Three-dimensional aerogel electrode preparation method, three-dimensional aerogel electrode and zinc battery

Abstract

The invention discloses a preparation method of a three-dimensional aerogel electrode, the three-dimensional aerogel electrode and a zinc battery, which are used for improving smooth transportation and high conductivity of zinc ions. Preparing graphene oxide; preparing an MXene aqueous solution; a TEMPO cellulose nanofiber is obtained; preparing an active response substance according to response items, wherein the response items comprise external pressure signal response and external optical signal response; the graphene oxide, the MXene aqueous solution, the TEMPO cellulose nanofiber, an active response substance and D-(+)-glucose are used, and the three-dimensional aerogel electrode is generated through a directional freezing method.

Description

TECHNICAL FIELD

[0001] The embodiment of the present application relates to the electrical field, in particular to a three-dimensional aerogel electrode preparation method, a three-dimensional aerogel electrode and a zinc battery. BACKGROUND

[0002] As a kind of wearable smart sensor equipment, electronic skin has attracted great research interest due to its application prospect in the field of artificial intelligence, medical devices, etc. However, in general, the work of the sensor in the wearable smart sensor equipment depends on the support of external power supply, which will inevitably lead to additional power cost efficiency and poor scalability limited by the volume of additional power supply.

[0003] On the basis of previous research, researchers explored the structure of linear motor based on triboelectric mode to manufacture self-powered sensors. However, due to the large internal resistance material required for the operation of linear motor, the output current provided by linear motor (usually in the range of 0-20 μA) is small, which casts a shadow on the accurate measurement of micro-current. Piezoelectric flexible self-powered sensors mainly use piezoelectric effect caused by dielectric torque to realize signal sensing. Electric dipole moment is generated by the deformation of oriented non-central symmetric crystal structure or porous polar body with continuous electric charge in the hole, which usually requires the use of harmful lead metal or organic ferroelectric compound materials. Moreover, this kind of sensor can only detect dynamic pressure signals, and cannot detect static pressure. Flexible pressure sensors are mainly divided into piezoresistive, capacitive and piezoelectric according to the stimulation response mechanism, among which piezoresistive sensors reflect the change of impedance belonging to state parameters, and have the ability of intuitive quantization and visualization of external stress stimulation even static pressure. However, piezoresistive effect does not generate electric charge, which sets a huge obstacle for the design of self-powered current source. Considering that the floating of impedance when powered by stable voltage source has a great influence on output current, flexible battery can be used in coupling with pressure sensor. Among various mainstream batteries, rechargeable zinc ion battery is concerned due to its high energy density, safe discharge process, non-toxic and inexpensive battery materials, simple preparation process and other advantages. Therefore, nowadays, sustainable pressure sensing materials can be used as an electrode, and then a suitable zinc ion battery system is designed to solve the above difficulties by formulating active material selection and optimizing battery configuration.

[0004] Flexible pressure sensors are generally composed of conductive electrodes, force-sensitive layers and flexible substrates. Stability and sensitivity are crucial when evaluating the performance of the sensor as needed. Currently, researchers are exploring hydrogels and aerogels with high porosity, excellent flexibility and electromechanical properties. Hydrogel sensors are prone to hysteresis and fluctuations, and have low sensitivity, while aerogels are prone to collapse under device deformation, which poses a stumbling block for cycle stability. Therefore, the balance between sensitivity and stability remains challenging. In addition, the positive electrode material of zinc ion battery essentially needs to ensure efficient and stable zinc storage, achieve smooth transport of zinc ions and high conductivity, which poses more stringent requirements for the cathode of the zinc ion hybrid pressure sensor with a dual identity. SUMMARY

[0005] The application discloses a three-dimensional aerogel electrode preparation method, a three-dimensional aerogel electrode and a zinc battery, which are used to improve the smooth transport and high conductivity of zinc ions.

[0006] The application aims to use a sustainable pressure sensing material as an electrode, load different active substances (such as manganese dioxide loading, molybdenum disulfide loading and zinc indium sulfide loading, etc.) on the pressure sensing material, and then use the electrode to design a suitable zinc ion battery system, which can perform pressure response or light response sensing detection without external power supply, saving energy, being environmentally friendly and sustainable, operating in an economical and scalable manner, and also expanding the application field due to the ability to load different active substances.

[0007] In a first aspect, embodiments of the application provide a three-dimensional aerogel electrode preparation method, comprising: preparing graphene oxide; preparing a MXene aqueous solution; obtaining TEMPO cellulose nanofibers; preparing active response substances according to response items, the response items including external pressure signal response and external light signal response; using graphene oxide, the MXene aqueous solution, TEMPO cellulose nanofibers, active response substances and D-(+)-glucose, and generating a three-dimensional aerogel electrode by a directional freezing method.

[0008] Optionally, the step of generating a three-dimensional aerogel electrode by a directional freezing method using graphene oxide, the MXene aqueous solution, TEMPO cellulose nanofibers, active response substances and D-(+)-glucose comprises: frozen-drying the TEMPO cellulose nanofibers; Put deionized water in beaker A, put graphene oxide into the deionized water in beaker A, and ultrasonically stir in beaker A to form a stable and uniform suspension; A predetermined weight of active response substance is weighed and added to beaker A, and ultrasonic stirring treatment is performed; A predetermined volume of MXene aqueous solution is measured and added to beaker A, and ultrasonic stirring treatment is performed; A predetermined weight of D-(+)-glucose is weighed and added to beaker A, and ultrasonic stirring treatment is performed; A predetermined weight of zinc ion-containing salt is weighed and added to beaker A, and ultrasonic stirring treatment is performed; Put deionized water in beaker B, weigh a predetermined weight of freeze-dried TEMPO cellulose nanofiber and put it into beaker B, and stir beaker B; Pour the mixture in beaker A into beaker B and stir; After stirring, take a predetermined volume of the mixture in an alumina crucible and place it on a pre-cooled copper block with liquid nitrogen, and continue to add liquid nitrogen around the alumina crucible for directional freezing; After all the freezing is completed, perform freeze-drying treatment; After freeze-drying is completed, place the alumina crucible in a moving tube furnace, and first introduce nitrogen to remove air in the tube; Heat at 300℃ for 1h, then heat at 700℃ for 2h, the heating rate is 5℃ / min, after annealing, naturally cool to room temperature, generate active response substance corresponding three-dimensional aerogel electrode.

[0009] Optionally, after using graphene oxide, MXene aqueous solution, TEMPO cellulose nanofiber, active response substance and D-(+)-glucose, and generating three-dimensional aerogel electrode by directional freezing method, the three-dimensional aerogel electrode preparation method further includes: Use graphene oxide, MXene aqueous solution, TEMPO cellulose nanofiber and D-(+)-glucose to prepare a special hydrophobic modifier; Use the hydrophobic modifier and combine the secondary directional freezing method to perform hydrophobic film attachment treatment on multiple surfaces of the three-dimensional aerogel electrode, and only one surface is reserved for ion exchange.

[0010] Optionally, the step of using graphene oxide, MXene aqueous solution, TEMPO cellulose nanofiber and D-(+)-glucose to prepare a special hydrophobic modifier includes: Freeze-drying treatment is performed on TEMPO cellulose nanofiber; Put deionized water in beaker C, put graphene oxide into the deionized water in beaker C, and ultrasonically stir in beaker C to form a stable and uniform suspension; Take a preset volume of MXene aqueous solution and add it to beaker C for ultrasonic stirring treatment; Weigh a preset weight of D-(+)-glucose and add it to beaker C for ultrasonic stirring treatment; Add a hydrophobic modifier to beaker C for ultrasonic stirring treatment; Put deionized water into beaker D, weigh a preset weight of freeze-dried TEMPO cellulose nanofiber and put it into beaker D, and stir beaker D; Pour the mixture in beaker C into beaker D and stir to generate a special hydrophobic modifier.

[0011] Optionally, after the step of obtaining TEMPO cellulose nanofiber, before the step of using graphene oxide, MXene aqueous solution, TEMPO cellulose nanofiber, active response substance and D-(+)-glucose to generate a three-dimensional aerogel electrode by directional freezing method, the three-dimensional aerogel electrode preparation method further comprises: Freeze-dry the TEMPO cellulose nanofiber; Put deionized water into beaker E, put graphene oxide into the deionized water in beaker E, and ultrasonically stir in beaker E to form a stable and uniform suspension; Take a preset volume of MXene aqueous solution and add it to beaker E for ultrasonic stirring treatment; Weigh a preset weight of D-(+)-glucose and add it to beaker E for ultrasonic stirring treatment; Weigh a preset weight of zinc ion-containing salt and add it to beaker E for ultrasonic stirring treatment; Put deionized water into beaker F, weigh a preset weight of freeze-dried TEMPO cellulose nanofiber and put it into beaker F, and stir beaker F; Pour the mixture in beaker E into beaker F and stir; After stirring, take a preset volume of the mixture in an alumina crucible and place it on a copper block pre-cooled with liquid nitrogen, and continue to add liquid nitrogen around the alumina crucible for directional freezing; After all the freezing is completed, perform freeze-drying treatment; After freeze-drying is completed, place the alumina crucible in a moving tube furnace, and first introduce nitrogen to remove air in the tube; Heat at 300℃ for 1h, then heat at 700℃ for 2h, the heating rate is 5℃ / min, after annealing, naturally cool to room temperature to generate a directional cold-dried sample; Test the assembly performance of the directional cold-dried sample; When the performance test result meets the preset condition, the directional cold-dried sample is determined to be a qualified sample.

[0012] Optionally, the step of performing the assembly performance test on the directional freeze-dried sample comprises: applying conductive silver paste on both ends of the glass slide and attaching copper wires; performing a drying process at a preset temperature to solidify the conductive silver paste and fix the copper wires; placing the directional freeze-dried sample on both ends, and performing a performance test using a linear motor and an electrochemical workstation.

[0013] Optionally, after the step of performing the assembly performance test on the directional freeze-dried sample, the three-dimensional aerogel electrode preparation method further comprises: preparing a non-directional freeze-dried sample, performing an assembly performance test using the non-directional freeze-dried sample, and performing a comparative analysis with the assembly performance test of the directional freeze-dried sample.

[0014] In a second aspect, the embodiments of the present application provide a three-dimensional aerogel electrode prepared by the three-dimensional aerogel electrode preparation method of any one of the first aspect.

[0015] In a third aspect, the embodiments of the present application provide a zinc battery, which is composed of an optical quartz sheet, a wire, a three-dimensional aerogel electrode of the second aspect, a battery separator treated by a 2 M ZnSO4 and 0.1 M MnSO4 immersion solution, and a zinc sheet, which are stacked in sequence. The three-dimensional aerogel electrode serves as a zinc ion sensing electrode. The wire comprises a pressure response type wire and a light response type wire, and the light response type wire has a hollow light response region.

