A comprehensive approach for the recycling of anode materials from spent lithium-ion batteries: Separation, lithium recovery, and graphite reutilization as environmental catalyst.

The effective recovery of valuables from anodes coming from spent lithium-ion batteries (LIBs) is of great importance to ensure resource supply and reduce the environmental burden for recycling. In this work, a simple and low energy consumption roasting method was proposed by employing low-temperature eutectic NaOH-KOH as reaction medium, in order to simultaneously separate graphite from Cu foils, extract lithium from it and set it up for reuse as environmental catalyst through one-step water washing process. Our results show that polyvinylidene difluoride (PVDF) was effectively deactivated due to dehydrofluorination/carbonization at a relatively low temperature and short time (150 °C, 20 min) when a mass ratio of 1:1 for eutectic NaOH-KOH to spent LIBs anodes was used, yielding 97.3 % of graphite detached. Moreover, a remarkable lithium extraction efficiency of 93.2 % was simultaneously obtained. Afterwards, the reusability of the recycled graphite was tested by employing it as a catalyst for the treatment of a contaminant organic dye (Rhodamine B) in the presence of NaClO. Our results show that a superior NaClO activation was obtained with the addition of recycled graphite, being this fact closely associated to the abundant active sites formed during the long-term charging/discharging cycles in the original battery. The alkaline-mediated roasting process presented in this work presents an energy-saving scheme to efficiently recover useful components from spent anodes, whereas the reusability example highlighted a useful option for repurposing the severely damaged graphite as an environmental catalyst rather than disposing it in landfills, turning waste into a valuable material.

Resource recovery and regeneration strategies for spent lithium-ion batteries: Toward sustainable high-value cathode materials.

Traditional cathode recycling methods have become outdated amid growing concerns for high-value output and environmental friendliness in spent Li-ion battery (LIB) recycling. Our study presents a closed-loop approach that involves selective sulfurization roasting, water leaching, and regeneration, efficiently transforming spent ternary Li batteries (i.e., NCM) into high-performance cathode materials. By combining experimental investigations with density functional theory (DFT) calculations, we elucidate the mechanisms within the NCM-C-S roasting system, providing a theoretical foundation for selective sulfidation. Utilizing in situ X-ray diffraction techniques and a series of consecutive experiments, the study meticulously tracks the evolution of regenerating cathode materials that use transition metal sulfides as their primary raw materials. The Li-rich regenerated NCM exhibits exceptional electrochemical performance, including long-term cycling, high-rate capabilities, reversibility, and stability. The closed-loop approach highlights the sustainability and environmental friendliness of this recycling process, with potential applications in other cathode materials, such as LiCoO2 and LiMn2O4. Compared with traditional methods, this short process approach avoids the complexity of leaching, solvent extraction, and reverse extraction, significantly increasing metal utilization and Li recovery rates while reducing pollution and resource waste.

In situ gold adsorption experiment at an acidic hot spring using a blue-green algal sheet.

Gold (Au), as one of the most precious metal resources that is used for both industrial products and private ornaments, is a global investment target, and mining companies are making huge investments to discover new Au deposits. Here, we report in situ Au adsorption in an acidic hot spring by a unique adsorption sheet made from blue-green algae with a high preferential adsorption ability for Au. The results of in situ Au adsorption experiments conducted for various reaction times ranging from 0.2 h to 7 months showed that a maximum Au concentration of 30 ppm was adsorbed onto the blue-green algal sheet after a reaction time of 7 months. The Au concentration in the hot spring water was below the detection limit (< 1 ppt); therefore, Au was enriched by preferential adsorption onto the blue-green algal sheet by a factor of more than ~ 3 × 107. Thus, our gold recovery method has a high potential to recover Au even from an Au-poor solution such as hot spring water or mine wastewater with a low impact on the environment.

Pelagic responses to oceanic anoxia during the Carnian Pluvial Episode (Late Triassic) in Panthalassa Ocean.

The Carnian Pluvial Episode (CPE) was a short interval of extreme rainfall in the Late Triassic that caused significant changes in marine ecosystems. Global warming induced by Wrangellia volcanism is thought to have resulted in oceanic anoxia during the CPE, but the global extent, duration, and severity of anoxia, and its effects on major marine taxa, remain unclear. To address this, we examined an equatorial record of conditions in the Panthalassa Ocean during the CPE, focusing on marine Os isotope data, redox conditions, and conodont and radiolarian biostratigraphy. The results show that Wrangellia volcanism peaked in the latest Julian (early Carnian), coinciding with development of reducing conditions in the deep-sea Panthalassa. A strong conodont turnover occurred during the period of oceanic anoxia, whereas radiolarians were less affected and their diversity increased after the recovery from anoxia. The increased radiolarian diversity during the early Tuvalian (late Carnian) can be attributed to chemical weathering and enhanced nutrient fluxes associated with global warming and the more humid climate of Pangea.

Chemical speciation changes of an all-solid-state lithium-ion battery caused by roasting determined by sequential acid leaching.

