MXene + rGO aerogel preparation method based on principle of corroding primary battery

Abstract

The invention relates to the technical field of energy storage materials, in particular to an MXene + rGO aerogel preparation method based on a corrosion primary battery principle. The method comprises the following steps: mixing hydrochloric acid and a solution A, and adjusting the pH value of the solution A to 6-7 to obtain a solution B; a square zinc sheet is soaked in the mixed solution B obtained in the step S3 in a culture dish; washing the black hydrogel obtained in the step S4 with deionized water; mixing hydrochloric acid with deionized water to obtain a solution C, soaking the hydrogel obtained in the step S5, and separating the hydrogel from the zinc sheet to obtain MXene + rGO hydrogel; the MXene + rGO hydrogel obtained in the step S6 is repeatedly washed with deionized water, and the MXene + rGO aerogel is obtained. According to the preparation method of the MXene + rGO aerogel based on the principle of corroding the primary battery, provided by the invention, a zinc sheet is treated in a manner of corroding the primary battery based on a solution for adjusting the pH value to obtain black hydrogel, and the MXene + rGO aerogel is obtained by treating the black hydrogel.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of energy storage materials, in particular to a preparation method of MXene+rGO aerogel based on the principle of corrosion primary cell. BACKGROUND

[0002] Nowadays, with the great innovation of flexible electronic devices, a large number of wearable, comfortable and portable electronic devices such as smart clothes, electronic skin and implantable medical devices emerge. In order to power these electronic devices, it is urgent to develop light, flexible and durable high-performance power supply. As a new type of efficient energy storage device, supercapacitors exceed batteries in many aspects such as high power density, long cycle life, fast charge and discharge rate, environmental protection and almost maintenance-free operation. The supercapacitors based on flexible fabric are light, comfortable, stretchable and cost-effective, which makes them particularly suitable for powering wearable electronic devices. Therefore, people have carried out extensive research on the manufacture of supercapacitors based on flexible fabric.

[0003] The application adopts the basic principle of additive-free pure MXene multi-dimensional architecture process based on the spontaneous oxidation-reduction reaction of MXene nanosheets on a metal template. This method effectively enhances the conductivity of MXene, while retaining the inherent hydrophilicity, which is attributed to the partial removal of oxygen functional groups after mild interfacial reduction. The obtained MXene assembly structure can not only be easily transferred or conformally coated on the surface of a substrate with precise sites of any shape, but also can be hybridized with other functional low-dimensional nanomaterials with different geometric dimensions. The MXene aerogel obtained by freeze-drying post-processing represents a typical 3D network structure with micrometer-sized pores. Excellent performance is provided.

[0004] The MXene sheets in the 3D hydrogel are stacked in parallel during air drying, and the water in the hydrogel evaporates, while the slow sublimation of ice can preserve the initial 3D structure of the self-assembled MXene gel structure during freeze-drying. The obtained 2D film can significantly improve the conductivity and electrochemical stability of the electrode material, thereby increasing the charge storage capacity of the electrode. On the basis of MXene self-assembly, the application composites rGO to further improve the performance of the MXene aerogel, However, to realize industrial application, it is still necessary to explore the optimization of the self-assembly of MXene nanosheets on a metal template and the potential combination of composite materials. The application provides a preparation method of MXene+rGO composite material, which can not only solve the conductivity and stability problems of existing materials, but also make breakthroughs in realizing large-scale production and reducing manufacturing costs. SUMMARY

[0005] Based on this, it is necessary to solve the above technical problems, provide a MXene+rGO aerogel preparation method based on the principle of corrosion primary battery, for solving the technical problems put forward in the background art.

[0006] In order to solve the above technical problems, the application adopts the following technical scheme: A MXene+rGO aerogel preparation method based on the principle of corrosion primary battery, the steps are as follows: S1: MAX-Ti3AlC2 powder is obtained, and the upper layer black liquid is obtained; S2: The upper layer black liquid obtained in step S1 is mixed with graphene oxide to obtain solution A; S3: Hydrochloric acid and solution A are mixed, the pH value of solution A is adjusted to 6-7, and solution B is obtained; S4: Square zinc sheet is soaked in the mixed solution B obtained in step S3 in a culture dish for 1 hour; S5: The black hydrogel obtained in step S4 is washed with deionized water, and the residual mixed solution B is removed; S6: Hydrochloric acid is mixed with deionized water to obtain solution C, and the hydrogel obtained in step S5 is soaked with solution C, and the hydrogel is separated from the zinc sheet to obtain MXene+rGO hydrogel; S7: The MXene+rGO hydrogel obtained in S6 is repeatedly washed with deionized water and freeze-dried to obtain MXene+rGO aerogel.

