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1.
Small ; 20(26): e2310843, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38247199

RESUMEN

LiNO3 has attracted intensive attention as a promising electrolyte additive to regulate Li deposition behavior as it can form favorable Li3N, LiNxOy species to improve the interfacial stability. However, the inferior solubility in carbonate-based electrolyte restricts its application in high-voltage Li metal batteries. Herein, an artificial composite layer (referred to as PML) composed of LiNO3 and PMMA is rationally designed on Li surface. The PML layer serves as a reservoir for LiNO3 release gradually to the electrolyte during cycling, guaranteeing the stability of SEI layer for uniform Li deposition. The PMMA matrix not only links the nitrogen-containing species for uniform ionic conductivity but also can be coordinated with Li for rapid Li ions migration, resulting in homogenous Li-ion flux and dendrite-free morphology. As a result, stable and dendrite-free plating/stripping behaviors of Li metal anodes are achieved even at an ultrahigh current density of 20 mA cm-2 (>570 h) and large areal capacity of 10 mAh cm-2 (>1200 h). Moreover, the Li||LiFePO4 full cell using PML-Li anode undergoes stable cycling for 2000 cycles with high-capacity retention of 94.8%. This facile strategy will widen the potential application of LiNO3 in carbonate-based electrolyte for practical LMBs.

2.
Small ; : e2400315, 2024 Mar 15.
Artículo en Inglés | MEDLINE | ID: mdl-38488741

RESUMEN

Currently, a major target in the development of Na-ion batteries is the concurrent attainment of high-rate capacity and long cycling stability. Herein, an advanced Na-ion battery with high-rate capability and long cycle stability based on Li/Ti co-doped P2-type Na0.67 Mn0.67 Ni0.33 O2 , a host material with high-voltage zero-phase transition behavior and fast Na+ migration/conductivity during dynamic de-embedding process, is constructed. Experimental results and theoretical calculations reveal that the two-element doping strategy promotes a mutually reinforcing effect, which greatly facilitates the transfer capability of Na+ . The cation Ti4+ doping is a dominant high voltage, significantly elevating the operation voltage to 4.4 V. Meanwhile, doping Li+ shows the function in charge transfer, improving the rate performance and prolonging cycling lifespan. Consequently, the designed P2-Na0.75 Mn0.54 Ni0.27 Li0.14 Ti0.05 O2 cathode material exhibits discharge capacities of 129, 104, and 85 mAh g- 1 under high voltage of 4.4 V at 1, 10, and 20 C, respectively. More importantly, the full-cell delivers a high initial capacity of 198 mAh g-1 at 0.1 C (17.3 mA g-1 ) and a capacity retention of 73% at 5 C (865 mA g-1 ) after 1000 cycles, which is seldom witnessed in previous reports, emphasizing their potential applications in advanced energy storage.

3.
Chemphyschem ; 25(11): e202300930, 2024 Jun 03.
Artículo en Inglés | MEDLINE | ID: mdl-38494679

RESUMEN

The intrinsically low electronic conductivity and slow ion diffusion kinetics limit further development of olivine LiFexMn1-xPO4 cathode materials. In this paper, with the aim of improving the performance of such materials and alleviating the Jahn-Taller effect of Mn3+ ion, a bimetallic oxalate precursor with gradient distribution of elemental concentration followed with an efficient process is applied to synthesize LiFe0.5Mn0.5PO4 nanocomposite. The results shown that with certain structural modulation of the precursor, the discharge capacity of synthesized LiFe0.5Mn0.5PO4 increased from 149 mAh g-1 to 156 mAh g-1 at 0.1 C, the cycling capacity was also remarkably improved. the Fe0.5Mn0.5C2O4 ⋅ 2H2O-1 precursor with gradient distribution of elemental concentration effectively restricts the reaction between electrode material and electrolyte, thereby alleviates the dissolution of Mn3+ ion, reduces the decay of capacity and improves the stability of the material.

