Revisit of Polyaniline as a High-Capacity Organic Cathode Material for Li-Ion Batteries.

Polyaniline (PANI) has long been explored as a promising organic cathode for Li-ion batteries. However, its poor electrochemical utilization and cycling instability cast doubt on its potential for practical applications. In this work, we revisit the electrochemical performance of PANI in nonaqueous electrolytes, and reveal an unprecedented reversible capacity of 197.2 mAh g-1 (244.8 F g-1) when cycled in a wide potential range of 1.5 to 4.4 V vs. Li+/Li. This ultra-high capacity derives from 70% -NH- transformed to =NH+- during deep charging/discharging process. This material also demonstrates a high average coulombic efficiency of 98%, an excellent rate performance with 73.5 mAh g-1 at 1800 mA g-1, and retains 76% of initial value after 100 cycles, which are among the best reported values for PANI electrodes in battery applications.

Scalable Synthesis of Bilayer Graphene at Ambient Temperature.

In this work, we develop for the first time a facile chemical lithiation-assisted exfoliation approach to the controllable and scalable preparation of bilayer graphene. Biphenyl lithium (Bp-Li), a strong reducing reagent, is selected to realize the spontaneous Li-intercalation into graphite at ambient temperature, forming lithium graphite intercalation compounds (Li-GICs). The potential of Bp-Li (0.11 V vs Li/Li+), which is just lower than the potential of stage-2 lithium intercalation (0.125 V), enables the precise lithiation of graphite to stage-2 Li-GICs (LiC12). Intriguingly, the exfoliation of LiC12 leads to the bilayer-favored production of graphene, giving a high selectivity of 78%. Furthermore, the mild intercalation-exfoliation procedure yields high-quality graphene with negligible structural deterioration. The obtained graphene exhibits ultralow defect density (ID/IG ∼ 0.14) and a considerably high C/O ratio (∼29.7), superior to most current state-of-the-art techniques. This simple and scalable strategy promotes the understanding of chemical Li-intercalation methods for preparing high-quality graphene and shows great potential for layer-controlled engineering.

Prognostic Assessment of Colorectal Cancer Patients after Laparoscopic Surgery: A Comprehensive Evaluation of the Glasgow Prognostic Score and Fibrinogen-to-Prealbumin Ratio.

BACKGROUND Previous studies have shown that systemic inflammation and suboptimal nutritional status are associated with poor cancer prognosis. This study aims to investigate the prognostic value of preoperative Glasgow prognostic score (GPS) and fibrinogen-to-prealbumin ratio (FPR) in patients with CRC (colorectal cancer) after laparoscopic surgery. MATERIAL AND METHODS In this study, the clinical data of 112 patients with CRC who underwent laparoscopic surgery were retrospectively analyzed, and the 3-year and 5-year survival rates of these patients were evaluated. In addition, the prognostic role of preoperative FPR and GPS in CRC patients was assessed using X-tile software, Kaplan-Meier analysis, and Cox regression analysis. Receiver operating characteristic (ROC) curves were generated to assess the predictive value of FPR, GPS, and FPR-GPS for the survival of these patients. RESULTS The results revealed a significant negative correlation between high FPR, elevated GPS, and overall survival (OS) in patients with CRC. Univariate and multivariate Cox regression analyses identified GPS (HR=3.207, 95% CI: 1.746~6.126), FPR (HR=2.669, 95% CI: 1.052~6.772), and lymph node metastasis (HR=2.222, 95% CI: 1.199~4.115) as independent prognostic indicators for overall survival. The ROC analysis demonstrated that the prediction based on FPR and GPS outperformed a single indicator in accurately predicting the prognosis of CRC patients. CONCLUSIONS Combining the preoperative FPR with the GPS contributes to accurate prognosis assessment for CRC patients after laparoscopic surgery. Patients exhibiting high FPR and GPS values are associated with a worse prognosis.

Controllable synthesis of a Na-enriched Na4V2(PO4)3 cathode for high-energy sodium-ion batteries: a redox-potential-matched chemical sodiation approach.

