Designer Lithium Reservoirs for Ultralong Life Lithium Batteries for Grid Storage.

The minimization of irreversible active lithium loss stands as a pivotal concern in rechargeable lithium batteries, particularly in the context of grid-storage applications, where achieving the utmost energy density over prolonged cycling is imperative to meet stringent demands, notably in terms of life cost. Departing from conventional methodologies advocating electrode prelithiation and/or electrolyte additives, a new paradigm is proposed here: the integration of a designer lithium reservoir (DLR) featuring lithium orthosilicate (Li4SiO4) and elemental sulfur. This approach concurrently addresses active lithium consumption through solid electrolyte interphase (SEI) formation and mitigates minor yet continuous parasitic reactions at the electrode/electrolyte interface during extended cycling. The remarkable synergy between the Li-ion conductive Li4SiO4 and the SEI-favorable elemental sulfur enables customizable compensation kinetics for active lithium loss throughout continuous cycling. The introduction of a minute quantity of DLR (3 wt% Li4SiO4@S) yields outstanding cycling stability in a prototype pouch cell (graphite||LiFePO4) with an ampere-hour-level capacity (≈2.3 Ah), demonstrating remarkable capacity retention (≈95%) even after 3000 cycles. This utilization of a DLR is poised to expedite the development of enduring lithium batteries for grid-storage applications and stimulate the design of practical, implantable rechargeable batteries based on related cell chemistries.

Volatile metabolomics reveals the characteristics of the unique flavor substances in oats.

Oats is a cereal well known for its high nutritional value and unique flavor. This study investigated the metabolomics data from oats, wheat, and barley using broadly targeted GC-MS metabonomic techniques. A total of 437 volatile organic compounds (VOCs) were identified, of which 414 were shared metabolites, with three metabolites unique to oats. Three hundred and seven differentially accumulated metabolites (DAMs) were screened from all the comparison groups, of which 27 metabolites were shared by oats and barley, and 121 shared by oats and wheat. Terpenoids and esters were the key metabolites determining the differences in flavor. A KEGG analysis indicated that the alpha-linolenic acid and phenylalanine pathways were the most significant metabolic pathways. The 42 DAMs found may be the main substances leading to the flavor differences between the different varieties. Overall, this study reveals the main reasons for the unique flavor of oats through metabolomic evidence.

Domino Reactions Enabling Sulfur-Mediated Gradient Interphases for High-Energy Lithium Batteries.

Silicon (Si)-based anodes are currently considered a feasible solution to improve the energy density of lithium-ion batteries owing to their sufficient specific capacity and natural abundance. However, Si-based anodes exhibit low electric conductivities and large volume changes during cycling, which could easily trigger continuous breakdown/reparation of the as-formed solid-electrolyte-interphase (SEI) layer, seriously hampering their practical application in current battery technology. To control the chemoelectrochemical instability of the conventional SEI layer, we herein propose the introduction of elemental sulfur into nonaqueous electrolytes, aiming to build a sulfur-mediated gradient interphase (SMGI) layer on Si-based anodes. The SMGI layer is generated through the domino reactions (i.e., electrochemical cascade reactions) involving the electrochemical reductions of elemental sulfur followed by nucleophilic substitutions of fluoroethylene carbonate, which endows the corresponding SEI layer with strong elasticity and chemomechanical stability and enables rapid transportation of Li+ ions. Consequently, the prototype Si||LiNi0.8Co0.1Mn0.1O2 cells attain a high-energy density of 622.2 W h kg-1 and a capacity retention of 88.8% after 100 cycles. Unlike previous attempts based on sophisticated chemical modifications of electrolyte components, this study opens a new avenue in interphase design for long-lived and high-energy rechargeable batteries.

Electrolysis Process-Facilitated Engineering of Primary Particles of Cobalt-Free LiNiO2 for Improved Electrochemical Performance.

