CN114974916A - Fibrous MXene loaded NiCoS composite material and preparation method and application thereof - Google Patents
Fibrous MXene loaded NiCoS composite material and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000005530 etching Methods 0.000 claims abstract description 36
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- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 20
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 20
- 239000003990 capacitor Substances 0.000 claims abstract description 18
- 239000007772 electrode material Substances 0.000 claims abstract description 17
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 10
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- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims abstract description 8
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 5
- FTTATHOUSOIFOQ-UHFFFAOYSA-N 1,2,3,4,6,7,8,8a-octahydropyrrolo[1,2-a]pyrazine Chemical compound C1NCCN2CCCC21 FTTATHOUSOIFOQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 3
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- 238000006243 chemical reaction Methods 0.000 claims description 8
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 7
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- 229910000474 mercury oxide Inorganic materials 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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 discloses a fibrous MXene loaded NiCoS composite material which is prepared from nickel acetate tetrahydrate, cobalt acetate, trimesic acid and 1, 4-diazabicyclo [2,2]Octane and sodium dodecyl sulfate are used as raw materials, and NiCo-MOFs is prepared through hydrothermal reaction; with Ti 3 AlC 2 The preparation method comprises the following steps of (1) taking lithium fluoride and concentrated hydrochloric acid as raw materials, and carrying out etching treatment and oscillation treatment to obtain fibrous MXene; finally, taking NiCo-MOFs as a precursor and fibrous MXene as a matrix, adding thioacetamide, and carrying out a second hydrothermal reaction to uniformly load a granular NiCoS composite material on the surface of the fibrous MXene; lamellar MXene has a lamellar structure of microns; the fibrous MXene is fibrous knot with diameter of 10-40nmStructuring; the diameter of the granular NiCoS is 5-30 nm. The preparation method comprises the following steps: 1, preparing NiCo-MOFs; 2, preparing fibrous MXene; 3, preparation of NiCoS @ MXene. Application of the material as an electrode material of a super capacitor, the specific capacitance is 1300-1500F g ‑1 (ii) a The energy density is as high as 63.3W h kg ‑1 (ii) a The cycling stability after 10000 cycles of cycling remained 73% of the original.
Description
Technical Field
The invention relates to the technical field of super capacitor electrode materials in new energy materials, and particularly relates to a fibrous MXene loaded metal sulfide composite material and a preparation method and application thereof.
Background
In recent years, the rapid growth of the population and the development of technology have increased global energy demand. However, the battery electrode material has various reactions inside, which causes the defects of short service life, long charging and discharging time, low power density and the like, and even has potential safety hazards of spontaneous combustion and explosion. Super Capacitors (SCs) as a new energy storage device attract a lot of attention due to their advantages of high power density, fast charge and discharge speed, wide working temperature range, long cycle life, etc., and become one of the most suitable energy storage and conversion devices. The electrochemical performance of the supercapacitor is mainly determined by electrode materials, and becomes a focus of research.
The MOFs have the advantages of flexible tailorability, excellent designability, unique pore channel structure and the like. Its large specific surface area, high porosity and structural adjustability, however, MOF S Has poor conductivity and cannot be directly used asElectrode materials, hence, MOFs S Are often used as templates or precursors to build derivatives or composites thereof. MOF S One such metal sulfide derivative is.
The transition metal sulfide has lower electronegativity, so that the sulfide combined with metal ions can have more electrochemical activity and stability, and can also generate multiple redox reactions, so that the sulfide has excellent electrochemical performance. However, there is still a need for improvement in that the electrochemical performance of these electrode materials is reduced due to structural destruction caused by volume expansion and contraction of the metal sulfide materials due to faradaic redox reaction during long-term charge and discharge.
To overcome these technical problems, one of the strategies that can be implemented is to combine MOFs and their derived sulfides with conductive materials, such as carbon, graphene, MXene, polyaniline, etc.
Among them, MXene having a typical two-dimensional structure is widely attracting attention. By treatment with hydrofluoric acid (HF) solution, a large number of surface functional groups (e.g., F) - 、O 2- 、OH - ) Is incorporated into the MXene material to render it hydrophilic. In addition, MXene of the laminated structure shows large surface area and good conductivity after etching treatment. MXene can be used not only as an electrode material directly but also combined with various materials by electrostatic assembly. The combination of MXene and other functional nanoparticles can realize synergistic effect, thereby improving electrochemical performance. Therefore, the metal sulfide/MXene composite material is beneficial to being used as an electrode material of a super capacitor.
