WO2022134423A1 - 一种动力电池逆向定位制备镍钴锰酸锂的方法和应用 - Google Patents

一种动力电池逆向定位制备镍钴锰酸锂的方法和应用 Download PDF

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WO2022134423A1
WO2022134423A1 PCT/CN2021/091663 CN2021091663W WO2022134423A1 WO 2022134423 A1 WO2022134423 A1 WO 2022134423A1 CN 2021091663 W CN2021091663 W CN 2021091663W WO 2022134423 A1 WO2022134423 A1 WO 2022134423A1
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cobalt
nickel
lithium
manganese alloy
powder
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PCT/CN2021/091663
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English (en)
French (fr)
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谢英豪
余海军
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
湖南邦普汽车循环有限公司
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Priority to US18/029,651 priority Critical patent/US11802055B1/en
Priority to EP21908434.0A priority patent/EP4206141A4/en
Publication of WO2022134423A1 publication Critical patent/WO2022134423A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/52—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [Mn2O4]2-, e.g. Li2(NixMn2-x)O4, Li2(MyNixMn2-x-y)O4
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/54—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [Mn2O4]-, e.g. Li(NixMn2-x)O4, Li(MyNixMn2-x-y)O4
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/56—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO3]2-, e.g. Li2[NixMn1-xO3], Li2[MyNixMn1-x-yO3
    • 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
    • C22B23/02—Obtaining nickel or cobalt by 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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
    • C01P2006/40—Electric properties
    • 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 relates to the technical field of lithium battery recycling, in particular to a method and application for preparing lithium nickel cobalt manganate by reverse positioning of power batteries.
  • the large-scale promotion of new energy vehicles has led to the large-scale use of power batteries.
  • Power batteries usually have a lifespan of 5-8 years. After a certain period of use, the performance of the battery deteriorates, which does not meet the needs of consumers and needs to be recycled and dismantled.
  • the traditional recovery and treatment method is to disassemble the power battery, and then take the battery cell to undergo pyrolysis, crushing, sorting, acid dissolution, impurity removal, extraction, back extraction, precipitation and other processes to recover and prepare nickel-cobalt-manganese hydroxide.
  • the cathode sheet is treated by the traditional method, aluminum needs to be treated as an impurity.
  • the traditional method has a long process flow, large consumption of raw and auxiliary materials, high energy consumption, and secondary waste water will be produced after treatment, and the secondary pollutant treatment cost is high and limited. obvious.
  • Reverse positioning refers to the process of making a product of equal (or better) quality in the same field after a product is scrapped within the life cycle boundary.
  • the reverse positioning cycle of waste power batteries to prepare nickel cobalt lithium manganate can shorten the treatment process, reduce secondary pollution, and reduce processing energy consumption, which is the future development direction.
  • the object of the present invention is to provide a method and application for preparing nickel-cobalt manganate lithium manganate by reverse positioning of power battery.
  • the process flow is short, the consumption of raw and auxiliary materials used is low, the energy consumption is low, the treatment cost is low, the pollutant discharge is low, and the whole process is environmentally friendly.
  • the present invention adopts the following technical solutions:
  • a method for preparing lithium nickel cobalt manganate comprising the following steps:
  • step (3) carrying out self-propagating reaction with the material after the mixing in step (2), cooling, and taking down the rough nickel-cobalt-manganese alloy of the lower layer;
  • the positive electrode material of the positive electrode sheet is nickel cobalt lithium manganate, wherein the molar ratio of nickel, cobalt and manganese is x:y:1-x-y, wherein 0 ⁇ x ⁇ 1, y>0, x+y ⁇ 1.
  • the slagging agent comprises one or more of calcium oxide, silicon dioxide or calcium fluoride, and the weight ratio of the positive electrode sheet and the slagging agent is (15-20): 1.
  • the slag-forming agent is a combination of calcium oxide and calcium fluoride, and the addition amount of calcium fluoride does not need to be particularly large, because the electrolyte will be contained on the pole piece after the battery is disassembled, and the electrolyte is in the air condition. It will decompose, and the electrolyte will decompose to generate lithium fluoride. Lithium fluoride reacts with calcium oxide at high temperature to obtain calcium fluoride, which makes full use of the characteristics of waste batteries.
