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WO2021209074A1 - 锂离子动力电池回收方法 - Google Patents

锂离子动力电池回收方法 Download PDF

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Publication number
WO2021209074A1
WO2021209074A1 PCT/CN2021/094537 CN2021094537W WO2021209074A1 WO 2021209074 A1 WO2021209074 A1 WO 2021209074A1 CN 2021094537 W CN2021094537 W CN 2021094537W WO 2021209074 A1 WO2021209074 A1 WO 2021209074A1
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Prior art keywords
friction
lithium
ion power
electrode
power battery
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English (en)
French (fr)
Inventor
维迪嘉德摩卡塞缪尔•迪米特里
王筝
赫尔菲利普
迈尔斯尼克
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University of Nottingham Ningbo China
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University of Nottingham Ningbo China
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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
    • H01M10/54—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
    • 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 solid waste and electronic garbage recycling, in particular to a lithium ion power battery recycling method.
  • the electrodes in lithium batteries are composed of positive and negative metal foils attached with active materials. Among them, there are many types of positive active materials with different characteristics. Most of their preparation materials involve scarce resources such as cobalt and nickel.
  • the positive pole piece is aluminum foil; the negative electrode material It is generally graphite, and the negative pole piece is copper foil, which has a great resource value.
  • waste power lithium-ion batteries there are three main methods for recycling waste power lithium-ion batteries: mechanical crushing and separation, pyrometallurgy and chemical methods. They mainly focus on the recovery of valuable metals cobalt, nickel and lithium, because these metals are scarce metals. Other metals have high recycling value. Most of the existing waste lithium battery recycling technologies have problems such as high energy consumption, low efficiency, and greater environmental impact.
  • the present invention proposes a lithium-ion power battery recovery method to provide technical support for the further development of lithium-ion power battery recovery.
  • a lithium ion power battery recovery method includes the following steps:
  • the electronic components of the lithium-ion power battery are removed
  • the crushed lithium-ion power battery is placed in a friction scrubbing machine to dissociate the positive and negative materials from the aluminum film and the copper film.
  • the materials from the friction scrubbing machine are sieved to obtain the oversize and the undersize including positive and negative materials
  • the sieve is put into a friction electrostatic separator to separate HDPE film, friction medium, copper foil and aluminum foil.
  • the under-sieve is put into a flat filter for dehydration
  • the dehydrated undersieve is put into a froth flotation machine to obtain separated negative electrode material and positive electrode material.
  • the electronic components include a control unit for controlling the lithium-ion power battery.
  • the cutting crusher crushes the dismantled lithium ion power battery.
  • the bottom screen of the cutting crusher has a hole diameter of 8-10 mm.
  • the speed of the impeller of the friction scrubbing machine is 1000-1200 revolutions per minute, and the slower speed can avoid the crushing of copper foil, aluminum foil and HDPE film in the process;
  • the friction medium is quartz sand, And the particle size range is 850-2360 ⁇ m, which is convenient for subsequent separation of quartz sand while ensuring the friction scrubbing effect;
  • the material ratio is optimized according to the efficiency of the friction scrubbing process, and the mass ratio of the crushed lithium-ion power battery to the friction medium is 10%-30 %, the density of the pulp is 60%-80%;
  • the friction scrubbing time is 10-20 minutes, and the selected liquid medium for the friction scrubbing process is water.
  • the wet vibrating screen sieving the material from the friction scrubbing machine, and the bottom sieve mesh diameter of the wet vibrating screen is 38 microns.
  • the particle size of the electrode active material is 1.5-7.8 microns, so a bottom sieve with a mesh diameter of 38 microns is used to process the material after friction and scrubbing to realize the separation of the electrode active material from other components.
  • the sieve is put into a friction electrostatic separator to separate the copper foil, the aluminum foil and the HDPE diaphragm.
  • the working temperature of the friction electrostatic separator is 20-25 degrees Celsius, the relative humidity is 40%-50%, and the rotation speed of the sorting drum is 40-60 revolutions per minute to ensure static electricity in the sorting process.
  • Transmission efficiency; working voltage is 20-30 kV, according to the conductivity of copper foil, aluminum foil, HDPE film and quartz sand, the distance between the ionization electrode and the sorting drum is 4-6 cm, and the distance between the repelling electrode and the sorting drum is 6 8 cm, based on the feeding position, the deflection angle of the ionization electrode is 35°, and the deflection angle of the repelling electrode is 50°.
