Molybdenum disulfide-based composite cathode material for aqueous zinc ion photorechargeable battery, preparation method and application thereof

Abstract

The present invention discloses a molybdenum disulfide-based composite positive electrode material for aqueous zinc-ion photorechargeable batteries, as well as its preparation method and application. The molybdenum disulfide-based composite positive electrode material comprises a 1T-phase MoS2 layer, a NiO nanoparticle layer, and a 2H-phase MoS2 layer, sequentially coated on a titanium mesh from bottom to top. The 1T-phase MoS2 layer is prepared from a 1T-phase MoS2 slurry, the NiO nanoparticle layer is prepared from a NiO nanoparticle slurry, and the 2H-phase MoS2 layer is prepared from a 2H-phase MoS2 slurry. The molybdenum disulfide-based composite positive electrode material of the present invention exhibits reversible, multi-cycle photorechargeability and is a potential application material for long-life aqueous zinc-ion photorechargeable batteries.

Description

Technical Field

[0001] The present invention relates to the field of materials science and electrochemical technology, and in particular to a molybdenum disulfide-based composite positive electrode material for aqueous zinc ion photorechargeable batteries, and a preparation method and application thereof. Background Art

[0002] Aqueous zinc-ion batteries consist of a zinc metal negative electrode, an aqueous electrolyte, and a zinc-storing positive electrode material. During constant current charge and discharge, zinc ions are transported back and forth between the positive and negative electrodes, enabling the conversion and storage of electrical energy. Aqueous zinc-ion photorechargeable batteries have a structure essentially identical to aqueous zinc-ion batteries, differing only in that a light-transmitting window is located on the positive electrode side of the battery, allowing light to directly reach the surface of the positive electrode material. After the battery completes constant current discharge, the external current and voltage are cut off, and light is applied to the battery. Recharging the battery solely through light, during which zinc ions escape from the interlayers of the positive electrode material and deposit on the surface of the zinc negative electrode, enabling energy storage.

[0003] The biggest structural difference between aqueous zinc-ion photovoltaic batteries and conventional photovoltaic batteries is that they lack distinct photovoltaic and energy storage modules. Instead, their cathode material (a single electrode sheet) serves as both a photovoltaic and energy storage medium, simultaneously performing photoelectric conversion and electrical energy storage. This design offers advantages such as reduced device size, lower costs, higher integration, and reduced energy loss.

[0004] Aqueous zinc-ion photorechargeable batteries are energy storage devices that integrate solar cells and aqueous zinc-ion energy storage batteries in a wire-free connection. As a portable self-powered energy source, they can be directly charged using sunlight. In addition, due to the inherent safety and low cost of aqueous zinc-ion batteries, aqueous zinc-ion photorechargeable batteries are considered to be one of the ideal power sources for future wearable electronics, portable smart electronics and other fields. Currently reported aqueous zinc-ion photorechargeable battery positive electrode materials are usually prepared based on vanadium oxide, but they generally have problems such as difficulty in reversible cycling, low overall efficiency of photoelectric conversion-energy storage, slow photorecharge rate, and high price of key materials, which limit their further application research and development. Therefore, aqueous zinc-ion photorechargeable batteries are still in urgent need of photorechargeable positive electrode materials that can undergo reversible photorecharge cycles, have long life, high overall efficiency, low price and high safety. Summary of the Invention

[0005] The present invention aims to overcome the shortcomings of the prior art and provides a molybdenum disulfide-based composite positive electrode material for aqueous zinc-ion photorechargeable batteries, as well as its preparation method and application. The present invention selects a molybdenum disulfide-based composite positive electrode material prepared layer by layer in the order of 1T-MoS2, NiO, and 2H-MoS2. When used as the positive electrode active material for aqueous zinc-ion photorechargeable batteries, the molybdenum disulfide-based composite positive electrode material exhibits reversible, multiple photorecharge cycle performance, making it a potential application material for long-life aqueous zinc-ion photorechargeable batteries.

[0006] To achieve the above purpose, the technical solution designed by the present invention is as follows:

[0007] The present invention provides a molybdenum disulfide-based composite positive electrode material for aqueous zinc ion photorechargeable batteries, wherein the molybdenum disulfide-based composite positive electrode material comprises a 1T phase MoS2 layer, a NiO nanoparticle layer, and a 2H phase MoS2 layer sequentially coated on a titanium mesh from bottom to top;

[0008] The thickness of the 1T phase MoS2 layer is 200~300 μm; the thickness of the NiO nanoparticle layer is 40~600 μm; and the thickness of the 2H phase MoS2 layer is 200~300 μm.

[0009] Furthermore, the 1T phase MoS2 layer is prepared from a 1T phase MoS2 slurry, the components of which include 1T phase MoS2, acetylene black and PVDF emulsion, wherein the mass ratio of 1T phase MoS2, acetylene black and PVDF emulsion is 6-8:2:1;

[0010] The NiO nanoparticle layer is prepared from NiO nanoparticle slurry, and the components of the NiO nanoparticle slurry include NiO nanoparticles, acetylene black and PVDF emulsion, wherein the mass ratio of NiO nanoparticles, acetylene black and PVDF emulsion is 6-8:2:1;

[0011] The 2H phase MoS2 layer is prepared from a 2H phase MoS2 slurry, wherein the components of the 2H phase MoS2 slurry include 2H phase MoS2, acetylene black and PVDF emulsion, wherein the mass ratio of 2H phase MoS2, acetylene black and PVDF emulsion is 6-8:2:1;

[0012] The 1T phase MoS 2、 The mass ratio of 2H phase MoS2 and NiO nanoparticles is 1:1:0.02~1;

[0013] The solid content of the PVDF emulsion is 9.5-11.5 mg / mL.

