Long-Cycle-Life Calcium Battery with a High-Capacity Conversion Cathode Enabled by a Ca/Li Hybrid Electrolyte.

Calcium (Ca) batteries represent an attractive option for electrochemical energy storage due to physicochemical and economic reasons. The standard reduction potential of Ca (-2.87 V) is close to Li and promises a wide voltage window for Ca full batteries, while the high abundance of Ca in the earth's crust implicates low material costs.

POM@ZIF Derived Mixed Metal Oxide Catalysts for Sustained Electrocatalytic Oxygen Evolution.

The design of efficient and stable oxygen evolution reaction (OER) catalysts based on noble-metal-free materials is crucial for energy conversion and storage. In this work, it was demonstrated how polyoxometalate (POM)-doped ZIF-67 can be converted into a stable oxygen evolution electrocatalyst by chemical etching, cation exchange, and thermal annealing steps. Characterization by X-ray photoelectron spectroscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy and Raman spectroscopy indicate that POM-doped ZIF-67 derived carbon-supported metal oxides were synthesized.

Molecular Engineering of Metalloporphyrins for High-Performance Energy Storage: Central Metal Matters.

Porphyrin derivatives represent an emerging class of redox-active materials for sustainable electrochemical energy storage. However, their structure-performance relationship is poorly understood, which confines their rational design and thus limits access to their full potential. To gain such understanding, we here focus on the role of the metal ion within porphyrin molecules.

Tetrathiafulvalene-Benzothiadiazole: A Metal-Free Photocatalyst for Hydrogen Production.

In this work, a series of hybrid tetrathiafulvalene-benzothiadiazole (TTF-BTD) are designed and applied as a metal-free photocatalyst for hydrogen production, particularly under visible light irradiation. Density functional theory calculations are used to shed light on the photophysical properties observed in the various TTF-BTD derivatives and investigated by the obtained data. Because band gap engineering has normally been used as an effective approach, we studied the effect of the various functional groups on the band gap to set a favorable band alignment with photocatalysts.

Probing Capacity Trends in MLiTiO Lithium-Ion Battery Anodes Using Calorimetric Studies.

Due to higher packing density, lower working potential, and area specific impedance, the MLiTiO (M = 2Na, Sr, Ba, and Pb) titanate family is a potential alternative to zero-strain LiTiO anodes used commercially in Li-ion batteries. However, the exact lithiation mechanism in these compounds remains unclear. Despite its structural similarity, MLiTiO behaves differently depending on charge and size of the metal ion, hosting 1.

Structures Controlled by Entropy: The Flexibility of Strychnine as Example.

To study the flexibility of strychnine, we performed molecular dynamics simulations with orientational tensorial constraints (MDOC). Tensorial constraints are derived from nuclear magnetic resonance (NMR) interaction tensors, for instance, from residual dipolar couplings (RDCs). Used as orientational constraints, they rotate the whole molecule and molecular parts with low rotational barriers.

Cation-controlled capture of polyoxovanadate-based organic-inorganic 1D architectures.

Metal cations are used to control the selective crystallization of organic-inorganic supramolecular polymers. Two complementary monomers, a dodecanuclear vanadate [VO(NO)] and the organic macrocycle cyclen assemble into hybrid host-guest aggregates. In the presence of Ba or La, supramolecular polymerization and crystallization is driven by a complex interplay of cyclene protonation, hydrogen-bonding and electrostatics.

Development of a Mg/O ReaxFF Potential to describe the Passivation Processes in Magnesium-Ion Batteries.

One of the key challenges preventing the breakthrough of magnesium-ion batteries (MIB) is the formation of a passivating boundary layer at the Mg anode. To describe the initial steps of Mg anode degradation by O impurities, a Mg/O ReaxFF (force field for reactive systems) parameter set was developed capable of accurately modeling the bulk, surface, adsorption, and diffusion properties of metallic Mg and the salt MgO. It is shown that O immediately dissociates upon first contact with the Mg anode (modeled as Mg(0001), Mg(10 0)A, and Mg(10 1)), heating the surface to several 1000 K.

Combining Deep Eutectic Solvents with TEMPO-based Polymer Electrodes: Influence of Molar Ratio on Electrode Performance.