  • the liquid medium of the froth flotation is water
  • the operating parameters during the flotation process are determined according to the surface activity characteristics of the positive electrode active material of the graphite
  • the impeller speed of the froth flotation machine is 1200-1800 revolutions per minute.
  • the content of methyl isobutyl methanol foaming agent is 15-25 microliters per liter
  • the content of n-dodecane capturing agent is 35-45 microliters per liter
  • the pH is 8
  • the foam height is 4 -8 cm
  • flotation time is 5-10 minutes.
  • the negative electrode material includes graphite.
  • the present invention is directed to recycled lithium ion power batteries and defective electrode sheets, including:
  • the battery cells in the battery module after the control unit, acquisition system, and cooling system are removed from the scrapped power battery, that is, the single battery cell that contains the electrolyte solution; and the residual electrode sheet produced in the industrial production, and the waste material of the electrode sheet .
  • the present invention has the following advantages:
  • the method of the present invention treats scrapped lithium ion batteries by cutting-type crushing, while realizing the dissociation of the battery structure while maintaining the unfolded state of the electrode metal foil, avoiding the electrode active material being wrapped in it and reducing the subsequent recovery efficiency.
  • the friction scrubbing technique is used to realize the dissociation of the electrode active material from the electrode metal foil while maintaining the unfolded state of the electrode metal foil, ensuring the efficiency of subsequent tribostatic separation.
  • the friction scrubbing medium quartz sand can be recycled and reused. Through friction electrostatic separation, the diversified recovery of copper foil, aluminum foil and HDPE diaphragm is realized.
  • the invention requires a small amount of chemical reagents to be used, the recovery process does not involve a high-energy-consumption process, and the environmental impact is small.
  • FIG. 1 is a schematic flowchart of a method for recycling a lithium-ion power battery according to an embodiment of the present invention
  • Figures 2(a) to 2(d) are schematic diagrams of scrap lithium-ion power batteries sorted and recovered according to an embodiment of the present invention
  • Figure 3 is a scanning electron micrograph of a positive electrode active material obtained according to an embodiment of the present invention.
  • Fig. 4 is a scanning electron micrograph of a negative active material obtained according to an embodiment of the present invention.
  • a lithium-ion power battery recycling method includes the following steps:
  • the electronic components of the lithium-ion power battery are removed
  • the crushed lithium-ion power battery is placed in a friction scrubbing machine to dissociate the positive and negative materials from the aluminum film and the copper film.
  • the materials from the friction scrubbing machine are sieved to obtain the oversize and the undersize including positive and negative materials
  • the sieve is put into a friction electrostatic separator to separate HDPE film, friction medium, copper foil and aluminum foil.
  • the under-sieve is put into a flat filter for dehydration
  • the dehydrated undersieve is put into a froth flotation machine to obtain separated negative electrode material and positive electrode material.
  • the electronic components include a control unit for controlling the lithium-ion power battery.
  • the cutting crusher crushes the dismantled lithium ion power battery
  • the bottom sieve of the cutting crusher has an aperture of 8-10 mm.
  • Cutting type crushing avoids curling of copper foil and aluminum foil, wrapping the electrode active material and affecting the subsequent recovery efficiency.
  • the smaller bottom screen aperture causes excessive crushing, causing the active material to be wrapped and reducing the recovery efficiency; the size of copper foil and aluminum foil is reduced, and the friction static electricity Sorting is difficult to achieve.
  • Larger bottom sieve aperture incomplete crushing makes it difficult to crush the battery structure.
  • the aperture of the present application can achieve an optimized comprehensive effect.
  • the speed of the impeller of the friction scrubbing machine is 1000-1200 revolutions per minute
  • the friction medium is quartz sand
  • the particle size range is 850-2360 ⁇ m.
  • the bottom sieve aperture of the cutting crusher is 8-10 mm
  • the size of the crushed battery material is generally no more than 5 mm, so the particle size range is 850-2360 ⁇ m, which can ensure higher scrubbing efficiency , While keeping the structure of copper foil and aluminum foil from being damaged.
  • the mass ratio of the crushed lithium-ion power battery to the friction medium is 10%-30%. The low mass ratio causes the medium consumption in the friction scrubbing process to increase, and the battery material processing efficiency is reduced.
  • the high mass ratio leads to a decrease in the dissociation efficiency of electrode material caused by friction scrubbing, and the friction time needs to be extended.
