废旧锂离子电池回收处理技术与资源化再生技术进展

近年来,随着消费电子商品、电动车和大规模储能市场的快速发展,作为目前占据最多市场份额的锂离子电池的产量也随之快速增长,随之产生的废旧锂离子电池的数量和重量呈现出了井喷式的上涨。从其巨大的数量、环境保护和资源再生的角度来看,废旧锂离子电池都具有很高的回收价值和潜力。本文主要从实验室研究和工业应用两个角度总结了目前主要的回收处理方法和流程,重点介绍了利用废旧锂离子电池电极材料重新再生和合成新的电极材料的研究进展。目前废旧锂离子电池回收处理存在的问题主要是：电极材料的复杂多样性导致分离提纯过程困难,回收过程易产生二次污染以及回收的经济激励不足。未来的发展趋势在于结合绿色环保和低成本经济,研究高效的回收处理工艺流程。     

A novel strategy of lithium recycling from spent lithium-ion batteries using imidazolium ionic liquid

In light of the increasing demand for environmental protection and energy conservation,the recovery of highly valuable metals,such as Li,Co,and Ni,from spent lithium-ion batteries (LIBs) has attracted wide-spread attention.Most conventional recycling strategies,however,suffer from a lack of lithium recycling,although they display high efficiency in the recovery of Co and Ni.In this work,we report an efficient extraction process of lithium from the spent LIBs by using a functional imidazolium ionic liquid.The extraction efficiency can be reached to 92.5％ after a three-stage extraction,while the extraction effi-ciency of Ni-Co-Mn is less than 4.0％.The new process shows a high selectivity of lithium ion.FTIR spec-troscopy and ultraviolet are utilized to characterize the variations in the functional groups during extraction to reveal that the possible extraction mechanism is cation exchange.The results of this work provide an effective and sustainable strategy of lithium recycling from spent LIBs.     

退役锂离子电池湿法回收生命周期和经济评价

锂离子电池（LIBs）具有能量密度高、输出功率大等优点被广泛应用,随之产生了大量退役LIBs。近年来,退役LIBs回收再利用逐渐受到了人们的关注,但目前回收体系尚不完善,存在发展动力和科学技术等方面的问题。从生命周期评价（LCA）和经济性评价两方面对典型的盐酸、硫酸-双氧水和电化学浸出3种回收方法进行分析讨论。使用SimaPro 9软件对回收过程进行生命周期评价,得到全球变暖潜能值、非生物资源耗竭潜能值和资源消耗量等,结果表明酸用量和能量消耗为主要的环境影响因素;并对回收再利用过程（包括预处理、浸出、再制备）进行经济性分析,得到相应的收益情况。结果表明,目前回收成本较高,整体呈现亏损状态。基于此,提出了相应的优化建议。     

A green approach for cohesive recycling and regeneration of electrode active materials from spent lithium-ion batteries

The implementation of the green energy transition by reducing reliance on fossil fuels has fueled the burgeoning demand for lithium-ion batteries in grid-level energy storage systems and electric vehicles. The growth of portable electronic devices has also contributed to this exponential demand, creating both logistical and environmental challenges in the supply of raw materials such as lithium and the management of end-of-life batteries. Current recycling methods for spent batteries are both energy-intensive and inefficient. To address these issues, a green approach using organic acid mixtures has been proposed to reclaim lithium from spent cathodes and recover and purify graphite from spent anodes, while also regenerating its structure. The effectiveness of this method is demonstrated through the use of organic acid mixtures to leach and reclaim lithium from NCM 622 batteries. On the anode side, a curing–leaching strategy using organic acids is employed to purify spent graphite, which is subsequently calcined to enhance its interlayer structure conducive to better intercalation of Li⁺ and improve electrochemical performance. Additionally, recovered graphite is tailored with carbon using water bath carbonization to repair structural defects caused by lithium intercalation and improve electrochemical performance while augmenting the regenerated graphite's quality, equipping it to be reused in batteries or upcycled applications.     