For sustainable energy storage, all-organic batteries based on redox-active polymers promise to become an alternative to lithium ion batteries. Yet, polymers contribute to the goal of an all-organic cell as electrodes or as solid electrolytes. Here, we replace the electrolyte with a deep eutectic solvent (DES) composed of sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) and N-methylacetamide (NMA), while using poly(2,2,6,6-tetramethylpiperidin-1-yl-oxyl methacrylate) (PTMA) as cathode.

Disclosing the Redox Pathway Behind the Excellent Performance of CuS in Solid-State Batteries.

Copper sulfide has attracted increasing attention as conversion-type cathode material for, especially, solid-state lithium-based batteries. However, the reaction mechanism behind its extraordinary electroactivity is not well understood, and the various explanations given by the scientific community are diverging. Herein, the CuS reaction dynamics are highlighted by examining the occurring redox processes via a cutting-edge methodology combining X-ray absorption fine structure spectroscopy, and chemometrics to overcome X-ray diffraction limitations posed by the poor material's crystallinity.

Locally Concentrated Ionic Liquid Electrolyte with Partially Solvating Diluent for Lithium/Sulfurized Polyacrylonitrile Batteries.

The development of Li/sulfurized polyacrylonitrile (SPAN) batteries requires electrolytes that can form stable electrolyte/electrode interphases simultaneously on lithium-metal anodes (LMAs) and SPAN cathodes. Herein, a low-flammability locally concentrated ionic liquid electrolyte (LCILE) employing monofluorobenzene (mFBn) as the diluent is proposed for Li/SPAN cells. Unlike non-solvating diluents in other LCILEs, mFBn partially solvates Li , decreasing the coordination between Li and bis(fluorosulfonyl)imide (FSI ).

Toward Dendrite-Free Metallic Lithium Anodes: From Structural Design to Optimal Electrochemical Diffusion Kinetics.

Lithium metal anodes are ideal for realizing high-energy-density batteries owing to their advantages, namely high capacity and low reduction potentials. However, the utilization of lithium anodes is restricted by the detrimental lithium dendrite formation, repeated formation and fracturing of the solid electrolyte interphase (SEI), and large volume expansion, resulting in severe "dead lithium" and subsequent short circuiting. Currently, the researches are principally focused on inhibition of dendrite formation toward extending and maintaining battery lifespans.

Single- to Few-Layer Nanoparticle Cathode Coating for Thiophosphate-Based All-Solid-State Batteries.

Bulk-type solid-state batteries (SSBs) composed of lithium thiophosphate superionic solid electrolytes (SEs) and high-capacity cathode active materials (CAMs) have recently attracted much attention for their potential application in next-generation electrochemical energy storage. However, compatibility issues between the key components in this kind of battery system are difficult to overcome. Here, we report on a protective cathode coating that strongly reduces the prevalence of detrimental side reactions between CAM and SE during battery operation.

Durable Nickel-Iron (Oxy)hydroxide Oxygen Evolution Electrocatalysts through Surface Functionalization with Tetraphenylporphyrin.

NiFe-based oxides are one of the best-known active oxygen evolution electrocatalysts. Unfortunately, they rapidly lost performance in Fe-purified KOH during the reaction. Herein, tetraphenylporphyrin (TPP) was loaded on a catalyst/electrolyte interface to alleviate the destabilization of NiFe (oxy)hydroxide.

Stability of Magnesium Binary and Ternary Compounds for Batteries Determined from First Principles.

Electrochemical stability is a critical performance parameter for the materials used as electrolytes and electrodes in batteries. Using first-principles electronic structure calculations, we have determined the electrochemical stability windows of magnesium binary and ternary spinel compounds. These materials are candidates for protective coatings, solid electrolytes, and cathodes in Mg batteries, which represent a promising sustainable alternative to Li-ion batteries that still dominate the battery market.

Hybrid Organic/Inorganic Interphase for Stabilizing a Zinc Metal Anode in a Mild Aqueous Electrolyte.

Aqueous rechargeable zinc-based batteries have recently gained tremendous attention because of their low cost and high safety. However, the issues associated with the zinc metal anode, including corrosion, H evolution, and dendrite growth, hinder their practical applications. Herein, we design a hybrid organic/inorganic interphase composed of poly(vinylidene fluoride-co-hexafluoropropylene), silica, and zinc triflate to stabilize the zinc metal anode in a mild aqueous electrolyte.

