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Considering the high cost of cobalt, cobalt‐free lithium nickel oxide (LiNiO2), which has an extremely high theoretical specific capacity, has become attractive. However, its application is hampered by continuous irreversible phase changes, unstable interfaces, and particle pulverization. Herein, an ≈35 nm‐thick selenium (Se) coating is applied to modify LiNiO2 using a combination of solid‐phase mixing and low‐temperature sintering. After 300 cycles, the selenium‐coated LiNiO2 (Se–LNO) cathode exhibits unusually high capacity retention of 82.09% at a charge cutoff voltage of 4.3 V. Furthermore, the coating modification improves the rate performance of the cathode materials, which exhibit considerable specific capacities of 168.7 and 149.6 mAh g−1 at current densities of 2 and 5 C, respectively. The significantly enhanced electrochemical performance can be attributed to the ability of the Se coating to enhance the structural stability of the cathode materials by suppressing phase transitions, stabilizing the interface, enhancing the kinetic behavior of the electrode, and reducing particle pulverization. According to the findings of this study, manipulating the Se coating in cathodes may provide a viable path for lower‐cost and higher‐energy‐density Co‐free lithium‐ion batteries. [ABSTRACT FROM AUTHOR]

Global low-carbon contracts, along with the energy and environmental crises, have encouraged the rapid development of the power battery industry. As the current first choice for power batteries, lithium-ion batteries have overwhelming advantages. However, the explosive growth of the demand for power lithium-ion batteries will likely cause crises such as resource shortages and supply–demand imbalances. This study adopts qualitative and quantitative research methods to comprehensively evaluate the power lithium-ion battery supply and demand risks by analyzing the global material flow of these batteries. The results show that the processes from resources to market of the power lithium-ion battery industry are highly concentrated with growing trends. The proportion of the top three power lithium-ion battery-producing countries grew from 71.79% in 2016 to 92.22% in 2020, increasing by 28%. The top three power lithium-ion battery-demand countries accounted for 83.07% of the demand in 2016 and 88.16% in 2020. The increasing concentration increases the severity of the supply risk. The results also imply that different processes are concentrated within different countries or regions, and the segmentation puts the development of the power lithium-ion battery industry at significant risk. It is urgent to address this situation so that this severe risk can be ameliorated. [ABSTRACT FROM AUTHOR]

A novel method for the recovery of Li from cathode material of waste ternary lithium-ion batteries is proposed, wherein water-based leaching of the reduction roasting product was conducted. First, the effects of leaching temperature, leaching time, liquid–solid ratio, and CO2 aeration rate on the recovery of Li were investigated, demonstrating that the leaching rate of Li can reach 79.95% under optimal conditions, i.e., a CO2 aeration rate of 200 mL/min, leaching time of 1.5 h, and liquid–solid ratio of 15:1, at 15°C. The leaching time and CO2 aeration rate had little impact, while the liquid–solid ratio and temperature were found to significantly affect the leaching rate of Li. Then, counter-current leaching experiments were carried out, and the total leaching rate of Li exceeded 98% after four stages with a liquid-to-solid ratio of 15:1. Battery-grade purity of the lithium carbonate product was obtained by evaporative crystallization. [ABSTRACT FROM AUTHOR]

Designing particles with a unique structure to accommodate volume variations on cycling is an effective strategy to improve the electrochemical performance of metal oxide anode materials for lithium-ion batteries (LIBs). Here, dandelion-like Co3O4 was prepared by a hydrothermal method following heat treatment. In a similar preparation method, by adding a structural modifier, i.e., sodium citrate, the dandelion-like Co3O4 could be transformed into multi-shelled hollow Co3O4 microspheres. These two different Co3O4 morphologies show different electrochemical behaviors as anode materials for LIBs. The multi-shelled hollow Co3O4 exhibited the better electrochemical performance. At a current density of 200 mA g−1, the reversible capacity after 200 cycles reached 1132 mAh g−1. Even at a very high current density, i.e., 1000 mA g−1, the reversible capacity was as high as 936 mAh g−1 after 300 cycles. Such an excellent electrochemical performance is mainly attributed to the multi-shelled hollow structure that can alleviate the volume variation during lithiation/delithiation; this further helps enhance the structural and cycling stability. It also proves that the electrochemical performance of the material can be enhanced by morphological modification. [ABSTRACT FROM AUTHOR]