4.
Amino Acids ; 56(1): 40, 2024 Jun 07.
Artículo en Inglés | MEDLINE | ID: mdl-38847939

RESUMEN

Pelodiscus sinensis meat is a nutritional food and tonic with angiotensin-converting enzyme (ACE) inhibitory activities. To identify the bioactive substances responsible, several bioinformatics methods were integrated to enable a virtual screening for bioactive peptides in proteins identified within a water-soluble protein fraction of Pelodiscus sinensis meat by Shotgun proteomics. The peptides were generated from the identified proteins by in silico proteolysis using six proteases. A comparison of the numbers of proteins suitable for digestion with each enzyme and the iBAQ (intensity-based absolute quantification) values for these proteins revealed that bromelain and papain were the most suitable proteases for this sample. Next, the water solubility, toxicity, and ADMET (absorption/distribution/metabolism/excretion/toxicity) properties of these peptides were evaluated in silico. Finally, a novel ACE inhibitory peptide IEWEF with an IC50 value of 41.33 µM was identified. The activity of the synthesized peptide was verified in vitro, and it was shown to be a non-competitive ACE inhibitor. Molecular docking revealed that IEWEF could tightly bind to C-ACE, and N-ACE with energies less than 0 kJ mol-1, and the peptide IEWEF can form hydrogen bonds with C-ACE and N-ACE respectively. These results provide evidence that bioactive peptides in the water-soluble protein fraction account for (at least) some of the ACE inhibitory activities observed in Pelodiscus sinensis meat. Furthermore, our research provides a workflow for the efficient identification of novel ACE inhibitory peptides from complex protein mixtures.


Asunto(s)
Inhibidores de la Enzima Convertidora de Angiotensina , Simulación del Acoplamiento Molecular , Péptidos , Hidrolisados de Proteína , Solubilidad , Inhibidores de la Enzima Convertidora de Angiotensina/química , Inhibidores de la Enzima Convertidora de Angiotensina/farmacología , Inhibidores de la Enzima Convertidora de Angiotensina/metabolismo , Hidrolisados de Proteína/química , Hidrolisados de Proteína/metabolismo , Animales , Péptidos/química , Péptidos/farmacología , Péptidos/metabolismo , Agua/química , Peptidil-Dipeptidasa A/química , Peptidil-Dipeptidasa A/metabolismo , Papaína/metabolismo , Papaína/antagonistas & inhibidores , Papaína/química , Proteínas de Peces/química , Proteínas de Peces/metabolismo
5.
BMC Plant Biol ; 23(1): 279, 2023 May 26.
Artículo en Inglés | MEDLINE | ID: mdl-37231351

RESUMEN

BACKGROUND: The myeloblastosis (MYB) superfamily is the largest transcription factor family in plants that play diverse roles during stress responses. However, the biotic stress-responsive MYB transcription factors of the grapevine have not been systematically studied. In China, grapevine berries are often infected with the grapevine berry inner necrosis virus (GINV), which eventually reduces the nutritional quality and commodity value. RESULTS: The present study identified and characterized 265 VvMYB or VvMYB-related genes of the "Crimson seedless" grapevine. Based on DNA-binding domain analysis, these VvMYB proteins were classified into four subfamilies, including MYB-related, 2R-MYB, 3R-MYB, and 4R-MYB. Phylogenetic analysis divided the MYB transcription factors into 26 subgroups. Overexpression of VvMYB58 suppressed GINV abundance in the grapevine. Further qPCR indicated that among 41 randomly selected VvMYB genes, 12 were induced during GINV infection, while 28 were downregulated. These findings suggest that VvMYB genes actively regulate defense response in the grapevine. CONCLUSION: A deeper understanding of the MYB TFs engaged in GINV defense response will help devise better management strategies. The present study also provides a foundation for further research on the functions of the MYB transcription factors.


