Rearrangement Of Ions Research Articles

Blood-based biomemristor for hyperglycemia and hyperlipidemia monitoring

Thanks to its structural characteristics and signal patterns similar to those of human brain synapses, memristors are widely believed to be applicable for neuromorphic computing. However, to our knowledge, memristors have not been effectively applied in the biomedical field, especially in disease diagnosis and health monitoring. In this work, a blood-based biomemristor was prepared for in vitro detection of hyperglycemia and hyperlipidemia. It was found that the device exhibits excellent resistance switching (RS) behavior at lower voltage biases. Through mechanism analysis, it has been confirmed that the RS behavior is driven by Ohmic conduction and ion rearrangement. Furthermore, the hyperglycemia and hyperlipidemia detection devices were constructed for the first time based on memristor logic circuits, and circuit simulations were conducted. These results confirm the feasibility of blood-based biomemristors in detecting hyperglycemia and hyperlipidemia, providing new prospects for the important application of memristors in the biomedical field.

Rearrangement, Elimination, and Ring-Opening Reactions of Cyclopropyl-Substituted Nitrenium Ions: A Computational and Experimental Investigation.

N-(4-Biphenylyl)-N-cyclopropyl nitrenium ion 5 and N-benzyl-N-cyclopropyl nitrenium ion (6) were generated through photolysis of their corresponding N-aminopyridinium ion photoprecursors. In the case of 5, stable products result from a combination of cyclopropyl ring expansion (N-biphenylazetium ion) and ethylene elimination (biphenylisonitrilium ion). When present in high concentrations, methanol can add to the cyclopropyl ring-forming N-3-methoxypropyl-N-biphenyl iminium ion. In contrast, the only detectable product from the N-benzyl-N-cyclopropyl nitrenium ion (6) is benzylisonitrile, resulting from the elimination of ethylene. Density functional theory (DFT) calculations predict the product distributions from the more stable biphenyl system 5 with reasonable accuracy. However, product distributions from the less stable benzyl system 6 are forecast with less accuracy.

Calcium-Pillar Boosting Smooth Phase Transition in Potassium Vanadate Nanobelts toward Superior Cycling Performance in Potassium-Ion Batteries.

The depletion of lithium resources has prompted exploration into alternative rechargeable energy storage systems, and potassium-ion batteries (PIBs) have emerged as promising candidates. As an active cathode material for PIBs, potassium vanadate (KxV2O5) usually suffers from structural damage during electrochemical K-ion insertion/extraction and hence leading to unsatisfactory cycling performance. Here, we introduce Ca2+ ions as pillars into the potassium vanadate to enhance its structural stability and smooth its phase transition behavior. The additional Ca2+ not only stabilizes the layered structure but also promotes the rearrangement of interlayer ions and leads to a smooth solid-solution phase transition. The optimal composition K0.36Ca0.05V2O5 (KCVO) exhibits outstanding cyclic stability, delivering a capacity of ∼90 mA h g-1 at 20 mA g-1 with negligible capacity decay even after 700 cycles at 500 mA g-1. Theoretical calculations indicate lower energy barriers for K+ diffusion, promoting rapid reaction kinetics. The excellent performances and detailed investigations offer insights into the structural regulation of layered vanadium cathodes.

