WO2022142583A1 - 一种磷酸铁锂废料的回收方法及其应用 - Google Patents

一种磷酸铁锂废料的回收方法及其应用 Download PDF

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WO2022142583A1
WO2022142583A1 PCT/CN2021/123412 CN2021123412W WO2022142583A1 WO 2022142583 A1 WO2022142583 A1 WO 2022142583A1 CN 2021123412 W CN2021123412 W CN 2021123412W WO 2022142583 A1 WO2022142583 A1 WO 2022142583A1
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lithium
iron phosphate
phosphate
lithium iron
recovery method
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PCT/CN2021/123412
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English (en)
French (fr)
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李�杰
段金亮
乔延超
陈若葵
李长东
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湖南邦普循环科技有限公司
广东邦普循环科技有限公司
湖南邦普汽车循环有限公司
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Priority to EP21913328.7A priority Critical patent/EP4269336A1/en
Publication of WO2022142583A1 publication Critical patent/WO2022142583A1/zh
Priority to US18/215,821 priority patent/US20230340637A1/en

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    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/008—Wet processes by an alkaline or ammoniacal leaching
    • 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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • 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
    • C01B25/30—Alkali metal phosphates
    • C01B25/305—Preparation from phosphorus-containing compounds by alkaline treatment
    • C01B25/306—Preparation from phosphorus-containing compounds by alkaline treatment from phosphates
    • 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
    • C01B25/30—Alkali metal phosphates
    • C01B25/305—Preparation from phosphorus-containing compounds by alkaline treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/08—Ferroso-ferric oxide [Fe3O4]
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
    • 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
    • H01M4/36—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
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using 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 disclosure belongs to the technical field of recycling waste battery materials, and in particular relates to a recycling method and application of lithium iron phosphate waste.
  • the stock of used power batteries has also ushered in an explosive growth, of which lithium iron phosphate batteries account for a large proportion.
  • the recycling methods of waste lithium iron phosphate batteries are divided into: fire recycling, wet recycling, high temperature solid phase repair technology and bioleaching technology.
  • the most widely used is the wet recovery process. Its main technical route is to use an acid-base solution to form a precipitate in the process of dissolving lithium iron phosphate, and each metal ion exists in the form of oxides and salts to remove copper and aluminum. and other impurity elements, with lithium salt and iron phosphate precipitation as the target product.
  • Aluminum ions are used as impurity elements in the sulfuric acid leaching solution.
  • a method for extracting lithium and iron phosphate from lithium iron phosphate waste has been disclosed.
  • the lithium iron phosphate powder is soaked in a NaOH solution, the concentration of the selected NaOH is 0.5-2 mol/L, and the soaking time is 30-180 min. After complete, the aluminum removal material is obtained.
  • the reaction system is not heated and stirred, resulting in low reaction rate and degree of reaction, and the actual aluminum removal effect is general.
  • the related art discloses a method for selectively extracting lithium from waste lithium iron phosphate materials by selecting an amount of NaOH added at 1.2-1.5 times the molar amount of aluminum, and reacting at 90-95° C. for 2-3 hours to obtain phosphoric acid after aluminum removal. Lithium iron powder.
  • the concentration of NaOH solution selected in this method is low, and the effect of removing aluminum is not ideal.
  • lithium iron phosphate batteries are mainly based on the recovery of lithium elements, and lithium carbonate, lithium phosphate or lithium dihydrogen phosphate are obtained by precipitation.
  • Lithium phosphate has strong heat resistance, no radioactivity, and has the advantages of short illumination but long light efficiency and low cost. It is an ideal material for producing color phosphors.
  • the nitrogen-containing lithium phosphate film is a widely used electrolyte film for all-solid-state thin-film lithium batteries, and can also be used to prepare lithium ferrous phosphate as a positive electrode material for lithium-ion batteries.
  • a method for recycling the cathode material of waste lithium iron phosphate battery is also disclosed.
