Preparation method and application of TMA-V2CTx / NSS composite material
By growing NSS nanospheres on TMA-V2CTx nanosheets to form a sandwich composite material, the problems of volume expansion and aggregation of supercapacitor electrode materials were solved, improving their conductivity and cycle stability in alkaline solutions and achieving high specific capacitance energy storage characteristics.
Patent Information
- Application Number
- CN202511463020.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-14
- Publication Date
- 2026-01-06
AI Technical Summary
Existing supercapacitor electrode materials suffer from volume expansion and aggregation issues during redox reactions, affecting their cycle stability and conductivity. Furthermore, traditional transition metal sulfides offer limited performance improvement in alkaline solutions.
NSS nanospheres were stably grown on TMA-V2CTx nanosheets using a simple hydrothermal method to form a sandwich composite material. TMA+ was used to modify the MXene surface to increase the interlayer spacing and reactive sites, thereby synergistically improving the conductivity.
The prepared TMA-V2CTx/NSS composite material exhibits excellent specific capacitance and energy storage characteristics in alkaline solution, improves cycle stability and conductivity, reduces material stacking, and enhances electrolyte permeability.
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Figure CN121282013A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a method for preparing MXene-based composite materials and their applications. Background Technology
[0002] Renewable energy sources such as wind and solar power play a vital role in modern lifestyles, but these sources are unstable and overly dependent on the natural environment. Therefore, how to store and effectively utilize renewable energy in practical applications has become a primary concern. In most cases, electricity is obtained from renewable or non-renewable energy sources using various conversion technologies and then applied to production and daily life. Electrochemical energy storage systems include lithium-ion batteries (LIBs), lithium-sulfur batteries, metal-air batteries, and supercapacitors. Both batteries and supercapacitors involve the transport and storage of ions and electrons in the electrode active materials. Batteries have high energy density but relatively low power density. Supercapacitors have attracted widespread attention due to their extremely high power density, rapid charge / discharge rates, and ultra-long cycle life.
[0003] The electrochemical performance of supercapacitors is mainly affected by the electrolyte and electrode materials, with the electrode material considered the primary factor influencing the energy density. Therefore, seeking an electrode material with large specific surface area, long cycle stability, and high conductivity is a current research focus. MXenes (transition metal carbides / nitrides / carbonitrides), as a new class of two-dimensional (2D) nanomaterials, have shown great application potential in the field of electrode materials since their initial discovery in 2011. MXene materials possess advantages such as high specific surface area and abundant active sites, tunable interlayer structure and ion transport channels, and controllable surface chemical properties. Among them, V2CT... x As an important member of the MXene family, vanadium exhibits significant advantages when used as an electrode material for supercapacitors: vanadium is one of the lightest atoms among all transition metals; its multivalent state characteristic, allowing it to flexibly switch between +2 and +5 valences, combined with the abundant active sites provided by surface end groups such as -OH and -O, can generate an extremely strong pseudocapacitive effect; and it is compatible with Ti3C2T x Compared to V2CT x The thin atomic layers of MXene result in a faster ion diffusion rate. In V2CT... x Intercalation of a large number of cations between layers and design of the structure of MXene-based materials are key to improving V2CT. x Effective methods for improving electrochemical performance.
[0004] As a component of battery-type electrode materials, transition metal sulfides are considered ideal candidate materials for supercapacitors due to their unique properties. They possess high conductivity, abundant redox active sites, excellent redox reversibility, good conductivity, and low electronegativity. Among various metal sulfides, nickel sulfide is considered one of the main electrode candidates for energy storage devices due to its excellent redox chemistry, high theoretical capacity, and excellent electronic conductivity. However, transition metal sulfides also suffer from the shortcomings of traditional transition metal-based materials, namely, volume expansion and aggregation during redox reactions.
