Chiral Molecular Coating of a LiNiCoMnO2 Cathode for High-Rate Capability Lithium-Ion Batteries.

The growing demand for energy has increased the need for battery storage, with lithium-ion batteries being widely used. Among those, nickel-rich layered lithium transition metal oxides [LiNi1-x-yCoxMnyO2 NCM (1 - x - y > 0.5)] are some of the promising cathode materials due to their high specific capacities and working voltages. In this study, we demonstrate that a thin, simple coating of polyalanine chiral molecules improves the performance of Ni-rich cathodes. The chiral organic coating of the active material enhances the discharge capacity and rate capability. Specifically, NCM811 and NCM622 electrodes coated with chiral molecules exhibit lower voltage hysteresis and better rate performance, with a capacity improvement of >10% at a 4 C discharge rate and an average improvement of 6%. We relate these results to the chirally induced spin selectivity effect that enables us to reduce the resistance of the electrode interface and to reduce dramatically the overpotential needed for the chemical process by aligning the electron spins.

Mitigating Interfacial Capacity Fading in Vanadium Pentoxide by Sacrificial Vanadium Sulfide Encapsulation for Rechargeable Mg-Ion Batteries.

Rechargeable Mg-ion Batteries (RMB) containing a Mg metal anode offer the promise of higher specific volumetric capacity, energy density, safety, and economic viability than lithium-ion battery technology, but their realization is challenging. The limited availability of suitable inorganic cathodes compatible with electrolytes relevant to Mg metal anode restricts the development of RMBs. Despite the promising capability of some oxides to reversibly intercalate Mg+2 ions at high potential, its lack of stability in chloride-containing ethereal electrolytes, relevant to Mg metal anode hinders the realization of a full practical RMB. Here the successful in situ encapsulation of monodispersed spherical V2 O5 (≈200 nm) is demonstrated by a thin layer of VS2 (≈12 nm) through a facile surface reduction route. The VS2 layer protects the surface of V2 O5 particles in RMB electrolyte solution (MgCl2 + MgTFSI in DME). Both V2 O5 and V2 O5 @VS2 particles demonstrate high initial discharge capacity. However, only the V2 O5 @VS2 material demonstrates superior rate performance, Coulombic efficiency (100%), and stability (138 mA h g-1 discharge capacity after 100 cycles), signifying the ability of the thin VS2 layer to protect the V2 O5 cathode and facilitate the Mg+2 ion intercalation/deintercalation into V2 O5 .

High-energy all-solid-state lithium batteries enabled by Co-free LiNiO2 cathodes with robust outside-in structures.

A critical current challenge in the development of all-solid-state lithium batteries (ASSLBs) is reducing the cost of fabrication without compromising the performance. Here we report a sulfide ASSLB based on a high-energy, Co-free LiNiO2 cathode with a robust outside-in structure. This promising cathode is enabled by the high-pressure O2 synthesis and subsequent atomic layer deposition of a unique ultrathin LixAlyZnzOδ protective layer comprising a LixAlyZnzOδ surface coating region and an Al and Zn near-surface doping region. This high-quality artificial interphase enhances the structural stability and interfacial dynamics of the cathode as it mitigates the contact loss and continuous side reactions at the cathode/solid electrolyte interface. As a result, our ASSLBs exhibit a high areal capacity (4.65 mAh cm-2), a high specific cathode capacity (203 mAh g-1), superior cycling stability (92% capacity retention after 200 cycles) and a good rate capability (93 mAh g-1 at 2C). This work also offers mechanistic insights into how to break through the limitation of using expensive cathodes (for example, Co-based) and coatings (for example, Nb-, Ta-, La- or Zr-based) while still achieving a high-energy ASSLB performance.

High-Entropy Co-Free O3-Type Layered Oxyfluoride: A Promising Air-Stable Cathode for Sodium-Ion Batteries.