  • the waste lithium iron phosphate is calcined and oxidized, leached with dilute sulfuric acid, filtered iron oxide, and ammonia water is added to the filtrate to adjust pH to precipitate iron phosphate and impurity copper in stages. , aluminum, etc., then add NaOH to the filtrate to adjust the pH to precipitate lithium phosphate, and obtain the product lithium phosphate after washing and drying.
  • this method can more comprehensively recover the metal elements in the positive electrode material and improve the resource recovery rate, the whole process route has been subjected to multiple roasting, the overall energy consumption is relatively large, and the recovery rate of the key element lithium is relatively low.
  • the embodiments of the present disclosure provide a method for recycling lithium iron phosphate waste and an application thereof. Aluminium removal is performed once before the wet recycling process, thereby improving the quality of iron phosphate products. It is then applied to the preparation of lithium phosphate and ferric oxide, which innovatively provides an oxidizing atmosphere in the process of removing aluminum by alkali leaching, partially oxidizes ferrous iron, and obtains ferric oxide, which is passed through the slag phase and the liquid. Phase transformation can effectively remove impurities such as copper and aluminum to obtain high-purity lithium phosphate.
  • the embodiments of the present disclosure provide:
  • a method for recycling lithium iron phosphate waste comprising the following steps:
  • the mass concentration of the ionic membrane liquid caustic soda is 30%, and the ionic membrane liquid caustic soda is diluted to a mass concentration of 3% to 10%; in another embodiment , diluted to a mass concentration of 5% to 7%.
  • step (2) the mass-to-volume ratio of the lithium iron phosphate powder to the ionic membrane liquid alkali is 1:(4-10).
  • the mass proportion of NaOH in the ionic membrane liquid caustic soda is 30%, and the sum of other impurities such as ClO ⁇ , CO 3 2 ⁇ , SO 4 2 ⁇ , SiO 2 , etc. does not exceed 0.05%.
  • the oxidizing atmosphere is one of an air atmosphere and an oxygen atmosphere.
  • step (2) the time of the water bath reaction is 0.5-2 h, and the temperature of the water bath reaction is 60°C to 90°C.
  • step (2) the rotational speed of the stirring is 300-500 r/min; in another embodiment, it is about 400 r/min.
  • step (3) the mass concentration of the ammonia solution is 8-10%.
  • step (3) the mass-volume ratio of the lithium phosphate slag and the aqueous ammonia solution is 1:(6-10).
  • the reaction atmosphere is one of nitrogen gas and argon gas.
  • step (3) the temperature of the reaction is 30°C-38°C, and the reaction time is 40-80 min.
  • step (3) it further includes performing magnetic separation on the filter residue to obtain Fe 3 O 4 .
  • the lithium iron phosphate powder obtained in step (1) is mixed with the ionic membrane liquid alkali to obtain a lithium iron phosphate slurry, and then a water bath reaction is performed, and filtered to obtain a leachate and lithium iron phosphate. slag; drying the lithium iron phosphate slag, and then performing a wet recovery process to obtain iron phosphate.
  • the temperature of the water bath reaction is between 60°C and 90°C; in another embodiment, it is about 80°C.
  • the water bath reaction time is 0.5-2 h; in another embodiment, it is about 1.5 h.
  • the drying temperature is 70°C-90°C; in another embodiment, it is about 80°C.
  • the aluminum in the lithium iron phosphate waste is removed, the leaching rate of aluminum is above 70%, and the leaching rate of iron, lithium and phosphorus in the solution is less than 3%.
  • the embodiments of the present disclosure also provide the application of the above-mentioned recycling method in battery recycling.
  • the aluminum content in the obtained lithium iron phosphate slag is 0.08%. No iron, indicating that the loss rate of iron is almost zero; the loss rate of lithium is 2.8-3.3%; the loss rate of phosphorus is 2.5-3.0%.