Asunto(s)
Factores de Transcripción , Vitis , Factores de Transcripción/genética , Factores de Transcripción/metabolismo , Frutas/genética , Frutas/metabolismo , Vitis/metabolismo , Filogenia , Necrosis/metabolismo , Regulación de la Expresión Génica de las Plantas , Proteínas de Plantas/genética , Proteínas de Plantas/metabolismo
6.
Plant Physiol ; 189(3): 1848-1865, 2022 06 27.
Artículo en Inglés | MEDLINE | ID: mdl-35485966

RESUMEN

Grapevine leafroll-associated virus 2 (GLRaV-2) is a prevalent virus associated with grapevine leafroll disease, but the molecular mechanism underlying GLRaV-2 infection is largely unclear. Here, we report that 24-kDa protein (p24), an RNA-silencing suppressor (RSS) encoded by GLRaV-2, promotes GLRaV-2 accumulation via interaction with the B3 DNA-binding domain of grapevine (Vitis vinifera) RELATED TO ABSCISIC ACID INSENSITIVE3/VIVIPAROUS1 (VvRAV1), a transcription factor belonging to the APETALA2/ETHYLENE RESPONSE FACTOR (AP2/ERF) superfamily. Salicylic acid-inducible VvRAV1 positively regulates the grapevine pathogenesis-related protein 1 (VvPR1) gene by directly binding its promoter, indicating that VvRAV1 may function in the regulation of host basal defense responses. p24 hijacks VvRAV1 to the cytoplasm and employs the protein to sequester 21-nt double-stranded siRNA together, thereby enhancing its own RSS activity. Moreover, p24 enters the nucleus via interaction with VvRAV1 and weakens the latter's binding affinity to the VvPR1 promoter, leading to decreased expression of VvPR1. Our results provide a mechanism by which a viral RSS interferes with both the antiviral RNA silencing and the AP2/ERF-mediated defense responses via the targeting of one specific host factor.


Asunto(s)
Closterovirus , Proteínas Virales/metabolismo , Vitis , Closterovirus/genética , Closterovirus/metabolismo , Enfermedades de las Plantas/genética , Interferencia de ARN , Factores de Transcripción/genética , Factores de Transcripción/metabolismo , Vitis/genética , Vitis/metabolismo
7.
Opt Express ; 31(3): 4216-4228, 2023 Jan 30.
Artículo en Inglés | MEDLINE | ID: mdl-36785395

RESUMEN

As a powerful molecular detection approach, tip-enhanced Raman scattering (TERS) spectroscopy has the advantages of nanoscale spatial resolution, label-free detection and high enhancement factor, therefore has been widely used in fields of chemistry, materials and life sciences. A TERS system enhanced by the focused gap-plasmon mode composed of Surface Plasmon Polariton (SPP) focus and the metal probe has been reported, however, its underlying enhancement mechanism for Raman excitation and scattering remains to be deeply explored. Here, we focus on the different performances of optical focus and SPP focus in the TERS system, and verify that the cooperation of these two focuses can produce maximum enhancement in a local electromagnetic field. Further, the Purcell effect on sample scattering in such a system is studied for the enhancement of Raman scattering collection in the far field. Finally, the local field enhancement and the sample far-field scattering enhancement are combined to show a full view of the whole process of TERS enhancement. This research can be applied to optimize the excitation and collection of Raman signals in TERS systems, which is of great value for the research and development of TERS technology.

