WO2024250134A1 - Procédé de préparation d'un matériau bleu de prusse, et matériau bleu de prusse et son utilisation - Google Patents

Procédé de préparation d'un matériau bleu de prusse, et matériau bleu de prusse et son utilisation 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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Prior art keywords
transition metal
preparation
prussian blue
solution
divalent
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English (en)
Chinese (zh)
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/fr
Publication of WO2024250134A1 publication Critical patent/WO2024250134A1/fr
Anticipated expiration legal-status Critical
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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

La présente divulgation appartient au domaine technique des matériaux bleu de Prusse, et concerne en particulier un procédé de préparation d'un matériau bleu de Prusse, ainsi qu'un matériau bleu de Prusse et son utilisation. Le matériau bleu de Prusse est préparé selon des principes électrochimiques, et des cations de métal de transition et des anions de cyanure de métal de transition sont séparés au moyen d'une membrane échangeuse de cations. Après excitation, les cations de métal de transition peuvent être lentement libérés et réagir avec les anions de cyanure de métal de transition, et la vitesse de formation de précipité peut être en outre commandée par commande d'un courant, de telle sorte que des défauts de structure provoqués par un taux de réaction très rapide sont évités. Le procédé de préparation est avantageux pour améliorer les performances électrochimiques d'un produit lorsqu'il est utilisé pour préparer un matériau d'électrode positive pour une batterie sodium-ion.
PCT/CN2023/098256 2023-06-05 2023-06-05 Procédé de préparation d'un matériau bleu de prusse, et matériau bleu de prusse et son utilisation Ceased WO2024250134A1 (fr)

Priority Applications (2)

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CN202380009316.4A CN116981797A (zh) 2023-06-05 2023-06-05 一种普鲁士蓝材料的制备方法、普鲁士蓝材料及应用
PCT/CN2023/098256 WO2024250134A1 (fr) 2023-06-05 2023-06-05 Procédé de préparation d'un matériau bleu de prusse, et matériau bleu de prusse et son utilisation

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PCT/CN2023/098256 WO2024250134A1 (fr) 2023-06-05 2023-06-05 Procédé de préparation d'un matériau bleu de prusse, et matériau bleu de prusse et son utilisation

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