Sodium-ion batteries have recently emerged as a promising alternative to lithium-based batteries, driven by an ever-growing demand for electricity storage systems. The present workproposes a cobalt-free high-capacity cathode for sodium-ion batteries, synthesized using a high-entropy approach. The high-entropy approach entails mixing more than five elements in a single phase; hence, obtaining the desired properties is a challenge since this involves the interplay between different elements. Here, instead of oxide, oxyfluoride is chosen to suppress oxygen loss during long-term cycling. Supplement to this, lithium is introduced in the composition to obtain high configurational entropy and sodium vacant sites, thus stabilizing the crystal structure, accelerating the kinetics of intercalation/deintercalation, and improving the air stability of the material. With the optimization of the cathode composition, a reversible capacity of 109 mAh g-1 (2-4 V) and 144 mAh g-1 (2-4.3 V) is observed in the first few cycles, along with a significant improvement in stability during prolonged cycling. Furthermore, in situ and ex situ diffraction studies during charging/discharging reveal that the high-entropy strategy successfully suppresses the complex phase transition. The impressive outcomes of the present work strongly motivate the pursuit of the high-entropy approach to develop efficient cathodes for sodium-ion batteries.

Anodic instability of carbon in non-alkaline Zn-air batteries.

Although non-alkaline rechargeable Zn-air batteries (RZABs) are promising for energy storage, their chemistry is still underdeveloped and unclear. It was suggested that using Zn(OAc)2 or Zn(OTf)2 aqueous solutions as electrolytes enables reversible, corrosion-free charge-discharge processes, but the anodic stability of carbon in these cells has remained poorly studied. We report that CO2 evolution is manifested during the oxygen evolution reaction in non-alkaline RZABs, which is associated with the corrosion of carbon scaffolds. This corrosion is observed for different electrolyte compositions, such as Zn(OAc)2, ZnSO4 and Zn(OTf)2 solutions of various concentrations. The corrosion rate decreases when the overpotentials during the oxygen evolution reaction are lower. This study underlines the importance of addressing the anodic instability of carbon in non-alkaline RZABs.

Multifunctional solvent molecule design enables high-voltage Li-ion batteries.

Elevating the charging cut-off voltage is one of the efficient approaches to boost the energy density of Li-ion batteries (LIBs). However, this method is limited by the occurrence of severe parasitic reactions at the electrolyte/electrode interfaces. Herein, to address this issue, we design a non-flammable fluorinated sulfonate electrolyte by multifunctional solvent molecule design, which enables the formation of an inorganic-rich cathode electrolyte interphase (CEI) on high-voltage cathodes and a hybrid organic/inorganic solid electrolyte interphase (SEI) on the graphite anode. The electrolyte, consisting of 1.9 M LiFSI in a 1:2 v/v mixture of 2,2,2-trifluoroethyl trifluoromethanesulfonate and 2,2,2-trifluoroethyl methanesulfonate, endows 4.55 V-charged graphite||LiCoO2 and 4.6 V-charged graphite||NCM811 batteries with capacity retentions of 89% over 5329 cycles and 85% over 2002 cycles, respectively, thus resulting in energy density increases of 33% and 16% compared to those charged to 4.3 V. This work demonstrates a practical strategy for upgrading the commercial LIBs.

Mussel-Inspired Polynorepinephrine/MXene-Based Magnetic Nanohybrid for Electromagnetic Interference Shielding in X-Band and Strain-Sensing Performance.

The current work delivers preparation of MXene-based magnetic nanohybrid coating for flexible electronic applications. Herein, we report carbon dot-triggered photopolymerized polynorepinepherene (PNE)-coated MXene and iron oxide hybrid deposited on the cellulose microporous membrane via a vacuum-assisted filtration strategy. The surface morphologies have been monitored by scanning electron microscopy analysis, and the coating thickness was evaluated by the gallium-ion-based focused ion beam method. Coated membranes have been tested against uniaxial tensile stretching and assessed by their fracture edges in order to assure flexibility and mechanical strength. Strain sensors and electromagnetic interference (EMI) shielding have both been tested on the material because of its electrical conductivity. The bending strain sensitivity has been stringent because of their fast 'rupture and reform' percolation network formation on the coated surface. Increased mechanical strength, solvent tolerance, cyclic deformation tolerance, and EMI shielding performance were achieved by decreasing interstitial membrane porosity. Considering a possible application, the membrane also has been tested against simulated static and dynamic water flow conditions that could infer its excellent robustness which also has been confirmed by elemental analysis via ICP-MS. Thus, as of nurturing the works of the literature, it could be believed that the developed material will be an ideal alternative of flexible lightweight cellulose for versatile electronic applications.

