Insights into the LiMn2O4 Cathode Stability in Aqueous Electrolytes.

LiMn2O4 (LMO) cathodes present large stability when cycled in aqueous electrolytes, contrasting with their behavior in conventional organic electrolytes in lithium-ion batteries (LIBs). To elucidate the mechanisms underlying this distinctive behavior, we employ unconventional characterization techniques, including variable energy positron annihilation lifetime spectroscopy (VEPALS), tip-enhanced Raman spectroscopy (TERS), and macro-Raman spectroscopy (with tens of µm-size laser spot). These still rather unexplored techniques in the battery field provide complementary information across different length scales, revealing previously hidden features. VEPALS offers atomic-scale insights, uncovering cationic defects and subnanometer pores that tend to collapse with cycling. TERS, operating in the nanometric range at the surface, captured the presence of Mn3O4 and its dissolution with cycling, elucidating dynamic changes during operation. Additionally, TERS highlights the accumulation of SO4 2- at grain boundaries. Macro-Raman spectroscopy focuses on the micrometer scale, depicting small changes in the cathode's long-range order, suggesting a slow but progressive loss of crystalline quality under operation. Integrating these techniques provides a comprehensive assessment of LMO cathode stability in aqueous electrolytes, offering multifaceted insights into phase and defect evolution that can help to rationalize the origin of such stability when compared with conventional organic electrolytes. Our findings advance the understanding of LMO behavior in aqueous environments and provide guidelines for its development for next-generation LIBs.

Superior Thermoelectric Performance of SiGe Nanowires Epitaxially Integrated into Thermal Micro-Harvesters.

Semiconductor nanowires have demonstrated fascinating properties with applications in a wide range of fields, including energy and information technologies. Particularly, increasing attention has focused on SiGe nanowires for applications in a thermoelectric generation. In this work, a bottom-up vapour-liquid-solid chemical vapour Deposition methodology is employed to integrate heavily boron-doped SiGe nanowires on thermoelectric generators. Thermoelectrical properties -, i.e., electrical and thermal conductivities and Seebeck coefficient - of grown nanowires are fully characterized at temperatures ranging from 300 to 600 K, allowing the complete determination of the Figure-of-merit, zT, with obtained values of 0.4 at 600 K for optimally doped nanowires. A correlation between doping level, thermoelectric performance, and elemental distribution is established employing advanced elemental mapping (synchrotron-based nano-X-ray fluorescence). Moreover, the operation of p-doped SiGe NWs integrated into silicon micromachined thermoelectrical generators is shown over standalone and series- and parallel-connected arrays. Maximum open circuit voltage of 13.8 mV and power output as high as 15.6 µW cm-2 are reached in series and parallel configurations, respectively, operating upon thermal gradients generated with hot sources at 200 °C and air flows of 1.5 m s-1 . These results pave the way for direct application of SiGe nanowire-based micro-thermoelectric generators in the field of the Internet of Things.

Nanoscaled LiMn2O4 for Extended Cycling Stability in the 3 V Plateau.

Extending the potential window toward the 3 V plateau below the typically used range could boost the effective capacity of LiMn2O4 spinel cathodes. This usually leads to an "overdischarge" of the cathode, which can cause severe material damage due to manganese dissolution into the electrolyte and a critical volume expansion (induced by Jahn-Teller distortions). As those factors determine the stability and cycling lifetime for all-solid-state batteries, the operational window of LiMn2O4 is usually limited to 3.5-4.5 V versus Li/Li+ in common battery cells. However, it has been reported that nano-shaped particles and thin films can potentially mitigate these detrimental effects. We demonstrate here that porous LiMn2O4 thin-film cathodes with a certain level of off-stoichiometry show improved cycling stability for the extended cycling range of 2.0-4.5 V versus Li/Li+. We argue through operando spectroscopic ellipsometry that the origin of this stability lies in the surprisingly small volume change in the layer during lithiation.

Photo-enhanced ionic conductivity across grain boundaries in polycrystalline ceramics.

Grain boundary conductivity limitations are ubiquitous in material science. We show that illumination with above-bandgap light can decrease the grain boundary resistance in solid ionic conductors. Specifically, we demonstrate the increase of the grain boundary conductance of a 3 mol% Gd-doped ceria thin film by a factor of approximately 3.5 at 250 °C and the reduction of its activation energy from 1.12 to 0.68 eV under illumination, while light-induced heating and electronic conductivity could be excluded as potential sources for the observed opto-ionic effect. The presented model predicts that photo-generated electrons decrease the potential barrier heights associated with space charge zones depleted in charge carriers between adjacent grains. The discovered opto-ionic effect could pave the way for the development of new electrochemical storage and conversion technologies operating at lower temperatures and/or higher efficiencies and could be further used for fast and contactless control or diagnosis of ionic conduction in polycrystalline solids.

Toward Controlling Filament Size and Location for Resistive Switches via Nanoparticle Exsolution at Oxide Interfaces.

