WO2024026991A1 - Modified prussian derivative, and preparation method therefor and use thereof - Google Patents

Modified prussian derivative, and preparation method therefor and use thereof Download PDF

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WO2024026991A1
WO2024026991A1 PCT/CN2022/119462 CN2022119462W WO2024026991A1 WO 2024026991 A1 WO2024026991 A1 WO 2024026991A1 CN 2022119462 W CN2022119462 W CN 2022119462W WO 2024026991 A1 WO2024026991 A1 WO 2024026991A1
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prussian
derivative
modified
vanadium compound
solution
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PCT/CN2022/119462
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French (fr)
Chinese (zh)
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徐学留
刘更好
阮丁山
李长东
李永光
李伟权
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the field of battery materials, and specifically relates to a modified Prussian derivative and its preparation method and application.
  • lithium-ion batteries have developed rapidly in the new energy industry and have been widely used in electric vehicles, portable electronic devices and smart daily necessities, resulting in an even scarcity of already rare lithium resources.
  • problems such as shortage of lithium resources and rising prices have seriously hindered the development of lithium-ion batteries.
  • Na elements of the same main group are more abundant in the earth's crust, and their distribution range is relatively wide, and the physical and chemical properties of the two are similar. Therefore, sodium-ion batteries are expected to become a new energy storage device to replace lithium-ion batteries.
  • Prussian derivative materials are currently one of the most promising materials as cathode materials for sodium-ion batteries. They have the characteristics of an open nanoframe structure, large space gaps and ion channels, high specific surface area, and controllable functionalization. , which is conducive to the rapid insertion and extraction of sodium ions. Therefore, Prussian derivative materials are very popular and have been extensively studied. However, Prussian derivative materials have two fatal shortcomings due to their structural properties: The first is that the structure of Prussian derivatives contains a large amount of lattice water and coordination water, resulting in a large water content in the material itself, which is harmful to The rate performance and cycle performance of the battery have a huge impact.
  • Prussian derivative materials are water absorbent and easily oxidized in the air, which seriously affects the specific capacity of batteries containing such materials. This has also become an urgent problem when using Prussian derivatives in cathode materials. thorny technical problems.
  • one of the objects of the present invention is to provide a modified Prussian derivative.
  • the second object of the present invention is to provide a method for preparing modified Prussian derivatives.
  • the third object of the present invention is to provide a cathode material.
  • the fourth object of the present invention is to provide a modified Prussian derivative for use in sodium-ion batteries or potassium-ion batteries.
  • a first aspect of the present invention provides a modified Prussian derivative, including a vanadium compound and a Prussian derivative; the Prussian derivative contains a vanadium compound on its surface and/or inside.
  • the modified Prussian derivative in the present invention is a Prussian derivative coated and modified with a vanadium compound.
  • the modified Prussian derivative in the present invention is a Prussian derivative modified by doping with a vanadium compound.
  • the modified Prussian derivative in the present invention is a Prussian derivative coated and doped with a vanadium compound.
  • Prussian white materials or Prussian blue materials have excellent sodium storage electrochemical properties, but in practical applications there are common problems such as low utilization, low efficiency, poor rate performance and unstable cycling.
  • the present invention solves the serious problems of water absorption and oxidation of the Prussian sodium cathode material when exposed to the air; at the same time, some cations in the vanadium compound enter the Prussian crystal and occupy the position of water in the crystal lattice of the material. , reducing the structural defects of Prussian-type materials. The reason is that metal cations with large radius occupy Na+ or K+ ion positions in part of the lattice of Prussian-type materials.
  • the cations with large ionic radius occupy more space, making the lattice water molecules It is forced to exclude, and the removal of lattice water reduces the defects of the material; at the same time, the coating and doping of Prussian-like surface and/or internal vanadium compounds can effectively inhibit the adsorption of surface adsorbed water, and the vanadium in the vanadium compound has Multiple valence states provide more redox potentials for the charging and discharging of the battery, thus increasing the specific capacity of the battery; secondly, cations with large ionic radius enter the crystal lattice, increasing the gap of the ion transmission channel and improving the sodium ion and electron transmission properties; this not only reduces the defects of Prussian derivatives, but also further improves the electrochemical properties of the material. This method solves the problems of low rate performance, poor cycle performance and serious water absorption of Prussian materials.
  • the chemical formula of the Prussian derivative is: Ax B y M z Na [(CN) 6 ] b ;
  • A is K or Na
  • B is K or Na
  • M is at least one of Co, Cu, Cr, Fe, Mn, Ni, Cr, and Zn;
  • N is Fe or Zn
  • 0.5 ⁇ x+y ⁇ 2, z is 1, 2 or 3; 0.5 ⁇ a ⁇ 3, 0.5 ⁇ b ⁇ 2.
  • the chemical formula of the Prussian derivative is: A x B y M z N a [(CN) 6 ] b ;
  • A is Na
  • M is at least one of Co, Cu, Cr, Fe, Mn, Ni, Cr, and Zn;
  • N is Fe or Zn
  • 0.5 ⁇ x+y ⁇ 2, x>y, z is 1, 2 or 3; 0.5 ⁇ a ⁇ 3, 0.5 ⁇ b ⁇ 2.
  • the Na content in the Prussian derivatives is greater than the K content; in other embodiments of the invention, the K content in the Prussian derivatives can also be greater than the Na content, or Prussian derivatives contain only K.
  • z is 1 or 3; further preferably, in the chemical formula of the Prussian derivative, z is 1.
  • the Prussian derivative in the chemical formula of the Prussian derivative, 0.7 ⁇ a ⁇ 3; further preferably, in the chemical formula of the Prussian derivative, 1 ⁇ a ⁇ 3; still further preferably, the Prussian derivative In the chemical formula of, a is 1, 2 or 3; more preferably, in the chemical formula of the Prussian derivative, a is 1 or 3.
  • the Prussian derivative in the chemical formula of the Prussian derivative, 0.7 ⁇ b ⁇ 2; further preferably, in the chemical formula of the Prussian derivative, 1 ⁇ b ⁇ 2; still further preferably, the Prussian derivative In the chemical formula, b is 1 or 2.
  • the chemical formula of the Prussian derivative is: A x B y M z N a [(CN) 6 ] b ;
  • A is K or Na
  • B is K or Na
  • M is at least one of Co, Cu, Cr, Fe, Mn, Ni, Cr, and Zn;
  • N is Fe or Zn
  • the vanadium compound is at least one of alkali metal vanadate, alkaline earth metal vanadate, and transition metal vanadate.
  • the alkali metal vanadate includes at least one of lithium vanadate, sodium vanadate, and potassium vanadate.
  • the alkaline earth metal vanadate includes at least one of calcium vanadate, magnesium vanadate, and strontium vanadate.
  • the transition metal vanadate includes at least one of manganese vanadate, iron vanadate, cobalt vanadate, nickel vanadate, copper vanadate, zinc vanadate, and silver vanadate.
  • the molar ratio of the vanadium compound and the Prussian derivative is (0.1-20):100; further preferably, the molar ratio of the vanadium compound and the Prussian derivative is (0.1-10) :100.
  • a second aspect of the present invention provides a method for preparing the modified Prussian derivative provided in the first aspect of the present invention, which includes the following steps:
  • the modified Prussian derivative is prepared by mixing and reacting the Prussian material with the vanadium compound.
  • the mixing reaction is specifically: making a Prussian material solution and a vanadium compound solution undergo a liquid phase reaction.
  • the liquid phase reaction temperature is 0 to 80°C; further preferably, the liquid phase reaction temperature is 5 to 80°C; still further preferably, the liquid phase reaction temperature is 5 to 40°C.
  • the liquid phase reaction time is 5 to 80 minutes; further preferably, the liquid phase reaction time is 10 to 60 minutes.
  • the stirring speed of the liquid phase reaction is 50-450rpm; further preferably, the stirring speed of the liquid phase reaction is 100-400rpm; still further preferably, the stirring speed of the liquid phase reaction is 200-400rpm. .
  • the Prussian material includes Na 2 MnFe(CN) 6 , Na 2 CoFe(CN) 6 , Na 2 NiFe(CN) 6 , Na 2 CuFe(CN) 6 , Na 2 Zn 3 [Fe(CN) 6 ] 2 , Na 2 FeFe(CN) 6 , Na 0.84 Ni[Fe(CN) 6 ] 0.7 1.
  • the vanadium compound is prepared by a mixed reaction of a vanadium-containing compound and a metal cation source. Further preferably, the preparation method of the vanadium compound is: mixing and reacting a vanadium-containing compound solution and a metal cation source solution to prepare a vanadium compound solution.
  • the vanadium-containing compound includes orthovanadate, pyrovanadate, metavanadate or vanadium oxide.
  • the orthovanadate includes sodium vanadate, potassium vanadate, lithium vanadate, manganese vanadate, nickel vanadate, iron vanadate, copper vanadate, cobalt vanadate, silver vanadate, chromium vanadate, At least one of calcium vanadate, magnesium vanadate, tin vanadate, and ruthenium vanadate.
  • the orthovanadate in the present invention is not limited to the types of orthovanadate listed above, other metal vanadates can also be used.
  • the metavanadate includes at least one of ammonium metavanadate, sodium metavanadate, potassium metavanadate, and silver metavanadate.
  • the pyrovanadate includes at least one of sodium pyrovanadate, ammonium pyrovanadate, and potassium pyrovanadate.
