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.

Operando Magnetometry Probing the Charge Storage Mechanism of CoO Lithium-Ion Batteries.

Cobalt oxide (CoO) is a promising electrode for high-energy-density Li-ion batteries (LIBs), where the charge storage is believed to take place solely during the electrochemical oxidation/reduction processes. However, this simple picture has been increasingly challenged by reported anomalously large storage capacities, indicating the existence of undiscovered extra charge reservoirs inside the system. Here, an advanced operando magnetometry technology is employed to monitor the magnetization variation of the CoO LIBs in real time and, in this particular system, it is clearly demonstrated that the anomalous capacity is associated with both the reversible formation of a spin capacitor and the growth of a polymeric film at low voltages. Furthermore, operando magnetometry provides direct evidence of the catalytic role of metallic Co in assisting the polymeric film formation. These critical findings help pave the way for better understanding of the charge storage mechanisms of transition-metal oxides and further utilizing them to design novel electrode materials.

Extra storage capacity in transition metal oxide lithium-ion batteries revealed by in situ magnetometry.

In lithium-ion batteries (LIBs), many promising electrodes that are based on transition metal oxides exhibit anomalously high storage capacities beyond their theoretical values. Although this phenomenon has been widely reported, the underlying physicochemical mechanism in such materials remains elusive and is still a matter of debate. In this work, we use in situ magnetometry to demonstrate the existence of strong surface capacitance on metal nanoparticles, and to show that a large number of spin-polarized electrons can be stored in the already-reduced metallic nanoparticles (that are formed during discharge at low potentials in transition metal oxide LIBs), which is consistent with a space charge mechanism. Through quantification of the surface capacitance by the variation in magnetism, we further show that this charge capacity of the surface is the dominant source of the extra capacity in the Fe3O4/Li model system, and that it also exists in CoO, NiO, FeF2 and Fe2N systems. The space charge mechanism revealed by in situ magnetometry can therefore be generalized to a broad range of transition metal compounds for which a large electron density of states is accessible, and provides pivotal guidance for creating advanced energy storage systems.

Reversible control of magnetization in Fe3O4 nanoparticles by a supercapacitor.

The manipulation of magnetism by electrical means is one of the most intensely pursued research topics of recent times aiming at the development of efficient and low-energy consumption devices in spintronics, microelectronics and bioelectronics. Herein, we successfully tuned the saturated magnetization of Fe3O4 by a supercapacitor. Through increasing the surface area of magnetic particles and activation of carbon cloth, fully reversible and robust saturation magnetization variation with low power consumption and remarkable switching speed can be realized on Fe3O4/ionic liquid interfaces at room temperature. The associated magnetism modulation can be attributed to ionic transition between Fe2+ and Fe3+ resulting from both electrostatic and electrochemical doping. This work paves the way for the development of high-performance spintronic devices.