Developing an abnormal high-Na-content P2-type layered oxide cathode with near-zero-strain for high-performance sodium-ion batteries.

Layered transition metal oxides (NaxTMO2) possess attractive features such as large specific capacity, high ionic conductivity, and a scalable synthesis process, making them a promising cathode candidate for sodium-ion batteries (SIBs). However, NaxTMO2 suffer from multiple phase transitions and Na+/vacancy ordering upon Na+ insertion/extraction, which is detrimental to their electrochemical performance. Herein, we developed a novel cathode material that exhibits an abnormal P2-type structure at a stoichiometric content of Na up to 1. The cathode material delivers a reversible capacity of 108 mA h g-1 at 0.2C and 97 mA h g-1 at 2C, retaining a capacity retention of 76.15% after 200 cycles within 2.0-4.3 V. In situ diffraction studies demonstrated that this material exhibits an absolute solid-solution reaction with a low volume change of 0.8% during cycling. This near-zero-strain characteristic enables a highly stabilized crystal structure for Na+ storage, contributing to a significant improvement in battery performance. Overall, this work presents a simple yet effective approach to realizing high Na content in P2-type layered oxides, offering new opportunities for high-performance SIB cathode materials.

Preferred Orientation Deposition via Multifunctional Gel Electrolyte with Molecular Anchor Enabling Highly Reversible Zn Anode.

The high activity of water molecules results in a series of awful parasitic reaction, which seriously impede the development of aqueous zinc batteries. Herein, a new gel electrolyte with multiple molecular anchors is designed by employing natural biomaterials from chitosan and chlorophyll derivative. The gel electrolyte firmly anchors water molecules by ternary hydrogen bonding to reduce the activity of water molecules and inhibit hydrogen evolution reaction. Meanwhile, the multipolar charged functional groups realize the gradient induction and redistribution of Zn2+ , which drives oriented Zn (002) plane deposition of Zn2+ and then achieves uniform Zn deposition and dendrite-free anode. As a result, it endows the Zn||Zn cell with over 1700 h stripping/plating processes and a high efficiency of 99.4% for the Zn||Cu cell. In addition, the Zn||V2 O5 full cells also exhibit capacity retention of 81.7% after 600 cycles at 0.5 A g-1 and excellent long-term stability over 1600 cycles at 2 A g-1 , and the flexible pouch cells can provide stable power for light-emitting diodes even after repeated bending. The gel electrolyte strategy provides a reference for reversible zinc anode and flexible wearable devices.

Remodeling Zinc Deposition via Multisite Zincophilic Chlorophyll for Powerful Aprotic Zinc Batteries.

The organic electrolyte can resolve the hurdle of hydrogen evolution in aqueous electrolytes but suffers from sluggish electrochemical reaction kinetics due to a compromised mass transfer process. Herein, we introduce a chlorophyll, zinc methyl 3-devinyl-3-hydroxymethyl-pyropheophorbide-a (Chl), as a multifunctional electrolyte additive for aprotic zinc batteries to address the related dynamic problems in organic electrolyte systems. The Chl exhibits multisite zincophilicity, which significantly reduces the nucleation potential, increases the nucleation sites, and induces uniform nucleation of Zn metal with a nucleation overpotential close to zero. Furthermore, the lower LUMO of Chl contributes to a Zn-N-bond-containing SEI layer and inhibits the decomposition of the electrolyte. Therefore, the electrolyte enables repeated zinc stripping/plating up to 2000 h (2 Ah cm-2 cumulative capacity) with an overpotential of only 32 mV and a high Coulomb efficiency of 99.4%. This work is expected to enlighten the practical application of organic electrolyte systems.

In Situ Buildup of Zinc Anode Protection Films with Natural Protein Additives for High-Performance Zinc Battery Cycling.

