High-entropy Prussian blue material and preparation method and application thereof

Abstract

The invention provides a high-entropy Prussian blue material and a preparation method and application thereof, and relates to the technical field of electrochemical material preparation and energy. The preparation method of the high-entropy Prussian blue material comprises the following steps: mixing a cobalt source, a nickel source, a copper source, a manganese source, a zinc source, an organic reducing compound and a first dispersing agent to obtain a first mixture; the molar ratio of the cobalt source to the nickel source to the copper source to the manganese source to the zinc source is 1: 1: 1: 1: 1; mixing the ferricyanide compound with a second dispersing agent to obtain a second mixture; and sequentially stirring and standing the first mixture and the second mixture to obtain the high-entropy Prussian blue material. The high-entropy Prussian blue material prepared by the method is stable in morphology, high in crystallinity and high in chemical stability, and can be applied to the field of electrochemical energy storage.

Description

Technical Field

[0001] This invention relates to the fields of electrochemical material preparation and energy technology, specifically to a high-entropy Prussian blue material, its preparation method, and its applications. Background Technology

[0002] In recent years, the diverse applications of high entropy in various materials have attracted widespread attention from researchers, promoting the rapid development of a series of single-phase multi-component (equimolar) materials. High-entropy alloys and high-entropy oxides, as typical high-entropy materials, have been applied in various fields such as environmental protection, electrochemical energy storage, and electrocatalysis. Recent reports indicate that battery materials obtained by introducing high-entropy structures can significantly improve cycle performance and have promising applications in the field of electrochemical energy storage.

[0003] Prussian blue analogues (PBAs), with the general chemical formula A x M A y [M B (CN)6] z ·□ m ·nH₂O (0≤x≤2), A represents Li + Na + K + Alkali metal ions, M A M B These represent ions of different valence states of transition metals such as Fe, Ni, and Co, where x, y, and z depend on M. A and M B The valence state is represented by □, where □ represents a vacancy, m represents the number of vacancies, and n represents the number of water molecules. PBAs have a face-centered cubic structure with space group Fm3m. In their lattice, M A and M B Located at the vertex position, formed by the cyano group (-C≡N-) located on the edge according to M B -C≡NM A Linear connection in the form of high-spin M A M coordinated with N, low-spin state B Coordinates with C to form M A N6 and M B C6 metallic octahedron, M A M BAll are located at the center of the complex, alternately connected to form a face-centered cubic structure, possessing an open three-dimensional framework. Prussian blue materials have a unique open framework structure that provides open channels, facilitating rapid ion conduction. The active sites for dual redox reactions can provide high capacity for the material. Moreover, the material synthesis process is simple, low-cost, and its morphology and species can be controlled. In 2004, Eftekhari et al. synthesized Prussian blue using an electrochemical deposition method (Volume 126, Issues 1–2, 16 February 2004, Pages 221-228), and for the first time studied the performance of Prussian blue as a potassium ion cathode material in non-aqueous electrolytes, finding that it has excellent electrochemical performance.

[0004] Studies have shown that high-entropy Prussian blue materials (HE-PBAs), which integrate highly dispersed active sites of high-entropy materials with unique 3D ion diffusion channels and redox active sites of Prussian blue analogues, have great potential for electrochemical applications. Wei Jiang et al. (Nano Energy 2021, 79, 105464) successfully synthesized a series of HE-PBAs combining mechanochemical and wet chemical properties at room temperature for the first time. Furthermore, in energy storage, Meng Du et al. (Angewandte Chemie International Edition 2022, 134, e202209350) reported on the application of HE-PBAs in lithium-sulfur batteries, and Jian Peng et al. (Angewandte Chemie International Edition 2023, 62, e202215865) reported on the application of HE-PBAs in sodium-ion batteries. Applications in zinc-ion storage have been rarely reported. Summary of the Invention

[0005] In view of this, the purpose of this invention is to provide a high-entropy Prussian blue material, its preparation method, and its applications. This invention employs a simple and convenient precipitation method to prepare a high-entropy Prussian blue material with stable morphology, high crystallinity, and uniform distribution of various metal elements, suitable for industrial-scale production. This invention applies the high-entropy Prussian blue material to the field of zinc ion storage, where it shows great promise.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a method for preparing high-entropy Prussian blue material, comprising the following steps: A cobalt source, a nickel source, a copper source, a manganese source, a zinc source, an organic reducing compound, and a first dispersant are mixed to obtain a first mixture; the molar ratio of the cobalt source, nickel source, copper source, manganese source, and zinc source is 1:1:1:1:1; The ferricyanide compound and the second dispersant are mixed to obtain a second mixture; The first mixture and the second mixture were stirred and allowed to stand in sequence to obtain the high-entropy Prussian blue material.

