WO2024130855A1 - 一种低铜铝无氟黑粉及其制备方法 - Google Patents

一种低铜铝无氟黑粉及其制备方法 Download PDF

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Publication number
WO2024130855A1
WO2024130855A1 PCT/CN2023/080229 CN2023080229W WO2024130855A1 WO 2024130855 A1 WO2024130855 A1 WO 2024130855A1 CN 2023080229 W CN2023080229 W CN 2023080229W WO 2024130855 A1 WO2024130855 A1 WO 2024130855A1
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Prior art keywords
black powder
aluminum
copper
preparation
low
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English (en)
French (fr)
Inventor
余海军
王涛
谢英豪
李爱霞
张学梅
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • 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
    • C22B1/02—Roasting processes
    • 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
    • C22B7/001—Dry processes
    • 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
    • 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
    • C22B7/007—Wet processes by acid leaching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • 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
    • C22B47/00—Obtaining manganese
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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 specifically relates to a low-copper-aluminum fluorine-free black powder and a preparation method thereof.
  • Lithium-ion batteries have the advantages of high voltage, small size, high energy density, low self-discharge, and high safety. They are widely used in various fields such as consumer electronics, power batteries, and industrial energy storage. In recent years, with the rapid growth in the production and use of lithium-ion batteries, the number of waste lithium-ion batteries has also become increasingly large. At present, the recycling and reuse of lithium-ion batteries has received more and more attention.
  • Waste battery black powder is a black powder containing metals such as nickel, cobalt, manganese, copper, aluminum, lithium and carbon powder obtained by disassembling, crushing, screening, pyrolysis and sorting of waste lithium-ion batteries.
  • the black powder is leached by wet leaching process to recover the valuable metals in it.
  • nickel, cobalt, manganese and lithium are leached in a sulfuric acid system with a reducing agent; the leached solution is subjected to impurity removal, extraction, stripping and other processes to obtain nickel sulfate, manganese sulfate and cobalt sulfate solutions respectively; finally, the final extract is evaporated and concentrated, and lithium carbonate is precipitated using a supersaturated sodium carbonate solution.
  • the aluminum metal in the battery will undergo an aluminothermic reaction at above 600°C, resulting in a sharp rise in instantaneous temperature and burning through the pyrolysis furnace, bringing about a greater safety risk; 2
  • the metallic copper and aluminum in the battery are oxidized in large quantities, resulting in a high impurity content in the battery powder, and during the subsequent acid leaching, the oxides dissolve to produce a large amount of copper and aluminum slag.
  • a large amount of acid and alkali is consumed during leaching and iron and aluminum removal, and the product added value is low, which brings great pressure to the subsequent purification.
  • the binder PVDF and lithium hexafluorophosphate in the electrolyte decompose and remain, resulting in a high fluoride content in the black powder. After wet treatment, it enters the wastewater, resulting in wastewater discharge not meeting standards.
  • the calcium fluoride slag produced after calcium solidification is a hazardous waste and requires special treatment by a qualified treatment manufacturer.
  • lithium fluoride is a precipitate, and some fluorine enters the lithium extraction solution, resulting in a decrease in the subsequent lithium extraction rate, a decrease in the purity of lithium carbonate, and an increase in the fluorine impurity content.
  • the present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a low-copper-aluminum fluorine-free black powder and a preparation method thereof, which can recover the copper and aluminum foil therein by low-temperature pyrolysis and perform defluorination treatment to prepare low-copper-aluminum fluorine-free black powder.
  • a low-copper-aluminum fluorine-free black powder wherein the water content of the low-copper-aluminum fluorine-free black powder is ⁇ 1.0wt%, the total content of nickel, cobalt and manganese metal elements is ⁇ 30.0wt%, the lithium content is ⁇ 3.3wt%, the copper content is ⁇ 0.8wt%, the aluminum content is ⁇ 1.0wt%, and the fluorine content is ⁇ 0.1wt%.
  • the particle size of the low copper and aluminum fluorine-free black powder is ⁇ 0.25 mm.
