Li Ratio Research Articles

Relevance of red blood cell Lithium concentration in the management of Lithium-treated bipolar and unipolar disorders: a systematic narrative review

BackgroundDespite a variability in response and a narrow therapeutic index, Lithium (Li) remains the gold standard treatment for bipolar disorders (BD), and a treatment of choice for unipolar disorders (UD). Red blood cell Li concentration (RBCLiC) and red blood cell/plasma Li ratio (LiR) have been studied in many areas of mood disorders (such as acute or chronic Li efficacy, adherence, side effects (SE), intoxication management) as well as in several research domains. This systematic review aims to synthesize the existing literature.MethodsWe conducted a systematic review, based on preferred reporting items for systematic reviews and Metanalysis (PRISMA) guidelines, of articles published between 1972 and February 2023, indexed in the following databases: EMBASE, MEDLINE, Cochrane Library. The search terms were combinations of the following headings: “Lithium AND Plasma AND Erythrocyte AND Mood disorders”. The systematic review protocol was published to PROSPERO (CRD42023406154).Results and conclusionOut of the 252 identified studies, 57 met the selection criteria. The articles investigated the interest of RBCLiC and other blood parameters (PLiC and LiR) in various areas: (i) disease management (31 articles) (compliance/adherence (5 articles), SE/toxicity (13 articles), prediction of Li response/therapeutic efficacy for acute episode or for relapse prevention (17 articles)), (ii) Li blood parameters as trait markers of mood disorders subtypes (UD, BDI, BDII) (16 articles), (iii) Li blood parameters as state markers of mood episodes (11 articles), (iv) factors influencing Li blood parameters (age, gender, ethnicity, dosage and duration of Li treatment, co-medications with other treatments, seasonality) associated with RBCLiC or LiR (24 articles), and (v) potential pathophysiological mechanisms (30 articles).ConclusionOverall, this review suggests that RBCLiC or LiR could be of interest for tolerance monitoring. However, the heterogeneity of methods and results, coupled with the limited amount of data, does not allow clear conclusions to be drawn in the other areas explored in this literature review. Given the potential interest in exploring brain Li pharmacokinetics (PK)s, this review calls for further research.

Antecedent Hydrologic Conditions Reflected in Stream Lithium Isotope Ratios During Storms

AbstractAntecedent hydrological conditions are recorded through the evolution of dissolved lithium isotope signatures (Li) by juxtaposing two storm events in an upland watershed subject to a Mediterranean climate. Discharge and Li are negatively correlated in both events, but mean Li ratios and associated ranges of variation are distinct between them. We apply a previously developed reactive transport model (RTM) for the site to these event‐scale flow perturbations, but observed shifts in stream Li are not reproduced. To reconcile the stability of the subsurface solute weathering profile with our observations of dynamic stream Li signatures, we couple the RTM to a distribution of fluid transit times that evolve based on storm hydrographs. The approach guides appropriate flux‐weighting of fluid from the RTM over a range of flow path lengths, or equivalently fluid residence times. This flux‐weighted RTM approach accurately reproduces dynamic storm Li‐discharge patterns distinguished by the antecedent conditions of the watershed.

Geofluid behavior prior to the 2018 Hokkaido Eastern Iburi earthquake: insights from groundwater geochemistry

A notable decrease of groundwater Na/K ratios was observed several months before the 2018 Hokkaido Eastern Iburi earthquake (M6.7) at a site approximately 20 km west of the earthquake’s epicenter. To investigate the cause of the decreased Na/K ratios, we analyzed groundwater samples (commercially bottled drinking water) to assess the contribution of deep-derived fluids using Li and Sr isotopic ratios, which are reliable indicators of deep fluid contributions. No pronounced changes in the 7Li/6Li and 87Sr/86Sr ratios were observed; thus, the pre-earthquake decrease of groundwater Na/K ratios did not result from the input of deep-derived fluids. The pre-earthquake decrease in the Na/K ratio observed in this study may instead be related to CO2 influx into the aquifer. The CO2 may have leaked from carbon dioxide capture and storage (CCS), because CCS was in operation near the epicenter of the 2018 Hokkaido Eastern Iburi earthquake. Decreases of the Na/K ratios and increases of the CO2 concentrations in groundwater have been reported before other large earthquakes; thus, CO2 influx into groundwater may be a common phenomenon preceding earthquakes.