  • the positive electrode sheet is ground to a particle size of 1-20 mm.
  • the drying temperature is 100°C-180°C.
  • step (2) the weight ratio of the mixture after the positive electrode sheet and the slag-forming agent is ground to the aluminum powder is (2-5):1.
  • the specific step of the self-propagating reaction is to place the material in a self-propagating reaction furnace, and ignite the self-propagating reaction with magnesium powder in an inert atmosphere, and the inert atmosphere is nitrogen, helium gas or argon.
  • the particle size of the coarse nickel-cobalt-manganese alloy after grinding is 1-10 ⁇ m.
  • the solid-to-liquid ratio of the grinding material of the crude nickel-cobalt-manganese alloy and the alkali solution is 1:(2-5) kg/L, and the concentration of the alkali solution is 0.5-3mol /L.
  • step (4) ultrasonic soaking is used for the soaking, the power density of the ultrasonic wave is 0.5-5 W/cm 2 , and the soaking time is 1-5 h.
  • the alkali solution is at least one of sodium hydroxide solution or potassium hydroxide solution.
  • the solid-to-liquid ratio of the porous nickel-cobalt-manganese alloy powder and the lithium salt solution is 1:(2-5) kg/L, and the concentration of the lithium salt solution is 1-3 mol/L .
  • step (5) the steps of stirring and dropping the lye solution are as follows: firstly, rapidly stir and disperse for 20-60min at a rotational speed of 1000-5000r/min, then reduce the rotational speed to 100-500r/min, and dropwise while stirring. Add 0.2-3mol/L lye.
  • the aging time is 5-10h.
  • the molar ratio of hydroxide in the alkali solution to lithium ion in the lithium salt solution is about 1:1, and the lithium ion in the lithium salt solution and the porous nickel-cobalt-manganese alloy powder have a molar ratio of about 1:1.
  • the molar ratio of the nickel-cobalt-manganese content is (1.1-1.3):1.
  • the process parameters of the sintering are: in an oxygen atmosphere, heating at 1-5°C/min to 1200-1400°C for 2-10min, and then naturally cooling to 700-1000°C for sintering 5 -30h.
  • the present invention also provides an application of the method in preparing a lithium ion battery.
  • the present invention utilizes self-propagating reaction to make nickel-cobalt lithium manganate react with metal aluminum, reversely locates the aluminum foil on the positive electrode sheet in the waste battery as the raw material for the treatment process, changes the traditional treatment method of treating aluminum as an impurity, and makes full use of the The characteristics of the components of the waste battery itself are processed to reduce the consumption of raw materials.
  • the obtained alloy is a nickel-cobalt-manganese alloy containing a certain amount of metal aluminum, so that the metal aluminum is dissolved in the alkaline washing process to form a porous nickel-cobalt-manganese alloy.
  • the aged lithium hydroxide penetrates into the nickel-cobalt-manganese alloy and fully fills the voids in the porous nickel-cobalt-manganese alloy.
  • the excess lithium hydroxide that does not enter the alloy is mixed with the alloy outside the alloy, so as to achieve a sufficiently uniform distribution of the lithium source from the inside of the material to the outside in the sintering process.
  • porous precursor powder is beneficial to reserve buffer space inside the material after sintering, eliminate material stress, and help the battery material to give space for material expansion and contraction during the charge-discharge cycle, so as to improve the cycle of the material. performance.
  • the present invention uses the reverse positioning treatment of waste batteries to re-prepare nickel-cobalt lithium manganate for batteries, realizes short-distance docking of wastes and raw materials, short technological process, low consumption of used raw and auxiliary materials, low energy consumption, low processing cost, and pollutant discharge. Less, the whole process is environmentally friendly.
  • Fig. 1 is the SEM image of the nickel-cobalt lithium manganate positive electrode material for battery prepared in Example 1;
  • FIG. 2 is a cycle life graph of Example 1 and Comparative Example.
