CN113675408B - MoS for high-performance potassium ion battery 2 /Ti 3 C 2 Preparation method of MXene composite material - Google Patents
MoS for high-performance potassium ion battery 2 /Ti 3 C 2 Preparation method of MXene composite material Download PDFInfo
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Abstract
The invention provides a MoS for a high-performance potassium ion battery 2 /Ti 3 C 2 The preparation method of the MXene composite material comprises the following steps: subjecting a plurality of layers of et-Ti 3 C 2 Dispersing MXene nano-sheet in intercalation agent solution, reacting at room temperature, centrifuging, washing, and drying to obtain in-Ti 3 C 2 MXene nanosheets; adding the mixed solution of a molybdenum precursor and a sulfur precursor into in-Ti under the conditions of ultrasound and stirring 3 C 2 In MXene nanosheet dispersion liquid, carrying out high-temperature reaction on the obtained mixed liquid; after the reaction is finished, centrifuging, washing and drying to obtain the catalyst. The composite material overcomes the defects of a single material and solves the problem that K is caused by + The problems of rapid reversible capacity attenuation and poor cycle stability caused by huge volume expansion and crushing of the electrode in the repeated embedding/separating process are solved, so that the cycle stability and the specific capacity of the potassium ion battery are obviously improved.
Description
Technical Field
The invention relates to a MoS for a high-performance potassium ion battery 2 /Ti 3 C 2 A preparation method of MXene composite material belongs to the technical field of potassium ion batteries.
Background
Currently, despite the successful commercialization of Lithium Ion Batteries (LIBs), future energy demands are still not met due to the high cost and uneven distribution of lithium resources. In recent years, potassium Ion Batteries (PIBs) have been considered as a promising alternative to LIBs due to their abundant potassium reserves, low cost and their electrochemical properties similar to lithium. Furthermore, K/K + Standard redox potential and Na/Na of (-2.93V vs Standard Hydrogen Electrode (SHE)) + (-2.71 Vvs SHE) is comparatively lower and closer to Li/Li + Standard redox potential of (-3.04V vs SHE). In addition, in the electrolyte of Propylene Carbonate (PC) solvent, with
And &>
In contrast, K + Has a minimum Stoke radius>
Further proving K + Fast diffusion kinetics in the electrolyte. However, due to +>
Is greater than->
And &>
Resulting in slow reaction kinetics and large volume expansion in the circulation process, fast capacity attenuation and poor rate capability. In this regard, suitable electrode materials are sought to accommodate rapid K + The large volume change during the insertion/extraction process is a major challenge in the development of PIBs.
At present, the transition metal sulfide is an alkali metal ion battery electrode material with great prospect due to large theoretical capacity and low cost, and has attracted wide attention of people at home and abroad. Wherein, molybdenum disulfide: (MoS 2 ) Has a unique layered structure, an open 2D diffusion path, an interlayer spacing (0.62 nm) greater than that of graphite (0.33 nm), and is a very promising K + The negative electrode material is rapidly inserted/removed. Furthermore, moS 2 Provides a large number of oxidation-reduction sites through multi-electron transfer and has higher theoretical specific capacity (670 mAh g) -1 ). However, pure MoS 2 The electrode is at K + The large volume expansion and pulverization during repeated intercalation/deintercalation can lead to problems of rapid capacity fade and poor cycle stability. In addition, its rapid charge/discharge capability is limited due to the inherently low conductivity. To solve this problem, many improvements to MoS have been proposed 2 Strategy for electrochemical performance, an effective and straightforward strategy is to take full advantage of the conductive substrate to prevent adjacent MoS 2 Agglomeration of the nanosheets and buffering of volume changes during cycling. Therefore, a new conductive substrate is explored to realize and reduce the layer MoS 2 Controlled surface coupling of nanoplatelets remains a significant challenge.
Among various conductive substrates, ti 3 C 2 MXene material has high conductivity (6.76X 10) 5 S m -1 ) The interlayer spacing is adjustable, the hydrophilicity is strong, and the like, and the material can be used as a substrate material for high-efficiency electron transportation and enhancement of alkali metal ion batteries and super capacitors. According to calculation, due to Ti 3 C 2 K of MXene + The diffusion barrier (0.103 eV) is lower than that of the pristine graphene (0.64 eV), so Ti 3 C 2 MXene negative electrode can realize faster K + Transport and higher charge/discharge rates. More importantly, ti 3 C 2 The abundant surface functional groups of MXene materials can also act as a conductive substrate for nucleation and loading of other active materials. Based on the advantages, the high specific energy few-layer MoS is reasonably designed 2 Nanosheet and high power Ti 3 C 2 MXene composites are very challenging and important for high performance PIBs. About MoS 2 The preparation of composites with MXene is also reported in the patent literature. For example, chinese patent document CN107660114a provides a preparation method of a molybdenum disulfide/MXene layered composite wave-absorbing material, which comprises the steps of: will disulfideMixing the molybdenum sulfide reaction solution with MXene material, preparing initial powder of the molybdenum disulfide/MXene layered composite material through hydrothermal reaction, washing and drying to obtain the molybdenum disulfide/MXene layered composite wave-absorbing material. The method has complex reaction process, and the prepared composite material is seriously stacked, which is not beneficial to the improvement of the wave absorption performance. Chinese patent document CN109671949A provides a preparation method of an MXene-based flexible composite anode material, wherein the preparation method comprises the following steps: mixing metal salt of transition metal element with a sulfur source, adding MXene material and alkaline solution to obtain a mixed solution, and carrying out hydrothermal reaction in a high-pressure reaction kettle to obtain the MXene/transition metal sulfide composite material. MXene prepared by HF etching only has thicker lamella and smaller interlayer spacing, which is not beneficial to the compounding with transition metal sulfide and the improvement of performance.