  • the vanadium oxide is vanadium oxide, vanadium trioxide, vanadium dioxide or vanadium pentoxide.
  • the Prussian material needs to be prepared into a solution when used; further preferably, the preparation method of the Prussian material solution is: mixing the Prussian material and water under the protection of a protective gas.
  • the protective gas is nitrogen or argon.
  • the preparation method of the modified Prussian derivative further includes the step of adding surfactants and/or additives.
  • the surfactants and additives are auxiliaries commonly used in the battery field.
  • the preparation method of the modified Prussian derivative specifically includes the following steps:
  • a third aspect of the present invention provides a cathode material, including the modified Prussian derivative provided by the first aspect of the present invention.
  • the fourth aspect of the present invention provides the use of the modified Prussian derivative provided in the first aspect of the present invention in sodium-ion batteries or potassium-ion batteries.
  • the modified Prussian derivative in the present invention has the characteristics of good thermal stability, regular morphology, and excellent electrochemical performance.
  • the present invention uses vanadium compounds to coat and/or dope Prussian derivatives, thereby improving the surface morphology and making the morphology of the material more regular.
  • the metal cations in the vanadium compounds can quickly enter the Prussian derivatives. In the crystal lattice of the derivative, it occupies the position of the original lattice water, reduces the structural defects of the material, increases the integrity of the crystal structure of the material, and removes the lattice water of internal defects in the material.
  • coating and/or doping with vanadium compounds can protect the Prussian derivatives, avoid moisture absorption and oxidation of the Prussian derivatives, and increase the rate performance of the battery.
  • vanadium is coated and doped in Prussian-type cathode materials, which can provide multiple redox sites and increase the relative theoretical capacity of battery materials.
  • the preparation method of the present invention has few technological processes, simple operation, low raw materials, and the solvent used is an aqueous solution, which is environmentally friendly and non-polluting, and the obtained product is easy to purify and separate, and can realize industrial large-scale production.
  • Figure 1 is an SEM image of the manganese-based Prussian white in Example 1;
  • Figure 2 is an SEM image of the modified Prussian derivative in Example 1;
  • Figure 3 is a TEM image of the modified Prussian derivative in Example 1.
  • Manganese-based Prussian white, nickel-based Prussian blue, cobalt-based Prussian white, zinc-based Prussian white, and iron-based Prussian white in the embodiments of the present invention can all be prepared by referring to the preparation method of Prussian-based complexes in the prior art.
  • the modified Prussian derivative in this example is a Prussian white derivative coated with K 2 V 6 O 16.
  • the chemical formula of the Prussian white derivative is: Na 1.85 K 0.15 MnFe(CN) 6 .
  • the modified Prussian derivative in this example is prepared by the following preparation method, which specifically includes the following steps:
  • step (3) Filter and wash the solution prepared in step (3), and dry it in an oven at 80°C overnight to prepare the modified Prussian derivative in this example, recorded as: Na 1.85 K 0.15 MnFe(CN) 6 ⁇ @K 2 V 6 O 16 .
  • a scanning electron microscope was used to test the SEM images of manganese-based Prussian white and modified Prussian derivatives in this example.
  • the SEM image of manganese-based Prussian white is shown in Figure 1, and the SEM image of modified Prussian derivatives.
  • Figure 2 by comparing Figure 1 and Figure 2, it can be seen that the surface of the modified Prussian derivative is more regular and has fewer structural defects.
  • the modified Prussian derivative in this example is manganese-based Prussian white coated and doped with Na 3 VO 4.
  • the chemical formula of manganese-based Prussian white is: Na 2 MnFe(CN) 6 .
  • the modified Prussian derivative in this example is prepared by the following preparation method, which specifically includes the following steps:
  • step (3) filter and wash the solution prepared in step (3), and dry it in an oven at 80°C overnight to obtain the modified Prussian derivative in this example, recorded as: Na 2 MnFe(CN) 6 ⁇ @Na 3 VO 4 .
  • the modified Prussian derivative in this example is coated with KVO 3 and doped with a Prussian blue derivative.
  • the chemical formula of the Prussian blue derivative is: Na 1.5 K 0.5 NiFe(CN) 6 .
  • the modified Prussian derivative in this example is prepared by the following preparation method, which specifically includes the following steps:
  • step (3) filter and wash the solution obtained in step (3), and dry it in an oven at 80°C overnight to obtain the modified Prussian derivative in this example, which is recorded as: Na 1.5 K 0.5 NiFe(CN ) 6 ⁇ @KVO 3 .
  • the modified Prussian derivative in this example is a Prussian white derivative coated with KVO 3.
  • the chemical formula of the Prussian white derivative is: Na 1.85 K 0.15 CoFe(CN) 6 .
  • the modified Prussian derivative in this example is prepared by the following preparation method, which specifically includes the following steps:
  • step (3) filter and wash the solution obtained in step (3), and dry it in an oven at 80°C overnight to obtain the modified Prussian derivative in this example, which is recorded as: Na 1.85 K 0.15 CoFe(CN ) 6 ⁇ @KVO 3 .
  • the modified Prussian derivative in this example is a Prussian white derivative coated with KVO 3.
  • the chemical formula of the Prussian white derivative is: Na 1.75 K 0.25 Zn 3 [Fe(CN) 6 ] 2 .
  • the modified Prussian derivative in this example is prepared by the following preparation method, which specifically includes the following steps:
  • step (3) filter and wash the solution prepared in step (3), and dry it in an oven at 80°C overnight to obtain the modified Prussian derivative in this example, which is recorded as: Na 1.75 K 0.25 Zn 3 [Fe(CN) 6 ] 2 ⁇ @KVO 3 .
  • the modified Prussian derivative in this example is a Prussian white derivative coated with KVO 3.
  • the chemical formula of the Prussian white derivative is: Na 1.56 K 0.44 FeFe(CN) 6 .
  • the modified Prussian derivative in this example is prepared by the following preparation method, which specifically includes the following steps:
  • step (3) filter and wash the solution obtained in step (3), and dry it in an oven at 80°C overnight to obtain the modified Prussian derivative in this example, recorded as: Na 1.56 K 0.44 FeFe(CN) 6 ⁇ @KVO 3 .
  • the modified Prussian derivative in this example is a Prussian white derivative coated with Na 3 VO 4.
  • the chemical formula of the Prussian white derivative is: Na 0.84 Ni[Fe(CN) 6 ] 0.71 .
  • the modified Prussian derivative in this example is prepared by the following preparation method, which specifically includes the following steps:
  • step (3) filter and wash the solution obtained in step (3), and dry it in an oven at 80°C overnight to obtain the modified Prussian derivative in this example, recorded as: Na 0.84 Ni[Fe(CN ) 6 ] 0.71 ⁇ @Na 3 VO 4 .
  • the modified Prussian derivatives prepared in Examples 1 to 7 can all be used as cathode materials.
  • Example 1 the manganese-based Prussian white (Na 2 MnFe(CN) 6 ) in Example 1 is used as the cathode material.
  • Examples 1 to 7 and Comparative Example 1 were used as positive electrode sheets and placed in a vacuum oven for drying (80°C, 3 h); and punched into discs with a diameter of 12 mm.
  • a dry electrode sheet is used as the positive electrode
  • a sodium sheet is used as the counter electrode for the negative electrode
  • the separator is a composite separator of glass fiber
  • the electrolyte is: 1 mol/L NaPF 6 + EC, DMC, DEC mixed solution (EC, DMC , The volume ratio of DEC is 1:1:1, EC refers to ethylene carbonate, DMC refers to dimethyl carbonate, and DEC refers to diethyl carbonate).
  • the discharge performance of the prepared half-cell was tested using the CT2001A battery testing system.
  • the cut-off voltage was 2.0-4.0V.
  • Discharge performance tests were conducted at 0.1C, 1C, 3C, and 5C. The specific test results are shown in Table 1 below.
  • Example 0.1C(mAh/g) 1C(mAh/g) 3C(mAh/g) 5C(mAh/g) Voltage range(V) Comparative example 1 130.1 105.3 97.9 64.2 2-4 Example 1 154.6 145.7 121.5 113.1 2-4 Example 2 162.2 151.9 140.6 122.7 2-4 Example 3 140.8 124.1 102.6 94.6 2-4 Example 4 160.4 144.2 135.4 125.9 2-4 Example 5 145.4 123.8 110.2 103.2 2-4 Example 6 146.7 129.5 114.9 105.3 2-4 Example 7 161.4 154.6 137.5 120.1 2-4
  • the modified Prussian derivatives prepared in Examples 1 to 7 of the present invention are coated and doped with vanadate compounds.
  • Hybrid modification, vanadium, as a multivalent metal element, is coated and doped on the Prussian derivative material, which can provide multiple redox sites and improve the relative theoretical capacity of the battery material, thereby improving the electrical performance of the battery. A substantial improvement.
  • the modified Prussian derivatives in the present invention after being coated and modified with vanadate compounds, can greatly reduce the water content in the Prussian derivative materials, which further shows that the vanadate compounds
  • the metal cations in the Prussian derivatives can quickly enter the crystal lattice of the Prussian derivatives, occupy the position of the original lattice water, remove the lattice water of internal defects of the Prussian derivatives, reduce the internal defects of the Prussian derivative materials, and increase the The integrity of the crystal structure of the Prussian derivative material is improved.

