WO2024066182A1 - Matériau d'électrode positive aux à ions sodium de type prusse et son procédé de recyclage - Google Patents

Matériau d'électrode positive aux à ions sodium de type prusse et son procédé de recyclage Download PDF

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WO2024066182A1
WO2024066182A1 PCT/CN2023/077899 CN2023077899W WO2024066182A1 WO 2024066182 A1 WO2024066182 A1 WO 2024066182A1 CN 2023077899 W CN2023077899 W CN 2023077899W WO 2024066182 A1 WO2024066182 A1 WO 2024066182A1
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solution
prussian
positive electrode
sodium ion
electrode material
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PCT/CN2023/077899
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English (en)
Chinese (zh)
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谢英豪
李爱霞
余海军
李长东
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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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Publication of WO2024066182A1 publication Critical patent/WO2024066182A1/fr

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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • 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
    • 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
    • H01M4/58—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the embodiments of the present application relate to the field of battery technology, for example, a Prussian sodium ion positive electrode material and a recovery method thereof.
  • Prussian sodium ion cathode materials are a type of sodium ion battery cathode materials with an open framework structure. It belongs to the metal-organic framework structure.
  • the metal and ferrocyanide in the lattice are arranged according to Fe—C ⁇ N—M to form a three-dimensional structural skeleton.
  • the Fe ions and metal M ions are arranged in a cubic shape, and the C ⁇ N roots are located on the edges of the cube.
  • This type of material belongs to the cubic crystal system, with a particle size of about 20 to 50 nm, and has a three-dimensional sodium ion insertion and extraction channel.
  • the embodiment of the present application provides a method for improving the recovery rate of ferrocyanate to reduce the pressure on the environment, and obtains a Prussian sodium ion positive electrode material with good regeneration performance and a recovery method thereof.
  • a method for recovering a Prussian sodium ion cathode material comprises the following steps:
  • the positive electrode material is cleaned or soaked with an acidic solution to obtain a solution A;
  • the solution C is filtered to obtain a filter residue
  • the filter residue is dried to obtain a Prussian sodium ion positive electrode material.
  • the acidic solution is a non-oxidizing acid solution.
  • the pH of the solution A is 3-6.
  • the complexing agent solution includes at least one of maleic acid, citric acid, citric acid, EDTA, sodium citrate and ammonia water.
  • the concentration of the complexing agent solution is 0.4 mol/L to 15 mol/L.
  • the preset concentration of the transition metal ion is 0.4 mol/L to 2 mol/L;
  • the preset concentration of ferrocyanate is 0.3 mol/L to 0.6 mol/L.
  • the preset concentration of the sodium ions is 0.3 mol/L to 0.6 mol/L.
  • the mixed reaction is carried out at a pH of 6.5 to 9.5 and an inert atmosphere.
  • the drying conditions are: temperature of 50° C. to 80° C., and time of 8 h to 12 h.
  • the filtrate obtained by filtering the solution C is recycled.
  • the acidic solution is an inorganic acid that does not react with the filtering metal.
  • a Prussian sodium ion positive electrode material is produced by the Prussian sodium ion positive electrode material recovery method described in any of the above embodiments.
  • the embodiments of the present application have at least the following advantages:
  • the above-mentioned Prussian sodium ion positive electrode material recovery method uses an acidic solution to clean or soak the positive electrode material so that the active substance on the positive electrode material can be dissolved in the acidic solution to obtain solution A, that is, the transition metal ions, sodium ions and acid-soluble substances such as ferrocyanate in the positive electrode material are free in the acidic solution to form solution A, and then the transition metal ion concentration, ferrocyanate concentration and sodium ion concentration in solution A are adjusted to a preset concentration, and then solution B and a complexing agent solution are mixed and reacted so that ferrocyanate can react with transition metal ions and sodium ions to precipitate to generate Prussian crystals, and finally solution C is filtered, and the filtered residue is dried to obtain a Prussian crystal with good regeneration performance.