Prior art 1[ Luo, L., Zhou, Y., Yan, W., et al. Construction of advanced charged animal bed frame derived cobalt catalysts/MXene compositions as high-performance electronics for supercapacitors.J. Colloid Interf Sci. 2022, 615, 282-292.]Luo et al hydrothermally grown ZIF-67-derived sulfide on flake MXene as an electrode material for a supercapacitor, 1A g -1 Has a specific capacitance of 602F g at a current density of -1 (ii) a Form asymmetric ultracapacitor system with active carbonCo 3 S 4 /Ti 3 C 2 T x // AC, at a power density of 800.3W/kg, showed a high energy density of 44.9 Wh/kg. The literature indicates that the excellent conductivity of MOFs-derived sulfides and MXene facilitates the charge transfer of electrons, and shows high capacity and energy density.
Prior art 2[ Li, H., Chen, X., Zalnezhad, E., et al., 3D thermal transition-metal resins disposed on MXene as binder-free electrode for high-performance supercapacitors.J Ind Eng Chem. 2022, 82, 309-316.]Li et al transition metal sulfide NiCo 2 S 4 Uniformly deposited on sheet MXene as an adhesive-free composite electrode material for supercapacitors at 1A g -1 Has a specific capacitance of 596.7C g at a current density of -1 ，MXene-NiCo 2 S 4 The super capacitor formed by the super capacitor and the activated carbon shows 27.24 Wh/kg at the power density of 0.48 kW/kg, and MXene and NiCo are shown in the literature 2 S 4 The junctions of (a) provide unique nanostructures, thereby providing greater surface area and exposing more redox sites in the electrolyte.
The prior art shows that the metal organic framework material has the advantages of rich pore structure, adjustable elements, controllable structure and the like, and is an ideal precursor for preparing transition metal sulfides. Although the metal sulfide shows high capacity and high conductivity, the further application of the metal sulfide in the electrode material of the super capacitor is limited by the defects of small surface area, easy accumulation, chemical instability and weak mechanical property, and is easily damaged by oxidation-reduction reaction in the long-term charge-discharge process, so that the rate performance and the cycle stability are poor, and therefore, the metal sulfide can be combined with MXene to realize a synergistic effect, the problems of accumulation of the metal sulfide, damage to the structure and the like are avoided, and the electrochemical performance is improved.
Therefore, the fibrous MXene is introduced as the matrix, so that the conductivity of the lamellar MXene is kept, the specific surface area of the lamellar MXene is improved, the appearance of the overall material is controlled, and the combination of the fibrous MXene and other functional nanoparticles can realize a synergistic effect, so that the electrochemical performance is improved; the shape of the material is controlled by a reasonable preparation method, and the NiCoS composite electrode material taking fibrous MXene as a matrix is obtained, so that NiCoS nano particles can be dispersed and prevented from being accumulated, the integral conductivity is provided, and the method is also an effective way for improving the material performance.
Disclosure of Invention
The invention aims to provide a fibrous MXene loaded NiCoS composite material as well as a preparation method and application thereof.
In order to solve the problems of improving the electrochemical performance and the electrochemical cycling stability of MOFs derived metal sulfide materials, the method adopted by the invention comprises the following steps: the fibrous MXene is obtained by etching a few-layer sheet-shaped MXene and further vibrating, and NiCoS nano particles are uniformly loaded on a fibrous MXene substrate material to prepare the NiCoS @ MXene composite material with a stable structure.
Wherein, the effect of loading NiCoS includes:
1. NiCoS belongs to a pseudo-capacitor electrode material;
2. the transition metal sulfide has excellent capacitance and conductivity relatively higher than MOFs, and has higher electrochemical activity and higher capacity;
3. NiCoS materials can undergo more redox reactions.
In addition, the effect of incorporating fibrous MXene as a base material has 3 aspects:
1. the overall conductivity of the material can be effectively improved;
2. the specific surface area of the composite material is increased, and the effect of controlling the overall appearance can be achieved;
3. the contact area of the composite material and the electrolyte is enlarged, and the diffusion of ions can be accelerated, so that the aim of improving the whole super-capacitive performance of the composite material is fulfilled.