8.
Small ; 18(1): e2105193, 2022 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-34786835

RESUMEN

Given the inherent characteristics of transition metal fluorides and open tunnel-type frameworks, intercalation-conversion-type FeF3 ·0.33H2 O has attracted widespread attention as a promising lithium-ion battery cathode material with high operating voltage and high energy density. However, its low electronic conductivity and poor structural stability impede its practical application in high-rate capacity and long-lifetime batteries. Herein, rod-like Nb-substituted FeF3 ·0.33H2 O (Nb-FeF3 ·0.33H2 O@C) nanocrystals with a carbon coating derived from in situ carbonization in an ionic liquid are deliberately designed and prepared. Based on first-principles calculations and electrochemical analysis, it is shown that substitution of Nb into a proportion of Fe sites can dramatically reduce the total energy of the system and the bandgap, thus boosting the structural stability and electronic conductivity of FeF3 ·0.33H2 O. Simultaneously, the combination of a surface conductive carbon coating and assembly of the nanoparticles into a rod-like mesoporous architecture can produce an omni-directional ion/electron transmission network and a robust 3D composite structure. The Nb-FeF3 ·0.33H2 O@C composite with 3% Nb-doping displays high capacity (583.2 mAh g-1 at 0.2 C), good rate capacity (187.8 mAh g-1 at a high rate of 5.0 C), and excellent long-term cycle stability (160.4 mAh g-1 after 300 long cycles).

9.
Phys Chem Chem Phys ; 24(24): 14877-14885, 2022 Jun 22.
Artículo en Inglés | MEDLINE | ID: mdl-35674009

RESUMEN

The two-dimensional layered niobium disulfide (NbS2), as a kind of anode material for Li-ion batteries, has received great attention because of its excellent electronic conductivity and structural stability. However, its ionic conductivity is far from desirable. Herein, we have proposed an effective way to acquire the rapid promotion of its Li-ion diffusion dynamics from the palladium doping effect. By first-principle calculations, we firstly investigated quantitative relations among lattice constants, mechanical properties, and Pd-doped concentration (x) for Pd doped NbS2 (PdxNbS2). It is found that the interlayer spacing of PdxNbS2 undergoes dramatic expansion, which contributes to affording its large space for Li-ion storage. And Pd0.25NbS2 has the best ductility, exhibiting its excellent destruction-resistant properties. Among PdxNbS2 (x = 0, 0.083, 0.167, 0.250, 0.333, and 0.417), it is also proved that Pd0.25NbS2 is the easiest to be prepared with the introduction of NbPd3 as the raw material for the Pd-dopant and it also exhibits excellent thermal stability at room temperature (300 K). Most importantly, by analysis with the climbing-image nudged elastic band method (CI-NEB), it is revealed that Pd0.25NbS2 shows the lowest Li-ion diffusion energy barrier of 0.26 eV, which is also much lower than that of NbS2 (0.43 eV). This is attributed to the inductive effect of the Pd-dopant in its layered structure, trying to maintain the Li-S six-coordinated structure at the initial state when Li-ions transfer to the saddle point. Accordingly, it induces a small structural difference in coordinate structures between initial states and transition states. Moreover, Pd0.25NbS2 undergoes a less obvious oxidation and reduction reaction, maintaining its excellent structural stability during Li intercalation/deintercalation. Additionally, the theoretical average voltage of Pd0.25NbS2 (1.75 V for Li0.75Pd0.25NbS2vs. Li/Li+) is also much lower than that of NbS2 (2.41 V vs. Li/Li+), implying that it can provide a higher power density. Therefore, our theoretical results pave a distinctive way to develop an ultrahigh-rate and long-life anode material for Li-ion batteries.

