网络首发时间: 2019-12-02 09:52
稀有金属 2021,45(04),493-501 DOI:10.13373/j.cnki.cjrm.xy19080040
废锂离子电池物理分选技术研究现状及展望
刘超 邱显扬 刘勇 何晓娟 陈志强 刘牡丹
广东省资源综合利用研究所稀有金属分离与综合利用国家重点实验室广东省矿产资源开发和综合利用重点实验室
摘 要:
为了应对能源安全和能源环境污染等问题,锂离子动力电池因其优越的性能在新能源汽车领域得到了广泛的运用。受制于锂离子动力电池的使用寿命和产品的更新换代,锂离子电池将在未来几年逐渐进入批量报废阶段,报废的锂离子电池含有钴、锂、铜、镍、石墨等有价组分,回收价值极大。另一方面,废锂离子电池中含有重金属离子、有机碳酸酯等有毒有害物质,若不妥善处置将对环境构成极大的威胁。为了实现资源化回收和无害化处理,废锂离子电池的回收已成为研究的热点。本文介绍了近年来国内外废锂离子电池物理分选技术研究现状,重点对破碎、筛分分选、重力分选和浮选等工艺进行了评述,提出应加强物理分选相关的技术研究,进一步提高分选产品纯度,指出废锂离子电池高效率、低成本、低污染的资源化回收技术是未来的发展方向。最后,对物理分选技术未来的发展前景进行了展望。
关键词:
废锂离子电池 ;资源与环境 ;物理分选 ;现状 ;展望 ;
中图分类号: X705
作者简介: 刘超(1988-),男,江西抚州人,硕士,工程师,研究方向:二次资源回收利用、选矿工艺研究,E-mail:courage0128@163.com;; *刘勇,教授级高级工程师,电话:020-37239216,E-mail:gzly11@163.com;
收稿日期: 2019-08-26
基金: 广东省科学院国家级科技创新平台创新能力提升专项(2019GDASYL-0402003); 广州市科技专项(201804020024); 广东省科技厅公益研究与能力建设专项(2017A070701020)资助;
Research Status and Prospects of Physical Separation Technology of Spent Lithium-Ion Batteries
Liu Chao Qiu Xianyang Liu Yong He Xiaojuan Chen Zhiqiang Liu Mudan
Guangdong Institute of Resource Comprehensive Utilization,State Key Laboratory of Rare Metals Separation and Comprehensive Utilization Guangzhou,Guangdong Province Key Laboratory of Mineral Resource and Comprehensive Utilization
Abstract:
In response to the increasingly prominent problems of security and environment of energy,lithium-ion power batteries were recognized as the most potential power battery to alleviate the difficulties because of its high energy density,fast charging and discharging speed,long cycle life environment friendly.Thanks to the strong support of the national support policy,it had been widely used in the field of new energy vehicles.The spent lithium-ion batteries contained valuable components such as cobalt,lithium,copper,nickel and graphite etc.with great recycling value,on the other hand,it contained toxic and harmful substances such as heavy metal ions and organic carbonates.So,it was obvious that the spent lithium-ion battery had both resource and hazard characteristics,which would pose a great threat to the environment if not treated properly.So,recycling and innocuity treatment of that had become a research