  • the rubbing time is 10-20 minutes.
  • the friction scrubbing time and the speed of the impeller in the friction scrubbing process together affect the friction scrubbing efficiency, and the increase of the speed can reduce the time to reach the target electrode material dissociation efficiency.
  • the lower pulp density weakens the friction between the friction medium and the electrode material, and reduces the dissociation efficiency.
  • Higher pulp density makes the pulp density too high, the fluidity of the pulp becomes worse, the friction effect is weakened, and the resistance of the impeller becomes larger, which is easy to cause deformation of the impeller and damage to the motor of the friction scrubber.
  • the pulp density is 60%-80% to achieve a comprehensive balance effect.
  • the wet vibrating screen screens the material from the friction scrubbing machine, and the bottom sieve mesh diameter of the wet vibrating screen is 38 microns.
  • the oversize is put into the friction static separator to separate the copper foil, the aluminum foil and the HDPE membrane.
  • the working temperature of the friction electrostatic separator is 20-25 degrees Celsius, and the relative humidity is 40%-50%, which ensures the efficiency of electrostatic conduction, and the rotation speed of the sorting drum is 40- 60 revolutions per minute, the working voltage is 20-30 kV, the distance between the ionization electrode and the sorting drum is 4-6 cm, the distance between the repelling electrode and the sorting drum is 6-8 cm, based on the feeding position, the ionization electrode is deflected The angle is 35°, and the deflection angle of the repelling electrode is 50°, which improves the sorting efficiency.
  • the speed of the impeller of the froth flotation machine is 1200-1800 revolutions per minute, and the content of the methyl isobutyl methanol foaming agent in the froth flotation machine is 15-25 micro Per liter, the low foaming agent content leads to insufficient foam generation and lower graphite recovery efficiency.
  • the high content of foaming agent makes it difficult to control the foam height and reduces the graphite recovery efficiency.
  • the content of n-dodecane capture agent is 35-45 microliters per liter, which is too low to reduce the capture efficiency of the cathode material, and too high waste.
  • 35-45ml/L can achieve a recovery efficiency of 90-95%, and a pH of 8 makes its work efficiency Significant improvement, the foam height is 4-8 cm, and the flotation time is 5-10 minutes lower than this time, resulting in low separation efficiency. A recovery efficiency of 90-95% can be achieved in 5-10 minutes.
  • the method includes:
  • the crusher used for crushing is a cutting crusher, and the bottom screen aperture is 8-10 mm;
  • the impeller speed is controlled at 1000-1200 revolutions per minute
  • the friction medium is quartz sand
  • the particle size range is controlled at 850-2360 ⁇ m
  • the pulp density is controlled at 60%-80%
  • the mass ratio of battery material to friction medium Control at 10%-30%, and control the rubbing time at 10-20 minutes;
  • the mesh diameter of the wet bottom sieve is 38 microns
  • the operating temperature of the friction electrostatic separation device is controlled at 20-25 degrees Celsius
  • the relative humidity is controlled at 0%-50%
  • the speed of the sorting drum is controlled at 40-60 revolutions per minute
  • the working voltage is controlled at 20-30 kV.
  • the deflection angle of the ionization electrode is 35°
  • the deflection angle of the repelling electrode is 50°.
  • the distance between the ionization electrode and the sorting drum is controlled at 4-6 cm
  • the distance between the repelling electrode and the sorting drum is 6-8 cm.
  • the speed of the froth flotation machine is controlled at 1200-1800 revolutions per minute
  • the content of methyl isobutyl methanol foaming agent is controlled at 15-25 microliters per liter
  • the content of n-dodecane trapping agent is controlled at 35-45 microliters Per liter
  • the pH is set to 8
  • the foam height is controlled at 4-8 cm
  • the time is controlled at 5-10 minutes.
  • the friction scrubbing process is controlled at 60% according to the pulp density, and the mass ratio of the battery material to the friction medium is 20%. Mix 200 grams of broken waste batteries, 800 grams of friction medium quartz sand and 667 grams of water, and put them into the friction scrubber. The particle size range of the quartz sand medium is controlled at 850-2360 ⁇ m, and the impeller speed of the friction scrubber is controlled at 1000 revolutions per minute. The scrubbing time is 10 minutes. The friction scrubbing of the above ratio can significantly increase the dissociation rate of the electrode active material from the electrode metal foil, while maintaining the unfolded state of the electrode metal foil, ensuring the efficiency of subsequent tribostatic separation.
