et al. | Hierarchical SnO2 nanoclusters wrapped functionalized carbonized cotton cloth for symmetrical supercapacitor | |
| Qu et al. | Graphene oxides-guided growth of ultrafine Co3O4 nanocrystallites from MOFs as high-performance anode of Li-ion batteries | |
| US11634332B2 (en) | Selenium-doped MXene composite nano-material, and preparation method and use thereof | |
| CN112233912B (en) | Foam nickel-loaded MnCo2O4.5Preparation method and application of/MXene composite nano material | |
| Yao et al. | Nanostructured transition metal vanadates as electrodes for pseudo-supercapacitors: a review | |
| CN107934965B (en) | Ti3C2-Co(OH)(CO3)0.5Process for preparing nano composite material | |
| Ren et al. | In-situ transformation of Ni foam into sandwich nanostructured Co1. 29Ni1. 71O4 nanoparticle@ CoNi2S4 nanosheet networks for high-performance asymmetric supercapacitors | |
| CN109941997B (en) | Hemoglobin-like Co3O4/Ti3C2Preparation method and application of nano composite material | |
| CN106783230A (en) | A kind of titanium carbide growth in situ CNTs three-dimensional composite materials and preparation method thereof | |
| Du et al. | Boosting the capacitance of NiCo2O4 hierarchical structures on nickel foam in supercapacitors | |
| CN108807008A (en) | A kind of lithium-ion capacitor nano whiskers flexibility lithium titanate/carbon nano tube/graphene composite material and preparation method | |
| CN114604945A (en) | Tungsten oxide/titanium carbide composite electrode material and preparation method and application thereof | |
| Chen et al. | High-performanced flexible solid supercapacitor based on the hierarchical MnCo2O4 micro-flower | |
| CN109786130B (en) | MnFe for super capacitor2O4Nanosheet array and preparation method thereof | |
| Ren et al. | Bimetal-organic framework-derived porous CoFe2O4 nanoparticles as biocompatible anode electrocatalysts for improving the power generation of microbial fuel cells | |
| Zhang et al. | Sol-gel method preparation and high-rate energy storage of high-entropy ceramic (FeCoCrMnNi) C porous powder | |
| CN111063549B (en) | Two-dimensional MOFs nanosheet-derived full-electrode material for hybrid capacitor | |
| KR20130047885A (en) | Method for fabrication of charge storage in multi-walled carbon nanotube-niooh nano composites | |
| Zhou et al. | Cu (OH) 2@ NiC2O4 core-shell structure: A novel class nanoarrays electrode materials for high-performance supercapacitor | |
| Zhou et al. | Evaporation induced uniform polypyrrole coating on CuO arrays for free-standing high lithium storage anode | |
| CN114784227B (en) | Graphene/metal oxide composite nano material, preparation method and application thereof, electrode plate and application thereof | |
| CN114446673B (en) | Three-dimensional net-shaped flake CoFe 2 O 4 @NiO composite material, preparation method and application | |
| CN111564317B (en) | Composite electrode material and preparation method thereof, and electrode of supercapacitor and preparation method thereof | |
| CN116130256A (en) | Preparation method and application of tungsten oxide nanowire/titanium carbide nanosheet composite material |
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 |