Currently, lithium-oxygen batteries (LOBs) suffer from unstable electrolytes, sluggish oxygen reaction kinetics, and lithium anode corrosion. This work systematically investigates propylene oxide and its halide additives, particularly epichlorohydrin (ECH), to modulate solid-liquid-gas interfaces and electrolyte properties. ECH enhances Li+ diffusion, alters Li-O reaction pathways, and suppresses Li dendrite growth. Batteries with ECH achieve an ultralow initial overpotential (similar to 0.2 V), a high discharge capacity of 11752 mAh g(-1), and over 40 cycles at a limited capacity of 1000 mAh g(-1). Combined DFT and experimental studies reveal that ECH regulates Li+ solvation, participates in forming a protective anode SEI layer, and leads to a new discharge product, ECH & centerdot;LiO2, reducing the initial overpotential to 0.16 V. This work reveals the synergistic mechanism of multifunctional electrolyte additives, offering a feasible path to achieve LOBs with long cycle life and high energy density.
Silicon, as a promising candidate for anode materials of next-generation lithium-ion batteries with high energy density, has suffered from severe capacity degradation and unstable solid electrolyte interface induced by the huge volume change during cycling. Employing yolk-shell design has been demonstrated as an effective strategy to alleviate this issue by incorporating void spaces and an electrolyte blocking layer into the structure. However, introduction of void spaces inevitably reduces the volumetric capacity of Si anodes. Herein, a rational yolk-shell structure with tailored void spaces targeting the expansion behaviors of polycrystalline silicon has been designed that achieved high void space utilization upon lithiation via a novel water-etching approach. Uniform and welldefined void spaces were formed in the one-step water etching process that accommodated the quasi-isotropic expansion of polycrystalline silicon nanoparticles with minimal redundant void spaces. The yolk-shell structure remained intact during cycling that enabled a stable solid electrolyte interface to be formed on the conformal double-walled shell. Such engineered yolk-shell endowed the Si-based anodes with maximized void space utilization and constant structural integrity, delivered a high volumetric capacity (1773 mAh cm- 3), an outstanding cycling stability (capacity retention of 90.4% after 1000 cycles), and a remarkable coulombic efficiency (99.88%).
PurposeNon-small cell lung cancer (NSCLC), including lung adenocarcinoma (LUAD) and lung squamous cell carcinoma (LUSC), exhibits marked tumor heterogeneity and poor prognosis. Metabolic reprogramming is a hallmark of cancer, and long non-coding RNAs (lncRNAs) have emerged as important regulators of tumor metabolism and immune interactions. This study aimed to systematically characterize metabolism-related lncRNAs in NSCLC using single-cell and bulk transcriptomic data, and to evaluate their associations with tumor heterogeneity, immune microenvironment, and clinical outcomes.MethodsRNA sequencing and clinical data for LUAD and LUSC were obtained from The Cancer Genome Atlas. Metabolism-related lncRNAs were identified through partial correlation analysis combined with KEGG pathway-based gene set enrichment analysis. Tumor microenvironment characteristics were assessed using CIBERSORTx. Consensus clustering based on the top 20 metabolism-related lncRNAs was applied to define molecular subtypes. Cis- and trans-regulatory relationships were explored using Spearman correlation, and competing endogenous RNA networks were constructed by integrating TargetScan-predicted miRNA-mRNA interactions. Findings were validated across six independent datasets, and single-cell transcriptomic data were used to assess cell-type-specific expression patterns.ResultsA subset of metabolism-related lncRNAs was significantly enriched among differentially expressed and survival-associated lncRNAs in NSCLC. AL365181.2 was identified as a key lncRNA associated with multiple metabolic pathways and poor prognosis. Single-cell analysis revealed immune cell-specific expression patterns, particularly in B cells, CD8+ T cells, and natural killer cells. Metabolic lncRNA-based clustering defined distinct molecular subtypes with significant differences in immune profiles and clinical outcomes.ConclusionsMetabolism-related lncRNAs contribute substantially to tumor heterogeneity and prognosis in NSCLC and may serve as valuable biomarkers for patient stratification and personalized therapeutic strategies.
