Wide-Temperature and High-Rate Operation of Lithium Metal Batteries Enabled by an Ionic Liquid Functionalized Quasi-Solid-State Electrolyte.

The development of high-energy-density solid-state lithium metal battery has been hindered by the unstable cycling of Ni-rich cathodes at high rate and limited wide-temperatures adoptability. In this study, an ionic liquid functionalized quasi-solid-state electrolyte (FQSE) is prepared to address these challenges. The FQSE features a semi-immobilized ionic liquid capable of anchoring solvent molecules through electrostatic interactions, which facilitates Li+ desolvation and reduces deleterious solvent-cathode reactions. The FQSE exhibits impressive electrochemical characteristics, including high ionic conductivity (1.9 mS cm-1 at 30 °C and 0.2 mS cm-1 at -30 °C) and a Li+ transfer number of 0.7. Consequently, Li/NCM811 cells incorporating FQSE demonstrate exceptional stability during high-rate cycling, enduring 700 cycles at 1 C. Notably, the Li/LFP cells with FQSE maintain high capacity across a wide temperature range, from -30 to 60 °C. This research provides a new way to promote the practical application of high-energy lithium metal batteries.

Designing a Refined Multi-Structural Polymer Electrolyte Framework for Highly Stable Lithium-Metal Batteries.

Rational structural designs of solid polymer electrolytes featuring rich interface-phase morphologies can improve electrolyte connection and rapid ion transport. However, these rigid interfacial structures commonly result in diminished or entirely inert ionic conductivity within their bulk phase, compromising overall electrolyte performance. Herein, a multi-component ion-conductive electrolyte was successfully designed based on a refined multi-structural polymer electrolyte (RMSPE) framework with uniform Li+ solvation chemistry and rapid Li+ transporting kinetics. The RMSPE framework is constructed via polymerization-induced phase separation based on a rational combination of lithiophilic components and rigid/flexible chain units with significant hydrophobic/hydrophilic contrasts. Further refined by coating a robust polymer network, this all-organic design endows a homogeneous micro-nano porous structure, providing a novel framework favorable for rapid ion transport in both its soft interfacial and bulk phases. The RMSPE exhibited excellent ion conductivity of 1.91 mS cm-1 at room temperature and a high Li+ transference number of 0.7. Assembled symmetrical Li cells realized stable cycling for over 2400 h at 3.0 mA cm-2. LiFePO4 full batteries demonstrated a long lifespan of 3300 cycles with a capacity retention of 93.5 % and stable cycling performance at -35 °C. This innovative design concept offers a promising perspective for achieving high-performance polymer-based Li metal batteries.

Multifunctional Interface Layer Constructed by Trace Zwitterions for Highly Reversible Zinc Anodes.

The inhomogeneous plating/stripping of Zn anode, attributed to dendrite growth and parasitic reactions at the electrode/electrolyte interface, severely restricts its cycling life-span. Here, trace zwitterions (trifluoroacetate pyridine, TFAPD) are introduced into the aqueous electrolyte to construct a multifunctional interface that enhances the reversibility of Zn anode. The TFA- anions with strong specific adsorption adhere onto the Zn surface to reconstruct the inner Helmholtz plane (IHP), preventing the hydrogen evolution and corrosion side reactions caused by free H2O. The Py+ cations accumulate on the outer Helmholtz plane (OHP) of Zn anode with the force of electric field during Zn2+ plating, forming a shielding layer to uniformize the deposition of Zn2+. Besides, the adsorbed TFA- and Py+ promote the desolvation process of Zn2+ resulting in fast reaction kinetics. Thus, the Zn||Zn cells present an outstanding cycling performance of more than 10000 hours. And even at 85 % utilization rate of Zn, it can stably cycle for over 200 hours at 10 mA cm-2 and 10 mAh cm-2. The Zn||I2 full cell exhibits a capacity retention of over 95 % even after 30000 cycles. Remarkably, the Zn||I2 pouch cells (95 mAh) deliver a high-capacity retention of 99 % after 750 cycles.

Activating and Stabilizing a Reversible four Electron Redox Reaction of I-/I+ for Aqueous Zn-Iodine Battery.