Currently, existing MoS 2 With Ti 3 C 2 The compounding method of the MXene composite material has the problems of common and complex reaction process, serious stacking of obtained products and difficult realization of MoS 2 And Ti 3 C 2 MXene has high synergistic effect. Chinese patent document CN106532015A proposes etching Ti with 49% HF 3 AlC 2 Precursor preparation of Ti with accordion shape 3 C 2 MXene cannot fundamentally solve the problem of Ti because the preparation material is not of a few-layer intercalation structure and does not have a three-dimensional stereo morphology 3 C 2 The self-stacking effect of MXene also fails to provide a better path for the transport of ions during electrochemical reaction. Therefore, the high specific energy few-layer MoS is reasonably designed 2 Nanosheet and high power Ti 3 C 2 The MXene material is coupled to obtain high-performance MoS 2 /Ti 3 C 2 MXene composite materials have great challenge and importance for high-performance potassium ion batteries. The invention is therefore proposed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a MoS for a high-performance potassium ion battery 2 /Ti 3 C 2 A preparation method of MXene composite material. The invention utilizes ion exchange and static electricityThe adsorption process successfully synthesizes MoS with 3D interconnection network 2 /Ti 3 C 2 MXene composite material, few-layer MoS in the obtained composite material 2 Nano sheet vertically loaded in Ti 3 C 2 On MXene. MoS of the invention 2 /Ti 3 C 2 MXene composite material incorporating Ti 3 C 2 MXene structure and few-layer MoS 2 The excellent characteristics of the nano-sheet, on one hand, the unique structure can effectively inhibit MoS 2 Aggregation and volume change of the nanosheets, thereby improving the conductivity of the composite material; on the other hand, moS 2 And Ti 3 C 2 The synergistic effect between these two components of MXene can significantly improve battery performance through novel battery capacitance Dual Mode Energy Storage (DMES) behavior. MoS of the invention 2 /Ti 3 C 2 The MXene composite material overcomes the defects of the traditional single material and solves the problem that K is generated + The problems of rapid reversible capacity attenuation and poor cycle stability caused by huge volume expansion and crushing of the electrode in the repeated embedding/separating process are solved, so that the cycle stability and the specific capacity of the potassium ion battery are obviously improved.
Description of terms:
room temperature: has a well-known meaning, in particular 25. + -. 5 ℃.
The technical scheme of the invention is as follows:
MoS for high-performance potassium ion battery 2 /Ti 3 C 2 The preparation method of the MXene composite material comprises the following steps:
(1) Subjecting a plurality of layers of et-Ti 3 C 2 Dispersing MXene nano-sheet in intercalation agent solution, reacting at room temperature, centrifuging, washing, and drying to obtain in-Ti 3 C 2 MXene nanosheets;
(2) Adding the mixed solution of a molybdenum precursor and a sulfur precursor into in-Ti under the conditions of ultrasound and stirring 3 C 2 In MXene nanosheet dispersion liquid, carrying out high-temperature reaction on the obtained mixed liquid; after the reaction is finished, centrifuging, washing and drying to obtain MoS 2 /Ti 3 C 2 MXene composite material.
According toet-Ti as described in step (1) of the present invention 3 C 2 The MXene nano-sheet takes HF as an etchant to selectively etch Ti 3 AlC 2 Obtained, which can be prepared according to the prior art; preferably, said et-Ti 3 C 2 The preparation method of the MXene nanosheet comprises the following steps:
mixing Ti 3 AlC 2 Slowly adding the powder into the HF solution for 0.5h, and stirring and reacting for 24h at 35 ℃; repeatedly washing the obtained substance with deionized water, centrifuging and decanting until the pH of the supernatant is 6-7, and freeze-drying the obtained precipitate at-30 ℃ for 24h to obtain et-Ti 3 C 2 MXene nanosheets; the mass fraction of the HF solution is 10-50 wt%, and the volume of the HF solution and Ti are 3 AlC 2 The mass ratio of the powder is 10-30 mL:1g of the total weight of the composition.
According to the present invention, preferably, the intercalation agent in step (1) is NaOH, liOH or KOH; the et-Ti 3 C 2 The mass ratio of the MXene nanosheets to the intercalating agent is 1.8-2.4, and more preferably 1:1-2; the intercalation agent can expand Ti 3 C 2 The interlayer spacing of MXene nano-sheets increases active sites.
According to the invention, the concentration of the intercalation solution in step (1) is preferably 1-3 mol/L.
According to the present invention, the reaction time in step (1) is preferably 5 to 8 hours.
