Amino-modified and interface-enhanced integrated flexible electrode and preparation method and application thereof

Abstract

The invention discloses an amino-modified and interface-enhanced integrated flexible electrode and a preparation method and application thereof, and belongs to the field of new energy materials and devices.Natural softwood pulp cellulose is modified with ethidene diamine, and a NiSe2 / Cel-NH2 / MoS2 cellulose flexible electrode NCMF is prepared through a phase transfer method and a solvothermal method; the electrochemical performance and the mechanical performance of the NCMF flexible electrode are remarkably improved, the area capacitance reaches 2475 mF cm <-2 > (3 mA cm <-2 >), and the capacitance retention rate after 2500 times of circulation is 92.1%; the tensile strength is 10.3 MPa, and bending / twisting deformation can be resisted; the energy density of the supercapacitor assembled by the flexible electrode can reach 1971.53 mu Wh cm <-2 >, and the capacitance retention rate after 2000 cycles is 72.73%.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of new energy materials and devices, in particular to an amino-modified and interface-enhanced integrated flexible electrode and its preparation method and application, which is suitable for the preparation of flexible supercapacitors. BACKGROUND

[0002] Flexible electronics is one of the hotspots in the development of science and technology in recent years. By combining electronic components with flexible materials, wearable, bendable and foldable electronic devices can be achieved. The development of this field is of great significance to the promotion of emerging industries such as smart wearable devices, flexible display screens and health monitoring systems. Traditional sandwich-structured flexible all-solid-state supercapacitors (FSCs) inevitably suffer physical damage when subjected to mechanical deformation, leading to electrolyte damage. At the same time, the weak intermolecular interaction between the electrode / electrolyte interface can cause interface dislocation, slip, and even short circuit and failure. Therefore, how to endow integrated FSCs with mechanical robustness and energy storage reliability is a problem that needs to be solved.

[0003] Cellulose, as a typical one-dimensional flexible substrate, can be functionalized by loading active materials. At the same time, cellulose has excellent hydrophilicity and self-supporting properties. Compared with the preparation method of traditional polymer binder-based electrode materials, the preparation of self-supporting fiber electrodes does not require additional binders, which can enable the active material to participate in the energy storage process to a greater extent, thereby improving the electrochemical performance of the device. High active materials can increase the energy density of self-supporting fiber electrodes and reduce manufacturing costs, which is beneficial to ion and electron transmission in the electrode. Although cellulose has the advantage of flexible substrate, its non-conductivity and weak binding force with active materials limit its application. In the prior art, transition metal sulfides such as MoS2 and NiSe2 have high pseudo-capacitive activity, but lack a stable interface connection mechanism with the cellulose substrate. SUMMARY

[0004] The technical problem solved by the present application is that the weak binding force between the conductive active material and the cellulose flexible substrate and the easy detachment of the active material during long-term charge / discharge cycling are addressed by providing an amino-modified and interface-enhanced integrated flexible electrode and its preparation method and application. The flower-like nanoflower structure of NiSe2 / Cell-NH2 / MoS2 (NCM) is coated to form a cellulose flexible electrode NCMF. Natural conifer pulp cellulose is used as the flexible substrate, and 3D flower-like transition metal chalcogenides are used as conductive active materials to meet the energy storage requirements of flexible supercapacitors. Cell-NH2 is introduced to bridge the interface between the active material and the cellulose substrate to improve the interface binding force of the substrate-type supercapacitor electrode material, thereby improving the cycle stability and mechanical properties of the flexible electrode and solving the problems of weak interface binding force between the active material and the cellulose substrate and poor cycle stability.

[0005] Technical solution: The preparation method of the amino-modified and interface-enhanced integrated flexible electrode comprises the following steps: Step 1, preparing amino-modified cellulose Cell-NH2: solvent exchange pretreatment is performed on cellulose raw materials, the pretreated cellulose is dissolved in a DMAc solution containing LiCl to form a cellulose solution; The cellulose is modified by SOCl2 and ethylenediamine EDA in sequence: SOCl2 reacts with the C6 hydroxyl group of cellulose to introduce a -Cl group through nucleophilic substitution reaction, obtaining chlorinated cellulose Cell-Cl; the primary amino group of EDA replaces the -Cl group in Cell-Cl, obtaining Cell-NH2; Step 2, preparing conductive active material NiSe2 / CM 12 : Cell-NH2 is reacted with a molybdenum source and a sulfur source through a solvothermal method to generate CM 12 , wherein the mass ratio of the molybdenum source to Cell-NH2 is 1:2; the CM 12 is mixed with a nickel source, NH4F and urea, a precursor is generated through a first solvothermal reaction, and the precursor is subjected to selenization treatment, and NiSe2 / CM 12 with a 3D flower-like structure is obtained through a second solvothermal reaction. Step 3, preparing flexible electrode NCMF: NiSe2 / CM 12 is blended with a cellulose solution, and a flexible electrode NCMF is obtained through defoaming, coating, solidification and film formation.

[0006] Preferably, the solvent exchange pretreatment step in step 1 is that the conifer pulp cellulose is sequentially immersed in water, methanol and DMAc for 1 h each time, the solvent is removed through vacuum filtration after each immersion, and the prepared product is dried at 70℃.

[0007] Preferably, the preparation step of the cellulose solution in step 1 is that LiCl is added into DMAc to prepare a 9 wt% solution at 80℃, the pretreated cellulose is added, the temperature is raised to 110℃ for activation for 1 h, the temperature is lowered to room temperature for stirring to form a transparent viscous liquid, and the liquid is coated into a film after vacuum defoaming, and the coating thickness is 80 μm.

[0008] Preferably, the preparation step of the CM 12 in step 2 is that 28 mL of octylamine, 26 mL of anhydrous ethanol, 77 mg of sulfur powder, 185.4 mg of ammonium molybdate tetrahydrate and a proportioned amount of Cell-NH2 are reacted at-200℃ for 24 h, and the product is washed and vacuum dried at 60℃ for 12 h.

[0009] Preferably, the preparation step of the NCM in step 2 is: First step solvothermal reaction: 581.6 mg Ni(NO3)2•6H2O, 370.4 mg NH4F, 1501.5 mg urea, 20-40 mg CM 12 dissolved in 40 mL deionized water, reacted at 120℃ for 16h; Second step selenization reaction: 0.1 g precursor, 157.9 mg Se powder, 300 mg NaOH were dissolved in 25 mL DMF, 0.14 mL 80% concentration N2H4•H2O was added dropwise under stirring, and reacted at 180℃ for 1h.

[0010] Preferably, the NCM addition amount in step 3 is 2.5 wt% of the mass of the cellulose solution; the coating thickness is 200 μm, the coating speed is 8 cm / s, and the electrode thickness after solidification is 120 μm.