In order to achieve the purpose of the invention, the invention adopts the technical scheme that:
a fibrous MXene loaded NiCoS composite material is prepared from nickel acetate tetrahydrate, cobalt acetate, trimesic acid, 1, 4-diazabicyclo [2,2]Octane and sodium dodecyl sulfate as originalCarrying out hydrothermal reaction on the materials to obtain NiCo-MOFs; simultaneously, with Ti 3 AlC 2 Etching to obtain lamellar MXene, and further vibrating to obtain fibrous MXene; and finally, taking NiCo-MOFs as a precursor, taking fibrous MXene as a matrix, adding thioacetamide, carrying out a second hydrothermal reaction, and uniformly loading a granular NiCoS composite material on the surface of the fibrous MXene to obtain the fibrous MXene loaded NiCoS composite material.
The lamellar MXene has a lamellar structure of micrometers; the fibrous MXene has a fibrous structure with a diameter of 10-40 nm; the diameter of the granular NiCoS is 5-30 nm.
A preparation method of a fibrous MXene loaded NiCoS composite material comprises the following steps:
in the step 1, the ratio of the amounts of nickel acetate tetrahydrate, cobalt acetate tetrahydrate, trimesic acid, 1, 4-diazabicyclo [2,2,2] octane and sodium dodecyl sulfate is 4: 2: 3: 6: 6;
the total concentration of the metal ions in the solution A is 0.0088 g/mL, and the total concentration of the metal ions in the solution B is 0.0036 g/mL;
the conditions of the first hydrothermal reaction are that the reaction temperature is 140-200 ℃, and the reaction time is 18-24 h;
step 2, preparing the fibrous MXene, namely preparing MAX into the lamellar MXene by etching treatment, and then preparing the lamellar MXene into the fibrous MXene by oscillating treatment;
etching treatment in the step 2, dissolving lithium fluoride in concentrated hydrochloric acid by using the lithium fluoride and the concentrated hydrochloric acid to meet a certain mass ratio, stirring under a certain condition to obtain etching solution, and then, adding Ti 3 AlC 2 Placing the obtained product in an etching solution, carrying out etching treatment under certain conditions, after the etching treatment is finished, carrying out centrifugal washing on the etching product under certain conditions, carrying out ultrasonic dispersion until the pH value of a supernatant is close to neutrality to obtain a dispersion solution, and carrying out freeze drying treatment on the dispersion solution to obtain the lamellar MXene;
the mass ratio of the lithium fluoride to the concentrated hydrochloric acid in the step 2 is 1 (5-10), the stirring conditions of the etching solution are that the stirring speed is 400-600 rpm, and the stirring time is 3-10 min;
the etching treatment conditions in the step 2 are that the etching temperature is 30-40 ℃, and the etching time is 20-36 h;
the centrifugation conditions of the step 2 are that the centrifugation rotating speed is 4000-6000rpm, and the centrifugation times are 10-20 times;
6. the production method according to claim 3, characterized in that: the step 2 of oscillating treatment, namely the preparation method of preparing the fibrous MXene from the lamellar MXene, comprises the following steps of carrying out ultrasonic dispersion on the lamellar MXene, carrying out oscillating treatment under certain conditions, washing an oscillating product by deionized water, and carrying out vacuum drying to obtain the fibrous MXene;
the ultrasonic dispersion condition in the step 2 is that ultrasonic dispersion is carried out for 20-40min in 6mol/L potassium hydroxide solution;
the oscillation treatment conditions in the step 2 are that the oscillation temperature is 20-30 ℃, the oscillation rotating speed is 120-180 rpm, and the oscillation time is 3-6 days;
step 3, preparing NiCoS @ MXene, namely mixing NiCo-MOFs obtained in the step 1 and fibrous MXene and thioacetamide obtained in the step 2 in an absolute ethyl alcohol solution, carrying out ultrasonic treatment on the NiCo-MOFs, the fibrous MXene and the thioacetamide to obtain a second hydrothermal reaction liquid, carrying out a second hydrothermal reaction on the second hydrothermal reaction liquid under a certain condition, washing a second hydrothermal product by distilled water and absolute ethyl alcohol, and drying to obtain a fibrous MXene loaded NiCoS composite material, namely NiCoS @ MXene for short;
in the step 3, the mass ratio of fibrous MXene, NiCo-MOFs and thioacetamide is 1: (3-5): (30-50);
the conditions of the second hydrothermal reaction in the step 3 are that the reaction temperature is 100-;
the drying condition of the step 3 is that the drying temperature is 60-80 ℃ and the drying time is 20-24 h.
