Preparation method and application of manganese-based Prussian blue material
By using a slow mixing method of a suspension of sodium oxalate and manganese salt and sodium ferrocyanide solution in manganese-based Prussian blue materials, a material with a gradient core-shell structure was prepared, which solved the problem of insufficient performance of existing materials in sodium ion batteries and significantly improved the electrochemical performance.
Patent Information
- Application Number
- CN202510292659.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-12
- Publication Date
- 2025-05-16
AI Technical Summary
The specific capacity and long cycle performance of existing manganese-based Prussian blue materials in sodium ion batteries are affected by Fe(CN)6 lattice defects and coordination water, which limits its development in the field of energy storage.
Sodium oxalate and manganese salt are dissolved in solvent to form a manganese oxalate suspension, and sodium ferrocyanide solution is slowly added under stirring state, and rare gas is protected, and the reaction is carried out in a water bath stirring reaction, and the precipitation, filtering and drying are allowed to stand to obtain a manganese-based Prussian blue material with a gradient core-shell structure.
By spontaneously growing the Prussian blue shell material with a concentration gradient change, the electrochemical performance of manganese-based Prussian blue materials is significantly improved, and its specific capacity and long cycle stability in sodium ion batteries are enhanced.
Smart Images
Figure CN120004289A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the field of batteries, and in particular relates to a preparation method and application of a manganese-based Prussian blue material. Background Art
[0002] Sodium-ion batteries have been widely studied in the field of energy storage due to their abundant reserves, low price, and similar working principles to lithium-ion batteries. Prussian blue and its analogs have been widely studied due to their rigid three-dimensional open framework structure, low cost, and high theoretical capacity. They can provide sufficient space for the rapid embedding of sodium ions to achieve high performance. However, the inherent Fe(CN)6 lattice defects and the presence of coordinated water in Prussian blue seriously affect the specific capacity and long cycle performance of the battery, limiting its further development in the field of energy storage. To solve the above problems, the current main research focuses on the construction and optimization of the crystal structure. The construction of a gradient core-shell structure is an effective strategy to improve the structural stability of high-energy-density manganese-based Prussian blue and inhibit the volume change during charging and discharging. However, the methods for constructing a gradient core-shell structure in most studies are costly and involve the flow control of multiple gradient raw materials in the co-precipitation process, and the operation steps are relatively complicated. Summary of the invention
[0003] The purpose of the present invention is to provide a method for preparing a manganese-based Prussian blue material and its application, so as to overcome at least one of the above-mentioned defects in the prior art.
[0004] To achieve this object, the present invention adopts the following technical solutions:
[0005] The invention provides a method for preparing a manganese-based Prussian blue material, comprising the following steps: S1: dissolving sodium oxalate and a manganese salt in a solvent to form a manganese oxalate suspension A, dissolving a metal salt in a solvent to form a solution B, and dissolving sodium ferrocyanide in a solvent to form a solution C; S2: slowly adding the solution B and the solution C into the suspension A at a fixed flow rate while stirring, introducing a rare gas for protection, stirring in a water bath for reaction, and then standing to precipitate, filtering and drying to obtain a manganese-based Prussian blue material with a gradient core-shell structure.
[0006] Preferably, the manganese salt is at least one of sulfate, chloride, oxalate, phosphate and carbonate of manganese, and the metal salt is at least one of sulfate, chloride, oxalate, phosphate and carbonate of Fe, Co, Ni, Cu or Zn.
[0007] Preferably, in step S1, the mass ratio of sodium oxalate to manganese salt is 1 / 3 to 3. More preferably, the mass ratio of sodium oxalate to manganese salt is 3:1, 2:1, 1:1, 1:2, 1:3.
[0008] Preferably, in step S1: the solvent is an organic solvent and / or water, and the organic solvent is at least one of ethanol, acetone, toluene, isopropanol, methanol and propanol.
[0009] Preferably, in step S2, the mass ratio of the manganese salt to the metal salt is 1 / 3 to 3. More preferably, the mass ratio of the manganese salt to the metal salt is 3:1, 2:1, 1:1, 1:2, 1:3.