采用盐酸溶液从废旧锂离子电池正极还原浸取钴

采用盐酸和双氧水体系为浸取液对废旧锂离子电池正极进行还原处理。正交实验表明,影响Co2+浸出率几种因素强度顺序为:HC l浓度>固液比>H2O2-HCl体积比>反应温度>反应时间。最佳浸取条件为:HCl浓度为3 mol/L,H2O2-HCl体积比为1∶15,反应时间90 min,反应温度80℃,固-液比(g/mL)为1∶50。此时,Co2+浸出率达到99.6%。     

Direct regeneration of LiNi0.5Co0.2Mn0.3O2 cathode material from spent lithium-ion batteries

At present, metal ions from spent lithium-ion batteries are mostly recovered by the acid leaching procedure, which unavoidably introduces potential pollutants to the environment. Therefore, it is necessary to develop more direct and effective green recycling methods. In this research, a method for the direct regeneration of anode materials is reported, which includes the particles size reduction of recovered raw materials by jet milling and ball milling, followed by calcination at high temperature after lithium supplementation. The regenerated LiNi_0.5Co_0.2Mn_0.3O₂ single-crystal cathode material possessed a relatively ideal layered structure and a complete surface morphology when the lithium content was n(Ni + Co + Mn):n(Li) = 1:1.10 at a sintering temperature of 920 ℃, and a sintering time of 12 h. The first discharge specific capacity was 154.87 mA·h·g^-1 between 2.75 V and 4.2 V, with a capacity retention rate of 90% after 100 cycles.     

废锂离子电池负极活性材料的分析测试

目前关于废锂离子电池资源化的研究主要集中在正极贵金属和负极铜材料的分离回收和精制方面,但对负极活性材料的资源化研究很少。本文采用XRD、SEM、GC-MS、ICP-AES等检测手段对废锂离子电池负极活性材料中石墨的结构、有机物的种类以及Li、Gu等金属的含量进行测试分析。结果显示,其主要组分石墨的本体结构基本无变化,仍保持完整的层状结构,但是其中含有一定量的有机物质,如有机电解质及增塑剂等。经过提纯,可以将其作为石墨原料进行资源化再利用;此外,稀有金属Li含量较高,为31.03 mg/g,分离回收的价值较高。     

采用湿法技术从废旧锂离子电池中回收有价金属

采取湿法回收技术对废旧锂离子电池进行处理,研究了回收铝、钴、锂金属元素的工艺条件.在90℃时,用10%NaOH浸出铝,其浸出率达到96%.在温度90℃、4mol·L-1H2SO4、固-液比1:8、反应时间100min的浸出条件下,钴、锂浸出率为92%.利用NaHCO3和Na2CO3,为沉淀剂,从酸浸出液分别制备得到Co...     

High performance MnO2 nanoflower supercapacitor electrode by electrochemical recycling of spent batteries

MnO₂ nanoflower is prepared by electrochemical conversion of Mn₃O₄ obtained by heat treatment of spent zinc‒carbon batteries cathode powder. The heat treated and converted powders were characterized by TGA, XRD, FTIR, FESEM and TEM techniques. XRD analyses show formation of Mn₃O₄ and MnO₂ phases for the heat treated and converted powders, respectively. FESEM images indicate the formation of porous nanoflower structure of MnO_2, while, condensed aggregated particles are obtained for Mn₃O₄. The energy band gap of MnO₂ is obtained from UV‒Vis spectra to be 2.4 eV. The electrochemical properties are investigated using cyclic voltammetry, galvanostatic charge‒discharge and electrochemical impedance techniques using three-electrode system. The specific capacitance of MnO₂ nanoflower (309 F g⁻¹ at 0.1 A g⁻¹) is around six times higher than those obtained from the heat treated one (54 F g⁻¹ at 0.1 A g⁻¹). Moreover, it has high capacitance retention up to 93% over 1650 cycles. Impedance spectra of MnO₂ nanoflower show very small resistances and high electrochemical active surface area (340 m² g⁻¹). The present work demonstrates a novel electrochemical approach to recycle spent zinc-carbon batteries into high value supercapacitor electrode.     

退役锂离子电池中有价金属回收研究进展

锂离子电池被广泛应用于电子产品、电动汽车和大规模储能材料等多个领域。随着电动车市场的快速发展,其使用量还将显著增加,随之产生数量极大的退役锂离子电池。退役锂离子电池的回收利用可以避免环境污染和资源浪费,尤其对实现锂资源供需平衡具有重要意义。综述了退役锂离子电池中有价金属元素回收技术研究现状,探讨了该领域未来发展方向。电池安全高效拆解技术与装备、有价元素整体化回收技术、电极材料再制备工艺以及避免二次污染环境是未来退役锂离子电池循环利用领域值得关注的重点。     

锂/钠离子电池过渡金属氟磷酸盐正极材料研究进展

便携式电子产品、电动汽车和储能领域的快速发展对电池能量密度的要求越来越高,正极材料是限制电池能量密度的主要因素。过渡金属氟磷酸盐（A₂MPO₄F,A=Li、Na,M=Mn、Fe、Co、Ni）是一类高比容量（~300 mA·h/g）和高能量密度（>1 000 W·h/kg）的新型正极材料。主要介绍了A₂MPO₄F的结构、合成方法与改性方面的最新进展。讨论了A₂MPO₄F所面临的主要挑战,特别是实现两电子反应所面临的困难。展望了它们的应用前景。     

