Development of Fluorine-Free Electrolytes for Aqueous-Processed Olivine-Type Phosphate Cathodes.

Environmental impacts and resource availability are significant concerns for the future of lithium-ion batteries. This study focuses on developing novel fluorine-free electrolytes compatible with aqueous-processed cobalt-free cathode materials. The new electrolyte contains lithium 1,1,2,3,3-pentacyanopropenide (LiPCP) salt. After screening various organic carbonates, a mixture of 30:70 wt.% ethylene carbonate and dimethyl carbonate was chosen as the solvent. The optimal salt concentration, yielding the highest conductivity of 9.6 mS·cm-1 at 20 °C, was 0.8 mol·kg-1. Vinylene carbonate was selected as a SEI-stabilizing additive, and the electrolyte demonstrated stability up to 4.4 V vs. Li+/Li. LiFePO4 and LiMn0.6Fe0.4PO4 were identified as suitable cobalt-free cathode materials. They were processed using sodium carboxymethyl cellulose as a binder and water as the solvent. Performance testing of various cathode compositions was conducted using cyclic voltammetry and galvanostatic cycling with the LiPCP-based electrolyte and a standard LiPF6-based one. The optimized cathode compositions, with an 87:10:3 ratio of active material to conductive additive to binder, showed good compatibility and performance with the new electrolyte. Aqueous-processed LiFePO4 and LiMn0.6Fe0.4PO4 achieved capacities of 160 mAh·g-1 and 70 mAh·g-1 at C/10 after 40 cycles, respectively. These findings represent the first stage of investigating LiPCP for the development of greener and more sustainable lithium-ion batteries.

Comparative Study of Cytotoxicity and Accumulation of Boron and Lithium-Containing Drugs in Skin Melanoma Cells In Vitro.

We studied cytotoxicity and accumulation of boron and lithium by cultured human fibroblasts and human and mouse skin melanoma cell cultures. The cytotoxicity of boron and lithium drugs was assessed by MTT tests in the boron and lithium concentration range of 10-640 µg/ml. Cell viability was significantly reduced after incubation with boron and lithium at concentrations >160 µg/ml. To assess accumulation of boron and lithium, the concentration of elements was measured using inductively coupled plasma atomic emission spectrometry. Melanoma cells more intensively accumulated lithium in comparison with boron. The results indicate the possibility of safe application of lithium salts in concentrations minimally required for successful neutron capture therapy.

Obstetric Outcomes in Women on Lithium: A Systematic Review and Meta-Analysis.

Background/Objectives: Lithium taken during pregnancy was linked in the past with increased risk for foetal/newborn malformations, but clinicians believe that it is worse for newborn children not to treat the mothers' underlying psychiatric illness. We set to review the available evidence of adverse foetal outcomes in women who received lithium treatment for some time during their pregnancy. Methods: We searched four databases and a register to seek papers reporting neonatal outcomes of women who took lithium during their pregnancy by using the appropriate terms. We adopted the PRISMA statement and used Delphi rounds among all the authors to assess eligibility and the Cochrane Risk-of-Bias tool to evaluate the RoB of the included studies. Results: We found 28 eligible studies, 10 of which met the criteria for inclusion in the meta-analysis. The studies regarded 1402 newborn babies and 2595 women exposed to lithium. Overall, the systematic review found slightly increased adverse pregnancy outcomes for women taking lithium for both the first trimester only and any time during pregnancy, while the meta-analysis found increased odds for cardiac or other malformations, preterm birth, and a large size for gestational age with lithium at any time during pregnancy. Conclusions: Women with BD planning a pregnancy should consider discontinuing lithium when euthymic; lithium use during the first trimester and at any time during pregnancy increases the odds for some adverse pregnancy outcomes. Once the pregnancy has started, there is no reason for discontinuing lithium; close foetal monitoring and regular blood lithium levels may obviate some disadvantages of lithium administration during pregnancy.

Entropy-Driven Hybrid Gel Electrolyte Enables Practical High-Voltage Lithium Metal Batteries.