Deuterium retention in co-deposition with lithium in Magnum-PSI: experimental analysis and comparison with SOLPS-ITER

The vapor-box, a liquid metal design for the divertor, utilizes lithium recirculation through evaporation and condensation. Safety concerns arise from Li-D/T formation and co-deposition on vapor-box walls and the first wall, affecting tritium retention. Additively manufactured tungsten capillary porous structure (CPS) samples with Li were exposed to high heat flux D plasmas in the linear plasma device Magnum-PSI, to study D retention in Li–D co-deposition dependence on substrate temperature (200 ∘ C–428 ∘ C) and distance from the plasma beam center (25–85 mm). The D:Li ratio was determined via in-situ ion beam diagnostics with simultaneously analyzed Nuclear Reaction Analysis and Elastic Backscattering Spectroscopy spectra to maximize the precision. Experimental results approach close to the theoretical maximum at 40:60 D:Li ratio and deposited film thickness ranging from 0.02 to 3.2 µm. Witness plate temperatures above 400 ∘ C yielded Li films under 150 nm in thickness with lower D:Li ratios (5:95 D:Li ratio). At this temperature LiD decomposition pressure is comparable with vessel pressure during plasma. SOLPS-ITER simulations narrowed CPS surface temperature to 650 ∘ C–700 ∘ C, indicating Li+ plasma dominance near the target surface. Redeposition ratio of lithium on the CPS surface was determined to be around 80 % , matching quartz crystal microbalance results. However, SOLPS-ITER simulations lacked accuracy in recreating observed Li and D deposition layers on WPs, improvements are needed to model plasmas with significant Li quantities. Extension of SOLPS-ITER simulations to include LiD molecules and enhance heat flux accuracy is crucial for better alignment with experimental data.

Efficient Leaching of Metal Ions from Spent Li-Ion Battery Combined Electrode Coatings Using Hydroxy Acid Mixtures and Regeneration of Lithium Nickel Manganese Cobalt Oxide

Extensive use of Li-ion batteries in electric vehicles, electronics, and other energy storage applications has resulted in a need to recycle valuable metals Li, Mn, Ni, and Co in these devices. In this work, an aqueous mixture of glycolic and lactic acid is shown as an excellent leaching agent to recover these critical metals from spent Li-ion laptop batteries combined with cathode and anode coatings without adding hydrogen peroxide or other reducing agents. An aqueous acid mixture of 0.15 M in glycolic and 0.35 M in lactic acid showed the highest leaching efficiencies of 100, 100, 100, and 89% for Li, Ni, Mn, and Co, respectively, in an experiment at 120 °C for 6 h. Subsequently, the chelate solution was evaporated to give a mixed metal-hydroxy acid chelate gel. Pyrolysis of the dried chelate gel at 800 °C for 15 h could be used to burn off hydroxy acids, regenerating lithium nickel manganese cobalt oxide, and the novel method presented to avoid the precipitation of metals as hydroxide or carbonates. The Li, Ni, Mn, and Co ratio of regenerated lithium nickel manganese cobalt oxide is comparable to this metal ratio in pyrolyzed electrode coating and showed similar powder X-ray diffractograms, suggesting the suitability of α-hydroxy carboxylic acid mixtures as leaching agents and ligands in regeneration of mixed metal oxide via pyrolysis of the dried chelate gel.

Soil low-density geochemical mapping of technology-critical elements (TCEs) and its environmental implications: The case of lithium in Portugal

Increased use of technology-critical elements (TCEs) like lithium (Li), and their socio-environmental impacts, make it an issue of national and global importance. In Portugal, new Li exploration/exploitation projects are a very likely scenario. Thus, it is essential to establish geochemical backgrounds/thresholds for Li in soil, which can have several applications. Here, Li contents were determined and mapped from a previous low-density geochemical survey that covered the entire continental area of Portugal, following UNESCO's IGCP 259 project recommendations. The sampling sites were chosen in undisturbed/uncultivated land to ensure a reliable representation of “natural” soils. A total of 152 samples (0–20 cm; <2 mm) were taken for this study. Soil Li analysis was carried out by Flame Atomic Absorption Spectrometry (FAAS) after aqua regia (AR) extraction (geoavailable Li), while a subset of 55 samples underwent further digestion with a strong acid mixture to measure total Li (FAAS). This was done to ascertain the relationship between the two Li fractions and its environmental significance. Soil Li spatial distribution was produced with GIS software. Median values of 14 mg/kg for geoavailable Li and 60 mg/kg for total Li were estimated from these datasets. The first value is comparable to the median Li (11 mg/kg) from an AR-extraction for agricultural/grazing soils in Europe (GEMAS project). Based on spatial analysis, Cambisols overlying granitoids in northern/central Portugal contain the highest AR-extractable Li (40 mg/kg). Such areas are recognized for hard-rock Li mineralizations, mainly associated with aplite-pegmatites. Principal Component Analysis identified an important Li-Al relationship, linked to Cambisols and Leptosols overlying granitoids/metamorphic rocks. The geoavailable/total Li ratios revealed that >60 % of the samples have a relatively high proportion (>45 %) of Li that can be mobilized/dispersed in the surface environment. These findings are intended to support the management of potential concerns regarding Li mining in mainland Portugal.

