Reinterpreting the Intercalation-Conversion Mechanism of FeP Anodes in Lithium/Sodium-Ion Batteries from Evolution of the Magnetic Phase.

Batteries with intercalation-conversion-type electrodes tend to achieve high-capacity storage, but the complicated reaction process often suffers from confusing electrochemical mechanisms. Here, we reinterpreted the essential issue about the potential of the conversion reaction and whether there is an intercalation reaction in a lithium/sodium-ion battery (LIB/SIB) with the FeP anode based on the evolution of the magnetic phase. Especially, the ever-present intercalation process in a large voltage range followed by the conversion reaction with extremely low potential was confirmed in FeP LIB, while it is mainly the conversion reaction for the sodium storage mechanism in FeP SIB. The insufficient conversion reaction profoundly limits the actual capacity to the expectedly respectable value. Accordingly, a graphene oxide modification strategy was proposed to increase the reversible capacity of FeP LIB/SIB by 99% and 132%, respectively. The results facilitate the development of anode materials with a high capacity and low operating potential.

Electrochemical interfacial catalysis in Co-based battery electrodes involving spin-polarized electron transfer.

Interfacial catalysis occurs ubiquitously in electrochemical systems, such as batteries, fuel cells, and photocatalytic devices. Frequently, in such a system, the electrode material evolves dynamically at different operating voltages, and this electrochemically driven transformation usually dictates the catalytic reactivity of the material and ultimately the electrochemical performance of the device. Despite the importance of the process, comprehension of the underlying structural and compositional evolutions of the electrode material with direct visualization and quantification is still a significant challenge. In this work, we demonstrate a protocol for studying the dynamic evolution of the electrode material under electrochemical processes by integrating microscopic and spectroscopic analyses, operando magnetometry techniques, and density functional theory calculations. The presented methodology provides a real-time picture of the chemical, physical, and electronic structures of the material and its link to the electrochemical performance. Using Co(OH)2 as a prototype battery electrode and by monitoring the Co metal center under different applied voltages, we show that before a well-known catalytic reaction proceeds, an interfacial storage process occurs at the metallic Co nanoparticles/LiOH interface due to injection of spin-polarized electrons. Subsequently, the metallic Co nanoparticles act as catalytic activation centers and promote LiOH decomposition by transferring these interfacially residing electrons. Most intriguingly, at the LiOH decomposition potential, electronic structure of the metallic Co nanoparticles involving spin-polarized electrons transfer has been shown to exhibit a dynamic variation. This work illustrates a viable approach to access key information inside interfacial catalytic processes and provides useful insights in controlling complex interfaces for wide-ranging electrochemical systems.

Improved Lithium Storage Performance of a TiO2 Anode Material Doped by Co.

TiO2 is a promising anode material for lithium-ion batteries (LIBs) due to its low cost, suitable operating voltage, and excellent structural stability. The inherent poor electron conductivity and low ion diffusion coefficient, however, severely limit its application in lithium storage. Here, Co-doped TiO2 is synthesized by a hydrothermal method as an anode material since Co@TiO2 possesses a large specific surface area and high electronic conductivity. Thanks to the Co dopants, the ion diffusion and electron transport are both greatly improved, which is very beneficial for cycle stability, coulombic efficiency (CE), reversible capacity, and rate performance. As a result, Co@TiO2 shows a high reversible capacity of 227 mAh g-1 at 3 C, excellent rate performance, and cycling stability with a capacity of about 125 mAh g-1 at 10C after 600 cycles (1 C = 170 mA g-1).

Space-Charge Control of Magnetism in Ferromagnetic Metals: Coupling Giant Magnitude and Robust Endurance.

