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1.
Angew Chem Int Ed Engl ; 62(52): e202315076, 2023 Dec 21.
Artículo en Inglés | MEDLINE | ID: mdl-37960950

RESUMEN

Polymer electrolytes provide a visible pathway for the construction of high-safety quasi-solid-state batteries due to their high interface compatibility and processability. Nevertheless, sluggish ion transfer at room temperature seriously limits their applications. Herein, a triangular synergy strategy is proposed to accelerate Na-ion conduction via the cooperation of polymer-salt, ionic liquid, and electron-rich additive. Especially, PVDF-HFP and NaTFSI salt acted as the framework to stably accommodate all the ingredients. An ionic liquid (Emim+ -FSI- ) softened the polymer chains through a weakening molecule force and offered additional liquid pathways for ion transport. Physicochemical characterizations and theoretical calculations demonstrated that electron-rich Nerolin with π-cation interaction facilitated the dissociation of NaTFSI and effectively restrained the competitive migration of large cations from EmimFSI, thus lowering the energy barrier for ion transport. The strategy resulted in a thin F-rich interphase dominated by NaTFSI salt's decomposition, enabling rapid Na+ transmission across the interface. These combined effects resulted in a polymer electrolyte with high ionic conductivity (1.37×10-3  S cm-1 ) and tNa+ (0.79) at 25 °C. The assembled cells delivered reliable rate capability and stability (200 cycles, 99.2 %, 0.5 C) with a good safety performance.

2.
J Am Chem Soc ; 145(39): 21661-21671, 2023 Oct 04.
Artículo en Inglés | MEDLINE | ID: mdl-37724914

RESUMEN

Constructing an inorganic-rich and robust solid electrolyte interphase (SEI) is one of the crucial approaches to improving the electrochemical performance of sodium metal batteries (SMBs). However, the low conductivity and distribution of common inorganics in SEI disturb Na+ diffusion and induce nonuniform sodium deposition. Here, we construct a unique SEI with evenly scattered high-conductivity inorganics by introducing a self-sacrifice LiTFSI into the sodium salt-base carbonate electrolyte. The reductive competition effect between LiTFSI and FEC facilitates the formation of the SEI with evenly scattered inorganics. In which the high-conductive Li3N and inorganics provide fast ions transport domains and high-flux nucleation sites for Na+, thus conducive to rapid sodium deposition at a high rate. Therefore, the SEI derived from LiTFSI and FEC enables the Na∥Na3V2(PO4)3 cell to show 89.15% capacity retention (87.62 mA h g-1) at an ultrahigh rate of 60 C after 10,000 cycles, while the cell without LiTFSI delivers only 48.44% capacity retention even after 8000 cycles. Moreover, the Na∥Na3V2(PO4)3 pouch cell with the special SEI presents a stable capacity retention of 92.05% at 10 C after 2000 cycles. This unique SEI design elucidates a new strategy to propel SMBs to operate under extreme high-rate conditions.

3.
ChemSusChem ; 16(24): e202300708, 2023 Dec 19.
Artículo en Inglés | MEDLINE | ID: mdl-37624682

RESUMEN

Interphases, especially the electrochemically formed solid electrolyte interphase (SEI), are significantly important for cycling stability, reaction kinetics and safety of rechargeable batteries. The structure and composition of the electric double layer (EDL) greatly affect the formation of the SEI and the performance of electrodes. However, as far as we know, there is no review discussing the theme specifically. Herein, the recent substantial progress for EDL and its impact on the formation of SEI in rechargeable batteries are reviewed and discussed. Firstly, the specific adsorption of electrolyte components on electrodes' surface and the ionic solvation structure are introduced. Furthermore, various methods for controlling EDL in different electrode systems are described. Finally, the potential future advancements of the SEI through the manipulation of EDL are discussed, aiming to enhance the electrochemical performance of rechargeable batteries.

4.
Adv Mater ; 35(15): e2203547, 2023 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-36649977

RESUMEN

Sodium storage batteries are one of the ever-increasing next-generation large-scale energy storage systems owing to the abundant resources and low cost. However, their viability is severely hampered by dendrite-related hazards on anodes. Herein, a novel ultrathin (8 µm) exterior-nonporous separator composed of honeycomb-structured fibers is prepared for homogeneous Na deposition and suppressed dendrite penetration. The unhindered ion transmission greatly benefits from honeycomb-structured fibers with huge electrolyte uptake (376.7%) and the polymer's inherent transport ability. Additionally, polar polymer chains consisting of polyethersulfone and polyvinylidene customize the highly aggregated solvation structure of electrolytes via substantial solvent immobilization, facilitating ion-conductivity-enhanced inorganic-rich solid-electrolyte interphase with remarkable interface endurance. With the reliable mechanical strength of the separator, the assembled sodium-ion full cell delivers significantly improved energy density and high safety, enabling stable operation under cutting and rolling. The as-prepared separator can further be generalized to lithium-based batteries for which apparent dendrite inhibition and cyclability are accessible and demonstrates its potential for practical application.