[0014] Furthermore, the mass ratio of the 1T phase MoS2, acetylene black and PVDF emulsion is 7:2:1;

[0015] The mass ratio of NiO nanoparticles, acetylene black, and PVDF emulsion was 7:2:1;

[0016] The mass ratio of 2H phase MoS2, acetylene black and PVDF emulsion is 7:2:1;

[0017] The 1T phase MoS 2、 The mass ratio of 2H phase MoS2 and NiO nanoparticles is 1:1:0.1.

[0018] The present invention also provides a method for preparing the molybdenum disulfide-based composite positive electrode material, comprising the following steps:

[0019] (1) According to the mass ratio of the above-mentioned 1T phase MoS2, acetylene black and PVDF emulsion, 1T phase MoS2, acetylene black and PVDF emulsion are weighed and mixed to prepare a slurry to obtain a 1T phase MoS2 slurry;

[0020] (2) According to the mass ratio of the 2H phase MoS2, acetylene black and PVDF emulsion, 2H phase MoS2, acetylene black and PVDF emulsion are weighed and mixed to prepare a slurry to obtain a 2H phase MoS2 slurry;

[0021] (3) According to the mass ratio of NiO nanoparticles, acetylene black and PVDF emulsion, NiO nanoparticles, acetylene black and PVDF emulsion are weighed and mixed to prepare a slurry to obtain NiO nanoparticle slurry;

[0022] (4) According to the above 1T phase MoS 2、 The mass ratio of 2H phase MoS2 and NiO nanoparticles was calculated by weighing 1T phase MoS2 slurry, NiO nanoparticle slurry and 2H phase MoS2 slurry;

[0023] (5) In the order of 1T phase MoS2 slurry, NiO nanoparticle slurry and 2H phase MoS2 slurry, they are drop-coated on the titanium mesh layer by layer. Each layer is dried after drop-coating to form a 1T phase MoS2 layer, a NiO nanoparticle layer and a 2H phase MoS2 layer on the titanium mesh in sequence, thereby obtaining a molybdenum disulfide-based composite positive electrode material for aqueous zinc ion photorechargeable batteries.

[0024] Furthermore, in step (1), the preparation method of the 1T phase MoS2 is as follows:

[0025] 1) Weigh ammonium molybdate tetrahydrate and urea, dissolve them in water, and mix to obtain a clear solution;

[0026] 2) Transfer the clarified solution to a reactor and heat at 150-170°C for 22-26 hours. After cooling, obtain the first black solid product.

[0027] 3) The first black solid product is washed and dried to obtain 1T phase MoS2.

[0028] Furthermore, the mass ratio of the ammonium molybdate tetrahydrate to urea is 2.35-2.55:3.5-3.7.

[0029] Furthermore, in step (2), the preparation method of the 2H phase MoS2 is as follows:

[0030] S1: Weigh ammonium molybdate tetrahydrate and urea, dissolve them in water, and mix to obtain a clear solution;

[0031] S2: Transfer the clear solution to a reactor and keep it at 210-230°C for 16-20 h. After cooling, a second black solid product is obtained.

[0032] S3: Wash and dry the second black solid product to obtain 2H phase MoS2.

[0033] Furthermore, the mass ratio of the ammonium molybdate tetrahydrate to urea is 2.35-2.55:3.5-3.7.

[0034] The present invention also provides an application of the molybdenum disulfide-based composite positive electrode material in the preparation of an aqueous zinc ion photorechargeable battery.

[0035] The present invention also provides an aqueous zinc ion photorechargeable battery, which comprises the molybdenum disulfide-based composite positive electrode material.

[0036] Principle of the present invention:

[0037] The molybdenum disulfide-based composite cathode material of the present invention is primarily composed of layers of 1T-phase MoS2, NiO nanoparticles, and 2H-phase MoS2 stacked together. The 2H-phase MoS2, as a semiconductor but unable to store zinc, performs photoelectric conversion, while the 1T-phase MoS2, as a metallic phase capable of storing zinc, stores zinc ions for energy storage. NiO, a commonly used hole transport layer material, efficiently transports holes and separates photogenerated carriers between the two MoS2 phases.

[0038] When the molybdenum disulfide-based composite positive electrode material of the present invention is applied to an aqueous zinc ion photorechargeable battery, the specific photorecharge mechanism is as follows: when light is irradiated to the surface of 2H phase MoS2, it undergoes photoelectric conversion, and the photogenerated electrons flow into the external circuit and then into the zinc negative electrode, inducing zinc metal deposition; the photogenerated holes are transported into the interior of the 1T phase MoS2 bulk phase via NiO, driving the zinc ions to escape from the 1T phase MoS2, thereby forming a complete photorecharge electrode reaction and realizing energy storage.

[0039] Beneficial effects of the present invention:

[0040] When the molybdenum disulfide-based composite positive electrode material of the present invention is selected as the positive electrode of the aqueous zinc ion photorechargeable battery, the positive electrode exhibits reversible photorecharge cycle performance and is a potential application material for long-life aqueous zinc ion photorechargeable batteries. Specifically, at 70 mW / cm 2 The device was photocharged for 2 hours under intense light and then discharged at a current density of 1000 mA / g, achieving 30 reversible cycles and a reversible capacity of 67 mAh / g. The process is simple, the raw materials are inexpensive and readily available, and the layer-by-layer drop coating method employed requires minimal equipment, making it easy to scale up production. Furthermore, the composite electrode exhibits reversible photocharging cycles and excellent photocharging performance. The resulting electrode exhibits good dispersibility, high photoelectric efficiency, and high yield, making it suitable for market promotion. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 This is the XRD pattern of the molybdenum disulfide-based composite cathode material of Example 1;

[0042] Figure 2 This is a Raman graph of the molybdenum disulfide-based composite cathode material of Example 1;

[0043] Figure 3 This is a diagram of the photocharging capacity of an aqueous zinc ion photorechargeable battery assembled with the molybdenum disulfide-based composite positive electrode material of Example 1;

[0044] Figure 4 This is a long photocharging cycle diagram of an aqueous zinc ion photorechargeable battery assembled with the molybdenum disulfide-based composite positive electrode material of Example 1. DETAILED DESCRIPTION

[0045] The present invention is further described in detail below with reference to specific embodiments so that those skilled in the art can understand.