  • Steps (1) and (2) in the embodiment of the present disclosure are equivalent to the pretreatment process of the wet recovery process.
  • the multi-stage aluminum removal makes the final aluminum removal rate reach more than 95%, and the process is simple, and the alkali leaching solution can be It can be recycled for many times within a suitable range, and the product has high value and considerable economic benefits.
  • the method of the embodiment of the present disclosure is used to recycle the lithium iron phosphate waste material, which can realize the comprehensive recovery of lithium, iron and phosphorus, wherein the recovery rate of lithium is more than 95%, and the process is simple, the product value is high, and there is considerable economic benefit .
  • FIG. 1 is a process flow diagram of Embodiment 1 of the present disclosure.
  • the conventional conditions or the conditions suggested by the manufacturer are used.
  • the raw materials, reagents, etc., which are not specified by the manufacturer, are all conventional products that can be purchased from the market.
  • step (3) the slurry obtained in step (2) was placed in a constant temperature water bath, the temperature was 80° C., air was introduced, and the reaction was carried out for 120 min, and filtered to obtain 2887ml of lye containing sodium metaaluminate and sodium phosphate, to obtain lithium phosphate, 409.2 grams of carbon powder and ferric oxide slag;
  • step (4) the slurry obtained in step (4) was reacted at normal temperature for 60min, and filtered to obtain 2355ml of ammonia aqueous solution containing lithium phosphate, and 237.8g of slag containing ferric oxide and carbon powder;
  • Fig. 1 is the process flow diagram of the disclosed embodiment 1. From Fig. 1, the pretreated lithium iron phosphate waste is pulverized and sieved to obtain lithium iron phosphate powder; mixed with the prepared sodium hydroxide solution to make a slurry Under a certain temperature, stirring rate and oxidative atmosphere, the leaching solution and lithium phosphate residue containing AlO 2 - , PO 4 3 - , Na + etc.
  • step (3) The slurry obtained in step (2) was placed in a constant temperature water bath, the temperature was 80 ° C, air was introduced, and the reaction was carried out for 120 min, and filtered to obtain 2905 ml of lye solution containing sodium metaaluminate and sodium phosphate, to obtain lithium phosphate, 408.8 grams of carbon powder and ferric oxide slag;
  • step (4) the slurry obtained in step (4) was reacted at normal temperature for 60min, filtered to obtain 2362ml of lithium phosphate-containing ammonia solution, and 238.2g of slag containing ferric oxide and carbon powder;
  • step (3) The slurry obtained in step (2) was placed in a constant temperature water bath, the temperature was 80 ° C, the reaction was performed for 90 min, and the lye solution containing sodium metaaluminate was filtered to obtain 2412 ml, and the slag 473.1 containing lithium iron phosphate and carbon powder was obtained. gram;
  • step (3) Take the leaching solution and lithium iron phosphate slag obtained in step (3), carry out processes such as dilution and slag melting, to obtain leaching rates of aluminum, phosphorus and lithium, which are 70.8%, 2.47%, and 2.82%, respectively.
  • step (3) The slurry obtained in step (2) was placed in a constant temperature water bath, the temperature was 80 ° C, the reaction was performed for 90 min, and 2406 ml of alkali solution containing sodium metaaluminate was obtained by filtration, and 466.9 ml of slag material containing lithium iron phosphate and carbon powder was obtained. gram;
  • step (3) Take the leaching solution and lithium iron phosphate slag obtained in step (3), carry out processes such as dilution and slag melting, to obtain leaching rates of aluminum, phosphorus and lithium, which are 70.5%, 2.93%, and 3.21%, respectively.