The particle morphology of LiNiO2 (LNO), the final product of Co-free high-Ni layered oxide cathode materials, must be engineered to prevent the degradation of electrochemical performance caused by the H2-H3 phase transition. Introducing a small amount of dopant oxides (Nb2O5 as an example) during the electrolysis synthesis of the Ni(OH)2 precursor facilitates the engineering of the primary particles of LNO, which is quick, simple, and inexpensive. In addition to the low concentration of Nb that entered the lattice structure, a combination of advanced characterizations indicates that the obtained LNO cathode material contains a high concentration of Nb in the primary particle boundaries in the form of lithium niobium oxide. This electrolysis method facilitated LNO (EMF-LNO) engineering successfully, reducing primary particle size and increasing particle packing density. Therefore, the EMF-LNO cathode material with engineered morphology exhibited increased mechanical strength and electrical contact, blocked electrolyte penetration during cycling, and reduced the H2-H3 phase transition effects.

Expandable Li Percolation Network: The Effects of Site Distortion in Cation-Disordered Rock-Salt Cathode Material.

Cation-disordered rock-salt (DRX) materials receive intensive attention as a new class of cathode candidates for high-capacity lithium-ion batteries (LIBs). Unlike traditional layered cathode materials, DRX materials have a three-dimensional (3D) percolation network for Li+ transportation. The disordered structure poses a grand challenge to a thorough understanding of the percolation network due to its multiscale complexity. In this work, we introduce the large supercell modeling for DRX material Li1.16Ti0.37Ni0.37Nb0.10O2 (LTNNO) via the reverse Monte Carlo (RMC) method combined with neutron total scattering. Through a quantitative statistical analysis of the material's local atomic environment, we experimentally verified the existence of short-range ordering (SRO) and uncovered an element-dependent behavior of transition metal (TM) site distortion. A displacement from the original octahedral site for Ti4+ cations is pervasive throughout the DRX lattice. Density functional theory (DFT) calculations revealed that site distortions quantified by the centroid offsets could alter the migration barrier for Li+ diffusion through the tetrahedral channels, which can expand the previously proposed theoretical percolating network of Li. The estimated accessible Li content is highly consistent with the observed charging capacity. The newly developed characterization method here uncovers the expandable nature of the Li percolation network in DRX materials, which may provide valuable guidelines for the design of superior DRX materials.

Staphylococcus aureus induces mitophagy to promote its survival within bovine mammary epithelial cells.

Mitophagy occurs in a variety of pathogenic infections. However, the role of mitophagy in the intracellular survival of Staphylococcus aureus (S.aureus) within bovine mammary epithelial cells (BMECs) and which molecules specifically mediate the induction of mitophagy remains unclear. Therefore, this study aims to investigate the role and mechanism of mitophagy in the intracellular survival of S.aureus. Here, we reported that S.aureus induced complete mitophagy to promote its survival within BMECs. The further mechanistic study showed that S. aureus induced mitophagy by activating the p38-PINK1-Parkin signaling pathway. These findings expand our knowledge of the intracellular survival mechanism of S.aureus in the host and provide a desirable therapeutic strategy against S.aureus and other intracellular infections.

Anion-enrichment interface enables high-voltage anode-free lithium metal batteries.

Aggressive chemistry involving Li metal anode (LMA) and high-voltage LiNi0.8Mn0.1Co0.1O2 (NCM811) cathode is deemed as a pragmatic approach to pursue the desperate 400 Wh kg-1. Yet, their implementation is plagued by low Coulombic efficiency and inferior cycling stability. Herein, we propose an optimally fluorinated linear carboxylic ester (ethyl 3,3,3-trifluoropropanoate, FEP) paired with weakly solvating fluoroethylene carbonate and dissociated lithium salts (LiBF4 and LiDFOB) to prepare a weakly solvating and dissociated electrolyte. An anion-enrichment interface prompts more anions' decomposition in the inner Helmholtz plane and higher reduction potential of anions. Consequently, the anion-derived interface chemistry contributes to the compact and columnar-structure Li deposits with a high CE of 98.7% and stable cycling of 4.6 V NCM811 and LiCoO2 cathode. Accordingly, industrial anode-free pouch cells under harsh testing conditions deliver a high energy of 442.5 Wh kg-1 with 80% capacity retention after 100 cycles.

