WO2024051095A1 - Procédé de recyclage pour matériau d'électrode positive de batterie au sodium de prusse usagée, et utilisation - Google Patents

Procédé de recyclage pour matériau d'électrode positive de batterie au sodium de prusse usagée, et utilisation Download PDF

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Publication number
WO2024051095A1
WO2024051095A1 PCT/CN2023/077130 CN2023077130W WO2024051095A1 WO 2024051095 A1 WO2024051095 A1 WO 2024051095A1 CN 2023077130 W CN2023077130 W CN 2023077130W WO 2024051095 A1 WO2024051095 A1 WO 2024051095A1
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WO
WIPO (PCT)
Prior art keywords
sodium
prussian
positive electrode
transition metal
cathode material
Prior art date
Application number
PCT/CN2023/077130
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English (en)
Chinese (zh)
Inventor
谢英豪
李爱霞
余海军
李长东
Original Assignee
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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Application filed by 广东邦普循环科技有限公司, 湖南邦普循环科技有限公司 filed Critical 广东邦普循环科技有限公司
Publication of WO2024051095A1 publication Critical patent/WO2024051095A1/fr

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Classifications

    • 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
    • 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

  • Embodiments of the present application relate to the field of battery materials, such as a recycling method and application of waste Prussian sodium battery cathode materials.
  • Prussian sodium-like cathode material is a type of sodium-ion battery cathode material with an open frame structure. It is a metal-organic frame structure material. The metal and ferricyanide in its lattice are arranged according to Fe—C ⁇ N—M to form a three-dimensional structure. In the skeleton, Fe and metal M are arranged in a cube shape, and 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 50nm, and has three-dimensional sodium ion intercalation and extraction channels.
  • This type of material has the following advantages: (1) The rigid framework structure and open large pores and sites of the Prussian sodium-like cathode material can ensure that sodium ions with a larger ionic radius can be reversibly deintercalated during the charge and discharge process. It will not change the structure of the cathode material; (2) The Prussian sodium-like cathode material is based on the double-electron redox mechanism, and its theoretical capacity is as high as 170mAh/g; (3) The Prussian sodium-like cathode material has a simple synthesis process, low toxicity and low cost. Suitable for mass production.
  • the embodiments of the present application provide a method for recycling waste Prussian sodium battery cathode materials.
  • This method precipitates and separates the transition metals in the Prussian sodium cathode materials through acid dissolution and simultaneously destroys the original complexation of each group in the material. , so that [Fe(CN) 6 ] 4- stably exists in the liquid phase, and the liquid phase can further obtain pure sodium ferrocyanide through heating/crystallization or extraction.
  • This solution has simple operation steps and does not require the introduction of highly toxic or violently reactive reagents. It can simultaneously recover and separate transition metal ions, sodium ions and ferrocyanide in the Prussian sodium cathode material.
  • a method for recycling used Prussian sodium battery cathode materials including the following steps:
  • the transition metal elements in the Prussian sodium cathode material can be completely separated and processed through a specific organic acid reaction system, and at the same time, it can also ensure that [Fe(CN) 6 ] 4- will not occur in the material.
  • the cyanide breaks down and reacts with sodium ions to exist stably in the liquid phase.
  • This liquid phase can be obtained through subsequent treatment to pure sodium ferrocyanide, which can be further used to prepare new Prussian sodium cathode materials.
  • the recycling method described in this application has simple operation steps, low requirements for reaction reagents, conditions and equipment, and the purity and yield of the obtained materials are high, making it very suitable for industrial-scale treatment of used batteries.
  • the Prussian-based sodium cathode material includes manganese-based Prussian-based derivative sodium cathode material, nickel-based Prussian-based derivative sodium cathode material, cobalt-based Prussian-based derivative sodium cathode material, copper-based Prussian-based derivative sodium cathode material , at least one of the zinc-based Prussian derivative sodium cathode materials.
  • the organic acid is at least one of oxalic acid and acetic acid.
  • the transition metal precipitate is further prepared by calcination to prepare a transition metal oxide.
  • the transition metal precipitate is manganese metal precipitate, which is calcined at 220-280°C to prepare manganous oxide.
  • the transition metal element in the material is manganese
  • the resulting precipitate is manganese oxalate.
  • This material can be calcined at a specific temperature to directly generate manganous oxide. After further acid dissolution, it can be used to prepare Prussian sodium Synthetic manganese sources are used in cathode materials and other products.
  • Another object of this application is to provide a preparation method of Prussian sodium cathode material, which includes the following steps:
  • step (1) also includes removal of organic acids in the filtrate, and the removal of organic acids is performed by heating or extraction.
  • the filtrate obtained by the recycling method of waste Prussian sodium battery cathode materials described in this application only contains sodium ions, [Fe(CN) 6 ] 4- and organic acids, and organic acids can generally be heated It can be removed by volatilization (applicable to small molecular organic acids that can volatilize at 150°C) or extraction without leaving any residue.
  • the liquid phase can be directly dried by heating or crystallized to obtain high-purity sodium ferrocyanide powder.
  • This product can be further directly mixed with Transition metal salts are directly combined to prepare Prussian sodium cathode materials.
  • the transition metal salt is prepared from transition metal precipitation obtained by the recycling method of used Prussian sodium battery cathode materials described in this application.
  • the organic acid precipitate obtained through the recovery method described in this application can be simply oxidized and converted to obtain pure transition metal salts, and the Prussian sodium cathode material can be obtained by using this salt and the sodium ferrocyanide powder mentioned above. Realize the integrated process of recycling waste lithium-ion battery materials and implement it with high economical and cost-effectiveness.
  • the transition metal salt may also be a new salt.
  • the beneficial effect of the embodiments of the present application is that the embodiments of the present application provide a method for recycling waste Prussian sodium battery cathode materials.
  • This method precipitates and separates the transition metals in the Prussian sodium battery cathode materials through acid dissolution and simultaneously destroys the materials.
  • the original complexation of each group makes [Fe(CN) 6 ] 4- stably exist in the liquid phase.
  • the liquid phase can be heated/crystallized or extracted to further obtain pure sodium ferrocyanide.
  • This solution has simple operation steps and does not require the introduction of highly toxic or violently reactive reagents. It can simultaneously recover and separate transition metal ions, sodium ions and ferrocyanide in the Prussian sodium cathode material.
  • This application also provides a method for preparing a Prussian sodium cathode material.
  • This method uses the liquid phase obtained by the recovery method described in this application to further purify it to obtain sodium ferrocyanide. This material can be directly transferred to new materials or the results obtained in this application. Transition metal salts obtained by metal precipitation and refining are used to prepare Prussian sodium cathode materials.
  • the preparation method has low raw material cost and is cost-effective to implement.
  • Figure 1 is a scanning electron microscope image of the Prussian sodium cathode material obtained in Example 1 of the present application.
  • Figure 2 is the charge and discharge curve of the Prussian sodium cathode material obtained in Example 1 of the present application.
  • step (2) Calcining the manganese oxalate precipitate obtained in step (2) for 6 hours at 250°C in an oxygen atmosphere to obtain manganous oxide, and then dissolving the manganous oxide in 1 mol/L dilute hydrochloric acid to obtain a manganous chloride solution;
  • step (2) Calculate the manganese acetate precipitate obtained in step (2) for 6 hours at 250°C in an oxygen atmosphere to obtain manganous oxide, and then dissolve the manganous oxide in 1 mol/L dilute hydrochloric acid to obtain a manganous chloride solution;
  • step (2) Calcining the manganese oxalate precipitate obtained in step (2) for 6 hours at 250°C in an oxygen atmosphere to obtain manganous oxide, and then dissolving the manganous oxide in 1 mol/L dilute hydrochloric acid to obtain a manganous chloride solution;
  • Example 1 The only difference between this comparative example and Example 1 is that the molar ratio of Prussian sodium cathode material:oxalic acid in step (2) is 12:1.
  • Example 1 The only difference between this comparative example and Example 1 is that the Prussian sodium normal The electrode material was soaked in the oxalic acid solution for 48 hours. In step (3), the molar ratio of sodium ions and [Fe(CN) 6 ] 4- in the filtrate was measured to be 2.61:1, [Fe(CN) 6 ] 4- The recovery rate is low and cannot meet the recycling requirements.
  • Example 1 The only difference between this comparative example and Example 1 is that the temperature at which the Prussian sodium cathode material separated in step (2) was immersed in the oxalic acid solution was 100°C.
  • step (3) the sodium ions and [ The molar ratio of Fe(CN) 6 ] 4- is 2.92:1, and the recovery rate of [Fe(CN) 6 ] 4- is low and cannot meet the recovery requirements.
  • the products of each example are processed at a rate of 0.1C
  • the first discharge specific capacity reached 147 ⁇ 155mAh/g, which is equivalent to or even slightly better than the 146mAh/g of the product of Comparative Example 1; the capacity retention rate of the products of each embodiment can still reach 94 ⁇ 95% after 150 cycles at 1C rate, which is the same as the 146mAh/g of the product of Comparative Example 1.
  • the products in Comparative Example 1 are the same, indicating that the manganese-based Prussian sodium cathode material recovered and prepared by the recycling method described in this application has excellent electrochemical properties and can completely replace commercial similar products prepared with new materials in the existing market.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Toxicology (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Primary Cells (AREA)