[0011] The application discloses an amino-modified and interface-enhanced integrated flexible electrode prepared by the above preparation method.

[0012] The application further discloses application of the above amino-modified and interface-enhanced integrated flexible electrode in positive and negative electrodes of a flexible all-solid-state supercapacitor.

[0013] Compared with the prior art, the application has at least the following beneficial effects: 1. The application adopts an amino-modified bridging mechanism, introduces -NH2 groups (Cell-NH2) into cellulose chains through EDA modification; the Cell-NH2 forms Mo-N / C-N coordination bonds with the active material MoS2 / NiSe2 and forms a hydrogen bond network with the cellulose substrate, realizes "triple interface enhancement", and prepares 3D flower-like NiSe2 / CM 12 (NCM) providing a high specific surface area and an ion diffusion channel; the cellulose network inhibits the collapse of the nanosheet skeleton and improves the mechanical stability; 2. The electrochemical performance and mechanical performance of the integrated flexible electrode prepared by the method are significantly improved, the area capacitance reaches 2475 mF cm -2 (3 mA cm -2 ), and the capacitance retention rate is 92.1% after 2500 cycles; the tensile strength is 10.3 MPa, and the bending / twisting deformation can be tolerated; the energy density of the supercapacitor assembled by using the flexible electrode can reach 1971.53 μWh cm -2 , and the capacitance retention rate is 72.73% after 2000 cycles. BRIEF DESCRIPTION OF DRAWINGS

[0014] Figure 1 It is a preparation flowchart of the integrated flexible electrode NCMF of the application; Figure 2 This is a scanning electron microscope image of NCM30, a conductive active material with a nanoflower structure obtained in this invention. Figure 3 The images show the scanning electron microscope (SEM) image, FTIR image, and XRD pattern of chemical composition analysis of the cellulose-based flower-shaped integrated flexible electrode NCMF prepared in this invention. Figure 4 The mechanical property test curves of the cellulose-based flower-shaped integrated flexible electrode NCMF prepared in this invention are shown. Figure 5 The conductive active material NCM with a nanoflower structure prepared in this invention 20 NCM 30 NCM 40 Electrochemical performance test results of NiSe2 electrode materials; Figure 6 The electrochemical performance test results of the cellulose-based flower-shaped integrated flexible electrode NCMF prepared in this invention are shown. Figure 7 The electrochemical test results are for an NCMF / / NCMF flexible all-solid-state supercapacitor assembled using cellulose-based flower-shaped integrated flexible electrode NCMF as the positive and negative electrode materials. Detailed Implementation

[0015] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the following will be described in conjunction with the accompanying drawings. Figures 1-7 The technical solutions of the embodiments of the present invention are clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. All other embodiments obtained by those skilled in the art based on the described embodiments of the present invention are within the scope of protection of the present invention.

[0016] like Figure 1 As shown, this invention discloses a method for preparing an integrated flexible electrode with amino modification and interface enhancement, comprising the following steps: (I) Preparation of Amino-Modified Cellulose Cell-NH2: The cellulose raw material was subjected to solvent exchange pretreatment. The activation pretreatment enhanced the diffusion of solvent into the crystalline regions of the cellulose molecular chain, thereby weakening the inter-polymer chain interactions. The pretreated cellulose was dissolved in a DMAc solution containing LiCl to form a cellulose solution. The solvent exchange pretreatment step was as follows: softwood pulp cellulose was successively immersed in water, methanol, and DMAc for 1 hour each. After each immersion, the solvent was removed by vacuum filtration and the solution was dried at 70°C for later use. The cellulose solution preparation step was as follows: LiCl was added to DMAc at 80°C to prepare a 9 wt% solution. After adding the pretreated cellulose, the temperature was raised to 110°C for activation for 1 hour. The solution was cooled to room temperature and stirred to form a transparent viscous liquid. After vacuum degassing, the solution was coated into a film with a thickness of 80 μm.

[0017] The cellulose is modified by SOCl2 and ethylenediamine (EDA) in sequence: SOCl2 reacts with the hydroxyl group at C6 of cellulose to introduce -Cl group by nucleophilic substitution reaction, to obtain chlorinated cellulose Cell-Cl; the primary amino group of EDA replaces the -Cl group in Cell-Cl, to obtain Cell-NH2.

[0018] (ii) Preparation of conductive active material NiSe2 / CM 12 (NCM): Cell-NH2 is reacted with a molybdenum source and a sulfur source by a solvothermal method to generate CM 12 , wherein the mass ratio of the molybdenum source to Cell-NH2 is 1:2; the preparation steps of CM 12 are as follows: 28 mL of octylamine, 26 mL of anhydrous ethanol, 77 mg of sulfur powder, 185.4 mg of ammonium molybdate tetrahydrate and a proportioned amount of Cell-NH2 are reacted at -200℃ for 24h, and the product is washed and vacuum dried at 60℃ for 12h.

[0019] CM 12 is mixed with a nickel source, NH4F and urea to generate a precursor by a first step of solvothermal reaction; wherein the first step of solvothermal reaction: 581.6 mg of Ni(NO3)2•6H2O, 370.4 mg of NH4F, 1501.5 mg of urea and 20-40 mg of CM 12 are dissolved in 40 mL of deionized water and reacted at 120℃ for 16h.

[0020] The precursor is subjected to selenization treatment, and NiSe2 / CM 12 with a 3D flower-like structure is obtained by a second step of solvothermal reaction; wherein the second step of selenization reaction: 0.1 g of the precursor, 157.9 mg of Se powder and 300 mg of NaOH are dissolved in 25 mL of DMF, 0.14 mL of 80% concentration of N2H4•H2O is added dropwise under stirring, and the mixture is reacted at 180℃ for 1h.

[0021] (iii) Preparation of flexible electrode NCMF: NiSe2 / CM 12 is blended with a cellulose solution, and a one-body flexible electrode NCMF is obtained by defoaming, coating, solidification and film formation; wherein the addition amount of NCM is 2.5 wt% of the mass of the cellulose solution; the coating thickness is 200 μm, the coating speed is 8 cm / s, and the thickness of the electrode after solidification is 120 μm.

[0022] The application discloses a one-body flexible electrode with amino modification and interface enhancement, which is prepared by the above preparation method.

[0023] The application further discloses application of the amino-modified and interface-enhanced integrated flexible electrode in positive and negative electrodes of a flexible all-solid-state supercapacitor.