High-Entropy Microdomain Interlocking Polymer Electrolytes for Advanced All-Solid-State Battery Chemistries.

All-solid-state polymer electrolytes (ASPEs) with excellent processivity are considered one of the most forward-looking materials for large-scale industrialization. However, the contradiction between improving the mechanical strength and accelerating the ionic migration of ASPEs has always been difficult to reconcile. Herein, a rational concept is raised of high-entropy microdomain interlocking ASPEs (HEMI-ASPEs), inspired by entropic elasticity well-known in polymer and biochemical sciences, by introducing newly designed multifunctional ABC miktoarm star terpolymers into polyethylene oxide for the first time. The tailor-made HEMI-ASPEs possess multifunctional polymer chains, which induce themselves to assemble into micro- and nanoscale dynamic interlocking networks with high topological structure entropy. HEMI-ASPEs achieve excellent toughness, considerable ionic conductivity, an appreciable lithium transference number (0.63), and desirable thermal stability (Td  > 400 °C) for all-solid-state lithium metal batteries. The Li|HEMI-ASPE-Li|Li symmetrical cell shows a stable Li plating/stripping performance over 4000 h, and a LiFePO4 |HEMI-ASPE-Li|Li full cell exhibits a high capacity retention (≈96%) after 300 cycles. This work contributes an innovative design concept introducing high-entropy supramolecular dynamic networks for ASPEs.

Bilayer Halide Electrolytes for All-Inorganic Solid-State Lithium-Metal Batteries with Excellent Interfacial Compatibility.

Inorganic solid-state electrolytes (ISSEs) have been extensively researched as the critical component in all-solid-state lithium-metal batteries (ASSLMBs). Many ISSEs exhibit high ionic conductivities up to 10-3 S cm-1. However, most of them suffer from poor interfacial compatibility with electrodes, especially lithium-metal anodes, limiting their application in high-performance ASSLMBs. To achieve good interfacial compatibility with a high-voltage cathode and a lithium-metal anode simultaneously, we propose Li3InCl6/Li2OHCl bilayer halide ISSEs with complementary advantages. In addition to the improved interfacial compatibility, the Li3InCl6/Li2OHCl bilayer halide ISSEs exhibit good thermal stability up to 160 °C. The Li-symmetric cells with sandwich electrolytes Li2OHCl/Li3InCl6/Li2OHCl exhibit long cycling life of over 300 h and a high critical current density of over 0.6 mA cm-2 at 80 °C. Moreover, the all-inorganic solid-state lithium-metal batteries (AISSLMBs) LiFePO4-Li3InCl6/Li3InCl6/Li2OHCl/Li fabricated by a facile cold-press method exhibit good rate performance and long-term cycling stability that stably cycle for about 3000 h at 80 °C. This work presents a facile and cost-effective method to construct bilayer halide ISSEs, enabling the development of high-performance AISSLMBs with good interfacial compatibility and thermal stability.

Anion Donicity of Liquid Electrolytes for Lithium Carbon Fluoride Batteries.