All-solid-state lithium-ion batteries (ASS-LIBs) are expected to replace current liquid-based LIBs in the near future owing to their high energy density and improved safety. It would be preferable if ASS-LIBs could be recycled by the current recycling processes used for liquid-based LIBs, but this possibility remains to be determined. Here, we subjected an ASS-LIB test cell containing an argyrodite-type solid electrolyte (Li6PS5Cl) and nickel-manganese-cobalt-type active material (Li(Ni0.5Mn0.3Co0.2)O2) to roasting, a treatment process commonly used for recycling of the valuable metals from liquid-based LIBs, and investigated the changes in chemical speciation. Roasting was performed at various temperatures (350-900 °C), for various times (60-360 min), and under various oxygen fugacity (air or O2) conditions. The chemical speciation of each metal element after roasting was determined by sequential elemental leaching tests and X-ray diffraction analysis. Li formed sulfates or phosphates over a wide temperature range. Ni and Co followed very complicated reaction paths owing to coexistence of S, P, and C, and they formed sulfides, phosphates, and complex oxides. The optimum conditions for minimizing formation of insoluble compounds, such as complex oxides, were a roasting temperature of 450-500 °C and a roasting time of 120 min. The results indicated that although ASS-LIBs can be treated by the same roasting processes as those used for current liquid-based LIBs, the optimal roasting conditions have narrow ranges. Thus, careful process control will be needed to achieve high extraction percentages of the valuable metals from ASS-LIBs.

Geochemical Modeling of Heavy Metal Removal from Acid Mine Drainage in an Ethanol-Supplemented Sulfate-Reducing Column Test.

A passive treatment process using sulfate-reducing bacteria (SRB) is known to be effective in removing heavy metals from acid mine drainage (AMD), though there has been little discussion of the mechanism involved to date. In this work, a sulfate-reducing column test was carried out using supplementary ethanol as an electron donor for microorganisms, and the reaction mechanism was examined using geochemical modeling and X-ray absorption fine structure (XAFS) analysis. The results showed that Cu was readily removed from the AMD on the top surface of the column (0-0.2 m), while Zn and Cd depletion was initiated in the middle of the column (0.2-0.4 m), where sulfide formation by SRB became noticeable. Calculations by a developed geochemical model suggested that ethanol decomposition by aerobic microbes contributed to the reduction of Cu, while sulfide produced by SRB was the major cause of Zn and Cd removal. XAFS analysis of column residue detected ZnS, ZnSO4 (ZnS oxidized by atmospheric exposure during the drying process), and CuCO3, thus confirming the validity of the developed geochemical model. Based on these results, the application of the constructed geochemical model to AMD treatment with SRB could be a useful approach in predicting the behavior of heavy metal removal.

Subseafloor sulphide deposit formed by pumice replacement mineralisation.

Seafloor massive sulphide (SMS) deposits, modern analogues of volcanogenic massive sulphide (VMS) deposits on land, represent future resources of base and precious metals. Studies of VMS deposits have proposed two emplacement mechanisms for SMS deposits: exhalative deposition on the seafloor and mineral and void space replacement beneath the seafloor. The details of the latter mechanism are poorly characterised in detail, despite its potentially significant role in global metal cycling throughout Earth's history, because in-situ studies require costly drilling campaigns to sample SMS deposits. Here, we interpret petrographic, geochemical and geophysical data from drill holes in a modern SMS deposit and demonstrate that it formed via subseafloor replacement of pumice. Samples from the sulphide body and overlying sediment at the Hakurei Site, Izena Hole, middle Okinawa Trough indicate that sulphides initially formed as aggregates of framboidal pyrite and matured into colloform and euhedral pyrite, which were replaced by chalcopyrite, sphalerite and galena. The initial framboidal pyrite is closely associated with altered material derived from pumice, and alternating layers of pumiceous and hemipelagic sediments functioned as a factory of sulphide mineralisation. We infer that anhydrite-rich layers within the hemipelagic sediment forced hydrothermal fluids to flow laterally, controlling precipitation of a sulphide body extending hundreds of meters.

Author Correction: Fish proliferation and rare-earth deposition by topographically induced upwelling at the late Eocene cooling event.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Fish proliferation and rare-earth deposition by topographically induced upwelling at the late Eocene cooling event.

The deep-sea clay that covers wide areas of the pelagic ocean bottom provides key information about open-ocean environments but lacks age-diagnostic calcareous or siliceous microfossils. The marine osmium isotope record has varied in response to environmental changes and can therefore be a useful stratigraphic marker. In this study, we used osmium isotope ratios to determine the depositional ages of pelagic clays extraordinarily rich in fish debris. Much fish debris was deposited in the western North and central South Pacific sites roughly 34.4 million years ago, concurrent with a late Eocene event, a temporal expansion of Antarctic ice preceding the Eocene-Oligocene climate transition. The enhanced northward flow of bottom water formed around Antarctica probably caused upwelling of deep-ocean nutrients at topographic highs and stimulated biological productivity that resulted in the proliferation of fish in pelagic realms. The abundant fish debris is now a highly concentrated source of industrially critical rare-earth elements.

A Miocene impact ejecta layer in the pelagic Pacific Ocean.