  • a method for preparing nickel cobalt lithium manganate by reverse positioning of a power battery comprising the following specific steps:
  • step (3) placing the mixed material in step (2) in a self-propagating reaction furnace, igniting magnesium powder to initiate a self-propagating reaction in a nitrogen atmosphere, removing the upper alumina-based smelting slag after cooling, and taking the lower layer to obtain a crude Nickel-cobalt-manganese alloy;
  • the precursor mixed powder is placed in an oxygen atmosphere, heated at 1°C/min to 1200°C for 2 minutes, then naturally cooled to 700°C for 5 hours, and cooled to room temperature to obtain a positive electrode material of nickel cobalt lithium manganate for batteries.
  • Figure 1 is the SEM image of the nickel-cobalt lithium manganate cathode material for batteries prepared in Example 1. It can be seen from the figure that the prepared nickel-cobalt lithium manganate has good sphericity and particle size distribution, and the material particles are complete , the surface has no obvious defects.
  • a method for preparing nickel cobalt lithium manganate by reverse positioning of a power battery comprising the following specific steps:
  • the precursor mixed powder is placed in an oxygen atmosphere, heated to 1300°C for 5 minutes at 3°C/min, then naturally cooled to 800°C for 10h sintering, and cooled to room temperature to obtain a nickel-cobalt lithium manganate cathode material for batteries.
  • a method for preparing nickel cobalt lithium manganate by reverse positioning of a power battery comprising the following specific steps:
  • the precursor mixed powder is placed in an oxygen atmosphere, heated to 1400°C for 10min at 5°C/min, then naturally cooled to 1000°C for 30h sintering, and cooled to room temperature to obtain a nickel-cobalt lithium manganate cathode material for batteries.