[0016] Optionally, the zinc battery further comprises a shell, and the shell is provided with a fixing hole, a pressure response hole, and a light response hole. The zinc sheet passes through the fixing hole. The wire passes through the pressure response hole, and the pressure response hole is provided with an extrusion area for displacement of the wire. The light response hole is used for transmitting light signals, so that the zinc battery can perform light response.

[0017] From the above technical solutions, it can be seen that the embodiments of the present application have the following advantages: The present application first prepares graphene oxide. A MXene aqueous solution is prepared. TEMPO cellulose nanofibers are obtained. According to the response project, an active response substance is prepared, and the response project includes an external pressure signal response and an external light signal response. The three-dimensional aerogel electrode is generated by using graphene oxide, the MXene aqueous solution, the TEMPO cellulose nanofiber, the active response substance, and D-(+)-glucose through a directional freeze-drying method.

[0018] The three-dimensional aerogel electrode prepared by the unique directional freezing method and the graphene oxide, MXene aqueous solution, TEMPO cellulose nanofiber, active response substance and D-(+)-glucose in the present application has high conductivity and high stress sensitivity due to the axial arrangement of the porous framework and the mutual cooperation of different components. And due to the low bending degree of the generated three-dimensional aerogel electrode aerogel framework, the active site is fully exposed, realizing fast ion diffusion and charge transfer kinetics, which can also detect without external power supply, while improving the smooth transport of zinc ions and high conductivity. BRIEF DESCRIPTION OF DRAWINGS

[0019] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or prior art description will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor.

[0020] Figure 1 An embodiment schematic diagram of the three-dimensional aerogel electrode preparation method of the present application; Figure 2 An embodiment schematic diagram of the method for preparing the three-dimensional aerogel electrode of the present application; Figure 3 An embodiment schematic diagram of the method for attaching the hydrophobic film of the present application; Figure 4 An embodiment schematic diagram of the method for generating a special hydrophobic modifier of the present application; Figure 5 An embodiment schematic diagram of the method for testing the directional dry sample of the present application; Figure 6 An embodiment schematic diagram of the method for testing the directional dry sample of the present application; Figure 7 An embodiment schematic diagram of the method for testing the non-directional dry sample of the present application; Figure 8 An embodiment schematic diagram of the three-dimensional aerogel electrode preparation device of the present application; Figure 9 An embodiment schematic diagram of the internal structure of the self-powered zinc ion hybrid pressure (light) sensor of the present application; Figure 10 An embodiment schematic diagram of the assembly mold of the self-powered zinc ion hybrid pressure (light) sensor of the present application; Figure 11 A scanning electron microscope image of manganese dioxide and molybdenum disulfide of the present application; Figure 12SEM top view of the DFD and NDFD of the present application; Figure 13 Current-time response curve of the DFD sensor of the present application in the range of 0.45-12.47 kPa; Figure 14 Cycling stability comparison of the NDFD, DFD, and DFD / Mn02cathode sensors of the present application; Figure 15 Test results of the DFD / Mn02cathode sensor of the present application under slow finger pressing; Figure 16 Cycling stability of the DFD / MoS2cathode sensor of the present application; Figure 17 Photocurrent response curve of the DFD / MoS2cathode sensor of the present application under light (AM 1.5, 200 mW cm -2 ) and dark conditions; Figure 18 Overall structure of the present application with hydrophobic film attached; Figure 19 Top surface with local film attached of the present application; Figure 20 Side view of the short side of the present application with film attached. DETAILED DESCRIPTION

[0021] In the following description, for purposes of explanation and not limitation, specific details are set forth such as particular architectures, technologies, techniques, etc. in order to provide a thorough understanding of the embodiments of the present application. However, it will be apparent to those skilled in the art that the present application can be practiced in other embodiments that depart from these specific details. In other instances, detailed descriptions of well-known systems, devices, circuits, and methods are omitted so as not to obscure the description of the present application with unnecessary detail.

[0022] It is to be understood that the terminology "includes", "has", "holds", "contains" and / or "comprising", when used in this specification and in the following claims, indicates the presence of the described features, integers, steps, operations, elements, and / or components, but does not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof.

[0023] It is also to be understood that the terminology "and / or" when used in this specification and in the following claims, refers to at least one of the items, or any combination of one or more of the items, and includes all possible combinations of one or more of the items.

[0024] As used in the specification and the appended claims of the application, the term "if' can be interpreted as meaning "when" or "upon" or "in response to determining" or "in response to detecting" depending on the context. Similarly, the phrase "if it is determined" or "if [the recited condition or event] is detected" can be interpreted as meaning "upon determining" or "in response to determining" or "upon detecting [the recited condition or event]" or "in response to detecting [the recited condition or event]" depending on the context.

[0025] In addition, in the description of the present application and the appended claims, the terms "first", "second", "third", etc. are only used to distinguish the description and cannot be understood as indicating or implying relative importance.

[0026] In the present application, the reference "one embodiment" or "some embodiments" and the like means that the specific features, structures or characteristics described in connection with the embodiment are included in one or more embodiments of the application. Therefore, the statements "in one embodiment", "in some embodiments", "in other some embodiments", "in further some embodiments" and the like appearing in different places in the specification are not necessarily all referring to the same embodiment, but mean "one or more but not all embodiments", unless otherwise specifically emphasized. The terms "include", "contain", "have" and their variants mean "include but not limited to", unless otherwise specifically emphasized.

[0027] In the prior art, a flexible pressure sensor is usually composed of a conductive electrode, a force-sensitive layer and a flexible substrate. When evaluating the performance of the sensor as needed, stability and sensitivity are crucial. At present, researchers are exploring hydrogels and aerogels with high porosity, excellent flexibility and electromechanical properties. Hydrogel sensors are prone to hysteresis and fluctuations, and have low sensitivity, while aerogels are prone to collapse under device deformation, which poses a stumbling block for cycle stability. Therefore, the balance between sensitivity and stability remains challenging. In addition, the positive electrode material of zinc ion battery essentially needs to ensure efficient and stable zinc storage, realizing smooth transport and high conductivity of zinc ions, which poses more stringent requirements on the cathode of the zinc ion hybrid pressure sensor with dual identity.

[0028] Based on this, the present application discloses a three-dimensional aerogel electrode preparation method, a three-dimensional aerogel electrode and a zinc battery, for improving the smooth transport and high conductivity of zinc ions.

[0029] With reference to the drawings of the embodiments of the present application, the technical solutions in the present application will be described clearly and completely. Obviously, the described embodiments are only a part of the embodiments of the present application, but not all the embodiments of the present application. Based on the embodiments of the present application, all the other embodiments obtained by a person of ordinary skill in the art without creative work are within the scope of protection of the present application.

[0030] The method of the present application can be applied to a server, a device, a terminal or other device with logical processing capability, and the present application is not limited in this regard. For the convenience of description, the following will be described taking the terminal as an example.

[0031] Please refer to Figure 1 The present application provides an embodiment of a three-dimensional aerogel electrode preparation method, comprising: 101. Preparing graphene oxide; In the embodiment, the method for preparing graphene oxide is as follows: 1. First, measure 20 mL of phosphoric acid and 180 mL of sulfuric acid, mix them in a 500 mL beaker, and place them in a 50 ℃ water bath for slow stirring for 15 min to make them uniformly mixed.

[0032] 2. Then add 1.5 g of carbon black to it, and slowly stir for 15 min to make them uniformly mixed. Then measure 9 g of potassium permanganate, and add a small amount of potassium permanganate to it every 2 min, and control the addition to be completed within 40 min (to prevent the reaction from exploding and the reaction heat from being too fast to exceed 50 ℃), and after all the potassium permanganate is added, keep it at 50 ℃ for slow stirring for 6 h.

[0033] 3. After the reaction is completed, measure 20 mL of hydrogen peroxide solution and 60 mL of deionized water in a 100 mL beaker, stir for 5 min to make them uniformly mixed, use a rubber bulb dropper to slowly drop a small amount of solution into the reaction each time (to prevent the gas bubbles from being generated too fast to explode and the reaction heat from being too fast to exceed 50 ℃, if it exceeds 50 ℃, immediately add tap water to the water bath to cool down), until the reaction no longer produces gas bubbles, and the color becomes yellow-green, then continue to keep it at 50 ℃ for slow stirring for 3 h.

[0034] 4、After the reaction is completed, slowly add deionized water to the 500 mL mark in three times and continuously stir evenly with a glass rod, seal at room temperature and stand for 8 h. After standing is completed, slowly suck the upper clear liquid with a rubber bulb dropper, leave the precipitate, repeat standing three times, continue to add an appropriate amount of deionized water and stir evenly, and centrifuge at 10000 r / min for 40 min, remove the upper clear liquid, leave the precipitate, repeat the addition of deionized water and centrifugal washing until it is neutral, collect the precipitate in a glass culture dish for freezing, and after freezing is completed, perform freeze-drying to obtain graphene oxide (GO).

[0035] 102、Preparation of MXene aqueous solution; Next, the MXene aqueous solution is prepared. First, 1 g of lithium fluoride is weighed in centrifuge tube A. Then, 12 mL of hydrochloric acid and 4 mL of deionized water are weighed in centrifuge tube B, and they are mixed evenly in an ice bath for 5 min. Then, the solution in centrifuge tube B is poured into centrifuge tube A, and the lithium fluoride is fully dissolved in an ice bath for 5 min. Then, 0.45 g of titanium aluminum carbide is weighed, and 0.15 g is added to centrifuge tube A at a time, and the addition is completed in three times, and each time the ice bath is stirred for 3 min. After the last addition, continue to stir in the ice bath for 20 min. Then, a pair of rubber gloves is tightly wrapped around the lid of centrifuge tube A with a rubber band (which can adjust the gas pressure balance and gas leakage of the reaction), and placed in a 40 ℃ oil bath for 48 h. After the reaction is completed, 40 mL of hydrochloric acid and 40 mL of deionized water are mixed in a beaker and stirred for 5 min, and then the solution is added to centrifuge tube A for acid washing. After shaking evenly, centrifuge at 4000 r / min for 5 min, and discard the supernatant. Repeat the acid washing three times. After acid washing is completed, repeat the above centrifugal operation by adding deionized water. After repeated washing three times, leave the precipitate in the refrigerator for 10 h. After the cold storage is completed, 100 mL of deionized water is weighed and the precipitate is dissolved in a beaker and ultrasonicated for 30 min. Then, centrifuge at 4000 r / min for 5 min to obtain the supernatant. Repeat the operation until all the MXene aqueous solution is separated.

[0036] 103、Obtaining TEMPO cellulose nanofiber; 104、Preparation of active response substance according to response project, which includes external pressure signal response and external light signal response; 105、Using graphene oxide, MXene aqueous solution, TEMPO cellulose nanofiber, active response substance and D-(+)-glucose, and generating a three-dimensional aerogel electrode by directional freezing method.