[0010] Preferably, in step S2: the mass of sodium ferrocyanide is a, the sum of the mass of manganese salt and metal salt is b, and a:b = 1 / 3 - 3. More preferably, a:b = 3:1, 2:1, 1:1, 1:2, 1:3.
[0011] Preferably, the ratio of sodium oxalate, sodium ferrocyanide, manganese salt, metal salt to the solvent is 1g: (0-100) mL. More preferably, the ratio of sodium oxalate, sodium ferrocyanide, manganese salt, metal salt to the solvent is 1g: 1mL, 1g: 5mL, 1g: 10mL, 1g: 15mL, 1g: 20mL, 1g: 25mL, 1g: 30mL, 1g: 35mL, 1g: 40mL, 1g: 45mL, 1g: 50mL, 1g: 55mL, 1g: 60mL, 1g: 65mL, 1g: 70mL, 1g: 75mL, 1g: 80mL, 1g: 85mL, 1g: 90mL, 1g: 95mL, 1g: 100mL.
[0012] Preferably, in step S2, the water bath temperature is 30-90°C. More preferably, the water bath temperature is 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, or 90°C.
[0013] Preferably, in step S2, the water bath time is 0.1-48h. More preferably, the water bath time is 0.1h, 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, 48h.
[0014] Preferably, in step S2, the standing time is 0.1-48 hours. More preferably, the standing time is 0.1 hours, 0.5 hours, 1 hours, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 48 hours.
[0015] Preferably, in step S2, the drying temperature is 60-200° C. More preferably, the drying temperature is 60° C., 70° C., 80° C., 90° C., 100° C., 110° C., 120° C., 130° C., 140° C., 150° C., 160° C., 170° C., 180° C., 190° C., or 200° C.
[0016] Preferably, in step S2, the drying time is 0.1-24 hours. More preferably, the drying time is 0.1 hours, 0.5 hours, 1 hours, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours.
[0017] Preferably, in step S2: vacuum drying or forced air drying is adopted, and the drying means includes at least one of spray drying, oven evaporation drying, rotary evaporation drying and freeze drying.
[0018] Preferably, the manganese-based Prussian blue material having a gradient core-shell structure includes a Prussian blue core material and a Prussian blue shell material, and the chemical formula of the Prussian blue core material is Na x Mn[Fe(CN)6] y · z H2O, where 0 <x≤2,0<y≤1,z> 0, the chemical formula of Prussian blue shell material is Na x M[Fe(CN)6] y · z H2O, wherein M is at least one of Fe, Co, Ni, Cu, and Zn, 0 <x≤2,0<y≤1,z> 0.
[0019] The present invention also provides a manganese-based Prussian blue material, which is prepared by the above-mentioned method for preparing the manganese-based Prussian blue material.
[0020] The present invention also provides a sodium ion battery positive electrode plate, comprising the above-mentioned manganese-based Prussian blue material.
[0021] The present invention also provides a sodium ion battery, comprising the above-mentioned sodium ion battery positive electrode sheet.
[0022] Preferably, it also includes a counter electrode and an electrolyte, the counter electrode is sodium metal, the solute of the electrolyte is NaPF6 or NaClO4, and the solvent of the electrolyte is PC, EC or DEC.
[0023] The beneficial effects of the present invention are:
[0024] Solid-phase manganese oxalate is used as a crystal seed. By utilizing the characteristic that the solubility of manganese-based Prussian blue materials is lower than that of manganese oxalate, all manganese oxalate precipitates are converted into manganese-based Prussian blue material precipitates. At the same time, the type and amount of the added metal salt are regulated in the co-precipitation reaction. Through its own step-by-step complexation and the complexation-dissociation competition between manganese ions and oxalate ions, there is no need to continuously adjust the raw material feed rate as in conventional gradient precipitation. A layer of Prussian blue shell material with a concentration gradient change (the inner core is manganese, and the manganese content of the outer shell gradually decreases), high crystallinity, and high sodium content can be spontaneously and gradually grown on the surface of the manganese-based Prussian blue material, which significantly improves the electrochemical properties of the manganese-based Prussian blue material. BRIEF DESCRIPTION OF THE DRAWINGS
[0025] Figure 1 This is a SEM image of the manganese-based Prussian blue material prepared in Comparative Example 1.
