WO2024082544A1 - 废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法 - Google Patents

废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法 Download PDF

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WO2024082544A1
WO2024082544A1 PCT/CN2023/083145 CN2023083145W WO2024082544A1 WO 2024082544 A1 WO2024082544 A1 WO 2024082544A1 CN 2023083145 W CN2023083145 W CN 2023083145W WO 2024082544 A1 WO2024082544 A1 WO 2024082544A1
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iron phosphate
lithium iron
positive electrode
solid
waste lithium
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PCT/CN2023/083145
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English (en)
French (fr)
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余海军
王涛
谢英豪
李爱霞
张学梅
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 WO2024082544A1 publication Critical patent/WO2024082544A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B2101/00—Type of solid waste
    • B09B2101/15—Electronic waste
    • B09B2101/16—Batteries
    • 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 invention belongs to the technical field of lithium battery recycling, and particularly relates to a method for preparing lithium iron phosphate positive electrode materials by directional circulation of waste lithium iron phosphate batteries.
  • Lithium iron phosphate power batteries are highly safe, can be quickly charged, and can be cycled up to 2,000 times. They have excellent safety performance and are gradually becoming a new choice for power batteries for electric vehicles. With the increasing market share and scrap volume of lithium iron phosphate power batteries, the recycling of lithium iron phosphate in waste lithium iron phosphate power batteries has also become one of the key contents of power battery recycling. Among a variety of lithium power batteries, only the positive electrode material of lithium iron phosphate power batteries does not contain precious metals, but is mainly composed of aluminum, lithium, iron, phosphorus and carbon elements. For this reason, companies are not enthusiastic about the recycling of lithium iron phosphate, and there is relatively little research on the recycling of lithium iron phosphate power batteries.
  • the present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes a method for preparing lithium iron phosphate positive electrode materials from waste lithium iron phosphate batteries in a directional cycle, which can recover lithium iron phosphate and then directional cycle to prepare lithium iron phosphate positive electrode materials, and the prepared positive electrode materials have a high specific capacity, thereby achieving full utilization of resources.
  • the method for preparing lithium iron phosphate positive electrode material by directional circulation of waste lithium iron phosphate batteries comprises the following steps:
  • step (2) adding phosphoric acid to the filtrate obtained in step (1) and performing thermal decomposition to obtain a dry material, and mixing the dry material with a lithium source, a ferrous source, and a carbon source to obtain a mixed material;
  • step (3) adding the mixture obtained in step (2) into ammonia water for hydrothermal reaction, then evaporating ammonia to obtain solid particles, and then The solid particles are calcined in an inert gas to obtain a lithium iron phosphate positive electrode material.
  • the alkali solution is at least one of a sodium hydroxide solution and a potassium hydroxide solution, and the mass percentage concentration of the alkali solution is 1%-10%.
  • the alkali solution is at least one of a sodium hydroxide solution and a potassium hydroxide solution, and the mass percentage concentration of the alkali solution is 2%-6%.
  • the liquid-to-solid ratio of the alkaline solution to the waste lithium iron phosphate battery black powder is (1-5) mL/g.
  • the liquid-to-solid ratio of the alkali solution to the waste lithium iron phosphate battery black powder is (2-4) mL/g.
  • the alkali leaching temperature is 30-100° C.
  • the alkali leaching time is 1-5 h.
  • the alkali leaching temperature is 50-90° C.
  • the alkali leaching time is 1-3 h.
  • the acid is at least one of hydrochloric acid and sulfuric acid, and the concentration of the acid is 1-3 mol/L.
  • the concentration of the acid is 2-2.5 mol/L.
  • the oxidant is hydrogen peroxide, and the concentration of the hydrogen peroxide is 3 vol%-20 vol%.
  • the oxidant is hydrogen peroxide, and the concentration of the hydrogen peroxide is 5 vol%-15 vol%.
  • the liquid-to-solid ratio of the mixed solution consisting of the acid and the oxidant to the solid slag is (2-9) mL/g.
  • the liquid-to-solid ratio of the mixed solution consisting of the acid and the oxidant to the solid slag is (4-6) mL/g.
  • the soaking temperature is 50-100° C. and the soaking time is 1-5 h.
  • the soaking temperature is 60-75° C. and the soaking time is 1-3 h.
  • the reducing agent is at least one of iron powder and copper powder.
  • the molar ratio of Fe to Cu in the filtrate is 100:(1-10).
  • step (1) the molar ratio of Fe to Cu in the filtrate is 100:(1-8).