Low capacity and poor cycle stability greatly inhibit the development of zinc-iodine batteries. Herein, a high-performance Zn-iodine battery has been reached by designing and optimizing both electrode and electrolyte. The Br- is introduced as the activator to trigger I+, and coupled with I+ forming interhalogen to stabilize I+ to achieve a four-electron reaction, which greatly promotes the capacity. And the Ni-Fe-I LDH nanoflowers serve as the confinement host to enable the reactions of I-/I+ occurring in the layer due to the spacious and stable interlayer spacing of Ni-Fe-I LDH, which effectively suppresses the iodine-species shuttle ensuring high cycling stability. As a result, the electrochemical performance is greatly enhanced, especially in specific capacity (as high as 350 mAh g-1 at 1 A g-1 far higher than two-electron transfer Zn-iodine batteries) and cycling performance (94.6 % capacity retention after 10000 cycles). This strategy provides a new way to realize high capacity and long-term stability of Zn-iodine batteries.

Reductive Competition Effect-Derived Solid Electrolyte Interphase with Evenly Scattered Inorganics Enabling Ultrahigh Rate and Long-Life Span Sodium Metal Batteries.

Constructing an inorganic-rich and robust solid electrolyte interphase (SEI) is one of the crucial approaches to improving the electrochemical performance of sodium metal batteries (SMBs). However, the low conductivity and distribution of common inorganics in SEI disturb Na+ diffusion and induce nonuniform sodium deposition. Here, we construct a unique SEI with evenly scattered high-conductivity inorganics by introducing a self-sacrifice LiTFSI into the sodium salt-base carbonate electrolyte. The reductive competition effect between LiTFSI and FEC facilitates the formation of the SEI with evenly scattered inorganics. In which the high-conductive Li3N and inorganics provide fast ions transport domains and high-flux nucleation sites for Na+, thus conducive to rapid sodium deposition at a high rate. Therefore, the SEI derived from LiTFSI and FEC enables the Na∥Na3V2(PO4)3 cell to show 89.15% capacity retention (87.62 mA h g-1) at an ultrahigh rate of 60 C after 10,000 cycles, while the cell without LiTFSI delivers only 48.44% capacity retention even after 8000 cycles. Moreover, the Na∥Na3V2(PO4)3 pouch cell with the special SEI presents a stable capacity retention of 92.05% at 10 C after 2000 cycles. This unique SEI design elucidates a new strategy to propel SMBs to operate under extreme high-rate conditions.

The impact of the initial operation of PTC in children on recurrence: 9-year experience in a single center.

PURPOSE: To summarize the treatment experience of single-center children with PTC and to explore the influence of initial surgery on the recurrence/metastasis of papillary thyroid carcinoma (PTC) in children. METHODS: A retrospective analysis of PTC case data of children (≤ 18 years old) who were admitted to and received surgical treatment in the First Affiliated Hospital of Kunming Medical University from January 2012 to December 2020. RESULTS: A total of 64 children with PTC were included, including 45 cases (70.31%) with a single lesion, and 19 cases (29.69%) with multiple lesions (≥ 2 lesions). Fifteen patients relapsed. Univariate analysis found that gender, thyroidectomy scope, central lymph node dissection, and lateral lymph node dissection were risk factors affecting reoperation; multi-factor analysis showed that central lymph node dissection was an independent risk factor affecting reoperation. According to Kaplan-Meier analysis, central lymph node dissection, total thyroidectomy (TT), lobectomy (LT), and disease-free survival (DFS) were statistically significant (p = 0.000, p = 0.000). CONCLUSION: At the time of diagnosis of PTC in children, the rate of lymph node metastasis in the central and lateral cervical regions is high. The vast majority of children with PTC should be treated with TT, and LT is chosen for a small number of patients. CND should be routinely lined.

A Temperature Self-Adaptive Electrolyte for Wide-Temperature Aqueous Zinc-Ion Batteries.

