WO2023273262A1 - 一种废旧锂电池安全热解除杂的方法和应用 - Google Patents

一种废旧锂电池安全热解除杂的方法和应用 Download PDF

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WO2023273262A1
WO2023273262A1 PCT/CN2021/142958 CN2021142958W WO2023273262A1 WO 2023273262 A1 WO2023273262 A1 WO 2023273262A1 CN 2021142958 W CN2021142958 W CN 2021142958W WO 2023273262 A1 WO2023273262 A1 WO 2023273262A1
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electrode
mesh
fragments
electrode material
waste lithium
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PCT/CN2021/142958
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English (en)
French (fr)
Inventor
余海军
钟应声
谢英豪
张学梅
李长东
Original Assignee
广东邦普循环科技有限公司
湖南邦普循环科技有限公司
湖南邦普汽车循环有限公司
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Priority to DE112021005045.1T priority Critical patent/DE112021005045T5/de
Priority to HU2200226A priority patent/HUP2200226A2/hu
Priority to ES202390051A priority patent/ES2976983A1/es
Priority to MX2023013229A priority patent/MX2023013229A/es
Priority to GB2313049.5A priority patent/GB2619190A/en
Priority to US18/265,860 priority patent/US20240030509A1/en
Priority to MA60468A priority patent/MA60468A1/fr
Publication of WO2023273262A1 publication Critical patent/WO2023273262A1/zh

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    • 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
    • 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
    • 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
    • C22B7/008—Wet processes by an alkaline or ammoniacal 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
    • H01M10/05—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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • 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 recycling electrode materials by a high-temperature method, and in particular relates to a method and an application for safely pyrolytically removing impurities from waste lithium batteries.
  • electrode materials are usually recovered by wet and high-temperature methods.
  • high-temperature method mechanical crushing is performed first, so that the metal casing of the waste lithium battery is broken into small particles, and the electrode material is detached from the waste electrode fragments through sieving, and the organic binder of the electrode material is pyrolyzed at the same time.
  • organic binders such as polyvinylidene fluoride, polytetrafluoroethylene
  • polyolefins in the separator such as polypropylene, polypropylene, etc.
  • conductive agent such as polypropylene, polypropylene, etc.
  • carbonates in the electrolyte such as ethylene carbonate, ethyl methyl carbonate
  • waste lithium battery plastic shell debris etc.
  • the first stage is a first stage
  • the above-mentioned second stage reaction rate is extremely fast, and a large amount of heat is released in a short time, causing the temperature of the reaction area to reach above 2800°C, which not only melts the electrode material near the reaction area, but also splashes the high-temperature molten material, which will further melt through the refractory material on the inner wall of the heating furnace. material and the inner wall of the heating furnace, which is very dangerous.
  • More impurities in the electrode material will not only affect the purity of the electrode material of the waste lithium battery, but also increase the complexity of the subsequent processing of the electrode material, cause damage to the equipment, and increase unsafe factors to the electrode material processing environment.
  • the present invention aims to solve at least one of the technical problems in the above-mentioned prior art. For this reason, the present invention proposes a method and application of safe thermal decontamination of waste batteries, which eliminates impurities such as organic binders, conductive agents, organic solvents, aluminum, etc. remaining in the electrode materials of waste lithium batteries, and improves the efficiency of the electrodes. The purity of the material and its safety during pyrolysis.
  • the present invention adopts the following technical solutions:
  • a method for safe pyrolysis of waste lithium batteries comprising the following steps:
  • the electrode fragments of waste lithium batteries are roasted once, quenched, and then layered and sieved to obtain current collector fragments and electrode materials;
  • the electrode powder is subjected to secondary firing to obtain the positive electrode material.
  • the electrode fragments of the waste lithium battery are obtained by discharging and crushing the waste lithium battery.
  • the above-mentioned crushing mainly reduces the production of fine particles of aluminum and copper, reduces the impurity particles in battery materials, and facilitates the recovery of fluid fragments.
  • the rapid cooling treatment is spraying a quick cooling agent to cool the spent lithium battery electrode fragments to ⁇ 50°C within 90s; the quick cooling agent is cold air with a temperature of ⁇ 15°C.
  • the temperature of the primary calcination is 420-600° C., and the time of the primary calcination is 45-90 minutes.
  • the atmosphere of the primary firing is air or oxygen.
