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A binary system of Li2TiO3–LiMnO2 is systematically examined by joint experimental and theoretical studies as electrode materials for Li storage applications. Increase in a fraction of Li2TiO3 effectively activates anionic redox, and thus holes are reversibly formed on oxygen by electrochemical oxidation. Such holes are energetically stabilized through π-type interaction with Mn t2g orbital as suggested by theoretical calculation. However, excess enrichment of Li2TiO3 fractions in this binary system results in the oxygen loss as an irreversible process on delithiation because of a non-bonding character for Ti–O bonds coupled with the formation of O–O dimers, which are chemically and electrochemically unstable species. Additionally, detailed electrochemical study clearly shows that Li migration kinetics is relatively slow, presumably coupled with low electronic conductivity. Nevertheless, nanosizing of primary particles is an effective strategy to overcome this limitation. The nanosized sample prepared by mechanical milling delivers a large reversible capacity, ∼300 mA h g−1, even at room temperature and shows much improved capacity retention. Formation and stabilization of holes for the nanosized sample are also directly evidenced by soft X-ray absorption spectroscopy. From these results, factors affecting the reversibility of anionic redox as emerging new chemistry and its possibility for energy storage applications are discussed in more details.

Lithium- and manganese-rich layered oxides (LMRs) are promising positive electrode materials for next-generation rechargeable lithium-ion batteries. Herein, the structural evolution of Li1.2Ni0.2Mn0.6O2 during the initial charge–discharge cycle was examined using synchrotron-radiation X-ray diffraction, X-ray absorption spectroscopy, and nuclear magnetic resonance spectroscopy to elucidate the unique delithiation behavior. The pristine material contained a composite layered structure composed of Ni-free and Ni-doped Li2MnO3 and LiMO2 (M = Ni, Mn) nanoscale domains, and Li ions were sequentially and inhomogeneously extracted from the composite structure. Delithiation from the LiMO2 domain was observed in the potential slope region associated with the Ni2+/Ni4+ redox couple. Li ions were then extracted from the Li2MnO3 domain during the potential plateau and remained mostly in the Ni-doped Li2MnO3 domain at 4.8 V. In addition, structural transformation into a spinel-like phase was partly observed, which is associated with oxygen loss and cation migration within the Li2MnO3 domain. During Li intercalation, cation remigration and mixing resulted in a domainless layered structure with a chemical composition similar to that of LiNi0.25Mn0.75O2. After the structural activation, the Li ions were reversibly extracted from the newly formed domainless structure.

Conversion-type iron trifluoride (FeF3) has attracted considerable attention as a positive electrode material for lithium secondary batteries due to its high energy density and low cost. However, t...

A 41.6MgO-27.1B2O3-31.2SiO2 glass was synthesized by container-less levitation method. B K-edge X-ray absorption near edge structure (XANES) spectroscopy was used to quantify the coordination of boron in the as-made glass, resulting in ~72% of boron in 3-fold coordination. Raman spectroscopy indicated that the glass structure includes depolymerized borate units, which are pyroborate (B2O54−) and ring and/or chain-type metaborate (B3O63−, (BO2O−)∞) groups. The structural changes in the glass under hydrostatic condition were investigated by high-pressure Raman spectroscopy within a diamond anvil cell at pressures up to 8.5 GPa. On the borate structure, metaborate groups decreased with pressure. In contrast, triborate groups, which include tetrahedrally coordinated boron and have a fully polymerized borate network, increased; suggesting that the coordination transformation of B and polymerization were induced via compression. However, the modification of the borate structure units seems to be reversible at least up to 8.5 GPa. As for the silicate network, Q0 and Q1 structures were responsible to compression. Specifically, Q0 could be replaced by Q1 with elevating pressure, which means that the silicate network becomes polymerized with pressure. Whereas, structure of glass samples recovered from the pressure higher than 5 GPa displayed depolymerized silicate network, as dissociation of Q2 to Q1. The observed structural changes in the silicate network implied a partial change of the coordination number of Si4+ ions, which can be enhanced by the presence of a modifier cation with high field strength such as Mg2+.

