A bamboo fiber supported nickel-cobalt bimetallic sulfide intercalated max film flexible electrode and a preparation method and application thereof

Abstract

The application discloses a kind of bamboo fiber support nickel cobalt double metal sulfide intercalation MAX film flexible electrode and its preparation method and application, the bamboo fiber support nickel cobalt double metal sulfide intercalation MAX film flexible electrode includes substrate, reinforcing material, layered Mxene material, metal sulfide doped material and anchoring material, the metal sulfide doped material growth in layered Mxene material interlayer forms MAX material, the reinforcing material and MAX material are loaded on substrate by anchoring material polypyrrole.The metal sulfide doped material of the present application grows in layered Mxene material interlayer, which not only can effectively prevent the aggregation of Mxene, increase its active site on surface, polypyrrole as conductive polymer also has certain energy storage function, intercalation and assembly together can play respective advantages, can play the role of synergistic energy storage, can greatly improve the electrochemical performance of flexible electrode.

Description

Technical Field

[0001] This invention relates to the field of new energy supercapacitor technology, and in particular to a bamboo fiber supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode, its preparation method and application. Background Technology

[0002] With the emergence of wearable electronic devices, the demand for high-performance energy storage devices is increasing. Compared to traditional rechargeable batteries and parallel-plate capacitors, new high-performance energy storage devices need to possess high energy density, high power density, and long cycle life, while also being flexible and deformable. Therefore, wearable energy storage devices with small size and flexibility have become a research hotspot.

[0003] Traditional flexible supercapacitor electrodes often use carbon fiber and metal as substrates, which have limitations in terms of environmental protection and sustainability. China is the world's richest country in bamboo resources, with enormous varieties, planting areas, and stock volumes. In recent years, bamboo-based composite materials and their derivatives, as a renewable resource, have emerged in the application research of flexible supercapacitors. Meanwhile, bamboo fiber is inexpensive, environmentally friendly, and highly flexible, making it a good substrate support material. Mxene (Ti3C2T) x As a novel electrode energy storage material, it possesses excellent conductivity, surface hydrophilicity, electrochemical stability, and the ability to store cations (such as H+). + Li + Na + K + The reversible embedding of Mxene (etc.) and its good mechanical flexibility make it an ideal 2D support matrix with great potential in electrochemical energy storage systems. However, the interlayer stacking of Mxene is prone to affect its electrochemical performance.

[0004] Meanwhile, transition metal sulfides (TMS), particularly nickel sulfide, have attracted considerable attention due to their excellent conductivity (approximately two orders of magnitude higher than that of oxides) and relatively high theoretical specific capacity. They can store charge through reversible, rapid redox reactions on their surfaces. However, their electrochemical performance is poor due to surface Faraday redox reactions and unfavorable reaction kinetics during rapid charge-discharge processes. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide a flexible electrode with good flexibility and excellent electrochemical performance, which is supported by bamboo fiber and has nickel-cobalt bimetallic sulfide intercalation MAX film. At the same time, the present invention also provides a method for preparing and applying the flexible electrode with bamboo fiber supported by nickel-cobalt bimetallic sulfide intercalation MAX film.

[0006] To solve the above-mentioned technical problems, the present invention adopts the following technical solution: A flexible electrode with bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalation MAX thin film includes a substrate, a reinforcing material, a layered Mxene material, a metal sulfide doped material, and an anchoring material. The metal sulfide doped material is grown between the layers of the layered Mxene material to form the MAX material. The Mxene material is Ti3C2T. x The MAX material is NiCoS x -Ti3C2T x The reinforcing material and NiCoS x -Ti3C2T x The membrane is anchored to a substrate, which is a bamboo fiber membrane, and the reinforcing material is bamboo fiber. The metal sulfide doping material is NiCoS. x The anchoring material is polypyrrole.

[0007] As a general inventive concept, this invention provides a method for preparing a bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode, comprising the following steps: S1. Disperse the layered MXene powder in a precursor solution containing metal ions, and carry out a hydrothermal reaction at 110-150℃ for 10-20 hours to allow the metal ions to insert into the layers of the MXene powder. After cooling and drying, obtain MAX powder. The precursor solution is a mixed solution containing nickel salt, cobalt salt, thioacetamide and an active agent, and the MXene powder is Ti3C2T. x The powder, wherein the MAX powder is NiCoS x -Ti3C2T x ; S2. Disperse MAX powder in a bamboo fiber solution to obtain a suspension, wherein the bamboo fiber solution is a mixed solution of bamboo fiber and pyrrole ethanol; S3. Using a bamboo fiber membrane impregnated with pyrrole ethanol solution as filter paper and a suspension as filtrate, MAX powder and bamboo fiber are filtered onto the filter paper to obtain a thin film. S4. Place the film at a temperature of 120-150℃ to polymerize pyrrole into polypyrrole. After drying, a bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode is obtained.

[0008] As a further improvement to the above technical solution: In step S1, the MXene powder is prepared by the following steps: immersing Ti3AlC2 powder in a mixture of LiF and HCl to etch out Al. 3+ The MXene powder was obtained by washing, centrifuging, and drying.