Abstract

The present application relates to a modified Prussian derivative, and a preparation method therefor and the use thereof. The modified Prussian derivative comprises a vanadium compound and a Prussian derivative, wherein the surface and/or interior of the Prussian derivative contains a vanadium compound. The modified Prussian derivative has the characteristics of good thermal stability, a regular morphology, and good electrochemical performance. By coating and doping a Prussian derivative with a vanadium compound, the surface morphology is improved, and the morphology of the material is more regular; and metal cations in the vanadium compound can quickly enter lattices of the Prussian derivative and occupy the original position of lattice water, thereby reducing the structure defects of the material, improving the integrity of the crystal structure of the material and removing lattice water of internal defects of the material. In addition, the coating and doping with the vanadium compound can perform a function of protecting the Prussian derivative, such that the moisture absorption and oxidation of the Prussian derivative are avoided, and the rate capacity of a battery is improved.

Description

一种改性的普鲁士类衍生物及其制备方法和应用A modified Prussian derivative and its preparation method and application 技术领域Technical field
本发明属于电池材料领域，具体涉及一种改性的普鲁士类衍生物及其制备方法和应用。The invention belongs to the field of battery materials, and specifically relates to a modified Prussian derivative and its preparation method and application.
背景技术Background technique
近几年来，锂离子电池在新能源行业高速发展，同时在电动汽车、便携式电子设备和智能生活用品中也得到了广泛应用，导致本就稀有的锂资源更加匮乏。同时，锂资源短缺和价格上涨等问题严重阻碍了锂离子电池的发展。然而同主族的Na元素在地壳中分布较为丰富，分布范围相对广泛，且两者物理化学性质相似。因此，钠离子电池有望成为替代锂离子电池的新的储能设备。In recent years, lithium-ion batteries have developed rapidly in the new energy industry and have been widely used in electric vehicles, portable electronic devices and smart daily necessities, resulting in an even scarcity of already rare lithium resources. At the same time, problems such as shortage of lithium resources and rising prices have seriously hindered the development of lithium-ion batteries. However, Na elements of the same main group are more abundant in the earth's crust, and their distribution range is relatively wide, and the physical and chemical properties of the two are similar. Therefore, sodium-ion batteries are expected to become a new energy storage device to replace lithium-ion batteries.
普鲁士类衍生物材料是目前最有希望作为钠离子电池正极材料的其中一类材料，其具有开放的纳米框架结构、较大的空间间隙和离子通道、高比表面积及可控的功能化等特点，有利于钠离子的快速嵌入和脱出，因此，普鲁士类衍生物材料备受青睐，也获得了广泛的研究。然而，普鲁士类衍生物材料由于本身结构属性原因存在着两个致命的缺点：第一个是普鲁士类衍生物结构中含有大量的晶格水和配位水，导致材料本身含水量较大，对电池的倍率性能和循环性能都造成巨大的影响。第二个是普鲁士类衍生物材料的吸水性和在空气中极易氧化性，严重影响了含有这类材料的电池的比容量，这也成为普鲁士类衍生物在正极材料中应用时亟需解决的棘手的技术难题。Prussian derivative materials are currently one of the most promising materials as cathode materials for sodium-ion batteries. They have the characteristics of an open nanoframe structure, large space gaps and ion channels, high specific surface area, and controllable functionalization. , which is conducive to the rapid insertion and extraction of sodium ions. Therefore, Prussian derivative materials are very popular and have been extensively studied. However, Prussian derivative materials have two fatal shortcomings due to their structural properties: The first is that the structure of Prussian derivatives contains a large amount of lattice water and coordination water, resulting in a large water content in the material itself, which is harmful to The rate performance and cycle performance of the battery have a huge impact. The second is that Prussian derivative materials are water absorbent and easily oxidized in the air, which seriously affects the specific capacity of batteries containing such materials. This has also become an urgent problem when using Prussian derivatives in cathode materials. thorny technical problems.
发明内容Contents of the invention
为了克服上述现有技术存在的问题，本发明的目的之一在于提供一种改性的普鲁士类衍生物。In order to overcome the above-mentioned problems in the prior art, one of the objects of the present invention is to provide a modified Prussian derivative.
本发明的目的之二在于提供一种改性的普鲁士类衍生物的制备方法。The second object of the present invention is to provide a method for preparing modified Prussian derivatives.
本发明的目的之三在于提供一种正极材料。The third object of the present invention is to provide a cathode material.
本发明的目的之四在于提供一种改性的普鲁士类衍生物在钠离子电池或钾离子电池中的应用。The fourth object of the present invention is to provide a modified Prussian derivative for use in sodium-ion batteries or potassium-ion batteries.
为了实现上述目的，本发明所采取的技术方案是：In order to achieve the above objects, the technical solutions adopted by the present invention are:
本发明的第一个方面提供了一种改性的普鲁士类衍生物，包括钒化合物和普鲁士类衍生物；所述普鲁士类衍生物表面和/或内部含有钒化合物。A first aspect of the present invention provides a modified Prussian derivative, including a vanadium compound and a Prussian derivative; the Prussian derivative contains a vanadium compound on its surface and/or inside.
当普鲁士类衍生物表面含有钒化合物时，则本发明中的改性的普鲁士类衍生物为钒化合物包覆改性的普鲁士类衍生物。当普鲁士类衍生物内部含有钒化合物时，则本发明中的改性 的普鲁士类衍生物为钒化合物掺杂改性的普鲁士类衍生物。当普鲁士类衍生物表面和内部含有钒化合物时，则本发明中的改性的普鲁士类衍生物为钒化合物包覆掺杂改性的普鲁士类衍生物。When the surface of the Prussian derivative contains a vanadium compound, the modified Prussian derivative in the present invention is a Prussian derivative coated and modified with a vanadium compound. When the Prussian derivative contains a vanadium compound inside, the modified Prussian derivative in the present invention is a Prussian derivative modified by doping with a vanadium compound. When the Prussian derivative contains vanadium compounds on the surface and inside, the modified Prussian derivative in the present invention is a Prussian derivative coated and doped with a vanadium compound.
普鲁士白类材料或普鲁士蓝类材料具有极佳的储钠电化学性能，但实际应用中普遍存在利用率低、效率低、倍率性能差和循环不稳定等问题。本发明通过钒化合物包覆和/或掺杂，解决了普鲁士类钠正极材料暴露空气中吸水和氧化较为严重的问题；同时钒化合物中部分阳离子进入普鲁士类晶体中，占据材料晶格水的位置，减少了普鲁士类材料的结构缺陷，原因是大半径的金属阳离子占据普鲁士类材料中部分晶格中的Na+或K+离子位置，离子半径大的阳离子占据了更多的空间，使晶格水分子被迫排除，而晶格水的去除减少了材料的缺陷；同时普鲁士类表面和/或内部的钒化合物的包覆掺杂能有效的抑制其表面吸附水的吸附，同时钒化合物中的钒具有多个价态，为电池的充放电提供了更多的氧化还原电位，从而增加了电池的比容量；其次，离子半径大的阳离子进入晶格，增加了离子传输通道的间隙，提高了钠离子和电子的传输性能；这样不但减少普鲁士类衍生物的缺陷，还进一步提高了材料的电化学性能，该方法解决普鲁士类材料存在的倍率性能低、循环性能差和吸水严重的问题。Prussian white materials or Prussian blue materials have excellent sodium storage electrochemical properties, but in practical applications there are common problems such as low utilization, low efficiency, poor rate performance and unstable cycling. By coating and/or doping with the vanadium compound, the present invention solves the serious problems of water absorption and oxidation of the Prussian sodium cathode material when exposed to the air; at the same time, some cations in the vanadium compound enter the Prussian crystal and occupy the position of water in the crystal lattice of the material. , reducing the structural defects of Prussian-type materials. The reason is that metal cations with large radius occupy Na+ or K+ ion positions in part of the lattice of Prussian-type materials. The cations with large ionic radius occupy more space, making the lattice water molecules It is forced to exclude, and the removal of lattice water reduces the defects of the material; at the same time, the coating and doping of Prussian-like surface and/or internal vanadium compounds can effectively inhibit the adsorption of surface adsorbed water, and the vanadium in the vanadium compound has Multiple valence states provide more redox potentials for the charging and discharging of the battery, thus increasing the specific capacity of the battery; secondly, cations with large ionic radius enter the crystal lattice, increasing the gap of the ion transmission channel and improving the sodium ion and electron transmission properties; this not only reduces the defects of Prussian derivatives, but also further improves the electrochemical properties of the material. This method solves the problems of low rate performance, poor cycle performance and serious water absorption of Prussian materials.
优选地，所述普鲁士类衍生物的化学式为：A xB yM zNa[(CN) 6] b； Preferably, the chemical formula of the Prussian derivative is: Ax B y M z Na [(CN) 6 ] b ;
其中，A为K或Na；Among them, A is K or Na;
B为K或Na；B is K or Na;
M为Co、Cu、Cr、Fe、Mn、Ni、Cr、Zn中的至少一种；M is at least one of Co, Cu, Cr, Fe, Mn, Ni, Cr, and Zn;
N为Fe或Zn；N is Fe or Zn;
0.5≤x+y≤2，z为1、2或3；0.5≤a≤3，0.5≤b≤2。0.5≤x+y≤2, z is 1, 2 or 3; 0.5≤a≤3, 0.5≤b≤2.