Petrogenesis of Mesozoic pegmatites in the Dahongliutan Li-mineralized belt (Western Kunlun, NW China)

The genesis of pegmatite and the associated Li-mineralization mechanism remain debated. The intimate temporal-spatial relationship between the pegmatites in the Dahongliutan Li-mineralized belt (incl. #509 Daoban and Akshay Li-poor pegmatites, and Akshay Li-rich pegmatite) and the Dahongliutan granite pluton allows us to discuss the origin of pegmatite and the Li-mineralization mechanism by conducting detailed geochemical and geochronological investigations on the two rock units in the Western Kunlun orogen (NW China). The Li-poor pegmatites in the Dahongliutan Li-mineralized belt exhibit similar or much lower Li, Rb, and Cs compared to the adjacent granite, and their εNd(t) values (-8.7–-10.0) are significantly lower than those of the granite (-7.5–-8.1) as well. However, the Akshay Li-rich pegmatite shows extremely high Li, Rb, Nb, Ta, and initial Sr isotopic ratios (0.7223–0.7227, obtained from apatite), in contrast to the Dahongliutan granite (ISr = 0.7108–0.7157). The whole-rock δ7Li values of the Dahongliutan granite, pegmatites, and the wall-rock Bayanharshan Group metapelite are + 0.76–+5.67 ‰, +0.8–+14.4 ‰, and −4.2–+2.8 ‰, respectively. Zircon and cassiterite U-Pb dating yielded 206Pb/238U ages of 216 ± 2 Ma and 195 ± 2 Ma for the #509 Daoban Li-poor pegmatite and Akshay Li-rich pegmatite, respectively. Modeling of trace elements and Li isotopes suggests that the pegmatites in the Dahongliutan Li-mineralized belt did not originate from fractional crystallization of granitic magma. Instead, they may have formed through direct anatexis under amphibolite-facies conditions. Abundant Li-rich claystone, occasionally accompanied by evaporite, may exist in the magma source of the Li-rich pegmatite, which is the key factor controlling pegmatitic Li mineralization.

Self-assembly formation of solid-electrolyte interphase in gel polymer electrolytes for high performance lithium metal batteries

Lithium-metal batteries (LMBs) using limited-Li anodes are imperative for realizing high-energy storage. Proper solid-electrolyte interphase (SEI) design to control Li-deposition behavior and enhance deposition reversibility is challenging. We engineer the self-assembly formation of SEI in a gel polymer electrolyte (GPE) comprising poly(vinylidene fluoride-co-hexafluoro propylene) (PVDF-co-HFP) dissolved in a LiPF6-LiNO3 dual-salt solution with multiple solvents. The components of this GPE present critical functions: (1) dielectric (PVDF‐co-HFP) dissociates ion pairs to facilitate Li+ transport in the electrolyte and regulate Li+ diffusion in the SEI to lower Li deposition overpotentials, and endows soft characteristics to the SEI; (2) dual-anion PF6−-NO3− in the Li+ solvation sheath facilitates facile Li+ desolvation and formation of rigid and ion-conductive Li3N–LiF-rich SEI. This GPE exhibits higher ionic conductivity and Li+ transference number than the corresponding liquid electrolytes. The capacity retention of an anode-free Cu|GPE|NMC811 battery, i.e., at an anodic-to-cathodic Li ratio (A/C) of 0, reaches 44% after 100 charge-discharge cycles. An LMB with limited-Li at A/C = 2, having energy of 616 Wh kg−1 based on electrode-material mass, exhibits a retention of 85% after 100 cycles. The strategy to regulate Li+-transport and Li-deposition through GPE is promising for realizing the application of LMBs.