[0009] In step S1, the mass ratio of nickel salt, cobalt salt, and thioacetamide in the precursor solution is 1:1:1-3.

[0010] In step S1, the nickel salt is NiCl26H2O, the cobalt salt is CoCl26H2O, and the activator is hexadecyltrimethylammonium bromide.

[0011] In step S1, the mass of the MXene powder is equal to the sum of the masses of the nickel salt, cobalt salt, and thioacetamide in the precursor solution.

[0012] In step S1, the hydrothermal reaction takes 8-24 hours.

[0013] In step S2, the mass ratio of the MAX powder to the bamboo fiber in the bamboo fiber solution is 0.5-2:0.5.

[0014] In step S2, the length of the bamboo fiber is <20 mm.

[0015] As a general inventive concept, the present invention also provides an application of the aforementioned bamboo fiber supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode or the bamboo fiber supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode prepared by the aforementioned method in a flexible supercapacitor.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention discloses a bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode (hereinafter referred to as bamboo-based flexible electrode), which uses a bamboo fiber film as a substrate and bamboo fiber as a reinforcing material. The metal sulfide dopant material is grown between the layers of the layered MAX material to form NiCoS. x -Ti3C2T x Metal sulfide doped materials (NiCoS) x ) grows on layered Mxene (Ti3C2T) x The layered structure of the material not only effectively prevents the aggregation of MXene and increases the number of metal ion sites on its surface, but also forms a stable "layered" structure to increase toughness. The three-dimensional network structure with MXene as the conductive matrix facilitates ultrafast electron transport, provides a larger contact area with the electrolyte, and accelerates ion diffusion, enabling bamboo-based flexible electrodes to exhibit excellent mechanical flexibility and electrochemical performance. Layered Ti3C2T x Metal sulfides (NiCoS) xBamboo fiber exhibits high specific capacitance, and polypyrrole (PPy), as a conductive polymer, also possesses certain energy storage capabilities. Therefore, intercalation and assembly of these materials can leverage their respective advantages to achieve synergistic energy storage, significantly improving the electrochemical performance of flexible electrodes. Furthermore, bamboo fiber membranes, as flexible substrates, benefit from the coating and anchoring of polypyrrole. This not only enhances the flexibility of bamboo and reduces electrolyte corrosion but, more importantly, can replace metal current collectors, offering significant advantages in cost reduction and environmental protection.

[0017] This invention discloses a method for fabricating a bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode, based on Mxene powder (Ti3C2T). x Theoretically, it has the advantages of high specific capacitance and large specific surface area. First, a hydrothermal method is used to process metal sulfides (NiCoS...). x Insert Ti3C2T x To prevent interlayer stacking and obtain MAX powder (NiCoS) x -Ti3C2T x At the same time, taking full advantage of the good flexibility and high specific strength of bamboo fiber, it is doped into NiCoS. x -Ti3C2T x The membrane serves as a supporting framework to enhance electrode flexibility. Due to the poor conductivity of bamboo fiber, using a bamboo fiber membrane impregnated with pyrrole ethanol solution as filter paper and a suspension as the filtrate, followed by filtration and placing the membrane in a pyrrole-containing container to form polypyrrole, not only improves conductivity but, more importantly, allows the bamboo fiber, bamboo fiber membrane, and NiCoS to be integrated. x -Ti3C2T x They are anchored together to prevent delamination and detachment. Attached Figure Description

[0018] Figure 1 These are electron microscope images and physical images of the bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode of Embodiment 1 of the present invention. Figure 1 (a) and Figure 1 (b) is a two-dimensional photograph. Figure 1 (c) is a photograph of the end face. Figure 1 (d) NiCoS x -Ti3C2T x @BF is a photo of a bent image.

[0019] Figure 2 The images show the TEM, mapping, and lattice diagram of the bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode of Embodiment 1 of the present invention. Figure 2 (a) and Figure 2 (b) is a TEM image. Figure 2 (c) shows the mapping photos of different elements. Figure 2(d) is a lattice photograph.

[0020] Figure 3 This is an electrochemical performance curve of the bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode of Embodiment 1 of the present invention. Figure 3 (a) shows the CV curves at different scan rates. Figure 3 (b) shows the GCD curves at different scan rates. Figure 3 (c) shows the specific capacitance plots under different current densities. Figure 3 (d) is the AC impedance diagram. Figure 3 (e) is a graph showing the cycle performance and coulomb efficiency.

[0021] Figure 4 These are the Ti3C2T samples from various embodiments and comparative examples of the present invention. x Electron micrographs of powder or MAX powder. Figure 4 (a) is Ti3C2T for Comparative Example 1 x Powder, Figure 4 (b) is the MAX powder of Comparative Example 2. Figure 4 (c) is the MAX powder of Example 2. Detailed Implementation

[0022] The present invention will be further described in detail below. Unless otherwise specified, the instruments or materials used in the present invention are commercially available.