[0046] Example 1

[0047] The preparation method of a molybdenum disulfide-based composite positive electrode material for aqueous zinc ion photorechargeable batteries specifically comprises the following steps:

[0048] 1) Weigh 2.47 g of ammonium molybdate tetrahydrate ((NH4)6Mo7O 24 ·4H2O) powder and 3.60 g urea (CO(NH2)2) powder in a glass beaker;

[0049] 2) Add 70 mL of deionized water to the glass beaker from step 1) and continue stirring until the solution becomes clear and transparent.

[0050] 3) The clear solution obtained in step 2) was transferred to a 100 mL Teflon reactor, kept at 160°C for 24 hours, and then naturally cooled to room temperature to obtain a first black solid product;

[0051] 4) The first black solid product obtained in 3) was washed three times with deionized water and anhydrous ethanol, respectively, and then dried in a vacuum drying oven at 60°C to obtain 1T phase MoS2 (1T-MoS2) powder;

[0052] 5) Repeat steps 1) and 2), transfer the clear solution obtained in step 2) to a 100 mL Teflon reactor, keep it at 220°C for 18 hours, and then cool it naturally to room temperature to obtain a second black solid product;

[0053] 6) The second black solid product obtained in 5) was washed three times with deionized water and anhydrous ethanol, respectively, and then dried in a vacuum drying oven at 60°C to obtain 2H phase MoS2 (2H-MoS2) powder;

[0054] 7) 1T phase MoS2, acetylene black, and PVDF emulsion (solid content 9.5-11.5 mg / mL) were mixed in a mass ratio of 7:2:1 to prepare a slurry to obtain a 1T phase MoS2 slurry containing 1.05 mg of 1T phase MoS2;

[0055] 8) 2H-phase MoS2, acetylene black, and PVDF emulsion were mixed in a mass ratio of 7:2:1 to prepare a slurry, thereby obtaining a 2H-phase MoS2 slurry containing 1.05 mg of 2H-phase MoS2;

[0056] 9) NiO nanoparticles, acetylene black, and PVDF emulsion were mixed in a mass ratio of 7:2:1 to prepare a slurry, thereby obtaining a NiO nanoparticle slurry containing 0.105 mg of NiO nanoparticles;

[0057] 10) 1T phase MoS2 slurry containing 1.05 mg of 1T phase MoS2, NiO nanoparticle slurry containing 0.105 mg of NiO nanoparticles, and 2H phase MoS2 slurry containing 1.05 mg of 2H phase MoS2 were respectively measured and drop-coated layer by layer on a 100-mesh titanium mesh in the order of 1T phase MoS2 slurry, NiO nanoparticle slurry, and 2H phase MoS2 slurry. After each layer was drop-coated, it was placed at 60°C for drying to form a 200-300 μm 1T phase MoS2 layer, a 100-200 μm NiO nanoparticle layer, and a 200-300 μm 2H phase MoS2 layer on the titanium mesh, thereby obtaining a molybdenum disulfide-based composite positive electrode material for aqueous zinc-ion rechargeable photocells.

[0058] Example 2

[0059] 1. The molybdenum disulfide-based composite cathode material of Example 1 was analyzed by X-ray diffractometer. Figure 1As shown, the crystal shape of the molybdenum disulfide-based composite positive electrode material is stable and the purity of MoS2 is high.

[0060] 2. The molybdenum disulfide-based composite cathode material of Example 1 was analyzed by laser confocal Raman spectroscopy (Raman). The results are as follows: Figure 2 As shown, it can be confirmed that MoS2 in the molybdenum disulfide-based composite positive electrode material exists in 1T and 2H phases respectively, and the phase purity is high.

[0061] 3. The molybdenum disulfide-based composite positive electrode material of Example 1 is used as the positive electrode of an aqueous zinc ion photorechargeable battery. The assembly method of the aqueous zinc ion photorechargeable battery is as follows:

[0062] 1) Cut an 8 mm diameter circular hole in the positive electrode shell of a CR2032 stainless steel battery. Then cut a 10 mm diameter flexible ITO disc. Use UV-curable adhesive to bond the flexible ITO disc to the outside of the hole in the positive electrode shell. Irradiate with UV light for 1 minute to complete the encapsulation of the light-transmitting window of the light-rechargeable battery.

[0063] 2) A button-type aqueous zinc ion photorechargeable battery was assembled using 3 M zinc trifluoromethanesulfonate (Zn(CF3SO3)2) dissolved in deionized water as the electrolyte, a zinc sheet as the negative electrode, the molybdenum disulfide-based composite positive electrode material of Example 1 as the positive electrode (2H phase MoS2 is close to the battery casing, and 1T phase MoS2 is close to the battery interior), GF-D glass fiber as the separator, and a CR2032 stainless steel battery casing.

[0064] 3) At 70 mW / cm 2 The aqueous zinc ion photorechargeable battery of this embodiment is irradiated with a light intensity of , so that it undergoes a photorecharge process.

[0065] The results are as follows Figure 3 As shown in the figure, the discharge current density is 1 A / g. After 2 h of photocharging, the voltage of the battery can be raised to 0.8 V, and the reversible capacity can reach 67 mAh / g, which is a relatively high level among batteries of the same type.