  • step (3) The slurry obtained in step (2) was placed in a constant temperature water bath, the temperature was 80 ° C, the reaction was performed for 120 min, and 2395 ml of alkali solution containing sodium metaaluminate was obtained by filtration, and 468.3 ml of slag containing lithium iron phosphate and carbon powder was obtained. gram;
  • step (3) Take the leaching solution and lithium iron phosphate slag obtained in step (3), carry out processes such as dilution and slag melting, to obtain leaching rates of aluminum, phosphorus, and lithium, which are 71.5%, 2.74%, and 3.08%, respectively.
  • lithium phosphate can be used as a raw material for the preparation of lithium iron phosphate cathode materials and other industrial applications
  • Fe 3 O 4 can be used as pigments, polishing agents, manufacturing audio tapes and telecommunication equipment, etc.

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Abstract

一种磷酸铁锂废料的回收方法及其应用，该方法包括以下步骤：将磷酸铁锂废料进行拆解、粉碎、过筛，得到磷酸铁锂粉料；将离子膜液碱进行稀释，加入磷酸铁锂粉料搅拌，氧化性氛围进行水浴反应，过滤，得到浸出液和磷酸锂渣；将磷酸锂渣烘干，加入氨水溶液进行反应，过滤，得到含磷酸锂的氨水溶液和滤渣；将含磷酸锂的氨水溶液进行蒸发，得到磷酸锂。经过本公开实施例氧化性氛围下的碱浸除铝后，得到的磷酸铁锂渣中铝含量为0.08％，通过多次实验，并对液相进行测定，发现液相中基本不含铁，表明铁的损失率几乎为零；锂的损失率在2.8-3.3％；磷的损失率在2.5-3.0％。

Description

一种磷酸铁锂废料的回收方法及其应用 技术领域
本公开属于废旧电池材料回收技术领域，具体涉及一种磷酸铁锂废料的回收方法及其应用。
背景技术
随着新能源行业的快速发展，废旧动力电池的存量也迎来了爆发式的增长，其中磷酸铁锂电池占据极大比重。目前，废旧磷酸铁锂电池的回收方法分为：火法回收、湿法回收、高温固相修复技术和生物浸出技术等。其中，应用较为广泛的是湿法回收工艺，它的主要技术路线是在溶解磷酸铁锂的过程中，使用酸碱溶液形成沉淀，各金属离子以氧化物和盐的形式存在，除去铜、铝等杂质元素，以锂盐和磷酸铁沉淀为目标产物。铝离子作为硫酸浸出液中的杂质元素，在后续以磷酸铁、碳酸锂的形式回收金属元素时，铝杂质的引入会生成磷酸铝，使得制备的磷酸铁纯度降低，导致后续以磷酸铁前驱体为原料制备的磷酸铁锂正极材料的电化学性能下降。