The application of the fibrous MXene loaded NiCoS composite material as the electrode material of the super capacitor discharges in the range of 0-0.55V and the discharge current density is 1A g -1 The specific capacitance is 1300-1500F g -1 ；
The active carbon and the active carbon form an asymmetric super capacitor which can be charged and discharged in the range of 0-1.7V and the power density of which is 850W kg -1 When the energy density is as high as 63.3W h kg -1 ；
The application of the fibrous MXene loaded NiCoS composite material as the electrode material of the supercapacitor is characterized in that: the active carbon and the super capacitor form an asymmetric super capacitor, and the discharge current density is 5A g -1 In this case, the cycle stability after 10000 cycles was maintained at 73% or more of the original cycle stability.
The obtained NiCoS @ MXene composite material with a stable structure is subjected to experimental detection, and the result is as follows:
the NiCoS @ MXene composite material is tested by X-ray diffraction (XRD), and diffraction crystal faces corresponding to different diffraction peaks meet a standard card, so that NiCoS can be successfully loaded on fibrous MXene;
the NiCoS @ MXene composite material is tested by a scanning electron microscope, and granular NiCoS can be seen to be uniformly distributed on a unique fibrous structure of MXene, so that the NiCoS @ MXene composite material with a stable structure is successfully prepared;
electrochemical test and electrochemical cycle stability test of NiCoS @ MXene composite:
discharging in the range of 0-0.55V and at a discharge current density of 1A g -1 Ratio of NiCoS @ MXene composite MaterialCapacitance of 1505F g -1 (ii) a The active carbon and the asymmetric super capacitor are charged and discharged in the range of 0-1.7V, and the power density is 850W kg -1 When the energy density is as high as 63.3W h kg -1 (ii) a Discharge current density of 5A g -1 The cycling stability after 10000 cycles of cycling was maintained at 73% or more of the original value.
Therefore, compared with the prior art, the NiCoS @ MXene composite material has the following advantages:
1. the invention adopts two-step hydrothermal method to successfully and uniformly load NiCoS nano particles derived from MOFs on a fibrous MXene carrier to prepare the NiCoS @ MXene composite material, realizes the effect of improving the stability of the supercapacitor, and has the specific capacitance of 1505F g -1 (ii) a The electrode material has low cost, simple synthesis method and process and easy large-scale production;
2, the MOFs derived NiCoS nano particles not only improve the problem of poor conductivity of the MOFs, but also provide additional pseudo capacitance for the matrix material, thereby improving the integral specific capacitance of the composite material;
3. the fibrous MXene prepared by modification can improve the conductivity of the composite material, increase the specific surface area of the composite material after the fibrous MXene is fibrous, play a role in controlling the overall morphology and avoid the aggregation of NiCoS nanoparticles, thereby improving the electrochemical activity of the material;
4. MXene with a fibrous structure is introduced as a substrate material, so that on one hand, the overall appearance of the material is effectively controlled, on the other hand, the contact area of the NiCoS @ MXene composite material and an electrolyte is increased, the diffusion of ions is accelerated, and the overall super-capacitor performance of the composite material is improved.
Therefore, the invention has wide application prospect in the field of super capacitor materials.