[0007] Preferably, the cobalt source includes one or more of cobalt nitrate, cobalt chloride, cobalt sulfate, and cobalt acetate; The nickel source includes one or more of nickel nitrate, nickel chloride, nickel sulfate, and nickel acetate; The copper source includes one or more of copper nitrate, copper chloride, copper sulfate, and copper acetate; The manganese source includes one or more of manganese nitrate, manganese chloride, manganese sulfate, and manganese acetate; The zinc source includes one or more of zinc nitrate, zinc chloride, zinc sulfate, and zinc acetate.

[0008] Preferably, the organic reducing compound includes one or more of sodium citrate, ascorbic acid, citric acid, potassium citrate, and glucose; The molar ratio of the organic reducing compound, cobalt source, nickel source, copper source, manganese source and zinc source is 4:1:1:1:1:1 to 6:1:1:1:1:1.

[0009] Preferably, the first dispersant is water; The total concentration of cobalt, nickel, copper, manganese and zinc sources in the first mixture is 0.004~0.04 mol / L.

[0010] Preferably, the ferricyanide compound includes one or more of potassium ferricyanide, sodium ferricyanide, potassium ferrocyanide, and sodium ferrocyanide; The molar ratio of the ferricyanide compound, cobalt source, nickel source, copper source, manganese source and zinc source is 4:1:1:1:1:1 to 6:1:1:1:1:1.

[0011] Preferably, the second dispersant is water; The concentration of ferricyanide in the second mixture is 0.01~0.08 mol / L.

[0012] Preferably, the stirring speed is 200~500 r / min; the stirring time is 16~30 h.

[0013] Preferably, the settling time is 16-30 hours; the settling temperature is room temperature.

[0014] This invention provides a high-entropy Prussian blue material prepared by the preparation method described in the above technical solution.

[0015] This invention provides the application of the high-entropy Prussian blue material described in the above technical solution in the field of zinc ion storage.

[0016] This invention provides a method for preparing high-entropy Prussian blue materials. The preparation method provided by this invention is a co-precipitation method, which is simple to operate, has universal experimental conditions, and can be directly used for large-scale industrial production. The high-entropy Prussian blue materials prepared by this invention have stable morphology, high crystallinity, and high chemical stability, and can be applied in the field of electrochemical energy storage, especially as high-power cathodes for energy storage devices such as zinc-ion batteries, zinc-ion capacitors, and hybrid ion capacitors, which have great application prospects.

[0017] In this invention, Prussian blue analogues (PBAs) can provide Zn with a three-dimensional open framework constructed by the coordination between the transition metal and the cyano group (-MN≡C-Fe-), and abundant active energy storage sites created by their multiple redox couplings. 2+ High-entropy materials, offering wide ion channels, are considered promising zinc electrode materials. They typically comprise five or more elements and can exhibit unique synergistic functions, resulting in useful properties. Furthermore, high-entropy materials possess open framework structures that are structurally stable, and their geometry changes little during zinc ion insertion, further mitigating capacity decay. This invention integrates highly dispersed active sites of high-entropy materials with 3D diffusion channels and redox active sites of Prussian blue analogs, creating high-entropy Prussian blue analogs (HE-PBAs) with immense potential for electrochemical energy storage applications. Attached Figure Description

[0018] Figure 1 The X-ray diffraction (XRD) spectrum of the high-entropy Prussian blue material prepared in Example 1; Figure 2 Scanning electron microscope (SEM) image of the high-entropy Prussian blue material prepared in Example 1; Figure 3 The image shows the spectral energy distribution surface scan (EDSMapping) of the high-entropy Prussian blue material prepared in Example 1. Figure 4 The charge-discharge diagram of the high-entropy Prussian blue material prepared in Example 1; Figure 5 The rate performance diagram of the high-entropy Prussian blue material prepared in Example 1; Figure 6 The cycling performance diagram shows the high-entropy Prussian blue material prepared in Example 1. Detailed Implementation

[0019] This invention provides a method for preparing high-entropy Prussian blue material, comprising the following steps: A cobalt source, a nickel source, a copper source, a manganese source, a zinc source, an organic reducing compound, and a first dispersant are mixed to obtain a first mixture; the molar ratio of the cobalt source, nickel source, copper source, manganese source, and zinc source is 1:1:1:1:1; The ferricyanide compound and the second dispersant are mixed to obtain a second mixture; The first mixture and the second mixture were stirred and allowed to stand in sequence to obtain the high-entropy Prussian blue material.