The uncontrolled growth of dendrites and serious side reactions, such as hydrogen evolution and corrosion, significantly hinder the industrial application and development of aqueous zinc-ion batteries (ZIBs). This article presents ovalbumin (OVA) as a multifunctional electrolyte additive for aqueous ZIBs. Experimental characterizations and theoretical calculations reveal that the OVA additive can replace the solvated sheath of recombinant hydrated Zn2+ through the coordination water, preferentially adsorb on the surface of the Zn anode, and construct a high-quality self-healing protective film. Notably, the OVA-based protective film with strong Zn2+ affinity will promote uniform Zn deposition and inhibit side reactions. As a result, Zn||Zn symmetrical batteries in ZnSO4 electrolytes containing OVA achieve a cycle life exceeding 2200 h. Zn||Cu batteries and Zn||MnO2 (2 A g-1) full batteries show excellent cycling stability for 2500 cycles, demonstrating promising application prospects. This study provides insights into utilizing natural protein molecules to modulate the kinetics of Zn2+ diffusion and enhance the stability of the anode interface.

Aspergillus Niger Derived Wrinkle-Like Carbon as Superior Electrode for Advanced Vanadium Redox Flow Batteries.

The scarcity of high electrocatalysis composite electrode materials has long been suppressing the redox reaction of V(II)/V(III) and V(IV)/V(V) couples in high performance vanadium redox flow batteries (VRFBs). Herein, through ingeniously regulating the growth of Aspergillus Niger, a wrinkle-like carbon (WLC) material that possesses edge-rich carbon, abundant heteroatoms, and nature wrinkle-like structure is obtained, which is subsequently successfully introduced and uniform dispersed on the surface of carbon fiber of graphite felt (GF). This composite electrode presents a lower overpotential and higher charge transfer ability, as the codoped multiheteroatoms increase the electrocatalysis activity and the wrinkled structure affords more abundant reaction area for vanadium ions in the electrolyte when compared with the pristine GF electrode, which is also supported by the density functional theory (DFT) calculations. Hence, the assembled battery using WLC electrodes achieves a high energy efficiency of 74.5% for 300 cycles at a high current density of 200 mA cm-2 , as well as the highest current density of 450 mA cm-2 . The WLC material not only uncovers huge potential in promoting the application of VRFBs, but also offers referential solution to synthesis microorganism-based high-performance electrode in other energy storage systems.

[Nitric Oxide Emissions from Chinese Upland Cropping Systems and Mitigation Strategies: A Meta-analysis].

Agroecosystems are a significant source of nitric oxide (NO), a potent atmospheric pollutant. It has been well documented that the NO emissions from upland cropping systems and their emission factors are large relative to those from paddy fields. However, a clear understanding of their uncertainty and regulating factors is still lacking. To date, various field experiments have been conducted to investigate NO emissions and mitigation, providing an opportunity for a Meta-analysis. The aims of this study were to 1 investigate the uncertainty and regulating factors of NO emissions and emission factors from maize-winter wheat rotations, non-waterlogging period in rice-winter wheat rotations, vegetable fields, tea plantations, and fruit orchards across China by extracting data from peer-reviewed publications, and 2 quantify the mitigation potential of management practices, such as reducing nitrogen fertilizer input, organic substitution with chemical fertilizers, and application of enhanced-efficiency nitrogen fertilizers or biochar by performing a pairwise Meta-analysis. A total of 49 references (published from 2006 to 2021) were collected. The results showed that annual NO emissions from the maize-winter wheat rotations, tea plantations, and fruit orchards averaged 1.44, 7.45, and 0.92 kg·hm-2, respectively, with significant differences among the three cropping systems (P<0.05). The seasonal NO emissions from the non-waterlogging period in rice-winter wheat rotations and vegetable fields within a single growth period averaged 2.13 kg·hm-2 and 2.09 kg·hm-2, respectively. The NO emissions positively related to nitrogen inputs in the maize-winter wheat rotations, non-waterlogging period in rice-winter wheat rotations, and tea plantations (P<0.01) but not in the vegetable fields and fruit orchards. The emission factors averaged 0.31%, 0.71%, 0.96%, 1.74%, and 0.13% in the maize-winter wheat rotations, non-waterlogging period in rice-winter wheat rotations, vegetable fields, tea plantations, and fruit orchards, respectively, with significant differences among the cropping systems (P<0.01), except between the maize-winter wheat rotations and non-waterlogging period in rice-winter wheat rotations or vegetable fields (P>0.05). Considering the substantial differences in emission factors among the cropping systems, a specific emission factor for each system should be applied when estimating an agricultural NO budget at a regional or national scale. Reducing nitrogen input only mitigated NO emissions (by 36%) at a reducing nitrogen ratio above 25% but did not impact emission factors. An optimal reducing nitrogen ratio has to be further evaluated without crop productivity penalties. Organic substitution in soils with organic carbon content<15 g·kg-1 or pH<7 and application of enhanced-efficiency fertilizers in the maize-winter wheat rotation simultaneously mitigated NO emissions (by -46%- -38%) and emission factors (by -62%- -45%). By contrast, biochar amendment had no significant effects on either NO emissions or emission factors. These findings highlight a possibility of choosing an effective NO mitigation strategy under specific field conditions.

