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1.
Chem Commun (Camb) ; 2024 Jun 21.
Artículo en Inglés | MEDLINE | ID: mdl-38904326

RESUMEN

CO2 capture by deep eutectic solvents (DESs) formed between 1,3-bis(isopropyl)imidazolium 1,2,4-triazolide ([IiPim][Triz]) and ethylene glycol (EG) is investigated in this study. [IiPim][Triz]-EG DESs exhibit a capacity of ∼1.0 mol CO2 per mol DES at 1.0 atm and 25 °C. Surprisingly, mechanistic results disclose that CO2 reacts with EG but does not bind with the C-2 site of the [IiPim]+ cation, which may be due to the high steric hindrance of the C-2 site of the N-heterocyclic carbene IiPim present in [IiPim][Triz]-EG DESs.

2.
Opt Express ; 32(9): 16199-16211, 2024 Apr 22.
Artículo en Inglés | MEDLINE | ID: mdl-38859254

RESUMEN

Single-crystal silicon (c-Si) is a vital component of photonic devices and has obvious advantages. Moreover, femtosecond-pulsed laser interactions with matter have been widely applied in micro/nanoscale processing. In this paper, we report the modification mechanisms of c-Si induced by a femtosecond laser (350 fs, 520 nm) at different pulse fluences, along with the mechanism of this technique to trim the phase error of c-Si-based devices. In this study, several distinct types of final micro/nanostructures, such as amorphization and ablation, were analyzed. The near-surface morphology was characterized using optical microscopy, scanning electron microscopy, and atomic force microscopy. The main physical modification processes were further analyzed using a two-temperature model. By employing Raman spectroscopy, we demonstrated that a higher laser fluence significantly contributes to the formation of more amorphous silicon components. The thickness of the amorphous layer was almost uniform (approximately 30 nm) at different induced fluences, as determined using transmission electron microscopy. From the ellipsometry measurements, we demonstrated that the refractive index increases for amorphization while the ablation decreases. In addition, we investigated the ability of the femtosecond laser to modify the effective index of c-Si microring waveguides by either amorphization or ablation. Both blue and red shifts of resonance spectra were achieved in the microring devices, resulting in double-direction trimming. Our results provide further insight into the femtosecond laser modification mechanism of c-Si and may be a practical method for dealing with the fabrication errors of c-Si-based photonic devices.

3.
Entropy (Basel) ; 26(5)2024 Apr 30.
Artículo en Inglés | MEDLINE | ID: mdl-38785643

RESUMEN

In this paper, the problem of joint transmission and computation resource allocation for a multi-user probabilistic semantic communication (PSC) network is investigated. In the considered model, users employ semantic information extraction techniques to compress their large-sized data before transmitting them to a multi-antenna base station (BS). Our model represents large-sized data through substantial knowledge graphs, utilizing shared probability graphs between the users and the BS for efficient semantic compression. The resource allocation problem is formulated as an optimization problem with the objective of maximizing the sum of the equivalent rate of all users, considering the total power budget and semantic resource limit constraints. The computation load considered in the PSC network is formulated as a non-smooth piecewise function with respect to the semantic compression ratio. To tackle this non-convex non-smooth optimization challenge, a three-stage algorithm is proposed, where the solutions for the received beamforming matrix of the BS, the transmit power of each user, and the semantic compression ratio of each user are obtained stage by stage. The numerical results validate the effectiveness of our proposed scheme.