  • Fig. 2(a) is the HDPE film material
  • Fig. 2(b) is the friction medium
  • Fig. 2(c) is the copper-aluminum film material
  • Fig. 2(d) is the electrode active material.
  • the friction scrubbing process can recover 83.8% of lithium and cobalt electrode materials; the non-conductive materials separated by the friction electrostatic device contain 95% of HDPE film materials, the conductive materials contain 97.7% of metal materials, and the remaining medium mineral products are 99% Grinding tool quartz sand; foam flotation primary flotation can achieve 71% recovery rate of cathode material, 49% purity, and the other components are graphite and quartz sand.
  • the recovery efficiency and purity can be improved by multi-stage flotation according to the requirements of recovered products.
  • the lithium-ion power battery to be recycled includes: the battery cells in the battery module after the control unit, the collection system, and the cooling system are removed from the scrap power battery, that is, the single battery piece that removes the contained electrolyte; and industrial production The inferior electrode sheet produced in the process, and the waste material of the electrode sheet.
  • the method of the present invention does not use organic solvents on the premise of omitting the process of manually disassembling a single cell, and can recover, sort and recycle the electrode materials in the cell, and can effectively sort and recover the positive and negative electrode materials, aluminum, and copper in the cell. As well as HDPE film materials, it expands the direction of lithium battery recycling and has broad industrial application prospects.

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Abstract

本发明公开了一种锂离子动力电池回收方法，方法包括以下步骤：拆除锂离子动力电池的电子元器件，破碎拆除后的锂离子动力电池，将破碎后的锂离子动力电池放入摩擦擦洗机中以从铝膜和铜膜上解离正负极材，筛分来自摩擦擦洗机的材料以得到筛上物和包括正负极材料的筛下物，筛上物放入摩擦静电分离器分离出HDPE薄膜、摩擦介质以及铜箔和铝箔，筛下物放入平板过滤器脱水，脱水后的筛下物放入泡沫浮选机中得到分离的负极材料和正极材料。