  • the pyrolysis method is spray pyrolysis.
  • the pyrolysis is carried out by placing the filtrate in a spray pyrolysis device with nitrogen as carrier.
  • the gas flow is sprayed for pyrolysis, the carrier gas flow rate is 60-150L/h, the pyrolysis temperature is 200-500°C, and fluoride ions and chloride ions are removed.
  • the pyrolysis method is to place the filtrate in a spray pyrolysis device, and perform spray pyrolysis with nitrogen as the carrier gas flow, the carrier gas flow rate is 80-120L/h, the pyrolysis temperature is 300-400°C, and fluoride ions and chloride ions are removed.
  • step (2) the molar ratio of Fe to P in the mixture is 1:1 and the molar ratio of Li to (Fe+2Cu) is (1.05-1.1):1.
  • the lithium source is at least one of lithium hydroxide, lithium carbonate and lithium oxalate.
  • the ferrous source is at least one of ferrous oxalate and ferrous acetate.
  • the molar amount of the carbon source added is 2-4 times the copper element in the dry material, and the carbon source is at least one of glucose, fructose, galactose, lactose and maltose.
  • the liquid-to-solid ratio of the aqueous ammonia to the mixed material is (1-5) mL/g, and the concentration of the aqueous ammonia is 3-10 mol/L.
  • the liquid-to-solid ratio of the aqueous ammonia to the mixed material is (2-3) mL/g, and the concentration of the aqueous ammonia is 4-6 mol/L.
  • step (3) the hydrothermal reaction is carried out in a closed container at a temperature of 100-200° C. for 2-10 hours.
  • step (3) the hydrothermal reaction is carried out in a closed container at a temperature of 140-160° C. for 4-8 hours.
  • the temperature of the ammonia evaporation is 80-100°C.
  • step (3) the temperature of the ammonia evaporation is 90-95°C.
  • the calcination temperature is 600-900° C.
  • the calcination time is 2-10 h.
  • the calcination temperature is 700-850° C.
  • the calcination time is 4-6 hours.
  • the method for preparing lithium iron phosphate positive electrode material by directional circulation of waste lithium iron phosphate batteries comprises the following steps:
  • a lithium source, a ferrous source, and a carbon source are added to form a mixture so that the molar ratio of Fe to P is 1:1 and the molar ratio of Li to (Fe+2Cu) is 1.05-1.1:1;
  • the lithium source is lithium hydroxide, lithium carbonate, lithium oxalate, and the ferrous source is ferrous oxalate or ferrous acetate;
  • the molar amount of the carbon source is 2-4 times that of the copper element in the solid particles;
  • the carbon source is glucose, fructose, galactose, lactose, or maltose;
  • the present invention firstly adds alkali to leach the black powder obtained by recycling waste lithium iron phosphate batteries, removes aluminum in the black powder, and avoids the formation of impurities in the subsequent leachate; then after washing, acid leaching is performed to obtain a leachate containing lithium, phosphorus, iron, copper, fluorine, and chlorine; iron powder/copper powder is added to reduce the trivalent iron in the leachate to avoid the direct generation of iron phosphate precipitation, adsorb impurity ions such as fluorine and chlorine, and cause the fluorine and chlorine impurities in the iron phosphate product to exceed the standard, affecting the subsequent preparation of lithium iron phosphate.
  • the present invention adds phosphoric acid to protect metal ions, and uses spray pyrolysis to treat the leachate to obtain the corresponding solid product.
  • the droplet concentration gradually increases, and a phosphate precipitate is first formed.
  • the residual fluorine ions and chloride ions are volatilized as hydrogen fluoride and hydrogen chloride.
  • the reaction principle is as follows: Fe 2+ +PO 4 3- ⁇ Fe 3 (PO 4 ) 2 Cu 2+ +PO 4 3- ⁇ Cu 3 (PO 4 ) 2 Li + +PO 4 3- ⁇ Li 3 PO 4 ;
  • the solid product produced by spray pyrolysis is recrystallized under hydrothermal conditions under the action of concentrated ammonia (ammonia can complex with copper ions and ferrous ions) to generate lithium iron phosphate and reduced copper.