Exploring a sodium-enriched cathode (i.e. Na4V2(PO4)3, which differs from its traditional stoichiometric counterpart Na3V2(PO4)3 that can provide extra endogenous sodium reserves to mitigate the irreversible capacity loss of the anode material (i.e. hard carbon), is an intriguing presodiation method for the development of high energy sodium-ion batteries. To meet this challenge, herein, we first propose a redox-potential-matched chemical sodiation approach, utilizing phenazine-sodium (PNZ-Na) as the optimal reagent to sodiate the Na3V2(PO4)3 precursor into Na-enriched Na4V2(PO4)3. The spontaneous sodiation reaction enables a fast reduction of one-half V ions from V3+ to V2+, followed by the insertion of one Na+ ion into the NASICON framework, which only takes 90 s to obtain the phase-pure Na4V2(PO4)3 product. When paired with a hard carbon anode, the resulting Na4VP‖HC full cell exhibits a high energy density of 251 W h kg-1, which is 58% higher than that of 159 W h kg-1 for the Na3VP‖HC control cell. Our chemical sodiation methodology provides an innovative approach for designing sodium-rich cathode materials and could serve as an impetus to the development of advanced sodium-ion batteries.

Preoperative Neutrophil-Lymphocyte Ratio (NLR)-Binding Fibrinogen-Albumin Ratio (FAR) Is Superior to Platelet-Lymphocyte Ratio (PLR)-Binding Fibrinogen-Albumin Ratio (FAR) and Lymphocyte-Monocyte (LMR)-Binding Fibrinogen-Albumin Ratio (FAR) as Predictors of Survival in Surgical Patients with Colorectal Adenocarcinoma.

BACKGROUND Studies have revealed that having systemic inflammation is linked to worse survival rates across a range of malignancies. This study aimed to evaluate the predictive significance of neutrophil-to-lymphocyte ratio (NLR), platelet-to-lymphocyte ratio (PLR), and lymphocyte-to-monocyte ratio (LMR) in combination with fibrinogen-to-albumin ratio (FAR) in surgical patients with colorectal adenocarcinoma (CRC). MATERIAL AND METHODS From January 2010 to December 2016, 200 patients with CRC had their preoperative NLR, PLR, LMR, and FAR assessed. Following that, univariate and multivariate analytic techniques were used to establish the prognostic value of these 4 indicators. Plotting the receiver operating characteristic (ROC) curves allowed researchers to assess whether the NLR-FAR, PLR-FAR, and LMR-FAR could be applied to predict survival. RESULTS High preoperative NLR (≥3.9 vs <3.9, P<0.001), high preoperative PLR (≥106 vs <106, P=0.039), low preoperative LMR (≥4.2 vs <4.2, P<0.001), and high preoperative FAR (≥0.09 vs <0.09, P=0.028) were significantly associated with worse overall survival in multivariate analysis, which was also confirmed with survival curves. The prediction outcomes of the combined components outperformed those of a single index. NLR-FAR outperformed PLR-FAR and LMR-FAR as a predictor of CRC, with an area under the curve (AUC) of 97.24% (95% confidence interval (CI)=0.9535 to 0.9915, P<0.0001), 92.57% (95% CI=0.8880 to 0.9634, P<0.0001), and 90.26% (95% CI=0.8515 to 0.9538, P<0.0001). CONCLUSIONS In patients with CRC, preoperative NLR, PLR, LMR, and FAR can be utilized as independent predictors of overall survival. Additionally, in the combined detection findings, NLR and FAR performed better as predictors of CRC patients than PLR-FAR and LMR-FAR.

Exfoliation of MoS2 Nanosheets Enabled by a Redox-Potential-Matched Chemical Lithiation Reaction.

Ion intercalation assisted exfoliation is the oldest and most popular method for the scalable synthesis of molybdenum disulfide (MoS2) nanosheets. The commonly used organolithium reagents for Li+ intercalation are n-butyllithium (n-BuLi) and naphthalenide lithium (Nap-Li); however, the highly pyrophoric nature of n-BuLi and the overly reducing power of Nap-Li hinder their extensive application. Here, a novel organolithium reagent, pyrene lithium (Py-Li), which has intrinsic safe properties and a well-matched redox potential, is reported for the intercalation and exfoliation of MoS2. The redox potential of Py-Li (0.86 V vs Li+/Li) is located just between the intercalation (1.13 V) and decomposition (0.55 V) potentials of bulk MoS2, thus allowing precise Li+ intercalation to form a lamellar LiMoS2 compound without undesirable structural damage. The lithiation reaction can be accomplished within 1 h at room temperature and the exfoliated nanosheets are almost single layer. This method also offers the advantages of low cost, high repeatability, and ease in realizing large-scale production.

