锂离子电池安全性特点及热模型研究

锂离子电池的安全问题越来越受到重视.本文从锂离子电池热安全性特点着手,分析了锂离子电池的着火、爆炸和电解液泄漏等安全事故特点.简单介绍了锂离子电池主要材料的产热特性、相互反应产热特性.讨论了锂离子电池热模型建立的两种途径,即量热仪途径和化学反应途径,通过这些热模型的建立,来指导锂离子电池的安全设计和管理.     

超声辅助生物淋滤废旧Zn-C电池锌锰溶出的研究

以氧化硫硫杆菌(A.thiooxidans)为淋滤菌株对废旧Zn-C电池电极材料中的Zn、Mn进行了生物浸提,比较研究了化学浸提、生物淋滤和不同超声辅助方法生物淋滤体系下的Zn、Mn的溶出效率及溶出动力学.结果表明:不同超声辅助方法中,超声+生物淋滤体系Zn、Mn溶出最优,Zn、Mn的最大溶出率分别为94.2%和65.5%,并提高了溶释速率.此外,对于Mn的溶出,化学淋滤体系符合边界层扩散控制模型,生物淋滤和超声+生物淋滤体系符合收缩核Stoke's regime模型,而Zn的溶出均符合化学反应控制模型.     

废旧锌锰电池锌锰元素的分析表征

为了解废旧锌锰电池的锌锰元素特征,以废旧碱性(A-A)和酸性(Zn-C)电池为研究对象,采用化学分析、BCR连续萃取技术、SEM-EDS和XRD等手段对拆分的电池正、负电极材料中的锌锰元素进行了分析表征.实验表明:废旧碱性(A-A)电池中Mn、Zn分别占到正极材料质量的49.2%、10.3%,以Zn Mn2O4四方体锌锰矿结构晶体存在;Zn占负极材料的52.5%,以Zn O晶体存在;废旧酸性(Zn-C)电池混合电解质中,Mn、Zn各占41.8%和25.2%,分别以Zn Mn2O4、Mn O2、Zn5(OH)8Cl2·H2O和Zn(NH3)2Cl2等晶体存在.BCR处理结果显示,A-A电池正极和Zn-C电池混合电解质中,Mn主要为残渣态较难酸释,而A-A电池负极中的Zn易于回收.     

废旧锌锰电池生物淋滤-水热法制备纳米锰锌铁氧体

以氧化硫硫杆菌(A.thiooxidans)和氧化亚铁钩端螺旋菌(L.ferrooxidans)为混合淋滤菌株对废旧锌锰电池进行了生物浸提,并以获取的淋滤液为前驱体,采用水热法制备出系列锰锌铁氧体软磁材料(Mn_(1-x)Zn_xFe_2O_4,x=0.2~0.8);结合X射线衍射(XRD)、扫描电镜-能谱(SEMEDX)、振动样品磁强计(VSM)、透射电镜(TEM)、红外光谱(FT-IR)、热重-差热分析(TG-DTA)等表征手段对制备材料的结构、形貌、磁学性能和稳定性进行分析.结果表明,在5%固液比(质量体积比,5 g/100 mL,以下均表述为"5%固液比")下,经过5 d的外源酸调控生物浸提,分别获得了84.5%、63.2%的Zn、Mn浸出效率;当Zn∶Mn∶Fe=0.4∶0.6∶2.0(物质的量比,即x=0.4)时,制备的纳米级Mn_(0.6)Zn_(0.4)Fe_2O_4性能最优,属纯相的立方尖晶石结构,颗粒分布均匀,饱和磁化强度(M_s)、剩余磁化强度(M_r)和矫顽力(H_c)分别为68.9 emu·g~(-1)、4.7 emu·g~(-1)和53.6 Oe,具有热稳定性和耐酸碱性,有望成为一种新型的水处理磁性材料.     

Multi-factor principle for electrolyte additive molecule design for facilitating the development of electrolyte chemistry

When I read the paper"Electrolytes enriched by potassium perfluorinated sulfonates for lithium metal batteries"from Prof. Jianmin Ma's group, which was published in Science Bulletin (doi.org/10.1016/j.scib.2020.09.018), I felt excited as presented a multi-factor principle for applying potassium perfluorinated sulfonates to suppress the dendrite growth and protect the cathode from the viewpoint of electrolyte additives. The effects of these additives are revealed through experimental results, molecular dynamics simulations and first-principle calculations. Specifically, it involves the influence of additives on Li+ solvation structure, solid electrolyte interphase (SEI), Li growth and nucleation. Following the guidance of the multi-factor principle, every part of the additive molecule should be utilized to regulate electrolytes. This multi-factor principle for electrolyte additive molecule design (EAMD) offers a unique insight on understanding the electrochemical behavior of ion-type electrolyte additives on both the Li metal anode and high-voltage cathode. In these regards, I would be delighted to write a highlight for this innovative work and, hopefully, it may raise more interest in the areas of electrolyte additives.     