Drawings
FIG. 1 is an XRD of NiCoS @ MXene composite prepared in step 3 of example 1;
FIG. 2 is a TEM image of an microlayer lamellar MXene material prepared in step 2.1 of example 1;
FIG. 3 is a SEM (scanning Electron microscope) image of a fibrous MXene material prepared in step 2.2 of example 1;
FIG. 4 is a SEM (scanning Electron microscope) image of NiCoS @ MXene composite prepared in step 3 of example 1;
FIG. 5 is a graph of the NiCoS @ MXene composite prepared in example 1 at a current density of 1A g -1 The following charge-discharge curve chart;
FIG. 6 shows that the current density of an asymmetric supercapacitor made of the NiCoS @ MXene composite material and activated carbon prepared in example 1 is 1A g -1 The following charge-discharge curve chart;
FIG. 7 is a graph of the cycle performance of the NiCoS @ MXene composite prepared in example 1;
FIG. 8 shows the NiCoS material prepared in comparative example 1 at a current density of 1A g -1 The following charge-discharge curve chart;
FIG. 9 is a graph of cycle performance of a NiCoS material prepared by practicing comparative example 1.
FIG. 10 is a graph of the NiCoS @ MXene-1 material prepared based on lamellar flake MXene of comparative example 2 at a current density of 1A g -1 The following charge-discharge curves.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, which are given by way of examples, but are not intended to limit the present invention.
Example 1
A preparation method of a fibrous MXene loaded NiCoS composite material comprises the following steps:
step 2, preparing the fibrous MXene, namely preparing MAX into the lamellar MXene through etching treatment, and then preparing the lamellar MXene into the fibrous MXene through oscillation treatment,
step 2.1, preparing lamellar MXene, firstly, precisely weighing 0.5 g of lithium fluoride powder and 10 mL of 9mol/L concentrated hydrochloric acid according to the mass ratio of 1:6.57, dissolving the lithium fluoride powder in 10 mL of 9mol/L concentrated hydrochloric acid, stirring the solution under the conditions of a stirring speed of 500 rpm and a stirring time of 5 min to obtain etching solution, and then weighing 0.5 g of Ti 3 AlC 2 The MAX is placed in an etching solution, etching treatment is carried out under the conditions that the etching temperature is 35 ℃, the etching time is 24 hours and stirring is carried out, the etching treatment effect is that an Al layer in the MAX phase is etched away, after the etching treatment is finished, an etching product is centrifugally washed for 15 times by deionized water until the pH value of a supernatant is close to neutrality, ultrasonic dispersion is carried out to obtain a dispersion liquid, and freeze drying treatment is carried out on the dispersion liquid to obtain the lamellar MXene;
step 2.2, fiberizing the flake MXene, namely placing 60mg of flake MXene in 60mL of 6mol/L potassium hydroxide solution for ultrasonic dispersion for 30min, then performing oscillation treatment in a constant-temperature oscillator under the conditions that the oscillation temperature is 25 ℃, the oscillation rotating speed is 150 rpm and the oscillation time is 5 days, washing the oscillation product for 3 times by deionized water and performing vacuum drying for 6h to obtain the flake MXene;
and 3, preparing NiCoS @ MXene, namely mixing 0.032g of NiCo-MOFs obtained in the step 1 and 0.008g of fibrous MXene and 0.32g of thioacetamide in an absolute ethyl alcohol solution according to the mass ratio of 4:1:40 to obtain a second hydrothermal reaction solution, carrying out a second hydrothermal reaction on the second hydrothermal reaction solution at the reaction temperature of 140 ℃ for 6 hours, washing the second hydrothermal product with distilled water and absolute ethyl alcohol, and drying at the drying temperature of 60 ℃ for 20 hours to obtain the fibrous MXene loaded NiCoS @ MXene composite material, namely NiCoS @ MXene for short.
In order to demonstrate the composition of the resulting NiCoS @ MXene, XRD testing was performed on NiCoS @ MXene. The test results are shown in FIG. 1, and the characteristic peaks at 16.2 °, 26.6 °, 31.3 °, 37.9 °, 50.1 ° and 54.8 ° correspond to Ni 3 S 4 And Co 3 S 4 The (111), (220), (311), (400), (511) and (440) diffraction crystal planes of (b). Wherein, NiCoS load is coated on the fibrous MXene, so that the fibrous MXene diffraction peak is not obviously shown. Test results show that the NiCoS @ MXene is successfully prepared by the method.
In order to prove the influence of the micro-morphology of the NiCoS @ MXene of the present invention, that is, the oscillation treatment on the micro-morphology of the material, the TEM and SEM tests were performed on the lamellar MXene obtained in step 2.1, the fibrous MXene obtained in step 2.2, and the NiCoS @ MXene obtained in step 3, respectively, and the test results are shown in fig. 2, fig. 3, and fig. 4, respectively.