  • Roasting the waste electrode fragments will reduce the adhesive performance of the binder (polyvinylidene fluoride, polytetrafluoroethylene), and the electrode material will become brittle; at the same time, the surface temperature of the waste electrode fragments will be rapidly reduced, and the current collector (aluminum foil, copper foil ) fragments have a thinner cut, the temperature of the cut part drops faster, and the shrinkage force is generated first, the cut of the current collector fragment is quickly curled, and the opening of the current collector fragment and the electrode material of the waste lithium battery is larger. After sieving, the waste lithium battery electrode materials are more likely to fall off.
  • the layered screening adopts an ultrasonic vibrating screening machine
  • the mesh number of the parent net of the ultrasonic vibrating screening machine is 16 mesh or 20 mesh
  • the mesh number of the transition net of the ultrasonic vibrating screening machine is 100
  • the mesh of the subnet of the ultrasonic vibrating screening machine is one of 500 mesh, 540 mesh or 600 mesh.
  • Ultrasonic vibrating screening machine is used for layered screening, and the high-precision and high-mesh screening function can also control the narrow particle size range of waste lithium battery electrode materials, which is conducive to improving the screening accuracy and the discharge efficiency can be increased by 20%. % ⁇ 50%.
  • one ultrasonic vibrating screening machine can be connected to multiple electric energy/sound energy converters at the same time, and can screen under different power and vibration frequencies.
  • Waste lithium battery electrode materials have the characteristics of certain adsorption and high static electricity when sieving.
  • the ultrasonic vibration sieving machine can solve this unfavorable characteristic. Therefore, the efficient separation of electrode materials and current collectors can be achieved through simple and sieving.
  • Screening and grading are carried out on the three-layer net of parent net, transition net and sub-net, which can well separate different types of material nets and recycle different materials in a targeted manner.
  • the parent network mainly retains current collector fragments
  • the transition network retains electrode material fragments containing more impurities
  • the sub-network retains coarse-grained electrode materials containing more impurities
  • the fine-grained electrode materials pass through the sub-network.
  • the electrode materials of different sizes and shapes intercepted by the parent grid, transition grid, and sub-net are collected by secondary screening.
  • the electrode material is electrode material fragments, coarse particle electrode material, and fine particle electrode material.
  • the electrode material fragments and the coarse particle electrode material are crushed and sieved to obtain the coarse current collector particles and the coarse particle electrode material, and the coarse particle electrode material is crushed and sieved to obtain the fine particle electrode material.
  • a pulverizer is used to further pulverize the electrode fragments and coarse-grained electrode materials through the sub-network, and at the same time, the coarse-grained current collector that is not easily crushed is also recovered.
  • the collector pieces are washed with water, dried, and the collector pieces are recovered.
  • the grinding aid is at least one of white carbon black, opal powder or quartz powder.
  • the main component of silica, opal powder or quartz powder is silicon dioxide
  • the mass ratio of the grinding aid to the electrode material is (0.1-0.5):100.
  • the grinding time is 30-120 min, and the rotation speed of the grinder used for grinding is 300-600 rpm.
  • the lye is one of sodium hydroxide, magnesium hydroxide, potassium hydroxide or calcium hydroxide.
  • the OH - concentration of the lye is 0.01-0.2 mol/L.
  • the soaking time is 10-15 minutes.
  • step (2) it also includes washing and drying the filter residue.
  • the filtered filtrate is supplemented with alkali, which can be used again to soak the ground electrode powder.
  • the temperature of the secondary calcination is 600-1000° C., and the time of the secondary calcination is 60-90 minutes.
  • the atmosphere of the secondary firing is air or oxygen.
  • the invention also provides the application of the method in recycling electrode materials.
  • the waste lithium battery electrode fragments are roasted once to reduce the adhesive performance of the binder, and at the same time, the surface temperature of the waste lithium battery electrode fragments is rapidly reduced. Since the cuts of the current collector (aluminum foil, copper foil) fragments are thinner, The temperature of the incision part drops faster, and the contraction force is generated first, and the incision of the current collector fragments is curled first, so the opening between the current collector fragments and the waste lithium battery electrode material increases, and after sieving, the waste lithium battery electrode material is easier to fall off.
  • the method of the present invention utilizes grinding aids to reduce the density of the electrode material and increase the uniformity of the electrode material after grinding, thereby avoiding the agglomeration phenomenon of the dry grinding electrode material, eliminating the electrostatic effect, and promoting the integration of aluminum in the electrode material and dilute Alkali reaction, reduce the temperature of secondary roasting, and then use lye to soak the electrode material to dissolve the residual aluminum powder, and the grinding aid will also dissolve in dilute alkali, so dilute alkali can simultaneously remove aluminum and grinding aid in the electrode material , and the filtered dilute alkali filtrate can be used again in the alkaline leaching of waste lithium battery electrode materials to reduce the consumption of alkali.
