Room-temperature sodium-ion batteries (SIBs) are regarded as promising candidates for smart grids and large-scale energy storage systems (EESs) due to their significant benefits of abundant and ...low-cost sodium resource. Among the previously reported cathode materials for SIBs, layered transition-metal oxides and polyanion-type materials are considered to be the most attractive options. Although many layered transition-metal oxides can provide high capacity due to their small molecular weight, their further application is hindered by low output voltage (mostly lower than 3.5 V), irreversible phase transition as well as storage instability. Comparatively, polyanion-type materials exhibit higher operating potentials due to the inductive effect of polyanion groups. Their robust 3D framework significantly decreases the structural variations during sodium ion de/intercalation. Moreover, the effect of strong X-O (X = S, P, Si,
etc.
) covalent bonds can effectively inhibit oxygen evolution. These advantages contribute to the superior cycle stability and high safety of polyanion-type materials. However, low electronic conductivity and limited capacity still restrict their further application. This review summarizes the recent progress of polyanion-type materials for SIBs, which include phosphates, fluorophosphates, pyrophosphates, mixed phosphates, sulfates, and silicates. We also discuss the remaining challenges and corresponding strategies for polyanion-type materials. We hope this review can provide some insights into the development of polyanionic materials.
This review summarizes the recent progress and remaining challenges of polyanion-type cathodes, providing guidelines towards high-performance cathodes for sodium ion batteries.
Realizing solid‐state lithium batteries with higher energy density and enhanced safety compared to the conventional liquid lithium‐ion batteries is one of the primary research and development goals ...set for next‐generation batteries in this decade. In this regard, polymer electrolytes have been widely researched as solid electrolytes due to their excellent processability, flexibility, and low weight. With high cationic transference numbers (tLi+ close to 1), single‐ion conducting polymer electrolytes (SICPEs) have tremendous advantages compared to polymer electrolyte systems (tLi+ < 0.4) because of their potential to reduce the buildup of ion concentration gradients and suppress growth of lithium dendrites. The current review covers the fundamentals of SICPEs, including anionic unit synthesis, polymer structure design, and film fabrication, along with simulation and experimental results in solid‐state lithium–metal battery applications. A perspective on current challenges, possible solutions, and potential research directions of SICPEs is also discussed to provide the research community with the critical technical aspects that may advance SICPEs as solid electrolytes in next‐generation energy storage systems.
This review covers the fundamentals of single‐ion conducting polymer electrolytes (SICPEs), including anionic unit synthesis, structure design, and film fabrication, along with simulation and experimental results in solid‐state lithium‐metal batteries. A perspective on current challenges, possible solutions, and research directions of SICPEs is also discussed to provide critical aspects that may advance SICPEs as solid electrolytes in lithium‐metal batteries.
P2‐type layered oxides suffer from an ordered Na+/vacancy arrangement and P2→O2/OP4 phase transitions, leading them to exhibit multiple voltage plateaus upon Na+ extraction/insertion. The deficient ...sodium in the P2‐type cathode easily induces the bad structural stability at deep desodiation states and limited reversible capacity during Na+ de/insertion. These drawbacks cause poor rate capability and fast capacity decay in most P2‐type layered oxides. To address these challenges, a novel high sodium content (0.85) and plateau‐free P2‐type cathode‐Na0.85Li0.12Ni0.22Mn0.66O2 (P2‐NLNMO) was developed. The complete solid‐solution reaction over a wide voltage range ensures both fast Na+ mobility (10−11 to 10−10 cm2 s−1) and small volume variation (1.7 %). The high sodium content P2‐NLNMO exhibits a higher reversible capacity of 123.4 mA h g−1, superior rate capability of 79.3 mA h g−1 at 20 C, and 85.4 % capacity retention after 500 cycles at 5 C. The sufficient Na and complete solid‐solution reaction are critical to realizing high‐performance P2‐type cathodes for sodium‐ion batteries.