Thermal Characterization of [C2Im][NO3] and Multivalent Nitrate Salts Mixtures

Due to their intrinsic properties, the current applicability of ionic liquids is enormous. In particular, their use in electrochemistry is beyond question. Numerous studies on these compounds and their mixtures, especially with lithium salts, focus on their use as electrolytes for batteries and other energy storage devices. This includes thermal energy storage devices, where 4th generation ionic liquids and their derivatives show a huge potential. Nevertheless, considering the uneven availability of the raw materials, such as lithium, research has extended to mixtures of these compounds with other salts of different metals that are more abundant and widely distributed, such as magnesium or aluminum. This work presents a comprehensive thermal characterization, using differential scanning calorimetry and thermogravimetry, of the protic ionic liquid ethylimidazolium nitrate and its mixture with magnesium and aluminum nitrate salts at different concentrations. Additionally, a comparison between these results and previous studies of mixtures of this ionic liquid with lithium nitrate, as well as mixtures of the protic ionic liquid EAN with the same metal salts, was also performed. The results indicated that the salt addition tends to broaden and reduce crystallization and melting peaks, while the glass transition becomes more visible and shifts to higher temperatures with increasing salt concentration. This is due to the disorder generated by the rearrangement of ions in the polar domains, which erodes the hydrogen bond network of the protic ionic liquid. Nevertheless, the thermal stability of the blended samples does not change significantly compared to the bulk ionic liquid.

Double Electrode Experiments Reveal the Processes Occurring at PEDOT-Coated Neural Electrode Arrays.

Neural electrodes have recently been developed with surface modifications of conductive polymers, in particular poly(3,4-ethylenedioxythiophene) (PEDOT), and extensively studied for their roles in recording and stimulation, aiming to improve their biocompatibility. In this work, the implications for the design of practical neural sensors are clarified, and systematic procedures for their preparation are reported. In particular, this study introduces the use of in vitro double electrode experiments to mimic the responses of neural electrodes with a focus on signal-recording electrodes modified with PEDOT. Specifically, potential steps on one unmodified electrode in an array are used to identify the responses for PEDOT doped with different anions and compared with that of a bare platinum (Pt) electrode. The response is shown to be related to the rearrangement of ions in solution near the detector electrode resulting from the potential step, with a current transient seen at the detector electrode. A rapid response for PEDOT doped with chloride (ca. 0.04 s) ions was observed and attributed to the fast movement of chloride ions in and out of the polymer film. In contrast, PEDOT doped with poly(styrenesulfonate) (PSS) responds much slower (ca. 2.2 s), and the essential immobility of polyanion constrains the direction of current flow.

Room‐Temperature Solid‐State Nitrogen‐Based Magneto‐Ionics in CoxMn1−xN Films

AbstractThe increasing energy demand in information technologies requires novel low‐power procedures to store and process data. Magnetic materials, central to these technologies, are usually controlled through magnetic fields or spin‐polarized currents that are prone to the Joule heating effect. Magneto‐ionics is a unique energy‐efficient strategy to control magnetism that can induce large non‐volatile modulation of magnetization, coercivity and other properties through voltage‐driven ionic motion. Recent studies have shown promising magneto‐ionic effects using nitrogen ions. However, either liquid electrolytes or prior annealing procedures are necessary to induce the desired N‐ion motion. In this work, magneto‐ionic effects are voltage‐triggered at room temperature in solid state systems of CoxMn1‐xN films, without the need of thermal annealing. Upon gating, a rearrangement of nitrogen ions in the layers is observed, leading to changes in the co‐existing ferromagnetic and antiferromagnetic phases, which result in substantial increase of magnetization at room temperature and modulation of the exchange bias effect at low temperatures. A detailed correlation between the structural and magnetic evolution of the system upon voltage actuation is provided. The obtained results offer promising new avenues for the utilization of nitride compounds in energy‐efficient spintronic and other memory devices.

Understanding the charge transfer effects of single atoms for boosting the performance of Na-S batteries.

The effective flow of electrons through bulk electrodes is crucial for achieving high-performance batteries, although the poor conductivity of homocyclic sulfur molecules results in high barriers against the passage of electrons through electrode structures. This phenomenon causes incomplete reactions and the formation of metastable products. To enhance the performance of the electrode, it is important to place substitutable electrification units to accelerate the cleavage of sulfur molecules and increase the selectivity of stable products during charging and discharging. Herein, we develop a single-atom-charging strategy to address the electron transport issues in bulk sulfur electrodes. The establishment of the synergistic interaction between the adsorption model and electronic transfer helps us achieve a high level of selectivity towards the desirable short-chain sodium polysulfides during the practical battery test. These finding indicates that the atomic manganese sites have an enhanced ability to capture and donate electrons. Additionally, the charge transfer process facilitates the rearrangement of sodium ions, thereby accelerating the kinetics of the sodium ions through the electrostatic force. These combined effects improve pathway selectivity and conversion to stable products during the redox process, leading to superior electrochemical performance for room temperature sodium-sulfur batteries.

