Flexible transparent aqueous zinc-ion battery polyaniline / vanadium oxide composite positive electrode sheet and preparation method thereof

Abstract

The application discloses a flexible transparent aqueous zinc ion battery polyaniline / vanadium oxide composite positive electrode sheet and a preparation method thereof, and belongs to the technical field of aqueous zinc ion batteries. The preparation method comprises the following steps: using vanadyl sulfate aqueous solution as an electroplating solution, using a gold grid / PET as a working electrode, and using a platinum sheet as a counter electrode to construct a two-electrode structure; a vanadium oxide layer is deposited on the surface of the gold grid / PET by adopting a constant-voltage electrochemical deposition method, and a vanadium oxide / gold grid / PET is prepared; sulfuric acid and polyaniline are added into deionized water to prepare an electroplating solution, the vanadium oxide / gold grid / PET is used as the working electrode, the platinum electrode is used as the counter electrode, and a saturated calomel electrode is used as a reference electrode to construct a three-electrode structure; a polyaniline layer is deposited on the surface of the vanadium oxide / gold grid / PET by adopting a constant-voltage electrochemical deposition method, and the composite positive electrode sheet is obtained.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of aqueous zinc ion batteries, and particularly relates to a flexible transparent aqueous zinc ion battery polyaniline / vanadium oxide composite positive electrode sheet and a preparation method thereof. BACKGROUND

[0002] In recent years, flexible transparent touch screens, smart wristbands, wearable sensors, electronic skin, implantable medical devices and other flexible transparent electronic products have developed rapidly. Flexible transparent energy storage electronic devices can provide energy supply for flexible electronic systems and are one of the core components of flexible electronic systems. Flexible transparent energy storage electronic devices need to have excellent flexibility and transparency while maintaining electrochemical performance. This requires the positive electrode, negative electrode, separator, electrolyte, current collector and packaging material of the device to have good light transmission and mechanical flexibility. Supercapacitors have simple structure, high reliability and good safety, but the low energy density restricts their application in flexible transparent electronic products. Although lithium ion batteries have excellent energy density, there are still great challenges in the construction of flexible transparent devices. Therefore, there is an urgent need to develop new energy storage devices with high flexibility, high transparency, high energy density and high safety.

[0003] Rechargeable zinc ion batteries have advantages such as high safety, high energy density, abundant resources and low cost, and are a new type of energy storage device with great market competitiveness. In recent years, with the rapid increase in demand for flexible electronic devices, the research and development of flexible zinc ion battery devices has rapidly developed, and a variety of flexible zinc ion battery materials and devices have been developed. However, due to the fact that flexible transparent metal electrodes are generally manufactured using vacuum plating technology, zinc has a low melting point and poor hardness, making it extremely challenging to produce flexible transparent zinc electrodes.

[0004] At present, manganese-based oxides, prussian blue analogues and vanadium-based oxides are actively explored as positive electrode materials for aqueous zinc ion batteries. However, in traditional alkaline plating solutions, the positive electrode material is often affected by dendrite growth and by-product problems, resulting in serious irreversibility, and most of them are plagued by limited capacity or poor cycle stability. Invention patent CN110190344A discloses a flexible aqueous zinc ion battery, in which the current collector layer includes a breathable layer and a substrate layer, and the substrate layer has at least one opening. The opening structure of the breathable layer and the substrate layer improves the cycle performance of the battery, and the aqueous zinc ion battery obtained by assembly has certain bending performance, but the battery cannot achieve transparent effect, and cannot meet the requirements of transparency of flexible electronic products and wearable devices.

[0005] Therefore, a flexible transparent aqueous zinc ion battery polyaniline / vanadium oxide composite positive electrode sheet and a preparation method thereof are proposed. SUMMARY

[0006] In view of the deficiencies of the prior art, the purpose of the present application is to provide a flexible transparent aqueous zinc ion battery polyaniline / vanadium oxide composite positive electrode sheet and a preparation method thereof, which solves the problems in the prior art.