  • the present invention also provides a method for preparing the low-copper-aluminum fluorine-free black powder, comprising the following steps:
  • the first oversize material is pyrolyzed at 300-400° C. in an inert atmosphere, and the material after pyrolysis is screened for the second time to obtain a second black powder and a second oversize material, and the second oversize material is color-sorted to obtain a copper foil and an aluminum-containing electrode;
  • step S1 the particle size of the crushed material obtained after the crushing is ⁇ 5 cm.
  • the waste lithium-ion battery is at least one of a ternary lithium-ion battery, a lithium cobalt oxide battery, a lithium manganese oxide battery or a lithium nickel oxide battery.
  • the sieve apertures of the first screening, the second screening, and the third screening are independently 0.2-0.3 mm.
  • step S2 the pyrolysis time is 3-5 hours.
  • step S3 the solid-liquid ratio of the aluminum-containing electrode to the ferric iron salt solution is 0.5-2.0 g/mL, and the concentration of iron ions in the ferric iron salt solution is 0.1-0.5 mol/L.
  • step S3 the reaction temperature is 40-90° C. Further, the reaction time is 0.5-1.0 h.
  • the trivalent iron salt solution is at least one of a ferric sulfate solution, a ferric nitrate solution or a ferric chloride solution.
  • step S3 the drying temperature is 100-120° C., and the drying time is 1-2 hours.
  • step S4 the flow rate of the air is 8-15 Nm 3 /min.
  • step S4 the calcination time is 0.5-1.0 h.
  • the battery is crushed by coarse crushing, and a part of the black powder that falls off during the crushing process is screened out.
  • the temperature of the whole process is controlled below 400°C through low-temperature pyrolysis, and pyrolysis is carried out under anaerobic conditions to avoid the combustion of electrolyte and diaphragm in the crushed material, avoid the phenomenon of temperature runaway caused by the occurrence of aluminothermic reaction, protect the pyrolysis furnace, reduce the degree of copper and aluminum oxidation, and carbonize the binder at the same time, and screen out a part of the black powder that falls off during the pyrolysis process again; due to the low-temperature reaction, the positive electrode powder is not completely desorbed, and the negative electrode binder decomposes at a slightly higher temperature and is easier to fall off, so the color sorting method is used to select the copper foil, and the aluminum-containing electrode enters the salt washing process; during the salt washing process, the principle of the reaction between trivalent iron ions and metallic aluminum
  • the obtained black powder is subjected to high-temperature defluorination.
  • the attached binder is completely carbonized and decomposed at high temperature, and fluorine is dissociated in the form of gas; on the other hand, during the decomposition process of the binder, fluorine will also combine with metal elements to form fluoride, which can be replaced and removed by high-temperature water vapor.
  • the reaction equation is:
  • FIG1 is a schematic diagram of the process flow of Example 1 of the present invention.
  • a method for reducing the copper, aluminum and fluorine content in battery black powder, the specific process is:
  • Step 1 after the waste ternary lithium-ion batteries are discharged and disassembled, they are crushed into crushed materials with a particle size of less than 5 cm;
  • Step 2 the crushed material is screened for the first time through a sieve with an aperture of 0.25 mm, and the undersize material is the first black powder and the first oversize material;
  • Step 3 adding the first screened material into the pyrolysis furnace, controlling the filling rate of the pyrolysis furnace to 5%, continuously introducing nitrogen, and raising the temperature to 300° C. for 5 hours;
  • Step 4 the pyrolyzed material is screened for the second time through a sieve with an aperture of 0.25 mm, and the undersize is the second black powder and the oversize is the second sieve;
  • Step 5 the material on the second sieve is color-sorted and separated by a color sorter to obtain copper foil and aluminum-containing electrode sheets;
  • Step 6 adding the aluminum-containing electrode to a ferric sulfate solution with an iron ion concentration of 0.1 mol/L at a solid-liquid ratio of 0.5 g/mL, and reacting at 90° C. for 0.5 h;
  • Step 7 screening the reacted mixture for the third time through a sieve with a pore size of 0.25 mm to obtain aluminum foil and slurry;
  • Step 8 filter-pressing the obtained slurry, and drying it at 100° C. for 2 hours to obtain a third black powder
  • Step 9 placing the first, second and third black powders obtained in a fluidized bed roasting furnace, blowing air into the furnace at 500° C. for 1.0 h, with a water vapor volume content of 40% in the air and an air flow rate of 15 Nm 3 /min;
  • Step 10 after dust collection at the outlet of the fluidized bed roasting furnace, black powder with low copper, aluminum and fluorine content is obtained.
