WO2024045513A1 - Method for recovering sodium vanadium phosphate positive electrode material - Google Patents

Method for recovering sodium vanadium phosphate positive electrode material Download PDF

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WO2024045513A1
WO2024045513A1 PCT/CN2023/077588 CN2023077588W WO2024045513A1 WO 2024045513 A1 WO2024045513 A1 WO 2024045513A1 CN 2023077588 W CN2023077588 W CN 2023077588W WO 2024045513 A1 WO2024045513 A1 WO 2024045513A1
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positive electrode
solution
sodium
ions
solution containing
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PCT/CN2023/077588
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French (fr)
Chinese (zh)
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徐学留
刘更好
阮丁山
李永光
李伟权
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 WO2024045513A1 publication Critical patent/WO2024045513A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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

  • This application relates to the technical field of development of cathode materials for sodium-ion batteries, and specifically, to a method for recycling sodium phosphovanadate cathode materials.
  • Sodium-ion batteries have attracted the attention of major enterprises and markets due to a series of outstanding physical and chemical properties such as low raw materials, abundant resources, safe performance, good low temperature resistance, good fast charging performance, and environmental friendliness. They are widely used in power vehicles, power tools, It has a wide range of applications in 3C digital, energy storage and other fields.
  • the current recycling technology is mainly aimed at used and retired lithium batteries, while there are very few reports on the recycling and utilization of sodium-ion battery cathode materials.
  • Sodium phosphovanadate is a NASICON type material, and its crystal structure belongs to the hexagonal crystal system. Sodium phosphovanadate has become one of the popular materials for sodium ion cathode materials due to its moderate voltage (3.4V), relatively ideal capacity, ultra-long cycle life and excellent rate performance.
  • the purpose of this application is to provide a method for recycling sodium vanadium phosphate cathode materials, which can fully recover decommissioned or used sodium vanadium phosphate cathode materials and is environmentally friendly.
  • This application provides a method for recycling sodium phosphovanadate cathode material, which includes the following steps:
  • the metal ion solution also contains M element and the M element does not contain Fe: first, M ions are precipitated and removed in the form of hydroxide to obtain V and solution, which will subsequently contain V and The solution is mixed with iron ions to make Complex with iron ions and solid-liquid separation to obtain iron phosphate precipitation and V-containing solution;
  • metal ion solution also contains M element and the M element is Fe, or when the metal ion solution does not contain M element, directly mix the metal ion solution containing V and P with iron ions to make Complex with iron ions and solid-liquid separation to obtain iron phosphate precipitation and V-containing solution;
  • the method further includes: mixing iron phosphate and sodium salt and sintering to obtain sodium iron phosphate.
  • the method further includes: mixing iron phosphate and lithium salt and sintering to obtain lithium iron phosphate.
  • the solution containing the Na y V 2-x M x (PO 4 ) 3 cathode material to be recovered and the strong alkali are mixed at 30-90°C for 10-100 hours; wherein, the cathode material The molar ratio to strong base is 1:1-10.
  • the precipitation of M ions in the form of hydroxide is achieved by adjusting the pH value of the corresponding metal ion solution.
  • the iron ions include at least one of Fe 2+ and Fe 3+ .
  • Complexation with iron ions is achieved in the following way: adding V and The pH value of the mixed solution with iron ions is adjusted to 2.5-3.
  • the solution containing Na y V 2-x M x (PO 4 ) 3 cathode material to be recovered is obtained in the following manner:
  • the positive electrode sheet in the Na y V 2-x M x (PO 4 ) 3 sodium ion positive electrode to be recovered is mixed and stirred with water to separate the carrier sheet from the positive electrode material, and then the carrier sheet is removed.
  • the positive electrode sheet is obtained by splitting the Na y V 2-x M x (PO 4 ) 3 sodium ion positive electrode discharge treatment to be recovered.
  • M is selected from any one of Ti, Mn, Fe, Cr and Al.
  • the synthetic source of M is a chloride salt, a sulfide salt, a nitrate salt, or an oxalate salt.
  • the recycling method of sodium phosphovanadate cathode material provided by this application has an ingenious process, simple operation, low raw materials, and the solvent used is a strong alkali, which is environmentally friendly and pollution-free.
  • the obtained product is easy to purify and separate, has a high recycling rate, and can be comprehensively used.
  • Efficiently recovering V and P elements in cathode materials has positive guiding significance for the recycling of sodium phosphovanadate cathode materials.
  • Figure 1 is a schematic flow chart of the recovery method of sodium phosphovanadate cathode material in Example 1 of the present application;
  • Figure 2 is an SEM image of the iron phosphate recovered in Example 1 of the present application.
  • Figure 3 is an XRD pattern of the iron phosphate recovered in Example 1 of the present application.
  • This application proposes a method for recycling sodium phosphovanadate cathode material, which includes the following steps:
  • M may be exemplarily selected from any one of Ti, Mn, Fe, Cr and Al.
  • Synthetic sources of M may be, for example, chloride salts, sulfide salts, nitrates or oxalates.
  • the strong base exemplarily includes at least one of sodium hydroxide and potassium hydroxide.
  • the molar ratio of cathode material to strong base can be 1:2-10, such as 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1 :10, etc., or any other value within the range of 1:2-10.
  • the temperature of the alkali washing reaction can be 30-90°C, such as 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C or 90°C °C, etc., can also be any other value within the range of 30-90 °C.
  • the time of the alkali washing reaction can be 10-100h, such as 10h, 20h, 30h, 40h, 50h, 60h, 70h, 80h, 90h or 100h, etc., or it can be any other value in the range of 10-100h.
  • the above-mentioned solution containing the Na y V 2-x M x (PO 4 ) 3 cathode material to be recovered can be obtained in the following manner: the Na y V 2-x M x (PO 4 ) 3 sodium to be recovered is The positive electrode sheet in the ion positive electrode is mixed and stirred with water to separate the carrier sheet from the positive electrode material, and then the carrier sheet (such as aluminum foil or copper foil, etc.) is removed.
  • the carrier sheet such as aluminum foil or copper foil, etc.
  • the above-mentioned positive electrode sheet is obtained by splitting the Na y V 2-x M x (PO 4 ) 3 sodium ion positive electrode to be recovered and then discharging.
  • the cathode material solution can be obtained by referring to the following methods:
  • Discharge the retired and/or used Na y V 2-x M x (PO 4 ) 3 sodium ion positive electrode (called sodium phosphovanadate battery in Figure 1), and then disassemble the positive electrode sheet, separator, and negative electrode sheet. Processed separately.
  • the stirring speed can be, for example, 500-1000 rpm
  • the stirring speed can be, for example, 500-1000 rpm
  • carrier sheets such as aluminum foil
  • carrier sheets can be collected through filtration, and then the collected aluminum foil can be recycled to an aluminum plant for reuse. The same goes for copper foil.
  • the metal ion solution also contains M element and the M element does not contain Fe: first precipitate M ions in the form of hydroxide and then remove them to obtain V and solution, which will subsequently contain V and The solution is mixed with iron ions to make Complex with iron ions and solid-liquid separation to obtain iron phosphate precipitation and V-containing solution;
  • the metal ion solution also contains M element and the M element is Fe, or when the metal ion solution does not contain M element, directly mix the metal ion solution containing V and P with iron ions to make It is complexed with iron ions and separated from solid to liquid to obtain iron phosphate precipitation and V-containing solution.
  • the M ions in the metal ion solution containing V, P and M (excluding Fe) are precipitated in the form of hydroxide and then removed to obtain V and M ions.
  • the solution Specifically, by adjusting the pH value of the corresponding metal ion solution, M ions are precipitated in the form of hydroxide.
  • Ti can be precipitated in the form of hydroxide by adjusting the pH of the corresponding metal ion solution to 2.5-3; Mn can be precipitated in the form of manganese ions by adjusting the pH of the corresponding metal ion solution to 8.6-10.8.
  • the iron ions used in the above process include at least one of Fe 2+ and Fe 3+ .
  • Complexation with iron ions is achieved in the following way: adding V and Adjust the pH value of the mixed solution with iron ions to 2.5-3 and let it stand. The added iron ions and the to-be-complexed The molar ratio is 1:1. The pH was adjusted with HCl.
  • it may also include S4: mixing and sintering iron phosphate with sodium salt (such as sodium carbonate or sodium hydroxide) to obtain sodium iron phosphate.
  • sodium salt such as sodium carbonate or sodium hydroxide
  • iron phosphate and lithium salt such as lithium carbonate are mixed and sintered to obtain lithium iron phosphate.
  • the obtained polar iron phosphate can be washed, roasted and ground before sintering.
  • the negative electrode sheet obtained by splitting the decommissioned and/or discarded Na y V 2-x M x (PO 4 ) 3 sodium ion positive electrode can also be subjected to high-temperature calcination and carbonization to obtain hard carbon.
