WO2024250134A1 - 一种普鲁士蓝材料的制备方法、普鲁士蓝材料及应用 - Google Patents

一种普鲁士蓝材料的制备方法、普鲁士蓝材料及应用 Download PDF

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WO2024250134A1
WO2024250134A1 PCT/CN2023/098256 CN2023098256W WO2024250134A1 WO 2024250134 A1 WO2024250134 A1 WO 2024250134A1 CN 2023098256 W CN2023098256 W CN 2023098256W WO 2024250134 A1 WO2024250134 A1 WO 2024250134A1
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transition metal
preparation
prussian blue
solution
divalent
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English (en)
French (fr)
Inventor
李爱霞
余海军
谢英豪
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Priority to CN202380009316.4A priority Critical patent/CN116981797A/zh
Priority to PCT/CN2023/098256 priority patent/WO2024250134A1/zh
Publication of WO2024250134A1 publication Critical patent/WO2024250134A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C3/00—Cyanogen; Compounds thereof
    • C01C3/08—Simple or complex cyanides of metals
    • C01C3/12—Simple or complex iron cyanides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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

Definitions

  • the present invention relates to the technical field of Prussian blue materials, and in particular to a preparation method of a Prussian blue material, a Prussian blue material and an application thereof.
  • sodium-sulfur batteries lithium-ion batteries
  • lead-acid batteries lead-carbon batteries
  • flow batteries sodium-ion batteries
  • sodium-ion batteries have the advantages of good safety, low cost, abundant resources, and environmental friendliness, making them very suitable for large-scale energy storage.
  • Prussian blue materials have an open framework structure that is conducive to the insertion and extraction of large-sized sodium ions. Therefore, they have the advantages of high capacity and good rate performance, making them very suitable as positive electrode materials for sodium-ion batteries.
  • Prussian blue cathode materials are usually obtained by coprecipitating a transition metal cyanide anion (such as M′(CN) 6 m- ) and a transition metal cation (such as Mn + ) in an aqueous solution, and the material has a three-dimensional skeleton crystal structure. Due to charge balance, M′(CN) 6 holes are easily generated in the crystals of Prussian blue cathode materials.
  • the molar ratio of the transition metal cation to the transition metal cyanide anion should be 2:1, so the proportion of M′(CN) 6 holes is as high as 50%.
  • the purpose of the present invention is to provide a method for preparing a Prussian blue material, a Prussian blue material and an application thereof. Reduce the formation of defects in materials and improve the electrochemical properties of materials.
  • the solution provided by the present disclosure includes a method for preparing a Prussian blue material, comprising: using a cation exchange membrane to separate transition metal cations and transition metal cyanide anions in two electrolytic cells of an electrochemical device, and preparing the material by an electrochemical method.
  • the method comprises: placing the first solution and the second solution in different electrolytic cells of an electrochemical device, respectively, and applying electricity;
  • the first solution includes: a first solvent and a metal salt containing a transition metal cation;
  • the second solution includes: a second solvent and a sodium salt containing a transition metal cyanide anion.
  • the current applied is 1A-20A.
  • the current applied is 5A-15A.
  • the transition metal cation in the metal salt is a divalent transition metal cation.
  • the divalent transition metal cation is selected from at least one of a divalent iron ion and a divalent manganese ion.
  • the divalent transition metal cation is a divalent iron ion.
  • the sodium salt containing a transition metal cyanide anion is sodium ferrocyanide or a hydrate thereof.
  • the ferrocyanide is sodium ferrocyanide or a hydrate of sodium ferrocyanide.
  • the molar ratio of the divalent transition metal cation to the transition metal cyanide anion is (1.0-1.2):1.
  • the molar ratio of the divalent transition metal cation to the transition metal cyanide anion is (1.05-1.15):1.
  • the first solution further contains an antioxidant.
  • the antioxidant is selected from at least one of ascorbic acid, citric acid, glucose and sucrose.
  • the antioxidant is ascorbic acid.
  • the molar ratio of the antioxidant to the transition metal cation is (0.5-0.8):1.
  • the molar ratio of the antioxidant to the transition metal cation is (0.6-0.7):1.
  • the concentration of the transition metal cation in the first solution is 0.15 mol/L-0.30 mol/L.
  • the concentration of the transition metal cyanide anion in the second solution is 0.1 mol/L-0.3 mol/L.
  • the first solvent and the second solvent are both water.
  • the material of the cation exchange membrane is selected from at least one of a polyetheretherketone homogeneous cation exchange membrane, a perfluoroethylene sulfonic acid homogeneous cation exchange membrane and a polysulfone homogeneous cation exchange membrane.
  • the method comprises placing a first solution in an anode region of an electrochemical device, placing a second solution in a cathode region of the electrochemical device, and then applying power to obtain a suspension of Prussian blue material.
  • the method comprises: placing a first solution in the anode region of an electrochemical device, applying power so that transition metal cations are adsorbed onto an electrode plate in the cathode region, and then disconnecting the power; placing a second solution in the anode region of the electrochemical device, and then applying power in the reverse direction so that the adsorbed transition metal cations are decomposed and enter the region where the transition metal cyanide anions are located to react, thereby obtaining a suspension of Prussian blue material.
  • the method further includes aging, washing, and separating the obtained suspension of Prussian blue material to obtain a solid material, and drying the solid material.
  • the aging time is 2h-5h.
  • the solution provided by the present disclosure also includes a Prussian blue material prepared by the preparation method in any of the above embodiments.
  • the chemical formula thereof is Na x M[Fe(CN) 6 ], wherein M represents divalent iron or divalent manganese, and 1.5 ⁇ x ⁇ 2.
  • the solution provided by the present disclosure also includes the use of the Prussian blue material in the above-mentioned embodiment as a positive electrode material for a sodium ion battery.
  • the solution provided by the present disclosure includes a sodium ion battery positive electrode plate, including a positive electrode collector and an active coating attached to the positive electrode collector, wherein the active coating contains the Prussian blue material in the above-mentioned embodiment.
  • the solution provided by the present disclosure includes a sodium ion battery, including the sodium ion battery positive electrode plate in the above embodiment.
  • the solution provided by the present disclosure includes an electrical device, including the sodium ion battery in the above embodiment.
  • the present disclosure adopts the principle of electrochemistry to prepare Prussian blue material, uses a cation exchange membrane to separate transition metal cations and transition metal cyanide anions, and after power is applied, the transition metal cations can be slowly released to react with transition metal cyanide anions.
  • the speed of precipitation formation can be further controlled by controlling the current, thereby avoiding structural defects caused by too fast a reaction rate and reducing the occurrence of the hole ratio.
  • the preparation method provided by the present disclosure is used to prepare a positive electrode material for a sodium ion battery, it is beneficial to improve the electrochemical performance of the product.
