Tomographic reconstruction of oxygen orbitals in lithium-rich battery materials.

The electrification of heavy-duty transport and aviation will require new strategies to increase the energy density of electrode materials1,2. The use of anionic redox represents one possible approach to meeting this ambitious target. However, questions remain regarding the validity of the O2-/O- oxygen redox paradigm, and alternative explanations for the origin of the anionic capacity have been proposed3, because the electronic orbitals associated with redox reactions cannot be measured by standard experiments. Here, using high-energy X-ray Compton measurements together with first-principles modelling, we show how the electronic orbital that lies at the heart of the reversible and stable anionic redox activity can be imaged and visualized, and its character and symmetry determined. We find that differential changes in the Compton profile with lithium-ion concentration are sensitive to the phase of the electronic wave function, and carry signatures of electrostatic and covalent bonding effects4. Our study not only provides a picture of the workings of a lithium-rich battery at the atomic scale, but also suggests pathways to improving existing battery materials and designing new ones.

Double-Layered Perovskite Oxyfluoride Cathodes with High Capacity Involving O-O Bond Formation for Fluoride-Ion Batteries.

Developing electrochemical high-energy storage systems is of crucial importance toward a green and sustainable energy supply. A promising candidate is fluoride-ion batteries (FIBs), which can deliver a much higher volumetric energy density than lithium-ion batteries. However, typical metal fluoride cathodes with conversion-type reactions cause a low-rate capability. Recently, layered perovskite oxides and oxyfluorides, such as LaSrMnO4 and Sr3Fe2O5F2, have been reported to exhibit relatively high rate performance and cycle stability compared to typical metal fluoride cathodes with conversion-type reactions, but their discharge capacities (∼118 mA h/g) are lower than those of typical cathodes used in lithium-ion batteries. Here, we show that double-layered perovskite oxyfluoride La1.2Sr1.8Mn2O7-δF2 exhibits (de) intercalation of two fluoride ions to rock-salt slabs and further (de) intercalation of excess fluoride ions to the perovskite layer, leading to a reversible capacity of 200 mA h/g. The additional fluoride-ion intercalation leads to the formation of O-O bond in the structure for charge compensation (i.e., anion redox). These results highlight the layered perovskite oxyfluorides as a new class of active materials for the construction of high-performance FIBs.

Fluoride Ion Storage and Conduction Mechanism in Fluoride Ion Battery Positive Electrode, Ruddlesden-Popper-Type Layered Perovskite La1.2Sr1.8Mn2O7 Crystal.

Structural characteristics on fluoride ion storage and conduction mechanism in La1.2Sr1.8Mn2O7, and its fluoridated materials, La1.2Sr1.8Mn2O7F and La1.2Sr1.8Mn2O7F2, for an all-solid-state fluoride ion battery positive electrode with a high volumetric capacity surpassing those of lithium-ion ones have been revealed using the Rietveld method and maximum entropy method. In La1.2Sr1.8Mn2O7, once the F- ions are taken into the NaCl slabs in its crystal through the charging process, it forms two stable fluoride compounds, La1.2Sr1.8Mn2O7F and La1.2Sr1.8Mn2O7F2, with the help of the Mn oxidation reaction. In these oxyfluorides, thermal vibrations of the F- ions inserted are much larger, especially in the a-b plane, than along the c axis. When surplus energy, such as an electric field for charging, is applied to these crystals at near room temperature or higher, the anions immediately begin to jump to their neighboring lattice sites, resulting in sufficiently rapid and large ionic conduction. The MEM analyses and density functional theory (DFT) calculations have revealed that the F- ions enable to easily travel along the ⟨110⟩ directions in the NaCl slabs of these crystals. These structural features thus make La1.2Sr1.8Mn2O7 and its fluorides possess both of two features incompatible with each other, ion storage and conduction, indispensable for rechargeable batteries.

Stacking Order Induced Anion Redox Regulation for Layer-Structured Na0.75 Li0.2 Mn0.7 Cu0.1 O2 Cathode Materials.

