A review on the recycling of spent lithium-ion batteries (LIBs) by the bioleaching approach.

This review discusses the latest trend in recovering valuable metals from spent lithium-ion batteries (LIBs) to meet the technological world's critical metal demands. Spent LIBs are a secondary source of valuable metals such as Li (5%-7%), Ni (5%-10%), Co (5%-25%), Mn (5-11%), and non-metal graphite. Recycling is essential for the battery industry to extract valuable critical metals from secondary sources to develop new and novel high-tech LIBs for various applications such as eco-friendly technologies, renewable energy, emission-free electric vehicles, and energy-saving lightings. LIB waste is currently undergoing high-temperature pyrometallurgical or hydrometallurgical processes to recover valuable metals, and these processes have proven to be successful and feasible. These methods, however, are not preferable due to the difficulties in controlling the process, secondary waste produced, high operational cost, and high risk of scaling up. Biotechnological approaches can be promising alternatives to pyrometallurgical and hydrometallurgical technologies in metal recovery from LIB waste. Microbiological metal dissolution or bioleaching has gained popularity for metal extraction from ores, concentrates, and recycled or residual materials in recent years. This technology is eco-friendly, safe to handle, and reduces operating costs and energy demands. The pre-treatment process (material preparation), microorganisms used in the bioleaching of LIBs, factors influencing the bioleaching process, methods of enhancing the leaching efficiency, regeneration of electrode materials, and future aspects have been discussed in detail.

Co3O4 Nanosheets as Battery-Type Electrode for High-Energy Li-Ion Capacitors: A Sustained Li-Storage via Conversion Pathway.

We report the excellent charge storage performance of high-energy Li-ion capacitors (LIC) fabricated from the mesoporous Co3O4 nanosheets as the conversion-type battery component and Jack fruit (Artocarpus heterophyllus) derived activated carbon as a supercapacitor electrode, especially at high temperatures (50 and 40 °C). Prior to the fabrication, the electrochemical prelithiation strategy was applied to Co3O4 to alleviate the irreversibility and enrich the Li-ions for electrochemical reactions (Co0 + Li2O). The LIC delivered a maximum energy density of ∼118 Wh kg-1 at a high temperature of 50 °C. The significant difference is observed at a high rate of 2.6 kW kg-1 at 50 °C with excellent cycle stability up to 3000 cycles, with a retention of ∼87% compared with the LIC cycled at room temperature (∼74%). The magnificent electrochemical performance clearly demonstrates that the mesoporous structure and residual carbon synergistically facilitated the Li+/electron transport and hinder undesirable side reactions with electrolytes to realize high-energy density at high temperatures.

Mesoporous Titanium Oxynitride Monoliths from Block Copolymer-Directed Self-Assembly of Metal-Urea Additives.

This report describes a simple one-pot soft-templating and ammonolysis-free approach to synthesize mesoporous crystalline titanium oxynitride by combining block copolymer-directed self-assembly with metal sol and urea precursors. The Pluronic F127 triblock copolymer was employed to structure-direct titanium-oxo-acetate sol nanoparticles and urea-formaldehyde into ordered hybrid mesostructured monoliths. The hybrid composites were directly converted into mesoporous crystalline titanium oxynitride and retained macroscale monolithic integrity up to 800 °C under nitrogen. Notably, the urea-formaldehyde additive provided nitrogen and rigid support to the inorganic mesostructure during crystallization. The resultant mesoporous titanium oxynitride exhibited good electrochemical catalytic activity toward hydrogen evolution reaction in 1 M KOH aqueous medium under applied bias. Our results suggest an inexpensive and safe pathway to generate ordered mesoporous crystalline metal oxynitride structures suitable for catalyst and energy-storage applications.

Combining Organic and Inorganic Wastes to Form Metal-Organic Frameworks.

This paper reports a simple method to recycle plastic-bottle and Li-ion-battery waste in one process by forming valuable coordination polymers (metal-organic frameworks, MOFs). Poly(ethylene terephthalate) from plastic bottles was depolymerized to produce an organic ligand source (terephthalate), and Li-ion batteries were dissolved as a source of metals. By mixing both dissolution solutions together, selective precipitation of an Al-based MOF, known as MIL-53 in the literature, was observed. This material can be recovered in large quantities from waste and presents similar properties of purity and porosity to as-synthesis MIL-53. This work illustrates the opportunity to form hybrid porous materials by combining different waste streams, laying the foundations for an achievable integrated circular economy from different waste cycle treatments (for batteries and plastics).