  • FIG1 is a first schematic diagram of a method for preparing a Prussian blue material provided by the present disclosure
  • FIG2 is a second schematic diagram of the method for preparing the Prussian blue material provided by the present disclosure; in the figure, (a) indicates that cations are adsorbed onto the cathode electrode plate by applying power; (b) indicates that the Prussian blue material is synthesized by applying power in the reverse direction;
  • FIG3 is an X-ray diffraction (XRD) pattern of the Prussian blue material prepared in Example 1;
  • FIG. 4 is a SEM image of the Prussian blue material prepared in Example 1.
  • any values of the ranges disclosed in this disclosure are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values.
  • the endpoint values of each range, the endpoint values of each range and the individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.
  • the disclosed embodiment provides a method for preparing a Prussian blue material, which is prepared using the principle of electrochemistry, using a cation exchange membrane to separate transition metal cations and transition metal cyanide anions, and after power is applied, the transition metal cations are slowly released to react with transition metal cyanide anions to form a precipitate.
  • transition metal cyanide anions M′(CN) 6 m-
  • transition metal cyanide anions M′(CN) 6 m-
  • the precipitation rate is too fast, resulting in a high proportion of M′(CN) 6 holes in the crystal structure of Prussian blue positive electrode materials, thereby increasing the proportion of interstitial water, and the material is very easy to form defects, which affects the actual specific capacity and electrochemical performance of the material.
  • the present invention utilizes an electrochemical method to slowly release transition metal cations through a cation exchange membrane, react with transition metal cyanide anions and precipitate.
  • the precipitation rate can be better controlled by controlling the current.
  • the operation is simple and flexible, and the problem of defects in the material structure caused by too fast precipitation during material preparation is solved.
  • a metal salt containing a transition metal cation and a first solvent are mixed to obtain a first solution, and a sodium salt containing a transition metal cyanide anion and a second solvent are mixed to obtain a second solution.
  • the first solution and the second solution are prepared for use.
  • the transition metal cation in the metal salt is a divalent transition metal cation, such as at least one of a divalent iron ion and a divalent manganese ion, and may be any one or more of the above.
  • the divalent transition metal cation is a divalent iron ion to improve the electrochemical performance of the prepared Prussian blue material for a positive electrode material of a sodium ion battery.
  • the metal salt corresponding to the divalent iron ion may be ferrous sulfate, ferrous chloride, ferrous nitrate, etc.
  • the sodium salt containing the transition metal cyanide anion can be at least one of sodium ferrocyanide or its hydrate, and can be any one or more of the above, and the sodium salt is used as a raw material to form a positive electrode material for a sodium ion battery after a one-step precipitation.
  • the ferrocyanide is sodium ferrocyanide or a hydrate of sodium ferrocyanide to improve the capacity and electrochemical performance of the material.
  • the molar ratio of the divalent transition metal cation and the transition metal cyanide anion is (1.0-1.2):1, preferably (1.05-1.15):1, such as 1.00:1, 1.05:1, 1.10:1, 1.15:1, 1.20:1, etc.
  • the first solution further contains an antioxidant to prevent oxidation of ferrous ions.
  • the specific type of the antioxidant is not limited, and can be selected from at least one of ascorbic acid, citric acid, glucose and sucrose, and can be any one or more of the above, preferably ascorbic acid.
  • the molar ratio of the antioxidant to the transition metal cation is (0.5-0.8):1, preferably (0.6-0.7):1, to achieve a better antioxidant effect.
  • the molar ratio of the antioxidant to the transition metal cation can be 0.5:1, 0.6:1, 0.7:1, 0.8:1, etc.
  • the concentration of transition metal cations in the first solution is 0.15 mol/L-0.30 mol/L, such as 0.15 mol/L, 0.20 mol/L, 0.25 mol/L, 0.30 mol/L, etc.
  • the concentration of transition metal cyanide anions in the second solution is 0.1 mol/L-0.3 mol/L, such as 0.10 mol/L, 0.15 mol/L, 0.20 mol/L, 0.25 mol/L, 0.30 mol/L, etc.
  • the first solvent and the second solvent may both be water, but are not limited thereto.
  • the first solution and the second solution are placed in different electrolytic cells of an electrochemical device respectively, and electricity is applied to the cells so that the transition metal cations are slowly released and react with the transition metal cyanide anions to form a precipitate.
  • the electrochemical device includes a cathode electrolyzer, an anode electrolyzer and a cation exchange membrane, wherein the cation exchange membrane separates the cathode electrolyzer from the anode electrolyzer, and electrode plates are disposed in both the cathode electrolyzer and the anode electrolyzer, and the two electrode plates are connected through an external circuit. After power is applied, cations enter the cathode electrolyzer through the cation exchange membrane to react with anions.
  • a first solution is placed in the anode region of an electrochemical device, and a second solution is placed in the The cathode region of the chemical device is then energized, and the transition metal cations in the anode region enter the cathode region through the cation exchange membrane, and react with the transition metal cyanide anions in the cathode region to obtain a suspension of Prussian blue material.
  • the first solution is placed in the anode region of the electrochemical device, and after power is applied, the transition metal cations are adsorbed onto the electrode plate in the cathode region (as shown in (a)), and then the power is turned off; the second solution is placed in the anode region of the electrochemical device, and then the power is applied in the reverse direction, so that the adsorbed transition metal cations are decomposed and enter the region where the transition metal cyanide anions are located to react (as shown in (b)), thereby obtaining a suspension of Prussian blue material.
  • the first solution is placed in the anode region of the electrochemical device, and then power is applied, so that the cathode is embedded with metal ions, and the anode is embedded with anions (as shown in (a));
  • the second solution is placed in the anode region of the electrochemical device, and after power is applied in the reverse direction, the original anode becomes the cathode, and the original cathode becomes the anode, so that the transition metal cations are decomposed and enter the region where the transition metal cyanide anions are located through the cation exchange membrane to react and form a precipitate.
  • the current is 1A-20A, and the power is turned off when no precipitation is observed; preferably, the current is 5A-15A.
  • the cation release rate can be controlled within a better range, which not only ensures a better reaction rate, but also avoids structural defects caused by too fast a deposition rate.
  • the electrode plates are all carbon electrode plates, but are not limited thereto.
  • the material of the cation exchange membrane is selected from at least one of polyetheretherketone homogeneous cation exchange membrane, perfluoroethylene sulfonic acid homogeneous cation exchange membrane and polysulfone homogeneous cation exchange membrane, and can be any one or more of the above materials.
  • the above cation exchange membranes are all commercially available materials.
  • the Prussian blue material is separated from the suspension obtained after the reaction is completed by post-treatment.
  • the post-treatment process includes aging, washing, and separating the obtained suspension of Prussian blue material to obtain a solid material, and drying the solid material to remove surface moisture and residual washing solvent.
  • aging can be carried out in a general aging kettle, and the aging time can be 2h-5h, such as 2h, 3h, 4h, 5h, etc. Washing can be performed multiple times.