The advancement of aqueous zinc-ion batteries (AZIBs) is often hampered by the dendritic zinc growth and the parasitic side reactions between the zinc anode and the aqueous electrolyte, especially under extreme temperature conditions. This study unveils the performance decay mechanism of zinc anodes in harsh environments, characterized by "dead zinc" at low temperatures and aggravated hydrogen evolution and adverse by-products at elevated temperatures. To address these issues, a temperature self-adaptive electrolyte (TSAE), founded on the competitive coordination principle of co-solvent and anions, is introduced. This electrolyte exhibits a dynamic solvation capability, engendering an inorganic-rich solid electrolyte interface (SEI) at low temperatures while an organic alkyl ether- and alkyl carbonate-containing SEI at elevated temperatures. The self-adaptability of the electrolyte significantly enhances the performance of the zinc anode across a broad temperature range. A Zn//Zn symmetrical cell, based on the TSAE, showcases reversible plating/stripping exceeding 16 800 h (>700 d) at room temperature under 1 mA cm-2 and 1 mAh cm-2, setting a record of lifespan. Furthermore, the TSAE enables stable operation of the zinc full batteries across an ultrawide temperature range of -35 to 75 °C. This work illuminates a pathway for optimizing AZIBs under extreme temperatures by fine-tuning the interfacial chemistry.

Insight into Sulfur-Containing Zwitter-Molecule Boosting Zn Anode: from Electrolytes to Electrodes.

Numerous organic electrolytes additives have been reported to improve Zn anode performance in aqueous Zn metal batteries (AZMBs). However, the modification mechanism needs to be further revealed in consideration of different environments for electrolytes and electrodes during the charge-discharge process. Herein, sulfur-containing zwitter-molecule (methionine, Met) is used as an additive for ZnSO4 electrolytes. In electrolytes, Met reduces the H2O coordination number and facilitates the desolvation process by virtue of functional groups (─COOH, ─NH2, C─S─C), accelerating Zn2+ transference kinetics and decreasing the amount of active water. On electrodes, Met prefers to adsorb on Zn (002) plane and further transforms into a zincophilic protective layer containing C─SOx─C through an in situ electrochemical oxidization, suppressing H2 evolution/corrosion reactions and guiding dendrite-free Zn deposition. By using Met-containing ZnSO4 electrolytes, the Zn//Zn cells show superior cycling performance under 30 mA cm-2/30 mA h cm-2. Moreover, the full cells Zn//NH4V4O10 full cells using the modified electrolytes exhibit good performance at temperatures from -8 to 60 °C. Notably, a high energy density of 105.30 W h kg-1 can be delivered using a low N/P ratio of 1.2, showing a promising prospect of Met electrolytes additives for practical use.

Recent advances in electrospinning nanofiber materials for aqueous zinc ion batteries.

Aqueous zinc ion batteries (AZIBs) are regarded as one of the most promising large-scale energy storage systems because of their considerable energy density and intrinsic safety. Nonetheless, the severe dendrite growth of the Zn anode, the serious degradation of the cathode, and the boundedness of separators restrict the application of AZIBs. Fortunately, electrospinning nanofibers demonstrate huge potential and bright prospects in constructing AZIBs with excellent electrochemical performance due to their controllable nanostructure, high conductivity, and large specific surface area (SSA). In this review, we first briefly introduce the principles and processing of the electrospinning technique and the structure design of electrospun fibers in AZIBs. Then, we summarize the recent advances of electrospinning nanofibers in AZIBs, including the cathodes, anodes, and separators, highlighting the nanofibers' working mechanism and the correlations between electrode structure and performance. Finally, based on insightful understanding, the prospects of electrospun fibers for high-performance AZIBs are also presented.

An advanced Ca/Zn hybrid battery enabled by the dendrite-free zinc anode and a reversible calcification/decalcification NASICON cathode.

The proposal of hybrid ion batteries, which can integrate the advantages of the single ion battery, opens up a new route for developing high-performance secondary batteries. Herein, we successfully constructed an aqueous hybrid battery comprised of polyanionic-type cathode material (Na3V2(PO4)3, NVP), Zn metal anode, and aqueous Ca2+/Zn2+ hybrid electrolyte. This exciting combination gives full play to not only the excellent diffusion dynamics of Ca2+ in the NASICON (sodium super ion conductors) structure but also the electrostatic shielding effect of Ca2+ with low reduction potential that inhibits the formation of zinc dendrites. As results, the NVP//Zn Zn/Ca hybrid battery delivers favorable specific capacity with outstanding rate performance (85.3 mAh g-1 capacity at 1 C, 60.5 mAh g-1 capacity at 20 C), and excellent cycle stability (74 % capacity retention after 1300 cycles).

An electrochemical activation strategy boosted alkaline Zinc-ion battery with Ultra-high energy density.