SiO2-based anode materials for lithium-ion batteries are attracting extensive attention due to their comprehensive advantages. As reported, when being modified with transition metals (TMs) via physical mixing, doping, or forming silicates, the lithium storage performance of SiO2 is significantly improved. However, the specific role of transition metals remains a subject of debate without a unified conclusion. This work employs density functional theory calculations to systematically study how representative TMs (Mn, Fe, Co, Ni, Cu, and Zn) modulate the surface electronic structure and lithium storage reactivity of α-SiO2 and β-SiO2. Co, Fe, and Ni significantly alter the electronic structure, enhancing the conductivity and lithium storage activity of α-SiO2 and β-SiO2. The strong hybridization between the 3d orbitals of TMs and the 2p orbitals of neighboring O atoms drives charge transfer from O atoms to the metals, forming localized electron accumulation regions and elongating the weakened Si-O bond. The charge redistribution effectively narrows the bandgap of SiO2 (e.g., reducing it to ~0.2 eV for Co), imparting a metallic-like conductivity, significantly improving charge-transport efficiency. The Li+ adsorption energy is strengthened to >0.5 eV (TM-α-SiO2) and >0.4 eV (TM-β-SiO2), while migration barrier is reduced to ~1 eV (TM-α-SiO2) and ~2 eV (TM-β-SiO2).
Electrochemical-thermally activated chemical (E-TAC) water splitting is an emerging hydrogen production technology. It temporally decouples hydrogen/oxygen evolution by electrochemically charging the anode without oxygen evolution and regenerating it via thermally activated water oxidation, theoretically enabling >100% electrolyzer efficiencies on a higher heating value (HHV) basis. However, limited charge capacity and sluggish water oxidation kinetics of conventional Ni(OH)2-based anodes have impeded their application. This work presents a high-performance E-TAC water splitting anode consisting of hierarchical NiCo/[Ni,Co](OH)2 composites. Vertically grown [Ni,Co](OH)2 nanoplates on a porous conductive NiCo alloy scaffold ensure high accessibility of the active hydroxide phase. The optimized electrode delivers a specific charge capacity 213% higher than pure [Ni,Co](OH)2 without oxygen evolution due to faster charge transfer kinetics. In repeated cycling tests at 50 mA cm−2, it achieves an energy efficiency of 103% based on electrical input and maintains a regeneration efficiency more than double that of pure [Ni,Co](OH)2. Kinetic analysis shows an exceptionally low apparent activation energy of 15.8 kJ mol−1 for the regeneration of NiCo/[Ni,Co](OH)2, suggesting enhanced reaction kinetics and reactant diffusion. This work provides insights into the mechanism of enhancing the performance of the anode materials and demonstrates a viable method of fabricating practical electrodes for E-TAC water splitting.
Metal-supported protonic ceramic fuel cells (PCFCs) require dense proton-conducting electrolyte films fabricated at reduced temperatures to avoid oxidation and degradation of metallic substrates during conventional high-temperature sintering. Here, a fast radio-frequency magnetron sputtering (RF-MS) process is developed to directly deposit dense BaZr0.Ce-1(0).Y-7(0).Yb-1(0).O-1(3-)delta (BZCYYb) electrolyte films at room temperature without post-deposition high-temperature sintering. By optimizing sputtering power and deposition geometry, deposition rates up to similar to 2.2 mu m h(-1) are achieved, among the highest reported for proton-conducting ceramic films prepared by magnetron sputtering. The as-deposited films are dense and crack-free and undergo controlled crystallization during subsequent moderate thermal treatment associated with cathode sintering. PCFCs fabricated with RF-MS BZCYYb electrolytes exhibit open-circuit voltages above 1.0 V and peak power densities of 491 mW cm(-2) for ceramic anode-supported cells and 442 mW cm(-2) for Ni-Fe metal-supported cells at 700 degrees C, comparable to those produced via conventional wet-coating and high-temperature sintering routes. Stable operation over 100 h under constant current load is also demonstrated. These results highlight fast RF-MS as an efficient and scalable strategy for low-temperature fabrication of high-quality proton-conducting electrolyte films, offering a promising pathway for metal-supported PCFCs and other protonic ceramic electrochemical devices.