[0007] The purpose of the present application can be achieved by the following technical solutions:

[0008] The preparation method of the flexible transparent aqueous zinc ion battery polyaniline / vanadium oxide composite positive electrode sheet comprises the following steps:

[0009] S1, vanadyl sulfate aqueous solution is used as an electroplating solution, gold mesh / PET is used as a working electrode, and platinum sheet is used as a counter electrode to construct a two-electrode structure, vanadium oxide layer is deposited on the surface of the gold mesh / PET by constant voltage electrochemical deposition, and vanadium oxide / gold mesh / PET is prepared.

[0010] S2, sulfuric acid and aniline are added to deionized water to prepare an electroplating solution, vanadium oxide / gold mesh / PET is used as a working electrode, platinum electrode is used as a counter electrode, and saturated mercury-mercury electrode is used as a reference electrode to construct a three-electrode structure, polyaniline layer is deposited on the surface of the vanadium oxide / gold mesh / PET by constant voltage electrochemical deposition, and the composite positive electrode sheet is obtained.

[0011] Further, the sheet resistance of the gold mesh / PET current collector is 1-2 Ω / sq, and the light transmittance is 80-90%.

[0012] Further, the concentration of the vanadyl sulfate aqueous solution is 0.05-0.2 mol / L.

[0013] Further, in S1, the two-electrode system is subjected to constant temperature stirring during the electrochemical deposition, the temperature is 50-80°C, and the stirring condition is 300 r / min-1000 r / min.

[0014] Further, in S1, the deposition potential interval of the constant voltage electrochemical deposition method is 0.8-2.0 V, and the deposition time is 10-25 min.

[0015] Further, in S2, the concentration of sulfuric acid in the prepared electroplating solution is 0.5-2 mol / L, and the concentration of aniline is 0.2-1 mol / L.

[0016] Further, in S2, the deposition potential interval of the constant voltage electrochemical deposition method is 0.55-0.95 V, and the deposition time is 30-120 s.

[0017] The flexible transparent aqueous zinc ion battery polyaniline / vanadium oxide composite positive electrode sheet is prepared by the above preparation method.

[0018] The application further discloses application of the flexible transparent aqueous zinc ion battery polyaniline / vanadium oxide composite positive electrode sheet in preparation of an aqueous zinc ion battery.

[0019] The application further discloses an aqueous zinc ion battery comprising the flexible transparent aqueous zinc ion battery polyaniline / vanadium oxide composite positive electrode sheet.

[0020] The application has the following beneficial effects:

[0021] 1. The flexible transparent aqueous zinc ion battery polyaniline / vanadium oxide / gold mesh / PET composite positive electrode sheet has high specific capacity, high cycle stability, high bending resistance and light transmittance. 2+ The rapid deintercalation between the vanadium oxide layers provides open channels.

[0022] 2. The water molecules in the structure can also shield the electric charges, reducing the electrostatic interaction between the host framework and the cations.

[0023] 3. The aqueous zinc ion battery polyaniline / vanadium oxide composite positive electrode sheet has excellent specific capacity, good mechanical flexibility, good transparency and stable cycle performance, and has good application potential and prospect as an energy storage component of wearable mobile devices. BRIEF DESCRIPTION OF DRAWINGS

[0024] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or prior art description. Obviously, for those skilled in the art, other drawings can also be obtained based on these drawings without any creative effort.

[0025] Figure 1 is an optical microscope and SEM image of the composite positive electrode sheet of the application;

[0026] Figure 2 is an optical photo of the flexible transparent aqueous zinc ion battery assembled by the composite positive electrode sheet of the application;

[0027] Figure 3 is a charge-discharge curve of the flexible transparent aqueous zinc ion battery assembled by the composite positive electrode sheet of the application. DETAILED DESCRIPTION

[0028] With reference to the accompanying drawings, the technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative effort should fall within the scope of the present application.

[0029] The preparation method of the flexible transparent aqueous zinc ion battery polyaniline / vanadium oxide composite positive electrode sheet comprises the following steps:

[0030] (1) Vanadyl sulfate powder is added to deionized water to prepare a vanadyl sulfate aqueous solution as an electroplating solution; a two-electrode structure is constructed with a gold grid / PET as a working electrode and a platinum plate as a counter electrode, and a vanadium oxide layer is deposited on the surface of the gold grid / PET by constant-voltage electrochemical deposition to prepare a vanadium oxide / gold grid / PET.