[0020] This invention involves mixing a cobalt source, a nickel source, a copper source, a manganese source, a zinc source, an organic reducing compound, and a first dispersant to obtain a first mixture. In this invention, the molar ratio of the cobalt source, nickel source, copper source, manganese source, and zinc source is 1:1:1:1:1.

[0021] In this invention, the cobalt source preferably includes one or more of cobalt nitrate, cobalt chloride, cobalt sulfate, and cobalt acetate, more preferably cobalt nitrate; the nickel source includes one or more of nickel nitrate, nickel chloride, nickel sulfate, and nickel acetate, more preferably nickel nitrate; the copper source includes one or more of copper nitrate, copper chloride, copper sulfate, and copper acetate, more preferably copper nitrate; the manganese source includes one or more of manganese nitrate, manganese chloride, manganese sulfate, and manganese acetate, more preferably manganese chloride; and the zinc source includes one or more of zinc nitrate, zinc chloride, zinc sulfate, and zinc acetate, more preferably zinc nitrate.

[0022] In this invention, the organic reducing compound preferably includes one or more of sodium citrate, ascorbic acid, citric acid, potassium citrate, and glucose, more preferably sodium citrate. In this invention, the molar ratio of the organic reducing compound, cobalt source, nickel source, copper source, manganese source, and zinc source is preferably 4:1:1:1:1:1 to 6:1:1:1:1:1, more preferably 22.5:4:4:4:4:4.

[0023] In this invention, the first dispersant is preferably water, and more preferably deionized water.

[0024] In this invention, the mixing of the cobalt source, nickel source, copper source, manganese source, zinc source, organic reducing compound, and first dispersant is preferably carried out under stirring conditions; the stirring temperature is preferably room temperature; and the stirring time is preferably 10 minutes. This invention does not have special requirements for the stirring rate; a stirring rate well known to those skilled in the art can be used.

[0025] In this invention, the total concentration of cobalt source, nickel source, copper source, manganese source and zinc source in the first mixture is preferably 0.004~0.04 mol / L, more preferably 0.008~0.02 mol / L.

[0026] This invention involves mixing a ferricyanide compound with a second dispersant to obtain a second mixture. In this invention, the ferricyanide compound preferably includes one or more of potassium ferricyanide, sodium ferricyanide, potassium ferrocyanide, and sodium ferrocyanide, more preferably potassium ferricyanide. In this invention, the molar ratio of the ferricyanide compound, cobalt source, nickel source, copper source, manganese source, and zinc source is preferably 4:1:1:1:1:1 to 6:1:1:1:1:1, more preferably 5:1:1:1:1:1:1.

[0027] In this invention, the second dispersant is preferably water, and more preferably ultrapure water.

[0028] In this invention, the mixing of the ferricyanide compound and the second dispersant is preferably carried out under stirring conditions; the stirring temperature is preferably room temperature; and the stirring time is preferably 10 minutes. This invention does not have special requirements for the stirring rate; any stirring rate well known to those skilled in the art can be used.

[0029] In this invention, the concentration of ferricyanide compound in the second mixture is preferably 0.01~0.08 mol / L, more preferably 0.04~0.06 mol / L.

[0030] After obtaining the first mixture and the second mixture, the present invention sequentially stirs and allows the first mixture and the second mixture to stand, thereby obtaining the high-entropy Prussian blue material. In the present invention, it is preferable to pour the first mixture into the second mixture, and then stir and allow it to stand. In the present invention, the stirring speed is preferably 200-500 r / min, more preferably 300-400 r / min; the stirring time is preferably 16-30 h, more preferably 20-24 h; and the stirring temperature is preferably room temperature. In the present invention, the standing time is preferably 16-30 h, more preferably 20-24 h; and the standing temperature is preferably room temperature.