Stacking order plays a key role in defining the electrochemical behavior and structural stability of layer-structured cathode materials. However, the detailed effects of stacking order on anionic redox in layer-structured cathode materials have not been investigated specifically and are still unrevealed. Herein, two layered cathodes with the same chemical formula but different stacking orders: P2-Na0.75 Li0.2 Mn0.7 Cu0.1 O2 (P2-LMC) and P3-Na0.75 Li0.2 Mn0.7 Cu0.1 O2 (P3-LMC) are compared. It is found that P3 stacking order is beneficial to improve the oxygen redox reversibility compared with P2 stacking order. By using synchrotron hard and soft X-ray absorption spectroscopies, three redox couples of Cu2+ /Cu3+ , Mn3.5+ /Mn4+ , and O2- /O- are revealed to contribute charge compensation in P3 structure simultaneously, and two redox couples of Cu2+ /Cu3+ and O2- /O- are more reversible than those in P2-LMC due to the higher electronic densities in Cu 3d and O 2p orbitals in P3-LMC. In situ X-ray diffraction reveals that P3-LMC exhibits higher structural reversibility during charge and discharge than P2-LMC, even at 5C rate. As a result, P3-LMC delivers a high reversible capacity of 190.3 mAh g-1 and capacity retention of 125.7 mAh g-1 over 100 cycles. These findings provide new insight into oxygen-redox-involved layered cathode materials for SIBs.

Adaptive Cation Pillar Effects Achieving High Capacity in Li-Rich Layered Oxide, Li2 MnO3 -LiMeO2 (Me = Ni, Co, Mn).

Intensive research is underway to further enhance the performance of lithium-ion batteries (LIBs). To increase the capacity of positive electrode materials, Li-rich layered oxides (LLO) are attracting attention but have not yet been put to practical use. The structural mechanisms through which LLO materials exhibit higher capacity than conventional materials remain unclear because their disordered phases make it difficult to obtain structural information by conventional analysis. The X-ray total scattering analysis reveals a disordered structure consisting of metal ions in octahedral and tetrahedral sites of Li layers as a result of cation mixing after the extraction of Li ions. Metal ions in octahedral sites act as rigid pillars. The metal ions move to the tetrahedral site of the Li layer, which functions as a Li-layer pillar during Li extraction, and returns to the metal site during Li insertion, facilitating Li diffusion as an adaptive pillar. Adaptive pillars are the specific structural features that differ from those of the conventional layered materials, and their effects are responsible for the high capacity of LLO materials. An essential understanding of the pillar effects will contribute to design guidelines for intercalation-type positive electrodes for next-generation LIBs.

Improvement of Visible-Light H2 Evolution Activity of Pb2 Ti2 O5.4 F1.2 Photocatalyst by Coloading of Rh and Pd Cocatalysts.

Pb2 Ti2 O5.4 F1.2 modified with various metal cocatalysts was studied as a photocatalyst for visible-light H2 evolution. Although unmodified Pb2 Ti2 O5.4 F1.2 showed negligible activity, modification of its surface with Rh led to the best observed promotional effect among the Pb2 Ti2 O5.4 F1.2 samples modified with a single metal cocatalyst. The H2 evolution activity was further enhanced by coloading with Pd; the Rh-Pd/Pb2 Ti2 O5.4 F1.2 photocatalyst showed 3.2 times greater activity than the previously reported Pt/Pb2 Ti2 O5.4 F1.2 . X-ray absorption fine-structure spectroscopy, photoelectrochemical, and transient absorption spectroscopy measurements indicated that the coloaded Rh and Pd species, which were partially alloyed on the Pb2 Ti2 O5.4 F1.2 surface, improved the electron-capturing ability, thereby explaining the high activity of the coloaded Rh-Pd/Pb2 Ti2 O5.4 F1.2 catalyst toward H2 evolution.

Single-shot laser-scattering technique refined for the real-time monitoring and sizing of individual nanoparticles and nanobubbles in bulk water.

Understanding the growth dynamics and transport mechanism of nanoparticles/nanobubbles in a solution is an important issue in nanoscience and nanotechnology. Using a standard CMOS camera and a nanosecond laser at 532 nm, we demonstrate the far-field detection of polystyrene nanoparticles in bulk water. Conveniently, the sizes of individual nanoparticles are found to be reliably estimated from the brightness of scattering signals under the single laser pulses. Since the scattering efficiency of polystyrene nanoparticles is similar to that of nanobubbles, our results imply that the detection of nanobubbles in bulk solution is also possible.