  • Electrode material powder Take waste batteries, disassemble, pyrolyze, crush and sort to obtain electrode material powder, dissolve the electrode material powder with hydrochloric acid, add lye to adjust pH to 9-10, filter, take filtrate, add lye to adjust pH >13, filter, take the filter residue, add lithium hydroxide in a molar ratio of 1:1 and mix well, and keep the temperature at 850°C for 20h to obtain lithium nickel cobalt manganate.
  • Example 1 The lithium nickel cobalt oxide obtained in Example 1 and the comparative example was used as the positive electrode, and the graphite was used as the negative electrode to assemble a battery.
  • the first discharge specific capacity and cycle performance of the nickel-cobalt lithium manganate cathode material recovered by the present invention are higher than those recovered by the traditional wet method, because the porous precursor powder used in this method is conducive to sintering.
  • the buffer space is reserved inside the rear material to eliminate the material stress, which is beneficial to the expansion and contraction of the material during the charging and discharging cycle of the battery material, and improves the cycle performance of the material.

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Abstract

本发明属于锂电池回收技术领域，提供一种动力电池逆向定位制备镍钴锰酸锂的方法和应用，该方法先将正极片和造渣剂混合磨碎，再烘干，冷却，加入铝粉，混匀，对混匀后的物料进行自蔓延反应，冷却，取下层粗制镍钴锰合金，将粗制镍钴锰合金磨碎，加入碱液，再浸泡，过滤，取滤渣清洗后烘干，得到多孔镍钴锰合金粉末，向多孔镍钴锰合金粉末加入锂盐溶液，搅拌和滴加碱液，陈化，过滤，取滤渣清洗后烘干，得到前驱体混合粉末，将前驱体混合粉末进行烧结和冷却，得到镍钴锰酸锂。本发明实现将废料与原料的短程对接，工艺流程短，所用原辅料消耗少，能耗低，处理成本低，污染物排放少，整个过程环境友好。

Description

一种动力电池逆向定位制备镍钴锰酸锂的方法和应用 技术领域
本发明涉及锂电池回收技术领域，特别是涉及一种动力电池逆向定位制备镍钴锰酸锂的方法和应用。
背景技术
据工信部数据，2019年，新能源汽车产销分别完成124.2万辆和120.6万辆。其中，纯电动汽车产销分别完成102万辆和97.2万辆，在新能源汽车产业带动下，动力电池产业得到飞速发展。
新能源汽车的大量推广带动动力电池的大量使用，动力电池通常寿命为5-8年，经过一定时间的使用后，电池性能衰减，不满足消费者的使用需求，需要回收拆解处理。传统回收处理方法是将动力电池拆解，取其电芯依次进行热解、破碎、分选、酸溶、除杂、萃取、反萃、沉淀等工艺回收制备镍钴锰氢氧化物。传统方法处理正极片时，铝作为杂质需要进行处理，传统方法工艺流程长，原辅料消耗大，能耗较高，且处理后会产能二次废水，二次污染物处理成本较高，局限性明显。