The increasing demand for high-energy powers have greatly incentivized the development of lithium carbon fluoride (Li||CFx ) cells. Five kinds of non-aqueous liquid electrolytes with various kinds of lithium salts (LiX, X=PF6 - , TFSI- , BF4 - , ClO4 - , and CF3 SO3 - ) were comparatively studied. Intriguingly, the LiBF4 -based electrolyte show relatively moderate ionic conductivities; yet, the corresponding Li||CFx cells deliver the highest discharge capacities among them. A combination of morphological and compositional analyses of the discharge CFx cathode suggest that the moderate donicity of BF4 - anion is accountable for favoring the breakdown of C-F bonds, and subsequently forming crystalline lithium fluoride as the main discharge products. This work brings not only fresh understanding on the role of salt anions for Li||CFx cells, but also inspire the electrolyte design for other conversion-type (sulfur and/or organosulfur) cathode materials desired for high-energy applications.

Designer Cathode Additive for Stable Interphases on High-Energy Anodes.

Rechargeable lithium-based batteries built with high-energy anode materials (e.g., silicon-based and silicon-derivative materials) are considered a feasible solution to satisfy the stringent requirements imposed by emerging markets, including electric vehicles and grid storage, due to their higher energy density compared to contemporary lithium-ion batteries. The robustness of the solid electrolyte interphase (SEI) layer on high-energy anodes is critical to achieve long-term and stable cycling performances of the batteries. Herein, we propose a new type of designer cathode additive (DCA), i.e., an ultrathin coating layer of elemental sulfur on the cathode, for the in situ formation of a thin and robust SEI layer on various types of high-energy anodes. The DCA elemental sulfur undergoes simultaneous oxidation and reduction paths, forming lithium alkyl sulfate (R-OSO2OLi) and poly(ethylene oxide) (PEO)-like polymers on the anode surface. The as-formed R-OSO2OLi/PEO-modified SEI layer has good lithium cation (Li+) permeability to facilitate fast ion transportation across the interphases and superior elasticity to adapt to large volume changes, which is particularly effective for improving the cycling efficiency of high-energy anodes (e.g., ca. 14-35% increase in capacity retention for the silicon-carbon composite (SiC) or silicon-tin alloy (Si-Sn)||LiFePO4 cells). The present work opens a new avenue toward the practical deployment of high-energy rechargeable lithium-based batteries.

Rational design of a topological polymeric solid electrolyte for high-performance all-solid-state alkali metal batteries.

Poly(ethylene oxide)-based solid-state electrolytes are widely considered promising candidates for the next generation of lithium and sodium metal batteries. However, several challenges, including low oxidation resistance and low cation transference number, hinder poly(ethylene oxide)-based electrolytes for broad applications. To circumvent these issues, here, we propose the design, synthesis and application of a fluoropolymer, i.e., poly(2,2,2-trifluoroethyl methacrylate). This polymer, when introduced into a poly(ethylene oxide)-based solid electrolyte, improves the electrochemical window stability and transference number. Via multiple physicochemical and theoretical characterizations, we identify the presence of tailored supramolecular bonds and peculiar morphological structures as the main factors responsible for the improved electrochemical performances. The polymeric solid electrolyte is also investigated in full lithium and sodium metal lab-scale cells. Interestingly, when tested in a single-layer pouch cell configuration in combination with a Li metal negative electrode and a LiMn0.6Fe0.4PO4-based positive electrode, the polymeric solid-state electrolyte enables 200 cycles at 42 mA·g-1 and 70 °C with a stable discharge capacity of approximately 2.5 mAh when an external pressure of 0.28 MPa is applied.

A Better Choice to Achieve High Volumetric Energy Density: Anode-Free Lithium-Metal Batteries.

Volumetric energy density is a critical but easily neglected index of lithium-metal batteries (LMBs). Compared with gravimetric energy density, the volumetric energy density (VED) of LMBs is much more sensitive to the anode/cathode (A/C) ratio due to the low density of lithium (Li) metal and the volume expansion of the Li-metal anode owing to its pulverization during cycles. Anode-free LMBs (AF-LMBs) have high theoretical VED due to the absence of an anode and high retention with relatively low cell expansion. Because Li plating highly depends on the mother substrate, Li plating on copper (Cu) substrates is more reversible and denser than that on Li substrates during cycling, which is beneficial for maintaining high volumetric capacity and efficient Li utilization. Therefore, considering that excess Li must be strictly limited to achieve competitive energy density, AF-LMBs (with bare Cu foil as the anode current collector) for high-volumetric-density batteries are recommended.