[0031] (2) Sulfuric acid and aniline are added to deionized water to prepare a mixed solution containing sulfuric acid and aniline as an electroplating solution, a three-electrode structure is constructed with the vanadium oxide / gold grid / PET prepared in step (1) as a working electrode, a platinum electrode as a counter electrode, and a saturated calomel electrode as a reference electrode, and a polyaniline layer is deposited on the surface of the vanadium oxide / gold grid / PET by constant-voltage electrochemical deposition to prepare a flexible transparent polyaniline / vanadium oxide / gold grid / PET composite positive electrode sheet.

[0032] In step (1), the sheet resistance of the gold grid / PET is 1-2 Ω / sq, and the light transmittance is 80-90%.

[0033] In step (1), the concentration of the vanadyl sulfate aqueous solution is 0.05-0.2 mol / L.

[0034] In step (1), the two-electrode system is subjected to constant-temperature stirring during the electrochemical deposition process, the temperature is 50-80℃, and the stirring condition is 300 r / min-1000 r / min; the deposition potential interval of the constant-voltage electrochemical deposition method is 0.8-2.0 V, and the deposition time is 10-25 min.

[0035] In step (2), the concentration of sulfuric acid in the mixed solution is 0.5-2 mol / L, and the concentration of aniline is 0.2-1 mol / L.

[0036] In step (2), the deposition potential interval of the constant-voltage electrochemical deposition method is 0.55-0.95 V, and the deposition time is 30-120 s.

[0037] The preparation process of the composite positive electrode sheet will be specifically described below through the following examples and comparative examples, wherein the raw materials used in the examples and comparative examples are as follows:

[0038] Gold mesh / PET was prepared by self-made, using crack template method and vacuum deposition process to prepare highly connected gold mesh on PET substrate, and gold mesh / PET was obtained. Specifically: the acrylic resin and ethanol were mixed uniformly according to the volume ratio of 2:1 to obtain a mixed solution; the mixed solution was coated on the surface of the plasma cleaned PET substrate; the sample was transferred to the vacuum drying oven, dried at 80℃ for 30min to obtain an acrylic resin crack network template sample; the sample was placed in a high vacuum metal evaporation film coating system, the vacuum degree was 2×10 -4 Pa, the substrate temperature was 100℃, and the gold film was vacuum deposited for 18nm; the sample was immersed in acetic acid and ultrasonically treated for 1min to remove the acrylic resin template layer; the sample was taken out and cleaned with ultrapure water and ethanol, and vacuum dried at 80℃ for 1h to obtain gold mesh / PET.

[0039] Acrylic resin: manufacturer: China Pharmaceutical Group Chemical Reagent Co., Ltd.; specification: AR;

[0040] Ethanol: manufacturer: China Pharmaceutical Group Chemical Reagent Co., Ltd.; specification: 99.9%;

[0041] Acetic acid: manufacturer: Shanghai Aladdin Biochemical Technology Co., Ltd.; specification: AR;

[0042] Gold particles: manufacturer: China Pharmaceutical Group Chemical Reagent Co., Ltd.; specification: 99.99%;

[0043] Vanadyl sulfate: manufacturer: Shanghai Aladdin Biochemical Technology Co., Ltd.; specification: AR; item number: V431627-25g;

[0044] Aniline: manufacturer: Shanghai Aladdin Biochemical Technology Co., Ltd.; specification: AR; item number: A112120-500ml;

[0045] Sulfuric acid: manufacturer: China Pharmaceutical Group Chemical Reagent Co., Ltd.; specification: AR; China Pharmaceutical Code: 10021661;

[0046] ITO / PET: manufacturer: Luoyang Tengchang Xukun Biological Technology Co., Ltd.; specification: square resistance 7 ohms.

[0047] Example 1

[0048] (1) 3.26 g vanadyl sulfate was added to 200 mL deionized water to prepare an electroplating solution, a gold grid / PET (2.5 cm x 2.5 cm) was used as a working electrode, a platinum plate was used as a counter electrode, and a saturated calomel electrode was used as a reference electrode. The solution was heated at a constant temperature of 50°C under stirring at 300 r / min, and constant voltage electrochemical deposition was performed at a deposition potential of 1.8 V for 15 min. Then the obtained sample was sequentially cleaned with deionized water and dried in an oven at 50°C for 2 h.