Electrolyte engineering plays a crucial role in enhancing the performance of lithium metal batteries (LMBs) featuring high-voltage cathodes and limited lithium anodes, thereby unlocking their potential for high-energy electrochemical storage. Herein, an entropy-driven hybrid gel electrolyte with enhanced diversity in Li-ion solvation structures is designed by incorporating substantial amounts of insoluble LiPO2F2 and LiNO3 salts into LiPF6-based carbonate electrolytes, followed by in situ thermal polymerization. Specifically, the Li+ solvation structures are modulated via ionophilic NO3- and PO2F2- to generate an anion-rich solvation sheath and thus promote anion reduction at the electrode-electrolyte interface. The interfaces enriched in anion-derived inorganic components facilitate rapid ionic transport, thus enabling smooth and dense Li morphology and ultimately enhancing the electrochemical performance of LMBs. As a result, this high-hybrid gel electrolyte confers LMBs employing high-voltage NCM cathodes, as demonstrated by sustained performance in both coin-cell (500 cycles at 4.5 V) and Ah-level pouch cell configurations under practical conditions (60 cycles, N/P: 1.92, and E/C: 2.0 g Ah -1).

Effects of Lithium Ions on tPA-Induced Hemorrhagic Transformation under Stroke.

Thrombolytic therapy with the tissue plasminogen activator (tPA) is a therapeutic option for acute ischemic stroke. However, this approach is subject to several limitations, particularly the increased risk of hemorrhagic transformation (HT). Lithium salts show neuroprotective effects in stroke, but their effects on HT mechanisms are still unknown. In our study, we use the models of photothrombosis (PT)-induced brain ischemia and oxygen-glucose deprivation (OGD) to investigate the effect of Li+ on tPA-induced changes in brain and endothelial cell cultures. We found that tPA did not affect lesion volume or exacerbate neurological deficits but disrupted the blood-brain barrier. We demonstrate that poststroke treatment with Li+ improves neurological status and increases blood-brain barrier integrity after thrombolytic therapy. Under conditions of OGD, tPA treatment increased MMP-2/9 levels in endothelial cells, and preincubation with LiCl abolished this MMP activation. Moreover, we observed the effect of Li+ on glycolysis in tPA-treated endothelial cells, which we hypothesized to have an effect on MMP expression.

Radical Polymer-based Positive Electrodes for Dual-Ion Batteries: Enhancing Performance with γ-Butyrolactone-based Electrolytes.

Dual-ion batteries (DIBs) represent a promising alternative for lithium ion batteries (LIBs) for various niche applications. DIBs with polymer-based active materials, here poly(2,2,6,6-tetramethylpiperidinyl-N-oxyl methacrylate) (PTMA), are of particular interest for high power applications, though they require appropriate electrolyte formulations. As the anion mobility plays a crucial role in transport kinetics, Li salts are varied using the well-dissociating solvent γ-butyrolactone (GBL). Lithium difluoro(oxalate)borate (LiDFOB) and lithium bis(oxalate)borate (LiBOB) improve cycle life in PTMA||Li metal cells compared to other Li salts and a LiPF6- and carbonate-based reference electrolyte, even at specific currents of 1.0 A g-1 (≈10C), whereas LiDFOB reveals a superior rate performance, i. e., ≈90 % capacity even at 5.0 A g-1 (≈50C). This is attributed to faster charge-transfer/mass transport, enhanced pseudo-capacitive contributions during the de-/insertion of the anions into the PTMA electrode and to lower overpotentials at the Li metal electrode.

Ether-Based High-Voltage Lithium Metal Batteries: The Road to Commercialization.

Ether-based high-voltage lithium metal batteries (HV-LMBs) are drawing growing interest due to their high compatibility with the Li metal anode. However, the commercialization of ether-based HV-LMBs still faces many challenges, including short cycle life, limited safety, and complex failure mechanisms. In this Review, we discuss recent progress achieved in ether-based electrolytes for HV-LMBs and propose a systematic design principle for the electrolyte based on three important parameters: electrochemical performance, safety, and industrial scalability. Finally, we summarize the challenges for the commercial application of ether-based HV-LMBs and suggest a roadmap for future development.

A Highly-Fluorinated Lithium Borate Main Salt Empowering Stable Lithium Metal Batteries.