[0024] The application successfully prepares the nanoflower-structured conductive active material NCM by using an in-situ solvothermal method, and prepares the NCMF flexible electrode by blending and coating the nanoflower-structured conductive active material NCM and the cellulose solution; the amino-modified cellulose is used as a raw material as a molecular bridge, and the interface bonding force, specific capacitance and cycle stability of the flexible electrode are successfully improved through a coordination bond strategy; and the obtained nanoflower-structured NiSe2 / CM 12 The active material exhibits high specific capacitance, excellent rate capability and electrochemical stability, and after being blended with the cellulose solution, the NCMF flexible electrode prepared by using a coating method can be assembled into an integrated flexible supercapacitor with excellent performance together with a hydrogel electrolyte; due to the strong interface bonding structure, the NCMF has excellent tensile stress; in addition, the flower-structured ion diffusion and the strong interface bonding stable mechanical structure are respectively helpful to obtaining high specific capacitance and long-term stable electrochemical performance under high load mass.

[0025] Embodiment 1: (I) Preparation of amino-modified cellulose Cell-NH2: The cellulose raw material is subjected to solvent exchange pretreatment, and the conifer pulp cellulose is sequentially immersed in water, methanol and DMAc for 1 h each time; after each immersion, the solvent is removed by vacuum filtration and dried at 70 DEG C for standby.

[0026] Preparation of the cellulose solution: LiCl is slowly added into DMAc under 80 DEG C and stirred until the solution is transparent; a DMAc solution containing 9wt% LiCl is prepared, 2.5wt% of the pretreated cellulose is added, and the temperature is raised to 110 DEG C for stirring and activation for 1 h; the temperature is lowered to room temperature, and the stirring is continued to obtain a transparent and uniform cellulose solution with a certain viscosity; the cellulose solution is subjected to vacuum filtration and degassing treatment for standby; the coating thickness of the coating machine is adjusted to 200 microns, and the speed is 8 cm / s; the film is uniformly scraped and coated, and then is placed in air for gelation for 1 h; then the film is placed in an ethanol coagulation bath for solidification; after natural air drying, the film is sealed for standby; the coating thickness is 80 microns; and the regenerated cellulose RCF is prepared.

[0027] Modification of the cellulose by sequentially passing SOCl2 and ethylenediamine EDA: 3 g of the pretreated conifer pulp cellulose is dissolved in 9wt% LiCl / DMAc solution, 20 mL of SOCl2 is added at 95 DEG C for reaction for 1 h, the reaction product is filtered, and the pH is adjusted to 7 by using ammonia water and deionized water to prepare chlorinated cellulose derivative Cell-Cl. 3 g of Cell-Cl is added into 100 mL of DMSO solvent and stirred uniformly, 3 mL of EDA is added at 90 DEG C for reaction for 12 h, and the filter is washed to be colorless by adding cold water overnight and vacuum filtration to prepare amino cellulose Cell-NH2.

[0028] The tensile strength of the regenerated synthetic RCF in the ethanol coagulation bath can reach 13.8 MPa, while also having a tensile strain capacity of 41%.

[0029] (ii) Preparation of conductive active material NiSe2 / CM 12 (NCM): 28 mL octylamine, 26 mL anhydrous ethanol, 77 mg sulfur powder, 185.4 mg ammonium molybdate tetrahydrate, and a proportioning amount of Cell-NH2 were reacted at -200℃ for 24h, and the product was washed and vacuum dried at 60℃ for 12h to prepare CM 12 .

[0030] 581.6 mg Ni(NO3)2•6H2O, 370.4 mg NH4F, 1501.5 mg urea, 20 mg CM 12 were dissolved in 40 mL of deionized water and stirred uniformly, transferred to a 50 mL PPL high-pressure reaction kettle, heated to 120℃ and kept for 16 h to form a precursor. 0.1 g of the precursor, 157.9 mg of Se powder, and 300 mg of NaOH were dissolved in 25 mL of DMF (N,N-dimethylformamide), and 0.14 mL of 80% concentration of N2H4•H2O was added dropwise under stirring conditions. The resulting mixture was heated to 180℃ in a 50 mL PPL high-pressure reaction kettle and kept for 1 h, and was washed by centrifugation with deionized water and ethanol to obtain a 3D flower-like structure of NiSe2 / CM 12 (NCM).

[0031] The synthesized cellulose-based flower-like electrode material NCM 20 (CM 12 has a specific capacitance of 925 F / g at a current density of 1A / g.

[0032] Example 2: (i) Preparation of amino-modified cellulose Cell-NH2: The raw material of cellulose was pretreated by solvent exchange, and the softwood pulp cellulose was immersed in water, methanol, and DMAc for 1h each time. After each immersion, the solvent was removed by vacuum filtration and dried at 70℃ for standby.

[0033] Preparation of cellulose solution: LiCl was slowly added into DMAc under stirring at 80℃ until the solution was transparent, a DMAc solution containing 9wt% LiCl was prepared, 2.5wt% pretreated cellulose was added, the temperature was raised to 110℃ and stirred for 1h for activation; the temperature was lowered to room temperature and the transparent and uniform cellulose solution with certain viscosity was continuously stirred, and vacuum filtration was used for defoaming treatment. The coating machine coating thickness was adjusted to 200 µm, the speed was 8 cm / s, and the film was uniformly scraped and coated, then it was placed in air for 1h for gelation, and then placed in an ethanol coagulation bath for solidification into a film, and after natural air drying, it was sealed for use. The coating thickness was 80 µm, and the regenerated cellulose RCF was prepared.

[0034] Cellulose was modified by SOCl2 and ethylenediamine EDA in turn: 3 g of pretreated conifer pulp cellulose was dissolved in 9wt% LiCl / DMAc solution, 20 mL of SOCl2 was added at 95℃ for 1h, the reaction product was filtered, washed with ammonia water and deionized water to pH=7, and chlorinated cellulose derivative Cell-Cl was prepared. 3g Cell-Cl was added into 100 mL DMSO solvent and stirred uniformly, and 3 mL EDA was added at 90℃ for 12h, and then added into cold water overnight, the filtrate was washed to colorless by vacuum filtration, and amino cellulose Cell-NH2 was prepared.

[0035] It was detected that the tensile strength of the regenerated synthetic RCF in the ethanol coagulation bath could reach 13.8 MPa, and it also had a tensile strain capacity of 41%.

[0036] (II) Preparation of conductive active material NiSe2 / CM 12 (NCM): 28 mL of octylamine, 26 mL of anhydrous ethanol, 77 mg of sulfur powder, 185.4 mg of ammonium molybdate tetrahydrate, and a certain amount of Cell-NH2 were reacted at -200℃ for 24h, and the product was washed and vacuum dried at 60℃ for 12h to prepare CM 12 .

[0037] 581.6 mg of Ni(NO3)2•6H2O, 370.4 mg of NH4F, 1501.5 mg of urea, 30 mg of CM 12The mixture was stirred in 40 mL of deionized water, transferred to a 50 mL PPL high-pressure reaction kettle, heated to 120°C and kept for 16 h to form a precursor. 0.1 g of the precursor, 157.9 mg of Se powder, and 300 mg of NaOH were dissolved in 25 mL of DMF (N,N-dimethylformamide), and 0.14 mL of 80% N2H4•H2O was added dropwise under stirring. The resulting mixture was heated to 180°C in a 50 mL PPL high-pressure reaction kettle and kept for 1 h, and then washed by centrifugation with deionized water and ethanol to obtain a 3D flower-like structure of NiSe2 / CM 12 (NCM).