  • the low-toxic [Fe(CN) 6 ] 4- in the discarded Prussian sodium battery can be recycled, avoiding the direct discard of the Prussian sodium ion positive electrode material causing greater pressure on the environment, thereby protecting the ecological balance.
  • the produced Prussian sodium ion positive electrode material has good regeneration performance, meets the market requirements, and can be directly put into production, thereby reducing the production cost of the Prussian sodium ion battery.
  • FIG1 is a flow chart of a method for recovering a Prussian sodium ion cathode material according to an embodiment of the present application
  • FIG. 2 is a SEM image of a Prussian sodium ion positive electrode material product according to an embodiment of the present application.
  • the embodiment of the present application provides a method for recovering a Prussian sodium ion positive electrode material, comprising the following steps: obtaining a positive electrode material; washing or soaking the positive electrode material with an acidic solution to obtain a solution A; The concentrations of transition metal ions, ferrocyanate and sodium ions in the solution A are adjusted to preset concentrations to obtain a solution B; a complexing agent solution is added to the solution B for a mixing reaction to obtain a solution C; the solution C is filtered to obtain a filter residue; the filter residue is dried to obtain a Prussian sodium ion positive electrode material.
  • the above-mentioned Prussian sodium ion positive electrode material recovery method uses an acidic solution to wash or soak the positive electrode material so that the active material on the positive electrode material can be dissolved in the acidic solution to obtain solution A, that is, the transition metal ions, sodium ions and acid-soluble substances such as ferrocyanate in the positive electrode material are free in the acidic solution to form solution A, and then the transition metal ion concentration, ferrocyanate concentration and sodium ion in solution A are adjusted to a preset concentration, and then solution B and the complexing agent solution are mixed and reacted so that ferrocyanate can react with transition metal ions and sodium ions to precipitate and generate Prussian crystals, and finally solution C is filtered, and the filtered residue is dried to obtain a Prussian sodium ion positive electrode material with good regeneration performance.
  • the above-mentioned recovery method can recycle the low-toxic [Fe(CN) 6 ] 4- in the discarded Prussian sodium battery, avoiding the direct discard of the Prussian sodium ion positive electrode material from causing greater pressure on the environment, thereby protecting the ecological balance.
  • the produced Prussian sodium-ion positive electrode material has good regeneration performance, meets market requirements, and can be directly put into production, thereby reducing the production cost of Prussian sodium-ion batteries.
  • a Prussian sodium ion cathode material recovery method includes some or all of the following steps:
  • solution A washing or soaking the positive electrode material with an acidic solution to obtain solution A.
  • the positive electrode material obtained from the waste Prussian sodium ion battery includes aluminum foil and active material
  • the positive electrode material is washed or soaked with an acidic solution to dissolve the active material, so that the transition metal ions, sodium ions and acid-soluble substances such as ferrocyanate in the active material are freed in the acidic solution to form solution A, thereby achieving separation of the aluminum foil and the active material, so that the active material can be better collected later.
  • the final Prussian sodium-ion battery positive electrode material often contains more ferrocyanide vacancy defects and crystal water.
  • ferrocyanide vacancy defects will reduce the structural stability of the Prussian sodium-ion battery positive electrode material, and the repeated insertion and extraction of sodium ions may cause the structure of the Prussian sodium-ion battery positive electrode material to collapse.
  • crystal water will occupy the position of ferrocyanide vacancy defects or the gap position of the crystal structure, thereby hindering the transport of sodium ions in the crystal structure, thereby reducing the conductivity of the Prussian sodium-ion battery.
  • the present application performs a mixed reaction on solution B and the complexing agent solution so that the complexing agent solution can effectively inhibit the reaction rate of the transition metal ions and ferrocyanide, thereby effectively avoiding the phenomenon that the vacancy defects of the Prussian crystals generated by the excessively fast reaction rate of the transition metal ions and ferrocyanide are more serious, so that the prepared Prussian sodium ion positive electrode material has good regeneration performance.
