Energie-Materialien

Developing thin, freestanding electrodes that work simultaneously as a current collector and electroactive material is pivotal to integrating portable and wearable chemical sensors. Herein, we have synthesized graphene/Prussian blue (PB) electrodes for hydrogen peroxide detection (H2O2) using a two-step method. First, an reduced graphene oxide/PAni/Fe2O3 freestanding film is prepared using a doctor blade technique, followed by the electrochemical deposition of PB nanoparticles over the films. The iron oxide nanoparticles work as the iron source for the heterogeneous electrochemical deposition of the nanoparticles in a ferricyanide solution. The size of the PB cubes electrodeposited over the graphene-based electrodes was controlled by the number of voltammetric cycles. For H2O2 sensing, the PB10 electrode achieved the lowest detection and quantification limits, 2.00 and 7.00 μM, respectively. The findings herein evidence the balance between the structure of the graphene/PB-based electrodes with the electrochemical performance for H2O2 detection and pave the path for developing new freestanding electrodes for chemical sensors.

The unsustainable dependence of nitrogen fertilizers (NFs) production on energy-intensive processes and its association with nitrate-laden wastewater that fuels harmful algal blooms (HABs) necessitate innovative solutions. Here, we propose a paradigm shift: repurposing HABs biomass as carbon-based catalysts (Cu1Mo1/NC) for the ambient-condition electrosynthesis of NFs from NO3− and CO2. Remarkably, Cu1Mo1/NC delivers a high NFs yield rate of 2303 μg h−1 mgcat−1 (772 μg h−1mgcat−1 for urea and 1531 μg h−1 mgcat−1 for ammonia) with a Faradaic efficiency (FE) of 68.4% (15.2% for urea and 53.2% for ammonia) at −1.05 V vs. RHE. Experimental and theoretical evidence reveal that Cu doping tunes the d-band center of Cu1Mo1/NC, bringing it closer to the Fermi level. This enhances the intermediate adsorption, thereby propelling the C-N coupling reaction. Carbon reduction potential analysis underscores the promising feasibility and sustainable value of the presented method.

Herein, we report polyphosphonate covalent organic frameworks (COFs) constructed via P-O-P linkages. The materials are synthesized via a single-step condensation reaction of the charge-assisted hydrogen-bonded organic framework, which is constructed from phenylphosphonic acid and 5,10,15,20‐tetrakis[p‐phenylphosphonic acid]porphyrin and is formed by simply heating its hydrogen-bonded precursor without using chemical reagents. Above 210 °C, it becomes an amorphous microporous polymeric structure due to the oligomerization of P-O-P bonds, which could be shown by constant-time solid-state double-quantum 31P nuclear magnetic resonance experiments. The polyphosphonate COF exhibits good water and water vapor stability during the gas sorption measurements, and electrochemical stability in 0.5 M Na2SO4 electrolyte in water. The reported family of COFs fills a significant gap in the literature by providing stable microporous COFs suitable for use in water and electrolytes. Additionally, we provide a sustainable synthesis route for the COF synthesis. The narrow pores of the COF effectively capture CO2.

Efficient separation of specific ions from aqueous media is crucial for advanced water treatment and resource recovery. Flow electrode capacitive deionization (FCDI) offers potential for selective ion removal through continuous operation. This study evaluates the performance of selective cation separation using a commercial activated carbon slurry in a multi-ion solution of monovalent (Li+, Na+, K+) and bivalent (Ca2+, Mg2+) cations. We assess ion removal and cation selectivity under different operational parameters, such as applied potential, slurry flow rate, and feed water flow rate. Our data show that bivalent cations, namely Ca2+ and Mg2+, are preferentially removal due to their higher charge-to-size ratio, aligning with hydrated ion sizes. The highest separation rate was observed for Ca2+ (5.7 μg cm−2 min−1), and the lowest for Li+ (0.2 μg cm−2 min−1). At the highest applied voltage (1.2 V), charge efficiencies reached 70 %, with an energy consumption of 41 Wh mol−1 for nearly complete cation removal. Optimal conditions were identified with a slurry flow rate of 6 mL min−1, feed water flow rate of 2 mL min−1, activated carbon content of 10 mass%, 1 mass% carbon black, and a cell voltage of 1.2 V. These findings highlight the importance of optimizing operational parameters to enhance ion removal.

This study explores the potential of re-purposing end-of-life commercial supercapacitors as electrochemical desalination cells, aligning with circular economy principles. A commercial 500-Farad supercapacitor was disassembled, and its carbon electrodes underwent various degrees of modification. The most straightforward modification involved NaOH-etching of the aluminum current collector to produce free-standing carbon films. More advanced modifications included CO2 activation and binder-added wet processing of the electrodes. When evaluated as electrodes for electrochemical desalination via capacitive deionization of low-salinity (20 mM) NaCl solutions, the minimally modified NaOH-etched carbon electrodes achieved an average desalination capacity of 5.8 mg g−1 and a charge efficiency of 80 %. In contrast, the CO2-activated, wet-processed electrodes demonstrated an improved desalination capacity of 7.9 mg g−1 and a charge efficiency above 90 % with stable performance over 20 cycles. These findings highlight the feasibility and effectiveness of recycling supercapacitors for sustainable water desalination applications, offering a promising avenue for resource recovery and re-purposing in pursuing environmental sustainability.

Organic materials have emerged as highly efficient electrodes for electrochemical energy storage, offering sustainable solutions independent from non-renewable resources. In this study, we showcase that mesoscale engineering can dramatically transform the electrochemical features of a molecular organic carboxylic anode. Through a sustainable, energy-efficient and environmentally benign self-assembly strategy, we developed a network of organic nanowires formed during water evaporation directly on the copper current collector, circumventing the need for harmful solvents, typically employed in such processes. The organic nanowire anode delivers high capacity and rate, reaching 1888 mA h g−1 at 0.1 A g−1 and maintaining 508 mA h g−1 at a specific current of 10 A g−1. Moreover, it exhibits superior thermal management during lithiation in comparison to graphite and other organic anodes. Comprehensive electrochemical evaluations and theoretical calculations reveal rapid charge transport mechanisms, with lithium diffusivity rates reaching 5 × 10−9 cm2 s−1, facilitating efficient and rapid interactions with 24 lithium atoms per molecule. Integrated as the negative electrode in a lithium-ion capacitor, paired with a commercially available porous carbon, the cell delivers a specific energy of 156 W h kg−1 at a specific power of 0.34 kW kg−1 and 60.2 W h kg−1 at 19.4 kW kg−1, establishing a benchmark among state-of-the-art systems in the field. These results underscore the critical role of supramolecular organization for optimizing the performance of organic electrode materials for practical and sustainable energy storage technologies.

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.