hotspot.Physical separation was a process to separate and purify the components of spent lithium-ion battery according to the differences in particle size,specific gravity,magnetism,wettability,friction charge and other physical properties.Physical separation technology was the method which could realize the pre-concentration of lithium,cobalt,copper,manganese and other metals in the treatment of spent lithium-ion batteries environmentally friendly and economically,which showed great potential in combination with other technologies to separate and purify the useful components.However,compared with metallurgical purification technology,the related research and reports of which were relatively few,and the systematic theory and efficient separation technology had not yet been formed.In this paper,the recovery of spent lithium-ion batteries by physical separation technology including crushing,screening,gravity separation and flotation and combination of which at home and abroad in recent years were introduced,and the advantages and disadvantages of each process were introduced and compared with detailed examples.The main conclusions were as follows:(1) In the process of crushing of spent lithium-ion battery cell,the selective crushing effect should be expanded as much as possible,so that the crushed products could be efficiently concentrated in the specific particle size fraction.Besides,special attention should be paid to the disposal of electrolyte,which was a safety problem that could not be ignored.(2) Flotation was an effective method to separate the cathode material and graphite from the electrode mixture,it had the advantages of low cost,low energy consumption,strong applicability and little harm to the environment.In the process of industrial application,low toxicity,economic and efficient removal of the binder which affected the flotation effect greatly was the most critical technical problem.