[0049] (2) 200 mL of a mixed solution of 1 mol / L dilute sulfuric acid and 0.5 mol / L polyaniline was taken, and the sample prepared in step (1) was used as a working electrode, a platinum electrode was used as a counter electrode, and a saturated calomel electrode was used as a reference electrode. Constant voltage electrochemical deposition was performed at a deposition potential of 0.75 V at room temperature for 60 s to prepare a sample, and then the obtained sample was sequentially cleaned with deionized water and anhydrous ethanol and dried in an oven at 50°C for 2 h to obtain a polyaniline / vanadium oxide / gold grid / PET composite positive electrode sheet with an area of 2.5 cm x 2.5 cm.

[0050] Figure 1 (a) and (b) in FIGS. 1-4 are, respectively, an optical microscope image and an SEM image of the prepared flexible transparent aqueous zinc ion battery polyaniline / vanadium oxide composite positive electrode sheet. As can be seen from FIGS. 1a and 1b, the polyaniline / vanadium oxide composite film layer grows uniformly on the gold grid / PET current collector. In addition, as can be seen from FIG. 1b, the surface of the polyaniline / vanadium oxide composite film is relatively rough, which is beneficial to reducing the interface impedance and improving the storage capacity for zinc ions.

[0051] Example 2

[0052] (1) 3.26 g vanadyl sulfate was added to 200 mL deionized water to prepare an electroplating solution, a gold grid / PET (2.5 cm x 2.5 cm) was used as a working electrode, a platinum plate was used as a counter electrode, and a saturated calomel electrode was used as a reference electrode. The solution was heated at a constant temperature of 50°C under stirring at 300 r / min, and constant voltage electrochemical deposition was performed at a deposition potential of 1.8 V for 15 min. Then the obtained sample was sequentially cleaned with deionized water and dried in an oven at 50°C for 2 h.

[0053] (2) Take 200 mL of 1 mol / L dilute sulfuric acid and 0.5 mol / L polyaniline mixed solution, use the sample prepared in step (1) as the working electrode, platinum electrode as the counter electrode, and saturated calomel electrode as the reference electrode, and prepare the sample by constant voltage electrochemical deposition at room temperature with deposition potential of 0.75 V and deposition time of 60 s, then wash the obtained sample with deionized water and anhydrous ethanol in sequence, dry in a 50℃ oven for 2 h, to obtain a polyaniline / vanadium oxide / gold grid / PET composite positive electrode sheet with an area of 2.5 cm x 2.5 cm.

[0054] Example 3

[0055] (1) Add 3.26 g of vanadyl sulfate to 200 mL of deionized water to prepare an electroplating solution, use gold grid / PET (2.5 cm x 2.5 cm) as the working electrode, platinum sheet as the counter electrode, and saturated calomel electrode as the reference electrode, and perform constant voltage electrochemical deposition under constant temperature heating at 50℃ in a water bath with stirring at 300 r / min, with deposition potential of 1.8 V and deposition time of 20 min. Then wash the obtained sample with deionized water in sequence, and dry in a 50℃ oven for 2 h.

[0056] (2) Take 200 mL of 1 mol / L dilute sulfuric acid and 0.5 mol / L polyaniline mixed solution, use the sample prepared in step (1) as the working electrode, platinum electrode as the counter electrode, and saturated calomel electrode as the reference electrode, and prepare the sample by constant voltage electrochemical deposition at room temperature with deposition potential of 0.75 V and deposition time of 60 s, then wash the obtained sample with deionized water and anhydrous ethanol in sequence, dry in a 50℃ oven for 2 h, to obtain a polyaniline / vanadium oxide / gold grid / PET composite positive electrode sheet with an area of 2.5 cm x 2.5 cm.

[0057] Example 4

[0058] (1) Add 3.26 g of vanadyl sulfate to 200 mL of deionized water to prepare an electroplating solution, use gold grid / PET (2.5 cm x 2.5 cm) as the working electrode, platinum sheet as the counter electrode, and saturated calomel electrode as the reference electrode, and perform constant voltage electrochemical deposition under constant temperature heating at 50℃ in a water bath with stirring at 300 r / min, with deposition potential of 1.8 V and deposition time of 25 min. Then wash the obtained sample with deionized water in sequence, and dry in a 50℃ oven for 2 h.