  • the regenerated Prussian sodium ion positive electrode material has good morphology and meets the requirements for market sales.
  • the above-mentioned Prussian sodium ion positive electrode material recovery method uses an acidic solution to wash or soak the positive electrode material so that the active material on the positive electrode material can be dissolved in the acidic solution to obtain solution A, that is, the transition metal ions, sodium ions and acid-soluble substances such as ferrocyanate in the positive electrode material are free in the acidic solution to form solution A, and then the transition metal ion concentration, ferrocyanate concentration and sodium ion in solution A are adjusted to a preset concentration, and then solution B and the complexing agent solution are mixed and reacted so that ferrocyanate can react with transition metal ions and sodium ions to precipitate and generate Prussian crystals, and finally solution C is filtered, and the filtered residue is dried to obtain a Prussian sodium ion positive electrode material with good regeneration performance.
  • the above-mentioned recovery method can recycle the low-toxic [Fe(CN) 6 ] 4- in the discarded Prussian sodium battery, avoiding the direct discard of the Prussian sodium ion positive electrode material from causing greater pressure on the environment, thereby protecting the ecological balance.
  • the above-mentioned recovery method is used to produce the Prussian sodium ion
  • the positive electrode material has good regeneration performance, meets market requirements, and can be directly put into production, thereby reducing the production cost of Prussian-type sodium-ion batteries.
  • the acidic solution is a non-oxidizing acid solution. It is understandable that since the cathode material obtained from the waste Prussian sodium ion battery contains a large amount of ferrocyanide, and ferrocyanide is easy to generate ferrocyanide under the oxidant, and ferrocyanide is more likely to undergo hydration than ferrocyanide to produce toxic hydrocyanic acid, thereby causing greater harm to the human body.
  • the acidic solution of the present application is a non-oxidizing acid, which can ensure that the transition metal ions, sodium ions and ferrocyanate on the active material are freed from the non-oxidizing acid to form solution A, and the added non-oxidizing acid can effectively inhibit the oxidation of ferrocyanide to ferrocyanide, so as to improve the recovery rate of ferrocyanide, and at the same time, it can also avoid the generation of ferrocyanide with higher toxicity, so as to ensure the safety of the Prussian sodium ion cathode material in the recovery process, so as to reduce the harm of toxic hydrocyanic acid to the human body and the environment.
  • the present application adopts a non-oxidizing acid, which can ensure that ferrocyanide is not easily decomposed under the conditions of non-oxidizing acid, so as to ensure that the structure of ferrocyanide will not change to the greatest extent, thereby improving the recovery rate of ferrocyanide.
  • the added non-oxidizing acid can also effectively inhibit the oxidation of ferrocyanide to ferrocyanide, so as to further improve the recovery rate of ferrocyanide.
  • it can also avoid the generation of highly toxic ferrocyanide, so as to ensure the safety of Prussian sodium ion positive electrode materials during the recovery process, so as to reduce the harm of toxic hydrocyanic acid to human body and environment.
  • the non-oxidizing acid solution includes at least one of a dilute HCl solution, a H 2 CO 3 solution, a dilute sulfuric acid solution, and a phosphoric acid solution. It is understood that the non-oxidizing acid solution refers to a type of acid solution that ionizes H + when dissolved in water and has weak oxidizing properties, so as to effectively avoid the decomposition of ferrocyanide and improve the recovery rate of ferrocyanide.
  • the pH of the solution A is 3 to 6. It can be understood that since ferrocyanide is easily oxidized to ferrocyanide under strong acidic conditions, the present application uses a non-oxidizing acid to directly dissolve the active substance and controls the pH of the solution A to be 3 to 6, which can provide a warm and stable environment for ferrocyanide. and conditions to better avoid the oxidative decomposition of ferrocyanide, thereby ensuring the recovery rate of ferrocyanide and avoiding the formation of ferrocyanide, thereby increasing the maximum benefit of recycling discarded Prussian sodium-ion batteries, thereby reducing harm to the environment and human body and improving the safety of the recycling process.