  • This embodiment provides a method for recycling decommissioned sodium cathode material Na 3 V 2 (PO 4 ) 3 (NASICON).
  • the flow diagram is shown in Figure 1, which specifically includes the following steps:
  • Step (1) Replace the retired and/or used Na 3 V 2 (PO 4 ) 3 sodium ion positive electrode (referred to as phosphorus vanadium in Figure 1 Sodium acid battery) is discharged, and then the positive electrode sheet, separator, and negative electrode sheet are disassembled and separated.
  • Na 3 V 2 (PO 4 ) 3 sodium ion positive electrode referred to as phosphorus vanadium in Figure 1 Sodium acid battery
  • the positive electrode sheet obtained after splitting is stirred with water at high speed in a container (rotation speed is 800 rpm) to separate the positive electrode material from the carrier sheet, and the carrier sheet is filtered to obtain a positive electrode material solution.
  • Step (2) Add sodium hydroxide solution to the Na 3 V 2 (PO 4 ) 3 positive electrode material solution to cause an alkali washing reaction.
  • the molar ratio of the positive electrode material to sodium hydroxide is 1:2. Stir vigorously (rotation speed is 800 rpm), react for 24 hours, and the reaction temperature is 30°C to obtain a solution containing V and P.
  • Step (3) Slowly add a certain amount of Fe 3+ solution to the solution containing V and P.
  • the molar ratio of Fe 3+ added to PO 4 3- is 1:1. Adjust the pH value to 2.8 so that A complete precipitation reaction occurs with Fe 3+ to generate FePO 4 precipitate (its SEM images and XRD images are shown in Figure 2 and Figure 3 respectively).
  • Step (4) Filter and collect the generated iron phosphate FePO 4 to obtain a V-containing filtrate.
  • the vanadium-containing filtrate is highly concentrated and crystallized to obtain the finished product of sodium vanadate.
  • Step (5) Mix the generated iron phosphate FePO 4 with a certain amount of lithium carbonate, and sinter at a high temperature of 800°C for 18 hours to obtain a lithium iron phosphate cathode material.
  • Step (6) Calcide and carbonize the negative electrode material at high temperature to obtain hard carbon.
  • This embodiment provides a method for recycling decommissioned sodium cathode material Na 3 VFe(PO 4 ) 3 , which specifically includes the following steps:
  • Step (1) Discharge the retired and/or discarded Na 3 VFe(PO 4 ) 3 sodium ion positive electrode, and then disassemble and separate the positive electrode sheet, separator, and negative electrode sheet.
  • the separated cathode sheets are stirred with water at high speed (500 prm) in a container to separate the cathode material from the carrier sheet.
  • the carrier sheet is filtered to remove the cathode material solution to obtain a cathode material solution.
  • Step (2) Add sodium hydroxide solution to the Na 3 VFe(PO 4 ) 3 positive electrode material solution to cause an alkali washing reaction.
  • the molar ratio of the positive electrode material to sodium hydroxide is 1:3. Stir vigorously (500prm), react for 24 hours, and the reaction temperature is 70°C to obtain a solution containing V, P, and Fe ions.
  • Step (3) Slowly add a certain amount of Fe 3+ solution to the solution containing V, P and Fe.
  • the molar ratio of Fe 3+ added is equal to The ratio is 1:1, adjust the pH value to 2.5, so that Occurs exactly with Fe 3+
  • the precipitation reaction produces FePO 4 precipitation.
  • Step (4) Filter and collect the generated iron phosphate FePO 4 to obtain a V-containing filtrate.
  • the vanadium-containing filtrate is highly concentrated and crystallized to obtain the finished product of sodium vanadate.
  • Step (5) Mix the generated iron phosphate FePO 4 with a certain amount of lithium carbonate, and sinter at a high temperature of 800°C for 18 hours to obtain a lithium iron phosphate cathode material.
  • This embodiment provides a method for recycling retired sodium cathode material Na 3 V 1.5 Al 0.5 (PO 4 ) 3 , which specifically includes the following steps:
  • Step (1) Discharge the retired and/or used Na 3 V 1.5 Al 0.5 (PO 4 ) 3 sodium ion positive electrode, and then disassemble and separate the positive electrode sheet, separator, and negative electrode sheet.
  • the separated cathode sheets are stirred with water at high speed (600 prm) in a container to separate the cathode material from the carrier sheet.
  • the carrier sheet is filtered to remove the cathode material solution to obtain a cathode material solution.
  • Step (2) Add sodium hydroxide solution to the Na 3 V 1.5 Al 0.5 (PO 4 ) 3 positive electrode material solution to cause an alkali washing reaction.
  • the molar ratio of the positive electrode material to sodium hydroxide is 1:3.
  • Stir vigorously (600prm) react for 24 hours, and the reaction temperature is 50°C to obtain a solution containing V, P, and Al ions. Adjust the pH value to precipitate Al ions and filter the residue.
  • Step (3) Slowly add a certain amount of Fe 3+ solution to the solution containing V and P.
  • the molar ratio of Fe 3+ added is equal to The ratio is 1:1, adjust the pH value to 2.7, so that It completely reacts with Fe 3+ to form FePO 4 precipitate.
  • Step (4) Filter and collect the generated iron phosphate FePO 4 to obtain a V-containing filtrate.
  • the vanadium-containing filtrate is highly concentrated and crystallized to obtain the finished product of sodium vanadate.
  • Step (5) Mix the generated iron phosphate FePO 4 with a certain amount of lithium carbonate, and sinter at a high temperature of 800°C for 18 hours to obtain a lithium iron phosphate cathode material.
  • This embodiment provides a method for recycling retired sodium cathode material Na 4 VMn (PO 4 ) 3 , which specifically includes the following steps:
  • Step (1) Discharge the retired and/or discarded Na 4 VMn(PO 4 ) 3 sodium ion positive electrode, and then disassemble and separate the positive electrode sheet, separator, and negative electrode sheet.
  • the separated cathode sheet is stirred with water at high speed (700 prm) in a container to separate the cathode material from the carrier sheet.
  • the carrier sheet is filtered to remove the cathode material solution to obtain a cathode material solution.
  • Step (2) Add sodium hydroxide solution to the Na 4 VMn(PO 4 ) 3 positive electrode material solution to cause an alkali washing reaction.
  • the molar ratio of the positive electrode material to sodium hydroxide is 1:3.
  • Stir vigorously (700prm) react for 24 hours, and the reaction temperature is 30°C to obtain a solution containing V, P, and Mn ions. Adjust the pH value to precipitate Mn ions and filter the residue.
  • Step (3) Slowly add a certain amount of Fe 3+ solution to the solution containing V and P.
  • the molar ratio of Fe 3+ added is equal to The ratio is 1:1, adjust the pH value to 2.6, so that It completely reacts with Fe 3+ to form FePO 4 precipitate.
  • Step (4) Filter and collect the generated iron phosphate FePO 4 to obtain a V-containing filtrate.
  • the vanadium-containing filtrate is highly concentrated and crystallized to obtain the finished product of sodium vanadate.
  • Step (5) Mix the generated iron phosphate FePO 4 with a certain amount of lithium carbonate, and sinter at a high temperature of 800°C for 18 hours to obtain a lithium iron phosphate cathode material.
  • This embodiment provides a method for recycling retired sodium cathode material Na 7 V 4 (P 2 O 7 ) 4 PO 4 , which specifically includes the following steps:
  • Step (1) Discharge the retired and/or discarded Na 7 V 4 (P 2 O 7 ) 4 PO 4 sodium ion positive electrode, and then disassemble and separate the positive electrode sheet, separator, and negative electrode sheet.
  • the separated cathode sheet is stirred with water at high speed (1000 prm) in a container to separate the cathode material from the carrier sheet.
  • the carrier sheet is filtered to remove the cathode material solution to obtain a cathode material solution.
  • Step (2) Add sodium hydroxide solution to the Na 7 V 4 (P 2 O 7 ) 4 PO 4 positive electrode material solution to cause an alkali washing reaction.
  • the molar ratio of the positive electrode material to sodium hydroxide is 1:8. Stir vigorously (1000prm), react for 24 hours, and the reaction temperature is 40°C to obtain a solution containing V and P ions.
  • Step (3) Slowly add a certain amount of Fe 3+ solution to the solution containing V and P.
  • the addition of Fe 3+ The molar ratio of The ratio is 1:1, adjust the pH value to 2.9, so that It completely reacts with Fe 3+ to form FePO 4 precipitate.
  • Step (4) Filter and collect the generated iron phosphate FePO 4 to obtain a V-containing filtrate.
  • the vanadium-containing filtrate is highly concentrated and crystallized to obtain the finished product of sodium vanadate.
  • Step (5) Mix the generated iron phosphate FePO 4 with a certain amount of lithium carbonate, and sinter at a high temperature of 800°C for 18 hours to obtain a lithium iron phosphate cathode material.