[0007] As a preferred embodiment of the MXene+rGO aerogel preparation method based on the principle of corrosion primary battery provided by the application, in step S2, 25 parts of the upper layer black liquid obtained in step S1 are mixed with 0:40:80:120:160 parts of graphene oxide to obtain solution A.

[0008] As a preferred embodiment of the MXene+rGO aerogel preparation method based on the principle of corrosion primary battery provided by the application, in step S4, square zinc sheet with an area of 1cm 2 is soaked in the mixed solution B obtained in step S3 in a culture dish for 1 hour.

[0009] As a preferred embodiment of the MXene+rGO aerogel preparation method based on the principle of corrosion primary battery provided by the application, in step S6, 10 parts of hydrochloric acid are mixed with 90 parts of deionized water to obtain solution C, and the hydrogel obtained in step S5 is soaked with solution C, and the hydrogel is separated from the zinc sheet to obtain MXene+rGO hydrogel.

[0010] As a preferred embodiment of the MXene+rGO aerogel preparation method based on the principle of corrosion primary cell provided by the application, in the S1 step, the MAX-Ti3AlC2 powder is obtained as the upper layer black liquid, and the steps are as follows: A. mixing deionized water and concentrated hydrochloric acid to obtain a first solution, and dissolving lithium fluoride in the first solution to obtain a second solution; B. adding 1 part of MAX-Ti3AlC2 powder into the second solution and continuing to stir for 24 hours; C. transferring the mixed solution obtained in step B into a centrifuge tube and washing and centrifuging; until the upper layer liquid is black; D. ultrasonicating the black liquid obtained in step C in an ice water bath for 30 minutes, and the temperature should be less than 20 DEG C; E. centrifuging the liquid after ultrasonicating in step D using a centrifuge to obtain the upper layer black liquid.

[0011] As a preferred embodiment of the MXene+rGO aerogel preparation method based on the principle of corrosion primary cell provided by the application, in step A, 10 parts of deionized water and 30 parts of concentrated hydrochloric acid are mixed to obtain a first solution, and 3.2 parts of lithium fluoride are dissolved in the first solution to obtain a second solution.

[0012] An application of the MXene+rGO aerogel based on the principle of corrosion primary cell.

[0013] It can be seen without doubt that the above technical solutions of the application can certainly solve the technical problems to be solved by the application.

[0014] Meanwhile, through the above technical solutions, the application at least has the following beneficial effects: The MXene+rGO aerogel preparation method based on the principle of corrosion primary cell provided by the application can treat zinc sheets by the principle of corrosion primary cell based on a solution for adjusting pH value, obtain black hydrogel, and obtain MXene+rGO aerogel by treating the black hydrogel.

[0015] 2. The MXene+rGO aerogel obtained by the application has high rate performance and cycle stability, and the electrochemical test shows that the specific capacitance is 604.57 F / g at 1 A / g, 364 F / g at 20 A / g, and the specific capacitance still has a retention rate of 60.2% at a higher current density, which indicates that the material has good rate performance.

[0016] 3, The present application adopts a simple and reliable pure MXene-based gelation principle, which is suitable for scalable micron-thick hydrogels; by simply immersing a zinc template of any shape into a water dispersion of MXene, a true self-assembly of MXene hydrogel on the surface of the template can be generated; this method can self-assemble in any shape of metal template, for example, superior to typical MXene films and high-rate, high-capacity supercapacitors. BRIEF DESCRIPTION OF DRAWINGS

[0017] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced. Obviously, the drawings in the following description are some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0018] Figure 1 Flow chart for self-assembly of MXene+rGO composite material of the present application; Figure 2 XRD pattern of MXene+rGO composite material of the present application; Figure 3 Cyclic voltammogram (CV) of MXene+rGO composite material of the present application; Figure 4 Cyclic voltammogram (CV) of MXene+rGO composite material of the present application; Figure 5 EIS diagram of MXene+rGO composite material of the present application; Figure 6 Rate performance diagram of MXene+rGO composite material of the present application. DETAILED DESCRIPTION

[0019] In order to make the purpose, technical scheme and advantages of the present application more clear, the present application will be further described in detail below in combination with the drawings and examples. It should be understood that the specific examples described herein are only used to explain the present application and do not limit the present application.

[0020] In order to make the person skilled in the art better understand the present application, the technical solutions in the embodiments of the present application will be described clearly and completely in combination with the drawings.

[0021] It should be noted that the embodiments in the present application and the features and technical solutions in the embodiments can be combined with each other without conflict.

[0022] It should be noted that like reference numerals and characters refer to like items throughout the drawings and that different items sharing the same reference numeral or character but having different suffixes are intended to represent different instances of the same item. Thus, once an item is defined in one drawing, it need not be further defined and explained in subsequent drawings.

