Formulation and Recycling of a Novel Electrolyte Based on Bio-Derived γ-Valerolactone and Lithium Bis(trifluoromethanesulfonyl)imide for Lithium-Ion Batteries.

This work introduces a novel electrolyte comprising lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt dissolved in bio-based γ-valerolactone (GVL) for lithium-ion batteries (LIBs). Moreover, a simple and sustainable aqueous-based recycling approach for recovering the imide-based lithium salt is proposed. Beyond the sustainable origin of the GVL solvent, this electrolyte exhibits reduced flammability risk, characterized by a flash point of 136 °C, along with favorable transport properties (conductivity of 6.

Cyanide Linkage Isomerization Induced by Cobalt Oxidation-State Changes at a Co-Fe Prussian-Blue Analogue/ZnO Interface.

Understanding the interfacial composition in heterostructures is crucial for tailoring heterogenous electrochemical and photoelectrochemical processes. This work aims to elucidate the structure of a series of Co-Fe Prussian blue analogue modified ZnO (PBA/ZnO) electrodes with interface-sensitive vibrational sum frequency generation (VSFG) spectroscopy. Our measurements revealed, for the first time, a cyanide linkage isomerism at the PBA/ZnO interface, when the composite is fabricated at elevated temperatures.

A Polarizable Forcefields for Glyoxal Acetals as Electrolyte Components for Lithium-Ion Batteries.

In this work we have derived the parameters of an AMOEBA-like polarizable forcefield for electrolytes based on tetramethoxy and tetraethoxy-glyoxal acetals, and propylene carbonate. The resulting forcefield has been validated using both ab-initio data and the experimental properties of the fluids. Using molecular dynamics simulations, we have investigated the structural features and the solvation properties of both the neat liquids and of the corresponding 1 M LiTFSI electrolytes at the molecular level.

Coordination and Diffusion in Glyoxal-Based Electrolytes for Potassium-Ion Batteries.

Glyoxal-based electrolytes have been identified as promising for potassium-ion batteries (PIBs). Here we investigate the properties of electrolytes containing potassium bis(fluorosulfonyl)imide (KFSI) in 1,1,2,2-tetra-ethoxy-ethane (tetra-ethyl-glyoxal, TEG) using density functional theory (DFT) calculations, Raman spectroscopy, and impedance spectroscopy. The coordination and configuration of the complexes possible to arise from coordination of the K ions by FSI and TEG were investigated both from an energetic point of view as well as qualitatively determined via comparing experimental and artificial Raman spectra.

Understanding the Role of Imide-Based Salts and Borate-Based Additives for Safe and High-Performance Glyoxal-Based Electrolytes in Ni-Rich NMC Cathodes for Li-Ion Batteries.

Herein, the design of novel and safe electrolyte formulations for high-voltage Ni-rich cathodes is reported. The solvent mixture comprising 1,1,2,2-tetraethoxyethane and propylene carbonate not only displays good transport properties, but also greatly enhances the overall safety of the cell thanks to its low flammability. The influence of the conducting salts, that is, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium bis(fluorosulfonyl)imide (LiFSI), and of the additives lithium bis(oxalato)borate (LiBOB) and lithium difluoro(oxalato)borate (LiDFOB) is examined.

Fluorine-Free Lithium-Ion Capacitor with Enhanced Sustainability and Safety Based on Bio-Based ƴ-Valerolactone and Lithium Bis(Oxalato)Borate Electrolyte.

In this work, the properties of a novel electrolyte based on the combination of bio-based ƴ-valerolactone (GVL) solvent with lithium bis(oxalato)borate (LiBOB) salt and its use for lithium-ion capacitors (LICs) are presented. It is shown that the 1 m LiBOB in GVL electrolyte displays good transport properties, high thermal stability, and the ability to prevent anodic dissolution. Its impact on the performance of both battery-type and capacitive-type electrodes is evaluated.

The "In situ electrolyte" as a sustainable alternative for the realization of high-power devices.

The "in situ electrolyte" displays a concept for electric double-layer- as well as metal-ion capacitors in which the by-products formed during carbon synthesis serve directly as electrolyte salt to minimize waste. In this work, the concept is applied for lithium- and sodium-based systems realizing EDLCs containing aqueous, "Water in Salt" (up to 1.8 V) as well as organic (2.

Electrochemical Sodium Storage in Hard Carbon Powder Electrodes Implemented in an Improved Cell Assembly: Insights from In-Situ and Ex-Situ Solid-State NMR.

In this work, we report on an improved cell assembly of cylindrical electrochemical cells for Na in-situ solid-state NMR (ssNMR) investigations. The cell set-up is suitable for using powder electrode materials. Reproducibility of our cell assembly is analyzed by preparing two cells containing hard carbon (HC) powder as working electrode and sodium metal as reference electrode.