  • a method for reducing the copper, aluminum and fluorine content in battery black powder, the specific process is:
  • Step 1 after the waste lithium cobalt oxide batteries are discharged and disassembled, they are crushed into crushed materials with a particle size of less than 5 cm;
  • Step 2 the crushed material is screened for the first time through a sieve with an aperture of 0.25 mm, and the undersize material is the first black powder and the first oversize material;
  • Step 3 adding the first screened material into the pyrolysis furnace, controlling the filling rate of the pyrolysis furnace to 10%, continuously introducing nitrogen, and raising the temperature to 350° C. for 4 hours;
  • Step 4 the pyrolyzed material is screened for the second time through a sieve with an aperture of 0.25 mm, and the undersize is the second black powder and the oversize is the second sieve;
  • Step 5 the material on the second sieve is color-sorted and separated by a color sorter to obtain copper foil and aluminum-containing electrode sheets;
  • Step 6 adding the aluminum-containing electrode to a ferric nitrate solution with an iron ion concentration of 0.3 mol/L according to a solid-liquid ratio of 1.0 g/mL, and reacting at 60° C. for 1.0 h;
  • Step 7 screening the reacted mixture for the third time through a sieve with a pore size of 0.25 mm to obtain aluminum foil and slurry;
  • Step 8 filter pressing the obtained slurry, and drying it at 110° C. for 1.5 hours to obtain a third black powder
  • Step 9 placing the first, second and third black powders obtained in a fluidized bed roasting furnace, blowing air into the furnace at 800° C. for 1.0 h, with a water vapor volume content of 20% in the air and an air flow rate of 12 Nm 3 /min;
  • Step 10 after dust collection at the outlet of the fluidized bed roasting furnace, black powder with low copper, aluminum and fluorine content is obtained.
  • a method for reducing the copper, aluminum and fluorine content in battery black powder, the specific process is:
  • Step 1 after the waste ternary lithium-ion batteries are discharged and disassembled, they are crushed into crushed materials with a particle size of less than 5 cm;
  • Step 2 the crushed material is screened for the first time through a sieve with an aperture of 0.25 mm, and the undersize material is the first black powder and the first oversize material;
  • Step 3 adding the first screened material into the pyrolysis furnace, controlling the filling rate of the pyrolysis furnace to 15%, continuously introducing nitrogen, and raising the temperature to 400° C. for 3 hours;
  • Step 4 the pyrolyzed material is screened for the second time through a sieve with an aperture of 0.25 mm, and the undersize is the second black powder and the oversize is the second sieve;
  • Step 5 the material on the second sieve is color-sorted and separated by a color sorter to obtain copper foil and aluminum-containing electrode sheets;
  • Step 6 adding the aluminum-containing electrode to a ferric chloride solution with an iron ion concentration of 0.5 mol/L according to a solid-liquid ratio of 2.0 g/mL, and reacting at 40° C. for 1.0 h;
  • Step 7 screening the reacted mixture for the third time through a sieve with a pore size of 0.25 mm to obtain aluminum foil and slurry;
  • Step 8 filter pressing the obtained slurry, and drying it at 120° C. for 1 hour to obtain a third black powder
  • Step 9 placing the first, second and third black powders obtained in a fluidized bed roasting furnace, blowing air into the furnace at 1000° C. for 0.5 h, with a water vapor volume content of 10% in the air and an air flow rate of 8 Nm 3 /min;
  • Step 10 after dust collection at the outlet of the fluidized bed roasting furnace, black powder with low copper, aluminum and fluorine content is obtained.