[0026] Figure 2 This is a SEM image of the manganese-based Prussian blue material with a gradient core-shell structure prepared in Example 1 of the present invention.
[0027] Figure 3 It is the XRD data diagram of comparative example 1 and embodiment 1.
[0028] Figure 4 It is the long cycle data diagram of ratio 1 and embodiment 1. DETAILED DESCRIPTION
[0029] The present invention will now be further described with reference to the accompanying drawings and specific implementation methods.
[0030] Comparative Example 1:
[0031] A method for preparing a conventional manganese-based Prussian blue material is provided, comprising the following steps:
[0032] S1: 2.0 g of sodium oxalate, 1.0 g of manganese sulfate and 1.0 g of ferrous sulfate were dissolved in 10 mL of pure water to form a manganese oxalate suspension A containing manganese oxalate precipitate, and 2.0 g of sodium ferrocyanide was dissolved in 10 mL of pure water to form a solution B.
[0033] S2: Slowly pump solution B into suspension A and introduce nitrogen for protection throughout the process. Stir the reaction in a 60°C water bath for 24 hours, then let it stand and settle for 1 hour, filter it with suction, and dry it in a vacuum drying oven at 120°C for 24 hours to obtain a manganese-based Prussian blue material.
[0034] In an argon glove box where both water and oxygen were less than 0.01 ppm, the manganese-based Prussian blue material prepared by the above-mentioned manganese-based Prussian blue material preparation method was used as a positive electrode material, and a sodium ion battery positive electrode sheet was prepared. Sodium metal was used as a counter electrode, and 1M NaPF6 EC / DEC=1:1 (v / v) + 2% FEC electrolyte was used to assemble a 2032 model button battery for performance testing.
[0035] Figure 1 This is a SEM image of the manganese-based Prussian blue material prepared in Comparative Example 1. It can be seen from the image that the sample presents large agglomerates of about 20 μm, and individual particles are 2-3 μm.
[0036] Embodiment 1:
[0037] A method for preparing a manganese-based Prussian blue material provided in this embodiment comprises the following steps:
[0038] S1: 2.0 g of sodium oxalate and 1.0 g of manganese sulfate were dissolved in 10 mL of pure water to form a manganese oxalate suspension A containing manganese oxalate precipitate, 2.0 g of ferrous sulfate was dissolved in 10 mL of pure water to form a solution B, and 2.0 g of sodium ferrocyanide was dissolved in 10 mL of pure water to form a solution C.
[0039] S2: While stirring, solution B and solution C are slowly pumped into suspension A at a fixed flow rate, and nitrogen is introduced for protection throughout the process. The reaction is stirred in a 60°C water bath for 24 hours, and then allowed to settle for 1 hour, filtered, and dried in a vacuum drying oven at 120°C for 24 hours to obtain a manganese-based Prussian blue material with a gradient core-shell structure. At the same time, other metal salts and sodium ferrocyanide solution required for the shell layer are pumped in at a fixed flow rate, and the manganese ions slowly dissociated from a large amount of manganese oxalate in the seed crystals are used to form the core. The oxalate has different complexing abilities with the manganese ions and other ions on the surface of the seed crystal, so that a manganese-based Prussian blue material with a gradient core-shell structure can be obtained.
[0040] The obtained manganese-based Prussian blue material with a gradient core-shell structure includes a Prussian blue core material and a Prussian blue shell material. The chemical formula of the Prussian blue core material of this embodiment is Na 1.75 Mn[Fe(CN)6] 0.95 .1.66H2O, the chemical formula of Prussian blue shell material is Na 1.54 Fe[Fe(CN)6] 0.83 .2.07H2O.
[0041] This embodiment also provides a manganese-based Prussian blue material, which is prepared by the above-mentioned method for preparing a manganese-based Prussian blue material.
[0042] This embodiment also provides a sodium ion battery positive electrode plate, including the above-mentioned manganese-based Prussian blue material.
[0043] This embodiment also provides a sodium ion battery, including the above-mentioned sodium ion battery positive electrode sheet, wherein it also includes a counter electrode and an electrolyte, the counter electrode is sodium metal, the solute of the electrolyte is NaPF6 or NaClO4, and the solvent of the electrolyte is PC, EC or DEC.
