ABSTRACT
Lithium metal is the ultimate anode material for pursuing the increased energy density of rechargeable batteries. However, fatal dendrites growth and huge volume change seriously hinder the practical application of lithium metal batteries (LMBs). In this work, a lithium host that preinstalled CoSe nanoparticles on vertical carbon vascular tissues (VCVT/CoSe) is designed and fabricated to resolve these issues, which provides sufficient Li plating space with a robust framework, enabling dendrite-free Li deposition. Their inherent N sites coupled with the in situ formed lithiophilic Co sites loaded at the interface of VCVT not only anchor the initial Li nucleation seeds but also accelerate the Li+ transport kinetics. Meanwhile, the Li2Se originated from the CoSe conversion contributes to constructing a stable solid-electrolyte interphase with high ionic conductivity. This optimized Li/VCVT/CoSe composite anode exhibits a prominent long-term cycling stability over 3000 h with a high areal capacity of 10 mAh cm-2. When paired with a commercial nickel-rich LiNi0.83Co0.12Mn0.05O2 cathode, the full-cell presents substantially enhanced cycling performance with 81.7% capacity retention after 300 cycles at 0.2 C. Thus, this work reveals the critical role of guiding Li deposition behavior to maintain homogeneous Li morphology and pave the way to stable LMBs.
ABSTRACT
Lithium-sulfur (Li-S) batteries show advantage of high theoretical capacity. However, the shuttle effect of polysulfides and sluggish sulfur redox kinetics seriously reduce their service life. Inspired by the porous structural features of biomass materials, herein, a functional interlayer is fabricated by silkworm excrement-derived three-dimensional porous carbon accommodating nano sized CoS2 particles (SC@CoS2 ). The porous carbon delivers a high specific surface area, which provides adequate adsorption sites, being responsible for suppressing the shuttle effect of polysulfides. Meanwhile, the porous carbon is favorable for hindering the aggregation of CoS2 and maintaining its high activity during extended cycles, which effectively accelerates the polysulfides conversion kinetics. Moreover, the SC@CoS2 functional interlayer effectively limits the formation of Li dendrites and promotes the uniform deposition of Li on the Li electrode surface. As a result, the CMK-3/S cathode achieves a high initial capacity of 1599.1â mAh g-1 at 0.2â C rate assisted by the polypropylene separator coated with the functional interlayer and 1208.3â mAh g-1 is maintained after the long cycling test. This work provides an insight into the designing of long-lasting catalysts for stable functional interlayer, which encourages the application of biomass-derived porous carbon in high-energy Li-S batteries.
ABSTRACT
Nickel-rich layered oxides (NLOs) are considered as one of the most promising cathode materials for next-generation high-energy lithium-ion batteries (LIBs), yet their practical applications are currently challenged by the unsatisfactory cyclability and reliability owing to their inherent interfacial and structural instability. Herein, we demonstrate an approach to reverse the unstable nature of NLOs through surface solid reaction, by which the reconstructed surface lattice turns stable and robust against both side reactions and chemophysical breakdown, resulting in improved cycling performance. Specifically, conformal La(OH)3 nanoshells are built with their thicknesses controlled at nanometer accuracy, which act as a Li+ capturer and induce controlled reaction with the NLO surface lattices, thereby transforming the particle crust into an epitaxial layer with localized Ni/Li disordering, where lithium deficiency and nickel stabilization are both achieved by transforming oxidative Ni3+ into stable Ni2+. An optimized balance between surface stabilization and charge transfer is demonstrated by a representative NLO material, namely, LiNi0.83Co0.07Mn0.1O2, whose surface engineering leads to a highly improved capacity retention and excellent rate capability with a strong capability to inhibit the crack of NLO particles. Our study highlights the importance of surface chemistry in determining chemical and structural behaviors and paves a research avenue in controlling the surface lattice for the stabilization of NLOs toward reliable high-energy LIBs.
