Superionic Conductivity in Sodium Zirconium Chloride-Based Compounds.

All-solid-state sodium batteries are attracting intensive attention, and chloride-based solid electrolytes are promising candidates for use in such batteries because of their high chemical stability and low Young's modulus. Here, we report new superionic conductors based on polyanion-added chloride-based materials. Na0.67 Zr(SO4 )0.33 Cl4 showed a high ionic conductivity of 1.6 mS cm-1 at room temperature. X-ray diffraction analysis indicated that the highly conducting materials are mainly a mixture of an amorphous phase and Na2 ZrCl6 . The conductivity might be dominated by the electronegativity of the central atom of the polyanion. Electrochemical measurements reveal that Na0.67 Zr(SO4 )0.33 Cl4 is a sodium ionic conductor and is suitable for use as a solid electrolyte in all-solid-state sodium batteries.

Preparation of a single-phase all-solid-state battery via the crystallization of amorphous sodium vanadium phosphate.

A single-phase all-solid-state battery was prepared from amorphous Na3V2(PO4)3 (NVP) powder, which was synthesized by mechanical milling of the crystalline NVP. It was found that the structure of the amorphous NVP was much different from that of the crystalline NVP from the FT-IR measurement. The charge-discharge curves of the half-cell using organic electrolyte were also much different from those in the case of crystalline NVP. By using amorphous NVP, a much higher ionic conductivity of the sintered pellet was observed compared with the case using crystalline NVP because of the high density of the pellet. The single-phase all-solid-state battery prepared from the amorphous NVP showed reasonable charge-discharge properties at room temperature.

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.

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.

Improvement of the rate capability of all-solid-state cells with Fe-based polysulfide positive electrode materials by modifying the microstructure.

We successfully prepared an Fe- and Li-containing polysulfide positive electrode material (Li8FeS5-Li2FeS2 composite) that shows a high specific capacity (>500 mA h g-1) with improved rate capability in all-solid-state cells. High-resolution TEM analysis indicated the coexistence of small crystallites of high-conductivity Li2FeS2 and FeS, as well as low-crystallinity Li2S, in the composite, and this microstructure is responsible for the improved battery performance.

High capacity all-solid-state lithium battery enabled by in situ formation of an ionic conduction path by lithiation of MgH2.

All-solid-state Li batteries have attracted significant attention because of their high energy density and high level of safety. In a solid-state Li-ion battery, the electrodes contain a solid electrolyte that does not contribute directly to the capacity. Therefore, a battery that does not require a solid electrolyte in its electrode mixture should exhibit a higher energy density. In this study, a MgH2 electrode was used as the negative electrode material without a solid electrolyte in its mixture. The resultant battery demonstrated excellent performance because of the formation of an ionic conduction path based on LiH in the electrode mixture. LiH and Mg clearly formed upon lithiation and returned to MgH2 upon delithiation as revealed by TEM-EELS analysis. This mechanism of in situ electrolyte formation enables the development of a solid-state battery with a high energy density.

Anion Redox in an Amorphous Titanium Polysulfide.

Amorphous transition-metal polysulfides are promising positive electrode materials for next-generation rechargeable lithium-ion batteries because of their high theoretical capacities. In this study, sulfur anion redox during lithiation of amorphous TiS4 (a-TiS4) was investigated by using experimental and theoretical methods. It was found that a-TiS4 has a variety of sulfur valence states such as S2-, S-, and Sδ-. The S2- species became the main component in the Li4TiS4 composition, indicating that sulfur is a redox-active element up to this composition. The simulated a-TiS4 structure changed gradually by lithium accommodation to form a-Li4TiS4: S-S bonds in the disulfide units and polysulfide chains were broken. Bader charge analysis suggested that the average S valency decreased drastically. Moreover, deep lithiation of a-TiS4 provided a conversion reaction to metallic Ti and Li2S, with a high practical capacity of ∼1000 mAh g-1 when a lower cutoff voltage was applied.

New insight derived from a two-compartment cell: electrochemical behavior of FeF3 positive electrode.

A designed two-compartment cell was applied to the degradation analysis of FeF3 having high theoretical energy density. Comparing with the result of the coin cell, the two-compartment cell gave us insight that the elution of Fe was responsible for the degradation of FeF3 and LiDFOB was found as an essentially effective additive for suppressing the degradation of FeF3.

Development of a half-cell for x-ray structural analysis of liquid electrolytes in rechargeable batteries.

A half-cell of the rechargeable Li-ion battery was developed to characterize an electrolyte structure using high energy x-ray total scattering measurements in combination with a two-dimensional x-ray detector. The scattering pattern consisted of strong Bragg peaks from electrodes and diffuse scatterings from sapphire windows, in addition to a weak halo pattern from the electrolyte. By selectively removing the signals of the electrodes and windows using specific numerical procedures, we could successfully extract the structural information of the electrolyte, which was in reasonable agreement with the reference data obtained from the electrolyte in a glass capillary. The present demonstration with a half-cell is expected to shed new light on operand characterization of the electrolyte structure during charging and discharging.

Structural characterization of an amorphous VS4 and its lithiation/delithiation behavior studied by solid-state NMR spectroscopy.

Vanadium sulfide (VS4) is one of the promising positive electrode materials for next-generation rechargeable lithium-ion batteries because of its high theoretical capacity (1196 mA h g-1). Crystalline VS4 has a unique structure, in which the Peierls-distorted one-dimensional chains of V-V bonds along the c axis are loosely connected to each other through van der Waals interactions. In this study, an amorphous VS4 is prepared by mechanical milling of the crystalline material, and its lithiation/delithiation behavior is investigated by solid-state nuclear magnetic resonance (NMR) spectroscopy. The amorphous VS4 shows a chain structure similar to that of crystalline VS4. The amorphous host structure is found to change drastically during the lithiation process to form Li3VS4: the V ions become tetrahedrally coordinated by S ions, in which the valence states of V and S ions simultaneously change from V4+ to V5+ and S- to S2-, respectively. When the Li insertion proceeds further, the valence state of V ions is reduced. After the 1st cycle, the amorphous VS4 recovers to the chain-like structure although it is highly disordered. No conversion to elemental V is observed, and a high capacity of 700 mA h g-1 is reversibly delivered between 1.5 and 2.6 V.