Traditional lithium salts are difficult to meet practical application demand of lithium metal batteries (LMBs) under high voltages and temperatures. LiPF6, as the most commonly used lithium salt, still suffers from notorious moisture sensitivity and inferior thermal stability under those conditions. Here, we synthesize a lithium salt of lithium perfluoropinacolatoborate (LiFPB) comprising highly-fluorinated and borate functional groups to address the above issues. It is demonstrated that the LiFPB shows superior thermal and electrochemical stability without any HF generation under high temperatures and voltages. In addition, the LiFPB can form a protective outer-organic and inner-inorganic rich cathode electrolyte interphase on LiCoO2 (LCO) surface. Simultaneously, the FPB- anions tend to integrate into lithium ion solvation structure to form a favorable fast-ion conductive LiBxOy based solid electrolyte interphase on lithium (Li) anode. All these fantastic features of LiFPB endow LCO (1.9 mAh cm-2)/Li metal cells excellent cycling under both high voltages and temperatures (e.g., 80 % capacity retention after 260 cycles at 60 °C and 4.45 V), and even at an extremely elevated temperature of 100 °C. This work emphasizes the important role of salt anions in determining the electrochemical performance of LMBs at both high temperature and voltage conditions.

Poly-Unsaturated Fatty Acids (PUFAs) from Cunninghamella elegans Grown on Glycerol Induce Cell Death and Increase Intracellular Reactive Oxygen Species.

Cunninghamella elegans NRRL-1393 is an oleaginous fungus able to synthesize and accumulate unsaturated fatty acids, amongst which the bioactive gamma-linolenic acid (GLA) has potential anti-cancer activities. C. elegans was cultured in shake-flask nitrogen-limited media with either glycerol or glucose (both at ≈60 g/L) employed as the sole substrate. The assimilation rate of both substrates was similar, as the total biomass production reached 13.0-13.5 g/L, c. 350 h after inoculation (for both instances, c. 27-29 g/L of substrate were consumed). Lipid production was slightly higher on glycerol-based media, compared to the growth on glucose (≈8.4 g/L vs. ≈7.0 g/L). Lipids from C. elegans grown on glycerol, containing c. 9.5% w/w of GLA, were transformed into fatty acid lithium salts (FALS), and their effects were assessed on both human normal and cancerous cell lines. The FALS exhibited cytotoxic effects within a 48 h interval with an IC50 of about 60 µg/mL. Additionally, a suppression of migration was shown, as a significant elevation of oxidative stress levels, and the induction of cell death. Elementary differences between normal and cancer cells were not shown, indicating a generic mode of action; however, oxidative stress level augmentation may increase susceptibility to anticancer drugs, improving chemotherapy effectiveness.

Lithium salts cytotoxicity and accumulation in melanoma cells in vitro.

Boron neutron capture therapy is a perspective selective technology for the destruction of cancer cells, while the use of lithium instead of boron may represent a new and promising vector for the development of neutron capture therapy (NCT). The aim of the study was a comparative assessment of the cytotoxicity of various lithium salts, as well as an analysis of the accumulation of lithium in tumor cells in vitro to determine the possibility of using lithium in NCT. The cytotoxicity of lithium salts was determined using MTT-test and colony forming assay on human fibroblasts BJ-5ta, human skin melanoma SK-Mel-28, and mouse skin melanoma B16 cell lines. An assessment of lithium concentration in cells was performed using inductively coupled plasma atomic emission spectrometry. Our results showed that three different lithium salts at a concentration of 40 µg/ml are not toxic for both tumor and normal cells. The highest uptake values were obtained on murine melanoma B16 cells when exposed to lithium carbonate (0.8 µg/106 cells); however, human melanoma SK-Mel-28 cells effectively accumulated both lithium carbonate and lithium citrate (about 0.46 µg/106 cells for two salts). Thus, our results demonstrate a range of non-toxic doses of lithium salts and a high uptake of lithium by tumor cells, which indicates the possibility to use the lithium in NCT.

Asymmetric Trihalogenated Aromatic Lithium Salt Induced Lithium Halide Rich Interface for Stable Cycling of All-Solid-State Lithium Batteries.