[0005] Based on the above research, using organic cations (TMA) + Intercalation methods for V2CT x Surface modification, specifically cation-modified MXene, significantly increases interlayer spacing and reactive sites, improves cycling stability, and further enhances its conductivity in alkaline solutions. Benefiting from the high oxidation state of Sn, and the fact that S doping systematically modulates the charge density of Ni and Sn and improves conductivity to enhance electrochemical performance, the performance of NSS is effectively improved. Transition metal sulfides are modified onto TMA-V2CT. x On nanosheets, this increases V2CT x The interlayer spacing reduces self-stacking and promotes complete electrolyte penetration. Due to TMA-V2CT x The synergistic effect between the composite material and transition metal sulfides, along with their inherent redox reactions, gives the prepared composite electrode excellent specific capacitance and energy storage characteristics. Summary of the Invention
[0006] The purpose of this invention is to solve the above-mentioned technical problems and provide a TMA-V2CT. x Preparation methods and applications of / NSS composite materials.
[0007] The objective of this invention is to stably grow NSS nanospheres on few-layer TMA-V2CT using a simple hydrothermal method. x TMA-V2CT was successfully designed and fabricated on nanosheets. x / NSS sandwich composite materials highlight the synergistic effect of inter-component structures with transition metal compounds. Through the study of TMA-V2CT... x The electrochemical properties of the / NSS composite material further expand the practical applications of MXene, and the structure-property relationship of MXene-based composite materials deepens the understanding of high-performance energy storage devices.
[0008] A method for preparing a TMA-MXene / NSS composite material is carried out according to the following steps:
[0009] 1. A TMA-V2CT x The preparation method and application of / NSS composite material, characterized by a TMA-V2CT x The preparation method of the / NSS composite material is completed according to the following steps:
[0010] I. Preparation of V2CT x MXene:
[0011] ① Dissolve lithium fluoride in hydrochloric acid and stir until homogeneous to obtain mixture I;
[0012] ② Dissolve V2AlC in mixture I and stir until homogeneous to obtain mixture II;
[0013] ③ Place mixture II in a polytetrafluoroethylene reactor for hydrothermal reaction. After the reaction is completed, allow it to cool naturally to room temperature to obtain reaction product I.
[0014] ④ Wash reaction product I by centrifugation with deionized water and anhydrous ethanol until the pH of the supernatant is higher than 6. Remove the supernatant to obtain precipitate V2CT. x MXene;
[0015] II. Preparation of TMA-V2CT x :
[0016] ① V2CT x The MXene precipitate was ultrasonically dispersed under a nitrogen atmosphere, and then centrifuged again to obtain precipitate I;
[0017] ② Add precipitate I to tetramethylammonium hydroxide solution, stir and mix evenly, transfer it to polytetrafluoroethylene reactor, and stir continuously at 25 ℃ for 12 h to obtain mixed solution I;
[0018] ③ Use deionized water and anhydrous ethanol to centrifuge and wash mixed solution I until the pH of the mixed solution is 7. Add an appropriate amount of deionized water again and sonicate under nitrogen atmosphere for 1 h. Centrifuge to separate, take the supernatant to obtain reaction product II.
[0019] ④ Dissolve reaction product II in lithium chloride solution, let stand, discard the supernatant, add deionized water and repeatedly centrifuge and wash until the supernatant turns black. After thorough mixing, perform ultrasonic and centrifugation, collect the supernatant to obtain TMA-V2CT. x ;
[0020] III. Preparation of TMA-V2CT x / NSS:
[0021] ① Add nickel nitrate hexahydrate, tin chloride pentahydrate and glycerol to isopropanol and stir until homogeneous to obtain mixture III;
[0022] ② Transfer mixture Ⅲ to a polytetrafluoroethylene reactor for hydrothermal reaction. After naturally cooling to room temperature, wash the reaction product several times with anhydrous ethanol and then vacuum dry to obtain reaction product Ⅲ.
[0023] ③ Dissolve sodium sulfide nonahydrate in deionized water and stir until homogeneous to obtain mixture IV;
[0024] ④. The TMA-V2CT x The solution was added to mixture IV and stirred until homogeneous to obtain mixture V;
[0025] ⑤ Add reaction product III to mixture V, stir well, and put it into a polytetrafluoroethylene reactor for hydrothermal reaction. After naturally cooling to room temperature, reaction product IV is obtained.
[0026] ⑥ Wash reaction product IV repeatedly with deionized water and dry it at 60 °C for 12 h to obtain powder sample TMA-V2CT. x / NSS, which stands for TMA-V2CT x / NSS composite material.