Chemically Presodiated Hard Carbon Anodes with Enhanced Initial Coulombic Efficiencies for High-Energy Sodium Ion Batteries.

Hard carbon (HC) is an attractive anode material for low-cost and high-energy density sodium-ion batteries (SIBs); however, its low initial Coulombic efficiency (ICE) limits its practical battery application. To overcome this problem, we reported a facile strategy to compensate the irreversible capacity loss of HC anodes simply by a chemical presodiation reaction of the HC electrode with a sodiation reagent (sodium biphenyl, Na-Bp). Benefiting from the strong sodiation ability of Na-Bp, HC anodes can be presodiated rapidly in a very short time and the presodiated HC (NaxHC) is found to have a desirable ICE of 100%. When coupled with the Na3V2(PO4)3 cathode to build a SIB full cell, the NaxHC||Na3V2(PO4)3 cell exhibits a high ICE of ∼95.0% and an elevated energy density of 218 W h kg-1, which are far superior to those of the control cell using a pristine HC anode (50% ICE and 120 W h kg-1, respectively), suggesting great advantages brought about by the chemical presodiation process. More importantly, this presodiation reaction is very mild and highly efficient and can be widely extended to a variety of Na-storage materials, offering a new route to develop high-performance Na-storage materials for practical battery applications.

Covalently Bonded Silicon/Carbon Nanocomposites as Cycle-Stable Anodes for Li-Ion Batteries.

Carbon coating is a popular strategy to boost the cyclability of Si anodes for Li-ion batteries. However, most of the Si/C nanocomposite anodes fail to achieve stable cycling due to the easy separation and peeling off of the carbon layer from the Si surface during extended cycles. To overcome this problem, we develop a covalent modification strategy by chemically bonding a large conjugated polymer, poly-peri-naphthalene (PPN), on the surfaces of nano-Si particles through a mechanochemical method, followed by a carbonization reaction to convert the PPN polymer into carbon, thus forming a Si/C composite with a carbon coating layer tightly bonded on the Si surface. Due to the strong covalent bonding interaction of the Si surface with the PPN-derived carbon coating layer, the Si/C composite can keep its structural integrity and provide an effective surface protection during the fluctuating volume changes of the nano-Si cores. As a consequence, the thus-prepared Si/C composite anode demonstrates a reversible capacity of 1512.6 mA h g-1, a stable cyclability over 500 cycles with a capacity retention of 74.2%, and a high cycling Coulombic efficiency of 99.5%, providing a novel insight for designing highly cyclable silicon anodes for new-generation Li-ion batteries.

Chemically Prelithiated Hard-Carbon Anode for High Power and High Capacity Li-Ion Batteries.

Hard carbons (HC) have potential high capacities and power capability, prospectively serving as an alternative anode material for Li-ion batteries (LIB). However, their low initial coulombic efficiency (ICE) and the resulting poor cyclability hinder their practical applications. Herein, a facile and effective approach is developed to prelithiate hard carbons by a spontaneous chemical reaction with lithium naphthalenide (Li-Naph). Due to the mild reactivity and strong lithiation ability of Li-Naph, HC anode can be prelithiated rapidly in a few minutes and controllably to a desirable level by tuning the reaction time. The as-formed prelithiated hard carbon (pHC) has a thinner, denser, and more robust solid electrolyte interface layer consisting of uniformly distributed LiF, thus demonstrating a very high ICE, high power, and stable cyclability. When paired with the current commercial LiCoO2 and LiFePO4 cathodes, the assembled pHC/LiCoO2 and pHC/LiFePO4 full cells exhibit a high ICE of >95.0% and a nearly 100% utilization of electrode-active materials, confirming a practical application of pHC for a new generation of high capacity and high power LIBs.

Hollow carbon nanofibers as high-performance anode materials for sodium-ion batteries.