[0037] In this embodiment, TEMPO cellulose nanofiber needs to be obtained, and active response substances are prepared according to response projects, which include external pressure signal response and external light signal response. Among them, the response projects include light response and pressure response, and the active response substances of the pressure response include MnO2, MnO2@Au. The active response substances of the light response also include MoS2, MoS2@Au, TiO2 / MoS2, TiO2 / MoS2@Au, ZnIn2S4, ZnIn2S4@Au, TiO2 / ZnIn2S4, TiO2 / ZnIn2S4@Au. The above active substances all need to be prepared and prepared into a form that can be loaded on a three-dimensional aerogel electrode. To generate a self-powered pressure response three-dimensional aerogel electrode (zinc ion hybrid pressure sensor, DFD / MnO2, DFD / MnO2@Au), DFD is a directional cold-drying sample. The self-powered zinc ion hybrid pressure sensor in this embodiment has high sensitivity, excellent surface capacitance / energy density and long cycle stability. In particular, the superior power supply capability can support real-time response to external pressure stimulation. And generate a self-powered light response three-dimensional aerogel electrode (zinc ion hybrid light response sensor, DFD / MoS2, DFD / MoS2@Au, DFD / TiO2 / MoS2, DFD / TiO2 / MoS2@Au and DFD / ZnIn2S4, DFD / ZnIn2S4@Au, DFD / TiO2 / ZnIn2S4, DFD / TiO2 / ZnIn2S4@Au), the zinc ion hybrid light response sensor in this embodiment can support real-time response to external light stimulation and has certain long cycle stability. In particular, the superior power supply capability can support real-time response to external light stimulation. The subsequent embodiments will be described in detail for the preparation of active response substances.

[0038] Finally, graphene oxide, MXene aqueous solution, TEMPO cellulose nanofiber, active response substance and D-(+)-glucose are used, and a three-dimensional aerogel electrode is generated by directional freezing method. This step is described in subsequent embodiments.

[0039] In this embodiment, graphene oxide is first prepared. MXene aqueous solution is prepared. TEMPO cellulose nanofiber is obtained. Active response substances are prepared according to response projects, which include external pressure signal response and external light signal response. Graphene oxide, MXene aqueous solution, TEMPO cellulose nanofiber, active response substance and D-(+)-glucose are used, and a three-dimensional aerogel electrode is generated by directional freezing method.

[0040] The three-dimensional aerogel electrode prepared by the directional freeze-drying method of the embodiment and the graphene oxide, the MXene aqueous solution, the TEMPO cellulose nanofiber, the active response substance and the D-(+)-glucose has high conductivity and high stress sensitivity due to the axial arrangement of the porous framework and the mutual cooperation of different components. Moreover, the three-dimensional aerogel electrode has low aerogel framework curvature, sufficient exposure of active sites, fast ion diffusion and charge transfer kinetics, and can improve the smooth transport of zinc ions and high conductivity without external power supply.

[0041] Moreover, in the embodiment, the honeycomb-like rGO / TOCNs / MXene / glucose aerogel prepared by the directional freeze-drying method described above is used as a cathode current collector (DFD) for loading manganese dioxide (MnO2) nanorods. The DFD has high conductivity and high stress sensitivity due to the axial arrangement of the porous framework and the mutual cooperation of different components. After the introduction of manganese dioxide, the aerogel framework has low curvature, sufficient exposure of active sites, fast ion diffusion and charge transfer kinetics, and can detect pressure without external power supply. Moreover, the cathode current collector (DFD) can also load molybdenum disulfide (MoS2) and other substances with light response performance. Since the 2H phase of MoS2 has light response and can also be used as a zinc ion battery, the DFD can detect light response without external power supply. The work can expand the ideas for the development of microelectronic sensors.

[0042] Please refer to Figure 2 An embodiment of a method for preparing a three-dimensional aerogel electrode is provided in the application, which comprises the following steps: 201. Freeze-drying the TEMPO cellulose nanofiber; 202. Deionized water is loaded into beaker A, graphene oxide is put into the deionized water in beaker A, and ultrasonic stirring is performed in beaker A to form a stable and uniform suspension; 203. A predetermined weight of active response substance is weighed and added to beaker A, and ultrasonic stirring is performed; 204. A predetermined volume of MXene aqueous solution is measured and added to beaker A, and ultrasonic stirring is performed; 205. A predetermined weight of D-(+)-glucose is weighed and added to beaker A, and ultrasonic stirring is performed; 206. A predetermined weight of zinc ion-containing salt is weighed and added to beaker A, and ultrasonic stirring is performed; 207. Deionized water is loaded into beaker B, a predetermined weight of freeze-dried TEMPO cellulose nanofiber is weighed and put into beaker B, and beaker B is stirred; 208. Pour the mixture in beaker A into beaker B and stir. 209. After stirring, take a predetermined volume of the mixture into an alumina crucible and place it on a copper block that has been pre-cooled with liquid nitrogen. Continue to add liquid nitrogen around the alumina crucible for directional freezing. 210. After all freezing is complete, perform freeze-drying. 211. After freeze-drying, place the alumina crucible in a movable tube furnace and first introduce nitrogen to remove air from the tube. 212. The electrode is kept at 300℃ for 1 hour, then at 700℃ for 2 hours, with a heating rate of 5℃ / min. After annealing, it is naturally cooled to room temperature to generate a three-dimensional aerogel electrode corresponding to the active responsive material.

[0043] The specific methods for preparing the active responsive materials, and how to generate the corresponding three-dimensional aerogel electrodes, will be described in detail below.

[0044] Example 1: Synthesis of Manganese Dioxide (MnO2). In this example, 0.973 g of potassium permanganate was first weighed into 120 mL of deionized water and stirred continuously for 30 min in beaker A until fully dissolved. Then, 2.27 g of manganese acetate (containing 4 molecules of water of crystallization) was weighed into 20 mL of deionized water and stirred continuously for 30 min in beaker B until fully dissolved. Then, the solution in beaker B was slowly added dropwise to beaker A using a dropper, while stirring continuously. After all the solution was added, stirring continued for 1 h. The mixture was then transferred to a 100 mL autoclave and subjected to a hydrothermal reaction at 120 °C for 12 h. After the hydrothermal reaction was completed and the mixture was allowed to cool naturally to room temperature, the dark brown product was washed three times with deionized water at 4000 r / min. Finally, the dark brown product was placed in a vacuum oven and dried for 12 h. After drying, it was ground into a dark brown powder to obtain manganese dioxide powder (in this example, beakers A and B are two new, independent beakers). Please refer to [reference needed]. Figure 11 , Figure 11 The images are scanning electron microscope (SEM) images of manganese dioxide and molybdenum disulfide. Specifically, (a) is a scanning electron microscope image of manganese dioxide (500 nm) and (b) is a scanning electron microscope image of molybdenum disulfide (1 μm).

[0045] Synthesis of DFD / MnO2, in this embodiment, the TEMPO cellulose nanofiber was first frozen for 12 h, and then freeze-dried for 14 h. Then 0.12 g of graphene oxide was weighed in 6 mL of deionized water, and ultrasonic stirring was performed in beaker A for 1 h to form a stable and uniform suspension. Then 0.04 g of MnO2 was weighed into beaker A and ultrasonic stirring was performed for 30 min. Then 6 mL of MXene aqueous solution was measured and added to beaker A, and ultrasonic stirring was continued for 30 min. Then 0.2 g of D-(+)-glucose was weighed into beaker A, and ultrasonic stirring was continued for 30 min. Then 0.1 g of zinc chloride (or zinc sulfate, zinc nitrate, etc. zinc ion containing salt) was weighed into beaker A, and ultrasonic stirring was continued for 30 min. Then 0.28 g of freeze-dried TEMPO cellulose nanofiber was weighed in 12 mL of deionized water, and stirred in beaker B for 30 min. The mixture in beaker A was poured into beaker B, and rapid stirring was performed for 6 h. After stirring, 2.2 mL of the mixture was taken with a rubber dropper and placed in a 30*20*10 mm alumina crucible (in addition to the rectangular alumina crucible, it can also be placed in any mold to make different shapes of electrode structure, that is, the shape of the electrode can be changed according to actual needs), and placed on a 100*100*10 mm copper block pre-cooled with liquid nitrogen, and liquid nitrogen was continuously added around the crucible for directional freezing. After the freezing was completed, freeze-drying was performed for 12 h. After freeze-drying, the crucible was placed in a movable tube furnace, and nitrogen was introduced for 20 min (to remove air in the tube), then heat treated at 300 °C for 1 h, and then heat treated at 700 °C for 2 h, with a heating rate of 5 °C / min. After annealing, it was naturally cooled to room temperature. The DFD / MnO2 sample was obtained.

[0046] Example Two: Synthesis of MnO2@Au, first 0.04 g of dry MnO2 powder was suspended in 20 mL of deionized water, and ultrasonic stirring was performed for 10 min to make the MnO2 powder uniform. Then 50 mL of 1 mM L-cysteine aqueous solution was added, and the mixture was ultrasonic stirred for 30 min. Then 50 mL of 0.3 mM HAuCl4 aqueous solution was added, and the mixture was stirred vigorously for 30 min. Then 100 mL of 5 mM L-ascorbic acid aqueous solution was quickly added. Finally, the reaction was carried out by rapid stirring for 3 h. After stirring, it was washed with deionized water three times. The MnO2 powder with gold nanoparticles grown on it was obtained.

[0047] Synthesis of DFD / MnO2@Au, in this embodiment, the TEMPO cellulose nanofiber is first frozen for 12 h, and then freeze-dried for 14 h. Then 0.12 g of graphene oxide is weighed in 6 mL of deionized water, and ultrasonic stirring is performed in beaker A for 1 h to form a stable and uniform suspension. Then 0.04 g of MnO2@Au powder is weighed and added to beaker A, and ultrasonic stirring is performed for 30 min. Then 6 mL of MXene aqueous solution is measured and added to beaker A, and ultrasonic stirring is continued for 30 min. Then 0.2 g of D-(+)-glucose is weighed and added to beaker A, and ultrasonic stirring is continued for 30 min. Then 0.1 g of zinc chloride (or zinc sulfate, zinc nitrate, etc. zinc ion containing salt) is weighed and added to beaker A, and ultrasonic stirring is continued for 30 min. Then 0.28 g of freeze-dried TEMPO cellulose nanofiber is weighed in 12 mL of deionized water, and stirred in beaker B for 30 min. Pour the mixture in beaker A into beaker B and stir quickly for 6 h. After stirring, 2.2 mL of the mixture is taken with a rubber dropper and placed in a 30*20*10 mm alumina crucible, which is placed on a 100*100*10 mm copper block pre-cooled with liquid nitrogen. Continue to add liquid nitrogen around the crucible for directional freezing. After the freezing is completed, the freeze-drying is carried out for 12 h. After the freeze-drying is completed, the crucible is placed in a movable tube furnace, and nitrogen is introduced for 20 min (to remove air in the tube), then heat treated at 300 ℃ for 1 h, and then heat treated at 700 ℃ for 2 h, with a heating rate of 5 ℃ / min. After annealing, the sample is naturally cooled to room temperature. The DFD / MnO2@Au sample is obtained.

