Preferentially selective extraction of lithium from spent LiCoO_(2)cathodes by medium-temperature carbon reduction roasting

Lithium recovery from spent lithium-ion batteries(LIBs)have attracted extensive attention due to the skyrocketing price of lithium.The medium-temperature carbon reduction roasting was proposed to preferential selective extraction of lithium from spent Li-CoO_(2)(LCO)cathodes to overcome the incomplete recovery and loss of lithium during the recycling process.The LCO layered structure was destroyed and lithium was completely converted into water-soluble Li2CO_(3)under a suitable temperature to control the reduced state of the cobalt oxide.The Co metal agglomerates generated during medium-temperature carbon reduction roasting were broken by wet grinding and ultrasonic crushing to release the entrained lithium.The results showed that 99.10%of the whole lithium could be recovered as Li2CO_(3)with a purity of 99.55%.This work provided a new perspective on the preferentially selective extraction of lithium from spent lithium batteries.

Direct Regeneration of Spent Lithium-Ion Battery Cathodes:From Theoretical Study to Production Practice

Direct regeneration method has been widely concerned by researchers in the field of battery recycling because of its advantages of in situ regeneration,short process and less pollutant emission.In this review,we firstly analyze the primary causes for the failure of three representative battery cathodes(lithium iron phosphate,layered lithium transition metal oxide and lithium cobalt oxide),targeting at illustrating their underlying regeneration mecha-nism and applicability.Efficient stripping of material from the collector to obtain pure cathode material has become a first challenge in recycling,for which we report several pretreatment methods currently available for subsequent regeneration processes.We review and discuss emphatically the research progress of five direct regeneration methods,including solid-state sintering,hydrothermal,eutectic molten salt,electrochemical and chemical lithiation methods.Finally,the application of direct regeneration technology in production practice is introduced,the problems exposed at the early stage of the industrialization of direct regeneration technol-ogy are revealed,and the prospect of future large-scale commercial production is proposed.It is hoped that this review will give readers a comprehensive and basic understanding of direct regeneration methods for used lithium-ion batteries and promote the industrial application of direct regeneration technology.

Preparation of lithium-ion battery anode materials from graphitized spent carbon cathode derived from aluminum electrolysis

Graphitized spent carbon cathode(SCC)is a hazardous solid waste generated in the aluminum electrolysis process.In this study,a flotation-acid leaching process is proposed for the purification of graphitized SCC,and the use of the purified SCC as an anode material for lithium-ion batteries is explored.The flotation and acid leaching processes were separately optimized through one-way experiments.The maximum SCC carbon content(93wt%)was achieved at a 90%proportion of−200-mesh flotation particle size,a slurry concentration of 10wt%,a rotation speed of 1600 r/min,and an inflatable capacity of 0.2 m^(3)/h(referred to as FSCC).In the subsequent acid leaching process,the SCC carbon content reached 99.58wt%at a leaching concentration of 5 mol/L,a leaching time of 100 min,a leaching temperature of 85°C,and an HCl/FSCC volume ratio of 5:1.The purified graphitized SCC(referred to as FSCC-CL)was utilized as an anode material,and it exhibited an initial capacity of 348.2 mAh/g at 0.1 C and a reversible capacity of 347.8 mAh/g after 100 cycles.Moreover,compared with commercial graphite,FSCC-CL exhibited better reversibility and cycle stability.Thus,purified SCC is an important candidate for anode material,and the flotation-acid leaching purification method is suitable for the resourceful recycling of SCC.

Oxidative exfoliation of spent cathode carbon:A two-in-one strategy for its decontamination and high-valued application

Spent cathode carbon(SCC)from aluminum electrolysis is a potential graphite resource.However,full use of the SCC remains a challenge,since it contains many hazardous substances(e.g.,fluoride salts,cyanides),encapsulated within the thick carbon layers and thus posing serious environmental concerns.This work presents a chemical oxidative exfoliation route to achieve the recycling of SCC and the decontaminated SCC with high-valued graphene oxide(GO)-like carbon structures(SCC-GO)is applied as an excellent adsorbent for organic pollutants.Specifically,after the oxidative exfoliation,the embedded hazardous constituents are fully exposed,facilitating their subsequent removal by aqueous leaching.Moreover,benefiting from the enhanced specific surface areas along with abundant O-containing functional groups,the as-produced SCC-GO,shows an adsorption capacity as high as 347 mg·g^(-1)when considering methylene blue as a pollutant model,which exceeds most of the recently reported carbon-based adsorbents.Our study provides a feasible solution for the efficient recycling of hazardous carbonaceous wastes.