Hollow carbon nanofibers (HCNFs) are successfully fabricated by pyrolyzation of a polyaniline hollow nanofiber precursor. The as-prepared HCNFs as sodium storage anode materials exhibit a high reversible charge capacity of 326 mA h g-1 at 20 mA g-1, high rate capability (85 mA h g-1 at 1.6 A g-1) and superior cycling stability (a capacity retention of 70% even after 5000 cycles at 1.6 A g-1). Such a high performance of HCNFs can be ascribed to the special hollow structure characteristics; they possess a well fabricated electronic transport path and can shorten the ion diffusion distance. Therefore, the HCNFs can be regarded as promising anode materials for advanced sodium ion batteries (SIBs).

Highly Electrochemically-Reversible Mesoporous Na2 FePO4 F/C as Cathode Material for High-Performance Sodium-Ion Batteries.

As promising cathode materials, iron-based phosphate compounds have attracted wide attention for sodium-ion batteries due to their low cost and safety. Among them, sodium iron fluorophosphate (Na2 FePO4 F) is widely noted due to its layered structure and high operating voltage compared with NaFePO4 . Here, a mesoporous Na2 FePO4 F@C (M-NFPF@C) composite derived from mesoporous FePO4 is synthesized through a facile ball-milling combined calcination method. Benefiting from the mesoporous structure and highly conductive carbon, the M-NFPF@C material exhibits a high reversible capacity of 114 mAh g-1 at 0.1 C, excellent rate capability (42 mAh g-1 at 10 C), and good cycling performance (55% retention after 600 cycles at 5 C). The high plateau capacity obtained (>90% of total capacity) not only shows high electrochemical reversibility of the as-prepared M-NFPF@C but also provides high energy density, which mainly originates from its mesoporous structure derived from the mesoporous FePO4 precursor. The M-NFPF@C serves as a promising cathode material with high performance and low cost for sodium-ion batteries.

In Situ Formation of Co9S8 Nanoclusters in Sulfur-Doped Carbon Foam as a Sustainable and High-Rate Sodium-Ion Anode.

Transition-metal sulfides hold great promise as anode materials for sodium-ion batteries due to the high theoretical capacity and excellent redox reversibility based on multielectron conversion reactions. In this work, an elaborate composite, cobalt sulfide nanoclusters embedded in honeycomb-like sulfur-doped carbon foam (Co9S8@S-CF), is prepared via a facile sulfur-assisting calcination strategy, which tactfully induces the co-occurrence of in situ pore-forming, sulfidation, sulfur doping, and carbonization. Notably, sulfur-doped carbon foam (S-CF) possesses abundant voids, which are subject to construction of three-dimensional ionic/electronic pathways, leading to high sodium-ion accessibility and ultrafast sodium-ion/electron transportation toward Co9S8 nanoclusters. When worked as an anode in sodium-ion batteries, it delivers a remarkable capacity of 373 mA h g-1 over 1000 cycles at 0.25 C, achieving superior capacity retention of 80%. Furthermore, this anode could achieve unprecedented rate capability with a reversible capacity of 180 mA h g-1 at 50 C (20 A g-1), which significantly precedes those reported previously.

Surface-Bound Silicon Nanoparticles with a Planar-Oriented N-Type Polymer for Cycle-Stable Li-Ion Battery Anode.

Silicon is now well-recognized to be a promising alternative anode for advanced lithium-ion batteries because of its highest capacity available today; however, its insufficiently high Coulombic efficiency upon cycling remains a major challenge for practical application. To overcome this challenge, we have developed a facile mechanochemical method to synthesize a core-shell-structured Si/polyphenylene composite (Si/PPP) with a n-type conductive PPP layer tightly bonded in a planar orientation to the surfaces of Si nanocores. Because of its compactness and flexibility, the outer PPP layer can protect the Si core from contacting the electrolyte and maintaining the structural stability of electrode/electrolyte interface during cycles. As a result, the Si/PPP anode demonstrated a high reversible capacity of ∼2387 mAh g-1, a stable cycleability with 88.5% capacity retention over 500 cycles, and, particularly, a high Coulombic efficiency of 99.7% upon extended cycling, offering a new insight for future development of high-capacity and cycle-stable Si anode.

NiGa2O4/rGO Composite as Long-Cycle-Life Anode Material for Lithium-Ion Batteries.