[0048] Example Three: Synthesis of Molybdenum Disulfide (MoS2), first, 1.0815 g of ammonium molybdate (containing 4 crystal waters) and 1.797 g of thiourea are dissolved in 54.9 mL of deionized water as molybdenum source and sulfur source respectively, and stirring is continued for 1 h. Then the mixture is transferred to a 100 mL autoclave and hydrothermal reaction is carried out at 210 ℃ for 18 h. After the hydrothermal reaction is completed, the black product is washed with deionized water and ethanol at 4000 r / min for three times respectively, and finally the black product is placed in a vacuum oven for drying for 12 h. After drying, the black powder is ground to obtain molybdenum disulfide powder.

[0049] Synthesis of DFD / MoS2, freeze TEMPO cellulose nanofiber for 12 h, then freeze dry for 14 h. Then weigh 0.12 g of graphene oxide in 6 mL of deionized water, ultrasonic stirring in beaker A for 1 h to form a stable and uniform suspension. Then weigh 0.85 g of MoS2 into beaker A, ultrasonic stirring for 30 min. Then weigh 6 mL of MXene aqueous solution into beaker A, continue to ultrasonic stirring for 30 min. Then weigh 0.2 g of D-(+)-glucose into beaker A, continue to ultrasonic stirring for 30 min. Then weigh 0.1 g of zinc chloride (or zinc sulfate, zinc nitrate, etc. zinc ion containing salt) into beaker A, continue to ultrasonic stirring for 30 min. Then weigh 0.28 g of freeze-dried TEMPO cellulose nanofiber in 12 mL of deionized water, stirring in beaker B for 30 min. Pour the mixture in beaker A into beaker B and stir quickly for 6 h. After stirring, use a rubber dropper to take 2.2 mL of the mixture into a 30*20*10 mm alumina crucible, and place it on a 100*100*10 mm copper block pre-cooled with liquid nitrogen. Continue to add liquid nitrogen around the crucible for directional freezing. After the freezing is completed, freeze dry for 12 h. After freeze drying, place the crucible in a moving tube furnace, first pass nitrogen for 20 min (remove air in the tube), then heat at 300 °C for 1 h, then heat at 700 °C for 2 h, the heating rate is 5 °C / min, after annealing, naturally cool to room temperature. Get DFD / MoS2 sample.

[0050] Example Four: Synthesis of MoS2@Au, take 0.85 g of dry MoS2 nanosheet powder and suspend it in 20 mL of deionized water, ultrasonic stirring for 10 min to mix the MoS2 nanosheet powder uniformly. Then add 50 mL of 1 mM L-cysteine aqueous solution, ultrasonic the mixture for 30 min. Then add 50 mL of 0.3 mM HAuCl4 aqueous solution, and stir vigorously for 30 min. Then quickly add 100 mL of 5 mM L-ascorbic acid aqueous solution. Finally, stir quickly for 3 h for reaction. After stirring, wash with deionized water three times. MoS2 nanosheet powder with gold nanoparticles grown on it is obtained.

[0051] Synthesis of DFD / MoS2@Au, freeze TEMPO cellulose nanofiber for 12 h, then freeze dry for 14 h. Then weigh 0.12 g of graphene oxide in 6 mL of deionized water, ultrasonic stirring in beaker A for 1 h to form a stable and uniform suspension. Then weigh 0.85 g of MoS2@Au powder into beaker A, ultrasonic stirring for 30 min. Then weigh 6 mL of MXene aqueous solution into beaker A, continue to ultrasonic stirring for 30 min. Then weigh 0.2 g of D-(+)-glucose into beaker A, continue to ultrasonic stirring for 30 min. Then weigh 0.1 g of zinc chloride (or zinc sulfate, zinc nitrate, etc. zinc ion containing salt) into beaker A, continue to ultrasonic stirring for 30 min. Then weigh 0.28 g of freeze-dried TEMPO cellulose nanofiber in 12 mL of deionized water, stirring in beaker B for 30 min. Pour the mixture in beaker A into beaker B and stir quickly for 6 h. After stirring, use a rubber dropper to take 2.2 mL of the mixture into a 30*20*10 mm alumina crucible, and place it on a 100*100*10 mm copper block pre-cooled with liquid nitrogen. Continue to add liquid nitrogen around the crucible for directional freezing. After the freezing is completed, freeze dry for 12 h. After freeze drying, place the crucible in a moving tube furnace, first introduce nitrogen for 20 min (to remove air in the tube), then heat at 300 ℃ for 1 h, then heat at 700 ℃ for 2 h, the heating rate is 5 ℃ / min. After annealing, cool to room temperature naturally. Get DFD / MoS2@Au sample.

[0052] Example Five: Synthesis of TiO2@MoS2 powder, 1.0815 g of ammonium molybdate (containing 4 crystal water) and 1.797 g of thiourea were dissolved in 54.9 mL of deionized water as molybdenum source and sulfur source respectively, a certain amount of TiO2 hollow sphere was added, and stirring was continued for 1 h. Then the mixture was transferred to a 100 mL autoclave and hydrothermal reaction was carried out at 210 ℃ for 18 h. After the hydrothermal reaction was completed, the product was cooled to room temperature naturally, then centrifuged with deionized water and ethanol respectively at 4000 r / min for three times, finally the product was placed in a vacuum oven for drying for 12 h. After drying, the powder was obtained, and TiO2@MoS2 powder was obtained.

[0053] Wherein, the synthesis of SiO2spheres, 9 mL of ammonia, 16.3 mL of ethanol and 24.8 mL of deionized water were mixed and stirred for 10 min, referred to as solution A. 4.5 mL of ethyl silicate (TEOS) and 45.5 mL of ethanol were mixed and stirred for 10 min, referred to as solution B. Solution B was quickly added to solution A, and after stirring for 2 h, the SiO2spheres were obtained by centrifugal washing with ethanol for 3 times. The synthesis of TiO2hollow spheres used SiO2spheres, first 0.2 g of SiO2spheres were dispersed in 150 mL of ethanol, then 1 mL of ammonium hydroxide was added, and stirred for 1 h. Then 2 mL of tetrabutyl titanate was added to the above solution at room temperature, and then reacted at 45 °C for 24 h. Then the product was washed with deionized water by centrifugation for three times, and vacuum dried at 60 °C for 10 h. Then the obtained SiO2@TiO2spheres were annealed in air atmosphere at 550 °C for 2 h. 10 g of KOH was dissolved in 100 mL of deionized water, and then the annealed SiO2@TiO2spheres were added to the solution and ultrasonicated for half an hour, and then stirred for 24 h. The TiO2hollow spheres were obtained by centrifugal washing with deionized water.

[0054] Synthesis of DFD / TiO2@MoS2, freeze TEMPO cellulose nanofiber for 12 h, then freeze dry for 14 h. Then weigh 0.12 g of graphene oxide in 6 mL of deionized water, ultrasonic stirring in beaker A for 1 h to form a stable and uniform suspension. Then weigh 0.85 g of TiO2@MoS2 powder into beaker A, ultrasonic stirring for 30 min. Then take 6 mL of MXene aqueous solution into beaker A, continue to ultrasonic stirring for 30 min. Then weigh 0.1 g of zinc chloride (or zinc sulfate, zinc nitrate, etc. zinc ion containing salt) into beaker A, continue to ultrasonic stirring for 30 min. Then weigh 0.2 g of D-(+)-glucose into beaker A, continue to ultrasonic stirring for 30 min. Then weigh 0.28 g of freeze-dried TEMPO cellulose nanofiber in 12 mL of deionized water, stir in beaker B for 30 min. Pour the mixture in beaker A into beaker B, quickly stir for 6 h. After stirring, take 2.2 mL of the mixture with a rubber dropper into a 30*20*10 mm alumina crucible, and place it on a 100*100*10 mm copper block pre-cooled with liquid nitrogen. Continue to add liquid nitrogen around the crucible for directional freezing. After the freezing is completed, freeze dry for 12 h. After freeze drying, place the crucible in a moving tube furnace, first introduce nitrogen for 20 min (to remove air in the tube), then heat at 300 °C for 1 h, then heat at 700 °C for 2 h, the heating rate is 5 °C / min, after annealing, naturally cool to room temperature. Get DFD / TiO2@MoS2 sample.

[0055] Example Six: Synthesis of TiO2 / MoS2@Au, 0.85 g of dry TiO2 / MoS2 powder was suspended in 20 mL of deionized water, ultrasonic stirring for 10 min to make ZnIn2S4 powder mixed uniformly. Then add 50 mL of 1 mM L-cysteine aqueous solution, ultrasonic the mixture for 30 min. Then add 50 mL of 0.3 mM HAuCl4 aqueous solution, and continue to stir vigorously for 30 min. Then quickly add 100 mL of 5 mM L-ascorbic acid aqueous solution. Finally, stir quickly for 3 h for reaction. After stirring, wash with deionized water three times. TiO2 / MoS2 powder with gold nanoparticles grown on it is obtained.

[0056] Synthesis of DFD / TiO2 / MoS2@Au, freeze TEMPO cellulose nanofiber for 12 h, then freeze drying for 14 h. Then weigh 0.12 g of graphene oxide in 6 mL of deionized water, ultrasonic stirring in beaker A for 1 h to form a stable and uniform suspension. Then weigh 0.5 g of TiO2 / MoS2@Au powder into beaker A, ultrasonic stirring for 30 min. Then weigh 6 mL of MXene aqueous solution into beaker A, continue to ultrasonic stirring for 30 min. Then weigh 0.1 g of zinc chloride (or zinc sulfate, zinc nitrate, etc. zinc ion containing salt) into beaker A, continue to ultrasonic stirring for 30 min. Then weigh 0.2 g of D-(+)-glucose into beaker A, continue to ultrasonic stirring for 30 min. Then weigh 0.28 g of freeze-dried TEMPO cellulose nanofiber in 12 mL of deionized water, stir in beaker B for 30 min. Pour the mixture in beaker A into beaker B, stir quickly for 6 h. After stirring, use a rubber dropper to take 2.2 mL of the mixture into a 30*20*10 mm alumina crucible, and place it on a 100*100*10 mm copper block pre-cooled with liquid nitrogen. Continue to add liquid nitrogen around the crucible for directional freezing. After the freezing is completed, freeze drying for 12 h. After freeze drying, place the crucible in a moving tube furnace, first pass nitrogen for 20 min (remove air in the tube), then heat at 300 ℃ for 1 h, then heat at 700 ℃ for 2 h, the heating rate is 5 ℃ / min, after annealing, naturally cool to room temperature. Get DFD / TiO2 / MoS2@Au sample.