An original recycling method for Li-ion batteries through large scale production of Metal Organic Frameworks.

A concept is proposed for the recycling of Li-ion batteries with an open-loop method that allows to reduce the volume of wastes and simultaneously to produce valuable materials in large amounts (Metal-Organic Frameworks, MOFs). After dissolution of Nickel, Manganese, Cobalt (NMC) batteries in acidic solution (HCl, HNO3 or H2SO4/H2O2), addition of organic moieties and a heat treatment, different MOFs are obtained. Solutions after precipitation are analyzed by inductively coupled plasma and materials are characterized by powder X-Ray diffraction, N2 adsorption, thermogravimetric analysis and Scanning electron microscope. With the use of Benzene-Tri-Carboxylic Acid as ligand, it has been possible to form selectively a MOF, based on Al metallic nodes, called MIL-96 in the literature, and known for its interesting properties in gas storage applications. The supernatant is then used again to precipitate other metals as MOFs after addition of a second batch of ligands. These two other MOFs are based on Cu (known as HKUST-1 in the literature) or Ni-Mn (with a new crystalline structure) depending of conditions. This method shows promising results at the lab scale (15 g of wastes can be converted in 10 g of MOFs), and opens interesting perspectives for the scaled-up production of MOFs.

Amorphous Fe-Ni-P-B-O Nanocages as Efficient Electrocatalysts for Oxygen Evolution Reaction.

Electrocatalysts are one of the most important parts for oxygen evolution reaction (OER) to overcome the sluggish kinetics. Herein, amorphous Fe-Ni-P-B-O (FNPBO) nanocages as efficient OER catalysts are synthesized by a simple low-cost and scalable method at room temperature. The samples are chemically stable, in clear contrast to reported unstable or even pyrophoric boride samples. The Fe/Ni ratio of the FNPBO nanocages can be continuously adjusted to optimize the OER catalytic performance. The FNPBO nanocages composed of multicomponent elements can weaken the metal-metal bonds, thus rearranging the electron density around the catalytic metal atom centers and reducing the energy barrier for intermediate formation. Hence the optimized FNPBO (Fe6.4Ni16.1P12.9B4.3O60.2) catalyst shows superior intrinsic electrocatalytic activity for OER. The low overpotential to afford the current density of 10 mA cm-2 (236 mV), the small Tafel slope (39 mV dec-1), and the high specific current density (26.44 mA cm-2) at a given overpotential of 300 mV make a sharp contrast to state-of-the-art RuO2 (327 mV, 136 mV dec-1, and 0.028 mA cm-2, respectively).

Layered Trichalcogenidophosphate: A New Catalyst Family for Water Splitting.

Due to the rapidly increasing demand for energy and environmental sustainability, stable and economical hydrogen production has received increasing attention in the past decades. In this regard, hydrogen production through photo- or electrocatalytic water splitting has continued to gain ever-growing interest. However, the existing catalysts are still unable to fulfill the demands of high-efficiency, low-cost, and sustainable hydrogen production. Layered metal trichalcogenidophosphate (MPQ3) is a newly developed two-dimensional material with tunable composition and electronic structure. Recently, MPQ3 has been considered a promising candidate for clean energy generation and related water splitting applications. In this minireview, we firstly introduce the structure and methods for the synthesis of MPQ3 materials. In the following sections, recent developments of MPQ3 materials for photo- and electrocatalytic water splitting are briefly summarized. The roles of MPQ3 materials in different reaction systems are also discussed. Finally, the challenges related to and prospects of MPQ3 materials are presented on the basis of the current developments.

CoSe2-Decorated NbSe2 Nanosheets Fabricated via Cation Exchange for Li Storage.

Though 2D transition metal dichalcogenides have attracted a lot of attention in energy-storage applications, the applications of NbSe2 for Li storage are still limited by the unsatisfactory theoretical capacity and uncontrollable synthetic approaches. Herein, a controllable oil-phase synthetic route for preparation of NbSe2 nanoflowers consisted of nanosheets with a thickness of ∼10 nm is presented. Significantly, a part of NbSe2 can be further replaced by orthorhombic CoSe2 nanoparticles via a post cation exchange process, and the predominantly 2D nanosheet-like morphology can be well-maintained, resulting in the formation of CoSe2-decorated NbSe2 (denoted as CDN) nanosheets. More interestingly, the CDN nanosheets exhibit excellent lithium-ion battery performance. For example, it achieves a highly reversible capacity of 280 mAh g-1 at 10 A g-1 and long cyclic stability with specific capacity of 364.7 mAh g-1 at 5 A g-1 after 1500 cycles, which are significantly higher than those of reported pure NbSe2.