Degradation Mechanism of Conversion-Type Iron Trifluoride: Toward Improvement of Cycle Performance.

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, the conversion process through which FeF3 operates leads it to suffer from capacity degradation upon repeated cycling. To improve the cycle performance, in this study we investigated the degradation mechanism of conversion-type FeF3 electrode material. Bulk analyses of FeF3 upon cycling reveal incomplete oxidation to Fe3+ concomitant with the aggregation of LiF at the charged state. In addition, surface analyses of FeF3 reveal that a film covered the electrode surface after 10 cycles, which leads to a remarkable increase in resistance. We show that the choice of the electrolyte formulation is crucial in preventing the formation of the film on the electrode surface; thus, FeF3 shows better performance in an electrolyte comprising LiBF4 solute in cyclic carbonate solvents than in chain carbonate-containing LiPF6 as the electrolyte. This study underpins that a careful selection of solvent, rather than solute, is significantly essential to improve the cycle performance of the FeF3 electrode.

A Reversible Rocksalt to Amorphous Phase Transition Involving Anion Redox.

The charge-discharge capacity of lithium secondary batteries is dependent on how many lithium ions can be reversibly extracted from (charge) and inserted into (discharge) the electrode active materials. In contrast, large structural changes during charging/discharging are unavoidable for electrode materials with large capacities, and thus there is great demand for developing materials with reversible structures. Herein, we demonstrate a reversible rocksalt to amorphous phase transition involving anion redox in a Li2TiS3 electrode active material with NaCl-type structure. We revealed that the lithium extraction during charging involves a change in site of the sulfur atom and the formation of S-S disulfide bonds, leading to a decrease in the crystallinity. Our results show great promise for the development of long-life lithium insertion/extraction materials, because the structural change clarified here is somewhat similar to that of optical phase-change materials used in DVD-RW discs, which exhibit excellent reversibility of the transition between crystalline and amorphous phase.

Rechargeable potassium-ion batteries with honeycomb-layered tellurates as high voltage cathodes and fast potassium-ion conductors.

Rechargeable potassium-ion batteries have been gaining traction as not only promising low-cost alternatives to lithium-ion technology, but also as high-voltage energy storage systems. However, their development and sustainability are plagued by the lack of suitable electrode materials capable of allowing the reversible insertion of the large potassium ions. Here, exploration of the database for potassium-based materials has led us to discover potassium ion conducting layered honeycomb frameworks. They show the capability of reversible insertion of potassium ions at high voltages (~4 V for K2Ni2TeO6) in stable ionic liquids based on potassium bis(trifluorosulfonyl) imide, and exhibit remarkable ionic conductivities e.g. ~0.01 mS cm-1 at 298 K and ~40 mS cm-1 at 573 K for K2Mg2TeO6. In addition to enlisting fast potassium ion conductors that can be utilised as solid electrolytes, these layered honeycomb frameworks deliver the highest voltages amongst layered cathodes, becoming prime candidates for the advancement of high-energy density potassium-ion batteries.

Rock-salt-type lithium metal sulphides as novel positive-electrode materials.

One way of increasing the energy density of lithium-ion batteries is to use electrode materials that exhibit high capacities owing to multielectron processes. Here, we report two novel materials, Li2TiS3 and Li3NbS4, which were mechanochemically synthesised at room temperature. When used as positive-electrode materials, Li2TiS3 and Li3NbS4 charged and discharged with high capacities of 425 mA h g(-1) and 386 mA h g(-1), respectively. These capacities correspond to those resulting from 2.5- and 3.5-electron processes. The average discharge voltage was approximately 2.2 V. It should be possible to prepare a number of high-capacity materials on the basis of the concept used to prepare Li2TiS3 and Li3NbS4.

Synthesis and characterization of the crystal structure, the magnetic and the electrochemical properties of the new fluorophosphate LiNaFe[PO4]F.

The new compound LiNaFe[PO(4)]F was synthesized by a solid state reaction route, and its crystal structure was determined using neutron powder diffraction data. LiNaFe[PO(4)]F was characterized by (57)Fe Mössbauer spectroscopy, magnetic susceptibility, specific heat capacity, and electrochemical measurements. LiNaFe[PO(4)]F crystallizes with orthorhombic symmetry, space group Pnma, with a = 10.9568(6) Å, b = 6.3959(3) Å, c = 11.4400(7) Å, V = 801.7(1) Å(3) and Z = 8. The structure consists of edge-sharing FeO(4)F(2) octahedra forming FeFO(3) chains running along the b axis. These chains are interlinked by PO(4) tetrahedra forming a three-dimensional framework with the tunnels and the cavities filled by the well-ordered sodium and lithium atoms, respectively. The specific heat and magnetization measurements show that LiNaFe[PO(4)]F undergoes a three-dimensional antiferromagnetic ordering at T(N) = 20 K. The neutron powder diffraction measurements at 3 K show that each FeFO(3) chain along the b-direction is ferromagnetic (FM), while these FM chains are antiferromagnetically coupled along the a and c-directions with a non-collinear spin arrangement. The galvanometric cycling showed that without any optimization, one mole of alkali metal is extractable between 1.0 V and 5.0 V vs. Li(+)/Li with a discharge capacity between 135 and 145 mAh g(-1).