目前有公开了一种从磷酸铁锂废料中提取锂和磷酸铁的方法，将磷酸铁锂粉末在NaOH溶液中浸泡，选用的NaOH浓度为0.5-2mol/L，浸泡时间为30-180min，反应完全后得到除铝料。该方法在进行碱浸除铝时，未对反应体系进行升温和搅拌，导致反应速率及反应程度较低，实际除铝效果一般。相关技术公开了一种废旧磷酸铁锂材料选择性提锂的方法中选取铝摩尔量的1.2-1.5倍的NaOH加入量，在90-95℃下反应2-3小时，得到除铝后的磷酸铁锂粉料。该方法选用的NaOH溶液浓度较低，除铝效果不理想。
此外，由于经济利益驱使，目前报道的废旧磷酸铁锂电池主要以回收锂元素为主，通过沉淀法得到碳酸锂、磷酸锂或磷酸二氢锂。磷酸锂耐热性强，没有放射性，具有光照短但光效长、成本低等优点，是生产彩色荧光粉的理想材料。而且含氮磷酸锂薄膜是应用于全固态薄膜锂电池较为广泛的电解质薄膜，还可用于制备锂离子电池正极材料磷酸亚铁锂。
目前还公开了一种废旧磷酸铁锂电池正极材料的回收方法，将废旧磷酸铁锂进行煅烧氧化，通过稀硫酸浸取，过滤氧化铁，滤液中加入氨水调pH分段沉淀磷酸铁及杂质铜、铝等，再向滤液中加入NaOH调pH沉淀磷酸锂，经过洗涤干燥后得到产品磷酸锂。该方法虽然可以较全面地回收正极材料中的金属元素，提高资源回收率用率，但是整个工艺路线中进行了 多次焙烧，整体耗能较大，且关键元素锂的回收率较低。
发明内容
本公开实施例提供一种磷酸铁锂废料的回收方法及其应用，在湿法回收工艺前进行一次除铝，提升了磷酸铁产品的品质。再将其应用于制备磷酸锂和四氧化三铁，该应用创新地在碱浸除铝的过程中提供氧化性氛围，将二价铁部分氧化，得到四氧化三铁，并通过渣相与液相的转化，有效除去铜、铝等杂质，得到高纯度的磷酸锂。
为实现上述目的，本公开实施例提供了：
一种磷酸铁锂废料的回收方法，包括以下步骤：
(1)将磷酸铁锂废料进行拆解、粉碎、过筛，得到磷酸铁锂粉料；
(2)将离子膜液碱进行稀释，加入磷酸铁锂粉料搅拌，在氧化性氛围下进行水浴反应，过滤，得到浸出液和磷酸锂渣；
(3)将所述磷酸锂渣烘干，加入氨水溶液进行反应，过滤，得到含磷酸锂的氨水溶液和滤渣；
(4)将所述含磷酸锂的氨水溶液进行蒸发，得到磷酸锂。
在一实施例中，步骤(2)中，所述离子膜液碱的质量浓度为30％，将所述离子膜液碱进行稀释至质量浓度为3％～10％；在又一实施例中，稀释至质量浓度为5％～7％。
在一实施例中，步骤(2)中，所述磷酸铁锂粉料和离子膜液碱的质量体积比为1:(4～10)。
在一实施例中，步骤(2)中，所述离子膜液碱中NaOH质量占比为30％，其他杂质如ClO -、CO 3 2-、SO 4 2-、SiO 2等的总和不超过0.05％。
在一实施例中，步骤(2)中，所述氧化性氛围为空气氛围和氧气氛围中的一种。
在一实施例中，步骤(2)中，所述水浴反应的时间为0.5～2h，水浴反应的温度为60℃～90℃。
在一实施例中，步骤(2)中，所述搅拌的转速为300～500r/min；在另一实施例中约为400r/min。
在一实施例中，步骤(3)中，所述氨水溶液的质量浓度为8-10％。
在一实施例中，步骤(3)中，所述磷酸锂渣和氨水溶液的质量体积比为1：(6～10)。
在一实施例中，步骤(3)中，所述反应的氛围为氮气和氩气中的一种。
在一实施例中，步骤(3)中，所述反应的温度为30℃-38℃，反应的时间为40-80min。
在一实施例中，步骤(3)中，还包括对所述滤渣进行磁选，得到Fe 3O 4。
在一实施例中，将步骤(1)制得的所述磷酸铁锂粉料与所述离子膜液碱混合，得到磷酸铁锂浆料，然后进行水浴反应，过滤，得到浸出液和磷酸铁锂渣；将所述磷酸铁锂渣烘干， 再进行湿法回收工艺，制得磷酸铁。