[0027] Compared with the prior art, the beneficial effects of the present invention are:
[0028] I. The TMA-V2CT prepared by this invention x / NSS composite materials can significantly increase interlayer spacing and reactive sites, improve cycle stability, reduce self-stacking, and promote complete electrolyte penetration, further enhancing their conductivity in alkaline solutions.
[0029] II. TMA-V2CT prepared according to the present invention x / NSS composite material, as an electrode material for supercapacitors, exhibits high specific capacitance, at 1 A g. -1 The lower specific capacitance is 1805.2 F g. -1 It can be applied to high energy density supercapacitors;
[0030] III. A TMA-V2CT prepared according to the present invention x The overall structure of the NSS composite material contains a two-dimensional layered structure of MXene and a large number of NSS nanoparticles distributed in TMA-V2CT. x On the interlayer and surface, a layered structure is formed, which can effectively prevent TMA-V2CT. x The collapse and accumulation of the lamellae mitigate the problems of self-structural pulverization and agglomeration of NSS nanoparticles during redox reactions;
[0031] IV. A TMA-V2CT prepared according to this embodiment x The method for preparing NSS composite materials is characterized by simple process, green and environmentally friendly preparation process, easy operation and low equipment requirements. Attached Figure Description
[0032] Figure 1 TMA-V2CT prepared for Example 1 x Scanning electron microscope image of / NSS;
[0033] Figure 2 TMA-V2CT prepared for Examples 1-2 x Comparison of cyclic voltammetry curves of NSS and NSS at the same scan rate;
[0034] Figure 3 TMA-V2CT prepared for Examples 1-2 x Comparison of constant current charging and discharging of / NSS and NSS at the same current density;
[0035] Figure 4 TMA-V2CT prepared for Examples 1-2 x Impedance comparison diagram of NSS and NSS;
[0036] Figure 5 TMA-V2CT prepared for Examples 1-2 x Comparison chart of the rate performance of / NSS and NSS;
[0037] Figure 6 TMA-V2CT prepared for Example 1 x Cyclic voltammetry curves of / NSS at different scan rates;
[0038] Figure 7 TMA-V2CT prepared for Example 1 x / NSS constant current charging and discharging diagrams at different current densities. Detailed Implementation
[0039] Specific Implementation Method 1: This implementation method is a preparation method of TMA-MXene / NSS composite material, which is specifically completed according to the following steps:
[0040] 1. A TMA-V2CT x The preparation method and application of / NSS composite material, characterized by a TMA-V2CT x The preparation method of the / NSS composite material is completed according to the following steps:
[0041] I. Preparation of V2CT x MXene:
[0042] ① Dissolve lithium fluoride in hydrochloric acid and stir until homogeneous to obtain mixture I;
[0043] ② Dissolve V2AlC in mixture I and stir until homogeneous to obtain mixture II;
[0044] ③ Place mixture II in a polytetrafluoroethylene reactor for hydrothermal reaction. After the reaction is completed, allow it to cool naturally to room temperature to obtain reaction product I.
[0045] ④ Wash reaction product I by centrifugation with deionized water and anhydrous ethanol until the pH of the supernatant is higher than 6. Remove the supernatant to obtain precipitate V2CT. x MXene;
[0046] II. Preparation of TMA-V2CT x :
[0047] ① V2CT x The MXene precipitate was ultrasonically dispersed under a nitrogen atmosphere, and then centrifuged again to obtain precipitate I;
[0048] ② Add precipitate I to tetramethylammonium hydroxide solution, stir and mix evenly, transfer it to polytetrafluoroethylene reactor, and stir continuously at 25 ℃ for 12 h to obtain mixed solution I;
[0049] ③ Use deionized water and anhydrous ethanol to centrifuge and wash mixed solution I until the pH of the mixed solution is 7. Add an appropriate amount of deionized water again and sonicate under nitrogen atmosphere for 1 h. Centrifuge to separate, take the supernatant to obtain reaction product II.