  • This embodiment provides a method for recycling decommissioned sodium cathode material Na 4 VCr(PO 4 ) 3 , which specifically includes the following steps:
  • Step (1) Discharge the retired and/or discarded Na 4 VCr(PO 4 ) 3 sodium ion positive electrode, and then disassemble and separate the positive electrode sheet, separator, and negative electrode sheet.
  • the separated cathode sheets are stirred with water at high speed (900 prm) in a container to separate the cathode material from the carrier sheet.
  • the carrier sheet is filtered to remove the cathode material solution to obtain a cathode material solution.
  • Step (2) Add sodium hydroxide solution to the Na 4 VCr(PO 4 ) 3 positive electrode material solution to cause an alkali washing reaction.
  • the molar ratio of the positive electrode material to sodium hydroxide is 1:2.
  • Stir vigorously (900prm) react for 10 hours, and the reaction temperature is 90°C to obtain a solution containing V, P, and Cr ions. Adjust the pH value to precipitate Cr ions and filter the residue.
  • Step (3) Slowly add a certain amount of Fe 3+ solution to the solution containing V and P.
  • the molar ratio of Fe 3+ added is equal to The ratio is 1:1, adjust the pH value to 2.8, so that It completely reacts with Fe 3+ to form FePO 4 precipitate.
  • Step (4) Filter and collect the generated iron phosphate FePO 4 to obtain a V-containing filtrate.
  • the vanadium-containing filtrate is highly concentrated and crystallized to obtain the finished product of sodium vanadate.
  • Step (5) Mix the generated iron phosphate FePO 4 with a certain amount of sodium carbonate, and sinter at a high temperature of 800°C for 18 hours to obtain a lithium iron phosphate cathode material.
  • This embodiment provides a method for recycling retired sodium cathode material Na 4 VTi(PO 4 ) 3 , which specifically includes: Next steps:
  • Step (1) Discharge the retired and/or discarded Na 4 VTi(PO 4 ) 3 sodium ion positive electrode, and then disassemble and separate the positive electrode sheet, separator, and negative electrode sheet.
  • the separated cathode sheets are stirred with water at high speed (900 prm) in a container to separate the cathode material from the carrier sheet.
  • the carrier sheet is filtered to remove the cathode material solution to obtain a cathode material solution.
  • Step (2) Add sodium hydroxide solution to the Na 4 VTi(PO 4 ) 3 positive electrode material solution to cause an alkali washing reaction.
  • the molar ratio of the positive electrode material to sodium hydroxide is 1:10.
  • Stir vigorously (900prm) react for 100h, and the reaction temperature is 30°C to obtain a solution containing V, P, and Ti ions. Adjust the pH value to precipitate Ti ions and filter the residue.
  • Step (3) Slowly add a certain amount of Fe 3+ solution to the solution containing V and P.
  • the molar ratio of Fe 3+ added is equal to The ratio is 1:1, adjust the pH value to 3.0, so that It completely reacts with Fe 3+ to form FePO 4 precipitate.
  • Step (4) Filter and collect the generated iron phosphate FePO 4 to obtain a V-containing filtrate.
  • the vanadium-containing filtrate is highly concentrated and crystallized to obtain the finished product of sodium vanadate.
  • Step (5) Mix the generated iron phosphate FePO 4 with a certain amount of sodium hydroxide, and sinter at a high temperature of 800°C for 18 hours to obtain a lithium iron phosphate cathode material.
  • the recycling process provided by this application is simple and ingenious, easy to operate, has low raw materials, the solvent used is a strong alkali, is environmentally friendly and pollution-free, and the resulting product is easy to purify and separate, and can achieve industrial large-scale production.
  • This application recycles sodium phosphovanadate cathode materials, solving problems such as environmental pollution and data waste.
  • the V and P elements can be fully recovered, while generating lithium iron phosphate or sodium iron phosphate cathode materials, which can be reused in lithium-ion batteries or sodium-ion battery materials.

Abstract

The present application relates to the technical field of sodium ion battery positive electrode material development, and discloses a method for recovering a sodium vanadium phosphate positive electrode material. The method comprises the following steps: mixing a solution containing a NayV2-xMx(PO4)3 positive electrode material to be recovered with a strong base to obtain a metal ion solution containing V and P, wherein M is a transition metal, 0≤x≤1, and 2≤y≤4; first precipitating M ions other than Fe in the form of a hydroxide and removing same, then mixing the solution containing V and PO4 3- with iron ions so that PO4 3- is complexed with iron ions, and performing solid-liquid separation to obtain iron phosphate precipitate and a solution containing V; and concentrating and crystallizing the solution containing V to obtain a sodium vanadate product. The recovery method has a simple process, low cost, and a high recycling rate, is environmentally friendly, allows for comprehensive and efficient recovery of V and P elements in positive electrode materials, and has positive guiding significance for recycling of sodium vanadium phosphate positive electrode materials.

Description

一种磷钒酸钠正极材料的回收方法A method for recycling sodium phosphovanadate cathode material 技术领域Technical field
本申请涉及钠离子电池正极材料开发技术领域，具体而言，涉及一种磷钒酸钠正极材料的回收方法。This application relates to the technical field of development of cathode materials for sodium-ion batteries, and specifically, to a method for recycling sodium phosphovanadate cathode materials.
背景技术Background technique
随着新能源行业的高速发展，其开发技术也日新月异。钠离子电池以原料低廉、资源丰富、性能安全、低温性好、快充性能好、对环境友好等一系列杰出的理化性能而备受各大企业和市场的关注，在动力汽车、电动工具、3C数码、以及储能等领域有着广泛的应用。随着钠离子电池的高速发展和投入使用，若大量的钠离子电池投入使用或报废后，如何高效的回收利用成为了一个难题。目前现有的回收技术主要针对的是废旧退役的锂电池，而关于钠离子电池正极材料的回收与利用的相关报道少之又少。With the rapid development of the new energy industry, its development technology is also changing with each passing day. Sodium-ion batteries have attracted the attention of major enterprises and markets due to a series of outstanding physical and chemical properties such as low raw materials, abundant resources, safe performance, good low temperature resistance, good fast charging performance, and environmental friendliness. They are widely used in power vehicles, power tools, It has a wide range of applications in 3C digital, energy storage and other fields. With the rapid development and use of sodium-ion batteries, if a large number of sodium-ion batteries are put into use or scrapped, how to efficiently recycle them has become a problem. The current recycling technology is mainly aimed at used and retired lithium batteries, while there are very few reports on the recycling and utilization of sodium-ion battery cathode materials.
磷钒酸钠是一种NASICON型材料，其晶体结构属于六方晶系。磷钒酸钠因具有适中的电压(3.4V)和比较理想的容量、超长的循环寿命和极佳的倍率性能，成为钠离子正极材料的热门材料之一。Sodium phosphovanadate is a NASICON type material, and its crystal structure belongs to the hexagonal crystal system. Sodium phosphovanadate has become one of the popular materials for sodium ion cathode materials due to its moderate voltage (3.4V), relatively ideal capacity, ultra-long cycle life and excellent rate performance.
目前，基本没有有关磷酸钒钠正极材料回收的现有技术。Currently, there are basically no existing technologies for recycling sodium vanadium phosphate cathode materials.
鉴于此，特提出本申请。In view of this, this application is filed.
发明内容Contents of the invention
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。The following is an overview of the topics described in detail in this article. This summary is not intended to limit the scope of the claims.
本申请的目的在于提供一种磷钒酸钠正极材料的回收方法，该方法能够全面回收退役或废旧的磷酸钒钠正极材料，且对环境无害。The purpose of this application is to provide a method for recycling sodium vanadium phosphate cathode materials, which can fully recover decommissioned or used sodium vanadium phosphate cathode materials and is environmentally friendly.