  • the reaction principle is as follows: Fe 3 (PO 4 ) 2 +6NH 3 ⁇ 3[Fe(NH 3 ) 2 ] 2+ +2PO 4 3- Cu 3 (PO 4 ) 2 +18NH 3 ⁇ 3[Cu(NH 3 ) 6 ] 2+ +2PO 4 3- 3NH 3 ⁇ H 2 O+Li 3 PO 4 ⁇ 3Li + +3OH - +3NH 4 + +PO 4 3- [Fe(NH 3 ) 2 ] 2+ +PO 4 3- +Li + ⁇ LiFePO 4 +2NH 3 ;
  • cupric ammonium ions Due to the strong complexing ability of copper and ammonia, it still exists in the form of cupric ammonium ions, which are hydrothermally reduced to form cuprous ammonium ions. As the ammonia evaporation reaction proceeds, the solution in the kettle decreases, the ammonia concentration decreases, and the copper and residual lithium are doped in the lithium iron phosphate particles in the form of lithium cuprous oxide.
  • the hydrothermally generated lithium iron phosphate is better crystallized, and on the other hand, the residual carbon source is further carbonized to form a conductive material, thereby improving the conductivity of the material. Due to the small particle size and low carbon content of the material obtained by the hydrothermal reaction, it has a higher specific capacity and cycle performance.
  • FIG1 is a process flow chart of Example 1 of the present invention.
  • FIG. 2 is a SEM image of the lithium iron phosphate positive electrode material prepared in Example 1 of the present invention.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • the method for preparing lithium iron phosphate positive electrode material by directional circulation of waste lithium iron phosphate batteries, as shown in FIG1 comprises the following steps:
  • lithium oxalate, ferrous oxalate and glucose are added, wherein the molar amount of glucose is 4 times that of the copper element in the solid particles; the molar ratio of Fe to P is 1:1 and the molar ratio of Li to (Fe+2Cu) is 1.05:1, to form a mixture;
  • the solid particles are placed in a nitrogen flow and calcined at 700° C. for 6 h to obtain a lithium iron phosphate positive electrode material.
  • the SEM image of the prepared lithium iron phosphate positive electrode material is shown in FIG. 2 .
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • the method for preparing lithium iron phosphate positive electrode material by directional circulation of waste lithium iron phosphate batteries comprises the following steps:
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • the method for preparing lithium iron phosphate positive electrode material by directional circulation of waste lithium iron phosphate batteries comprises the following steps:
  • the method for preparing lithium iron phosphate positive electrode material by directional circulation of waste lithium iron phosphate batteries comprises the following steps:
  • lithium oxalate and ferrous oxalate are added to form a mixture so that the molar ratio of Li, Fe and P is 1.05:1:1;
  • the method for preparing lithium iron phosphate positive electrode material by directional circulation of waste lithium iron phosphate batteries comprises the following steps:
  • the lithium iron phosphate positive electrode material obtained in the embodiment and the comparative example, acetylene black as a conductive agent, PVDF as a binder, are mixed at a mass ratio of 8:1:1, and a certain amount of organic solvent NMP is added, and then coated on an aluminum foil after stirring to make a positive electrode sheet, and a metal lithium sheet is used as the negative electrode;
  • the diaphragm is a Celgard2400 polypropylene porous membrane;
  • the solvent in the electrolyte is a solution composed of EC, DMC and EMC at a mass ratio of 1:1:1, the solute is LiPF 6 , and the concentration of LiPF 6 is 1.0 mol/L; 2023 button cells are assembled in a glove box.
  • the battery is tested for charge and discharge cycle performance, and the 0.2C discharge specific capacity is tested within the cut-off voltage range of 2.0-3.65V; the electrochemical performance test results are shown in Table 1 below.
  • the lithium iron phosphate positive electrode material obtained by the method for preparing lithium iron phosphate positive electrode material from waste lithium iron phosphate batteries through directional circulation of the present invention has a high discharge capacity and excellent cycle performance, and its 0.2C discharge capacity can reach 160.7 mAh/g, and its capacity retention rate after 100 cycles at 1C is above 98.1%.