[0057] Example Seven: Synthesis of Sulfur Indium Zinc Powder (ZnIn2S4), 0.3 g of thioacetamide, 0.27 g of zinc chloride and 0.44 g of indium chloride were added to 100 mL of deionized water (and the pH was adjusted to 2.5 with hydrochloric acid) and stirred for 20 min, then placed in an 80 ℃ oil bath. After stirring for 2 h, the resulting product was washed with deionized water and ethanol three times by centrifugation, and dried at 60 ℃ under vacuum for 10 h. ZnIn2S4 powder was obtained.

[0058] Synthesis of DFD / ZnIn2S4, first freeze TEMPO cellulose nanofiber for 12 h, then freeze dry for 14 h. Then weigh 0.12 g graphene oxide in 6 mL deionized water, ultrasonic stirring in beaker A for 1 h to form a stable and uniform suspension. Then weigh 0.85 g ZnIn2S4 into beaker A, ultrasonic stirring for 30 min. Then take 6 mL MXene aqueous solution into beaker A, continue to ultrasonic stirring for 30 min. Then weigh 0.2 g D-(+)-glucose into beaker A, continue to ultrasonic stirring for 30 min. Then weigh 0.1 g zinc chloride (or zinc sulfate, zinc nitrate, etc. zinc ion containing salt) into beaker A, continue to ultrasonic stirring for 30 min. Then weigh 0.28 g freeze-dried TEMPO cellulose nanofiber in 12 mL deionized water in beaker B, stirring for 30 min. Pour the mixture in beaker A into beaker B, quickly stir for 6 h. After stirring, take 2.2 mL mixture with a rubber dropper into a 30*20*10 mm alumina crucible, and place it on a 100*100*10 mm copper block pre-cooled with liquid nitrogen. Continue to add liquid nitrogen around the crucible for directional freezing. After freezing is completed, freeze dry for 12 h. After freeze drying, place the crucible in a moving tube furnace, first pass in 20 min nitrogen (remove air in the tube), then heat at 300 °C for 1 h, then heat at 700 °C for 2 h, the heating rate is 5 °C / min, after annealing, naturally cool to room temperature. Get DFD / ZnIn2S4 sample.

[0059] Example Eight: Synthesis of ZnIn2S4@Au, take 0.85 g of dry ZnIn2S4 powder and suspend it in 20 mL of deionized water, ultrasonic stirring for 10 min to mix the MoS2 nanosheet powder uniformly. Then add 50 mL of 1 mM L-cysteine aqueous solution, ultrasonic the mixture for 30 min. Then add 50 mL of 0.3 mM HAuCl4 aqueous solution, and stir vigorously for 30 min. Then quickly add 100 mL of 5 mM L-ascorbic acid aqueous solution. Finally, stir quickly for 3 h to react. After stirring, wash with deionized water three times. Get ZnIn2S4 powder with gold nanoparticles grown on it.

[0060] Synthesis of DFD / ZnIn2S4@Au, first freeze TEMPO cellulose nanofiber for 12 h, then freeze drying for 14 h. Then weigh 0.12 g of graphene oxide in 6 mL of deionized water, ultrasonic stirring in beaker A for 1 h to form a stable and uniform suspension. Then weigh 0.85 g of ZnIn2S4@Au powder into beaker A, ultrasonic stirring for 30 min. Then take 6 mL of MXene aqueous solution into beaker A, continue to ultrasonic stirring for 30 min. Then weigh 0.2 g of D-(+)-glucose into beaker A, continue to ultrasonic stirring for 30 min. Then weigh 0.1 g of zinc chloride (or zinc sulfate, zinc nitrate, etc. zinc ion containing salt) into beaker A, continue to ultrasonic stirring for 30 min. Then weigh 0.28 g of freeze-dried TEMPO cellulose nanofiber in 12 mL of deionized water, stir in beaker B for 30 min. Pour the mixture in beaker A into beaker B, stir quickly for 6 h. After stirring, take 2.2 mL of the mixture with a rubber dropper into a 30*20*10 mm alumina crucible, and place it on a 100*100*10 mm copper block pre-cooled with liquid nitrogen. Continue to add liquid nitrogen around the crucible for directional freezing. After the freezing is completed, freeze drying for 12 h. After freeze drying, place the crucible in a moving tube furnace, first pass nitrogen for 20 min (to remove air in the tube), then heat at 300 ℃ for 1 h, then heat at 700 ℃ for 2 h, the heating rate is 5 ℃ / min, after annealing, naturally cool to room temperature. Get DFD / ZnIn2S4@Au sample.

[0061] Example Nine: Synthesis of TiO2@ZnIn2S4 powder, 45-150 mg of TiO2 hollow sphere is added to 100 mL of deionized water (and the pH is adjusted to 2.5 with hydrochloric acid) and stirred for 20 min, then 0.3 g of thioacetamide, 0.27 g of zinc chloride and 0.44 g of indium chloride are added, the resulting mixed solution is stirred for 10 min, then put into an 80 ℃ oil bath, stir for 2 h, then the resulting product is washed with deionized water and ethanol respectively for 3 times, and dried at 60 ℃ under vacuum for 10 h. Obtain TiO2@ZnIn2S4 sample.

[0062] Synthesis of DFD / TiO2@ZnIn2S4, first freeze TEMPO cellulose nanofiber for 12 h, then freeze dry for 14 h. Then weigh 0.12 g of graphene oxide in 6 mL of deionized water, ultrasonic stirring in beaker A for 1 h to form a stable and uniform suspension. Then weigh 0.85 g of TiO2@ZnIn2S4 powder into beaker A, ultrasonic stirring for 30 min. Then take 6 mL of MXene aqueous solution into beaker A, continue to ultrasonic stirring for 30 min. Then weigh 0.2 g of D-(+)-glucose into beaker A, continue to ultrasonic stirring for 30 min. Then weigh 0.1 g of zinc chloride (or zinc sulfate, zinc nitrate, etc. zinc ion containing salt) into beaker A, continue to ultrasonic stirring for 30 min. Then weigh 0.28 g of freeze-dried TEMPO cellulose nanofiber in 12 mL of deionized water, stir in beaker B for 30 min. Pour the mixture in beaker A into beaker B and stir quickly for 6 h. After stirring, take 2.2 mL of the mixture with a rubber dropper into a 30*20*10 mm alumina crucible, and place it on a 100*100*10 mm copper block pre-cooled with liquid nitrogen. Continue to add liquid nitrogen around the crucible for directional freezing. After the freezing is completed, freeze dry for 12 h. After freeze drying, place the crucible in a moving tube furnace, first introduce nitrogen for 20 min (to remove air in the tube), then heat at 300 ℃ for 1 h, then heat at 700 ℃ for 2 h, the heating rate is 5 ℃ / min. After annealing, cool to room temperature naturally. Get DFD / TiO2@ZnIn2S4 sample.

[0063] Example Ten: Synthesis of TiO2 / ZnIn2S4@Au, take 0.85 g of dried TiO2 / ZnIn2S4 powder and suspend it in 20 mL of deionized water, ultrasonic stirring for 10 min to mix the TiO2 / ZnIn2S4 powder uniformly. Then add 50 mL of 1 mM L-cysteine aqueous solution, ultrasonic the mixture for 30 min. Then add 50 mL of 0.3 mM HAuCl4 aqueous solution, and stir vigorously for 30 min. Then quickly add 100 mL of 5 mM L-ascorbic acid aqueous solution. Finally, stir quickly for 3 h to react. After stirring, wash with deionized water three times. TiO2 / ZnIn2S4 powder with gold nanoparticles grown on it is obtained.

[0064] Synthesis of DFD / TiO2 / ZnIn2S4@Au, first freeze TEMPO cellulose nanofiber for 12 h, then freeze dry for 14 h. Then weigh 0.12 g of graphene oxide in 6 mL of deionized water, ultrasonic stirring in beaker A for 1 h to form a stable and uniform suspension. Then weigh 0.5 g of TiO2 / MoS2@Au powder into beaker A, ultrasonic stirring for 30 min. Then weigh 6 mL of MXene aqueous solution into beaker A, continue to ultrasonic stirring for 30 min. Then weigh 0.2 g of D-(+)-glucose into beaker A, continue to ultrasonic stirring for 30 min. Then weigh 0.1 g of zinc chloride (or zinc sulfate, zinc nitrate, etc. zinc ion containing salt) into beaker A, continue to ultrasonic stirring for 30 min. Then weigh 0.28 g of freeze-dried TEMPO cellulose nanofiber in 12 mL of deionized water, stir in beaker B for 30 min. Pour the mixture in beaker A into beaker B and stir quickly for 6 h. After stirring, use a rubber dropper to take 2.2 mL of the mixture into a 30*20*10 mm alumina crucible, and place it on a 100*100*10 mm copper block pre-cooled with liquid nitrogen. Continue to add liquid nitrogen around the crucible for directional freezing. After the freezing is completed, freeze dry for 12 h. After freeze drying, place the crucible in a moving tube furnace, first introduce nitrogen for 20 min (to remove air in the tube), then heat at 300 ℃ for 1 h, then heat at 700 ℃ for 2 h, the heating rate is 5 ℃ / min, after annealing, naturally cool to room temperature. Get DFD / TiO2 / ZnIn2S4@Au sample.

[0065] In the above synthesis method, the preparation process solves the problem of cracking of the prepared sample by introducing zinc ions (zinc chloride, zinc nitrate, zinc sulfate, etc. zinc ion containing salt), greatly improving the yield.

[0066] Please refer to Figure 3 An embodiment of the application provides a method for hydrophobic film attachment treatment, comprising: 301. Using graphene oxide, MXene aqueous solution, TEMPO cellulose nanofiber and D-(+)-glucose to prepare a special hydrophobic film; 302. Using the hydrophobic film and combining the secondary directional freezing method to perform hydrophobic film attachment treatment on multiple surfaces of the three-dimensional aerogel electrode, and only one surface is reserved for ion exchange.

[0067] In this embodiment, graphene oxide, MXene aqueous solution, TEMPO cellulose nanofiber and D-(+)-glucose are needed to prepare a special hydrophobic film, and the hydrophobic film is attached to the multiple faces of the three-dimensional aerogel electrode using the hydrophobic film and combined with the secondary directional freezing method, and only one face is left for ion exchange.