This work reports a novel Ga-based material, NiGa2O4, which is typically used as a photocatalyst for water splitting, as an anode for Li-ion battery with a long cycle life. High-surface-area reduced graphene oxide (rGO) has been used as the conductive substrate to avoid the aggregation of NiGa2O4 nanoparticles (NPs). Because the size and shape of NiGa2O4 are very sensitive to the pH of the precursor, ethylene glycol has been employed as the solvent, as well as the reduction agent to reduce GO, to avoid using extra surfactants and also to avoid the variation of pH of the precursor. The obtained NiGa2O4/rGO composite possesses high capacity and long cycle life (2000 cycles, 2 A/g), with NiGa2O4 NPs around 3-4 nm that are uniformly distributed on the rGO surface. Full cell performance with LiCoO2 as cathode has also been studied, with the average loss of 0.04% per cycle after 100 cycles (C/2 of LiCoO2). The long cycle life of the composite was ascribed to the self-healing feature of Ga0 formed during charging.

High-Performance Ga2O3 Anode for Lithium-Ion Batteries.

There is a great deal of interest in developing battery systems that can exhibit self-healing behavior, thus enhancing cyclability and stability. Given that gallium (Ga) is a metal that melts near room temperature, we wanted to test if it could be employed as a self-healing anode material for lithium-ion batteries (LIBs). However, Ga nanoparticles (NPs), when directly applied, tended to aggregate upon charge/discharge cycling. To address this issue, we employed carbon-coated Ga2O3 NPs as an alternative. By controlling the pH of the precursor solution, highly dispersed and ultrafine Ga2O3 NPs, embedded in carbon shells, could be synthesized through a hydrothermal carbonization method. The particle size of the Ga2O3 NPs was 2.6 nm, with an extremely narrow size distribution, as determined by high-resolution transmission electron microscopy and Brunauer-Emmett-Teller measurements. A lithium-ion battery anode based on this material exhibited stable charging and discharging, with a capacity of 721 mAh/g after 200 cycles. The high cyclability is due to not only the protective effects of the carbon shell but also the formation of Ga0 during the lithiation process, as indicated by operando X-ray absorption near-edge spectroscopy.

Suppression of Dendritic Lithium Growth by in Situ Formation of a Chemically Stable and Mechanically Strong Solid Electrolyte Interphase.

The growth and proliferation of Li dendrites during repeated Li cycling has long been a crucial issue that hinders the development of secondary Li-metal batteries. Building a stable and robust solid state electrolyte interphase (SEI) on the Li-anode surface is regarded as a promising strategy to overcome the dendrite issues. In this work, we report a simple strategy to engineer the interface chemistry of Li-metal anodes by using tiny amounts of dimethyl sulfate (DMS, C2H6SO4) as the SEI-forming additive. With the preferential reduction of DMS, an SEI layer composed of Li2S/Li2O forms on the Li surface. This inorganic SEI layer features high structural modulus and low interfacial resistant, enabling a dense and dendrite-free Li deposition as evidenced by scanning electron microscopy, atomic force microscopy, and in situ optical images. In addition, this SEI layer can prevent the deposited Li from direct contact with corrosive electrolytes, thus rendering an improved cycling stability of Li anodes with an average Coulombic efficiency of 97% for up to 150 cycles. When the DMS additive is introduced into a Li/NCM full cell, the cycle life of Li-metal batteries can be also improved significantly. This work demonstrates a feasible route to suppress Li dendrite growth by designing appropriate film-forming additives to regulate the interfacial properties of the SEI layer, and also the sulfonyl-based derivatives revealed in this work represent a large variety of new film-forming molecules, providing a broad selectivity for constructing high efficiency and cycle-stable Li anodes to address the intrinsic problems of rechargeable Li-metal batteries.

Multinuclear NMR Study of the Solid Electrolyte Interface Formed in Lithium Metal Batteries.