Morphology Changes in Perfluorosulfonated Ionomer from Thickness and Thermal Treatment Conditions.

The morphological changes of Nafion thin films with thicknesses from 10 to 200 nm on Pt substrate with various annealing histories (unannealed to 240 °C) were systematically investigated using grazing incidence small-angle X-ray scattering (GISAXS) and grazing incidence wide-angle X-ray scattering (GIWAXS). The results revealed that the hydrophilic ionic domain and hydrophobic backbone in Nafion thin films changed significantly when the annealing treatment exceeded the cluster transition temperature, which decreased proton conductivity, due to the constrained hydrophilic/hydrophobic phase separation, and increased the crystalline-rich domain. This research contributed to the understanding of ionomer thermal stability in the catalyst layer, which is subjected to thermal annealing during the hot-pressing process.

Electrochemical phase transformation accompanied with Mg extraction and insertion in a spinel MgMn2O4 cathode material.

One of the key challenges when developing magnesium rechargeable batteries (MRB) is to develop Mg-intercalation cathodes exhibiting higher redox potentials with larger specific capacities. Although Mg-transition-metal spinel oxides have been shown to be excellent candidates as MRB cathode materials by utilizing the valence change from trivalent to divalent of transition metals starting from Mg insertion, there is no clear evidence to date that Mg can be indeed extracted from the initial spinel hosts by utilizing the change from trivalent to quadrivalent. In this work, we clearly present various experimental evidences of the electrochemical extraction of Mg from spinel MgMn2O4. The present electrochemical charge, i.e., extraction treatment of Mg, was performed in an ionic liquid at 150 °C to ensure Mg hopping in the spinel host. Our analyses show that Mg can be extracted from Mg1-xMn2O4 up to x = 0.4 and, afterwards, successively be inserted into the Mg-extracted (demagnesiated) host via a two-phase reaction between tetragonal and cubic spinels. Finally, we also discuss the difference in electrochemical features between LiMn2O4 and MgMn2O4.

Mechanistic Insight on the Formation of GaN:ZnO Solid Solution from Zn-Ga Layered Double Hydroxide Using Urea as the Nitriding Agent.

A solid solution of GaN and ZnO (GaN:ZnO) is promising as a photocatalyst for visible-light-driven overall water splitting to produce H2. However, several obstacles still exist in the conventional preparation procedure of GaN:ZnO. For example, the atomic distributions of Zn and Ga are nonuniform in GaN:ZnO when a mixture of the metal oxides, i.e. Ga2O3 and ZnO, is used as a precursor. In addition, GaN:ZnO is generally prepared under a harmful NH3 flow for long durations at high temperatures. Here, a facile synthesis of GaN:ZnO with homogeneous atomic composition via a simple and safe procedure is reported. A layered double hydroxide (LDH) containing Zn2+ and Ga3+ was used to increase the uniformity of the atomic distributions of Zn and Ga in GaN:ZnO. We employed urea as a nitriding agent instead of gaseous NH3 to increase the safety of the reaction. Through the optimization of reaction conditions such as heat treatment temperature and content of urea, single-phase GaN:ZnO was successfully obtained. In addition, the nitridation mechanism using urea was investigated in detail. NH3 released from the thermal decomposition of urea did not directly nitride the LDH precursor. X-ray absorption and infrared  spectroscopies revealed that Zn(CN2)-like intermediate species were generated at the middle temperature range and Ga-N bonds formed at high temperature along with dissociation of CO and CO2.

Undoped Layered Perovskite Oxynitride Li2 LaTa2 O6 N for Photocatalytic CO2 Reduction with Visible Light.