[0068] Specifically, different embodiments also have different hydrophobic film attachment methods, which are illustrated as follows. Take out the well-stirred PTFE (or MTMS, FPU, etc.) hydrophobic modifier and add 0.5 mL to the mold. Place the top surface of the DFD / MnO2 sample on the hydrophobic modifier, and the added hydrophobic modifier should slightly cover the top surface (ensure complete encapsulation). Then place it on the 100*100*10 mm copper block pre-cooled with liquid nitrogen, and continue to add liquid nitrogen around the crucible for secondary directional freezing. At this time, it should be noted that because the internal channel direction of the sample is from the bottom to the top, when the other four sides are subjected to secondary freeze-drying and hydrophobic modifier attachment, first place the sample side on the hydrophobic modifier, and the added hydrophobic modifier should slightly cover the side (ensure complete encapsulation). Then place the 100*100*10 mm copper block pre-cooled with liquid nitrogen on the side of the sample (i.e. the bottom surface of the sample, ensuring that the position of the copper block is perpendicular to the internal channel direction of the sample). After the five surfaces are completely frozen, freeze-drying is performed for 12 h. After completion, the hydrophobic modifier becomes a hydrophobic film and is attached to the surface of the sample.

[0069] Take out the well-stirred PTFE (or MTMS, FPU, etc.) hydrophobic modifier and add 0.5 mL to the mold. Place the top surface of the DFD / MnO2@Au sample on the hydrophobic modifier, and the added hydrophobic modifier should slightly cover the top surface (ensure complete encapsulation). Then place it on the 100*100*10 mm copper block pre-cooled with liquid nitrogen, and continue to add liquid nitrogen around the crucible for secondary directional freezing. At this time, it should be noted that because the internal channel direction of the sample is from the bottom to the top, when the other four sides are subjected to secondary freeze-drying and hydrophobic modifier attachment, first place the sample side on the hydrophobic modifier, and the added hydrophobic modifier should slightly cover the side (ensure complete encapsulation). Then place the 100*100*10 mm copper block pre-cooled with liquid nitrogen on the side of the sample (i.e. the bottom surface of the sample, ensuring that the position of the copper block is perpendicular to the internal channel direction of the sample). After the five surfaces are completely frozen, freeze-drying is performed for 12 h. After completion, the hydrophobic modifier becomes a hydrophobic film and is attached to the surface of the sample.

[0070] Please refer to Figures 18 to 20 , Figure 18The whole structure schematic diagram of the hydrophobic film attached, the sample is DFD / MnO2 and DFD / MnO2@Au, the outside is the mold for fixing, the mold inside has a hydrophobic modifier, the lower side is a copper block, Figure 19 The top surface attached local schematic diagram, it can be seen that the position relationship of the sample, the hydrophobic modifier and the copper block, the position plane of the copper block and the channel direction are perpendicular, Figure 20 The side surface attached schematic diagram, in the left and right side surface attached schematic diagram, the channel direction is perpendicular to the copper block position, and the copper block is located below.

[0071] Please refer to Figure 4 The application provides an embodiment of a method for generating a special hydrophobic modifier, which comprises the following steps: 401. Freeze-drying treatment of TEMPO cellulose nanofiber; 402. Deionized water is loaded in beaker A, and graphene oxide is put into the deionized water in beaker C, and ultrasonic stirring is performed in beaker C to form a stable and uniform suspension; 403. A preset volume of MXene aqueous solution is measured and added to beaker C, and ultrasonic stirring treatment is performed; 404. A preset weight of D-(+)-glucose is weighed and added to beaker C, and ultrasonic stirring treatment is performed; 405. The hydrophobic modifier is added to beaker C, and ultrasonic stirring treatment is performed; 406. Deionized water is loaded in beaker D, and a preset weight of freeze-dried TEMPO cellulose nanofiber is weighed and put into beaker D, and beaker D is stirred; 407. The mixture in beaker C is poured into beaker D, and stirring treatment is performed to generate a special hydrophobic modifier.

[0072] In this embodiment, a professional hydrophobic film needs to be generated. First, the TEMPO cellulose nanofiber is frozen for 12 hours, and then freeze-dried for 14 hours. Then 0.12 g of graphene oxide is weighed in 6 mL of deionized water, and ultrasonic stirring is performed in beaker C for 1 hour to form a stable and uniform suspension. 6 mL of MXene aqueous solution is measured and added to beaker C, and ultrasonic stirring is continued for 30 minutes. 0.2 g of D-(+)-glucose is weighed and added to beaker C, and ultrasonic stirring is continued for 30 minutes. 1 wt% of polytetrafluoroethylene (PTFE) (or methyltrimethoxysilane (MTMS), fluorinated polyurethane (FPU), etc. hydrophobic modifier) is added, and ultrasonic stirring is continued for 30 minutes. 0.1 g of zinc chloride (or zinc sulfate, zinc nitrate, etc. zinc ion-containing salt) is weighed and added to beaker C, and ultrasonic stirring is continued for 30 minutes. Then 0.28 g of freeze-dried TEMPO cellulose nanofiber is weighed in 12 mL of deionized water, and stirred in beaker D for 30 minutes. The mixture in beaker A is poured into beaker D, and stirred quickly for 6 hours. After stirring, a special hydrophobic modifier is generated.

[0073] The test sample (DFD / MnO2, DFD / MnO2@Au) is used in the secondary freeze-drying technology on the other 5 surfaces except the surface in contact with the separator. The prepared polytetrafluoroethylene (PTFE) hydrophobic film (or hydrophobic film prepared by methyltrimethoxysilane (MTMS), fluorinated polyurethane (FPU), etc. hydrophobic modifier) is tightly attached to the surface, so that the test sample has a hydrophilic surface and a hydrophobic surface on the other 5 surfaces, greatly reducing the loss of electrolyte during the application test of the self-powered zinc ion hybrid pressure sensor (because the assembled self-powered zinc ion hybrid pressure sensor is also a zinc ion battery, a certain amount of electrolyte needs to be added, and the electrolyte will be squeezed out from the other 5 surfaces not in contact with the separator during compression, resulting in loss of electrolyte. After using the hydrophobic film to package it, the loss of electrolyte during compression can be greatly reduced. ), also making the sensor waterproof and allowing it to detect external pressure in wet and rainy bad weather.

[0074] Please refer to Figure 5 An embodiment of a method for testing a directional cold-dried sample is provided, comprising: 501. Freeze-drying TEMPO cellulose nanofiber; 502. Deionized water is added to beaker E, and graphene oxide is added to the deionized water in beaker E, and ultrasonic stirring is performed in beaker E to form a stable and uniform suspension; 503. A predetermined volume of MXene aqueous solution is measured and added to beaker E, and ultrasonic stirring is performed; 504、Weigh a preset weight of D-(+)-glucose into beaker E, and perform ultrasonic stirring treatment; 505、Weigh a preset weight of zinc ion-containing salt into beaker E, and perform ultrasonic stirring treatment; 506、Fill beaker F with deionized water, weigh a preset weight of freeze-dried TEMPO cellulose nanofiber into beaker F, and perform stirring treatment on beaker F; 507、Pour the mixture in beaker E into beaker F, and perform stirring treatment; 508、After stirring, take a preset volume of the mixture into an alumina crucible, and place the alumina crucible on a copper block pre-cooled with liquid nitrogen, continue to add liquid nitrogen around the alumina crucible to perform directional freezing; 509、After all the freezing is completed, perform freeze-drying treatment; 510、After the freeze-drying is completed, place the alumina crucible in a movable tube furnace, and first introduce nitrogen to remove air in the tube; 511、Heat at 300℃ for 1h, and then heat at 700℃ for 2h, with a heating rate of 5℃ / min, and after the annealing is completed, naturally cool to room temperature to generate a directional freeze-dried sample; 512、Perform assembly performance test on the directional freeze-dried sample; 513、When the performance test result reaches a preset condition, determine that the directional freeze-dried sample is a qualified sample.

[0075] In this embodiment, a DFD (directional freeze-dried sample) containing no active response substance needs to be generated for testing.

[0076] First, freeze TEMPO cellulose nanofiber for 12 h, then freeze dry for 14 h. Then weigh 0.12 g of graphene oxide in 6 mL of deionized water, ultrasonic stirring in beaker E for 1 h to form a stable and uniform suspension. Then take 6 mL of MXene aqueous solution into beaker E and continue to ultrasonic stirring for 30 min. Then weigh 0.2 g of D-(+)-glucose into beaker E and continue to ultrasonic stirring for 30 min. Then weigh 0.1 g of zinc chloride (or zinc sulfate, zinc nitrate, etc. containing zinc ion salt) into beaker E and continue to ultrasonic stirring for 30 min. Then weigh 0.28 g of freeze-dried TEMPO cellulose nanofiber in 12 mL of deionized water and stir in beaker F for 30 min. Pour the mixture in beaker E into beaker F and stir quickly for 6 h. After stirring, take 2.2 mL of the mixture with a rubber dropper into a 30*20*10 mm alumina crucible and place it on a 100*100*10 mm copper block pre-cooled with liquid nitrogen. Continue to add liquid nitrogen around the crucible for directional freezing. After the whole freezing is completed, freeze dry for 12 h. After freeze drying, place the crucible in a moving tube furnace, first introduce nitrogen for 20 min (to remove air in the tube), then heat at 300 ℃ for 1 h, then heat at 700 ℃ for 2 h, the heating rate is 5 ℃ / min. After annealing, cool to room temperature naturally. Get DFD sample (directional freeze-dried sample). Please refer to Figure 12 , Figure 12 are scanning electron microscope top views of DFD and NDFD, specifically Figure 12 (a) is a scanning electron microscope top view of DFD (directional freeze-dried sample), Figure 12 (b) is a scanning electron microscope top view of NDFD (non-directional freeze-dried sample). The DFD (directional freeze-dried sample) generated by this scheme has more axially arranged porous skeletons, which is conducive to the diffusion of ions. The sample made by conventional non-directional freeze-drying is mostly a flaky wall structure, which is not conducive to the diffusion of ions.

[0077] The following data comparison, please refer to Figure 13 , Figure 13 is an I-t curve diagram of DFD sensor under different pressures, specifically, Figure 13The current-time response curve of the DFD sensor in the range of 0.45-12.47 kPa shows that the response current of the two electrodes of the sensor increases in parallel with the increase of the force under the action of pressure. Under a larger applied pressure, the mutual contact and communication between adjacent sheets stimulate more contact pathways, resulting in an increase in conductivity, thereby showing a large current. Based on this, the DFD sensor can perceive and distinguish different degrees of force. Moreover, the response current under the same pressure is also certain, indicating that it has a good pressure current response mechanism. The NDFD sensor cannot perform I-t curve testing under different pressures because it does not have resilience.