5.
Angew Chem Int Ed Engl ; 62(10): e202216450, 2023 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-36599807

RESUMEN

Solid-electrolyte interphase (SEI) seriously affects battery's cycling life, especially for high-capacity anode due to excessive electrolyte decomposition from particle fracture. Herein, we report an ultrathin SEI (3-4 nm) induced by Cu+ -tailored double electrical layer (EDL) to suppress electrolyte consumption and enhance cycling stability of CuS anode in sodium-ion batteries. Unique EDL with SO3 CF3 -Cu complex absorbing on CuS in NaSO3 CF3 /diglyme electrolyte is demonstrated by in situ surface-enhanced Raman, Cyro-TEM and theoretical calculation, in which SO3 CF3 -Cu could be reduced to CuF2 -rich SEI. Dispersed CuF2 and F-containing compound can provide good interfacial contact for formation of ultrathin and stable SEI film to minimize electrolyte consumption and reduce activation energy of Na+ transport. As a result, the modified CuS delivers high capacity of 402.8 mAh g-1 after 7000 cycles without capacity decay. The insights of SEI construction pave a way for high-stability electrode.

6.
Angew Chem Int Ed Engl ; 60(20): 11481-11486, 2021 May 10.
Artículo en Inglés | MEDLINE | ID: mdl-33686746

RESUMEN

High initial coulombic efficiency is highly desired because it implies effective interface construction and few electrolyte consumption, indicating enhanced batteries' life and power output. In this work, a high-capacity sodium storage material with FeS2 nanoclusters (≈1-2 nm) embedded in N, S-doped carbon matrix (FeS2 /N,S-C) was synthesized, the surface of which displays defects-repaired characteristic and detectable dot-matrix distributed Fe-N-C/Fe-S-C bonds. After the initial discharging process, the uniform ultra-thin NaF-rich (≈6.0 nm) solid electrolyte interphase was obtained, thereby achieving verifiable ultra-high initial coulombic efficiency (≈92 %). The defects-repaired surface provides perfect platform, and the catalysis of dot-matrix distributed Fe-N-C/Fe-S-C bonds to the rapid decomposing of NaSO3 CF3 and diethylene glycol dimethyl ether successfully accelerate the building of two-dimensional ultra-thin solid electrolyte interphase. DFT calculations further confirmed the catalysis mechanism. As a result, the constructed FeS2 /N,S-C provides high reversible capacity (749.6 mAh g-1 at 0.1 A g-1 ) and outstanding cycle stability (92.7 %, 10 000 cycles, 10.0 A g-1 ). Especially, at -15 °C, it also obtains a reversible capacity of 211.7 mAh g-1 at 10.0 A g-1 . Assembled pouch-type cell performs potential application. The insight in this work provides a bright way to interface design for performance improvement in batteries.

7.
Small ; 17(9): e1903194, 2021 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-31544320

RESUMEN

High-energy batteries with low cost are urgently needed in the field of large-scale energy storage, such as grid systems and renewable energy sources. Sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs) with alloy-based anodes provide huge potential due to their earth abundance, high capacity, and suitable working potential, and are recognized as attractive alternatives for next-generation batteries system. Although some important breakthroughs have been reported, more significant improvements are still required for long lifetime and high energy density. Herein, the latest progress for alloy-based anodes for SIBs and PIBs is summarized, mainly including Sn, Sb, Ge, Bi, Si, P, and their oxides, sulfides, selenides, and phosphides. Specifically, the material designs for the desired Na+ /K+ storage performance, phase transform, ionic/electronic transport kinetics, and specific chemical interactions are discussed. Typical structural features and research strategies of alloy-based anodes, which are used to facilitate processes in battery development for SIBs and PIBs, are also summarized. The perspective of future research of SIBs and PIBs is outlined.