在又一实施例中，所述水浴反应的温度为60℃-90℃；在另一实施例中约为80℃。
在又一实施例中，所述水浴反应的时间为0.5～2h；在另一实施例中约为1.5h。
在又一实施例中，所述烘干的温度为70℃-90℃；在另一实施例中约为80℃。
根据本公开实施例的方法除去磷酸铁锂废料中的铝，铝的浸出率在70％以上，且溶液中铁、锂、磷的浸出率在3％以下。
本公开实施例还提供了上述的回收方法在电池回收中的应用。
本公开实施例的优点：
(1)经过本公开实施例在氧化性氛围下的碱浸除铝后，得到的磷酸铁锂渣中铝含量为0.08％，通过多次实验，并对液相进行测定，发现液相中基本不含铁，表明铁的损失率几乎为零；锂的损失率在2.8-3.3％；磷的损失率在2.5-3.0％。
(2)本公开实施例的步骤(1)和(2)相当于湿法回收工艺的预处理过程，多段除铝使得最终铝去除率可达95％以上，且工艺简单，碱浸液可在合适的范围内多次循环使用，产品价值高，具有可观的经济效益。
(3)采用本公开实施例的方法回收磷酸铁锂废料，可以实现锂、铁、磷的综合回收，其中锂的回收率在95％以上，且工艺简单，产品价值高，具有可观的经济效益。
附图说明
图1为本公开实施例1的工艺流程图。
具体实施方式
为了对本公开进行深入的理解，下面结合实例对本公开若干实施方案进行描述，以进一步地说明本公开的特点和优点，任何不偏离本公开主旨的变化或者改变能够为本领域的技术人员所理解，本公开的保护范围由所属权利要求范围确定。
本公开实施例中未注明具体条件者，按照常规条件或者制造商建议的条件进行。所用未注明生产厂商者的原料、试剂等，均为可以通过市售购买获得的常规产品。
实施例1
本实施例的磷酸铁锂废料的回收方法，包括以下步骤：
(1)将磷酸铁锂废料进行拆解、粉碎、过筛，得到磷酸铁锂粉料；
(2)称取500g质量分数为67.7％的磷酸铁锂粉料，配置3000ml质量分数10％的NaOH溶液，混合得到磷酸铁锂浆料；
(3)将步骤(2)得到的浆料置于恒温水浴中，温度为80℃，通入空气，反应120min， 过滤得到含偏铝酸钠和磷酸钠的碱液2887ml，得到含磷酸锂、碳粉和四氧化三铁的渣料409.2克；
(4)称取步骤(3)磷酸锂、碳粉和四氧化三铁的渣料300g，配置2400ml质量分数10％的氨水溶液，在氮气气氛下混合得到磷酸锂浆料；
(5)将步骤(4)得到的浆料在常温下反应60min，过滤得到含磷酸锂的氨水溶液2355ml，以及含四氧化三铁和碳粉的渣料237.8g；
(6)将步骤(5)磷酸锂的氨水溶液进行蒸发，得到纯磷酸锂产品58.8g。
图1为本公开实施例1的工艺流程图，从图1可得将经过预处理的磷酸铁锂废料粉碎过筛，得到磷酸铁锂粉料；与配制好的氢氧化钠溶液混合制成浆料；在一定温度、搅拌速率及氧化性氛围下，反应一段时间后过滤得到含AlO 2 -、PO 4 3-、Na +等的浸出液和磷酸锂渣；配制合适浓度的氨水溶液与磷酸锂渣混合，调整好固液比，并在保护性气氛下进行反应，得到含磷酸锂的氨水溶液和含Fe 3O 4、Cu、C等成分的渣料；含磷酸锂的氨水溶液进行蒸发，得到纯磷酸锂产品；对渣相进行磁选，得到纯Fe 3O 4。
实施例2
本实施例的磷酸铁锂废料的回收方法，包括以下步骤：
(1)将磷酸铁锂废料进行拆解、粉碎、过筛，得到磷酸铁锂粉料；
(2)称取500g质量分数为67.7％的磷酸铁锂粉料，配置3000ml质量分数12％的NaOH溶液，混合得到磷酸铁锂浆料；
(3)将步骤(2)得到的浆料置于恒温水浴中，温度为80℃，通入空气，反应120min，过滤得到含偏铝酸钠和磷酸钠的碱液2905ml，得到含磷酸锂、碳粉和四氧化三铁的渣料408.8克；