[0066] The results are as follows Figure 4 As shown, in an environment where charging is only dependent on light, the aqueous zinc ion photorechargeable battery of this embodiment continuously cycles under 2 h photocharging conditions, exhibiting a reversible discharge specific capacity and achieving more than 30 reversible photorecharge cycles.

[0067] Example 3

[0068] The preparation method of a molybdenum disulfide-based composite positive electrode material for aqueous zinc ion photorechargeable batteries specifically comprises the following steps:

[0069] 1) Weigh 2.47 g (NH4)6Mo7O 244H2O powder and 3.60 g CO(NH2)2 powder in a glass beaker;

[0070] 2) Add 70 mL of deionized water to the glass beaker from step 1) and continue stirring until the solution becomes clear and transparent.

[0071] 3) The clear solution obtained in step 2) was transferred to a 100 mL Teflon reactor, kept at 160°C for 24 hours, and then naturally cooled to room temperature to obtain a first black solid product;

[0072] 4) The first black solid product obtained in 3) was washed three times with deionized water and anhydrous ethanol respectively, and then dried in a vacuum drying oven at 60°C to obtain 1T phase MoS2 powder;

[0073] 5) Repeat steps 1) and 2), transfer the clear solution obtained in step 2) to a 100 mL Teflon reactor, keep it at 220°C for 18 hours, and then cool it naturally to room temperature to obtain a second black solid product;

[0074] 6) The second black solid product obtained in 5) was washed three times with deionized water and anhydrous ethanol, respectively, and then dried in a vacuum drying oven at 60°C to obtain 2H phase MoS2 powder;

[0075] 7) 1T phase MoS2, acetylene black, and PVDF emulsion were mixed in a mass ratio of 7:2:1 to prepare a slurry, thereby obtaining a 1T phase MoS2 slurry containing 1.05 mg of 1T phase MoS2;

[0076] 8) 2H-phase MoS2, acetylene black, and PVDF emulsion were mixed in a mass ratio of 7:2:1 to prepare a slurry, thereby obtaining a 2H-phase MoS2 slurry containing 1.05 mg of 2H-phase MoS2;

[0077] 9) NiO nanoparticles, acetylene black, and PVDF emulsion were mixed in a mass ratio of 7:2:1 to prepare a slurry, thereby obtaining a NiO nanoparticle slurry containing 0.021 mg of NiO nanoparticles;

[0078] 10) 1T phase MoS2 slurry containing 1.05 mg of 1T phase MoS2, NiO nanoparticle slurry containing 0.021 mg of NiO nanoparticles, and 2H phase MoS2 slurry containing 1.05 mg of 2H phase MoS2 were respectively measured and drop-coated layer by layer on a 100-mesh titanium mesh in the order of 1T phase MoS2 slurry, NiO nanoparticle slurry, and 2H phase MoS2 slurry. After each layer was drop-coated, it was placed at 60°C for drying to form a 200-300 μm 1T phase MoS2 layer, a 20-40 μm NiO nanoparticle layer, and a 200-300 μm 2H phase MoS2 layer on the titanium mesh, thereby obtaining a molybdenum disulfide-based composite positive electrode material for aqueous zinc-ion rechargeable photocells.

[0079] The molybdenum disulfide-based composite positive electrode material obtained in this embodiment was used as the positive electrode to assemble an aqueous zinc ion photorechargeable battery according to the method of Example 2. The aqueous zinc ion photorechargeable battery of this embodiment was 100 nm at 70 mW / cm 2 The photocharging cycle was carried out under a light intensity of , achieving 30 reversible photocharging cycles with a reversible capacity of 7.99 mAh / g.

[0080] Example 4

[0081] The preparation method of a molybdenum disulfide-based composite positive electrode material for aqueous zinc ion photorechargeable batteries specifically comprises the following steps:

[0082] 1) Weigh 2.47 g (NH4)6Mo7O 24 4H2O powder and 3.60 g CO(NH2)2 powder in a glass beaker;

[0083] 2) Add 70 mL of deionized water to the glass beaker from step 1) and continue stirring until the solution becomes clear and transparent.

[0084] 3) The clear solution obtained in step 2) was transferred to a 100 mL Teflon reactor, kept at 160°C for 24 hours, and then naturally cooled to room temperature to obtain a first black solid product;

[0085] 4) The first black solid product obtained in 3) was washed three times with deionized water and anhydrous ethanol respectively, and then dried in a vacuum drying oven at 60°C to obtain 1T phase MoS2 powder;

[0086] 5) Repeat steps 1) and 2), transfer the clear solution obtained in step 2) to a 100 mL Teflon reactor, keep it at 220°C for 18 hours, and then cool it naturally to room temperature to obtain a second black solid product;

[0087] 6) The second black solid product obtained in 5) was washed three times with deionized water and anhydrous ethanol, respectively, and then dried in a vacuum drying oven at 60°C to obtain 2H phase MoS2 powder;

[0088] 7) 1T phase MoS2, acetylene black, and PVDF emulsion were mixed in a mass ratio of 7:2:1 to prepare a slurry to obtain a 1T phase MoS2 slurry containing 1.05 mg of 1T phase MoS2;

[0089] 8) 2H-phase MoS2, acetylene black, and PVDF emulsion were mixed in a mass ratio of 7:2:1 to prepare a slurry to obtain a 2H-phase MoS2 slurry containing 1.05 mg of MoS2;

[0090] 9) NiO nanoparticles, acetylene black, and PVDF emulsion were mixed in a mass ratio of 7:2:1 to prepare a slurry to obtain a NiO nanoparticle slurry containing 0.053 mg of NiO;

[0091] 10) 1T phase MoS2 slurry containing 1.05 mg 1T phase MoS2, NiO nanoparticle slurry containing 0.053 mg NiO, and 2H phase MoS2 slurry containing 1.05 mg MoS2 were respectively measured and drop-coated layer by layer on a 100-mesh titanium mesh in the order of 1T phase MoS2 slurry, NiO nanoparticle slurry, and 2H phase MoS2 slurry. After each layer was drop-coated, it was placed at 60°C for drying to form a 200-300 μm 1T phase MoS2 layer, a 50-100 μm NiO nanoparticle layer, and a 200-300 μm 2H phase MoS2 layer on the titanium mesh, thereby obtaining a molybdenum disulfide-based composite positive electrode material for aqueous zinc-ion rechargeable photocells.