The major challenge facing lithium–oxygen batteries is the insulating and bulk lithium peroxide discharge product, which causes sluggish decomposition and increasing overpotential during recharge. Here, we demonstrate an improved round-trip efficiency of ~80% by means of a mesoporous carbon electrode, which directs the growth of one-dimensional and amorphous lithium peroxide. Morphologically, the one-dimensional nanostructures with small volume and high surface show improved charge transport and promote delithiation (lithium ion dissolution) during recharge and thus plays a critical role in the facile decomposition of lithium peroxide. Thermodynamically, density functional calculations reveal that disordered geometric arrangements of the surface atoms in the amorphous structure lead to weaker binding of the key reaction intermediate lithium superoxide, yielding smaller oxygen reduction and evolution overpotentials compared to the crystalline surface. This study suggests a strategy to enhance the decomposition rate of lithium peroxide by exploiting the size and shape of one-dimensional nanostructured lithium peroxide., While lithium-oxygen batteries offer a green method to power vehicles, the sluggish decomposition of lithium peroxide limits device performance. Here, the authors direct lithium peroxide formation into amorphous nanostructures to enable its facile decomposition and improve charging efficiency.

Li2MnO3 is an important parent component in lithium- and manganese-rich layered oxides (LMRs), which are one of the promising positive electrode materials for next-generation lithium ion rechargeable batteries. Here, we report the layered-to-spinel phase transformation in Li2MnO3 during the initial charging process to characterise its unique delithiation behaviour, which gives an insight into the relationship between the structure, superior capacities and degradation of LMR electrodes. The atomic-scale observation using scanning transmission electron microscopy (STEM) techniques suggests that the structural transformation occurs in a biphasic manner within a single particle. The formed phase has a Li-defect spinel structure, indicating that the delithiation leads to Mn migration from the transition-metal layer to the Li layer, accompanied by some oxygen release. This layered-to-spinel phase transformation is an essential bulk process in the initial activation of Li2MnO3. During the lithiation in the 1st discharge, the Mn remigration occurs and the layered structure is again formed with significant disordering. During the multiple cycles, the defect spinel structure is stabilised and becomes more oxygen-deficient with a lower Mn valency. As a consequence, the amount of inserted Li decreases, which corresponds to the capacity and voltage fading observed in Li2MnO3 and LMRs.

Unique heterogeneous catalase-like activity was observed for metallosupramolecular ionic crystals [AuI4CoIII2(dppe)2(d-pen)4]X n ([1]X n ; dppe = 1,2-bis(diphenylphosphino)ethane; d-pen = d-penicillaminate; X n = (Cl-)2, (ClO4-)2, (NO3-)2 or SO42-) consisting of AuI4CoIII2 complex cations, [1]2+, and inorganic anions, X- or X2-. Treatment of the ionic crystals with an aqueous H2O2 solution led to considerable O2 evolution with a high turnover frequency of 1.4 × 105 h-1 for the heterogeneous cobalt complexes, which was dependent on their size and shape as well as the arrangement of cationic and anionic species. These dependencies were rationalized by the presence of cobalt(ii) centers on the crystal surface and their efficient exposure on the (111) plane rather than the (100) plane based on morphological and theoretical studies.

In lithium oxygen (Li–O2) batteries, controlling the structure of lithium peroxide (Li2O2) can reduce the large overpotential of the charge process as this affects the ionic and electronic conductivities of Li2O2. We demonstrate, for the first time, the in situ structural tuning of Li2O2 during the discharge process by virtue of the surface properties of carbon nanotube electrodes. We tailored carbon nanotube surfaces to decouple oxygen functional groups, defective edges, and graphitization, which directly influence the surface-binding affinity of O2 and LiO2. Consequently, conformal and completely amorphous Li2O2 films form in the presence of oxygen functional groups, which can facilely decompose in the subsequent charge. In contrast, crystalline Li2O2 particles grow in more ordered carbon electrodes and consequently require higher overpotential for decomposition. Our comprehensive study reveals the possibility of facile decomposition of Li2O2 by the surface engineering of carbon electrode and gives insi...