Oxynitrides are promising visible-light-responsive photocatalysts, but their structures are almost confined with three-dimensional (3D) structures such as perovskites. A phase-pure Li2 LaTa2 O6 N with a layered perovskite structure was successfully prepared by thermal ammonolysis of a lithium-rich oxide precursor. Li2 LaTa2 O6 N exhibited high crystallinity and visible-light absorption up to 500 nm. As opposed to well-known 3D oxynitride perovskites, Li2 LaTa2 O6 N supported by a binuclear RuII complex was capable of stably and selectively converting CO2 into formate under visible light (λ>400 nm). Transient absorption spectroscopy indicated that, as compared to 3D oxynitrides, Li2 LaTa2 O6 N possesses a lower density of mid-gap states that work as recombination centers of photogenerated electron/hole pairs, but a higher density of reactive electrons, which is responsible for the higher photocatalytic performance of this layered oxynitride.

Amorphous Metal Polysulfides: Electrode Materials with Unique Insertion/Extraction Reactions.

A unique charge/discharge mechanism of amorphous TiS4 is reported. Amorphous transition metal polysulfide electrodes exhibit anomalous charge/discharge performance and should have a unique charge/discharge mechanism: neither the typical intercalation/deintercalation mechanism nor the conversion-type one, but a mixture of the two. Analyzing the mechanism of such electrodes has been a challenge because fewer tools are available to examine the "amorphous" structure. It is revealed that the electrode undergoes two distinct structural changes: (i) the deformation and formation of S-S disulfide bonds and (ii) changes in the coordination number of titanium. These structural changes proceed continuously and concertedly for Li insertion/extraction. The results of this study provide a novel and unique model of amorphous electrode materials with significantly larger capacities.

In operando quantitation of Li concentration for a commercial Li-ion rechargeable battery using high-energy X-ray Compton scattering.

Compton scattering is one of the most promising probes for quantitating Li under in operando conditions, since high-energy X-rays, which have high penetration power, are used as the incident beam and the Compton-scattered energy spectrum has specific line-shapes for each element. An in operando quantitation method to determine the Li composition in electrodes has been developed by using line-shape (S-parameter) analysis of the Compton-scattered energy spectrum. In this study, S-parameter analysis has been applied to a commercial coin cell Li-ion rechargeable battery and the variation of the S-parameters during the charge/discharge cycle at the positive and negative electrodes has been obtained. By using calibration curves for Li composition in the electrodes, the change in Li composition of the positive and negative electrodes has been determined using the S-parameters simultaneously.

Pressure-Stabilized Cubic Perovskite Oxyhydride BaScO2H.

We report a scandium oxyhydride BaScO2H prepared by solid state reaction under high pressure. Rietveld refinements against powder synchrotron X-ray and neutron diffraction data revealed that BaScO2H adopts the ideal cubic perovskite structure (Pm3̅m), where oxide (O2-) and hydride (H-) anions are disordered. 1H nuclear magnetic resonance (NMR) spectroscopy provides a positive chemical shift of about +4.4 ppm, which can be understood by the distance to the nearest (and possibly the next nearest) cation from the H nucleus. A further analysis of the NMR data and calculations based on ab initio random structure searches suggest a partial cis preference in ScO4H2 octahedra. The present oxyhydride, if compositionally or structurally tuned, may become a candidate for H- conductors.

Anti-site mixing governs the electrochemical performances of olivine-type MgMnSiO4 cathodes for rechargeable magnesium batteries.

Rechargeable magnesium batteries are deemed as the next-generation secondary battery systems because of their high theoretical capacity and the terrestrial abundance of magnesium, which is used as the anode in these batteries. The cathode material is an important factor to improve the energy density of the magnesium batteries. In this study, we investigate olivine-type MgMnSiO4 cathode materials owing to their high theoretical capacity (>300 mA h g(-1)). The low-temperature synthesis of MgMnSiO4 suppresses anti-site mixing between Mg and Mn, which drastically improves the charge-discharge capacities of the magnesium battery cathode. Our results show that the suppression of the degree of anti-site mixing between Mg and Mn enhances the diffusion of Mg(2+) during magnesium (de)insertion, and therefore, it is a dominant factor that affects the electrochemical performance of olivine-type MgMnSiO4.

Phase transition kinetics of LiNi0.5Mn1.5O4 analyzed by temperature-controlled operando X-ray absorption spectroscopy.