According to the present invention, preferably, the washing in step (1) is 6 times by deionized water; the drying is to freeze-dry the washed product at-30 ℃ for 24h.
According to the present invention, it is preferable that in-Ti is mentioned in the step (2) 3 C 2 The concentration of the MXene nanosheet dispersion is 5.0 to 8.0mg/mL, and more preferably 6.6 to 6.7mg/mL.
According to the present invention, preferably, the molybdenum precursor in the step (2) is sodium molybdate dihydrate (Na) 2 MoO 4 ·2H 2 O) or ammonium molybdate ((NH) 4 ) 2 MoO 4 )。
According to the present invention, it is preferable that said in the step (2)Molybdenum element and in-Ti in molybdenum precursor 3 C 2 The mass ratio of the MXene nano-sheets is 1:3-5.
According to the present invention, preferably, the sulfur precursor in step (2) is thioacetamide (CH) 3 CSNH 2 ) Or thiourea (NH) 2 CSNH 2 )。
According to the present invention, it is preferable that elemental sulfur and in-Ti in the sulfur precursor in the step (2) 3 C 2 The mass ratio of the MXene nanosheets is 1:2-3.
According to the invention, preferably, the mixed solution of the molybdenum precursor and the sulfur precursor in the step (2) is obtained by dissolving the molybdenum precursor and the sulfur precursor in deionized water, wherein the mass concentration of the molybdenum precursor in the mixed solution is 2-6 mg/mL, and the mass concentration of the sulfur precursor in the mixed solution is 4-8 mg/mL; the mixed solution of the molybdenum precursor and the sulfur precursor is added into the system in a dropwise manner.
According to the present invention, it is preferable that the reaction temperature in step (2) is 180 to 220 ℃ and the reaction time is 18 to 36 hours.
According to the present invention, it is preferable that the washing in the step (2) is centrifugal washing with water and absolute ethyl alcohol for 4 to 6 times, respectively; the drying is freeze drying at-30 ℃ for 24-48 h.
According to the invention, the MoS prepared by the preparation method 2 /Ti 3 C 2 The MXene composite material is used as a negative electrode material and applied to a potassium ion battery, and the application method comprises the following steps:
mixing MoS 2 /Ti 3 C 2 Mixing an MXene composite material, a polyvinylidene fluoride (PVDF) binder and conductive carbon black (super-PLI) according to a mass ratio of 70; the mass of the N-methyl pyrrolidone is MoS 2 /Ti 3 C 2 2-3 times of the total mass of the MXene composite material, the polyvinylidene fluoride binder and the conductive carbon black.
The invention has the following technical characteristics and beneficial effects:
1. the invention utilizes intercalation agent to let-Ti 3 C 2 Intercalation treatment is carried out on MXene nano-sheets, and cations of the intercalating agent are inserted into Ti 3 C 2 T x Interlamination, meanwhile, the-OH in the intercalation agent can replace the-F surface functional group to obtain in-Ti with larger interlayer spacing 3 C 2 MXene nano-sheet. Ti with larger interlayer spacing 3 C 2 The MXene framework provides larger specific surface area and ion exchange sites, is favorable for full contact of electrode materials and electrolyte, and improves the charge transfer efficiency. Then, through ion exchange and electrostatic adsorption processes, the MoS of few layers 2 The nano-sheets are uniformly loaded on the surface of the nano-sheet with a 3D interconnection network structure in-Ti 3 C 2 MXene, thereby exposing more active sites and improving the storage capacity of potassium. The preparation method solves the problem of MoS 2 The aggregation and the volume change of the nano sheets, thereby obviously improving the cycling stability and the specific capacity of the potassium ion battery.
2. MoS prepared by the invention 2 /Ti 3 C 2 In the MXene composite material, the conductive in-Ti is uniformly loaded 3 C 2 Few-layer MoS on MXene substrate 2 The nanoplatelets have enhanced conductivity and reduced volume expansion and aggregation during cycling, resulting in high capacity and stable energy storage. At the same time, in-Ti 3 C 2 And MoS 2 The components have strong Mo-C covalent bonds, so that atom charge polarization is further caused, charge absorption is improved, effective interface electron transfer is realized, the capacitance performance is enhanced, faster and more stable energy storage is ensured, and the method has great significance in preparing the potassium ion battery cathode. The preparation method adopts a specific adding sequence of the molybdenum source and the sulfur source, the molybdenum source and the sulfur source are basically nucleated in the process of stirring in deionized water in the ion exchange process in the early stage, and then the molybdenum source and the sulfur source are electrically conducted in-Ti 3 C 2 Uniformly growing MXene substrate into MoS 2 If the adding sequence of the molybdenum source or the sulfur source is changed, part of the sulfur source or the molybdenum source can excessively change in-Ti 3 C 2 Chemical properties and charge of MXene surfaceDistributed, moS with uniform appearance and excellent performance can not be obtained 2 /Ti 3 C 2 MXene composite material.