  • a method for preparing black powder which is different from Example 1 in that the crushed material is directly subjected to low-temperature pyrolysis and screening, and the specific process is as follows:
  • Step 1 after the waste ternary lithium-ion batteries are discharged and disassembled, they are crushed into crushed materials with a particle size of less than 5 cm;
  • Step 2 adding the crushed material into the pyrolysis furnace, controlling the filling rate of the pyrolysis furnace to 5%, continuously introducing nitrogen, and raising the temperature to 300° C. for 5 hours;
  • Step 3 the pyrolyzed material is sieved through a sieve with an aperture of 0.25 mm to obtain black powder under the sieve and copper powder on the sieve.
  • Step 4 color sorting and separation of copper and aluminum foil to obtain copper foil and aluminum foil.
  • a method for preparing black powder which is different from Example 2 in that the crushed material is directly subjected to low-temperature pyrolysis and screening, and the specific process is as follows:
  • Step 1 after the waste lithium cobalt oxide batteries are discharged and disassembled, they are crushed into crushed materials with a particle size of less than 5 cm;
  • Step 2 adding the crushed material into the pyrolysis furnace, controlling the filling rate of the pyrolysis furnace to 10%, continuously introducing nitrogen, and raising the temperature to 350° C. for 4 hours;
  • Step 3 sieving the pyrolyzed material through a sieve with an aperture of 0.25 mm to obtain black powder under the sieve and copper and aluminum foil over the sieve;
  • Step 4 color sorting and separation of copper and aluminum foil to obtain copper foil and aluminum foil.