Bio-Waste-Derived Hard Carbon Anodes Through a Sustainable and Cost-Effective Synthesis Process for Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) are postulated as sustainable energy storage devices for light electromobility and stationary applications. The anode of choice in SIBs is hard carbon (HC) due to its electrochemical performance. Among different HC precursors, bio-waste resources have attracted significant attention due to their low-cost, abundance, and sustainability.

Bimetallic Alloys b-AsP at High Concentration Differences: Ideal for Photonic Devices.

Black arsenic phosphorus (b-AsP) is expected to be one of the primary materials for future photonic devices. However, the -factor is randomly estimated and applied in photonic devices in current studies, rather than systematically analyzing it for a comprehensive understanding. Herein, AsP switches from a direct band gap semiconductor to an indirect band gap one at = 0.

Potential-Dependent Pt(111)/Water Interface: Tackling the Challenge of a Consistent Treatment of Electrochemical Interfaces.

The interface between an electrode and an electrolyte is where electrochemical processes take place for countless technologically important applications. Despite its high relevance and intense efforts to elucidate it, a description of the interfacial structure and, in particular, the dynamics of the electric double layer at the atomic level is still lacking. Here we present reactive force-field molecular dynamics simulations of electrified Pt(111)/water interfaces, shedding light on the orientation of water molecules in the vicinity of the Pt(111) surface, taking into account the influence of potential, adsorbates, and ions simultaneously.

Enabling High-Stability of Aqueous-Processed Nickel-Rich Positive Electrodes in Lithium Metal Batteries.

Lithium batteries occupy the large-scale electric mobility market raising concerns about the environmental impact of cell production, especially regarding the use of poly(vinylidene difluoride) (teratogenic) and N-methyl-2-pyrrolidone (NMP, harmful). To avoid their use, an aqueous electrode processing route is utilized in which a water-soluble hybrid acrylic-fluoropolymer together with sodium carboxymethyl cellulose is used as binder, and a thin phosphate coating layer is in situ formed on the surface of the nickel-rich cathode during electrode processing. The resulting electrodes achieve a comparable performance to that of NMP-based electrodes in conventional organic carbonate-based electrolyte (LP30).

Important Impact of the Slurry Mixing Speed on Water-Processed LiTiO Lithium-Ion Anodes in the Presence of HPO as the Processing Additive.

The aqueous processing of lithium transition metal oxides into battery electrodes is attracting a lot of attention as it would allow for avoiding the use of harmful -methyl-2-pyrrolidone (NMP) from the cell fabrication process and, thus, render it more sustainable. The addition of slurry additives, for instance phosphoric acid (PA), has been proven to be highly effective for overcoming the corresponding challenges such as aluminum current collector corrosion and stabilization of the active material particle. Herein, a comprehensive investigation of the effect of the ball-milling speed on the effectiveness of PA as a slurry additive is reported using LiTiO (LTO) as an exemplary lithium transition metal oxide.

Local Volume Conservation in Concentrated Electrolytes Is Governing Charge Transport in Electric Fields.

While ion transport processes in concentrated electrolytes, e.g., based on ionic liquids (IL), are a subject of intense research, the role of conservation laws and reference frames is still a matter of debate.

Insights into the Reaction Mechanisms of Nongraphitic High-Surface Porous Carbons for Application in Na- and Mg-Ion Batteries.

The fabrication of low-cost carbon materials and high-performance sodium- and magnesium-ion batteries comprising hierarchical porous electrodes and superior electrolytes is necessary for complementing Li-ion energy storage. In this work, nongraphitic high-surface porous carbons (NGHSPCs) exhibited an unprecedented formation of -stages (stage-1 and stage-2) due to the co-intercalation of sodium (Na(dgm)C) with diglyme. X-ray diffraction patterns, Patterson diagram, Raman spectra, and IR spectra suggested the presence of -stages.

Novel sulfur-doped single-ion conducting multi-block copolymer electrolyte.

Solid-state lithium batteries are considered one of the most promising candidates for future electrochemical energy storage. However, both inorganic solid electrolytes (such as oxide-based or sulfide-based materials) and polymer electrolytes still have to overcome several challenges to replace the currently used liquid organic electrolytes. An increasingly adopted approach to overcome these challenges relies on the combination of different electrolyte systems.