3. The invention uses Ti 3 C 2 Compared with the traditional carbon materials such as graphene and the like, the MXene nano-sheet is used as a substrate material, and Ti 3 C 2 MXene has fast ion diffusion capacity, the MoS of the invention 2 With Ti 3 C 2 The coupling mode of MXene materials can greatly improve MoS 2 /Ti 3 C 2 Reversible capacity, cycle life and rate capability of MXene electrodes. Experiments prove that the MoS prepared by the invention 2 /Ti 3 C 2 MXene negative pole material, 0.1A g -1 After circulating for 200 times under the current density of (2), 360.0mAh g can be provided -1 And at 0.5A g -1 After 1300 cycles, the reversible capacity is 195.5mAh g -1 Has long cycle stability, and the attenuation rate of each cycle is only 0.01 percent.
4. The preparation method successfully prepares the novel MoS through simple and convenient ion exchange and electrostatic adsorption processes 2 /Ti 3 C 2 The MXene composite material can be popularized to the preparation of other composite materials, and plays a certain reference role in widening an energy material system. The invention provides a new idea for developing a high-performance potassium storage anode material with a DMES mechanism. The method has the advantages of simple operation, easily obtained raw materials, low cost and easy large-scale industrial popularization and application.
Drawings
FIG. 1 is the MoS prepared in example 1 2 /Ti 3 C 2 SEM (a-b) and TEM (c-d) images of MXene composite materials.
FIG. 2 shows in-Ti prepared in example 1 3 C 2 SEM image of MXene nanosheet.
FIG. 3 is Ti 3 AlC 2 、et-Ti 3 C 2 MXene, in-Ti prepared in comparative example 1 3 C 2 MXene and MoS prepared in example 1 2 /Ti 3 C 2 XRD pattern of MXene composite material.
FIG. 4 shows an embodimentMoS prepared in example 1 2 /Ti 3 C 2 Mapping map of MXene composite material.
FIG. 5 is a MoS prepared in comparative example 2 2 SEM (a) and TEM (b) images of the material.
FIG. 6 is an in-Ti alloy prepared in comparative example 3 3 C 2 SEM image of MXene nano-sheet, wherein (a) is in-Ti obtained by low intercalation agent concentration 3 C 2 SEM image of MXene nano-sheet, wherein (b) is in-Ti obtained by high intercalator concentration 3 C 2 SEM images of MXene nanoplatelets.
FIG. 7 is the MoS prepared in comparative example 3 2 /Ti 3 C 2 SEM image of MXene composite material, in which (a) MoS obtained by low intercalation agent concentration 2 /Ti 3 C 2 SEM image of MXene composite material, image (b) is MoS obtained by high intercalator concentration 2 /Ti 3 C 2 SEM images of MXene composite.
FIG. 8 shows MoS obtained in comparative example 4 2 /Ti 3 C 2 SEM images of MXene composites.
FIG. 9 shows MoS prepared in comparative example 2 of test example 1 2 Nanosheet, in-Ti prepared in comparative example 1 3 C 2 MXene materials and MoS prepared in example 1 2 /Ti 3 C 2 Cycle performance curve of MXene composite.
FIG. 10 shows MoS prepared in example 1 of Experimental example 1 2 /Ti 3 C 2 Long cycle performance curve of MXene composite.
FIG. 11 is the MoS prepared in comparative example 3 2 /Ti 3 C 2 Cyclic performance curve of MXene composite.
FIG. 12 is a MoS prepared in comparative example 4 2 /Ti 3 C 2 Cycle performance curve of MXene composite.
Detailed Description
The present invention is further described below with reference to the following drawings and examples, but is not limited thereto.
The raw materials used in the examples are all conventional raw materials and can be obtained commercially, unless otherwise specified; the methods used in the examples are prior art unless otherwise specified.
Example 1
MoS for high-performance potassium ion battery 2 /Ti 3 C 2 The preparation method of the MXene composite material comprises the following steps:
(1) Preparation of et-Ti 3 C 2 MXene nano-sheet
1g of Ti with the grain diameter of less than 38 mu m 3 AlC 2 Slowly adding the powder into 20mL of HF solution with the mass fraction of 40wt% for 0.5h to avoid overheating exothermic reaction, and stirring for reaction at 35 ℃ for 24h; repeatedly washing the obtained product with deionized water, centrifuging and decanting until the pH of the supernatant is 6-7, and freeze-drying the obtained precipitate at-30 deg.C for 24h to obtain et-Ti 3 C 2 MXene nano-sheet.
(2) Preparation of in-Ti 3 C 2 MXene nano-sheet
1g of et-Ti 3 C 2 MXene nanosheets are dispersed in 20mL of 1.8mol/L NaOH solution, and the obtained mixture is continuously stirred and reacted for 6 hours at room temperature; after the reaction is finished, centrifuging, washing the obtained precipitate for 6 times by using deionized water, and freeze-drying the product obtained by washing at-30 ℃ for 24 hours to obtain in-Ti 3 C 2 MXene nanosheets.