本申请可这样实现：This application can be implemented as follows:
本申请提供一种磷钒酸钠正极材料的回收方法，包括以下步骤：This application provides a method for recycling sodium phosphovanadate cathode material, which includes the following steps:
S1、将含待回收的NayV2-xMx(PO4)3正极材料的溶液与强碱混合，得到含V、P的金属离子溶液；其中，M为过渡金属，0≤x≤1，2≤y≤4； S1. Mix the solution containing the Na y V 2-x M x (PO 4 ) 3 cathode material to be recovered with a strong base to obtain a metal ion solution containing V and P; where M is a transition metal, 0≤x≤ 1,2≤y≤4;
S2、根据金属离子溶液中所含元素的情况，分别按以下方式处理：S2. According to the elements contained in the metal ion solution, process them in the following ways:
a、当金属离子溶液中还含有M元素且M元素中不含Fe时：先将M离子以氢氧化物的形式沉淀除去后，得到含V和的溶液，随后将含V和的溶液与铁离子混合，使与铁离子络合，固液分离，得到磷酸铁沉淀和含V的溶液；a. When the metal ion solution also contains M element and the M element does not contain Fe: first, M ions are precipitated and removed in the form of hydroxide to obtain V and solution, which will subsequently contain V and The solution is mixed with iron ions to make Complex with iron ions and solid-liquid separation to obtain iron phosphate precipitation and V-containing solution;
b、当金属离子溶液中还含有M元素且M元素为Fe时，或者当金属离子溶液中不含M元素时，均直接将含V和P的金属离子溶液与铁离子混合，使与铁离子络合，固液分离，得到磷酸铁沉淀和含V的溶液；b. When the metal ion solution also contains M element and the M element is Fe, or when the metal ion solution does not contain M element, directly mix the metal ion solution containing V and P with iron ions to make Complex with iron ions and solid-liquid separation to obtain iron phosphate precipitation and V-containing solution;
S3、将含V的溶液进行浓缩结晶，得到钒酸钠产品。S3. Concentrate and crystallize the solution containing V to obtain the sodium vanadate product.
在可选的实施方式中，还包括：将磷酸铁与钠盐混合烧结，得到磷酸铁钠。In an optional embodiment, the method further includes: mixing iron phosphate and sodium salt and sintering to obtain sodium iron phosphate.
在可选的实施方式中，还包括：将磷酸铁与锂盐混合烧结，得到磷酸铁锂。In an optional embodiment, the method further includes: mixing iron phosphate and lithium salt and sintering to obtain lithium iron phosphate.
在可选的实施方式中，含待回收的NayV2-xMx(PO4)3正极材料的溶液与强碱是于30-90℃的条件下混合10-100h；其中，正极材料与强碱的摩尔比为1:1-10。In an optional embodiment, the solution containing the Na y V 2-x M x (PO 4 ) 3 cathode material to be recovered and the strong alkali are mixed at 30-90°C for 10-100 hours; wherein, the cathode material The molar ratio to strong base is 1:1-10.
在可选的实施方式中，M离子以氢氧化物的形式沉淀是通过调节相应金属离子溶液的pH值实现。In an optional embodiment, the precipitation of M ions in the form of hydroxide is achieved by adjusting the pH value of the corresponding metal ion solution.
在可选的实施方式中，铁离子包括Fe2+和Fe3+中的至少一种。In alternative embodiments, the iron ions include at least one of Fe 2+ and Fe 3+ .
在可选的实施方式中，与铁离子络合经以下方式实现：将含V和的溶液与铁离子的混合溶液的pH值调节至2.5-3。In an alternative implementation, Complexation with iron ions is achieved in the following way: adding V and The pH value of the mixed solution with iron ions is adjusted to 2.5-3.
在可选的实施方式中，含待回收的NayV2-xMx(PO4)3正极材料的溶液经以下方式获得：In an optional embodiment, the solution containing Na y V 2-x M x (PO 4 ) 3 cathode material to be recovered is obtained in the following manner:
将待回收的NayV2-xMx(PO4)3钠离子正极中的正极片与水混合搅拌，使载体片与正极材料分离，随后除去载体片。The positive electrode sheet in the Na y V 2-x M x (PO 4 ) 3 sodium ion positive electrode to be recovered is mixed and stirred with water to separate the carrier sheet from the positive electrode material, and then the carrier sheet is removed.
在可选的实施方式中，正极片经待回收的NayV2-xMx(PO4)3钠离子正极放电处理后拆分而得。In an optional embodiment, the positive electrode sheet is obtained by splitting the Na y V 2-x M x (PO 4 ) 3 sodium ion positive electrode discharge treatment to be recovered.
在可选的实施方式中，M选自Ti、Mn、Fe、Cr和Al中的任意一种。In alternative embodiments, M is selected from any one of Ti, Mn, Fe, Cr and Al.
在可选的实施方式中，M的合成来源为氯化盐、硫化盐、硝酸盐或草酸盐。 In alternative embodiments, the synthetic source of M is a chloride salt, a sulfide salt, a nitrate salt, or an oxalate salt.
本申请的有益效果包括：The beneficial effects of this application include:
本申请提供的磷钒酸钠正极材料的回收方法，其流程巧妙，操作简单，原料低廉，所用溶剂为强碱，对环境友好无污染，并且所得产物易提纯分离，回收利用率高，可全面高效地回收正极材料中的V和P元素，对磷钒酸钠正极材料的回收利用有着积极的指导意义。The recycling method of sodium phosphovanadate cathode material provided by this application has an ingenious process, simple operation, low raw materials, and the solvent used is a strong alkali, which is environmentally friendly and pollution-free. The obtained product is easy to purify and separate, has a high recycling rate, and can be comprehensively used. Efficiently recovering V and P elements in cathode materials has positive guiding significance for the recycling of sodium phosphovanadate cathode materials.
在阅读并理解了附图和详细描述后，可以明白其他方面。Other aspects will be apparent after reading and understanding the drawings and detailed description.
附图说明Description of drawings
为了更清楚地说明本申请实施例的技术方案，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申请的某些实施例，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。In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required to be used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present application and therefore do not It should be regarded as a limitation of the scope. For those of ordinary skill in the art, other relevant drawings can be obtained based on these drawings without exerting creative efforts.
图1为本申请实施例1中磷钒酸钠正极材料的回收方法的流程示意图；Figure 1 is a schematic flow chart of the recovery method of sodium phosphovanadate cathode material in Example 1 of the present application;
图2为本申请实施例1回收得到的磷酸铁的SEM图；Figure 2 is an SEM image of the iron phosphate recovered in Example 1 of the present application;
图3为本申请实施例1回收得到的磷酸铁的XRD图。Figure 3 is an XRD pattern of the iron phosphate recovered in Example 1 of the present application.
具体实施方式Detailed ways
为使本申请实施例的目的、技术方案和优点更加清楚，下面将对本申请实施例中的技术方案进行清楚、完整地描述。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。In order to make the purpose, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below. If the specific conditions are not specified in the examples, the conditions should be carried out according to the conventional conditions or the conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not indicated, they are all conventional products that can be purchased commercially.
下面对本申请提供的磷钒酸钠正极材料的回收方法进行具体说明。The following is a detailed description of the recovery method of the sodium phosphovanadate cathode material provided in this application.
本申请提出一种磷钒酸钠正极材料的回收方法，包括以下步骤：This application proposes a method for recycling sodium phosphovanadate cathode material, which includes the following steps:
S1：将含待回收的NayV2-xMx(PO4)3正极材料的溶液与强碱混合(即碱洗反应)，得到含V、P和M的金属离子溶液；其中，M为过渡金属，0≤x≤1，2≤y≤4。S1: Mix the solution containing the Na y V 2-x M x (PO 4 ) 3 cathode material to be recovered with a strong alkali (i.e., alkali washing reaction) to obtain a metal ion solution containing V, P and M; where, M It is a transition metal, 0≤x≤1, 2≤y≤4.
作为参考地，M示例性地可选自Ti、Mn、Fe、Cr和Al中的任意一种。M的合成来源例如可以为氯化盐、硫化盐、硝酸盐或草酸盐。For reference, M may be exemplarily selected from any one of Ti, Mn, Fe, Cr and Al. Synthetic sources of M may be, for example, chloride salts, sulfide salts, nitrates or oxalates.
强碱示例性地包括氢氧化钠和氢氧化钾中的至少一种。 The strong base exemplarily includes at least one of sodium hydroxide and potassium hydroxide.
正极材料与强碱的摩尔比可以为1:2-10，如1:2、1:3、1:4、1:5、1:6、1:7、1:8、1:9或1:10等，也可以为1:2-10范围内的其它任意值。The molar ratio of cathode material to strong base can be 1:2-10, such as 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1 :10, etc., or any other value within the range of 1:2-10.
碱洗反应的温度可以为30-90℃，如30℃、35℃、40℃、45℃、50℃、55℃、60℃、65℃、70℃、75℃、80℃、85℃或90℃等，也可以为30-90℃范围内的其它任意值。The temperature of the alkali washing reaction can be 30-90℃, such as 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃ or 90℃ ℃, etc., can also be any other value within the range of 30-90 ℃.
碱洗反应的时间可以为10-100h，如10h、20h、30h、40h、50h、60h、70h、80h、90h或100h等，也可以为10-100h范围内的其它任意值。The time of the alkali washing reaction can be 10-100h, such as 10h, 20h, 30h, 40h, 50h, 60h, 70h, 80h, 90h or 100h, etc., or it can be any other value in the range of 10-100h.