[0092] The molybdenum disulfide-based composite positive electrode material obtained in this embodiment was used as the positive electrode to assemble an aqueous zinc ion photorechargeable battery according to the method of Example 2. The aqueous zinc ion photorechargeable battery of this embodiment was 100 nm at 70 mW / cm 2 The photocharging cycle was carried out under a light intensity of , achieving 30 reversible photocharging cycles with a reversible capacity of 5.65 mAh / g.

[0093] Example 5

[0094] The preparation method of a molybdenum disulfide-based composite positive electrode material for aqueous zinc ion photorechargeable batteries specifically comprises the following steps:

[0095] 1) Weigh 2.47 g (NH4)6Mo7O 24 4H2O powder and 3.60 g CO(NH2)2 powder in a glass beaker;

[0096] 2) Add 70 mL of deionized water to the glass beaker from step 1) and continue stirring until the solution becomes clear and transparent.

[0097] 3) The clear solution obtained in step 2) was transferred to a 100 mL Teflon reactor, kept at 160°C for 24 hours, and then naturally cooled to room temperature to obtain a first black solid product;

[0098] 4) The first black solid product obtained in 3) was washed three times with deionized water and anhydrous ethanol respectively, and then dried in a vacuum drying oven at 60°C to obtain 1T phase MoS2 powder;

[0099] 5) Repeat steps 1) and 2), transfer the clear solution obtained in step 2) to a 100 mL Teflon reactor, keep it at 220°C for 18 hours, and then cool it naturally to room temperature to obtain a second black solid product;

[0100] 6) The second black solid product obtained in 5) was washed three times with deionized water and anhydrous ethanol, respectively, and then dried in a vacuum drying oven at 60°C to obtain 2H phase MoS2 powder;

[0101] 7) 1T phase MoS2, acetylene black, and PVDF emulsion were mixed in a mass ratio of 7:2:1 to prepare a slurry, thereby obtaining a 1T phase MoS2 slurry containing 1.05 mg of 1T phase MoS2;

[0102] 8) 2H-phase MoS2, acetylene black, and PVDF emulsion were mixed in a mass ratio of 7:2:1 to prepare a slurry, thereby obtaining a 2H-phase MoS2 slurry containing 1.05 mg of 2H-phase MoS2;

[0103] 9) NiO nanoparticles, acetylene black, and PVDF emulsion were mixed in a mass ratio of 7:2:1 to prepare a slurry, thereby obtaining a NiO nanoparticle slurry containing 0.21 mg of NiO nanoparticles;

[0104] 10) 1T phase MoS2 slurry containing 1.05 mg of 1T phase MoS2, NiO nanoparticle slurry containing 0.21 mg of NiO nanoparticles, and 2H phase MoS2 slurry containing 1.05 mg of 2H phase MoS2 were respectively measured and drop-coated layer by layer on a 100-mesh titanium mesh in the order of 1T phase MoS2 slurry, NiO nanoparticle slurry, and 2H phase MoS2 slurry. After each layer was drop-coated, it was placed at 60°C for drying to form a 200-300 μm 1T phase MoS2 layer, a 300-400 μm NiO nanoparticle layer, and a 200-300 μm 2H phase MoS2 layer on the titanium mesh, thereby obtaining a molybdenum disulfide-based composite positive electrode material for aqueous zinc-ion rechargeable photocells.

[0105] The molybdenum disulfide-based composite positive electrode material obtained in this embodiment was used as the positive electrode to assemble an aqueous zinc ion photorechargeable battery according to the method of Example 2. The aqueous zinc ion photorechargeable battery of this embodiment was 100 nm at 70 mW / cm 2 The photocharging cycle was carried out under a light intensity of , achieving 30 reversible photocharging cycles with a reversible capacity of 21.26 mAh / g.

[0106] Example 6

[0107] The preparation method of a molybdenum disulfide-based composite positive electrode material for aqueous zinc ion photorechargeable batteries specifically comprises the following steps:

[0108] 1) Weigh 2.47 g (NH4)6Mo7O 24 4H2O powder and 3.60 g CO(NH2)2 powder in a glass beaker;

[0109] 2) Add 70 mL of deionized water to the glass beaker from step 1) and continue stirring until the solution becomes clear and transparent.

[0110] 3) The clear solution obtained in step 2) was transferred to a 100 mL Teflon reactor, kept at 160°C for 24 hours, and then naturally cooled to room temperature to obtain a first black solid product;

[0111] 4) The first black solid product obtained in 3) was washed three times with deionized water and anhydrous ethanol respectively, and then dried in a vacuum drying oven at 60°C to obtain 1T phase MoS2 powder;

[0112] 5) Repeat steps 1) and 2), transfer the clear solution obtained in step 2) to a 100 mL Teflon reactor, keep it at 220°C for 18 hours, and then cool it naturally to room temperature to obtain a second black solid product;

[0113] 6) The second black solid product obtained in 5) was washed three times with deionized water and anhydrous ethanol, respectively, and then dried in a vacuum drying oven at 60°C to obtain 2H phase MoS2 powder;

[0114] 7) 1T phase MoS2, acetylene black, and PVDF emulsion were mixed in a mass ratio of 7:2:1 to prepare a slurry, thereby obtaining a 1T phase MoS2 slurry containing 1.05 mg of 1T phase MoS2;

