3D High-Resolution Chemical Characterization of Sputtered Li-Rich NMC811 Thin Films Using TOF-SIMS.

Massive demand for Li-ion batteries stimulates the research of new materials such as high-capacity cathodes, metal anodes, and solid electrolytes, which should ultimately lead to new generations of batteries such as all-solid-state batteries. Such material discovery often requires knowledge on lithium's content and local distribution in complex Li-containing systems, which is a challenging analytical task. The state-of-the-art time-of-flight secondary-ion mass spectrometry (TOF-SIMS) is one of the few chemical analysis techniques allowing for parallel detection of all sample components and representing their distributions in 3D with nanoscale resolution. In this work, we explore the outstanding potential of TOF-SIMS for comprehensive chemical and nano-/micro-structural characterization of novel Li-rich nickel manganese cobalt oxide thin films, which are potential cathode materials for the future generation batteries. Off-stoichiometric thin films of Li- and Ni-rich layered oxide with the composition of LixNi0.8Mn0.1Co0.1O2 (LR-NMC811, x > 1) were deposited using reactive magnetron sputtering. Such thin films do not contain any conductive additives or binders and therefore serve as model 2D systems to investigate compositional fluctuations, surface and interface phenomena, and their aging. TOF-SIMS revealed the presence of 400 ± 100 nm overlithiated grains and 100 ± 30 nm nanoparticles with an increased 7Li16O+ ion content in the buried part of LR-NMC811. The Li-rich agglomerates could potentially serve as Li reservoirs for compensating Li losses during cathode fabrication and cell operation. Interestingly, these sub-micron structures decomposed in time upon exposure to ambient conditions for 30 days.

Influence of amorphous carbon interlayers on nucleation and early growth of lithium metal at the current collector-solid electrolyte interface.

Nucleation and early growth of Li metal is critical to the performance of anode-free solid-state batteries. We report the use of amorphous carbon deposited by direct current magnetron sputtering as an intermediate layer between the Cu current collector and the Lipon solid electrolyte. The density, conductivity, and microstructure of the carbon interlayer are varied and their influence on the reversible formation and removal of the Li metal anode is investigated. It is shown that thin films of amorphous carbon act as seed layers, reducing the overpotential for Li plating and increasing the critical current density for Li plating and stripping from 2 up to 8 mA cm-2. It is further demonstrated that the ionic conductivity of the Li ions in the carbon interlayers determines their optimum thickness to be 100 nm or less, and that the initial Li loss due to interphase formation can be reduced to a few tens of nm by decreasing the density of the carbon films.

Detection of Au+ Ions During Fluorine Gas-Assisted Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) for the Complete Elemental Characterization of Microbatteries.

Due to excellent electric conductivity and chemical inertness, Au can be used in new microdevices for energy applications, microelectronics, and biomedical solutions. However, the chemical analysis of Au-containing systems using time-of-flight secondary ion mass spectrometry (TOF-SIMS) can be difficult because of the negative ionization of Au, as most metals form positive ions, and therefore cannot be detected from the same analytical volume. In this work, we present the potential of fluorine gas coinjection for altering the polarity, from the negative to positive, of Au secondary ions generated under Ga+ beam bombardment. The importance of detecting Au+ ions and representing their spatial distribution in nanoscale was demonstrated using a novel solid electrolyte for Li-ion solid-state batteries, amorphous Li7La3Zr2O12 (aLLZO). This allowed for assessing the migration of mobile Li+ ions outside the aLLZO layer and alloying the Au layer with Li, which explained the presence of an internal electric field observed during the polarization measurements. Remarkably, during fluorine gas-assisted TOF-SIMS measurements, the trace amount of Au content (5 ppm) was detected in a Pt layer (unattainable under standard vacuum conditions). In conclusion, fluorine gas-assisted TOF-SIMS can help understanding operation mechanisms and potential degradation processes of microdevices and therefore help optimizing their functionality.

Millisecond photonic sintering of iron oxide doped alumina ceramic coatings.