Improved Cycling Stability of LiNi0.8 Co0.1 Mn0.1 O2 Cathode Material via Variable Temperature Atomic Surface Reduction with Diethyl Zinc.

High-Ni-rich layered oxides [e.g., LiNix Coy Mnz O2 ; x > 0.5, x + y + z = 1] are considered one of the most promising cathodes for high-energy-density lithium-ion batteries (LIB). However, extreme electrode-electrolyte reactions, several interfacial issues, and structural instability restrict their practical applicability. Here, a shortened unconventional atomic surface reduction (ASR) technique is demonstrated on the cathode surface as a derivative of the conventional atomic layer deposition (ALD) process, which brings superior cell performances. The atomic surface reaction (reduction process) between diethyl-zinc (as a single precursor) and Ni-rich NMC cathode [LiNi0.8 Co0.1 Mn0.1 O2 ; NCM811] material is carried out using the ALD reactor at different temperatures. The temperature dependency of the process through advanced spectroscopy and microscopy studies is demonstrated and it is shown that thin surface film is formed at 100 °C, whereas at 200 °C a gradual atomic diffusion of Zn ions from the surface to the near-surface regions is taking place. This unique near-surface penetration of Zn ions significantly improves the electrochemical performance of the NCM811 cathode. This approach paves the way for utilizing vapor phase deposition processes to achieve both surface coatings and near-surface doping in a single reactor to stabilize high-energy cathode materials.

Selective Catalyst Surface Access through Atomic Layer Deposition.

Catalyst poisoning is a prominent issue, reducing the lifetime of catalysts and increasing the costs of the processes that rely on them. The electrocatalysts that enable green energy conversion and storage, such as proton exchange membrane fuel cells and hydrogen bromine redox flow batteries, also suffer from this issue, hindering their utilization. Current solutions to protect electrocatalysts from harmful species fall short of effective selectivity without inhibiting the required reactions. This article describes the protection of a standard 50% Pt/C catalyst with a V2O5 coating through atomic layer deposition (ALD). The ALD selectively deposited V2O5 on the Pt, which enhanced hydrogen transport to the Pt surface and resulted in a higher mass activity in alkaline electrolytes. Cyclic voltammetry and X-ray photoelectron spectroscopy showed that the Pt was protected by the coating in the HBr/Br2 electrolyte which dissolved the uncoated 50% Pt/C in under 3 min.

Improvement of the Electrochemical Performance of LiNi0.8Co0.1Mn0.1O2 via Atomic Layer Deposition of Lithium-Rich Zirconium Phosphate Coatings.

Owing to its high energy density, LiNi0.8Co0.1Mn0.1O2 (NMC811) is a cathode material of prime interest for electric vehicle battery manufacturers. However, NMC811 suffers from several irreversible parasitic reactions that lead to severe capacity fading and impedance buildup during prolonged cycling. Thin surface protection films coated on the cathode material mitigate degradative chemomechanical reactions at the electrode-electrolyte interphase, which helps to increase cycling stability. However, these coatings may impede the diffusion of lithium ions, and therefore, limit the performance of the cathode material at a high C-rate. Herein, we report on the synthesis of zirconium phosphate (ZrxPOy) and lithium-containing zirconium phosphate (LixZryPOz) coatings as artificial cathode-electrolyte interphases (ACEIs) on NMC811 using the atomic layer deposition technique. Upon prolonged cycling, the ZrxPOy- and LixZryPOz-coated NMC811 samples show 36.4 and 49.4% enhanced capacity retention, respectively, compared with the uncoated NMC811. Moreover, the addition of Li ions to the LixZryPOz coating enhances the rate performance and initial discharge capacity in comparison to the ZrxPOy-coated and uncoated samples. Using online electrochemical mass spectroscopy, we show that the coated ACEIs largely suppress the degradative parasitic side reactions observed with the uncoated NMC811 sample. Our study demonstrates that providing extra lithium to the ACEI layer improves the cycling stability of the NMC811 cathode material without sacrificing its rate capability performance.