[0031] In this invention, the obtained product is preferably subjected to centrifugal washing, drying, and grinding sequentially after settling to obtain the high-entropy Prussian blue material. In this invention, the centrifugal washing preferably includes centrifugal washing three times each with deionized water and ethanol. In this invention, the drying temperature is preferably 60°C, and the drying time is preferably 10 hours.

[0032] This invention provides a high-entropy Prussian blue material prepared by the preparation method described above. In this invention, the high-entropy Prussian blue material comprises cobalt, nickel, copper, manganese, zinc, and iron.

[0033] This invention provides the application of the high-entropy Prussian blue material described above in the field of zinc-ion storage, preferably in zinc-ion batteries, zinc-ion capacitors, or hybrid ion capacitors. In this invention, the high-entropy Prussian blue material is preferably used as a positive electrode material.

[0034] In a specific embodiment of the present invention, the high-entropy Prussian blue material, acetylene black, and binder described in the above technical solution are ground evenly, stirred into a paste using N-methylpyrrolidone as a solvent, coated onto carbon paper, and dried to obtain the positive electrode material; zinc metal is used as the negative electrode, a glass fiber membrane is used as the separator, an electrolyte is added, and a coin cell is assembled. In the present invention, the binder is preferably polyvinylidene fluoride. In the present invention, the mass ratio of the high-entropy Prussian blue material, acetylene black, and binder is preferably 7:2:1. In the present invention, the drying temperature is preferably 60°C, and the drying time is preferably 12 hours. In the present invention, the electrolyte is preferably 3M zinc trifluoromethanesulfonate.

[0035] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0036] Example 1 At room temperature, 0.0004 mol cobalt nitrate, 0.0004 mol nickel nitrate, 0.0004 mol copper nitrate, 0.0004 mol manganese chloride, 0.0004 mol zinc nitrate, and 0.00225 mol sodium citrate were added to 50 mL of deionized water and stirred for 10 min to obtain the first mixture. Add 0.002 mol potassium ferricyanide to 50 mL of ultrapure water and stir for 10 min to obtain the second mixture; The first mixture and the second mixture were mixed and stirred for 24 h, then allowed to stand for 24 h. The resulting solid precipitate was washed three times each with deionized water and ethanol by centrifugation, dried at 60°C for 10 h, and then ground to obtain the high-entropy Prussian blue material.

[0037] Figure 1 The XRD pattern of the high-entropy Prussian blue material prepared in Example 1 is shown below. Figure 1 It can be seen that it has a single-phase structure and contains no impurities.

[0038] Figure 2 The image shows a SEM image of the high-entropy Prussian blue material prepared in Example 1. Figure 2It can be seen that the high-entropy Prussian blue material is composed of nanoscale particles with a cubic morphology.

[0039] Figure 3 The image shows the EDS mapping of the high-entropy Prussian blue material prepared in Example 1, where a is a scanning transmission electron microscope (SEM) image of the sample, b is the elemental distribution map of zinc, c is the elemental distribution map of cobalt, d is the elemental distribution map of nickel, e is the elemental distribution map of copper, and f is the elemental distribution map of manganese. Analysis shows that zinc, cobalt, nickel, copper, and manganese are uniformly distributed in the high-entropy Prussian blue material.

[0040] Example 2 At room temperature, 0.0004 mol cobalt nitrate, 0.0004 mol nickel nitrate, 0.0004 mol copper nitrate, 0.0004 mol manganese nitrate, 0.0004 mol zinc nitrate, and 0.00225 mol sodium citrate were added to 50 mL of deionized water and stirred for 10 min to obtain the first mixture. Add 0.002 mol potassium ferricyanide to 50 mL of ultrapure water and stir for 10 min to obtain the second mixture; The first mixture and the second mixture were mixed and stirred for 24 h, then allowed to stand for 24 h. The resulting solid precipitate was centrifuged three times each with deionized water and ethanol, dried at 60 ℃ for 10 h, and then ground to obtain high-entropy Prussian blue material.

[0041] Example 3 At room temperature, 0.0004 mol cobalt nitrate, 0.0004 mol nickel nitrate, 0.0004 mol copper nitrate, 0.0004 mol manganese nitrate, 0.0004 mol zinc nitrate, and 0.00225 mol potassium citrate were added to 50 mL of deionized water and stirred for 10 min to obtain the first mixture. Add 0.002 mol potassium ferricyanide to 50 mL of ultrapure water and stir for 10 min to obtain the second mixture; The first mixture and the second mixture were mixed and stirred for 24 h, then allowed to stand for 24 h. The resulting solid precipitate was centrifuged three times each with deionized water and ethanol, dried at 60 ℃ for 10 h, and then ground to obtain high-entropy Prussian blue material.