High-Crystallinity Urchin-like VS4 Anode for High-Performance Lithium-Ion Storage.

VS4 anode materials with controllable morphologies from hierarchical microflower, octopus-like structure, seagrass-like structure to urchin-like structure have been successfully synthesized by a facile solvothermal synthesis approach using different alcohols as solvents. Their structures and electrochemical properties with various morphologies are systematically investigated, and the structure-property relationship is established. Experimental results reveal that Li+ ion storage behavior in VS4 significantly depends on physical features such as the morphology, crystallite size, and specific surface area. According to this study, electrochemical performance degrades on the order of urchin-like VS4 > octopus-like VS4 > seagrass-like VS4 > flower-like VS4. Among them, urchin-like VS4 demonstrates the best electrochemical performance benefiting from its peculiar structure which possesses large surface area that accommodates the volume change to a certain extent, and single-crystal thorns that provide fast electron transportation. Kinetic parameters derived from EIS spectra and sweep-rate-dependent CV curves, such as charge-transfer resistances, Li+ ion apparent diffusion coefficients and stored charge ratio of capacitive and intercalation contributions, both support this claim well. In addition, the EIS measurement was conducted during the first discharge/charge process to study the solid electrolyte interface (SEI) formation on urchin-like VS4 and kinetics behavior of Li+ ion diffusion. A better fundamental understanding on Li+ storage behavior in VS4 is promoted, which is applicable to other vanadium-based materials as well. This study also provides invaluable guidance for morphology-controlled synthesis tailored for optimal electrochemical performance.

Synthesis of high volumetric capacity graphene oxide-supported tellurantimony Na- and Li-ion battery anodes by hydrogen peroxide sol gel processing.

High-charge-capacity sodium-ion battery anodes made of Sb2Te3@reduced graphene oxide are reported for the first time. Uniform nano-coating of graphene oxide is carried out from common sol of peroxotellurate and peroxoantimonate under room temperature processing. Reduction by hydrazine under glycerol reflux yields Sb2Te3@reduced graphene oxide. The electrodes exhibit exceptionally high volumetric charge capacity, above 2300mAhcm-3 at 100mAg-1 current density, showing very good rate capabilities and retaining 60% of this capacity even at 2000mAg-1. A comparison of sodiation and lithiation shows that lithiation exhibits better volumetric charge capacity, but surprisingly only marginally better relative rate capability retention at 2000mAg-1. Tellurium-based electrodes are attractive due to the high volumetric charge capacity of Te, its very high electric conductivity, and the low relative expansion upon lithiation/sodiation.

Melt-Spun Fe-Sb Intermetallic Alloy Anode for Performance Enhanced Sodium-Ion Batteries.

Owing to the high theoretical sodiation capacities, intermetallic alloy anodes have attracted considerable interest as electrodes for next-generation sodium-ion batteries (SIBs). Here, we demonstrate the fabrication of intermetallic Fe-Sb alloy anode for SIBs via a high-throughput and industrially viable melt-spinning process. The earth-abundant and low-cost Fe-Sb-based alloy anode exhibits excellent cycling stability with nearly 466 mAh g-1 sodiation capacity at a specific current of 50 mA g-1 with 95% capacity retention after 80 cycles. Moreover, the alloy anode displayed outstanding rate performance with ∼300 mAh g-1 sodiation capacity at 1 A g-1. The crystalline features of the melt-spun fibers aid in the exceptional electrochemical performance of the alloy anode. Further, the feasibility of the alloy anode for real-life applications was demonstrated in a sodium-ion full-cell configuration which could deliver a sodiation capacity of over 300 mAh g-1 (based on anode) at 50 mA g-1 with more than 99% Coulombic efficiency. The results further exhort the prospects of melt-spun alloy anodes to realize fully functional sodium-ion batteries.

Practical Li-Ion Battery Assembly with One-Dimensional Active Materials.