Ferromagnetic metals show great prospects in ultralow-power-consumption spintronic devices, due to their high Curie temperature and robust magnetization. However, there is still a lack of reliable solutions for giant and reversible voltage control of magnetism in ferromagnetic metal films. Here, a novel space-charge approach is proposed which allows for achieving a modulation of 30.3 emu/g under 1.3 V in Co/TiO2 multilayer granular films. The robust endurance with more than 5000 cycles is demonstrated. Similar phenomena exist in Ni/TiO2 and Fe/TiO2 multilayer granular films, which shows its universality. The magnetic change of 107% in Ni/TiO2 underlines its potential in a voltage-driven ON-OFF magnetism. Such giant and reversible voltage control of magnetism can be ascribed to space-charge effect at the ferromagnetic metals/TiO2 interfaces, in which spin-polarized electrons are injected into the ferromagnetic metal layer with the adsorption of lithium-ions on the TiO2 surface. These results open the door for a promising method to modulate the magnetization in ferromagnetic metals, paving the way toward the development of ionic-magnetic-electric coupled applications.

Revealing An Intercalation-Conversion-Heterogeneity Hybrid Lithium-Ion Storage Mechanism in Transition Metal Nitrides Electrodes with Jointly Fast Charging Capability and High Energy Output.

The performance of electrode materials depends intensively on the lithium (Li)-ion storage mechanisms correlating ultimately with the Coulombic efficiency, reversible capacity, and morphology variation of electrode material upon cycling. Transition metal nitrides anode materials have exhibited high-energy density and superior rate capability; however, the intrinsic mechanism is largely unexplored and still unclear. Here, a typical 3D porous Fe2 N micro-coral anode is prepared and, an intercalation-conversion-heterogeneity hybrid Li-ion storage mechanism that is beyond the conventional intercalation or conversion reaction is revealed through various characterization techniques and thermodynamic analysis. Interestingly, using advanced in situ magnetometry, the ratio (ca. 24.4%) of the part where conversion reaction occurs to the entire Fe2 N can further be quantified. By rationally constructing a Li-ion capacitor comprising 3D porous Fe2 N micro-corals anode and commercial AC cathode, the hybrid full device delivers a high energy-density (157 Wh kg-1 ) and high power-density (20 000 W kg-1 ), as well as outstanding cycling stability (93.5% capacitance retention after 5000 cycles). This research provides an original and insightful method to confirm the reaction mechanism of material related to transition metals and a fundamental basis for emerging fast charging electrode materials to be efficiently explored for a next-generation battery.

A comparative study of electrochemical and electrostatic doping modulation of magnetism in Fe3O4via ultracapacitor structure.

Electric field control of magnetism can boost energy efficiency and have brought revolutionary breakthroughs in the development of widespread applications in spintronics. Electrolyte gating plays an important role in magnetism modulation. In this work, reversible room-temperature electric field control of saturation magnetization in Fe3O4via a supercapacitor structure is demonstrated with three types of traditional gate electrolytes for comparison. Different magnetization response and responsible mechanisms are revealed by Operando magnetometry PPMS/VSM and XPS characterization. The main mechanism in Na2SO4, KOH aqueous electrolytes is electrochemical effect, while both electrochemical and electrostatic effects were found in LiPF6organic electrolyte. This work offers a kind of reference basis for selecting appropriate electrolyte in magnetism modulation by electrolyte-gating in the future, meanwhile, paves its way towards practical use in magneto-electric actuation, voltage-assisted magnetic storage, facilitating the development of high-performance spintronic devices.

Reacquainting the Electrochemical Conversion Mechanism of FeS2 Sodium-Ion Batteries by Operando Magnetometry.

In spite of the excellent electrochemical performance in lithium-ion batteries (LIBs), transition-metal compounds usually show inferior capacity and cyclability in sodium-ion batteries (SIBs), implying different reaction schemes between these two types of systems. Herein, coupling operando magnetometry with electrochemical measurement, we peformed a comprehensive investigation on the intrinsic relationship between the ion-embedding mechanisms and the electrochemical properties of the typical FeS2/Na (Li) cells. Operando magnetometry together with ex-situ transmission electron microscopy (TEM) measurement reveal that only part of FeS2 is involved in the conversion reaction process, while the unreactive parts form "inactive cores" that lead to the low capacity. Through quantification with Langevin fitting, we further show that the size of the iron grains produced by the conversion reaction are much smaller in SIBs than that in LIBs, which may lead to more serious pulverization, thereby resulting in worse cycle performance. The underlying reason for the above two above phenomena in SIBs is the sluggish kinetics caused by the larger Na-ion radius. Our work paves a new way for the investigation of novel SIB materials with high capacity and long durability.