Visualizing the Atomic Configuration of Carbonate Groups in a (Cu,C)Ba2 Ca3 Cu4 O11+δ Superconductor.

Carbonates (CO3 2- ) have always been known as impurities to degrade the superconductivity in cuprate high-Tc superconductors. Herein, the atomic arrangement of carbonates is directly visualized in (Cu,C)Ba2 Ca3 Cu4 O11+δ via integrated differential phase contrast (iDPC) combined with state-of-the-art scanning transmission electron microscopy. The carbon atoms replace Cu atoms in the charge-reservoir layers, contributing to the formation of carbonates through strong orbital hybridization with the surrounding oxygen atoms. Using first-principles calculations, the spatial configuration of the carbonate groups is confirmed and their influence on the local crystal lattice and electronic states is further investigated. The carbonates not only accommodate distortions by improving the flatness of the outer CuO2 layers but also reduce the density of states at the Fermi level. These two factors play competitive roles to affect the superconductivity. This study provides direct evidence of the presence of CO3 2- groups and gains an insight into the underlying mechanism of superconductivity in oxycarbonate superconductors.

Phase and Band Structure Engineering via Linear Additive in NBT-ST for Excellent Energy Storage Performance with Superior Thermal Stability.

Lead-free relaxor ferroelectric ceramics with ultrahigh energy-storage performance are vital for pulsed power systems. We herein propose a strategy of phase and band structure engineering for high-performance energy storage. To demonstrate the effectiveness of this strategy, (1 - x)(0.75Na0.5Bi0.5TiO3-0.25SrTiO3)-xCaTi0.875Nb0.1O3 (NBT-ST-xCTN, x = 0.1, 0.2, 0.3, 0.4, and 0.5) samples were designed and fabricated via the solid-state reaction method. The linear dielectric CTN was used as a modulator to tune both phase and band structures of the tested system. Our results show that both rhombohedral phase (R-phase) and tetragonal phase (T-phase) coexist in the samples. The R/T ratio decreases, while the band gap increases with increasing CTN content. The best energy-storage properties with large energy storage density (Wrec = 7.13 J/cm3), a high efficiency (η = 90.3%), and an ultrafast discharge time (25 ns) were achieved in the NBT-ST-0.4CTN sample with R/T = 0.121. Importantly, along with its excellent energy-storage performance, the sample exhibited superior thermal stability with the variations of Wrec ≤ 7% and η ≤ 10% over the wide temperature range of 233-413 K. This work suggests that this engineering of phase and band structures is a promising strategy to achieve superior energy-storage properties in lead-free ceramics.