Low-Temperature and Fast-Charge Sodium Metal Batteries.

Low-temperature operation of sodium metal batteries (SMBs) at the high rate faces challenges of unstable solid electrolyte interphase (SEI), Na dendrite growth, and sluggish Na+ transfer kinetics, causing a largely capacity curtailment. Herein, low-temperature and fast-charge SMBs are successfully constructed by synergetic design of the electrolyte and electrode. The optimized weak-solvation dual-salt electrolyte enables high Na plating/stripping reversibility and the formation of NaF-rich SEI layer to stabilize sodium metal. Moreover, an integrated copper sulfide electrode is in situ fabricated by directly chemical sulfuration of copper current collector with micro-sized sulfur particles, which significantly improves the electronic conductivity and Na+ diffusion, knocking down the kinetic barriers. Consequently, this SMB achieves the reversible capacity of 202.8 mAh g-1 at -20 °C and 1 C (1 C = 558 mA g-1 ). Even at -40 °C, a high capacity of 230.0 mAh g-1 can still be delivered at 0.2 C. This study is encouraging for further exploration of cryogenic alkali metal batteries, and enriches the electrode material for low-temperature energy storage.

Low-temperature anode-free potassium metal batteries.

In contrast to conventional batteries, anode-free configurations can extend cell-level energy densities closer to the theoretical limit. However, realizing alkali metal plating/stripping on a bare current collector with high reversibility is challenging, especially at low temperature, as an unstable solid-electrolyte interphase and uncontrolled dendrite growth occur more easily. Here, a low-temperature anode-free potassium (K) metal non-aqueous battery is reported. By introducing Si-O-based additives, namely polydimethylsiloxane, in a weak-solvation low-concentration electrolyte of 0.4 M potassium hexafluorophosphate in 1,2-dimethoxyethane, the in situ formed potassiophilic interface enables uniform K deposition, and offers K||Cu cells with an average K plating/stripping Coulombic efficiency of 99.80% at -40 °C. Consequently, anode-free Cu||prepotassiated 3,4,9,10-perylene-tetracarboxylicacid-dianhydride full batteries achieve stable cycling with a high specific energy of 152 Wh kg-1 based on the total mass of the negative and positive electrodes at 0.2 C (26 mA g-1) charge/discharge and -40 °C.

Rechargeable Potassium-Ion Full Cells Operating at -40 °C.

Potassium-ion batteries (PIBs) are promising for cryogenic energy storage. However, current researches on low-temperature PIBs are limited to half cells utilizing potassium metal as an anode, and realizing rechargeable full cells is challenged by lacking viable anode materials and compatible electrolytes. Herein, a hard carbon (HC)-based low-temperature potassium-ion full cell is successfully fabricated for the first time. Experimental evidence and theoretical analysis revealed that potassium storage behaviors of HC anodes in the matched low-temperature electrolyte involve defect adsorption, interlayer co-intercalation, and nanopore filling. Notably, these unique potassiation processes exhibited low interfacial resistances and small reaction activation energies, enabling an excellent cycling performance of HC with a capacity of 175 mAh g-1 at -40 °C (68 % of its room-temperature capacity). Consequently, the HC-based full cells demonstrated impressive rechargeability and high energy density above 100 Wh kg-1 cathode at -40 °C, representing a significant advancement in the development of PIBs.

Identification of a Novel ACE Inhibitory Hexapeptide from Camellia Seed Cake and Evaluation of Its Stability.

The camellia seed cake proteins (CP) used in this study were individually hydrolyzed with neutral protease, alkaline protease, papain, and trypsin. The results showed that the hydrolysate had the highest ACE inhibitory activity at 67.36 ± 0.80% after four hours of neutral protease hydrolysis. Val-Val-Val-Pro-Gln-Asn (VVVPQN) was then obtained through ultrafiltration, Sephadex G-25 gel chromatography separation, LC-MS/MS analysis, and in silico screening. VVVPQN had ACE inhibitory activity with an IC50 value of 0.13 mg/mL (198.66 µmol/L), and it inhibited ACE in a non-competitive manner. The molecular docking indicated that VVVPQN can combine with ACE to form eight hydrogen bonds. The results of the stability study showed that VVVPQN maintained high ACE-inhibitory activity in weakly acidic and neutral environments and that heat treatment (20-80 °C) and Na+, Mg2+, as well as Fe3+ metal ions had little effect on the activity of VVVPQN. Moreover, it remained relatively stable after in vitro simulated gastrointestinal digestion. These results revealed that VVVPQN identified in camellia seed cake has the potential to be applied in functional food or antihypertensive drugs.

Hybrid Lamellar Superlattices with Monoatomic Platinum Layers and Programmable Organic Ligands.