[0059] (2) Take 200 mL of 1 mol / L dilute sulfuric acid and 0.5 mol / L polyaniline mixed solution, use the sample prepared in step (1) as the working electrode, platinum electrode as the counter electrode, and saturated calomel electrode as the reference electrode, and prepare the sample by constant voltage electrochemical deposition at room temperature with deposition potential of 0.75 V and deposition time of 60 s, then wash the obtained sample with deionized water and anhydrous ethanol in sequence, dry in a 50℃ oven for 2 h, to obtain a polyaniline / vanadium oxide / gold grid / PET composite positive electrode sheet with an area of 2.5 cm x 2.5 cm.

[0060] Example 5

[0061] (1) Add 3.26 g of vanadyl sulfate to 200 mL of deionized water to prepare an electroplating solution, use gold grid / PET (2.5 cm x 2.5 cm) as the working electrode, platinum sheet as the counter electrode, and saturated calomel electrode as the reference electrode, and perform constant voltage electrochemical deposition under constant temperature heating at 50℃ in a water bath with stirring at 300 r / min, with deposition potential of 1.8 V and deposition time of 15 min. Then wash the obtained sample with deionized water in sequence, and dry in a 50℃ oven for 2 h.

[0062] (2) Take 200 mL of 1 mol / L dilute sulfuric acid and 0.5 mol / L polyaniline mixed solution, use the sample prepared in step (1) as the working electrode, platinum electrode as the counter electrode, and saturated calomel electrode as the reference electrode, and prepare the sample by constant voltage electrochemical deposition at room temperature with deposition potential of 0.75 V and deposition time of 30 s, then wash the obtained sample with deionized water and anhydrous ethanol in sequence, dry in a 50℃ oven for 2 h, to obtain a polyaniline / vanadium oxide / gold grid / PET composite positive electrode sheet with an area of 2.5 cm x 2.5 cm.

[0063] Example 6

[0064] (1) Add 3.26 g of vanadyl sulfate to 200 mL of deionized water to prepare an electroplating solution, use gold grid / PET (2.5 cm x 2.5 cm) as the working electrode, platinum sheet as the counter electrode, and saturated calomel electrode as the reference electrode, and perform constant voltage electrochemical deposition under constant temperature heating at 50℃ in a water bath with stirring at 300 r / min, with deposition potential of 1.8 V and deposition time of 15 min. Then wash the obtained sample with deionized water in sequence, and dry in a 50℃ oven for 2 h.

[0065] (2) Take 200 mL of a mixed solution of dilute sulfuric acid with a concentration of 1 mol / L and polyaniline with a concentration of 0.5 mol / L, use the sample prepared in step (1) as the working electrode, a platinum electrode as the counter electrode, and a saturated calomel electrode as the reference electrode, perform constant-voltage electrochemical deposition at room temperature with a deposition potential of 0.75 V and a deposition time of 90 s to prepare a sample, then wash the obtained sample with deionized water and anhydrous ethanol in sequence, dry in a 50°C oven for 2 h, and obtain a polyaniline / vanadium oxide / gold grid / PET composite positive electrode sheet with an area of 2.5 cm x 2.5 cm.

[0066] Example 7

[0067] (1) Add 3.26 g of vanadyl sulfate to 200 mL of deionized water to configure an electroplating solution, use a gold grid / PET (2.5 cm x 2.5 cm) as the working electrode, a platinum sheet as the counter electrode, and a saturated calomel electrode as the reference electrode, perform constant-voltage electrochemical deposition under constant temperature heating at 50°C with stirring at 300 r / min, a deposition potential of 1.8 V, and a deposition time of 15 min. Then wash the obtained sample with deionized water in sequence, dry in a 50°C oven for 2 h.

[0068] (2) Take 200 mL of a mixed solution of dilute sulfuric acid with a concentration of 1 mol / L and polyaniline with a concentration of 0.5 mol / L, use the sample prepared in step (1) as the working electrode, a platinum electrode as the counter electrode, and a saturated calomel electrode as the reference electrode, perform constant-voltage electrochemical deposition at room temperature with a deposition potential of 0.75 V and a deposition time of 120 s to prepare a sample, then wash the obtained sample with deionized water and anhydrous ethanol in sequence, dry in a 50°C oven for 2 h, and obtain a polyaniline / vanadium oxide / gold grid / PET composite positive electrode sheet with an area of 2.5 cm x 2.5 cm.