优选地，所述普鲁士类衍生物的化学式为：A xB yM zN a[(CN) 6] b； Preferably, the chemical formula of the Prussian derivative is: A x B y M z N a [(CN) 6 ] b ;
其中，A为Na；Among them, A is Na;
B为K；B is K;
M为Co、Cu、Cr、Fe、Mn、Ni、Cr、Zn中的至少一种；M is at least one of Co, Cu, Cr, Fe, Mn, Ni, Cr, and Zn;
N为Fe或Zn；N is Fe or Zn;
0.5≤x+y≤2，x＞y，z为1、2或3；0.5≤a≤3，0.5≤b≤2。0.5≤x+y≤2, x>y, z is 1, 2 or 3; 0.5≤a≤3, 0.5≤b≤2.
在本发明中的一些优选实施方案中，普鲁士类衍生物中的Na含量大于K的含量；在本发明的其他实施方案中，普鲁士类衍生物中的K的含量也可以大于Na的含量，或者普鲁士类衍生物中仅含有K。In some preferred embodiments of the present invention, the Na content in the Prussian derivatives is greater than the K content; in other embodiments of the invention, the K content in the Prussian derivatives can also be greater than the Na content, or Prussian derivatives contain only K.
优选地，所述普鲁士类衍生物的化学式中，0.8≤x+y≤2；进一步优选地，所述普鲁士类衍生物的化学式中，1≤x+y≤2；再进一步优选地，所述普鲁士类衍生物的化学式中，x+y≤2； 更优选地，所述普鲁士类衍生物的化学式中，x+y＝2。Preferably, in the chemical formula of the Prussian derivative, 0.8≤x+y≤2; further preferably, in the chemical formula of the Prussian derivative, 1≤x+y≤2; still further preferably, the In the chemical formula of the Prussian derivative, x+y≤2; more preferably, in the chemical formula of the Prussian derivative, x+y=2.
优选地，所述普鲁士类衍生物的化学式中，z为1或3；进一步优选地，所述普鲁士类衍生物的化学式中，z为1。Preferably, in the chemical formula of the Prussian derivative, z is 1 or 3; further preferably, in the chemical formula of the Prussian derivative, z is 1.
优选地，所述普鲁士类衍生物的化学式中，0.7≤a≤3；进一步优选地，所述普鲁士类衍生物的化学式中，1≤a≤3；再进一步优选地，所述普鲁士类衍生物的化学式中，a为1、2或3；更优选地，所述普鲁士类衍生物的化学式中，a为1或3。Preferably, in the chemical formula of the Prussian derivative, 0.7≤a≤3; further preferably, in the chemical formula of the Prussian derivative, 1≤a≤3; still further preferably, the Prussian derivative In the chemical formula of, a is 1, 2 or 3; more preferably, in the chemical formula of the Prussian derivative, a is 1 or 3.
优选地，所述普鲁士类衍生物的化学式中，0.7≤b≤2；进一步优选地，所述普鲁士类衍生物的化学式中，1≤b≤2；再进一步优选地，所述普鲁士类衍生物的化学式中，b为1或2。Preferably, in the chemical formula of the Prussian derivative, 0.7≤b≤2; further preferably, in the chemical formula of the Prussian derivative, 1≤b≤2; still further preferably, the Prussian derivative In the chemical formula, b is 1 or 2.
优选地，所述普鲁士类衍生物的化学式为：A xB yM zN a[(CN) 6] b； Preferably, the chemical formula of the Prussian derivative is: A x B y M z N a [(CN) 6 ] b ;
其中，A为K或Na；Among them, A is K or Na;
B为K或Na；B is K or Na;
M为Co、Cu、Cr、Fe、Mn、Ni、Cr、Zn中的至少一种；M is at least one of Co, Cu, Cr, Fe, Mn, Ni, Cr, and Zn;
N为Fe或Zn；N is Fe or Zn;
x+y＝2，z为1，a为1或3，b为1或2。x+y=2, z is 1, a is 1 or 3, and b is 1 or 2.
优选地，所述钒化合物为碱金属钒酸盐、碱土金属钒酸盐、过渡金属钒酸盐中的至少一种。Preferably, the vanadium compound is at least one of alkali metal vanadate, alkaline earth metal vanadate, and transition metal vanadate.
优选地，所述碱金属钒酸盐包括钒酸锂、钒酸钠、钒酸钾中的至少一种。Preferably, the alkali metal vanadate includes at least one of lithium vanadate, sodium vanadate, and potassium vanadate.
优选地，所述碱土金属钒酸盐包括钒酸钙、钒酸镁、钒酸锶中的至少一种。Preferably, the alkaline earth metal vanadate includes at least one of calcium vanadate, magnesium vanadate, and strontium vanadate.
优选地，所述过渡金属钒酸盐包括钒酸锰、钒酸铁、钒酸钴、钒酸镍、钒酸铜、钒酸锌、钒酸银中的至少一种。Preferably, the transition metal vanadate includes at least one of manganese vanadate, iron vanadate, cobalt vanadate, nickel vanadate, copper vanadate, zinc vanadate, and silver vanadate.
优选地，所述钒化合物和所述普鲁士类衍生物的摩尔比为(0.1～20)：100；进一步优选地，所述钒化合物和所述普鲁士类衍生物的摩尔比为(0.1～10)：100。Preferably, the molar ratio of the vanadium compound and the Prussian derivative is (0.1-20):100; further preferably, the molar ratio of the vanadium compound and the Prussian derivative is (0.1-10) :100.
本发明的第二个方面提供了本发明第一个方面提供的改性的普鲁士类衍生物的制备方法，包括以下步骤：A second aspect of the present invention provides a method for preparing the modified Prussian derivative provided in the first aspect of the present invention, which includes the following steps:
使普鲁士类材料与钒化合物混合反应，制得所述改性的普鲁士类衍生物。The modified Prussian derivative is prepared by mixing and reacting the Prussian material with the vanadium compound.
优选地，所述混合反应具体为：使普鲁士类材料溶液和钒化合物溶液进行液相反应。Preferably, the mixing reaction is specifically: making a Prussian material solution and a vanadium compound solution undergo a liquid phase reaction.
优选地，所述液相反应温度为0～80℃；进一步优选地，所述液相反应温度为5～80℃；再进一步优选地，所述液相反应温度为5～40℃。Preferably, the liquid phase reaction temperature is 0 to 80°C; further preferably, the liquid phase reaction temperature is 5 to 80°C; still further preferably, the liquid phase reaction temperature is 5 to 40°C.
优选地，所述液相反应时间为5～80min；进一步优选地，所述液相反应时间为10～60min。Preferably, the liquid phase reaction time is 5 to 80 minutes; further preferably, the liquid phase reaction time is 10 to 60 minutes.
优选地，所述液相反应的搅拌速度为50-450rpm；进一步优选地，所述液相反应的搅拌 速度为100-400rpm；再进一步优选地，所述液相反应的搅拌速度为200-400rpm。Preferably, the stirring speed of the liquid phase reaction is 50-450rpm; further preferably, the stirring speed of the liquid phase reaction is 100-400rpm; still further preferably, the stirring speed of the liquid phase reaction is 200-400rpm. .
优选地，所述普鲁士类材料包括Na 2MnFe(CN) 6、Na 2CoFe(CN) 6、Na 2NiFe(CN) 6、Na 2CuFe(CN) 6、Na 2Zn 3[Fe(CN) 6] 2、Na 2FeFe(CN) 6、Na 0.84Ni[Fe(CN) 6] 0.71、Na 2CrFe(CN) 6、K 2MnFe(CN) 6、K 2CoFe(CN) 6、K 2NiFe(CN) 6、K 2CuFe(CN) 6、K 2Zn 3[Fe(CN) 6] 2、K 2CrFe(CN) 6、Na 1.63FeFe(CN) 6中的至少一种。 Preferably, the Prussian material includes Na 2 MnFe(CN) 6 , Na 2 CoFe(CN) 6 , Na 2 NiFe(CN) 6 , Na 2 CuFe(CN) 6 , Na 2 Zn 3 [Fe(CN) 6 ] 2 , Na 2 FeFe(CN) 6 , Na 0.84 Ni[Fe(CN) 6 ] 0.7 1. Na 2 CrFe(CN) 6 , K 2 MnFe(CN) 6 , K 2 CoFe(CN) 6 , K At least one of 2 NiFe(CN) 6 , K 2 CuFe(CN) 6 , K 2 Zn 3 [Fe(CN) 6 ] 2 , K 2 CrFe(CN) 6 , and Na 1.63 FeFe(CN) 6 .
优选地，所述钒化合物是由含钒的化合物与金属阳离子源混合反应制得。进一步优选地，所述钒化合物的制备方法为：将含钒的化合物溶液与金属阳离子源溶液混合反应，制得钒化合物溶液。Preferably, the vanadium compound is prepared by a mixed reaction of a vanadium-containing compound and a metal cation source. Further preferably, the preparation method of the vanadium compound is: mixing and reacting a vanadium-containing compound solution and a metal cation source solution to prepare a vanadium compound solution.
优选地，所述含钒的化合物包括正钒酸盐、焦钒酸盐、偏钒酸盐或钒氧化物。Preferably, the vanadium-containing compound includes orthovanadate, pyrovanadate, metavanadate or vanadium oxide.