Solid polymer electrolytes (SPEs) are the key components for all-solid-state lithium metal batteries with high energy density and intrinsic safety. However, the low lithium ion transference number (t+) of a conventional SPE and its unstable electrolyte/electrode interface cannot guarantee long-term stable operation. Herein, asymmetric trihalogenated aromatic lithium salts, i.e., lithium (3,4,5-trifluorobenzenesulfonyl)(trifluoromethanesulfonyl)imide (LiFFF) and lithium (4-bromo-3,5-difluorobenzenesulfonyl)(trifluoromethanesulfonyl)imide (LiFBF), are synthesized for polymer electrolytes. They exhibit higher t+ values and better compatibility with Li metal than conventional lithium bis(trifluoromethanesulfonyl) imide (LiTFSI). Due to the trihalogenated aromatic anions, LiFFF- and LiFBF-based electrolytes are prone to generate an LiF- and LiBr-rich solid electrolyte interphase (SEI), therefore increasing the stability of the solid electrolyte/anode interface. Particularly, LiFBF could induce a LiF/LiBr hybrid SEI, where LiF shows a high Young's modulus and high surface energy for homogenizing Li ion flux and LiBr exhibits an extremely low Li ion diffusion barrier in the SEI layer. As a result, the Li/Li symmetric cells could remain stable for more than 1200 h without a short circuit and the LiFePO4/Li batteries showed superb electrochemical performance over 1200 cycles at 1 C. This work provides valuable insights from the perspective of lithium salt molecular structures for high-performance all-solid-state lithium metal batteries.

Effect of Lithium Salts on the Properties of Cassava Starch Solid Biopolymer Electrolytes.

This study evaluates the effect of lithium salts on the structural, electrochemical, and thermal properties of cassava starch solid biopolymer electrolytes (SBPEs). Films of SBPEs were synthesized using plasticizing agents and lithium salts (LiCl, Li2SO4, and CF3LiSO3) via thermochemical method. The SBPEs with lithium salts exhibited characteristic FTIR bands starch, with slight variations in the vibration oxygen-related functional groups compared to salt-free biopolymer spectra. The RCOH/COC index (short-range crystallinity) was higher in the films synthesized without lithium salt and the lowest value was established in the films synthesized with Li2SO4. Thermal degradation involved dehydration between 40 to 110 °C and molecular decomposition between 245 to 335 °C. Degradation temperatures were close when synthesized with salts but differed in films without lithium salt. DSC revealed two endothermic processes: one around 65 °C linked to crystalline structure changes and the second at approximately 271 °C associated with glucose ring decomposition. The electrochemical behavior of the SBPEs varied with the salts used, resulting in differences in the potential and current of peaks from the redox processes and its conductivity, presenting the lowest value (8.42 × 10-5 S cm-1) in the SBPE films without salt and highest value (9.54 × 10-3 S cm-1) in the films with Li2SO4. It was concluded that the type of lithium salt used in SBPEs synthesis affected their properties. SBPEs with lithium triflate showed higher molecular ordering, thermal stability, and lower redox potentials in electrochemical processes.

Water Molecules' and Lithium Cations' Mobility in Sulfonated Polystyrene Studied by Nuclear Magnetic Resonance.

The hydration of ions and charge groups controls electro mass transfer through ion exchange systems. The self-diffusion and local mobility of water molecules as well as lithium cations in poly (4-styrenesulfonic acid) and its lithium, sodium and cesium salts were investigated for the first time using pulsed-field gradient NMR (PFG NMR) and NMR relaxation techniques. The temperature dependences of the water molecule and Li+ cation self-diffusion coefficients exhibited increasing self-diffusion activation energy in temperature regions below 0 °C, which is not due to the freezing of parts of the water. The self-diffusion coefficients of water molecules and lithium cations, as measured using PFG NMR, are in good agreement with the self-diffusion coefficients calculated based on Einstein's equation using correlation times obtained from spin-lattice relaxation data. It was shown that macroscopic water molecules' and lithium cations' transfer is controlled by local particles jumping between neighboring sulfonated groups. These results are similar to the behavior of water and cations in sulfonic cation exchanger membranes and resins. It was concluded that polystyrenesulfonic acid is appropriate model of the ionogenic part of membranes based on this polymer.

Viscoelastic Properties of Water-Absorbed Poly(methyl methacrylate) Doped with Lithium Salts with Various Anions.