Polyoxometalate-Modified Amphiphilic Polystyrene--poly(2-(dimethylamino)ethyl methacrylate) Membranes for Heterogeneous Glucose to Formic Acid Methyl Ester Oxidation.

Herein, we present a new heterogeneous catalyst active toward glucose to formic acid methyl ester oxidation. The catalyst was fabricated via electrostatic immobilization of the inorganic polyoxometalate HPA-5 catalyst H[PMoVO] onto the pore surface of amphiphilic block copolymer membranes prepared via non-solvent-induced phase separation (NIPS). The catalyst immobilization was achieved via wet impregnation due to strong coulombic interactions between protonated tertiary amino groups of the polar poly(2-(dimethylamino)ethyl methacrylate) block and the anionic catalyst.

Coordinative Stabilization of Single Bismuth Sites in a Carbon-Nitrogen Matrix to Generate Atom-Efficient Catalysts for Electrochemical Nitrate Reduction to Ammonia.

Electrochemical nitrate reduction to ammonia powered by renewable electricity is not only a promising alternative to the established energy-intense and non-ecofriendly Haber-Bosch reaction for ammonia generation but also a future contributor to the ever-more important denitrification schemes. Nevertheless, this reaction is still impeded by the lack of understanding for the underlying reaction mechanism on the molecular scale which is necessary for the rational design of active, selective, and stable electrocatalysts. Herein, a novel single-site bismuth catalyst (Bi-N-C) for nitrate electroreduction is reported to produce ammonia with maximum Faradaic efficiency of 88.

pH-Regulated Refinement of Pore Size in Carbon Spheres for Size-Sieving of Gaseous C , C and C Hydrocarbon Pairs.

Selective separation of industrial important C , C and C hydrocarbon pairs by physisorbents can greatly reduce the energy intensity related to the currently used cryogenic distillation techniques. The achievement of size-sieving based on carbonaceous materials is desirable, but commonly hindered by the random structure of carbons often with a broad pore size distribution. Herein, a pH-regulated pre-condensation strategy was introduced to control the carbon pore architecture by the sp /sp hybridization of precursor.

Sensing of chemical oxygen demand (COD) by amperometric detection-dependence of current signal on concentration and type of organic species.

The standard method to determine chemical oxygen demand (COD) with KCrO uses harmful chemicals, has a long analysis time, and cannot be used for on-site online monitoring. It is therefore necessary to find a fast, cheap, and harmless alternative. The amperometric determination of COD on boron-doped diamond (BDD) electrodes is a promising approach.

Glyoxylic-Acetal-Based Electrolytes for Sodium-Ion Batteries and Sodium-Ion Capacitors.

A comprehensive study on the properties and implementation of glyoxylic-acetals in sodium-ion energy storage systems is presented. Electrolytes containing 1,1,2,2-tetramethoxyethane (tetramethoxyglyoxal, TMG), 1,1,2,2-tetraethoxyethane (tetraethoxyglyoxal, TEG) and a mixture of the latter with propylene carbonate (PC) exhibit increased thermal stabilities and higher flash points compared to classical electrolytes based on carbonates as solvents. Due to its favorable properties, 1 m NaTFSI in TEG/PC (3 : 7), has been selected and used for sodium-ion energy storage systems based on a Prussian Blue (PB) positive electrode and a hard carbon (HC) negative electrode.

Application of Thermal Response Measurements to Investigate Enhanced Water Adsorption Kinetics in Ball-Milled C N-Type Materials.

Sorption-based water capture is an attractive solution to provide potable water in arid regions. Heteroatom-decorated microporous carbons with hydrophilic character are promising candidates for water adsorption at low humidity, but the strong affinity between the polar carbon pore walls and water molecules can hinder the water transport within the narrow pore system. To reduce the limitations of mass transfer, C N-type carbon materials obtained from the thermal condensation of a molecular hexaazatriphenylene-hexacarbonitrile (HAT-CN) precursor were treated mechanochemically via ball milling.

γ-Valerolactone as Sustainable and Low-Toxic Solvent for Electrical Double Layer Capacitors.

In this work, γ-valerolactone (GVL), a green solvent based on largely available biomass (carbohydrates), highly biodegradable, and with low eco-toxicological profile, was used as electrolyte component in energy storage devices. This solvent allowed the realization of electrolytes with good transport properties and high thermal stability, which could be successfully applied in electrical double layer capacitors (EDLCs). GVL-based EDLCs could operate at 2.

Electrochemical Generation of Catalytically Active Edge Sites in C N-Type Carbon Materials for Artificial Nitrogen Fixation.