4.
Artículo en Inglés | MEDLINE | ID: mdl-38435123

RESUMEN

Background: Some patients with chronic obstructive pulmonary disease (COPD) benefit from glucocorticoid (GC) treatment, but its mechanism is unclear. Objective: With the help of the Gene Expression Omnibus (GEO) database, the key genes and miRNA-mRNA related to the treatment of COPD by GCs were discussed, and the potential mechanism was explained. Methods: The miRNA microarray dataset (GSE76774) and mRNA microarray dataset (GSE36221) were downloaded, and differential expression analysis were performed. Gene Ontology (GO) function and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway enrichment analyses were performed on the differentially expressed genes (DEGs). The protein interaction network of the DEGs in the regulatory network was constructed with the STRING database, and the key genes were screened through Cytoscape. Potential downstream target genes regulated by differentially expressed miRNAs (DEMs) were predicted by the miRWalk3.0 database, and miRNA-mRNA regulatory networks were constructed. Finally, some research results were validated. Results: ① Four DEMs and 83 DEGs were screened; ② GO and KEGG enrichment analysis mainly focused on the PI3K/Akt signalling pathway, ECM receptor interaction, etc.; ③ CD2, SLAMF7, etc. may be the key targets of GC in the treatment of COPD; ④ 18 intersection genes were predicted by the mirwalk 3.0 database, and 9 pairs of miRNA-mRNA regulatory networks were identified; ⑤ The expression of miR-320d-2 and TFCP2L1 were upregulated by dexamethasone in the COPD cell model, while the expression of miR-181a-2-3p and SLAMF7 were downregulated. Conclusion: In COPD, GC may mediate the expression of the PI3K/Akt signalling pathway through miR-181a-2-3p, miR-320d-2, miR-650, and miR-155-5p, targeting its downstream signal factors. The research results provide new ideas for RNA therapy strategies of COPD, and also lay a foundation for further research.


Asunto(s)
MicroARNs , Enfermedad Pulmonar Obstructiva Crónica , Humanos , Glucocorticoides/farmacología , Glucocorticoides/uso terapéutico , ARN Mensajero/genética , Fosfatidilinositol 3-Quinasas , Proteínas Proto-Oncogénicas c-akt , Enfermedad Pulmonar Obstructiva Crónica/diagnóstico , Enfermedad Pulmonar Obstructiva Crónica/tratamiento farmacológico , Enfermedad Pulmonar Obstructiva Crónica/genética , MicroARNs/genética
5.
Small Methods ; : e2301742, 2024 Mar 10.
Artículo en Inglés | MEDLINE | ID: mdl-38461542

RESUMEN

Vanadium-based polyanionic materials are promising electrode materials for sodium-ion batteries (SIBs) due to their outstanding advantages such as high voltage, acceptable specific capacity, excellent structural reversibility, good thermal stability, etc. Polyanionic compounds, moreover, can exhibit excellent multiplicity performance as well as good cycling stability after well-designed carbon covering and bulk-phase doping and thus have attracted the attention of multiple researchers in recent years. In this paper, after the modification of carbon capping and bulk-phase nitrogen doping, compared to pristine Na3 V2 (PO4 )3 , the well optimized Na3 V(PO3 )3 N/C possesses improved electromagnetic induction strength and structural stability, therefore exhibits exceptional cycling capability of 96.11% after 500 cycles at 2 C (1 C = 80 mA g-1 ) with an elevated voltage platform of 4 V (vs Na+ /Na). Meanwhile, the designed Na3 V(PO3 )3 N/C possesses an exceptionally low volume change of ≈0.12% during cycling, demonstrating its quasi-zero strain property, ensuring an impressive capacity retention of 70.26% after 10,000 cycles at 2 C. This work provides a facial and cost-effective synthesis method to obtain stable vanadium-based phosphate materials and highlights the enhanced electrochemical properties through the strategy of carbon rapping and bulk-phase nitrogen doping.