We investigated the effects of water absorption on the dynamic mechanical properties of poly(methyl methacrylate) doped with various generic lithium salts, such as lithium perchlorate trihydrate (LiClO4), lithium trifluoromethanesulfonate (LiCF3SO3), lithium nonafluorobutanesulfonate (LiC4F9SO3), and lithium bis(trifluoromethanesulfonyl)imide (LiN(CF3SO2)). The rates of weight change during water absorption of lithium salt-doped samples were higher in the following order: LiClO4, LiCF3SO3, LiC4F9SO3, and LiN(CF3SO2). Interestingly, the aforementioned order was the same as the order of the terminal relaxation times in the flow region of the viscoelastic measurement in the melting-state. This implies that the water absorption of the salt-doped PMMA occurs due to the factors that affect the pinning of the PMMA molecular chains in the places.

Slow glycosylation: Activation of trichloroacetimidates under mild conditions using lithium salts and the role of counterions.

Glycosylations were carried out with the two glycosyl donors 4-O-acetyl-2,3-O-isopropylidene-1-O-trichloroacetimidoyl-α-l-rhamnopyranose and 2,3,4-tri-O-benzyl-1-O-trichloro-acetimidoyl-α-l-rhamnopyranose in combination with the two alcohols 1-adamantanol and l-menthol as model glycosyl acceptors. As catalysts, the five lithium salts LiNTf2, LiI, LiClO4, LiPF6 and LiOTf were investigated. We demonstrated that both lithium and the respective counterions are playing a role in the activation of trichloroacetimidate glycosyl donors at rt. Under these very mild conditions, the glycosylations are slow and completed in two to eight days. Depending on the counterion, the rate and yield of the reaction differs; however, the selectivity of all investigated lithium salts is deficient.

Single-Ion Lithium Conducting Polymers with High Ionic Conductivity Based on Borate Pendant Groups.

A family of single-ion lithium conducting polymer electrolytes based on highly delocalized borate groups is reported. The effect of the nature of the substituents on the boron atom on the ionic conductivity of the resultant methacrylic polymers was analyzed. To the best of our knowledge the lithium borate polymers endowed with flexible and electron-withdrawing substituents presents the highest ionic conductivity reported for a lithium single-ion conducting homopolymer (1.65×10-4  S cm-1 at 60 °C). This together with its high lithium transference number t Li + =0.93 and electrochemical stability window of 4.2 V vs Li0 /Li+ show promise for application in lithium batteries. To illustrate this, a lithium borate monomer was integrated into a single-ion gel polymer electrolyte which showed good performance on lithium symmetrical cells (<0.85 V at ±0.2 mA cm-2 for 175 h).

Utilization of Interfacial Charge Storage toward Ultra-high Capacity: Li2SO4 Sealed Micron Sized Iron Oxides as Anode for Lithium Batteries.

The interfacial charge storage is derived from spin-polarized electrons stored on the surface of iron metal nanoparticles, and reasonable utilization can achieve a capacity far beyond the traditional conversion mechanism. Generally, iron oxide is easy to crack, pulverize, and fall off due to its poor conductivity and large volume change during cycling, and causes serious side reactions with the electrolyte. Herein, this pulverization phenomenon was intentionally utilized to in situ form nano-sized iron particles and create a large number of Fe/Li2O interfaces. Specifically, a Li+ conductor like Li2SO4 was utilized to seal micron sized iron oxides and also work as an aggregation barrier. Thus, the in situ formed nanoparticles were separated from the electrolyte and could provide huge capacity through interfacial charge storage. Therefore, the specific capacity of this unique composite continues to rise upon activation cycling and finally reaches 1708 mA h g-1, which is more than twice its theoretical capacity based on the conversion mechanism. The gradually increasing interfacial charge storage capacity was also directly confirmed by X-ray photoelectron spectroscopy tests. This novel strategy provides new opportunities for the design and commercialization of advanced energy storage systems.

Controlled Experiments and Optimized Theory of Absorption Spectra of Li Metal and Salts.