Research activities on the development of one-dimensional (1D) nanostructures and their successful implementation in the fabrication of high-performance practical Li-ion batteries (LIBs) are described. Although numerous 1D-structured materials have been explored for use in LIBs as anodes, cathodes, and separator-cum-electrolytes, only a very limited number of studies report the practical assembly of LIBs using these components. As a result, the salient features of using 1D materials in charge-storage devices have not been realized from an application perspective. Exceptional battery performance is reported when all-1D-based electro-active materials are used to fabricate LIBs. Using all-1D nanostructures not only provides high power capability, energy density, and durability, it also opens up new avenues for developing high-performance next-generation Li-ion power packs.

ß-Co(OH)2 Nanosheets: A Superior Pseudocapacitive Electrode for High-Energy Supercapacitors.

In this work, ß-Co(OH)2 nanosheets are explored as efficient pseudocapacitive materials for the fabrication of 1.6 V class high-energy supercapacitors in asymmetric fashion. The as-synthesized ß-Co(OH)2 nanosheets displayed an excellent electrochemical performance owing to their unique structure, morphology, and reversible reaction kinetics (fast faradic reaction) in both the three-electrode and asymmetric configuration (with activated carbon, AC). For example, in the three-electrode set-up, ß-Co(OH)2 exhibits a high specific capacitance of ∼675 F g-1 at a scan rate of 1 mV s-1 . In the asymmetric supercapacitor, the ß-Co(OH)2 ∥AC cell delivers a maximum energy density of 37.3 Wh kg-1 at a power density of 800 W kg-1 . Even at harsh conditions (8 kW kg-1 ), an energy density of 15.64 Wh kg-1 is registered for the ß-Co(OH)2 ∥AC assembly. Such an impressive performance of ß-Co(OH)2 nanosheets in the asymmetric configuration reveals the emergence of pseudocapacitive electrodes towards the fabrication of high-energy electrochemical charge storage systems.

Polymeric Nanomaterials Based on the Buckybowl Motif: Synthesis through Ring-Opening Metathesis Polymerization and Energy Storage Applications.

Ring-opening metathesis polymerization (ROMP) of buckybowl corannulene-based oxa-norbornadiene monomer is shown to give rise to polymeric nanomaterials with an average pore size of about 1.4 nm and a surface area of 49.2 m2/g. Application in supercapacitor devices show that the corannulene-based nanomaterials exhibit a specific capacitance of 134 F·g-1 (1.0 V voltage window) in a three-electrode cell configuration. Moreover, the electrode assembled from these materials in a symmetric configuration (1.6 V voltage window) exhibits long-term cyclability of 90% capacitance retention after undergoing 10000 cycles. This work demonstrates that ROMP is a valuable method in synthesizing nanostructured corannulene polymers, and that materials based on the nonplanar polycyclic aromatic motif represents an attractive active component for fabrication of devices targeted at electrochemical energy storage applications.

Controllable Preparation of Square Nickel Chalcogenide (NiS and NiSe2) Nanoplates for Superior Li/Na Ion Storage Properties.

A facile and bottom-up approach has been presented to prepare 2D Ni-MOFs based on cyanide-bridged hybrid coordination polymers. After thermally induced sulfurization and selenization processes, Ni-MOFs were successfully converted into NiS and NiSe2 nanoplates with carbon coating due to the decomposition of its organic parts. When evaluated as anodes of Li-ion batteries (LIBs) and Na-ion batteries (NIBs), NiS and NiSe2 nanoplates show high specific capacities, excellent rate capabilities, and stable cycling stability. The NiS plates show good Li storage properties, while NiSe2 plates show good Na storage properties as anode materials. The study of the diffusivity of Li(+) in NiS and Na(+) in NiSe2 shows consistent results with their Li/Na storage properties. The 2D MOFs-derived NiS and NiSe2 nanoplates reported in this work explore a new approach for the large-scale synthesis of 2D metal sulfides or selenides with potential applications for advanced energy storage.

Red Mud and Li-Ion Batteries: A Magnetic Connection.