  • the primary roasting of the present invention is to pyrolyze impurities such as most of the organic binders (such as polyvinylidene fluoride, polytetrafluoroethylene), conductive agents, organic solvents, etc.
  • the secondary roasting is to pyrolyze and carbonize impurities that cannot be obtained in the primary roasting. A small portion of residual impurities that are pyrolyzed.
  • Fig. 1 is the process flow chart of embodiment 1 of the present invention.
  • Fig. 1 is the process flow chart of the embodiment 1 of the present invention, can obtain from Fig. 1 that the waste lithium battery is discharged, initially crushed, and waste electrode sheet fragments are obtained, and then roasted, cooled, sieved, and sieved, and an ultrasonic vibrating sieve is used
  • the sub-machine performs layered screening, that is, the three-layer network of the parent network, transitional network and sub-network is screened and classified, so that fine particle electrode materials will be obtained, and then the electrode powder will be obtained through dilute alkali removal, filtration, and secondary roasting. .
  • waste lithium batteries for discharge and initial crushing to obtain waste electrode fragments with a length and width of 2 to 3 cm and a mass of 8.79 kg.
  • a temperature of 550 ° C and oxygen flow place them in a heating furnace for 69 minutes of roasting. After roasting, move it to the mesh basket, spray air-conditioning at a temperature of 10°C for rapid cooling, and use an ultrasonic vibrating screener to sieve (20 mesh for the parent mesh, 100 mesh for the transition mesh, and 540 mesh for the subnet), and the parent mesh collects the fluid Debris, the transition network collects electrode material fragments containing impurities, and the sub-network collects coarse particle electrode materials containing more impurities;
  • waste lithium batteries for discharge and initial crushing to obtain waste electrode fragments with a length and width of 2 to 3 cm and a mass of 8.37 kg. Put them in a heating furnace for 57 minutes at a temperature of 580 ° C and oxygen flow, and after roasting Move to the mesh basket, spray air-conditioning at a temperature of 10°C for rapid cooling, and use an ultrasonic vibrating screener to sieve (20 mesh for the parent mesh, 100 mesh for the transition mesh, and 600 mesh for the subnet).
  • the parent mesh collects fluid debris
  • the transition net collects electrode material fragments containing impurities
  • the sub-net collects coarse particle electrode materials containing more impurities;
  • waste lithium batteries for discharge and primary crushing to obtain waste electrode fragments with a length and width of 2 to 3 cm and a mass of 7.83 kg. Put them in a heating furnace for 68 minutes at a temperature of 490 ° C and oxygen flow, and after roasting Move to the mesh basket, spray air-conditioning at a temperature of 10°C for rapid cooling, and use an ultrasonic vibrating screener to screen (select 16 mesh for the parent mesh, 200 mesh for the transition mesh, and 600 mesh for the subnet).
  • the parent mesh collects fluid debris
  • the transition net collects electrode material fragments containing impurities
  • the sub-net collects coarse particle electrode materials containing more impurities;
  • the opal powder and electrode material are sent into an oscillating ball mill with a rotation speed of 540rpm to grind for 69min according to the mass ratio of 0.14:100, and then moved to 0.175mol/L dilute potassium hydroxide solution for OH- concentration after grinding. Soak for 15 minutes and filter to obtain filtrate and filter residue. The filtrate is supplemented with alkali, which can be used to soak electrode powder again, and the filter residue is washed with water and dried to obtain electrode powder;
  • the method for the safe pyrolysis of waste lithium batteries of this comparative example comprises the following steps:
  • waste lithium batteries for discharge and initial crushing to obtain waste electrode fragments with a length and width of 2 to 3 cm and a mass of 7.45 kg. Put them in a heating furnace for 53 minutes at a temperature of 615°C and pass oxygen, and cool at room temperature , using an ultrasonic vibrating screening machine for screening (choose 16 mesh for the main net, 140 mesh for the transition net, and 500 mesh for the sub net).
  • the main net collects fluid debris
  • the transition net collects electrode material fragments containing impurities
  • the sub net collects debris Coarse particle electrode material with many impurities;
  • the method for the safe pyrolysis of waste lithium batteries of this comparative example comprises the following steps:
  • waste lithium batteries for discharge and primary crushing to obtain waste electrode fragments with a length and width of 2 to 3 cm and a mass of 8.07 kg.