本申请中，上述含待回收的NayV2-xMx(PO4)3正极材料的溶液可经以下方式获得：将待回收的NayV2-xMx(PO4)3钠离子正极中的正极片与水混合搅拌，使载体片与正极材料分离，随后除去载体片(如铝箔或铜箔等)。In this application, the above-mentioned solution containing the Na y V 2-x M x (PO 4 ) 3 cathode material to be recovered can be obtained in the following manner: the Na y V 2-x M x (PO 4 ) 3 sodium to be recovered is The positive electrode sheet in the ion positive electrode is mixed and stirred with water to separate the carrier sheet from the positive electrode material, and then the carrier sheet (such as aluminum foil or copper foil, etc.) is removed.
上述正极片经待回收的NayV2-xMx(PO4)3钠离子正极放电处理后拆分而得。The above-mentioned positive electrode sheet is obtained by splitting the Na y V 2-x M x (PO 4 ) 3 sodium ion positive electrode to be recovered and then discharging.
具体的，正极材料溶液可参照以下方式得到：Specifically, the cathode material solution can be obtained by referring to the following methods:
将退役和/或废旧的NayV2-xMx(PO4)3钠离子正极(图1中称为磷钒酸钠电池)进行放电处理，然后将正极片、隔膜、负极片进行拆分处理。Discharge the retired and/or used Na y V 2-x M x (PO 4 ) 3 sodium ion positive electrode (called sodium phosphovanadate battery in Figure 1), and then disassemble the positive electrode sheet, separator, and negative electrode sheet. Processed separately.
将拆分后所得的正极片放入带有搅拌的特定容器中，容器里加入大量的纯水，进行剧烈的高速搅拌(搅拌转速例如可以为500-1000rpm)处理，使载体片和正极材料分离，然后过滤处理，除去载体片，即可得到正极材料溶液。Put the separated cathode sheets into a special container with stirring, add a large amount of pure water to the container, and perform vigorous high-speed stirring (the stirring speed can be, for example, 500-1000 rpm) to separate the carrier sheets and cathode materials. , and then filtered to remove the carrier sheet to obtain the cathode material solution.
在某些实施方式中，可通过过滤方式，收集载体片(如铝箔)，随后将收集的铝箔回收至铝厂回用。铜箔同理。In some embodiments, carrier sheets (such as aluminum foil) can be collected through filtration, and then the collected aluminum foil can be recycled to an aluminum plant for reuse. The same goes for copper foil.
S2：根据金属离子溶液中所含元素的情况，分别按以下方式处理：S2: According to the elements contained in the metal ion solution, process them in the following ways:
a、当金属离子溶液中还含有M元素且M元素中不含Fe时：先将M离子以氢氧化物的形式沉淀后除去后，得到含V和的溶液，随后将含V和的溶液与铁离子混合，使与铁离子络合，固液分离，得到磷酸铁沉淀和含V的溶液；a. When the metal ion solution also contains M element and the M element does not contain Fe: first precipitate M ions in the form of hydroxide and then remove them to obtain V and solution, which will subsequently contain V and The solution is mixed with iron ions to make Complex with iron ions and solid-liquid separation to obtain iron phosphate precipitation and V-containing solution;
b、当金属离子溶液中还含有M元素且M元素为Fe时，或者当金属离子溶液中不含M元素时，均直接将含V和P的金属离子溶液与铁离子混合，使 与铁离子络合，固液分离，得到磷酸铁沉淀和含V的溶液。b. When the metal ion solution also contains M element and the M element is Fe, or when the metal ion solution does not contain M element, directly mix the metal ion solution containing V and P with iron ions to make It is complexed with iron ions and separated from solid to liquid to obtain iron phosphate precipitation and V-containing solution.
也即，将含V、P和M(不含Fe)的金属离子溶液中的M离子以氢氧化物的形式沉淀后除去，得到含V和的溶液。具体的，通过调节相应金属离子溶液的pH值，使M离子以氢氧化物的形式沉淀。That is, the M ions in the metal ion solution containing V, P and M (excluding Fe) are precipitated in the form of hydroxide and then removed to obtain V and M ions. The solution. Specifically, by adjusting the pH value of the corresponding metal ion solution, M ions are precipitated in the form of hydroxide.
作为参考地，Ti可通过将相应金属离子溶液的pH调节至2.5-3以使钛离子以氢氧化物的形式沉淀；Mn可通过将相应金属离子溶液的pH调节至8.6-10.8以使锰离子以氢氧化物的形式沉淀；Cr可通过将相应金属离子溶液的pH调节至4.6-5.6以使铬离子以氢氧化物的形式沉淀；Al可通过将相应金属离子溶液的pH调节至6-10以使铝离子以氢氧化物的形式沉淀。As a reference, Ti can be precipitated in the form of hydroxide by adjusting the pH of the corresponding metal ion solution to 2.5-3; Mn can be precipitated in the form of manganese ions by adjusting the pH of the corresponding metal ion solution to 8.6-10.8. Precipitate in the form of hydroxide; Cr can be precipitated in the form of hydroxide by adjusting the pH of the corresponding metal ion solution to 4.6-5.6; Al can be precipitated in the form of hydroxide by adjusting the pH of the corresponding metal ion solution to 6-10 to precipitate aluminum ions in the form of hydroxides.
上述过程所用的铁离子包括Fe2+和Fe3+中的至少一种。The iron ions used in the above process include at least one of Fe 2+ and Fe 3+ .
与铁离子络合经以下方式实现：将含V和的溶液与铁离子的混合溶液的pH值调节至2.5-3，静置。加入的铁离子与待络合的的摩尔比为1:1。pH采用HCl调节。 Complexation with iron ions is achieved in the following way: adding V and Adjust the pH value of the mixed solution with iron ions to 2.5-3 and let it stand. The added iron ions and the to-be-complexed The molar ratio is 1:1. The pH was adjusted with HCl.
该过程涉及的化学反应方程式如下： The chemical reaction equation involved in this process is as follows:
S3：将含V的溶液进行浓缩结晶，得到钒酸钠产品。S3: Concentrate and crystallize the V-containing solution to obtain sodium vanadate product.
进一步地，还可包括S4：将磷酸铁与钠盐(如碳酸钠或氢氧化钠)混合烧结，得到磷酸铁钠。或者，将磷酸铁与锂盐(如碳酸锂)混合烧结，得到磷酸铁锂。Further, it may also include S4: mixing and sintering iron phosphate with sodium salt (such as sodium carbonate or sodium hydroxide) to obtain sodium iron phosphate. Alternatively, iron phosphate and lithium salt (such as lithium carbonate) are mixed and sintered to obtain lithium iron phosphate.
较佳地，烧结前，可将得到的磷酸铁极性洗涤焙烧和碾碎。Preferably, the obtained polar iron phosphate can be washed, roasted and ground before sintering.
此外，还可将退役将退役和/或废旧的NayV2-xMx(PO4)3钠离子正极拆分得到的负极片进行高温煅烧和碳化处理，得到硬碳。In addition, the negative electrode sheet obtained by splitting the decommissioned and/or discarded Na y V 2-x M x (PO 4 ) 3 sodium ion positive electrode can also be subjected to high-temperature calcination and carbonization to obtain hard carbon.
以下结合实施例对本申请的特征和性能作进一步的详细描述。The features and performance of the present application will be described in further detail below in conjunction with examples.
实施例1Example 1
本实施例提供一种退役钠正极材料Na3V2(PO4)3(NASICON)的回收方法，流程示意图如图1所示，具体包括以下步骤：This embodiment provides a method for recycling decommissioned sodium cathode material Na 3 V 2 (PO 4 ) 3 (NASICON). The flow diagram is shown in Figure 1, which specifically includes the following steps:
步骤(1)：将退役和/或废旧的Na3V2(PO4)3钠离子正极(图1中称为磷钒 酸钠电池)进行放电处理，然后将正极片、隔膜、负极片进行拆解分离。Step (1): Replace the retired and/or used Na 3 V 2 (PO 4 ) 3 sodium ion positive electrode (referred to as phosphorus vanadium in Figure 1 Sodium acid battery) is discharged, and then the positive electrode sheet, separator, and negative electrode sheet are disassembled and separated.
将拆分后所得的正极片在容器中与水进行高速搅拌(转速为800rpm)，使正极材料与载体片分离，过滤除去载体片，得到正极材料溶液。The positive electrode sheet obtained after splitting is stirred with water at high speed in a container (rotation speed is 800 rpm) to separate the positive electrode material from the carrier sheet, and the carrier sheet is filtered to obtain a positive electrode material solution.
步骤(2)：在Na3V2(PO4)3正极材料溶液中加入氢氧化钠溶液发生碱洗反应，正极材料的与氢氧化钠的摩尔比为1:2。剧烈搅拌(转速为800rpm)，反应24h，反应温度为30℃，得到含V和P的溶液。Step (2): Add sodium hydroxide solution to the Na 3 V 2 (PO 4 ) 3 positive electrode material solution to cause an alkali washing reaction. The molar ratio of the positive electrode material to sodium hydroxide is 1:2. Stir vigorously (rotation speed is 800 rpm), react for 24 hours, and the reaction temperature is 30°C to obtain a solution containing V and P.