逆向定位指在生命周期边界内，产品报废后，经过一定的处理，使之成为相同领域同等(或更优)品质产品的过程。废旧动力电池逆向定位循环制备镍钴锰酸锂可以缩短处理流程、减少二次污染，降低处理能耗，是未来的发展方向。
发明内容
本发明的目的在于提供一种动力电池逆向定位制备镍钴锰酸锂的方法和应用，该方法以废旧电池逆向定位处理重新制备电池用镍钴锰酸锂，实现将废料与原料的短程对接，工艺流程短，所用原辅料消耗少，能耗低，处理成本低，污染物排放少，整个过程环境友好。
为实现上述目的，本发明采用以下技术方案：
一种制备镍钴锰酸锂的方法，包括以下步骤：
(1)将废电池拆解，分离，得到正极片、负极片和隔膜；
(2)将正极片和造渣剂混合磨碎，再烘干，冷却，加入铝粉，混匀；
(3)将步骤(2)混匀后的物料进行自蔓延反应，冷却，取下层粗制镍钴锰合金；
(4)将所述粗制镍钴锰合金磨碎，加入碱液，再浸泡，过滤，取滤渣清洗后烘干，得到多孔镍钴锰合金粉末；
(5)向所述多孔镍钴锰合金粉末加入锂盐溶液，搅拌和滴加碱液，陈化，过滤，取滤渣清洗后烘干，得到前驱体混合粉末；
(6)将所述前驱体混合粉末进行烧结和冷却，得到所述镍钴锰酸锂。
所述正极片的正极材料为镍钴锰酸锂，其中镍、钴、锰摩尔比为x：y：1-x-y，其中0＜x＜1，y＞0，x+y≤1。
优选地，步骤(2)中，所述造渣剂包括氧化钙、二氧化硅或氟化钙的一种或者多种，所述正极片和造渣剂的重量比为(15-20):1。更优选地，所述造渣剂为氧化钙和氟化钙的组合，其中氟化钙的加入量不需要特别的多，因为电池拆解后极片上会含有电解液，电解液在空气条件下会分解，电解液分解后生成氟化锂，氟化锂在高温下与氧化钙反应可得到氟化钙，这充分利用了废电池的特点。
优选地，步骤(2)中，所述正极片磨碎至粒度为1-20mm。
优选地，步骤(2)中，所述烘干的温度为100℃-180℃。
优选地，步骤(2)中，正极片和造渣剂磨碎后的混合料与所述铝粉的重量比为(2-5):1。
优选地，步骤(3)中，所述自蔓延反应的具体步骤是将物料放在自蔓延反应炉内，在惰性气氛下，用镁粉点燃引发自蔓延反应，所述惰性气氛为氮气、氦气或氩气。
优选地，步骤(4)中，所述粗制镍钴锰合金磨碎后的粒径为1-10μm。
优选地，步骤(4)中，所述粗制镍钴锰合金的磨碎料与碱液的固液比为1:(2-5)kg/L，所述碱液的浓度为0.5-3mol/L。
优选地，步骤(4)中，所述浸泡采用超声浸泡，超声波的功率密度为0.5～5W/cm 2，浸泡的时间为1-5h。
优选地，步骤(4)中，所述碱液为氢氧化钠溶液或氢氧化钾溶液中的至少一种。
优选地，步骤(5)中，所述多孔镍钴锰合金粉末和锂盐溶液的固液比为1:(2-5)kg/L，所述锂盐溶液的浓度为1-3mol/L。
优选地，步骤(5)中，所述搅拌和滴加碱液的步骤为：先以转速1000-5000r/min快速搅拌分散20-60min，再降低转速至100-500r/min，边搅拌边滴加0.2-3mol/L的碱 液。
优选地，步骤(5)中，所述陈化的时间为5-10h。
优选地，步骤(5)中，所述碱液中的氢氧根与锂盐溶液中锂离子的摩尔比约为1:1，锂盐溶液中锂离子与所述多孔镍钴锰合金粉末中的镍钴锰合量的摩尔比为(1.1-1.3):1。
优选地，步骤(6)中，所述烧结的工艺参数为：在氧气气氛下，以1-5℃/min升温至1200-1400℃恒温2-10min，然后自然降温至700-1000℃烧结5-30h。
本发明还提供一种所述的方法在制备锂离子电池中的应用。
本发明的优点：
1、本发明利用自蔓延反应使镍钴锰酸锂与金属铝反应，逆向定位将废旧电池中正极片上的铝箔作为处理过程的原料，改变传统处理方式的将铝作为杂质的处理思路，充分利用废电池自身组分的特点进行处理，减少原辅料的消耗。
2、在自蔓延反应中，适当加入过量的金属铝，使得到的合金为含一定金属铝的镍钴锰合金，使得在碱洗工艺溶解金属铝，形成多孔的镍钴锰合金。
3、在锂盐沉淀环节，经陈化后的氢氧化锂渗透进入镍钴锰合金内部，充分填满多孔镍钴锰合金中的空隙。未进入合金内部过量的氢氧化锂在合金外部与合金混合，以便于烧结环节中实现锂源从材料内部到外部的充分均匀分布。
4、采用多孔前驱体粉末有利于在烧结后材料内部预留出缓冲的空间，消除材料应力，有利于电池材料在充放电循环的过程中给出材料膨胀和收缩的空间，以提升材料的循环性能。
5、本发明以废旧电池逆向定位处理重新制备电池用镍钴锰酸锂，实现将废料与原料的短程对接，工艺流程短，所用原辅料消耗少，能耗低，处理成本低，污染物排放少，整个过程环境友好。
附图说明
本发明的上述和/或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和容易理解，其中：