  • a temperature of 585 ° C and oxygen flow place them in a heating furnace for a 45 min roasting , moved to the mesh basket after roasting, sprayed air-conditioning at a temperature of 10°C for rapid cooling, and selected an ultrasonic vibrating screener for screening (choose 16 mesh for the parent mesh, 200 mesh for the transition mesh, and 600 mesh for the subnet).
  • the transition net collects electrode material fragments containing impurities
  • the subnet collects coarse particle electrode materials containing more impurities;
  • the electrode material is sent into a vibrating ball mill with a rotation speed of 540rpm and ground for 78min. After grinding, it is moved to 0.094mol / L dilute potassium hydroxide solution for immersion, soaked for 15min and filtered to obtain filtrate, filter residue, and filtrate. Alkali is added to the medium, which can be used to soak the electrode powder again, and the filter residue is washed with water and dried to obtain the electrode powder;
  • Comparative example 2 does not add grinding aid, and agglomeration phenomenon can occur, and agglomeration phenomenon is unfavorable for particle dispersion, and can cause particle size to be bigger, is unfavorable for the dispersal of the carbonized incrustation such as roasting binder, conductive agent, organic solvent, just It is not conducive to the reaction between aluminum and dilute alkali, resulting in aluminum residue after dilute alkali treatment.

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Abstract

本发明公开了一种废旧锂电池安全热解除杂的方法和应用，该方法包括以下步骤：将废旧锂电池电极碎片进行一次焙烧，急冷，再进行筛分，得到集流体碎片和电极材料；将电极材料和助磨剂混合研磨，加入碱液中浸泡，过滤取滤渣，得到电极粉；将电极粉进行二次焙烧，得到正极材料。本发明的方法对废旧锂电池电极碎片进行一次焙烧降低粘结剂的粘合性能，同时快速降低废弃锂电池电极碎片表面温度，由于集流体(铝箔、铜箔)碎片的切口更薄，该切口部分温度下降更快，先产生收缩力，集流体碎片切口快速卷曲，因而集流体碎片与废弃锂电池电极材料开口更大，筛分后，废旧锂电池电极材料则更容易脱落。

Description

一种废旧锂电池安全热解除杂的方法和应用 技术领域
本发明属于高温法回收电极材料技术领域，具体涉及一种废旧锂电池安全热解除杂的方法和应用。