8.
J Phys Chem Lett ; 11(4): 1435-1442, 2020 Feb 20.
Artículo en Inglés | MEDLINE | ID: mdl-31922750

RESUMEN

Conversion-type anode materials for sodium ion batteries have received extensive attention because of their relatively high theoretical capacity. However, multiple challenging obstacles stand in the way of their commercial application, especially their poor cycling stability resulting from the bad reversibility of the conversion reaction. Herein, Ni-Co bimetal sulfide was selected and investigated with the goal of improving the reversibility of the conversion reaction owing to the similarity of Ni and Co. As expected, when three-dimensional hierarchical Ni@NiCo2S4 (NiCo2S4 nanowires growing on the Ni foam) was applied as the free-standing anode for sodium ion batteries, it demonstrated high capacity and excellent cycling stability (90.65%, 100 cycles) compared with those of monometallic sulfides. Various characterization [in situ X-ray diffraction (XRD), ex situ XRD, ex situ X-ray photoelectron spectroscopy, FESEM mapping, and high-resolution transmission electron microscopy] tests confirmed that the Ni-Co alloy was formed during the discharge process and effectively prevented the crystalline grain growth of conversion reaction products, improving the reaction kinetics and reversibility.

9.
Cell Rep ; 9(6): 2034-42, 2014 Dec 24.
Artículo en Inglés | MEDLINE | ID: mdl-25533343

RESUMEN

Conversion from fibroblasts to neurons has recently been successfully induced. However, the underlying mechanisms are poorly understood. Here, we find that depletion of p53 alone converts fibroblasts into all three major neural lineages. The induced neuronal cells express multiple neuron-specific proteins and generate action potentials and transmitter-receptor-mediated currents. Surprisingly, depletion does not affect the well-known tumorigenic p53 target, p21. Instead, knockdown of p53 upregulates neurogenic transcription factors, which in turn boosts fibroblast-neuron conversion. p53 binds the promoter of the neurogenic transcription factor Neurod2 and regulates its expression during fibroblast-neuron conversion. Furthermore, our method provides a high efficiency of conversion in late-passage fibroblasts. Genome-wide transcriptional analysis shows that the p53-deficiency-induced neurons exhibit an expression profile different from parental fibroblasts and similar to control-induced neurons. The results may help to understand and improve neural conversion mechanisms to develop robust neuron-replacement therapy strategies.


Asunto(s)
Fibroblastos/citología , Neurogénesis , Neuronas/citología , Proteína p53 Supresora de Tumor/metabolismo , Animales , Factores de Transcripción con Motivo Hélice-Asa-Hélice Básico/genética , Factores de Transcripción con Motivo Hélice-Asa-Hélice Básico/metabolismo , Línea Celular , Fibroblastos/metabolismo , Humanos , Ratones , Células-Madre Neurales/citología , Células-Madre Neurales/metabolismo , Células-Madre Neurales/trasplante , Neuronas/metabolismo , Neuropéptidos/genética , Neuropéptidos/metabolismo , Proteína p53 Supresora de Tumor/genética
10.
Assay Drug Dev Technol ; 10(1): 24-36, 2012 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-22280060

RESUMEN

Traditional drug discovery efforts have resulted in the approval of a handful of receptor tyrosine kinase (RTK) inhibitors; however, their discovery relied solely on screening recombinant kinases, often with poor cellular activity outcome. The ability to screen RTKs in their natural environment is sought as an alternative approach. We have adapted a novel strategy utilizing a green fluorescent protein-labeled SRC homology 2 domain-based biosensor as a surrogate reporter of endogenous epidermal growth factor receptor (EGFR) activity in A549 cells. Upon activation of the receptor, EGFR function in live cells is measured by the number of green granules that form. Here we describe assay miniaturization and demonstrate specificity for EGFR through its chemical inhibition and RNAi-dependent knockdown resulting in complete abrogation of granule formation. Gefitinib and PD 153035 were identified as hits in a pilot screen. This approach allows for the identification of novel EGFR modulators in high-throughput formats for screening chemical and RNAi libraries.


Asunto(s)
Antineoplásicos/análisis , Técnicas Biosensibles/métodos , Ensayos de Selección de Medicamentos Antitumorales/métodos , Receptores ErbB/fisiología , Antineoplásicos/farmacología , Línea Celular Tumoral , Relación Dosis-Respuesta a Droga , Receptores ErbB/antagonistas & inhibidores , Humanos , Proyectos Piloto , ARN Interferente Pequeño/genética
11.
Plant J ; 45(4): 616-29, 2006 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-16441352