  • the concentration of the non-oxidizing acid solution is 0.05mol/L to 0.5mol/L. It is understandable that if the concentration is lower than 0.05mol/L, it is difficult to ensure that the non-oxidizing acid solution can fully dissolve the active substance from the aluminum foil, which is likely to cause a low recovery rate of ferrocyanide; if the concentration of the non-oxidizing acid solution is higher than 0.5mol/L, it is easy to cause ferrocyanide to decompose. Therefore, the present application controls the concentration of the non-oxidizing acid solution to 0.05mol/L to 0.5mol/L.
  • the added non-oxidizing acid solution can not only fully dissolve the active substance on the aluminum foil, but also avoid the phenomenon that ferrocyanide is easily oxidized to ferrocyanide with higher toxicity. In this way, not only the recovery rate of ferrocyanide is improved, but also the safety of the recovery process is ensured.
  • the following step is also included: dismantling the discarded Prussian sodium ion battery to separate the positive electrode material, the negative electrode material and the separator, so as to obtain the positive electrode material.
  • the step of washing or soaking the positive electrode material with an acidic solution includes the following specific steps: scraping the active substance on the aluminum foil into a non-oxidizing acid solution to obtain a mixed solution to quickly separate the aluminum foil from the active substance, thereby improving production efficiency; washing or soaking the positive electrode material with the mixed solution to fully dissolve the active substance remaining on the aluminum foil to achieve comprehensive recovery of ferrocyanide in the positive electrode material, thereby improving the recovery rate of ferrocyanide.
  • the following step is also included: detecting the concentrations of transition metal ions, ferrocyanate and sodium ions in the solution A.
  • the concentrations of transition metal ions, ferrocyanate and sodium ions in solution A are detected by using an ICP (Inductive Coupled Plasma Emission Spectrometer) inductively coupled plasma spectrometer to quickly obtain the actual concentrations of transition metal ions, ferrocyanate and sodium ions in solution A, so as to better adjust the concentrations of transition metal ions, ferrocyanate and sodium ions in solution A to meet the requirements for preparing regenerated Prussian sodium ion positive electrode materials.
  • ICP Inductive Coupled Plasma Emission Spectrometer
  • each detection unit can detect the concentration of a corresponding element, so that It is able to realize the rapid detection of transition metal ions, ferrocyanate and sodium ions in solution A, thereby improving the recovery efficiency.
  • the complexing agent solution includes at least one of maleic acid, citric acid, citric acid, EDTA, sodium citrate and ammonia water.
  • the complexing agent solution is a mixture of maleic acid, EDTA and sodium citrate. It can be understood that since the added maleic acid has good scale inhibition performance, can adsorb impurities, has good colloidal properties and dispersing effects, it can not only improve the dispersibility of the complexing agent to ensure the preparation of uniform Prussian crystals with less impurities, but also cooperate with the use of EDTA and sodium citrate. The added EDTA and sodium citrate can effectively improve the complexing ability, complexing capacity and biodegradability of the complexing agent to obtain a complexing agent with higher complexing capacity, stronger complexing ability and good biodegradability.
  • the addition of the compounded complexing agent is beneficial to the dispersibility of the complexing agent in solution B on the one hand, thereby facilitating the generation of uniform Prussian crystals with less impurities, so as to reduce the vacancy defects and crystal water content of the Prussian crystals, and obtain Prussian sodium ion positive electrode materials with excellent electrochemical properties; on the other hand, it helps to improve the biodegradability of the complexing agent to reduce the pressure on the environment, and on the other hand, it also ensures that the complexing capacity is higher to improve the recovery rate of ferrocyanide and the Prussian crystals with more stable complexing ability are obtained, so as to ensure that the Prussian crystals with more stable structure are obtained.
