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.

Revisiting Metal-Organic Frameworks Porosimetry by Positron Annihilation: Metal Ion States and Positronium Parameters.

Metal-organic frameworks (MOFs) stand as pivotal porous materials with exceptional surface areas, adaptability, and versatility. Positron Annihilation Lifetime Spectroscopy (PALS) is an indispensable tool for characterizing MOF porosity, especially micro- and mesopores in both open and closed phases. Notably, PALS offers porosity insights independent of probe molecules, which is vital for detailed characterization without structural transformations. This study explores how metal ion states in MOFs affect PALS results. We find significant differences in measured porosity due to paramagnetic or oxidized metal ions compared to simulated values. By analyzing CPO-27(M) (M = Mg, Co, Ni), with identical pore dimensions, we observe distinct PALS data alterations based on metal ions. Paramagnetic Co and Ni ions hinder and quench positronium (Ps) formation, resulting in smaller measured pore volumes and sizes. Mg only quenches Ps, leading to underestimated pore sizes without volume distortion. This underscores the metal ions' pivotal role in PALS outcomes, urging caution in interpreting MOF porosity.

Unravelling the Water Adsorption Mechanism in Hierarchical MOFs: Insights from In Situ Positron Annihilation Lifetime Studies.

Atmospheric water harvesting with metal-organic frameworks (MOFs) is a new technology providing a clean, long-term water supply in arid areas. In-situ positron annihilation lifetime spectroscopy (PALS) is proposed as a valid methodology for the mechanistic understanding of water sorption in MOFs and the selection of prospective candidates for desired applications. DUT-67-Zr and DUT-67-Hf frameworks are used as model systems for method validation because of their hierarchical pore structure, high adsorption capacity, and chemical stability. Both frameworks are characterized using complementary techniques, such as nitrogen (77 K) and water vapor (298 K) physisorption, SEM, and PXRD. DUT-67-Zr and DUT-67-Hf are investigated by PALS upon exposure to humidity for the first time, demonstrating the stepwise pore filling mechanism by water molecules for both MOFs. In addition to exploring the potential of PALS as a tool for probing MOFs during in situ water loading, this work offers perspectives on the design and use of MOFs for water harvesting.

Millisecond flash lamp curing for porosity generation in thin films.

Flash lamp annealing (FLA) with millisecond pulse durations is reported as a novel curing method for pore precursor's degradation in thin films. A case study on the curing of dielectric thin films is presented. FLA-cured films are being investigated by means of positron annihilation spectroscopy (PAS) and Fourier-transform infrared (FTIR) spectroscopy in order to quantify the nm-scale porosity and post-treatment chemistry, respectively. Results from positron annihilation reveal the onset of the formation of porous voids inside the samples at 6 ms flash treatment time. Moreover, parameter's adjustment (flash duration and energy density) allows for identifying the optimum conditions of effective curing. Within such a systematic investigation, positron results indicate that FLA is able to decompose the porogen (pore precursors) and to generate interconnected (open porosity) or isolated pore networks with self-sealed pores in a controllable way. Furthermore, FTIR results demonstrate the structural evolution after FLA, that help for setting the optimal annealing conditions whereby only a residual amount of porogen remains and at the same time a well-densified matrix, and a hydrophobic porous structures are created. Raman spectroscopy suggests that the curing-induced self-sealing layer developed at the film surface is a graphene oxide-like layer, which could serve as the outside sealing of the pore network from intrusions.

Regulating Oxygen Ion Transport at the Nanoscale to Enable Highly Cyclable Magneto-Ionic Control of Magnetism.

Magneto-ionics refers to the control of magnetic properties of materials through voltage-driven ion motion. To generate effective electric fields, either solid or liquid electrolytes are utilized, which also serve as ion reservoirs. Thin solid electrolytes have difficulties in (i) withstanding high electric fields without electric pinholes and (ii) maintaining stable ion transport during long-term actuation. In turn, the use of liquid electrolytes can result in poor cyclability, thus limiting their applicability. Here we propose a nanoscale-engineered magneto-ionic architecture (comprising a thin solid electrolyte in contact with a liquid electrolyte) that drastically enhances cyclability while preserving sufficiently high electric fields to trigger ion motion. Specifically, we show that the insertion of a highly nanostructured (amorphous-like) Ta layer (with suitable thickness and electric resistivity) between a magneto-ionic target material (i.e., Co3O4) and the liquid electrolyte increases magneto-ionic cyclability from <30 cycles (when no Ta is inserted) to more than 800 cycles. Transmission electron microscopy together with variable energy positron annihilation spectroscopy reveals the crucial role of the generated TaOx interlayer as a solid electrolyte (i.e., ionic conductor) that improves magneto-ionic endurance by proper tuning of the types of voltage-driven structural defects. The Ta layer is very effective in trapping oxygen and hindering O2- ions from moving into the liquid electrolyte, thus keeping O2- motion mainly restricted between Co3O4 and Ta when voltage of alternating polarity is applied. We demonstrate that this approach provides a suitable strategy to boost magneto-ionics by combining the benefits of solid and liquid electrolytes in a synergetic manner.