10.
Phys Chem Chem Phys ; 21(48): 26358-26367, 2019 Dec 11.
Artículo en Inglés | MEDLINE | ID: mdl-31793574

RESUMEN

Herein, we implement first-principles calculations to design Li7P3S11-xOx at an atomic scale, aiming to obtain stable Li7P3S11-xOx-type solid electrolyte materials with good Li+ conductivity. After searching for chemical potentials, Li2O2 is expected to be the potential raw material, and it can afford the most favorable growth environment for the synthesis of Li7P3S11-xOx (x = 0.25, 0.50, 0.75 and 1). Among these compounds, it is found that Li7P3S10.25O0.75 exhibits the most desirable Li+ conductivity of 109 mS cm-1 at 300 K, which is far higher than that of Li7P3S11 (50 mS cm-1 at 300 K). By structural analysis, it is demonstrated that the Li diffusion pathway in Li7P3S10.25O0.75 is significantly broadened relative to that in Li7P3S11 (71.38 Å3vs. 69.48 Å3), which breaks the bottleneck during Li diffusion. Moreover, the resistance of Li ion diffusion in Li7P3S10.25O0.75 decreases due to the balance of interactions between Li and its neighbouring atoms at the transition state, which induces a much lesser energy barrier of Li7P3S10.25O0.75 than that of Li7P3S11 (0.20 eV vs. 0.31 eV). Moreover, introducing Li vacancies is unlikely to alter the essence of the inherent superionic conductivity of Li7P3S10.25O0.75. Furthermore, Li7P3S10.25O0.75 can maintain good thermal stability and similar electrochemical stability to Li7P3S11. This study successfully clarifies the role of oxygen in enhancing the Li+ conductivity of Li7P3S11-xOx. Moreover, it affords a new strategy to design other solid-state electrolytes with good Li+ conductivity.

11.
Small ; 14(49): e1803134, 2018 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-30358110

RESUMEN

The commercialization of lithium-sulfur (Li-S) batteries is greatly hindered due to serious capacity fading caused by the polysulfide shuttling effect. Optimizing the structural configuration, enhancing reaction kinetics of the sulfur cathode, and increasing areal sulfur loading are of great significance for promoting the commercial applications of Li-S batteries. Herein, the multifunctional polysulfide scavengers based on nitrogen, sulfur co-doped carbon cloth (DCC), which is supported by flower-like MoS2 (1T-2H) decorated with BaMn0.9 Mg0.1 O3 perovskite particle (PrNP) and carbon nanotubes (CNTs), namely, DCC@MoS2 /PrNP/CNTs, are delicately designed and synthesized. The physical confinement, chemical coupling, and catalysis conversion for active sulfur are achieved simultaneously in this polysulfide motif. Due to these merits, the as-fabricated self-supported DCC@MoS2 /PrNP/CNTs/S manifests an excellent reversible areal capacity of 4.75 mAh cm-2 with an ultrahigh sulfur loading of 5.2 mg cm-2 at the 50th cycle. The outstanding cycling stability is obtained upon 800 cycles with a large reversible capacity of 871 mAh g-1 and a negligible fading rate of 0.02% per cycle at a rate of 1.0 C, suggesting its promising prospects for the commercial success of high-performance Li-S batteries toward flexible electronic devices and energy storage equipment.

12.
Molecules ; 23(8)2018 Jul 24.
Artículo en Inglés | MEDLINE | ID: mdl-30042340

RESUMEN

Wolfiporia cocos is a fungus containing triterpenoids and is widely used as an herbal medicine. However, it is unknown whether its main triterpenoid contents differ in different tissues. In this study, we identified dehydrotumulosic acid, polyporenic acid C, pachymic acid, dehydrotrametenolic acid, and dehydroeburicoic acid as the five main triterpenoids in W. cocos. We also systematically profiled the contents and distribution of these main triterpenoids in different tissues of W. cocos. High contents of all five triterpenoids were found in the surface layer of W. cocos. Intriguingly, we noted that the highest contents of the five triterpenoids were found in the surface layer of the sclerotium grown under pollution-controlled cultivation; the second-highest contents were found in the surface layer of the natural sclerotium. These results indicate that environmentally friendly cultivation of the sclerotium of W. cocos is a practical way to increase the productivity of W. cocos. In addition, our findings suggest that the triterpenoids may contribute to the pharmacological activity of W. cocos, and the surface layer of sclerotium in W. cocos might be a promising raw material for applications in health care and the development of functional medical products.


