A New Sodium Thioborate Fast Ion Conductor: Na3 B5 S9.

We report a new sodium fast-ion conductor, Na3 B5 S9 , that exhibits a high Na ion total conductivity of 0.80 mS cm-1 (sintered pellet; cold-pressed pellet=0.21 mS cm-1 ). The structure consists of corner-sharing B10 S20 supertetrahedral clusters, which create a framework that supports 3D Na ion diffusion channels. The Na ions are well-distributed in the channels and form a disordered sublattice spanning five Na crystallographic sites. The combination of structural elucidation via single crystal X-ray diffraction and powder synchrotron X-ray diffraction at variable temperatures, solid-state nuclear magnetic resonance spectra and ab initio molecular dynamics simulations reveal high Na-ion mobility (predicted conductivity: 0.96 mS cm-1 ) and the nature of the 3D diffusion pathways. Notably, the Na ion sublattice orders at low temperatures, resulting in isolated Na polyhedra and thus much lower ionic conductivity. This highlights the importance of a disordered Na ion sublattice-and existence of well-connected Na ion migration pathways formed via face-sharing polyhedra-in dictating Na ion diffusion.

Innovative Approaches to Li-Argyrodite Solid Electrolytes for All-Solid-State Lithium Batteries.

ConspectusAs the world transitions away from fossil energy to green and renewable energy, electrochemical energy storage increasingly becomes a vital component of the mix to conduct this transition. The central goal in developing next-generation batteries is to maximize the gravimetric and volumetric energy density and battery cycle life and improve safety. All solid-state batteries using a solid electrolyte and a lithium metal anode represent one of the most promising technologies that can achieve this goal. Highly conductive solid electrolytes (>10 mS·cm-1) are the key component to remove the safety concerns inherent with flammable organic liquid electrolytes and achieve high energy density by enabling high active material loading. Considering a range of inorganic solid electrolytes that have been developed to date, sulfide solid electrolytes exhibit the highest ionic conductivities, which even surpass those of conventional organic liquid electrolytes. Argyrodite-structured sulfide solid electrolytes are among the most promising materials in this class and are currently the dominantly used solid electrolytes for all-solid-state battery fabrication. Argyrodite solid electrolytes are particularly appealing because of their ultrahigh Li-ion conductivity, quasi-stable solid-electrolyte interphase (SEI) formed with Li metal, and ability to be prepared via scalable solution-assisted synthesis approaches. These factors are all vital for commercial applications.In this Account, we afford an overview of our recent development of several argyrodite superionic conductors, including Li6.6Si0.6Sb0.5S5I (24 mS·cm-1), Li6.6Ge0.6P0.4S5I (18 mS·cm-1), and Li5.5PS4.5Cl1.5 (12 mS·cm-1), and a comprehensive understanding of the origin of the underlying high conductivity, namely, sulfide/halide anion site disorder and Li cation site disorder. A high degree of sulfide/halide anion site disorder (changes in anion distribution) modifies the anionic charge, which in turn strongly influences the lithium distribution. A more inhomogeneous charge distribution in anion-disordered systems generates a spatially diffuse and delocalized lithium density, resulting in faster ionic transport. Lithium cation site disorder generated by increasing Li carrier concentration through aliovalent substitution creates high-energy interstitial sites for Li ion diffusion, which activate concerted ion migration and flatten the energy landscape for Li ion diffusion. This enables high conductivity in Li-rich argyrodite superionic conductors. These concepts are also expected to promote the design of rational new solid electrolytes and fundamental understanding of the structure-ion transport relationships in inorganic ionic conductors.Collectively, a comprehensive and deep understanding of the interphase formation between argyrodite solid electrolytes and cathode active materials/Li metal and the failure mechanism of all-solid-state batteries with argyrodite solid electrolytes will lead to the bottom-up engineering of the cathode/anode-solid electrolyte interfaces, which will accelerate the development of safe, high-energy-density all-solid-state lithium batteries.

New Family of Argyrodite Thioantimonate Lithium Superionic Conductors.