优选地，所述正钒酸盐包括钒酸钠、钒酸钾、钒酸锂、钒酸锰、钒酸镍、钒酸铁、钒酸铜、钒酸钴、钒酸银、钒酸铬、钒酸钙、钒酸镁、钒酸锡、钒酸钌中的至少一种。本发明中的正钒酸盐并不限于上述列举的正钒酸盐的种类，还可以采用其他金属钒酸盐。Preferably, the orthovanadate includes sodium vanadate, potassium vanadate, lithium vanadate, manganese vanadate, nickel vanadate, iron vanadate, copper vanadate, cobalt vanadate, silver vanadate, chromium vanadate, At least one of calcium vanadate, magnesium vanadate, tin vanadate, and ruthenium vanadate. The orthovanadate in the present invention is not limited to the types of orthovanadate listed above, other metal vanadates can also be used.
优选地，所述偏钒酸盐包括偏钒酸铵、偏钒酸钠、偏钒酸钾、偏钒酸银中的至少一种。Preferably, the metavanadate includes at least one of ammonium metavanadate, sodium metavanadate, potassium metavanadate, and silver metavanadate.
优选地，所述焦钒酸盐包括焦钒酸钠、焦钒酸铵、焦钒酸钾中的至少一种。Preferably, the pyrovanadate includes at least one of sodium pyrovanadate, ammonium pyrovanadate, and potassium pyrovanadate.
优选地，所述钒氧化物为氧化钒、三氧化二钒、二氧化钒或五氧化二钒。Preferably, the vanadium oxide is vanadium oxide, vanadium trioxide, vanadium dioxide or vanadium pentoxide.
优选地，所述普鲁士类材料在使用时需要配制成溶液；进一步优选地，所述普鲁士类材料溶液的制备方法为：在保护气体的保护下，将普鲁士类材料与水混合制得。Preferably, the Prussian material needs to be prepared into a solution when used; further preferably, the preparation method of the Prussian material solution is: mixing the Prussian material and water under the protection of a protective gas.
优选地，所述保护气体为氮气或氩气。Preferably, the protective gas is nitrogen or argon.
优选地，所述改性的普鲁士类衍生物的制备方法中还包括加入表面活性剂和/或添加剂的步骤。Preferably, the preparation method of the modified Prussian derivative further includes the step of adding surfactants and/or additives.
优选地，所述表面活性剂和添加剂均为电池领域通常使用的助剂。Preferably, the surfactants and additives are auxiliaries commonly used in the battery field.
优选地，所述改性的普鲁士类衍生物的制备方法具体包括以下步骤：Preferably, the preparation method of the modified Prussian derivative specifically includes the following steps:
(1)将普鲁士类材料与水混合，搅拌，加入反应釜，通入保护气体，得到普鲁士类材料溶液；(1) Mix the Prussian material with water, stir, add it to the reaction kettle, and pass in protective gas to obtain a Prussian material solution;
(2)将含钒的化合物和金属离子源溶液混合反应，制得钒化合物溶液；(2) Mix and react the vanadium-containing compound and the metal ion source solution to prepare a vanadium compound solution;
(3)将所述钒化合物溶液与普鲁士类材料溶液在温度为0～80℃时反应5～80min，然后过滤、洗涤、干燥，制得所述改性的普鲁士类衍生物。(3) React the vanadium compound solution and the Prussian material solution at a temperature of 0 to 80°C for 5 to 80 minutes, and then filter, wash, and dry to obtain the modified Prussian derivative.
本发明的第三个方面提供了一种正极材料，包括本发明第一方面提供的改性的普鲁士类衍生物。A third aspect of the present invention provides a cathode material, including the modified Prussian derivative provided by the first aspect of the present invention.
本发明的第四个方面提供了本发明第一个方面提供的改性的普鲁士类衍生物在钠离子电池或钾离子电池中的应用。The fourth aspect of the present invention provides the use of the modified Prussian derivative provided in the first aspect of the present invention in sodium-ion batteries or potassium-ion batteries.
本发明的有益效果是：本发明中的改性的普鲁士类衍生物具备热稳定性好、形貌规整、电化学性能优良的特点。The beneficial effects of the present invention are: the modified Prussian derivative in the present invention has the characteristics of good thermal stability, regular morphology, and excellent electrochemical performance.
具体而言：本发明通过采用钒化合物对普鲁士类衍生物进行包覆和/或掺杂，改善了表面形貌，使材料的形貌更加规整，钒化合物中的金属阳离子能够快速的进入普鲁士类衍生物的晶格中，占据原来晶格水的位置，减少材料的结构缺陷，增加了材料的晶体结构的完整性，去除了材料内部缺陷的晶格水。此外，钒化合物包覆和/或掺杂可以起到保护普鲁士类衍生物的作用，避免普鲁士类衍生物吸湿和氧化，增加了电池的倍率性能。钒作为一个多价的金属元素，包覆掺杂在普鲁士类正极材料中，能提供多个氧化还原性位点，提高电池材料的相对理论容量。Specifically: the present invention uses vanadium compounds to coat and/or dope Prussian derivatives, thereby improving the surface morphology and making the morphology of the material more regular. The metal cations in the vanadium compounds can quickly enter the Prussian derivatives. In the crystal lattice of the derivative, it occupies the position of the original lattice water, reduces the structural defects of the material, increases the integrity of the crystal structure of the material, and removes the lattice water of internal defects in the material. In addition, coating and/or doping with vanadium compounds can protect the Prussian derivatives, avoid moisture absorption and oxidation of the Prussian derivatives, and increase the rate performance of the battery. As a multivalent metal element, vanadium is coated and doped in Prussian-type cathode materials, which can provide multiple redox sites and increase the relative theoretical capacity of battery materials.
本发明中的制备方法工艺流程少，操作简单，原料低廉，所用溶剂为水溶液，对环境友好无污染，并且所得产物易提纯分离，能实现工业化大规模生产。The preparation method of the present invention has few technological processes, simple operation, low raw materials, and the solvent used is an aqueous solution, which is environmentally friendly and non-polluting, and the obtained product is easy to purify and separate, and can realize industrial large-scale production.
附图说明Description of the drawings
图1为实施例1中的锰基普鲁士白的SEM图；Figure 1 is an SEM image of the manganese-based Prussian white in Example 1;
图2为实施例1中改性的普鲁士类衍生物的SEM图；Figure 2 is an SEM image of the modified Prussian derivative in Example 1;
图3为实施例1中改性的普鲁士类衍生物的TEM图。Figure 3 is a TEM image of the modified Prussian derivative in Example 1.
具体实施方式Detailed ways
以下结合附图和实例对本发明的具体实施作进一步详细说明，但本发明的实施和保护不限于此。需要指出的是，以下若为有未特别详细说明之过程，均是本领域技术人员可参照现有技术实现或理解的。所用试剂或仪器未注明生产厂商者，视为可以通过市售购买得到的常规产品。The specific implementation of the present invention will be further described in detail below with reference to the accompanying drawings and examples, but the implementation and protection of the present invention are not limited thereto. It should be noted that any process that is not specifically described in detail below can be implemented or understood by those skilled in the art with reference to the existing technology. If the manufacturer of the reagents or instruments used is not indicated, they are regarded as conventional products that can be purchased commercially.
本发明实施例中的锰基普鲁士白、镍基普鲁士蓝、钴基普鲁士白、锌基普鲁士白、铁基普鲁士白均可以参照现有技术中的普鲁士类配合物的制备方法制得。Manganese-based Prussian white, nickel-based Prussian blue, cobalt-based Prussian white, zinc-based Prussian white, and iron-based Prussian white in the embodiments of the present invention can all be prepared by referring to the preparation method of Prussian-based complexes in the prior art.
实施例1Example 1
本例中的改性的普鲁士类衍生物是采用K 2V 6O 16包覆掺杂普鲁士白衍生物，普鲁士白衍生物的化学式为：Na 1.85K 0.15MnFe(CN) 6。 The modified Prussian derivative in this example is a Prussian white derivative coated with K 2 V 6 O 16. The chemical formula of the Prussian white derivative is: Na 1.85 K 0.15 MnFe(CN) 6 .
本例中的改性的普鲁士类衍生物采用以下制备方法制得，具体包括以下步骤：The modified Prussian derivative in this example is prepared by the following preparation method, which specifically includes the following steps:
(1)称取1mol锰基普鲁士白(Na 2MnFe(CN) 6)溶于500mL的去离子水中，剧烈搅拌使锰基普鲁士白充分溶解于水中，搅拌速率为400rpm，然后置于冰浴条件下，温度控制在5℃，得到A溶液。 (1) Weigh 1 mol of manganese-based Prussian white (Na 2 MnFe(CN) 6 ) and dissolve it in 500 mL of deionized water. Stir vigorously to fully dissolve the manganese-based Prussian white in the water. The stirring rate is 400 rpm, and then placed in an ice bath. , and the temperature was controlled at 5°C to obtain solution A.
(2)称取3mol偏钒酸铵和1mol的氯化钾溶解在250mL的去离子水溶液中，剧烈搅拌使偏钒酸铵和氯化钾溶于水并充分反应，得到B溶液。(2) Weigh 3 mol of ammonium metavanadate and 1 mol of potassium chloride and dissolve them in 250 mL of deionized water solution. Stir vigorously to dissolve the ammonium metavanadate and potassium chloride in the water and fully react to obtain solution B.
(3)将B溶液缓慢的滴入含锰基普鲁士白的A溶液中，缓慢搅拌，反应温度控制在5℃，陈化反应10min。(3) Slowly drop solution B into solution A containing manganese-based Prussian white, stir slowly, control the reaction temperature at 5°C, and age the reaction for 10 minutes.