[0038] The synthesized cellulose-based flower-like electrode material NCM 30 (CM 12 The specific capacitance of the cellulose-based flower-like electrode material NCM

[0039] Example 3: (I) Preparation of amino-modified cellulose Cell-NH2: The cellulose raw material was subjected to solvent exchange pretreatment, and the conifer pulp cellulose was sequentially immersed in water, methanol, and DMAc for 1 h each time. After each immersion, the solvent was removed by vacuum filtration and dried at 70°C for standby use.

[0040] Preparation of a cellulose solution: LiCl was slowly added to DMAc at 80°C under stirring until the solution was transparent, and a DMAc solution containing 9 wt% LiCl was prepared. The pretreated cellulose was added at 2.5 wt%, and the temperature was raised to 110°C for 1 h of stirring activation. The temperature was lowered to room temperature, and the transparent and uniform cellulose solution with certain viscosity was continuously stirred and degassed by vacuum filtration for standby use. The coating thickness of the coating machine was adjusted to 200 µm, and the speed was adjusted to 8 cm / s. The film was formed by uniform scraping, and then it was placed in air for 1 h of gelation, and then it was placed in an ethanol coagulation bath for solidification into a film. After natural air drying, it was sealed for standby use. The coating thickness was 80 µm, and the regenerated cellulose RCF was prepared.

[0041] Modification of cellulose by SOCl2 and ethylenediamine EDA in sequence: 3 g of pretreated conifer pulp cellulose was dissolved in 9 wt% LiCl / DMAc solution, 20 mL of SOCl2 was added at 95°C for 1 h of reaction, and the reaction product was filtered and washed with ammonia water and deionized water until pH=7 to prepare the cellulose derivative Cell-Cl. 3 g of Cell-Cl was added to 100 mL of DMSO solvent and stirred uniformly, and 3 mL of EDA was added at 90°C for 12 h of reaction. The filtrate was washed to colorless by vacuum filtration after being added to cold water overnight. The amino cellulose Cell-NH2 was prepared.

[0042] The tensile strength of the regenerated synthetic RCF in an ethanol coagulation bath can reach 13.8 MPa, while also having a tensile strain capacity of 41%.

[0043] (ii) Preparation of conductive active material NiSe2 / CM 12 (NCM): 28 mL octylamine, 26 mL anhydrous ethanol, 77 mg sulfur powder, 185.4 mg ammonium molybdate tetrahydrate, and a proportioning amount of Cell-NH2 were reacted at -200℃ for 24h, and the product was washed and vacuum dried at 60℃ for 12h to prepare CM 12 .

[0044] 581.6 mg Ni(NO3)2•6H2O, 370.4 mg NH4F, 1501.5 mg urea, 40 mg CM 12 were dissolved in 40 mL of deionized water and stirred uniformly, transferred to a 50 mL PPL high-pressure reaction kettle, heated to 120℃ and kept for 16 h to form a precursor. 0.1 g of the precursor, 157.9 mg of Se powder, and 300 mg of NaOH were dissolved in 25 mL of DMF (N,N-dimethylformamide), and 0.14 mL of 80% concentration of N2H4•H2O was added dropwise under stirring. The obtained mixture was heated to 180℃ in a 50 mL PPL high-pressure reaction kettle and kept for 1 h, and then washed by centrifugation with deionized water and ethanol to obtain a 3D flower-like structure of NiSe2 / CM 12 (NCM).

[0045] The synthesized cellulose-based flower-like electrode material NCM 30 (CM 12 has a specific capacitance of 1405 F / g at a current density of 1A / g.

[0046] Example 4: (i) Preparation of amino-modified cellulose Cell-NH2: The raw material of cellulose was pretreated by solvent exchange, and the softwood pulp cellulose was sequentially immersed in water, methanol, and DMAc for 1h each time. After each immersion, the solvent was removed by vacuum filtration and dried at 70℃ for standby.

[0047] Preparation of cellulose solution: LiCl was slowly added to DMAc at 80℃ and stirred until the solution became clear. A DMAc solution containing 9wt% LiCl was prepared, and 2.5wt% pretreated cellulose was added. The mixture was heated to 110℃ and stirred for 1 h to activate it. The solution was then cooled to room temperature and stirred continuously to form a clear, homogeneous cellulose solution with a certain viscosity. The solution was then degassed using vacuum filtration for later use. The coating thickness was adjusted to 200 µm and the speed to 8 cm / s. The coating was uniformly applied to form a film, which was then allowed to stand in the air to gel for 1 h. Finally, the film was placed in an ethanol coagulation bath to solidify. After natural drying, the film was sealed for later use. The coating thickness was 80 µm, thus obtaining regenerated cellulose RCF.

[0048] Cellulose was modified sequentially using SOCl2 and ethylenediamine (EDA): 3 g of pretreated softwood pulp cellulose was dissolved in a 9 wt% LiCl / DMAc solution, and 20 mL of SOCl2 was added at 95 °C for 1 h. The reaction product was filtered and washed with ammonia and deionized water until pH=7 to prepare the chlorinated cellulose derivative Cell-Cl. 3 g of Cell-Cl was added to 100 mL of DMSO solvent and stirred until homogeneous. 3 mL of EDA was added at 90 °C and reacted for 12 h. The mixture was then incubated in cold water overnight, and the filtrate was washed until colorless to prepare aminocellulose Cell-NH2.

[0049] Tests showed that the regenerated and synthesized RCF achieved a tensile strength of 13.8 MPa in an ethanol coagulation bath, while also possessing a tensile strain capacity of 41%.

[0050] (II) Preparation of conductive active material NiSe2 / CM 12 (NCM): 28 mL of octylamine, 26 mL of anhydrous ethanol, 77 mg of sulfur powder, 185.4 mg of ammonium molybdate tetrahydrate, and a specified amount of Cell-NH2 were reacted at -200 °C for 24 h. The product was washed and then vacuum dried at 60 °C for 12 h to obtain CM. 12 .

[0051] 581.6 mg Ni(NO3)2•6H2O, 370.4 mg NH4F, 1501.5 mg urea, and 30 mg CM 12Dissolved in 40 mL of deionized water, stirred evenly, transferred to a 50 mL PPL high-pressure reactor, heated to 120°C and kept for 16 h to form a precursor. 0.1 g of the precursor, 157.9 mg of Se powder, 300 mg of NaOH were dissolved in 25 mL of DMF (N, N-dimethylformamide), 0.14 mL of 80% concentration of N2H4•H2O was added dropwise under stirring, and the obtained mixture was heated to 180°C in a 50 mL PPL high-pressure reactor and kept for 1 h, and then washed by centrifugation with deionized water and ethanol to obtain a 3D flower-like structure of NiSe2 / CM 12 (NCM).