[0023] Example 1 A flexible electrode with bamboo fiber supported nickel-cobalt bimetallic sulfide intercalation MAX film according to this embodiment uses bamboo fiber film as substrate and bamboo fiber as reinforcing material. The metal doping material includes multiple layered Ti3C2T x and NiCoS located between the lamellar structures x NiCoS x Grown in Mxene (Ti3C2T) x (between layers)

[0024] The bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode of the present invention is a multilayer film: Ti3C2T x It has a layered structure, NiCoS x -Ti3C2T x It is in the Ti3C2T layer x NiCoS was inserted x The layered structure of the substrate bamboo fiber membrane is also a membrane structure, which is of great significance for improving the flexibility and service life of the electrode.

[0025] A method for fabricating a bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode according to this embodiment includes the following steps: 1) Ti3AlC2 powder was soaked in a mixed solution of LiF and HCl at a concentration of 2 mol / L (LiF and HCl were both 2 mol / L, mixed in a 1:1 mass ratio), dispersed at high speed for 48 hours, then washed with distilled water until neutral, centrifuged, and dried to obtain lamellar Ti3C2T x Powder.

[0026] 2) Weigh NiCl26H2O, CoCl26H2O and CH4N2S (thioacetamide) in a mass ratio of 1:1:3, mix them evenly to prepare a mixed solution, and add hexadecyltrimethylammonium bromide (1% of the mass of NiCl26H2O) to obtain a precursor solution.

[0027] 3) Place the precursor solution into a reaction vessel lined with polytetrafluoroethylene, and add Ti3C2T with a mass equal to the sum of the masses of NiCl26H2O, CoCl26H2O, and CH4N2S. x The powder was ultrasonically dispersed for 2 hours. Then, it was kept at 120 °C for 10 hours, and after natural cooling and drying, Ni and Co sulfide-doped MAX powder (NiCoS) was obtained. x -Ti3C2T x ).

[0028] 4) Disperse 0.5 g of bamboo fiber (length < 20 mm) ultrasonically in 100 mL of a 5% pyrrole (Py) ethanol solution. After the solution has fully permeated the bamboo fiber, add 0.5 g of NiCoS. x -Ti3C2T x The powder was ultrasonically dispersed for 2 hours to obtain NiCoS. x -Ti3C2T x - Bamboo fiber suspension.

[0029] 5) Using bamboo fiber membranes impregnated with pyrrole ethanol solution as filter paper, NiCoS x -Ti3C2T x - The bamboo fiber suspension is used as the filtrate, and NiCoS x -Ti3C2T x Bamboo fiber is evenly filtered onto filter paper and assembled into a membrane.

[0030] 6) The above membrane was sealed in a sealing bag and heated at 120 °C for 20 min to polymerize pyrrole (Py) into polypyrrole (Ppy). After drying, a bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode (NiCoS) was obtained. x -Ti3C2Tx @BF flexible electrode).

[0031] Figure 1 These are electron microscope images and physical images of the bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode of Embodiment 1 of the present invention. Figure 1 As can be seen from the SEM images and magnified views in (a) and (b), bamboo fibers are coated with NiCoS. x -Ti3C2T x It covers, but also provides support, thus forming a flexible electrode film. Figure 1 (c) shows the end face of the flexible electrode, from which NiCoS can be seen. x -Ti3C2T x Intertwined with each other. Figure 1 (d) is NiCoS x -Ti3C2T x The large-angle bending photo of the @BF flexible electrode shows that the electrode has good flexibility.

[0032] Figure 2 This is the bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode (NiCoS) of Embodiment 1 of the present invention. x -Ti3C2T x TEM, mapping, and lattice diagram of @BF. Figure 2 As can be seen from the TEM images (a) and (b), NiCoS x -Ti3C2T x @BF exhibits a porous structure. Figure 2 The mapping image in (c) shows that Ti, Ni, S, Co and other elements are evenly distributed, indicating that NiCoS x Doping successful. Figure 2 The lattice and selected area electron diffraction patterns in (d) further demonstrate that NiCoS x The existence of.

[0033] Figure 3 This is an electrochemical performance diagram of the bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode of Example 1 of the present invention. Figure 3 (a) shows the CV curves of the composite membrane at different scan rates. It has an approximately rectangular shape with a large closed area, indicating good reversibility and ion response capacitance behavior, and the double layer capacitance dominates in neutral electrolyte. Figure 3 (b) is the charge-discharge curve, which is an isosceles triangle, indicating good charge-discharge reversibility. Figure 3(c) shows the specific capacitance variation at different current densities. As can be seen from the figure, the specific capacitance decreases with increasing current density, but even at a current density of 10 A / g, the specific capacitance still exceeds 200 F / g. This indicates that the electrode liquid has good specific capacitance even at higher current densities. Figure 3 (d) is the EIS spectrum. The curves show a parabola and a vertical line in the high and low frequency regions, respectively, indicating that it has good capacitance performance. Figure 3 (e) shows the cyclic stability and coulombic efficiency of the electrode. After 3000 cycles at a current density of 10 A / g, the specific capacitance is retained at 87.23%, while the coulombic efficiency hardly decays, indicating that the electrode has good stability.