[0042] Example 4 At room temperature, 0.0004 mol cobalt chloride, 0.0004 mol nickel chloride, 0.0004 mol copper chloride, 0.0004 mol manganese chloride, 0.0004 mol zinc chloride, and 0.00225 mol potassium citrate were added to 50 mL of deionized water and stirred for 10 min to obtain the first mixture. Add 0.002 mol potassium ferricyanide to 50 mL of ultrapure water and stir for 10 min to obtain the second mixture; The first mixture and the second mixture were mixed and stirred for 24 h, then allowed to stand for 24 h. The resulting solid precipitate was centrifuged three times each with deionized water and ethanol, dried at 60 ℃ for 10 h, and then ground to obtain high-entropy Prussian blue material.

[0043] Example 5 At room temperature, 0.0004 mol cobalt nitrate, 0.0004 mol nickel nitrate, 0.0004 mol copper nitrate, 0.0004 mol manganese nitrate, 0.0004 mol zinc nitrate, and 0.00225 mol ascorbic acid were added to 50 mL of deionized water and stirred for 10 min to obtain the first mixture. Add 0.002 mol potassium ferricyanide to 50 mL of ultrapure water and stir for 10 min to obtain the second mixture; The first mixture and the second mixture were mixed and stirred for 24 h, then allowed to stand for 24 h. The resulting solid precipitate was centrifuged three times each with deionized water and ethanol, dried at 60 ℃ for 10 h, and then ground to obtain high-entropy Prussian blue material.

[0044] Example 6 At room temperature, 0.0004 mol cobalt chloride, 0.0004 mol nickel chloride, 0.0004 mol copper chloride, 0.0004 mol manganese chloride, 0.0004 mol zinc chloride, and 0.00225 mol citric acid were added to 50 mL of deionized water and stirred for 10 min to obtain the first mixture. Add 0.002 mol potassium ferricyanide to 50 mL of ultrapure water and stir for 10 min to obtain the second mixture; The first mixture and the second mixture were mixed and stirred for 24 h, then allowed to stand for 24 h. The resulting solid precipitate was centrifuged three times each with deionized water and ethanol, dried at 60 ℃ for 10 h, and then ground to obtain high-entropy Prussian blue material.

[0045] Example 7 At room temperature, 0.0004 mol cobalt sulfate, 0.0004 mol nickel sulfate, 0.0004 mol copper sulfate, 0.0004 mol manganese sulfate, 0.0004 mol zinc sulfate, and 0.00225 mol potassium citrate were added to 50 mL of deionized water and stirred for 10 min to obtain the first mixture. Add 0.002 mol potassium ferricyanide to 50 mL of ultrapure water and stir for 10 min to obtain the second mixture; The first mixture and the second mixture were mixed and stirred for 24 h, then allowed to stand for 24 h. The resulting solid precipitate was centrifuged three times each with deionized water and ethanol, dried at 60 ℃ for 10 h, and then ground to obtain high-entropy Prussian blue material.

[0046] Example 8 At room temperature, 0.0004 mol cobalt acetate, 0.0004 mol nickel acetate, 0.0004 mol copper acetate, 0.0004 mol manganese acetate, 0.0004 mol zinc acetate, and 0.00225 mol potassium citrate were added to 50 mL of deionized water and stirred for 10 min to obtain the first mixture. Add 0.002 mol potassium ferricyanide to 50 mL of ultrapure water and stir for 10 min to obtain the second mixture; The first mixture and the second mixture were mixed and stirred for 24 h, then allowed to stand for 24 h. The resulting solid precipitate was centrifuged three times each with deionized water and ethanol, dried at 60 ℃ for 10 h, and then ground to obtain high-entropy Prussian blue material.