[0050] ④ Dissolve reaction product II in lithium chloride solution, let stand, discard the supernatant, add deionized water and repeatedly centrifuge and wash until the supernatant turns black. After thorough mixing, perform ultrasonic and centrifugation, collect the supernatant to obtain TMA-V2CT. x ;
[0051] III. Preparation of TMA-V2CT x / NSS:
[0052] ① Add nickel nitrate hexahydrate, tin chloride pentahydrate and glycerol to isopropanol and stir until homogeneous to obtain mixture III;
[0053] ② Transfer mixture Ⅲ to a polytetrafluoroethylene reactor for hydrothermal reaction. After naturally cooling to room temperature, wash the reaction product several times with anhydrous ethanol and then vacuum dry to obtain reaction product Ⅲ.
[0054] ③ Dissolve sodium sulfide nonahydrate in deionized water and stir until homogeneous to obtain mixture IV;
[0055] ④. The TMA-V2CT x The solution was added to mixture IV and stirred until homogeneous to obtain mixture V;
[0056] ⑤ Add reaction product III to mixture V, stir well, and put it into a polytetrafluoroethylene reactor for hydrothermal reaction. After naturally cooling to room temperature, reaction product IV is obtained.
[0057] ⑥ Wash reaction product IV repeatedly with deionized water and dry it at 60 °C for 12 h to obtain powder sample TMA-V2CT. x / NSS, which stands for TMA-V2CT x / NSS composite material.
[0058] Specific Implementation Method Two: The difference between this implementation method and Specific Implementation Method One is that the mass concentration of the tetramethylammonium hydroxide solution mentioned in step two ② is 5 wt.%; the other steps are the same as in Specific Implementation Method One.
[0059] Specific Implementation Method 3: This implementation method differs from Specific Implementation Method 1 or 2 in that: the molar ratio of nickel nitrate hexahydrate to tin chloride pentahydrate in step 3① is 14:1; the volume ratio of isopropanol to glycerol is 2.5:1; and the mass ratio of tin chloride pentahydrate to isopropanol is 1.9 mg:1 mL. Other steps are the same as in Specific Implementation Method 1 or 2.
[0060] Specific Implementation Method Four: This implementation method differs from Specific Implementation Methods One to Three in that the hydrothermal reaction temperature in step three ② is 160 ℃, and the hydrothermal reaction time is 12 h. The other steps are the same as in Specific Implementation Methods One to Three.
[0061] Specific Implementation Method Five: The difference between this implementation method and Specific Implementation Methods One to Four is that the mass concentration of sodium sulfide nonahydrate mentioned in step three ③ is 2 mg / mL. -1 The other steps are the same as those in implementation methods one through four.
[0062] Specific Implementation Method Six: The difference between this implementation method and Specific Implementation Methods One through Five is that the added TMA-V2CT mentioned in step three (④) is... x Concentration of 4 mg / mL -1 The other steps are the same as those in implementation methods one through five.
[0063] Specific Implementation Method Seven: The difference between this implementation method and Specific Implementation Methods One through Six is: the mass of reaction product III mentioned in step three (⑤) and TMA-V2CT xThe volume ratio was 100 mg:1 mL, the reaction temperature was 130 °C, and the reaction time was 6 h. Other steps were the same as in specific embodiments one through six.
[0064] Specific Implementation Method Eight: The difference between this implementation method and Specific Implementation Methods One through Seven is that: a TMA-V2CT x / NSS composite material is used as an electrode material for supercapacitors. Other steps are the same as in specific embodiments one through seven.
[0065] The beneficial effects of the present invention are verified using the following embodiments:
[0066] Example 1: A TMA-V2CT x The preparation method of the / NSS composite material is carried out according to the following steps:
[0067] I. Preparation of V2CT x MXene:
[0068] ① Dissolve 2.0 g of lithium fluoride in 20 mL of a 12 mol / L solution. -1 In hydrochloric acid, stir until homogeneous to obtain mixture I;
[0069] ② Dissolve 1.0 g of V2AlC in mixture I and stir for 10 min until homogeneous to obtain mixture II;
[0070] ③ Place mixture II in a polytetrafluoroethylene reactor for hydrothermal reaction at a temperature of 90°C for 72 hours. Allow it to cool naturally to room temperature to obtain reaction product I.
[0071] ④ Wash reaction product I with deionized water and anhydrous ethanol by centrifugation until the pH of the supernatant is higher than 6. Centrifuge multiple times at 8500 rpm to remove the supernatant and obtain the precipitate V2CT. x MXene;
[0072] II. Preparation of TMA-V2CT x :
[0073] ① V2CT x The MXene precipitate was sonicated under nitrogen for 0.5 h and then centrifuged again. The precipitate was then collected for later use.