[0034] The NiCoS prepared in this embodiment x -Ti3C2T x A three-electrode system was constructed using a BF flexible electrode as the working electrode, a platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. The electrochemical performance of the composite membrane electrode was tested using 2M NaCl as the electrolyte. At 1 A / g, NiCoS… x -Ti3C2T x The specific capacitance of the @BF flexible electrode is 363.5 F / g.

[0035] Comparative Example 1 (without interpolation) A method for preparing the bamboo fiber flexible electrode of this comparative example includes the following steps: 1) Ti3AlC2 powder was soaked in a mixed solution of LiF and HCl at a concentration of 2 mol / L (LiF and HCl were both 2 mol / L, mixed in a 1:1 mass ratio), dispersed at high speed for 48 hours, then washed with distilled water until neutral, centrifuged, and dried to obtain lamellar Ti3C2T x Powder.

[0036] 2) Disperse 0.5 g of bamboo fiber (length < 20 mm) ultrasonically in 100 mL of 5% pyrrole (Py) ethanol solution. After the solution has fully permeated the bamboo fiber, add 0.5 g of Ti3C2T. x Powder was ultrasonically dispersed for 2 hours to obtain Ti3C2T x - Bamboo fiber suspension.

[0037] 3) Using bamboo fiber membranes impregnated with pyrrole ethanol solution as filter paper, Ti3C2T x - The bamboo fiber suspension is used as the filtrate, and Ti3C2T x Bamboo fiber is evenly filtered onto filter paper and assembled into a membrane.

[0038] 4) The above membrane was sealed in a sealing bag and heated at 120 °C for 20 min to polymerize Py into PPy. After drying, bamboo fiber flexible electrode (Ti3C2T) was obtained. x @BF flexible electrode).

[0039] The Ti3C2T prepared in this comparative example x A three-electrode system was constructed using a BF flexible electrode as the working electrode, a platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. The electrochemical performance of the composite membrane electrode was tested using 2M NaCl as the electrolyte. At 1 A / g, Ti3C2T… x The specific capacitance of the @BF flexible electrode is 183.5 F / g.

[0040] Comparative Example 2 (Intercalation not ideal) A method for preparing the bamboo fiber flexible electrode of this comparative example includes the following steps: 1) Ti3AlC2 powder was soaked in a mixed solution of LiF and HCl at a concentration of 2 mol / L (LiF and HCl were both 2 mol / L, mixed in a 1:1 mass ratio), dispersed at high speed for 48 hours, then washed with distilled water until neutral, centrifuged, and dried to obtain lamellar Ti3C2T x Powder.

[0041] 2) Weigh NiCl26H2O, CoCl26H2O and CH4N2S (thioacetamide) in a mass ratio of 1:1:3, mix them evenly to prepare a mixed solution of a certain concentration, and add hexadecyltrimethylammonium bromide (1% of the mass of NiCl26H2O) to obtain the precursor solution.

[0042] 3) Place the precursor solution into a reaction vessel lined with polytetrafluoroethylene, and add Ti3C2T with a mass equal to the sum of the masses of NiCl26H2O, CoCl26H2O, and CH4N2S. x The powder was ultrasonically dispersed for 2 hours. Then, it was kept at 100 °C for 6 hours, and after natural cooling and drying, Ni-Co sulfide-doped MAX powder (NiCoS) was obtained. x -Ti3C2T x ).

[0043] 4) Disperse 0.5 g of bamboo fiber (length < 20 mm) ultrasonically in 100 mL of a 5% pyrrole (Py) ethanol solution. After the solution has fully permeated the bamboo fiber, add 0.5 g of NiCoS. x -Ti3C2T x The powder was ultrasonically dispersed for 2 hours to obtain NiCoS. x -Ti3C2T x- Bamboo fiber suspension.

[0044] 5) Using bamboo fiber membranes impregnated with pyrrole ethanol solution as filter paper, NiCoS x -Ti3C2T x - The bamboo fiber suspension is used as the filtrate, and NiCoS x -Ti3C2T x Bamboo fiber is evenly filtered onto filter paper and assembled into a membrane.

[0045] 6) The above membrane was sealed in a sealing bag and heated at 120 °C for 20 min to polymerize Py into PPy. After drying, a bamboo fiber flexible electrode (NiCoS) was obtained. x -Ti3C2T x @BF flexible electrode).

[0046] NiCoS in this comparative example x -Ti3C2T x A three-electrode system was constructed using a BF flexible electrode as the working electrode, a platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. The electrochemical performance of the composite membrane electrode was tested using 2M NaCl as the electrolyte. At 1 A / g, NiCoS… x -Ti3C2T x The specific capacitance of the @BF flexible electrode is 253.3 F / g. After 5000 cycles, the specific capacitance retention rate is 83.5%.