Influence of pH on spectroscopic and interfacial features of phenol in aqueous cetrimonium bromide solutions of different concentrations

Phenol is an aromatic compound with toxic effects on the environment and living organisms. Cetrimonium bromide (CTAB) is a cationic, quaternary ammonium surfactant, constituent in industrial formulations, and is employed for solubilization as well as removal of pollutants. This study explores the impact of pH on the behavior of phenol in the micellar solution of CTAB via UV–Visible spectroscopy and surface tension measurements at room temperature. Binding coefficient (Kb), free energy change of binding (ΔGb), change in molar absorptivity (Δε), partition coefficient (Kc), free energy change of partitioning (ΔGp) and number of molecules per micelle (n) were determined at different pH. Results showed that phenol exhibits no appreciable interaction with the CTAB, however phenolate ions have the tendency to bind with CTAB micelles and penetrate in the palisade layer of CTAB.Surface properties such as surface excess (τmax), minimum area per molecule (Amin), packing parameter (P), surface area per head group (as), free energy changes of micellization (ΔGm), adsorption ΔGads, and transfer (ΔGtrans), and surface pressure (Π) for CTAB, and phenol in CTAB solutions were also determined. Interfacial studies supported the role of phenol in facilitating micellization of CTAB thermodynamically and hence a fall in CMC values of CTAB except for pH 7.11. Calculated interfacial parameters established the influence of phenol over rearrangement and surface adsorption of CTAB molecular ions at air/water interface. Surface tension results also showed that unionized phenol molecules have low surface activity (62.23mN/m), but when phenol is ionized into phenolate ion surface dramatically increased (44.17 mN/m).

High-energy CID tandem TOF-MS of various types of precursor ions of selected diether phospholipids: Diagnostic known and unexpected fragmentation pathways

The fragmentation behavior of some selected synthetic (1,2-diphytanyl- and 1,2-dihexadecyl-glycerophosphatidylethanolamine, 1,2-diphytanyl- and 1,2-dihexadecyl-glycerophosphatidylcholine) as well as of one natural diether phospholipid (2,3-diphytanyl-glycerophosphatidylinositol), the latter obtained from extracts of the archaeon Sulfolobus acidocaldaricus, was described by negative- and positive-ion MALDI high-energy CID tandem time-flight mass spectrometry for the first time. In contrast to the fragmentation pathways of classical diester glycerophospholipids, whose fragmentation behavior is already well described, the investigated diether glycerophospholipids exhibited a very different fragmentation behavior. The [M–H]−-precursor ions (ethanolamine, inositol) showed abundant high-mass charge-remote site fragmentation of the alkyl chains with easy determination of all methyl branching points (if present). Corresponding low mass product ions elucidated the identity of the polar head group. In contrast, [M+H]+-precursor ions of ethanolamine derivatives showed unusual loss of H3PO4 directly from the precursor ion and McLafferty-like rearrangements of selected product ions differing between sn1-and sn2-substituents, [R1O+58]+ and [R2O+42]+ ions, respectively. No diagnostic low mass product ions or high mass charge-remote site fragmentations are observed. A yet undescribed rearrangement reaction for protonated diether phosphocholine derivates was found by an intramolecular transesterification rearrangement of the precursor ion forming protonated O-alkyl glycerophosphatidylcholine. Besides, high mass charge-remote site fragmentation of the alkyl chains was observed. High-energy CID-spectra of [M+Na]+-precursor ions showed only little fragmentation (ethanolamine, inositol) with abundant partial polar head group losses and low mass head group product ions. In contrast, the [M+Na]+-precursor ions of corresponding choline derivatives showed significant charge-remote site fragmentation of the alkyl chains and diagnostic low mass head group ions. In case of the ethanolamine derivatives the [M+2Na–H]+-precursor ions exhibited abundant polar head group losses and high mass charge-remote site fragmentation with diagnostic low mass head group product ions. The inositol derivative mainly yielded disodiated dehydrated inositol phosphate as product ions. Finally, two diether phospholipid-specific product ions, the newly described K- and L-type ions, are described for the first time for all lipid derivatives and their mechanism of formation is described in detail.

