P-type binary copper oxide semiconductor films for various O2 flow rates and total pressures (Pt) were prepared using the reactive magnetron sputtering method. Their morphologies and structures were detected by X-ray diffraction, Raman spectrometry, and SEM. A phase diagram with Cu2O, Cu4O3, CuO, and their mixture was established. Moreover, based on Kelvin Probe Force Microscopy (KPFM) and conductive AFM (C-AFM), by measuring the contact potential difference (VCPD) and the field emission property, the work function and the carrier concentration were obtained, which can be used to distinguish the different types of copper oxide states. The band gaps of the Cu2O, Cu4O3, and CuO thin films were observed to be (2.51 ± 0.02) eV, (1.65 ± 0.1) eV, and (1.42 ± 0.01) eV, respectively. The resistivities of Cu2O, Cu4O3, and CuO thin films are (3.7 ± 0.3) × 103 Ω·cm, (1.1 ± 0.3) × 103 Ω·cm, and (1.6 ± 6) × 101 Ω·cm, respectively. All the measured results above are consistent.

All-solid-state Li-metal batteries (ASSLBs) are highly desirable, due to their inherent safety and high energy density; however, the irregular and uncontrolled growth of Li filaments is detrimental to interfacial stability and safety. Herein, we report on the incorporation of piezo-/ferroelectric BaTiO 3 (BTO) nanofibers into solid electrolytes and determination of electric-field distribution due to BTO inclusion that effectively regulates the nucleation and growth of Li dendrites. Theoretical simulations predict that the piezoelectric effect of BTO embedded in solid electrolyte reduces the driving force of dendrite growth at high curvatures, while its ferroelectricity reduces the overpotential, which helps to regularize Li deposition and Li + flux. Polarization reversal of soft solid electrolytes was identified, confirming a regular deposition and morphology alteration of Li. As expected, the ASSLBs operating with LiFePO 4 /Li and poly(ethylene oxide) (PEO)/garnet solid electrolyte containing 10% BTO additive showed a steady and long cycle life with a reversible capacity of 103.2 mAh g −1 over 500 cycles at 1 C. Furthermore, the comparable cyclability and flexibility of the scalable pouch cells prepared and the successful validation in the sulfide electrolytes, demonstrating its universal and promising application for the integration of Li metal anodes in solid-state batteries.

It is notoriously difficult to distinguish the stoichiometric LiCoO2 (LCO) with a O3-I structure from its lithium defective O3-II phase because of their similar crystal symmetry. Interestingly, moreover, the O3-II phase shows metallic conductivity, whereas the O3-I phase is an electronic insulator. How to effectively reveal the intrinsic mechanism of the conductivity difference and nonequilibrium phase transition induced by the lithium deintercalation is of vital importance for its practical application and development. Based on the developed technology of in situ peak force tunneling atomic force microscopy (PF-TUNA) in liquids, the phase transition from O3-I to O3-II and consequent insulator-to-metal transition of LCO thin-film electrodes with preferred (003) orientation nanorods designed and prepared via magnetron sputtering were observed under an organic electrolyte for the first time in this work. Then, studying the post-mortem LCO thin-film electrode by using ex situ time-dependent XRD and conductive atomic force microscopy, we find the phase relaxation of LCO electrodes after the nonequilibrium deintercalation, further proving the differences of the electronic conductivity and work function between the O3-I and O3-II phases. Moreover, X-ray absorption spectroscopy results indicate that the oxidation of Co ions and the increasing of O 2p–Co 3d hybridization in the O3-II phase lead to electrical conductivity improvement in Li1–x CoO2. Simultaneously, it is found that the nonequilibrium deintercalation at a high charging rate can result in phase-transition hysteresis and the O3-I/O3-II coexistence at the charging end, which is explained well by an ionic blockade model with an antiphase boundary. At last, this work strongly suggests that PF-TUNA can be used to reveal the unconventional phenomena on the solid/liquid interfaces.

The solid electrolyte interphase in rechargeable Li-ion batteries, its dynamics and, significantly, its nanoscale structure and composition, hold clues to high-performing and safe energy storage. Unfortunately, knowledge of solid electrolyte interphase formation is limited due to the lack of in situ nano-characterization tools for probing solid-liquid interfaces. Here, we link electrochemical atomic force microscopy, three-dimensional nano-rheology microscopy and surface force-distance spectroscopy, to study, in situ and operando, the dynamic formation of the solid electrolyte interphase starting from a few 0.1 nm thick electrical double layer to the full three-dimensional nanostructured solid electrolyte interphase on the typical graphite basal and edge planes in a Li-ion battery negative electrode. By probing the arrangement of solvent molecules and ions within the electric double layer and quantifying the three-dimensional mechanical property distribution of organic and inorganic components in the as-formed solid electrolyte interphase layer, we reveal the nanoarchitecture factors and atomistic picture of initial solid electrolyte interphase formation on graphite-based negative electrodes in strongly and weakly solvating electrolytes.