A Sodium Bis(fluorosulfonyl)imide (NaFSI)-based Multifunctional Electrolyte Stabilizes the Performance of NaNi1/3Fe1/3Mn1/3O2/hard carbon Sodium-ion Batteries.

A sodium bis(fluorosulfonyl)imide (NaFSI)-based multifunctional electrolyte is developed by partially replacing NaPF6 salt in the electrolyte to improve the wide temperature range working capability of NaNi1/3Fe1/3Mn1/3O2/hard carbon (NNFM111/HC) sodium-ion batteries (SIBs). The capacity retention of the SIBs with NaFSI-NaPF6 dual salt electrolyte increases from 47.2% to 75.5% after 250 cycles at 25 oC, and from 51.0% to 82.3% after 80 cycles at 45 oC, and the 1 C discharge capacity retention at the low temperature of -20 oC also increases 26.8%. In the single salt system, NaPF6 effectively passivate the aluminum foil and NaFSI passivate the electrode/electrolyte interface. The synergistic effect of NaPF6 and NaFSI greatly improves the battery performance in a wide temperature range. This NaFSI-based dual salt electrolyte also effectively overcomes the flaws when the SIBs using NaFSI or NaPF6 independently, and makes it more suitable for SIBs, indicating promising prospects in the commercial application of NNFM111/HC SIBs.

M335, a novel small-molecule STING agonist activates the immune response and exerts antitumor effects.

In the context of antitumor immune responses, the activation of the stimulator of interferon genes (STING) assumes a critical role and imparts enhanced immunogenicity. An effective strategy for exogenously activating the immune system involves the utilization of STING agonists, and prior investigations primarily concentrated on modifying endogenous cyclic dinucleotides (CDNs) to achieve this. Nevertheless, the practical utility of CDNs was restricted due to limitations associated with their physicochemical attributes and administration protocols. In this article, we present the discovery of a novel small-molecule agonist denoted as M335, identified through high-throughput screening using surface plasmon resonance (SPR). M335 demonstrates the ability to activate the TBK1-IRF3-IFN axis in a STING-dependent manner in vitro. Through experimentation on mouse models bearing tumors, we observed that the administration of M335 resulted in the activation of immune cells. Notably, significant antitumor effects were achieved with both intratumoral and intraperitoneal administration of M335. These findings suggest the potential of M335 as a promising agent for cancer immunotherapy, which will promote the development of STING agonists in anti-tumor applications.

A Functional Electrolyte Containing P-Phenyl Diisothiocyanate (PDITC) Additive Achieves the Interphase Stability of High Nickel Cathode in a Wide Temperature Range.

The lithium-ion batteries (LIBs) with high nickel cathode have high specific energy, but as the nickel content in the cathode active material increases, batteries are suffering from temperature limitations, unstable performance, and transition metal dissolution during long cycling. In this work, a functional electrolyte with P-phenyl diisothiocyanate (PDITC) additive is developed to stabilize the performance of LiNi0.8 Co0.1 Mn0.1 O2 (NCM811)/graphite LIBs over a wide temperature range. Compared to the batteries without the additive, the capacity retention of the batteries with PDITC-containing electrolyte increases from 23 % to 74 % after 1400 cycles at 25 °C, and from 15 % to 85 % after 300 cycles at 45 °C. After being stored at 60 °C, the capacity retention rate and capacity recovery rate of the battery are also improved. In addition, the PDITC-containing battery has a higher discharge capacity at -20 °C, and the capacity retention rate increases from 79 % to 90 % after 500 cycles at 0 °C. Both theoretical calculations and spectroscopic results demonstrate that PDITC is involved in constructing a dense interphase, inhibiting the decomposition of the electrolyte and reducing the interfacial impedance. The application of PDITC provides a new strategy to improve the wide-temperature performance of the NCM811/graphite LIBs.

A Brush-like Li-Ion Exchange Polymer as Potential Artificial Solid Electrolyte Interphase for Dendrite-Free Lithium Metal Batteries.

Artificial polymeric solid electrolyte interfaces (APSEIs) are an emerging material that enables use of a lithium metal anode as a lithium metal battery technique with high energy density. However, the poor ionic conductivity, low lithium transference number, and bad compatibity with lithium metal anode lead to a large dissipative loss of energy capacity. Here we report that, by properly constructing a brush-like structure in cellulose nanofibril (CNF) based APSEIs, a good ion-aggregation morphology with interconnected ionic conducting channels can be built, such that the Li-ion conduction in the APSEI layer becomes highly efficient. The optimal approach to constructing such an ionic highway is proved computationally using coarse-grained molecular dynamics (CGMD) simulations and implemented experimentally based on transmission electron microscopy (TEM) and atomic force microscopy (AFM). In addition, Li-ion exchange structures and hydroxyl-abundant structures endow the APSEIs with good ability to suppress dendrite growth and excellent compatibility with the anode surface.

