Phase Relations in the Li2O-V2O3-V2O5 System at 700 C: Correlations with Magnetic Defect Concentration in Heavy Fermion LiV2O4

The phase relations in the Li2O-V2O3-V2O5 ternary system at 700 C for compositions in equilibrium with LiV2O4 are reported. This study clarified the synthesis conditions under which low and high magnetic defect concentrations can be obtained within the spinel structure of LiV2O4. We confirmed that the LiV2O4 phase can be obtained containing low (0.006 mol%) to high (0.83 mol%) magnetic defect concentrations n{defect} and with consistently high magnetic defect spin S values between 3 and 6.5. The high n{defect} values were obtained in the LiV2O4 phase in equilibrium with V2O3, Li3VO4, or LiVO2 and the low values in the LiV2O4 phase in equilibrium with V3O5. A model is suggested to explain this correlation.Comment: 6 pages, 7 figures; Phys. Rev. B (accepted

Dynamic behaviour of interphases and its implication on high-energy-density cathode materials in lithium-ion batteries

Undesired electrode-electrolyte interactions prevent the use of many high-energy-density cathode materials in practical lithium-ion batteries. Efforts to address their limited service life have predominantly focused on the active electrode materials and electrolytes. Here an advanced three-dimensional chemical and imaging analysis on a model material, the nickel-rich layered lithium transition-metal oxide, reveals the dynamic behaviour of cathode interphases driven by conductive carbon additives (carbon black) in a common nonaqueous electrolyte. Region-of-interest sensitive secondary-ion mass spectrometry shows that a cathode-electrolyte interphase, initially formed on carbon black with no electrochemical bias applied, readily passivates the cathode particles through mutual exchange of surface species. By tuning the interphase thickness, we demonstrate its robustness in suppressing the deterioration of the electrode/electrolyte interface during high-voltage cell operation. Our results provide insights on the formation and evolution of cathode interphases, facilitating development of in situ surface protection on high-energy-density cathode materials in lithium-based batteries.ope

Hole concentration and phonon renormalization in Ca-doped YBa_2Cu_3O_y (6.76 < y < 7.00)

In order to access the overdoped regime of the YBa_2Cu_3O_y phase diagram, 2% Ca is substituted for Y in YBa_2Cu_3O_y (y = 7.00,6.93,6.88,6.76). Raman scattering studies have been carried out on these four single crystals. Measurements of the superconductivity-induced renormalization in frequency (Delta \omega) and linewidth (\Delta 2\gamma) of the 340 cm^{-1} B_{1g} phonon demonstrate that the magnitude of the renormalization is directly related to the hole concentration (p), and not simply the oxygen content. The changes in \Delta \omega with p imply that the superconducting gap (\Delta_{max}) decreases monotonically with increasing hole concentration in the overdoped regime, and \Delta \omega falls to zero in the underdoped regime. The linewidth renormalization \Delta 2\gamma is negative in the underdoped regime, crossing over at optimal doping to a positive value in the overdoped state.Comment: 18 pages; 5 figures; submitted to Phys. Rev. B Oct. 24, 2002 (BX8292

Magnetic and Charge Correlations in La{2-x-y}Nd_ySr_xCuO_4: Raman Scattering Study

Two aspects in connection with the magnetic properties of La_{2-x-y}Nd_ySr_xCuO_4 single crystals are discussed. The first is related to long wavelength magnetic excitations in x = 0, 0.01, and 0.03 La_{2-x}Sr_xCuO_4 detwinned crystals as a function of doping, temperature and magnetic field. Two magnetic modes were observed within the AF region of the phase diagram. The one at lower energies was identified with the spin-wave gap induced by the antisymmetric DM interaction and its anisotropic properties in magnetic field could be well explained using a canonical form of the spin Hamiltonian. A new finding was a magnetic field induced mode whose dynamics allowed us to discover a spin ordered state outside the AF order which was shown to persist in a 9 T field as high as 100 K above the N\'eel temperature T_N for x = 0.01. For these single magnon excitations we map out the Raman selection rules in magnetic fields and demonstrate that their temperature dependent spectral weight is peaked at the N\'eel temperature. The second aspect is related to phononic and magnetic Raman scattering in La_{2-x-y}Nd_ySr_xCuO_4 with three doping concentrations: x = 1/8, y = 0; x = 1/8, y = 0.4; and x = 0.01, y = 0. We observed that around 1/8 Sr doping and independent of Nd concentration there exists substantial disorder in the tilt pattern of the CuO_6 octahedra in both the orthorhombic and tetragonal phases which persist down to 10 K and are coupled to bond disorder in the cation layers. The weak magnitude of existing charge/spin modulations in the Nd doped structure did not allow us to detect specific Raman signatures on lattice dynamics or two-magnon scattering around 2200 cm-1.Comment: 26 pages, 22 figure