背景技术
目前，通常以湿法和高温法来回收电极材料。在高温法中，先机械破碎，使得废旧锂电池金属外壳碎成小颗粒，通过筛分处理，电极材料从废极片碎片上脱落，同时热解掉电极材料的有机粘结剂(例如聚偏氟乙烯、聚四氟乙烯)、导电剂、有机溶剂等。高温焙烧后，但电极材料中杂质较多，不能有效的将之彻底热解：有机粘结剂(例如聚偏氟乙烯、聚四氟乙烯)、隔膜中的聚烯烃类(例如聚丙烯、聚乙烯)、导电剂、电解液中的碳酸酯类(例如碳酸乙烯酯、碳酸甲乙酯)、废旧锂电池塑料壳碎屑等在高温热解后因受热不均导致的碳化结痂仍残留在电极材料颗粒中；同时机械破碎、筛分处理并不能将电极材料颗粒中残留的残余小部分铝粉、铜粉去掉。高温(>1200℃)通空气或氧气下，电极材料中的正极材料、铜粉均可与铝粉发生反应，反应如下：
第一阶段：
LiNi eCo fMn gO 2→LiO+eNiO+f CoO+g MnO，e+f+g＝1；(主反应)
2Cu+O 2→2CuO。
第二阶段：
eNiO+fCoO+gMnO+2/3(e+f+g)Al→1/3(e+f+g)Al 2O 3+eNi+fCo+gMn；(主反应)
3CuO+2Al→3Cu+Al 2O 3。
上述第二阶段反应速率极快，短时间放出大量的热，致使反应区域温度达到2800℃以上，不仅能熔融反应区域附近的电极材料，高温熔融物飞溅，进一步将会熔穿加热炉内壁的耐火材料以及加热炉内壁，十分危险。
电极材料中较多的杂质，不仅影响废弃锂电池电极材料的纯度，也将加大后续处理电极材料流程的复杂程度，也对设备产生损害，对电极材料处理环境增加不安全因素。
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，本发明提出一种废电池安全热解除杂的方法和应用，该方法消除了废弃锂电池电极材料中残留的有机粘结剂、导电剂、有机溶剂、铝等杂质，并提高了电极材料的纯度以及热解时的安全性。
为实现上述目的，本发明采用以下技术方案：
一种废旧锂电池安全热解除杂的方法，包括以下步骤：
(1)将废旧锂电池电极碎片进行一次焙烧，急冷，再进行分层筛分，得到集流体碎片和电极材料；
(2)将所述电极材料和助磨剂混合研磨，加入碱液中浸泡，过滤取滤渣，得到电极粉；
(3)将所述电极粉进行二次焙烧，得到正极材料。
优选地，步骤(1)中，所述废旧锂电池电极碎片是由废旧锂电池放电，破碎，即得。
上述的破碎，主要减少细颗粒铝、铜的产生，降低减少电池材料中杂质颗粒，便于回收集流体碎片。
优选地，步骤(1)中，所述急冷处理是喷撒速冷剂，在90s内将废旧锂电池电极碎片冷却至<50℃；所述速冷剂为温度＜15℃的冷气。
优选地，步骤(1)中，所述一次焙烧的温度为420～600℃，一次焙烧的时间为45～90min。
优选地，步骤(1)中，所述一次焙烧的气氛为空气或氧气。
焙烧废极片碎片，粘结剂(聚偏氟乙烯、聚四氟乙烯)粘合性能降低，电极材料变脆；同时快速降低废极片碎片表面温度，废极片上集流体(铝箔、铜箔)碎片的切口更薄，该切口部分温度下降更快，先产生收缩力，集流体碎片切口快速卷曲，集流体碎片与废弃锂电池电极材料开口更大。经过筛分，废弃锂电池电极材料则更容易脱落。
优选地，步骤(1)中，所述分层筛分采用超声波振动筛分机，超声波振动筛分机的母网的目数为16目或20目，超声波振动筛分机的过渡网的目数为100目、140目或200目中的一种，超声波振动筛分机的子网的目数为500目、540目或600目中的一种。
采用超声波振动筛分机进行分层筛分，利用高精度、高网目的筛分功能同时，也能 控制废弃锂电池电极材料较窄的粒度范围，利于提高筛分的精度，出料效率可提高20％～50％。在三层筛分网连用时，一台超声波振动筛分机可同时连接多个电能/声能转换器，能在不同功率、振动频率下筛分。废弃锂电池电极材料在筛分时具有一定吸附性、高静电的特点，采用超声波振动筛分机能解决该不利的特点，因此通过简单的、筛分即可实现电极材料、集流体的高效分离。
母网、过渡网、子网三层网进行筛分、分级处理，能很好的将不同类型材料网筛分开，针对性的回收不同材料。母网主要截留集流体碎片，过渡网截留含较多杂质电极材料碎片，子网截留部分含较多杂质的粗颗粒电极材料，过子网的为细颗粒电极材料。母网、过渡网、子网截留的大小形状不同的电极材料进行二次筛分收集。
优选地，步骤(1)中，所述电极材料为电极材料碎片、粗颗粒电极材料、细颗粒电极材料。