(4)称取步骤(3)磷酸锂、碳粉和四氧化三铁的渣料300g，配置2400ml质量分数8％的氨水溶液，在氮气气氛下混合得到磷酸锂浆料；
(5)将步骤(4)得到的浆料在常温下反应60min，过滤得到含磷酸锂的氨水溶液2362ml，以及含四氧化三铁和碳粉的渣料238.2g；
(6)将步骤(5)磷酸锂的氨水溶液进行蒸发，得到纯磷酸锂产品57.9g。
实施例3
本实施例的磷酸铁锂废料的回收方法，包括以下步骤：
(1)将磷酸铁锂废料进行拆解、粉碎、过筛，得到磷酸铁锂粉料；
(2)称取500g质量分数为67.7％的磷酸铁锂粉料，配置2500ml质量分数5％的NaOH 溶液，混合得到磷酸铁锂浆料；
(3)将步骤(2)得到的浆料置于恒温水浴中，温度为80℃，反应90min，过滤得到含偏铝酸钠的碱液2412ml，得到含磷酸铁锂和碳粉的渣料473.1克；
(4)取步骤(3)得到的浸出液和磷酸铁锂渣，进行稀释、熔渣等过程，得到铝、磷、锂的浸出率分别为70.8％、2.47％、2.82％。
实施例4
本实施例的磷酸铁锂废料的回收方法，包括以下步骤：
(1)将磷酸铁锂废料进行拆解、粉碎、过筛，得到磷酸铁锂粉料；
(2)称取500g质量分数为67.7％的磷酸铁锂粉料，配置2500ml质量分数6％的NaOH溶液，混合得到磷酸铁锂浆料；
(3)将步骤(2)得到的浆料置于恒温水浴中，温度为80℃，反应90min，过滤得到含偏铝酸钠的碱液2406ml，得到含磷酸铁锂和碳粉的渣料466.9克；
(4)取步骤(3)得到的浸出液和磷酸铁锂渣，进行稀释、熔渣等过程，得到铝、磷、锂的浸出率分别为70.5％、2.93％、3.21％。
实施例5
本实施例的磷酸铁锂废料的回收方法，包括以下步骤：
(1)将磷酸铁锂废料进行拆解、粉碎、过筛，得到磷酸铁锂粉料；
(2)称取500g质量分数为67.7％的磷酸铁锂粉料，配置2500ml质量分数5％的NaOH溶液，混合得到磷酸铁锂浆料；
(3)将步骤(2)得到的浆料置于恒温水浴中，温度为80℃，反应120min，过滤得到含偏铝酸钠的碱液2395ml，得到含磷酸铁锂和碳粉的渣料468.3克；
(4)取步骤(3)得到的浸出液和磷酸铁锂渣，进行稀释、熔渣等过程，得到铝、磷、锂的浸出率分别为71.5％、2.74％、3.08％。
表1实施例1的用料和成本
辅料 30％离子膜碱 20％氨水 氮气 总计
加入量/m 3 1.55 2.4 0.5  
价格/元 1152 1223 12 2387
表2实施例1制得的磷酸锂含量
指标 主含量 Ni/ppm Co/ppm Mn/ppm Ca/ppm Mg/ppm
数值 99.13 2.54 2.72 41.99 19.74 24.97
Al/ppm Zn/ppm Ti/ppm Zr/ppm Na/ppm K/ppm  
24.43 4.1 548 35.1 126.6 9.47  
表3实施例1制得的Fe 3O 4含量
指标 主含量 Ni/ppm Co/ppm Mn/ppm Ca/ppm Mg/ppm
数值 99.01 0.72 3.08 7.89 8.55 16.27
Al/ppm Zn/ppm Zr/ppm Na/ppm K/ppm    
40.61 11.08 93.84 54.72 32.31    
从表1-3可得，本公开实施例的成本低，其中锂的回收率在95％以上，制备的磷酸锂和Fe 3O 4纯度高。其中，磷酸锂可用做制备磷酸铁锂正极材料和其它工业化应用的原料，Fe 3O 4可用做颜料、抛光剂、制造录音磁带和电讯器材等。