The electrochemical nitrogen reduction reaction (NRR) to ammonia (NH ) is a potentially carbon-neutral and decentralized supplement to the established Haber-Bosch process. Catalytic activation of the highly stable dinitrogen molecules remains a great challenge. Especially metal-free nitrogen-doped carbon catalysts do not often reach the desired selectivity and ammonia production rates due to their low concentration of NRR active sites and possible instability of heteroatoms under electrochemical potential, which can even contribute to false positive results.

Schiff-bases for sustainable battery and supercapacitor electrodes.

The quest for more efficient ways to store electrical energy prompted the development of different storage devices over the last decades. This includes but is not limited to different battery concepts and supercapacitors. However, modern batteries rely on electrochemical principles that often involve transition metals which can for instance suffer from toxicity or limited availability.

New Diglyme-based Gel Polymer Electrolytes for Na-based Energy Storage Devices.

This work presents for the first time a new diglyme-based gel polymer (DOBn-GPE) suitable for Na-based energy storage devices. The DOBn-GPE, which contains a methacrylate-based polymer, exhibited an excellent high ionic conductivity (2.3 mS cm at 20 °C), broad electrochemical stability (>5.

Water in Protic Ionic Liquid Electrolytes: From Solvent Separated Ion Pairs to Water Clusters.

The large electrochemical and cycling stability of "water-in-salt" systems have rendered promising prospective electrolytes for batteries. The impact of addition of water on the properties of ionic liquids has already been addressed in several publications. In this contribution, we focus on the changes in the state of water.

Toward Efficient Synthesis of Porous All-Carbon-Based Nanocomposites for Enantiospecific Separation.

Chiral separation and asymmetric synthesis and catalysis are crucial processes for obtaining enantiopure compounds, which are especially important in the pharmaceutical industry. The efficiency of the separation processes is readily increased by using porous materials as the active material can interact with a larger surface area. Silica, metal-organic frameworks, or chiral polymers are versatile porous materials that are established in chiral applications, but their instability under certain conditions in some cases requires the use of more stable porous materials such as carbons.

The Functional Chameleon of Materials Chemistry-Combining Carbon Structures into All-Carbon Hybrid Nanomaterials with Intrinsic Porosity to Overcome the "Functionality-Conductivity-Dilemma" in Electrochemical Energy Storage and Electrocatalysis.

Nanoporous carbon materials can cover a remarkably wide range of physicochemical properties. They are widely applied in electrochemical energy storage and electrocatalysis. As a matter of fact, all these applications combine a chemical process at the electrode-electrolyte interface with the transport (and possibly the transfer) of electrons.

Emulsion Polymerizations for a Sustainable Preparation of Efficient TEMPO-based Electrodes.

Organic polymer-based batteries represent a promising alternative to present-day metal-based systems and a valuable step toward printable and customizable energy storage devices. However, most scientific work is focussed on the development of new redox-active organic materials, while straightforward manufacturing and sustainable materials and production will be a necessary key for the transformation to mass market applications. Here, a new synthetic approach for 2,2,6,6-tetramethyl-4-piperinidyl-N-oxyl (TEMPO)-based polymer particles by emulsion polymerization and their electrochemical investigation are reported.

Silica based ionogels: interface effects with aprotic and protic ionic liquids with lithium.

In the frame of the development of solid ionogel electrolytes with enhanced ion transport properties, this paper investigates ionogel systems constituted by ∼80 wt% of ionic liquids (ILs) confined in meso-/macroporous silica monolith materials. The anion-cation coordination for two closely related ILs, either aprotic (AIL) butylmethylpyrrolidinium or protic (PIL) butylpyrrolidinium, both with bis(trifluoromethylsulfonyl)imide (TFSI) anions, with and without lithium cations, is studied in depth. The ILs are confined within silica with well-defined mesoporosities (8 to 16 nm).

Polyimide@Ketjenblack Composite: A Porous Organic Cathode for Fast Rechargeable Potassium-Ion Batteries.

Potassium-ion batteries (PIBs) configurated by organic electrodes have been identified as a promising alternative to lithium-ion batteries. Here, a porous organic Polyimide@Ketjenblack is demonstrated in PIBs as a cathode, which exhibits excellent performance with a large reversible capacity (143 mAh g at 100 mA g ), high rate capability (125 and 105 mAh g at 1000 and 5000 mA g ), and long cycling stability (76% capacity retention at 2000 mA g over 1000 cycles). The domination of fast capacitive-like reaction kinetics is verified, which benefits from the porous structure synthesized using in situ polymerization.

A Comparative Review of Electrolytes for Organic-Material-Based Energy-Storage Devices Employing Solid Electrodes and Redox Fluids.

Electrolyte chemistry is critical for any energy-storage device. Low-cost and sustainable rechargeable batteries based on organic redox-active materials are of great interest to tackle resource and performance limitations of current batteries with metal-based active materials. Organic active materials can be used not only as solid electrodes in the classic lithium-ion battery (LIB) setup, but also as redox fluids in redox-flow batteries (RFBs).