(3) Preparation of MoS 2 /Ti 3 C 2 MXene composite material
0.2g of in-Ti prepared in the step (2) 3 C 2 Dispersing MXene nano-sheets in 30mL of deionized water, and carrying out ultrasonic treatment for 30min to obtain in-Ti 3 C 2 MXene nanosheet dispersion; then 0.12g of sodium molybdate dihydrate (Na) 2 MoO 4 ·2H 2 O) and 0.2g of thioacetamide (CH) 3 CSNH 2 ) Dissolving the molybdenum precursor and the sulfur precursor in 30mL of deionized water, and magnetically stirring to obtain a mixed solution of the molybdenum precursor and the sulfur precursor; under the conditions of ultrasonic and magnetic stirring, dropwise adding the mixed solution of a molybdenum precursor and a sulfur precursor into in-Ti 3 C 2 Continuously stirring the MXene nanosheet dispersion liquid for 1h, transferring the obtained mixed liquid into a 100mL stainless steel autoclave with a polytetrafluoroethylene lining, and reacting for 24h at 200 ℃; after the mixture is naturally cooled to the room temperature,centrifugally washing the obtained black precipitate with deionized water and anhydrous ethanol for 5 times, and freeze-drying the washed product at-30 deg.C for 24h to obtain MoS 2 /Ti 3 C 2 MXene composite material.
MoS prepared in this example 2 /Ti 3 C 2 SEM and TEM images of MXene composite are shown in FIG. 1, and from FIG. 1, it can be seen that MoS is a few layers 2 The nano-sheets are uniformly supported on Ti 3 C 2 And on MXene, a 3D interconnected conductive network structure is formed, so that more active sites are exposed, and the storage capacity of potassium is improved.
in-Ti prepared in this example 3 C 2 The SEM image of MXene nanosheets is shown in FIG. 2, and as can be seen from FIG. 2, the obtained in-Ti 3 C 2 The MXene nano-sheet has an accordion structure with uniform appearance.
MoS prepared in this example 2 /Ti 3 C 2 The XRD pattern of MXene composite material is shown in FIG. 3. From FIG. 3, it can be seen that the material prepared by this example has Ti 3 C 2 MXene and MoS 2 Diffraction peaks common to both and compared to et-Ti 3 C 2 MXene material, the interlamellar spacing of the obtained composite material is obviously enlarged; as can also be seen in FIG. 3, in-Ti 3 C 2 Interlayer spacing of MXene nanosheets compared with et-Ti 3 C 2 MXene nanosheets are significantly enlarged.
MoS prepared in this example 2 /Ti 3 C 2 The mapping diagram of MXene composite material is shown in FIG. 4, and from FIG. 4, moS can be seen 2 Nanosheet being in Ti 3 C 2 Uniform growth on MXene.
Example 2
MoS for high-performance potassium ion battery 2 /Ti 3 C 2 The preparation method of the MXene composite material comprises the following steps:
(1) Preparation of et-Ti 3 C 2 MXene nano-sheet
1g of Ti with the grain diameter of less than 38 mu m 3 AlC 2 Slowly adding 20mL of the powder with the mass fraction of 40wt%In the HF solution (2), the reaction is carried out for 0.5h to avoid overheat exothermic reaction, and the reaction is stirred for 24h at the temperature of 35 ℃; repeatedly washing the obtained product with deionized water, centrifuging and decanting until the pH of the supernatant is 6-7, and freeze-drying the obtained precipitate at-30 deg.C for 24h to obtain et-Ti 3 C 2 MXene nanosheets.
(2) Preparation of in-Ti 3 C 2 MXene nano-sheet
1g of et-Ti 3 C 2 MXene nano-sheets are dispersed in 30mL of 1.8mol/LNaOH solution, and the obtained mixture is continuously stirred and reacted for 6h at room temperature; after the reaction is finished, centrifuging, washing the obtained precipitate for 6 times by using deionized water, and freeze-drying the product obtained by washing at-30 ℃ for 24 hours to obtain in-Ti 3 C 2 MXene nano-sheet.
(3) Preparation of MoS 2 /Ti 3 C 2 MXene composite material
0.2g of in-Ti prepared in the step (2) 3 C 2 Dispersing MXene nano-sheets in 30mL of deionized water, and carrying out ultrasonic treatment for 30min to obtain in-Ti 3 C 2 MXene nanosheet dispersion; then 0.12g of sodium molybdate dihydrate (Na) 2 MoO 4 ·2H 2 O) and 0.2g of thioacetamide (CH) 3 CSNH 2 ) Dissolving the molybdenum precursor and the sulfur precursor in 30mL of deionized water, and magnetically stirring to obtain a mixed solution of the molybdenum precursor and the sulfur precursor; under the conditions of ultrasonic and magnetic stirring, dropwise adding the mixed solution of a molybdenum precursor and a sulfur precursor into in-Ti 3 C 2 Continuously stirring the MXene nanosheet dispersion liquid for 1h, transferring the obtained mixed liquid into a 100mL stainless steel autoclave with a polytetrafluoroethylene lining, and reacting for 24h at 200 ℃; naturally cooling to room temperature, respectively centrifugally washing the obtained black precipitate with deionized water and absolute ethyl alcohol for 5 times, and freeze-drying the washed product at-30 ℃ for 24 hours to obtain MoS 2 /Ti 3 C 2 MXene composite material.