  • a method for preparing black powder which is different from Example 3 in that the crushed material is directly subjected to low-temperature pyrolysis and screening, and the specific process is as follows:
  • Step 1 after the waste ternary lithium-ion batteries are discharged and disassembled, they are crushed into crushed materials with a particle size of less than 5 cm;
  • Step 2 adding the crushed material into the pyrolysis furnace, controlling the filling rate of the pyrolysis furnace to 15%, continuously introducing nitrogen, and raising the temperature to 400°C for 3 hours;
  • Step 3 sieving the pyrolyzed material through a sieve with an aperture of 0.25 mm to obtain black powder under the sieve and copper and aluminum foil over the sieve;
  • Step 4 color sorting and separation of copper and aluminum foil to obtain copper foil and aluminum foil.

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Abstract

本发明公开了一种低铜铝无氟黑粉及其制备方法，废旧电池经破碎和筛分得到第一黑粉和第一筛上物，第一筛上物热解，筛分得第二黑粉和第二筛上物，将第二筛上物进行色选得铜箔和含铝极片，含铝极片在铁盐溶液中反应，筛分得铝箔和浆料，浆料固液分离得第三黑粉，第一黑粉、第二黑粉和第三黑粉在含水蒸气的空气中焙烧，得到低铜铝无氟黑粉。本发明采用低温热解、色选分离、盐洗脱附、火法脱氟的联合工艺，回收得到了高价值的铜箔、铝箔以及黑粉。

Description

一种低铜铝无氟黑粉及其制备方法 技术领域
本发明属于锂电池回收技术领域，具体涉及一种低铜铝无氟黑粉及其制备方法。
背景技术
锂离子电池具有电压高、体积小、能量密度大、自放电小、安全性高等优点，被广泛地应用于消费类电子产品、动力电池、工业储能等各个领域。近年来，随着锂离子电池生产数量和使用数量的快速增长，废旧锂离子电池的数量也越来越庞大。目前，锂离子电池的回收再利用已经受到人们越来越多的重视。
废电池黑粉是废锂离子电池经拆解、破碎、筛分、热解、分选等工序得到的含镍、钴、锰、铜、铝和锂等金属及碳粉的黑色粉体。
通常，黑粉采用湿法浸出工艺来回收其中的有价金属。具体为：在加有还原剂的硫酸体系下浸出镍、钴、锰和锂；浸出液经除杂、萃取、反萃等工序分别得到硫酸镍、硫酸锰、硫酸钴溶液；最后，将最终的萃取液蒸发浓缩，采用过饱和碳酸钠溶液沉淀碳酸锂。
然而，在黑粉的制备过程中，采用的热解预处理工艺在现有的工业生产中使用的较为广泛，但其中也存在一些较大的问题，如：①常规热解的温度在500℃以上，由于物料种类复杂，在此温度下，电解液及隔膜出现燃烧，极易造成热解炉内局部反应剧烈，造成温度失控，电池中的铝金属在600℃以上时会发生铝热反应，导致瞬间温度急剧上升，烧穿热解炉，带来较大的安全风险；②在此温度下，电池中的金属铜铝被大量氧化，导致电池粉中杂质含量高，且在后续酸液浸出时，氧化物溶解，产生大量的铜铝渣，在浸出和除铁铝时消耗酸碱量大、产品附加值低，给后续净化提纯带来了较大压力。虽然可以采用通惰性气体进行无氧热解改善铜铝氧化情况，但是目前的设备很难做到完全密封，铜铝仍然有部分被氧化；③热解过程中粘结剂PVDF以及电解液中的六氟磷酸锂等分解并残留，使黑粉中氟化物含量较高，通过湿法处理后，进入废水中导致废水排放不达标，通过钙固化后产生的氟化钙渣又属于危险废物，需要具备资质的处理厂家专门处理，且氟化锂属于沉淀，部分氟进入提锂液中，导致后续的锂提取率降低，碳酸锂纯度降低，氟杂质含量升高。