步骤(3)：缓慢的加入定量的Fe3+溶液到含V和P的溶液中，Fe3+的加入的摩尔比与PO4 3-的比值为1:1，调节pH值至2.8，使与Fe3+完全发生沉淀发反应，生成FePO4沉淀(其SEM图以及XRD图分别如图2和图3所示)。Step (3): Slowly add a certain amount of Fe 3+ solution to the solution containing V and P. The molar ratio of Fe 3+ added to PO 4 3- is 1:1. Adjust the pH value to 2.8 so that A complete precipitation reaction occurs with Fe 3+ to generate FePO 4 precipitate (its SEM images and XRD images are shown in Figure 2 and Figure 3 respectively).
步骤(4)：将生成的磷酸铁FePO4过滤收集，得到含V的滤液，将含钒滤液进行高度浓缩结晶，得到钒酸钠成品。Step (4): Filter and collect the generated iron phosphate FePO 4 to obtain a V-containing filtrate. The vanadium-containing filtrate is highly concentrated and crystallized to obtain the finished product of sodium vanadate.
步骤(5)：将生成的磷酸铁FePO4与定量的碳酸锂进行混料，800℃高温烧结18h，得到磷酸铁锂正极材料。Step (5): Mix the generated iron phosphate FePO 4 with a certain amount of lithium carbonate, and sinter at a high temperature of 800°C for 18 hours to obtain a lithium iron phosphate cathode material.
步骤(6)：将负极材料进行高温煅烧和碳化，得到硬碳。Step (6): Calcide and carbonize the negative electrode material at high temperature to obtain hard carbon.
实施例2Example 2
本实施例提供一种退役钠正极材料Na3VFe(PO4)3的回收方法，具体包括以下步骤：This embodiment provides a method for recycling decommissioned sodium cathode material Na 3 VFe(PO 4 ) 3 , which specifically includes the following steps:
步骤(1)：将退役和/或废旧的Na3VFe(PO4)3钠离子正极进行放电处理，然后将正极片、隔膜、负极片进行拆解分离。Step (1): Discharge the retired and/or discarded Na 3 VFe(PO 4 ) 3 sodium ion positive electrode, and then disassemble and separate the positive electrode sheet, separator, and negative electrode sheet.
将拆分得到的正极片在容器中与水进行高速搅拌(500prm)，使正极材料与载体片分离，过滤除去载体片，得到正极材料溶液。The separated cathode sheets are stirred with water at high speed (500 prm) in a container to separate the cathode material from the carrier sheet. The carrier sheet is filtered to remove the cathode material solution to obtain a cathode material solution.
步骤(2)：在Na3VFe(PO4)3正极材料溶液中加入氢氧化钠溶液发生碱洗反应，正极材料的与氢氧化钠的摩尔比为1:3。剧烈搅拌(500prm)，反应24h，反应温度为70℃，得到含V、P、Fe离子的溶液。Step (2): Add sodium hydroxide solution to the Na 3 VFe(PO 4 ) 3 positive electrode material solution to cause an alkali washing reaction. The molar ratio of the positive electrode material to sodium hydroxide is 1:3. Stir vigorously (500prm), react for 24 hours, and the reaction temperature is 70°C to obtain a solution containing V, P, and Fe ions.
步骤(3)：缓慢的加入定量的Fe3+溶液到含V、P和Fe的溶液中，Fe3+的加入的摩尔比与的比值为1:1，调节pH值至2.5，使与Fe3+完全发生 沉淀发反应，生成FePO4沉淀。Step (3): Slowly add a certain amount of Fe 3+ solution to the solution containing V, P and Fe. The molar ratio of Fe 3+ added is equal to The ratio is 1:1, adjust the pH value to 2.5, so that Occurs exactly with Fe 3+ The precipitation reaction produces FePO 4 precipitation.
步骤(4)：将生成的磷酸铁FePO4过滤收集，得到含V的滤液，将含钒滤液进行高度浓缩结晶，得到钒酸钠成品。Step (4): Filter and collect the generated iron phosphate FePO 4 to obtain a V-containing filtrate. The vanadium-containing filtrate is highly concentrated and crystallized to obtain the finished product of sodium vanadate.
步骤(5)：将生成的磷酸铁FePO4与定量的碳酸锂进行混料，800℃高温烧结18h，得到磷酸铁锂正极材料。Step (5): Mix the generated iron phosphate FePO 4 with a certain amount of lithium carbonate, and sinter at a high temperature of 800°C for 18 hours to obtain a lithium iron phosphate cathode material.
实施例3Example 3
本实施例提供一种退役钠正极材料Na3V1.5Al0.5(PO4)3的回收方法，具体包括以下步骤：This embodiment provides a method for recycling retired sodium cathode material Na 3 V 1.5 Al 0.5 (PO 4 ) 3 , which specifically includes the following steps:
步骤(1)：将退役和/或废旧的Na3V1.5Al0.5(PO4)3钠离子正极进行放电处理，然后将正极片、隔膜、负极片进行拆解分离。Step (1): Discharge the retired and/or used Na 3 V 1.5 Al 0.5 (PO 4 ) 3 sodium ion positive electrode, and then disassemble and separate the positive electrode sheet, separator, and negative electrode sheet.
将拆分得到的正极片在容器中与水进行高速搅拌(600prm)，使正极材料与载体片分离，过滤除去载体片，得到正极材料溶液。The separated cathode sheets are stirred with water at high speed (600 prm) in a container to separate the cathode material from the carrier sheet. The carrier sheet is filtered to remove the cathode material solution to obtain a cathode material solution.
步骤(2)：在Na3V1.5Al0.5(PO4)3正极材料溶液中加入氢氧化钠溶液发生碱洗反应，正极材料的与氢氧化钠的摩尔比为1:3。剧烈搅拌(600prm)，反应24h，反应温度为50℃，得到含V、P、Al离子的溶液。调节pH值，使Al离子发生沉淀，过滤滤渣。Step (2): Add sodium hydroxide solution to the Na 3 V 1.5 Al 0.5 (PO 4 ) 3 positive electrode material solution to cause an alkali washing reaction. The molar ratio of the positive electrode material to sodium hydroxide is 1:3. Stir vigorously (600prm), react for 24 hours, and the reaction temperature is 50°C to obtain a solution containing V, P, and Al ions. Adjust the pH value to precipitate Al ions and filter the residue.
步骤(3)：缓慢的加入定量的Fe3+溶液到含V和P的溶液中，Fe3+的加入的摩尔比与的比值为1:1，调节pH值至2.7，使与Fe3+完全发生沉淀发反应，生成FePO4沉淀。Step (3): Slowly add a certain amount of Fe 3+ solution to the solution containing V and P. The molar ratio of Fe 3+ added is equal to The ratio is 1:1, adjust the pH value to 2.7, so that It completely reacts with Fe 3+ to form FePO 4 precipitate.
步骤(4)：将生成的磷酸铁FePO4过滤收集，得到含V的滤液，将含钒滤液进行高度浓缩结晶，得到钒酸钠成品。Step (4): Filter and collect the generated iron phosphate FePO 4 to obtain a V-containing filtrate. The vanadium-containing filtrate is highly concentrated and crystallized to obtain the finished product of sodium vanadate.
步骤(5)：将生成的磷酸铁FePO4与定量的碳酸锂进行混料，800℃高温烧结18h，得到磷酸铁锂正极材料。Step (5): Mix the generated iron phosphate FePO 4 with a certain amount of lithium carbonate, and sinter at a high temperature of 800°C for 18 hours to obtain a lithium iron phosphate cathode material.
实施例4Example 4
本实施例提供一种退役钠正极材料Na4VMn(PO4)3的回收方法，具体包括以下步骤： This embodiment provides a method for recycling retired sodium cathode material Na 4 VMn (PO 4 ) 3 , which specifically includes the following steps:
步骤(1)：将退役和/或废旧的Na4VMn(PO4)3钠离子正极进行放电处理，然后将正极片、隔膜、负极片进行拆解分离。Step (1): Discharge the retired and/or discarded Na 4 VMn(PO 4 ) 3 sodium ion positive electrode, and then disassemble and separate the positive electrode sheet, separator, and negative electrode sheet.
将拆分得到的正极片在容器中与水进行高速搅拌(700prm)，使正极材料与载体片分离，过滤除去载体片，得到正极材料溶液。The separated cathode sheet is stirred with water at high speed (700 prm) in a container to separate the cathode material from the carrier sheet. The carrier sheet is filtered to remove the cathode material solution to obtain a cathode material solution.