Example 3
MoS for high-performance potassium ion battery 2 /Ti 3 C 2 The preparation method of the MXene composite material comprises the following steps:
(1) Preparation of et-Ti 3 C 2 MXene nano-sheet
1g of Ti with the grain diameter of less than 38 mu m 3 AlC 2 Slowly adding the powder into 20mL of HF solution with the mass fraction of 40wt% for 0.5h to avoid overheat exothermic reaction, and stirring for reaction at 35 ℃ for 24h; repeatedly washing the obtained substance with deionized water, centrifuging and decanting until the pH of the supernatant is 6-7, and freeze-drying the obtained precipitate at-30 deg.C for 24h to obtain et-Ti 3 C 2 MXene nano-sheet.
(2) Preparation of in-Ti 3 C 2 MXene nano-sheet
1g of et-Ti 3 C 2 MXene nanosheets are dispersed in 20mL of 1.8mol/L NaOH solution, and the obtained mixture is continuously stirred and reacted for 6 hours at room temperature; after the reaction is finished, centrifuging, washing the obtained precipitate for 6 times by using deionized water, and freeze-drying the product obtained by washing at-30 ℃ for 24 hours to obtain in-Ti 3 C 2 MXene nanosheets.
(3) Preparation of MoS 2 /Ti 3 C 2 MXene composite material
0.2g of in-Ti prepared in the step (2) 3 C 2 Dispersing MXene nano-sheets in 30mL of deionized water, and carrying out ultrasonic treatment for 30min to obtain in-Ti 3 C 2 MXene nanosheet dispersion; then 0.12g of sodium molybdate dihydrate (Na) 2 MoO 4 ·2H 2 O) and 0.2g of thioacetyl (CH) 3 CSNH 2 ) Dissolving the molybdenum precursor and the sulfur precursor in 30mL of deionized water, and magnetically stirring to obtain a mixed solution of the molybdenum precursor and the sulfur precursor; under the conditions of ultrasonic and magnetic stirring, dropwise adding the mixed solution of a molybdenum precursor and a sulfur precursor into in-Ti 3 C 2 Continuously stirring the MXene nanosheet dispersion liquid for 1h, transferring the obtained mixed liquid into a 100mL stainless steel autoclave with a polytetrafluoroethylene lining, and reacting for 24h at 180 ℃; naturally cooling to room temperature, respectively centrifugally washing the obtained black precipitate with deionized water and absolute ethyl alcohol for 5 times, and freeze-drying the washed product at-30 ℃ for 24 hours to obtain MoS 2 /Ti 3 C 2 MXene composite material.
Comparative example 1
in-Ti 3 C 2 The preparation method of the MXene material comprises the following steps:
(1) The procedure was as described in step (1) of example 1.
(2) 1g of et-Ti 3 C 2 MXene nanosheets are dispersed in 20mL of 1.8mol/L NaOH solution, and the obtained mixture is continuously stirred and reacted for 6 hours at room temperature; after the reaction is finished, centrifuging, washing the obtained precipitate for 6 times by using deionized water, and freeze-drying the product obtained by washing at-30 ℃ for 24 hours to obtain in-Ti 3 C 2 MXene nano-sheet.
in-Ti prepared in this comparative example 3 C 2 The XRD pattern of MXene material is shown in FIG. 3.
Comparative example 2
MoS 2 The preparation method of the nano sheet comprises the following steps:
0.12g of sodium molybdate dihydrate (Na) 2 MoO 4 ·2H 2 O) and 0.2g of thioacetamide (CH) 3 CSNH 2 ) Dissolved in 60mL of deionized water to form a homogeneous solution under magnetic stirring, and the resulting mixture was transferred to a 100mL polytetrafluoroethylene-lined stainless steel autoclave and reacted at 200 ℃ for 24h. After the reaction is finished, naturally cooling to room temperature, centrifuging, respectively centrifugally washing the obtained black precipitate for 5 times by using deionized water and absolute ethyl alcohol, and then freeze-drying at-30 ℃ for 24 hours to obtain MoS 2 Nanosheets.
MoS prepared in this comparative example 2 SEM and TEM photographs of the nanosheets are shown in FIG. 5, and it can be seen from FIG. 5 that the MoS was prepared 2 The stacking of the nanosheets is severe.
Comparative example 3
MoS 2 /Ti 3 C 2 MXene composite was prepared as described in example 1, except that: the concentration of the NaOH solution in the step (2) is 0.5mol/L and 4mol/L respectively.
in-Ti prepared in this comparative example 3 C 2 The SEM image of MXene nanosheets is shown in FIG. 6, and it can be seen from FIG. 6a that et-Ti 3 C 2 Partial proportion of MXene nano-sheet and intercalation agentLow, no significant intercalation, as can be seen in FIG. 6b, et-Ti 3 C 2 Too high ratio of MXene nanosheet to intercalating agent results in-Ti 3 C 2 The nanosheet is damaged.