[0023] Embodiment one Reference Figure 1 and Figure 2 A MXene+rGO aerogel preparation method based on the principle of corrosion galvanic cell is provided, and the steps are as follows: S1: MAX-Ti3AlC2 powder is added to obtain a black liquid on the top; Preferably, in the S1 step, MAX-Ti3AlC2 powder is added to obtain a black liquid on the top, and the steps are as follows: A. 10 parts of deionized water and 30 parts of concentrated hydrochloric acid are mixed to obtain a first solution, and 3.2 parts of lithium fluoride is dissolved in the first solution to obtain a second solution; Further, step A should be carried out in a polytetrafluoroethylene beaker.

[0024] B. 1 part of MAX-Ti3AlC2 powder is added to the second solution and stirring is continued for 24 hours; Further, the speed of adding MAX-Ti3AlC2 powder in step B should be slow, at least 5 min / g, and the stirring should start before the powder is added, and the stirring in step B uses an oil bath heater, and the stirring speed should be fast, and the temperature is 45°C.

[0025] C. The mixed solution obtained in step B is transferred to a centrifuge tube for washing and centrifugation; until the upper liquid turns black; Further, in step C, the obtained mixed solution is first washed and centrifuged twice with 1M hydrochloric acid solution, and finally washed and centrifuged with deionized water until the upper liquid turns black, and the centrifugation rate in step C should be greater than 4000rmp / min.

[0026] D. The black liquid obtained in step C is ultrasonicated in an ice water bath for 30 minutes, and the temperature should be less than 20°C; E. The liquid after ultrasonication in step D is centrifuged using a centrifuge to obtain a black liquid on the top; Further, the centrifugation in step E uses a centrifuge with a centrifugation rate of 3500rmp / min for 15 minutes.

[0027] S2: 25 parts of the black liquid on the top obtained in step S1 are mixed with 0:40:80:120:160 parts of graphene oxide to obtain solution A; S3: Hydrochloric acid and solution A are mixed to adjust the pH value of solution A to 6-7 to obtain solution B; S4: In a culture dish, 1 cm2 square zinc pieces with an area of 1 cm S5: washing the black hydrogel obtained in step S4 with deionized water to remove residual mixed solution B; S6: mixing 10 parts of hydrochloric acid with 90 parts of deionized water to obtain solution C, and immersing the hydrogel obtained in step S5 in solution C, and separating the hydrogel from the zinc pieces to obtain MXene+rGO hydrogel; S7: repeatedly washing the MXene+rGO hydrogel obtained in S6 with deionized water, and freeze-drying to obtain MXene+rGO aerogel.

[0028] The specific implementation of the embodiment is as follows: Mixing 10 parts of deionized water and 30 parts of concentrated hydrochloric acid to obtain a first solution, dissolving 3.2 parts of lithium fluoride in the first solution to obtain a second solution, adding 1 part of MAX-Ti3AlC2 powder to the second solution at a speed of 5 min / g and continuing to stir for 24 h, and transferring the obtained mixed solution to a centrifuge tube and washing and centrifuging until the upper liquid turns black; ultrasonicating the black liquid in an ice water bath for 30 min, and the temperature should be less than 20℃; after ultrasonicating, centrifuging using a centrifuge to obtain the upper black liquid; mixing 25 parts of the upper black liquid with graphene oxide to obtain solution A, mixing hydrochloric acid and solution A, adjusting the pH value of solution A to obtain solution B; immersing square zinc pieces with an area of 1 cm 2 square zinc pieces with an area of 1 cm

[0029] Example Two On the basis of the above-mentioned example one, the application of MXene+rGO aerogel based on the principle of corrosion primary cell is disclosed. The MXene+rGO aerogel is applied to the negative electrode of supercapacitor.

[0030] The MXene+rGO aerogel is applied to lithium ion battery, Example

[0031] Reference Figures 3-6 , the content of the above-mentioned example one is verified.

[0032] (1) Figure 3The figure shows the CV curves of the MXene+rGO composite material at scan rates from 5 mV / s to 60 mV / s. As can be seen from the figure, the MXene+rGO composite material exhibits a relatively obvious redox reversible peak at different scan rates from 5 mV / s to 60 mV / s, indicating that this material can undergo redox reactions to store charge. Furthermore, the figure shows that the MXene+rGO composite material has a wide voltage window. Even when the scan rate increases to 60 mV / s, the shape of the CV curve remains unchanged, indicating that the MXene+rGO composite material maintains good charge-discharge performance at relatively fast scan rates. (2) Figure 4 The figure shows the GCD curves of the MXene+rGO composite material at current densities ranging from 1 A / g to 20 A / g. As can be seen from the figure, the GCD curves of the MXene+rGO composite material deviate from an isosceles triangle (a typical characteristic of double-layer capacitance). The GCD curves still maintain good symmetry even at high current densities, indicating that... It has excellent reversible charge and discharge capability; Calculated using the specific capacitance formula:

[0033] Where C is the specific capacitance (F / g), I is the charge / discharge current (A), t is the discharge time (s), ΔV is the potential window (V), and m is the mass of the active material (g). According to the calculation results of the formula, the MXene+rGO composite material has a specific capacitance of 604.57 F / g at a current density of 1 A / g, 604.57 F / g at a current density of 1 A / g, 474.4 F / g at a current density of 4 A / g, 431.4 F / g at a current density of 10 A / g, and 364 F / g at a current density of 20 A / g. (3) By Figure 4 According to (2), the specific capacitance of the MXene+rGO composite material at a high current density of 20A / g is 60.2% of that at a current density of 1A / g. This indicates that the MXene+rGO composite material has good rate performance when used as an electrode material for supercapacitors. (4) By Figure 5 As shown, the MXene+rGO composite material exhibits a negligible semi-circular shape in the high-frequency region, indicating that the sample has a low charge transfer resistance.

[0034] Unless otherwise specified, the experimental methods used in the following examples are conventional methods, and the materials, reagents, methods and instruments used are conventional materials, reagents, methods and instruments in the art, which can be obtained by those skilled in the art through commercial channels.

[0035] The preferred embodiments of the application disclosed above are only to facilitate the elucidation of the application. The preferred embodiments do not describe all the details of the application, nor limit the application to the specific embodiments described. Obviously, many modifications and variations are possible in light of the above teachings. The embodiments were chosen and described in order to provide the best illustration of the principles of the application and its practical application, and to thereby enable one of ordinary skill in the art to best utilize the application. The application is only to be limited by the claims and their full scope and equivalents.

Claims

1. A method for preparing MXene+rGO aerogel based on the principle of corrosion galvanic cells, characterized in that, The steps are as follows: S1: A black liquid was obtained from the MAX-Ti3AlC2 powder. S2: Mix the upper black liquid obtained in step S1 with graphene oxide to obtain solution A; S3: Mix hydrochloric acid and solution A, adjust the pH of solution A to 6-7, and obtain solution B; S4: Immerse the square zinc sheet in the mixed solution B obtained in step S3 in a petri dish for 1 hour; S5: Wash the black hydrogel obtained in step S4 with deionized water and remove the residual mixed solution B; S6: Mix hydrochloric acid with deionized water to obtain solution C, and soak the hydrogel obtained in step S5 with solution C. Separate the hydrogel from the zinc sheet to obtain MXene+rGO hydrogel. S7; The MXene+rGO hydrogel obtained in S6 was repeatedly washed with deionized water and freeze-dried to obtain MXene+rGO aerogel.

2. The method for preparing MXene+rGO aerogel based on the principle of corrosion galvanic cells according to claim 1, characterized in that, In step S2, 25 parts of the upper black liquid obtained in step S1 are mixed with 0:40:80:120:160 parts of graphene oxide to obtain solution A.

3. The method for preparing MXene+rGO aerogel based on the principle of corrosion galvanic cell according to claim 1, characterized in that, In step S4, a 1 cm² area is placed in the petri dish. 2 The square zinc sheet is immersed in the mixed solution B obtained in step S3 for 1 hour.

4. The method for preparing MXene+rGO aerogel based on the principle of corrosion galvanic cells according to claim 1, characterized in that, In step S6, 10 parts of hydrochloric acid and 90 parts of deionized water are mixed to obtain solution C, and the hydrogel obtained in step S5 is soaked in solution C. The hydrogel is then separated from the zinc sheet to obtain MXene+rGO hydrogel.

5. The method for preparing MXene+rGO aerogel based on the principle of corrosion galvanic cell according to claim 1, characterized in that, In step S1, the MAX-Ti3AlC2 powder is processed to obtain an upper black liquid, as follows: A. Mix deionized water and concentrated hydrochloric acid to obtain a first solution, and dissolve lithium fluoride in the first solution to obtain a second solution; B. Add 1 part of MAX-Ti3AlC2 powder to the second solution and continue stirring for 24 hours; C. Transfer the mixed solution obtained in step B to a centrifuge tube, wash and centrifuge until the upper liquid turns black; D. Sonicate the black liquid obtained in step C in an ice water bath for 30 minutes, with the temperature below 20°C. E. Centrifuge the sonicated liquid from step D to obtain the upper black liquid.

6. The method for preparing MXene+rGO aerogel based on the principle of corrosion galvanic cells according to claim 5, characterized in that, In step A, 10 parts of deionized water and 30 parts of concentrated hydrochloric acid are mixed to obtain a first solution, and 3.2 parts of lithium fluoride are dissolved in the first solution to obtain a second solution.

7. An application of MXene+rGO aerogel based on the principle of corrosion galvanic cell.

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