Consumer electronics (CE) and electric vehicles (EVs) associated with renewable and sustainable energy have been rapidly changing human lifestyles and transportation habits since 1990s. These active innovations have resulted in a large amount of spent lithium-ion batteries (LiBs) in China. At least two problems are declining the sustainability of production and final disposal of LiBs: one is potential environmental and health risk, and the other is that more and more valuable resources are being stored in spent LiBs without appropriate recycling. We found that a lack of effective regulation, collection systems and recycling technologies are major barriers and challenges to solve the problems. And in order to develop a comprehensive management scheme for this waste stream in China, we proposed a three-pronged approach: (1) new regulation or policy is quite a necessity to deal with the challenges unique to spent LiBs recycling; (2) collection systems for CE and EV batteries can be substantially established based upon past experience of general e-waste management and extended producer responsibility, respectively; and (3) more emphasis needs to be placed on new technology for spent LiBs recycling, to tackle the large quantities of stored spent LiBs. [ABSTRACT FROM AUTHOR]

With the booming of consumer electronics (CE) and electric vehicle (EV), a large number of spent lithium-ion battery (LIBs) have been generated worldwide. Resource depletion and environmental concern driven from the sustainable industry of CE and EV have motivated spent LIBs should be recovered urgently. However, the conventional process combined with leaching, precipitating, and filtering was quite complicated to recover cobalt and lithium from spent LIBs. In this work, we developed a novel recovery process, only combined with oxalic acid leaching and filtering. When the optimal parameters for leaching process is controlled at 150 min retention time, 95 °C heating temperature, 15 g L −1 solid–liquid ratio, and 400 rpm rotation rate, the recovery rate of lithium and cobalt from spent LIBs can reach about 98% and 97%, respectively. Additionally, we also tentatively discovered the leaching mechanism of lithium cobalt oxide (LiCoO 2 ) using oxalic acid, and the leaching order of the sampling LiCoO 2 of spent LIBs. All the obtained results can contribute to a short-cut and high-efficiency process of spent LIBs recycling toward a sound closed-loop cycle. [ABSTRACT FROM AUTHOR]

Lithium-ion battery (LIB) applications in consumer electronics and electric vehicles are rapidly growing, resulting in boosting resources demand, including cobalt and lithium. So recycling of batteries will be a necessity, not only to decline the consumption of energy, but also to relieve the shortage of rare resources and eliminate the pollution of hazardous components, toward sustainable industries related to consumer electronics and electric vehicles. The authors review the current status of the recycling processes of spent LIBs, introduce the structure and components of the batteries, and summarize all available single contacts in batch mode operation, including pretreatment, secondary treatment, and deep recovery. Additionally, many problems and prospect of the current recycling processes will be presented and analyzed. It is hoped that this effort would stimulate further interest in spent LIBs recycling and in the appreciation of its benefits. [ABSTRACT FROM PUBLISHER]

Highlights: [•] Manual dismantling is superior in spent high-power LiBs recycling. [•] Heated ionic liquid can effectively separate Al and cathode materials. [•] Fourier’s law was adopted to determine the heat transfer mechanism. [•] The process of spent LiBs recycling with heated ionic liquid dismantling was proposed. [ABSTRACT FROM AUTHOR]

Abstract: This work proposes a new process of recovering Co from spent Li-ion batteries (LIBs) by a combination of crushing, ultrasonic washing, acid leaching and precipitation, in which ultrasonic washing was used for the first time as an alternative process to improve the recovery efficiency of Co and reduce energy consumption and pollution. Spent LIBs were crushed with a 12mm aperture screen, and the undersize products were put into an ultrasonic washing container to separate electrode materials from their support substrate. The washed materials were filtered through a 2mm aperture screen to get underflow products, namely recovered electrodes. Ninety two percent of the Co was transferred to the recovered electrodes where Co accounted for 28% of the mass and impurities, including Al, Fe, and Cu, accounted for 2%. The valuable materials left in 2–12mm products, including Cu, Al, and Fe, were presented as thin sheets, and could be easily separated. The recovered electrodes were leached with 4.0M HCl for 2.0h, at 80°C, along with concurrent agitation. Ninety seven percent of the Li and 99% of the Co in recovered electrodes could be dissolved. The impurities could be removed at pH 4.5–6.0 with little loss of Co by chemical precipitation. This process is feasible for recycling spent LIBs in scale-up. [Copyright &y& Elsevier]