Description

锂离子动力电池回收方法 技术领域
本发明属于固体废物、电子垃圾回收技术领域，特别是一种锂离子动力电池回收方法。
背景技术
最近几年，随着移动电子设备与新能源车产量、保有量的持续增长，既带来了规模庞大的锂离子电池需求，也给相应的回收行业带来了巨大的机遇与挑战。随着锂离子电池需求量的日益上升，报废电池的处理和利用变成了一个新的难题。锂电池中电极由附着活性材料的正负极金属箔片构成，其中正极活性材料种种类众多，特性各异，其制备材料大多涉及如钴、镍等稀缺资源，正极极片为铝箔；负极材料一般为石墨，负极极片为铜箔，具有较大的资源化价值。
目前废旧动力锂离子电池资源化回收主要有三种方式：机械破碎分离法、高温冶金法与化学法，主要集中在对有价金属钴、镍和锂的回收，因为这些金属属于稀缺金属，相对于其他金属具有较高的回收价值。现有废弃锂电池回收技术手段多存在高能耗、低效率、环境影响较大等问题。
在背景技术部分中公开的上述信息仅仅用于增强对本发明背景的理解，因此可能包含不构成在本国中本领域普通技术人员公知的现有技术的信息。
发明内容
为了克服现有技术中存在的不足，实现正负极活性材料以及铜铝 箔片的多元化综合回收工艺，本发明提出锂离子动力电池回收方法，为锂离子动力电池回收的进一步发展提供技术支持。
本发明的目的是通过以下技术方案予以实现，一种锂离子动力电池回收方法包括以下步骤：
第一步骤中，拆除锂离子动力电池的电子元器件，
第二步骤中，破碎拆除后的锂离子动力电池，
第三步骤中，将破碎后的锂离子动力电池放入摩擦擦洗机中以从铝膜和铜膜上解离正负极材，
第四步骤中，筛分来自摩擦擦洗机的材料以得到筛上物和包括正负极材料的筛下物，
第五步骤中，筛上物放入摩擦静电分离器分离出HDPE薄膜、摩擦介质以及铜箔和铝箔，
第六步骤中，筛下物放入平板过滤器脱水，
第七步骤中，脱水后的筛下物放入泡沫浮选机中得到分离的负极材料和正极材料。
所述的方法中，第一步骤中，电子元器件包括用于控制锂离子动力电池的控制单元。
所述的方法中，第二步骤中，切割式破碎机破碎拆除后的锂离子动力电池。为了避免过度粉碎带来的铜箔、铝箔卷曲，包裹电极活性材料而影响后续回收效率，切割式破碎机的底筛孔径为8-10毫米。
所述的方法中，第三步骤中，摩擦擦洗机的叶轮转速为1000-1200转每分钟，较慢的转速可以避免过程中对于铜箔、铝箔以及HDPE薄 膜的破碎；摩擦介质为石英砂，且粒度范围为850-2360μm，在保证摩擦擦洗效果的同时便于后续分选石英砂再次利用；根据摩擦擦洗过程效率优化物质比例，破碎后的锂离子动力电池与摩擦介质质量比为10％-30％，矿浆密度60％-80％；摩擦擦洗时间为10-20分钟，摩擦擦洗过程所选液体媒介为水。
所述的方法中，第四步骤中，湿式振动筛筛分来自摩擦擦洗机的材料，所述湿式振动筛的底筛筛孔直径为38微米。电极活性材料粒径为1.5-7.8微米，因此采用筛孔直径为38微米的底筛处理摩擦擦洗后的材料，实现电极活性材料与其他组分的分离。
所述的方法中，第五步骤中，筛上物放入摩擦静电分离器分离得到铜箔、铝箔以及HDPE隔膜。
所述的方法中，第五步骤中，摩擦静电分离器工作温度为20-25摄氏度，相对湿度为40％-50％，分选滚筒转速为40-60转每分钟，以确保分选过程静电传输效率；工作电压为20-30千伏，根据铜箔、铝箔、HDPE薄膜以及石英砂的导电性，电离电极与分选滚筒距离为4-6厘米，排斥电极与分选滚筒距离为6-8厘米，以给料位置为基准，电离电极偏转角为35°，排斥电极偏转角为50°。
所述的方法中，第七步骤中，泡沫浮选液体媒介为水，浮选过程中运行参数根据石墨有正极活性材料表面活性特征而确定，泡沫浮选机叶轮转速为1200-1800转每分钟，泡沫浮选机中，甲基异丁基甲醇起泡剂含量为15-25微升每升，正十二烷捕获剂含量为35-45微升每升，pH为8，泡沫高度为4-8厘米，浮选时间为5-10分钟。
所述的方法中，所述负极材料包括石墨。
本发明针对回收的锂离子动力电池及残次电极片，包括：
报废动力电池中除去控制单元、采集系统、冷却系统后的电池模块中的电池单体，即去除所含电解液的单个电池片；以及工业生产中产生的残次电极片、制作电极片的废料。