MoS obtained in this comparative example 2 /Ti 3 C 2 The SEM image of the MXene composite is shown in FIG. 7, and it can be seen from FIG. 7a that et-Ti 3 C 2 The ratio of MXene nano-sheet to intercalation agent is low, and the obtained MoS 2 /Ti 3 C 2 MoS in MXene composite material 2 The nano-sheets are distributed in Ti 3 C 2 MXene nanosheet surface with only a small amount of embedded Ti 3 C 2 MXene nanosheet interlayer; from FIG. 7b, it can be seen that et-Ti 3 C 2 The ratio of MXene nano-sheet to intercalation agent is too high, resulting in-Ti 3 C 2 The nanosheet was damaged and MoS could not be obtained 2 The nano-sheets are uniformly supported on Ti 3 C 2 MXene surface and interlaminar morphology.
Comparative example 4
MoS 2 /Ti 3 C 2 The preparation method of the MXene composite material comprises the following steps:
(1) Preparation of et-Ti 3 C 2 MXene nano-sheet
1g of Ti with the grain diameter of less than 38 mu m 3 AlC 2 Slowly adding the powder into 20mL of HF solution with the mass fraction of 40wt% for 0.5h to avoid overheat exothermic reaction, and stirring for reaction at 35 ℃ for 24h; repeatedly washing the obtained product with deionized water, centrifuging and decanting until the pH of the supernatant is 6-7, and freeze-drying the obtained precipitate at-30 deg.C for 24h to obtain et-Ti 3 C 2 MXene nanosheets.
(2) Preparation of MoS 2 /Ti 3 C 2 MXene composite material
0.2g of et-Ti prepared in step (1) 3 C 2 Dispersing MXene nano-sheets in 30mL of deionized water, and carrying out ultrasonic treatment for 30min to obtain et-Ti 3 C 2 An MXene nanosheet dispersion; then 0.12g of sodium molybdate dihydrate (Na) 2 MoO 4 ·2H 2 O) and 0.2g of thioAcetamide (CH) 3 CSNH 2 ) Dissolving the molybdenum precursor and the sulfur precursor in 30mL of deionized water, and magnetically stirring to obtain a mixed solution of the molybdenum precursor and the sulfur precursor; under the conditions of ultrasonic and magnetic stirring, dropwise adding a mixed solution of a molybdenum precursor and a sulfur precursor into et-Ti 3 C 2 Continuously stirring the MXene nanosheet dispersion liquid for 1h, transferring the obtained mixed liquid into a 100mL stainless steel autoclave with a polytetrafluoroethylene lining, and reacting for 24h at 180 ℃; naturally cooling to room temperature, respectively centrifugally washing the obtained black precipitate with deionized water and absolute ethyl alcohol for 5 times, and freeze-drying the washed product at-30 ℃ for 24 hours to obtain MoS 2 /Ti 3 C 2 MXene composite material.
MoS was obtained in this comparative example 2 /Ti 3 C 2 The SEM image of the MXene composite material is shown in FIG. 8, and it can be seen from FIG. 8 that Ti 3 C 2 MXene close packing with only a small amount of MoS 2 Embedding between layers, moS cannot be obtained 2 Nanosheet being in Ti 3 C 2 MXene surface and interlaminar vertically loaded composites.
Test example 1
MoS obtained in example 1 2 /Ti 3 C 2 MXene composite Material in-Ti obtained in comparative example 1 3 C 2 MXene Material MoS obtained in comparative example 2 2 Nanosheets, comparative example 3 and MoS prepared in comparative example 4 2 /Ti 3 C 2 The MXene composite material is used as a negative electrode material to be applied to a potassium ion battery, and the electrochemical performance of the MXene composite material is tested by the following specific method:
MoS obtained in example 1 2 /Ti 3 C 2 MXene composite Material in-Ti obtained in comparative example 1 3 C 2 MXene materials, moS obtained in comparative example 2 2 Nanosheets, moS prepared in comparative example 3 and comparative example 4 2 /Ti 3 C 2 The MXene composite material is an active substance, the active substance, polyvinylidene fluoride (PVDF, HSV 900) binder and conductive carbon black (super-PLI) are mixed according to the mass ratio of 703 times of the total mass of the substance, the polyvinylidene fluoride binder and the conductive carbon black), stirring for 12h, preparing uniform slurry, uniformly coating the slurry on a copper foil, and performing vacuum drying at 80 ℃ for 12h to obtain the negative electrode material for the potassium ion battery. Potassium metal as counter electrode, glass fiber membrane (GF/D whatman) as diaphragm, potassium hexafluorophosphate (KPF) 6 ) A solution obtained by dissolving a mixed solvent of Ethylene Carbonate (EC) and diethyl carbonate (DEC) was used as an electrolyte (the volume ratio of ethylene carbonate to diethyl carbonate was 1:1, the concentration of potassium hexafluorophosphate in the electrolyte is 0.8 mol/L), and assembling the button cell 2025 in a vacuum glove box.
MoS obtained in example 1 2 /Ti 3 C 2 MXene composite, in-Ti obtained in comparative example 1 3 C 2 MXene materials, moS obtained in comparative example 2 2 The cycle performance curve of the electrode with the nanosheet as the negative electrode material is shown in fig. 9, and it can be seen from fig. 9 that the MoS prepared in the embodiment 1 of the invention 2 /Ti 3 C 2 MXene composite material electrode in 0.1Ag -1 After 200 cycles at a current density of 360.0mAhg -1 Has a reversible capacity significantly better than that of in-Ti of comparative example 1 3 C 2 MXene and MoS 2 Reversible capacities of nanosheet electrodes 158.6 and 63.9mAhg -1 And excellent cycle performance is shown.
