Capacitive tendency concept alongside supervised machine-learning toward classifying electrochemical behavior of battery and pseudocapacitor materials.

In recent decades, more than 100,000 scientific articles have been devoted to the development of electrode materials for supercapacitors and batteries. However, there is still intense debate surrounding the criteria for determining the electrochemical behavior involved in Faradaic reactions, as the issue is often complicated by the electrochemical signals produced by various electrode materials and their different physicochemical properties. The difficulty lies in the inability to determine which electrode type (battery vs. pseudocapacitor) these materials belong to via simple binary classification. To overcome this difficulty, we apply supervised machine learning for image classification to electrochemical shape analysis (over 5500 Cyclic Voltammetry curves and 2900 Galvanostatic Charge-Discharge curves), with the predicted confidence percentage reflecting the shape trend of the curve and thus defined as a manufacturer. It's called "capacitive tendency". This predictor not only transcends the limitations of human-based classification but also provides statistical trends regarding electrochemical behavior. Of note, and of particular importance to the electrochemical energy storage community, which publishes over a hundred articles per week, we have created an online tool to easily categorize their data.

Unveiling LiTFSI Precipitation as a Key Factor in Solid Electrolyte Interphase Formation in Li-Based Water-in-Salt Electrolytes.

A water-in-salt electrolyte is a highly concentrated aqueous solution (i.e., 21 mol LiTFSI in 1 kg H2 O) that reduces the number of water molecules surrounding salt ions, thereby decreasing the water activity responsible for decomposition. This electrolyte widens the electrochemical stability window via the formation of a solid electrolyte interphase (SEI) at the electrode surface. However, using high concentration electrolytes in Li-ion battery technology to enhance energy density and increase cycling stability remains challenging. A parasitic reaction, called the hydrogen evolution reaction, occurs when the reaction operates at a lower voltage. It is demonstrated here that a micrometric white layer is indeed a component of the SEI layer, not just on the nanoscale, through the utilization of an operando high-resolution optical microscope. The results indicate that LiTFSI precipitation is the primary species present in the SEI layer. Furthermore, the passivation layer is found to be dynamic since it dissolves back into the electrolyte during open circuit voltage.

Continuous medium approach to approximate the high concentrated aqueous electrolyte with different types of electrochemical structure.

Superconcentrated aqueous electrolytes have recently emerged as a new class of electrolytes, called water-in-salt electrolytes. They are distinguished, in both weight and volume, by a quantity of salt greater than water. Currently, these electrolytes are attracting major interest, particularly for application in aqueous rechargeable batteries. These electrolytes have only a small amount of free water due to an ultrahigh salt concentration. Consequently, the electrochemical stability window of water is wider than the predicted thermodynamic value of 1.23 V. Hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) have been shown to be shifted to more negative and positive potentials, respectively. The decrease in free water population is recognized as being involved in the increase in the electrochemical stability window of water. Here, we study the quantitative contribution of the decrease in the free water molecule concentration to the permittivity of the solution and of the activity of water to the OER and HER overpotentials when the salt concentration increases. We compare our model with that of Kornyshev and get three types of electrolyte structures: diluted, gradient of water contents, and aggregation. The theoretical calculation of the redox potentials of the OER and HER is compared with the experimentally determined electrochemical properties of aqueous LiTFSI electrolytes.

Unprecedented energy storage in metal-organic complexes via constitutional isomerism.

The essence of any electrochemical system is engraved in its electrical double layer (EDL), and we report its unprecedented reorganization by the structural isomerism of molecules, with a direct consequence on their energy storage capability. Electrochemical and spectroscopic analyses in combination with computational and modelling studies demonstrate that an attractive field-effect due to the molecule's structural-isomerism, in contrast to a repulsive field-effect, spatially screens the ion-ion coulombic repulsions in the EDL and reconfigures the local density of anions. In a laboratory-level prototype supercapacitor, those with ß-structural isomerism exhibit nearly 6-times elevated energy storage compared to the state-of-the-art electrodes, by delivering ∼535 F g-1 at 1 A g-1 while maintaining high performance metrics even at a rate as high as 50 A g-1. The elucidation of the decisive role of structural isomerism in reconfiguring the electrified interface represents a major step forward in understanding the electrodics of molecular platforms.