A binary system of NaCrO2–TiO2, NaxCrxTi1–xO2 (1.0 ≥ x ≥ 0.5), is systematically examined, and the electrodes’ performance is tested in Na cells. Different layered phases, O3, Na-deficient O3, P2, and P3, are found in this system, as confirmed by X-ray and neutron diffraction techniques. Among them, P2-type Na2/3Cr2/3Ti1/3O2 and P3-type Na0.58Cr0.58Ti0.42O2 show excellent electrode performance as positive and negative electrode materials, respectively. P2 Na2/3Cr2/3Ti1/3O2 shows excellent rate capability as a positive electrode, and average voltage based on Cr3+/Cr4+ redox in a Na cell is increased compared with that of O3-type NaCrO2. The operating voltage of Cr3+/Cr4+ is also enhanced because of an inductive effect of Ti4+ substitution for Cr3+. However, the reversible range is limited to x < 1/3 in Na2/3–xCr2/3Ti1/3O2 associated with partial Cr oxidation to Cr6+ and migration into tetrahedral sites upon charging, as found by X-ray diffraction and X-ray absorption spectroscopy. P3 Na0.58Cr0.58Ti0.42O2 d...

In lithium-oxygen (Li-O2) batteries, it is believed that lithium peroxide (Li2O2) electrochemically forms thin films with thicknesses less than 10 nm resulting in capacity restrictions due to limitations in charge transport. Here we show unexpected Li2O2 film growth with thicknesses of ∼60 nm on a three-dimensional carbon nanotube (CNT) electrode incorporated with cerium dioxide (ceria) nanoparticles (CeO2 NPs). The CeO2 NPs favor Li2O2 surface nucleation owing to their strong binding toward reactive oxygen species (e.g., O2 and LiO2). The subsequent film growth results in thicknesses of ∼40 nm (at cutoff potential of 2.2 V vs Li/Li(+)), which further increases up to ∼60 nm with the addition of trace amounts of H2O that enhances the solution free energy. This suggests the involvement of solvated superoxide species (LiO2(sol)) that precipitates on the existing Li2O2 films to form thicker films via disproportionation. By comparing toroidal Li2O2 formed solely from LiO2(sol), the thick Li2O2 films formed from surface-mediated nucleation/thin-film growth following by LiO2(sol) deposition provides the benefits of higher reversibility and rapid surface decomposition during recharge.

Li-rich layered oxides have attracted attention as promising positive electrode materials for next-generation lithium-ion secondary batteries because of their high energy storage capacity. The participation of the oxygen anion has been hypothesized to contribute to these oxides' high capacity. In the present study, we used O K-edge and Mn L-edge X-ray absorption spectroscopy (XAS) to study the reversible redox reactions that occur in single-phase Li-rich layered manganese oxide, Li2MnO3. We semiquantitatively analyzed the oxygen and manganese reactions by dividing the charge/discharge voltage region into two parts. The O K-edge XAS indicated that the electrons at the oxygen site reversibly contributed to the charge compensation throughout the charge/discharge processes at operating voltages between 2.0 and 4.8 V vs. Li+/Li0. The Mn L-edge XAS spectra indicated that the Mn redox reaction occurred only in the lower-voltage region. Thus, at higher potentials, the electrons, mainly at the oxygen site, contributed to the charge compensation. Peaks whose energies were similar to peroxide appeared in and then disappeared from the O K-edge spectra obtained during the reversible redox cycles. These results indicate that the reorganization of the oxygen network in the crystal structure affects the redox components. By using two kinds of detection modes with different probing depths in XAS measurements, it was found that these redox reactions are bulk phenomena in the electrode.

We investigated the oxygen contributions on delithiation process of different types of layered 3d transition metal oxides, Li2TiO3, Li2MnO3, and LiCoO2, using X-ray spectroscopies with the aid of density functional theory calculations. In delithiatied LiCoO2, electrons are extracted from highly hybridized Co 3d and O 2p orbitals without O2 loss. In Li2TiO3, the hybridized Ti 3d and O 2p orbitals at the valence band is mainly contributed by O 2p orbitals, and delithiated Li2TiO3 loses oxygen as the electrons are extracted. Li2MnO3 exhibits some hybridization. In delithiated Li2MnO3, a certain amount of oxygen is lost, but the large amount of oxidized O anions remains as peroxide and superoxide-like states, which would work as the redox active species. Therefore, the degree of hybridization between metal 3d and O 2p orbitals is a key factor to influence the stability of O anion redox during the oxidation process, which determines the electrode performance.