The TEM test result of the flaky MXene is shown in FIG. 2, and the morphology of the MXene without oscillation treatment is micron-scale flaky;
the SEM test result of the fibrous MXene is shown in FIG. 3, and the morphology of the fibrous MXene after oscillation treatment is about 20nm fibrous;
the results of SEM testing of NiCoS @ MXene are shown in FIG. 4, where fibrous MXene was uniformly loaded with granular NiCoS.
As can be seen by comparing fig. 2 and fig. 3, the micron-sized sheet MXene is converted from a sheet structure into a fibrous structure by the oscillation treatment;
as can be seen from a comparison between fig. 3 and fig. 4, granular NiCoS is uniformly loaded on the surface of the fibrous MXene, and the fiber structure of the loaded NiCoS @ MXene is changed from 20nm before loading to about 50 nm.
The electrochemical test method adopted by the invention comprises the following specific steps: the material to be tested is taken as a working electrode, a mercury oxide electrode and a platinum electrode are respectively taken as a reference electrode and an auxiliary electrode, the material is immersed in 6M KOH solution to be tested in a three-electrode system, NiCoS @ MXene is taken as a positive electrode, activated carbon is taken as a negative electrode, and electrolyte is taken as 6M KOH, and the asymmetric supercapacitor is assembled to be tested.
The results of the electrochemical performance test of NiCoS @ MXene are as follows:
the results of the NiCoS @ MXene electrochemical performance test are shown in FIG. 5, and the NiCoS @ MXene electrochemical performance test is performed in a three-electrode system under the conditions that the discharge current density is 1A g and the discharge is in a range of 0-0.55V -1 When the specific capacitance of NiCoS @ MXene is 1505F g -1 ；
The results of the electrochemical performance test of the asymmetric device composed of NiCoS @ MXene and activated carbon are shown in FIG. 6, and the device is discharged in the range of 0-1.7V and is discharged in the range of 1A g -1 When the specific capacitance is 157.8F g -1 Calculated at a power density of 850W kg -1 The energy density is as high as 63.3W h kg -1 ；
The result of the cycle stability test of the asymmetric device composed of NiCoS @ MXene and activated carbon is shown in FIG. 7, and the discharge current density is 5A g -1 Then, the cycle stability after 10000 cycles of charge and discharge was maintained to 73% or more of the original cycle stability.
To demonstrate the effect of fiberization on material properties, comparative examples 1 and 2 are provided. Wherein, the comparative example 1 is NiCoS material, namely NiCoS material prepared without adding fibrous MXene, as the basic reference; comparative example 2 is NiCoS @ MXene based on lamellar-less MXene, for the purpose of comparing fibrous MXene with lamellar-less MXene.
Comparative example 1
A method for preparing a NiCoS material, the steps not specifically described being the same as those of example 1, except that: and (3) not performing the step 2, and not adding the fibrous MXene in the step 3 to obtain the NiCoS material, namely NiCoS for short.
The results of the NiCoS electrochemical performance test are shown in FIG. 8, and the NiCoS electrochemical performance test is performed under a three-electrode system, wherein the NiCoS electrochemical performance test is performed under the conditions that the discharge current density is 1A g and the discharge is within the range of 0-0.5V -1 Specific capacitance of 1174F g -1 ；
The cycling stability of the asymmetric NiCoS and activated carbon devices is shown in FIG. 9, at a discharge current density of 5A g -1 In the process, the circulation stability after 3000 cycles is only kept as the original 60%;
compared with the example 1, the specific capacitance is improved by 28.2% and the cycle stability is greatly improved by introducing the fibrous MXene matrix. Experimental results show that the fibrous MXene conductive substrate is beneficial to ultrahigh-speed transportation of electrons, and meanwhile, the specific surface area of the fibrillated MXene is increased, NiCoS nano particles are prevented from being aggregated, and oxidation-reduction reaction of sulfide on the surface is facilitated.
Comparative example 2
A method of making a NiCoS @ MXene material based on lamellar flake MXene, the steps not specifically described being the same as in example 1, except that: in the step 2, only the step 2.1 is performed, the step 2.2 is not performed, and the small-layer lamellar MXene is added in the step 3 to replace the fiberized MXene, so that the NiCoS @ MXene material, which is referred to as NiCoS @ MXene-1 for short, can be obtained.