(3) Physical separation created favorable conditions for subsequent separation in treatment of spent lithium-ion batteries,it was pointed out that the combined pretreatment by combined processes had showed a good application prospect.In order to further improve the purity of separation products,it was pointed out that it must strengthen the research of physical separation technology to improve the purity of sorting products,and the process of high efficiency,low cost,low pollution was the development direction of in future.To overcome the weakness of physical separation such as low product purity and incomplete disposal of harmful substances,some effective managements must be taken in:(1) According to the material and structure characteristics of different spent lithium-ion batteries,the crushing methods should be selected to expand the selective crushing effect,and the study on the properties of crushed products should be strengthened,so as to lay the foundation for the formulation of reasonable physical separation process.(2) In the process of physical separation and pretreatment of spent lithium-ion battery,it was necessary to strengthen the research on low-cost and high-efficiency recovery technology of useful components such as separator,anode material and electrolyte of them.Special attention should be paid to the treatment of toxic and harmful substances of waste batteries,no matter what process was selected.(3) When selecting the treatment process,interdisciplinary integration should be emphasized to change or optimize the physical and chemical properties such as magnetism,specific gravity and floatability of some components of spent lithium-ion battery by appropriate methods,so as to achieve the purpose of green,efficient and economic recycling.(4) Physical separation should not be simply regarded as the pretreatment process in the recovery process.The combination of physical separation with hydrometallurgy,pyrometallurgy and bio-metallurgy would be an important research content of recycling spent lithium-ion batteries in the future.
Keyword:
spent lithium-ion batteries; resources and environment; physical separation technology; current situation; prospect;
Received: 2019-08-26
在全球石化资源日益枯竭和污染问题日益加剧的时代背景下,能源的安全、清洁等问题成为了全球关注的焦点,锂离子电池因其能量密度高、容量大、无记忆性等优点,被公认为是最具发展潜力的动力电池
[1 ,2 ,3 ,4 ]
。近年来,以锂离子电池为主要动力源的新能源汽车取得了长足的进步和发展。预计2030年新能源汽车销量占比将达到40%
[5 ]