[0047] Comparative Example 3 (without pyrrole anchoring) A method for preparing the bamboo fiber flexible electrode of this comparative example includes the following steps: 1) Ti3AlC2 powder was soaked in a mixed solution of LiF and HCl at a concentration of 2 mol / L (LiF and HCl were both 2 mol / L, mixed in a 1:1 mass ratio), dispersed at high speed for 48 hours, then washed with distilled water until neutral, centrifuged, and dried to obtain lamellar Ti3C2T x Powder.

[0048] 2) Weigh NiCl26H2O, CoCl26H2O and CH4N2S (thioacetamide) in a mass ratio of 1:1:3, mix them evenly to prepare a mixed solution of a certain concentration, and add hexadecyltrimethylammonium bromide (1% of the mass of NiCl26H2O) to obtain the precursor solution.

[0049] 3) Place the precursor solution into a reaction vessel lined with polytetrafluoroethylene, and add Ti3C2T with a mass equal to the sum of the masses of NiCl26H2O, CoCl26H2O, and CH4N2S. xThe powder was ultrasonically dispersed for 2 hours. Then, it was kept at 120 °C for 10 hours, and after natural cooling and drying, Ni and Co sulfide-doped MAX powder (NiCoS) was obtained. x -Ti3C2T x ).

[0050] 4) Disperse 0.5 g of bamboo fiber (length < 20 mm) ultrasonically in 100 mL of a 5% pyrrole (Py) ethanol solution. After the solution has fully permeated the bamboo fiber, add 0.5 g of NiCoS. x -Ti3C2T x The powder was ultrasonically dispersed for 2 hours to obtain NiCoS. x -Ti3C2T x - Bamboo fiber suspension.

[0051] 5) Using bamboo fiber membrane (unimpregnated with pyrrole ethanol solution) as filter paper, NiCoS x -Ti3C2T x - The bamboo fiber suspension is used as the filtrate, and NiCoS x -Ti3C2T x Bamboo fiber is evenly filtered onto filter paper and assembled into a membrane.

[0052] 6) After drying the above membrane, a bamboo fiber flexible electrode (NiCoS) is obtained. x -Ti3C2T x @BF flexible electrode).

[0053] With NiCoS x -Ti3C2T x A three-electrode system was constructed using a BF flexible electrode as the working electrode, a platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. The electrochemical performance of the composite membrane electrode was tested using 2M NaCl as the electrolyte. At 1 A / g, NiCoS… x -Ti3C2T x The specific capacitance of the @BF flexible electrode is 283.7 F / g. After 200 charge-discharge cycles, the specific capacitance is 173.9 F / g, a decrease of 38.7%.

[0054] Example 2 A method for fabricating a bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode according to this embodiment includes the following steps: 1) Ti3AlC2 powder was soaked in a mixed solution of LiF and HCl at a concentration of 2 mol / L (LiF and HCl were both 2 mol / L, mixed in a 1:1 mass ratio), dispersed at high speed for 48 hours, then washed with distilled water until neutral, centrifuged, and dried to obtain lamellar Ti3C2T x Powder.

[0055] 2) Weigh NiCl26H2O, CoCl26H2O and CH4N2S (thioacetamide) in a mass ratio of 1:1:2.5, mix them evenly to prepare a mixed solution of a certain concentration, and add hexadecyltrimethylammonium bromide (1% of the mass of NiCl26H2O) to obtain the precursor solution.

[0056] 3) Place the precursor solution into a reaction vessel lined with polytetrafluoroethylene, and add Ti3C2T with a mass equal to the sum of the masses of NiCl26H2O, CoCl26H2O, and CH4N2S. x The powder was ultrasonically dispersed for 2 hours. Then, it was kept at 110 °C for 10 hours, and after natural cooling and drying, Ni and Co sulfide-doped MAX powder (NiCoS) was obtained. x -Ti3C2T x ).

[0057] 4) Disperse 0.5 g of bamboo fiber (length < 20 mm) ultrasonically in 100 mL of 8% pyrrole (Py) ethanol solution. After the solution has fully permeated the bamboo fiber, add 2.0 g of NiCoS. x -Ti3C2T x The powder was ultrasonically dispersed for 2 hours to obtain NiCoS. x -Ti3C2T x - Bamboo fiber suspension.

[0058] 5) Using bamboo fiber membranes impregnated with pyrrole ethanol solution as filter paper, NiCoS x -Ti3C2T x - The bamboo fiber suspension is used as the filtrate, and NiCoS x -Ti3C2T x Bamboo fiber is evenly filtered onto filter paper and assembled into a membrane.

[0059] 6) The above membrane was sealed in a sealing bag and heated at 120 °C for 20 min to polymerize Py into PPy. After drying, a bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode (NiCoS) was obtained. x -Ti3C2T x @BF flexible electrode).

[0060] With NiCoS x -Ti3C2T x A three-electrode system was constructed using a BF flexible electrode as the working electrode, a platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. The electrochemical performance of the composite membrane electrode was tested using 2M NaCl as the electrolyte. At 1 A / g, NiCoS… x -Ti3C2Tx The specific capacitance of the @BF flexible electrode is 423.7 F / g.