6.
Opt Express ; 32(3): 3006-3030, 2024 Jan 29.
Artículo en Inglés | MEDLINE | ID: mdl-38297534

RESUMEN

In direct time-of-flight (D-TOF) light detection and ranging (LIDAR), accuracy and full-scale range (FSR) are the main performance parameters to consider. Particularly, in single-photon avalanche diodes (SPAD) based systems, the photon-counting statistics plays a fundamental role in determining the LIDAR performance. Also, the intrinsic performance ultimately depends on the system parameters and constraints, which are set by the application. However, the best-achievable performance directly depends on the selected depth estimation method and is not necessarily equal to intrinsic performance. We evaluate a D-TOF LIDAR system, in the particular context of smartphone applications, in terms of parameter trade-offs and estimation efficiency. First, we develop a simulation model by combining radiometry and photon-counting statistics. Next, we perform a trade-off analysis to study dependencies between system parameters and application constraints, as well as non-linearities caused by the detection method. Further, we derive an analytical model to calculate the Cramér-Rao lower bound (CRLB) of the LIDAR system, which analytically accounts for the shot noise. Finally, we evaluate a depth estimation method based on artificial intelligence (AI) and compare its performance to the CRLB. We demonstrate that the AI-based estimator fully compensates the non-linearity in depth estimation, which varies depending on application conditions such as target reflectivity.

7.
Chem Sci ; 14(47): 13924-13933, 2023 Dec 06.
Artículo en Inglés | MEDLINE | ID: mdl-38075638

RESUMEN

Ni-rich cathodes with a radial ordered microstructure have been proved to enhance materials' structural stability. However, the construction process of radial structures has not yet been clearly elaborated. Herein, the formation process of radial structures induced by different doped elements has been systematically investigated. The advanced Electron Back Scatter Diffraction (EBSD) characterization reveals that W-doped materials are more likely to form a low-angle arrangement between crystal planes of the primary particles and exhibit twin growth during sintering than a B-doped cathode. The corresponding High Angle Annular Dark Field-Scanning Transmission Electron Microscopy (HAADF-STEM) analysis further proves that the twin growth induced by W doping can promote the migration of Li+. Simultaneously, the W-doped sample reduces the (003) plane surface energy and promotes the retention of the crystal plane, which can effectively alleviate the structural degradation caused by Li+ (de)intercalation. At a cut-off voltage of 4.6 V, the W-doped cathode displays a capacity retention rate of 94.1% after 200 cycles at 1C. This work unveils the influence of different element doping on the structure from the perspective of crystal plane orientation within primary particles and points out the importance of the exposure and orientation of the crystal plane of the particles.

8.
Eur Urol Oncol ; 2023 Dec 28.
Artículo en Inglés | MEDLINE | ID: mdl-38158249

RESUMEN

BACKGROUND: Despite the use of multiparametric magnetic resonance imaging (mpMRI)-guided targeted biopsy (TB) to identify suspicious prostate lesions, it may still miss clinically significant prostate cancer (csPCa) or result in false-negative findings. Recent evidence suggests that combining biopsies taken from within and around magnetic resonance imaging (MRI) lesions can improve the detection of csPCa. OBJECTIVE: This study aimed to compare the diagnostic performance of the regional saturation biopsy (RSB) method, involving template-based nine-core biopsies for suspected regions, with that of the MRI-directed TB and/or the systematic biopsy (SB) methods in biopsy-naïve patients with prostate-specific antigen (PSA) levels ranging from 4 to 20 ng/ml. DESIGN, SETTING, AND PARTICIPANTS: A prospective, single-center, randomized controlled trial included 434 biopsy-naïve patients with suspected lesions on mpMRI and PSA levels between 4 and 20 ng/ml (from January 2022 to July 2023). OUTCOME MEASUREMENTS AND STATISTICAL ANALYSIS: The detection rates of csPCa for the RSB, TB, and SB methods were analyzed using the McNemar test for intrapatient comparisons. The Fisher's exact test was used for comparisons between RSB and TB. RESULTS AND LIMITATIONS: The RSB approach yielded a significantly higher detection rate of csPCa than both the TB approach (44.1% vs 31.8%, p = 0.01) and the SB approach (44.1% vs 34.1%, p = 0.03). The RSB approach exhibited a comparable detection rate of csPCa (44.1% vs. 40.7%, p = 0.3) to the combined approach (TB + SB), while requiring fewer biopsy cores and a higher positive core number to avoid sampling the entire prostate gland (32.7% vs 18.3%, p < 0.001). Upon conducting a whole-mount histopathological analysis, it was observed that the RSB approach successfully identified 97% (32 out of 33) of the prostate cancer foci as the index lesion, whereas only 59.18% (29 out of 49) were classified as index lesions using the SB approach. Furthermore, mpMRI underestimated the average diameter of histological tumor size by a median of 0.76 cm, highlighting the importance of an optimal biopsy area for the RSB procedure. CONCLUSIONS: For patients with suspected lesions on mpMRI and PSA levels between 4 and 20 ng/ml, the RSB approach has shown improved detection of clinically significant prostate cancer, accurately identifying index lesions, and minimizing biopsy cores compared with the MRI-directed TB and SB approaches. PATIENT SUMMARY: For patients with suspected lesions on multiparametric magnetic resonance imaging and prostate-specific antigen levels between 4 and 20 ng/ml, the regional saturation biopsy method provides enhanced detection of clinically significant prostate cancer, as well as precise identification of index lesions, surpassing both magnetic resonance imaging-directed targeted biopsy and the systematic biopsy method.