MoS prepared according to the invention in example 1 2 /Ti 3 C 2 The long cycle performance curve of MXene composite is shown in FIG. 10, and can be seen from FIG. 10 at 0.5A g -1 The current density of (2) can provide 195.5mAh g after 1300 cycles -1 The reversible capacity of (2) shows an excellent long-cycle stability, with a rate of decay per cycle of only 0.01%.
MoS prepared in comparative example 3 2 /Ti 3 C 2 The cycle performance curve of the electrode using MXene composite material as the negative electrode material is shown in FIG. 11, and it can be seen from FIG. 11 that MoS is obtained by using low-concentration and high-concentration intercalators 2 /Ti 3 C 2 MXene composite material electrode is 0.1A g -1 Respectively has a current density of 95.9mAhg after 200 cycles -1 And 108.8mAhg -1 The reversible capacity of (a) is fast in performance decay during the circulation process, and is obviously inferior to that of the embodiment 1 of the invention. From the above, it can be seen that the intercalator concentration and ratio are such that a high performance long life MoS is produced 2 /Ti 3 C 2 The MXene composite material electrode has extremely important function.
MoS prepared in comparative example 3 2 /Ti 3 C 2 The cycle performance curve of the electrode using MXene composite material as the negative electrode material is shown in FIG. 12, and the obtained MoS can be seen from FIG. 12 2 /Ti 3 C 2 The MXene composite material is used as the cathode of the potassium ion battery at 0.1A g -1 The performance decays very fast at the current density of (c).
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as would be obvious to one skilled in the art be included within the scope of the appended claims.
Claims (8)
1. MoS for high-performance potassium ion battery 2 /Ti 3 C 2 The preparation method of the MXene composite material comprises the following steps:
(1) A plurality of layers of et-Ti 3 C 2 Dispersing MXene nano-sheet in intercalation agent solution, reacting at room temperature, centrifuging, washing, and drying to obtain in-Ti 3 C 2 MXene nanosheets; the intercalation agent is NaOH, liOH or KOH; the et-Ti 3 C 2 The mass ratio of the MXene nanosheet to the intercalator is 1; the concentration of the intercalation solution is 1 to 3 mol/L;
(2) Adding the mixed solution of a molybdenum precursor and a sulfur precursor into in-Ti under the conditions of ultrasound and stirring 3 C 2 In MXene nanosheet dispersion liquid, carrying out high-temperature reaction on the obtained mixed liquid; after the reaction is finished, centrifuging, washing and drying to obtain MoS 2 /Ti 3 C 2 MXene composite material; the molybdenum precursor is sodium molybdate dihydrate or ammonium molybdate; molybdenum in the molybdenum precursorElement and in-Ti 3 C 2 The mass ratio of the MXene nanosheets is 1 to 3-5; the sulfur precursor is thioacetamide or thiourea; the sulfur precursor contains sulfur element and in-Ti 3 C 2 The mass ratio of the MXene nanosheets is 1 to 2 to 3.
2. The MoS of claim 1 2 /Ti 3 C 2 The preparation method of the MXene composite material is characterized in that the et-Ti in the step (1) 3 C 2 The mass ratio of the MXene nanosheets to the intercalator is 1 to 2.
3. The MoS of claim 1 2 /Ti 3 C 2 The preparation method of the MXene composite material is characterized in that the reaction time in the step (1) is 5 to 8 hours; the washing is washing for 6 times by deionized water; the drying is to freeze-dry 24h at-30 ℃ of the product obtained by washing.
4. The MoS of claim 1 2 /Ti 3 C 2 The preparation method of the MXene composite material is characterized in that the in-Ti in the step (2) 3 C 2 The concentration of the MXene nanosheet dispersion is 5.0-8.0 mg/mL.
5. The MoS of claim 1, wherein 2 /Ti 3 C 2 The preparation method of the MXene composite material is characterized in that the in-Ti in the step (2) 3 C 2 The concentration of the MXene nanosheet dispersion is 6.6 to 6.7mg/mL.
6. The MoS of claim 1 2 /Ti 3 C 2 The preparation method of the MXene composite material is characterized in that the mass concentration of a molybdenum precursor in the mixed solution in the step (2) is 2-6 mg/mL, and the mass concentration of a sulfur precursor in the mixed solution is 4-8 mg/mL; the mixed solution of the molybdenum precursor and the sulfur precursor is added into the system in a dropwise manner.
7. The MoS of claim 1, wherein 2 /Ti 3 C 2 The preparation method of the MXene composite material is characterized in that the reaction temperature in the step (2) is 180-220 ℃, and the reaction time is 18-36 h.
8. The MoS of claim 1 2 /Ti 3 C 2 The preparation method of the MXene composite material is characterized in that the washing in the step (2) is 4~6 times of centrifugal washing by water and ethanol respectively; the drying is carried out for 24 to 48 hours at the temperature of minus 30 ℃.
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