We report on a new family of argyrodite lithium superionic conductors, as solid solutions Li6+xMxSb1-xS5I (M = Si, Ge, Sn), that exhibit superionic conductivity. These represent the first antimony argyrodites to date. Exploration of the series using a combination of single crystal X-ray and synchrotron/neutron powder diffraction, combined with impedance spectroscopy, reveals that an optimal degree of substitution (x), and substituent induces slight S2-/I- anion site disorder-but more importantly drives Li+ cation site disorder. The additional, delocalized Li-ion density is located in new high energy lattice sites that provide intermediate interstitial positions (local minima) for Li+ diffusion and activate concerted ion migration, leading to a low activation energy of 0.25 eV. Excellent room temperature ionic conductivity of 14.8 mS·cm-1 is exhibited for cold-pressed pellets-up to 24 mS·cm-1 for sintered pellets-among the highest values reported to date. This enables all-solid-state battery prototypes that exhibit promising properties. Furthermore, even at -78 °C, suitable bulk ionic conductivity of the electrolyte is retained (0.25 mS·cm-1). Selected thioantimonate iodides demonstrate good compatibility with Li metal, sustaining over 1000 h of Li stripping/plating at current densities up to 0.6 mA·cm-2. The significantly enhanced Li ion conduction and lowered activation energy barrier with increasing site disorder reveals an important strategy toward the development of superionic conductors.

Elastic and Li-ion-percolating hybrid membrane stabilizes Li metal plating.

Lithium metal batteries are capable of revolutionizing the battery marketplace for electrical vehicles, owing to the high capacity and low voltage offered by Li metal. Current exploitation of Li metal electrodes, however, is plagued by their exhaustive parasitic reactions with liquid electrolytes and dendritic growth, which pose concerns to both cell performance and safety. We demonstrate that a hybrid membrane, both elastic and Li+-ion percolating, can stabilize Li plating/stripping with high Coulombic efficiency. The compact packing of a Li+ solid electrolyte phase offers percolated Li+-conducting channels and the consequent infiltration of an elastic polymer endows membrane flexibility to accommodate volume changes. The protected electrode allows Li plating with 95.8% efficiency for 200 cycles and stable operation of an LTO|Li cell for 2,000 cycles. This rationally structured membrane represents an interface engineering approach toward stabilized Li metal electrodes.

Size distribution, directional source contributions and pollution status of PM from Chengdu, China during a long-term sampling campaign.

Long-term and synchronous monitoring of PM10 and PM2.5 was conducted in Chengdu in China from 2007 to 2013. The levels, variations, compositions and size distributions were investigated. The sources were quantified by two-way and three-way receptor models (PMF2, ME2-2way and ME2-3way). Consistent results were found: the primary source categories contributed 63.4% (PMF2), 64.8% (ME2-2way) and 66.8% (ME2-3way) to PM10, and contributed 60.9% (PMF2), 65.5% (ME2-2way) and 61.0% (ME2-3way) to PM2.5. Secondary sources contributed 31.8% (PMF2), 32.9% (ME2-2way) and 31.7% (ME2-3way) to PM10, and 35.0% (PMF2), 33.8% (ME2-2way) and 36.0% (ME2-3way) to PM2.5. The size distribution of source categories was estimated better by the ME2-3way method. The three-way model can simultaneously consider chemical species, temporal variability and PM sizes, while a two-way model independently computes datasets of different sizes. A method called source directional apportionment (SDA) was employed to quantify the contributions from various directions for each source category. Crustal dust from east-north-east (ENE) contributed the highest to both PM10 (12.7%) and PM2.5 (9.7%) in Chengdu, followed by the crustal dust from south-east (SE) for PM10 (9.8%) and secondary nitrate & secondary organic carbon from ENE for PM2.5 (9.6%). Source contributions from different directions are associated with meteorological conditions, source locations and emission patterns during the sampling period. These findings and methods provide useful tools to better understand PM pollution status and to develop effective pollution control strategies.

Seasonal and regional variations of source contributions for PM10 and PM2.5 in urban environment.

To characterize the sources of to PM10 and PM2.5, a long-term, speciate and simultaneous dataset was sampled in a megacity in China during the period of 2006-2014. The PM concentrations and PM2.5/PM10 were higher in the winter. Higher percentages of Al, Si, Ca and Fe were observed in the summer, and higher concentrations of OC, NO3(-) and SO4(2-) occurred in the winter. Then, the sources were quantified by an advanced three-way model (defined as an ABB three-way model), which estimates different profiles for different sizes. A higher percentage of cement and crustal dust was present in the summer; higher fractions of coal combustion and nitrate+SOC were observed in the winter. Crustal and cement contributed larger portion to coarse part of PM10, whereas vehicular and secondary source categories were enriched in PM2.5. Finally, potential source contribution function (PSCF) and source regional apportionment (SRA) methods were combined with the three-way model to estimate geographical origins. During the sampling period, the southeast region (R4) was an important region for most source categories (0.6%-11.5%); the R1 (centre region) also played a vital role (0.3-6.9%).

