Energy Materials

Lithium-ion batteries (LIBs) are at the forefront of technological innovation in the current global energy-transition paradigm, driving surging demand for electric vehicles and renewable energy-storage solutions. Despite their widespread use and superior energy densities, the environmental footprint and resource scarcity associated with LIBs necessitate sustainable recycling strategies. This comprehensive review critically examines the existing landscape of battery recycling methodologies, including pyrometallurgical, hydrometallurgical, and direct recycling techniques, along with emerging approaches such as bioleaching and electrochemical separation. Our analysis not only underscores the environmental and efficiency challenges posed by conventional recycling methods but also highlights the promising potential of electrochemical techniques for enhancing selectivity, reducing energy consumption, and mitigating secondary waste production. By delving into recent advancements and juxtaposing various recycling methodologies, we pinpoint electrochemical recycling as a pivotal technology for efficiently recovering valuable metals, such as Li, Ni, Co, and Mn, from spent LIBs in an environmentally benign manner. Our discussion extends to the scalability, economic viability, and future directions of electrochemical recycling, and advocates for their integration into global battery-recycling infrastructure to address the dual challenges of resource depletion and environmental sustainability.

Microporous carbonaceous electrode materials store charge by ion electrosorption onto the electrode surface. Despite significant efforts to understand this phenomenon, a definitive picture of the adsorption mechanisms within these complex nanoscale structures is lacking. Here, we use nuclear magnetic resonance (NMR) spectroscopy to directly observe and quantify aqueous adsorbate partitioning behavior driven by spontaneous physisorption within the micropores. Our results show that the solvation properties of the electrolyte ions influence the ionophilicity/ionophobicity of the adsorbate-carbon system, with ionophilic and ionophobic systems exhibiting distinct behavior concerning the electrolyte loading volume. Micropore diameter is also shown to influence spontaneous electrolyte partitioning behavior and disturb ion solvation. In situ NMR spectroscopy using a working supercapacitor comprising microporous carbon electrodes with aqueous sodium sulfate and aqueous sodium bis(trifluoromethane)sulfonimide electrolytes indicates that spontaneous electrolyte partitioning behavior influences the charge-balancing mechanism. Our results suggest that spontaneously ionophilic systems favor charge-balancing by counter-ion adsorption under an applied voltage, and spontaneously ionophobic systems favor a co-ion ejection mechanism under an applied potential. These results provide new molecular-level insight into the role of electrolyte properties on spontaneous physisorption behavior and charged electrosorption behavior within microporous carbon electrodes.

Li–S batteries with an improved cycle life of over 1000 cycles have been achieved using cathodes of sulfur-infiltrated nanoporous carbon with carbonate-based electrolytes. In these cells, a protective cathode–electrolyte interphase (CEI) is formed, leading to solid-state conversion of S to Li2S in the nanopores. This prevents the dissolution of polysulfides and slows capacity fade. However, there is currently little understanding of what limits the capacity and rate performance of these Li–S batteries. Here, we aim to deepen our understanding of the capacity and rate limitation using a variety of structure-sensitive and electrochemical techniques, such as operando small-angle neutron scattering (SANS), operando X-ray diffraction (XRD), electrochemical impedance spectroscopy, and galvanostatic charge/discharge. Operando SANS and XRD data give direct evidence of CEI formation and solid-state sulfur conversion occurring inside the nanopores. Electrochemical measurements using two nanoporous carbons with different pore sizes suggest that charge transfer at the active material interfaces and the specific CEI/active material structure in the nanopores play the dominant role in defining capacity and rate performance. This work helps define strategies to increase the sulfur loading while maximizing sulfur usage, rate performance, and cycle life.

Coating laser-patterned stainless-steel surfaces with carbon nanotubes (CNT) or carbon onions (CO) forms a tribological system that provides effective solid lubrication. Lubricant retention represents the fundamental mechanism of this system, as storing the particles inside the pattern prevents lubricant depletion in the contact area. In previous works, we used direct laser interference patterning to create line patterns with three different structural depths on AISI 304 stainless-steel platelets. Electrophoretic deposition subsequently coated the patterned surfaces with either CNTs or COs. Ball-on-disc friction tests were conducted to study the effect of structural depth on the solid lubricity of as-described surfaces. The results demonstrated that the shallower the textures, the lower the coefficient of friction, regardless of the applied particle type. This follow-up study examines the carbon nanoparticles’ structural degradation after friction testing on substrates patterned with different structural depths (0.24, 0.36, and 0.77 µm). Raman characterization shows severe degradation of both particle types and is used to classify their degradation state within Ferrari’s three-stage amorphization model. It was further shown that improving CNT lubricity translates into increasing particle defectivity. This is confirmed by electron microscopy, which shows decreasing crystalline domains. Compared to CNTs, CO-derived tribofilms show even more substantial structural degradation.

The development of hierarchically porous block copolymer (BCP) membranes via the application of the self-assembly and non-solvent induced phase separation (SNIPS) process is one important achievement in BCP science in the last decades. In this work, we present the synthesis of polyacrylonitrile-containing amphiphilic BCPs and their unique microphase separation capability, as well as their applicability for the SNIPS process leading to isoporous integral asymmetric membranes. Poly(styrene-co-acrylonitrile)-b-poly(2-hydroxyethyl methacrylate)s (PSAN-b-PHEMA) are synthesized via a two-step atom transfer radical polymerization (ATRP) procedure rendering PSAN copolymers and BCPs with overall molar masses of up to 82 kDa while maintaining low dispersity index values in the range of Đ = 1.13–1.25. The polymers are characterized using size-exclusion chromatography (SEC) and NMR spectroscopy. Self-assembly capabilities in the bulk state are examined using transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) measurements. The fabrication of isoporous integral asymmetric membranes is investigated, and membranes are examined by scanning electron microscopy (SEM). The introduction of acrylonitrile moieties within the membrane matrix could improve the membranes’ mechanical properties, which was confirmed by nanomechanical analysis using atomic force microscopy (AFM).