The composition of the solid electrolyte interphase (SEI) layers formed in Cu|Li cells using lithium bis(fluorosulfonyi)imide (LiFSI) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in 1,2-dimethoxyethane (DME) electrolytes is determined by a multinuclear solid-state MAS NMR study at high magnetic field. It is found that the "dead" metallic Li is largely reduced in the SEI layers formed in a 4 M LiFSI-DME electrolyte system compared with those formed in a 1 M LiFSI-DME electrolyte system. This finding relates directly to the safety of Li metal batteries, as one of the main safety concerns for these batteries is associated with the "dead" metallic Li formed after long-term cycling. It is also found that a large amount of LiF, which exhibits superior mechanical strength and good Li+ ionic conductivity, is observed in the SEI layer formed in the concentrated 4 M LiFSI-DME and 3 M LiTFSI-DME systems but not in the diluted 1 M LiFSI-DME system. Quantitative 6Li MAS NMR results indicate that the SEI associated with the 4 M LiFSI-DME electrolyte is denser than those formed in the 1 M LiFSI-DME and 3 M LiTFSI-DME systems. These studies reveal the fundamental mechanisms behind the excellent electrochemical performance associated with higher concentration LiFSI-DME electrolyte systems.

Graphene-Scaffolded Na3V2(PO4)3 Microsphere Cathode with High Rate Capability and Cycling Stability for Sodium Ion Batteries.

High voltage, high rate, and cycling-stable cathodes are urgently needed for development of commercially viable sodium ion batteries (SIBs). Herein, we report a facile spray-drying method to synthesize graphene-scaffolded Na3V2(PO4)3 microspheres (NVP@rGO), in which nanocrystalline Na3V2(PO4)3 is embedded in graphene sheets to form porous microspheres. Benefiting from the highly conductive graphene framework and porous structure, the NVP@rGO material exhibits a high reversible capacity (115 mAh g-1 at 0.2 C), long-term cycle life (81% of capacity retention up to 3000 cycles at 5 C), and excellent rate performance (44 mAh g-1 at 50 C). The electrochemical properties of a full Na-ion cell with the NVP@rGO cathode and Sb/C anode are also investigated. The present results suggest promising applications of the NVP@rGO material as a high performance cathode for sodium ion batteries.

Dual Core-Shell Structured Si@SiOx@C Nanocomposite Synthesized via a One-Step Pyrolysis Method as a Highly Stable Anode Material for Lithium-Ion Batteries.

Silicon (Si) has been regarded as a promising high-capacity anode material for developing advanced lithium-ion batteries (LIBs), but the practical application of Si anodes is still unsuccessful mainly due to the insufficient cyclability. To deal with this issue, we propose a new route to construct a dual core-shell structured Si@SiOx@C nanocomposite by direct pyrolysis of poly(methyl methacrylate) (PMMA) polymer on the surface of Si nanoparticles. Since the PMMA polymers can be chemically bonded on the nano-Si surface through the interaction between ester group and Si surface group, and thermally decomposed in the subsequent pyrolysis process with their alkyl chains converted to carbon and the residue oxygen recombining with Si to form SiOx, the dual core-shell structure can be conveniently formed in a one-step procedure. Benefiting from the strong buffering effect of the SiOx interlayer and the efficient blocking action of dense outer carbon layer in preventing electrolyte permeation, the obtained nanocomposite demonstrates a high capacity of 1972 mA h g-1, a stable cycling performance with a capacity retention of >1030 mA h g-1 over 500 cycles, and particularly a superiorly high Coulombic efficiency of >99.5% upon extended cycling, exhibiting a great promise for practical uses. More importantly, the synthetic method proposed in this work is facile and low cost, making it more suitable for large-scale production of high capacity anode for advanced LIBs.

The Impact of Li Grain Size on Coulombic Efficiency in Li Batteries.

One of the most promising means to increase the energy density of state-of-the-art lithium Li-ion batteries is to replace the graphite anode with a Li metal anode. While the direct use of Li metal may be highly advantageous, at present its practical application is limited by issues related to dendrite growth and low Coulombic efficiency, CE. Here operando electrochemical scanning transmission electron microscopy (STEM) is used to directly image the deposition/stripping of Li at the anode-electrolyte interface in a Li-based battery. A non-aqueous electrolyte containing small amounts of H2O as an additive results in remarkably different deposition/stripping properties as compared to the "dry" electrolyte when operated under identical electrochemical conditions. The electrolyte with the additive deposits more Li during the first cycle, with the grain sizes of the Li deposits being significantly larger and more variable. The stripping of the Li upon discharge is also more complete, i.e., there is a higher cycling CE. This suggests that larger grain sizes are indicative of better performance by leading to more uniform Li deposition and an overall decrease in the formation of Li dendrites and side reactions with electrolyte components, thus potentially paving the way for the direct use of Li metal in battery technologies.