废旧电池资源化、无害化

对当前国内外在废旧电池的处理处置方面进行了综合性论述,对废旧电池的危害及当前应采取的对策进行分析。     

Technological improvements in automotive battery recycling

Recycling of automotive batteries for the recovery of secondary lead is extremely important in Brazil, for the country does not possess large reserves of this metal. Lead is one of the most widely used metals in the world, but it is highly toxic, posing risks for humans and for the environment if not utilized or treated adequately. Industrial waste containing lead in Brazil are classified by the Brazilian Residue Code (NBR—10004:2004) as hazardous. The lead recycling process employed by the recycling industry in Brazil is the pyrometallurgical process in a rotary furnace. This process consists of four stages: (1) grinding of the battery to separate plastic, electrolyte and lead plates; (2) lead reduction in a rotary furnace; (3) separation of metallic lead from slag; and (4) refining of recycled lead. The purpose of this work is to propose process improvements aimed primarily at increasing production output by reducing the loss of lead in slag and particulates, thereby providing a healthier work environment in line with Brazilian environmental and labor laws.     

Novel mesoporous microspheres of Al and Ni doped LMO spinels and their performance as cathodes in secondary lithium ion batteries

A facile, scalable, and solution-based technique is used to fabricate Al and Ni-doped (LiAl_0.1Mn_1.9O₄ and LiAl_0.1Ni_0.1Mn_1.8O₄) microspheres of lithium manganese oxide (LMO) spinels for use as reversible cathode materials for lithium ion batteries (LIBs). The spheres of the two samples exhibit different porosities. Cells with these LMO-based cathodes are then cycled between 4.5 V and 2 V to study their stabilities while simultaneously being subjected to the undesirable Jahn-Teller distortion that occurs around the ~3 V regime. The LiAl_0.1Mn_1.9O₄ (LAMO) and the LiAl_0.1Ni_0.1Mn_1.8O₄ (LANMO) cells exhibit comparable open circuit voltages (OCV) of 2.94 V and 2.97 V, respectively. During cell cycling, the LAMO cell exhibits a maximum specific capacity of 122.51 mAh g^?1 with a capacity fade of 65.35% after 75 cycles. The LiAl_0.1Ni_0.1Mn_1.8O₄ (LAMO) sample fares better and exhibits a maximum of 140.49 mAh g^?1 and a capacity drop of 52.59%. Detailed structural studies indicate that Ni doping and the greater degree of porosity of the LANMO sample to be a stabilizing factor. This is further confirmed by cyclic voltammetry (CV) and AC impedance spectra analysis.     

Chemical and process mineralogical characterizations of spent lithium-ion batteries: An approach by multi-analytical techniques

Mineral processing operation is a critical step in any recycling process to realize liberation, separation and concentration of the target parts. Developing effective recycling methods to recover all the valuable parts from spent lithium-ion batteries is in great necessity. The aim of this study is to carefully undertake chemical and process mineralogical characterizations of spent lithium-ion batteries by coupling several analytical techniques to provide basic information for the researches on effective mechanical crushing and separation methods in recycling process. The results show that the grade of Co, Cu and Al is fairly high in spent lithium ion batteries and up to 17.62 wt.%, 7.17 wt.% and 21.60 wt.%. Spent lithium-ion batteries have good selective crushing property, the crushed products could be divided into three parts, they are Al-enriched fraction (+2 mm), Cu and Al-enriched fraction (?2 + 0.25 mm) and Co and graphite-enriched fraction (?0.25 mm). The mineral phase and chemical state analysis reveal the electrode materials recovered from ?0.25 mm size fraction keep the original crystal forms and chemical states in lithium-ion batteries, but the surface of the powders has been coated by a certain kind of hydrocarbon. Based on these results a flowsheet to recycle spent LiBs is proposed.     

A mechanical pre-treatment process for the valorization of useful fractions from spent batteries

In this paper the authors propose a full-scale plant aimed to pre-treat spent batteries in order to obtain cleaned useful fractions (magnetic and non-magnetic metals, paper, plastic, a fine-sized material made of a metal-carbon mixture). The treating process was designed after having analyzed and tested a representative sample coming from the whole amount of spent batteries collected in 1 month by the public service in and around Turin. The analyses performed on the sample allowed the authors to determine its in-percentage composition in term of type of batteries: 60-70% b.w. (by weight) alkaline, 25-30% b.w. Zn-C and 5-10% b.w. other types. For each type, the composition in term of size (AAA or LR03; AA or LR6; C or LR14; D or LR20; 9 V or 6F22A; 4.5 V or 3R12A) has also been determined.The treatment for the recovery of secondary raw materials foresees the following phases:

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separation of useful types/sizes of exhaust batteries to undergo further treatments by means of a first sieving process;

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liberation of the single components taking advantage of a crushing operation;

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separation of a fine-sized material (to subject to pyro or hydro metallurgic recovery) from a coarse-sized material (to send to secondary smelt foundries and incinerators) by means of a second sieving phase.

On the basis of the results obtained from the crushing/sieving laboratory tests and the chemical characterization, a full-scale plant able to treat about 76,000 t/y of spent batteries has been designed. The cost analysis performed on the proposed treatment plant has given back a unit pre-treatment cost equal to 3€ per ton of processed spent batteries.