Interfacial Engineering of Na3 V2 (PO4 )2 F3 Hollow Spheres through Atomic Layer Deposition of TiO2 : Boosting Capacity and Mitigating Structural Instability.

To mitigate the associated challenges of instability and capacity improvement in Na3 V2 (PO4 )2 F3  (NVPF), rationally designed uniformly distributed hollow spherical NVPF and coating the surface of NVPF with ultrathin (≈2 nm) amorphous TiO2  by atomic layer deposition is demonstrated. The coating facilitates higher mobility of the ion through the cathode electrolyte interphase (CEI) and enables higher capacity during cycling. The TiO2 @NVPF exhibit discharge capacity of >120 mAhg-1 , even at 1C rates, and show lower irreversible capacity in the first cycle. Further, nearly 100% capacity retention after rate performance in high current densities and 99.9% coulombic efficiency after prolonged cycling in high current density is reported. The improved performance in TiO2 @NVPF is ascribed to the passivation behavior of TiO2  coating which protects the surface of NVPF from volume expansion, significantly less formation of carbonates, and decomposition of electrolyte, which is also validated through post cycling analysis. The study shows the importance of ultrathin surface protection artificial CEI for advanced sodium-ion battery cathodes. The protection layer is diminishing parasitic reaction, which eventually enhances the Na ion participation in reaction and stabilizes the cathode structure.

Diethylzinc-Assisted Atomic Surface Reduction to Stabilize Li and Mn-Rich NCM.

Li and Mn-rich nickel cobalt manganese oxide (LMR-NCM) is one of the most promising cathode materials for realizing next-generation Li-ion batteries due to its high specific capacity of >250 mA h g-1 and operating potential > 4.5 V. Nevertheless, being plagued by severe capacity fading and voltage decay, the commercialization of LMR-NCM appears to be a distant goal. The anionic activity of oxygen and associated phase transformations are the reasons behind the unstable electrochemical performance. The tendency of LMR-NCM to react with CO2 and moisture further makes it prone to interfacial instability and degradation. Here, we report a neoteric method to mitigate the stability issues and improve the electrochemical performance of LMR-NCM by changing the electronic configuration of constituting O and transition metals via diethylzinc-assisted atomic surface reduction (Zn-ASR) using an extremely facile protocol. With the proposed Zn-ASR, a 2-3 nm thin layer of a reduced surface enriched with complex ZnOx or ZnOxRy was obtained on the LMR-NCM particles. X-ray photoelectron spectroscopy suggested the transfer of ethyl groups of diethylzinc to O atoms on the LMR-NCM surface, which ultimately led to the reduction of near-surface Mn and Ni atoms and impeded irreversible anionic activity. The presence of ZnOx/ZnOxRy also resulted in superior charge transfer and resistance against HF. As a result, in contrast to LMR-NCM, the Zn-ASR-treated sample exhibited substantially improved rate capabilities, facilitated charge transfer, enhanced capacity retention, reduced parasitic reactions, and long-term stability as reflected from in-depth electrochemical analysis, in operando gaseous evolution studies, and post-mortem microscopic analysis.

AZ31 Magnesium Alloy Foils as Thin Anodes for Rechargeable Magnesium Batteries.