Regeneration of spent LiFePO4 as a high-performance cathode material by a simultaneous coating and doping strategy

With the number of decommissioned electric vehicles increasing annually,a large amount of discarded power battery cathode material is in urgent need of treatment.However,common leaching methods for recovering metal salts are economically inefficient and polluting.Meanwhile,the recycled material obtained by lithium remediation alone has limited performance in cycling stability.Herein,a short method of solid-phase reduction is developed to recover spent LiFePO4 by simultaneously introducing Mg2+ions for hetero-atom doping.Issues of particle agglomeration,carbon layer breakage,lithium loss,and Fe3+defects in spent LiFePO4 are also addressed.Results show that Mg2+addition during regeneration can remarkably enhance the crystal structure stability and improve the Li+diffusion coefficient.The regenerated LiFePO4 exhibits significantly improved electrochemical performance with a specific discharge capacity of 143.2 mAh·g^(−1)at 0.2 C,and its capacity retention is extremely increased from 37.9%to 98.5%over 200 cycles at 1 C.Especially,its discharge capacity can reach 95.5 mAh·g^(−1)at 10 C,which is higher than that of spent LiFePO4(55.9 mAh·g^(−1)).All these results show that the proposed regeneration strategy of simultaneous carbon coating and Mg2+doping is suitable for the efficient treatment of spent LiFePO4.

Regeneration of Al-doped LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) cathode material by simulated hydrometallurgy leachate of spent lithium-ion batteries

A uniform Al-doped LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) cathode material was prepared using a coprecipitation method to take advantage of the positive effect of Al on regenerated NCM(Ni,Co,Mn)cathode materials and ameliorate cumbersome and high-cost impurity removal processes during lithium-ion battery recycling.When the Al^(3+) content in the leachate was 1 at.%with respect to the total amount of transition metals(Ni,Co,and Mn),the produced Al-doped NCM cathode material increased concentrations of lattice oxygen and Ni^(2+).The initial specific capacity at 0.1C was 167.4 mA·h/g,with a capacity retention of 79.1%after 400 cycles at 1C.Further,this Al-doped sample showed improved rate performance and a smaller electrochemical impedance.These findings provide a reference for developing industrial processes to resynthesize cathode materials with improved electrochemical performance by incorporating Al^(3+) impurities produced during lithium-ion battery recycling.

Removal of nickel from spent electroless nickel-plating bath with nickel foam cathode

The electrochemical method was used to remove nickel ion from spent electroless nickel plating bath (pH=5 3). An electrolytic cell was composed of a porous nickel foam cathode and an inert RuO 2/Ti anode. Nickel ions were reduced and deposited on the surface of the nickel foam cathode. The effect of current density (i), linear velocity of wastewater(v), gap between cathode and anode(d C/A) and reaction time(t) on nickel removal rate and current efficiency were studied. As reaction time prolonged, nickel removal rate increased while current efficiency decreased. And larger v and smaller d C/A can enhance nickel removal rate and increase current efficiency by promoting mass transfer and dropping concentration polarization. The effect of current density on nickel removal by electrochemistry was related to other parameters. After three hours’ electrolysis with i=1 0 A/dm2, v=18 5 cm/min and d C/A=0 5 cm, nickel removal rate and current efficiency reached 85 6% and 29 1%, respectively.

An environmentally benign and sustainable process for carbon recovery and efficient defluorination of spent carbon cathode

A systematic and green low-temperature sulfation roasting−water leaching strategy was put forward to achieve a very high fluorine removal rate of 97.82%for spent carbon cathode(SCC),which was believed as a hazardous solid waste.And the carbon could be recycled with a purity of 90.29 wt.%in the flaky microstructure.Thermodynamic analysis and the results of SEM,XRD and EDS indicate that most of the fluoride could convert into water-soluble sulfate at low temperature.And the highest fluorine removal rate could be obtained when<0.15 mm SCC particles were mixed with sulfuric acid at a liquid-to-solid ratio of 1:1,and then roasted at 300℃ for 0.5 h.The sulfate was removed to purify the carbon via water-leaching process.Avrami exponents and corresponding activation energy for the roasting and leaching process demonstrated that both processes are controlled by diffusion.