以上对本公开提供的一种磷酸铁锂废料的回收方法及其应用进行了详细的介绍，本文中应用了具体实施例对本公开的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本公开的方法及其核心思想，包括若干方式，并且也使得本领域的任何技术人员都能够实践本公开，包括制造和使用任何装置或系统，和实施任何结合的方法。应当指出，对于本技术领域的普通技术人员来说，在不脱离本公开原理的前提下，还可以对本公开进行若干改进和修饰，这些改进和修饰也落入本公开权利要求的保护范围内。本公开专利保护的范围通过权利要求来限定，并可包括本领域技术人员能够想到的其他实施例。如果这些其他实施例具有不是不同于权利要求文字表述的结构要素，或者如果它们包括与权利要求的文字表述无实质差异的等同结构要素，那么这些其他实施例也应包含在权利要求的范围内。

Claims (10)

  1. 一种磷酸铁锂废料的回收方法，包括以下步骤：
    (1)将磷酸铁锂废料进行拆解、粉碎、过筛，得到磷酸铁锂粉料；
    (2)将离子膜液碱进行稀释，加入所述磷酸铁锂粉料，搅拌，氧化性氛围下进行水浴反应，过滤，得到浸出液和磷酸锂渣；
    (3)将所述磷酸锂渣烘干，加入氨水溶液进行反应，过滤，得到含磷酸锂的氨水溶液和滤渣；
    (4)将所述含磷酸锂的氨水溶液进行蒸发，得到磷酸锂。
  2. 根据权利要求1所述的回收方法，其中，步骤(2)中，所述离子膜液碱的质量浓度为30％，将所述离子膜液碱进行稀释至质量浓度为3％～10％。
  3. 根据权利要求1所述的回收方法，其中，步骤(2)中，所述磷酸铁锂粉料和离子膜液碱的质量体积比为1:(4～10)。
  4. 根据权利要求1所述的回收方法，其中，步骤(2)中，所述水浴反应的温度为60℃～90℃；步骤(2)中，所述水浴反应的时间为0.5～2h。
  5. 根据权利要求1所述的回收方法，其中，步骤(2)中，所述氧化性氛围为空气氛围和氧气氛围中的一种。
  6. 根据权利要求1所述的回收方法，其中，步骤(2)中，所述搅拌的转速为300～500r/min。
  7. 根据权利要求1所述的回收方法，其中，步骤(3)中，所述反应的氛围为氮气和氩气中的一种；步骤(3)中，所述反应的温度为30℃-38℃，反应的时间为40-80min。
  8. 根据权利要求1所述的回收方法，其中，步骤(3)中，所述氨水溶液的质量浓度为8-10％。
  9. 根据权利要求1所述的回收方法，其中，步骤(3)中，还包括对所述滤渣进行磁选，得到Fe 3O 4。
  10. 权利要求1-9中任一项所述的回收方法在电池回收中的应用。
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CN108929956A (zh) * 2018-07-11 2018-12-04 方嘉城 一种废弃磷酸铁锂中间料的处理方法
CN109179512A (zh) * 2018-09-13 2019-01-11 郑忆依 一种磷酸铁锂废料的处理方法
CN110331288A (zh) * 2019-06-28 2019-10-15 湖南邦普循环科技有限公司 一种废旧磷酸铁锂材料选择性提锂的方法
CN110482511A (zh) * 2019-07-12 2019-11-22 湖南大学 一种废旧磷酸铁锂电池正极材料的回收方法
CN112694074A (zh) * 2020-12-28 2021-04-23 湖南邦普循环科技有限公司 一种磷酸铁锂废料的回收方法及其应用

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