[0074] ② Prepare a 5 wt.% intercalating agent solution with 5 mL of tetramethylammonium hydroxide (TMAOH) and pour it into the above-mentioned prepared precipitate. Stir well and then transfer it to a polytetrafluoroethylene reactor. Stir at 25 °C for 12 h to obtain mixed solution I.
[0075] ③ Wash the mixed solution I by centrifugation with deionized water and anhydrous ethanol until the pH of the mixed solution is 7. Add an appropriate amount of deionized water again and sonicate under nitrogen atmosphere for 1 h. Centrifuge at 3000 rpm for 15 min, collect the supernatant, and obtain reaction product II.
[0076] ④ Dissolve reaction product II in lithium chloride solution, let stand for 24 h, discard the supernatant, add deionized water and repeatedly centrifuge and wash until the supernatant turns black. After thorough mixing, sonicate for 30 min, centrifuge, collect the supernatant to obtain TMA-V2CT. x ;
[0077] III. Preparation of TMA-V2CT x / NSS:
[0078] ① Add nickel nitrate hexahydrate, tin chloride pentahydrate and glycerol to isopropanol and stir until homogeneous to obtain mixture III;
[0079] In step 3①, the molar ratio of nickel nitrate hexahydrate to tin chloride pentahydrate is 14:1; the volume ratio of isopropanol to glycerol is 2.5:1; and the mass ratio of tin chloride pentahydrate to isopropanol is 1.9 mg:1 mL.
[0080] ② The mixture Ⅲ was transferred to a polytetrafluoroethylene reactor for hydrothermal reaction at 160 °C for 1.5 h. After naturally cooling to room temperature, the reaction product was washed several times with anhydrous ethanol and then dried under vacuum at 60 °C for 12 h to obtain reaction product Ⅲ, which was named NiSn-glycerate.
[0081] ③ Dissolve sodium sulfide nonahydrate in deionized water and stir for 10 min until homogeneous to obtain mixture IV;
[0082] The mass concentration of sodium sulfide nonahydrate mentioned in step 3③ is 2 mg / mL. -1 ;
[0083] ④ Add 1 mL of TMA-V2CT x The solution was added to mixture IV and stirred until homogeneous to obtain mixture V;
[0084] The TMA-V2CT described in steps three and four x The concentration is 4 mg / mL -1 ;
[0085] ⑤ Add reaction product III to mixture V, stir for 30 min, then put it into a polytetrafluoroethylene reactor for hydrothermal reaction at 130 ℃ for 6 h. After naturally cooling to room temperature, reaction product IV is obtained.
[0086] ⑥ Wash reaction product IV repeatedly with deionized water and dry it at 60 °C for 12 h to obtain powder sample TMA-V2CT. x / NSS, which stands for TMA-V2CT x / NSS composite material.
[0087] Example 2: The difference between this example and Example 1 is that TMA-V2CT was not added in step three. x In step three (⑤), mixture IV is mixed with reaction product III, wherein the mass ratio of reaction product III (NiSn-glycerate) to sodium sulfide nonahydrate is 2:1. Other steps and parameters are the same as in step three of Example 1.
[0088] The product obtained in Example 2 was NSS (NiSn-LDH / Ni7S6).
[0089] This experiment used a three-electrode system: the electrolyte solution was a 6 M potassium hydroxide solution, the counter electrode was a platinum electrode, the reference electrode was a mercury / mercury oxide electrode, and the working electrodes were TMA-V2CT. x / NSS, TMA-V2CT x 、NSS.
[0090] Figure 1 TMA-V2CT prepared for Example 1 x Scanning electron microscope image of / NSS;
[0091] like Figure 1 As shown, the prepared TMA-V2CT x The structure of / NSS observed under scanning electron microscopy consists of a large number of NSS nanoparticles distributed in TMA-V2CT. x On the interlayer and surface, a layered structure is formed, which can effectively prevent TMA-V2CT. x The structure effectively mitigates the collapse and accumulation of the layers and also alleviates the problems of self-structural pulverization and agglomeration of NSS nanoparticles during redox reactions, enabling more direct ion transport with the electrolyte. Therefore, the composite sandwich structure enhances structural stability to a certain extent and provides a larger contact area with the electrolyte, achieving a synergistic effect.