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Abstract

本发明公开了废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法，包括以下步骤：(1)将废旧磷酸铁锂电池黑粉用碱液碱浸后固液分离，得到固体渣，将所述固体渣与酸、氧化剂混合浸泡后，再加入还原剂，然后固液分离，得到滤液；(2)向步骤(1)得到的所述滤液中加入磷酸后热解，得到干燥料，将所述干燥料与锂源、亚铁源及碳源混合，得到混合料；(3)将步骤(2)得到的混合料加入氨水中进行水热反应，然后蒸氨得到固体颗粒，再将所述固体颗粒在惰性气体中焙烧得到磷酸铁锂正极材料。该方法制备得到的正极材料具备较高的比容量，从而达到资源的充分利用。

Description

废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法 技术领域
本发明属于锂电池回收技术领域，特别涉及废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法。
背景技术
磷酸铁锂动力电池的安全性高，可快速充电且循环次数能达到2000次，具有很好的安全性能，逐渐成为电动汽车用动力电池的新选择。随着磷酸铁锂动力电池市场占有量和报废量的日益上升，废旧磷酸铁锂动力电池中的磷酸铁锂回收利用也成为动力电池回收的重点内容之一。在多种锂动力电池中，只有磷酸铁锂动力电池正极材料不含贵金属，而是主要由铝、锂、铁、磷和碳元素组成。正因如此，企业对磷酸铁锂的回收利用并不热心，针对磷酸铁锂动力电池回收的研究也比较少。
现有的对废旧磷酸铁锂动力电池的回收工艺中，会引入大量的杂质离子，造成后续碳酸铁锂的纯度降低，导致无法直接使用回收得到的碳酸铁锂制备成正极材料或者制备成正极材料后的比容量较低。
因此急需开发新的对废旧磷酸铁锂动力电池的回收方法。
发明内容
本发明旨在至少解决现有技术中存在的技术问题之一。为此，本发明提出一种废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法，该方法能将磷酸铁锂回收后定向循环制备磷酸铁锂正极材料，且制备得到的正极材料具备较高的比容量，从而达到资源的充分利用。
本发明的上述技术目的是通过以下技术方案得以实现的：
废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法，包括以下步骤：
(1)将废旧磷酸铁锂电池黑粉用碱液碱浸后固液分离，得到固体渣，将所述固体渣与酸、氧化剂混合浸泡后，再加入还原剂，然后固液分离，得到滤液；
(2)向步骤(1)得到的所述滤液中加入磷酸后热解，得到干燥料，将所述干燥料与锂源、亚铁源及碳源混合，得到混合料；
(3)将步骤(2)得到的混合料加入氨水中进行水热反应，然后蒸氨得到固体颗粒，再将 所述固体颗粒在惰性气体中焙烧得到磷酸铁锂正极材料。
优选的，步骤(1)中，所述碱液为氢氧化钠溶液与氢氧化钾溶液中的至少一种，所述碱液的质量百分比浓度为1％-10％。
进一步优选的，步骤(1)中，所述碱液为氢氧化钠溶液与氢氧化钾溶液中的至少一种，所述碱液的质量百分比浓度为2％-6％。
优选的，步骤(1)中，所述碱液与所述废旧磷酸铁锂电池黑粉的液固比为(1-5)mL/g。
进一步优选的，步骤(1)中，所述碱液与所述废旧磷酸铁锂电池黑粉的液固比为(2-4)mL/g。
优选的，步骤(1)中，所述碱浸的温度为30-100℃，碱浸的时间为1-5h。
进一步优选的，步骤(1)中，所述碱浸的温度为50-90℃，碱浸的时间为1-3h。
优选的，步骤(1)中，所述酸为盐酸及硫酸中的至少一种，所述酸的浓度为1-3mol/L。
进一步优选的，步骤(1)中，所述酸的浓度为2-2.5mol/L。
优选的，步骤(1)中，所述氧化剂为双氧水，所述双氧水的浓度为3vol％-20vol％。
进一步优选的，步骤(1)中，所述氧化剂为双氧水，所述双氧水的浓度为5vol％-15vol％。
优选的，步骤(1)中，所述酸与所述氧化剂组成的混合液与所述固体渣的液固比为(2-9)mL/g。
进一步优选的，步骤(1)中，所述酸与所述氧化剂组成的混合液与所述固体渣的液固比为(4-6)mL/g。
优选的，步骤(1)中，所述浸泡的温度为50-100℃，浸泡时间为1-5h。