Population dynamics of Arctica islandica off Long Island (USA): an analysis of sex-based demographics and regional comparisons

The boreal bivalve Arctica islandica is an important fishery in the United States (US), yet very little is known about the resiliency of this species to fishing activity due to limited understanding of localized population demographics. Demographics including age frequency, recruitment patterns, mortality rates, and sexual dimorphism were evaluated for a population sampled off Long Island (LI, 40.09658°N 73.01057°W) and compared with samples from Georges Bank (GB, 40.72767°N, 67.79850°W) collected in 2015 and 2017, where GB was described in a previous study. This study supports evidence that this species is sexually dimorphic. Earlier assumptions of prolonged lapses in recruitment were not substantiated for either the GB or LI populations; yearly cohorts were observed for the past century, and both populations presented recruitment pulses in approximately 8-y periods. Estimated ages from this study are older than previously reported for the US Mid-Atlantic with the oldest animal represented by a 310-year-old male collected from LI. Simulated total mortality was higher at GB than LI, and higher for GB females than GB males, with simulated mean longevity estimates greater at LI than GB. The population sex ratio at GB was 1:1.1 (female:male), whereas the LI ratio was 1:1.4 and relatively deficient in large females. Recruitment into the populations occurs routinely with substantial hiatuses being rare and substantive year classes occurring at least decadally with lesser, but contributing, recruitment in most years in between. Routine recruitment may insulate this species from risks posed by overfishing to an extent not typical for other long-lived species.

Selective recovery of lithium from spent LiFePO4 battery via a self-catalytic air oxidation method

To achieve the long-term healthy development of new energy vehicles and energy storage industries, the recycling of spent lithium-ion batteries is extremely significant. Air oxidation leaching at room temperature can achieve the efficient recovery of lithium from LFP scrap (generated in LiFePO4 material production), but this method is unsuitable for the treatment of cathode materials from spent LFP batteries. In this work, cyclic voltammetry measurements were first innovatively employed to clarify the reasons for the ineffective leaching of lithium from spent LFP materials via air oxidation leaching and provide the theoretical basis for intensified leaching. Subsequently, a novel method of self-catalytic air pressure leaching was proposed to selectively recover lithium from spent LFP batteries, which ingeniously employs green and cost-free air as the oxidant and self-owned Fe in the LiFePO4 as the O2 deliverer and catalyst. 98.9% Li and only 0.41% Fe, and 3.01% P were leached from spent LFP materials under 0.4 MPa of air pressure, n (H2SO4)/n (Li) ratio of 0.5, liquid to solid ratio of 20 mL/g, 90 °C, and 5 h. The leaching kinetic study was performed and it indicated that the leaching kinetics of Li was controlled by chemical reaction. By combining the results of the thermodynamic analysis and various characterization methods, the reaction course of this self-catalytic air pressure leaching was clarified. In particular, AC-TEM and SEM-EDS analysis showed that the dispersed carbon bands covered on the LiFePO4 particles have been destroyed during the oxidation leaching, which significantly promotes the lithium recovery rate. Finally, the economic feasibility and environmental impact evaluations demonstrated that the proposed method has the advantages of high recycling profits, environmental friendliness, and low carbon emissions.

Contiguous High-Mobility Interphase Surrounding Nano-Precipitates in Polymer Matrix Solid Electrolyte

We establish that an interfacial region develops around amorphous Li1.3Al0.3Ti1.7(PO4)3 (LATP) nanoparticles in a poly(ethylene oxide) (PEO), which exhibits a 30 times higher Li+ mobility than the polymer matrix. To take advantage of this gain throughout the material, nanoparticles must be uniformly dispersed across the matrix, so that the interphase formation is minimally blocked by LATP particle agglomeration. This is achieved using a water-based in situ precipitation method, carefully controlling the temperature schedule during processing. A maximum conductivity of 3.80 × 10-4 S cm-1 at 20 °C for an ethylene oxide to Li ratio of 10 is observed at 25 wt % (12.5 vol %) particle loading, as predicted by our tri-phase model. Comparative infrared spectroscopy reveals softening and broadening of the C-O-C stretching modes, reflecting increased disorder in the polymer backbone that is consistent with opening passageways for cation migration. A transition state theory-based approach for analyzing the temperature dependence of the ionic conductivity reveals that thermally activated processes within the interphase benefit more from higher activation entropy than from the decrease in activation enthalpy. The lithium infusion from LATP particles is small, and the charge carriers tend to concentrate in a space-charge configuration near the particle/polymer interface.