A high sodium content (0.85) and plateau‐free P2‐type cathode, Na0.85Li0.12Ni0.22Mn0.66O2, is developed for sodium‐ion batteries. The sodium content promises a large specific capacity of 123.4 mA h g−1 with an average working voltage as high as 3.5 V. The complete solid‐solution reaction over a wide voltage range ensures small volume variation (1.7 %) and fast Na+ kinetics (10−10 to 10−11 cm2 s−1), contributing to both excellent cycling stability and rate capability.
Electrochemical CO2 reduction reaction (CO2RR) is a promising approach to convert CO2 to carbon‐neutral fuels using external electric powers. Here, the Bi2S3‐Bi2O3 nanosheets possessing substantial ...interface being exposed between the connection of Bi2S3 and Bi2O3 are prepared and subsequently demonstrate to improve CO2RR performance. The electrocatalyst shows formate Faradaic efficiency (FE) of over 90% in a wide potential window. A high partial current density of about 200 mA cm−2 at −1.1 V and an ultralow onset potential with formate FE of 90% are achieved in a flow cell. The excellent electrocatalytic activity is attributed to the fast‐interfacial charge transfer induced by the electronic interaction at the interface, the increased number of active sites, and the improved CO2 adsorption ability. These collectively contribute to the faster reaction kinetics and improved selectivity and consequently, guarantee the superb CO2RR performance. This study provides an appealing strategy for the rational design of electrocatalysts to enhance catalytic performance by improving the charge transfer ability through constructing a functional heterostructure, which enables interface engineering toward more efficient CO2RR.
The heterostructured Bi2S3‐Bi2O3 nanosheets with substantial amount of interface are designed, which demonstrate the enhanced CO2 electroreduction performance. The fast‐interfacial charge transfer induced by the electronic interaction at the interface, together with the increased number of active sites and the improved CO2 adsorption ability, collectively contribute to the improved electrocatalytic performance.
A synergistic catalytic method combining photoredox catalysis, hydrogen‐atom transfer, and proton‐reduction catalysis for the dehydrogenative silylation of alkenes was developed. With this approach, ...a highly concise route to substituted allylsilanes has been achieved under very mild reaction conditions without using oxidants. This transformation features good to excellent yields, operational simplicity, and high atom economy. Based on control experiments, a possible reaction mechanism is proposed.
A synergistic catalytic method of combining photoredox catalysis, hydrogen‐atom transfer, and proton‐reduction catalysis for the dehydrogenative silylation of alkenes was developed. The reaction features high regioselectivity, excellent tolerance of functional groups, wide substrate scope, and mild reaction conditions. Moreover, this oxidant‐free system offers a cleaner and more efficient method beyond traditional catalysis, which requires either stoichiometric or excess amounts of oxidants.
High‐Energy Aqueous Sodium‐Ion Batteries Jin, Ting; Ji, Xiao; Wang, Peng‐Fei ...
Angewandte Chemie International Edition,
May 17, 2021, Letnik:
60, Številka:
21
Journal Article
Recenzirano
Water‐in‐salt electrolytes (WISE) have largely widened the electrochemical stability window (ESW) of aqueous electrolytes by formation of passivating solid electrolyte interphase (SEI) on anode and ...also absorption of the hydrophobic anion‐rich double layer on cathode. However, the cathodic limiting potential of WISE is still too high for most high‐capacity anodes in aqueous sodium‐ion batteries (ASIBs), and the cost of WISE is also too high for practical application. Herein, a low‐cost 19 m (m: mol kg−1) bi‐salts WISE with a wide ESW of 2.8 V was designed, where the low‐cost 17 m NaClO4 extends the anodic limiting potential to 4.4 V, while the fluorine‐containing salt (2 m NaOTF) extends the cathodic limiting potential to 1.6 V by forming the NaF–Na2O–NaOH SEI on anode. The 19 m NaClO4–NaOTF–H2O electrolyte enables a 1.75 V Na3V2(PO4)3∥Na3V2(PO4)3 full cell to deliver an appreciable energy density of 70 Wh kg−1 at 1 C with a capacity retention of 87.5 % after 100 cycles.