[0069] Comparative Example 1

[0070] Add 3.26 g of vanadyl sulfate to 200 mL of deionized water to configure an electroplating solution, use a gold grid / PET (2.5 cm x 2.5 cm) as the working electrode, a platinum sheet as the counter electrode, and a 50°C water bath for constant temperature heating, perform constant-voltage electrochemical deposition with stirring at 300 r / min, a deposition potential of 1.8 V, and a deposition time of 15 min. Then wash the obtained sample with deionized water and anhydrous ethanol in sequence, dry in a 50°C oven for 2 h, and obtain a vanadium oxide / gold grid / PET electrode sheet with an area of 2.5 cm x 2.5 cm.

[0071] Comparative Example 2

[0072] A 200 mL mixed solution of dilute sulfuric acid with a concentration of 1 mol / L and polyaniline with a concentration of 0.5 mol / L was taken, a gold mesh / PET (2.5 cm x 2.5 cm) was used as the working electrode, a platinum electrode was used as the counter electrode, and a saturated calomel electrode was used as the reference electrode, a sample was prepared by constant-voltage electrochemical deposition at room temperature with a deposition potential of 0.75 V and a deposition time of 60 s, then the obtained sample was sequentially cleaned with deionized water and anhydrous ethanol, and dried in an oven at 50°C for 2 h to obtain a polyaniline / gold mesh / PET electrode with an area of 2.5 cm x 2.5 cm.

[0073] Comparative Example 3

[0074] (1) 3.26 g of vanadyl sulfate was added to 200 mL of deionized water to prepare an electroplating solution, an ITO / PET current collector (2.5 cm x 2.5 cm) was used as the working electrode, a platinum sheet was used as the counter electrode, and a saturated calomel electrode was used as the reference electrode, constant-temperature heating was performed in a water bath at 50°C, the stirring condition was 300 r / min, constant-voltage electrochemical deposition was performed, the deposition potential was 1.8 V, and the deposition time was 15 min. Then the obtained sample was sequentially cleaned with deionized water and dried in an oven at 50°C for 2 h.

[0075] (2) A 200 mL mixed solution of dilute sulfuric acid with a concentration of 1 mol / L and polyaniline with a concentration of 0.5 mol / L was taken, the sample prepared in step (1) was used as the working electrode, a platinum electrode was used as the counter electrode, and a saturated calomel electrode was used as the reference electrode, a sample was prepared by constant-voltage electrochemical deposition at room temperature with a deposition potential of 0.75 V and a deposition time of 60 s, then the obtained sample was sequentially cleaned with deionized water and anhydrous ethanol, and dried in an oven at 50°C for 2 h to obtain a polyaniline / vanadium oxide / ITO / PET composite positive electrode with an area of 2.5 cm x 2.5 cm.

[0076] Experimental Test

[0077] 1) Preparation of negative electrode of flexible transparent aqueous zinc ion battery and assembly of battery

[0078] Zinc sulfate 3 g, sodium sulfate 3 g, PEI solution 0.08 g, and boric acid 0.5 g were dissolved in 20 mL of deionized water to prepare a zinc negative electrode plating solution. A piece of zinc foil was used as the anode, and a gold mesh / PET (2.5 cm x 2.5 cm) was used as the working electrode, then electrodeposition was performed at a constant voltage of -0.2 V for 1 h. The obtained sample was gently rinsed with deionized water and then dried in air for 2 h to obtain a transparent zinc metal mesh negative electrode.

[0079] A conductive tape is pasted on the edge of the transparent positive electrode and negative electrode, respectively, for transmitting electrons; a piece of PAM / ZnSO4 hydrogel electrolyte with a suitable size is sandwiched between the positive and negative electrodes, and then the air is squeezed out by gently pressing, and then the whole device is packaged with an acrylic transparent tape to assemble the flexible transparent aqueous zinc ion battery as shown in Figure 2 The effective working area of the flexible transparent aqueous zinc ion battery is 4 cm 2 (2 cm x 2 cm).