进一步优选的，步骤(1)中，所述浸泡的温度为60-75℃，浸泡时间为1-3h。
优选的，步骤(1)中，所述还原剂为铁粉及铜粉中的至少一种。
优选的，步骤(1)中，所述滤液中Fe与Cu的摩尔比＝100:(1-10)。
进一步优选的，步骤(1)中，所述滤液中Fe与Cu的摩尔比＝100:(1-8)。
优选的，步骤(2)中，加入所述磷酸后，所述滤液中离子摩尔量满足以下条件：3Li++1.5(Fe2++Cu2+)＝2PO4 3-。
优选的，步骤(2)中，所述热解的方式为喷雾热解。
优选的，步骤(2)中，所述热解的方式为将所述滤液置于喷雾热解装置中，以氮气为载 气气流进行喷雾热解，载气流量为60-150L/h，热解温度为200-500℃，去除氟离子、氯离子。
进一步优选的，步骤(2)中，所述热解的方式为将所述滤液置于喷雾热解装置中，以氮气为载气气流进行喷雾热解，载气流量为80-120L/h，热解温度为300-400℃，去除氟离子、氯离子。
优选的，步骤(2)中，所述混合料中Fe与P的摩尔比＝1:1且Li与(Fe+2Cu)的摩尔比＝(1.05-1.1):1。
优选的，步骤(2)中，所述锂源为氢氧化锂、碳酸锂及草酸锂中的至少一种。
优选的，步骤(2)中，所述亚铁源为草酸亚铁及醋酸亚铁中的至少一种。
优选的，步骤(2)中，添加所述碳源的摩尔量为所述干燥料中铜元素的2-4倍，所述碳源为葡萄糖、果糖、半乳糖、乳糖及麦芽糖中的至少一种。
优选的，步骤(3)中，所述氨水与所述混合料的液固比为(1-5)mL/g，所述氨水的浓度为3-10mol/L。
进一步优选的，步骤(3)中，所述氨水与所述混合料的液固比为(2-3)mL/g，所述氨水的浓度为4-6mol/L。
优选的，步骤(3)中，所述的水热反应为在温度为100-200℃下的密闭容器中反应2-10h。
进一步优选的，步骤(3)中，所述的水热反应为在温度为140-160℃下的密闭容器中反应4-8h。
优选的，步骤(3)中，所述蒸氨的温度为80-100℃。
进一步优选的，步骤(3)中，所述蒸氨的温度为90-95℃。
优选的，步骤(3)中，所述焙烧的温度为600-900℃，所述焙烧的时间为2-10h。
进一步优选的，步骤(3)中，所述焙烧的温度为700-850℃，所述焙烧的时间为4-6h。
优选的，废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法，包括以下步骤：
(1)按液固比2-4mL/g，将废旧磷酸铁锂电池黑粉用2-6％的液碱在50-90℃下浸出1-3h；
(2)固液分离，将固体渣用纯水洗涤后，按液固比4-6mL/g，将固体渣用用盐酸及双氧水的混合液在60-75℃下浸出1-3h，盐酸的浓度2-2.5mol/L，双氧水的浓度为5vol％-15vol％；
(3)按照还原剂：三价铁的摩尔比1.05-1.1:1，向浸出液中加入还原剂，除去三价铁离子；还原剂为铁粉、铜粉中的至少一种，使浸出液中Fe与Cu的摩尔比＝100:1-8；
(4)固液分离后，向滤液中加入磷酸，调节滤液中离子摩尔量满足以下条件： 3Li++1.5(Fe2++Cu2+)＝2PO4 3-；
(5)将滤液置于喷雾热解装置中，以氮气为载气气流进行喷雾热解，载气流量为100-150L/h，热解温度为350-500℃，去除氟离子、氯离子；
(6)将喷雾热解产生的固体颗粒收集后，加入锂源、亚铁源、碳源，使Fe与P的摩尔比＝1:1且Li与(Fe+2Cu)的摩尔比＝1.05-1.1:1，形成混合料；锂源为氢氧化锂、碳酸锂、草酸锂，亚铁源为草酸亚铁、醋酸亚铁；碳源的摩尔量是固体颗粒中铜元素的2-4倍；碳源为葡萄糖、果糖、半乳糖、乳糖、麦芽糖；
(7)按照液固比2-3mL/g，将混合料加入至4-6mol/L的氨水中，在温度为140-160℃下密闭反应釜中水热反应时间4-8h；
(8)水热反应结束后，打开反应釜，继续加热温度为90-95℃，蒸氨，直至完全干燥，得到固体颗粒；
(9)将固体颗粒置于氮气流中，在700-850℃下高温焙烧4-6h，即得磷酸铁锂正极材料。
本发明的有益效果是：
本发明首先将废旧的磷酸铁锂电池回收得到的黑粉进行加碱浸出，除去黑粉中的铝，避免在后续浸出液中形成杂质；而后经洗涤后，采用酸浸，得到含锂、磷、铁、铜、氟、氯的浸出液；通过加入铁粉/铜粉还原浸出液中三价铁，避免直接产生磷酸铁沉淀，吸附氟氯等杂质离子，造成磷酸铁产品氟氯杂质超标，影响后续磷酸铁锂的制备。本发明通过加入磷酸保护金属离子，并采用喷雾热解的方式对浸出液进行处理，得到对应的固体产物，喷雾热解过程中，液滴浓度逐渐升高，首先形成磷酸盐沉淀，残留的氟离子、氯离子则以氟化氢、氯化氢挥发出去，反应原理如下：