  • the added sodium citrate can also provide sodium ions to provide sufficient sodium source for Prussian crystals, thereby ensuring that ferrocyanide, transition metal ions and sodium ions can fully and comprehensively react to improve the recovery rate of ferrocyanide.
  • the mass ratio of maleic acid, EDTA and sodium citrate is 1: (0.5-0.8): 1. It can be understood that by compounding maleic acid, EDTA and sodium citrate in a mass ratio of 1: (0.5-0.8): 1, a complexing agent with good dispersibility, easy degradation, high complexing capacity and strong complexing ability can be obtained.
  • the concentration of the complexing agent solution is 0.4 mol/L to 15 mol/L, so as to ensure that the complexing agent can better control the reaction rate of ferrocyanide and transition metal ions, so as to effectively slow down the speed of forming Prussian crystals, reduce the vacancy defects and crystal water content of Prussian crystals, and obtain Prussian sodium ion positive electrode materials with excellent electrochemical properties.
  • the step of adjusting the concentrations of transition metal ions, ferrocyanate and sodium ions in the solution A to preset concentrations includes the following specific steps: first adjusting the concentration of ferrocyanate, then adjusting the concentration of transition metal ions, and finally adjusting the concentration of sodium ions.
  • the present application first adjusts the ferrocyanate in solution A to increase the concentration of ferrocyanate in solution A, thereby reducing the vacancy defects of ferrocyanate generated by Prussian crystals, that is, ensuring that under the condition of a higher concentration of ferrocyanate, the vacancy defects of ferrocyanate formed by ferrocyanate in Prussian crystals are less, which is conducive to the generation of Prussian crystals with fewer vacancy defects, and then replenishes the concentration of transition metal ions to a preset concentration to ensure that the recovered transition metal ions can fully react with ferrocyanate, and then ferrocyanate reacts with the subsequently added transition metal ions, that is, the transition metal ions and ferrocyanate react in stages to better slow down the excessive reaction rate of the transition metal ions and ferrocyanate to cause the generation of Prussian crystals with more serious vacancy defects, and finally adjusts the sodium ions so that the generated Prussian crystals can meet the requirements of regeneration performance.
  • the transition metal ion concentration is adjusted by using a transition metal salt so that the transition metal ion concentration reaches a preset requirement.
  • the preset concentration of the transition metal ion is 0.4 mol/L to 2 mol/L to ensure that the transition metal ions in solution B meet the production requirements of the regenerated Prussian sodium ion positive electrode material.
  • the concentration of transition metal ions is adjusted by using ferrocyanate, so that the concentration of ferrocyanate reaches the preset requirement.
  • the preset concentration of ferrocyanate is 0.3 mol/L to 0.6 mol/L, so as to ensure that the ferrocyanate in solution B reaches the production requirement of the regenerated Prussian sodium ion positive electrode material.
  • sodium salt is used to adjust the transition metal ion concentration so that the ferrocyanate concentration reaches a preset requirement.
  • the preset concentration of sodium ions is 0.3 mol/L to 0.6 mol/L to ensure that the sodium ions in solution B meet the production requirements of the regenerated Prussian sodium ion positive electrode material.
  • the transition metal salt includes at least one of a divalent Mn salt, a divalent Fe salt, a divalent Co salt, a divalent Ni salt, a divalent Cu salt and a divalent Zn salt, so as to adjust the transition metal concentration.
  • the divalent Mn salt includes at least one of MnCl 2 and MnSO 4 .
  • the divalent Fe salt includes at least one of FeCl 2 and FeSO 4 .
  • the divalent Co salt includes at least one of CoCl 2 and CoSO 4 .
  • the divalent Ni salt includes at least one of NiCl 2 and NiSO 4 .
  • the divalent Cu salt includes at least one of CuCl 2 and CuSO 4 .