  • the specific method of separation is not limited, and can be centrifugal separation, but is not limited thereto.
  • Drying can be carried out in a general vacuum drying oven, and the drying temperature is approximately 120°C-320°C, and the drying time is approximately 12h-48h.
  • the present disclosure also provides a Prussian blue material, which is prepared by the above-mentioned preparation method and has a complete lattice morphology, a low proportion of crystal water, and also has a higher capacity, a longer cycle life and relatively excellent rate performance.
  • the chemical formula is Na x M[Fe(CN) 6 ], wherein M represents divalent iron or divalent manganese, such as the chemical formula may be Na x Fe[Fe(CN) 6 ], 1.5 ⁇ x ⁇ 2.
  • the value of x may be 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, etc.
  • the present disclosure also provides a sodium ion battery positive electrode plate, including a positive electrode collector and an active coating attached to the positive electrode collector, wherein the active coating contains the above-mentioned Prussian blue material.
  • the improvement of the performance of the Prussian blue material can further improve the performance of the sodium ion battery positive electrode plate.
  • the preparation process of the positive electrode plate of the sodium ion battery can refer to the existing technology, and the main steps include: mixing Prussian blue material, conductive agent, binder and solvent to form a slurry, coating the slurry on the positive electrode collector, and forming a coating after drying.
  • the present disclosure also provides a sodium ion battery, including the above-mentioned sodium ion battery positive electrode plate, and also includes a negative electrode plate, an electrolyte, a diaphragm, etc., and the specific material types are not limited.
  • the present disclosure also provides an electrical device, including the sodium ion battery, which is used to supply power, and the specific electrical device is not limited.
  • the electrochemical devices used in the following examples all include: an anode electrolyzer, a cathode electrolyzer, a cation exchange membrane (made of a homogeneous cation exchange membrane of perfluoroethylene sulfonic acid), and a carbon-containing electrode plate (graphite electrode), wherein the cation exchange membrane separates the anode electrolyzer and the cathode electrolyzer.
  • the test temperature is 26°C.
  • This embodiment provides a method for preparing a Prussian blue material, comprising the following steps:
  • Ferrous sulfate and ascorbic acid were dissolved in 500 ml of deionized water to obtain solution I.
  • the concentration of ferrous sulfate in solution I was 0.22 mol/L, and the concentration of ascorbic acid was 0.14 mol/L.
  • Sodium ferrocyanide decahydrate was dissolved in 500 ml of deionized water to obtain a solution II having a sodium ferrocyanide concentration of 0.2 mol/L.
  • Solution I was added to the anode region of the electrochemical device, and solution II was added to the cathode region of the electrochemical device.
  • the device was powered on at a current of 10A.
  • Ferrous ions entered the cathode region through the cation exchange membrane and formed precipitation with cyanide anions (M′(CN) 6 m -). When no precipitation was observed, the power was turned off to obtain a suspension of Prussian blue material.
  • the suspension was aged for 3 hours, washed with water for 3 times, and centrifuged to obtain a solid material, which was then vacuum dried at 200° C. for 24 hours.
  • the molar ratio of the divalent transition metal cation to the transition metal cyanide anion is 1.1:1, and the molar ratio of the antioxidant to the transition metal cation is 0.64:1.
  • This embodiment provides a method for preparing a Prussian blue material, comprising the following steps:
  • Ferrous sulfate and ascorbic acid were dissolved in 500 ml of deionized water to obtain solution I.
  • the concentration of ferrous sulfate in solution I was 0.24 mol/L, and the concentration of ascorbic acid was 0.19 mol/L.
  • Sodium ferrocyanide decahydrate was dissolved in 500 ml of deionized water to obtain a solution II having a sodium ferrocyanide concentration of 0.2 mol/L.
  • Solution I was added to the anode region of the electrochemical device, and the current was 20A for 550 minutes, so that the ferrous ions were completely adsorbed on the cathode electrode plate (as shown in Figure 2 (a)), and then the power was turned off;
  • Solution II was added to the anode region of the electrochemical device, and the electrochemical device was reversely powered at a current of 15A.
  • the ferrous ions entered the cathode region (the cathode region after reverse power-on) through the cation exchange membrane and began to form precipitation with the cyanide anion (M′(CN) 6 m- ). When no precipitation was observed, the power was turned off to obtain a suspension of Prussian blue material.
  • the suspension was aged for 3 hours, washed with water for 3 times, and centrifuged to obtain a solid material, which was then vacuum dried at 200° C. for 24 hours.
  • Example 1 The only difference from Example 1 is that the current is 5A.
  • Example 1 The only difference from Example 1 is that the current is 15A.
  • Example 1 The only difference from Example 1 is that the current is 20A.
  • Example 1 The only difference from Example 1 is that the current is 25A.
  • Example 1 The only difference from Example 1 is that the current is 1A.
  • Example 1 The only difference from Example 1 is that the concentration of sodium ferrocyanide in solution II is 0.24 mol/L, so that the molar ratio of the divalent transition metal cation to the transition metal cyanide anion is 1.0:1.
  • Example 1 The only difference from Example 1 is that the concentration of sodium ferrocyanide in solution II is 0.18 mol/L, so that the molar ratio of the divalent transition metal cation to the transition metal cyanide anion is 1.2:1.
  • Example 1 The only difference from Example 1 is that the concentration of sodium ferrocyanide in solution II is 0.275 mol/L, so that the molar ratio of the divalent transition metal cation to the transition metal cyanide anion is 0.8:1.
  • Example 1 The only difference from Example 1 is that the concentration of sodium ferrocyanide in solution II is 0.147 mol/L, so that the molar ratio of the divalent transition metal cation to the transition metal cyanide anion is 1.5:1.
  • Example 1 The only difference from Example 1 is that in Solution I, ascorbic acid is replaced by an equimolar amount of glucose.
  • Example 1 The only difference from Example 1 is that the concentration of ascorbic acid in solution I is 0.11 mol/L, so that the molar ratio of the antioxidant to the transition metal cation is 0.5:1.
  • Example 1 The only difference from Example 1 is that the concentration of ascorbic acid in solution I is 0.176 mol/L, so that the molar ratio of the antioxidant to the transition metal cation is 0.8:1.
  • Example 1 The only difference from Example 1 is that the concentration of ascorbic acid in solution I is 0.066 mol/L, so that the molar ratio of the antioxidant to the transition metal cation is 0.3:1.
  • Example 1 The only difference from Example 1 is that the concentration of ascorbic acid in solution I is 0.22 mol/L, so that the molar ratio of the antioxidant to the transition metal cation is 1.0:1.
  • This comparative example provides a traditional method for preparing Prussian blue material, comprising the following steps:
  • Sodium ferrocyanide decahydrate was dissolved in 50 ml of deionized water to obtain a solution II having a sodium ferrocyanide concentration of 0.2 mol/L.