[0047] Example 9 At room temperature, 0.0004 mol cobalt nitrate, 0.0004 mol nickel nitrate, 0.0004 mol copper nitrate, 0.0004 mol manganese nitrate, 0.0004 mol zinc nitrate, and 0.00225 mol sodium citrate were added to 50 mL of deionized water and stirred for 10 min to obtain the first mixture. Add 0.002 mol potassium ferrocyanide to 50 mL of ultrapure water and stir for 10 min to obtain the second mixture; The first mixture and the second mixture were mixed and stirred for 24 h, then allowed to stand for 24 h. The resulting solid precipitate was centrifuged three times each with deionized water and ethanol, dried at 60 ℃ for 10 h, and then ground to obtain high-entropy Prussian blue material.

[0048] Application examples The high-entropy Prussian blue material, acetylene black, and polyvinylidene fluoride binder prepared in Example 1 were weighed in a mass ratio of 70:20:10. After being ground evenly, the mixture was stirred thoroughly into a paste using N-methylpyrrolidone as a solvent. The paste was then evenly coated onto carbon paper cut to a suitable size and dried thoroughly at 60 °C for 12 h. The resulting material was used as the positive electrode. Zinc metal was used as the negative electrode, a glass fiber membrane was used as the separator, and a 3 mol / L zinc trifluoromethanesulfonate solution (water as the solvent) was used as the electrolyte to assemble a coin cell. Charge and discharge tests were then performed on the Land battery testing system.

[0049] The high-entropy Prussian blue material prepared in Example 1 was tested at 0.2 A·g. -1Charge-discharge curves, rate performance at different rates, and 1 A·g -1 The lifespan curve after 1000 cycles is as follows: Figure 4 , 5 As shown in Figures 6 and 7, the reversible specific capacity of the high-entropy Prussian blue material prepared in Example 1 can reach 65 mAh·g. -1 1 A·g -1 The cycle retention rate reached 65%.

[0050] The test results from the examples show that the high-entropy Prussian blue material prepared by the present invention has a uniform distribution of various metal elements, good product stability and consistency, and good zinc storage performance.

[0051] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a high-entropy Prussian blue material, characterized in that, Includes the following steps: A cobalt source, a nickel source, a copper source, a manganese source, a zinc source, an organic reducing compound, and a first dispersant are mixed to obtain a first mixture; the molar ratio of the cobalt source, nickel source, copper source, manganese source, and zinc source is 1:1:1:1:1; The ferricyanide compound and the second dispersant are mixed to obtain a second mixture; The first mixture and the second mixture were stirred and allowed to stand in sequence to obtain the high-entropy Prussian blue material.

2. The preparation method according to claim 1, characterized in that, The cobalt source includes one or more of cobalt nitrate, cobalt chloride, cobalt sulfate, and cobalt acetate; The nickel source includes one or more of nickel nitrate, nickel chloride, nickel sulfate, and nickel acetate; The copper source includes one or more of copper nitrate, copper chloride, copper sulfate, and copper acetate; The manganese source includes one or more of manganese nitrate, manganese chloride, manganese sulfate, and manganese acetate; The zinc source includes one or more of zinc nitrate, zinc chloride, zinc sulfate, and zinc acetate.

3. The preparation method according to claim 1, characterized in that, The organic reducing compound includes one or more of sodium citrate, ascorbic acid, citric acid, potassium citrate, and glucose; The molar ratio of the organic reducing compound, cobalt source, nickel source, copper source, manganese source and zinc source is 4:1:1:1:1:1 to 6:1:1:1:1:

1.

4. The preparation method according to claim 1, characterized in that, The first dispersant is water; The total concentration of cobalt, nickel, copper, manganese and zinc sources in the first mixture is 0.004~0.04 mol / L.

5. The preparation method according to claim 1, characterized in that, The ferricyanide compound includes one or more of potassium ferricyanide, sodium ferricyanide, potassium ferrocyanide, and sodium ferrocyanide. The molar ratio of the ferricyanide compound, cobalt source, nickel source, copper source, manganese source and zinc source is 4:1:1:1:1:1 to 6:1:1:1:1:

1.

6. The preparation method according to claim 1 or 5, characterized in that, The second dispersant is water; The concentration of ferricyanide in the second mixture is 0.01~0.08 mol / L.

7. The preparation method according to claim 1, characterized in that, The stirring speed is 200~500 r / min; the stirring time is 16~30 h.

8. The preparation method according to claim 1, characterized in that, The settling time is 16-30 hours; the settling temperature is room temperature.

9. The high-entropy Prussian blue material prepared by the preparation method according to any one of claims 1 to 8.

10. The application of the high-entropy Prussian blue material of claim 9 in the field of zinc ion storage.

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