[0044] Specifically, in an argon glove box with water and oxygen less than 0.01 ppm, the manganese-based Prussian blue material with a gradient core-shell structure obtained by the above-mentioned Prussian blue material preparation method was used as a positive electrode material, and a sodium ion battery positive electrode sheet was prepared. Sodium metal was used as a counter electrode, and 1M NaPF6 EC / DEC=1:1 (v / v) + 2% FEC electrolyte was used to assemble 2032-type button batteries for performance testing.
[0045] Figure 2 This is an SEM image of the manganese-based Prussian blue material with a gradient core-shell structure prepared in Example 1. It can be seen from the figure that the sample presents large agglomerates of about 20 μm, which is similar to the overall morphology of Comparative Example 1, but the surface of the particles are uniformly coated with nano-scale particles. Through the line scan of the particle profile elements, it can be seen that the inner core is all manganese, the manganese content in the surface layer gradually decreases, and the iron content of the coating gradually increases, indicating that the manganese-based Prussian blue material with a gradient core-shell structure was successfully prepared.
[0046] Figure 3 These are the XRD data of Comparative Example 1 and Example 1. It can be seen from the figure that the overall peak shapes are similar, but the sodium content of the core-shell structure sample is lower.
[0047] Figure 4 These are the long cycle data of Comparative Example 1 and Example 1. It can be seen from the figure that the core-shell structured sample is superior to the single-structured Prussian blue material in terms of both capacity and long cycle stability.
[0048] Embodiment 2:
[0049] A method for preparing a manganese-based Prussian blue material provided in this embodiment comprises the following steps:
[0050] S1: 5.0 g of sodium oxalate and 1.0 g of manganese sulfate were dissolved in 10 mL of pure water to form a manganese oxalate suspension A containing manganese oxalate precipitate, 2.0 g of zinc sulfate was dissolved in 10 mL of pure water to form a solution B, and 2.0 g of sodium ferrocyanide was dissolved in 10 mL of pure water to form a solution C.
[0051] S2: While stirring, solution B and solution C were slowly pumped into suspension A at a fixed flow rate, and nitrogen was introduced for protection throughout the process. The mixture was stirred in a 50°C water bath for 24 hours, then allowed to settle for 8 hours, filtered, and dried in a vacuum drying oven at 150°C for 24 hours to obtain a manganese-based Prussian blue material with a gradient core-shell structure.
[0052] The chemical formula of the Prussian blue core material in this embodiment is Na 1.76 Mn[Fe(CN)6] 0.991 .1.67H2O, the chemical formula of Prussian blue shell material is Na 1.75 Zn[Fe(CN)6] 0.82 .1.56H2O.
[0053] In an argon glove box with less than 0.01 ppm of water and oxygen, the manganese-based Prussian blue material with a gradient core-shell structure prepared by the above-mentioned manganese-based Prussian blue material preparation method was used as a positive electrode material, and a sodium ion battery positive electrode sheet was prepared. Sodium metal was used as a counter electrode, and 1M NaPF6 EC / DEC=1:1 (v / v) + 2% FEC electrolyte was used to assemble a 2032-type button battery for performance testing.
[0054] Embodiment 3:
[0055] A method for preparing a manganese-based Prussian blue material provided in this embodiment comprises the following steps:
[0056] S1: 10.0 g of sodium oxalate and 2.0 g of manganese sulfate were dissolved in 10 mL of pure water to form a manganese oxalate suspension A containing manganese oxalate precipitate, 2.0 g of nickel sulfate was dissolved in 10 mL of pure water to form a solution B, and 2.0 g of sodium ferrocyanide was dissolved in 10 mL of pure water to form a solution C.
[0057] S2: While stirring, solution B and solution C were slowly pumped into suspension A at a fixed flow rate, and nitrogen was introduced for protection throughout the process. The mixture was stirred in a 95°C water bath for 24 hours, then allowed to settle for 4 hours, filtered, and dried in a vacuum drying oven at 120°C for 48 hours to obtain a manganese-based Prussian blue material with a gradient core-shell structure.