Lithium and strontium isotopic systematics in the Nalenggele River catchment of Qaidam basin, China: Quantifying contributions to lithium brines and deciphering lithium behavior in hydrological processes

The salt lakes fed by the Nalenggele River in the Qaidam Basin, located on the northeastern Qinghai Tibetan Plateau (QTP), are major brine lithium reservoirs in China. The quantitative identifications of the Li sources and their dynamic behavior shed light on the formation mechanism of the brine Li deposits in closed-basin of arid regions. This study presents Li and Sr isotope ratios (δ7Li, 87Sr/86Sr) and other hydrogeochemical parameters for river waters, springs, spring river waters, shallow groundwaters, surface brines, and intercrystalline brines around the Nalenggele River Basin (NRB) and its adjacent small watersheds. The results indicate that the Nalenggele River water is a mixing product of hot springs and regional surface meltwater, and the source of dissolved Li in the NRB is mainly supplied by the hot springs. With multi-tracer models, it is confirmed that around 84.9 %−93.4 % of dissolved Li is provided by the Li-rich hot spring waters, which account for only 3–5 % of the total water input. Furthermore, the dissolved Li in the streams of different hydrological regions shows various isotopic fractionation behavior. In general, the lower average δ7Li values (average of +5.6 ‰) with more enriched Li with respect to Na in the waters of the piedmont Gobi region indicates a significant additional input of dissolved Li from bedrock and sediments. The second-stage alluvial fan of the NRB produces 7Li enrichments and Li-depleted waters (compared with Na), which can be explained by the adsorption of clay or Fe (Mn) oxide phases that fractionate Li isotopes. The highest average δ7Li values (+12.76 ‰) are observed when Li is not adsorbed by the scarce fine clastic sediments in the hypersaline environment of the salt lake region. It can be concluded that the continuous halite precipitation during the brine evolution not only causes the abnormal enrichment of Li in the brine (compared with Na) but also continuously sequesters the 6Li from the brines, resulting in a significant 7Li enrichment. Overall, these findings advance the understanding of the lithium sources of Li-rich brines and its enrichment and metallogenic process during water migration in hyper-arid regions and have crucial indicative significance for lithium cycling under a strong evaporation environment.

Lithium Recovery from NCM Lithium Ion Battery by Carbonation Roasting Followed by Water Leaching

Lithium is a representative rare metal and ranks 32nd in abundance among elements in the earth’s crust. Lithium is used in a variety of applications, including the production of organolithium compounds, as an alloying addition to aluminum and magnesium, and as the anode in rechargeable lithium ion batteries especially for electronic devices and electric vehicles. Today, lithium is an indispensable metal in our daily lives. It is important to recycle lithium from used lithium-ion batteries to prepare for lithium shortages and protect lithium resources. The active cathode material of a lithium ion battery contains other valuable metals including Ni, Co, and Mn. In this study, the effect of carbonation temperature on Li recovery from NCM (LiNixCoyMnzO2) powder as Li2CO3 was investigated. First, a carbonation roasting was performed to convert the Li in the NCM powder into Li2CO3 at various temperature using a thermo-gravimetric analyzer. The roasted cinder leached into the water to dissolve the Li2CO3. The results showed that in Ar gas atmosphere the NCM phase was decomposed into Li2O and Li1-xM1+xO2 phases and the weight decreased by 4.7%, but in a CO2 atmosphere Li2CO3 was formed, resulting in a 12.1% increase in weight. In the isothermal experiment, the weight and carbon concentration of cinder increased with temperature, and the Li ratio in the NCM gradually decreased. The NCM powder was able to react with CO2 above 853 K, while some nickel, cobalt and manganese were regenerated into different Li1-xM1+xO2 crystalline phases. The maximum Li recovery rate of 76% wsa achieved for 2 h carbonation roasting at 1073 K followed by water leaching, filtering and an evaporative crystallization process.

Generative shaping and material-forming (GSM) enables structure engineering of complex-shaped Li4SiO4 ceramics based on 3D printing of ceramic/polymer precursors