Efficient bifunctional electrocatalysts for Li-O-2 batteries can optimize the generation and decomposition of LiOx, but it is challenging to design and optimize catalyst components and structures to ensure both catalytic performance and stability. Herein, we propose a strategy to design and explore mixed-valent catalysts via catalyst self-regulation within the cell and to investigate their working mechanism through experiments and computations, using Sn as a case study. Unlike conventional catalysts with nanostructures and complex compositions, micrometer-sized Sn (micro-Sn) is used as a catalyst with large particles (0.5-3.0 mu m) and smooth surfaces. After an activation process, it presents a low charge plateau of similar to 3.6 V. Ex-situ techniques confirm the Li-O reaction mechanism of the activated micro-Sn, where ultrathin SnOx/SnO2 nanolayers (similar to 10 nm thick) grow on micro-Sn. The density functional theory calculation shows that SnOx and SnO2 boost the oxygen reduction and evolution reactions, respectively, yielding film-like and network-like LiOx. Therefore, the performance is greatly improved. Moreover, the mixed-valent Sn@SnOx/SnO2 is obtained outside the cell by thermal oxidation, showing similar, and even better, performance without the activation process. This result further verifies the catalytic effect of Sn@SnOx/SnO2 and expands the preparation routes of catalysts with similar components and structures.
Solid-state polymer electrolytes in lithium-metal batteries face significant challenges, including interfacial contact, ion-transport kinetics, and electrode-side reactions. Although conventional in-situ curing strategies partially alleviate interfacial contact issues, the random initiation of polymerization and the poor stability remain unresolved. Herein, we propose an electrode/electrolyte interface film-induced in-situ curing (IFIC) strategy via site-specific polymerization during the pre-cycling. An azo-based initiator (azobisisobutyronitrile) and its reactive derivatives are directionally distributed within the interface films on both the anode and the cathode, guiding the spatially selective polymerization of monomers at the electrode/electrolyte interface, resulting in a solid-state electrolyte with uniform structure and excellent interfacial compatibility. Various electrochemical tests, characterization, and computational simulations are combined to systematically elucidate the polymerization process and the correlation between interfacial chemical composition, microstructural evolution, and battery performance. An inorganic-organic composite interface layer is formed on the anode, significantly enhancing Li+ transport and uniform Li deposition/stripping. The Li||LiFePO4 battery assembled using this IFIC strategy maintains an exceptionally thin (similar to 7 nm), uniform, and intact interface layer on the cathode after hundreds of cycles, with 90.0% capacity retention at 1C after 1000 cycles.
The limited theoretical capacity and rate performance of graphite-based anodes are increasingly struggling to meet the growing demands of electric vehicles, aircraft, and smart grids. Combining SiOx with graphite is recognized as an effective strategy to enhance the comprehensive battery performance. However, the inherently low initial coulombic efficiency and sluggish lithiation kinetics of SiOx significantly hinder its advantages and practical applications. This work constructs a novel double-core-shelled G@Ni2SiO4-Ni@C material by in situ growth of Ni2SiO4 nanolayers (<15 nm thick) and Ni(OH)2 nanoplates (<8 nm), followed by pyrolytic carbon encapsulation of pitch. SEM, TEM, EDS, XRD, XPS, and TGA provide an adequate characterization of the formation trajectory. Benefiting from the unique double core-shell structure and Ni catalysis, G@Ni2SiO4-Ni@C exhibits superior lithium storage performance, with an initial coulombic efficiency of 87.2% at 500 mA/g, much higher than that of the Ni-free sample (63.9%); the reversible capacity after 1000 cycles is 585.6 mAh/g (1.57 times the theoretical capacity of graphite), with a capacity retention of 115.8%. Ex-situ XPS and density functional theory calculations reveal the role of Ni in activating Li-Si-O and Li-O bonds and enhancing interfacial electronic transport, thereby enabling the release of more Li+ ions and improving rate performance.