A NaClO4/NaOTF electrolyte was designed for aqueous Na‐ion batteries (ASIBs). The solid electrolyte interphase (SEI) containing NaF–Na2O–NaOH forming on the anode extended the cathodic limiting potential of electrolyte to 1.6 V, and the hydrophobic anions extend the anodic to 4.4 V. A 1.75 V Na3V2(PO4)3∥Na3V2(PO4)3 cell achieved a high energy density of 70 Wh kg−1 with 87.5 % capacity retention after 100 cycles.
Objectives
This study was conducted in order to establish and validate a radiomics model for predicting lymph node (LN) metastasis of intrahepatic cholangiocarcinoma (IHC) and to determine its ...prognostic value.
Methods
For this retrospective study, a radiomics model was developed in a primary cohort of 103 IHC patients who underwent curative-intent resection and lymphadenectomy. Radiomics features were extracted from arterial phase computed tomography (CT) scans. A radiomics signature was built based on highly reproducible features using the least absolute shrinkage and selection operator (LASSO) method. Multivariate logistic regression analysis was adopted to establish a radiomics model incorporating radiomics signature and other independent predictors. Model performance was determined by its discrimination, calibration, and clinical usefulness. The model was internally validated in 52 consecutive patients.
Results
The radiomics signature comprised eight LN-status–related features and showed significant association with LN metastasis in both cohorts (
p
< 0.001). A radiomics nomogram that incorporates radiomics signature and CA 19-9 level showed good calibration and discrimination in the primary cohort (AUC 0.8462) and validation cohort (AUC 0.8921). Promisingly, the radiomics nomogram yielded an AUC of 0.9224 in the CT-reported LN-negative subgroup. Decision curve analysis confirmed the clinical utility of this nomogram. High risk for metastasis portended significantly lower overall and recurrence-free survival than low risk for metastasis (both
p
< 0.001). The radiomics nomogram was an independent preoperative predictor of overall and recurrence-free survival.
Conclusions
Our radiomics model provided a robust diagnostic tool for prediction of LN metastasis, especially in CT-reported LN-negative IHC patients, that may facilitate clinical decision-making.
Key Points
• The radiomics nomogram showed good performance for prediction of LN metastasis in IHC patients, particularly in the CT-reported LN-negative subgroup.
• Prognosis of high-risk patients remains dismal after curative-intent resection.
• The radiomics model may facilitate clinical decision-making and define patient subsets benefiting most from surgery.
Bambusoideae is the only subfamily that contains woody members in the grass family, Poaceae. In phylogenetic analyses, Bambusoideae, Pooideae and Ehrhartoideae formed the BEP clade, yet the internal ...relationships of this clade are controversial. The distinctive life history (infrequent flowering and predominance of asexual reproduction) of woody bamboos makes them an interesting but taxonomically difficult group. Phylogenetic analyses based on large DNA fragments could only provide a moderate resolution of woody bamboo relationships, although a robust phylogenetic tree is needed to elucidate their evolutionary history. Phylogenomics is an alternative choice for resolving difficult phylogenies.
Here we present the complete nucleotide sequences of six woody bamboo chloroplast (cp) genomes using Illumina sequencing. These genomes are similar to those of other grasses and rather conservative in evolution. We constructed a phylogeny of Poaceae from 24 complete cp genomes including 21 grass species. Within the BEP clade, we found strong support for a sister relationship between Bambusoideae and Pooideae. In a substantial improvement over prior studies, all six nodes within Bambusoideae were supported with ≥0.95 posterior probability from Bayesian inference and 5/6 nodes resolved with 100% bootstrap support in maximum parsimony and maximum likelihood analyses. We found that repeats in the cp genome could provide phylogenetic information, while caution is needed when using indels in phylogenetic analyses based on few selected genes. We also identified relatively rapidly evolving cp genome regions that have the potential to be used for further phylogenetic study in Bambusoideae.