步骤(2)：在Na4VMn(PO4)3正极材料溶液中加入氢氧化钠溶液发生碱洗反应，正极材料的与氢氧化钠的摩尔比为1:3。剧烈搅拌(700prm)，反应24h，反应温度为30℃，得到含V、P、Mn离子的溶液。调节pH值，使Mn离子发生沉淀，过滤滤渣。Step (2): Add sodium hydroxide solution to the Na 4 VMn(PO 4 ) 3 positive electrode material solution to cause an alkali washing reaction. The molar ratio of the positive electrode material to sodium hydroxide is 1:3. Stir vigorously (700prm), react for 24 hours, and the reaction temperature is 30°C to obtain a solution containing V, P, and Mn ions. Adjust the pH value to precipitate Mn ions and filter the residue.
步骤(3)：缓慢的加入定量的Fe3+溶液到含V和P的溶液中，Fe3+的加入的摩尔比与的比值为1:1，调节pH值到2.6，使与Fe3+完全发生沉淀发反应，生成FePO4沉淀。Step (3): Slowly add a certain amount of Fe 3+ solution to the solution containing V and P. The molar ratio of Fe 3+ added is equal to The ratio is 1:1, adjust the pH value to 2.6, so that It completely reacts with Fe 3+ to form FePO 4 precipitate.
步骤(4)：将生成的磷酸铁FePO4过滤收集，得到含V的滤液，将含钒滤液进行高度浓缩结晶，得到钒酸钠成品。Step (4): Filter and collect the generated iron phosphate FePO 4 to obtain a V-containing filtrate. The vanadium-containing filtrate is highly concentrated and crystallized to obtain the finished product of sodium vanadate.
步骤(5)：将生成的磷酸铁FePO4与定量的碳酸锂进行混料，800℃高温烧结18h，得到磷酸铁锂正极材料。Step (5): Mix the generated iron phosphate FePO 4 with a certain amount of lithium carbonate, and sinter at a high temperature of 800°C for 18 hours to obtain a lithium iron phosphate cathode material.
实施例5Example 5
本实施例提供一种退役钠正极材料Na7V4(P2O7)4PO4的回收方法，具体包括以下步骤：This embodiment provides a method for recycling retired sodium cathode material Na 7 V 4 (P 2 O 7 ) 4 PO 4 , which specifically includes the following steps:
步骤(1)：将退役和/或废旧的Na7V4(P2O7)4PO4钠离子正极进行放电处理，然后将正极片、隔膜、负极片进行拆解分离。Step (1): Discharge the retired and/or discarded Na 7 V 4 (P 2 O 7 ) 4 PO 4 sodium ion positive electrode, and then disassemble and separate the positive electrode sheet, separator, and negative electrode sheet.
将拆分得到的正极片在容器中与水进行高速搅拌(1000prm)，使正极材料与载体片分离，过滤除去载体片，得到正极材料溶液。The separated cathode sheet is stirred with water at high speed (1000 prm) in a container to separate the cathode material from the carrier sheet. The carrier sheet is filtered to remove the cathode material solution to obtain a cathode material solution.
步骤(2)：在Na7V4(P2O7)4PO4正极材料溶液中加入氢氧化钠溶液发生碱洗反应，正极材料的与氢氧化钠的摩尔比为1:8。剧烈搅拌(1000prm)，反应24h，反应温度为40℃，得到含V、P离子的溶液。Step (2): Add sodium hydroxide solution to the Na 7 V 4 (P 2 O 7 ) 4 PO 4 positive electrode material solution to cause an alkali washing reaction. The molar ratio of the positive electrode material to sodium hydroxide is 1:8. Stir vigorously (1000prm), react for 24 hours, and the reaction temperature is 40°C to obtain a solution containing V and P ions.
步骤(3)：缓慢的加入定量的Fe3+溶液到含V和P的溶液中，Fe3+的加入 的摩尔比与的比值为1:1，调节pH值至2.9，使与Fe3+完全发生沉淀发反应，生成FePO4沉淀。Step (3): Slowly add a certain amount of Fe 3+ solution to the solution containing V and P. The addition of Fe 3+ The molar ratio of The ratio is 1:1, adjust the pH value to 2.9, so that It completely reacts with Fe 3+ to form FePO 4 precipitate.
步骤(4)：将生成的磷酸铁FePO4过滤收集，得到含V的滤液，将含钒滤液进行高度浓缩结晶，得到钒酸钠成品。Step (4): Filter and collect the generated iron phosphate FePO 4 to obtain a V-containing filtrate. The vanadium-containing filtrate is highly concentrated and crystallized to obtain the finished product of sodium vanadate.
步骤(5)：将生成的磷酸铁FePO4与定量的碳酸锂进行混料，800℃高温烧结18h，得到磷酸铁锂正极材料。Step (5): Mix the generated iron phosphate FePO 4 with a certain amount of lithium carbonate, and sinter at a high temperature of 800°C for 18 hours to obtain a lithium iron phosphate cathode material.
实施例6Example 6
本实施例提供一种退役钠正极材料Na4VCr(PO4)3的回收方法，具体包括以下步骤：This embodiment provides a method for recycling decommissioned sodium cathode material Na 4 VCr(PO 4 ) 3 , which specifically includes the following steps:
步骤(1)：将退役和/或废旧的Na4VCr(PO4)3钠离子正极进行放电处理，然后将正极片、隔膜、负极片进行拆解分离。Step (1): Discharge the retired and/or discarded Na 4 VCr(PO 4 ) 3 sodium ion positive electrode, and then disassemble and separate the positive electrode sheet, separator, and negative electrode sheet.
将拆分得到的正极片在容器中与水进行高速搅拌(900prm)，使正极材料与载体片分离，过滤除去载体片，得到正极材料溶液。The separated cathode sheets are stirred with water at high speed (900 prm) in a container to separate the cathode material from the carrier sheet. The carrier sheet is filtered to remove the cathode material solution to obtain a cathode material solution.
步骤(2)：在Na4VCr(PO4)3正极材料溶液中加入氢氧化钠溶液发生碱洗反应，正极材料的与氢氧化钠的摩尔比为1:2。剧烈搅拌(900prm)，反应10h，反应温度为90℃，得到含V、P、Cr离子的溶液。调节pH值，使Cr离子发生沉淀，过滤滤渣。Step (2): Add sodium hydroxide solution to the Na 4 VCr(PO 4 ) 3 positive electrode material solution to cause an alkali washing reaction. The molar ratio of the positive electrode material to sodium hydroxide is 1:2. Stir vigorously (900prm), react for 10 hours, and the reaction temperature is 90°C to obtain a solution containing V, P, and Cr ions. Adjust the pH value to precipitate Cr ions and filter the residue.
步骤(3)：缓慢的加入定量的Fe3+溶液到含V和P的溶液中，Fe3+的加入的摩尔比与的比值为1:1，调节pH值到2.8，使与Fe3+完全发生沉淀发反应，生成FePO4沉淀。Step (3): Slowly add a certain amount of Fe 3+ solution to the solution containing V and P. The molar ratio of Fe 3+ added is equal to The ratio is 1:1, adjust the pH value to 2.8, so that It completely reacts with Fe 3+ to form FePO 4 precipitate.
步骤(4)：将生成的磷酸铁FePO4过滤收集，得到含V的滤液，将含钒滤液进行高度浓缩结晶，得到钒酸钠成品。Step (4): Filter and collect the generated iron phosphate FePO 4 to obtain a V-containing filtrate. The vanadium-containing filtrate is highly concentrated and crystallized to obtain the finished product of sodium vanadate.
步骤(5)：将生成的磷酸铁FePO4与定量的碳酸钠进行混料，800℃高温烧结18h，得到磷酸铁锂正极材料。Step (5): Mix the generated iron phosphate FePO 4 with a certain amount of sodium carbonate, and sinter at a high temperature of 800°C for 18 hours to obtain a lithium iron phosphate cathode material.
实施例7Example 7
本实施例提供一种退役钠正极材料Na4VTi(PO4)3的回收方法，具体包括以 下步骤：This embodiment provides a method for recycling retired sodium cathode material Na 4 VTi(PO 4 ) 3 , which specifically includes: Next steps:
步骤(1)：将退役和/或废旧的Na4VTi(PO4)3钠离子正极进行放电处理，然后将正极片、隔膜、负极片进行拆解分离。Step (1): Discharge the retired and/or discarded Na 4 VTi(PO 4 ) 3 sodium ion positive electrode, and then disassemble and separate the positive electrode sheet, separator, and negative electrode sheet.
将拆分得到的正极片在容器中与水进行高速搅拌(900prm)，使正极材料与载体片分离，过滤除去载体片，得到正极材料溶液。The separated cathode sheets are stirred with water at high speed (900 prm) in a container to separate the cathode material from the carrier sheet. The carrier sheet is filtered to remove the cathode material solution to obtain a cathode material solution.