Exceptional Li-ion battery performance is presented with the oxide component of the anode was extracted from red mud by simple magnetic separation and applied directly without any further processing. The extracted material has γ-Fe2 O3 as the major phase with inter-dispersed phases of Ti, Al, and Si oxides. In a half-cell assembly, the phase displayed a reversible capacity (∼697 mA h g(-1) ) with excellent stability upon cycling. Interestingly, the stability is rendered by the multiphase constitution of the material with the presence of other electrochemically inactive metal oxides, such as Al2 O3 , SiO2 , and Fe2 TiO4 , which could accommodate the strain and facilitate release during the charge-discharge processes in the electrochemically active maghemite component. We fabricated the full-cell assembly with eco-friendly cathode LiMn2 O4 by adjusting the mass loading. Prior to full-cell assembly, an electrochemical pre-lithiation was enforced to overcome the irreversible capacity loss obtained from the anode. The full-cell delivered a capacity of ∼100 mA h g(-1) (based on cathode loading) with capacity retention of ∼61 % after 2000 cycles under ambient conditions.

Two-Dimensional Tin Disulfide Nanosheets for Enhanced Sodium Storage.

Sodium-ion batteries (SIBs) are considered as complementary alternatives to lithium-ion batteries for grid energy storage due to the abundance of sodium. However, low capacity, poor rate capability, and cycling stability of existing anodes significantly hinder the practical applications of SIBs. Herein, ultrathin two-dimensional SnS2 nanosheets (3-4 nm in thickness) are synthesized via a facile refluxing process toward enhanced sodium storage. The SnS2 nanosheets exhibit a high apparent diffusion coefficient of Na(+) and fast sodiation/desodiation reaction kinetics. In half-cells, the nanosheets deliver a high reversible capacity of 733 mAh g(-1) at 0.1 A g(-1), which still remains up to 435 mAh g(-1) at 2 A g(-1). The cell has a high capacity retention of 647 mA h g(-1) during the 50th cycle at 0.1 A g(-1), which is by far the best for SnS2, suggesting that nanosheet morphology is beneficial to improve cycling stability in addition to rate capability. The SnS2 nanosheets also show encouraging performance in a full cell with a Na3V2(PO4)3 cathode. In addition, the sodium storage mechanism is investigated by ex situ XRD coupled with high-resolution TEM. The high specific capacity, good rate capability, and cycling durability suggest that SnS2 nanosheets have great potential working as anodes for high-performance SIBs.

One-Pot Synthesis of Tunable Crystalline Ni3 S4 @Amorphous MoS2 Core/Shell Nanospheres for High-Performance Supercapacitors.

Transition metal sulfides gain much attention as electrode materials for supercapacitors due to their rich redox chemistry and high electrical conductivity. Designing hierarchical nanostructures is an efficient approach to fully utilize merits of each component. In this work, amorphous MoS(2) is firstly demonstrated to show specific capacitance 1.6 times as that of the crystalline counterpart. Then, crystalline core@amorphous shell (Ni(3)S(4)@MoS(2)) is prepared by a facile one-pot process. The diameter of the core and the thickness of the shell can be independently tuned. Taking advantages of flexible protection of amorphous shell and high capacitance of the conductive core, Ni(3)S(4) @amorphous MoS(2) nanospheres are tested as supercapacitor electrodes, which exhibit high specific capacitance of 1440.9 F g(-1) at 2 A g(-1) and a good capacitance retention of 90.7% after 3000 cycles at 10 A g(-1). This design of crystalline core@amorphous shell architecture may open up new strategies for synthesizing promising electrode materials for supercapacitors.

Ultralong Durability of Porous α-Fe2O3 Nanofibers in Practical Li-Ion Configuration with LiMn2O4 Cathode.

Prelithiated, electrospun α-Fe2O3 nanofibers display an exceptional cycleability when it is paired with commercial LiMn2O4 cathode in full-cell assembly. The performance of such α-Fe2O3 nanofibers is mainly due to the presence of unique morphology with porous structure, appropriate mass balance, and working potential. Also, synthesis technique cannot be ruled out for the performance.

Electrospun nanofibers: a prospective electro-active material for constructing high performance Li-ion batteries.

In the present review, we describe the development of a high energy density LIB fabricated with all 1D nanofibers as the anode and cathode, as well as a separator-cum-electrolyte prepared by an electrospinning technique without compromising the power capability and cycle life. Such a unique assembly certainly enables realizing the advantages of using 1D nanostructures in practical LIBs, irrespective of the anode or cathode in the presence of gelled polyvinylidene fluoride-co-hexafluoropropylene as the separator-cum-electrolyte. Outstanding cycling profiles with high power densities were noted for all the configurations evaluated. This excellent performance opens up new avenues for the development of high performance Li-ion power packs with a long cycle life and high energy and power densities to drive zero emission transportation applications in the near future, and opens up new research activities in this field as well.