9.
Nanotechnology ; 34(45)2023 Aug 25.
Artículo en Inglés | MEDLINE | ID: mdl-37527639

RESUMEN

As the price of the precious metal cobalt continues to rise, there is an urgent need for a cobalt-free or low-cobalt electrode material to reduce the cost of lithium-ion batteries, which are widely used commercially, while maintaining their performance as much as possible. With the introduction of the new concept of high entropy (HE) materials into the battery field, low cobalt and cobalt free HE novel lithium-ion batteries have attracted great attention. It possesses important research value to use HE materials to reduce the use of cobalt metal in electrode materials. In this perspective, the comparison between the new cathode materials of low cobalt and cobalt-free HE lithium-ion battery and traditional cathode materials and the latest progress in maintaining structural stability and conductivity are introduced. It is believed that low cobalt and cobalt-free and HE layered oxides can be used to replace the function of cobalt in the cathode materials of lithium-ion batteries. Finally, the future research directions and the synthesis method of HE cathode materials for lithium-ion batteries are also discussed.

10.
J Agric Food Chem ; 71(33): 12417-12430, 2023 Aug 23.
Artículo en Inglés | MEDLINE | ID: mdl-37578298

RESUMEN

d-Aspartate is critical in maintaining hormone secretion and reproductive development in mammals. This study investigated the mechanism of different d-aspartate levels (0, 0.005, 0.05, and 0.5% d-aspartate) in low-protein diets on growth performance and meat quality by mediating the gut microbiota alteration in pigs. We found that adding 0.005% d-aspartate to a low-protein diet could dramatically improve the growth performance during the weaned and growing periods. Dietary d-aspartate with different levels markedly increased the back fat, and 0.5% d-aspartate significantly increased the redness in 24 h and reduced the shear force of the longissimus dorsi (LD) muscle. Moreover, d-aspartate treatments decreased the mRNA expression of MyHC II a and MyHC IIx in the LD muscle. The protein expression of MyH1, MyH7, TFAM, FOXO1, CAR, UCP2, and p-AMPK was upregulated by 0.005% d-aspartate. Additionally, the abundance of Alistipes, Akkermansia, and the [Eubacterium]_coprostanoligenes_group in the intestinal chyme of pigs was significantly decreased by d-aspartate treatments at the genus level, which was also accompanied by a significant decrease in acetate content. These differential microorganisms were significantly correlated with meat quality characteristics. These results indicated that d-aspartate in low-protein diets could improve the growth performance and meat quality in pigs by regulating energy and lipid metabolism via the alteration of gut microbiota.