Aqueous zinc ion batteries (AZIBs) have broad prospects in many fields because of their high theoretical capacity, high hydrogen overpotential, low equilibrium potential, low cost and high safety. However, the surface chemical reactivity of cathode is usually limited by the utilization of active materials, resulting in insensitive edge position and unsatisfactory capacity. In this paper, a simple and convenient strategy is reported, in which the bimetallic phosphide nano-interfaces are constructed only by electrochemical high-voltage activation, so as to increase the electrode capacity of about 150 % (compared to the original NiCoP electrode). Under the combined action of water and oxygen, a coating of NiCo-OH nanosheet is formed on the NiCoP nano-wall, and the surfaces are rich in low-priced mixed state with remarkable reactivity and structural stability, which is theoretically confirmed by density functional theory (DFT). As a result, the 3D cathode has an ultra-high capacity of 544.9 mAh g-1 and excellent rate performance (still about 69.5 % at 30 A g-1). The assembled NCPOH//Zn battery has excellent reversibility and long life (maintained 97 % of initial capacity after 2000 cycles) and achieves a remarkable energy density of 933.5 Wh kg-1. Our work explores the relationship between interface corrosion mechanism and corrosion surface activity, which is a powerful strategy to build metal phosphides with high surface electrochemical activity as advanced energy storage devices.

Simultaneously Stabilizing Both Electrodes and Electrolytes by a Self-Separating Organometallics Interface for High-Performance Zinc-Ion Batteries at Wide Temperatures.

Rechargeable aqueous zinc-ion batteries are of great potential as one of the next-generation energy-storage devices due to their low cost and high safety. However, the development of long-term stable electrodes and electrolytes still suffers from great challenges. Herein, a self-separation strategy is developed for an interface layer design to optimize both electrodes and electrolytes simultaneously. Specifically, the coating with an organometallics (sodium tricyanomethanide) evolves into an electrically responsive shield layer composed of nitrogen, carbon-enriched polymer network, and sodium ions, which not only modulates the zinc-ion migration pathways to inhibit interface side reactions but also adsorbs onto Zn perturbations to induce planar zinc deposition. Additionally, the separated ions from the coating can diffuse to the electrolyte to affect the Zn2+ solvation structure and maintain the cathode structural stability by forming a stable cathode-electrolyte interface and sodium ions' equilibrium, confirmed by in situ spectroscopy and electrochemical analysis. Due to these unique advantages, the symmetric zinc batteries exhibit an extralong cycling lifespan of 3000 h and rate performance at 20 mA cm-2 at wide temperatures. The efficiency of the self-separation strategy is further demonstrated in practical full batteries with an ultralong lifespan over 10 000 cycles from -35 to 60 °C.

Towards advanced aqueous zinc battery by exploiting synergistic effects between crystalline phosphide and amorphous phosphate.

High-performance aqueous zinc batteries are expected to be realized, rooting from component synergistic effects of the hierarchical composite electrode materials. Herein, hierarchical crystalline Ni-Co phosphide coated with amorphous phosphate nanoarrays (C-NiCoP@A-NiCoPO4) self-supporting on the Ni foam are constructed as cathode material of an aqueous zinc battery. In this unique core-shell structure, the hexagonal phosphide with high conductivity offers ultra-fast electronic transmission and amorphous phosphate with high stability, and open-framework provides more favorable ion diffusivity and a stable protective barrier. The synergistic effects of this intriguing core-shell structure endow the electrode material with outstanding reaction kinetics and structural stability, which is theoretically confirmed by density functional theory (DFT) calculations. As a result, the C-NiCoP@A-NiCoPO4 electrode exhibits a higher specific capacity of 350.6 mA h g-1 and excellent cyclic stability with 92.6% retention after 10 000 cycles. Moreover, the C-NiCoP@A-NiCoPO4 is coupled with Zn anode to assemble an aqueous pouch battery that delivers ultra-high energy density (626.33 W h kg-1 at 1.72 kW kg-1) with extraordinary rate performance (452.05 W h kg-1 at 33.56 kW kg-1). Moreover, the corresponding quasi-solid flexible battery with polyacrylamide hydrogel electrolyte exhibits favorable durability under frequent mechanical strains, which indicates the great promise of crystalline/amorphous hierarchical electrodes in the field of energy storage.