Fe2++PO4 3-→Fe3(PO4)2
Cu2++PO4 3-→Cu3(PO4)2
Li++PO4 3-→Li3PO4；
喷雾热解产生的固体产物，在浓氨水的作用下，(氨水可与铜离子、亚铁离子络合)在水热条件下进行重结晶，生成磷酸铁锂和还原铜。反应原理如下：
Fe3(PO4)2+6NH3→3[Fe(NH3)2]2++2PO4 3-
Cu3(PO4)2+18NH3→3[Cu(NH3)6]2++2PO4 3-
3NH3·H2O+Li3PO4→3Li++3OH-+3NH4 ++PO4 3-
[Fe(NH3)2]2++PO4 3-+Li+→LiFePO4+2NH3；
由于铜与氨的络合能力较强，仍以铜氨离子的形式存在，经水热还原生成亚铜氨离子，随着进一步蒸氨反应的进行，釜内溶液减少，氨浓度降低，铜与残留的锂以氧化亚铜锂的形式掺杂于磷酸铁锂颗粒中。
通过后续进一步烧结，一方面，使水热生成的磷酸铁锂更好的结晶，另一方面，残留的碳源也进一步碳化，形成导电材料，从而提高材料的电导率。由于采用了水热反应得到的材料颗粒度较小，且掺碳量低，具有较高比容量和循环性能。
附图说明
图1为本发明实施例1的工艺流程图。
图2为本发明实施例1制备得到的磷酸铁锂正极材料的SEM图。
具体实施方式
下面结合具体实施例对本发明做进一步的说明。
实施例1：
废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法，如图1所示，包括如下步骤：
(1)按液固比4mL/g，将废旧磷酸铁锂电池黑粉用质量百分比浓度为2％的氢氧化钠溶液在90℃下浸出3h；
(2)固液分离，将固体渣用纯水洗涤后，按液固比6mL/g，将固体渣用盐酸及双氧水的混合液在75℃下浸出3h，盐酸的浓度为2mol/L，双氧水的浓度为5vol％；
(3)按照还原剂：三价铁的摩尔比1.05:1，向浸出液中加入还原剂，除去三价铁离子；还原剂为铁粉、铜粉中的至少一种，使浸出液中Fe与Cu的摩尔比＝100:1；
(4)固液分离后，向滤液中加入磷酸，调节滤液中离子摩尔量满足以下条件：3Li++1.5(Fe2++Cu2+)＝2PO4 3-；
(5)将滤液置于喷雾热解装置中，以氮气为载气气流进行喷雾热解，载气流量为100L/h，热解温度为350℃，去除氟离子、氯离子；
(6)将喷雾热解产生的固体颗粒收集后，加入草酸锂、草酸亚铁、葡萄糖，葡萄糖的摩尔量是固体颗粒中铜元素的4倍；使Fe与P的摩尔比＝1:1且Li与(Fe+2Cu)的摩尔比＝1.05:1，形成混合料；
(7)按照液固比2mL/g，将混合料加入至6mol/L的氨水中，在温度为140℃下密闭反应釜 中水热反应时间4h；
(8)水热反应结束后，打开反应釜，继续加热温度为90℃，蒸氨，直至完全干燥，得到固体颗粒；
(9)将固体颗粒置于氮气流中，在700℃下高温焙烧6h，即得磷酸铁锂正极材料，制得的磷酸铁锂正极材料的SEM图如图2所示。
实施例2：
废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法，包括如下步骤：
(1)按液固比3mL/g，将废旧磷酸铁锂电池黑粉用质量百分比浓度为4％的氢氧化钠溶液在70℃下浸出2h；
(2)固液分离，将固体渣用纯水洗涤后，按液固比5mL/g，将固体渣用盐酸及双氧水的混合液在68℃下浸出2h，盐酸的浓度为2.5mol/L，双氧水的浓度为10vol％；
(3)按照还原剂：三价铁的摩尔比1.1:1，向浸出液中加入还原剂，除去三价铁离子；还原剂为铁粉、铜粉中的至少一种，使浸出液中Fe与Cu的摩尔比＝100:4；
(4)固液分离后，向滤液中加入磷酸，调节滤液中离子摩尔量满足以下条件：3Li++1.5(Fe2++Cu2+)＝2PO4 3-；
(5)将滤液置于喷雾热解装置中，以氮气为载气气流进行喷雾热解，载气流量为125L/h，热解温度为420℃，去除氟离子、氯离子；
(6)将喷雾热解产生的固体颗粒收集后，加入氢氧化锂、醋酸亚铁、果糖，果糖是固体颗粒中铜元素的3倍，使Fe与P的摩尔比＝1:1且Li与(Fe+2Cu)的摩尔比＝1.1:1，形成混合料；