  • Test method (1) Assembly of button sodium ion battery: The Prussian blue positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) prepared in the example are mixed in a mass ratio of 7:2:1, and the mixed slurry is coated on aluminum foil, dried and cut into discs as the positive electrode; the metal sodium sheet is used as the negative electrode, and Whatman glass fiber (GF/D) is used as the separator; the organic electrolyte is prepared by NaClO 4 , EC (ethylene carbonate), DEC (diethyl carbonate) and FEC (fluoroethylene carbonate), the NaClO 4 concentration is 1.0 mol/L, the volume ratio of EC to DEC is 1:1, and the mass fraction of FEC in the electrolyte is 5%; the sodium ion battery is assembled in an argon glove box;
  • PVDF polyvinylidene fluoride
  • the cycle performance was tested at 25°C (1C/1C 2.0 ⁇ 4.3V); the gram capacity was tested at a current of 25mA/g.
  • the material prepared in this scheme has the advantage of better capacity retention rate.
  • Example 1 and Examples 3-7 It can be seen from the test results of Example 1 and Examples 3-7 that the applied current has a certain influence on the performance of the product, and Example 1, Example 3 and Example 4 have the best effects, that is, the applied current is preferably 5A-15A.
  • Example 1 It can be seen from Example 1 and Examples 8-11 that the molar ratio of the divalent transition metal cation to the transition metal cyanide anion is 0.8-1.5:1, which can enable the product to have a good capacity retention rate.
  • Example 1 It can be seen from Example 1 and Examples 12-17 that the type and amount of antioxidant have little effect on the performance of the product.
  • Example 1 has a certain influence on the defects of the product, and Example 1, Example 3 and Example 4 have the best effects, that is, the applied current is preferably 5A-15A.
  • Example 1 It can be seen from Example 1 and Examples 8-11 that the molar ratio of the divalent transition metal cation to the transition metal cyanide anion is 0.8-1.5:1, which can significantly reduce product defects.
  • Example 1 It can be seen from Example 1 and Examples 12-17 that the type and amount of antioxidant have little effect on the defects of the product.
  • the XRD pattern of the Prussian blue material prepared in Test Example 1 is shown in Figure 3. It can be seen that the prepared product is a pure-phase cubic Prussian blue positive electrode material; the sharp peak shape indicates that the prepared Prussian blue positive electrode material has a high degree of crystallinity.
  • the SEM image of the Prussian blue material prepared in Test Example 1 is shown in Figure 4. It can be seen that the prepared Prussian blue positive electrode material is in a cubic shape and has a smooth surface.
