Recycling and Reutilization of Metals Aided by Deep Eutectic Solvents: from NMC Cathodes of Spent Li-ion Batteries to Electrolytes for Supercapacitors.

With the rapidly increasing demand for lithium ion batteries (LIBs), recycling the metals found in spent cathodes is mandatory to both alleviate shortages resulting from the mining of natural metal ores and manage the disposal of spent LIBs. The use of deep eutectic solvents (DESs) for metals recovery from spent cathodes of LIBs (e. g., LCO and NMC types) offers a sustainable yet efficient alternative to conventional hydrometallurgical processes. Nonetheless, g efforts are required to use milder temperatures and higher mass loadings, thus ensuring cost-effectiveness. In this latter regard, addressing the reutilization of DESs in subsequent stages of metal extraction, and streamlining or eliminating the chemical procedures employed for metal separation, is even more crucial to guarantee the economic feasibility of the recycling process. Herein, we have prepared a DES that provides extraction efficiencies of ca. 100 % for every metal of NMC cathodes even at mild experimental conditions (e. g., 60 °C) and for loadings as high as 70 mgNMC/gDES. Moreover, we have pioneered the direct use of leachates containing DESs and metals as electrolytes for supercapacitors. This approach enables the reintroduction of DESs and the recovered metals into the value chain with a minimal economic and environmental impact.

From Green to Black Gold: Highly Microporous Carbons from Pistachio Shells by a Controlled Physical Activation Process.

Highly microporous carbons with BET surface areas of up to ca. 3300 m2 g-1 and pore volumes of up to 1.6 cm3 g-1 have been successfully synthesized from pistachio shells, a waste whose generation is growing on account of the nutritive value of pistachios and the resilience of this crop to climate change. Such a high pore development has been achieved by a simple and benign CO2 physical activation process assisted by a custom pre-treatment of the biomass. Herein, different approaches have been explored for the transformation into carbon materials with diverse microstructures, mineral matter content and particle size/morphology, tuning thereby their reactivities towards CO2 and diffusion kinetics and, in this way, pore development. In particular, the most efficient route for the production of highly microporous carbons involves a hydrothermal carbonization process which increases the degree of aromatization and effectively removes the mineral matter, enhancing thereby the efficiency of both carbon production and porosity generation. By increasing the activation temperature, substantial shortening of the operation time can be achieved without compromising pore development. This work provides new integral strategies towards the production of biomass-based, CO2-activated carbons with a focus on optimizing pore structure, minimizing energy consumption and maximizing product yield.

Cork-Derived Carbon Sheets for High-Performance Na-Ion Capacitors.

S-doped carbon sheets have been easily prepared by deconstructing the 3D cellular structure of a fully sustainable and renewable biomass material such as cork through a mild ball-milling process. S-doping of the material (>14 wt % S) has been achieved by using sulfur as an earth-abundant, cost-effective, and environmentally benign S-dopant. Such synthesized materials provide large Na storage capacities in the range of 300-550 mAh g-1 at 0.1 A g-1 and can handle large current densities of 10 A g-1, providing 55-140 mAh g-1. Their increased packing density compared to the 3D pristine structure allows them to also provide good volumetric capacities in the range of 285-522 mAh cm-3 at 0.1 A g-1 and 53-133 mAh cm-3 at 10 A g-1. In addition, highly porous carbon sheets (SBET > 2700 m2 g-1) have been produced from the same carbon precursor by rationally designing the chemical activation approach. These materials are able to provide good anion storage capacities/capacitances of up to 100-114 mAh g-1/163-196 F g-1. A sodium-ion capacitor assembled with the optimized S-doped carbon sheets and the highly porous carbon sheets with mass matching ratios provided the best energy/power characteristics (90 Wh kg-1 at 29 kW kg-1) in combination with robust cycling stability over 10,000 cycles, with a capacity fade of only 0.0018% per cycle.

Eco-Friendly Synthesis of 3D Disordered Carbon Materials for High-Performance Dual Carbon Na-Ion Capacitors.

An eco-friendly and sustainable salt-templating approach was proposed for the production of anode materials with a 3D sponge-like structure for sodium-ion capacitors using gluconic acid as carbon precursor and sodium carbonate as water-removable template. The optimized carbon material combined porous thin walls that provided short diffusional paths, a highly disordered microstructure with dilated interlayer spacing, and a large oxygen content, all of which facilitated Na ion transport and provided plenty of active sites for Na adsorption. This material provided a capacity of 314 mAh g-1 at 0.1 A g-1 and 130 mAh g-1 at 10 A g-1 . When combined with a 3D highly porous carbon cathode (SBET ≈2300 m2 g-1 ) synthesized from the same precursor, the Na-ion capacitor showed high specific energy/power, that is 110 Wh kg-1 at low power and still 71 Wh kg-1 at approximately 26 kW kg-1 , and a good capacity retention of 70 % over 10000 cycles.