Imidazolium-Type Poly(ionic liquid) Endows the Composite Polymer Electrolyte Membrane with Excellent Interface Compatibility for All-Solid-State Lithium Metal Batteries.

Developing a poly(ethylene oxide) (PEO)-based polymer electrolyte with high ionic conductivity and robust mechanical property is beneficial for real applications of all-solid-state lithium metal batteries (ASSLMBs). Herein, an excellent organic/inorganic interface compatibility of all-solid-state composite polymer electrolytes (CPEs) is achieved using a novel imidazolium-type poly(ionic liquid) with strong electrostatic interactions, providing insights into the achievement of highly stable CPEs. The key properties such as micromorphologies, thermal behavior, crystallinity, tLi+, mechanical property, lithium anode surficial morphology, and electrochemical performance are systematically investigated. The combined experimental and density functional theory (DFT) simulation results exhibit that the strong electrostatic interaction and ion-dipole interaction cooperated to improve the compatibility of the CPE, with a high ionic conductivity of 1.46 × 10-4 S cm-1 at 40 °C and an incredible mechanical strain of 2000% for dendrite-free and highly stable all-solid-state LMBs. This work affords a promising strategy to accelerate the development of PEO-based polymer electrolytes for real applications in ASSLMBs.

Insight into the Contribution of Nitriles as Electrolyte Additives to the Improved Performances of the LiCoO2 Cathode.

Nitriles have been successfully used as electrolyte additives for performance improvement of commercialized lithium-ion batteries based on the LiCoO2 cathode, but the underlying mechanism is unclear. In this work, we present an insight into the contribution of nitriles via experimental and theoretical investigations, taking for example succinonitrile. It is found that succinonitrile can be oxidized together with PF6- preferentially on LiCoO2 compared to the solvents in the electrolyte, making it possible to avoid the formation of hydrogen fluoride from the electrolyte oxidation decomposition, which is detrimental to the LiCoO2 cathode. Additionally, inorganic LiF and -NH group-containing polymers are formed from the preferential oxidation of succinonitrile, constructing a protective interphase on LiCoO2, which suppresses electrolyte oxidation decomposition and prevents LiCoO2 from structural deterioration. Consequently, the LiCoO2 cathode presents excellent stability under cycling and storing at high voltages.

1,2,3,4-Tetrakis(2-cyanoethoxy)butane (TCEB)-Assisted Construction of Self-Repair Electrode Interface Films to Improve the Performance of 4.5 V Pouch LiCoO2/Artificial Graphite Full Cells Operating at 45 °C.

1,2,3,4-Tetrakis(2-cyanoethoxy)butane (TCEB) is first evaluated as a functional electrolyte additive to increase the charge cutoff voltage and energy density of pouch LiCO2 (LCO)/artificial graphite (AG) lithium-ion batteries (LIBs) at a high temperature of 45 °C. The charge (0.7 C) and discharge (1 C) tests show that TCEB effectively improves the cycle stability of cells under a high charge cutoff voltage of 4.5 V. At 25 °C, the capacity retention of the cells with TCEB increases from 0.0% to 72.1% after 1200 cycles. At 45 °C, the capacity retention of the cells without TCEB after 50 cycles is close to 0.0%, while the capacity retention of the cells with TCEB is still 81.6%, even after 350 cycles. The spectroscopic characterization results demonstrate that the TCEB electrolyte additive participates in the construction of a self-repair electrode/electrolyte interface film. Subsequently, low impedance and strong protective layers are formed on the two electrode surfaces. The quantitative analysis results and a theoretical calculation also show that TCEB effectively inhibits the dissolution of Co3+ and maintains the structural integrity of electrode materials. These results indicate that TCEB endows LIBs with excellent cycle stability and is a promising electrolyte additive for the high-voltage and high-temperature conditions of LCO-based LIBs.

Tailoring Low-Temperature Performance of a Lithium-Ion Battery via Rational Designing Interphase on an Anode.