Direct regeneration of LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) 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_(0.5)Co_(0.2)Mn_(0.3)O_(2) 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 0 C,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.

Preparation of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 cathode materials from spent Li-ion batteries

A recycling process including separation of electrode materials by ultrasonic treatment,acid leaching,Fe-removing,precipitation of cobalt,nickel,manganese and lithium has been applied successfully to recycle spent lithium-ion batteries and to synthesize LiNi1/3Co1/3Mn1/3O2. When ultrasonic treatment with 2-nitroso-4-methylphenol(NMP) at 40 ℃ for 15 min,the electrode materials are separated completely. Above 99% of Co,Ni,Mn and Li,95% of Fe in the separated electrodes are acid-leached in the optimized conditions of 2 mol/L H2SO4,1∶2 H2O2-H2SO4(molar ratio),70 ℃,1∶10 initial S∶L ratio,and 1 h. 99.5% of Fe and less than 1% of Co,Ni,Mn in the leaching solution can be removed in the conditions of initial pH value 2.0-2.5 adjusted by adding 18% Na2CO3,90 ℃ and stirring time 3 h. After adjusted to be equal by adding NiSO4,CoSO4 and MnSO4 solution,97.1% of Ni,Co,Mn in the Fe-removing surplus leaching solution can be recovered as Ni1/3Co1/3Mn1/3(OH)2. 94.5% of Li in the surplus filtrate after the deposition of Co,Ni and Mn can be recovered as Li2CO3. The LiNi1/3Co1/3Mn1/3O2,prepared from the recovered compounds,is found to have good characteristics of the layered structure and elecrtochemical performance.

Hydrometallurgical recovery of lithium carbonate and iron phosphate from blended cathode materials of spent lithium-ion battery

The recycling of cathode materials from spent lithium-ion battery has attracted extensive attention,but few research have focused on spent blended cathode materials.In reality,the blended materials of lithium iron phosphate and ternary are widely used in electric vehicles,so it is critical to design an effective recycling technique.In this study,an efficient method for recovering Li and Fe from the blended cathode materials of spent LiFePO_(4)and LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)batteries is proposed.First,87%A1 was removed by alkali leaching.Then,91.65%Li,72.08%Ni,64.6%Co and 71.66%Mn were further separated by selective leaching with H_(2)SO_(4)and H_(2)O_(2).Li,Ni,Co and Mn in solution were recovered in the form of Li_(2)CO_(3)and hydroxide respectively.Subsequently,98.38%Fe was leached from the residue by two stage process,and it is recovered as FePO_(4)·2H_(2)O with a purity of 99.5%by precipitation.Fe and P were present in FePO_(4)·2H_(2)O in amounts of 28.34%and 15.98%,respectively.Additionally,the drift and control of various components were discussed,and cost-benefit analysis was used to assess the feasibility of potential application.

Converting intercalation-type cathode in spent lithium-ion batteries into conversion-type cathode

The widespread applications of lithium-ion batteries(LIBs)generate tons of spent LIBs.Therefore,recycling LIBs is of paramount importance in protecting the environment and saving the resources.Current commercialized LIBs mostly adopt layered oxides such as LiCoO_(2)(LCO)or LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)(NMC)as the cathode materials.Converting the intercalation-type spent oxides into conversion-type cathodes(such as metal fluorides(MFs))offers a valid recycling strategy and provides substantially improved energy densities for LIBs.Herein,two typical Co-based cathodes,LCO and LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(NMC622),in spent LIBs were successfully converted to CoF_(2) and(Ni_(x)Co_(y)Mn_(z))F_(2) cathodes by a reduction and fluorination technique.The as converted CoF_(2) and(Ni_(x)Co_(y)Mn_(z))F_(2) delivered cell energy densities of 650 and 700 Wh/kg,respectively.Advanced atomic-level electron microscopy revealed that the used LCO and NMC622 were converted to highly phase pure Co metal and Ni_(0.6)Co_(0.2)Mn_(0.2) alloys in the used graphite-assisted reduction roasting,simultaneously producing the important product of Li_(2)CO_(3) using only environment friendly solvent.Our study provided a versatile strategy to convert the intercalation-type Co-based cathode in the spent LIBs into conversion-type MFs cathodes,which offers a new avenue to recycle the spent LIBs and substantially increase the energy densities of next generation LIBs.