[0052] (Three) Preparation of flexible electrode NCMF: 2.5 wt% NCM 30 was added to the cellulose solution, stirred at room temperature for 12 h, and then vacuum degassing treatment was performed to obtain NCM 30 film-forming solution, the coating thickness was adjusted to 200 µm, and the coating speed was 8 cm / s. The conductive cellulose electrode was obtained by coating, and after drying, an integrated flexible electrode NCMF with a thickness of 120 µm was obtained.

[0053] It was detected that the maximum tensile stress of the synthesized cellulose-based flower-like integrated flexible electrode NCMF was 10.3 MPa, and the elongation at break was only 7.2%; at a current density of 3 mA / cm 2 , the area specific capacitance of the NCMF flexible electrode was 2475 mF / cm 2 , which was nearly 8 times higher than that of the CMF (388.6 mF / cm 2 ); and the capacitance retention rate was 92.1% after 2500 cycles at a current density of 7 mA / cm 2 .

[0054] Comparative Example 1: (One) Preparation of amino-modified cellulose Cell-NH2: The cellulose raw material was pretreated by solvent exchange, and the softwood pulp cellulose was immersed in water, methanol and DMAc for 1 h respectively. After each immersion, the solvent was removed by vacuum filtration and dried at 70°C for standby.

[0055] Preparation of cellulose solution: LiCl was slowly added into DMAc under stirring at 80℃ until the solution was transparent, a DMAc solution containing 9wt% LiCl was prepared, 2.5wt% of pretreated cellulose was added, and the temperature was raised to 110℃ for 1h of stirring activation; the temperature was lowered to room temperature, and the transparent and uniform cellulose solution with certain viscosity was continuously stirred, and vacuum filtration defoaming treatment was used for standby. The coating thickness of the coating machine was adjusted to 200 µm, the speed was 8 cm / s, and the film was uniformly scraped and coated, and then it was placed in air for 1h of gelation, and then placed in an ethanol coagulation bath for solidification into a film, and after natural air drying, it was sealed for standby, the coating thickness was 80 µm, and the regenerated cellulose RCF was prepared.

[0056] Modification of cellulose by SOCl2 and ethylenediamine EDA in sequence: 3 g of pretreated softwood pulp cellulose was dissolved in a 9wt% LiCl / DMAc solution, 20 mL of SOCl2 was added at 95℃ for 1h of reaction, the reaction product was filtered, washed with ammonia water and deionized water to pH=7, and the chlorinated cellulose derivative Cell-Cl was prepared. 3g of Cell-Cl was uniformly stirred in 100 mL of DMSO solvent, and 3 mL of EDA was added at 90℃ for 12h of reaction, and then added to cold water overnight, and the filtrate was washed to colorless by vacuum filtration, and the amino cellulose Cell-NH2 was prepared.

[0057] It was detected that the tensile strength of the regenerated and synthesized RCF in the ethanol coagulation bath could reach 13.8 MPa, and it also had a tensile strain capacity of 41%.

[0058] (II) Preparation of conductive active material NiSe2 / CM 12 (NCM): Cell-NH2 was reacted with 28 mL of octylamine, 26 mL of anhydrous ethanol, 77 mg of sulfur powder, 185.4 mg of ammonium molybdate tetrahydrate, and molybdenum source ((NH4)6Mo7O 24 4H2O) at a mass ratio of 1:1 at -200℃ for 24h, and the product was washed and vacuum dried at 60℃ for 12h to prepare CM 12 .

[0059] 2.5wt% of CM 12 was added to the cellulose solution, and the stirring was continuously carried out at room temperature for 12h, and after uniform mixing, the CM 12 cellulose film forming solution was obtained by vacuum defoaming treatment, the coating thickness was adjusted to 200 µm, and the scraping speed was 8 cm / s, and the CM 12 cellulose flexible electrode was obtained by coating, and after drying, the CMF flexible electrode with a thickness of 120 µm was obtained.

[0060] The synthesized CMF flexible electrode can withstand external forces such as bending, twisting, stretching and tearing, and the maximum stress can reach 8.1 MPa; when the current density is 1 mA / cm 2 , the area specific capacitance is 388.6 mF / cm 2 , and the capacitance retention rate still maintains 100% after 2500 continuous cycles.

[0061] Comparative Example 2: 581.6 mg of Ni(NO3)2·6H2O, 370.4 mg of NH4F and 1501.5 mg of urea were dissolved in 40 mL of deionized water and stirred uniformly, and then transferred to a 50 mL PPL high-pressure reaction kettle and heated to 120 DEG C and kept for 16 h, and the precipitate was collected and centrifuged and washed and dried. 0.1 g of the product obtained in the above step, 157.9 mg of Se powder and 300 mg of NaOH were dissolved in 25 mL of DMF (N,N-dimethylformamide), and 0.14 mL of 80% concentration of N2H4·H2O was added dropwise under stirring, and the obtained mixture was heated to 180 DEG C in a 50 mL PPL high-pressure reaction kettle and kept for 1 h, and the NiSe2 product was obtained by centrifugal washing with deionized water and ethanol.

[0062] It is detected that the specific capacitance of the synthesized NiSe2 electrode material is 1207 F / g when the current density is 1 A / g.

[0063] The materials used in Examples 1-4 and Comparative Examples 1-2 of the present application are all conventional commercially available products, which can be purchased.

[0064] The detection method of the capacitance of the integrated flexible electrode material prepared in Examples 1-4 and Comparative Examples 1-2 of the present application is as follows: The CHI660E electrochemical workstation is used for electrochemical performance test of the electrode, the three-electrode system is working electrode, Pt sheet as counter electrode, Hg / HgO as reference electrode, the electrolyte is 1M KOH, the scan rate of cyclic voltammetry (CV) is 5-200 mV / s; the galvanostatic charge / discharge (GCD) uses different current densities to test the charge / discharge time of the electrode; the electrochemical impedance spectroscopy (EIS) test frequency is 0.01-100 kHz. The mass specific capacitance of the electrode material is calculated by the following formula: ; In the formula: is the current; is the discharge time; For electrode material active substance quality; For voltage window.

[0065] The mechanical property detection method of the prepared integrated flexible electrode material prepared by the embodiments 1-4 and the comparative examples 1-2 is as follows: at room temperature, a universal testing machine is used for testing: the electrode sample is cut into 15 mm wide and 200 mm long, and the thickness of 5 randomly selected points is measured and averaged; the clamp spacing is set to 100 mm, the speed is 5 mm / min, the sample is pulled apart, and each group is tested for 3 times.