Asunto(s)
Lanosterol/análogos & derivados , Triterpenos/aislamiento & purificación , Wolfiporia/química , Cromatografía Líquida de Alta Presión , Lanosterol/química , Lanosterol/aislamiento & purificación , Extracción Líquido-Líquido/métodos , Metanol/química , Micelio/química , Micelio/metabolismo , Solventes/química , Triterpenos/química , Wolfiporia/metabolismo
13.
Acta Chim Slov ; 64(1): 95-101, 2017.
Artículo en Inglés | MEDLINE | ID: mdl-28380221

RESUMEN

A novel high-performance gel polymer electrolyte (GPE) based on poly(vinylidene fluoride) (PVDF), thermoplastic polyurethane (TPU) and polystyrene (PS) has been prepared. Its characteristics are investigated by scanning electron microscopy (SEM), thermal analysis (DSC), universal testing machines (UTM), galvanostatic charge-discharge and electrochemical impedance spectroscopy. The GPE based on TPU/PVDF/PS (10 wt.%) show a high ionic conductivity of 5.28 × 10-3 S cm-1 with the electrochemical stability window of 5.0 V. In addition, its first charge-discharge capacity reached to 169.5 mAh g-1, high mechanical strength and stability to allow safe operation in rechargeable lithium ion polymer batteries.

14.
Opt Express ; 24(10): 11002-8, 2016 May 16.
Artículo en Inglés | MEDLINE | ID: mdl-27409922

RESUMEN

Planar lenses are attractive photonic devices due to its minimized size and easy to integrate. However, planar lenses designed in traditional ways are restricted by the diffraction limit. They have difficulties in further reducing the focal spot size beyond the diffraction limit. Super-oscillation provides a possible way to solve the problem. However, lenses based on super-oscillation have always been affected by huge sidelobes, which resulted in limited field of view and difficulties in real applications. To address the problem, in the paper, a far-field sub-diffraction lens based on binary amplitude-phase mask was demonstrated under illumination of linearly polarized plane wave at wavelength 632.8 nm. The lens realized a long focal length of 148λ (94 µm), and the full width at half maximum of the focal line was 0.406λ, which was super-oscillatory. More important is that such a flat lens has small sidelobes and wide field of view. Within the measured range of [-132λ, + 120λ], the maximum sidelobe observed on the focal plane was less than 22% of the central peak. Such binary amplitude-phase planar lens can also be extended to long focal length far-field sub-diffraction focusing lens for other spectrum ranges.

15.
Biotechnol Appl Biochem ; 62(2): 186-92, 2015.
Artículo en Inglés | MEDLINE | ID: mdl-24888716

RESUMEN

Atherosclerosis (AS) is a progressive disease characterized by endothelial injury and lipid aggregation in the arterial walls. Studies have reported that endothelial progenitor cells (EPCs) derived from the bone marrow (BM) might provide an endogenous repair mechanism by differentiating into endothelial cells to replace the dysfunctional endothelium. Our study aims to investigate the effect of EPCs derived from rat BM on AS. EPCs transduced by recombinant adeno-associated virus-green fluorescent protein (GFP) were transplanted into a rat AS model. After 2 months of transplantation, the localization of GFP-labeled cells, morphology, and lipid content in the aorta were examined. GFP-labeled EPCs were found in the endothelial monolayer of the artery vessel in the GFP/EPC group. Hematoxylin and eosin staining suggested that the lipid deposits in the aortic endothelium in the EPC/GFP group were less compared with those in the untreated group. Oil Red O staining of liver slices showed that lipid droplets were obviously decreased in the GFP/EPC group. The endothelial nitric oxide synthase and apolipoprotein E mRNA levels in the GFP/EPC group were significantly higher, but the intercellular cell adhesion molecule-1 mRNA level was significantly lower compared with the control group. The results suggest that EPCs derived from the BM can repair the injured endothelium and promote an atherosclerotic lesion regression. Therefore, EPCs may provide a useful tool for the treatment of AS.