[0078] Please refer to Figure 14 , Figure 14 The cycle stability comparison diagram of NDFD, DFD, and DFD / MnO2 cathode sensors (the left side is the capacity retention rate, and the right side is the coulombic efficiency, which is similar), from which it can be seen that the DFD / MnO2 (directional freeze-drying / manganese dioxide) cathode battery has obvious advantages in charge-discharge performance, and still retains 82.41% of the initial capacity after 1000 cycles at a current density of 2 mA cm -2 . In contrast, the capacity retention rate of DFD (directional freeze-drying) after 1000 cycles is significantly reduced to 50.97%, and NDFD (non-directional freeze-drying) only retains 32.54% of the initial capacity. It also shows that the sample prepared by the directional freeze-drying method in this embodiment is beneficial to the infiltration of electrolyte and the diffusion of ions due to the many axially arranged porous frameworks.

[0079] Please refer to Figure 15 , Figure 15 The test result diagram of the DFD / MnO2 cathode sensor under slow finger pressing shows that an external bias voltage of 0 V means no external power supply. The DFD / MnO2 cathode sensor prepared by the directional freeze-drying method in this embodiment can still respond to pressure in real time without an external power supply.

[0080] Please refer to Figure 16 , Figure 16 The cycle stability diagram of the DFD / MoS2 cathode sensor shows that the DFD / MoS2 cathode battery still retains 80.89% of the initial capacity after 500 cycles at a current density of 2 mA cm -2 , still having a quite good capacity retention rate.

[0081] Please refer to Figure 17 , Figure 17 The DFD / MoS2 cathode sensor illumination (AM 1.5, 200 mW cm-2 ) and the schematic diagram of the photocurrent response curve under dark condition, the DFD sensor loaded with MoS2 can respond to light in time.

[0082] Please refer to Figure 6 The present application provides an embodiment of a method for testing the assembly performance of a directional freeze-dried sample, comprising: 601. Apply conductive silver paste to both ends of the glass slide and attach copper wires; 602. Perform drying treatment at a predetermined temperature to solidify the conductive silver paste and fix the copper wires; 603. Place the directional freeze-dried sample on both ends, and use a linear motor and an electrochemical workstation to perform performance testing.

[0083] In this embodiment, conductive silver paste is applied to both ends of the glass slide and copper wires are attached to serve as conductive wires, with a distance of 1 cm between the two ends. The glass slide is dried at 80°C for 2 hours to solidify the conductive silver paste and fix the copper wires. Then, the directional freeze-dried sample (DFD) is placed on both ends, and a linear motor and an electrochemical workstation are used to perform performance testing. In this embodiment, in addition to testing the directional freeze-dried sample (DFD) without adding a load, the directional freeze-dried sample (DFD) with added load can also be tested again, in a similar manner to the testing of the directional freeze-dried sample (DFD).

[0084] Please refer to Figure 7 The present application provides an embodiment of a method for testing a non-directional freeze-dried sample, comprising: 701. Prepare a non-directional freeze-dried sample, use the non-directional freeze-dried sample to perform assembly performance testing, and perform comparative analysis with the assembly performance testing of the directional freeze-dried sample.

[0085] In this embodiment, in order to perform comparative analysis, an NDFD sample needs to be prepared under the same conditions.

[0086] First, the TEMPO cellulose nanofiber is frozen for 12 h, and then freeze-dried for 14 h. Then, 0.12 g of graphene oxide is weighed in 6 mL of deionized water, and ultrasonic stirring is performed in beaker A (here, beaker A and beaker B are not the same as the previous ones, but two new beakers) for 1 h to form a stable and uniform suspension. Then, 6 mL of the MXene aqueous solution is measured and added to beaker A, and ultrasonic stirring is continued for 30 min. Then, 0.2 g of D-(+)-glucose is weighed and added to beaker A, and ultrasonic stirring is continued for 30 min. Then, 0.1 g of zinc chloride (or zinc sulfate, zinc nitrate, etc. containing zinc ion salt) is weighed, and 0.28 g of freeze-dried TEMPO cellulose nanofiber is weighed in 12 mL of deionized water in beaker B and stirred for 30 min. The mixture in beaker A is poured into beaker B, and rapid stirring is performed for 6 h. After stirring is completed, 2.2 mL of the mixture is taken with a rubber dropper and placed in a 30*20*10 mm alumina crucible, and non-directional freezing is performed in a refrigerator. After the freezing is completed, freeze-drying is performed for 12 h. After freeze-drying is completed, the crucible is placed in a movable tube furnace, nitrogen is introduced for 20 min (to remove air in the tube), then heat preservation is performed at 300 ℃ for 1 h, and then heat preservation is performed at 700 ℃ for 2 h, the heating rate is 5 ℃ / min, and after annealing is completed, natural cooling is performed to room temperature. The NDFD sample is obtained.

[0087] Please refer to Figure 8 The application provides a three-dimensional aerogel electrode preparation device, which comprises: The processor 801, the memory 802, the input / output unit 803 and the bus 804.

[0088] The processor 801 is connected with the memory 802, the input / output unit 803 and the bus 804.

[0089] The memory 802 stores a program, and the processor 801 calls the program to perform the three-dimensional aerogel electrode preparation method as shown in Figure 1 、 Figure 2 and Figure 3 、 Figure 4 , and 5, Figure 6 .

[0090] The application provides a computer readable storage medium, and the computer readable storage medium stores a program, and the program performs the three-dimensional aerogel electrode preparation method as shown in Figure 1 、 Figure 2 and Figure 3 、 Figure 4 , and 5, Figure 6 when the computer executes the program.

[0091] Please refer to Figure 9 and Figure 10 ,Figure 9 A schematic diagram of the internal structure of a self-powered zinc ion hybrid pressure (light) sensor. Figure 10 This is a schematic diagram of the assembly mold for a self-powered zinc-ion hybrid pressure (optical) sensor. It can be seen that the zinc battery (self-powered zinc-ion hybrid pressure (optical) sensor) is composed of an optical quartz sheet, wires, a three-dimensional aerogel electrode, a battery separator treated with a solution of 2 M ZnSO4 and 0.1 M MnSO4, and a zinc sheet stacked sequentially. The three-dimensional aerogel electrode serves as the zinc-ion sensing electrode. The wires include pressure-responsive wires and light-responsive wires; the light-responsive wires have a hollow light-response region. (Total...) Figure 10 See, the zinc battery also includes a casing with mounting holes, pressure response holes, and light response holes. The zinc sheet passes through the mounting holes. The wires pass through the pressure response holes, which have a compression area for wire displacement. The light response holes allow light signals to pass through, enabling the zinc battery to respond to light.

[0092] Specifically, the construction methods of different responsive active substances are slightly different, and the construction methods are all adapted to the characteristics of the corresponding responsive active substances. The following is a detailed introduction to the assembly and testing of the self-powered photoresponse sensor.

[0093] Example 1: A self-powered zinc-ion hybrid pressure sensor with a hydrophobic film attached, a zinc plate, and a separator treated with 2 M ZnSO4 + 0.1 M MnSO4 immersion solution were assembled in a hamburger structure (note: the side without the hydrophobic film attached is in close contact with the separator). To study the performance of the obtained battery, the system analyzed constant current charge-discharge (GCD), cyclic voltammetry (CV) curves, and electrochemical impedance spectroscopy (EIS).

[0094] Example 2: A self-powered zinc-ion hybrid pressure sensor with a hydrophobic film attached, a zinc plate, and a separator treated with 2 M ZnSO4 + 0.1 M MnSO4 solution were assembled in a hamburger structure. To study the performance of the obtained battery, the system analyzed constant current charge-discharge (GCD), cyclic voltammetry (CV) curves, and electrochemical impedance spectroscopy (EIS).

[0095] Example 3: The self-powered zinc-ion hybrid photoresponse sensor was constructed by first coating all surfaces of DFD / MoS2 except the side in contact with the separator with a layer of polytetrafluoroethylene to form a hydrophobic surface. This surface was then assembled with a zinc plate and a separator treated with 2 M ZnSO4 in a hamburger-like structure. To study the performance of the obtained battery, the photocurrent performance, galvanostatic charge-discharge (GCD), cyclic voltammetry (CV) curves, and electrochemical impedance spectroscopy (EIS) were systematically analyzed.

[0096] Example four: the self-powered zinc ion hybrid light response sensor is formed by coating the DFD / MoS2@Au with a polytetrafluoroethylene layer on the other surface except the surface in contact with the separator to form a hydrophobic surface, and then assembling it with a zinc plate and a separator treated with a 2 M ZnS04solution in the form of a hamburger structure. In order to study the performance of the obtained battery, the photocurrent performance, galvanostatic charge-discharge (GCD), cyclic voltammetry (CV) curves and electrochemical impedance spectroscopy (EIS) and other performances are analyzed.

[0097] Example five: the self-powered zinc ion hybrid light response sensor is formed by coating the DFD / TiO2@MoS2 with a polytetrafluoroethylene layer on the other surface except the surface in contact with the separator to form a hydrophobic surface, and then assembling it with a zinc plate and a separator treated with a 2 M ZnS04solution in the form of a hamburger structure. In order to study the performance of the obtained battery, the photocurrent performance, galvanostatic charge-discharge (GCD), cyclic voltammetry (CV) curves and electrochemical impedance spectroscopy (EIS) and other performances are analyzed.

[0098] Example six: the self-powered zinc ion hybrid light response sensor is formed by coating the DFD / TiO2 / MoS2@Au with a polytetrafluoroethylene layer on the other surface except the surface in contact with the separator to form a hydrophobic surface, and then assembling it with a zinc plate and a separator treated with a 2 M ZnS04solution in the form of a hamburger structure. In order to study the performance of the obtained battery, the photocurrent performance, galvanostatic charge-discharge (GCD), cyclic voltammetry (CV) curves and electrochemical impedance spectroscopy (EIS) and other performances are analyzed.

[0099] Example seven: the self-powered zinc ion hybrid light response sensor is formed by coating the DFD / ZnIn2S4 with a polytetrafluoroethylene layer on the other surface except the surface in contact with the separator to form a hydrophobic surface, and then assembling it with a zinc plate and a separator treated with a 2 M ZnS04solution in the form of a hamburger structure. In order to study the performance of the obtained battery, the photocurrent performance, galvanostatic charge-discharge (GCD), cyclic voltammetry (CV) curves and electrochemical impedance spectroscopy (EIS) and other performances are analyzed.

[0100] Example eight: the self-powered zinc ion hybrid light response sensor is formed by coating the DFD / ZnIn2S4@Au with a polytetrafluoroethylene layer on the other surface except the surface in contact with the separator to form a hydrophobic surface, and then assembling it with a zinc plate and a separator treated with a 2 M ZnS04solution in the form of a hamburger structure. In order to study the performance of the obtained battery, the photocurrent performance, galvanostatic charge-discharge (GCD), cyclic voltammetry (CV) curves and electrochemical impedance spectroscopy (EIS) and other performances are analyzed.