(4)将步骤(3)中制备的溶液过滤、洗涤，放在80℃烘箱中干燥过夜，制得本例中的改性的普鲁士类衍生物，记为：Na 1.85K 0.15MnFe(CN) 6·@K 2V 6O 16。 (4) Filter and wash the solution prepared in step (3), and dry it in an oven at 80°C overnight to prepare the modified Prussian derivative in this example, recorded as: Na 1.85 K 0.15 MnFe(CN) 6 ·@K 2 V 6 O 16 .
使用扫描电子显微镜分别测试本例中锰基普鲁士白和改性的普鲁士类衍生物的SEM图，其中，锰基普鲁士白的SEM图如图1所示，改性的普鲁士类衍生物的SEM图如图2所示，通过对比图1和图2可知，改性的普鲁士类衍生物表面更加规整，结构缺陷更少。A scanning electron microscope was used to test the SEM images of manganese-based Prussian white and modified Prussian derivatives in this example. The SEM image of manganese-based Prussian white is shown in Figure 1, and the SEM image of modified Prussian derivatives. As shown in Figure 2, by comparing Figure 1 and Figure 2, it can be seen that the surface of the modified Prussian derivative is more regular and has fewer structural defects.
使用透射电子显微镜测试本例中改性的普鲁士类衍生物的TEM图，测试结果如图3所示，由图3可知，K 2V 6O 16成功包覆在Na 1.85K 0.15MnFe(CN) 6的表面，从而在Na 1.85K 0.15MnFe(CN) 6上形成包覆层，包覆层的厚度约为5～10nm。 Use a transmission electron microscope to test the TEM image of the modified Prussian derivative in this example. The test results are shown in Figure 3. From Figure 3, it can be seen that K 2 V 6 O 16 is successfully coated in Na 1.85 K 0.15 MnFe(CN) 6 , thereby forming a coating layer on Na 1.85 K 0.15 MnFe(CN) 6. The thickness of the coating layer is about 5 to 10 nm.
实施例2Example 2
本例中的改性的普鲁士类衍生物是采用Na 3VO 4包覆掺杂锰基普鲁士白，锰基普鲁士白的化学式为：Na 2MnFe(CN) 6。 The modified Prussian derivative in this example is manganese-based Prussian white coated and doped with Na 3 VO 4. The chemical formula of manganese-based Prussian white is: Na 2 MnFe(CN) 6 .
本例中的改性的普鲁士类衍生物采用以下制备方法制得，具体包括以下步骤：The modified Prussian derivative in this example is prepared by the following preparation method, which specifically includes the following steps:
(1)称取1mol锰基普鲁士白(Na 2MnFe(CN) 6)溶于500mL的去离子水中，剧烈搅拌使锰基普鲁士白充分溶解于水中，搅拌速率为400rpm，然后置于冰浴条件下，温度控制在5℃，得到A溶液。 (1) Weigh 1 mol of manganese-based Prussian white (Na 2 MnFe(CN) 6 ) and dissolve it in 500 mL of deionized water. Stir vigorously to fully dissolve the manganese-based Prussian white in the water. The stirring rate is 400 rpm, and then placed in an ice bath. , and the temperature was controlled at 5°C to obtain solution A.
(2)称取1mol的偏钒酸铵和3mol的氯化钠溶解在250mL的去离子水溶液中，作为B溶液；剧烈搅拌使偏钒酸铵和氯化钠充分溶于水。(2) Weigh 1 mol of ammonium metavanadate and 3 mol of sodium chloride and dissolve it in 250 mL of deionized water solution as solution B; stir vigorously to fully dissolve ammonium metavanadate and sodium chloride in the water.
(3)将B溶液缓慢的滴入含锰基普鲁士白的A溶液中，不停的搅拌，温度保持在5℃，陈化反应1h。(3) Slowly drop solution B into solution A containing manganese-based Prussian white, stir continuously, keep the temperature at 5°C, and age for 1 hour.
(4)最后将步骤(3)中制得的溶液过滤、洗涤，放在80℃烘箱中干燥过夜，制得本例中的改性的普鲁士类衍生物，记为：Na 2MnFe(CN) 6·@Na 3VO 4。 (4) Finally, filter and wash the solution prepared in step (3), and dry it in an oven at 80°C overnight to obtain the modified Prussian derivative in this example, recorded as: Na 2 MnFe(CN) 6 ·@Na 3 VO 4 .
实施例3Example 3
本例中的改性的普鲁士类衍生物是采用KVO 3包覆掺杂普鲁士蓝衍生物，普鲁士蓝衍生物的化学式为：Na 1.5K 0.5NiFe(CN) 6。 The modified Prussian derivative in this example is coated with KVO 3 and doped with a Prussian blue derivative. The chemical formula of the Prussian blue derivative is: Na 1.5 K 0.5 NiFe(CN) 6 .
本例中的改性的普鲁士类衍生物采用以下制备方法制得，具体包括以下步骤：The modified Prussian derivative in this example is prepared by the following preparation method, which specifically includes the following steps:
(1)称取1mol镍基普鲁士蓝(Na 2NiFe(CN) 6)溶于500mL的去离子水中，剧烈搅拌使镍基普鲁士蓝充分溶解于水中，搅拌速率为400rpm，然后置于冰浴条件下，温度控制在10℃，得到A溶液。 (1) Weigh 1 mol of nickel-based Prussian blue (Na 2 NiFe(CN) 6 ) and dissolve it in 500 mL of deionized water. Stir vigorously to fully dissolve the nickel-based Prussian blue in the water. The stirring rate is 400 rpm, and then placed in an ice bath. , and the temperature was controlled at 10°C to obtain solution A.
(2)称取2mol偏钒酸铵和2mol的氯化钾溶解在250mL的去离子水溶液中，作为B溶 液；剧烈搅拌使偏钒酸铵和氯化钾充分溶于水。(2) Weigh 2 mol of ammonium metavanadate and 2 mol of potassium chloride and dissolve them in 250 mL of deionized water solution as solution B; stir vigorously to fully dissolve ammonium metavanadate and potassium chloride in the water.
(3)将B溶液缓慢的滴入含镍基普鲁士蓝的A溶液中，不停的搅拌，温度控制在10℃，陈化反应45min。(3) Slowly drop solution B into solution A containing nickel-based Prussian blue, stir continuously, control the temperature at 10°C, and age for 45 minutes.
(4)最后将步骤(3)制得的溶液过滤、洗涤，放在80℃烘箱中干燥过夜，制得了本例中的改性的普鲁士类衍生物，记为：Na 1.5K 0.5NiFe(CN) 6·@KVO 3。 (4) Finally, filter and wash the solution obtained in step (3), and dry it in an oven at 80°C overnight to obtain the modified Prussian derivative in this example, which is recorded as: Na 1.5 K 0.5 NiFe(CN ) 6 ·@KVO 3 .
实施例4Example 4
本例中的改性的普鲁士类衍生物是采用KVO 3包覆掺杂普鲁士白衍生物，普鲁士白衍生物的化学式为：Na 1.85K 0.15CoFe(CN) 6。 The modified Prussian derivative in this example is a Prussian white derivative coated with KVO 3. The chemical formula of the Prussian white derivative is: Na 1.85 K 0.15 CoFe(CN) 6 .
本例中的改性的普鲁士类衍生物采用以下制备方法制得，具体包括以下步骤：The modified Prussian derivative in this example is prepared by the following preparation method, which specifically includes the following steps:
(1)称取1mol钴基普鲁士白(Na 2CoFe(CN) 6)溶于500mL的去离子水中，剧烈搅拌使钴基普鲁士白充分溶解于水中，搅拌速率为400rpm，然后在冰浴条件下，温度控制在3℃，得到A溶液。 (1) Weigh 1 mol of cobalt-based Prussian white (Na 2 CoFe(CN) 6 ) and dissolve it in 500 mL of deionized water. Stir vigorously to fully dissolve the cobalt-based Prussian white in the water. The stirring rate is 400 rpm, and then place it in an ice bath. , the temperature was controlled at 3°C, and solution A was obtained.
(2)称取2mol偏钒酸铵和2mol的氯化钾溶解在250mL的去离子水溶液中，作为B溶液；剧烈搅拌使偏钒酸铵和氯化钾充分溶于水。(2) Weigh 2 mol of ammonium metavanadate and 2 mol of potassium chloride and dissolve them in 250 mL of deionized water solution as solution B; stir vigorously to fully dissolve ammonium metavanadate and potassium chloride in the water.
(3)将B溶液缓慢的滴入含钴基普鲁士白的A溶液中，不停的搅拌，温度保持在3℃，陈化反应20min。(3) Slowly drop solution B into solution A containing cobalt-based Prussian white, stir continuously, keep the temperature at 3°C, and age for 20 minutes.
(4)最后将步骤(3)制得的溶液过滤、洗涤，放在80℃烘箱中干燥过夜，制得本例中的改性的普鲁士类衍生物，记为：Na 1.85K 0.15CoFe(CN) 6·@KVO 3。 (4) Finally, filter and wash the solution obtained in step (3), and dry it in an oven at 80°C overnight to obtain the modified Prussian derivative in this example, which is recorded as: Na 1.85 K 0.15 CoFe(CN ) 6 ·@KVO 3 .