[Display omitted] • Sn 4 P 3 /P-doped C@CNs composites were prepared by simple and environmentally friendly synthesis method. • The composites were composed of ultra-small Sn 4 P 3 and 3D P-doped porous carbon nanosheets. • The Sn 4 P 3 /P-doped C@CNs exhibited excellent electrochemical performance. • The role of P-doped CNs and ultra-small Sn 4 P 3 were investigated. Transition-metal phosphides (TMPs) with high theoretical specific capacity and appropriate reaction potential have been recognized as prospective anode materials for lithium-ion batteries (LIBs). However, the practical application is still hindered by the inferior rate capability and worse cycling stability, which is mainly arising from large volume variations and inferior electric conductivities of TMPs. Herein, ultra-small Sn 4 P 3 particles are fully embedded into three-dimensionally interconnected P-doped porous carbon nanosheets (Sn 4 P 3 /P-C@CNs), which is fabricated by a feasible and environmentally friendly synthesis strategy with phytic acid as phosphorus source. The ultra-small Sn 4 P 3 particles and the conductive P-doped 3D carbon backbone is advantage to alleviate the volume changes of Sn 4 P 3 nanoparticles, reduce side reaction with electrolyte and promote the transfer of ions/electrons, leading to a significant improvement in electrochemical performance. Consequently, the Sn 4 P 3 /P-C@CNs composite electrode delivers a high reversible capacity of 770 mA h g−1 at 0.1 A/g upon 100 cycles, and exhibits 717 mA h g−1 at 1 A/g after 1000 loops. The lithium storage mechanism is investigated by density functional theory calculations. This research could offer a sensible and facile design strategy for TMPs-based electrode materials and make it hopeful for the applications in next-generation high-energy–density LIBs. [ABSTRACT FROM AUTHOR]

In the electrodes of spent lithium-ion batteries, graphite, due to its layered structure and crystalline composition, presents significant recyclable value, yet it has not been fully utilized. This study proposes a modified mechanical exfoliation method (MEM), which employs leaching-drying pretreatment to transform waste graphite into two-dimensional graphene. Three drying methods were evaluated, among which freeze drying was found to be the most conducive for exfoliation. Pneumatic drying, being basic and simple, did not exhibit any special effects that benefit exfoliation. XRD results showed that leaching restores the lamellar structure of graphite, with peak intensity (× 105) increasing from 6.5 to 8.9–10.1. XPS analysis revealed that vacuum roasting drying leads to dehydration condensation of hydroxyl groups between layers, resulting in the obtained graphite having the best dehydration effect and the lowest oxygen content, at only 1.89%, but this enhances interlayer forces, which is counterproductive for exfoliation. In contrast, freeze drying, through the volumetric expansion caused by the freezing of water, disrupts the interlayer forces, achieving an interlayer spacing of 337.5 nm, which facilitates the exfoliation of graphene. This was confirmed by TEM results. This method effectively overcomes the problem of impurity contamination in waste graphite, providing a new approach for the high-value utilization and green recycling of graphite in spent lithium batteries. [Display omitted] • Dehydration condensation of vacuum drying results in a tighter graphite layer. • Volume expansion from water freezing can break the interlayer force of graphite. • The modified MEM can remove impurities and avoid secondary contamination. • Graphite wastes in spent LIBs can be environmentally upcycled into 2D graphene. [ABSTRACT FROM AUTHOR]

Lithium-ion battery (LIBs) applications using antimony (Sb) based anodes with high specific capacity and suitable operating voltage have showed tremendous potential. However, the large volume variation during electrochemical cycling limits their application. In this paper, M-Sb (M=Co, Ni) nanoparticles embedded in nitrogen doped carbon nanofibers have been prepared by an electrospinning method, 3D interconnected M-Sb@CN (NiSb@CN and Sb/CoSb 2 @CN) fiber composites are obtained finally. M-Sb nanoparticles are uniformly distributed in N-doped carbon nanofibers, which can prevent their direct exposure to the electrolyte. Compared with bare Sb-M and Sb-C binary electrodes, the M-Sb-C three-component composite electrodes show smaller volume change and stronger charge transport ability. The introduction of the transition metal (Co, Ni) not only serves as buffer substrate for volume change, but also regulates the properties of carbon fibers as a catalyst. High reversible capacities of 647.4 and 620.2 mA h g−1 of NiSb@CN and Sb/CoSb 2 @CN fiber composites can be maintained after 600 cycles at a current rate of 500 mA g−1. First principles calculation demonstrates that N-doping and the incorporation of transition metal M have favorable effect on the improved Li binding energy, offering a possibility for the material design of the high-performance LIBs. [ABSTRACT FROM AUTHOR]