步骤(2)：在Na4VTi(PO4)3正极材料溶液中加入氢氧化钠溶液发生碱洗反应，正极材料的与氢氧化钠的摩尔比为1:10。剧烈搅拌(900prm)，反应100h，反应温度为30℃，得到含V、P、Ti离子的溶液。调节pH值，使Ti离子发生沉淀，过滤滤渣。Step (2): Add sodium hydroxide solution to the Na 4 VTi(PO 4 ) 3 positive electrode material solution to cause an alkali washing reaction. The molar ratio of the positive electrode material to sodium hydroxide is 1:10. Stir vigorously (900prm), react for 100h, and the reaction temperature is 30°C to obtain a solution containing V, P, and Ti ions. Adjust the pH value to precipitate Ti ions and filter the residue.
步骤(3)：缓慢的加入定量的Fe3+溶液到含V和P的溶液中，Fe3+的加入的摩尔比与的比值为1:1，调节pH值到3.0，使与Fe3+完全发生沉淀发反应，生成FePO4沉淀。Step (3): Slowly add a certain amount of Fe 3+ solution to the solution containing V and P. The molar ratio of Fe 3+ added is equal to The ratio is 1:1, adjust the pH value to 3.0, so that It completely reacts with Fe 3+ to form FePO 4 precipitate.
步骤(4)：将生成的磷酸铁FePO4过滤收集，得到含V的滤液，将含钒滤液进行高度浓缩结晶，得到钒酸钠成品。Step (4): Filter and collect the generated iron phosphate FePO 4 to obtain a V-containing filtrate. The vanadium-containing filtrate is highly concentrated and crystallized to obtain the finished product of sodium vanadate.
步骤(5)：将生成的磷酸铁FePO4与定量的氢氧化钠进行混料，800℃高温烧结18h，得到磷酸铁锂正极材料。Step (5): Mix the generated iron phosphate FePO 4 with a certain amount of sodium hydroxide, and sinter at a high temperature of 800°C for 18 hours to obtain a lithium iron phosphate cathode material.
综上所述，本申请提供的回收方法至少具有以下优势：To sum up, the recycling method provided by this application has at least the following advantages:
(1)本申请提供的回收工艺流程简单巧妙，操作简单，原料低廉，所用溶剂为强碱，对环境友好无污染，并且所得产物易提纯分离，能实现工业化大规模生产。(1) The recycling process provided by this application is simple and ingenious, easy to operate, has low raw materials, the solvent used is a strong alkali, is environmentally friendly and pollution-free, and the resulting product is easy to purify and separate, and can achieve industrial large-scale production.
(2)本申请将磷钒酸钠正极材料进行回收利用，解决了环境污染、资料浪费等问题。能够将其中的V和P元素全面加以回收，同时生成磷酸铁锂或磷酸铁钠正极材料，可重复用于锂离子电池或钠离子电池材料中。(2) This application recycles sodium phosphovanadate cathode materials, solving problems such as environmental pollution and data waste. The V and P elements can be fully recovered, while generating lithium iron phosphate or sodium iron phosphate cathode materials, which can be reused in lithium-ion batteries or sodium-ion battery materials.
以上仅为本申请的优选实施例而已，并不用于限制本申请，对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进、组合等，均应包含在本申请的保护范围之 内。 The above are only preferred embodiments of the present application and are not intended to limit the present application. For those skilled in the art, the present application may have various modifications and changes. Any modifications, equivalent substitutions, improvements, combinations, etc. made within the spirit and principles of this application shall be included in the protection scope of this application. Inside.

Claims (10)

  1. 一种磷钒酸钠正极材料的回收方法，其中，包括以下步骤：A method for recycling sodium phosphovanadate cathode material, which includes the following steps:
    S1、将含待回收的NayV2-xMx(PO4)3正极材料的溶液与强碱混合，得到含V和P的金属离子溶液；其中，M为过渡金属，0≤x≤1，2≤y≤4；S1. Mix the solution containing the Na y V 2-x M x (PO 4 ) 3 cathode material to be recovered with a strong base to obtain a metal ion solution containing V and P; where M is a transition metal, 0≤x≤ 1,2≤y≤4;
    S2、根据金属离子溶液中所含元素的情况，分别按以下方式处理：S2. According to the elements contained in the metal ion solution, process them in the following ways:
    a、当所述金属离子溶液中还含有M元素且M元素中不含Fe时：先将M离子以氢氧化物的形式沉淀除去后，得到含V和的溶液，随后将含V和的溶液与铁离子混合，使与铁离子络合，固液分离，得到磷酸铁沉淀和含V的溶液；a. When the metal ion solution also contains M element and the M element does not contain Fe: first, M ions are precipitated and removed in the form of hydroxide to obtain V and solution, which will subsequently contain V and The solution is mixed with iron ions to make Complex with iron ions and solid-liquid separation to obtain iron phosphate precipitation and V-containing solution;
    b、当所述金属离子溶液中还含有M元素且M元素为Fe时，或者当所述金属离子溶液中不含M元素时，均直接将含V和P的金属离子溶液与铁离子混合，使与铁离子络合，固液分离，得到磷酸铁沉淀和含V的溶液；b. When the metal ion solution also contains M element and the M element is Fe, or when the metal ion solution does not contain M element, directly mix the metal ion solution containing V and P with iron ions, make Complex with iron ions and solid-liquid separation to obtain iron phosphate precipitation and V-containing solution;
    S3、将含V的溶液进行浓缩结晶，得到钒酸钠产品。S3. Concentrate and crystallize the solution containing V to obtain the sodium vanadate product.
  2. 根据权利要求1所述的回收方法，其中，还包括：将磷酸铁与钠盐混合烧结，得到磷酸铁钠。The recycling method according to claim 1, further comprising: mixing iron phosphate and sodium salt and sintering to obtain sodium iron phosphate.
  3. 根据权利要求1所述的回收方法，其中，还包括：将磷酸铁与锂盐混合烧结，得到磷酸铁锂。The recycling method according to claim 1, further comprising: mixing iron phosphate and lithium salt and sintering to obtain lithium iron phosphate.
  4. 根据权利要求1所述的回收方法，其中，含待回收的NayV2-xMx(PO4)3正极材料的溶液与强碱是于30-90℃的条件下混合10-100h；其中，正极材料与强碱的摩尔比为1:1-10。The recovery method according to claim 1, wherein the solution containing the Na y V 2-x M x (PO 4 ) 3 cathode material to be recovered and the strong alkali are mixed at 30-90°C for 10-100 hours; Among them, the molar ratio of positive electrode material to strong alkali is 1:1-10.
  5. 根据权利要求1所述的回收方法，其中，M离子以氢氧化物的形式沉淀是通过调节相应金属离子溶液的pH值实现。The recovery method according to claim 1, wherein the precipitation of M ions in the form of hydroxide is achieved by adjusting the pH value of the corresponding metal ion solution.
  6. 根据权利要求1所述的回收方法，其中，铁离子包括Fe2+和Fe3+中的至少一种。The recycling method according to claim 1, wherein the iron ions include at least one of Fe 2+ and Fe 3+ .
  7. 根据权利要求1所述的回收方法，其中，与铁离子络合经以下方式实现：将含V和的溶液与铁离子的混合溶液的pH值调节至2.5-3。The recycling method according to claim 1, wherein, Complexation with iron ions is achieved in the following way: adding V and The pH value of the mixed solution with iron ions is adjusted to 2.5-3.
  8. 根据权利要求1所述的回收方法，其中，所述含待回收的NayV2-xMx(PO4)3 正极材料的溶液经以下方式获得：The recycling method according to claim 1, wherein the Na y V 2-x M x (PO 4 ) 3 containing Na y V 2-x M x (PO 4 ) 3 to be recycled The solution of cathode material is obtained in the following way:
    将待回收的NayV2-xMx(PO4)3钠离子正极中的正极片与水混合搅拌，使载体片与正极材料分离，随后除去载体片。The positive electrode sheet in the Na y V 2-x M x (PO 4 ) 3 sodium ion positive electrode to be recovered is mixed and stirred with water to separate the carrier sheet from the positive electrode material, and then the carrier sheet is removed.
  9. 根据权利要求8所述的回收方法，其中，所述正极片经待回收的NayV2-xMx(PO4)3钠离子正极放电处理后拆分而得。The recycling method according to claim 8, wherein the positive electrode sheet is obtained by splitting the Na y V 2-x M x (PO 4 ) 3 sodium ion positive electrode discharge treatment to be recovered.
  10. 根据权利要求1所述的回收方法，其中，M选自Ti、Mn、Fe、Cr和Al中的任意一种；M的合成来源为氯化盐、硫化盐、硝酸盐或草酸盐。 The recovery method according to claim 1, wherein M is selected from any one of Ti, Mn, Fe, Cr and Al; the synthetic source of M is chloride salt, sulfide salt, nitrate or oxalate.
PCT/CN2023/077588 2022-08-29 2023-02-22 Method for recovering sodium vanadium phosphate positive electrode material WO2024045513A1 (en)

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