Electrolytes for Multivalent Metal-Ion Batteries: Current Status and Future Prospect.

Electrochemical energy storage has experienced unprecedented advancements in recent years and extensive discussions and reviews on the progress of multivalent metal-ion batteries have been made mainly from the aspect of electrode materials, but relatively little work comprehensively discusses and provides an outlook on the development of electrolytes in these systems. Under this circumstance, this Review will initially introduce different types of electrolytes in current multivalent metal-ion batteries and explain the basic ion conduction mechanisms, preparation methods, and pros and cons. On this basis, we will discuss in detail the research and development of electrolytes for multivalent metal-ion batteries in recent years, and finally, critical challenges and prospects for the application of electrolytes in multivalent metal-ion batteries will be put forward.

Formulating High-Rate and Long-Cycle Heterostructured Layered Oxide Cathodes by Local Chemistry and Orbital Hybridization Modulation for Sodium-Ion Batteries.

It is still very urgent and challenging to simultaneously develop high-rate and long-cycle oxide cathodes for sodium-ion batteries (SIBs) because of the sluggish kinetics and complex multiphase evolution during cycling. Here, the concept of accurately manipulating structural evolution and formulating high-performance heterostructured biphasic layered oxide cathodes by local chemistry and orbital hybridization modulation is reported. The P2-structure stoichiometric composition of the cathode material shows a layered P2- and O3-type heterostructure that is explicitly evidenced by various macroscale and atomic-scale techniques. Surprisingly, the heterostructured cathode displays excellent rate performance, remarkable cycling stability (capacity retention of 82.16% after 600 cycles at 2 C), and outstanding compatibility with hard carbon anode because of the integrated advantages of intergrowth structure and local environment regulation. Meanwhile, the formation process from precursors during calcination and the highly reversible dynamic structural evolution during the Na+ intercalation/deintercalation process are clearly articulated by a series of in situ characterization techniques. Also, the intrinsic structural properties and corresponding electrochemical behavior are further elucidated by the density of states and electron localization function of density functional theory calculations. Overall, this strategy, which finely tunes the local chemistry and orbitals hybridization for high-performance SIBs, will open up a new field for other materials.

[Effects of Stalk Incorporation on Soil Carbon Sequestration, Nitrous Oxide Emissions, and Global Warming Potential of a Winter Wheat-Summer Maize Field in Guanzhong Plain].