The cp genome of Bambusoideae evolved slowly, and phylogenomics based on whole cp genome could be used to resolve major relationships within the subfamily. The difficulty in resolving the diversification among three clades of temperate woody bamboos, even with complete cp genome sequences, suggests that these lineages may have diverged very rapidly.
Celotno besedilo
Dostopno za:
DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
As one of the most promising cathode candidates for room‐temperature sodium‐ion batteries (SIBs), P2‐type layered oxides face the challenge of simultaneously realizing high‐rate performance while ...achieving long cycle life. Here, a stable Na2/3Ni1/6Mn2/3Cu1/9Mg1/18O2 cathode material is proposed that consists of multiple‐layer oriented stacking nanoflakes, in which the nickel sites are partially substituted by copper and magnesium, a characteristic of the material that is confirmed by multiscale scanning transmission electron microscopy and electron energy loss spectroscopy techniques. Owing to the optimal morphology structure modulation and chemical element substitution strategy, the electrode displays remarkable rate performance (73% capacity retention at 30C compared to 0.5C) and outstanding cycling stability in Na half‐cell system couple with unprecedented full battery performance. The underlying thermal stability, phase stability, and Na+ storage mechanisms are clearly elucidated through the systematical characterizations of electrochemical behaviors, in situ X‐ray diffraction at different temperatures, and operando X‐ray diffraction upon Na+ deintercalation/intercalation. Surprisingly, a quasi‐solid‐solution reaction is switched to an absolute solid‐solution reaction and a capacitive Na+ storage mechanism is demonstrated via quantitative electrochemical kinetics calculation during charge/discharge process. Such a simple and effective strategy might reveal a new avenue into the rational design of excellent rate capability and long cycle stability cathode materials for practical SIBs.
A stable copper and magnesium cosubstituted Na2/3Ni1/6Mn2/3Cu1/9Mg1/18O2 cathode material consisting of multiple‐layer oriented stacking nanoflakes is reported. An optimal structure design and a chemical element substitution strategy are demonstrated to greatly improve Na+ transport kinetics and structural stability of P2‐type cathode material, resulting in high‐rate and long cycle life for a sodium‐ion battery.
As one of the most promising cathodes for rechargeable sodium‐ion batteries (SIBs), O3‐type layered transition metal oxides commonly suffer from inevitably complicated phase transitions and sluggish ...kinetics. Here, a NaLi0.05Ni0.3Mn0.5Cu0.1Mg0.05O2 cathode material with the exposed {010} active facets by multiple‐layer oriented stacking nanosheets is presented. Owing to reasonable geometrical structure design and chemical substitution, the electrode delivers outstanding rate performance (71.8 mAh g−1 and 16.9 kW kg−1 at 50C), remarkable cycling stability (91.9% capacity retention after 600 cycles at 5C), and excellent compatibility with hard carbon anode. Based on the combined analyses of cyclic voltammograms, ex situ X‐ray absorption spectroscopy, and operando X‐ray diffraction, the reaction mechanisms behind the superior electrochemical performance are clearly articulated. Surprisingly, Ni2+/Ni3+ and Cu2+/Cu3+ redox couples are simultaneously involved in the charge compensation with a highly reversible O3–P3 phase transition during charge/discharge process and the Na+ storage is governed by a capacitive mechanism via quantitative kinetics analysis. This optimal bifunctional regulation strategy may offer new insights into the rational design of high‐performance cathode materials for SIBs.
An O3‐type NaLi0.05Ni0.3Mn0.5Cu0.1Mg0.05O2 cathode material with exposed {010} active facets by multiple‐layer oriented stacking nanosheets is successfully constructed via reasonable structure design and chemical substitution. An optimal bifunctional regulation is demonstrated to be an efficient strategy to restrain the unfavorable multiphase transformation and greatly improve Na+ transport kinetics resulting in excellent performance for sodium‐ion batteries.
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