Raising the Intrinsic Safety of Layered Oxide Cathodes by Surface Re-Lithiation with LLZTO Garnet-Type Solid Electrolytes.

Battery safety concerns are becoming more and more prominent with the increasing demands of lithium-ion batteries (LIBs) with higher energy density. The greatest threat to battery safety derives from the easy release of oxygen from the high-capacity layered oxide cathodes at highly delithiated states and subsequent exothermic reactions with reductive agents in batteries. Herein, it is demonstrated that solid electrolyte Li6.5 La3 Zr1.5 Ta0.5 O12 (LLZTO) can supply lithium ions to re-lithiate the charged LiCoO2 at elevated temperatures. Such a re-lithiation process can lower the state-of-charge of LiCoO2 , and thus, inherently postpones its structural decomposition and the associated release of oxygen during the heating process. The LiCoO2 /graphite full cell with 1 wt% addition of LLZTO demonstrates remarkably enhanced safety performances. This work proposes a strategy that through the adoption of solid electrolytes to solve safety issues raised from both flammable liquid electrolytes and high capacity cathodes, to achieve intrinsically safe LIBs or solid-state batteries.

Aqueous interphase formed by CO2 brings electrolytes back to salt-in-water regime.

Super-concentrated water-in-salt electrolytes make high-voltage aqueous batteries possible, but at the expense of high cost and several adverse effects, including high viscosity, low conductivity and slow kinetics. Here, we observe a concentration-dependent association between CO2 and TFSI anions in water that reaches maximum strength at 5 mol kg-1 LiTFSI. This TFSI-CO2 complex and its reduction chemistry allow us to decouple the interphasial responsibility of an aqueous electrolyte from its bulk properties, hence making high-voltage aqueous Li-ion batteries practical in dilute salt-in-water electrolytes. The CO2/salt-in-water electrolyte not only inherits the wide electrochemical stability window and non-flammability from water-in-salt electrolytes but also successfully circumvents the numerous disadvantages induced by excessive salt. This work represents a deviation from the water-in-salt pathway that not only benefits the development of practical aqueous batteries, but also highlights how the complex interactions between electrolyte components can be used to manipulate interphasial chemistry.

Electrolyzed Ni(OH)2 Precursor Sintered with LiOH/LiNiO3 Mixed Salt for Structurally and Electrochemically Stable Cobalt-Free LiNiO2 Cathode Materials.

Cobalt-free LiNiO2 cathode materials offer a higher energy density at a lower cost than high Co-containing cathode materials. However, Ni(OH)2 precursors for LiNiO2 cathodes are traditionally prepared by the coprecipitation method, which is expensive, complex, and time-consuming. Herein, we report a fast, facile, and inexpensive electrolysis process to prepare a Ni(OH)2 precursor, which was mixed with LiOH/LiNO3 salts to obtain a LiNiO2 cathode material. A combination of advanced characterization techniques revealed that the LiNiO2 cathode material prepared in this way exhibited an excellent layered structure with negligible Li/Ni site mixing and surface structural distortion. Electrochemical cycling of the LiNiO2 cathode material showed an initial discharge capacity of 235.2 mA h/g and a capacity retention of 80.2% after 100 cycles (at 1 C) between 2.75 and 4.3 V. The degradation of the cycling performance of the LiNiO2 cathode material was mainly attributed to the formation of a surface solid-electrolyte interface and a ∼5 nm rock salt-like structure, while the bulk structure of the cathode after cycling was generally stable.

Amorphous Redox-Rich Polysulfides for Mg Cathodes.