A solid electrolyte interphase (SEI) formed on a model LiCoO2 electrode was analyzed by the ultra-soft X-ray absorption spectroscopy (XAS). The data of Li K-, B K-, C K-, O K-, and Co L-edges spectra for the SEI film on the electrode were collected using three detection methods with different probing depths. The electrode was prepared by a pulsed laser deposition method. All the spectral data consistently indicated that the SEI film containing lithium carbonate was instantly formed just after the soak of the electrode into the electrolyte solution and that it decomposed during the repeated charge–discharge reactions. The decomposition of the SEI film seems to cause the deterioration in lithium ion battery cycle performance. By adding lithium bis(oxalate) borate (LiBOB) to the electrolyte the decomposition could be suppressed leading to longer cycle life. It was found that some of the Co ions at the electrode surface were reduced to Co(II) during the charge–discharge reactions and this reaction could also be suppressed by the addition of LiBOB.

Recently synthesized Rh-Ni trinuclear complexes hexacoordinated with sulfur ions, 3-aminopropanethiolate (apt) metalloligand [Ni{Rh(apt)$_{3}$}$_{2}$](NO$_{3}$)$_{n}$ ($n$ = 2, 3, 4), are found to be chemically interconvertible between the nominal Ni$^{2+}$ and Ni$^{4+}$ states. In order to clarify the origins of their interconvertible nature and the stability of such a high oxidation state as the tetravalency from the physical point of view, we have systematically investigated the local 3$d$ electronic structures of [Ni{Rh(apt)$_{3}$}$_{2}$](NO$_{3}$)$_{n}$ by means of soft X-ray core-level absorption spectroscopy (XAS). The experimental data have been reproduced by the single-site configuration-interaction cluster-model simulations, which indicate that the charge-transferred configurations are more stable than the nominal $d$-electron-number configuration for $n=3,4$ leading to the prominent charge-transfer effects. These are also supported by S $K$-edge XAS of [Ni{Rh(apt)$_{3}$}$_{2}$](NO$_{3}$)$_{n}$. Our results imply that the found charge-transfer effects have a key role to realize the interconvertible nature as well as the stability of the high oxidization state of the Ni ions., Comment: 16 pages, 4 figures

To realize the development of rechargeable sodium batteries, new positive electrode materials without less abundant elements are explored. Enrichment of sodium contents in host structures is required to increase the theoretical capacity as electrode materials, and therefore Na-excess compounds are systematically examined in a binary system of Na2 TiO3 -NaMnO2 . After several trials, synthesis of Na-excess compounds with a cation disordered rocksalt structure is successful by adapting a mechanical milling method. Among the tested electrode materials, Na1.14 Mn0.57 Ti0.29 O2 in this binary system delivers a large reversible capacity of ≈200 mA h g-1 , originating from reversible redox reactions of cationic Mn3+ /Mn4+ and anionic O2- /On - redox confirmed by X-ray absorption spectroscopy. Holes in oxygen 2p orbitals, which are formed by electrochemical oxidation, are energetically stabilized by electron donation from Mn ions. Moreover, reversibility of anionic redox is significantly improved compared with a former study on a binary system of Na3 NbO3 -NaMnO2 tested as model electrode materials.

Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g−1 based on solid-state redox reaction of oxide ions., Energy storage by metal redox reactions sets strict limits on capacity in metal oxide cathode materials used in lithium-ion batteries. Here authors study stabilization of redox reactions at oxygen sites and demonstrate a cathode with a high reversible capacity enabled by the process.

A perfluorinated alkyl chain grafted to carbon nanotubes is employed in the lithium–oxygen (Li–O2) cell. We demonstrate a highly localized Li–O2 electrochemical reaction in close proximity to the perfluorinated moiety owing to its high O2 affinity. This hydrophobic modification can provide an enhancement in capacity for a very thin microbattery system.