Vat photopolymerization (VPP) 3D printing of ceramics normally uses ceramic slurries directly made of the target ceramic powder. It may become challenging when the ceramic powders are difficult-to-make and thus are expensive or rarely accessible. We have previously proposed a generative shaping and material-forming (GSM) 3D printing strategy, which involves the use of low-cost multi-component inorganic ceramic precursors as powder sources. The shaping of complex structures was realized through VPP, followed by reaction sintering to form the target ceramic material. In the current study, as a step further, ceramic (Li 2 CO 3 ) and polymer (methyl polysiloxane) combined precursors were employed as an alternative material source for the first time to go through the 3D printing and reaction sintering processes, complementing the application range of the proposed GSM strategy. The slurry formulation and printability, the sinterability of the printed parts and the microstructures and mechanical performance of the sintered parts were characterized and optimized in accordance with the ingredient contents, particularly the stoichiometric ratios of Si:Li in the precursors. As a result, complex-structured Li 4 SiO 4 ceramics with high purity were fabricated based on the use of Li 2 CO 3 ceramic and Si-rich polymer as precursors. Through the advanced characterization and analysis of material phase and microstructural evolution, it was found that the fabricated complex-structured Li 4 SiO 4 ceramics based on a precursor slurry with a solid content of 40 vol%, a Si:Li ratio of 1:2.5, and a sintering temperature of 850 ℃ showed a high phase purity of 97.23% and a compressive strength of 15.24 ± 0.33 MPa, with a skeleton’s relative density of 65.31% is achieved. The results showed greatly enhanced strength at much higher porosities, which might be advantageous and beneficial to structure engineering for mechanical enhancement and the improvement of tritium release effectiveness. Compared with the previous study using multi-component ceramic powder precursors, the ceramics prepared in this study exhibited enhanced microstructural stability and higher phase purity with an advantageously lower sintering temperature. Further analysis revealed that compared with the high temperature solid-state reaction of multi-component ceramic powder precursors, the involvement of the Si-rich polymer precursor enabled the more efficient and complete synthesis of Li 4 SiO 4 as a result of the accelerated covering and cleavage of Si–O–Si bonds on the Li 2 CO 3 particles at a much lower temperature. The present work suggests that the GSM strategy using combined ceramic and polymer precursors as proposed in this study is a promising alternative method to produce high quality Li 4 SiO 4 components with complex structures. • Our GSM strategy is extended to 3D printing using ceramic/polymer precursors. • Slurry formulation and printability, sinterability of parts and microstructures of sintered parts were characterized. • High material phase purity and strength for the skeleton were achieved with lower sintering temperature. • Improved strength by GSM enabled structure engineering with complete synthesis/rearrangement of material/microstructures.

Radiative properties of ‘Eu’in Li–Al–Si–O ceramics: Effect of ‘Si’ to ‘Li’ ratio

Four Li–Al–Si– O -based ceramic compounds with varying Si to Li ratios were synthesized via a high-temperature reaction route and characterized by X-Ray diffraction, scanning electron microscopy, and photoluminescence techniques. Eu was used as an activator in these four compositions namely, LiAlSiO 4 , LiAlSi 2 O 6 , LiAlSi 3 O 8 , and LiAlSi 4 O 10 , and the radiative properties were evaluated. The activator concentration was optimized in all these samples to 2 mol%. The photoluminescence emission intensity and decay time values increased with the Si to Li ratio. The relative intensities of the emission spectra and the lifetime values indicated that the rare earth ion stabilizes itself at interstitial positions in the lattice having approximately C 2v symmetry. The chromaticity indices for the four ceramic samples doped with Eu were calculated that showed near red emission for all. To get an idea about their commercial utility, color purity, quantum efficiencies for the phosphors were evaluated. The emission profile of the prepared samples was compared with a commercial sample. The Judd-Ofelt parameters, transition probabilities, branching ratios, and quantum efficiencies were also calculated for these systems. It was observed that the metal-ligand bond covalency decreased with an increase in the Si to Li ratio which was responsible for the increase in the emission intensities and luminescence decay time values.

Ionic Conductivity of Hybrid Composite Solid Polymer Electrolytes of PEOnLiClO4-Cubic Li7La3Zr2O12 Films

Ionic conductivity of the polyethylene oxide-LiClO4 (PEOnLiClO4) solid polymer electrolyte (SPE) films with an EO:Li ratio (n) of 10, 12, 15, as well as the hybrid composite solid polymer electrolyte (CSPE) films of PEOnLiClO4 containing 50 wt% of cubic-Li7La3Zr2O12 (LLZO) sub-micron sized particles, have been studied by varying Li-salt content in the films. The complex AC dielectric permittivity and conductivity data obtained from electrical impedance measurements were fitted using a generalized power-law, including the effects of electrode polarization applied at low AC frequencies to obtain various relaxation times. In addition to increased mechanical and thermal robustness, the CSPE films show higher values of ionic conductivity, &gt;10−4 S/cm at room temperature compared to those of SPE films with n = 12 and 15. On the contrary, the ionic conductivity of CSPE with n = 10 decreases by a factor of three compared to the corresponding SPE film due to increased polymer structural reorientation and Li-ion pairing effects. The Vogel–Tammann–Fulcher behavior of the temperature-dependent conductivity data indicates a close correlation between the ionic conductivity and polymer segmental relaxation. The PEO12LiClO4-LLZO film shows the lowest activation energy of ~0.05 eV.