。新能源汽车电池组的寿命通常为4~6年,将导致未来废旧锂离子电池爆发式的增长,我国汽车动力电池报废量如图1所示
[6 ,7 ,8 ]
。由于报废的锂离子电池兼具资源性和危害性特征,势必带来极大的资源和环境问题。因此,废锂离子电池的无害化处理和资源化利用势在必行。
废锂离子电池回收过程中的物理分选技术一般作为冶金提纯前的预处理工序,用来富集高含量的物质,其分选结果直接关系到后续工艺的选择、提纯难易程度、经济环保等关键性问题,在整个回收利用环节中起到重要的承上启下的作用
[9 ,10 ]
。然而,目前物理分选并没有引起足够的重视,缺乏系统的理论和高效的分选技术,严重制约了废锂离子电池回收的工业化和无害化处置进展
[11 ,12 ]
。因此,为了加深对废锂离子电池物理分选技术现状的认识和理解,对当前的物理分选技术进行了综合论述,可为废锂离子电池的资源化和无害化处理提供参考。
图1 锂离子动力电池年报废量
Fig.1 Quantity of spent lithium-ion power batteries in China
1废锂离子电池的资源特点
当前绝大部分已商品化的锂离子动力电池正极材料普遍为三元材料、锰酸锂和磷酸铁锂
[13 ,14 ]
,其中三元材料电池和磷酸铁锂电池的市场占有量达45%左右
[15 ]
。报废的锂离子电池通常含Co 5%~20%,Ni 5%~10%,Li 5%~7%,其他金属(Cu,Al,Fe等)5%~10%、有机物15%以及塑料7%
[16 ]
,其质量分数如图2所示。有价金属的含量高于矿石本身甚至加工后的矿石精矿,废锂离子电池被誉为名副其实的“金属矿山”
[15 ]
。相较于其它电池,锂离子电池通常被认为是清洁、绿色的能源,但由于锂离子电池含有重金属离子、六氟磷酸锂、有机碳酸酯等有毒有害物质,若不妥善处理依旧对水质、土壤和大气造成严重污染
[18 ]
。因此,废锂离子的安全无害化处理和资源的绿色回收处理,是循环经济的必由之路,具有重大的资源、经济和环保等效益。
废锂离子电池的组成一般包括正极材料、负极材料、电解质、隔膜和外壳5个部分,结构如图3所示。正极材料主要成分为钴酸锂、镍酸锂和磷酸铁锂等,其质量分数约占电池的25%~30%,制作成本约占电池的40%,可见该组分是回收利用的重点;负极材料为优质石墨等碳材料,其质量分数约占电池的14%~19%;负极的电骨架为铜箔,正极的电骨架为铝箔,电池外壳则大部分以不锈钢和铁为主,这些金属单质的质量分数约占电池的30%~40%
[8 ,11 ,13 ,19 ]
。由此可见,废锂离子电池的正极材料、负极材料、铜箔、铝箔、金属外壳是主要回收对象。
2废锂离子电池物理分选现状
物理分选是根据废锂离子电池各组分在粒度、比重、磁性、润湿性、摩擦荷电性等物理性质的差异实现各组分分离和提纯的过程
[20 ,21 ]
,包括筛分分选、重力分选、磁力分选和浮选等。具有经济、环保、流程短、简化后续冶金处理工艺等优点,在实际运用中物理分选大多作为废锂离子电池回收过程中的预处理工序,用来预先富集高含量的物质。
2.1破碎、筛分分选
图2 废锂离子电池有价组分质量分数
Fig.2 Mass fraction of valuable components in spent lithium-ion power batteries
图3 锂离子电池结构
Fig.3 Construction of lithium-ion batteries
破碎是废锂离子电池资源回收过程中的关键环节,电池放电后经切割、剪切或者冲击粉碎等方式减小了电池的金属外壳及内部组分的粒度,废锂离子电池中的各组分破碎后往往在特定的粒级会产生富集,表现出明显的选择性破碎特点。
张涛
[11 ]
将废弃锂电池经过一次冲击破碎和筛分,金属外壳和大片隔膜富集在+2 mm破碎产物中,金属箔片和纤维状隔膜富集在0.25~2 mm破碎产物中,电极活性材料钴酸锂和石墨富集在-0.25mm破碎产物中。周旭等
[22 ]
对废锂离子电池负极材料采用锤振破碎和振动筛分,得到的+0.250 mm粒级中铜品位为92.4%,-0.125 mm粒级中碳粉品位为96.6%,-0.125~+0.250 mm粒级再经气流分选,实现了铜与碳粉的有效分离。李建波
[23 ]
针对传统破碎法存在的粒度差不显著、粒度分布不均匀等问题,采用规则破碎法,在破碎产物中负极材料与铝箔和铜箔的粒度差极大,隔膜性质未发生明显变化,经筛分实现了正负极材料与铝箔和铜箔的分离。Li等
[24 ]
对废锂离子电池破碎筛分得到-12mm粒级产品,利用超声波对破碎产品进行清洗,清洗后的产品再利用2 mm筛网筛分分选,得到的筛上产品为易于分选的铜、铝和铁薄片,筛下产品为电极材料。利用超声波清洗使得电极材料中的92%的Co从其支撑薄板上充分脱落,为后续分选创造了有利条件。因此,废锂离子电池的破碎目的在于应设法尽可能扩大选择性破碎效果,使破碎产物高效地集中在特定的粒级当中,为后续分选创造有利条件。
值得注意的是,废锂离子电池中电解液的处置是破碎过程中不可忽视的安全问题
[25 ]