The net greenhouse gas emissions from upland soils, as indicated by global warming potential (GWP), mainly depend on the soil carbon sequestration and nitrous oxide (N2O) emissions. The annual changes in surface (0-20 cm) soil organic carbon (SOC) content from 2010 to 2017 and the N2O emissions from 2014 to 2017 were measured within a long-term fertilization experiment. The objective was to quantify the effect of stalk incorporation on the soil carbon sequestration, annual N2O emissions, and GWP of a winter wheat-summer maize field in the Guanzhong Plain. The field experiment included three treatments:conventional fertilization (CF), conventional fertilization plus maize stalks (CFS), and an unfertilized control (CK). The CF and CFS treatments received the same amount of urea per year, with nitrogen (N) input at 165 kg·hm-2 and 188 kg·hm-2 in the winter wheat season and summer maize season, respectively. The CF treatment retained the stubbles (about 10 cm above ground) when harvesting the winter wheat and summer maize crops. The CFS treatment retained the same wheat stubbles and all maize stalks (containing approximately 40 kg·hm-2 of N). The CK treatment was unfertilized throughout the year, with the stubble management the same as that in the CF treatment. The results showed that the CK treatment displayed few changes in SOC content and low N2O emissions, with GWP varying from 0.04 to 0.11 t·(hm2·a)-1. The SOC contents in the CF and CFS treatments increased linearly with the fertilization years (P<0.001), and their SOC sequestration rates were 0.69 t·(hm2·a)-1 and 0.97 t·(hm2·a)-1, respectively. The N2O emissions from the CF and CFS treatments varied from 1.65 to 5.36 kg·(hm2·a)-1 and from 3.08 to 7.73 kg·(hm2·a)-1, respectively. The annual N2O emissions from the CFS treatment were 43%-94% higher than those from the CF treatment, whereas the difference was only significant between 2015 and 2016 (P<0.05). The GWP of the CF and CFS treatments varied from -1.95 to -0.28 t·(hm2·a)-1 and from -2.59 to -0.35 t·(hm2·a)-1, respectively. The cumulative GWP of the CFS treatment was 42% lower than that of the CF treatment between 2014 and 2017. In summary, the studied winter wheat-summer maize field acted as a sink of greenhouse gases under the conventional fertilization regime. The stalk incorporation further favored greenhouse gas mitigation despite the trade-offs between SOC sequestration and N2O emissions.

A dual conducting network corbelled hydrated vanadium pentoxide cathode for high-rate aqueous zinc-ion batteries.

Aqueous zinc-ion batteries (ZIBs) are widely recognized for their excellent safety and high theoretical capacity but are hindered by the scarcity of cathode materials with high-rate performance and stability. Herein, a dual conducting network corbelled hydrated vanadium pentoxide that involves structural water as a pillar to enlarge the layer spacing of vanadium pentoxide and ensure cycling stability was reported. Along with the proton co-insertion, the hydrated vanadium pentoxide delivers nearly theoretical specific capacities of 524.6 mA h g-1 at 0.3 A g-1 and 258.7 mA h g-1 at 10 A g-1, which was largely due to non-faradaic contribution, and retains 196.8 mA h g-1 at 4.8 A g-1 after 1100 cycles. Notably, a high energy density of 409.3 W h kg-1 at 0.3 A g-1 and a power density of 6666.4 W kg-1 at 10 A g-1 have also been achieved. The design strategy offers a potential path to develop high-rate ZIBs.

Formulating the Electrolyte Towards High-Energy and Safe Rechargeable Lithium-Metal Batteries.

Rechargeable lithium-metal batteries with a cell-level specific energy of >400 Wh kg-1 are highly desired for next-generation storage applications, yet the research has been retarded by poor electrolyte-electrode compatibility and rigorous safety concerns. We demonstrate that by simply formulating the composition of conventional electrolytes, a hybrid electrolyte was constructed to ensure high (electro)chemical and thermal stability with both the Li-metal anode and the nickel-rich layered oxide cathodes. By employing the new electrolyte, Li∥LiNi0.6 Co0.2 Mn0.2 O2 cells show favorable cycling and rate performance, and a 10 Ah Li∥LiNi0.8 Co0.1 Mn0.1 O2 pouch cell demonstrates a practical specific energy of >450 Wh kg-1 . Our findings shed light on reasonable design principles for electrolyte and electrode/electrolyte interfaces toward practical realization of high-energy rechargeable batteries.

Revealing the Superiority of Fast Ion Conductor in Composite Electrolyte for Dendrite-Free Lithium-Metal Batteries.

Composite electrolytes composed of a nanoceramic and polymer have been widely studied because of their high ionic conductivity, good Li-ion transference number, and excellent machinability, whereas the intrinsic reason for the improvement of performance is ambiguous. Herein, we have designed a functional polymer skeleton with different types of nanofiller to reveal the superiority of fast ion conductors in composite electrolyte. Three types of ceramics with different dielectric constants and Li-ion transfer ability were selected to prepare composite electrolytes, the composition, structure, and electrochemical performances of which were systematically investigated. It was found that the addition of fast ion conductive ceramics could provide a high Li-ion transference ability and decreased diffusion barrier because the additional pathways existed in the ceramic, which are revealed by experiment and density functional theory calculations. Benefiting from the superiority of fast ion conductor, Li-metal batteries with this advanced composite electrolyte exhibit an impressive cycling stability and enable a dendrite-free Li surface after cycling. Our work enriches the understanding of the function of fast ion conductors in composite electrolyte and guides the design for other high-performance composite electrolytes in rechargeable solid batteries.