The results of the electrochemical performance test of NiCoS @ MXene-1 are shown in FIG. 10, and the three-electrode system can realize charge discharge within the range of 0-0.53V and discharge current density of 1A g -1 When the specific capacitance of NiCoS @ MXene-1 loaded on flaky MXene is 1255F g -1 ；
Compared with the example 1, the MXene is introduced as the matrix, and the specific capacitance of the fiber MXene subjected to oscillation treatment is improved by 19.9% compared with that of the fiber MXene with few layers. Experimental results show that the fibrous MXene not only can retain the conductivity of the flaky MXene, but also can increase the specific surface area of the flaky MXene, and plays a role in controlling the overall morphology of the composite material, so that the NiCoS nano-particles are prevented from being accumulated, and the oxidation-reduction reaction of sulfide on the surface is facilitated.
The following conclusions can be drawn from the above comparative examples 1, 2 and examples:
1. when the fibrous MXene is used as a carrier to load NiCoS, the electrochemical performance of the composite material is improved to a certain extent compared with that of single NiCoS, the reason is that the fibrous MXene is used as a substrate material to have a decisive influence on the overall appearance of the NiCoS @ MXene material, the fibrous MXene is used as a conductive substrate, the aggregation of NiCoS nano particles can be avoided, the ultra-high speed transport of electrons is facilitated, the contact area of the NiCoS @ MXene material and an electrolyte is enlarged, and the diffusion of ions is accelerated;
2. the fibrous MXene can not only keep the conductivity of the lamellar MXene, but also increase the specific surface area of the lamellar MXene, and play a role in controlling the overall morphology of the material, and compared with the lamellar MXene, the fibrous MXene can better avoid the accumulation of NiCoS nanoparticles and is beneficial to the oxidation-reduction reaction of sulfides on the surface.
Claims (10)
1. A fibrous MXene loaded NiCoS composite material is characterized in that: nickel acetate tetrahydrate, cobalt acetate, trimesic acid and 1, 4-diazabicyclo [2,2]Octane and sodium dodecyl sulfate are used as raw materials, and NiCo-MOFs is prepared through hydrothermal reaction; simultaneously, with Ti 3 AlC 2 The lithium fluoride and the concentrated hydrochloric acid are used as raw materials, the flaky MXene is obtained through etching treatment, and the fibrous MXene is obtained through further oscillation treatment; and finally, taking NiCo-MOFs as a precursor, taking fibrous MXene as a matrix, adding thioacetamide, carrying out a second hydrothermal reaction, and uniformly loading a granular NiCoS composite material on the surface of the fibrous MXene to obtain the fibrous MXene loaded NiCoS composite material.
2. The fibrous MXene-loaded NiCoS composite material of claim 1, wherein: the lamellar MXene has a lamellar structure of micrometers; the fibrous MXene has a fibrous structure with a diameter of 10-40 nm; the diameter of the granular NiCoS is 5-30 nm.
3. A preparation method of a fibrous MXene loaded NiCoS composite material is characterized by comprising the following steps:
step 1, preparing NiCo-MOFs, namely dissolving nickel acetate tetrahydrate, cobalt acetate tetrahydrate, trimesic acid, 1, 4-diazabicyclo [2,2,2] octane and sodium dodecyl sulfate in water to prepare a solution A, simultaneously dissolving trimesic acid and 1, 4-diazabicyclo [2,2,2] octane in a mixed solvent of absolute ethyl alcohol and N, N-dimethylformamide to prepare a solution B, mixing the solution A and the solution B, adding sodium dodecyl sulfate to obtain a first hydrothermal reaction liquid, then carrying out a first hydrothermal reaction on the first hydrothermal reaction liquid under a certain condition, washing and drying a first hydrothermal product by distilled water and absolute ethyl alcohol to obtain the NiCo-MOFs;
step 2, preparing the fibrous MXene, namely preparing MAX into the lamellar MXene by etching treatment, and then preparing the lamellar MXene into the fibrous MXene by oscillating treatment;
and 3, preparing NiCoS @ MXene, namely mixing NiCo-MOFs obtained in the step 1 and fibrous MXene and thioacetamide obtained in the step 2 in an absolute ethyl alcohol solution according to a certain mass ratio, carrying out ultrasonic treatment on the NiCo-MOFs, the fibrous MXene and the thioacetamide to obtain a second hydrothermal reaction liquid, carrying out a second hydrothermal reaction on the second hydrothermal reaction liquid under a certain condition, washing a second hydrothermal product by distilled water and absolute ethyl alcohol, and drying to obtain the fibrous MXene loaded NiCoS composite material, namely NiCoS @ MXene for short.