,电解液的成分一般包括有机碳酸脂类和锂盐,电解液中的六氟磷酸锂(Li PF6 )在55℃以上的热稳定性差,如公式所示:Li PF6 ?Li F(s)+PF5 (g),PF5 与溶剂反应生成剧毒化学品并引发溶剂聚合,与此同时,Li PF6 极易与水反应产生有毒气体HF
[26 ]
,此外,电解液中有机溶剂的闪点和沸点均很低,易引起热失控
[27 ]
。Batrec工艺将锂离子电池在拆解成单个电芯后,置于二氧化碳气氛中进行破碎,释放出来的锂和二氧化碳发生反应,减少了破碎过程中有毒有害物质的危害
[28 ]
。Recupyl工艺利用氩、二氧化碳或两种气体的适当混合物制成惰性气体的密闭装置对废锂离子破碎,确保破碎过程的安全
[29 ]
。国内部分处理厂家将拆解后的废锂离子电芯置于密闭的环境中整体破碎,破碎后在一定的温度下和密封的装置中使电解液挥发,收集后再进行集中处理,避免了电解液在回收过程中对环境和人体的直接危害。
2.2重力分选
重力分选是利用破碎后各组分的比重差异,借助风力或水力介质来实现不同组分的分离,重力分选是物理分选处理废锂离子电池重要的方法之一,重选设备结构简单、成本低、无污染,主要用来分离废锂离子电池的隔膜材料和金属材料。
金泳勋等
[30 ]
利用立式剪碎机和振动筛对废锂离子电池进行破碎筛分,对1700μm破碎产品进行重力分选,分离得到轻产品(隔膜)和重产品(铜、铝等)。李建波等
[31 ]
根据隔膜的物理性质,研制了重力分选机,在进水流量为0.51 m3 ·h-1 ,搅拌速率为250 r·min-1 的条件下,隔膜的回收率最大为99.84%,实现了隔膜的分离。Bertuol等
[32 ]
对废锂离子电池进行锤式破碎和筛分,对-0.211 mm产品在淘析式喷动床装置中进行气流分选,通过调节垂直上升气流大小,得到了3种不同密度的产品,再分别对气流分选产品进行检查筛分,最后得到了产率为17.2%的铜铝金属混合物,产率为15.8%的铝金属外壳,产率为42.7%的钴酸锂和石墨组成的电极材料和产率为6.1%的聚合物,回收的工艺流程图如图4所示。张雨
[33 ]
对剪切破碎和立式冲击破碎后的-2.00~+0.25 mm物料,利用主动脉动气流装置对模拟物料和实际物料进行了气流分选试验,通过调节气流速度、脉动频率、给料速率得到最佳的分选条件,取得较好的试验效果,实现了铜箔和铝箔的分离。
图4 废锂离子重力分选工艺流程图
Fig.4 Flow sheet for gravity separation of spent lithium-ion batteries
2.3磁力分选
磁力分选在物理分选过程中的回收对象大多为含磁性的铁质,可选择性地分离废锂离子电池金属外壳等铁质材料
[34 ]
或冶金工艺处理后的磁性物质。Shin等
[35 ]
报道了一种工业化应用前景广阔的回收废锂离子电池中有价金属的方法,其中机械处理部分包括了利用磁力分选来分离钢壳。Li等
[36 ]
提出来一种从破碎后的细粒级电极材料粉末清洁环保回收钴、锂、活性炭的工艺,将钴酸锂和活性炭置于氮气气氛中焙烧,两者发生反应生成Co,Li2 CO3 和气体,通过选择性的溶解Li2 CO3 ,再利用Co具有铁磁性和活性炭的非磁性特点,采用湿式磁选方法实现了Co和活性炭的分离,获得了钴,锂和活性炭的回收率分别为95.72%,98.93%和91.05%。Yamaji等
[37 ]
针对剪切破碎和筛分后的废锂离子电池,利用磁选分离出+1 mm粒级颗粒中的钢壳,非磁性产品经涡流电选分离出塑料,最后通过气流重力分选实现铝和铜的分离,实现了对+1 mm粒级颗粒塑料、铝、铁、铜的分离,分选工艺流程图如图5所示。
2.4浮选
浮选是利用物料表面物理化学性质的差异,借助于泡沫的浮力实现颗粒分离的过程,具有成本低、能耗低、适用性强、对环境危害小等优点。在废锂离子电池回收利用过程中,浮选主要的处置对象为破碎筛分后的细粒级富钴粉体,其主要成分为钴酸锂颗粒和石墨颗粒
[38 ,39 ,40 ]
,由于钴酸锂表面表现出天然的亲水性,而石墨为典型的分子晶体结构,具有较强的天然疏水性,较大的润湿性差异使二者的浮选分离成为了可能。
图5 废锂离子电池物理分选工艺流程图
Fig.5 Flow sheet for physical separation of spent lithium-ion batteries
李红等
[41 ]
对比研究了废弃锂离子电池富钴破碎产物与商品化电极材料的浮选行为,研究表明商品化钴酸锂和石墨的天然可浮性差异较大,而废弃锂离子电池富钴破碎产物的钴酸锂颗粒和石墨颗粒表面粗糙,有杂质附着,使钴酸锂和石墨颗粒表面润湿性发生改变,并提出了在浮选前必须对富钴破碎产物进行表面改性,增大钴酸锂和石墨表面可浮性差异,才能实现二者的浮选分离。
黄红军和黄秋森
[42 ]
采用球磨-低温热处理两阶段流程可以将阻碍钴酸锂和石墨浮选分离的电极材料表面有机物膜去除,增大了钴酸锂与石墨间的可浮性差异,经浮选流程获得了钴酸锂回收率和品位高达90.32%和88.03%的良好分选效果。
Yu等
[43 ]