  • the present invention adopts the principle of electrochemistry to prepare Prussian blue material, uses a cation exchange membrane to separate transition metal cations and transition metal cyanide anions, and after power is applied, the transition metal cations can be slowly released to react with transition metal cyanide anions, and the speed of forming precipitation can be further controlled by controlling the current, thereby avoiding structural defects caused by too fast a reaction rate and reducing the occurrence of the hole ratio.
  • the reaction can be completed using a simple electrochemical device, the operation is convenient, and the reaction rate is easy to accurately control, which has very good industrial practicability.

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Abstract

本公开属于普鲁士蓝材料技术领域，具体涉及一种普鲁士蓝材料的制备方法、普鲁士蓝材料及应用。采用电化学的原理制备普鲁士蓝材料，用阳离子交换膜将过渡金属阳离子和过渡金属氰化物阴离子分隔开，通电后过渡金属阳离子可以缓慢释放与过渡金属氰化物阴离子反应，通过控制电流可以进一步控制形成沉淀的速度，避免了由于反应速率过快导致的结构缺陷。该制备方法用于制备钠离子电池正极材料时，有利于提高产品的电化学性能。

Description

一种普鲁士蓝材料的制备方法、普鲁士蓝材料及应用 技术领域
本公开属于普鲁士蓝材料技术领域，具体而言，涉及一种普鲁士蓝材料的制备方法、普鲁士蓝材料及应用。
背景技术
目前常见的储能电池有钠硫电池、锂离子电池、铅酸电池、铅碳电池、液流电池等。这几类电池中，钠离子电池具有安全性好、成本低且资源丰富，并对环境友好等综合优点，非常适合应用于大规模储能。在钠离子电池中，普鲁士蓝类材料由于结构中含有开放的框架结构，有利于大尺寸的钠离子的脱嵌，因此具有容量较高、倍率性能好等优点，非常适合作为钠离子电池正极材料。
普鲁士蓝类正极材料通常是通过将一种过渡金属氰化物阴离子(如M′(CN)6 m-)与一种过渡金属阳离子(如Mn+)在水溶液中共沉淀而得，材料为三维的骨架晶体结构。出于电荷平衡的缘故，普鲁士蓝类正极材料晶体中极易产生M′(CN)6空穴，比如在+2价的过渡金属阳离子与带四个负电荷的过渡金属氰化物阴离子(其中过渡金属的价态也是+2价)共沉淀得到的普鲁士蓝类正极材料晶体中，为了保持电荷平衡，过渡金属阳离子与过渡金属氰化物阴离子的摩尔比应为2:1，因此M′(CN)6空穴的比例高达50％。
在普鲁士蓝类正极材料中，每个空穴的存在会产生六个配位水，使正极材料的吸水性大大增强，且在普鲁士蓝类正极材料晶体结构的孔道中的空隙水由于易和配位水形成氢键，从而增加了去除空隙水的难度。这些空隙水的存在会占据普鲁士蓝类正极材料晶体结构的孔道中的部分空间，阻碍了碱金属或碱土金属离子(例如Na+或Li+)的传输。同时，这些孔隙水的存在还会游离到电解液中，并与电解液发生副反应，引起电解液消耗、负极SEI膜不稳定、阻抗增大，导致电化学储能装置出现容量衰减、胀气等不良后果。
因此，如何减少合成的普鲁士蓝类正极材料的空穴比例，已经成为目前亟需解决的技术问题。
鉴于此，特提出本公开。
发明内容
本公开的目的包括提供一种普鲁士蓝材料的制备方法、普鲁士蓝材料及应用，旨 在减少材料中缺陷的形成，提高材料的电化学性能。
为了实现本公开的上述目的，可采用以下技术方案：
第一方面，本公开的提供的方案包括一种普鲁士蓝材料的制备方法，包括：利用阳离子交换膜将过渡金属阳离子和过渡金属氰化物阴离子分隔在电化学装置的两个电解槽中，通过电化学的方法进行制备。
在本公开的一些实施方式中，包括：将第一溶液和第二溶液分别置于电化学装置不同的电解槽中，进行通电；
其中，第一溶液中包括：第一溶剂和含过渡金属阳离子的金属盐；
第二溶液中包括：第二溶剂和含过渡金属氰化物阴离子的钠盐。
在本公开的一些实施方式中，通电电流为1A-20A。
在本公开的一些实施方式中，通电电流为5A-15A。
在本公开的一些实施方式中，金属盐中的过渡金属阳离子为二价过渡金属阳离子。
在本公开的一些实施方式中，二价过渡金属阳离子选自二价铁离子和二价锰离子中的至少一种。
在本公开的一些实施方式中，二价过渡金属阳离子为二价铁离子。
在本公开的一些实施方式中，含过渡金属氰化物阴离子的钠盐为亚铁氰化钠或其水合物。
在本公开的一些实施方式中，亚铁氰化物为亚铁氰化钠或亚铁氰化钠的水合物。
在本公开的一些实施方式中，二价过渡金属阳离子和过渡金属氰化物阴离子的摩尔比为(1.0-1.2):1。
在本公开的一些实施方式中，二价过渡金属阳离子和过渡金属氰化物阴离子的摩尔比为(1.05-1.15):1。
在本公开的一些实施方式中，在第一溶液中还含有抗氧化剂。
在本公开的一些实施方式中，抗氧化剂选自抗坏血酸、柠檬酸、葡萄糖和蔗糖中的至少一种。
在本公开的一些实施方式中，抗氧化剂为抗坏血酸。
在本公开的一些实施方式中，抗氧化剂和过渡金属阳离子的摩尔比为(0.5-0.8):1。
在本公开的一些实施方式中，抗氧化剂和过渡金属阳离子的摩尔比为(0.6-0.7):1。
在本公开的一些实施方式中，在第一溶液中过渡金属阳离子的浓度为0.15mol/L-0.30mol/L。
在本公开的一些实施方式中，在第二溶液中过渡金属氰化物阴离子的浓度为0.1mol/L-0.3mol/L。
在本公开的一些实施方式中，第一溶剂和第二溶剂均为水。
在本公开的一些实施方式中，阳离子交换膜的材质选自聚醚醚酮均相阳离子交换膜、全氟乙烯磺酸均相阳离子交换膜和聚砜均相阳离子交换膜中的至少一种。
在本公开的一些实施方式中，包括：将第一溶液置于电化学装置的阳极区中，将第二溶液置于电化学装置的阴极区中，然后进行通电，得到普鲁士蓝材料的悬浮液。
在本公开的一些实施方式中，包括：将第一溶液置于电化学装置的阳极区，通电后使过渡金属阳离子吸附至阴极区的电极板上，然后断电；将第二溶液置于电化学装置的阳极区，然后反向通电，使吸附的过渡金属阳离子解析后进入过渡金属氰化物阴离子所在区域反应，得到普鲁士蓝材料的悬浮液。
在本公开的一些实施方式中，还包括：将得到的普鲁士蓝材料的悬浮液进行陈化、洗涤、分离得到固体物料，将固体物料进行干燥。
在本公开的一些实施方式中，陈化时间为2h-5h。
第二方面，本公开的提供的方案还包括一种普鲁士蓝材料，通过上述任意实施方式中的制备方法制备而得。
在本公开的一些实施方式中，其化学式为NaxM[Fe(CN)6]，其中，M表示二价铁或二价锰，1.5<x<2。
第三方面，本公开的提供的方案还包括上述实施方式中的普鲁士蓝材料作为钠离子电池正极材料的应用。