[0058] The chemical formula of the Prussian blue core material in this embodiment is Na 1.92 Mn[Fe(CN)6] 0.99 .1.02H2O, the chemical formula of Prussian blue shell material is Na 1.71 Ni[Fe(CN)6] 0.86 .2.03H2O.
[0059] In an argon glove box with less than 0.01 ppm of water and oxygen, the manganese-based Prussian blue material with a gradient core-shell structure prepared by the above-mentioned preparation method of the manganese-based Prussian blue material was used as a positive electrode material, and a sodium ion battery positive electrode sheet was prepared. Sodium metal was used as a counter electrode, and 1M NaPF6 EC / DEC=1:1 (v / v) + 2% FEC electrolyte was used to assemble a 2032-type button battery for performance testing.
[0060] Embodiment 4:
[0061] A method for preparing a manganese-based Prussian blue material provided in this embodiment comprises the following steps:
[0062] S1: 2.0 g of sodium oxalate and 1.0 g of manganese sulfate were dissolved in 10 mL of pure water to form a manganese oxalate suspension A containing manganese oxalate precipitate, 1.0 g of copper sulfate was dissolved in 10 mL of pure water to form a solution B, and 2.0 g of sodium ferrocyanide was dissolved in 10 mL of pure water to form a solution C.
[0063] S2: While stirring, solution B and solution C were slowly pumped into suspension A at a fixed flow rate, and nitrogen was introduced for protection throughout the process. The mixture was stirred in a 70°C water bath for 24 hours, then allowed to settle for 1 hour, filtered, and dried in a vacuum drying oven at 120°C for 24 hours to obtain a manganese-based Prussian blue material with a gradient core-shell structure.
[0064] The chemical formula of the Prussian blue core material in this embodiment is Na 1.79 Mn[Fe(CN)6] 0.98 .1.43H2O, the chemical formula of Prussian blue shell material is Na 1.71 Cu[Fe(CN)6] 0.82 .1.83H2O.
[0065] In an argon glove box with less than 0.01 ppm of water and oxygen, the manganese-based Prussian blue material with a gradient core-shell structure prepared by the above-mentioned manganese-based Prussian blue material preparation method was used as a positive electrode material, and a sodium ion battery positive electrode sheet was prepared. Sodium metal was used as a counter electrode, and 1M NaPF6 EC / DEC=1:1 (v / v) + 2% FEC electrolyte was used to assemble a 2032-type button battery for performance testing.
[0066] Embodiment 5:
[0067] A method for preparing a manganese-based Prussian blue material provided in this embodiment comprises the following steps:
[0068] S1: 2.0 g of sodium oxalate and 1.0 g of manganese sulfate were dissolved in 10 mL of pure water to form a manganese oxalate suspension A containing manganese oxalate precipitate, 1.0 g of ferrous sulfate and 1.0 g of nickel sulfate were dissolved in 10 mL of pure water to form a solution B, and 2.0 g of sodium ferrocyanide was dissolved in 10 mL of pure water to form a solution C.
[0069] S2: While stirring, solution B and solution C were slowly pumped into suspension A at a fixed flow rate, and nitrogen was introduced for protection throughout the process. The mixture was stirred in a 60°C water bath for 24 hours, then allowed to stand and precipitate for 1 hour, filtered, and dried in a vacuum drying oven at 120°C for 48 hours to obtain a manganese-based Prussian blue material with a gradient core-shell structure.
[0070] The chemical formula of the Prussian blue core material in this embodiment is Na 1.75 Mn[Fe(CN)6] 0.95 .1.66H2O, the chemical formula of Prussian blue shell material is Na 1.63 Ni 0.34 Fe 0.61 [Fe(CN)6] 0.85 .1.77H2O.
[0071] In an argon glove box with less than 0.01 ppm of water and oxygen, the manganese-based Prussian blue material with a gradient core-shell structure prepared by the above-mentioned manganese-based Prussian blue material preparation method was used as a positive electrode material, and a sodium ion battery positive electrode sheet was prepared. Sodium metal was used as a counter electrode, and 1M NaPF6 EC / DEC=1:1 (v / v) + 2% FEC electrolyte was used to assemble a 2032-type button battery for performance testing.