进一步优选地，将所述电极材料碎片和粗颗粒电极材料粉碎，筛分，得到粗集流体颗粒和粗颗粒电极材料，将粗颗粒电极材料粉碎，过筛得到细颗粒电极材料。
基于前面除去大部分铝、铜，采用粉碎机，进一步将电极碎片、粗颗粒电极材粉碎过子网，同时也将不易粉碎的粗颗粒集流体回收。
优选地，步骤(1)中，对所述集流体碎片水洗、干燥，回收集流体碎片。
优选地，步骤(2)中，所述助磨剂为白炭黑、蛋白石粉或石英粉中的至少一种。(白炭黑、蛋白石粉或石英粉的主要成分为二氧化硅)
优选地，步骤(2)中，所述助磨剂和电极材料的质量比为(0.1～0.5)：100。
优选地，步骤(2)中，所述研磨的时间为30～120min，研磨使用研磨机的转数为300～600rpm。
优选地，步骤(2)中，所述碱液为氢氧化钠、氢氧化镁、氢氧化钾或氢氧化钙中的一种。
进一步优选地，所述碱液的OH -浓度为0.01～0.2mol/L。
优选地，步骤(2)中，所述浸泡的时间为10～15min。
优选地，步骤(2)中，还包括对所述滤渣进行水洗、烘干。
优选地，步骤(2)中，所述过滤后的滤液中补充碱，可再次用于浸泡研磨后的电极粉。
优选地，步骤(3)中，所述二次焙烧的温度为600～1000℃，二次焙烧的时间为60～90min。
优选地，步骤(3)中，所述二次焙烧的气氛为空气或氧气。
本发明还提供所述的方法在回收电极材料中的应用。
相对于现有技术，本发明的有益效果如下：
1、本发明的方法对废弃锂电池电极碎片进行一次焙烧降低粘结剂的粘合性能，同时快速降低废弃锂电池电极碎片表面温度，由于集流体(铝箔、铜箔)碎片的切口更薄，该切口部分温度下降更快，先产生收缩力，集流体碎片切口先卷曲，因而集流体碎片与废弃锂电池电极材料开口增大，筛分后，废弃锂电池电极材料则更容易脱落。
2、本发明的方法利用助磨剂减小电极材料的密度和增加研磨出电极材料的均匀性，从而避免干磨电极材料则呈现出团聚现象、消除静电效应，促进电极材料中的铝与稀碱反应、降低二次焙烧的温度，再利用碱液浸泡电极材料可溶解残留的铝粉，同时助磨剂也将溶于稀碱，因此稀碱能同步除去电极材料中的铝、助磨剂，而且过滤后的稀碱滤液能再次用于碱浸废弃锂电池电极材料中，减少碱的消耗。
3、本发明的一次焙烧是为了热解大部分有机粘结剂(例如聚偏氟乙烯、聚四氟乙烯)、导电剂、有机溶剂等杂质，二次焙烧是为了热解碳化一次焙烧中无法热解掉的残余小部分杂质。
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
本实施例的废旧锂电池安全热解除杂的方法，包括以下步骤：
(1)回收废旧锂电池放电、初破碎，得到长宽为2～3cm废电极片碎片，质量为7.34kg， 在温度为586℃和通氧情况下，置于加热炉中进行一次焙烧45min，焙烧后移至网篮中，喷温度为10℃的冷气进行急冷，选用超声波振动筛分机进行筛分(母网选16目，过渡网为100目，子网选540目)，母网收集流体碎片，过渡网收集含杂质的电极材料碎片，子网收集含较多杂质的粗颗粒电极材料；
(2)将母网截留的集流体碎片水洗、干燥，回收集流体碎片，过渡网截留的电极材料碎片和子网截留的粗颗粒电极材料经过粉碎机碎成细颗粒，第二次用超声波筛分机的过渡网、子网筛分，第二次筛分中，过渡网截留的为粗集流体颗粒，并进行收集，子网截留的粗颗粒电极材料再次用于上述粉碎机碎成细颗粒，子网过筛得电极材料；
(3)将白炭黑和电极材料按质量比为0.41:100送入转数为540rpm的振荡球磨机中研磨87min，研磨后移至OH -浓度在0.031mol/L的氢氧化钠溶液中浸泡，浸泡12min过滤，得滤液、滤渣，滤液中补充碱，可再次用于浸泡电极粉，滤渣进行水洗、烘干得电极粉；
(4)将电极粉移至加热炉中，通空气下，在加热炉中温度为755℃焙烧87min，得5.37kg正极材料。
图1为本发明实施例1的工艺流程图，从图1可得将废旧锂电池放电、初破碎、得到废电极片碎片，再进行一次焙烧、冷却、筛分、筛分，使用超声波振动筛分机进行分层筛分，即母网、过渡网、子网三层网进行筛分、分级处理，从而将得到细颗粒电极材料，再通过稀碱除杂、过滤、二次焙烧、得到电极粉。
实施例2
本实施例的废旧锂电池安全热解除杂的方法，包括以下步骤：
(1)回收废旧锂电池放电、初破碎，得到长宽为2～3cm废电极片碎片，质量为8.79kg，在温度为550℃和通氧情况下，置于加热炉中进行一次焙烧69min，焙烧后移至网篮中，喷温度为10℃的冷气进行急冷，选用超声波振动筛分机进行筛分(母网选20目，过渡网为100目，子网选540目)，母网收集流体碎片，过渡网收集含杂质的电极材料碎片，子网收集含较多杂质的粗颗粒电极材料；