Asunto(s)
Microbioma Gastrointestinal , Carne de Cerdo , Carne Roja , Porcinos , Animales , Dieta con Restricción de Proteínas , Ácido D-Aspártico , Ácido Aspártico , Metabolismo de los Lípidos , Dieta/veterinaria , Carne/análisis , Alimentación Animal/análisis , Mamíferos
11.
Molecules ; 28(14)2023 Jul 17.
Artículo en Inglés | MEDLINE | ID: mdl-37513333

RESUMEN

The choline prolinate ([Ch][Pro]) as a hydrogen bond acceptor and ethylene glycol (EG) as a hydrogen bond donor are both used to synthesize the deep eutectic solvents (DESs) [Ch][Pro]-EG to capture CO2. The CO2 capacity of [Ch][Pro]-EG is determined, and the nuclear magnetic resonance (NMR) and infrared (IR) spectrum are used to investigate the CO2 capture mechanism. The results indicate that CO2 reacts with both the amino group of [Pro]- anion and the hydroxyl group of EG, and the mechanism found in this work is different from that reported in the literature for the [Ch][Pro]-EG DESs.

12.
Nanoscale ; 15(31): 13076-13085, 2023 Aug 10.
Artículo en Inglés | MEDLINE | ID: mdl-37498536

RESUMEN

All-solid-state batteries are one of the most important game changers in electrochemical energy storage since they are free from the risk of leakage of hazardous flammable liquid solvents. Among the various types of solid-state electrolytes, Li7-xLa3Zr2-xTaxO12 garnets possess many desirable advantages to be considered a suitable candidate for lithium-ion batteries. However, their practical application has been hindered by premature short-circuits due to lithium dendrite growth, nonnegligible electronic conductivity and interfacial air sensitivity issues. Herein, we propose a multifunctional layer strategy to simultaneously address both the interface and electronic conductivity issues. With the help of a facile chemical process based on reactive cobalt boride, electron leakage was effectively blocked and the electrochemical performance/stability could be well maintained over extended cycles. The cobalt boride-coating layer also possessed an impressive Li metal wetting ability while sustaining a low interfacial resistance. A full cell paired with a commercialized cathode showed satisfactory performance with low overpotentials and a high specific capacity over 150 mA h g-1. Moreover, first-principle calculations further revealed the status of the rearrangement of the electron cloud behind the charge-density difference, and the nature of the low diffusion energy barrier of the reactive cobalt boride protective layer. Our strategy highlights the necessity of designing proper multifunctional layers in the garnet-type solid-state lithium-ion battery system.

13.
Antioxidants (Basel) ; 13(1)2023 Dec 20.
Artículo en Inglés | MEDLINE | ID: mdl-38275631

RESUMEN

Breast cancer, especially the aggressive triple-negative subtype, poses a serious health threat to women. Unfortunately, effective targets are lacking, leading to a grim prognosis. Research highlights the crucial role of c-MYC overexpression in this form of cancer. Current inhibitors targeting c-MYC focus on stabilizing its G-quadruplex (G4) structure in the promoter region. They can inhibit the expression of c-MYC, which is highly expressed in triple-negative breast cancer (TNBC), and then regulate the apoptosis of breast cancer cells induced by intracellular ROS. However, the clinical prospects for the application of such inhibitors are not promising. In this research, we designed and synthesized 29 acridone derivatives. These compounds were assessed for their impact on intracellular ROS levels and cell activity, followed by comprehensive QSAR analysis and molecular docking. Compound N8 stood out, significantly increasing ROS levels and demonstrating potent anti-tumor activity in the TNBC cell line, with excellent selectivity shown in the docking results. This study suggests that acridone derivatives could stabilize the c-MYC G4 structure. Among these compounds, the small molecule N8 shows promising effects and deserves further investigation.