LiNi0.5Mn1.5O4 (LNMO) is a promising positive electrode material for lithium ion batteries because it shows a high potential of 4.7 V vs. Li/Li(+). Its charge-discharge reaction includes two consecutive phase transitions between LiNi0.5Mn1.5O4 (Li1) ↔ Li0.5Ni0.5Mn1.5O4 (Li0.5) and Li0.5 ↔ Ni0.5Mn1.5O4 (Li0) and the complex transition kinetics that governs the rate capability of LNMO can hardly be analyzed by simple electrochemical techniques. Herein, we apply temperature-controlled operando X-ray absorption spectroscopy to directly capture the reacting phases from -20 °C to 40 °C under potential step (chronoamperometric) conditions and evaluate the phase transition kinetics using the apparent first-order rate constants at various temperatures. The constant for the Li1 ↔ Li0.5 transition (process 1) is larger than that for the Li0.5 ↔ Li0 transition (process 2) at all the measured temperatures, and the corresponding activation energies are 29 and 46 kJ mol(-1) for processes 1 and 2, respectively. The results obtained are discussed to elucidate the limiting factor in this system as well as in other electrode systems.

Compton scattering imaging of a working battery using synchrotron high-energy X-rays.

Results of studies on Compton scattering imaging using synchrotron high-energy X-rays are reported. The technique is applied to a discharging coin cell, and the intensity of Compton scattered X-rays from the inside of the cell has been measured as a function of position and time. The position-time intensity map captures the migration of lithium ions in the positive electrode and reveals the structural change due to the volume expansion of the electrode. This experiment is a critical step in developing synchrotron-based Compton scattering imaging for electrochemical cells at a product level.

Charge-Compensation-Driven Failure Mechanism of Ni Redox in Fe-Rich Ni/Fe/Mn-Based O3-Type Layered Oxide Sodium-Ion Cathodes.

For cathode materials of sodium-ion batteries, O3-type Ni/Fe/Mn-based (Na-NFM) layered oxides have garnered extensive attention because of high economic viability, environmental friendliness, and the potential for high energy density. Among them, Fe-rich compositions exhibit higher initial charge capacity and lower bill-of-material costs, while they fade rapidly and exhibit low initial coulombic efficiency, hindering their commercialization prospects. In this work, we investigate the failure of Fe-rich Na-NFM materials through X-ray absorption spectroscopy methods. The results reveal a combined failure mechanism that encompasses not only the conventional theory of Fe migration but also an abnormal Ni-redox deterioration, which has not yet been reported. More factors related to the failure of Fe-rich Na-NFM layered oxides are discussed in detail. These findings are expected to inspire targeted research efforts toward Fe-rich Na-NFM materials, thereby accelerating the practical application of sodium-ion batteries.

Quantitating the lattice strain dependence of monolayer Pt shell activity toward oxygen reduction.

Lattice strain of Pt-based catalysts reflecting d-band status is the decisive factor of their catalytic activity toward oxygen reduction reaction (ORR). For the newly arisen monolayer Pt system, however, no general strategy to isolate the lattice strain has been achieved due to the short-range ordering structure of monolayer Pt shells on different facets of core nanoparticles. Herein, based on the extended X-ray absorption fine structure of monolayer Pt atoms on various single crystal facets, we propose an effective methodology for evaluating the lattice strain of monolayer Pt shells on core nanoparticles. The quantitative lattice strain establishes a direct correlation to monolayer Pt shell ORR activity.

Direct observation of a metastable crystal phase of Li(x)FePO4 under electrochemical phase transition.

The phase transition between LiFePO4 and FePO4 during nonequilibrium battery operation was tracked in real time using time-resolved X-ray diffraction. In conjunction with increasing current density, a metastable crystal phase appears in addition to the thermodynamically stable LiFePO4 and FePO4 phases. The metastable phase gradually diminishes under open-circuit conditions following electrochemical cycling. We propose a phase transition path that passes through the metastable phase and posit the new phase's role in decreasing the nucleation energy, accounting for the excellent rate capability of LiFePO4. This study is the first to report the measurement of a metastable crystal phase during the electrochemical phase transition of LixFePO4.