(7)按照液固比2.5mL/g，将混合料加入至5mol/L的氨水中，在温度为150℃下密闭反应釜中水热反应时间6h；
(8)水热反应结束后，打开反应釜，继续加热温度为93℃，蒸氨，直至完全干燥，得到固体颗粒；
(9)将固体颗粒置于氮气流中，在780℃下高温焙烧5h，即得磷酸铁锂正极材料。
实施例3：
废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法，包括如下步骤：
(1)按液固比2mL/g，将废旧磷酸铁锂电池黑粉用质量百分比浓度为6％的氢氧化钾溶液在50℃下浸出1h；
(2)固液分离，将固体渣用纯水洗涤后，按液固比4mL/g，将固体渣用盐酸及双氧水的混合液在60℃下浸出1h，盐酸的浓度为2.5mol/L，双氧水的浓度为15vol％；
(3)按照还原剂：三价铁的摩尔比1.08:1，向浸出液中加入还原剂，除去三价铁离子；还原剂为铁粉、铜粉中的至少一种，使浸出液中Fe与Cu的摩尔比＝100:8；
(4)固液分离后，向滤液中加入磷酸，调节滤液中离子摩尔量满足以下条件：3Li++1.5(Fe2++Cu2+)＝2PO4 3-；
(5)将滤液置于喷雾热解装置中，以氮气为载气气流进行喷雾热解，载气流量为150L/h，热解温度为500℃，去除氟离子、氯离子；
(6)将喷雾热解产生的固体颗粒收集后，加入碳酸锂、醋酸亚铁、乳糖，乳糖是固体颗粒中铜元素的2倍，使Fe与P的摩尔比＝1:1且Li与(Fe+2Cu)的摩尔比＝1.08:1，形成混合料；
(7)按照液固比3mL/g，将混合料加入至4mol/L的氨水中，在温度为160℃下密闭反应釜中水热反应时间8h；
(8)水热反应结束后，打开反应釜，继续加热温度为95℃，蒸氨，直至完全干燥，得到固体颗粒；
(9)将固体颗粒置于氮气流中，在850℃下高温焙烧4h，即得磷酸铁锂正极材料。
对比例1：
废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法，包括如下步骤：
(1)按液固比4mL/g，将废旧磷酸铁锂电池黑粉用质量百分比浓度为2％的氢氧化钠溶液在90℃下浸出3h；
(2)固液分离，将固体渣用纯水洗涤后，按液固比6mL/g，将固体渣用盐酸及双氧水的混合液在75℃下浸出3h，盐酸的浓度为2mol/L，双氧水的浓度为5vol％；
(3)按照铁粉：(三价铁+铜离子)的摩尔比1.05:1，向浸出液中加入铁粉，除去铜离子；
(4)固液分离后，向滤液中加入磷酸，调节滤液中离子摩尔量满足以下条件：3Li++1.5Fe2+＝2PO4 3-；
(5)将滤液置于喷雾热解装置中，以氮气为载气气流进行喷雾热解，载气流量为100L/h，热解温度为350℃，去除氟离子、氯离子；
(6)将喷雾热解产生的固体颗粒收集后，加入草酸锂、草酸亚铁，使Li、Fe与P的摩尔比＝1.05:1:1，形成混合料；
(7)按照液固比2mL/g，将混合料加入至6mol/L的氨水中，在温度为140℃下密闭反应釜中水热反应时间4h；
(8)水热反应结束后，打开反应釜，继续加热温度为90℃，蒸氨，直至完全干燥，得到固体颗粒；
(9)将固体颗粒置于氮气流中，在700℃下高温焙烧6h，即得磷酸铁锂正极材料。
对比例2：
废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法，包括如下步骤：
(1)按液固比3mL/g，将废旧磷酸铁锂电池黑粉用质量百分比浓度为4％的氢氧化钠溶液在70℃下浸出2h；
(2)固液分离，将固体渣用纯水洗涤后，按液固比5mL/g，将固体渣用盐酸及双氧水的混合液在68℃下浸出2h，盐酸的浓度为2.5mol/L，双氧水的浓度为10vol％；
(3)按照铁粉：(三价铁+铜离子)的摩尔比1.1:1，向浸出液中加入铁粉，除去铜离子；
(4)固液分离后，向滤液中加入磷酸、醋酸亚铁，使Fe与P的摩尔比＝1:1，形成混合液；
(5)向混合液中加入双氧水，并调节pH为1.9，得到磷酸铁沉淀；
(6)固液分离后，用去离子水洗涤沉淀物，并在800℃下煅烧0.5h，得到磷酸铁材料；
(7)按照化学式中各元素的摩尔比为Li:P:Fe:葡萄糖＝1:1:1:1，将磷酸铁与葡萄糖、碳酸锂加入去离子水，在混合搅拌缸里面充分混合、搅拌，再经喷雾干燥后在惰性气氛、700℃下保持6小时，粉碎，得磷酸铁锂正极材料。
试验例：