[0066] Figure 1 (a) is the dissolution and regeneration process of regenerated cellulose and a physical diagram, the raw material conifer pulp cellulose molecular chain contains a large number of intermolecular and intramolecular hydrogen bonds, when it is added into LiCl / DMAc solvent, the small molecules of the solvent will penetrate into the cellulose, swell and open the amorphous region of the cellulose, so that the cellulose molecular chain gradually stretches, and finally uniformly disperses in the solvent to form a homogeneous system, at this time the cellulose is completely dissolved and dissociated, the main reason is that Li + combined with DMAc, Cl - forms hydrogen bonds with the -OH on the cellulose molecular chain, destroys the original structure of cellulose, and destroys the original hydrogen bond network of cellulose by forming hydrogen bonds between the solvent and the cellulose molecules to realize the dissolution of cellulose. Figure 1 (b) is the preparation process and principle of Cell-NH2 and NCMF, first, Cell-NH2 is prepared, the pretreated cellulose raw material is fully dissolved, then SOCl2 and EDA are used for modification treatment, SOCl2 performs site nucleophilic substitution reaction on the -OH at C6 position of the long chain of cellulose, introduces -Cl, and then replaces -Cl through the primary amino group at the end of EDA molecule, finally Cell-NH2 is prepared; secondly, the Cell-NH2 is mixed with selenium source and nickel source to prepare flower-shaped structure NCM by hydrothermal method, and finally NCM is mixed with cellulose solution to obtain NCMF.

[0067] Figure 2 is a scanning electron microscope image of the prepared nanoflower structure conductive active substance NCM 30 Figure 2 ​As can be seen from (a)-2(b), the cellulose fibril microstructure is relatively complete and presents long filamentous shape, and the surface is rough. When the cellulose concentration is 2.5 wt%, the cellulose fibers swell during the dissolution process, break into short bamboo-shaped pieces, and are basically completely dissolved, finally forming a uniform and viscous transparent solution. In general, the higher the cellulose concentration in the solution, the better the performance of RCF. However, when the cellulose solution has a too high concentration, the viscosity is also large, which can result in poor flowability during the coating process, making it difficult to be coated by scraping, and the uniformity of the film is poor, and large holes appear on the surface, which greatly affects the mechanical properties of the cellulose film. In addition, the ideal skeleton support material of the flexible supercapacitor needs to have good hydrophilicity. The large amount of -OH in the cellulose macromolecule has hydrophilic properties, which helps to adsorb aqueous electrolyte, and the cellulose skeleton can be used as an internal storage place for electrolyte, which can attract electrolyte to diffuse to the surface of the flexible electrode active material. Further tests show that the contact angle of RCF is 41.2°, which proves that it has good electrolyte wettability, and RCF can be used as a flexible skeleton for supercapacitor electrodes. Figure 2 (c)-2(d) are scanning electron microscope images of the modified Cell-NH2. The diameter of the unmodified cellulose is about 20 µm, and the surface is smooth. After modification with SOCl2 and EDA, the fiber surface changes from long sheet to loose cluster distribution, and the morphology presents a loose and disordered accumulation structure. The fiber surface is rougher, and a large number of hole structures and spherical particles with a diameter of about 1 nm appear.(NH4)6Mo7O 24 · When the mass ratio of (NH4)6Mo7O 12 The micro-morphology of CM Figure 2 (e)-2(f) shows that a large number of uniformly distributed 3D hollow structure nanotubes can be observed, which are formed by the spontaneous assembly of MoS2 layers in the solution. It is measured that the diameter of CM 12 The sample has a diameter of about 180-210 nm and a length of about 12 µm. Compared with the pure MoS2 tube wall, the tube wall is thicker, and the thickness increases by about 2 nm. This is because the Cell-NH2 nanoparticles are uniformly distributed on the outer wall, resulting in an increase in the outer diameter of the nanotube and a decrease in the inner diameter. EDS energy spectrum analysis of CM 12 shows that Mo elements and S elements from MoS2 and N elements from Cell-NH2 are uniformly distributed.

[0068] Figure 2 (g)-2(k) shows that NCM exhibits different micro-morphologies with different amounts of CM 12 introduction; Figure 2 (g) is the original morphology of NiSe2, which presents a state of accumulation of nanoparticle clusters. When the amount of CM 12 introduction is 20 mg, as shown in Figure 2As shown in (h), the nanoparticles gradually grow into large particles, but no 3D tubular CMs were observed. 12 This is because under these hydrothermal conditions, CM 12 The tubular structure was broken down into individually dispersed nanoparticles. When CM was increased... 12 When the dose introduced is 30 mg, such as Figure 2 In (i)-2(j), the geometry of the nanoparticles underwent significant changes, and the NiSe2 and CM nanoparticle structures... 12 Assemble and generate novel nanoflower-like structures NCM 30 Furthermore, there are scattered nanoparticle fragments on the petals; and Figure 2 (j) NCM 30 The EDS elemental distribution images show that Se, Mo, S, and Ni are uniformly distributed on the surface of the nanoflowers, indicating that NiSe2 and C are compatible. 12 They successfully reconciled. Figure 3 In (k), when CM 12 When the dosage is increased to 40 mg, NCM 40 The appearance of collapsed and broken nanosheets is likely due to the collapse of the nanoflower structure grown in NiSe2. In summary, CM 12 The introduction of [a specific substance] affects the nucleation and growth of NCM, guiding the direction of crystal growth and promoting the orderly arrangement of selenium and nickel atoms, leading to directional growth into nanoflower structures; furthermore, [the specific substance] determines [the specific structure] of NCM. 12 When the dose introduced is 30 mg, NCM 30 It possesses a large number of active sites and superior nanomorphology.

[0069] Figure 3 The images show the scanning electron microscope (SEM) image, FTIR image, and XRD pattern for chemical composition analysis of the cellulose-based flower-like integrated flexible electrode NCMF prepared according to this invention. Figure 3 As shown in (a)-3(b), the NCMF surface is rough and has a large number of randomly dispersed particles and obvious phase interfaces, which is due to the poor compatibility between cellulose and NCM particles. Figure 3 (c) is an EDS image of Se, Ni, Mo and S elements on the NCMF surface. It can be observed that these four elements are uniformly distributed, which shows that NCM can be uniformly distributed in cellulose.