和现有技术相比，本发明具有以下优点：
本发明所述的方法通过切割式破碎处理报废锂离子电池，在实现电池结构解离的同时保持电极金属箔片的展开状态，避免了电极活性材料被包裹在其中而降低后续回收效率。通过摩擦擦洗技术实现电极活性材料从电极金属箔片上的解离，同时保持电极金属箔片的展开状态，保证了后续摩擦静电分选的效率。摩擦擦洗介质石英砂可回收反复利用。通过摩擦静电分选，实现了铜箔、铝箔与HDPE隔膜的多元化回收。本发明所需化学试剂使用量较小，回收工艺不涉及高能耗过程，环境影响较少。
附图说明
通过阅读下文优选的具体实施方式中的详细描述，本发明各种其他的优点和益处对于本领域普通技术人员将变得清楚明了。说明书附图仅用于示出优选实施方式的目的，而并不认为是对本发明的限制。显而易见地，下面描述的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。而且在整个附图中，用相同的附图标记表示相同的部件。
在附图中：
图1是根据本发明一个实施例的锂离子动力电池回收方法的流程示意图；
图2(a)至图2(d)是根据本发明一个实施例的分选回收的报废锂离子动力电池示意图；
图3是根据本发明一个实施例的获得的正极活性材料扫描电镜图；
图4是根据本发明一个实施例的获得的负极活性材料扫描电镜图。
以下结合附图和实施例对本发明作进一步的解释。
具体实施方式
下面将参照附图1至附图4更详细地描述本发明的具体实施例。虽然附图中显示了本发明的具体实施例，然而应当理解，可以以各种形式实现本发明而不应被这里阐述的实施例所限制。相反，提供这些实施例是为了能够更透彻地理解本发明，并且能够将本发明的范围完整的传达给本领域的技术人员。
需要说明的是，在说明书及权利要求当中使用了某些词汇来指称特定组件。本领域技术人员应可以理解，技术人员可能会用不同名词来称呼同一个组件。本说明书及权利要求并不以名词的差异来作为区分组件的方式，而是以组件在功能上的差异来作为区分的准则。如在通篇说明书及权利要求当中所提及的“包含”或“包括”为一开放式用语，故应解释成“包含但不限定于”。说明书后续描述为实施本发 明的较佳实施方式，然所述描述乃以说明书的一般原则为目的，并非用以限定本发明的范围。本发明的保护范围当视所附权利要求所界定者为准。
为便于对本发明实施例的理解，下面将结合附图以具体实施例为例做进一步的解释说明，且各个附图并不构成对本发明实施例的限定。
为了更好地理解，一种锂离子动力电池回收方法包括以下步骤：
第一步骤中，拆除锂离子动力电池的电子元器件，
第二步骤中，破碎拆除后的锂离子动力电池，
第三步骤中，将破碎后的锂离子动力电池放入摩擦擦洗机中以从铝膜和铜膜上解离正负极材，
第四步骤中，筛分来自摩擦擦洗机的材料以得到筛上物和包括正负极材料的筛下物，
第五步骤中，筛上物放入摩擦静电分离器分离出HDPE薄膜、摩擦介质以及铜箔和铝箔，
第六步骤中，筛下物放入平板过滤器脱水，
第七步骤中，脱水后的筛下物放入泡沫浮选机中得到分离的负极材料和正极材料。
所述的方法的优选实施方式中，第一步骤中，电子元器件包括用于控制锂离子动力电池的控制单元。
所述的方法的优选实施方式中，第二步骤中，切割式破碎机破碎拆除后的锂离子动力电池，切割式破碎机的底筛孔径为8-10毫米。切割式破碎避免出现铜箔、铝箔卷曲，包裹电极活性材料而影响后续 回收效率，较小的底筛孔径导致过度破碎，造成活性材料被包裹，降低回收效率；铜箔铝箔尺寸变小，摩擦静电分选难以实现。较大的底筛孔径：破碎不完全，难以破碎电池结构，本申请的孔径能够实现优化的综合效果。
所述的方法的优选实施方式中，第三步骤中，摩擦擦洗机的叶轮转速为1000-1200转每分钟，摩擦介质为石英砂，且粒度范围为850-2360μm，摩擦介质粒度与破碎后的电池材料对应，第二步骤中切割式破碎机的底筛孔径为8-10毫米，破碎电池材料的尺寸一般不大于5毫米，因此且粒度范围为850-2360μm，这样可以保证较高的擦洗效率，同时保持铜箔铝箔结构不被破坏。破碎后的锂离子动力电池与摩擦介质质量比为10％-30％，低质量比导致摩擦擦洗过程介质用量变大，电池材料处理效率降低。高质量比导致摩擦擦洗带来的电极材料解离效率降低，摩擦时间需要延长。摩擦擦洗时间为10-20分钟。摩擦擦洗时间与摩擦擦洗过程叶轮转速共同影响摩擦擦洗效率，转速提高可以降低达到目标电极材料解离效率的时间。