图1为实施例1制得的电池用镍钴锰酸锂正极材料的SEM图；
图2为实施例1和对比例的循环寿命图。
具体实施方式
为了对本发明进行深入的理解，下面结合实例对本发明优选实验方案进行描述， 以进一步的说明本发明的特点和优点，任何不偏离本发明主旨的变化或者改变能够为本领域的技术人员理解，本发明的保护范围由所属权利要求范围确定。
实施例1
一种动力电池逆向定位制备镍钴锰酸锂的方法，包括以下具体步骤：
(1)将废电池拆解，分离后得到电芯、外壳、极耳，取电芯，将电芯拆解，分离后得到正极材料为镍钴锰酸锂的正极片、负极片、隔膜；
(2)将正极片和造渣剂氧化钙按重量比15：1混合，将正极片磨碎至粒度为1mm，于100℃下烘干，冷却至室温后按重量比2:1比例加入金属铝粉，混匀；
(3)将步骤(2)混匀后的物料放在自蔓延反应炉内，在氮气气氛下，用镁粉点燃引发自蔓延反应，冷却后除去上层氧化铝基熔炼渣，取下层得到粗制镍钴锰合金；
(4)将粗制镍钴锰合金磨碎至粒径1μm；
(5)按固液比1:2kg/L将粉末放入0.5mol/L氢氧化钠溶液中，在功率密度为0.5W/cm 2的超声波振动下浸泡1h，过滤，取滤渣，用水清洗后烘干，得到多孔镍钴锰合金粉末；
(6)取1mol/L的锂盐溶液，按固液比1:2kg/L加入多孔镍钴锰合金粉末，以转速1000r/min快速搅拌分散20min，降低转速至100r/min，边搅拌边滴加0.2mol/L的碱液，陈化5h，控制所滴加的碱液中氢氧根与所加入的锂盐中锂离子的摩尔比为1:1，同时控制锂离子与镍钴锰合量摩尔比为1.1:1，过滤，取滤渣，用水清洗后烘干，得到前驱体混合粉末；
(7)将前驱体混合粉末置于氧气气氛下，以1℃/min升温至1200℃恒温2min，然后自然降温至700℃烧结5h，冷却至室温，得到电池用镍钴锰酸锂正极材料。
图1为实施例1制得的电池用镍钴锰酸锂正极材料的SEM图，从图中可以看出，制备得到的镍钴锰酸锂具有较好的球形度及粒度分布，材料颗粒完整，表面无明显的缺陷。
实施例2
一种动力电池逆向定位制备镍钴锰酸锂的方法，包括以下具体步骤：
(1)将废电池拆解，分离后得到电芯、外壳、极耳，取电芯，将电芯拆解，分离后得到正极材料为镍钴锰酸锂的正极片、负极片、隔膜；
(2)将正极片和造渣剂氧化钙按重量比17：1混合，将正极片磨碎至粒度为10mm，于150℃下烘干，冷却至室温后按重量比3:1比例加入金属铝粉，混匀；
(3)将物料放在自蔓延反应炉内，在氮气气氛下，用镁粉点燃引发自蔓延反应，冷却后除去上层氧化铝基熔炼渣，取下层得到粗制镍钴锰合金；
(4)将粗制镍钴锰合金磨碎至粒径5μm；
(5)按固液比1:3kg/L将粉末放入1mol/L氢氧化钠溶液中，在功率密度为2W/cm 2的超声波振动下浸泡3h，过滤，取滤渣，用水清洗后烘干，得到多孔镍钴锰合金粉末。
(6)取2mol/L的锂盐溶液，按固液比1:3kg/L加入多孔镍钴锰合金粉末，以转速2000r/min快速搅拌分散40min，降低转速至300r/min，边搅拌边滴加1mol/L的碱液，陈化8h，控制所滴加的碱液中氢氧根与所加入的锂盐中锂离子的摩尔比为1:1，同时控制锂离子与镍钴锰合量摩尔比为1.2:1，过滤，取滤渣，用水清洗后烘干，得到前驱体混合粉末；
(7)将前驱体混合粉末置于氧气气氛下，以3℃/min升温至1300℃恒温5min，然后自然降温至800℃烧结10h，冷却至室温，得到电池用镍钴锰酸锂正极材料。
实施例3
一种动力电池逆向定位制备镍钴锰酸锂的方法，包括以下具体步骤：
(1)将废电池拆解，分离后得到电芯、外壳、极耳，取电芯，将电芯拆解，分离后得到正极材料为镍钴锰酸锂的正极片、负极片、隔膜；
(2)将正极片和造渣剂氧化钙按重量比20：1混合，将正极片磨碎至粒度为20mm，于180℃下烘干，冷却至室温后按重量比5:1比例加入金属铝粉，混匀；
(3)将物料放在自蔓延反应炉内，在氮气气氛下，用镁粉点燃引发自蔓延反应，冷却后除去上层氧化铝基熔炼渣，取下层得到粗制镍钴锰合金；
(4)将粗制镍钴锰合金磨碎至粒径10μm；
(5)按固液比1:5kg/L将粉末放入3mol/L氢氧化钠溶液中，在功率密度为5W/cm 2的超声波振动下浸泡5h，过滤，取滤渣，用水清洗后烘干，得到多孔镍钴锰合金粉末；
(6)取3mol/L的锂盐溶液，按固液比1:5kg/L加入多孔镍钴锰合金粉末，以转速5000r/min快速搅拌分散60min，降低转速至500r/min，边搅拌边滴加3mol/L的碱液，陈化10h，控制所滴加的碱液中氢氧根与所加入的锂盐中锂离子的摩尔比为1:1，同时控制锂离子与镍钴锰合量摩尔比为1.3:1，过滤，取滤渣，用水清洗后烘干，得到前驱体混合粉末；