[0061] Example 3 A method for fabricating a bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode according to this embodiment includes the following steps: 1) Ti3AlC2 powder was soaked in a mixed solution of LiF and HCl at a concentration of 2 mol / L (LiF and HCl were both 2 mol / L, mixed in a 1:1 mass ratio), dispersed at high speed for 48 hours, then washed with distilled water until neutral, centrifuged, and dried to obtain lamellar Ti3C2T x Powder.

[0062] 2) Weigh NiCl26H2O, CoCl26H2O and CH4N2S (thioacetamide) in a mass ratio of 1:1:2.5, mix them evenly to prepare a mixed solution of a certain concentration, and add hexadecyltrimethylammonium bromide (1% of the mass of NiCl26H2O) to obtain the precursor solution.

[0063] 3) Place the precursor solution into a reaction vessel lined with polytetrafluoroethylene, and add Ti3C2T with a mass equal to the sum of the masses of NiCl26H2O, CoCl26H2O, and CH4N2S. x The powder was ultrasonically dispersed for 2 hours. Then, it was kept at 110 °C for 10 hours, and after natural cooling and drying, Ni and Co sulfide-doped MAX powder (NiCoS) was obtained. x -Ti3C2T x ).

[0064] 4) Disperse 0.5 g of bamboo fiber (length < 20 mm) ultrasonically in 100 mL of 8% pyrrole (Py) ethanol solution. After the solution has fully permeated the bamboo fiber, add 2.0 g of NiCoS. x -Ti3C2T x The powder was ultrasonically dispersed for 2 hours to obtain NiCoS. x -Ti3C2T x - Bamboo fiber suspension.

[0065] 5) Using bamboo fiber membranes impregnated with pyrrole ethanol solution as filter paper, NiCoS x -Ti3C2T x - The bamboo fiber suspension is used as the filtrate, and NiCoS x -Ti3C2T x Bamboo fiber is evenly filtered onto filter paper and assembled into a membrane.

[0066] 6) The above membrane was sealed in a sealing bag and heated at 120 °C for 20 min to polymerize Py into PPy. After drying, a bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode (NiCoS) was obtained. x -Ti3C2T x @BF flexible electrode).

[0067] With bent NiCoS x -Ti3C2T x A three-electrode system was constructed using a BF flexible electrode as the working electrode, a platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. The electrochemical performance of the composite membrane electrode was tested using 2M NaCl as the electrolyte. At 1 A / g, NiCoS… x -Ti3C2T x The specific capacitance of the @BF flexible electrode at bending angles of 60°, 90°, and 120° are 418.3 F / g, 415.7 F / g, and 413.9 F / g, respectively.

[0068] Example 4 A method for fabricating a bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode according to this embodiment includes the following steps: 1) Ti3AlC2 powder was soaked in a mixed solution of LiF and HCl at a concentration of 2 mol / L (LiF and HCl were both 2 mol / L, mixed in a 1:1 mass ratio), dispersed at high speed for 48 hours, then washed with distilled water until neutral, centrifuged, and dried to obtain lamellar Ti3C2T x Powder.

[0069] 2) Weigh NiCl26H2O, CoCl26H2O and CH4N2S (thioacetamide) in a mass ratio of 1:1:3, mix them evenly to prepare a mixed solution of a certain concentration, and add hexadecyltrimethylammonium bromide (1% of the mass of NiCl26H2O) to obtain the precursor solution.

[0070] 3) Place the precursor solution into a reaction vessel lined with polytetrafluoroethylene, and add Ti3C2T with a mass equal to the sum of the masses of NiCl26H2O, CoCl26H2O, and CH4N2S. x The powder was ultrasonically dispersed for 2 hours. Then, it was kept at 130 °C for 10 hours, and after natural cooling and drying, Ni-Co sulfide-doped MAX powder (NiCoS) was obtained. x -Ti3C2T x ).

[0071] 4) Disperse 0.5 g of bamboo fiber (length < 20 mm) ultrasonically in 100 mL of a 10% pyrrole (Py) ethanol solution. After the solution has fully permeated the bamboo fiber, add 1.0 g of NiCoS. x -Ti3C2T x The powder was ultrasonically dispersed for 2 hours to obtain NiCoS. x -Ti3C2T x - Bamboo fiber suspension.

[0072] 5) Using bamboo fiber membranes impregnated with pyrrole ethanol solution as filter paper, NiCoS x -Ti3C2T x - The bamboo fiber suspension is used as the filtrate, and NiCoS x -Ti3C2T x Bamboo fiber is evenly filtered onto filter paper and assembled into a membrane.

[0073] 6) The above membrane was sealed in a sealing bag and heated at 120 °C for 20 min to polymerize Py into PPy. After drying, a bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode (NiCoS) was obtained. x -Ti3C2T x @BF flexible electrode).

[0074] With NiCoS x -Ti3C2T x A three-electrode system was constructed using a BF flexible electrode as the working electrode, a platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. The electrochemical performance of the composite membrane electrode was tested using 2M NaCl as the electrolyte. At 2 A / g, NiCoS… x -Ti3C2T x The specific capacitance of the @BF flexible electrode is 387.2 F / g.