Multifunctional semi-interpenetrating polymer network-nanoencapsulated cathode materials for high-performance lithium-ion batteries

As a promising power source to boost up advent of next-generation ubiquitous era, high-energy density lithium-ion batteries with reliable electrochemical properties are urgently requested. Development of the advanced lithium ion-batteries, however, is staggering with thorny problems of performance deterioration and safety failures. This formidable challenge is highly concerned with electrochemical/thermal instability at electrode material-liquid electrolyte interface, in addition to structural/chemical deficiency of major cell components. Herein, as a new concept of surface engineering to address the abovementioned interfacial issue, multifunctional conformal nanoencapsulating layer based on semi-interpenetrating polymer network (semi-IPN) is presented. This unusual semi-IPN nanoencapsulating layer is composed of thermally-cured polyimide (PI) and polyvinyl pyrrolidone (PVP) bearing Lewis basic site. Owing to the combined effects of morphological uniqueness and chemical functionality (scavenging hydrofluoric acid that poses as a critical threat to trigger unwanted side reactions), the PI/PVP semi-IPN nanoencapsulated-cathode materials enable significant improvement in electrochemical performance and thermal stability of lithium-ion batteries.open

A Biomass-Based Integral Approach Enables Li-S Full Pouch Cells with Exceptional Power Density and Energy Density

Lithium-sulfur (Li-S) batteries, as part of the post-lithium-ion batteries (post-LIBs), are expected to deliver significantly higher energy densities. Their power densities, however, are today considerably worse than that of the LIBs, limiting the Li-S batteries to very few specific applications that need low power and long working time. With the rapid development of single cell components (cathode, anode, or electrolyte) in the last few years, it is expected that an integrated approach can maximize the power density without compromising the energy density in a Li-S full cell. Here, this goal is achieved by using a novel biomass porous carbon matrix (PCM) in the anode, as well as N-Co9S8 nanoparticles and carbon nanotubes (CNTs) in the cathode. The authors' approach unlocks the potential of the electrodes and enables the Li-S full pouch cells with unprecedented power densities and energy densities (325 Wh kg−1 and 1412 W kg−1, respectively). This work addresses the problem of low power densities in the current Li-S technology, thus making the Li-S batteries a strong candidate in more application scenarios

Delithiation/lithiation behavior of LiNi<inf>0.5</inf>Mn<inf>1.5</inf>O<inf>4</inf> studied by in situ and ex situ ^6,7Li NMR spectroscopy

Delithiation and lithiation behaviors of ordered spinel LiNi0.5Mn1.5O4 and disordered spinel LiNi0.4Mn1.6O4 were investigated by using in situ (in operando) 7Li NMR and ex situ 6Li MAS NMR spectroscopy. The in situ 7Li monitoring of the ordered spinel revealed a clear appearance and subsequent disappearance of a new signal from the well-defined phase Li0.5Ni0.5Mn1.5O4, suggesting the two-phase reaction processes among Li1.0Ni0.5Mn1.5O4, Li0.5Ni0.5Mn1.5O4, and Li0.0Ni0.5Mn1.5O4. Also, for the disordered spinel, Li0.5Ni0.4Mn1.6O4 was identified with a broad distribution in Li environment. High-resolution 6Li MAS NMR spectra were also acquired for the delithiated and lithiated samples to understand the detailed local structure around Li ions. We suggested that the nominal Li-free phase Li0.0Ni0.5Mn1.5O4 can accommodate a small amount of Li ions in its structure. The tetragonal phases Li2.0Ni0.5Mn1.5O4 and Li2.0Ni0.4Mn1.6O4, which occurred when the cell was discharged down to 2.0 V, were very different in the Li environment from each other. It is found that 6, 7Li NMR is highly sensitive not only to the Ni/Mn ordering in LiNi0.5Mn1.5O4 but also to the valence changes of Ni and Mn on charge-discharge process