  • the divalent Zn salt includes at least one of ZnCl 2 and ZnSO 4 .
  • the ferrocyanide-containing salt includes at least one of potassium ferrocyanide and sodium ferrocyanide.
  • the sodium salt includes at least one of NaCl 2 and NaSO 4 .
  • the step of mixing the solution B and the complexing agent solution comprises the following specific steps: adding water to the reactor for preheating, and passing the solution B and the complexing agent solution into the reactor for mixing reaction, so as to achieve the mixing reaction of the solution B and the complexing agent solution.
  • the mixing reaction is carried out under the conditions of pH 6.5 to 9.5 and inert atmosphere to ensure the normal reaction of the solution B and the complexing agent solution.
  • the flow ratio of the solution B and the complexing agent solution is 1 to 1, so as to ensure that the complexing agent solution can be better mixed with the solution B, so as to more effectively suppress the speed of generating Prussian crystals, so as to obtain Prussian crystals with fewer vacancy defects.
  • the preheating temperature is 40°C to 50°C.
  • the following step is further included: performing an aging reaction on the solution C.
  • the aging reaction on the solution C is conducive to the formation of Prussian crystals, so as to avoid the formation of Prussian crystals with more vacancy defects.
  • the aging time is 8h to 10h.
  • the drying conditions are: temperature of 50°C to 80°C, time of 8h to 12h, so as to effectively remove moisture from the filter residue to ensure that a Prussian sodium ion positive electrode material with good regeneration performance is obtained.
  • the filtrate obtained by filtering the solution C is recycled. It can be understood that since the filtrate obtained after filtration is a complexing agent solution, the complexing agent solution can be recycled to reduce the production cost of recycling.
  • the present application embodiment also provides a Prussian sodium ion positive electrode material, which is produced by the Prussian sodium ion positive electrode material recovery method described in any of the above embodiments. It can be understood that the Prussian sodium ion positive electrode material produced by the above Prussian sodium ion positive electrode material recovery method can obtain a good regeneration performance, that is, the electrical performance of the Prussian sodium ion positive electrode material sold on the market can be achieved, thereby realizing the recycling of the low-toxic [Fe(CN) 6 ] 4- in the discarded Prussian sodium battery, avoiding the direct discard of the Prussian sodium ion positive electrode material causing greater pressure on the environment, thereby protecting the ecological balance.
  • the embodiments of the present application have at least the following advantages:
  • the above-mentioned Prussian sodium ion positive electrode material recovery method uses an acidic solution to wash or soak the positive electrode material so that the active material on the positive electrode material can be dissolved in the acidic solution to obtain solution A, that is, the transition metal ions, sodium ions and acid-soluble substances such as ferrocyanate in the positive electrode material are free in the acidic solution to form solution A, and then the transition metal ion concentration, ferrocyanate concentration and sodium ion in solution A are adjusted to a preset concentration, and then solution B and the complexing agent solution are mixed and reacted so that ferrocyanate can react with transition metal ions and sodium ions to precipitate and generate Prussian crystals, and finally solution C is filtered, and the filtered residue is dried to obtain a Prussian sodium ion positive electrode material with good regeneration performance.
  • the above-mentioned recovery method can recycle the low-toxic [Fe(CN) 6 ] 4- in the discarded Prussian sodium battery, avoiding the direct discard of the Prussian sodium ion positive electrode material from causing greater pressure on the environment, thereby protecting the ecological balance.