因此，为避免给湿法处理黑粉的下游厂家带来诸多麻烦，亟需对前端工艺进行改进，以制取得到低铜铝氟含量的黑粉。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出一种低铜铝无氟黑粉及其制备方法，能够通过低温热解回收其中的铜铝箔，并进行脱氟处理，制备出低铜铝无氟的黑粉。
根据本发明的一个方面，提出了一种低铜铝无氟黑粉，所述低铜铝无氟黑粉的含水量≤1.0wt％，镍钴锰金属元素总含量≥30.0wt％，锂元素含量≥3.3wt％，铜元素含量≤0.8wt％，铝含量≤1.0wt％，氟含量≤0.1wt％。
在本发明的一些实施方式中，所述低铜铝无氟黑粉的颗粒度≤0.25mm。
本发明还提供所述的低铜铝无氟黑粉的制备方法，包括以下步骤：
S1：废旧锂离子电池经放电、拆解、破碎和第一次筛分，得到第一黑粉和第一筛上物；
S2：所述第一筛上物在惰性气氛下300-400℃进行热解，热解后物料进行第二次筛分，得到第二黑粉和第二筛上物，将所述第二筛上物进行色选分离，得到铜箔和含铝极片；
S3：将所述含铝极片置于三价铁盐溶液中进行反应，所得反应物料进行第三次筛分，得到铝箔和浆料，将所述浆料进行固液分离，所得固体进行烘干，得到第三黑粉；
S4：将所述第一黑粉、第二黑粉和第三黑粉在500-1000℃下鼓入空气进行焙烧，且空气中的水蒸气体积含量为10％-40％，得到所述低铜铝无氟黑粉。
在本发明的一些实施方式中，步骤S1中，所述破碎后所得破碎料的粒度≤5cm。
在本发明的一些实施方式中，步骤S1中，所述废旧锂离子电池为三元锂离子电池、钴酸锂电池、锰酸锂电池或镍酸锂电池中的至少一种。
在本发明的一些实施方式中，所述第一次筛分、第二次筛分、第三次筛分的筛网孔径独立为0.2-0.3mm。
在本发明的一些实施方式中，步骤S2中，所述热解在热解炉中进行，所述第一筛上物在所述热解炉中的填充率为5％-15％。
在本发明的一些实施方式中，步骤S2中，所述热解的时间为3-5h。
在本发明的一些实施方式中，步骤S3中，所述含铝极片与三价铁盐溶液的固液比为0.5-2.0g/mL，所述三价铁盐溶液中铁离子的浓度为0.1-0.5mol/L。
在本发明的一些实施方式中，步骤S3中，所述反应的温度为40-90℃。进一步地，所述反应的时间为0.5-1.0h。
在本发明的一些实施方式中，步骤S3中，所述三价铁盐溶液为硫酸铁溶液、硝酸铁溶液或氯化铁溶液中的至少一种。
在本发明的一些实施方式中，步骤S3中，所述烘干的温度为100-120℃，烘干的时间为1-2h。
在本发明的一些实施方式中，步骤S4中，所述空气的流量为8-15Nm3/min。
在本发明的一些实施方式中，步骤S4中，所述焙烧的时间为0.5-1.0h。
根据本发明的一种优选的实施方式，至少具有以下有益效果：
1、本发明中，针对废旧锂离子电池在较高热解温度下极易出现安全隐患、铜铝大面积被氧化以及黑粉残留氟的问题，采用低温热解、色选分离、盐洗脱附、火法脱氟的联合工艺，回收得到了高价值的铜箔、铝箔以及黑粉。
2、首先，通过粗破碎，将电池破碎，并筛分出破碎过程脱落的一部分黑粉，再经低温热解，使全过程的温度控制在400℃以下，并在无氧条件下热解，避免了破碎料中电解液及隔膜的燃烧，避免了铝热反应的发生导致温度失控的现象，保护了热解炉，降低了铜铝氧化的程度，同时使粘结剂出现碳化，再次筛分出热解过程脱落的一部分黑粉；由于低温反应，正极粉脱附不彻底，而负极粘结剂稍高温度就分解，比较容易脱落，故采用色选法将铜箔选出，含铝极片则进入盐洗工序；盐洗过程中，利用三价铁离子与金属铝反应的原理，对铝进行腐蚀，实现黑粉的脱落，反应方程式为：
Al+3Fe3+→Al3++3Fe2+
3、对所得黑粉进行高温脱氟，一方面，高温下附带的粘结剂彻底碳化分解，氟以气体形式解离；另一方面，在粘结剂的分解过程中，氟还会与金属元素结合，生成氟化物，通过高温水蒸气可将氟置换脱除，其反应方程式为：
2LiF+H2O→Li2O+2HF
MeF2+H2O→MeO+2HF(Me＝Ni,Co,Mn)
附图说明