Silicon's potential as a lithium-ion battery (LIB) anode is limited by extensive volume expansion, low intrinsic electrical conductivity, and high interfacial reactivity of lithium silicide (LixSi). Herein, we present a novel molten-assisted etching strategy that enables the construction of a potentially porous silicon framework with a spatially controlled gradient boron distribution. By utilizing molten boron oxide (B2O3) as both an etchant and a boron source, a one-step high-temperature reaction simultaneously induces pore formation and generates an in situ boron-rich silicide (SiBx) passivation layer on the silicon surface. Meanwhile, boron atoms diffuse inward along a concentration gradient, generating a boron-doped porous silicon. Subsequent carbon coating further drives boron incorporation into the carbon layer, thereby enhancing the overall conductivity. This multiscale architecture design effectively mitigates lithiation-induced mechanical stress and promotes the formation of a thin and robust solid electrolyte interphase (SEI) through a synergistic dual-passivation effect from both the carbon and SiBx layers. As a result, the optimized electrode delivers a high reversible capacity of 1617.5 mAh g-1 at 4 A g-1, excellent cycling stability with 80 % capacity retention after 800 cycles, and an impressive average Coulombic efficiency of 99.91 %. Moreover, this concurrent etching-doping strategy presents a cost-effective and scalable pathway for the development of advanced silicon-based anodes, contributing to the advancement of next-generation high-energy lithium-ion batteries.
Silicon-based materials are considered promising next-generation anode candidates for lithium-ion batteries due to their high theoretical capacity and natural abundance. However, severe volume expansion (similar to 300 %) during cycling and intrinsically low electrical conductivity significantly hinder their practical applications. Surface coating modification has been recognized as an effective strategy for silicon-based materials. However, common coating materials, such as C and metal oxides, are limited by weak interfacial bonding, insufficient stress buffering, and cracking of the coating layer, making it challenging to construct uniform, durable, and multifunctional shells. This work constructs a double core-shell structured nanocomposite, Si@Co2SiO4@C. The composite leverages the buffering and conductive properties of the double shells, as well as the catalytic effect of newly generated Co-0, to facilitate reversible lithiation of the Li-Si-O compounds, thereby achieving high capacity and long-term cycling stability. As a result, the composite delivers a reversible capacity of 1296 mA h g(-1) after 200 cycles at a current density of 300 mA g(-1). The role of the double-shell structure is investigated through electrochemical measurements and structure characterization. This double core-shell structure, utilizing a transition metal silicate intermediate layer, provides a novel approach to developing high-performance Si-based anodes with distinct advantages for balancing high capacity and structural stability.
The practical application of polyethylene oxide (PEO) based solid-state electrolytes is severely limited by their low room-temperature ion transport, narrow electrochemical window, and unstable Li/PEO interfaces. This work introduces pentafluorobenzene boronic acid (PFBBA), with -C6F5 and -B(OH)2 ligands, as an advanced additive to resolve these problems. At 30 degrees C, the electrolyte containing 1.0% PFBBA shows the best performance with an ionic conductivity of 3.09 x 10-5 S cm-1, an Li+ ion transference number of 0.342, and an electrochemical window up to 5.0 V (vs. Li/Li+). The Li//Li battery can stably deposit/peel Li for 1000 h without a short circuit. The reversible capacity of Li//LiFePO4 full batteries at 0.5C after 500 cycles is 124.8 mA h g-1. The modification mechanism is studied by experimental and computational methods. The electron-withdrawing -C6F5 endows B in PFBBA with stronger Lewis acidity and better affinity with F in LiTFSI by forming pi-pi coordination. The hydrogen bonding interaction between B-OH in PFBBA and -O- in PEO changes the crystallinity of PEO. These two aspects enhanced Li+ ion transport and widened the electrochemical stability window. More importantly, PFBBA participates in in situ forming a LiF/Li-B-O rich SEI layer on the Li anode surface, enhancing the SEI film's mechanical strength and Li+ ion flux. PFBBA modifies PEO-based electrolytes by endowing B atoms with stronger Lewis acidity and forming a LiF/Li-B-O rich SEI film.