In recent decades, rechargeable Mg batteries (RMBs) technologies have attracted much attention because the use of thin Mg foil anodes may enable development of high-energy-density batteries. One of the most critical challenges for RMBs is finding suitable electrolyte solutions that enable efficient and reversible Mg cells operation. Most RMB studies concentrate on the development of novel electrolyte systems, while only few studies have focused on the practical feasibility of using pure metallic Mg as the anode material. Pure Mg metal anodes have been demonstrated to be useful in studying the fundamentals of nonaqueous Mg electrochemistry. However, pure Mg metal may not be suitable for mass production of ultrathin foils (<100 microns) due to its limited ductility. The metals industry overcomes this problem by using ductile Mg alloys. Herein, the feasibility of processing ultrathin Mg anodes in electrochemical cells was demonstrated by using AZ31 Mg alloys (3 % Al; 1 % Zn). Thin-film Mg AZ31 anodes presented reversible Mg dissolution and deposition behavior in complex ethereal Mg electrolytes solutions that was comparable to that of pure Mg foils. Moreover, it was demonstrated that secondary Mg battery prototypes comprising ultrathin AZ31 Mg alloy anodes (≈25 µm thick) and Mgx Mo6 S8 Chevrel-phase cathodes exhibited cycling performance equal to that of similar cells containing thicker pure Mg foil anodes. The possibility of using ultrathin processable Mg metal anodes is an important step in the realization of rechargeable Mg batteries.

Carbon-Dots-Initiated Photopolymerization: An In Situ Synthetic Approach for MXene/Poly(norepinephrine)/Copper Hybrid and its Application for Mitigating Water Pollution.

The current work presents a facile and green synthesis of carbon quantum dots (C-dots), which could serve as initiators for polymerization. Herein, C-dots have been synthesized from an easily available green herb, dill leaves, by a single-step hydrothermal method. These C-dots were efficiently utilized as initiators for the photopolymerization of the polymer poly(norepinephrine) (PNE) for the first time. The photopolymerization is discussed by a factorial design, and the optimized synthesis conditions were evaluated by a third-order regression model of three reaction parameters: monomer concentration, C-dots concentration, and UV exposure time. The sign convention of the factorial design mode indicated that monomer concentration and time of exposure are the most important factors for polymerization. The photopolymerized poly(norepinephrine) was extensively studied using Fourier transform infrared (FTIR) analysis, X-ray photoelectron spectroscopy (XPS), mass spectra, scanning electron microscopy (SEM), atomic force microscopy (AFM), contact angle measurement, and thermogravimetric analysis (TGA). UV-assisted deposition of PNE on six different types of substrates was performed, and their water contact angle and surface morphology were studied to evaluate the coating. This UV-triggered polymerization technique was further applied to fabricate sandwich-like composite catalyst MXene/poly(norepinephrine)/copper nanoparticles. This catalyst displayed good performance in the reduction of 4-NP (4-nitrophenol) at ambient temperature, and the first-order rate constant of the catalysis was 9.39 × 10-3 s-1. The reusability of the catalyst was evaluated in terms of the conversion factor. After 10 catalytic cycles, the conversion to catalyze 4-NP was still greater than 91%. The catalytic performance was also evaluated in the continuous flow condition through a membrane, fabricated from a cellulose filter paper coated with MXene/poly(norepinephrine)/copper nanoparticles. This composite catalyst not only offers a practical mode for the catalytic reaction of MXene-based materials but also lays down the foundation for the development of new catalysts.

Structure and Functionality of an Alkylated LixSiyOz Interphase for High-Energy Cathodes from DNP-ssNMR Spectroscopy.

Degradation processes at the cathode-electrolyte interface are a major limitation in the development of high-energy lithium-ion rechargeable batteries. Deposition of protective thin coating layers on the surface of high-energy cathodes is a promising approach to control interfacial reactions. However, rational design of effective protection layers is limited by the scarcity of analytical tools that can probe thin, disordered, and heterogeneous phases. Here we propose a new structural approach based on solid-state nuclear magnetic resonance spectroscopy coupled with dynamic nuclear polarization (DNP) for characterizing thin coating layers. We demonstrate the approach on an efficient alkylated LixSiyOz coating layer. By utilizing different sources for DNP, exogenous from nitroxide biradicals and endogenous from paramagnetic metal ion dopants, we reveal the outer and inner surface layers of the deposited artificial interphase and construct a structural model for the coating. In addition, lithium isotope exchange experiments provide direct evidence for the function of the surface layer, shedding light on its role in the enhanced rate performance of coated cathodes. The presented methodology and results advance us in identifying the key properties of effective coatings and may enable rational design of protective and ion-conducting surface layers.