(2)将母网截留的集流体碎片水洗、干燥，回收集流体碎片，过渡网截留的电极材料碎片和子网截留的粗颗粒电极材料经过粉碎机碎成细颗粒，第二次用超声波筛分机的过渡网、子网筛分，第二次筛分中，过渡网截留的为粗集流体颗粒，并进行收集，子网截留的粗颗粒电极材料再次用于上述粉碎机碎成细颗粒，子网过筛得电极材料；
(3)将白炭黑和电极材料按质量比为0.27:100送入转数为480rpm的振荡球磨机中研磨104min，研磨后移至OH -浓度在0.157mol/L的稀氢氧化钠溶液中浸泡，浸泡10min过滤，得滤液、滤渣，滤液中补充碱，可再次用于浸泡电极粉，滤渣进行水洗、烘干得电极粉；
(4)将电极粉移至加热炉中，通空气下，在加热炉中，温度为695℃下焙烧78min，得到6.64kg正极材料。
实施例3
本实施例的废旧锂电池安全热解除杂的方法，包括以下步骤：
(1)回收废旧锂电池放电、初破碎，得到长宽为2～3cm废电极片碎片，质量为8.37kg，在温度为580℃和通氧情况下，置于加热炉中进行57min，焙烧后移至网篮中，喷温度为10℃的冷气进行急冷，选用超声波振动筛分机进行筛分(母网选20目，过渡网为100目，子网选600目)，母网收集流体碎片，过渡网收集含杂质的电极材料碎片，子网收集含较多杂质的粗颗粒电极材料；
(2)将母网截留的集流体碎片水洗、干燥，回收集流体碎片，过渡网截留的电极材料碎片和子网截留的粗颗粒电极材料经过粉碎机碎成细颗粒，第二次用超声波筛分机的过渡网、子网筛分，第二次筛分中，过渡网截留的为粗集流体颗粒，并进行收集，子网截留的粗颗粒电极材料再次用于上述粉碎机碎成细颗粒，子网过筛得电极材料；
(3)将白炭黑和电极材料按质量比为3:100送入转数为540rpm的振荡球磨机中研磨76min，研磨后移至OH -浓度在0.138mol/L的稀氢氧化钠溶液中浸泡，浸泡15min过滤，得滤液、滤渣，滤液中补充碱，可再次用于浸泡电极粉，滤渣进行水洗、烘干得电极粉；
(4)将电极粉移至加热炉中，通空气下，置于加热炉中在845℃下焙烧67min，得6.31kg正极材料。
实施例4
本实施例的废旧锂电池安全热解除杂的方法，包括以下步骤：
(1)回收废旧锂电池放电、初破碎，得到长宽为2～3cm废电极片碎片，质量为7.83kg，在温度为490℃和通氧情况下，置于加热炉中进行68min，焙烧后移至网篮中，喷温度为10℃的冷气进行急冷，选用超声波振动筛分机进行筛分(母网选16目，过渡网为200目，子网选600目)，母网收集流体碎片，过渡网收集含杂质的电极材料碎片，子网收 集含较多杂质的粗颗粒电极材料；
(2)将母网截留的集流体碎片水洗、干燥，回收集流体碎片，过渡网截留的电极材料碎片和子网截留的粗颗粒电极材料经过粉碎机碎成细颗粒，第二次用超声波筛分机的过渡网、子网筛分，第二次筛分中，过渡网截留的为粗集流体颗粒，并进行收集，子网截留的粗颗粒电极材料再次用于上述粉碎机碎成细颗粒，子网过筛得电极材料；
(3)将蛋白石粉和电极材料按质量比为0.14:100送入转数为540rpm的振荡球磨机中研磨69min，研磨后移至OH -浓度在0.175mol/L的稀氢氧化钾溶液中浸泡，浸泡15min过滤，得滤液、滤渣，滤液中补充碱，可再次用于浸泡电极粉，滤渣进行水洗、烘干得电极粉；
(4)将电极粉移至加热炉中，通空气下，加热炉中755℃下焙烧75min，得5.64kg正极材料。
对比例1
本对比例的废旧锂电池安全热解除杂的方法，包括以下步骤：
(1)回收废旧锂电池放电、初破碎，得到长宽为2～3cm废电极片碎片，质量为7.45kg，在温度为615℃和通氧情况下，置于加热炉中进行53min，常温冷却，选用超声波振动筛分机进行筛分(母网选16目，过渡网为140目，子网选500目)，母网收集流体碎片，过渡网收集含杂质的电极材料碎片，子网收集含较多杂质的粗颗粒电极材料；
(2)将母网截留的集流体碎片水洗、干燥，回收集流体碎片，过渡网截留的电极材料碎片和子网截留的粗颗粒电极材料经过粉碎机碎成细颗粒，第二次用超声波筛分机的过渡网、子网筛分，第二次筛分中，过渡网截留的为粗集流体颗粒，并进行收集，子网截留的粗颗粒电极材料再次用于上述粉碎机碎成细颗粒，子网过筛得电极材料；