HfO 2 shows an obvious activation behavior and excellent performance, accompanied by reversible oxygen defect regulation.
Lithium-air batteries have attracted much attention because of their high energy density. However, the sluggish kinetics of the Li-O reaction leads to high charge/discharge overpotentials and poor reversibility. Therefore, exploring efficient and low-cost cathode catalysts in promoting the Li-O reaction is crucial. Herein, the first principles calculation method, for the first time, is used to study the catalytic performance based on Pt-like /3-Mo2C by modifying the C sites with B, N, and O. The N modification decreases the d-band center of Mo atoms from 0.11 eV (/3-Mo2C) to-0.23 eV, resulting in optimal adsorption energy and charge transfer. In comparison, B and O have a negative effect. The N modification changes the rate-determining step of the entire catalytic process from the decomposition of LiO2 (/3-Mo2C, B-/3-Mo2C, O-/3-Mo2C) to the decomposition of Li2O2. The electronic structure and Bader charge analysis show that N-modified /3-Mo2C has a significantly lower work function than other structures, which increases the charge transfer ability between the catalyst and LiO2. This work provides a valuable scheme for adjusting the transition metal electronic structure in low-cost MXene for lithium-air batteries.
Silicon (Si) stands out as a highly promising anode material for next-generation lithium-ion batteries. However, its low intrinsic conductivity and the severe volume changes during the lithiation/delithiation process adversely affect cycling stability and hinder commercial viability. Rational design of electrode architecture to enhance charge transfer and optimize stress distribution of Si is a transformative way to enhance cycling stability, which still remains a great challenge. In this work, we fabricated a stable integrated Si electrode by combining two-dimensional graphene sheets (G), one-dimensional Si nanowires (SiNW), and carbon nanotubes (CNT) through the cyclization process of polyacrylonitrile (PAN). The integrated electrode features a G/SiNW framework enveloped by a conformal coating consisting of cyclized PAN (cPAN) and CNT. This configuration establishes interconnected electron and lithium-ion transport channels, coupled with a rigid-flexible encapsulated coating, ensuring both high conductivity and resistance against the substantial volume changes in the electrode. The unique multidimensional structural design enhances the rate performance, cyclability, and structural stability of the integrated electrode, yielding a gravimetric capacity (based on the total mass of the electrode) of 650 mAh g-1 after 1000 cycles at 3.0 A g-1. When paired with a commercial LiNi0.5Co0.2Mn0.3O2 cathode, the resulting full cell retains 84.8% of its capacity after 160 cycles at 2.0 C and achieves an impressive energy density of 435 Wh kg-1 at 0.5 C, indicating significant potential for practical applications. This study offers valuable insights into comprehensive electrode structure design at the electrode level for Si-based materials.
The slow reaction kinetics of Li-O is currently the most pressing technical obstacle to the development of lithium-oxygen batteries. The Li2O2 ' s growth/decomposition pathways dominate the battery performance and can be optimized by exploring efficient cathode catalysts. Herein, we prepare regular, polycrystalline, oxygen vacancy (V-O)-riched PrOx uniformly anchored on few-layered graphene (FLG) nanosheets to boost the Li-O reactions. XRD, TGA, XPS, SEM, TEM, SEAD, and electrochemical test techniques are used to study their chemical composition, microstructure, battery performance, and the effect of FLG on the formation of polycrystalline and V-O. It is confirmed that FLG provides a large specific surface area and good electron transport. Moreover, it works as an anchoring substrate to transform PrOx from single crystal to polycrystalline, which is beneficial for exposing catalytic sites and V-O and improving the battery performance. This unique composition and structure offer efficient active sites, accelerate electron transport, and regulate the Li2O2 ' s nucleation to form nanofilms or nanosheets on the catalyst. With this cathode catalyst, the battery achieved an ultralow total overpotential of 0.618 V, with a discharge capacity of 11489 mAh g(-1) in the ultimate-capacity mode and a superior cyclability of 85 cycles under the limited capacity of 500 mAh g(-1).