[0070] Figure 3 (d) is the NCMF infrared FTIR image, due to 3337 cm⁻¹. -1 This is the stretching vibration peak of the -OH group on the cellulose molecular chain, at 2900 cm⁻¹. -1 The absorption peak at 1092 cm⁻¹ originates from the bending vibration of CH in cellulose. -1 The absorption peak originates from the stretching vibration of the COC bond in the six-membered ring of cellulose; it passes through 899 cm⁻¹.-1 Weak absorption peaks appeared, confirming that the glucose units of cellulose were connected by β-glycosidic bonds; compared with the chemical structure of the amino-modified cellulose, the stretching vibration peak at 2973 cm -1 The in-plane vibration absorption peak of δNHwas located at 1640 cm -1 The absorption peak at 1236 cm -1 was caused by the stretching vibration of C-N, and the absorption peak at 804 cm -1 was caused by the out-of-plane deformation vibration of N-H specific to the primary amine in EDA, thus proving the success of the preparation of the amino-modified cellulose. Further comparison of the -OH peak area at 3700 cm -1 -3000 cm -1 It was observed that the -OH peak area of Cell-NH2was smaller than that of the cellulose before modification, because the -OH on the cellulose after modification was consumed, and the -NH2was successfully introduced into the cellulose molecular chain.

[0071] Figure 4 (e) To determine the changes in the crystal structure and crystallinity of the cellulose before and after modification by XRD analysis, the diffraction peaks of the cellulose raw material at 2θ = 16°, 22.7°, and 34.7° correspond to the (110), (110), (200), and (040) crystal planes of type I cellulose, and Cell-NH2shows a peak at 2θ = 22.1° corresponding to the (021) crystal plane of type II cellulose. The intensity of this crystal plane diffraction peak is also reduced compared with the cellulose raw material. By calculation, the crystallinity of Cell-NH2decreased to 40%, while the crystallinity of the cellulose raw material was 87.47%. This is because the -NH2replaced the -OH on the surface of the cellulose, and the crystalline region of the fiber was destroyed, resulting in a decrease in crystallinity.

[0072] Figure 4 The mechanical property test curve of the cellulose-based flower-shaped integrated flexible electrode NCMF; Figure 4 (a) is the stress-strain curve of MF, CMF, and RCF. RCF can withstand a stress of 13.8 MPa. The introduction of CM 12 After the introduction of CM 12The introduction of particles reduces the continuity of RCF, the surface flatness of CMF decreases, and the internal defects of CMF increase; but the tensile strength of CMF is still higher than that of MF sample, because Cell-NH2 forms a hydrogen bond network with the -OH of the cellulose substrate, which inhibits crack propagation during stretching; the structural orientation of fibers during coating forms a physical cross-linked fiber network in the ethanol coagulation bath, and the strong self-aggregation force (hydrogen bond) between adjacent cellulose chains forms a tightly stacked and cross-linked film with ultra-high toughness after air drying.

[0073] Figure 4 (b) stress-strain curve of flexible electrode NCMF; the real object diagram before and after the fracture of NCMF is shown in the upper left corner of Figure 4 (b), the maximum tensile stress of NCMF is 10.3 MPa, and the elongation at break is only 7.2%, Figure 5 (b), the upper left corner of the inset is the real object diagram before and after the fracture of NCMF, the maximum stress of flexible electrode NCMF increases compared with flexible electrode CMF, and the elongation at break decreases, because there is a phase interface between NCM and cellulose, when NCMF is subjected to external stress, the interfacial force is transmitted, that is, from the cellulose matrix to the filler, and the transmission efficiency depends on the strength of the interfacial region, because the filler and the matrix in NCM interact through hydrogen bonds and coordination bonds, which enhances the resistance of NCMF to external stress, and the addition of conductive filler reduces the flexibility of cellulose molecular chain and the continuity of self-crosslinking, thus leading to the decrease of elongation at break of NCMF.

[0074] Figure 5 The three-electrode system was used to study the NCM 20 , NCM 30 , NCM 40 and NiSe2 as supercapacitor electrode material electrochemical energy storage performance test figure, electrolyte is 1 M KOH solution; from Figure 6 , when CM 12 the amount of introduction is 30 mg, the area wrapped by CV curve is the largest, indicating that NCM 30 has the largest specific capacitance; when the current density is 1 A / g, the nanoflower structure of NCM 30 is beneficial to increase the contact area of electrolyte ions, resulting in the longest charge / discharge time of NCM 30 , and the calculated specific capacitance is the largest, which is 1405 F / g, so the optimal amount of CM 12 is 30 mg. Compared with NiSe2 and CM 12 , the NCM 30 electrode R ct value is the smallest, which is 0.3 Ω; NCM 30Ni has strong electrical conductivity and electron transport capabilities as an electrode material; specifically... 2+ / Ni 3+ The various valence changes in the transformation process promote efficient redox reactions, and also provide electron donors and acceptors during charging / discharging.

[0075] Figure 6 The electrochemical performance test results of the flexible electrode NCMF; by Figure 7 It can be seen that the pseudocapacitance contribution rate of the NCMF electrode is 53%, indicating that the charge storage mechanism is mainly based on surface redox reactions. At a current density of 3 mA / cm², 2 At that time, the areal capacitance of the NCMF flexible electrode was 2475 mF / cm². 2 The specific capacitance was nearly 8 times higher than that of CMF, which may be due to the increased charge transfer between Mo and Ni cations, resulting in a richer pool of electroactive sites involved in redox reactions; at a current density of 20 mA / cm². 2 The capacitance at that time was still 880 mF / cm 2 NCMF's R ct With an impedance of approximately 0.4 Ω and minimal arc-shaped region, NCMF exhibits low impedance, rapid redox reactions, and strong electron and ion transport capabilities, thus demonstrating superior energy storage characteristics. The NCMF electrode operates at 7 mA / cm². 2 After 2500 cycles at a current density, the capacitance retention rate was 92.1%. During this process, the electrode material and electrolyte underwent an incompletely reversible reaction during charging / discharging, which resulted in a slight decrease in the cycle stability of the NCMF electrode compared to the CMF electrode.

[0076] ​ The electrochemical test results are for an NCMF / / NCMF flexible all-solid-state supercapacitor assembled using cellulose-based flower-shaped integrated flexible electrode NCMF as the positive and negative electrode materials; when the current density is from 0.5 mA / cm²... 2 Increased to 25 mA / cm 2 At that time, the areal capacitance of the flexible all-solid-state supercapacitor increased from 56.78 mF / cm². 2 It decreased to 8.6 mF / cm 2 The decrease is significant because at higher current densities, the effectiveness of ion diffusion in the electrolyte (ion diffusion from the electrolyte to the surface of the electroactive material) decreases, thus reducing the utilization rate of the electroactive material; at 10 mA / cm 2The flexible all-solid-state supercapacitor can be easily bent under external force, indicating that it still has excellent flexibility.