(7)将前驱体混合粉末置于氧气气氛下，以5℃/min升温至1400℃恒温10min，然后自然降温至1000℃烧结30h，冷却至室温，得到电池用镍钴锰酸锂正极材料。
对比例
取废旧电池，经拆解、热解、破碎、分选，得到的电极材料粉，将电极材料粉采用盐酸溶解，加入碱液调节pH至9～10，过滤，取滤液，加入碱液调节pH＞13，过滤，取滤渣，按金属量摩尔比1:1加入氢氧化锂混匀，在850℃恒温20h，得到镍钴锰酸锂。
性能检测：
分别以上述实施例1和对比例制得的镍钴酸锂为正极，以石墨为负极，组装成电池，以1C倍率进行首次放电测试和2500次充放电循环测试，结果如表1所示。
表1
  比容量(mAh/g) 容量保持率
实施例1 210.8 84.3％
对比例 172.3 68.3％
由表1可以看出，本发明回收的镍钴锰酸锂正极材料的首次放电比容量和循环性能均比传统湿法回收的高，这是由于本方法采用的多孔前驱体粉末有利于在烧结后材料内部预留出缓冲的空间，消除材料应力，有利于电池材料在充放电循环的过程中给出材料膨胀和收缩的空间，提升了材料的循环性能。
以上对本发明提供的动力电池逆向定位制备镍钴锰酸锂的方法和应用进行了详细的介绍，本文中应用了具体实施例对本发明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发明的方法及其核心思想，包括最佳方式，并且也使得本领域的任何技术人员都能够实践本发明，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，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。本发明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. 一种制备镍钴锰酸锂的方法，其特征在于，包括以下步骤：
    (1)将废电池拆解，分离，得到正极片、负极片和隔膜；
    (2)将正极片和造渣剂混合磨碎，再烘干，冷却，加入铝粉，混匀，得到物料；
    (3)将所述物料进行自蔓延反应，冷却，取下层粗制镍钴锰合金；
    (4)将所述粗制镍钴锰合金磨碎，加入碱液，再浸泡，过滤，取滤渣清洗后烘干，得到多孔镍钴锰合金粉末；
    (5)向所述多孔镍钴锰合金粉末加入锂盐溶液，搅拌和滴加碱液，陈化，过滤，取滤渣清洗后烘干，得到前驱体混合粉末；
    (6)将所述前驱体混合粉末进行烧结和冷却，得到所述镍钴锰酸锂。
  2. 根据权利要求1所述的方法，其特征在于，步骤(2)中，所述造渣剂包括氧化钙、二氧化硅或氟化钙的一种或者多种，所述正极片和造渣剂的重量比为(15-20):1。
  3. 根据权利要求1所述的方法，其特征在于，步骤(2)中，正极片和造渣剂磨碎后的混合料与所述铝粉的重量比为(2-5):1。
  4. 根据权利要求1所述的方法，其特征在于，步骤(3)中，所述自蔓延反应的步骤是将物料放在自蔓延反应炉内，在惰性气氛下，用镁粉点燃引发自蔓延反应。
  5. 根据权利要求1所述的方法，其特征在于，步骤(4)中，所述粗制镍钴锰合金的磨碎料与碱液的固液比为1:(2-5)kg/L，所述碱液的浓度为0.5-3mol/L。
  6. 根据权利要求1所述的方法，其特征在于，步骤(5)中，所述多孔镍钴锰合金粉末和锂盐溶液的固液比为1:(2-5)kg/L，所述锂盐溶液的浓度为1-3mol/L。
  7. 根据权利要求1所述的方法，其特征在于，步骤(5)中，所述搅拌和滴加碱液的步骤为：先以转速1000-5000r/min快速搅拌分散20-60min，再降低转速至100-500r/min，边搅拌边滴加0.2-3mol/L的碱液。
  8. 根据权利要求1所述的方法，其特征在于，步骤(5)中，所述碱液中的氢氧根与锂盐溶液中锂离子的摩尔比为(1-1.3):1，锂盐溶液中锂离子与所述多孔镍钴锰合金粉末中的镍钴锰合量的摩尔比为(1.1-1.3):1。
  9. 根据权利要求1所述的方法，其特征在于，步骤(6)中，所述烧结的工艺参数为：在氧气或空气的气氛下，以1-5℃/min升温至1200-1400℃恒温2-10min，然后降温至700-1000℃ 烧结5-30h。
  10. 权利要求1-9任一项所述的方法在制备锂离子电池中的应用。
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