Investigation of Li metal and ionic compounds through experimental and theoretical spectroscopy has been of tremendous interest due to their prospective applications in Li-metal and Li-ion batteries. Li K-edge soft X-ray absorption spectroscopy (sXAS) provides the most direct spectroscopic characterization; unfortunately, due to the low core-level energy and the highly reactive surface, Li-K sXAS of Li metal has been extremely challenging, as evidenced by many controversial reports. Here, through controlled and ultra-high energy resolution experiments of two kinds of in situ prepared samples, we report the intrinsic Li-K sXAS of Li-metal that displays a prominent leading peak that has not been revealed before. Furthermore, theoretical simulations show that, due to the low number of valence electrons in Li, the Li-K sXAS is strongly affected by the response of the valence electrons to the core hole. We successfully reproduce the Li-K sXAS by state-of-the-art calculations with considerations of a number of relevant parameters such as temperature, energy resolution, and, especially, contributions from transitions which are forbidden in the single-particle treatment. Such a comparative experimental and theoretical investigation is further extended to a series of Li ionic compounds, which highlight the importance of considering the total and single-particle energies for obtaining an accurate alignment of the spectra. Our work provides the first reliable Li-K sXAS of the Li metal surface with advanced theoretical calculations. The experimental and theoretical results provide a critical benchmark for studying Li chemistry in both metallic and ionic states.

Lithium carbonate: Updated reproductive and developmental toxicity assessment using scientific literature and guideline compliant studies.

The current publication describes most recent so far unpublished (key) guideline and GLP compliant reproductive and developmental toxicity studies of lithium carbonate in rats, including their interpretation and conclusions in terms of human hazard assessment when compared to existing literature. Particular attention was paid to the target organs and dose response of lithium ion related effects to differentiate between a primary (pharmacokinetic/pharmacodynamic) action and secondary effects as a result of systemic and target organ toxicity. In the key two-generation reproduction toxicity (OECD TG 416) study in rats, doses of 5, 15 and 45 mg/kg bw/d (0.95, 2.9 and 8.6 mg Li+/kg bw/d) were given by oral gavage, resulting in clear NOAELs of 15 mg/kg bw/d (2.9 mg Li+/kg bw/d) for systemic parental toxicity and 45 mg/kg bw/d (8.6 mg Li+/kg bw/d) for reproductive toxicity and fetal toxicity. Target organ changes were consistently observed in liver (cytoplasmic rarefaction) and kidney (dilated tubuli). In the key developmental toxicity (OECD TG 414) study in rats, doses given by oral gavage were 10, 30 and 90 mg/kg bw/d (1.9, 5.7 and 17.1 mg Li+/kg bw/d) was investigated resulting in NO(A)ELs of 30 mg/kg bw/d (5.7 mg Li+/kg bw/d) (maternal toxicity) and 90 mg/kg bw/d (17 mg Li+/kg bw/d) (fetal toxicity and teratogenicity). The highest dose of 90 mg/kg bw/day resulted in clear signs of toxicity and peak plasma concentrations at the toxic range (>1.0 mEq lithium/L). Toxic effects of lithium carbonate were not seen in the reproductive and developmental organs. No adverse effects on sperm (total motility, progressive motility and morphology of testicular and cauda epididymal sperm) were observed in the two-generation rat reproduction toxicity study. There was also no impact on fertility indices or on litter sizes in this study, nor were there any fetal effects in the two-generation reproduction toxicity and developmental toxicity study at doses causing already systemic toxicity in the dams. Secondary effects such as decreased weight (gain) and food consumption were reported in the developmental toxicity study. The absence of any reproductive/developmental findings at dose levels causing clear systemic toxicity in the test animals in these key mammalian studies, does not suggest an immediate concern for possible human reproductive or developmental toxicity effects from exposure to lithium during drug use.

Additive Effects of Lithium Salts with Various Anionic Species in Poly (Methyl Methacrylate).

We report that lithium salts in lithium-ion batteries effectively modify the physical properties of poly (methyl methacrylate) (PMMA). The glass transition temperature (Tg) is an indicator of the heat resistance of amorphous polymers. The anionic species of the salts strongly affected the glass transition behavior of PMMA. We focused on the additive effects of various lithium salts, such as LiCF3SO3, LiCOOCF3, LiClO4, and LiBr, on the Tg of PMMA. The large anions of the former three salts caused them to form macroscopic aggregates that acted as fillers in the PMMA matrix and to combine the PMMA domains, increasing Tg. On the other hand, LiBr salts dispersed microscopically in the PMMA matrix at the molecular scale, leading to the linking of the PMMA chains. Thus, the addition of LiBr to PMMA increased Tg as well as the relaxation time in the range of glass to rubber transition.