Revealing the Structural Evolution of Electrode/Electrolyte Interphase Formation during Magnesium Plating and Stripping with operando EQCM‐D

Rechargeable magnesium batteries could provide future energy storage systems with high energy density. One remaining challenge is the development of electrolytes compatible with the negative Mg electrode, enabling uniform plating and stripping with high Coulombic efficiencies. Often improvements are hindered by a lack of fundamental understanding of processes occurring during cycling, as well as the existence and structure of a formed interphase layer at the electrode/electrolyte interface. Here, a magnesium model electrolyte based on magnesium bis(trifluoromethanesulfonyl)imide (Mg(TFSI)$_2$) and MgCl$_2$ with a borohydride as additive, dissolved in dimethoxyethane (DME), was used to investigate the initial galvanostatic plating and stripping cycles operando using electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D). We show that side reactions lead to the formation of an interphase of irreversibly deposited Mg during the initial cycles. EQCM-D based hydrodynamic spectroscopy reveals the growth of a porous layer during Mg stripping. After the first cycles, the interphase layer is in a dynamic equilibrium between the formation of the layer and its dissolution, resulting in a stable thickness upon further cycling. This study provides operando information of the interphase formation, its changes during cycling and the dynamic behavior, helping to rationally develop future electrolytes and electrode/electrolyte interfaces and interphases

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. The successful combination of a DES with a polymer electrode is reported here for the first time. The electrochemical stability of PTMA electrodes in the DES at the eutectic molar ratio of 1 : 6 is comparable to conventional battery electrolytes. More viscous electrolytes with higher salt concentration can hinder cycling at high rates. Lower salt concentration leads to decreasing capacities and faster decomposition. The eutectic mixture of 1 : 6 is best suited uniting high stability and moderate viscosity

Charge Tunable GaAs Quantum Dots in a Photonic n-i-p Diode

In this submission, we discuss the growth of charge-controllable GaAs quantum dots embedded in an n-i-p diode structure, from the perspective of a molecular beam epitaxy grower. The QDs show no blinking and narrow linewidths. We show that the parameters used led to a bimodal growth mode of QDs resulting from low arsenic surface coverage. We identify one of the modes as that showing good properties found in previous work. As the morphology of the fabricated QDs does not hint at outstanding properties, we attribute the good performance of this sample to the low impurity levels in the matrix material and the ability of n- and p-doped contact regions to stabilize the charge state. We present the challenges met in characterizing the sample with ensemble photoluminescence spectroscopy caused by the photonic structure used. We show two straightforward methods to overcome this hurdle and gain insight into QD emission properties

Chromophores, fluorophores and robust ancillary ligands for molecular catalysts: 1,3-Bis(2-pyridylimino)isoindolines

Since the first report in the early 1950s, 1,3-bis(2-pyridylimino)isoindolines (BPIs) have found widespread applications in organic, inorganic and materials chemistry. This microreview focuses on recent progress towards chiral BPI derivatives as ligands for enantioselective catalysis as well as developments in the use of BPI complexes in materials science, focusing on luminescent and birefringent materials

Revealing the Structural Evolution of Electrode/Electrolyte Interphase Formation during Magnesium Plating and Stripping with operando EQCM-D

Rechargeable magnesium batteries could provide future energy storage systems with high energy density. One remaining challenge is the development of electrolytes compatible with the negative Mg electrode enabling uniform plating and stripping with high Coulombic efficiencies. Often improvements are hindered by a lack of fundamental understanding of processes occurring during cycling as well as the existence and structure of a formed interphase layer at the electrode/electrolyte interface. Here, a magnesium model electrolyte based on magnesium bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2) and MgCl2 with a borohydride as additive, dissolved in dimethoxyethane (DME), was used to investigate the initial galvanostatic plating and stripping cycles under operation conditions using electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D). We show that side reactions lead to the formation of an interphase of irreversibly deposited Mg during the initial cycles. EQCM-D based hydrodynamic spectroscopy reveals the growth of a porous layer during Mg stripping. After the first cycles, the interphase layer is in a dynamic equilibrium between the formation of the layer and its dissolution, resulting in a stable thickness upon further cycling. This study provides operando information of the interphase formation, its changes during cycling and the dynamic behavior, helping to rationally develop future electrolytes and electrode/electrolyte interfaces and interphases

Revealing the Structural Evolution of Electrode/Electrolyte Interphase Formation during Magnesium Plating and Stripping with operando EQCM-D

Rechargeable magnesium batteries could provide future energy storage systems with high energy density. One remaining challenge is the development of electrolytes compatible with the negative Mg electrode, enabling uniform plating and stripping with high Coulombic efficiencies. Often improvements are hindered by a lack of fundamental understanding of processes occurring during cycling, as well as the existence and structure of a formed interphase layer at the electrode/electrolyte interface. Here, a magnesium model electrolyte based on magnesium bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2) and MgCl2 with a borohydride as additive, dissolved in dimethoxyethane (DME), was used to investigate the initial galvanostatic plating and stripping cycles operando using electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D). We show that side reactions lead to the formation of an interphase of irreversibly deposited Mg during the initial cycles. EQCM-D based hydrodynamic spectroscopy reveals the growth of a porous layer during Mg stripping. After the first cycles, the interphase layer is in a dynamic equilibrium between the formation of the layer and its dissolution, resulting in a stable thickness upon further cycling. This study provides operando information of the interphase formation, its changes during cycling and the dynamic behavior, helping to rationally develop future electrolytes and electrode/electrolyte interfaces and interphases

Insight into the Synthesis Process of an Industrial Ziegler-Natta Catalyst

In Ziegler–Natta catalysis, the catalyst particle size has a strong influence not only on catalyst performance but also on the morphology and particle size distribution of the final polymer particles. Fundamental insight into the catalyst particle formation process is therefore of industrial importance when addressing specific requirements in the final products. In the present work, we fully characterize a single-step catalyst preparation process, which comprises a reactive precipitation of a MgCl2-supported Ziegler–Natta catalyst, through decomposition of the hetero-bimetallic complex, Mg(OR)2·Ti(OR)4, by addition of ethyl aluminum dichloride (EADC). We track the evolution of both of the concentrations of the metals (Mg, Ti, Al) as well as Cl in the liquid phase and the size of the formed catalyst particles. It is observed that the liquid-phase composition is governed by the EADC feed rate under fully Cl-starved conditions. The process can be divided into two stages: The first stage is dominated by the precipitation of the Mg-based support, and the second stage involves complex adsorption–precipitation of the Ti species. The growth of the catalyst particle size occurs only in the first stage and is controlled by the aggregation and breakage events during the MgCl2 precipitation. It follows that the hydrodynamic stress in the reactor plays the essential role in controlling the catalyst size. In the second stage, no further particle growth occurs, not only because of the depletion of Mg in the liquid phase but also because the adsorbed Ti complex stabilizes the particles against aggregation. Finally, we have performed polymerization tests with the prepared catalysts and found that the size distribution of the polymer particles indeed closely replicates the one of the used catalyst particles.ISSN:1520-5045ISSN:0888-588

Ziegler-Natta catalyst sonofragmentation for controlling size and size distribution of the produced polymer particles

ISSN:1547-5905ISSN:0001-154