[0075] Example 5 A method for fabricating a bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode according to this embodiment includes the following steps: 1) Ti3AlC2 powder was soaked in a mixed solution of LiF and HCl at a concentration of 2 mol / L (LiF and HCl were both 2 mol / L, mixed in a 1:1 mass ratio), dispersed at high speed for 48 hours, then washed with distilled water until neutral, centrifuged, and dried to obtain lamellar Ti3C2T x Powder.

[0076] 2) Weigh NiCl26H2O, CoCl26H2O and CH4N2S (thioacetamide) in a mass ratio of 1:1:3, mix them evenly to prepare a mixed solution of a certain concentration, and add hexadecyltrimethylammonium bromide (1% of the mass of NiCl26H2O) to obtain the precursor solution.

[0077] 3) Place the precursor solution into a reaction vessel lined with polytetrafluoroethylene, and add Ti3C2T with a mass equal to the sum of the masses of NiCl26H2O, CoCl26H2O, and CH4N2S. x The powder was ultrasonically dispersed for 2 hours. Then, it was kept at 120 °C for 10 hours, and after natural cooling and drying, Ni and Co sulfide-doped MAX powder (NiCoS) was obtained. x -Ti3C2T x ).

[0078] 4) Disperse 0.5 g of bamboo fiber (length < 20 mm) ultrasonically in 100 mL of a 5% pyrrole (Py) ethanol solution. After the solution has fully permeated the bamboo fiber, add 0.5 g of NiCoS. x -Ti3C2T x The powder was ultrasonically dispersed for 2 hours to obtain NiCoS. x -Ti3C2T x - Bamboo fiber suspension.

[0079] 5) Using bamboo fiber membranes impregnated with pyrrole ethanol solution as filter paper, NiCoS x -Ti3C2T x - The bamboo fiber suspension is used as the filtrate, and NiCoS x -Ti3C2T x Bamboo fiber is evenly filtered onto filter paper and assembled into a membrane.

[0080] 6) The above membrane was sealed in a sealing bag and heated at 120 °C for 20 min to polymerize Py into PPy. After drying, a bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode (NiCoS) was obtained. x -Ti3C2T x @BF flexible electrode).

[0081] Using NiCoS in this embodiment x -Ti3C2T x A three-electrode system was constructed using a BF flexible electrode as the working electrode, a platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. The electrochemical performance of the composite membrane electrode was tested using 2M NaCl as the electrolyte. At 10 A / g, NiCoS… x -Ti3C2T xThe specific capacitance of the @BF flexible electrode is 217.6 F / g.

[0082] Example 6 A method for fabricating a bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode according to this embodiment includes the following steps: 1) Ti3AlC2 powder was soaked in a mixed solution of LiF and HCl at a concentration of 2 mol / L (LiF and HCl were both 2 mol / L, mixed in a 1:1 mass ratio), dispersed at high speed for 48 hours, then washed with distilled water until neutral, centrifuged, and dried to obtain lamellar Ti3C2T x Powder.

[0083] 2) Weigh NiCl26H2O, CoCl26H2O and CH4N2S (thioacetamide) in a mass ratio of 1:1:1, mix them evenly to prepare a mixed solution of a certain concentration, and add hexadecyltrimethylammonium bromide (1% of the mass of NiCl26H2O) to obtain the precursor solution.

[0084] 3) Place the precursor solution into a reaction vessel lined with polytetrafluoroethylene, and add Ti3C2T with a mass equal to the sum of the masses of NiCl26H2O, CoCl26H2O, and CH4N2S. x The powder was ultrasonically dispersed for 2 hours. Then, it was kept at 120 °C for 10 hours, and after natural cooling and drying, Ni and Co sulfide-doped MAX powder (NiCoS) was obtained. x -Ti3C2T x ).

[0085] 4) Disperse 0.5 g of bamboo fiber (length < 2 mm) ultrasonically in 100 mL of 7% pyrrole (Py) ethanol solution. After the solution has fully permeated the bamboo fiber, add 1.0 g of NiCoS. x -Ti3C2T x The powder was ultrasonically dispersed for 2 hours to obtain NiCoS. x -Ti3C2T x - Bamboo fiber suspension.

[0086] 5) Using bamboo fiber membranes impregnated with pyrrole ethanol solution as filter paper, NiCoS x -Ti3C2T x - The bamboo fiber suspension is used as the filtrate, and NiCoS x -Ti3C2T x Bamboo fiber is evenly filtered onto filter paper and assembled into a membrane.

[0087] 6) The above membrane was sealed in a sealing bag and heated at 120 °C for 20 min to polymerize Py into PPy. After drying, a bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode (NiCoS) was obtained. x -Ti3C2T x @BF flexible electrode).