ABSTRACT
The development of potassium-ion batteries (PIBs) is challenged by the shortage of stable cathode materials capable of reversibly hosting the large-sized K+ (1.38 Å), which is prone to cause severe structural degradation and complex phase evolution during the potassiation/depotassiation process. Here, we identified that anionic doping of the layered oxides for PIBs is effective to combat their capacity fading at high voltage (>4.0 V). Taking P2-type K2/3Mn7/9Ni1/9Ti1/9O17/9F1/9 (KMNTOF) as an example, we showed that the partial substitution of O2- by F- enlarged the interlayer distance of the K2/3Mn7/9Ni1/9Ti1/9O2 (KMNTO), which becomes more favorable for fast K+ transition without violent structural destruction. Meanwhile, based on the experimental data and theoretical results, we identified that the introduction of F- anions effectively increased the redox-active Mn cationic concentration by lowering the average valence of the Mn element, accordingly providing more reversible capacity derived from the Mn3+/4+ redox couple, rather than oxygen redox. This anionic doping strategy enables the KMNTOF cathode to deliver a high reversible capacity of 132.5 mAh g-1 with 0.53 K+ reversible (de)intercalation in the structure. We expect that the discovery provides new insights into structural engineering for pursuing stable cathodes to facilitate the future applications of high-performance PIBs.
ABSTRACT
A Li3PO4 nanocoating around a nickel-rich cathode material was successfully constructed via controlling the reaction between the electrode material and a preformed phosphorus-containing polymeric nanoshell; this not only effectively tackles the alkali residue challenge, but it also contributes to much-improved electrochemical performance being shown by a high-energy cathode.
ABSTRACT
BACKGROUND AND AIMS: The study objective was to compare the effectiveness of microwave ablation (MWA) and laparoscopic liver resection (LLR) on solitary 3-5-cm HCC over time. APPROACH AND RESULTS: From 2008 to 2019, 1289 patients from 12 hospitals were enrolled in this retrospective study. Diagnosis of all lesions were based on histopathology. Propensity score matching was used to balance all baseline variables between the two groups in 2008-2019 (n = 335 in each group) and 2014-2019 (n = 257 in each group) cohorts, respectively. For cohort 2008-2019, during a median follow-up of 35.8 months, there were no differences in overall survival (OS) between MWA and LLR (HR: 0.88, 95% CI 0.65-1.19, p = 0.420), and MWA was inferior to LLR regarding disease-free survival (DFS) (HR 1.36, 95% CI 1.05-1.75, p = 0.017). For cohort 2014-2019, there was comparable OS (HR 0.85, 95% CI 0.56-1.30, p = 0.460) and approached statistical significance for DFS (HR 1.33, 95% CI 0.98-1.82, p = 0.071) between MWA and LLR. Subgroup analyses showed comparable OS in 3.1-4.0-cm HCCs (HR 0.88, 95% CI 0.53-1.47, p = 0.630) and 4.1-5.0-cm HCCs (HR 0.77, 95% CI 0.37-1.60, p = 0.483) between two modalities. For both cohorts, MWA shared comparable major complications (both p > 0.05), shorter hospitalization, and lower cost to LLR (all p < 0.001). CONCLUSIONS: MWA might be a first-line alternative to LLR for solitary 3-5-cm HCC in selected patients with technical advances, especially for patients unsuitable for LLR.
Subject(s)
Carcinoma, Hepatocellular , Catheter Ablation , Laparoscopy , Liver Neoplasms , Carcinoma, Hepatocellular/pathology , Hepatectomy , Humans , Liver Neoplasms/pathology , Microwaves/therapeutic use , Propensity Score , Retrospective Studies , Treatment OutcomeABSTRACT
The application of solid-state batteries (SSBs) is challenged by the inherently poor interfacial contact between the solid-state electrolyte (SSE) and the electrodes, typically a metallic lithium anode. Building artificial intermediate nanofilms is effective in tackling this roadblock, but their implementation largely relies on vapor-based techniques such as atomic layer deposition, which are expensive, energy-intensive, and time-consuming due to the monolayer deposited per cycle. Herein, an easy and low-cost wet-chemistry fabrication process is used to engineer the anode/solid electrolyte interface in SSBs with nanoscale precision. This coordination-assisted deposition is initiated with polyacrylate acid as a functional polymer to control the surface reaction, which modulates the distribution and decomposition of metal precursors to reliably form a uniform crack-free and flexible nanofilm of a large variety of metal oxides. For demonstration, artificial Al2O3 interfacial nanofilms were deposited on a ceramic SSE, typically garnet-structured Li6.5La3Zr1.5Ta0.5O12 (LLZT), that led to a significant decrease in the Li/LLZT interfacial resistance (from 2079.5 to 8.4 Ω cm2) as well as extraordinarily long cycle life of the assembled SSBs. This strategy enables the use of a nickel-rich LiNi0.83Co0.07Mn0.1O2 cathode to deliver a reversible capacity of 201.5 mAh g-1 at a considerable loading of 4.8 mg cm-2, featuring performance metrics for an SSB that is competitive with those of traditional Li-ion systems. Our study demonstrates the potential of solution-based routes as an affordable and scalable manufacturing alternative to vapor-based deposition techniques that can accelerate the development of SSBs for practical applications.