Analysis of survival rates and prognosis of hepatoblastoma in children: a retrospective study from a single center in China.

Hepatoblastoma (HB) is the most common liver cancer in children, this study aims at analyzing the prognostic factors affecting the survival rates and summarizing the treatment experience. In this study, we reviewed patients with primary HB under the age of 14 years who underwent complete tumor resection from June 1997 to March 2019. The data of 72 patients were collected. Survival analysis was performed by Kaplan-Meier, multivariate Cox proportional hazards regression and linear mixed model for repeated measures (LMMRM). The 5-year and the 10-year event-free survival (EFS) of all patients were 78.2% and 73%, respectively. Both the 5-year and 10-year overall survival (OS) were 85.7%. Kaplan-Meier survival analysis showed that patients with tumor capsule infiltration (TCI) and patients with surgical margin less than 1 cm may also have a good prognosis. The Cox proportional hazards regression model analysis results were similar to the Kaplan-Meier analysis results. LMMRM analysis showed that there were significant differences in platelet, alpha-fetoprotein, C-reactive protein and hemoglobin values after surgery in the metastasis group (P < 0.05). This study suggests that patients with TCI or narrow surgical margin (<1 cm) may also have a good prognosis, and the risk stratification of HB can be used as the latest grading standard to evaluate the prognosis of patients.

Spontaneous regression of stage III neuroblastoma: A case report.

BACKGROUND: Neuroblastoma (NB) is the most common type of extracranial solid tumour in children. The overall prognosis of NB is poor, but at the same time, NB shows significant clinical diversity. NB can demonstrate spontaneous regression or can differentiate into benign ganglioneuroma. CASE SUMMARY: This study retrospectively analyzed the clinical data of a patient with spontaneous regression of stage III NB who was admitted in May 2015. Studies of the spontaneous regression of NB published from October 1946 to September 2019 were retrieved through PubMed. The clinical manifestations, diagnosis, treatment, and follow-up results were analysed. CONCLUSION: Spontaneous regression of stage III NB is rare in the clinic. The report of this case is an important supplement to the study of the spontaneous regression of NB.

Enabling a Durable Electrochemical Interface via an Artificial Amorphous Cathode Electrolyte Interphase for Hybrid Solid/Liquid Lithium-Metal Batteries.

A hybrid solid/liquid electrolyte with superior security facilitates the implementation of high-energy-density storage devices, but it suffers from inferior chemical compatibility with cathodes. Herein, an optimal lithium difluoro(oxalato)borate salt was introduced to build in situ an amorphous cathode electrolyte interphase (CEI) between Ni-rich cathodes and hybrid electrolyte. The CEI preserves the surface structure with high compatibility, leading to enhanced interfacial stability. Meanwhile, the space-charge layer can be prominently mitigated at the solid/solid interface via harmonized chemical potentials, acquiring promoted interfacial dynamics as revealed by COMSOL simulation. Consequently, the amorphous CEI integrates the bifunctionality to provide an excellent cycling stability, high Coulombic efficiency, and favorable rate capability in high-voltage Li-metal batteries, innovating the design philosophy of functional CEI strategy for future high-energy-density batteries.

Preparation of a porous graphite felt electrode for advance vanadium redox flow batteries.

Rapid mass transfer and great electrochemical activity have become the critical points for designing electrodes in vanadium redox flow batteries (VRFBs). In this research, we show a porous graphite felt (GF@P) electrode to improve the electrochemical properties of VRFBs. The generation of pores on graphite felt electrodes is based on etching effects of iron to carbon. The voltage and energy efficiencies of VRFB based on the GF@P electrode can reach 72.6% and 70.7% at a current density of 200 mA cm-2, respectively, which are 8.3% and 7.9% better than that of untreated GF@U (graphite felt). Further, the VRFBs based on GF@P electrodes possess supreme stability after over 500 charge-discharge cycles at 200 mA cm-2. The high-efficiency approach reported in this study offers a new strategy for designing high-performance electrode materials applied in VRFBs.