Recent advancements in hydrometallurgical recycling technologies of spent lithium-ion battery cathode materials

The rapidly increasing production of lithium-ion batteries(LIBs)and their limited service time increases the number of spent LIBs,eventually causing serious environmental issues and resource wastage.From the perspectives of clean production and the development of the LIB industry,the effective recovery and recycling of spent LIBs require urgent solutions.This study provides an overview of the current hydrometallurgical processes employed in the recycling of spent cathode materials,focusing on the leaching of valuable metals and their postprocessing.In particular,this research reviews the various leaching systems(inorganic acid,organic acid,and ammonia)and the separation of valuable metals,and then,recommendations for subsequent study are offered in an attempt to contribute to the development of highly efficient methods for recycling spent cathode materials.In addition,a range of existing technologies,such as solvent extraction,chemical precipitation,electrochemical deposition,and regeneration,for the postprocessing of leaching solutions are summarized.Finally,the promising technologies,existing challenges and suggestions with respect to the development of effective and environmentally friendly recycling methods for handling spent cathode materials are identified.

A Sustainable Strategy for Spent Cathode Carbon Blocks Hazardous Waste Recycling Using Binary Molten Salt Thermal Treatment

Waste-to-Energy treatment is a promising path to environment and energy management in the future.This work detailed a binary molten salt thermal treatment methodology for the detoxification of spent cathode carbon block(SCCB)waste and the recycling of carbonaceous materials.The thermal behavior of SCCB and SCCB blended with molten salts was investigated.It was found that the NaCl-Na_(2)CO_(3)binary molten salts significantly contributed to reducing pyrolysis onset temperature by 334.3 K compared to that of SCCB itself(i.e.,activation energy of pyrolysis reaction was reduced from 4.24×10^(5)to 2.30×10^(5)J/mol),thus helping to lower thermal treatment energy consumption.With the addition of binary molten salts,the residue after thermal treatment in a horizontal tube furnace experiment was separated into two layers.The bottom-layer residue was mainly composed of molten salts.The fluorine content in the form of NaF and CaF_(2)of top-layer residue was reduced significantly while the carbon content remained unchanged.Specifically,the leaching concentration of fluoride ion was decreased from 4620 mg/L to 856 mg/L.It is noted that the NaF and CaF_(2)can be removed through water-leaching and hydrothermal acid-leaching methods and thus the carbonaceous materials with a calorific value of 17.5 MJ/kg were obtained.

A closed-loop process for recycling LiNi_xCo_yMn_((1-x-y))O_2 from mixed cathode materials of lithium-ion batteries

With the rapid development of consumer electronics and electric vehicles(EV), a large number of spent lithium-ion batteries(LIBs) have been generated worldwide. Thus, effective recycling technologies to recapture a significant amount of valuable metals contained in spent LIBs are highly desirable to prevent the environmental pollution and resource depletion. In this work, a novel recycling technology to regenerate a LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 cathode material from spent LIBs with different cathode chemistries has been developed. By dismantling, crushing,leaching and impurity removing, the LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2(selected as an example of LiNi_xCo_yMn_(1-x-y)O_2) powder can be directly prepared from the purified leaching solution via co-precipitation followed by solid-state synthesis. For comparison purposes, a fresh-synthesized sample with the same composition has also been prepared using the commercial raw materials via the same method. X-ray diffraction(XRD), scanning electron microscopy(SEM) and electrochemical measurements have been carried out to characterize these samples. The electrochemical test result suggests that the re-synthesized sample delivers cycle performance and low rate capability which are comparable to those of the freshsynthesized sample. This novel recycling technique can be of great value to the regeneration of a pure and marketable LiNi_xCo_yMn_(1-x-y)O_2 cathode material with low secondary pollution.