Micrometer-sized Si particles are beneficial to practical lithium-ion batteries in regard to low cost and high volumetric energy density in comparison with nanostructured Si anodes. However, both the issues of electrical contact loss and overgrowth of solid electrolyte interface for microscale Si induced by colossal volume change still remain to be addressed. Herein, a scalable and template-free method is introduced to fabricate yolk-shell structured Si anode from commercially available Si microparticles. The void is created via a one-step alkali etching process with the remaining silicon core as the yolk, and a double-walled shell is formed from simultaneous in situ growth of the conformal native oxide layer and subsequent carbon coating. In this configuration, the well-defined void spaces allow the Si core to expand without compromising structural integrity, while the double-walled shell acts as a static capsule to confine silicon fragments despite likely particle fracture. Therefore, electrical connectivity is maintained on both the particle and electrode level during deep galvanostatic cycling, and the solid-electrolyte interface is stabilized on the shell surface. Owing to the benefits of tailored design, excellent cycling stability (capacity retention of 95% after 100 cycles) and high coulombic efficiency (99.5%) are realized in a practical full-cell demonstration.
Rational composition and structural design of electrode substances are critical for lithium-ion batteries (LIBs) supercapacitors (SCs) with good cycling steadiness and superb rate capability. Therefore, we report a electrode material consisting of V2O3 quantum dots (QDs, about 6.64 nm) well-distributed on mesoporous carbon (MC) nanosheets. V2O3 has high intrinsic conductivity and an open tunnel-like lattice structure, facilitating electron transfer and ion intercalation. The composite architectures can offer more electrochemical active shorten ion/electron diffusion paths, and reduce volume swings during the charging/discharging process. synergic effect of these merits significantly improves the reaction kinetics and prevents structural damage to entire electrode. As a result, V2O3-QDs/MC nanosheets exhibit a large capacity/capacitance, excellent cycling steadiness, and high rate performance. For LIBs, V2O3-QDs/MC displays a great reversible capacity of 931 g- 1 at 0.2 A g-1 over 500 cycles and fast and stable lithium storage behaviors with 822 mAh g-1 at 2 A g-1 1000 cycles. For SCs, V2O3-QDs/MC manifests a considerable specific capacitance of 270 F g-1 at 1 A g-1 satisfactory durability for at least 5000 cycles at 10 A g-1. This work informs a good structure design for structing advanced metal oxide-based nanostructured electrode materials.
Lithium-oxygen (Li-O2) batteries are facing challenges in capacity, cycling stability, and kinetics for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Advanced catalysts should have a high and bifunctional catalytic activity for ORR and OER. Moreover, the trade-off carbon in catalysts should have good oxidation resistance and high electronic conductivity and be used in a tiny amount. Up to now, it is still a challenge. Therefore, this work introduces a low-carbon CeOx/Ru@RuO2 nanosheet as efficient cathode catalysts for Li-O2 batteries and studies the preparation and working mechanisms using a variety of characterization and electrochemical techniques. The air oxidation treatment oxidizes Ru into Ru@RuO2 and simultaneously removes unstable C into CO2, leaving a tiny amount of stable carbon. CeOx/Ru@RuO2 has enormous mesopores, well-distributed sub-5 nm CeOx and Ru@RuO2 nanocrystals, a tiny amount of antioxidation carbon (1.2 %), and a high specific surface area of 159.3 m2 g-1. These aspects optimize the Li-O reaction and regulate the Li2O2 nucleation to form uniform and ultrathin Li2O2 nanoflakes. As a result, the ORR and OER overpotentials are only 0.17 V and 0.45 V, respectively. This work provides a novel material combination and structure design for developing bifunctional catalyst materials in Li-O2 batteries.(c) 2022 Elsevier B.V. All rights reserved.
Highly porous carboxymethyl cellulose lithium (CMC-Li) aerogel frameworks are used as a novel, robust, high-conductivity support for PEO-based electrolytes, offering a low melting point (30.43 °C) and high tensile strength (3.85 Mpa). The ionic conductivity, Li+ ion transference number, and electrochemical window at 30 °C are 2.59 × 10−4 S cm−1, 0.646, and 5.3 V, respectively.