退役锂离子电池电化学还原浸出及热力学研究

近年来锂离子电池的需求量快速增长,产生了大量退役锂离子电池（LIBs）。回收退役LIBs对保障中国的清洁能源安全具有重要意义。电化学浸出退役LIBs正极材料是一种绿色经济的回收方法。目前,电化学法回收退役LIBs存在浸出时间长、电流效率低、槽压高的问题。基于此,提出了一种牺牲阳极的电化学还原回收退役LIBs的方法。该方法以退役LIBs正极材料为阴极,以铜板为阳极,在盐酸体系下进行电化学浸出。在最佳条件下锂离子和钴离子的浸出率均达到99.9%、电流效率高达99.8%、槽压小于0.427 V。使用基于Eh-pH和Matlab的热力学计算方法,对电化学还原浸出体系进行了热力学研究。研究结果表明,温度升高,配合物种类增多、配位物种占比增大,有助于浸出反应平衡正向移动。     

A biomass-derived biochar-supported NiS/C anode material for lithium-ion batteries

Nickel sulfides are perfect anode materials for high-capacity and low-cost lithium-ion batteries (LIBs); however, with the shortcoming of polysulfide intermediate dissolution, volume expansion exceeding the limit during cycling also restricts their development. Herein, NiS/C composite materials are successfully anchored on chestnut shell fluff (CSF)-derived biochar by a glucose-auxiliary hydrothermal method along with an annealing treatment. The CSF biochar acts as an effective electron transmission channel for the rapid lithiation/delithiation of NiS and as a fixed sulfur carrier for inhibiting the dissolution of polysulfide. Glucose restrains the accumulation of NiS particles and then transforms into uniform amorphous carbon during annealing, which is more effective in buffering for rapid volume variation. Moreover, the CSF-NiS/C electrode exhibits a remarkable specific capacity of 1522.8 mAh g^-1 (0.1 A g^-1) and distinguished rate performance with 295 mAh g^-1 capacity (3 A g^-1), which are better than those of the pure NiS/C anode material displays. Researchers may be inspired by both of these reasonable design and synthesis strategies that are beneficial for the development of high-performance nickel-based sulfide anode materials for LIBs.     

Erosion mechanism of refractories in a pyro-processing furnace for recycling lithium-ion secondary batteries

The refractory lining in a furnace is always damaged and peels off when spent lithium-ion secondary batteries (LIB) are pyro-processed in a rotary kiln. To develop highly durable refractories and to elucidate the erosion behavior, various analyses such as scanning electron microscopy/energy dispersive X-ray spectroscopy, laser-induced breakdown spectroscopy, inductively coupled plasma atomic emission spectroscopy, ion chromatography, and X-ray diffraction were performed on the linings sampled from different sections of a refractory. Our results suggested the following mechanisms in Al₂O₃–SiO₂–CaO refractory damage during pyro-processing of spent LIB packs. First, Li₂O, P₂O₅, LiF, and HF were formed by thermal decomposition of electrolyte constituents of the lithium-ion secondary batteries. When HF reacts with SiO₂, Al₂O₃, and CaO on the surface of the refractory, each fluoride that forms vaporizes and melts. When Li₂O and P₂O₅ (as well as LiF) react with the Al₂O₃–SiO₂ refractory, an Li₂O–Al₂O₃–SiO₂–P₂O₅(-LiF) phase with a low melting point forms and penetrates into the refractory through pores, grain boundaries, and cracks, resulting in peeling off.     

Coaxial MnO/C nanotubes as anodes for lithium-ion batteries

Coaxial MnO/C nanotubes with an average diameter of about 450 nm, a wall thickness of about 150 nm, a length of 1–5 μm and a 10 nm thick carbon layer have been prepared using β-MnO₂ nanotubes as self-templates in acetylene at 600 °C. The microstructure of the product has been characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, and Raman spectroscopy. The electrochemical performance of the product has been evaluated by galvanostatic charge/discharge cycling. It is found that the product exhibits a reversible capacity of nearly 500 mAh g⁻¹ at a current density of 188.9 mA g⁻¹, and 83.9% of capacity retention, higher than bare MnO nanotubes (58.2%) and MnO nanoparticles (25.8%). The results reveal that coaxial MnO/C nanotubes would be a promising anode material for next-generation lithium-ion batteries.     