第四方面，本公开的提供的方案包括一种钠离子电池正极极片，包括正极集流体和附着在正极集流体上的活性涂层，活性涂层中含有上述实施方式中的普鲁士蓝材料。
第五方面，本公开的提供的方案包括一种钠离子电池，包括上述实施方式中的钠离子电池正极极片。
第六方面，本公开的提供的方案包括一种用电装置，包括上述实施方式中的钠离子电池。
本公开采用电化学的原理制备普鲁士蓝材料，用阳离子交换膜将过渡金属阳离子和过渡金属氰化物阴离子分隔开，通电后过渡金属阳离子可以缓慢释放与过渡金属氰化物阴离子反应，通过控制电流可以进一步控制形成沉淀的速度，避免了由于反应速率过快导致的结构缺陷，减少空穴比例的发生。本公开所提供的制备方法用于制备钠离子电池正极材料时，有利于提高产品的电化学性能。
附图说明
为了更清楚地说明本公开实施例的技术方案，下面将对实施例中所需要使用的附 图作简单地介绍，应当理解，以下附图仅示出了本公开的某些实施例，因此不应被看作是对范围的限定，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他相关的附图。
图1为本公开所提供普鲁士蓝材料的制备方法的第一原理图；
图2为本公开所提供普鲁士蓝材料的制备方法的第二原理图；图中，(a)表示通电使阳离子吸附到阴极区电极板上；(b)表示反向通电合成普鲁士蓝材料；
图3为实施例1制备的普鲁士蓝材料的X射线衍射(XRD)图谱；
图4为实施例1制备的普鲁士蓝材料的SEM图。
具体实施方式
下面将结合实施例对本公开的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本公开，而不应视为限制本公开的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
在本公开中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本公开实施例提供一种普鲁士蓝材料的制备方法，采用电化学的原理进行制备，利用阳离子交换膜将过渡金属阳离子和过渡金属氰化物阴离子分隔开，通电后使过渡金属阳离子缓慢释放与过渡金属氰化物阴离子反应形成沉淀。
需要说明的是，传统的制备普鲁士蓝材料的方法，当过渡金属氰化物阴离子(M′(CN)6 m-)与过渡金属阳离子一混合立即就生成沉淀，沉淀速度过快致使普鲁士蓝类正极材料晶体结构中M′(CN)6空穴的比例很高，从而使得空隙水的比例增多，材料极易形成缺陷，材料实际比容量和电化学性能均受到影响。本公开利用电化学的方法，使过渡金属阳离子通过阳离子交换膜缓慢释放，与过渡金属氰化物阴离子反应而沉淀下来，通过控制电流可以更好地控制沉淀速率，操作简便灵活，解决材料制备过程中沉淀过快导致材料结构形成缺陷的问题。
具体而言，可以包括如下步骤：
S1、溶液配制
将含过渡金属阳离子的金属盐和第一溶剂混合得到第一溶液，将含过渡金属氰化物阴离子的钠盐和第二溶剂混合得到第二溶液，配制得到第一溶液和第二溶液备用。
在一些实施方式中，金属盐中的过渡金属阳离子为二价过渡金属阳离子，如可以为二价铁离子和二价锰离子中的至少一种，可以为以上任意一种或几种。优选地，二价过渡金属阳离子为二价铁离子，以提升制备得到普鲁士蓝材料用于钠离子电池正极材料的电化学性能。具体地，二价铁离子所对应的金属盐可以为硫酸亚铁、氯化亚铁、硝酸亚铁等。
在一些实施方式中，含过渡金属氰化物阴离子的钠盐可以为亚铁氰化钠或其水合物中的至少一种，可以为以上任意一种或几种，采用钠盐为原料以通过一步沉淀之后形成钠离子电池用正极材料。优选地，亚铁氰化物为亚铁氰化钠或亚铁氰化钠的水合物，以提升材料的容量和电化学性能。
在一些实施方式中，通过控制第一溶液和第二溶液中的离子用量，使二价过渡金属阳离子和过渡金属氰化物阴离子的摩尔比为(1.0-1.2):1，优选为(1.05-1.15):1，如可以为1.00:1、1.05:1、1.10:1、1.15:1、1.20:1等。
在一些实施方式中，在第一溶液中还含有抗氧化剂，以防止亚铁离子氧化。抗氧化剂的具体种类不限，可以选自抗坏血酸、柠檬酸、葡萄糖和蔗糖中的至少一种，可以为以上任意一种或几种，优选为抗坏血酸。
进一步地，抗氧化剂和过渡金属阳离子的摩尔比为(0.5-0.8):1，优选为(0.6-0.7):1，以起到更好的抗氧化效果。具体地，抗氧化剂和过渡金属阳离子的摩尔可以为0.5:1、0.6:1、0.7:1、0.8:1等。
在一些实施方式中，在第一溶液中过渡金属阳离子的浓度为0.15mol/L-0.30mol/L，如可以为0.15mol/L、0.20mol/L、0.25mol/L、0.30mol/L等。在第二溶液中过渡金属氰化物阴离子的浓度为0.1mol/L-0.3mol/L，如可以为0.10mol/L、0.15mol/L、0.20mol/L、0.25mol/L、0.30mol/L等。
在一些实施方式中，第一溶剂和第二溶剂可以均为水，但不限于此。
S2、利用电化学的方法进行反应
将第一溶液和第二溶液分别置于电化学装置不同的电解槽中，进行通电，使过渡金属阳离子缓慢释放与过渡金属氰化物阴离子反应形成沉淀。
在一些实施方式中，电化学装置包括阴极电解槽、阳极电解槽和阳离子交换膜，阳离子交换膜将阴极电解槽和阳极电解槽分隔开，在阴极电解槽和阳极电解槽中均设置有电极板，两个电极板通过外部线路连通。通电后，阳离子通过阳离子交换膜进入阴极电解槽与阴离子发生反应。
为实现阳离子的缓慢释放，可以有如下两种实现方式，但不限于此：
(1)如图1所示，将第一溶液置于电化学装置的阳极区中，将第二溶液置于电化 学装置的阴极区中，然后进行通电，阳极区中的过渡金属阳离子通过阳离子交换膜进入阴极区，与阴极区中的含过渡金属氰化物阴离子进行反应得到普鲁士蓝材料的悬浮液。
(2)如图2所示，将第一溶液置于电化学装置的阳极区，通电后使过渡金属阳离子吸附至阴极区的电极板上(如(a)所示)，然后断电；将第二溶液置于电化学装置的阳极区，然后反向通电，使吸附的过渡金属阳离子解析后进入过渡金属氰化物阴离子所在区域反应(如(b)所示)，得到普鲁士蓝材料的悬浮液。具体地，将第一溶液置于电化学装置的阳极区，然后通电，使阴极上嵌入金属离子，阳极上嵌入阴离子(如(a)所示)；将第二溶液置于电化学装置的阳极区，反向通电之后，原来的阳极变成阴极，原来的阴极变成阳极，使过渡金属阳离子解析下来，通过阳离子交换膜进入过渡金属氰化物阴离子所在区域反应，形成沉淀。
在一些实施方式中，通电电流为1A-20A，当观察到无沉淀产生后进行断电；优选地，通电电流为5A-15A。通过进一步控制通电电流可以使阳离子释放速率控制在较好范围内，既保证较好的反应速率，也避免了由于沉积速率过快导致的结构缺陷。
在一些实施方式中，电极板均为碳电极板，但不限于此。
在一些实施方式中，阳离子交换膜的材质选自聚醚醚酮均相阳离子交换膜、全氟乙烯磺酸均相阳离子交换膜和聚砜均相阳离子交换膜中的至少一种，可以为以上材质中的任意一种或多种，以上几种阳离子交换膜均为市购材料。
S3、后处理
通过后处理从反应完成后得到的悬浮液中分离得到普鲁士蓝材料。
在一些实施例中，后处理的过程包括将得到的普鲁士蓝材料的悬浮液进行陈化、洗涤、分离得到固体物料，将固体物料进行干燥，以去除表面水分和残留洗涤溶剂。