14.
ACS Appl Mater Interfaces ; 14(51): 56808-56816, 2022 Dec 28.
Artículo en Inglés | MEDLINE | ID: mdl-36516879

RESUMEN

Organic electrode materials face two outstanding issues in the practical applications in lithium-ion batteries (LIBs), dissolution and poor electronic conductivity. Herein, we fabricate a nanocomposite of an anthraquinone carboxylate lithium salt (LiAQC) and graphene to address the two issues. LiAQC is synthesized via a green and facile one-pot reaction and then ball-milled with graphene to obtain a nanocomposite (nr-LiAQC/G). For comparison, single LiAQC is also ball-milled to form a nanorod (nr-LiAQC). Together with pristine LiAQC, the three samples are used as cathodes for LIBs. Results show that good cycling performance can be obtained by introducing the -CO2Li hydrophilic group on anthraquinone. Furthermore, the nr-LiAQC/G demonstrates not only a high initial discharge capacity of 187 mAh g-1 at 0.1 C but also good cycling stability (reversible capacity: ∼165 mAh g-1 at 0.1 C after 200 cycles) and good rate capability (the average discharge capacity of 149 mAh g-1 at 2 C). The superior electrochemical properties of the nr-LiAQC/G profit from graphene with high electronic conductivity, the nanorod structure of LiAQC shortening the transport distance for lithium ions and electrons, and the introduction of the -CO2Li hydrophilic group decreasing the dissolution of LiAQC in the electrolyte. Meanwhile, density functional theory calculations support the roles of graphene and -CO2Li groups. The fabrication is general and facile, ready to be extended to other organic electrode materials.

15.
Sci Bull (Beijing) ; 67(15): 1589-1602, 2022 Aug 15.
Artículo en Inglés | MEDLINE | ID: mdl-36546287

RESUMEN

Sodium layered oxides generally suffer from deep-desodiation instability in P2 structure and sluggish kinetics in O3 structure. It will be great to design P2/O3 biphasic materials that bring the complementary merits of both structures. However, such exploration is hindered by the ambiguous mechanism of material formation. Herein, supported by theoretical simulations and various spectroscopies, we prove that P2/O3 biphasic structures essentially originate from the internal heterogeneity of cationic potential, which can be realized by constraining the temperature-driven ion diffusion during solid-state reactions. Consequently, P2/O3 biphasic Na0.7Ni0.2Cu0.1Fe0.2Mn0.5O2-δ with well-designed quaternary composition is successfully obtained, exhibiting much-improved rate capabilities (62 mAh g-1 at 2.4 A g-1) and cycling stabilities (84% capacity retention after 500 cycles) than its single-phase analogues. Furthermore, synchrotron-based diffraction and X-ray absorption spectroscopy are employed to unravel the underlying sodium-storage mechanism of the P2/O3 biphasic structure. This work presents new insights toward the rational design of advanced layered cathodes for sodium-ion batteries.

16.
Adv Sci (Weinh) ; 9(23): e2201896, 2022 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-35661447

RESUMEN

Activation of oxygen redox during the first cycle has been reported as the main trigger of voltage hysteresis during further cycles in high-energy-density Li-rich 3d-transition-metal layered oxides. However, it remains unclear whether hysteresis only occurs due to oxygen redox. Here, it is identified that the voltage hysteresis can highly correlate to cationic reduction during discharge in the Li-rich layered oxide, Li1.2 Ni0.4 Mn0.4 O2 . In this material, the potential region of discharge accompanied by hysteresis is apparently separated from that of discharge unrelated to hysteresis. The quantitative analysis of soft/hard X-ray absorption spectroscopies discloses that hysteresis is associated with an incomplete cationic reduction of Ni during discharge. The galvanostatic intermittent titration technique shows that the inevitable energy consumption caused by hysteresis corresponds to an overpotential of 0.3 V. The results unveil that hysteresis can also be affected by cationic redox in Li-rich layered cathodes, implying that oxygen redox cannot be the only reason for the evolution of voltage hysteresis. Therefore, appropriate control of both cationic and anionic redox of Li-rich layered oxides will allow them to reach their maximum energy density and efficiency.