废旧锂电池电极材料浮选行为及表面性质

锂离子电池中含有丰富的金属元素和多种毒害性物质,废旧锂电池回收不仅能实现资源循环利用,而且能防止环境污染.本文以废旧动力锰酸锂电池为研究对象,利用“焙烧强化浮选”的方法解决锰酸锂电池资源化回收过程中正负极电极材料难以浮选分离的问题,即通过焙烧去除电极材料表面的有机粘附物,从而增大电极材料表面润湿性差异,进而强化浮选分离过程.结果表明,商品化锰酸锂和商品化石墨具有相反的浮选行为,而废旧锰酸锂和废旧石墨具有相似的疏水性浮选行为.废旧锰酸锂电极材料浮选分离时,锰酸锂和石墨浮选分离效率低,而商品化锰酸锂和石墨的浮选分离效率高.XRD、XPS、SEM、FT-IR及接触角分析表明,废旧锂电池电极材料表面均包裹一层含C、O、F等元素的有机物,导致正负极电极材料具有相似的表面性质,因而表现出相似的浮选行为,导致两者的浮选分离难度大.不同焙烧参数下电极材料的浮选分离试验结果表明,550℃焙烧2 h后锰酸锂和石墨的浮选分离效率明显优于未焙烧的电极材料.此时,浮选精矿中锰酸锂的品位由未焙烧的63.10%提高到90.98%;小型闭路浮选精矿中石墨残留量少,锰酸锂的纯度达到99%.

橙皮还原浸出废旧锂电池正极材料有价金属

为了促进废旧锂电池的高效环保浸出,研究了一种利用橙皮作为有机还原剂,高效浸出废旧锂电池正极材料中金属的方法。结果表明:橙皮的添加显著提高了柠檬酸浸出剂的性能,实现了锂、镍、钴和锰的高浸出率,最佳浸出条件为柠檬酸浓度2 mol/L、橙皮用量40 g/L、浸出温度95℃、液固比20∶1、搅拌速度300 r/min、浸出时间120 min。利用Design Expert 10推导出了一个浸出模型,能精确预测金属的浸出率。动力学研究表明,锂、镍、钴和锰的表观活化能分别为64.95、67.71、66.65和72.8 kJ/mol,说明正极材料浸出过程主要受化学反应控制。通过对比OP浸出前后的SEM像,验证了橙皮还原能力可用还原糖理论进行解释。

基于过期葡萄糖酸亚铁和废锂箔制备高性能LiFePO_(4)/C正极的研究

近几年,锂离子电池的市场需求剧增,导致原材料价格暴涨。为此,分别将过期葡萄糖酸亚铁和废锂箔与H_(3)PO_(4)反应生成Fe_(3)(PO_(4))2/葡萄糖酸钠磷酸酯和Li_(3)PO_(4)粉末,然后采用磷酸铁工艺制备LiFePO_(4)/C纳米颗粒,并研究其储锂性能。研究结果表明,LiFePO_(4)/C正极在1.0C循环300圈后的可逆容量和容量保持率分别高达129.3mAh/g和97.0%,与商业LiFePO_(4)正极材料性能相当,这可能归功于纳米颗粒及碳层之间的协同效应。该研究降低了LiFePO_(4)的制备成本和环境排放。

退役LiFePO_(4)正极材料强化解离技术研究现状及展望

随着新能源汽车产业及储能领域快速发展,退役LiFePO_(4)电池的规模化综合回收已成为我国新能源领域可持续发展面临的关键挑战与迫切需求。总结了退役LiFePO_(4)电池正极材料的主要强化解离技术,包括火法冶金、湿法冶金、机械化学、电化学冶金等的原理、优缺点及研究应用现状,进一步阐述了强化解离技术在提高有价组分回收效率、降低成本和减少环境影响方面的创新进展,并对未来发展趋势进行了展望。

铝电解大修渣废旧阴极炭的处理技术研究现状及展望

铝电解槽大修渣废旧阴极炭的无害化处理和资源化利用是电解铝行业实现绿色可持续发展的瓶颈所在。介绍了铝电解废阴极炭中的有毒组分及有毒元素的迁移规律,重点总结了高温火法、液相浸出法和协同处理法的原理、研究现状及优缺点,并对未来发展趋势进行了展望。