The conventional recycling methods of spent lithium-ion batteries (LIBs) regard Al/Cu foils as impurities, which are usually removed by deep screening or alkali leaching. Deep screening refers to the process of over-screening the electrode materials by passing the crushed materials of spent LIBs through a screen with a pore size of only 0.075 mm. However, the serious hole-blocking phenomenon of deep screening and the environmental hazards of alkali leaching restrict their practical application. Herein, a combination of mild screening, reduction leaching and selective purification is proposed to achieve green and sustainable recycling of spent LIBs. Specifically, spent LIBs are subjected to discharge, crushing and mild screening to obtain fine-mixture materials under 4-mm sieving, leaving large pieces of Cu/Al foils on the screen mesh, which can be separated as crude products by color sorting. Then, dilute H 2 SO 4 is employed to dissolve the valuable elements in underflow fractions, where residual Cu/Al foils serve as reductants to assist leaching. Eventually, through multi-step precipitates and hydrothermal treatment, a series of promising products (CuO, NaAlCO 3 (OH) 2 , precursor and Li 2 CO 3) are obtained, at high quality. This route provides a clever strategy for fine management and cascade recovery of the valuable components from spent LIBs. Image 1 • The fine management and cascade recovery of Cu/Al foils are first proposed. • Thermodynamic analysis of Cu/Al foils as reducing agent was carried out. • Multi-step precipitation and hydrothermal method were used for purification. • The deep screening problem has been solved in a green and sustainable way. [ABSTRACT FROM AUTHOR]

As a renewable energy source, hydrogen production from biomass pyrolysis is one of the effective ways to promote global sustainable development. Herein, the inherent Al foils and typical LiCoO 2 cathodes in spent lithium ion batteries are jointly employed as the catalyst to reform sawdust pyrolysis gas to produce hydrogen-rich synthesis gas. It is the introduction of Al element that triggers the in-situ atomic replacement reaction to immobilize volatile lithium, thereby inducing the formation of a similar Li-CO 2 battery system, which efficiently converts CO 2 into CO. Furthermore, a new adsorption-enhanced in-situ-assembled porous structure has been discovered and proved to obtain ~95% surface vacancy oxygen content and various hydrogen evolution sites. Eventually, the yields and volume fractions of H 2 are 11.31 mmol/g and 65.79%, respectively, and the purity of syngas (H 2 +CO) reaches 91.82%, which verify its excellent performance in hydrogen reforming and CO 2 conversion. In the pyrolysis of spent Lithium-ion batteries, the inherent Al foils and LiCoO 2 undergo an atomic substitution reaction, and spontaneously form a sorption-enhanced catalytic materials, which consists of Co nanoflowers and LiAlO 2 @CoO nanoporous network. The LiAlO 2 @CoO nanoporous network can not only pre-adsorb the hydrogen-containing functional groups, but also disperse the Co nanoflowers, further enhancing the hydrogen evolution behavior of the newborn nano-transition metal. Therefore, this in-situ surface engineering makes an important contribution to the preparation of H 2 -rich syngas. [Display omitted] • Al foils and LiCoO 2 cathodes are employed to reform sawdust pyrolysis gas. • A new adsorption-enhanced in-situ-assembled porous structure is discovered. • Volatile Li is fixed to form a similar Li-CO 2 battery to convert CO 2 to CO. • The volume fractions of H 2 and syngas are 65.79% and 91.82%, respectively. [ABSTRACT FROM AUTHOR]

The rapid development of lithium-ion batteries (LIBs) in emerging markets is pouring huge reserves into, and triggering broad interest in the battery sector, as the popularity of electric vehicles (EVs)is driving the explosive growth of EV LIBs. These mounting demands are posing severe challenges to the supply of raw materials for LIBs and producing an enormous quantity of spent LIBs, bringing difficulties in the areas of resource allocation and environmental protection. This review article presents an overview of the global situation of power LIBs, aiming at different methods to treat spent power LIBs and their associated metals. We provide a critical review of power LIB supply chain, industrial development, waste treatment strategies and recycling, etc. Power LIBs will form the largest proportion of the battery industry in the next decade. The analysis of the sustainable supply of critical metal materials is emphasized, as recycling metal materials can alleviate the tight supply chain of power LIBs. The existing significant recycling practices that have been recognized as economically beneficial can promote metal closed-loop recycling. Scientific thinking needs to innovate sustainable and cost-effective recycling technologies to protect the environment because of the chemicals contained in power LIBs. [Display omitted] • The comprehensive information of power lithium-ion batteries and associated critical metal recycling was summarized. • The inductive structure of the development of the power lithium-ion battery industry including the impact factors was built. • Recycling critical metal materials can alleviate the tight supply of raw materials for manufacturing lithium-ion batteries. • The existing recycling technologies and practices can push the spent power lithium-ionbattery closed-loop recycling. [ABSTRACT FROM AUTHOR]