4. The production method according to claim 3, characterized in that: in the step 1, the mass ratio of nickel acetate tetrahydrate, cobalt acetate tetrahydrate, trimesic acid, 1, 4-diazabicyclo [2,2,2] octane to sodium dodecyl sulfate is 4: 2: 3: 6: 6;
the total concentration of the metal ions in the solution A is 0.0088 g/mL, and the total concentration of the metal ions in the solution B is 0.0036 g/mL;
the conditions of the first hydrothermal reaction are that the reaction temperature is 140-200 ℃ and the reaction time is 18-24 h.
5. The production method according to claim 3, characterized in that: etching treatment in the step 2, dissolving lithium fluoride in concentrated hydrochloric acid by using the lithium fluoride and the concentrated hydrochloric acid to meet a certain mass ratio, stirring under a certain condition to obtain etching solution, and then, adding Ti 3 AlC 2 Placing the obtained product in an etching solution, carrying out etching treatment under certain conditions, carrying out centrifugal washing on the etching product under certain conditions after the etching treatment is finished, carrying out ultrasonic dispersion until the pH value of a supernatant is close to neutral to obtain a dispersion solution, and carrying out freeze drying treatment on the dispersion solution to obtain the lamellar MXene;
the mass ratio of the lithium fluoride to the concentrated hydrochloric acid in the step 2 is 1 (5-10), the stirring conditions of the etching solution are that the stirring speed is 400-600 rpm, and the stirring time is 3-10 min;
the etching treatment conditions in the step 2 are that the etching temperature is 30-40 ℃ and the etching time is 20-36 h;
the centrifugation conditions of the step 2 are that the centrifugation rotating speed is 4000-6000rpm, and the centrifugation times are 10-20 times.
6. The production method according to claim 3, characterized in that: the step 2 of oscillating treatment, namely the preparation method of preparing the fibrous MXene from the lamellar MXene, comprises the following steps of carrying out ultrasonic dispersion on the lamellar MXene, carrying out oscillating treatment under certain conditions, washing an oscillating product by deionized water, and carrying out vacuum drying to obtain the fibrous MXene;
the ultrasonic dispersion condition of the step 2 is that ultrasonic dispersion is carried out for 20-40min in 6mol/L potassium hydroxide solution;
the oscillation treatment conditions in the step 2 are that the oscillation temperature is 20-30 ℃, the oscillation rotation speed is 120-180 rpm, and the oscillation time is 3-6 days.
7. The production method according to claim 3, characterized in that: in the step 3, the mass ratio of fibrous MXene, NiCo-MOFs and thioacetamide is 1: (3-5): (30-50);
the conditions of the second hydrothermal reaction in the step 3 are that the reaction temperature is 100-160 ℃, and the reaction time is 4-8 h;
the drying condition of the step 3 is that the drying temperature is 60-80 ℃ and the drying time is 20-24 h.
8. The application of the fibrous MXene loaded NiCoS composite material as the electrode material of the supercapacitor is characterized in that: discharging in the range of 0-0.55V and at a discharge current density of 1A g -1 The specific capacitance is 1300-1500F g -1 。
9. Fibrous MXene loaded NiCoS composite material as supercapacitor electrode materialThe application is characterized in that: the active carbon and the active carbon form an asymmetric super capacitor which can be charged and discharged in the range of 0-1.7V and the power density of which is 850W kg -1 When the energy density is as high as 63.3W h kg -1 。
10. The application of the fibrous MXene loaded NiCoS composite material as the electrode material of the supercapacitor is characterized in that: the active carbon and the super capacitor form an asymmetric super capacitor, and the discharge current density is 5A g -1 In this case, the cycle stability after 10000 cycles was maintained at 73% or more of the original cycle stability.
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