Meteorite impacts have caused catastrophic perturbations to the global environment and mass extinctions throughout the Earth's history. Here, we present petrographic and geochemical evidence of a possible impact ejecta layer, dating from about 11 Ma, in deep-sea clayey sediment in the Northwest Pacific. This clay layer has high platinum group element (PGE) concentrations and features a conspicuous negative Os isotope anomaly (187Os/188Os as low as ~0.2), indicating an influx of extraterrestrial material. It also contains abundant spherules that include pseudomorphs suggestive of porphyritic olivine as well as spinel grains with euhedral, dendritic and spherical forms and NiO contents as great as 23.3 wt%, consistent with impact ejecta. Osmium isotope stratigraphy suggests a most plausible depositional age of ~11 Ma (Miocene) for this layer, as determined by fitting with the seawater evolution curve. No large impact crater of this age is known on land, even within the relatively large uncertainty range of the relative Os age. Thus, we suggest that an unrecognised impact event in the middle or late Miocene produced the impact ejecta layer of the Northwest Pacific.

The tremendous potential of deep-sea mud as a source of rare-earth elements.

Potential risks of supply shortages for critical metals including rare-earth elements and yttrium (REY) have spurred great interest in commercial mining of deep-sea mineral resources. Deep-sea mud containing over 5,000 ppm total REY content was discovered in the western North Pacific Ocean near Minamitorishima Island, Japan, in 2013. This REY-rich mud has great potential as a rare-earth metal resource because of the enormous amount available and its advantageous mineralogical features. Here, we estimated the resource amount in REY-rich mud with Geographical Information System software and established a mineral processing procedure to greatly enhance its economic value. The resource amount was estimated to be 1.2 Mt of rare-earth oxide for the most promising area (105 km2 × 0-10 mbsf), which accounts for 62, 47, 32, and 56 years of annual global demand for Y, Eu, Tb, and Dy, respectively. Moreover, using a hydrocyclone separator enabled us to recover selectively biogenic calcium phosphate grains, which have high REY content (up to 22,000 ppm) and constitute the coarser domain in the grain-size distribution. The enormous resource amount and the effectiveness of the mineral processing are strong indicators that this new REY resource could be exploited in the near future.

Rapid growth of mineral deposits at artificial seafloor hydrothermal vents.

Seafloor massive sulphide deposits are potential resources for base and precious metals (Cu-Pb-Zn ± Ag ± Au), but difficulties in estimating precise reserves and assessing environmental impacts hinder exploration and commercial mining. Here, we report petrological and geochemical properties of sulphide chimneys less than 2 years old that formed where scientific boreholes vented hydrothermal fluids in the Iheya-North field, Okinawa Trough, in East China Sea. One of these infant chimneys, dominated by Cu-Pb-Zn-rich sulphide minerals, grew a height of 15 m within 25 months. Portions of infant chimneys are dominated by sulphate minerals. Some infant chimneys are sulphide-rich similar to high-grade Cu-Pb-Zn bodies on land, albeit with relatively low As and Sb concentrations. The high growth rate reaching the 15 m height within 25 months is attributed to the large hydrothermal vent more than 50 cm in diameter created by the borehole, which induced slow mixing with the ambient seawater and enhanced efficiency of sulphide deposition. These observations suggest the possibility of cultivating seafloor sulphide deposits and even controlling their growth and grades through manipulations of how to mix and quench hydrothermal fluids with the ambient seawater.

Post-drilling changes in seabed landscape and megabenthos in a deep-sea hydrothermal system, the Iheya North field, Okinawa Trough.

There has been an increasing interest in seafloor exploitation such as mineral mining in deep-sea hydrothermal fields, but the environmental impact of anthropogenic disturbance to the seafloor is poorly known. In this study, the effect of such anthropogenic disturbance by scientific drilling operations (IODP Expedition 331) on seabed landscape and megafaunal habitation was surveyed for over 3 years using remotely operated vehicle video observation in a deep-sea hydrothermal field, the Iheya North field, in the Okinawa Trough. We focused on observations from a particular drilling site (Site C0014) where the most dynamic change of landscape and megafaunal habitation was observed among the drilling sites of IODP Exp. 331. No visible hydrothermal fluid discharge had been observed at the sedimentary seafloor at Site C0014, where Calyptogena clam colonies were known for more than 10 years, before the drilling event. After drilling commenced, the original Calyptogena colonies were completely buried by the drilling deposits. Several months after the drilling, diffusing high-temperature hydrothermal fluid began to discharge from the sedimentary subseafloor in the area of over 20 m from the drill holes, 'artificially' creating a new hydrothermal vent habitat. Widespread microbial mats developed on the seafloor with the diffusing hydrothermal fluids and the galatheid crab Shinkaia crosnieri endemic to vents dominated the new vent community. The previously soft, sedimentary seafloor was hardened probably due to barite/gypsum mineralization or silicification, becoming rough and undulated with many fissures after the drilling operation. Although the effects of the drilling operation on seabed landscape and megafaunal composition are probably confined to an area of maximally 30 m from the drill holes, the newly established hydrothermal vent ecosystem has already lasted 2 years and is like to continue to exist until the fluid discharge ceases and thus the ecosystem in the area has been altered for long-term.