  • the abandoned Prussian sodium-ion battery is disassembled to separate the positive electrode material, the negative electrode material and the separator to obtain the positive electrode material; the positive electrode material is washed or soaked with a 0.05 mol/L dilute HCl solution to obtain a solution A with a pH of 6; the solution A is detected with an ICP inductively coupled plasma spectrometer, and potassium ferrocyanide, MnCl2 and NaCl2 are sequentially added to the solution A to make the concentration of [Fe(CN)6] 4- in the solution B reach 0.3 mol/L, the concentration of Mn2 + reach 0.4 mol/L, and the concentration of Na + reach 0.3 mol/L, to obtain a solution B;
  • Solution B and 0.4 mol/L maleic acid solution are introduced into the reactor for a mixed reaction, wherein the conditions for the mixed reaction are to control the flow ratio of solution B and the complexing agent solution to be 1:1 and the pH of the mixed reaction to be 6.5 under an inert atmosphere, the solution C is aged for 8 hours, and then the solution C is filtered to obtain a filter residue and a filtrate; the filtrate obtained by filtering the solution C is recycled, and the filter residue is dried at a temperature of 80° C. for 8 hours to obtain a Prussian sodium ion positive electrode material.
  • the discarded Prussian sodium ion battery is disassembled to separate the positive electrode material, the negative electrode material and the separator to obtain the positive electrode material; the positive electrode material is cleaned or soaked with a 0.30 mol/L H 2 CO 3 solution; A solution A with a pH of 5 is obtained; an ICP inductively coupled plasma spectrometer is used to detect the solution A, and sodium ferrocyanide, FeSO 4 and NaSO 2 are sequentially added to the solution A to make the concentration of [Fe(CN)6] 4- in the solution B reach 0.45 mol/L, the concentration of Fe 2+ reach 1.2 mol/L, and the concentration of Na + reach 0.45 mol/L, thereby obtaining a solution B;
  • Prussian sodium ion positive electrode material Water is added to the reactor to preheat to 45°C, and solution B and 7.7 mol/LEDTA solution are introduced into the reactor for mixed reaction, wherein the mixed reaction conditions are to control the flow ratio of solution B and complexing agent solution to be 1:1 and the pH of the mixed reaction to be 8 under inert atmosphere conditions, and the solution C is aged for 9 hours, and then the solution C is filtered to obtain filter residue and filtrate; the filtrate obtained by filtering the solution C is recycled, and the filter residue is dried at a temperature of 65°C for 10 hours to obtain a Prussian sodium ion positive electrode material.
  • the produced Prussian sodium ion positive electrode material has good regeneration performance, meets market requirements, and can be directly put into production, thereby reducing the production cost of Prussian sodium ion batteries.
  • Dismantle discarded Prussian sodium-ion batteries to separate positive electrode materials, negative electrode materials and separators to obtain positive electrode materials; use 0.5 mol/L dilute sulfuric acid solution to wash or soak the positive electrode materials to obtain solution A with a pH of 3; use an ICP inductively coupled plasma spectrometer to detect solution A, and add sodium ferrocyanide, NiCl2 and NaCl2 to solution A in sequence to make the concentration of [Fe(CN)6] 4- in solution B reach 0.6 mol/L, the concentration of Ni2 + reach 2 mol/L, and the concentration of Na + reach 0.6 mol/L, thereby obtaining solution B;
  • Solution B and 15 mol/L sodium citrate solution are introduced into the reactor for a mixed reaction, wherein the conditions for the mixed reaction are to control the flow ratio of solution B and the complexing agent solution to be 1:1 and the pH of the mixed reaction to be 9.5 under an inert atmosphere, the solution C is aged for 10 hours, and then the solution C is filtered to obtain a filter residue and a filtrate; the filtrate obtained by filtering the solution C is recycled, and the filter residue is dried at a temperature of 50° C. for 12 hours to obtain a Prussian sodium ion positive electrode material.