[0080] The transparent zinc metal mesh negative electrode prepared by the above experimental process and the positive electrode prepared in each example and the comparative example are used to prepare the flexible transparent aqueous zinc ion battery device according to the above assembly process, and the performance test is carried out.

[0081] 2) Performance test

[0082] The prepared electrode and the assembled transparent aqueous zinc ion battery are tested for light transmittance by using an ultraviolet spectrophotometer. The flexible transparent aqueous zinc ion battery device assembled by the positive electrode prepared in Example 1 is tested for charge and discharge under a charge and discharge current of 100 μA·cm -2 The charge and discharge curve is shown in Figure 3 From the figure, it can be seen that the charge and discharge voltage window of the battery is 0.2-1.5 V, and the charge and discharge specific capacity is about 22 μAh·cm -2 It is shown that the electrochemical performance of the battery is stable and the reversibility is good. At the same time, the batteries assembled by the electrodes prepared in other examples and the comparative example are tested under the same parameters, and the discharge specific capacity data of each device is obtained. In addition, the assembled flexible transparent aqueous zinc ion battery device is tested for 200 cycles under a charge and discharge current of 100 μA·cm -2 The capacity retention rate of the battery is obtained. The assembled flexible transparent aqueous zinc ion battery device is cycled and bent at an angle of 60° for 500 times, and the discharge capacity retention rate of the battery after 500 cycles of 60° cycle bending is tested.

[0083] 3) Analysis of test results

[0084] The test results are shown in Table 1:

[0085] Table 1: Performance data of batteries assembled by electrodes prepared in each example and the comparative example

[0086]

[0087] From Table 1, it can be seen that:

[0088] Compared with the sample of comparative example 1 and comparative example 2, the sample of comparative example 2 only deposited polyaniline on the gold grid, and although the capacity retention rate of the battery assembled by the sample reached 88% after 200 cycles, the discharge specific capacity was only 5 μAh·cm-2, which was much lower than that of the sample of comparative example 1. It is proved that vanadium oxide can provide higher specific capacity for the battery due to its good layered structure.

[0089] Compared with the sample of comparative example 1 and comparative example 2, the sample of comparative example 2 only deposited polyaniline on the gold grid, and although the capacity retention rate of the battery assembled by the sample reached 88% after 200 cycles, the discharge specific capacity was only 5 μAh·cm-2, which was much lower than that of the sample of comparative example 1. It is proved that vanadium oxide can provide higher specific capacity for the battery due to its good layered structure. -2 ; It is proved that vanadium oxide can provide higher specific capacity for the battery due to its good layered structure.

[0090] Compared with the sample of comparative example 1 and comparative example 3, the sample of comparative example 3 changed the gold grid / PET substrate to ITO / PET. Due to the uniform conductivity of the whole ITO / PET surface, the light transmittance of the positive electrode sheet and the battery assembled after the preparation is low. In addition, ITO / PET as a water-based zinc ion positive electrode current collector will undergo oxidation reaction at high potential, resulting in a decrease in conductivity, thereby making the battery cycle retention rate as low as 32%. In addition, due to the poor mechanical properties of ITO, the sample of comparative example 3 has poor bending resistance after being assembled into a battery. After 500 cycles of 60° bending, the ITO layer is broken, and the discharge capacity retention rate of the battery is as low as 15%. It is proved that the gold grid / PET has the characteristics of the metal layer with a network morphology and strong adhesion to the substrate, and gold also has good electrochemical stability. These characteristics help the flexible transparent water-based zinc ion battery to achieve high cycle stability, high light transmittance and high bending resistance.

[0091] Compared with example 2, example 3 and example 4, the deposition time of vanadium oxide in example 1 is longer than that in example 2 but shorter than that in example 3 and example 4. The discharge specific capacity of the battery assembled by the sample ranks example 2 < example 1 < example 3 < example 4, and the ranking of light transmittance is just the opposite, example 2 > example 1 > example 3 > example 4. This shows that the deposition time of vanadium oxide mainly affects the discharge specific capacity of the battery and the light transmittance of the battery. The longer the deposition time, the more the deposition amount of vanadium oxide, so the higher the capacity of the battery, and the higher the coverage rate of vanadium oxide on the electrode sheet, resulting in lower light transmittance. Among them, due to the higher capacity contribution rate of vanadium oxide, its influence on the discharge specific capacity is more obvious.