下面结合附图和实施例对本发明做进一步的说明，其中：
图1为本发明实施例1的工艺流程示意图。
具体实施方式
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施例，而不是全部实施例，基于本发明的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本发明保护的范围。
实施例1
一种降低电池黑粉中铜铝氟含量的方法，具体过程为：
步骤1，废旧三元锂离子电池经放电、拆解后，破碎成粒度为5cm以下的破碎料；
步骤2，将破碎料经孔径为0.25mm的筛网进行第一次筛分，得到筛下物为第一黑粉和第一筛上物；
步骤3，将第一筛上物加入到热解炉中，控制热解炉填充率为5％，持续通入氮气，并升温至300℃，持续5h；
步骤4，将热解后的物料经孔径为0.25mm的筛网进行第二次筛分，得到筛下物为第二黑粉和第二筛上物；
步骤5，将第二筛上物经色选机进行色选分离，得到铜箔和含铝极片；
步骤6，按照固液比0.5g/mL，将含铝极片加入到铁离子浓度0.1mol/L的硫酸铁溶液中，在90℃下反应0.5h；
步骤7，将反应后的混合物料经孔径为0.25mm的筛网进行第三次筛分，得到铝箔和浆料；
步骤8，对所得浆料进行压滤，并在100℃下烘干2h，得到第三黑粉；
步骤9，将所得第一、二、三黑粉置于流化床焙烧炉中，在500℃下鼓入空气，持续1.0h，空气中的水蒸气体积含量为40％，空气流量为15Nm3/min；
步骤10，在流化床焙烧炉出口进行收尘后，即得低铜铝氟含量的黑粉。
监测热解炉内情况：炉内无明显火星。
实施例2
一种降低电池黑粉中铜铝氟含量的方法，具体过程为：
步骤1，废旧钴酸锂电池经放电、拆解后，破碎成粒度为5cm以下的破碎料；
步骤2，将破碎料经孔径为0.25mm的筛网进行第一次筛分，得到筛下物为第一黑粉和第一筛上物；
步骤3，将第一筛上物加入到热解炉中，控制热解炉填充率为10％，持续通入氮气，并升温至350℃，持续4h；
步骤4，将热解后的物料经孔径为0.25mm的筛网进行第二次筛分，得到筛下物为第二黑粉和第二筛上物；
步骤5，将第二筛上物经色选机进行色选分离，得到铜箔和含铝极片；
步骤6，按照固液比1.0g/mL，将含铝极片加入到铁离子浓度0.3mol/L的硝酸铁溶液中，在60℃下反应1.0h；
步骤7，将反应后的混合物料经孔径为0.25mm的筛网进行第三次筛分，得到铝箔和浆料；
步骤8，对所得浆料进行压滤，并在110℃下烘干1.5h，得到第三黑粉；
步骤9，将所得第一、二、三黑粉置于流化床焙烧炉中，在800℃下鼓入空气，持续1.0h，空气中的水蒸气体积含量为20％，空气流量为12Nm3/min；
步骤10，在流化床焙烧炉出口进行收尘后，即得低铜铝氟含量的黑粉。
监测热解炉内情况：炉内无明显火星。
实施例3
一种降低电池黑粉中铜铝氟含量的方法，具体过程为：
步骤1，废旧三元锂离子电池经放电、拆解后，破碎成粒度为5cm以下的破碎料；
步骤2，将破碎料经孔径为0.25mm的筛网进行第一次筛分，得到筛下物为第一黑粉和第一筛上物；
步骤3，将第一筛上物加入到热解炉中，控制热解炉填充率为15％，持续通入氮气，并升温至400℃，持续3h；
步骤4，将热解后的物料经孔径为0.25mm的筛网进行第二次筛分，得到筛下物为第二黑粉和第二筛上物；
步骤5，将第二筛上物经色选机进行色选分离，得到铜箔和含铝极片；
步骤6，按照固液比2.0g/mL，将含铝极片加入到铁离子浓度0.5mol/L的氯化铁溶液中，在40℃下反应1.0h；
步骤7，将反应后的混合物料经孔径为0.25mm的筛网进行第三次筛分，得到铝箔和浆料；
步骤8，对所得浆料进行压滤，并在120℃下烘干1h，得到第三黑粉；
步骤9，将所得第一、二、三黑粉置于流化床焙烧炉中，在1000℃下鼓入空气，持续0.5h，空气中的水蒸气体积含量为10％，空气流量为8Nm3/min；
步骤10，在流化床焙烧炉出口进行收尘后，即得低铜铝氟含量的黑粉。
监测热解炉内情况：炉内无明显火星。
对比例1
一种黑粉的制备方法，与实施例1的区别在于，破碎料直接进行低温热解和筛分，具体过程为：
步骤1，废旧三元锂离子电池经放电、拆解后，破碎成粒度为5cm以下的破碎料；