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.

Defect Nanostructure and its Impact on Magnetism of α-Cr2 O3 Thin Films.

Thin films of the magnetoelectric insulator α-Cr2 O3 are technologically relevant for energy-efficient magnetic memory devices controlled by electric fields. In contrast to single crystals, the quality of thin Cr2 O3 films is usually compromised by the presence of point defects and their agglomerations at grain boundaries, putting into question their application potential. Here, the impact of the defect nanostructure, including sparse small-volume defects and their complexes is studied on the magnetic properties of Cr2 O3 thin films. By tuning the deposition temperature, the type, size, and relative concentration of defects is tailored, which is analyzed using the positron annihilation spectroscopy complemented with electron microscopy studies. The structural characterization is correlated with magnetotransport measurements and nitrogen-vacancy microscopy of antiferromagnetic domain patterns. Defects pin antiferromagnetic domain walls and stabilize complex multidomain states with a domain size in the sub-micrometer range. Despite their influence on the domain configuration, neither small open-volume defects nor grain boundaries in Cr2 O3 thin films affect the Néel temperature in a broad range of deposition parameters. The results pave the way toward the realization of spin-orbitronic devices where magnetic domain patterns can be tailored based on defect nanostructures without affecting their operation temperature.

Insights into the pores of microwave-assisted metal-imidazolate frameworks showing enhanced gas sorption.

Microwave heating (MW)-assisted synthesis has been widely applied as an alternative method for the chemical synthesis of organic and inorganic materials. In this work, we report MW-assisted synthesis of three isostructural 3D frameworks with a flexible linker arm of the chelating linker 2-substituted imidazolate-4-amide-5-imidate, named IFP-7-MW (M = Zn, R = OMe), IFP-8-MW (M = Co; R = OMe) and IFP-10-MW (M = Co; R = OEt) (IFP = Imidazolate Framework Potsdam). These chelating ligands were generated in situ by partial hydrolysis of 2-substituted 4,5-dicyanoimidazoles under MW- and also conventional electrical heating (CE)-assisted conditions in DMF. The structure of these materials was determined by IR spectroscopy and powder X-ray diffraction (PXRD) and the identity of the materials synthesized under CE-conditions was established. Materials obtained from MW-heating show many fold enhancement of CO2 and H2 uptake capacities, compared to the analogous CE-heating method based materials. To understand the inner pore-sizes of IFP structures and variations of gas sorptions, we performed positron annihilation lifetime spectroscopy (PALS), which shows that MW-assisted materials have smaller pore sizes than materials synthesized under CE-conditions. The "kinetically controlled" MW-synthesized material has an inherent ability to trap extra linkers, thereby reducing the pore sizes of CE-materials to ultra/micropores. These ultramicropores are responsible for high gas sorption.

Study of the Discrepancies between Crystallographic Porosity and Guest Access into Cadmium-Imidazolate Frameworks and Tunable Luminescence Properties by Incorporation of Lanthanides.

An extended member of the isoreticular family of metal-imidazolate framework structures, IFP-6 (IFP=imidazolate framework Potsdam), based on cadmium metal and an in situ functionalized 2-methylimidazolate-4-amide-5-imidate linker is reported. A porous 3D framework with 1D hexagonal channels with accessible pore windows of 0.52 nm has been synthesized by using an ionic liquid (IL) linker precursor. IFP-6 shows significant gas uptake capacity only for CO2 and CH4 at elevated pressure, whereas it does not adsorb N2 , H2 , and CH4 under atmospheric conditions. IFP-6 is assumed to deteriorate at the outside of the material during the activation process. This closing of the metal-organic framework (MOF) pores is proven by positron annihilation lifetime spectroscopy (PALS), which revealed inherent crystal defects. PALS results support the conservation of the inner pores of IFP-6. IFP-6 has also been successfully loaded with luminescent trivalent lanthanide ions (Ln(III) =Tb, Eu, and Sm) in a bottom-up one-pot reaction through the in situ generation of the linker ligand and in situ incorporation of photoluminescent Ln ions into the constituting network. The results of photoluminescence investigations and powder XRD provide evidence that the Ln ions are not doped as connectivity centers into the frameworks, but are instead located within the pores of the MOFs. Under UV light irradiation, Tb@IFP-6 and Eu@IFP-6 (λexc =365 nm) exhibit observable emission changes to a greenish and reddish color, respectively, as a result of strong Ln 4 f emissions.