Blue-Emitting Cs(Pb,Cd)Br3 Nanocrystals Resistant to Electric Field-Induced Ion Segregation.

High-performance solution-processed perovskite light-emitting diodes (PeLEDs) have emerged as a good alternative to the well-established technology of epitaxially grown AIIIBV semiconductor alloys. Colloidal cesium lead halide perovskite nanocrystals (CsPbX3 NCs) exhibit room-temperature excitonic emission that can be spectrally tuned across the entire visible range by varying the content of different halogens at the X-site. Therefore, they present a promising platform for full color display manufacturing. Engineering of highly efficient PeLEDs based on bromide and iodide perovskite NCs emitting green and red light, respectively, does not face major challenges except low operational stability of the devices. Meanwhile, mixed-halide counterparts demonstrating blue luminescence suffer from the electric field-induced phase separation (ion segregation) phenomenon described by the rearrangement (demixing) of mobile halide ions in the crystal lattice. This phenomenon results in an undesirable temporal redshift of the electroluminescence spectrum. However, to realize spectral tuning and, at the same time, address the issue of ion segregation less mobile Cd2+ ion could be introduced in the lattice at Pb2+-site that leads to the band gap opening. Herein, we report an original synthesis of CsPb0.88Cd0.12Br3 perovskite NCs and study their structural and optical properties, in particular electroluminescence. Multilayer PeLEDs based on the obtained NCs exhibit single-peak emission centered at 485 nm along with no noticeable change in the spectral line shape for 30 min which is a significant improvement of the device performance.

Are SAXS and SANS suitable to extract information on the role of water for electric-double-layer formation at the carbon-aqueous-electrolyte interface?

This study reports on the applicability of X-ray transmission (XRT), small- and wide-angle X-ray scattering (SAXS/WAXS) and small-angle neutron scattering (SANS) for investigating fundamental processes taking place in the working electrode of an electric double-layer capacitor with 1 M RbBr aqueous electrolyte at different applied potentials. XRT and incoherent neutron scattering are employed to determine global ion- and water-concentration changes and associated charge-balancing mechanisms. We showcase the suitability of SAXS and SANS, respectively, to get complementary information on local ion and solvent rearrangement in nanoconfinement, but also underscore the limitations of simple qualitative models, asking for more quantitative descriptions of water-water and ion-water interactions via detailed atomistic modelling approaches.

Mass Spectrometry Rearrangement Ions and Metabolic Pathway-Based Discovery of Indole Derivatives during the Aging Process in Citrus reticulata 'Chachi'.

The rapid analysis and characterization of compounds using mass spectrometry (MS) may overlook trace compounds. Although targeted analysis methods can significantly improve detection sensitivity, it is hard to discover novel scaffold compounds in the trace. This study developed a strategy for discovering trace compounds in the aging process of traditional Chinese medicine based on MS fragmentation and known metabolic pathways. Specifically, we found that the characteristic component of C. reticulata 'Chachi', methyl N-methyl anthranilate (MMA), fragmented in electrospray ionization coupled with collision-induced dissociation (CID) to produce the rearrangement ion 3-hydroxyindole, which was proven to exist in trace amounts in C. reticulata 'Chachi' based on comparison with the reference substance using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Combining the known metabolic pathways of 3-hydroxyindole and the possible methylation reactions that may occur during aging, a total of 10 possible indole derivatives were untargeted predicted. These compounds were confirmed to originate from MMA using purchased or synthesized reference substances, all of which were detected in C. reticulata 'Chachi' through LC-MS/MS, achieving trace compound analysis from untargeted to targeted. These results may contribute to explaining the aging mechanism of C. reticulata 'Chachi', and the strategy of using the CID-induced special rearrangement ion-binding metabolic pathway has potential application value for discovering trace compounds.