[0101] Example 9: The self-powered zinc ion hybrid light response sensor is formed by coating the DFD / TiO2@ZnIn2S4 with a polytetrafluoroethylene layer on the other surface except the surface in contact with the separator to form a hydrophobic surface, and then assembling it with a zinc plate and a separator treated with a 2 M ZnSO4 solution in the form of a hamburger structure. In order to study the performance of the resulting battery, the system analyzes the photocurrent performance, galvanostatic charge-discharge (GCD), cyclic voltammetry (CV) curves and electrochemical impedance spectroscopy (EIS) and other performances.

[0102] Example 10: The self-powered zinc ion hybrid light response sensor is formed by coating the active response material (DFD / TiO2 / ZnIn2S4@Au) with a polytetrafluoroethylene layer on the other surface except the surface in contact with the separator to form a hydrophobic surface, and then assembling it with a zinc plate and a separator treated with a 2 M ZnSO4 solution in the form of a hamburger structure. In order to study the performance of the resulting battery, the system analyzes the photocurrent performance, galvanostatic charge-discharge (GCD), cyclic voltammetry (CV) curves and electrochemical impedance spectroscopy (EIS) and other performances.

[0103] Those skilled in the art can clearly understand that, for the convenience and brevity of description, the specific working process of the system, device and unit described above can refer to the corresponding process in the foregoing method embodiments, which will not be repeated here.

[0104] In several embodiments provided in the present application, it should be understood that the disclosed system, device and method can be implemented in other ways. For example, the device embodiments described above are only schematic, for example, the division of the units is only a logical function division, and actual implementation can have another division manner, for example, a plurality of units or components can be combined or integrated into another system, or some features can be ignored or not executed. In addition, the coupling or direct coupling or communication connection between the units shown or discussed can be indirect coupling or communication connection through some interface, device or unit, which can be electrical, mechanical or other forms.

[0105] The units described as separate components can or can not be physically separated, and the components shown as units can or can not be physical units, i.e. they can be located in one place or distributed on a plurality of network units. Part or all of the units can be selected according to actual needs to achieve the purpose of the embodiments of the present application.

[0106] In addition, each functional unit in each embodiment of the present application can be integrated in one processing unit, or each unit can exist physically, or two or more units can be integrated in one unit. The above integrated unit can be realized in the form of hardware or in the form of software functional unit.

[0107] The integrated unit, if implemented in the form of a software functional unit and sold or used as an independent product, can be stored in a computer-readable storage medium. Based on such understanding, the technical solutions of the present application, essentially or in other words, the part that contributes to the prior art or the whole or part of the technical solutions can be embodied in the form of a software product. The computer software product is stored in a storage medium and includes a number of instructions for causing a computer device (which can be a personal computer, a server, or a network device, etc.) to execute all or part of the steps of the methods described in the various embodiments of the present application. The aforementioned storage medium includes: a U disk, a mobile hard disk, a read-only memory (ROM, read-only memory), a random access memory (RAM, random access memory), a magnetic disk or an optical disk, and various media that can store program codes.

Claims

1. A method for preparing a three-dimensional aerogel electrode, characterized by, Comprising: preparing graphene oxide; preparing MXene aqueous solution; obtaining TEMPO cellulose nanofiber; preparing active response substance according to response project, the response project including external pressure signal response and external light signal response; using the graphene oxide, the MXene aqueous solution, the TEMPO cellulose nanofiber, active response substance and D-(+)-glucose, and generating three-dimensional aerogel electrode by directional freezing method.

2. The method of claim 1, wherein the three-dimensional aerogel electrode is prepared by a process comprising: The step of using the graphene oxide, the MXene aqueous solution, the TEMPO cellulose nanofiber, active response substance and D-(+)-glucose, and generating three-dimensional aerogel electrode by directional freezing method comprises: frozen drying treatment is performed on the TEMPO cellulose nanofiber; Deionized water is loaded into beaker A, the graphene oxide is put into the deionized water in beaker A, ultrasonic stirring is performed in beaker A, and a stable and uniform suspension is formed; A preset weight of active response substance is weighed and added into beaker A, and ultrasonic stirring treatment is performed; A preset volume of MXene aqueous solution is measured and added into beaker A, and ultrasonic stirring treatment is performed; A preset weight of D-(+)-glucose is weighed and added into beaker A, and ultrasonic stirring treatment is performed; A preset weight of zinc ion-containing salt is weighed and added into beaker A, and ultrasonic stirring treatment is performed; Deionized water is loaded into beaker B, a preset weight of frozen and dried TEMPO cellulose nanofiber is weighed and put into beaker B, and stirring treatment is performed on beaker B; The mixture in beaker A is poured into beaker B, and stirring treatment is performed; After stirring is completed, a preset volume of the mixture is taken in an alumina crucible, and is placed on a copper block pre-cooled with liquid nitrogen, and directional freezing is continued by adding liquid nitrogen around the alumina crucible; After all the freezing is completed, frozen drying treatment is performed; After the frozen drying is completed, the alumina crucible is placed in a movable tube furnace, and nitrogen is first introduced to remove air in the tube; At 300 DEG C, heat preservation is performed for 1 h, and then at 700 DEG C, heat preservation is performed for 2 h, the heating rate is 5 DEG C / min, after annealing is completed, natural cooling is performed to room temperature, and a three-dimensional aerogel electrode corresponding to the active response substance is generated.

3. The method of claim 1, wherein the three-dimensional aerogel electrode is prepared by a process comprising: After the step of using the graphene oxide, the MXene aqueous solution, the TEMPO cellulose nanofiber, active response substance and D-(+)-glucose, and generating three-dimensional aerogel electrode by directional freezing method, the three-dimensional aerogel electrode preparation method further comprises: using the graphene oxide, the MXene aqueous solution, the TEMPO cellulose nanofiber and D-(+)-glucose to prepare a special hydrophobic modifier; using the hydrophobic modifier and combining secondary directional freezing method to perform hydrophobic film attachment treatment on multiple surfaces of the three-dimensional aerogel electrode, and only one surface is reserved for ion exchange.

4. The method of claim 3, wherein the three-dimensional aerogel electrode is prepared by the steps of: The step of using the graphene oxide, the MXene aqueous solution, the TEMPO cellulose nanofiber and D-(+)-glucose to prepare a special hydrophobic modifier comprises: frozen drying treatment is performed on the TEMPO cellulose nanofiber; In beaker C, deionized water is loaded, and the graphene oxide is put into the deionized water in the beaker C, ultrasonic stirring is carried out in the beaker C to form a stable and uniform suspension; A preset volume of MXene aqueous solution is measured and added to the beaker C, and ultrasonic stirring treatment is carried out; A preset weight of D-(+)-glucose is weighed and added to the beaker C, and ultrasonic stirring treatment is carried out; A hydrophobic modifier is added to the beaker C, and ultrasonic stirring treatment is carried out; In beaker D, deionized water is loaded, and a preset weight of freeze-dried TEMPO cellulose nanofiber is weighed and put into the beaker D, and the beaker D is stirred; The mixture in the beaker C is poured into the beaker D, and stirring treatment is carried out to generate a special hydrophobic modifier.

5. The method of claim 1 to 4, wherein, After the step of obtaining the TEMPO cellulose nanofiber, before the step of generating the three-dimensional aerogel electrode by using the graphene oxide, the MXene aqueous solution, the TEMPO cellulose nanofiber, the active response substance and the D-(+)-glucose through the directional freezing method, the three-dimensional aerogel electrode preparation method further comprises: The TEMPO cellulose nanofiber is subjected to freeze-drying treatment; In beaker E, deionized water is loaded, and the graphene oxide is put into the deionized water in the beaker E, ultrasonic stirring is carried out in the beaker E to form a stable and uniform suspension; A preset volume of MXene aqueous solution is measured and added to the beaker E, and ultrasonic stirring treatment is carried out; A preset weight of D-(+)-glucose is weighed and added to the beaker E, and ultrasonic stirring treatment is carried out; A preset weight of zinc ion-containing salt is weighed and added to the beaker E, and ultrasonic stirring treatment is carried out; In beaker F, deionized water is loaded, and a preset weight of freeze-dried TEMPO cellulose nanofiber is weighed and put into the beaker F, and the beaker F is stirred; The mixture in the beaker E is poured into the beaker F, and stirring treatment is carried out; After the stirring is completed, a preset volume of the mixture is taken in an alumina crucible, and is placed on a copper block pre-cooled with liquid nitrogen, and liquid nitrogen is continuously added around the alumina crucible for directional freezing; After all the freezing is completed, freeze-drying treatment is carried out; After the freeze-drying is completed, the alumina crucible is placed in a movable tube furnace, and nitrogen is first introduced to remove the air in the tube; At 300°C, heat preservation is carried out for 1h, and then at 700°C, heat preservation is carried out for 2h, the heating rate is 5°C / min, after the annealing is completed, natural cooling is carried out to room temperature to generate a directional cold-dried sample; The directional cold-dried sample is subjected to assembly performance test; When the performance test result reaches a preset condition, the directional cold-dried sample is determined as a qualified sample.

6. The method of claim 5, wherein the three-dimensional aerogel electrode is prepared by the steps of: The step of testing the assembly performance of the directional cold-dried sample comprises: Conductive silver paste is applied to both ends of the glass slide and copper wires are attached; Drying treatment is carried out at a preset temperature to cure the conductive silver paste and fix the copper wires; The directional cold-dried sample is placed on the two end points, and a linear motor and an electrochemical workstation are used for performance test.

7. The method for preparing a three-dimensional aerogel electrode according to claim 5, characterized in that, After the step of testing the assembly performance of the directional cold-dried sample, the three-dimensional aerogel electrode preparation method further comprises: Preparation of non-oriented cold-drying samples, use of the non-oriented cold-drying samples for assembly performance tests, and comparison analysis with the assembly performance tests of the oriented cold-drying samples.

8. A three-dimensional aerogel electrode, characterized in that, Prepared by the preparation method of the three-dimensional aerogel electrode according to any one of claims 1 to 7.

9. A zinc battery, characterized in that, Composed of optical quartz sheet, wire, the three-dimensional aerogel electrode according to claim 8, battery diaphragm treated by 2 M ZnSO4 plus 0.1 M MnSO4 immersion liquid, and zinc sheet, which are stacked in sequence; The three-dimensional aerogel electrode is used as a zinc ion sensing electrode; The wire includes a pressure response type wire and a light response type wire, and the light response type wire has a hollow light response region.

10. The zinc battery of claim 9, wherein, The zinc battery further includes a shell, and the shell is provided with a fixing hole, a pressure response hole, and a light response hole; The zinc sheet passes through the fixing hole; The wire passes through the pressure response hole, and the pressure response hole is provided with an extrusion region for wire displacement; The light response hole is used for transmitting light signals, so that the zinc battery can perform light response.

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