[0092] Figure 2 TMA-V2CT prepared for Examples 1-2 x Comparison of cyclic voltammetry curves of NSS and NSS at the same scan rate;
[0093] like Figure 2 As shown, this is TMA-V2CT. xThe cyclic voltammetry curves of / NSS and NSS at the same scan rate; the voltage test range of the cyclic voltammetry is 0-0.6 V; from Figure 2 It can be observed that for both samples, a pair of distinct Faraday redox peaks are visible, with relatively large potential separation, exhibiting typical battery-type electrochemical energy storage behavior. Compared to NSS, TMA-V2CT... x / NSS has the largest redox current and closing area, indicating that TMA-V2CT x / NSS has the best electrochemical performance.
[0094] Figure 3 TMA-V2CT prepared for Examples 1-2 x Comparison of constant current charging and discharging of / NSS and NSS at the same current density;
[0095] like Figure 3 As shown, this is TMA-V2CT. x / NSS, NSS in 1 A g -1 Charge-discharge performance test curves under current density; the voltage test window for constant current charge-discharge is 0-0.5 V; from Figure 3 It can be seen from this that: TMA-V2CT x The discharge time of / NSS is longer than that of NSS, meaning its electrode specific capacity is larger. According to the formula Cs = I × ∆t / m × V(F g) -1 ) Calculation, TMA-V2CT x / NSS in 1 A g -1 The specific capacitance at that time was 1805.2 F g. -1 However, at the same current density, the specific capacitance of NSS is only 1507.2 F g. -1 .
[0096] Figure 4 TMA-V2CT prepared for Examples 1-2 x Impedance comparison diagram of NSS and NSS;
[0097] from Figure 4 It can be seen that in the high-frequency region, TMA-V2CT x The arc diameter of the / NSS composite material is significantly smaller than that of NSS, indicating that TMA-V2CT x The / NSS composite material exhibits low charge transfer resistance. Furthermore, the Nyquist plot shows that TMA-V2CT... x The / NSS electrode exhibits an approximately linear slope in the low-frequency region, indicating that the composite material has better capacitive behavior than the NSS electrode.
[0098] Figure 5TMA-V2CT prepared for Examples 1-2 x Comparison of capacitance retention rates of / NSS and NSS under different current densities;
[0099] from Figure 5 It can be seen that: TMA-V2CT x / NSS maintains a capacitance retention of 63% even at high current densities, a significant improvement compared to NSS's 46.2% rate performance. This indicates that MXene's larger specific surface area accelerates ion transport in the electrolyte, enhancing the material's rate performance.
[0100] Figure 6 TMA-V2CT prepared for Example 1 x / CV curves of NSS at different scan rates;
[0101] from Figure 6 It can be seen that as the scan rate increases, due to the influence of polarization effect, TMA-V2CT... x The anodic and cathodic peaks of / NSS shifted in the positive and negative directions, respectively. As the scan rate increased, the shape of the CV curve remained largely consistent, without significant changes, indicating that TMA-V2CT... x The / NSS electrode material maintains stable electrochemical properties at different scan rates.
[0102] Figure 7 TMA-V2CT prepared for Example 1 x / NSS constant current charging and discharging diagrams at different current densities;
[0103] from Figure 7 TMA-V2CT can be seen from x / NSS in 1-10 A g -1 The GCD curves at different current densities are all nonlinear, exhibiting a clear charge-discharge plateau, and possessing the characteristic current density of 1 A g for typical battery-type materials. -1 At this point, the specific capacitance is at its maximum, reaching 1805.2 F g. -1 .
[0104] In summary: The TMA-V2CT prepared in Example 1 x / NSS composite materials have high capacitor performance and excellent stability, and can be used as active materials for supercapacitors.