较低矿浆密度使得摩擦介质与电极材料间摩擦作用减弱，解离效率降低。较高矿浆密度使得矿浆密度过高，矿浆流动性变差，摩擦作用减弱，同时叶轮阻力变大，容易造成叶轮变形，摩擦擦洗机电机损坏。矿浆密度60％-80％达到综合平衡效果。
所述的方法的优选实施方式中，第四步骤中，湿式振动筛筛分来自摩擦擦洗机的材料，所述湿式振动筛的底筛筛孔直径为38微米。
所述的方法的优选实施方式中，第五步骤中，筛上物放入摩擦静 电分离器分离得到铜箔、铝箔以及HDPE隔膜。
所述的方法的优选实施方式中，第五步骤中，摩擦静电分离器工作温度为20-25摄氏度，相对湿度为40％-50％，这确保了静电传导效率，分选滚筒转速为40-60转每分钟，工作电压为20-30千伏，电离电极与分选滚筒距离为4-6厘米，排斥电极与分选滚筒距离为6-8厘米，以给料位置为基准，电离电极偏转角为35°，排斥电极偏转角为50°，提高了分选效率。
所述的方法的优选实施方式中，第七步骤中，泡沫浮选机叶轮转速为1200-1800转每分钟，泡沫浮选机中，甲基异丁基甲醇起泡剂含量为15-25微升每升，起泡剂含量低导致泡沫生成量不足，石墨回收效率降低。起泡剂含量高导致泡沫高度难以控制，石墨回收效率降低。正十二烷捕获剂含量为35-45微升每升，过低降低正极材料的捕捉效率，过高浪费，35-45ml/L可实现90-95％回收效率，pH为8使得其工作效能显著提升，泡沫高度为4-8厘米，浮选时间为5-10分钟低于该时间导致分离效率低。5-10分钟可实现90-95％的回收效率。
为了进一步理解本发明，在一个实施方式中，如图1所示，方法包括：
S101、拆除废旧电池上的电子元器件；
S102、将拆解后的废旧电池破碎，
其中，破碎所用破碎机为切割式破碎机，且底筛孔径为8-10毫米；
S103、将破碎废旧电池放入摩擦擦洗机中，得到从铝、铜膜上解 离的正负极材，
其中，摩擦擦洗机中，叶轮速度控制在1000-1200转每分钟，摩擦介质为石英砂，且粒度范围控制在850-2360μm，矿浆密度控制在60％-80％，电池材料与摩擦介质质量比控制在10％-30％，摩擦擦洗时间控制在10-20分钟；
S104、将解离后混合材料于电极片放入湿式振动筛，得到分离的活性电极材料，
其中，中湿式底筛筛孔直径为38微米；
S201、将过筛后的筛上物放入摩擦静电分离器，将混合物分为HDPE薄膜、摩擦介质与铜箔铝箔三个组分；
其中，摩擦静电分选装置操作温度控制在20-25摄氏度，相对湿度控制在0％-50％，分选滚筒转速控制在40-60转每分钟，工作电压控制在20-30千伏。以给料位置为基准，电离电极偏转角为35°，排斥电极偏转角为50°。电离电极与分选滚筒距离控制在4-6厘米，排斥电极与分选滚筒距离在6-8厘米。
S202、将过筛后的筛下物放入平板过滤器脱水；
S203、将过滤后混合电极材料放入泡沫浮选机中，得到分离的负极材料和正极材料，
其中，泡沫浮选机转速控制在1200-1800转每分钟，甲基异丁基甲醇起泡剂含量控制在15-25微升每升，正十二烷捕获剂含量控制在35-45微升每升，pH设置为8，泡沫高度控制在4-8厘米，时间控制在5-10分钟。
下面详细介绍本发明的一个应用实施例来具体说明。
实施例
S101、拆除废旧电池上的电子元器件；
S102、将200克拆解后的废旧电池用切割式破碎机破碎，底筛选用8毫米底筛；
S103、摩擦擦洗过程按照矿浆密度控制在60％，电池材料与摩擦介质质量比20％。将200克破碎废旧电池、800克摩擦介质石英砂与667克水混合，放入摩擦擦洗机中，石英砂介质粒度范围控制在850-2360μm，摩擦擦洗机叶轮速度控制在1000转每分钟，摩擦擦洗时间为10分钟。上述比例的摩擦擦洗能够显著提高电极活性材料从电极金属箔片上的解离率，同时保持电极金属箔片的展开状态，保证了后续摩擦静电分选的效率。
S104、将解离后混合材料于电极片放入湿式振动筛，设置振动筛工作时间为20分钟，湿式底筛筛孔直径为38微米；
S201、将过筛后的筛上物放入摩擦静电分离器，将混合物分为HDPE薄膜、摩擦介质与铜箔铝箔三个组分。摩擦静电分选装置操作温度控制在25摄氏度，相对湿度控制在50％，分选滚筒转速控制在50转每分钟，工作电压控制在25千伏。以给料位置为基准，电离电极偏转角为35°，排斥电极偏转角为50°。电离电极与分选滚筒距离控制在5厘米，排斥电极与分选滚筒距离在7厘米。上述参数能够显著提高HDPE薄膜与铜箔铝箔的分选效率。