以实施例和对比例得到的磷酸铁锂正极材料，乙炔黑为导电剂，PVDF为粘结剂，按质量比8:1:1进行混合，并加入一定量的有机溶剂NMP，搅拌后涂覆于铝箔上制成正极片，负极采用金属锂片；隔膜为Celgard2400聚丙烯多孔膜；电解液中溶剂为EC、DMC和EMC按质量比1:1:1组成的溶液，溶质为LiPF6，LiPF6的浓度为1.0mol/L；在手套箱内组装2023型扣式电池。对电池进行充放电循环性能测试，在截止电压2.0-3.65V范围内，测试0.2C放电比容量；测试电化学性能结果如下表1所示。
表1：电化学性能测试结果

由表1可知，本发明废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法得到的磷酸铁锂正极材料具有较高的放电容量及优异的循环性能，其0.2C放电容量能达到160.7mAh/g，其1C下循环100次容量保持率在98.1％以上。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法，其特征在于：包括以下步骤：
    (1)将废旧磷酸铁锂电池黑粉用碱液碱浸后固液分离，得到固体渣，将所述固体渣与酸、氧化剂混合浸泡后，再加入还原剂，然后固液分离，得到滤液；
    (2)向步骤(1)得到的所述滤液中加入磷酸后热解，得到干燥料，将所述干燥料与锂源、亚铁源及碳源混合，得到混合料；
    (3)将步骤(2)得到的混合料加入氨水中进行水热反应，然后蒸氨得到固体颗粒，再将所述固体颗粒在惰性气体中焙烧得到磷酸铁锂正极材料。
  2. 根据权利要求1所述的废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法，其特征在于：步骤(1)中，所述碱浸的温度为30-100℃，碱浸的时间为1-5h。
  3. 根据权利要求1所述的废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法，其特征在于：步骤(1)中，所述酸为盐酸及硫酸中的至少一种，所述酸的浓度为1-3mol/L。
  4. 根据权利要求1所述的废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法，其特征在于：步骤(1)中，所述氧化剂为双氧水，所述双氧水的浓度为3vol％-20vol％。
  5. 根据权利要求1所述的废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法，其特征在于：步骤(1)中，所述还原剂为铁粉及铜粉中的至少一种。
  6. 根据权利要求1所述的废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法，其特征在于：步骤(2)中，加入所述磷酸后，所述滤液中离子摩尔量满足以下条件：3Li++1.5(Fe2++Cu2+)＝2PO4 3-。
  7. 根据权利要求1所述的废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法，其特征在于：步骤(2)中，所述热解的方式为喷雾热解。
  8. 根据权利要求1所述的废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法，其特征在于：步骤(2)中，所述混合料中Fe与P的摩尔比＝1:1且Li与(Fe+2Cu)的摩尔比＝(1.05-1.1):1。
  9. 根据权利要求1所述的废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法，其特征在于：步骤(3)中，所述氨水与所述混合料的液固比为1-5mL/g，所述氨水的浓度为3-10mol/L。
  10. 根据权利要求1所述的废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法，其特征在于：步骤(3)中，所述的水热反应为在温度为100-200℃下的密闭容器中反应2-10h。
PCT/CN2023/083145 2022-10-21 2023-03-22 废旧磷酸铁锂电池定向循环制取磷酸铁锂正极材料的方法 WO2024082544A1 (zh)

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