Effect of Li Ratio in Li-Naphthalenide Solution on Li Pre-Doping to Si Negative Electrode for Next-Generation Batteries

In order to realize a carbon-free society, there is a strong need to increase the energy density of secondary batteries such as Li-ion batteries (LIB). In recent years, study on next-generation batteries such as Li-air O2 (LAB) and Li-S has been actively conducted. Si is one of the most attractive materials for the negative electrode of these secondary batteries, with the high theoretical capacity of 3580 mAh g-1 based on Li3.75Si. When Si is used as the negative electrode of LAB and Li-S batteries, however, it is a critical issue to add Li resource to the electrode since the positive electrode also does not contain Li resource. One of the solutions is to conduct Li pre-doping to the Si electrodes. Various methods have been reported, including direct contact of Li metal foil with Si electrode, electrochemical Li pre-doping, and mixing Li metal and active materials method [1].We reported that Si electrodes pre-doped with Li by the solution method, in which a Si electrode is attached to a Li metal through a separator and immersed in Li-naphthalenide (Li-NTL) solutions with different ether solvents [2]. In particular, 2-methyltetrahydrofuran (MeTHF), a solvent of Li-NTL solution, showed a higher Li pre-doping capacity and Li3.75Si crystal phase was identified on a 24 h pre-doping electrode. In this way, deep Li doped level and relatively uniform Li doping was achieved with this method. DFT calculation showed that MeTHF has a higher unoccupied molecular orbital (LUMO) energy than the other ester, meaning that the Li-NTL solution using MeTHF solvent is difficult to be subjected a reductive decomposition. We exhibited that the Li-NTL solution having a low equilibrium potentials provided a deeper pre-doping capacity of Li. On the other hand, Yus et al. revealed that Li-NTL/THF solution contained the two types of NTL anions, i.e. radical anion (Li+NTL· -) and dianion (Li+ 2NTL2 -), and the ratio is changed by the Li concentration [3]. It is considered that the same phenomena should be occurred in the case of MeTHF solvent and probably affects it on Li-doped capacity.In this study, we investigated the effect of Li concentration of Li-NTL/MeTHF solution in order to improve the Li pre-doping capacity and to elucidate the Li pre-doping mechanism using the Li-NTL solution. Si electrodes with a weight ratio of Si : Ketjen black : polyimide binder = 80:5:15 were prepared and pre-doped with Li for 24 h using 0.5 M Li-NTL solution (Li : naphthalene = 0.5 : 1.0 or 1.0 : 1.0 by molar ratio). The pre-doping capacity was confirmed by the discharge capacity of the electrochemical delithiation reaction from open circuit voltage (OCV) to 1.5 V. Figure 1 shows the equilibrium potentials of Li-NTL solutions obtained in a two-electrode cells with a Li metal and a Ni mesh electrode immersed in 1.0 M LiPF6/EC+DMC (1:1 by vol.) electrolyte solution and Li-NTL solution, respectively, and two solutions were separated by a solid-state electrolyte Li7La3Zr2O12 (LLC). The equilibrium potential linearly decreased with increasing temperature, and drastically increased with the molar ratio of Li : naphthalene. Therefore, a higher Li concentration will provide a higher Li pre-doping capacity. The change in the Li pre-doping capacity, cycleablity, and pre-doping mechanism by using the Li-NTL dianion solution will be discussed in the meeting.This work was partially supported by NEDO RISING2 project (JPNP16001).

Combined density functional theory/kinetic Monte Carlo investigation of surface morphology during cycling of Li-Cu electrodes

We employed a combined density functional theory and kinetic Monte Carlo approach in order to investigate the nanoscale behavior of lithium stripping and plating on lithium-copper nanoalloys. Density functional theory calculations were used to develop an atom-by-atom understanding of the nucleation behavior of lithium on copper surfaces with different surface morphologies. We found that nanometric pits resulted in significantly more favorable lithium deposition when compared to pristine or lightly-defective Cu surfaces, which is in agreement with previous experimental studies. We then used density functional theory and constrained ab initio molecular dynamics to develop interaction and reaction parameters for a larger-scale kinetic Monte Carlo model in order to provide insight into the stripping and plating behavior of nanostructured Li-Cu nanoalloy anodes. Substantial losses in capacity and strong indications of morphological change were observed for a wide range of Cu:Li ratios over 100 cycles. We observed a complex relationship between the nanoparticle composition and the properties of the formed solid-electrolyte interphase.