实施例5Example 5
本例中的改性的普鲁士类衍生物是采用KVO 3包覆掺杂普鲁士白衍生物，普鲁士白衍生物的化学式为：Na 1.75K 0.25Zn 3[Fe(CN) 6] 2。 The modified Prussian derivative in this example is a Prussian white derivative coated with KVO 3. The chemical formula of the Prussian white derivative is: Na 1.75 K 0.25 Zn 3 [Fe(CN) 6 ] 2 .
本例中的改性的普鲁士类衍生物采用以下制备方法制得，具体包括以下步骤：The modified Prussian derivative in this example is prepared by the following preparation method, which specifically includes the following steps:
(1)称取1mol锌基普鲁士白Na 2Zn 3[Fe(CN) 6] 2·H 2O溶于500mL的去离子水中，剧烈搅拌使锌基普鲁士白充分溶解于水中，搅拌速率为400rpm，然后置于冰浴条件下，温度控制在10℃，得到A溶液。 (1) Weigh 1 mol of zinc-based Prussian white Na 2 Zn 3 [Fe(CN) 6 ] 2 ·H 2 O and dissolve it in 500 mL of deionized water. Stir vigorously to fully dissolve the zinc-based Prussian white in the water. The stirring rate is 400 rpm. , and then placed in an ice bath with the temperature controlled at 10°C to obtain solution A.
(2)称取2mol V 2O 3和2mol的氯化钾溶解在250mL的去离子水溶液中，作为B溶液；剧烈搅拌使V 2O 3和氯化钾充分溶于水。 (2) Weigh 2 mol V 2 O 3 and 2 mol potassium chloride and dissolve them in 250 mL of deionized water solution as solution B; stir vigorously to fully dissolve V 2 O 3 and potassium chloride in water.
(3)将B溶液缓慢的滴入含锌基普鲁士白的A溶液中，不停的搅拌，温度保持在10℃，陈化反应30min。(3) Slowly drop solution B into solution A containing zinc-based Prussian white, stir continuously, keep the temperature at 10°C, and age for 30 minutes.
(4)最后将步骤(3)制得的溶液过滤、洗涤，放在80℃烘箱中干燥过夜，得到了制得本例中的本例中的改性的普鲁士类衍生物，记为：Na 1.75K 0.25Zn 3[Fe(CN) 6] 2·@KVO 3。 (4) Finally, filter and wash the solution prepared in step (3), and dry it in an oven at 80°C overnight to obtain the modified Prussian derivative in this example, which is recorded as: Na 1.75 K 0.25 Zn 3 [Fe(CN) 6 ] 2 ·@KVO 3 .
实施例6Example 6
本例中的改性的普鲁士类衍生物是采用KVO 3包覆掺杂普鲁士白衍生物，普鲁士白衍生物的化学式为：Na 1.56K 0.44FeFe(CN) 6。 The modified Prussian derivative in this example is a Prussian white derivative coated with KVO 3. The chemical formula of the Prussian white derivative is: Na 1.56 K 0.44 FeFe(CN) 6 .
本例中的改性的普鲁士类衍生物采用以下制备方法制得，具体包括以下步骤：The modified Prussian derivative in this example is prepared by the following preparation method, which specifically includes the following steps:
(1)称取1mol铁基普鲁士白(Na 2FeFe(CN) 6·3.1H 2O)溶于500mL的去离子水中，剧烈搅拌使铁基普鲁士白充分溶解于水中，搅拌速率为400rpm，然后置于冰浴条件下，温度控制在15℃，得到A溶液。 (1) Weigh 1 mol of iron-based Prussian white (Na 2 FeFe(CN) 6 ·3.1H 2 O) and dissolve it in 500 mL of deionized water. Stir vigorously to fully dissolve the iron-based Prussian white in the water. The stirring rate is 400 rpm, and then Place in an ice bath and control the temperature at 15°C to obtain solution A.
(2)称取2mol的偏钒酸铵和2mol的氯化钾溶解在250mL的去离子水溶液中，作为B溶液；剧烈搅拌使偏钒酸铵和氯化钾充分溶于水。(2) Weigh 2 mol of ammonium metavanadate and 2 mol of potassium chloride and dissolve them in 250 mL of deionized water solution as solution B; stir vigorously to fully dissolve ammonium metavanadate and potassium chloride in the water.
(3)将B溶液缓慢的滴入含铁基普鲁士白的A溶液中，不停的搅拌，温度控制在15℃，陈化反应40min。(3) Slowly drop solution B into solution A containing iron-based Prussian white, stir continuously, control the temperature at 15°C, and age for 40 minutes.
(4)最后将步骤(3)制得的溶液过滤、洗涤，放在80℃烘箱中干燥过夜，制得本例中的本例中的改性的普鲁士类衍生物，记为：Na 1.56K 0.44FeFe(CN) 6·@KVO 3。 (4) Finally, filter and wash the solution obtained in step (3), and dry it in an oven at 80°C overnight to obtain the modified Prussian derivative in this example, recorded as: Na 1.56 K 0.44 FeFe(CN) 6 ·@KVO 3 .
实施例7Example 7
本例中的改性的普鲁士类衍生物是采用Na 3VO 4包覆掺杂普鲁士白衍生物，普鲁士白衍生物的化学式为：Na 0.84Ni[Fe(CN) 6] 0.71。 The modified Prussian derivative in this example is a Prussian white derivative coated with Na 3 VO 4. The chemical formula of the Prussian white derivative is: Na 0.84 Ni[Fe(CN) 6 ] 0.71 .
本例中的改性的普鲁士类衍生物采用以下制备方法制得，具体包括以下步骤：The modified Prussian derivative in this example is prepared by the following preparation method, which specifically includes the following steps:
(1)称取1mol镍基普鲁士白Na 0.84Ni[Fe(CN) 6] 0.71·6H 2O溶于500mL的去离子水中，剧烈搅拌使镍基普鲁士白充分溶解于水中，搅拌速率为400rpm，然后在冰浴条件下，温度控制在5℃，得到A溶液。 (1) Weigh 1 mol of nickel-based Prussian white Na 0.84 Ni[Fe(CN) 6 ] 0.71 ·6H 2 O and dissolve it in 500 mL of deionized water. Stir vigorously to fully dissolve the nickel-based Prussian white in the water. The stirring rate is 400 rpm. Then under ice bath conditions, the temperature was controlled at 5°C to obtain solution A.
(2)称取2mol偏钒酸铵和6mol的氯化钠溶解在250mL的去离子水溶液中，作为B溶液；剧烈搅拌使偏钒酸铵和氯化钠充分溶于水。(2) Weigh 2 mol of ammonium metavanadate and 6 mol of sodium chloride and dissolve them in 250 mL of deionized water solution as solution B; stir vigorously to fully dissolve ammonium metavanadate and sodium chloride in the water.
(3)将B溶液缓慢的滴入含镍基普鲁士白的A溶液中，不停的搅拌，缓慢升温到80℃，陈化反应20min。(3) Slowly drop solution B into solution A containing nickel-based Prussian white, stir continuously, slowly raise the temperature to 80°C, and age for 20 minutes.
(4)最后将步骤(3)制得的溶液过滤、洗涤，放在80℃烘箱中干燥过夜，制得本例中的改性的普鲁士类衍生物，记为：Na 0.84Ni[Fe(CN) 6] 0.71·@Na 3VO 4。 (4) Finally, filter and wash the solution obtained in step (3), and dry it in an oven at 80°C overnight to obtain the modified Prussian derivative in this example, recorded as: Na 0.84 Ni[Fe(CN ) 6 ] 0.71 ·@Na 3 VO 4 .
实施例1～7中制得的改性的普鲁士类衍生物均可以用作正极材料。The modified Prussian derivatives prepared in Examples 1 to 7 can all be used as cathode materials.
对比例1Comparative example 1
本例是将实施例1中的锰基普鲁士白(Na 2MnFe(CN) 6)作为正极材料。 In this example, the manganese-based Prussian white (Na 2 MnFe(CN) 6 ) in Example 1 is used as the cathode material.
分别将实施例1～7和对比例1中制得的材料作为正极极片放置在真空烘箱内进行干燥(80℃，3h)；并冲切成直径为12mm的圆片。在半电池中，正极使用干燥的电极片，负极使 用钠片为对电极，隔膜为玻璃纤维的复合隔膜，电解液：1mol/L的NaPF 6+EC、DMC、DEC的混合溶液(EC、DMC、DEC的体积比为1：1：1，EC指的是碳酸亚乙酯，DMC指的是碳酸二甲酯，DEC指的是碳酸二乙酯)。利用CT2001A型电池检测系统测试制备的半电池的放电性能，其中，截止电压为2.0-4.0V，先0.2C下恒流充至4.0V，再恒压4.0V充至电流≤0.05C，分别在0.1C、1C、3C、5C下进行了放电性能测试，具体测试结果如下表1所示。 The materials prepared in Examples 1 to 7 and Comparative Example 1 were used as positive electrode sheets and placed in a vacuum oven for drying (80°C, 3 h); and punched into discs with a diameter of 12 mm. In the half-cell, a dry electrode sheet is used as the positive electrode, a sodium sheet is used as the counter electrode for the negative electrode, the separator is a composite separator of glass fiber, and the electrolyte is: 1 mol/L NaPF 6 + EC, DMC, DEC mixed solution (EC, DMC , The volume ratio of DEC is 1:1:1, EC refers to ethylene carbonate, DMC refers to dimethyl carbonate, and DEC refers to diethyl carbonate). The discharge performance of the prepared half-cell was tested using the CT2001A battery testing system. The cut-off voltage was 2.0-4.0V. First, it was charged to 4.0V at a constant current of 0.2C, and then charged to a current of ≤0.05C at a constant voltage of 4.0V. Discharge performance tests were conducted at 0.1C, 1C, 3C, and 5C. The specific test results are shown in Table 1 below.