Performances of lithium-ion batteries at subambient temperatures are extremely restricted by the resistive interphases originated from electrolyte decomposition, especially on the anode surface. This work reports a novel strategy that an anode interphase of low impedance is constructed by applying an electrolyte additive dimethyl sulfite (DMS). Electrochemical measurements indicate that the as-constructed interphase provides graphite/LiNi0.5Co0.2Mn0.3O2 pouch cells with excellent low-temperature performance, outperforming the interphase constructed by 1,3,2-dioxathiolane 2,2-dioxide (DTD), a common commercially used electrolyte additive. Spectral characterizations in combination with theoretical calculations demonstrate that the improved performance is attributed to the unique molecular structure of DMS, which presents appropriate reduction activity and constructs the more stable and ionically conductive anode interphase due to the weaker combination of its reduction product with lithium ions than DTD. This rational design of interphases via an additive structure has been proven to be a low cost but rather an effective approach to tailor the performances of lithium-ion batteries.

Stabilizing a High-Voltage Lithium-Rich Layered Oxide Cathode with a Novel Electrolyte Additive.

We report a novel electrolyte additive, bis(trimethylsilyl)carbodiimide, that effectively stabilizes high-voltage lithium-rich oxide cathode. Charge/discharge tests demonstrate that even trace amounts of bis(trimethylsilyl)carbodiimide in a baseline electrolyte improve the cycling stability of this cathode significantly, either in Li-based half cells or graphite-based full cells, where the capacity retention after 200 cycles between 2 and 4.8 V at 0.5C is enhanced from 40 to 72% and 49 to 77%, respectively. Analyses using physical characterization and theoretical calculations reveal that this additive not only builds a protective film on the cathode but also eliminates detrimental hydrogen fluoride via its strong coordination with hydrogen fluoride or protons.

Lithium Bis(oxalate)borate Reinforces the Interphase on Li-Metal Anodes.

Li metal provides an ideal anode for the highest energy density batteries, but its reactivity with electrolytes brings poor cycling stability. Electrolyte additives have been employed to effectively improve the cycling stability, often with the underlying mechanism poorly understood. In this work, applying lithium bis(oxalate)borate (LiBOB) as a chemical source for a dense and protective interphase, we investigate this issue with combined techniques of electrochemical/physical characterizations and theoretical calculations. It was revealed that the solid electrolyte interphase (SEI) formed by Li and the carbonate electrolyte is unstable and responsible for the fast deterioration of the Li anode. When LiBOB is present in the electrolyte, a reinforced SEI was formed, enabling significant improvement in cycling stability due to the preferential reduction of the BOB anion over the carbonate molecules and the strong combination of its reduction products with the species from the electrolyte reduction. The effectiveness of such new SEI chemistry on the Li anode supports excellent performance of a Li/LiFePO4 cell. This approach provides a pathway to rationally design an interphase on the Li anode so that high energy density batteries could be realized.

Stabilizing LiCoO2/Graphite at High Voltages with an Electrolyte Additive.

The energy density of commercial Li-ion batteries (LIBs) using LiCoO2 is adversely affected by the limited access to the Li stored in the CoO2 lattice, which is imposed partially by the instability of carbonate-based electrolytes at potentials higher than 4.5 V. In this work, we report a novel approach to fully utilize these extra Li via simultaneously stabilizing anode and cathode interfaces with a designed additive, 4-propyl-[1,3,2]dioxathiolane-2,2-dioxide (PDTD), which strongly coordinates with Co ions dissolved in electrolytes while decomposing to form protective interphases on both cathode and anode surfaces. The Co ions present in the electrolyte deposit on the anode in the form of a coordination complex with PDTD, avoiding the formation of Co metal that will catalyze the reduction decomposition of the additive-free electrolyte. The presence of PDTD in the electrolyte enables a higher charging potential of 4.45 V for LiCoO2/graphite cells, which significantly improves the energy density and cycling stability of this cathode chemistry that has already been used extensively in commercial LIBs.

2,3,4,5,6-Pentafluorophenyl Methanesulfonate as a Versatile Electrolyte Additive Matches LiNi0.5Co0.2Mn0.3O2/Graphite Batteries Working in a Wide-Temperature Range.