Memristive devices are among the most prominent candidates for future computer memory storage and neuromorphic computing. Though promising, the major hurdle for their industrial fabrication is their device-to-device and cycle-to-cycle variability. These occur due to the random nature of nanoionic conductive filaments, whose rupture and formation govern device operation. Changes in filament location, shape, and chemical composition cause cycle-to-cycle variability. This challenge is tackled by spatially confining conductive filaments with Ni nanoparticles. Ni nanoparticles are integrated on the bottom La0.2 Sr0.7 Ti0.9 Ni0.1 O3- δ electrode by an exsolution method, in which, at high temperatures under reducing conditions, Ni cations migrate to the perovskite surface, generating metallic nanoparticles. This fabrication method offers fine control over particle size and density and ensures strong particle anchorage in the bottom electrode, preventing movement and agglomeration. In devices based on amorphous SrTiO3 , it is demonstrated that as the exsolved Ni nanoparticle diameter increases up to ≈50 nm, the ratio between the ON and OFF resistance states increases from single units to 180 and the variability of the low resistance state reaches values below 5%. Exsolution is applied for the first time to engineer solid-solid interfaces extending its realm of application to electronic devices.

Nanoscale Correlations between Metal-Insulator Transition and Resistive Switching Effect in Metallic Perovskite Oxides.

Strongly correlated perovskite oxides are a class of materials with fascinating intrinsic physical functionalities due to the interplay of charge, spin, orbital ordering, and lattice degrees of freedom. Among the exotic phenomena arising from such an interplay, metal-insulator transitions (MITs) are fundamentally still not fully understood and are of large interest for novel nanoelectronics applications, such as resistive switching-based memories and neuromorphic computing devices. In particular, rare-earth nickelates and lanthanum strontium manganites are archetypical examples of bandwidth-controlled and band-filling-controlled MIT, respectively, which are used in this work as a playground to correlate the switching characteristics of the oxides and their MIT properties by means of local probe techniques in a systematic manner. These findings suggest that an electric-field-induced MIT can be triggered in these strongly correlated systems upon generation of oxygen vacancies and establish that lower operational voltages and larger resistance ratios are obtained in those films where the MIT lies closer to room temperature. This work demonstrates the potential of using MITs in the next generation of nanoelectronics devices.

Lithium-Battery Anode Gains Additional Functionality for Neuromorphic Computing through Metal-Insulator Phase Separation.

Specialized hardware for neural networks requires materials with tunable symmetry, retention, and speed at low power consumption. The study proposes lithium titanates, originally developed as Li-ion battery anode materials, as promising candidates for memristive-based neuromorphic computing hardware. By using ex- and in operando spectroscopy to monitor the lithium filling and emptying of structural positions during electrochemical measurements, the study also investigates the controlled formation of a metallic phase (Li7 Ti5 O12 ) percolating through an insulating medium (Li4 Ti5 O12 ) with no volume changes under voltage bias, thereby controlling the spatially averaged conductivity of the film device. A theoretical model to explain the observed hysteretic switching behavior based on electrochemical nonequilibrium thermodynamics is presented, in which the metal-insulator transition results from electrically driven phase separation of Li4 Ti5 O12 and Li7 Ti5 O12 . Ability of highly lithiated phase of Li7 Ti5 O12 for Deep Neural Network applications is reported, given the large retentions and symmetry, and opportunity for the low lithiated phase of Li4 Ti5 O12 toward Spiking Neural Network applications, due to the shorter retention and large resistance changes. The findings pave the way for lithium oxides to enable thin-film memristive devices with adjustable symmetry and retention.

Electrochemical Tuning of Metal Insulator Transition and Nonvolatile Resistive Switching in Superconducting Films.

Modulation of carrier concentration in strongly correlated oxides offers the unique opportunity to induce different phases in the same material, which dramatically change their physical properties, providing novel concepts in oxide electronic devices with engineered functionalities. This work reports on the electric manipulation of the superconducting to insulator phase transition in YBa2Cu3O7-δ thin films by electrochemical oxygen doping. Both normal state resistance and the superconducting critical temperature can be reversibly manipulated in confined active volumes of the film by gate-tunable oxygen diffusion. Vertical and lateral oxygen mobility may be finely modulated, at the micro- and nano-scale, by tuning the applied bias voltage and operating temperature thus providing the basis for the design of homogeneous and flexible transistor-like devices with loss-less superconducting drain-source channels. We analyze the experimental results in light of a theoretical model, which incorporates thermally activated and electrically driven volume oxygen diffusion.

Spontaneous formation of spiral-like patterns with distinct periodic physical properties by confined electrodeposition of Co-In disks.

Spatio-temporal patterns are ubiquitous in different areas of materials science and biological systems. However, typically the motifs in these types of systems present a random distribution with many possible different structures. Herein, we demonstrate that controlled spatio-temporal patterns, with reproducible spiral-like shapes, can be obtained by electrodeposition of Co-In alloys inside a confined circular geometry (i.e., in disks that are commensurate with the typical size of the spatio-temporal features). These patterns are mainly of compositional nature, i.e., with virtually no topographic features. Interestingly, the local changes in composition lead to a periodic modulation of the physical (electric, magnetic and mechanical) properties. Namely, the Co-rich areas show higher saturation magnetization and electrical conductivity and are mechanically harder than the In-rich ones. Thus, this work reveals that confined electrodeposition of this binary system constitutes an effective procedure to attain template-free magnetic, electric and mechanical surface patterning with specific and reproducible shapes.