Visualizing Water Reduction with Diazonium Grafting on a Glassy Carbon Electrode Surface in a Water-in-Salt Electrolyte.

Aqueous batteries are regaining interest, thanks to the extended working stability voltage window in a highly concentrated electrolyte, namely the water-in-salt electrolyte. A solid-electrolyte interphase (SEI) forms on the negative electrode to prevent water access to the electrode surface. However, we further reported that the formed SEI layer was not uniform on the surface of the glassy carbon electrode. The SEI after passivation will also show degradation during the remaining time of open-circuit voltage (OCV); hence, it calls for a more stable passivation layer to cover the electrode surface. Here, a surface modification was successfully achieved via artificial diazonium grafting using monomers, such as poly(ethylene glycol), α-methoxy, ω-allyloxy (PEG), and allyl glycidyl cyclocarbonate (AGC), on glassy carbon. Physical and electrochemical measurements indicated that the hydrophobic layer composed of PEG or AGC species was well grafted on the electrode surface. The grafted hydrophobic coatings could protect the electrode surface from the water molecules in the bulk electrolyte and then suppress the free water decomposition (from LSV) but still migrating lithium ions. Furthermore, multiple cycles of CV with one-hour resting OCV identified the good stability of the hydrophobic grafting layer, which is a highlight compared with our precious work. These findings relying on the diazonium grafting design may offer a new strategy to construct a stable artificial SEI layer that can well protect the electrode surface from the free water molecule.

Energy-efficient hydrogen production over a high-performance bifunctional NiMo-based nanorods electrode.

Electrochemical water splitting to hydrogen fuel is highly desirable yet challenging mainly limited by sluggish cathodic oxygen evolution reaction (OER). Urea electrolysis can produce hydrogen more energy-savingly by replacing OER process with urea oxidation reaction (UOR) due to favorable thermodynamic potential, however lacking efficient UOR catalysts restricts the industrial application. Here we reported novel NiMo-based nanorods, Ni/Ni0.2Mo0.8N/MoO3, by thermal ammonolysis of NiMo-based precursor as excellent catalyst for OER and hydrogen evolution reaction (HER) with small overpotentials of 252 mV, and 103 mV to achieve a current density of 10 mA cm-2 in 1.0 M KOH. Moreover, the Ni/Ni0.2Mo0.8N/MoO3 shows fabulous catalytic UOR activity with a low potential of 1.349 V at 10 mA cm-2, outperforming most recently reported non-noble metal catalysts and commercial RuO2. More importantly, the cell voltage of urea electrolysis using Ni/Ni0.2Mo0.8N/MoO3 as cathode for HER and anode for UOR is significantly reduced from 1.52 V of traditional water electrolysis to 1.356 V to deliver 10 mA cm-2 with excellent stability for over 400 h, superior to almost recently reported catalysts. The high performances result from the synergistic effect between highly active and conductive metal nickel and nitride, and nanorods arrays grown on 3D substrate. This work demonstrates that this material holds encouraging potential in large-scale energy-saving H2 production and urea-related wastewater treatment.

Synthesis of d-f coordination polymer nanoparticles and their application in phosphorescence and magnetic resonance imaging.

Magneto-phosphorescent d-f coordination polymer nanoparticles (f-CPPs) were conveniently synthesized by phosphorescent carboxyl-functionalized iridium complexes as building blocks and magnetic Gd(III) ions as metallic nodes. They reveal uniform hollow spheres with an average diameter of around 60 nm and wall thickness of about 10 nm. Water soluble f-CPPs were obtained by polyvinylpyrolidone modification (denoted as f-CPPs@PVP), which had an intense red phosphorescence, moderate longitudinal relaxivity (r(1)) and low cytotoxicity. Furthermore, inductively coupled plasma atomic emission spectroscopy (ICP-AES) and confocal laser scanning microscopy (CLSM) confirmed f-CPPs@PVP could be taken up by living cells effectively. Therefore, they should be a novel nano-bioprobe for the multimodal imaging of cancer cells.