A Mechanism Study on the (+)-ESI-TOF/HRMS Fragmentation of Some PPI Prazoles and Their Related Substances.

Fragmentation mechanisms of some prazoles and their related substances were newly investigated in this paper via positive mode ESI-TOF HRMS1 and HRMS2. Some novel fragmentation rules or ions were found or detected in the research. The pyridine and the benzoimidazole ring remained in most cases during the ionization, and heterolytic fragmentations often occurred near the -S(O)nCH2- linker to give the [1,3]-H migration ion or [1,7]-H migration ion rearranging across the benzoimdazole ring. Smiles rearrangement ionizations also frequently occurred, initiated by the attack of the lone pair electrons from the pyridine ring, and the sulfones gave special N-(2-benzoimdazolyl) pyridine ions (11b and 12c) by a direct extraction from SO2, and the thioethers gave similar framework ions (8c, 9c and 10c) via the rearrangement and a further homolytic cleavage of SH radicals. However, the sulfoxides were seldom detected in the corresponding Smiles rearrangement ions during our measurement, and the N'-oxides of the pyridines did not undergo the Smiles rearrangement ionization due to the absence of the lone pair electrons. The 5/6-membered chelating ions with Na+ or K+ were frequently detected as the molecular and further fragment ions. Some novel and interesting fragment ions containing bivalent (8b and 9b), tetravalent (4b, 5c and 6c) or hexavalent (15b and 16b) sulfurs were first reported here.

Nucleation and Crystallization of Ferrous Phosphate Hydrate via an Amorphous Intermediate.

The fundamental processes of nucleation and crystallization are widely observed in systems relevant to material synthesis and biomineralization; yet most often, their mechanism remains unclear. In this study, we unravel the discrete stages of nucleation and crystallization of Fe3(PO4)2·8H2O (vivianite). We experimentally monitored the formation and transformation from ions to solid products by employing correlated, time-resolved in situ and ex situ approaches. We show that vivianite crystallization occurs in distinct stages via a transient amorphous precursor phase. The metastable amorphous ferrous phosphate (AFEP) intermediate could be isolated and stabilized. We resolved the differences in bonding environments, structure, and symmetric changes of the Fe site during the transformation of AFEP to crystalline vivianite through synchrotron X-ray absorption spectroscopy at the Fe K-edge. This intermediate AFEP phase has a lower water content and less distorted local symmetry, compared to the crystalline end product vivianite. Our combined results indicate that a nonclassical, hydration-induced nucleation and transformation driven by the incorporation and rearrangement of water molecules and ions (Fe2+ and PO43-) within the AFEP is the dominating mechanism of vivianite formation at moderately high to low vivianite supersaturations (saturation index ≤ 10.19). We offer fundamental insights into the aqueous, amorphous-to-crystalline transformations in the Fe2+-PO4 system and highlight the different attributes of the AFEP, compared to its crystalline counterpart.

Integrating I(I)/I(III) catalysis in reaction cascade design enables the synthesis of gem-difluorinated tetralins from cyclobutanols

Partially saturated, fluorine-containing rings are ubiquitous across the drug discovery spectrum. This capitalises upon the biological significance of the native structure and the physicochemical advantages conferred by fluorination. Motivated by the significance of aryl tetralins in bioactive small molecules, a reaction cascade has been validated to generate novel gem-difluorinated isosteres from 1,3-diaryl cyclobutanols in a single operation. Under the Brønsted acidity of the catalysis conditions, an acid-catalysed unmasking/fluorination sequence generates a homoallylic fluoride in situ. This species serves as the substrate for an I(I)/I(III) cycle and is processed, via a phenonium ion rearrangement, to an (isolable) 1,3,3-trifluoride. A final C(sp3)-F bond activation event, enabled by HFIP, forges the difluorinated tetralin scaffold. The cascade is highly modular, enabling the intermediates to be intercepted: this provides an expansive platform for the generation of structural diversity.