Compositional evolution of the muscovite of Renli pegmatite-type rare-metal deposit, northeast Hunan, China: Implications for its petrogenesis and mineralization potential

The Renli deposit is the largest known pegmatite-type Ta–Nb deposit in south China. Its rare-metal pegmatites show regular zoning of pegmatite types and rare-metal mineralization assemblages from northeast to southwest. One hundred and forty major outcropping pegmatite dikes throughout the deposit can be approximately divided into four zones outward from the Mufushan batholith: microcline pegmatite zone (P1); microcline–albite pegmatite zone (P2); albite pegmatite zone (P3); and albite–spodumene pegmatite zone (P4). The sizes of the dikes decrease with distance from the batholith, and their rare-metal mineralization type changes as follows: Be → Nb–Ta (–Be) → Li (–Nb–Ta). Field geological characteristics, chronological and Lu–Hf and Sr–Nb–Pb isotopic studies indicate that these rare-metal pegmatites have a close petrogenetic relationship with the Mufushan complex granitic intrusions. However, because of the similarities in geochemical characteristics, magma source properties, and emplacement ages of these different granitic intrusions, identifying the parental rock of rare-metal pegmatites is challenging.Muscovites are common throughout the granitic intrusions and four types of pegmatites in the Renli deposit, and are intimately associated with rare-metal mineralization. The geochemistry of muscovite obtained from granites and pegmatites can be used to demonstrate the parental relationships of rare-metal pegmatites and Mufushan granites, allowing pegmatite evolution trends and the mineralization potential of the Renli deposit to be evaluated. The K/Rb versus Cs, Rb, Li, Nb, and Ta ratios and Ta/Nb versus Li, Ta, and TiO2 ratios in muscovites from the granites and pegmatites show that they form an association with the following sequence of evolution: biotite monzogranite → two-mica monzogranite → microcline pegmatite → microcline–albite pegmatite → albite pegmatite → albite–spodumene pegmatite. The above complete evolution sequence represents the magmatic stage of the deposit and the lepidolite-quartz core in pegmatite with well internal zoning represents the fluid-rich stage of the deposit. The Al4Si–3□–1 exchange vector (where □ represents a vacancy) is shown to have played an important role in the first magmatic stage of the Renli deposit when compositional changes in Li-poor muscovite formed in the magmatic stage involved this substitution. During the late fluid-rich stage formed by highly differentiated magma at the end of the magmatic evolution of the deposit, Li was incorporated into micas by Li3Al–1□–2. Many pegmatite dikes with transitional boundaries can be observed in the outcrops of two-mica monzogranite (RLG2), and geochemical characteristics of muscovite suggest that this monzogranite show the highest differentiation degree in Renli granites, whose average K/Rb and Ta/Nb ratios are close to those of the Renli pegmatites. This indicates that the two-mica monzogranite (RLG2) has the closest petrogenetic relationship with the Renli rare-metal pegmatites. Combined with the data from this and previous studies, the K/Rb ratio, Li and Cs contents of muscovite can be used to distinguish the barren pegmatite and different types (Be, Nb–Ta, or Li type) of rare-metal pegmatites to a certain degree. Therefore, muscovite can indicate the metallogenic type and economic potential in a pegmatite-type rare-metal deposit.

Preparation and Characterization of Lithium Ion Conductive Organic/Inorganic Composite Solid Electrolyte.

The purpose of this study was to improve the ionic conductivity and physical properties of a polymer electrolyte by complexing it with ceramic particles. First, a polymer/ceramic composite solid electrolyte was prepared by synthesizing a super porous silica aerogel powder and adding it to a slurry containing a polyethylene oxide (PEO)-based polymer electrolyte; then, the electrochemical properties of electrolyte of different compositions were confirmed. PEO and polymethyl methacrylate (PMMA) were copolymerized, the optimum ratio of lithium salt, plasticizer, and silica aerogel was determined, and ion conductivity of the composite electrolyte was improved. When the EO:Li ratio was 10:1, the glass transition temperature was the lowest, and the room-temperature ion conductivity was improved to 3.0 × 10-5 S/cm. As a result of XRD and thermal analysis, it was confirmed that the stability and durability of the electrolyte interface can also be improved by complexation of the polymer electrolyte with ceramic particles.