[0115] 8) 2H-phase MoS2, acetylene black, and PVDF emulsion were mixed in a mass ratio of 7:2:1 to prepare a slurry, thereby obtaining a 2H-phase MoS2 slurry containing 1.05 mg of 2H-phase MoS2;

[0116] 9) NiO nanoparticles, acetylene black, and PVDF emulsion were mixed in a mass ratio of 7:2:1 to prepare a slurry, thereby obtaining a NiO nanoparticle slurry containing 0.525 mg of NiO nanoparticles;

[0117] 10) 1T phase MoS2 slurry containing 1.05 mg of 1T phase MoS2, NiO nanoparticle slurry containing 0.525 mg of NiO nanoparticles, and 2H phase MoS2 slurry containing 1.05 mg of 2H phase MoS2 were respectively measured and drop-coated layer by layer on a 100-mesh titanium mesh in the order of 1T phase MoS2 slurry, NiO nanoparticle slurry, and 2H phase MoS2 slurry. After each layer was drop-coated, it was placed at 60°C for drying to form a 200-300 μm 1T phase MoS2 layer, a 400-450 μm NiO nanoparticle layer, and a 200-300 μm 2H phase MoS2 layer on the titanium mesh, thereby obtaining a molybdenum disulfide-based composite positive electrode material for aqueous zinc-ion rechargeable photocells.

[0118] The molybdenum disulfide-based composite positive electrode material obtained in this embodiment was used as the positive electrode to assemble an aqueous zinc ion photorechargeable battery according to the method of Example 2. The aqueous zinc ion photorechargeable battery of this embodiment was 100 nm at 70 mW / cm 2 The photocharging cycle was carried out under a light intensity of , achieving 30 reversible photocharging cycles with a reversible capacity of 34.85 mAh / g.

[0119] Example 7

[0120] The preparation method of a molybdenum disulfide-based composite positive electrode material for aqueous zinc ion photorechargeable batteries specifically comprises the following steps:

[0121] 1) Weigh 2.47 g (NH4)6Mo7O 24 4H2O powder and 3.60 g CO(NH2)2 powder in a glass beaker;

[0122] 2) Add 70 mL of deionized water to the glass beaker from step 1) and continue stirring until the solution becomes clear and transparent.

[0123] 3) The clear solution obtained in step 2) was transferred to a 100 mL Teflon reactor, kept at 160°C for 24 hours, and then naturally cooled to room temperature to obtain a first black solid product;

[0124] 4) The first black solid product obtained in 3) was washed three times with deionized water and anhydrous ethanol respectively, and then dried in a vacuum drying oven at 60°C to obtain 1T phase MoS2 powder;

[0125] 5) Repeat steps 1) and 2), transfer the clear solution obtained in step 2) to a 100 mL Teflon reactor, keep it at 220°C for 18 hours, and then cool it naturally to room temperature to obtain a second black solid product;

[0126] 6) The second black solid product obtained in 5) was washed three times with deionized water and anhydrous ethanol, respectively, and then dried in a vacuum drying oven at 60°C to obtain 2H phase MoS2 powder;

[0127] 7) 1T phase MoS2, acetylene black, and PVDF emulsion were mixed in a mass ratio of 7:2:1 to prepare a slurry, thereby obtaining a 1T phase MoS2 slurry containing 1.05 mg of 1T phase MoS2;

[0128] 8) 2H-phase MoS2, acetylene black, and PVDF emulsion were mixed in a mass ratio of 7:2:1 to prepare a slurry, thereby obtaining a 2H-phase MoS2 slurry containing 1.05 mg of 2H-phase MoS2;

[0129] 9) NiO nanoparticles, acetylene black, and PVDF emulsion were mixed in a mass ratio of 7:2:1 to prepare a slurry, thereby obtaining a NiO nanoparticle slurry containing 1.05 mg of NiO nanoparticles;

[0130] 10) 1T phase MoS2 slurry containing 1.05 mg of 1T phase MoS2, NiO nanoparticle slurry containing 1.05 mg of NiO nanoparticles, and 2H phase MoS2 slurry containing 1.05 mg of 2H phase MoS2 were respectively measured and drop-coated layer by layer on a 100-mesh titanium mesh in the order of 1T phase MoS2 slurry, NiO nanoparticle slurry, and 2H phase MoS2 slurry. After each layer was drop-coated, it was placed at 60°C for drying to form a 200-300 μm 1T phase MoS2 layer, a 500-600 μm NiO nanoparticle layer, and a 200-300 μm 2H phase MoS2 layer on the titanium mesh, thereby obtaining a molybdenum disulfide-based composite positive electrode material for aqueous zinc-ion rechargeable photocells.

[0131] The molybdenum disulfide-based composite positive electrode material obtained in this embodiment was used as the positive electrode to assemble an aqueous zinc ion photorechargeable battery according to the method of Example 2. The aqueous zinc ion photorechargeable battery of this embodiment was 100 nm at 70 mW / cm 2 The photocharging cycle was carried out under a light intensity of , achieving 30 reversible photocharging cycles with a reversible capacity of 30.23 mAh / g.

[0132] Example 8

[0133] The preparation method of a molybdenum disulfide-based composite positive electrode material for aqueous zinc ion photorechargeable batteries specifically comprises the following steps:

[0134] 1) Weigh 2.35 g (NH4)6Mo7O 24 4H2O powder and 3.70 g CO(NH2)2 powder in a glass beaker;

[0135] 2) Add 70 mL of deionized water to the glass beaker from step 1) and continue stirring until the solution becomes clear and transparent.