RESUMEN

Gateway cloning technology facilitates high-throughput cloning of target sequences by making use of the bacteriophage lambda site-specific recombination system. Target sequences are first captured in a commercially available "entry vector" and are then recombined into various "destination vectors" for expression in different experimental organisms. Gateway technology has been embraced by a number of plant laboratories that have engineered destination vectors for promoter specificity analyses, protein localization studies, protein/protein interaction studies, constitutive or inducible protein expression studies, gene knockdown by RNA interference, or affinity purification experiments. We review the various types of Gateway destination vectors that are currently available to the plant research community and provide links and references to enable additional information to be obtained concerning these vectors. We also describe a set of "pEarleyGate" plasmid vectors for Agrobacterium-mediated plant transformation that translationally fuse FLAG, HA, cMyc, AcV5 or tandem affinity purification epitope tags onto target proteins, with or without an adjacent fluorescent protein. The oligopeptide epitope tags allow the affinity purification, immunolocalization or immunoprecipitation of recombinant proteins expressed in vivo. We demonstrate the utility of pEarleyGate destination vectors for the expression of epitope-tagged proteins that can be affinity captured or localized by immunofluorescence microscopy. Antibodies detecting the FLAG, HA, cMyc and AcV5 tags show relatively little cross-reaction with endogenous proteins in a variety of monocotyledonous and dicotyledonous plants, suggesting broad utility for the tags and vectors.


Asunto(s)
Vectores Genéticos , Genómica , Plantas/genética , Proteómica , Secuencia de Aminoácidos , Secuencia de Bases , Cromatografía de Afinidad , ADN de Plantas , Datos de Secuencia Molecular , Proteínas Recombinantes de Fusión/genética
12.
BMC Evol Biol ; 5: 73, 2005 Dec 20.
Artículo en Inglés | MEDLINE | ID: mdl-16368004

RESUMEN

BACKGROUND: Rates of synonymous nucleotide substitutions are, in general, exceptionally low in plant mitochondrial genomes, several times lower than in chloroplast genomes, 10-20 times lower than in plant nuclear genomes, and 50-100 times lower than in many animal mitochondrial genomes. Several cases of moderate variation in mitochondrial substitution rates have been reported in plants, but these mostly involve correlated changes in chloroplast and/or nuclear substitution rates and are therefore thought to reflect whole-organism forces rather than ones impinging directly on the mitochondrial mutation rate. Only a single case of extensive, mitochondrial-specific rate changes has been described, in the angiosperm genus Plantago. RESULTS: We explored a second potential case of highly accelerated mitochondrial sequence evolution in plants. This case was first suggested by relatively poor hybridization of mitochondrial gene probes to DNA of Pelargonium hortorum (the common geranium). We found that all eight mitochondrial genes sequenced from P. hortorum are exceptionally divergent, whereas chloroplast and nuclear divergence is unexceptional in P. hortorum. Two mitochondrial genes were sequenced from a broad range of taxa of variable relatedness to P. hortorum, and absolute rates of mitochondrial synonymous substitutions were calculated on each branch of a phylogenetic tree of these taxa. We infer one major, approximately 10-fold increase in the mitochondrial synonymous substitution rate at the base of the Pelargonium family Geraniaceae, and a subsequent approximately 10-fold rate increase early in the evolution of Pelargonium. We also infer several moderate to major rate decreases following these initial rate increases, such that the mitochondrial substitution rate has returned to normally low levels in many members of the Geraniaceae. Finally, we find unusually little RNA editing of Geraniaceae mitochondrial genes, suggesting high levels of retroprocessing in their history. CONCLUSION: The existence of major, mitochondrial-specific changes in rates of synonymous substitutions in the Geraniaceae implies major and reversible underlying changes in the mitochondrial mutation rate in this family. Together with the recent report of a similar pattern of rate heterogeneity in Plantago, these findings indicate that the mitochondrial mutation rate is a more plastic character in plants than previously realized. Many molecular factors could be responsible for these dramatic changes in the mitochondrial mutation rate, including nuclear gene mutations affecting the fidelity and efficacy of mitochondrial DNA replication and/or repair and--consistent with the lack of RNA editing--exceptionally high levels of "mutagenic" retroprocessing. That the mitochondrial mutation rate has returned to normally low levels in many Geraniaceae raises the possibility that, akin to the ephemerality of mutator strains in bacteria, selection favors a low mutation rate in plant mitochondria.


Asunto(s)
ADN Mitocondrial/genética , ADN de Plantas/genética , Evolución Molecular , Geraniaceae/genética , Secuencia de Bases , Cloroplastos/genética , Variación Genética , Genoma de Planta , Geraniaceae/clasificación , Mitocondrias/genética , Pelargonium/genética , Filogenia , Plantago/genética , Reacción en Cadena de la Polimerasa
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