Differentiating Toxic and Nontoxic Tricresyl Phosphate Isomers Using Ion–Molecule Reactions with Oxygen

Ortho-substituted isomers of tricresyl phosphates (TCPs) and their toxic metabolites (e.g., CBDP: cresyl saligenin phosphate) can cause neurotoxic effects in humans. When TCP is introduced to an atmospheric pressure chemical ionization source using gas chromatography, radical cations M•+ are formed by charge exchange. The mass spectrum of an ortho-substituted isomer displays two intense peaks that are absent in the spectra of non-ortho-substituted isomers, leading us to propose structure-diagnostic ion-molecule reactions between ions M•+ and oxygen species present in the source. However, the mechanisms of these reactions have not yet been established. In this study, we propose a mechanism and provide support through computational and experimental analyses using density functional theory and cyclic ion mobility-mass spectrometry. The mechanism consists of a multistep reaction starting with the rearrangement of the molecular ion into a distonic isomer followed by an oxidation step and then decomposition into [CBDP-H]+. This proposal is consistent with the results obtained from a series of isotopically labeled analogues. Cyclic ion mobility experiments with a tri-o-cresyl phosphate standard reveal the presence of at least two hydrogen shift isomers of the product ion [CBDP-H]+ that are connected by a low-lying barrier. The selectivity of the ion-molecule reactions toward ortho-substituted cresyl TCP isomers provides us with an identification tool that can select potentially neurotoxic triaryl phosphate esters present in complex mixtures that are produced in large volume by industry.

Effect of N-doping-derived solvent adsorption on electrochemical double layer structure and performance of porous carbon

N-doped porous carbon has been extensively investigated for broad electrochemical applications. The performance is significantly impacted by the electrochemical double layer (EDL), which is material dependent and hard to characterize. Limited understanding of doping-derived EDL structure hinders insight into the structure–performance relations and the rational design of high-performance materials. Thus, we analyzed the mass and chemical composition variation of EDL within electrochemical operation by electrochemical quartz crystal microbalance, in-situ X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry. We found that N-doping triggers specifically adsorbed propylene carbonate solvent in the inner Helmholtz plane (IHP), which prevents ion rearrangement and enhances the migration of cations. However, this specific adsorption accelerated solvent decomposition, rendering rapid performance degradation in practical devices. This work reveals that the surface chemistry of electrodes can cause specific adsorption of solvents and change the EDL structure, which complements the classical EDL theory and provide guidance for practical applications.

Formation mechanism of thiadiamondoids: evidence from thermochemical sulfate reduction simulation experiments with model compounds

High concentrations of thiadiamondoids together with elevated H2S are indicative of the occurrence and extent of thermochemical sulfate reduction (TSR). However, the obscure formation mechanism and accumulation timing of thiadiamondoids restricts their application in TSR evaluation. In this study, TSR simulation experiments with MgSO4 and three model compounds, namely adamantane, 1-methyladamantane, and diamantane, were performed in gold tubes in high pressure reactors. The gaseous hydrocarbons and liquid products generated from the model compounds by TSR were identified and quantified. According to the H2S yields from the three model compounds, the susceptibility to TSR of three model compounds is 1-meththyladamantane > adamantane > diamantane. Four types of compound groups with diamondoid structure were detected in the liquid products: from high to low abundance these are diamondoidyl ketones, diamondoidyl alcohols, diamondoidthiols and thiadiamondoids, respectively. Thiadiamondoids can be generated from C0-alkylated diamondoid species by TSR. During the TSR process, the concentrations of both diamondoidyl alcohols and diamondoidthiols first increased within the maturity range 0.89–1.09 Easy%Ro and then decreased at maturity > 1.09 Easy%Ro. The rapid decrease in concentration of diamondoidthiols does not correspond to increasing thiadiamondoids, suggesting that diamondoidthiols may not be reaction intermediates for thiadiamondoids in laboratory experiment conditions. In the TSR simulation experiments, slowly increasing concentrations of diamondoidyl ketones correspond to slowly increasing concentrations of thiadiamondoids. For the synthesis mechanism of thiaadamantanes derived from thiaadaamantane-4,8-dione, we propose that the diamondoidyl ketones could be reaction intermediates in thiadiamondoid formation. The thiadiamondoids in petroleum could have two different formation mechanisms: (1) low-temperature cationic carbon ion rearrangement in diagenesis to early catagenesis stages, in which thiadiamondoids are derived from the diagenetic products of polycyclic thiols in the source rock; and (2) a free sulfur radical mechanism that occurs in the TSR process at high temperature in the middle catagenesis to metagenesis stages. During the TSR process, free sulfur radicals attack the diamondoidyl ketones generated in the first stage of TSR and open the cage structure. Then the carbonyl carbon atom is replaced by a sulfur atom, followed by cyclization to form thiadiamondoids. Based on the H2S yields in the TSR simulation experiments with diamondoid model compounds, most thiadiamondoids formed in the second stage of the autocatalyzed TSR process within the maturity range of 1.09–1.21 Easy%Ro.