[0092] Compared with example 5, example 6 and example 7, the polyaniline deposition time of example 1 is longer than example 5, but shorter than example 6 and example 7; the cycle stability of the sample after assembling the battery is ranked as example 5 < example 1 < example 6 < example 7, and the transmittance is ranked as example 5 > example 1 > example 6 > example 7; this shows that the deposition time of polyaniline mainly affects the cycle stability and transmittance of the battery, the longer the deposition time is, the more the deposition amount is, the higher the cycle stability of the battery is, and the lower the transmittance is.

[0093] In the description of the present specification, the description referring to the terms "one embodiment", "an example", "a specific example" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Also, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0094] The basic principles, main features and advantages of the present application are shown and described above. It should be understood by those skilled in the art that the present application is not limited by the above examples, and the above examples and descriptions in the specification are only to illustrate the principles of the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the claimed present application.

Claims

1. A method for preparing a flexible transparent aqueous zinc-ion battery polyaniline / vanadium oxide composite cathode electrode sheet, characterized in that, Comprise the following steps: S1, vanadyl sulfate aqueous solution as the electroplating solution, gold grid / PET as the working electrode, platinum sheet as the counter electrode, to build a two-electrode structure, using constant voltage electrochemical deposition method to deposit vanadium oxide layer on the surface of gold grid / PET, to prepare vanadium oxide / gold grid / PET; S2, sulfuric acid and aniline are added to deionized water to prepare an electroplating solution, vanadium oxide / gold grid / PET as the working electrode, platinum electrode as the counter electrode, saturated calomel electrode as the reference electrode, to build a three-electrode structure, using constant voltage electrochemical deposition method to deposit polyaniline layer on the surface of vanadium oxide / gold grid / PET, to obtain the composite positive electrode sheet.

2. The method of making a flexible transparent aqueous zinc-ion battery polyaniline / vanadium oxide composite cathode electrode sheet according to claim 1, wherein, The sheet resistance of the gold grid / PET current collector is 1-2Ω / sq, and the light transmittance is 80-90%.

3. The method of making a flexible transparent aqueous zinc-ion battery polyaniline / vanadium oxide composite cathode electrode sheet according to claim 1, wherein, The concentration of the vanadyl sulfate aqueous solution is 0.05-0.2mol / L.

4. The method of making a flexible transparent aqueous zinc-ion battery polyaniline / vanadium oxide composite cathode electrode sheet of claim 1, wherein, In S1, the two-electrode system is stirred at constant temperature during the electrochemical deposition process, the temperature is 50-80℃, and the stirring condition is 300r / min-1000r / min.

5. The method of making a flexible transparent aqueous zinc-ion battery polyaniline / vanadium oxide composite cathode electrode sheet according to claim 1 or 4, characterized in that, In S1, the deposition potential range of the constant voltage electrochemical deposition method is 0.8-2.0V, and the deposition time is 10-25min.

6. The method of making a flexible transparent aqueous zinc-ion battery polyaniline / vanadium oxide composite cathode electrode sheet of claim 1, wherein, In S2, the concentration of sulfuric acid in the prepared electroplating solution is 0.5-2mol / L, and the concentration of aniline is 0.2-1mol / L.

7. The method of making a flexible transparent aqueous zinc-ion battery polyaniline / vanadium oxide composite cathode electrode sheet of claim 1, wherein, In S2, the deposition potential range of the constant voltage electrochemical deposition method is 0.55-0.95V, and the deposition time is 30-120s.

8. A flexible transparent aqueous zinc-ion battery polyaniline / vanadium oxide composite cathode electrode sheet, characterized in that, Prepared by the preparation method of any one of claims 1-7.

9. The application of the flexible transparent aqueous zinc-ion battery polyaniline / vanadium oxide composite positive electrode sheet of claim 8 in the preparation of an aqueous zinc-ion battery.

10. An aqueous zinc-ion battery, characterized in that, The flexible transparent aqueous zinc-ion battery polyaniline / vanadium oxide composite positive electrode sheet of claim 8.

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