(3)将白炭黑和电极材料按质量比为0.43:100送入转数为480rpm的振荡球磨机中研磨72min，研磨后移至OH -浓度在0.076mol/L的稀氢氧化钠溶液中浸泡，浸泡14min过滤，得滤液、滤渣，滤液中补充碱，可再次用于浸泡电极粉，滤渣进行水洗、烘干得电极粉；
(4)将电极粉移至加热炉中，通空气下，加热炉中850℃焙烧74min，即得正极材料。
对比例2
本对比例的废旧锂电池安全热解除杂的方法，包括以下步骤：
(1)回收废旧锂电池进行放电、初破碎，得到长宽为2～3cm废电极片碎片，质量为8.07kg，在温度为585℃和通氧情况下，置于加热炉中进行一次焙烧45min，焙烧后移至网篮中，喷温度为10℃的冷气进行急冷，选用超声波振动筛分机进行筛分(母网选16目，过渡网为200目，子网选600目)，母网收集流体碎片，过渡网收集含杂质的电极材料碎片，子网收集含较多杂质的粗颗粒电极材料；
(2)将母网截留的集流体碎片水洗、干燥，回收集流体碎片，过渡网截留的电极材料碎片和子网截留的粗颗粒电极材料经过粉碎机碎成细颗粒，第二次用超声波筛分机的过渡网、子网筛分，第二次筛分中，过渡网截留的为粗集流体颗粒，并进行收集，子网截留的粗颗粒电极材料再次用于上述粉碎机碎成细颗粒，子网过筛得电极材料；
(3)将电极材料送入转数为540rpm的振荡球磨机中研磨78min，研磨后移至OH -浓度在0.094mol/L的稀氢氧化钾溶液中浸泡，浸泡15min过滤，得滤液、滤渣，滤液中补充碱，可再次用于浸泡电极粉，滤渣进行水洗、烘干得电极粉；
(4)将电极粉移至加热炉中，通空气下，加热炉中780℃焙烧87min，得6.24kg正极材料。
表1 实施例1、2、3、4和对比例1、2电极材料中铝、碳检测值
Figure PCTCN2021142958-appb-000001
Figure PCTCN2021142958-appb-000002
由表1可得，利用本发明实施例1-4的方法热解除杂的正极材料，含铝量低，而对比例1由于是常温下缓慢冷却，不利于集流体碎片切口卷曲度小，导致集流体碎片与废弃锂电池电极材料开口减小，经过筛分废弃锂电池电极材料不易脱落，导致稀碱处理前铝含量高。对比例2不加入助磨剂，会出现团聚现象，团聚现象不利于颗粒分散，会造成颗粒粒径较大，不利于焙烧粘结剂、导电剂、有机溶剂等碳化结痂的分散，也就不利于铝和稀碱反应，造成稀碱处理后还有铝残留。
上面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. 一种废旧锂电池安全热解除杂的方法，其特征在于，包括以下步骤：
    (1)将废旧锂电池电极碎片进行一次焙烧，急冷，再进行分层筛分，得到集流体碎片和电极材料；
    (2)将所述电极材料和助磨剂混合研磨，加入碱液中浸泡，过滤取滤渣，得到电极粉；
    (3)将所述电极粉进行二次焙烧，得到正极材料。
  2. 根据权利要求1所述的方法，其特征在于，步骤(1)中，所述一次焙烧的温度为420～600℃，一次焙烧的时间为45～90min，一次焙烧的气氛为空气或氧气。
  3. 根据权利要求1所述的方法，其特征在于，步骤(1)中，所述筛分使用超声波振动筛分机，超声波振动筛分机的母网的目数为16目或20目，超声波振动筛分机的过渡网的目数为100目、140目或200目中的一种，超声波振动筛分机的子网的目数为500目、540目或600目中的一种。
  4. 根据权利要求1所述的方法，其特征在于，步骤(1)中，所述急冷处理是喷撒速冷剂，在90s内将废旧锂电池电极碎片冷却至<50℃；所述速冷剂为温度＜15℃的冷气。
  5. 根据权利要求1所述的方法，其特征在于，步骤(2)中，所述助磨剂为白炭黑、蛋白石粉或石英粉中的至少一种。
  6. 根据权利要求1所述的方法，其特征在于，步骤(2)中，所述助磨剂和电极材料的质量比为(0.1～0.5)：100。
  7. 根据权利要求1所述的方法，其特征在于，步骤(2)中，所述碱液为氢氧化钠、氢氧化镁、氢氧化钾或氢氧化钙中的一种。
  8. 根据权利要求1所述的方法，其特征在于，步骤(2)中，所述碱液的OH -浓度为0.01～0.2mol/L。
  9. 根据权利要求1所述的方法，其特征在于，步骤(3)中，所述二次焙烧的温度为600～1000℃，二次焙烧的时间为60～90min。
  10. 权利要求1-9任一项所述的方法在回收电极材料中的应用。
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