进一步地，陈化可以是在一般的陈化釜中进行，陈化时间可以为2h-5h，如可以为2h、3h、4h、5h等。洗涤可以是进行多次水洗。分离的具体方法不限，可以为离心分离的方式，但不限于此。干燥可以是在一般的真空干燥箱中进行，干燥温度大致为120℃-320℃，干燥时间大致为12h-48h。
本公开还提供一种普鲁士蓝材料，通过上述制备方法制备而得，具有完整的晶格形貌、低比例的结晶水，同时还具有较高的容量、较长的循环寿命和较为优异的倍率性能。
在一些实施方式中，其化学式为NaxM[Fe(CN)6]，其中，M表示二价铁或二价锰，如化学式可以为NaxFe[Fe(CN)6]，1.5<x<2。x的取值可以为1.5、1.6、1.7、1.8、1.9、2.0等。
本公开还提供一种钠离子电池正极极片，包括正极集流体和附着在正极集流体上的活性涂层，活性涂层中含有上述普鲁士蓝材料，由于普鲁士蓝材料性能的提升可以进一步提升钠离子电池正极极片的性能。
具体地，钠离子电池正极极片的制备过程可以参照现有技术，主要步骤包括：将普鲁士蓝材料、导电剂、粘结剂和溶剂混合形成浆料，将浆料涂覆在正极集流体上，干燥后形成涂层。
本公开还提供一种钠离子电池，包括上述钠离子电池正极极片，还包括负极极片、电解液、隔膜等，具体的材料种类不限。
本公开还提供一种用电装置，包括上述钠离子电池，利用钠离子电池进行供电，具体的用电器不限。
以下结合实施例对本公开的特征和性能作进一步的详细描述。
需要说明的是，以下实施例采用的电化学装置均包括：阳极电解槽、阴极电解槽、阳离子交换膜(材质为全氟乙烯磺酸均相阳离子交换膜)、含碳电极板(石墨电极)，阳离子交换膜将阳极电解槽、阴极电解槽分隔开。试验温度为26℃。
实施例1
本实施例提供了一种普鲁士蓝材料的制备方法，包括以下步骤：
(1)溶液配制
取硫酸亚铁、抗坏血酸分别溶于500毫升去离子水中得到溶液I，溶液I中硫酸亚铁浓度为0.22mol/L，抗坏血酸浓度为0.14mol/L。
将十水合亚铁氰化钠溶解于500毫升去离子水中，得到亚铁氰化钠浓度为0.2mol/L的溶液II。
(2)利用电化学的方法进行反应
将溶液I加入到电化学装置的阳极区中，将溶液II加入到电化学装置的阴极区。进行通电，通电电流为10A，亚铁离子通过阳离子交换膜进入负极区域，与氰化物阴离子(M′(CN)6 m-)形成沉淀，当观察到无沉淀产生后进行断电，得到普鲁士蓝材料的悬浮液。
(3)后处理
将上述悬浮液经陈化3小时，再经3次水洗、离心分离后得到固体物料，将固体物料在200℃的条件下真空干燥24h。
注：本实施例中，二价过渡金属阳离子和过渡金属氰化物阴离子的摩尔比为1.1:1，抗氧化剂和过渡金属阳离子的摩尔比为0.64:1。
实施例2
本实施例提供了一种普鲁士蓝材料的制备方法，包括以下步骤：
(1)溶液配制
取硫酸亚铁、抗坏血酸分别溶于500毫升去离子水中得到溶液I，溶液I中硫酸亚铁浓度为0.24mol/L，抗坏血酸浓度为0.19mol/L。
将十水合亚铁氰化钠溶解于500毫升去离子水中，得到亚铁氰化钠浓度为0.2mol/L的溶液II。
(2)利用电化学的方法进行反应
将溶液I加入到电化学装置的阳极区，通电电流为20A，通电时间为550min，使亚铁离子完全被吸附到阴极区电极板上(如图2中(a)所示)，然后断电；将溶液II加入到电化学装置的阳极区，对电化学装置进行反向通电，通电电流为15A，亚铁离子通过阳离子交换膜进入负极区域(反向通电后的负极区域)，与氰化物阴离子(M′(CN)6 m-)开始形成沉淀，当观察到无沉淀产生后进行断电，得到普鲁士蓝材料的悬浮液。
(3)后处理
将上述悬浮液经陈化3小时，再经3次水洗、离心分离后得到固体物料，将固体物料在200℃的条件下真空干燥24h。
实施例3
与实施例1的区别仅在于：通电电流为5A。
实施例4
与实施例1的区别仅在于：通电电流为15A。
实施例5
与实施例1的区别仅在于：通电电流为20A。
实施例6
与实施例1的区别仅在于：通电电流为25A。
实施例7
与实施例1的区别仅在于：通电电流为1A。
实施例8
与实施例1的区别仅在于：溶液II中亚铁氰化钠浓度为0.24mol/L，使二价过渡金属阳离子和过渡金属氰化物阴离子的摩尔比为1.0:1。
实施例9
与实施例1的区别仅在于：溶液II中亚铁氰化钠浓度为0.18mol/L，使二价过渡金属阳离子和过渡金属氰化物阴离子的摩尔比为1.2:1。
实施例10
与实施例1的区别仅在于：溶液II中亚铁氰化钠浓度为0.275mol/L，使二价过渡金属阳离子和过渡金属氰化物阴离子的摩尔比为0.8:1。
实施例11
与实施例1的区别仅在于：溶液II中亚铁氰化钠浓度为0.147mol/L，使二价过渡金属阳离子和过渡金属氰化物阴离子的摩尔比为1.5:1。
实施例12
与实施例1的区别仅在于：溶液I中将抗坏血酸替换为等摩尔量的柠檬酸。
实施例13
与实施例1的区别仅在于：溶液I中将抗坏血酸替换为等摩尔量的葡萄糖。
实施例14
与实施例1的区别仅在于：溶液I中抗坏血酸的浓度为0.11mol/L，使抗氧化剂和过渡金属阳离子的摩尔比为0.5:1。
实施例15
与实施例1的区别仅在于：溶液I中抗坏血酸的浓度为0.176mol/L，使抗氧化剂和过渡金属阳离子的摩尔比为0.8:1。
实施例16
与实施例1的区别仅在于：溶液I中抗坏血酸的浓度为0.066mol/L，使抗氧化剂和过渡金属阳离子的摩尔比为0.3:1。
实施例17
与实施例1的区别仅在于：溶液I中抗坏血酸的浓度为0.22mol/L，使抗氧化剂和过渡金属阳离子的摩尔比为1.0:1。
对比例1
本对比例提供一种传统的制备普鲁士蓝材料的方法，包括如下步骤：
(1)取硫酸亚铁、抗坏血酸分别溶于50毫升去离子水中得到溶液I，溶液I中硫酸亚铁浓度为0.22mol/L，抗坏血酸浓度为0.14mol/L。
将十水合亚铁氰化钠溶解于50毫升去离子水中，得到亚铁氰化钠浓度为0.2mol/L的溶液II。
(2)将溶液I和溶液II同时加入到100毫升去离子水中，在26℃下经共沉淀反应，形成普鲁士蓝悬浮液。
(3)将上述悬浮液经陈化3小时，再经3次水洗、离心分离后得到固体物料，将固体物料在200℃的条件下真空干燥24h。
试验例1
测试实施例和对比例制备得到的普鲁士蓝正极材料的性能，结果如表1所示。
测试方法：(1)纽扣钠离子电池的组装：将实施例中所制备的普鲁士蓝正极材料、乙炔黑以及聚偏氟乙烯(PVDF)按照7:2:1的质量比进行混合，并将混合均匀后的浆料涂覆在铝箔上，干燥后剪切成圆片，作为正极；金属钠片作为负极，Whatman玻璃纤维(GF/D)为隔膜；有机系电解液由NaClO4、EC(碳酸乙烯酯)、DEC(碳酸二乙酯)和FEC(氟代碳酸乙烯酯)配制而成，NaClO4浓度为1.0mol/L，EC与DEC的体积比为1:1，FEC在电解液中的质量分数为5％；在氩气手套箱内组装成钠离子电池；
其中，循环性能在25℃(1C/1C 2.0～4.3V)下进行测试；克容量在25mA/g大小的电流下进行测试。
表1普鲁士蓝正极材料的电化学性能测试结果