A Long-Life, High-Rate Lithium/Sulfur Cell: A Multifaceted Approach to Enhancing Cell Performance

Lithium/sulfur (Li/S) cells are receiving significant attention as an alternative power source for zero-emission vehicles and advanced electronic devices due to the very high theoretical specific capacity (1675 mA·h/g) of the sulfur cathode. However, the poor cycle life and rate capability have remained a grand challenge, preventing the practical application of this attractive technology. Here, we report that a Li/S cell employing a cetyltrimethyl ammonium bromide (CTAB)-modified sulfur-graphene oxide (S-GO) nanocomposite cathode can be discharged at rates as high as 6C (1C = 1.675 A/g of sulfur) and charged at rates as high as 3C while still maintaining high specific capacity (~ 800 mA·h/g of sulfur at 6C), with a long cycle life exceeding 1500 cycles and an extremely low decay rate (0.039% per cycle), perhaps the best performance demonstrated so far for a Li/S cell. The initial estimated cell-level specific energy of our cell was ~ 500 W·h/kg, which is much higher than that of current Li-ion cells (~ 200 W·h/kg). Even after 1500 cycles, we demonstrate a very high specific capacity (~ 740 mA·h/g of sulfur), which corresponds to ~ 414 mA·h/g of electrode: still higher than state-of-the-art Li-ion cells. Moreover, these Li/S cells with lithium metal electrodes can be cycled with an excellent Coulombic efficiency of 96.3% after 1500 cycles, which was enabled by our new formulation of the ionic liquid-based electrolyte. The performance we demonstrate herein suggests that Li/S cells may already be suitable for high-power applications such as power tools. Li/S cells may now provide a substantial opportunity for the development of zero-emission vehicles with a driving range similar to that of gasoline vehicles

Somatic Mutations in UBA1 and Severe Adult-Onset Autoinflammatory Disease

BACKGROUND Adult-onset inflammatory syndromes often manifest with overlapping clinical features. Variants in ubiquitin-related genes, previously implicated in autoinflammatory disease, may define new disorders. METHODS We analyzed peripheral-blood exome sequence data independent of clinical phenotype and inheritance pattern to identify deleterious mutations in ubiquitin-related genes. Sanger sequencing, immunoblotting, immunohistochemical testing, flow cytometry, and transcriptome and cytokine profiling were performed. CRISPR-Cas9–edited zebrafish were used as an in vivo model to assess gene function. RESULTS We identified 25 men with somatic mutations affecting methionine-41 (p.Met41) in UBA1, the major E1 enzyme that initiates ubiquitylation. (The gene UBA1 lies on the X chromosome.) In such patients, an often fatal, treatment-refractory inflammatory syndrome develops in late adulthood, with fevers, cytopenias, characteristic vacuoles in myeloid and erythroid precursor cells, dysplastic bone marrow, neutrophilic cutaneous and pulmonary inflammation, chondritis, and vasculitis. Most of these 25 patients met clinical criteria for an inflammatory syndrome (relapsing polychondritis, Sweet’s syndrome, polyarteritis nodosa, or giant-cell arteritis) or a hematologic condition (myelodysplastic syndrome or multiple myeloma) or both. Mutations were found in more than half the hematopoietic stem cells, including peripheral-blood myeloid cells but not lymphocytes or fibroblasts. Mutations affecting p.Met41 resulted in loss of the canonical cytoplasmic isoform of UBA1 and in expression of a novel, catalytically impaired isoform initiated at p.Met67. Mutant peripheral-blood cells showed decreased ubiquitylation and activated innate immune pathways. Knockout of the cytoplasmic UBA1 isoform homologue in zebrafish caused systemic inflammation. CONCLUSIONS Using a genotype-driven approach, we identified a disorder that connects seemingly unrelated adult-onset inflammatory syndromes. We named this disorder the VEXAS (vacuoles, E1 enzyme, X-linked, autoinflammatory, somatic) syndrome. (Funded by the NIH Intramural Research Programs and the EU Horizon 2020 Research and Innovation Program.