Site-Independent Hydrogenation Reactions on Oxide-Supported Au Nanoparticles Facilitated by Intraparticle Hydrogen Atom Diffusion.

Metal-support interactions have been widely utilized for optimizing the catalytic reactivity of oxide-supported Au nanoparticles. Optimized reactivity was mainly detected with small (1-5 nm) oxide-supported Au nanoparticles and correlated to highly reactive sites at the oxide-metal interface. However, catalytically active sites are not necessarily restricted to the interface but reside as well on the Au surface. Uncovering the interconnection between reactive sites located at the interface and those situated at the metal surface is of crucial importance for understanding the reaction mechanism on Au nanoparticles. Herein, high-spatial-resolution IR nanospectroscopy measurements were conducted to map the localized reactivity in hydrogenation reactions on oxide-supported Au particles while using nitro-functionalized ligands as probes molecules. Comparative analysis of the reactivity pattern on single particles supported on various oxides revealed that oxide-dependent reactivity enhancement was not limited to the oxide-metal interface but was detected throughout the Au particle, leading to site-independent reactivity. These results indicate that reactive Au sites on both the oxide-metal interface and metal surface can activate the nitro groups toward hydrogenation reactions. The observed influence of oxide support (TiO2 > SiO2 > Al2O3) on the overall reactivity pattern specified that hydrogen dissociation occurred at the oxide-metal interface, followed by highly efficient intraparticle hydrogen atom diffusion to the interior parts of the Au particle. In contrast to Au particles, the oxide-metal interface had only a minor impact on the reactivity of supported Pt particles in which hydrogen dissociation and nitro group reduction were effectively activated on Pt sites. Single-particle measurements provided insights into the relative reactivity pattern of oxide-supported Au particles, revealing that the less-reactive Au metal sites can activate hydrogenation reactions in the presence of hydrogen atoms that diffuse from the Au/oxide boundary.

Electrochemical Activation of Li2MnO3 Electrodes at 0 °C and Its Impact on the Subsequent Performance at Higher Temperatures.

This work continues our systematic study of Li- and Mn- rich cathodes for lithium-ion batteries. We chose Li2MnO3 as a model electrode material with the aim of correlating the improved electrochemical characteristics of these cathodes initially activated at 0 °C with the sstructural evolution of Li2MnO3, oxygen loss, formation of per-oxo like species (O22-) and the surface chemistry. It was established that performing a few initial charge/discharge (activation) cycles of Li2MnO3 at 0 °C resulted in increased discharge capacity and higher capacity retention, and decreased and substantially stabilized the voltage hysteresis upon subsequent cycling at 30 °C or at 45 °C. In contrast to the activation of Li2MnO3 at these higher temperatures, Li2MnO3 underwent step-by-step activation at 0 °C, providing a stepwise traversing of the voltage plateau at >4.5 V during initial cycling. Importantly, these findings agree well with our previous studies on the activation at 0 °C of 0.35Li2MnO3·0.65Li[Mn0.45Ni0.35Co0.20]O2 materials. The stability of the interface developed at 0 °C can be ascribed to the reduced interactions of the per-oxo-like species formed and the oxygen released from Li2MnO3 with solvents in ethylene carbonate-methyl-ethyl carbonate/LiPF6 solutions. Our TEM studies revealed that typically, upon initial cycling both at 0 °C and 30 °C, Li2MnO3 underwent partial structural layered-to-spinel (Li2Mn2O4) transition.

Scalable Synthesis of Few-Layered 2D Tungsten Diselenide (2H-WSe2) Nanosheets Directly Grown on Tungsten (W) Foil Using Ambient-Pressure Chemical Vapor Deposition for Reversible Li-Ion Storage.