[0088] Using NiCoS in this embodiment x -Ti3C2T x A three-electrode system was constructed using a BF flexible electrode as the working electrode, a platinum sheet as the counter electrode, and an Ag / AgCl electrode as the reference electrode. The electrochemical performance of the composite membrane electrode was tested using 2M NaCl as the electrolyte. At 5 A / g, NiCoS… x -Ti3C2T x The specific capacitance of the @BF flexible electrode when bent at 90° is 313.7 F / g.

[0089] Figure 4 These are the Ti3C2T samples from various embodiments and comparative examples of the present invention. x Electron micrographs of powder or MAX powder. Figure 4 (a) is Ti3C2T as Comparative Example 1 x Powder, Figure 4 (b) is the MAX powder of Comparative Example 2. Figure 4 (c) is the MAX powder from Example 2. From Figure 4 As can be seen from the comparative example 1 without intercalation treatment, Ti3C2T x Although exhibiting a layered structure, the layers are stacked together; in Comparative Example 2, the intercalation structure of the MAX powder collapses; the MAX powder of Example 2 exhibits a better layered structure with gaps between layers, and petal-shaped NiCoS can be seen in the magnified partial image. x This indicates that the reaction temperature and time are key factors in whether metal sulfides can be successfully inserted into Mxene powder to form stable MAX powder.

[0090] While the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the invention. Any person skilled in the art can make many possible variations and modifications to the technical solutions of the present invention, or modify them into equivalent embodiments, without departing from the scope of the present invention. Therefore, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention, without departing from the scope of the present invention, should fall within the protection scope of the present invention.

Claims

1. A flexible electrode with bamboo fiber supported nickel-cobalt bimetallic sulfide intercalation MAX thin film, characterized in that: The material comprises a substrate, a reinforcing material, a layered Mxene material, a metal sulfide doped material, and an anchoring material. The metal sulfide doped material is grown between the layers of the layered Mxene material to form a MAX material. The Mxene material is Ti3C2T. x The MAX is NiCoS x -Ti3C2T x The reinforcing material and the MAX material are loaded onto a substrate via an anchoring material, wherein the substrate is a bamboo fiber membrane, the reinforcing material is bamboo fiber, and the metal sulfide doping material is NiCoS. x The anchoring material is polypyrrole.

2. A method for preparing a bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode, characterized in that: Includes the following steps: S1. Disperse the layered Mxene powder in a precursor solution containing metal ions, and carry out a hydrothermal reaction at 110-150℃ for 10-20 hours to allow the metal ions to insert into the layers of the Mxene powder. After cooling and drying, obtain MAX powder. The precursor solution is a mixed solution containing nickel salt, cobalt salt, thioacetamide and an active agent, and the Mxene powder is Ti3C2T. x The powder, wherein the MAX powder is NiCoS x -Ti3C2T x ; S2. Disperse MAX powder in a bamboo fiber solution to obtain a suspension, wherein the bamboo fiber solution is a mixed solution of bamboo fiber and pyrrole ethanol; S3. Using a bamboo fiber membrane impregnated with pyrrole ethanol solution as filter paper and a suspension as filtrate, MAX powder and bamboo fiber are filtered onto the filter paper to obtain a thin film. S4. Place the film at a temperature of 120-150℃ to polymerize pyrrole into polypyrrole. After drying, a bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode is obtained.

3. The method for preparing a bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode according to claim 2, characterized in that: In step S1, the MXene powder is prepared by the following steps: immersing Ti3AlC2 powder in a mixture of LiF and HCl to etch out Al. 3+ The mixture was washed, centrifuged, and dried to obtain Mxene powder.

4. The method for preparing a bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode according to claim 2, characterized in that: In step S1, the mass ratio of nickel salt, cobalt salt, and thioacetamide in the precursor solution is 1:1:1-3.

5. The method for preparing the bamboo fiber supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode according to claim 4, characterized in that: In step S1, the nickel salt is NiCl2 6H2O, the cobalt salt is CoCl2 6H2O, and the activator is hexadecyltrimethylammonium bromide.

6. The method for preparing a bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode according to any one of claims 2 to 5, characterized in that: In step S1, the mass of the MXene powder is equal to the sum of the masses of the nickel salt, cobalt salt, and thioacetamide in the precursor solution.

7. The method for preparing a bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode according to claim 6, characterized in that: In step S1, the hydrothermal reaction takes 8-24 hours.

8. The method for preparing a bamboo fiber-supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode according to any one of claims 2 to 5, characterized in that: In step S2, the mass ratio of the MAX powder to the bamboo fiber in the bamboo fiber solution is 0.5-2:0.

5.

9. The method for preparing the bamboo fiber supported nickel-cobalt bimetallic sulfide intercalated MAX thin film flexible electrode according to claim 8, characterized in that: In step S2, the length of the bamboo fiber is <20 mm.

10. The application of a flexible bamboo fiber supported nickel-cobalt bimetallic sulfide intercalated MAX thin film electrode prepared by the method of preparing the flexible bamboo fiber supported nickel-cobalt bimetallic sulfide intercalated MAX thin film electrode according to claim 1 or any one of claims 2 to 9 in a flexible supercapacitor.

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