Asunto(s)
Aterosclerosis/fisiopatología , Aterosclerosis/terapia , Células Progenitoras Endoteliales/trasplante , Animales , Aterosclerosis/patología , Células Cultivadas , Masculino , Ratas , Ratas Sprague-Dawley , Resultado del Tratamiento
16.
J Nanosci Nanotechnol ; 14(7): 5157-65, 2014 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-24757995

RESUMEN

Supercapacitors are successfully prepared from ordered mesoporous carbon (OMC) synthesized by employing the mesoporous silica, SBA-15 as template and furfuryl alcohol as carbon source. It is found that the carbonized temperature greatly influences the physical properties of the synthesized mesoporous carbon materials. The optimal carbonized temperature is measured to be 600 degrees C under which OMC with the specific surface area of 1219 m2/g and pore volume of 1.31 cm3/g and average pore diameter of - 3 nm are synthesized. The OMC materials synthesized under different carbonized temperature are used as electrode material of supercapacitors and the electrochemical properties of the OMC materials are compared by using cyclic voltammetry, electrochemical impedance spectroscopy, galvanostatic charge-discharge and self-discharge tests. The results show that the electrochemical properties of the OMC materials are directly related to the specific surface area and pore volume of the mesoporous carbon and the electrode prepared from the OMC synthesized under the carbonized temperature of 600 degrees C (OMC-600) exhibits the most excellent electrochemical performance with the specific capacitance of 207.08 F/g obtained from cyclic voltammetry at the scan rate of 1 mV/s, small resistance and low self-discharge rate. Moreover, the supercapacitor based on the OMC-600 material exhibits good capacitance properties and stable cycle behavior with the specific capacitance of 105 F/g at the current density of 700 mA/g, and keeps a specific capacitance of 98 F/g after 20000 consecutive charge/discharge cycles.

17.
Artículo en Inglés | MEDLINE | ID: mdl-38914535

RESUMEN

The irreversible oxygen-redox reactions in the high-voltage region of sodium-layered cathode materials lead to poor capacity retention and structural instability during cycling, presenting a significant challenge in the development of high-energy-density sodium-ion batteries. This work introduces a high-entropy design for layered Na0.67Li0.1Co0.1Cu0.1Ni0.1Ti0.1Mn0.5O2 (Mn-HEO) cathode with a self-regulating mechanism to extend specific capacity and energy density. The oxygen redox reaction was activated during the initial charging process, accompanied by the self-regulation of active elements, enhancing the ionic bonds to form a vacancy wall near the TM vacancies and thus preventing the migration of transition metal elements. Systematic in situ/ex situ characterizations and theoretical calculations comprehensively support the understanding of the self-regulation mechanism of Mn-HEO. As a result, the Mn-HEO cathode exhibits a stable structure during cycling. It demonstrates almost zero strain within a wide voltage range of 2.0-4.5 V with a remarkable specific capacity (177 mAh g-1 at 0.05 C) and excellent long-term cycling stability (87.6% capacity retention after 200 cycles at 2 C). This work opens a new pathway for enhancing the stability of oxygen-redox chemistry and revealing a mechanism of crystal structure evolution for high-energy-density layered oxides.