An electrolyte using 2,3,4,5,6-pentafluorophenyl methanesulfonate (PFPMS) as a versatile additive is investigated through calculating the molecular orbital energies of additives and solvents and designing the electrolyte composition, and the comparative performances of LiNi0.5Co0.2Mn0.3O2/graphite cells operating in a wide-temperature range are improved. It is revealed that PFPMS can form interfacial films on both the cathode and anode surfaces, resulting in a decrease of the cell impedance and the side reactions between the active materials and electrolyte. Compared to the cells without additive of 74.9% and those with vinylene carbonate (VC) of 76.7%, the cycling retention of the cell with 1.0 wt % PFPMS reaches 91.7% after 400 cycles at room temperature. In particular, for the high-temperature storage at 60 °C for 7 d, the cell containing 1.0 wt % PFPMS exhibits optimal capacity retention of 86.3% and capacity recovery of 90.6%; for the low-temperature discharge capacity retention at -20 °C, the cell with 1.0 wt % PFPMS maintains at 66.3% at 0.5 C, while for the cells without additive and containing 1.0 wt % VC, their retention values are 55.0 and 62.1%, respectively. The excellent cycling, wide-temperature practicability, and rate capability of the cells with PFPMS demonstrate that the electrolyte with PFPMS additive is promising for applications in LiNi0.5Co0.2Mn0.3O2/graphite batteries.

Constructing Unique Cathode Interface by Manipulating Functional Groups of Electrolyte Additive for Graphite/LiNi0.6Co0.2Mn0.2O2 Cells at High Voltage.

A novel electrolyte additive, 1-(2-cyanoethyl) pyrrole (CEP), has been investigated to improve the electrochemical performance of graphite/LiNi0.6Co0.2Mn0.2O2 cells cycling up to 4.5 V vs Li/Li+. The 4.5 V cycling results present that after 50 cycles, up to 4.5 V capacity retention of the graphite/LiNi0.6Co0.2Mn0.2O2 cell is improved significantly from 27.4 to 81.5% when adding 1% CEP to baseline electrolyte (1 M LiPF6 in EC/EMC 1:2, by weight). Ex situ characterization results support the mechanism of CEP for enhancing the electrochemical performance. On one hand, the significant enhancement is ascribed to a formed superior cathode interfacial film by preferential oxidation of CEP on the cathode electrode surface suppressing electrolyte decomposition at high voltage. On the other hand, the duo Lewis base functional groups can effectively capture dissociation product PF5 from LiPF6 with the presence of an unavoidable trace amount of water or aprotic impurities in the electrolyte. Thus this mitigates the hydrofluoric acid (HF) generation that leads to the reduction of transition-metal dissolution in the electrolyte upon cycling at high voltage. The theoretical modeling suggests that CEP has a mechanism of stabilizing electrolyte via combination of -C≡N: functional group and H2O. The work presented here also shows nuclear magnetic resonance spectra analysis to prove the capability of CEP reducing HF generation and X-ray photoelectron spectroscopy analysis to observe cathode surface composition.

[Expressions of pannexin proteins in I-10 Leydig tumor cells and TM3 Leydig cells and their regulatory effect on the channel function in mice].

OBJECTIVE: To investigate the expressions of the pannexin (Panx) proteins in I-10 Leydig tumor cells and TM3 Leydig cells and their regulatory effect on the Panx channel function in mice. METHODS: The expressions of the Panx-1 and Panx-2 proteins in the mouse Leydig tumor cells were determined by Western blot. The I-10 Leydig tumor cells were treated with carbenoxolone (CBX) at 100 µmol/L or probenecid (PBN) at 200 µmol/L, the fluorescence resonance energy transfer (FRET) detected by time-lapse fluorescence imaging, and the extracellular adenosine 5'-triphosphate (eATP) level measured with the commercial detection kit. Molecular biological methods were used to interfere with shRNA and overexpress mPanx-1 the Panx-1 gene and regulate the expression and function of the Panx-1 protein. RESULTS: The expressions of Panx-1 (ï¼»289.5 ± 55.8ï¼½%) and Panx-2 (ï¼»264.5 ± 24.6ï¼½%) were significantly increased in the I-10 Leydig tumor cells as compared with those in the normal TM3 Leydig cells (both P < 0.05). FRET was remarkably reduced after treated with CBX (ï¼»87.5 ± 17.7ï¼½%) and PBN (ï¼»89.3 ± 14.3ï¼½%) in comparison with that in the control group (both P < 0.01). At 8, 16 and 24 hours, the eATP level was decreased by (57.3 ± 7.2)%, (56.4 ± 9.6)% and (63.4 ± 6.4)% in the CBX group (P < 0.01) and (61.7 ± 2.5)%, (35.8 ± 1.6)% and (13.5 ± 8.3)% in the PBN group (P < 0.01). Molecular biological treatment down-regulated the expression of Panx-1 by (38.3 ± 5.2)% and (31.8 ± 5.1)% in the shRNA1 and shRNA2 groups, respectively (both P < 0.01), but up-regulated that of Panx-1 by (128.4 ± 7.5)% in the mPanx-1 group (P < 0.01) as compared with the negative control. FRET was reduced by (72.4 ± 39.4)% in the shRNA group (P < 0.01) and the eATP level by (14.7 ± 0.1)%, (13.7 ± 0.3)% and (13.1 ± 0.3)% at 8, 16 and 24 hours, respectively (P < 0.01) while FRET elevated by (122.5 ± 17.1)% in the mPanx-1 group (P < 0.01) and the eATP level by (886.1 ± 82.1)%, (885.8 ± 83.3)% and (841.5 ± 21.8)% at 8, 16 and 24 hours, respectively (P < 0.01). CONCLUSIONS: The expressions of Panx-1 and Panx-2 are increased in I-10 mouse Leydig tumor cells, and inhibiting the Panx channel with CBX, PBN and shRNA reduces FRET and the eATP level in the I-10 cells.