锂离子电池二硫化钼基负极材料研究进展

锂离子电池以其便携、无记忆效应、循环寿命长等特点广泛应用于移动电子设备、电动汽车等领域。负极材料的改进是制备新型高性能锂离子电池的重要环节。具有类石墨烯结构的二硫化钼是极具发展潜力的锂离子电池用负极材料。但纯二硫化钼导电性差、充放电过程中体积膨胀率高,导致其可逆容量低、容量保持率差。复合化与纳米化是解决上述问题的有效途径。综述了近年来用于锂离子电池负极材料的二硫化钼基复合材料研究进展,重点介绍了二硫化钼/碳和二硫化钼/过渡金属化合物体系的形貌特征、比容量、循环稳定性等,并对二硫化钼基负极材料的发展趋势进行了展望。     

废锂离子电池正极材料中锂元素选择性回收的研究进展

随着新能源汽车市场的蓬勃发展,锂离子电池作为新能源汽车的关键部件,面临着关键金属资源尤其是锂资源供给不足的风险,回收废锂离子电池中所含的二次锂资源将成为解决锂资源供需问题、推动行业可持续发展的重要途经。因此为实现废锂离子电池中锂元素的高效提取,分步或优先提取的选择性提锂工艺备受研究者们关注。本文介绍了火法、湿法、机械化学法和电化学法四种当前主流的选择性提锂工艺,在阐述其基础反应机理的基础上,总结归纳了各工艺最新的研究成果,并从提取过程中的工艺能耗、物耗、回收率、选择性、环境影响等多个角度对各工艺的优势和不足进行了深入分析。最后,对废锂离子电池中有价金属资源化回收的发展趋势及前景进行了展望,为未来研发更加清洁高效的回收工艺提供参考。     

On the electrochemical performance of anthracite-based graphite materials as anodes in lithium-ion batteries

The electrochemical performance as potential negative electrode in lithium-ion batteries of graphite materials that were prepared from two Spanish anthracites of different characteristics by heat treatment in the temperature interval 2400-2800 °C are investigated by galvanostatic cycling. The interlayer spacing, d₀₀₂, and crystallite sizes along the c axis, L_c, and the a axis, L_a, calculated from X-ray diffractometry (XRD) as well as the relative intensity of the Raman D-band, I_D/I_t, are used to assess the degree of structural order of the graphite materials. The galvanostatic cycling are carried out in the 2.1-0.003 V potential range at a constant current and C/10 rate during 50 cycles versus Li/Li⁺. Larger reversible lithium storage capacities are obtained from those anthracite-based graphite materials with higher structural order and crystal orientation. Reasonably good linear correlations were attained between the electrode reversible charge and the materials XRD and Raman crystal parameters. The graphite materials prepared show excellent cyclability as well as low irreversible charge; the reversible capacity being up to ∼250 mA h g⁻¹. From this study, the utilization of anthracite-based graphite materials as negative electrode in lithium-ion batteries appears feasible. Nevertheless, additional work should be done to improve the structural order of the graphite materials prepared and therefore, the reversible capacity.     

Synthesis of MnOx/reduced graphene oxide nanocomposite as an anode electrode for lithium-ion batteries

We report the high performance of the manganese oxide/reduced graphene oxide (MnOx/rGO) nanocomposite as an anode electrode of a lithium-ion battery. The composite is synthesized by a low temperature (83 °C) chemical solution reaction, and shows relatively high specific capacities (660 mAh g⁻¹) after 50 cycles. For MnOx/rGO composites, the cycling stability is increased remarkably as compared to that seen with individual MnOx, and this is due to the synergistic effects of both the components in the composite. The rGO acts as a conductive buffer layer that suppresses the volume change of MnOx, and simultaneously promotes the conductivity of MnOx. The functional groups of graphene oxide facilitate MnOx formation at low temperature, and this retains the MnOx-graphene oxide connection, thus improving the capacity and cycling stability.     

Hematite nanoflakes as anode electrode materials for rechargeable lithium-ion batteries

Hematite (α-Fe₂O₃) nanoflakes and nanocubes were synthesized by liquid-solid-solution method and their properties as anode electrode materials for rechargeable Li⁺-ion batteries were measured. When changing the water to ethanol volume ratio in the synthesis system, the nanocrystals can be changed from α-Fe₂O₃ to α-FeOOH, with shapes being tuned from nanoflakes to nanocubes, non-uniform particles and nanowires. When assembled as the anode electrode materials in rechargeable Li⁺-ion batteries, the hematite nanoflakes showed one more plateau in the first discharge progress of the voltage-composition curves than hematite nanocrystals with other shapes in the literature. X-ray diffraction, high-resolution transmission electron microscope and electrochemical data showed that this extra plateau came from the formation of Li₂Fe₃O₄ nanoclusters and amorphous Li₂O. This experiment showed that like sizes, shapes of nanocrystals may also affect the detailed electrochemical progress.