The lack of appropriate cathodes is restraining the advances of Mg batteries. Crystalline cathode materials suffer from sluggish reaction kinetics and low-capacity delivery. The finite type of crystalline structure further confines the rational design of cathode materials. Herein, we proposed amorphization and anion enrichment as a brand-new strategy to not only enhance the solid-state ion diffusion and provide more ion-storage sites in amorphous structure but also contribute to the local transfer of multiple electrons through the additional anionic redox centers. Accordingly, a series of amorphous titanium polysulfides (a-TiS x , x = 2, 3, and 4) were designed, which significantly outperformed their crystalline counterparts and achieved a highly competitive energy density of ∼260 Wh/kg. The unique Mg2+ storage mechanism involves the dissociation/formation of S-S bonds and changes in the coordination number of Ti, namely, a mixture of conversion and intercalation reaction, accompanied by the joint cationic (Ti) and anionic (S) redox-rich chemistry. Our proposed amorphous and redox-rich design philosophy might provide an innovative direction for developing high-performance cathode materials for multivalent-ion batteries.

Comprehensive Analysis of the Expression and Prognosis for E2Fs in Human Clear Cell Renal Cell Carcinoma.

Background: E2F transcription factors is a family of transcription factors, and lots of studies have shown that they play a key role in the occurrence and development of many tumors. However, the association between expression, prognostic value, and immune infiltration in the tumor microenvironment of the eight E2Fs members in ccRCC is still unclear. Method: s. We used online databases, such as ONCOMINE, UALCAN, Kaplan-Meier plotter, GEPIA, Metascape, TIMER, and cBioPortal, to analyze the effect of mRNA expression of E2Fs family members in ccRCC on the prognosis of patients and the relationship with immune infiltration. Results: Except for E2F5, other seven members of the family of E2Fs mRNA expression levels in ccRCC tissues were significantly higher than control tissues. And the high expression of E2Fs mRNA in ccRCC patients was related to cancer stage and tumor grade. Survival analysis results suggested that elevated mRNA expression levels of E2F1/2/3/4/7/8 were significantly related to the shorter overall survival (OS) in ccRCC patients (P = 3.9E - 06), while high mRNA expression of E2F6 is not related to OS (P = 0.061). Mutations of E2Fs were correlated with shorter OS of ccRCC patients (P = 7.094E - 5). In addition, mRNA expression of E2F1/2/3/4/7/8 was positively correlated with infiltration of six types of immune cells, including B cells, CD8+ T cells, CD4+ T cells, macrophages, neutrophils, and dendritic cells. Conclusions: These results indicate that E2F1/2/3/4/7/8 may be used as a prognostic marker for the survival of ccRCC patients and laid the foundation for studying the immune infiltration role of E2Fs family members in tumors.

Reaction Mechanisms of Ta-Substituted Cubic Li7La3Zr2O12 with Solvents During Storage.

The reactivity of garnet solid electrolytes toward humid air hinders their practical application despite their attractive, superior properties such as high Li+ conductivity and wide electrochemical window. Sealing garnets with organic solvents can not only prevent them from reacting with humid air but also render them compatible with other processing technologies. Therefore, the chemical and structural stability of garnets in organic solvents must be studied. In this study, we selected several commonly used organic solvents with different representative functional groups to investigate their stability with garnets and reaction mechanisms. The experiments and theoretical calculations revealed that all of the solvents reacted with garnets through Li-H exchange, and solvent acidity determined the reaction strength. Furthermore, the solvent acidity was closely correlated to the functional groups connected to H atoms, which can affect charge distribution. Solvents or the tautomer of the solvents with hydroxyl groups such as alcohol, acetone, and N-methyl pyrrolidone, which are relatively more acidic, can lead to a violent reaction with changes in the lattice parameters of garnets. Ether compounds and saturated aliphatic hydrocarbons with relatively low acidity are highly stable against garnets. The proposed reaction mechanisms and rules may help in selecting appropriate solvents for different applications of garnets.