Claims
1. A TMA-V2C x Method for the preparation of TMA-V2C A TMA-V2CT x The method for preparing the / NSS composite material is accomplished in the following steps: I. Preparation of V2CT x MXene: ①, the lithium fluoride is dissolved in hydrochloric acid, stirring, to obtain a mixture I; ②, V2AlC is dissolved in mixture I, stirring, to obtain mixture II; ③, the mixture II is placed in a polytetrafluoroethylene reactor for hydrothermal reaction, after the reaction is completed, the natural cooling to room temperature, to obtain the reaction product I; IV. Centrifuging and washing the reaction product I with deionized water and anhydrous ethanol until the pH value of the supernatant is higher than 6, removing the supernatant, and obtaining the precipitate V2CT x MXene; II. Preparation of TMA-V2CT x : ①, V2CT x MXene precipitate was ultrasonically dispersed under a nitrogen atmosphere, and after centrifugation again, precipitate I was obtained; ②, the precipitate I is added to the tetramethylammonium hydroxide solution, stirring, mixing, it is transferred to a polytetrafluoroethylene reactor, 25 ℃ continuous stirring for 12 h, to obtain a mixed solution I; ③, the mixed solution I is centrifuged with deionized water and anhydrous ethanol, until the pH of the mixed solution is 7, again adding a proper amount of deionized water and ultrasonic treatment under nitrogen atmosphere for 1 h, centrifugal separation, take the supernatant, to obtain the reaction product II; IV. The reaction product II is dissolved in a lithium chloride solution, left to stand, the supernatant is decanted, deionized water is added and repeatedly washed by centrifugation until the supernatant is black. After thorough shaking, the supernatant is collected by ultrasonic and centrifugal treatment to obtain TMA-V2CT x ; III. Preparation of TMA-V2CT x / NSS: ①, the nickel nitrate hexahydrate, tin chloride pentahydrate and glycerol are added to isopropyl alcohol, stirring, to obtain a mixture III; ②, the mixture III is transferred to a polytetrafluoroethylene reactor for hydrothermal reaction, after the natural cooling to room temperature, the reaction product is washed with anhydrous ethanol for several times and vacuum dried, to obtain the reaction product III; ③, the sodium sulfide nonahydrate is dissolved in deionized water, stirring, to obtain a mixture IV; IV. adding TMA-V2CT to mixture III x solution to mixture IV, and stirring to obtain mixture V; ⑤, the reaction product III is added to the mixture V, stirring, it is loaded into a polytetrafluoroethylene reactor for hydrothermal reaction, after the natural cooling to room temperature, to obtain the reaction product IV; ⑥, the reaction product IV is repeatedly washed with deionized water, and dried at 60 °C for 12 h to obtain a powder sample TMA-V2CT x / NSS, i.e. TMA-V2CT x / NSS composite material.
2. A TMA-V2C according to claim 1 x Process for the production of / NSS composite materials, characterized in that The mass concentration of the tetramethylammonium hydroxide solution in step two ② is 5 wt.%.
3. A TMA-V2C according to claim 1 x Process for the production of / NSS composite materials, characterized in that The molar ratio of the nickel nitrate hexahydrate and the tin chloride pentahydrate in step three ① is 14:1; the volume ratio of the isopropyl alcohol and the glycerol is 2.5:1; the mass of the tin chloride pentahydrate to the volume of the isopropyl alcohol is 1.9 mg:1 mL.
4. A TMA-V2C according to claim 1 x Process for the production of / NSS composite materials, characterized in that The temperature of the hydrothermal reaction in step three ② is 160 ℃, and the time of the hydrothermal reaction is 12 h.
5. A TMA-V2C according to claim 1 x Method for the production of / NSS composite materials, characterized in that The mass concentration of the nine water sodium sulfide described in step three ③ is 2 mg mL -1 .
6. A TMA-V2C according to claim 1 x Method for the production of / NSS composite materials, characterized in that The TMA-V2CT added in step three (iv) as described above x at a concentration of 4 mg mL -1 .
7. A TMA-V2C according to claim 1 x Process for the production of / NSS composite materials, characterized in that The mass of the reaction product III in step three (v) and the volume of TMA-V2CT x were 100 mg: 1 mL, the reaction temperature was 130 °C, and the time was 6 h.
8. A TMA-V2C according to claim 1 x Method for the production of / NSS composite materials, characterized in that A TMA-V2CT x / NSS composites as electrode materials for supercapacitors.