The sintering of alumina (Al2O3) traditionally occurs at high temperatures (up to ca. 1700 °C) and in significantly long times (up to several hours), which are required for the consolidation of the material by diffusion processes. Here we investigate the photonic sintering of alumina particles using millisecond flash lamp irradiation with extreme heating rates up to 108 K/min. The limitation of the low visible light absorption of alumina is resolved by adding colored α-Fe2O3 nanoparticles, which initiated the grain growth during sintering. After the millisecond-long light pulses from a xenon flash lamp, a bimodal mixture of α-Al2O3 precursor particles was sintered and iron segregation at the grain boundaries was observed. The proposed photonic sintering approach based on doping with colored centers may be extended to other refractory ceramics with low absorption in the visible light range once appropriate high-absorbing dopants are identified.

Synaptic transistors with aluminum oxide dielectrics enabling full audio frequency range signal processing.

The rapid evolution of the neuromorphic computing stimulates the search for novel brain-inspired electronic devices. Synaptic transistors are three-terminal devices that can mimic the chemical synapses while consuming low power, whereby an insulating dielectric layer physically separates output and input signals from each other. Appropriate choice of the dielectric is crucial in achieving a wide range of operation frequencies in these devices. Here we report synaptic transistors with printed aluminum oxide dielectrics, improving the operation frequency of solution-processed synaptic transistors by almost two orders of magnitude to 50 kHz. Fabricated devices, yielding synaptic response for all audio frequencies (20 Hz to 20 kHz), are employed in an acoustic response system to show the potential for future research in neuro-acoustic signal processing with printed oxide electronics.

Fast Charge Transfer across the Li7La3Zr2O12 Solid Electrolyte/LiCoO2 Cathode Interface Enabled by an Interphase-Engineered All-Thin-Film Architecture.

Lithium garnet Li7La3Zr2O12 (LLZO) is being investigated as a potential solid electrolyte for next-generation solid-state batteries owing to its high ionic conductivity and electrochemical stability against metallic lithium and high potential cathodes. While the LLZO/Li metal anode interface has been thoroughly investigated to achieve almost negligible interface resistances, the LLZO/cathode interface still suffers from high interfacial resistances mainly due to the high-temperature sintering required for proper ceramic bonding. In this work, the LLZO solid electrolyte/LiCoO2 (LCO) cathode interface is investigated in an all-thin-film model system. This architecture provides an easy access to the interface for in situ and ex situ characterization, allowing one to identify the degradation processes taking place under high-temperature cosintering and to test solutions such as interface modifications. Introducing an in situ-lithiated Nb2O5 diffusion barrier at the interface, we were able to lower the LLZO/LCO charge transfer resistance to about 50 Ω cm2, a 3-fold reduction with respect to previously reported values. The low interfacial resistance combined with the high conductance through the LLZO thin-film electrolyte allows one to investigate the charge transfer at high charge-discharge rates, unlike in bulk systems. At 1C, discharge capacities of about 140 mA h g-1 were measured, and at 10C, 60% of the theoretical capacity was retained with a cycle life over 100 cycles. Besides the role of this architecture in the interface investigation, this work also constitutes a milestone in the development of thin-film solid-state batteries with higher power densities.

Sorption-desorption tests to assess the risk derived from metal contamination in mineral and organic soils.

We obtained the sorption isotherms of Cd, Cu, Pb and Zn from seven soils with contrasting properties, including mineral and organic soils. The distribution coefficients (Kd) were determined from batch tests in a solution that simulated the soil solution cationic composition. The Kd values of the target metals varied greatly depending on soil type and initial metal concentration. Sorption isotherms were fitted to Freundlich and Langmuir models, and derived parameters were correlated to soil properties through the construction of a correlation matrix and application of Principal Component Analysis. The batch Kd showed a satisfactory agreement with the Kd obtained from field-contaminated soils. The sorption tests were complemented with the estimation of the reversibility of metal sorption by the application of an extraction test. The extraction yields, which did not relate to the initial metal concentration, depended on the metal-soil combination, and showed no correlation to batch Kd values. The risk derived from a contamination event was estimated through the quantification of a Retention Factor, defined as the ratio of the Kd versus the extraction yield. Results showed that this was an excellent index to highlight which metal and soil represent the most vulnerable scenarios after a contamination event.