Green Light Photoelectrocatalysis with Sulfur-Doped Carbon Nitride: Using Triazole-Purpald for Enhanced Benzylamine Oxidation and Oxygen Evolution Reactions.

Materials dictate carbon neutral industrial chemical processes. Visible-light photoelectrocatalysts from abundant resources will play a key role in exploiting solar irradiation. Anionic doping via pre-organization of precursors and further co-polymerization creates tuneable semiconductors. Triazole derivative-purpald, an unexplored precursor with sulfur (S) container, combined in different initial ratios with melamine during one solid-state polycondensation with two thermal steps yields hybrid S-doped carbon nitrides (C3 N4 ). The series of S-doped/C3 N4 -based materials show enhanced optical, electronic, structural, textural, and morphological properties and exhibit higher performance in organic benzylamine photooxidation, oxygen evolution, and similar energy storage (capacitor brief investigation). 50M-50P exhibits the highest photooxidation conversion (84 ± 3%) of benzylamine to imine at 535 nm - green light for 48 h, due to a discrete shoulder (≈700) nm, high sulfur content, preservation of crystal size, new intraband energy states, structural defects by layer distortion, and 10-16 nm pores with arbitrary depth. This work innovates by studying the concomitant relationships between: 1) the precursor decomposition while C3 N4 is formed, 2) the insertion of S impurities, 3) the S-doped C3 N4 property-activity relationships, and 4) combinatorial surface, bulk, structural, optical, and electronic characterization analysis. This work contributes to the development of disordered long-visible-light photocatalysts for solar energy conversion and storage.

Monolithic All-Solid-State High-Voltage Li-Metal Thin-Film Rechargeable Battery.

The substitution of an organic liquid electrolyte with lithium-conducting solid materials is a promising approach to overcome the limitations associated with conventional lithium-ion batteries. These constraints include a reduced electrochemical stability window, high toxicity, flammability, and the formation of lithium dendrites. In this way, all-solid-state batteries present themselves as ideal candidates for improving energy density, environmental friendliness, and safety. In particular, all-solid-state configurations allow the introduction of compact, lightweight, high-energy-density batteries, suitable for low-power applications, known as thin-film batteries. Moreover, solid electrolytes typically offer wide electrochemical stability windows, enabling the integration of high-voltage cathodes and permitting the fabrication of higher-energy-density batteries. A high-voltage, all-solid-state lithium-ion thin-film battery composed of LiNi0.5Mn1.5O4 cathode, a LiPON solid electrolyte, and a lithium metal anode has been deposited layer by layer on low-cost stainless-steel current collector substrates. The structural and electrochemical properties of each electroactive component of the battery had been analyzed separately prior to the full cell implementation. In addition to a study of the internal solid-solid interface, comparing them was done with two similar cells assembled using conventional lithium foil, one with thin-film solid electrolyte and another one with thin-film solid electrolyte plus a droplet of LP30 liquid electrolyte. The thin-film all-solid state cell developed in this work delivered 80.5 mAh g-1 in the first cycle at C/20 and after a C-rate test of 25 cycles at C/10, C/5, C/2, and 1C and stabilized its capacity at around 70 mAh g-1 for another 12 cycles prior to the start of its degradation. This cell reached gravimetric and volumetric energy densities of 333 Wh kg-1 and 1,212 Wh l-1, respectively. Overall, this cell showed a better performance than its counterparts assembled with Li foil, highlighting the importance of the battery interface control.

Growth Parameters and Diffusion Barriers for Functional High-Voltage Thin-Film Batteries Based on Spinel LiNi0.5Mn1.5O4 Cathodes.

