Despite the impressive merits of low-cost and high-safety electrochemical energy storage for aqueous zinc ion batteries, researchers have long struggled against the unresolved issues of dendrite growth and the side reactions of zinc metal anodes. Herein, a new strategy of zinc-electrolyte interface charge engineering induced by amino acid additives is demonstrated for highly reversible zinc plating/stripping. Through electrostatic preferential absorption of positively charged arginine molecules on the surface of the zinc metal anode, a self-adaptive zinc-electrolyte interface is established for the inhibition of water adsorption/hydrogen evolution and the guidance of uniform zinc deposition. Consequently, an ultra-long stable cycling up to 2200 h at a high current density of 5 mA cm −2 is achieved under an areal capacity of 4 mAh cm −2 . Even cycled at an ultra-high current density of 10 mA cm −2 , 900 h-long stable cycling is still demonstrated, demonstrating the reliable self-adaptive feature of the zinc-electrolyte interface. This work provides a new perspective of interface charge engineering in realizing highly reversible bulk zinc anode that can prompt its practical application in aqueous rechargeable zinc batteries.
Ferroelectric materials are fascinating for their non-volatile switchable electric polarizations induced by the spontaneous inversion-symmetry breaking. However, in all of the conventional ferroelectric compounds, at least two constituent ions are required to support the polarization switching1,2. Here, we report the observation of a single-element ferroelectric state in a black phosphorus-like bismuth layer3, in which the ordered charge transfer and the regular atom distortion between sublattices happen simultaneously. Instead of a homogenous orbital configuration that ordinarily occurs in elementary substances, we found the Bi atoms in a black phosphorous-like Bi monolayer maintain a weak and anisotropic sp orbital hybridization, giving rise to the inversion-symmetry-broken buckled structure accompanied with charge redistribution in the unit cell. As a result, the in-plane electric polarization emerges in the Bi monolayer. Using the in-plane electric field produced by scanning probe microscopy, ferroelectric switching is further visualized experimentally. Owing to the conjugative locking between the charge transfer and atom displacement, we also observe the anomalous electric potential profile at the 180° tail-to-tail domain wall induced by competition between the electronic structure and electric polarization. This emergent single-element ferroelectricity broadens the mechanism of ferroelectrics and may enrich the applications of ferroelectronics in the future.
Ferroelectricity exists in a variety of three-and two-dimensional materials and is of great significance for the development of electronic devices. However, the presence of ferroelectricity in one-dimensional materials is extremely rare. Here, we predict ferroelectricity in one-dimensional SbN and BiN nanowires. Their polarization strengths are 1 order of magnitude higher than ever reported values in one-dimensional structures. Moreover, we find that spontaneous spin polarization can be generated in SbN and BiN nanowires by moderate hole doping. This is the first time the coexistence of both ferroelectricity and ferromagnetism in a one-dimensional system has been reported. Our finding not only broadens the family of one-dimensional ferroelectric materials but also offers a promising platform for novel electronic and spintronic applications.
:Inter-twisted bilayers of two-dimensional (2D) materials can host low-energy flat bands, which offer opportunity to investigate many intriguing physics associated with strong electron correlations. In the existing systems, ultra-flat bands only emerge at very small twist angles less than a few degrees, which poses challenge for experimental study and practical applications. Here, we propose a new design principle to achieve low-energy ultra-flat bands with increased twist angles. The key condition is to have a 2D semiconducting material with large energy difference of band edges controlled by stacking. We show that the interlayer interaction leads to defect-like states under twisting, which forms a flat band in the semiconducting band gap with dispersion strongly suppressed by the large energy barriers in the moiré superlattice even for large twist angles. We explicitly demonstrate our idea in bilayer α-In2Se3 and bilayer InSe. For bilayer α-In2Se3, we show that a twist angle ~13.2˚ is sufficient to achieve the band flatness comparable to that of twist bilayer graphene at the magic angle ~1.1˚. In addition, the appearance of ultra-flat bands here is not sensitive to the twist angle as in bilayer graphene, and it can be further controlled by external gate fields. Our finding provides a new route to achieve ultra-flat bands other than reducing the twist angles and paves the way towards engineering such flat bands in a large family of 2D materials.
Ferroelectricity in ultrathin two-dimensional (2D) materials has attracted broad interest due to potential applications in nonvolatile memory, nanoelectronics and optoelectronics. However, ferroelectricity is barely explored in materials with native centro or mirror symmetry, especially in the 2D limit. Here, we report the first experimental realization of room-temperature ferroelectricity in van der Waals layered GaSe down to monolayer with mirror symmetric structures, which exhibits strong intercorrelated out-of-plane and in-plane electric polarization. The origin of ferroelectricity in GaSe comes from intralayer sliding of the Se atomic sublayers, which breaks the local structural mirror symmetry and forms dipole moment alignment. Ferroelectric switching is demonstrated in nano devices fabricated with GaSe nanoflakes, which exhibit exotic nonvolatile memory behavior with a high channel current on/off ratio. Our work reveals that intralayer sliding is a new approach to generate ferroelectricity within mirror symmetric monolayer, and offers great opportunity for novel nonvolatile memory devices and optoelectronics applications.
Safe and efficient hydrogen storage is one of the key technologies for the widespread utilization of hydrogen energy. Formic acid (FA) is regarded as a safe and convenient chemical hydrogen storage material. However, the lack of highly efficient heterogeneous catalysts hinders its practical application. Herein, we presented a facile wet-impregnated deposition method to synthesize ultrafine AuPd alloy nanoparticles anchored on TiO nanosheets (AuPd/TiO nanosheets) which were used as high efficient catalysts for the dehydrogenation of FA. TiO nanosheets were calcined at different temperatures to modify the catalytic activity of catalyst. AuPd/TiO nanosheets-400 exhibits the superior activity for catalyzing the FA to release 96% of overall hydrogen content with an initial turnover frequency value of 592 mol H mol metal h at 25 °C and low activation energy of 11.8 kJ mol. Detailed characterizations show that the superior catalytic performance can be ascribed to the alloy structure of AuPd centers, the phase and crystallinity of TiO nanosheets, and the strong electron transfer interaction between AuPd nanoparticles and TiO nanosheets substrate.
Bandgap engineering is an efficient strategy for controlling the physical properties of semiconductor materials. For flexible two-dimensional (2D) materials, strain provides a nondestructive and adjustable method for bandgap adjustment. Here, we propose that, in 2D materials with out-of-plane ferroelectricity, the antibonding nature of the valence band maximum and conduction band minimum and polarized charge distribution induced by ferroelectricity give rise to giant changes of the bandgap under curvature strain field. This hypothesis was proven by scanning tunneling microscopy/spectroscopy measurements on monolayer α-In2Se3 that revealed that the bandgap of α-In2Se3 increases significantly due to bending. Both experiments and theoretical calculations indicated that the bandgap increases monotonically with the degree of bending of the α-In2Se3 layer. Our work suggests that bending is an effective method for tuning the gaps of 2D ferroelectric materials, providing a new platform for bandgap engineering under the combination of ferroelectricity and strain field.
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