Phosphorus and oxygen co-doped composite electrode with hierarchical electronic and ionic mixed conducting networks for vanadium redox flow batteries.

The hierarchical electronic and ionic mixed conducting networks build in graphite felt electrodes possess excellent electrocatalytic activity and faster electronic and ionic conduction, resulting in an enhanced energy efficiency of vanadium redox flow batteries with durable life for 1000 cycles and a high discharge capacity of 10.1 A h L-1 at a current density of 350 mA cm-2.

Engineering Janus Interfaces of Ceramic Electrolyte via Distinct Functional Polymers for Stable High-Voltage Li-Metal Batteries.

The fast-ionic-conducting ceramic electrolyte is promising for next-generation high-energy-density Li-metal batteries, yet its application suffers from the high interfacial resistance and poor interfacial stability. In this study, the compatible solid-state electrolyte was designed by coating Li1.4Al0.4Ti1.6(PO4)3 (LATP) with polyacrylonitrile (PAN) and polyethylene oxide (PEO) oppositely to satisfy deliberately the disparate interface demands. Wherein, the upper PAN constructs soft-contact with LiNi0.6Mn0.2Co0.2O2, and the lower PEO protects LATP from being reduced, guaranteeing high-voltage tolerance and improved stability toward Li-metal anode performed in one ceramic. Moreover, the core function of LATP is amplified to guide homogeneous ions distribution and hence suppresses the formation of a space-charge layer across interfaces, uncovered by the COMSOL Multiphysics concentration field simulation. Thus, such a bifunctional modified ceramic electrolyte integrates the respective superiority to render Li-metal batteries with excellent cycling stability (89% after 120 cycles), high Coulombic efficiency (exceeding 99.5% per cycle), and a dendrite-free Li anode at 60 °C, which represents an overall design of ceramic interface engineering for future practical solid battery systems.

Suppression of Monoclinic Phase Transitions of O3-Type Cathodes Based on Electronic Delocalization for Na-Ion Batteries.

As high capacity cathodes, O3-type Na-based oxides always suffer from a series of monoclinic transitions upon sodiation/desodiation, mainly caused by Na+/vacancy ordering and Jahn-Teller (J-T) distortion, leading to rapid structural degradation and serious performance fading. Herein, a simple modulation strategy is proposed to address this issue based on refrainment of electron localization in expectation to alleviate the charge ordering and change of electronic structure, which always lead to Na+/vacancy ordering and J-T distortion, respectively. According to density functional theory calculations, Fe3+ with slightly larger radius is introduced into NaNi0.5Mn0.5O2 with the intention of enlarging transition metal layers and facilitating electronic delocalization. The obtained NaFe0.3Ni0.35Mn0.35O2 exhibits a reversible phase transition of O3hex-P3hex without any monoclinic transitions in striking contrast with the complicated phase transitions (O3hex-O'3mon-P3hex-P'3mon-P3'hex) of NaNi0.5Mn0.5O2, thus excellently improving the capacity retention with a high rate kinetic. In addition, the strategy is also effective to enhance the air stability, proved by direct observation of atomic-scale ABF-STEM for the first time.

Unveiling the Role of Heteroatom Gradient-Distributed Carbon Fibers for Vanadium Redox Flow Batteries with Long Service Life.

The fundamental understanding of electrocatalytic reaction process is anticipated to guide electrode upgradation and acquirement of high-performance vanadium redox flow batteries (VRFBs). Herein, a carbon fiber prototype system with a heteroatom gradient distribution has been developed with enlarged interlayer spacing and a high graphitization that improve the electronic conductivity and accelerate the electrocatalytic reaction, and the mechanism by which gradient-distributed heteroatoms enhance vanadium redox reactions was elucidated with the assistance of density functional theory calculations. All these contributions endow the obtained electrode prominent redox reversibility and durability with only 1.7% decay in energy efficiency over 1000 cycles at 150 mA cm-2 in the VRFBs. Our work sheds light on the significance of elaborated electrode design and impels the in-depth investigation of VRFBs with long service life.