17.
Small Methods ; 6(7): e2200455, 2022 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-35620961

RESUMEN

Organic materials have attracted much attention in sodium ion batteries (SIBs) because of their advantages such as being environmentally benign and having high designability. Capacities and cycle life of organic materials are the most important parameters in most research which has been paid much effort to obtain an impressive electrochemical performance on the material level, and the sodium-detachable ability of these materials to directly match with the sodium-free anode is neglected. In this work, one organic sodium salt (C6 H2 Na2 O6 ) exhibits the unique ability (charging first in half cell) unlike other reported organic cathode materials (normally discharging first) for SIBs. The redox mechanism and structure change are investigated by in situ and ex situ tests to give a better understanding for C6 H2 Na2 O6 . Satisfying electrochemical performance (74% capacity retention after 600 cycles at 0.05 A g-1 and 63% capacity retention at 5 A g-1 when compared with capacity at 0.05 A g-1 ) is achieved by the C6 H2 Na2 O6 electrode. In addition, matched with hard carbon, full cells are assembled successfully like other transition metal containing cathode materials because C6 H2 Na2 O6 electrode can deliver its sodium ions to a sodium-free anode directly without any presodiation.

19.
J Am Chem Soc ; 144(17): 7929-7938, 2022 May 04.
Artículo en Inglés | MEDLINE | ID: mdl-35468290

RESUMEN

The Jahn-Teller effect (JTE) is one of the most important determinators of how much stress layered cathode materials undergo during charge and discharge; however, many reports have shown that traces of superstructure exist in pristine layered materials and irreversible phase transitions occur even after eliminating the JTE. A careful consideration of the energy of cationic distortion using a Taylor expansion indicated that second-order JTE (pseudo-JTE) is more widespread than the aforementioned JTE because of the various bonding states that occur between bonding and antibonding molecular orbitals in transition-metal octahedra. As a model case, a P2-type Mn-rich cathode (Na3/4MnO2) was investigated in detail. MnO6 octahedra are well known to undergo either elongation or contraction in a specific direction due to JTE. Here, the substitution of Li for Mn (Na3/4(Li1/4Mn3/4)O2) helped to oxidize Mn3+ to Mn4+ suppressing JTE; however, the MnO6 octahedra remained asymmetric with a clear trace of the superstructure. With various advanced analyses, we disclose the pseudo-JTE as a general reason for the asymmetric distortions of the MnO6 octahedra. These distortions lead to the significant electrochemical degradation of Na3/4Li1/4Mn3/4O2. The suppression of the pseudo-JTE modulates phase transition behaviors during Na intercalation/deintercalation and thereby improves all of the electrochemical properties. The insight obtained by coupling a theoretical background for the pseudo-JTE with verified layered cathode material lattice changes implies that many previous approaches can be rationalized by regulating pseudo-JTE. This suggests that the pseudo-JTE should be thought more important than the well-known JTE for layered cathode materials.

20.
Chem Commun (Camb) ; 58(22): 3591-3600, 2022 Mar 15.
Artículo en Inglés | MEDLINE | ID: mdl-35254369

RESUMEN

The extraordinarily high capacity exhibited by lithium-rich oxides has motivated intensive investigations towards both the cationic and anionic redox processes. With recent main focus on the anionic redox behavior, the anionic redox chemistry has emerged as a new orientation to pursue higher-energy cathodes for lithium-ion batteries. However, the key practical issues such as voltage decay, voltage hysteresis, and irreversible oxygen loss of lithium-rich oxides have triggered researchers to act on the ligand by designing novel lithium-rich sulfides/selenides. In light of this, we herein provide a timely and in-depth perspective on the development of these lithium-rich sulfides/selenides with various structures and coordinations. We highlighted both the variations of phases and structures, lithium storage mechanism, detailed change of sulfur/selenide through anionic redox, and potentials for higher energy densities. We also outlined the main academic and commercial obstacles or challenges for these Li-rich sulfides/selenides for next-generation lithium-ion batteries.

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