Compared with layered materials such as graphite and transitional metal dichalcogenides with highly anisotropic in-plane covalent bonds, freestanding metallic two-dimensional (2D) films with atomic thickness are intrinsically more difficult to achieve. The omnidirectional nature of typical metallic bonds prevents the formation of highly anisotropic atomically thin metallic layers. Herein, we report a ligand regulation strategy to stabilize monoatomic platinum layers by forming a unique lamellar superlattice structure with self-assembled organic ligand layers. We show that the interlayer spacings and coordination environments could be systematically tuned by varying programmable molecular ligands with the designed length and structural motifs, which further modulate the electronic states and catalytic performances. The strategy can be extended for preparing lamellar superlattices with monoatomic metallic layers from silver and gold. Such general and delicate synthetic control provides an exciting model system for systematic investigation of the intriguing structure-property correlation of monoatomic layers and promises a molecular design pathway for heterogeneous catalysts.

Low-Temperature High-Areal-Capacity Rechargeable Potassium-Metal Batteries.

High mass loading and high areal capacity are key metrics for commercial batteries, which are usually limited by the large charge-transfer impedance in thick electrodes. This can be kinetically deteriorated under low temperatures, and the realization of high-areal-capacity batteries in cold climates remains challenging. Herein, a low-temperature high-areal-capacity rechargeable potassium-tellurium (K-Te) battery is successfully fabricated by knocking down the kinetic barriers in the cathode and pairing it with stable anode. Specifically, the in situ electrochemical self-reconstruction of amorphous Cu1.4 Te in a thick electrode is realized simply by coating micro-sized Te on the Cu collector, significantly improving its ionic conductivity. Meanwhile, the optimized electrolyte enables fast ion transportation and a stable K-metal anode at a large current density and areal capacity. Consequently, this K-Te battery achieves a high areal capacity of 1.25 mAh cm-2 at -40 °C, which greatly exceeds those of most reported works. This work highlights the significance of electrode design and electrolyte engineering for high areal capacity at low temperatures, and represents a critical step toward practical applications of low-temperature batteries.

Dynamic Biomolecular "Mask" Stabilizes Zn Anode.

Zn anode is confronted with serious Zn dendrite growth and water-induced parasitic reactions, which severely hinders the rapid development and practical application of aqueous zinc metal batteries (AZMBs). Herein, inspired by sodium hyaluronate (SH) biomolecules in living organisms featured with the functions of water retention, ion-transport regulation, and film-formation, the SH working as a dynamic and self-adaptive "mask" is proposed to stabilize Zn anode. Benefiting from the abundant functional groups with high hydrophilicity and zincophilicity, SH molecule can constrain active water molecules on the Zn-electrolyte interface and participate in Zn2+ solvation structure to suppress parasitic reactions. Furthermore, the dynamical adsorption of SH with high-density negative charge on the Zn surface could serve as Zn2+ reservoirs to guide uniform Zn deposition. Consequently, stable Zn plating and an ultrahigh cumulative plating capacity (CPC) of 4.8 Ah cm-2 are achieved even at 20 mA cm-2 (20 mAh cm-2 ) in a Zn||Zn symmetric battery, reaching a record level in AZMBs. In addition, the Zn||ß-MnO2 full battery exhibits a substantially improved cycle stability. This work presents a route to realize a highly reversible and stable Zn metal anode by learning from nature.

2,3-diaminophenazine as a high-rate rechargeable aqueous zinc-ion batteries cathode.

Organic materials are attracting extensive attention as promising cathodes for rechargeable aqueous zinc-ion batteries (ZIBs). However, most of them fail to implement the requirement of batteries with combined high-rate and long-cycle performance. Herein, we report a flexible organic molecule 2,3-diaminophenazine (DAP) which exhibits ultrahigh rate performance up to 500C and high capacity retention of 80% after 10,000 cycles at 100C (25.5 A g-1). Moreover, the Zn2+ storage mechanism in the DAP electrode is revealed by ex-situ characterization technologies and theoretical calculation, and the redox active centers CN participate in the reversible electrochemical reaction process. Furthermore, electrochemical analyses show that surface-controlled electrochemical behavior contributes to the high-rate performance of DAP cathodes. Besides, its excellent long-cycle performance can be ascribed to the suppressed DAP dissolubility by using a modified glass fiber separator with carbon nanotubes (CNT) film. Our work provides useful insight into the design of high-rate and long-life ZIBs.

Flexible Electron-Rich Ion Channels Enable Ultrafast and Stable Aqueous Zinc-Ion Storage.