Molybdenum carbides, oxides, and mixed anionic carbide–nitride–oxides Mo(C,N,O)x are potential anode materials for lithium-ion batteries. Here we present the preparation of hybrid inorganic–organic precursors by a precipitation reaction of ammonium heptamolybdate ((NH4)6Mo7O24) with para-phenylenediamine in a continuous wet chemical process known as a microjet reactor. The mixing ratio of the two components has a crucial influence on the chemical composition of the obtained material. Pyrolysis of the precipitated precursor compounds preserved the size and morphology of the micro- to nanometer-sized starting materials. Changes in pyrolysis conditions such as temperature and time resulted in variations of the final compositions of the products, which consisted of mixtures of Mo(C,N,O)x, MoO2, Mo2C, Mo2N, and Mo. We optimized the reaction conditions to obtain carbide-rich phases. When evaluated as an anode material for application in lithium-ion battery half-cells, one of the optimized materials shows a remarkably high capacity of 933 mA h g−1 after 500 cycles. The maximum capacity is reached after an activation process caused by various conversion reactions with lithium.

As part of humankind’s path towards more sustainable water technologies, redox flow desalination (RFD) has emerged as a promising technology due to its high energy efficiency and easy operation. So far, RFD research has focused on removing and recovering inorganic salts such as lithium-ions, heavy metal ions, or phosphate and nitrate ions. Thus, the potential of RFD in water desalination and resource recovery processes has not been fully demonstrated. Therefore, this study aimed to assess RFD for the valorization of tetramethylammonium hydroxide (TMAH) as value-added organic compounds from wastewater beyond inorganic elements, which is widely being used as an etching solvent, photoresist developer, and surfactant in semiconductor and display industries. By applying a low cell voltage (<1.2 V), a reversible redox reaction allowed a continuous removal of TMAH from the wastewater stream and a simultaneous recovery for reuse as a form of tetramethylammonium cation. The TMAH removal rate was approximately 4.3 mM/g/h with a 40% recovery ratio. With various operational conditions (i.e., TMAH concentration, cell voltage, and flow rate), our system exhibited a high potential for the valorization of TMAH with 60% reduction in capital cost compared to conventional desalination processes.

Abstract Binder is a crucial component in present-day battery electrodes but commonly contains fluorine and requires coating processing using organic (often toxic) solvents. Preparing binder-free electrodes is an attractive strategy to make battery electrode production and its end-of-use waste greener and safer. Here, electrospinning is employed to prepare binder-free and self-standing electrodes. Such electrodes often suffer from low flexibility, and the correlation between performance and flexibility is usually overlooked. Processing parameters affect the mechanical properties of the electrodes, and for the first time it is reported that mechanical flexibility directly influences the electrochemical performance of the electrode. The importance is highlighted when processing parameters advantageous to powder materials, such as a higher heat treatment temperature, harm self-standing electrodes due to deterioration of fiber flexibility. Other strategies, such as conductive carbon addition, can be employed to improve the cell performance, but their effect on the mechanical properties of the electrodes must be considered. Rapid heat treatment achieves self-standing V2O3 with a capacity of 250 mAh g−1 at 250 mA g−1 and 390 mAh g−1 at 10 mA g−1

Hexacyanometallates, known as Prussian blue (PB) and its analogues (PBAs), are a class of coordination
compounds with a regular and porous open structure. The PBAs are formed by the self-assembly of
metallic species and cyanide groups. A uniform distribution of each element makes the PBAs robust
templates to prepare hollow and highly porous (hetero)nanostructures of metal oxides, sulfides, carbides,
nitrides, phosphides, and (N-doped) carbon, among other compositions. In this review, we examine
methods to derive materials from PBAs focusing on the correlation between synthesis steps and
derivative morphologies and composition. Insights into catalytic and electrochemical properties resulting
from different derivatization strategies are also presented. We discuss challenges in manipulating the
derivatives' properties, give perspectives of synthetic approaches for the target applications and present
an outlook on less investigated grounds in Prussian blue derivatives

MBenes are post-MXene materials that contain boron in their structure instead of carbon and nitrogen. This unique composition offers an opportunity to explore the role of boron in the performance of 2D materials. However, wet-chemical etching and delamination of the starting MoAlB phase are challenging due to the persistent bonding of aluminum atoms with their neighboring elements. Herein, it is overcome by processing MoAlB for 24, 48, and 72 h with an aqueous HCl/H2O2 solution. The time-wise etching and delamination delivers individual single-to-few layered 48-MBene flakes. The theoretical-to-experimental XRD analysis revealed the best-delaminated 48-MBene having Mo2B2 orthorhombic lattice arrangement. The presence of Mo oxide allows direct 1.2 eV and indirect 0.2 eV optical band gaps and outstanding photocatalytic activity in decomposing methylene blue as a model organic contaminant. The 48-MBene photocatalyst achieves about 90% of MB decomposition under ultraviolet and simulated white light irradiation with three times faster kinetics outperforming even hybridized MXenes. In addition, 48-MBene appeared best suited to utilize the full spectrum of visible light into reactive oxygen species. Conversely, 24-MBene and 72-MBene shows incomplete delamination or oxidation, hampering their photocatalytic activity. The obtained results open an experimental pathway to apply MBenes in environmental remediation.