表1实施例1～7和对比例1中制得的材料的电性能Table 1 Electrical properties of materials prepared in Examples 1 to 7 and Comparative Example 1
实施例Example 0.1C(mAh/g)0.1C(mAh/g) 1C(mAh/g)1C(mAh/g) 3C(mAh/g)3C(mAh/g) 5C(mAh/g)5C(mAh/g) 电压范围(V)Voltage range(V)
对比例1Comparative example 1 130.1130.1 105.3105.3 97.997.9 64.264.2 2-42-4
实施例1Example 1 154.6154.6 145.7145.7 121.5121.5 113.1113.1 2-42-4
实施例2Example 2 162.2162.2 151.9151.9 140.6140.6 122.7122.7 2-42-4
实施例3Example 3 140.8140.8 124.1124.1 102.6102.6 94.694.6 2-42-4
实施例4Example 4 160.4160.4 144.2144.2 135.4135.4 125.9125.9 2-42-4
实施例5Example 5 145.4145.4 123.8123.8 110.2110.2 103.2103.2 2-42-4
实施例6Example 6 146.7146.7 129.5129.5 114.9114.9 105.3105.3 2-42-4
实施例7Example 7 161.4161.4 154.6154.6 137.5137.5 120.1120.1 2-42-4
由上表1可知，相对于对比例1中的锰基普鲁士白正极材料而言，本发明实施例1～7中制得的改性的普鲁士类衍生物采用钒酸盐类化合物进行包覆掺杂改性，钒作为一个多价的金属元素，包覆掺杂在普鲁士类衍生物材料上，能提供多个氧化还原性位点，提高电池材料的相对理论容量，从而使电池的电性能有了较大幅度的提升。As can be seen from Table 1 above, compared with the manganese-based Prussian white cathode material in Comparative Example 1, the modified Prussian derivatives prepared in Examples 1 to 7 of the present invention are coated and doped with vanadate compounds. Hybrid modification, vanadium, as a multivalent metal element, is coated and doped on the Prussian derivative material, which can provide multiple redox sites and improve the relative theoretical capacity of the battery material, thereby improving the electrical performance of the battery. A substantial improvement.
分别测试实施例1～7中制得的改性的普鲁士类衍生物在包覆前和包覆后材料中的水含量值，具体测试结果记录在下表2中。The water content values of the modified Prussian derivatives prepared in Examples 1 to 7 before and after coating were tested respectively. The specific test results are recorded in Table 2 below.
表2实施例1～7中的改性的普鲁士类衍生物的水含量测试Table 2 Water content test of modified Prussian derivatives in Examples 1 to 7
Figure PCTCN2022119462-appb-000001
Figure PCTCN2022119462-appb-000001
Figure PCTCN2022119462-appb-000002
Figure PCTCN2022119462-appb-000002
由上表2可知，本发明中的改性的普鲁士类衍生物在采用钒酸盐类化合物包覆改性后，能极大地降低了普鲁士类衍生物材料中的水含量，进而表明钒酸盐类化合物中的金属阳离子能够快速的进入普鲁士类衍生物的晶格中，占据原来晶格水的位置，除去普鲁士类衍生物内部缺陷的晶格水，减少普鲁士类衍生物材料的内部缺陷，增加了普鲁士类衍生物材料的晶体结构的完整性。As can be seen from Table 2 above, the modified Prussian derivatives in the present invention, after being coated and modified with vanadate compounds, can greatly reduce the water content in the Prussian derivative materials, which further shows that the vanadate compounds The metal cations in the Prussian derivatives can quickly enter the crystal lattice of the Prussian derivatives, occupy the position of the original lattice water, remove the lattice water of internal defects of the Prussian derivatives, reduce the internal defects of the Prussian derivative materials, and increase the The integrity of the crystal structure of the Prussian derivative material is improved.
上面对本发明实施例作了详细说明，但是本发明不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下做出各种变化。此外，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。The embodiments of the present invention have been described in detail above. However, the present invention is not limited to the above-mentioned embodiments. Various changes can be made within the knowledge scope of those of ordinary skill in the art without departing from the gist of the present invention. In addition, the embodiments of the present invention and the features in the embodiments may be combined with each other without conflict.

Claims (10)

  1. 一种改性的普鲁士类衍生物，其特征在于，包括钒化合物和普鲁士类衍生物；所述普鲁士类衍生物表面和/或内部含有钒化合物。A modified Prussian derivative, characterized in that it includes a vanadium compound and a Prussian derivative; the Prussian derivative contains a vanadium compound on its surface and/or inside.
  2. 根据权利要求1所述的改性的普鲁士类衍生物，其特征在于，所述普鲁士类衍生物的化学式为：A xB yM zNa[(CN) 6] b； The modified Prussian derivative according to claim 1, wherein the chemical formula of the Prussian derivative is: Ax By By M z Na [(CN) 6 ] b ;
    其中，A为K或Na；Among them, A is K or Na;
    B为K或Na；B is K or Na;
    M为Co、Cu、Cr、Fe、Mn、Ni、Cr、Zn中的至少一种；M is at least one of Co, Cu, Cr, Fe, Mn, Ni, Cr, and Zn;
    N为Fe或Zn；N is Fe or Zn;
    0.5≤x+y≤2，z为1、2或3；0.5≤a≤3，0.5≤b≤2。0.5≤x+y≤2, z is 1, 2 or 3; 0.5≤a≤3, 0.5≤b≤2.
  3. 根据权利要求1或2所述的改性的普鲁士类衍生物，其特征在于，所述钒化合物为碱金属钒酸盐、碱土金属钒酸盐、过渡金属钒酸盐中的至少一种。The modified prussian derivative according to claim 1 or 2, characterized in that the vanadium compound is at least one of an alkali metal vanadate, an alkaline earth metal vanadate, and a transition metal vanadate.
  4. 根据权利要求1或2所述的改性的普鲁士类衍生物，其特征在于，所述钒化合物和所述普鲁士类衍生物的摩尔比为(0.1～20)：100。The modified Prussian derivative according to claim 1 or 2, wherein the molar ratio of the vanadium compound and the Prussian derivative is (0.1-20):100.
  5. 权利要求1～4任一项所述的改性的普鲁士类衍生物的制备方法，其特征在于，包括以下步骤：The preparation method of modified Prussian derivatives according to any one of claims 1 to 4, characterized in that it includes the following steps:
    使普鲁士类材料与钒化合物混合反应，制得所述改性的普鲁士类衍生物。The modified Prussian derivative is prepared by mixing and reacting the Prussian material with the vanadium compound.
  6. 根据权利要求5所述的改性的普鲁士类衍生物的制备方法，其特征在于，所述混合反应具体为：使普鲁士类材料溶液和钒化合物溶液进行液相反应。The method for preparing modified Prussian derivatives according to claim 5, characterized in that the mixing reaction is specifically: making a Prussian material solution and a vanadium compound solution undergo a liquid phase reaction.
  7. 根据权利要求6所述的改性的普鲁士类衍生物的制备方法，其特征在于，所述液相反应温度为0～80℃，液相反应时间为5～80min。The method for preparing modified Prussian derivatives according to claim 6, characterized in that the liquid phase reaction temperature is 0 to 80°C, and the liquid phase reaction time is 5 to 80 minutes.
  8. 根据权利要求5所述的改性的普鲁士类衍生物的制备方法，其特征在于，所述普鲁士类材料包括Na 2MnFe(CN) 6、Na 2CoFe(CN) 6、Na 2NiFe(CN) 6、Na 2CuFe(CN) 6、Na 2Zn 3[Fe(CN) 6] 2、Na 2FeFe(CN) 6、Na 0.84Ni[Fe(CN) 6] 0.71、Na 2CrFe(CN) 6、K 2MnFe(CN) 6、K 2CoFe(CN) 6、K 2NiFe(CN) 6、K 2CuFe(CN) 6、K 2Zn 3[Fe(CN) 6] 2、K 2CrFe(CN) 6、Na 1.63FeFe(CN) 6中的至少一种。 The method for preparing modified Prussian derivatives according to claim 5, characterized in that the Prussian materials include Na 2 MnFe(CN) 6 , Na 2 CoFe(CN) 6 , Na 2 NiFe(CN) 6 , Na 2 CuFe(CN) 6 , Na 2 Zn 3 [Fe(CN) 6 ] 2 , Na 2 FeFe(CN) 6 , Na 0.84 Ni[Fe(CN) 6 ] 0.71 , Na 2 CrFe(CN) 6 , K 2 MnFe(CN) 6 , K 2 CoFe(CN) 6 , K 2 NiFe(CN) 6 , K 2 CuFe(CN) 6 , K 2 Zn 3 [Fe(CN) 6 ] 2 , K 2 CrFe( CN) 6 and Na 1.63 FeFe(CN) 6 .
  9. 一种正极材料，其特征在于，包括权利要求1～4任一项所述的改性的普鲁士类衍生物。A cathode material, characterized by comprising the modified Prussian derivative according to any one of claims 1 to 4.
  10. 权利要求9所述的正极材料在钠离子电池或钾离子电池中的应用。Application of the cathode material according to claim 9 in sodium-ion batteries or potassium-ion batteries.
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