Aqueous zinc-ion batteries (ZIBs) are regarded as a promising candidate for ultrafast charge storage owing to the high ionic conductivity of aqueous electrolytes and high theoretical capacity of zinc metal anodes. However, the strong electrostatic interaction between high-charge-density zinc ions and host materials generally leads to sluggish ion-transport kinetics and structural collapse of rigid cathode materials during the charge/discharge process, so searching for suitable cathode materials for ultrafast and long-term stable ZIBs remains a great challenge. Herein, flexible electron-rich ion channels enabling fast-charging and stable aqueous ZIBs have been demonstrated. Because of the nitrogen-rich conjugated structure of organic phenazine (PNZ) molecules, electron-rich ion channels are formed with the C═N redox centers situated on the channel surface, where zinc ions can transport rapidly and react with active moieties directly. Meanwhile, the π-conjugated systems and inherent flexibility of PNZ molecules can accommodate rapid strain changes and maintain their structural stability during zinc-ion intercalation/deintercalation. Consequently, they exhibit a high capacity of 94.2 mAh g-1 at an ultrahigh rate of 700C (208.6 A g-1) and an ultralong life over 100,000 cycles at 100C, which are superior to those of previously reported aqueous ZIBs. Our work presents a new way for developing ultrafast and ultrastable aqueous ZIBs.

Rechargeable Aqueous Aluminum Organic Batteries.

Aqueous aluminum-ion batteries (AABs) are regarded as promising next-generation energy storage devices, and the current reported cathodes for AABs mainly focused on inorganic materials which usually implement a typical Al3+ ions (de)insertion mechanism. However, the strong electrostatic forces between Al3+ and the host materials usually lead to sluggish kinetics, poor reversibility and inferior cycling stability. Herein, we employ an organic compound with redox-active moieties, phenazine (PZ), as the cathode material in AABs. Different from conventional inorganic materials confined by limited lattice spacing and rigid structure, the flexible organic molecules allow a large-size Al-complex co-intercalation through reversible redox active centers (-C=N-) of PZ. This co-intercalation behavior can effectively reduce desolvation penalty, and substantially lower the Coulombic repulsion during the ion (de)insertion process. Consequently, this organic cathode exhibits a high capacity and excellent cyclability, which exceeds those of most reported electrode materials for AABs. This work highlights the anion co-intercalation chemistry of redox-active organic materials, which is expected to boost the development of high-performance multivalent-ion battery systems.

Nanopile Interlocking Separator Coating toward Uniform Li Deposition of the Li Metal Anodes.

Uncontrollable growth of lithium (Li) dendrite has severely hindered the development of Li metal anodes, while separator modification is regarded as a simple and effective way to mitigate the growth of Li dendrite. However, the "drop-dregs" phenomenon of coating layer desquamated from polyolefin separator due to their different Young's modulus would induce a nonuniform Li ionic flux, finally resulting in deteriorative electrochemical performance and even thermal runaway of the battery. Herein, we introduce a novel nanopile mechanical interlocking strategy to create delamination-free separator modification, which could stably generate a homogeneous Li ionic flux to guide long-term uniform Li deposition. Both experimental and simulation results demonstrate a strong bonding strength between the coating layer and membrane matrix based on this physical interlocking mechanism. Consequently, with a nearly dendrite-free Li deposition and a largely reduced interface impedance, 1000 h stable cycling of Li/Li half cells enrolled this modified separator is successfully achieved. Also, a significant improvement in Li/LiFePO4 full cells in long-term cycling stability to 500 cycles further indicates its promising practical potential. Moreover, this presented approach without any binding agents or surface activation procedures could be facilely scaled up, providing an applicable and durable separator modification solution toward stable Li metal anodes.

Bio-Inspired Isoalloxazine Redox Moieties for Rechargeable Aqueous Zinc-Ion Batteries.

Organic electrode materials hold great potential for fabricating sustainable energy storage systems, however, the development of organic redox-active moieties for rechargeable aqueous zinc-ion batteries is still at an early stage. Here, we report a bio-inspired riboflavin-based aqueous zinc-ion battery utilizing an isoalloxazine ring as the redox center for the first time. This battery exhibits a high capacity of 145.5 mAh g-1 at 0.01 A g-1 and a long-life stability of 3000 cycles at 5 A g-1 . We demonstrate that isoalloxazine moieties are active centers for reversible zinc-ion storage by using optical and photoelectron spectroscopies as well as theoretical calculations. Through molecule-structure tailoring of riboflavin, the obtained alloxazine and lumazine molecules exhibit much higher theoretical capacities of 250.3 and 326.6 mAh g-1 , respectively. Our work offers an effective redox-active moiety for aqueous zinc batteries and will enrich the valuable material pool for electrode design.