对废锂离子电池进行破碎筛分,对-0.074 mm的细粒电极材料粉末进行磨矿-浮选,取得了Li Co O2 的品位为97.13%,石墨的品位为73.56%的回收指标,研究表明磨矿破坏了石墨的层状结构,使其暴露在外并产生新的疏水表面,同时对有机隔膜的磨损有利于恢复Li Co O2 颗粒的表面亲水性。
He等
[44 ]
将废锂离子电池冲击破碎后的-0.25mm物料经Fenton试剂改性,改变了石墨和正极活性物质钴酸锂的表明润湿性,经浮选法使二者得到了有效的分离,获得了钴酸锂精矿含锂39.91%,回收率为98.99%的分选指标。可见,浮选可以实现电极材料中钴酸锂和石墨的分离,能否低毒、经济和高效的去除正极材料粘结剂的不利影响是能否实现工业化应用的关键。
2.5联合分选
物理分选一般作为冶金提纯前的预处理工序来富集高含量的物质
[45 ,46 ,47 ]
,但随着锂离子电池技术水平的提高,锂离子电池在组成和结构不断出现新的变化,尤其是正极活性材料的革新,对以后的回收工艺提出了新的要求。根据废锂离子电池不同的回收需求,物理分选的方式和程度是不同的,往往需要将多种工艺组合起来对报废锂离子电池进行处理
[48 ]
,多种工艺联合处理废锂离子电池展现了良好的运用前景。
Sony/Sumitomo公司研发了一种废锂离子电池分选回收工艺,该工艺先将未拆解的废锂离子电池直接于1000℃下进行煅烧,煅烧打开了电池结构并消除电解液和隔膜等有机质,然后对煅烧后的残余进行破碎、筛分、磁选,使得Fe,Cu,Al相互分离,筛下的物料主要是碳粉、Li Co O2 和/或Li Cox Ni(1-x) O2
[49 ]
。该工艺通过火法冶金与物理分选相结合实现了不同组分的分离。
金泳勋等
[30 ]
利用立式剪碎机、分离摇床和振动筛将废锂离子分级,分别得到轻产品隔膜、金属产品(铝和铜等)和电极材料(锂钴氧化物和石墨混合粉末),将电极材料置于马弗炉中773 K温度下热处理2 h,脱除粉末表面的有机粘结剂,扩大石墨与钴锂氧化物可浮性差异,利用浮选对二者进行分离,得到锂和钴的含量高于93%,锂和钴的回收率为92%。该工艺在物理分选过程中,利用火法处理脱除了有机粘结剂,使浮选分离钴锂化合物和石墨成为可能。
Huang等
[50 ]
对主要成分为Li Fe PO4 ,Li Mn2 O4 和石墨的混合阴极材料,先通过盐酸和双氧水选择性的浸出得到了含Fe,Mn,Li浸出液,利用离子浮选选择性从浸出液中回收Fe3+ 得到Fe Cl3 产品,再通过添加KMn O4 沉淀Mn2+ 得到Mn O2 /Mn2 O3 沉淀,最后向富Li+ 溶液中添加Na3 PO4 溶液沉淀回收Li+ 得到Li3 PO4 ,全流程Li,Fe和Mn的回收率分别为80.93%±0.16%,85.40%±0.12%和81.02%±0.08%,工艺流程如图6所示。该工艺深度融合了离子浮选和湿法冶金,为工业有效分离和回收废锂离子电池阴极有价金属提供了一种新的途径。
图6 回收废锂离子电池的联合工艺工艺流程图
Fig.6 Flow sheet of recovery of spent lithium-ion batteries by combined process
3总结与展望
随着锂离子动力电池在未来几年逐渐进入批量报废阶段,鉴于废锂离子电池的资源性和危害性特征,废锂离子电池的低污染、高效率、低成本、增加回收物质种类的资源化回收技术是未来的发展方向。物理分选技术在处理废锂离子电池中可以清洁、环保、经济地实现锂、钴、铜、锰等金属的预先富集,在与其它技术相结合进一步实现有用组分的分离和提纯展现了巨大的潜力。近年来,国内外学者利用物理分选技术在废锂离子预处理和回收有价金属方面做了大量的研究,但相较于冶金提纯技术,物理分选技术研究相比较少,尚未形成系统的理论和高效的分选技术,物理分选存在产品纯度不高,对有害物质的处置不彻底等问题。因此,加强物理分选技术研究和开发是废锂离子电池高效利用的重要课题之一。
为了提高物理分选的分选效率和回收率,应从以下方面考虑和加强相关技术研究:
1.应根据废锂离子电池自身的材质和结构特征,针对性的选择破碎方法,扩大选择性破碎效果,应加强对破碎产物的性质特征的研究,充分了解各组分的组成、结构及相互关系等,从而为制定合理物理分选工艺的基础。
2.在废锂离子电池物理分选预处理过程中,应加强废锂离子电池中隔膜、负极材料、电解液等有用组分的低成本、高效率回收技术研究,在选择处理工艺时要特别注意废电池的有毒有害物质的处理。
3.在制定回收处理的工艺过程中,应注重多学科交叉融合,运用适当的方法来改变废锂离子电池某些组分的磁性、比重、可浮性等物理化学性质或优化处理工艺,扩大不同组分间的物理化学性质差异,从而利用物理分选技术以达到绿色、高效、经济的回收目的。
4.随着锂电池技术的发展,锂电池在材料和结构出现了新的变化,对废锂离子电池的绿色化和资源化回收提出了新的要求,不应简单的把物理分选仅仅作为回收过程中的预处理工序,物理分选与湿法冶金、火法冶金和生物冶金等其它工艺的深度融合的联合处理工艺是未来回收废锂离子电池的重要研究内容。
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