Abstract

La présente demande concerne le domaine des matériaux de batterie. La demande porte sur un procédé de recyclage pour un matériau d'électrode positive de batterie au sodium de Prusse usagée, et une utilisation. Le procédé de recyclage selon la présente demande comprend les étapes suivantes consistant à : (1) démonter une batterie au sodium-ion usagée, séparer un matériau d'électrode positive au sodium de Prusse sur une feuille d'électrode positive d'un collecteur de courant, et effectuer un lavage et un tamisage ; et (2) tremper le matériau d'électrode positive au sodium de Prusse séparé dans une solution d'acide organique pendant 2-24 h à 20-60°C, et filtrer pour obtenir un précipité de métal de transition et un filtrat contenant des ions sodium et [Fe(CN)6]4-, le rapport molaire entre le matériau d'électrode positive au sodium de Prusse séparé et un acide organique contenu dans la solution d'acide organique étant de (7-10) : 1. Selon cette solution, les étapes de l'opération sont simples, il n'est pas nécessaire d'introduire un réactif présentant une toxicité élevée ou provoquant une réaction violente, et les ions de métal de transition, les ions sodium et le ferrocyanure contenus dans le matériau d'électrode positive au sodium de Prusse peuvent être simultanément recyclés et séparés. La présente demande concerne en outre un procédé de préparation d'un matériau d'électrode positive au sodium de Prusse à partir d'un produit obtenu par le procédé de recyclage.
PCT/CN2023/077130 2022-09-05 2023-02-20 Procédé de recyclage pour matériau d'électrode positive de batterie au sodium de prusse usagée, et utilisation WO2024051095A1 (fr)

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CN202211087961.1A CN115472943B (zh) 2022-09-05 2022-09-05 一种废旧普鲁士类钠电池正极材料的回收方法及应用

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CN115472943B (zh) * 2022-09-05 2023-12-12 广东邦普循环科技有限公司 一种废旧普鲁士类钠电池正极材料的回收方法及应用

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