ABSTRACT
Background: Tumor status can affect patient prognosis. Prognostic nutritional index (PNI), as a nutritional indicator, is closely related to the prognosis of cancer. However, few studies have examined the combined prognostic value of CEA and PNI in patients. This study investigated the relationship between CEA/PNI and prognosis of colon cancer patients. Methods: A total of 513 patients with stage II-III colon cancer who underwent curative resection at two medical centers from 2009 to 2019 were included. Clinicopathological factors were assessed and overall survival (OS) was assessed in a cohort of 413 patients. Multivariate analysis was used to identify independent prognostic variables to construct histograms predicting 1-year and 3-year OS. Data from 100 independent patients in the validation group was used to validate the prognostic model. Results: The median OS time was 33.6 months, and mortality was observed in 54 patients. Multivariate analysis revealed that preoperative CEA/PNI, lymph node metastasis, peripheral nerve invasion, operation mode, and postoperative chemotherapy were independent factors for prognosis evaluation and thus were utilized to develop the nomogram. The C-index was 0.788 in the learning set and 0.836 in the validation set. The calibration curves reached favorable consensus among the 1-, 3-year OS prediction and actual observation. Conclusion: The combined use of CEA and PNI is an independent prognostic factor and thus can serve as a basis for a model to predict the prognosis of patients with stage II-III colon cancer.
ABSTRACT
Due to the obvious advantage in potassium reserves, potassium-ion batteries (PIBs) are now receiving increasing research attention as an alternative energy storage system for lithium-ion batteries (LIBs). Unfortunately, the large size of K+ makes it a challenging task to identify suitable electrode materials, particularly cathode ones that determine the energy density of PIBs, capable of tolerating the serious structural deformation during the continuous intercalation/deintercalation of K+ . It is therefore of paramount importance that proper design principles of cathode materials be followed to ensure stable electrochemical performance if a practical application of PIBs is expected. Herein, the current knowledge on the structural engineering of cathode materials acquired during the battle against its performance degradation is summarized. The K+ storage behavior of different types of cathodes is discussed in detail and the structure-performance relationship of materials sensitive to their different lattice frameworks is highlighted. The key issues facing the future development of different categories of cathode materials are also highlighted and perspectives for potential approaches and strategies to promote the further development of PIBs are provided.
ABSTRACT
Hollow carbon-based nanospheres (HCNs) have been demonstrated to show promising potential in a large variety of research fields, particularly electrochemical devices for energy conversion/storage. The current synthetic protocols for HCNs largely rely on template-based routes (TBRs), which are conceptually straightforward in creating hollow structures but challenged by the time-consuming operations with a low yield in product as well as serious environmental concerns caused by hazardous etching agents. Meanwhile, they showed inadequate ability to build complex carbon-related architectures. Innovative strategies for HCNs free from extra templates thus are highly desirable and are expected to not only ensure precise control of the key structural parameters of hollow architectures with designated functionalities, but also be environmentally benign and scalable approaches suited for their practical applications.In this Account, we outline our recent research progress on the development of template-free protocols for the creation of HCNs with a focus on the acquired mechanical insight into the hollowing mechanism when no extra templates were involved. We demonstrated that carbon-based particles themselves could act as versatile platforms to create hollow architectures through an effective modulation of their inner chemistry. By means of reaction control, the precursor particles were synthesized into solid ones with a well-designed inhomogeneity inside in the form of different chemical parameters such as molecular weight, crystallization degree, and chemical reactivity, by which we not only can create hollow structures inside particles but also have the ability to tune the key features including compositions, porosity, and dimensional architectures. Accordingly, the functionalities of the prepared HCNs could be systematically altered or optimized for their applications. Importantly, the discussed synthesis approaches are facile and environmentally benign processes with potential for scale-up production.The nanoengineering of HNCs is found to be of special importance for their application in a large variety of electrochemical energy storage and conversion systems where the charge transfer and structural stability become a serious concern. Particular attention in this Account is therefore directed to the potential of HCNs in battery systems such as sodium ion batteries (NIBs) and potassium ion batteries (KIBs), whose electrochemical performances are plagued by the destructive volumetric deformation and sluggish charge diffusion during the intercalation/deintercalation of large-size Na+ or K+. We demonstrated that precise control of the multidimensional factors of the HCNs is critical to offer an optimized design of sufficient reactive sites, excellent charge and mass transport kinetics, and resilient electrode structure and also provide a model system suitable for the study of complicated metal-ion storage mechanisms, such as Na+ storage in a hard carbon anode. We expect that this Account will spark new endeavors in the development of HCNs for various applications including energy conversion and storage, catalysis, biomedicine, and adsorption.