Cobalt-free spinel LiNi0.5Mn1.5O4 is one of the most promising and environmentally friendly cathodes, based on its high specific theoretical capacity (147 mAh·g-1) and high electrochemical potential (4.7 V vs Li+/Li), as well as good electronic and Li-ion conductivities. In this work, we present the fabrication of LiNi0.5Mn1.5O4 thin-film cathodes deposited by the industrially scalable AC magnetron sputtering technique on functional and cost-effective stainless steel current collectors. This is the first step toward battery downscaling, envisioning the fabrication of compact microbatteries for low-power energy supply. The thin-film strategy is crucial also for solid electrolyte fabrication that will allow the integration of high-energy-density batteries while overcoming most of the current battery challenges. In this work, the effect of film thickness on the material's electrochemical performance is discussed, correlating the observed structural and morphological evolution with the final electrochemical response. Moreover, the effect of iron diffusion from the current collector substrate into the cathode film is analyzed. The addition of a stable CrN barrier layer in between the substrate and the film is proposed to prevent Fe diffusion, with a direct positive influence on the electrochemical behavior. All in all, the obtained results will facilitate the practical implementation of LiNi0.5Mn1.5O4 thin films as high-voltage cathodes in functional cost-effective microbatteries.

Role of the voltage window on the capacity retention of P2-Na2/3[Fe1/2Mn1/2]O2 cathode material for rechargeable sodium-ion batteries.

P2-Na2/3[Fe1/2Mn1/2]O2 layered oxide is a promising high energy density cathode material for sodium-ion batteries. However, one of its drawbacks is the poor long-term stability in the operating voltage window of 1.5-4.25 V vs Na+/Na that prevents its commercialization. In this work, additional light is shed on the origin of capacity fading, which has been analyzed using a combination of experimental techniques and theoretical methods. Electrochemical impedance spectroscopy has been performed on P2-Na2/3[Fe1/2Mn1/2]O2 half-cells operating in two different working voltage windows, one allowing and one preventing the high voltage phase transition occurring in P2-Na2/3[Fe1/2Mn1/2]O2 above 4.0 V vs Na+/Na; so as to unveil the transport properties at different states of charge and correlate them with the existing phases in P2-Na2/3[Fe1/2Mn1/2]O2. Supporting X-ray photoelectron spectroscopy experiments to elucidate the surface properties along with theoretical calculations have concluded that the formed electrode-electrolyte interphase is very thin and stable, mainly composed by inorganic species, and reveal that the structural phase transition at high voltage from P2- to "Z"/OP4-oxygen stacking is associated with a drastic increased in the bulk electronic resistance of P2-Na2/3[Fe1/2Mn1/2]O2 electrodes which is one of the causes of the observed capacity fading.

Revealing In Situ Li Metal Anode Surface Evolution upon Exposure to CO2 Using Ambient Pressure X-Ray Photoelectron Spectroscopy.

Because they deliver outstanding energy density, next-generation lithium metal batteries (LMBs) are essential to the advancement of both electric mobility and portable electronic devices. However, the high reactivity of metallic lithium surfaces leads to the low electrochemical performance of many secondary batteries. Besides, Li deposition is not uniform, which has been attributed to the low ionic conductivity of the anode surface. In particular, lithium exposure to CO2 gas is considered detrimental due to the formation of carbonate on the solid electrolyte interphase (SEI). In this work, we explored the interaction of Li metal with CO2 gas as a function of time using ambient pressure X-ray photoelectron spectroscopy to clarify the reaction pathway and main intermediates involved in the process during which oxalate formation has been detected. Furthermore, when O2 gas is part of the surrounding environment with CO2 gas, the reaction pathway is bypassed to directly promote carbonate as a single product.

Toward Stable Electrode/Electrolyte Interface of P2-Layered Oxide for Rechargeable Na-Ion Batteries.

The electrochemical properties of P2-Na2/3Mn0.8Fe0.1Ti0.1O2 layered oxide, which is a promising cathode material for rechargeable Na-ion batteries (NIBs), are evaluated with an optimized in-house ionic liquid (IL)-based electrolyte, and its performance is compared with that using carbonate-based electrolyte. The IL-based system reveals better electrochemical performance at room temperature than the carbonate electrolyte-based one at 0.1C and 1C, especially in terms of cycling stability, with a 97% capacity retention after 100 deep cycles (0.1C). The electrode/electrolyte interface is thoroughly studied in both systems by means of X-ray photoelectron spectroscopy and scanning electron microscopy so as proof that the formed interface is crucial to optimizing the electrochemical performance of NIBs. The carbonate-based system shows a thin, inhomogeneous, and unstable interface layer, while the IL-based one exhibits an even thinner but homogeneous and more stable interface, which may result in safer and longer-lasting NIBs.