More Sustainable Chemical Activation Strategies for the Production of Porous Carbons.

The preparation of porous carbons attracts a great deal of attention given the importance of these materials in many emerging applications, such as hydrogen storage, CO2 capture, and energy storage in supercapacitors and batteries. In particular, porous carbons produced by applying chemical activation methods are preferred because of the high pore development achieved. However, given the environmental risks associated with conventional activating agents such as KOH, the development of greener chemical activation methodologies is an important objective. This Review summarizes recent progress in the production of porous carbons by using more sustainable strategies based on chemical activation. The use of less-corrosive chemical agents as an alternative to KOH is thoroughly reviewed. In addition, progress achieved to date by using emerging self-activation methodologies applied to organic salts and biomass products is also discussed.

Straightforward synthesis of Sulfur/N,S-codoped carbon cathodes for Lithium-Sulfur batteries.

An upgrade of the scalable fabrication of high-performance sulfur-carbon cathodes is essential for the widespread commercialization of this technology. Herein we present a simple, cost-effective and scalable approach for the fabrication of cathodes comprising sulfur and high-surface area, N,S-codoped carbons. The method involves the use of a sulfur salt, i.e. sodium thiosulfate, as activating agent, sulfur precursor and S-dopant, and polypyrrole as carbon precursor and N-dopant. In this way, the production of the porous host and the incorporation of sulfur are combined in the same procedure. The porous hosts thus produced have BET surface areas in excess of 2000 m2 g-1, a micro-mesoporous structure, as well as sulfur and nitrogen contents of 5-6 wt% and ~2 wt%, respectively. The elemental sulfur content in the composites can be precisely modulated in the range of 24 to ca. 90 wt% by controlling the amount of sodium thiosulfate used. Remarkably, these porous carbons are able to accommodate up to 80 wt% sulfur exclusively within their porosity. When analyzed in lithium-sulfur batteries, these sulfur-carbon composites show high specific capacities of 1100 mAh g-1 at a low C-rate of 0.1 C and above 500 mAh g-1 at a high rate of 2 C for sulfur contents in the range of 50-80 wt%. Remarkably, the composites with 51-65 wt% S can still provide above 400 mAh g-1 at an ultra-fast rate of 4 C (where a charge and discharge cycle takes only ten minutes). The good rate capability and sulfur utilization was additionally assessed for cathodes with a high sulfur content (65-74%) and a high sulfur loading (>5 mg cm-2). In addition, cathodes of 4 mg cm-2 successfully cycled for 260 cycles at 0.2 C showed only a low loss of 0.12%/cycle.

Publisher Correction: Fabrication of high-performance dual carbon Li-ion hybrid capacitor: mass balancing approach to improve the energy-power density and cycle life.

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

Fabrication of high-performance dual carbon Li-ion hybrid capacitor: mass balancing approach to improve the energy-power density and cycle life.

Most lithium-ion capacitor (LIC) devices include graphite or non-porous hard carbon as negative electrode often failing when demanding high energy at high power densities. Herein, we introduce a new LIC formed by the assembly of polymer derived hollow carbon spheres (HCS) and a superactivated carbon (AC), as negative and positive electrodes, respectively. The hollow microstructure of HCS and the ultra large specific surface area of AC maximize lithium insertion/diffusion and ions adsorption in each of the electrodes, leading to individual remarkable capacity values and rate performances. To optimize the performance of the LIC not only in terms of energy and power densities but also from a stability point of view, a rigorous mass balance study is also performed. Optimized LIC, using a 2:1 negative to positive electrode mass ratio, shows very good reversibility within the operative voltage region of 1.5-4.2 V and it is able to deliver a specific cell capacity of 28 mA h-1 even at a high current density of 10 A g-1. This leads to an energy density of 68 W h kg-1 at an extreme power density of 30 kW kg-1. Moreover, this LIC device shows an outstanding cyclability, retaining more than 92% of the initial capacity after 35,000 charge-discharge cycles.

Tailoring micro-mesoporosity in activated carbon fibers to enhance SO2 catalytic oxidation.

Enhanced SO2 adsorption of activated carbon fibers is obtained by tailoring a specific micro-mesoporous structure in the fibers. This architecture is obtained via metal catalytic activation of the fibers with a novel precursor, cobalt naphthenate, which contrary to other precursors, also enhances spinnability and carbon fiber yield. In the SO2 oxidation, it is demonstrated that the combination of micropores and large mesopores is the main factor for an enhanced catalytic activity which is superior to that observed in other similar microporous activated carbon fibers. This provides an alternative way for the development of a new generation of catalytic material.