18.
J Colloid Interface Sci ; 670: 519-529, 2024 Sep 15.
Artículo en Inglés | MEDLINE | ID: mdl-38776687

RESUMEN

The high theoretical energy density and specific capacity of lithium-sulfur (Li-S) batteries have garnered considerable attention in the prospective market. However, ongoing research on Li-S batteries appears to have encountered a bottleneck, with unresolved key technical challenges such as the significant shuttle effect and sluggish reaction kinetics. This investigation explores the catalytic efficacy of three catalysts for Li-S batteries and elucidates the correlation between their structure and catalytic impacts. The results suggest that the combined utilization of lithium-insertion technology and a proton exchange approach for δ-MnO2 can optimize its electronic structure, resulting in an optimal catalyst (H/Li inserted δ-MnO2, denoted as HLM) for the sulfur reduction reaction. The replacement of Mn sites in δ-MnO2 with Li atoms can enhance the structural stability of the catalyst, while the introduction of H atoms between transition metal layers contributes to the satisfactory catalytic performance of HLM. Theoretical calculations demonstrate that the bond length of Li2S4 adsorbed by the HLM molecule is elongated, thereby facilitating the dissociation process of Li2S4 and enhancing the reaction kinetics in Li-S batteries. Consequently, the Li-S battery utilizing HLM as a catalyst achieves a high areal specific capacity of 4.2 mAh cm-2 with a sulfur loading of 4.1 mg cm-2 and a low electrolyte/sulfur (E/S) ratio of 8 µL mg-1. This study introduces a methodology for designing effective catalysts that could significantly advance practical developments in Li-S battery technology.

19.
ACS Appl Mater Interfaces ; 16(9): 11349-11360, 2024 Mar 06.
Artículo en Inglés | MEDLINE | ID: mdl-38381529

RESUMEN

P2-type Fe-Mn-based oxides offer excellent discharge specific capacity and are as affordable as typical layered oxide cathode materials for sodium-ion batteries (SIBs). After Cu modification, though they can improve the cycling performance and air stability, the discharge specific capacity will be reduced. Considering the complementary nature of biphasic phases in electrochemistry, hybridizing P2/O3 hybrid phases can enhance both the storage performance of the battery and specific capacity. Herein, a hybrid phase composite with high capacity and good cycle performance is deliberately designed and successfully prepared by controlling the amount of Mg doping in the layered oxide. It has been found that the introduction of Mg can activate anion redox in the oxide layer, resulting in a significant increase in the specific discharge capacity of the material. Meanwhile, the dual-phase structure can produce an interlocking effect, thus effectively alleviating structure strain. The degradation of cycling performance caused by structural damage during the high-voltage charging and discharging process is clearly mitigated. The results show that the specific discharge capacity of Na0.67Cu0.2Mg0.1Fe0.2Mn0.5O2 is as high as 212.0 mAh g-1 at 0.1C rate and 186.2 mAh g-1 at 0.2C rate. After 80 cycles, the capacity can still maintain 88.1%. Moreover, the capacity and cycle performance as well as the stability can still remain stable even in the high-voltage window. Therefore, this work offers an insightful exploration for the development of composite cathode materials for SIBs.

20.
J Colloid Interface Sci ; 669: 126-136, 2024 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-38713952

RESUMEN

The shuttle effect and sluggish redox kinetics of polysulfides have hindered the development of lithium-sulfur batteries (LSBs) as premier energy storage devices. To address these issues, a high-entropy metal phosphide (NiCoMnFeCrP) was synthesized using the sol-gel method. NiCoMnFeCrP, with its rich metal species, exhibits strong synergistic effects and provides numerous catalytic active sites for the conversion of polysulfides. These active sites, possessing significant polarity, can bond with polysulfides. In situ ultraviolet-visible were conducted to monitor the dynamic changes in species and concentrations of polysulfides, validating the ability of NiCoMnFeCrP to facilitate the conversion of polysulfides. The batteries with the NiCoMnFeCrP catalyst as functional separators exhibited minimal capacity decay rates of 0.04 % and 0.23 % after 100 cycles at 0 °C and 60 °C, respectively. This indicates that the NiCoMnFeCrP catalyst possesses good thermal stability. Meanwhile, its area capacity can reach 4.78 mAh cm-2 at a high sulfur load of 4.54 mg cm-2. In conclusion, NiCoMnFeCrP achieves the objective of mitigating the shuttle effect and accelerating the kinetics of the redox reaction, thereby facilitating the commercialization of LSBs.

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