步骤2，将破碎料加入到热解炉中，控制热解炉填充率为5％，持续通入氮气，并升温至300℃，持续5h；
步骤3，将热解后的物料经孔径为0.25mm的筛网进行筛分，得到筛下物黑粉和筛上物铜 铝箔；
步骤4，色选分离铜铝箔，得到铜箔和铝箔。
监测热解炉内情况：炉内无明显火星。
对比例2
一种黑粉的制备方法，与实施例2的区别在于，破碎料直接进行低温热解和筛分，具体过程为：
步骤1，废旧钴酸锂电池经放电、拆解后，破碎成粒度为5cm以下的破碎料；
步骤2，将破碎料加入到热解炉中，控制热解炉填充率为10％，持续通入氮气，并升温至350℃，持续4h；
步骤3，将热解后的物料经孔径为0.25mm的筛网进行筛分，得到筛下物黑粉和筛上物铜铝箔；
步骤4，色选分离铜铝箔，得到铜箔和铝箔。
监测热解炉内情况：炉内无明显火星。
对比例3
一种黑粉的制备方法，与实施例3的区别在于，破碎料直接进行低温热解和筛分，具体过程为：
步骤1，废旧三元锂离子电池经放电、拆解后，破碎成粒度为5cm以下的破碎料；
步骤2，将破碎料加入到热解炉中，控制热解炉填充率为15％，持续通入氮气，并升温至400℃，持续3h；
步骤3，将热解后的物料经孔径为0.25mm的筛网进行筛分，得到筛下物黑粉和筛上物铜铝箔；
步骤4，色选分离铜铝箔，得到铜箔和铝箔。
监测热解炉内情况：炉内无明显火星。
对实施例1-3与对比例1-3所得黑粉进行检测，结果如表1所示。
表1

由表1可见，对比例1-3中，黑粉中氟含量较高，说明氟化物残留较多；对比例1-3热解温度不足，热解反应难以完全发生，镍钴锰总含量低，说明正极粉脱附率较低。
上面结合附图对本发明实施例作了详细说明，但是本发明不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。此外，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。

Claims (10)

  1. 一种低铜铝无氟黑粉，其特征在于，所述低铜铝无氟黑粉的含水量≤1.0wt％，镍钴锰金属元素总含量≥30.0wt％，锂元素含量≥3.3wt％，铜元素含量≤0.8wt％，铝含量≤1.0wt％，氟含量≤0.1wt％。
  2. 如权利要求1所述的低铜铝无氟黑粉的制备方法，其特征在于，包括以下步骤：
    S1：废旧锂离子电池经放电、拆解、破碎和第一次筛分，得到第一黑粉和第一筛上物；
    S2：所述第一筛上物在惰性气氛下300-400℃进行热解，热解后物料进行第二次筛分，得到第二黑粉和第二筛上物，将所述第二筛上物进行色选分离，得到铜箔和含铝极片；
    S3：将所述含铝极片置于三价铁盐溶液中进行反应，所得反应物料进行第三次筛分，得到铝箔和浆料，将所述浆料进行固液分离，所得固体进行烘干，得到第三黑粉；
    S4：将所述第一黑粉、第二黑粉和第三黑粉在500-1000℃下鼓入空气进行焙烧，且空气中的水蒸气体积含量为10％-40％，得到所述低铜铝无氟黑粉。
  3. 根据权利要求2所述的制备方法，其特征在于，步骤S1中，所述破碎后所得破碎料的粒度≤5cm。
  4. 根据权利要求2所述的制备方法，其特征在于，步骤S1中，所述废旧锂离子电池为三元锂离子电池、钴酸锂电池、锰酸锂电池或镍酸锂电池中的至少一种。
  5. 根据权利要求2所述的制备方法，其特征在于，所述第一次筛分、第二次筛分、第三次筛分的筛网孔径独立为0.2-0.3mm。
  6. 根据权利要求2所述的制备方法，其特征在于，步骤S2中，所述热解的时间为3-5h。
  7. 根据权利要求2所述的制备方法，其特征在于，步骤S3中，所述含铝极片与三价铁盐溶液的固液比为0.5-2.0g/mL，所述三价铁盐溶液中铁离子的浓度为0.1-0.5mol/L。
  8. 根据权利要求2所述的制备方法，其特征在于，步骤S3中，所述反应的温度为40-90℃。
  9. 根据权利要求2所述的制备方法，其特征在于，步骤S3中，所述三价铁盐溶液为硫酸铁溶液、硝酸铁溶液或氯化铁溶液中的至少一种。
  10. 根据权利要求2所述的制备方法，其特征在于，步骤S4中，所述空气的流量为8-15Nm3/min。
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