A new receptor model-incremental lifetime cancer risk method to quantify the carcinogenic risks associated with sources of particle-bound polycyclic aromatic hydrocarbons from Chengdu in China.

PM10 and PM2.5 samples were simultaneously collected during a one-year monitoring period in Chengdu. The concentrations of 16 particle-bound polycyclic aromatic hydrocarbons (Σ16PAHs) were measured. Σ16PAHs concentrations varied from 16.85 to 160.24 ng m(-3) and 14.93 to 111.04ngm(-3) for PM10 and PM2.5, respectively. Three receptor models (principal component analysis (PCA), positive matrix factorization (PMF), and Multilinear Engine 2 (ME2)) were applied to investigate the sources and contributions of PAHs. The results obtained from the three receptor models were compared. Diesel emissions, gasoline emissions, and coal and wood combustion were the primary sources. Source apportionment results indicated that these models were able to track the ΣPAHs. For the first time, the cancer risks for each identified source were quantitatively calculated for ingestion and dermal contact routes by combining the incremental lifetime cancer risk (ILCR) values with the estimated source contributions. The results showed that gasoline emissions posed the highest cancer risk, even though it contributed less to Σ16PAHs. The results and method from this work can provide useful information for quantifying the toxicity of source categories and studying human health in the future.

Using an improved Source Directional Apportionment method to quantify the PM(2.5) source contributions from various directions in a megacity in China.

The transport of particulate matter (PM) and chemical species is an essential mechanism for determining the fate of PM pollutants and their effects. To determine source transport quantitatively, an ambient PM2.5 dataset from a megacity in China was analysed using a novel method called "Source Directional Apportionment" (SDA). The SDA method is developed in this work to quantify contributions of each source category from various directions. The three steps of SDA are (1) to estimate source categories and time series of source contributions to PM with a factor analysis model, (2) to identify directions by trajectory cluster analysis and (3) to quantify source directional contributions for each source category by combining the time series of source contributions to the back trajectories in each direction. For PM2.5 in Chengdu, crustal dust, vehicular exhaust, coal combustion and secondary sulphate are all important contributors to PM; secondary nitrate and cement dust are relatively less influential. Four potential source directions were identified in Chengdu during the sampling period from 2009 to 2011. The percentages of source directional contributions from Directions 1-4 (northeast, southwest to south, southwest and west) were estimated as follows: crustal dust (7.9%, 9.1%, 6.4% and 6.2%, respectively), cement dust (1.0%, 1.2%, 1.3% and 1.1%, respectively), vehicular exhaust (6.4%, 6.0%, 5.6% and 7.0%, respectively), secondary sulphate (5.1%, 5.2%, 5.6% and 8.6%, respectively) and secondary nitrate (2.0%, 2.4%, 2.5% and 2.3%, respectively). Finally, the source directional contributions to important chemical species were quantified to determine their transport from sources to receptor.

Long-term variation of the levels, compositions and sources of size-resolved particulate matter in a megacity in China.

To investigate the long-term trends and variations of the levels, compositions, size distribution and sources of particulate matter (PM), long-term monitoring campaigns of PM10 and PM2.5 were performed in a megacity in China (Chengdu) during the period from 2009 to 2011. The average concentration of PM10 was 172.01±89.80 µg/m(3) and that of PM2.5 was 103.15±59.83 µg/m(3), with an average PM2.5/PM10 of 0.60. Enrichments of the important species indicated that the fractions of crustal elements were higher in PM10 than those in PM2.5, while the abundance of organic carbon (OC) and secondary ions was enriched in the fine PM. Quantitative source apportionments of both PM10 and PM2.5 were performed by PMF. PM10 and PM2.5 in Chengdu were influenced by similar source categories, and their percentage contributions were in the same order: crustal dust was the highest contributor, followed by vehicular exhaust, secondary sulfate, secondary nitrate and cement dust. Crustal dust and cement dust contributed a higher percentage to PM10 than to PM2.5, while vehicular exhaust and secondary particles provided higher percentage contributions to PM2.5. In addition, PMF-HCA was performed to investigate the characteristics of the sources of the clustered samples, identifying three periods: crustal dust dominant-period, secondary sulfate dominant-period and comprehensive source influenced-period. Planting, reduction of precursors, and banning high-emission vehicles should be implemented to control crustal dust, secondary particles and vehicular exhaust in Chengdu. Furthermore, the size-resolved and the period-resolved control would be more effective.