Utilization of acid/base or corrosive reagents is currently the preferred way to recover valuable metals from spent lithium−ion batteries (LIBs), but it is still likely to cause serious environmental risks. Herein we report an acid−free process for selective recycling of Li from cathode materials of spent LIBs, via an ionic substitution stimulated by mechanochemistry. The key innovation is that selective regeneration of Li 2 CO 3 is easily achieved with safe and low−cost NaCl and SiO 2 as mechanochemical reaction reagents, and Na 2 CO 3 as precipitation reagent, via a sustainable recycling process. The corresponding ionic substitution reaction mechanism between Li+ and Na+ was explored and verified. Based on the ionic substitution reaction induced by mechanical forces, Li+ in the α−NaFeO 2 layered structure of LiCoO 2 was first successfully replaced by Na+ from NaCl. The separation of the generated LiCl, the recovery of Li 2 CO 3 , and the regeneration of NaCl were then simultaneously achieved by a sustainable chemical precipitation process using only Na 2 CO 3 as the precipitant. The engineering applications confirmed that the designed mechanochemical approach can successfully achieve the selective recovery of Li 2 CO 3 from various cathode materials of spent LIBs in a green manner and could be therefore applied as a preceding process for spent LIBs recycling. Image 1 • Selective regeneration of Li 2 CO 3 from cathode materials of spent LIBs was proposed. • NaCl and SiO 2 were selected as the co-grinding mechanochemical reaction reagents. • Li+ in LiCoO 2 was replaced by Na+ under the induction of mechanochemical forces. • The designed approach can be applied for Li recovery from various spent LIBs. [ABSTRACT FROM AUTHOR]

• SEI film, electrolyte and binders remain on the surface of waste graphite. • Li 2 CO 3 and CuO have invaded the crystal structure of waste graphite. • Modified Hummers method can remove impurities without secondary pollution. • Graphite in spent LIBs can be prepared directly into 2D graphene oxide. The graphite electrodes of spent lithium-ion batteries (LIBs) have a good crystalline composition and layered structure, and the recovery potential is promising. However, the internal and external surfaces of the waste graphite are often polluted with various organic and inorganic impurities, which seriously restrict its high-value utilization. Herein, the microstructure and surface analysis of waste graphite at variable scales were carried out systematically to reveal the types and occurrence status of impurities and their influence on the preparation of graphene oxide (GO) using a modified Hummers method. The results show that the graphite surface contaminants are polyvinylidene fluoride binder, LiPF 6 electrolyte and LiF residue from the solid electrolyte interface, while residual lithium (Li 2 CO 3) and CuO were found to have invaded the crystal structure of graphite. Fortunately, the modified Hummers method can effectively remove these complicated associated impurities and prevent their re-contamination on the GO surface. More importantly, the modified Hummers method can not only destroy the longitudinal molecular bonds between graphite layers, but also splice them horizontally to form 2D GO, which is verified by high-resolution transmission electron microscope (HR-TEM) images. This paper provides theoretical support and practical guidance for the high-value utilization of waste graphite in spent LIBs. [ABSTRACT FROM AUTHOR]

• A low-toxicity, high-efficiency, and low-cost deep eutectic solvent was synthesized. • Choline chloride-glycerol deep eutectic solvent was applied to separate Al foil and cathode materials of spent LIBs. • The deactivation of PVDF can be attributed to an alkali degradation process of PVDF in deep eutectic solvent. The separation of cathode materials from aluminum (Al) foil is a key issue worthy of attention in the process of resource utilization of spent lithium-ion batteries (LIBs). Traditional technologies for the Al foil and cathode materials separation have the disadvantages of the use of corrosive acid/alkali, release of HF hazards, and environment and healthy risks of the toxicity reagent. In this study, a low-toxicity, high-efficiency, and low-cost deep eutectic solvent (DES), choline chloride-glycerol, was synthesized and applied to solving the separation dilemma of Al foil and cathode materials in spent LIBs. The experimental results show that separation of the Al foil and cathode materials can be achieved under optimal conditions designed by the response surface method: heating temperature 190 ℃, choline chloride: glycerol molar ratio 2.3:1, and heating time 15.0 min; the peeling percentage of cathode material can reach 99.86 wt%. Mechanism analysis results confirm that the separation of Al foil and cathode materials was the result of the deactivation of the organic binder polyvinylidene fluoride (PVDF), which can be attributed to an alkali degradation process caused by the attack of the hydroxide of choline chloride on the acidic hydrogen atom in PVDF. [ABSTRACT FROM AUTHOR]