[0077] The application adopts an amino modification bridging mechanism, introduces a -NH2 group (Cell-NH2) into a cellulose chain through EDA modification; the Cell-NH2 forms a Mo-N / C-N coordination bond with the active substance MoS2 / NiSe2 and forms a hydrogen bond network with the cellulose substrate, realizes "triple interface enhancement", and prepares 3D flower-like NiSe2 / CM 12 (NCM) provide high specific surface area and ion diffusion channels; the cellulose network inhibits the collapse of the nanosheet skeleton and improves the mechanical stability. The application utilizes a phase transfer method and a solvothermal method to synthesize a cellulose-based flexible supercapacitor electrode with excellent interface bonding force and electrochemical performance. On the one hand, the cellulose polyhydroxy structure is a good electrolyte ion conductor; on the other hand, the cellulose film prepared by a dissolution regeneration method usually has a crystallinity of less than 60%, and water can easily penetrate into the fibers, having good hydrophilicity. This makes the cellulose substrate suitable for aqueous electrolyte, which helps to reduce the interface resistance, improve the specific capacitance and cycle stability of the electrode material. In terms of flexibility, the cellulose film can be stretched, bent, twisted, and even cut into any shape. However, cellulose itself does not have conductivity, and its application in the field of flexible electrode materials is limited. Therefore, MoS2 and NiSe2 are used as pseudocapacitive energy storage materials, which have excellent electrochemical activity and resource abundance. The conductive active substance loaded on the flexible substrate is prone to fall off during long-term charging and discharging process, so it is necessary to consider how to establish an effective and stable force connection between the conductive active substance and the cellulose substrate. Cell-NH2 which can form coordination with transition metals is selected as a bridging agent, and is compounded with conductive active substances through a solvothermal method to establish a durable and stable interaction force between the conductive active substance and the cellulose substrate. At the same time, the cellulose network with high aspect ratio can effectively inhibit the collapse of the nanosheet skeleton of the conductive filler, further improving the stability and electrochemical performance of the flexible electrode.

[0078] The application modifies natural conifer pulp cellulose by using ethylenediamine, and prepares a NiSe2 / Cell-NH2 / MoS2 cellulose flexible electrode NCMF through a phase transfer method and a solvothermal method; the amino-modified cellulose Cell-NH2 serves as a "bridge" between NiSe2 and MoS2, improving the interface bonding force of the flexible electrode; the electrochemical performance and mechanical performance of the integrated flexible electrode are significantly improved, and the area capacitance reaches 2475 mF cm -2 (3 mA cm -2), the capacitance retention rate is 92.1% after 2500 cycles; the tensile strength is 10.3 MPa, and the bending / twisting deformation can be tolerated; and the energy density of the supercapacitor assembled by using the flexible electrode can reach 1971.53 μWh cm -2 , the capacitance retention rate is 72.73% after 2000 cycles.

[0079] The above is the preferred embodiment of the present application, it should be noted that, for those skilled in the art, without departing from the principles of the present application, can make a number of improvements and refinements, these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A method for preparing an integrated flexible electrode with amino modification and interface enhancement, characterized in that, Includes the following steps: Step 1, Preparation of amino-modified cellulose Cell-NH2: The cellulose raw material is pretreated by solvent exchange, and the pretreated cellulose is dissolved in a DMAc solution containing LiCl to form a cellulose solution; Cellulose was modified sequentially by SOCl2 and ethylenediamine (EDA): SOCl2 reacted with the C6 hydroxyl group of cellulose via a nucleophilic substitution reaction to introduce a -Cl group, yielding chlorocellulose Cell-Cl; the primary amino group of EDA substituted the -Cl group in Cell-Cl to obtain Cell-NH2. Step 2, Preparation of conductive active material NiSe2 / CM 12 Cell-NH2 is reacted with a molybdenum source and a sulfur source via a solvothermal method to generate CM. 12 The molybdenum source:Cell-NH2 mass ratio is 1:2; CM 12 The precursor is generated by mixing with a nickel source, NH4F, and urea in a first-step solvothermal reaction. The precursor is then selenized, followed by a second-step solvothermal reaction to obtain a 3D flower-like NiSe2 / CM. 12 ; Step 3, Fabrication of flexible electrode NCMF: NiSe2 / CM 12 The NCMF (non-carbonated flexible electrode) is obtained by blending with a cellulose solution, followed by degassing, coating, and curing to form a film.

2. The method for preparing the integrated flexible electrode with amino modification and interface enhancement according to claim 1, characterized in that, The solvent exchange pretreatment step in step 1 is as follows: cellulose from softwood pulp is sequentially immersed in water, methanol, and DMAc for 1 hour each. After each immersion, the solvent is removed by vacuum filtration and the pulp is dried at 70°C for later use.

3. The method for preparing the integrated flexible electrode with amino modification and interface enhancement according to claim 1, characterized in that, The preparation steps of the cellulose solution in step 1 are as follows: LiCl is added to DMAc at 80℃ to prepare a 9 wt% solution, and after adding pretreated cellulose, the temperature is raised to 110℃ for 1 h for activation; the temperature is lowered to room temperature and stirred to form a transparent viscous liquid, which is then degassed under vacuum and coated into a film with a coating thickness of 80 μm.

4. The method for preparing the integrated flexible electrode with amino modification and interface enhancement according to claim 1, characterized in that, The CM mentioned in step 2 12 The preparation steps are as follows: 28 mL of octylamine, 26 mL of anhydrous ethanol, 77 mg of sulfur powder, 185.4 mg of ammonium molybdate tetrahydrate and the specified amount of Cell-NH2 are reacted at -200℃ for 24 h. After washing, the product is dried under vacuum at 60℃ for 12 h.

5. The method for preparing the integrated flexible electrode with amino modification and interface enhancement according to claim 1, characterized in that, The preparation steps of NCM in step 2 are as follows: Step 1: Solvent-thermal reaction: 581.6 mg Ni(NO3)2•6H2O, 370.4 mg NH4F, 1501.5 mg urea, and 20-40 mg CM are reacted. 12 Dissolve in 40 mL of deionized water and react at 120℃ for 16 h; The second step is the selenization reaction: 0.1 g of precursor, 157.9 mg of Se powder and 300 mg of NaOH are dissolved in 25 mL of DMF, and 0.14 mL of 80% N2H4•H2O is added dropwise under stirring. The reaction is carried out at 180℃ for 1 h.

6. The method for preparing the integrated flexible electrode with amino modification and interface enhancement according to claim 1, characterized in that, In step 3, the amount of NCM added was 2.5 wt% of the cellulose solution mass; the coating thickness was 200 μm, the coating speed was 8 cm / s, and the electrode thickness after curing was 120 μm.

7. An integrated flexible electrode with amino-modified and interface-reinforced properties, characterized in that, It is prepared by any one of the preparation methods described in claims 1 to 6.

8. The application of an integrated flexible electrode with amino modification and interface enhancement as described in claim 7 in the positive and negative electrodes of a flexible all-solid-state supercapacitor.

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