3,3'-(Ethylenedioxy)dipropiononitrile as an Electrolyte Additive for 4.5 V LiNi1/3Co1/3Mn1/3O2/Graphite Cells.

3,3'-(Ethylenedioxy)dipropiononitrile (EDPN) has been introduced as a novel electrolyte additive to improve the oxidation stability of the conventional carbonate-based electrolyte for LiNi1/3Co1/3Mn1/3O2/graphite pouch batteries cycled under high voltage. Mixing 0.5 wt % EDPN into the electrolyte greatly improved the capacity retention, from 32.5% to 83.9%, of cells cycled for 100 times in the range 3.0-4.5 V with a rate of 1C. The high rate performance (3C and 5C) was also improved, while the cycle performance was similar to that of the cell without EDPN when cycled between 3.0 and 4.2 V. Further evidence of a stable protective interphase film can be formed on the LiNi1/3Co1/3Mn1/3O2 electrode surface due to the presence of EDPN in the electrolyte. This process effectively suppresses the oxidative decomposition of electrolyte and the growth in the charge-transfer resistance of the LiNi1/3Co1/3Mn1/3O2 electrode and greatly improves the high-voltage electrochemical properties for the cells. In contrast, EDPN has no positive effect on the cyclic performance of the LiNi0.5Co0.2Mn0.3O2-based cell under high operating voltage.

Selective recognition of sulfate anions in a 95% ethanol solvent with a simple neutral salicylaldehyde dansyl hydrazine Schiff base tuned by Brønsted-Lowry acid-base reaction.

A new Schiff base compound, 5-(dimethylamino)-N'-(2-hydroxybenzylidene)naphthalene-1-sulfonohydrazide (R), has been synthesized, characterized, and employed as a selective fluorescence receptor for the recognition of sulfate anions. UV-vis absorption, fluorescence emission, (1)H NMR spectra and DFT calculation studies on the system have been carried out to determine the nature of the interactions between R and anions. The results reveal that the deprotonation of the phenol without the need of a strong base leads to the formation of a hydrogen-bonding complex with a -SO2-NH- group, which is responsible for the spectra changes. The deprotonation process for the selectivity recognition of sulfate can be tuned by the Brønsted-Lowry acid-base reaction in nonaqueous solutions, revealing that suitable phenolic hydroxyl acidity is the key factor for anion recognition selectivity.

A dinuclear zinc complex with (E)-4-dimethyl-amino-N'-(2-hy-droxy-benzyl-idene)benzohydrazide.

The title compound, bis-[µ-(E)-2-({2-[4-(dimethyl-amino)-benzo-yl]hydrazinyl-idene}meth-yl)phenolato]bis-[formato-zinc], [Zn(2)(C(16)H(16)N(3)O(2))(2)(CHO(2))(2)], is a dinuclear Zn(II) complex containing two Zn(II) cations, two monovalent anions of a Schiff base ligand, 4-dimethyl-amino-N'-(2-hy-droxy-benzyl-idene)benzohydrazide (L), and two formate ions. Each Zn(II) atom chelates with the hy-droxy O atom of salicyl-aldehyde, the imine N atom, the carbonyl O atom, the formate carboxyl-ate O atom and the hy-droxy O atom of the salicyl-aldehyde moiety in a symmetry-related unit. The five-coordinate Zn(II) atoms form a dimeric centrosymmetric unit with a central parallelepiped Zn(2)O(2) core and parallel faces derived from the Schiff base ligands. The crystal packing is stabilized by inter-molecular N-H⋯O hydrogen bonds between the amide N atom and the formate carboxyl-ate O atom.