ABSTRACT
Sodium-ion batteries (SIBs) are promising candidates for large-scale electric energy storage with abundant sodium resources. However, their development is challenged by the availability of satisfactory cathode materials with stable framework to accommodate the transportation of large-sized Na+ (1.02 Å), whose continuous insertion/extraction can easily cause irreversible volumetric deformation in the crystalline material, leading to inevitable structural failure and capacity fading. Here, different from the previous synthesis efforts targeting at Na+ containing compounds, we unveil the possibility of achieving a highly reversible sodiation/desodiation process by resorting to a K+-based layered metal oxide formulated as K0.5Mn0.7Fe0.2Ti0.1O2 (KMFT), which is a P2 type in structure with a wide interlayer spacing to sit K+ (1.38 Å). We demonstrate that an initial K+/Na+ exchange can introduce Na+ into the lattice while a small amount of K+ remains inside, which plays a significant role in ensuring enlarged channels for a fast and stable Na+ diffusion. The KMFT electrode delivers a high initial discharge capacity of 147.1 mA h g-1 at 10 mA g-1 and outstanding long cycling stability with capacity retention of 71.5% after 1000 cycles at 500 mA g-1. These results provide a new design strategy for the development of stable SIBs cathodes to facilitate their future applications.
ABSTRACT
Potassium ion batteries (KIBs) have emerged as a promising energy storage system, but the stability and high rate capability of their electrode materials, particularly carbon as the most investigated anode ones, become a primary challenge. Here, it is identified that pitch-derived soft carbon, a nongraphitic carbonaceous species which is paid less attention in the battery field, holds special advantage in KIB anodes. The structural flexibility of soft carbon makes it convenient to tune its crystallization degree, thereby modulating the storage behavior of large-sized K+ in the turbostratic carbon lattices to satisfy the need in structural resilience, low-voltage feature, and high transportation kinetics. It is confirmed that a simple thermal control can produce structurally optimized soft carbon that has much better battery performance than its widely reported carbon counterparts such as graphite and hard carbon. The findings highlight the potential of soft carbon as an interesting category suitable for high-performance KIB electrode and provide insights for understanding the complicated K+ storage mechanisms in KIBs.
ABSTRACT
Hollow carbon nanospheres (HCNs) have found broad applications in a large variety of application fields. Unfortunately, HCNs are known for their tedious operations and are incompetent for scalable synthesis for those widely adopted nanocasting-based routes. Here, we report a facile and highly efficient method for the creation of hollow carbon structures by tuning the growth kinetics of its polymeric precursor. We identified that a controlled polymerization of Cu2+-poly(m-phenylenediamine) (Cu-PmPD) could form nanospheres with modulated inner chemical inhomogeneity, where the core of the particles was low in polymerization degree and water soluble, whereas the outer part was water insoluble. Therefore, a simple water washing of the prepared polymeric particles directly formed hollow nanospheres with a good control on the structural features including their cavity size and shell thickness. HCNs were formed through a following heat treatment and were able to exhibit promising potential as a stable anode material when tested in potassium-ion batteries.
ABSTRACT
A self-hollowing process was demonstrated for the creation of hollow MoS2 nanospheres starting from their amorphous solid precursor, which were spontaneously transformed into a hollow structure during the rearrangement of crystal lattices initiated by a high-temperature treatment, forming hollow-structured materials favorable for their application in sodium ion batteries.
ABSTRACT
As lithium-ion batteries continue to climb to even higher energy density, they meanwhile cause serious concerns on their stability and reliability during operation. To make sure the electrode materials, particularly cathode materials, are stable upon extended cycles, surface modification becomes indispensable to minimize the undesirable side reaction at the electrolyte-cathode interface, which is known as a critical factor to jeopardizing the electrode performance. This Review is targeted at a precise surface control of cathode materials with focus on the synthetic strategies suitable for a maximized surface protection ensured by a uniform and conformal surface coating. Detailed discussions are taken on the formation mechanism of the designated surface species achieved by either wet-chemistry routes or instrumental ones, with attention to the optimized electrochemical performance as a result of the surface control, accordingly drawing a clear image to describe the synthesis-structure-performance relationship to facilitate further understanding of functional electrode materials. Finally, perspectives regarding the most promising and/or most urgent developments for the surface control of high-energy cathode materials are provided.