[0136] 3) The clear solution obtained in step 2) was transferred to a 100 mL Teflon reactor, kept at 150°C for 26 hours, and then naturally cooled to room temperature to obtain a first black solid product;

[0137] 4) The first black solid product obtained in 3) was washed three times with deionized water and anhydrous ethanol respectively, and then dried in a vacuum drying oven at 60°C to obtain 1T phase MoS2 powder;

[0138] 5) Repeat steps 1) and 2), transfer the clear solution obtained in step 2) to a 100 mL Teflon reactor, keep it at 210°C for 20 hours, and then cool it naturally to room temperature to obtain a second black solid product;

[0139] 6) The second black solid product obtained in 5) was washed three times with deionized water and anhydrous ethanol, respectively, and then dried in a vacuum drying oven at 60°C to obtain 2H phase MoS2 powder;

[0140] 7) 1T phase MoS2, acetylene black, and PVDF emulsion were mixed in a mass ratio of 6:2:1 to prepare a slurry, thereby obtaining a 1T phase MoS2 slurry containing 1.05 mg of 1T phase MoS2;

[0141] 8) 2H-phase MoS2, acetylene black, and PVDF emulsion were mixed in a mass ratio of 6:2:1 to prepare a slurry, thereby obtaining a 2H-phase MoS2 slurry containing 1.05 mg of 2H-phase MoS2;

[0142] 9) NiO nanoparticles, acetylene black, and PVDF emulsion were mixed in a mass ratio of 6:2:1 to prepare a slurry, thereby obtaining a NiO nanoparticle slurry containing 0.105 mg of NiO nanoparticles;

[0143] 10) 1T phase MoS2 slurry containing 1.05 mg of 1T phase MoS2, NiO nanoparticle slurry containing 0.105 mg of NiO nanoparticles, and 2H phase MoS2 slurry containing 1.05 mg of 2H phase MoS2 were respectively measured and drop-coated layer by layer on a 100-mesh titanium mesh in the order of 1T phase MoS2 slurry, NiO nanoparticle slurry, and 2H phase MoS2 slurry. After each layer was drop-coated, it was placed at 60°C for drying to form a 200-300 μm 1T phase MoS2 layer, a 100-200 μm NiO nanoparticle layer, and a 200-300 μm 2H phase MoS2 layer on the titanium mesh, thereby obtaining a molybdenum disulfide-based composite positive electrode material for aqueous zinc-ion rechargeable photocells.

[0144] The molybdenum disulfide-based composite positive electrode material obtained in this embodiment was used as the positive electrode to assemble an aqueous zinc ion photorechargeable battery according to the method of Example 2. The aqueous zinc ion photorechargeable battery of this embodiment was 100 nm at 70 mW / cm 2 The photocharging cycle was carried out under a light intensity of , achieving 30 reversible photocharging cycles with a reversible capacity of 17.83 mAh / g.

[0145] Example 9

[0146] The preparation method of a molybdenum disulfide-based composite positive electrode material for aqueous zinc ion photorechargeable batteries specifically comprises the following steps:

[0147] 1) Weigh 2.55 g (NH4)6Mo7O 24 4H2O powder and 3.50 g CO(NH2)2 powder in a glass beaker;

[0148] 2) Add 70 mL of deionized water to the glass beaker from step 1) and continue stirring until the solution becomes clear and transparent.

[0149] 3) The clear solution obtained in step 2) was transferred to a 100 mL Teflon reactor, kept at 170°C for 22 hours, and then naturally cooled to room temperature to obtain a first black solid product;

[0150] 4) The first black solid product obtained in 3) was washed three times with deionized water and anhydrous ethanol respectively, and then dried in a vacuum drying oven at 60°C to obtain 1T phase MoS2 powder;

[0151] 5) Repeat steps 1) and 2), transfer the clear solution obtained in step 2) to a 100 mL Teflon reactor, keep it at 230°C for 16 hours, and then cool it naturally to room temperature to obtain a second black solid product;

[0152] 6) The second black solid product obtained in 5) was washed three times with deionized water and anhydrous ethanol, respectively, and then dried in a vacuum drying oven at 60°C to obtain 2H phase MoS2 powder;

[0153] 7) 1T phase MoS2, acetylene black, and PVDF emulsion were mixed in a mass ratio of 8:2:1 to prepare a slurry, thereby obtaining a 1T phase MoS2 slurry containing 1.05 mg of 1T phase MoS2;

[0154] 8) 2H-phase MoS2, acetylene black, and PVDF emulsion were mixed in a mass ratio of 8:2:1 to prepare a slurry, thereby obtaining a 2H-phase MoS2 slurry containing 1.05 mg of 2H-phase MoS2;

[0155] 9) NiO nanoparticles, acetylene black, and PVDF emulsion were mixed in a mass ratio of 8:2:1 to prepare a slurry, thereby obtaining a NiO nanoparticle slurry containing 0.105 mg of NiO nanoparticles;

[0156] 10) 1T phase MoS2 slurry containing 1.05 mg of 1T phase MoS2, NiO nanoparticle slurry containing 0.105 mg of NiO nanoparticles, and 2H phase MoS2 slurry containing 1.05 mg of 2H phase MoS2 were respectively measured and drop-coated layer by layer on a 100-mesh titanium mesh in the order of 1T phase MoS2 slurry, NiO nanoparticle slurry, and 2H phase MoS2 slurry. After each layer was drop-coated, it was placed at 60°C for drying to form a 200-300 μm 1T phase MoS2 layer, a 100-200 μm NiO nanoparticle layer, and a 200-300 μm 2H phase MoS2 layer on the titanium mesh, thereby obtaining a molybdenum disulfide-based composite positive electrode material for aqueous zinc-ion rechargeable photocells.