Microgravimetric contributions of multivalent metal ions, water molecules and protons to the energy storage at the electrolyte/electrode interface of aqueous ion batteries

The aqueous battery employing multivalent metal ions as charge carriers is theoretically a high energy density electrochemical energy storage device due to the fact that it carries more charges. However, the storage mechanism of multivalent metal ions, especially Al3+ ions, in TiO2 materials has not been established.A new model associated with the contribution of multivalent metal ions, water molecules and protons in the charging/discharging process of the electrode is established in this work. The storage mechanism of aqueous Al3+ ion batteries is revealed from a new perspective by studying the relationship between the charge inside the TiO2 film and the mass at the interface. More importantly, a highlighted work is to reveal the changes in the amount of interfacial free water molecules and the hydration number of Al3+ ions due to the adsorption/desorption of hydrated ions during the charging/discharging process.The present work is of great significance for revealing the mechanism of multivalent cations on metal oxide surfaces in aqueous batteries, and meanwhile, the model established can also be extended to other fields such as supercapacitors, photovoltaics, and photocatalysis. The results obtained in this work may have an impact on the performance of energy storage batteries, especially the influence of the rearrangement of interface hydration ions and water molecules on the energy storage mechanism.

Realization of superior ionic conductivity by manipulating the atomic rearrangement in Al-doped Li7La3Zr2O12

High ionic conductivity is usually observed in the cubic phase of garnet Li7La3Zr2O12 (LLZO), which can be stabilized by dopants including Ca2+, Fe3+, Al3+, Ga3+, Ti4+, and Si4+. However, the ionic conductivity shows a strong dependence on both the lithium and the dopant atomic occupancy of the garnet LLZO crystal structure (space group Ia 3‾ d), i.e., the 24d (LiO4) or 96 h (LiO6) sites. Dopants occupying the 24d site can induce a strong local electric field which blocks the Li+ diffusion path. The sparking plasma sintering (SPS) process, which limits the diffusion and relaxation time of the material, introduces a metastable state of the cubic LLZO with strong lattice distortion and inadequate ion distribution. Post-annealing promotes ion rearrangement, especially the Al3+ migration from the 24d to 96 h sites, which is driven by the mitigation of the metastable state as identified by structure and composition analysis. Ionic conductivity as high as 3.3 × 10−4 S cm−1 is achieved along with low electronic conductivity of 5.17 × 10−7 S cm−1 by post-annealing at 500 °C in an oxygen environment after the SPS process, meanwhile, the activation energy of is SPS500 as low as 0.36 eV, representing the low energy barriers for ion transportation. This work demonstrated a strategy to fabricate LLZO solid-state electrolyte with high ionic conductivity by manipulating its metastable state and reveal atomic occupation is a vital factor in influencing ionic conductivity besides doping content and bulk density.