  • the abandoned Prussian sodium-ion battery is disassembled to separate the positive electrode material, the negative electrode material and the separator to obtain the positive electrode material; the positive electrode material is washed or soaked with a 0.05 mol/L dilute HCl solution to obtain a solution A with a pH of 6; the solution A is detected with an ICP inductively coupled plasma spectrometer, and potassium ferrocyanide, MnCl 2 and NaCl 2 are added to the solution A in sequence to reduce the [Fe(CN) 6]
  • the concentration of 4- reaches 0.3 mol/L, the concentration of Mn 2+ reaches 0.4 mol/L, and the concentration of Na + reaches 0.3 mol/L, and solution B is obtained;
  • Solution B Water is added to the reactor to preheat it to 40°C, and solution B, 0.4 mol/L maleic acid solution, 0.4 mol/L EDTA and 0.4 mol/L sodium citrate are introduced into the reactor for mixed reaction, wherein the mass ratio of maleic acid solution, EDTA and sodium citrate is 1:0.5:1, and the conditions for the mixed reaction are to control the flow ratio of solution B and complexing agent solution to be 1:1 and the pH of the mixed reaction to be 6.5 under inert atmosphere conditions, and the solution C is aged for 8 hours, and then the solution C is filtered to obtain a filter residue and a filtrate; the filtrate obtained by filtering the solution C is recycled, and the filter residue is dried at a temperature of 80°C for 8 hours to obtain a Prussian sodium ion positive electrode material.
  • Example 1 The difference from Example 1 is that the order of adding potassium ferrocyanide, MnCl 2 and NaCl 2 to solution A is different, that is, in Comparative Example 1, MnCl 2 , potassium ferrocyanide and NaCl 2 are added to solution A in sequence.
  • the other conditions are the same as in Example 1.
  • Example 1 The difference from Example 1 is that the pH of solution A is 1.5, and the other conditions are the same as those in Example 1.
  • D10, D50, and D90 represent the particle size parameters of the Prussian sodium ion positive electrode material, which means that 10%, 50%, and 90% of the particle sizes are within the measured size values;
  • BET represents the total surface area of particles per unit volume or unit mass.
  • TD tap density

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Abstract

Un matériau d'électrode positive à ions sodium de type Prusse et son procédé de recyclage sont divulgués dans la présente demande. La présente demande décrite concerne le procédé de recyclage du matériau d'électrode positive à ions sodium de type Prusse, comprenant les étapes suivantes consistant à : obtenir un matériau d'électrode positive ; nettoyer ou tremper le matériau d'électrode positive au moyen d'une solution acide ; réguler les concentrations d'ions de métal de transition, de radicaux de ferrocyanure et d'ions sodium dans la solution A selon des concentrations prédéfinies ; ajouter une solution d'agent complexant dans la solution B aux fins d'une réaction de mélange ; filtrer la solution C pour obtenir des résidus de filtre ; et sécher les résidus de filtre pour obtenir le matériau d'électrode positive à ions sodium de type Prusse. Le procédé de recyclage du matériau d'électrode positive à ions sodium de type Prusse peut recycler du [Fe(CN)6]4- à faible toxicité dans des batteries au sodium de type Prusse usagées, et éviter ainsi une grande pression exercée sur l'environnement par des matériaux d'électrode positive à ions sodium de type Prusse directement mis au rebut, ce qui permet de protéger l'équilibre écologique. De plus, le matériau d'électrode positive à ions sodium de type Prusse produit présente de bonnes performances de régénération et peut ainsi satisfaire aux exigences commerciales.
PCT/CN2023/077899 2022-09-29 2023-02-23 Matériau d'électrode positive aux à ions sodium de type prusse et son procédé de recyclage WO2024066182A1 (fr)

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CN111252814A (zh) * 2020-01-19 2020-06-09 广西师范大学 一种废旧三元锂离子电池正极材料的回收方法
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CN115058598A (zh) * 2022-07-06 2022-09-16 山东大学 一种废旧钠离子电池的回收方法
CN115579539A (zh) * 2022-09-29 2023-01-06 广东邦普循环科技有限公司 普鲁士类钠离子正极材料及其回收方法

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JP2014114470A (ja) * 2012-12-07 2014-06-26 Sumitomo Metal Mining Co Ltd アルミニウムの分離除去方法、並びにリチウムイオン電池からの有価金属の回収方法
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