[0157] The molybdenum disulfide-based composite positive electrode material obtained in this embodiment was used as the positive electrode to assemble an aqueous zinc ion photorechargeable battery according to the method of Example 2. The aqueous zinc ion photorechargeable battery of this embodiment was 100 nm at 70 mW / cm 2 The photocharging cycle was carried out under a light intensity of , achieving 30 reversible photocharging cycles with a reversible capacity of 35.19 mAh / g.

[0158] Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of them. People can also obtain other embodiments based on this embodiment without inventiveness, and these embodiments all fall within the scope of protection of the present invention.

Claims

1. A molybdenum disulfide-based composite cathode material for aqueous zinc-ion photorechargeable batteries, characterized in that: The molybdenum disulfide-based composite cathode material comprises a 1T phase MoS2 layer, a NiO nanoparticle layer, and a 2H phase MoS2 layer coated on a titanium mesh in sequence from bottom to top; The thickness of the 1T phase MoS2 layer is 200~300 μm; the thickness of the NiO nanoparticle layer is 40~600 μm; and the thickness of the 2H phase MoS2 layer is 200~300 μm.

2. The molybdenum disulfide-based composite cathode material according to claim 1, characterized in that: The 1T phase MoS2 layer is prepared from a 1T phase MoS2 slurry, wherein the components of the 1T phase MoS2 slurry include 1T phase MoS2, acetylene black and PVDF emulsion, wherein the mass ratio of 1T phase MoS2, acetylene black and PVDF emulsion is 6-8:2:1; The NiO nanoparticle layer is prepared from NiO nanoparticle slurry, and the components of the NiO nanoparticle slurry include NiO nanoparticles, acetylene black and PVDF emulsion, wherein the mass ratio of NiO nanoparticles, acetylene black and PVDF emulsion is 6-8:2:1; The 2H phase MoS2 layer is prepared from a 2H phase MoS2 slurry, wherein the components of the 2H phase MoS2 slurry include 2H phase MoS2, acetylene black and PVDF emulsion, wherein the mass ratio of 2H phase MoS2, acetylene black and PVDF emulsion is 6-8:2:1; The 1T phase MoS 2、 The mass ratio of 2H phase MoS2 and NiO nanoparticles is 1:1:0.02~1; The solid content of the PVDF emulsion is 9.5-11.5 mg / mL.

3. The molybdenum disulfide-based composite cathode material according to claim 2, characterized in that: The mass ratio of the 1T phase MoS2, acetylene black and PVDF emulsion is 7:2:1; The mass ratio of NiO nanoparticles, acetylene black, and PVDF emulsion was 7:2:1; The mass ratio of 2H phase MoS2, acetylene black and PVDF emulsion is 7:2:1; The 1T phase MoS 2、 The mass ratio of 2H phase MoS2 and NiO nanoparticles is 1:1:0.

1.

4. A method for preparing the molybdenum disulfide-based composite positive electrode material according to claim 2 or 3, characterized in that: The following steps are involved: (1) According to the mass ratio of the above-mentioned 1T phase MoS2, acetylene black and PVDF emulsion, 1T phase MoS2, acetylene black and PVDF emulsion are weighed and mixed to prepare a slurry to obtain a 1T phase MoS2 slurry; (2) According to the mass ratio of the 2H phase MoS2, acetylene black and PVDF emulsion, 2H phase MoS2, acetylene black and PVDF emulsion are weighed and mixed to prepare a slurry to obtain a 2H phase MoS2 slurry; (3) According to the mass ratio of NiO nanoparticles, acetylene black and PVDF emulsion, NiO nanoparticles, acetylene black and PVDF emulsion are weighed and mixed to prepare a slurry to obtain NiO nanoparticle slurry; (4) According to the above 1T phase MoS 2、 The mass ratio of 2H phase MoS2 and NiO nanoparticles was calculated by weighing 1T phase MoS2 slurry, NiO nanoparticle slurry and 2H phase MoS2 slurry; (5) In the order of 1T phase MoS2 slurry, NiO nanoparticle slurry and 2H phase MoS2 slurry, they are drop-coated on the titanium mesh layer by layer. Each layer is dried after drop-coating to form a 1T phase MoS2 layer, a NiO nanoparticle layer and a 2H phase MoS2 layer on the titanium mesh in sequence, thereby obtaining a molybdenum disulfide-based composite positive electrode material for aqueous zinc ion photorechargeable batteries.

5. The preparation method according to claim 4, characterized in that: In the step (1), the preparation method of the 1T phase MoS2 is specifically as follows: 1) Weigh ammonium molybdate tetrahydrate and urea, dissolve them in water, and mix to obtain a clear solution; 2) Transfer the clarified solution to a reactor and heat at 150-170°C for 22-26 hours. After cooling, obtain the first black solid product. 3) The first black solid product is washed and dried to obtain 1T phase MoS2.

6. The preparation method according to claim 5, characterized in that: The mass ratio of the ammonium molybdate tetrahydrate to urea is 2.35-2.55:3.5-3.

7.

7. The preparation method according to claim 4, characterized in that: In the step (2), the preparation method of the 2H phase MoS2 is as follows: S1: Weigh ammonium molybdate tetrahydrate and urea, dissolve them in water, and mix to obtain a clear solution; S2: Transfer the clear solution to a reactor and keep it at 210-230°C for 16-20 h. After cooling, a second black solid product is obtained. S3: Wash and dry the second black solid product to obtain 2H phase MoS2.

8. The preparation method according to claim 7, characterized in that: The mass ratio of the ammonium molybdate tetrahydrate to urea is 2.35-2.55:3.5-3.

7.

9. Use of the molybdenum disulfide-based composite cathode material according to any one of claims 1 to 3 in the preparation of an aqueous zinc ion photorechargeable battery.

10. An aqueous zinc ion photorechargeable battery, characterized in that: The aqueous zinc ion photorechargeable battery comprises the molybdenum disulfide-based composite positive electrode material according to any one of claims 1 to 3.

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