ABSTRACT
Surface cobalt doping is an effective and economic way to improve the electrochemical performance of cathode materials. Herein, by tuning the precipitation kinetics of Co2+, we demonstrate an aqueous-based protocol to grow uniform basic cobaltous carbonate coating layer onto different substrates, and the thickness of the coating layer can be adjusted precisely in nanometer accuracy. Accordingly, by sintering the cobalt-coated LiNi0.5Mn1.5O4 cathode materials, an epitaxial cobalt-doped surface layer will be formed, which will act as a protective layer without hindering charge transfer. Consequently, improved battery performance is obtained because of the suppression of interfacial degradation.
ABSTRACT
K-ion batteries (KIBs) are now drawing increasing research interest as an inexpensive alternative to Li-ion batteries (LIBs). However, due to the large size of K+, stable electrode materials capable of sustaining the repeated K+ intercalation/deintercalation cycles are extremely deficient especially if a satisfactory reversible capacity is expected. Herein, we demonstrated that the structural engineering of carbon into a hollow interconnected architecture, a shape similar to the neuron-cell network, promised high conceptual and technological potential for a high-performance KIB anode. Using melamine-formaldehyde resin as the starting material, we identify an interesting glass blowing effect of this polymeric precursor during its carbonization, which features a skeleton-softening process followed by its spontaneous hollowing. When used as a KIB anode, the carbon scaffold with interconnected hollow channels can ensure a resilient structure for a stable potassiation/depotassiation process and deliver an extraordinary capacity (340 mAh g-1 at 0.1 C) together with a superior cycling stability (no obvious fading over 150 cycles at 0.5 C).
ABSTRACT
A surface doping strategy is demonstrated for the stabilization of LiMn2O4, which is achieved by the surface solid reaction between the LiMn2O4 particle and its ZnO nanoshell. The surface treated sample shows a much improved high temperature performance with evidently suppressed Mn dissolution.
ABSTRACT
D-dimer, one of the canonical markers of hypercoagulability, was reported to be a potential prognostic marker of colorectal cancer. However, an inconsistent conclusion existed in several published studies. Thus, we performed this meta-analysis to provide a comprehensive insight into the prognostic role for pretreatment D-dimer in colorectal cancer. Six databases (English: Pubmed, Embase and Web of Science; Chinese: CNKI, Wangfang and VIP) were utilized for the literature retrieval. Hazard ratio (HR) was pooled by Stata 12.0. A total of fifteen studies (2283 cases) corresponded to this meta-analysis and provided available data to evaluate the prognostic role of D-dimer for colorectal cancer. The pooled HR reached 2.167 (95%. CI (confidence interval): 1.672-2.809, P < 0.001) utilizing random effect model due to obvious heterogeneity among the included studies (I2: 73.3%; P < 0.001). To explore the heterogeneity among the studies, we conducted a sensitivity analysis and found a heterogeneous study. After removing it, the heterogeneity reduced substantially (I2: 0%; P = 0.549) and we obtained a more convincing result by fixed effect model (HR = 2.143, 95% CI = 1.922-2.390, P < 0.001, 14 studies with 2179 cases). In summary, high pretreatment plasma D-dimer predicts poor survival of colorectal cancer based on the current evidence. Further prospective researches are necessary to confirm the role of D-dimer in colorectal cancer.
ABSTRACT
BACKGROUND: Studies have shown the existence of gender- and age-related differences in the incidence and anatomic distribution of colorectal cancers. The purposes of this study were to analyze the distribution characteristics of colorectal cancer patients regarding gender, age, location and tumor size in the course of colonoscopy. MATERIALS AND METHODS: All colorectal cancer patients who underwent colonoscopy in the First Affiliated Hospital of Guangxi Medical University from 2003 to 2012 were included in our retrospective study. Demographic information (age and gender) and colonoscopy report information (tumor size and location) were collected and analyzed. To compare the gender differences in tumor location and tumor size, as well as the size differences in tumor location, the chi-square test was used. RESULTS: A total of 3, 369 colorectal cancer patients (2, 007 men vs 1, 362 women) were included in our study. Statistical analysis showed there was no gender difference in the anatomic distribution of the tumors (p>0.05). However, there was a gender difference in tumor size (p>0.05). In addition, our study found there was a significant difference in tumor size between rectal and colon tumors (p>0.001). CONCLUSIONS: There was no gender difference in the anatomic distribution of colorectal tumors. In addition, tumors observed in men were larger than in women.