[0072] The present invention adopts solid-phase manganese oxalate as a crystal seed, utilizes the characteristic that the solubility of manganese-based Prussian blue materials is lower than that of manganese oxalate, and completely transforms manganese oxalate precipitates into manganese-based Prussian blue material precipitates. Meanwhile, the type and amount of the added metal salt are regulated in the coprecipitation reaction. Through its own step-by-step complexation and the complexation-dissociation competition between manganese ions and oxalate ions, there is no need to continuously adjust the raw material feeding speed as in conventional gradient precipitation, and a layer of Prussian blue shell material with a concentration gradient change (the inner core is manganese, and the manganese content of the outer shell gradually decreases), high crystallinity and high sodium content can be spontaneously and gradually grown on the surface of the manganese-based Prussian blue material, thereby significantly improving the electrochemical performance of the manganese-based Prussian blue material.
[0073] The present invention provides a method for preparing a manganese-based Prussian blue material with a gradient core-shell structure by simply using seed crystals, and application of the material in sodium ion battery energy storage.
[0074] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, it should be understood by those skilled in the art that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features thereof may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims
1. A method for preparing a manganese-based Prussian blue material, characterized in that: The following steps are involved: S1: dissolving sodium oxalate and manganese salt in a solvent to form a manganese oxalate suspension A, dissolving a metal salt in a solvent to form a solution B, and dissolving sodium ferrocyanide in a solvent to form a solution C; S2: While stirring, solution B and solution C are slowly added to suspension A at a fixed flow rate, and a rare gas is introduced for protection. The mixture is stirred in a water bath for reaction, and then allowed to stand for precipitation. After filtering and drying, a manganese-based Prussian blue material with a gradient core-shell structure is obtained.
2. The method for preparing a manganese-based Prussian blue material according to claim 1, characterized in that: The manganese salt is at least one of manganese sulfate, chloride, oxalate, phosphate and carbonate; The metal salt is at least one of sulfate, chloride, oxalate, phosphate and carbonate of Fe, Co, Ni, Cu or Zn; The usage ratio of sodium oxalate, sodium ferrocyanide, manganese salt, metal salt and solvent is 1g:(0-100)mL.
3. The method for preparing a manganese-based Prussian blue material according to claim 1, characterized in that: In step S1: The mass ratio of sodium oxalate to manganese salt is 1 / 3-3; The solvent is an organic solvent and / or water; The organic solvent is at least one of ethanol, acetone, toluene, isopropanol, methanol and propanol.
4. The method for preparing a manganese-based Prussian blue material according to claim 1, characterized in that: In step S2: The mass ratio of manganese salt to metal salt is 1 / 3-3; The mass of sodium ferrocyanide is a, the sum of the masses of manganese salt and metal salt is b, a:b=1 / 3-3.
5. The method for preparing a manganese-based Prussian blue material according to claim 1, characterized in that: In step S2: The water bath temperature is 30-90°C; The water bath time is 0.1-48h; The standing time is 0.1-48h; Drying temperature is 60-200℃; Drying time is 0.1-24h; Use vacuum drying or air drying.
6. The method for preparing a manganese-based Prussian blue material according to claim 1, characterized in that: The manganese-based Prussian blue material with a gradient core-shell structure includes a Prussian blue core material and a Prussian blue shell material; The chemical formula of Prussian blue nuclear material is Na x Mn[Fe(CN)6] y · z H2O, where 0 <x≤2,0<y≤1,z> 0; The chemical formula of Prussian blue shell material is Na x M[Fe(CN)6] y · z H2O, wherein M is at least one of Fe, Co, Ni, Cu, and Zn, 0 <x≤2,0<y≤1,z> 0.
7. Manganese-based Prussian blue materials, characterized in that: The material is prepared by the method for preparing a manganese-based Prussian blue material as described in any one of claims 1 to 6.
8. A sodium ion battery positive electrode, characterized in that: Including the manganese-based Prussian blue material as described in claim 7.
9. A sodium ion battery, characterized in that: Including the sodium ion battery positive electrode sheet as described in claim 8.
10. The sodium ion battery according to claim 9, characterized in that: Also includes a counter electrode, and an electrolyte; The counter electrode is sodium metal; The solute of the electrolyte is NaPF6 or NaClO4; The solvent of the electrolyte is PC, EC or DEC.