S202、将过筛后的筛下物放入平板过滤器；
S203、取20克通过过滤器将的混合电极材料放入泡沫浮选机中，得到分离的负极材料和正极材料，泡沫浮选机转速控制在1500转每分钟，并加入20微升甲基异丁基甲醇起泡剂，以及40微升正十二烷捕获剂，pH设置为8，泡沫高度控制为4厘米，运行时间控制为5分钟，并每隔30秒收集产生泡沫。
应用实施例的方法生产的回收产品如图2(a)至图4所示。其中，图2(a)为HDPE膜材料，图2(b)为摩擦介质，图2(c)为铜铝膜材料，图2(d)为电极活性材料。摩擦擦洗流程可回收83.8％的锂、钴电极材料；摩擦静电装置分选出的非导电材料中含有95％的HDPE膜材料，导电材料中含有97.7％金属材料，剩余中矿产物为99％的研磨工具石英砂；泡沫浮选一级浮选可实现正极材料回收率71％，纯度49％，其他成分为石墨与石英砂。回收效率与纯度可以根据回收产品要求，通过多级浮选进行提高。
从上述数据我们可以得出，摩擦擦洗流程可以有效的分选回收锂、钴、石墨电极材料，而后续的摩擦静电流程以及泡沫浮选流程可以有效的分选出摩擦擦洗的各类产物。
本发明中，待回收的锂离子动力电池包括：报废动力电池中除去控制单元、采集系统、冷却系统后的电池模块中的电池单体，即去除所含电解液的单个电池片；以及工业生产中产生的残次电极片、制作电极片的废料。本发明方法在省略人工拆解单个电池片的流程的前提下，不使用有机溶剂，对电池片中电极材料的回收分选及回收，并且可以有效分选回收电池片中正负极材料、铝、铜以及HDPE膜材料， 为锂电池回收领域拓展了方向，具有广阔的工业应用前景。
综上所述，以上实施例仅用以说明本公开的技术方案，而非对其限制；尽管参照前述实施例对本公开进行了详细的说明，本领域技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本公开的各实施例技术方案的范围。

Claims (9)

  1. 一种锂离子动力电池回收方法，所述方法包括以下步骤：
    第一步骤中，拆除锂离子动力电池的电子元器件，
    第二步骤中，破碎拆除后的锂离子动力电池，
    第三步骤中，将破碎后的锂离子动力电池放入摩擦擦洗机中以从铝膜和铜膜上解离正负极材，
    第四步骤中，筛分来自摩擦擦洗机的材料以得到筛上物和包括正负极材料的筛下物，
    第五步骤中，筛上物放入摩擦静电分离器分离出HDPE薄膜、摩擦介质以及铜箔和铝箔，
    第六步骤中，筛下物放入平板过滤器脱水，
    第七步骤中，脱水后的筛下物放入泡沫浮选机中得到分离的负极材料和正极材料。
  2. 根据权利要求1所述的方法，其中，第一步骤中，电子元器件包括用于控制锂离子动力电池的控制单元。
  3. 根据权利要求1所述的方法，其中，第二步骤中，切割式破碎机破碎拆除后的锂离子动力电池，切割式破碎机的底筛孔径为8-10毫米。
  4. 根据权利要求1所述的方法，其中，第三步骤中，摩擦擦洗机的叶轮转速为1000-1200转每分钟，摩擦介质为石英砂，且粒度范围为850-2360μm，破碎后的锂离子动力电池与摩擦介质质量比为10％-30％，摩擦擦洗时间为10-20分钟。
  5. 根据权利要求1所述的方法，其中，第四步骤中，湿式振动筛 筛分来自摩擦擦洗机的材料，所述湿式振动筛的底筛筛孔直径为38微米。
  6. 根据权利要求5所述的方法，其中，第五步骤中，筛上物放入摩擦静电分离器分离得到铜箔、铝箔以及HDPE隔膜。
  7. 根据权利要求1所述的方法，其中，第五步骤中，摩擦静电分离器工作温度为20-25摄氏度，相对湿度为40％-50％，分选滚筒转速为40-60转每分钟，工作电压为20-30千伏，电离电极与分选滚筒距离为4-6厘米，排斥电极与分选滚筒距离为6-8厘米，以给料位置为基准，电离电极偏转角为35°，排斥电极偏转角为50°。
  8. 根据权利要求1所述的方法，其中，第七步骤中，泡沫浮选机叶轮转速为1200-1800转每分钟，泡沫浮选机中，甲基异丁基甲醇起泡剂含量为15-25微升每升，正十二烷捕获剂含量为35-45微升每升，pH为8，泡沫高度为4-8厘米，浮选时间为5-10分钟。
  9. 根据权利要求1所述的方法，其中，所述负极材料包括石墨。
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