We report a facile two-furnace APCVD synthesis of 2H-WSe2. A systematic study of the process parameters is performed to show the formation of the phase-pure material. Extensive characterization of the bulk and exfoliated material confirm that 2H-WSe2 is layered (i.e., 2D). X-ray diffraction (XRD) confirms the phase, while high-resolution scanning electron microscopy (HRSEM), high-resolution transmission electron microscopy (HRTEM), and atomic force microscopy (AFM) clarify the morphology of the material. Focused ion beam scanning electron microscopy (FIB-SEM) estimates the depth of the 2H-WSe2 formed on W foil to be around 5-8 µm, and Raman/UV-vis measurements prove the quality of the exfoliated 2H-WSe2. Studies on the redox processes of lithium-ion batteries (LiBs) show an increase in capacity up to 500 cycles. On prolonged cycling, the discharge capacity up to the 50th cycle at 250 mA/g of the material shows a stable value of 550 mAh/g. These observations indicate that exfoliated 2H-WSe2 has promising applications as an LiB electrode material.

Modification of Li- and Mn-Rich Cathode Materials via Formation of the Rock-Salt and Spinel Surface Layers for Steady and High-Rate Electrochemical Performances.

We demonstrate a novel surface modification of Li- and Mn-rich cathode materials 0.33Li2MnO3·0.67LiNi0.4Co0.2Mn0.4O2 for lithium-ion batteries (high-energy Ni-Co-Mn oxides, HE-NCM) via their heat treatment with trimesic acid (TA) or terephthalic acid at 600 °C under argon. We established the optimal regimes of the treatment-the amounts of HE-NCM, acid, temperature, and time-resulting in a significant improvement of the electrochemical behavior of cathodes in Li cells. It was shown that upon treatment, some lithium is leached out from the surface, leading to the formation of a surface layer comprising rock-salt-like phase Li0.4Ni1.6O2. The analysis of the structural and surface studies by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy confirmed the formation of the above surface layer. We discuss the possible reactions of HE-NCM with the acids and the mechanism of the formation of the new phases, Li0.4Ni1.6O2 and spinel. The electrochemical characterizations were performed by testing the materials versus Li anodes at 30 °C. Importantly, the electrochemical results disclose significantly improved cycling stability (much lower capacity fading) and high-rate performance for the treated materials compared to the untreated ones. We established a lower evolution of the voltage hysteresis with cycling for the treated cathodes compared to that for the untreated ones. Thermal studies by differential scanning calorimetry also demonstrated lower (by ∼32%) total heat released in the reactions of the materials treated with fluoroethylene carbonate (FEC)-dimethyl carbonate (DEC)/LiPF6 electrolyte solutions, thus implying their significant surface stabilization because of the surface treatment. It was established by a postmortem analysis after 400 cycles that a lower amount of transition-metal cations dissolved (especially Ni) and a reduced number of surface cracks were formed for the 2 wt % TA-treated HE-NCMs compared to the untreated ones. We consider the proposed method of surface modification as a simple, cheap, and scalable approach to achieve a steady and superior electrochemical performance of HE-NCM cathodes.

Lithium-Oxygen Batteries and Related Systems: Potential, Status, and Future.

The goal of limiting global warming to 1.5 °C requires a drastic reduction in CO2 emissions across many sectors of the world economy. Batteries are vital to this endeavor, whether used in electric vehicles, to store renewable electricity, or in aviation. Present lithium-ion technologies are preparing the public for this inevitable change, but their maximum theoretical specific capacity presents a limitation. Their high cost is another concern for commercial viability. Metal-air batteries have the highest theoretical energy density of all possible secondary battery technologies and could yield step changes in energy storage, if their practical difficulties could be overcome. The scope of this review is to provide an objective, comprehensive, and authoritative assessment of the intensive work invested in nonaqueous rechargeable metal-air batteries over the past few years, which identified the key problems and guides directions to solve them. We focus primarily on the challenges and outlook for Li-O2 cells but include Na-O2, K-O2, and Mg-O2 cells for comparison. Our review highlights the interdisciplinary nature of this field that involves a combination of materials chemistry, electrochemistry, computation, microscopy, spectroscopy, and surface science. The mechanisms of O2 reduction and evolution are considered in the light of recent findings, along with developments in positive and negative electrodes, electrolytes, electrocatalysis on surfaces and in solution, and the degradative effect of singlet oxygen, which is typically formed in Li-O2 cells.