可见，相较于常规的普鲁士蓝制备方法，本方案制备的材料具有容量保持率较好的优势。
从实施例1和实施例3-7的测试结果可以看出，施加电流对产品的性能有一定影响，实施例1、实施例3和实施例4效果最好，即施加电流为5A-15A为宜。
从实施例1和实施例8-11可以看出，二价过渡金属阳离子和过渡金属氰化物阴离子的摩尔比为0.8-1.5:1，均能够使产品具有较好的容量保持率。
从实施例1和实施例12-17可以看出，抗氧化剂的种类和用量对产品的性能影响不大。
试验例2
采用电感耦合等离子体发射光谱仪(ICP)，对所制备的普鲁士蓝正极材料每分子含缺陷数进行测试，其结果如表2所示。
表2普鲁士蓝正极材料的缺陷情况测试结果
可以看出，实施例制备得到的普鲁士蓝正极材料的缺陷数明显小于对比例1。
从实施例1和实施例3-6的测试结果可以看出，施加电流对产品的缺陷情况有一定影响，实施例1、实施例3和实施例4效果最好，即施加电流为5A-15A为宜。
从实施例1和实施例8-11可以看出，二价过渡金属阳离子和过渡金属氰化物阴离子的摩尔比为0.8-1.5:1，均能够显著降低产品缺陷。
从实施例1和实施例12-17可以看出，抗氧化剂的种类和用量对产品的缺陷情况影响不大。
试验例3
测试实施例1制备得到普鲁士蓝材料的XRD图，如图3所示。可以看出，说明所制备的产物是纯相的立方体型普鲁士蓝正极材料；尖锐的峰型说明所制备的普鲁士蓝正极材料结晶度很高。
测试实施例1制备得到普鲁士蓝材料的SEM图，如图4所示。可以看出，所制备的普鲁士蓝正极材料为立方体形状，且具有平滑的表面。
以上详细描述了本公开的优选实施方式，但是，本公开并不限于此。在本公开的技术构思范围内，可以对本公开的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本公开所公开的内容，均属于本公开的保护范围。
工业实用性
本公开采用电化学的原理制备普鲁士蓝材料，用阳离子交换膜将过渡金属阳离子和过渡金属氰化物阴离子分隔开，通电后过渡金属阳离子可以缓慢释放与过渡金属氰化物阴离子反应，通过控制电流可以进一步控制形成沉淀的速度，避免了由于反应速率过快导致的结构缺陷，减少空穴比例的发生。利用简便的电化学装置即可完成反应，操作方便，且反应速率便于精确控制，具有非常好的工业实用性。

Claims (30)

  1. 一种普鲁士蓝材料的制备方法，其特征在于，包括：利用阳离子交换膜将过渡金属阳离子和过渡金属氰化物阴离子分隔在电化学装置的两个电解槽中，通过电化学的方法进行制备。
  2. 根据权利要求1所述的制备方法，其特征在于，包括：将第一溶液和第二溶液分别置于所述电化学装置不同的电解槽中，进行通电；
    其中，所述第一溶液中包括：第一溶剂和含所述过渡金属阳离子的金属盐；
    所述第二溶液中包括：第二溶剂和含所述过渡金属氰化物阴离子的钠盐。
  3. 根据权利要求2所述的制备方法，其特征在于，通电电流为1A-20A。
  4. 根据权利要求3所述的制备方法，其特征在于，通电电流为5A-15A。
  5. 根据权利要求2-4中任一项所述的制备方法，其特征在于，所述金属盐中的所述过渡金属阳离子为二价过渡金属阳离子。
  6. 根据权利要求5所述的制备方法，其特征在于，所述二价过渡金属阳离子选自二价铁离子和二价锰离子中的至少一种。
  7. 根据权利要求6所述的制备方法，其特征在于，所述二价过渡金属阳离子为二价铁离子。
  8. 根据权利要求5-7中任一项所述的制备方法，其特征在于，含所述过渡金属氰化物阴离子的钠盐为亚铁氰化钠或其水合物。
  9. 根据权利要求8所述的制备方法，其特征在于，含所述过渡金属氰化物阴离子的钠盐为亚铁氰化钠或其水合物。
  10. 根据权利要求9所述的制备方法，其特征在于，所述二价过渡金属阳离子和所述过渡金属氰化物阴离子的摩尔比为(1.0-1.2):1。
  11. 根据权利要求10所述的制备方法，其特征在于，所述二价过渡金属阳离子和所述过渡金属氰化物阴离子的摩尔比为(1.05-1.15):1。
  12. 根据权利要求2-11中任一项所述的制备方法，其特征在于，在所述第一溶液中还含有抗氧化剂。
  13. 根据权利要求12所述的制备方法，其特征在于，所述抗氧化剂选自抗坏血酸、柠檬酸、葡萄糖和蔗糖中的至少一种。
  14. 根据权利要求13所述的制备方法，其特征在于，所述抗氧化剂为抗坏血酸。
  15. 根据权利要求12-14中任一项所述的制备方法，其特征在于，所述抗氧化剂和所述过渡金属阳离子的摩尔比为(0.5-0.8):1。
  16. 根据权利要求15所述的制备方法，其特征在于，所述抗氧化剂和所述过渡金属 阳离子的摩尔比为(0.6-0.7):1。
  17. 根据权利要求2-16中任一项所述的制备方法，其特征在于，在所述第一溶液中过渡金属阳离子的浓度为0.15mol/L-0.30mol/L。
  18. 根据权利要求2-17中任一项所述的制备方法，其特征在于，在所述第二溶液中过渡金属氰化物阴离子的浓度为0.1mol/L-0.3mol/L。
  19. 根据权利要求2-18中任一项所述的制备方法，其特征在于，所述第一溶剂和所述第二溶剂均为水。
  20. 根据权利要求2-19中任一项所述的制备方法，其特征在于，所述阳离子交换膜的材质选自聚醚醚酮均相阳离子交换膜、全氟乙烯磺酸均相阳离子交换膜和聚砜均相阳离子交换膜中的至少一种。
  21. 根据权利要求2-20中任一项所述的制备方法，其特征在于，包括：将所述第一溶液置于所述电化学装置的阳极区中，将所述第二溶液置于所述电化学装置的阴极区中，然后进行通电，得到普鲁士蓝材料的悬浮液。
  22. 根据权利要求2-20中任一项所述的制备方法，其特征在于，包括：将所述第一溶液置于所述电化学装置的阳极区，通电后使过渡金属阳离子吸附至阴极区的电极板上，然后断电；将所述第二溶液置于所述电化学装置的阳极区，然后反向通电，使吸附的过渡金属阳离子解析后进入所述过渡金属氰化物阴离子所在区域反应，得到普鲁士蓝材料的悬浮液。
  23. 根据权利要求21或22所述的制备方法，其特征在于，还包括：将得到的所述普鲁士蓝材料的悬浮液进行陈化、洗涤、分离得到固体物料，将所述固体物料进行干燥。
  24. 根据权利要求23所述的制备方法，其特征在于，陈化时间为2h-5h。
  25. 一种普鲁士蓝材料，其特征在于，通过权利要求1-24中任一项所述的制备方法制备而得。
  26. 根据权利要求25所述的普鲁士蓝材料，其特征在于，其化学式为NaxM[Fe(CN)6]，其中，M表示二价铁或二价锰，1.5<x<2。
  27. 权利要求26所述的普鲁士蓝材料作为钠离子电池正极材料的应用。
  28. 一种钠离子电池正极极片，其特征在于，包括正极集流体和附着在所述正极集流体上的活性涂层，所述活性涂层中含有权利要求26中所述普鲁士蓝材料。
  29. 一种钠离子电池，其特征在于，包括权利要求28所述的钠离子电池正极极片。
  30. 一种用电装置，其特征在于，包括权利要求29所述的钠离子电池。
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