Hydrogen Bond Networks Stabilized High-Capacity Organic Cathode for Lithium-Ion Batteries.

High-capacity small organic materials are plagued by their high solubility. Here we proposed constructing hydrogen bond networks (HBN) via intermolecular hydrogen bonds to suppress the solubility of active material. The illustrated 2, 7- diamino-4, 5, 9, 10-tetraone (PTO-NH2 ) molecule with intermolecular hydrogen (H) bond between O in -C=O and H in -NH2 , which make PTO-NH2 presents transverse two-dimensional extension and longitudinal π-π stacking structure. In situ Fourier transform infrared spectroscopy (FTIR) has tracked the reversible evolution of H-bonds, further confirming the existence of HBN structure can stabilize the intermediate 2-electron reaction state. Therefore, PTO-NH2 with HBN structure has higher active site utilization (95 %), better cycle stability and rate performance. This study uncovers the H-bond effect and evolution during the electrochemical process and provides a strategy for materials design.

Quinone Electrodes for Alkali-Acid Hybrid Batteries.

Aqueous batteries are promising candidates for large-scale energy storage but face either limited energy density (lead-acid batteries), cost/resource concerns (Ni-MH batteries), or safety issues due to metal dendrite growth at high current densities (zinc batteries). We report that through designing electrochemical redox couples, quinones as intrinsic dendrite-free and sustainable anode materials demonstrate the theoretical energy density of 374 W h kg-1 coupling with affordable Mn2+/MnO2 redox reactions on the cathode side. Due to the fast K-ion diffusion in the electrolyte, low K-ion desolvation energy at the interface, and fast quinone/phenol reaction, the optimized poly(1,4-anthraquinone) in the KOH electrolyte shows specific capacities of 295 mA h g-1 at 300 C-rate and 225 mA h g-1 at 240 mA cm-2. Further constructed practical aqueous batteries exhibit an output voltage of 2 V in alkali-acid hybrid electrolyte systems with exceptional electrochemical kinetics, which can release/store over 95% of the theoretical capacity in less than 40 s (25 000 mA g-1). The scaled Ah level aqueous battery with the upgradation of interfacial chemistry on the electrode current collector exhibits an overall energy density of 92 W h kg-1, exceeding commercial aqueous lead-acid and Ni-MH batteries. The rapid response, intrinsic dendrite-free existence, and cost efficiency of quinone electrodes provide promising application interests for regulating the output of the electricity grid generated by intermittent solar and wind energy.

Hydrogen Bond Shielding Effect for High-Performance Aqueous Zinc Ion Batteries.

Manganese oxides are highly desirable for the cathode of rechargeable aqueous zinc ion batteries (AZIBs) owing to their low cost and high abundance. However, the terrible structure stability of manganese oxide limits its practical application. Here, it is demonstrated that the hydrogen-bond shielding effect can improve the electrochemical performance of manganese oxide. Briefly, (NH4 )0.125 MnO2 (NHMO) is prepared by introducing NH4 + into the tunnel structure of α-MnO2 . The robust hydrogen bonds between N-H and host O atoms can stabilize the lattice structure of α-MnO2 and suppress the dissolution of Mn element. More importantly, it can also accelerate ions mobility kinetics by weakening the electrostatic interaction of host O atoms. Thus, the fabricated Zn||NHMO battery possesses impressive cycling life (99.5% of capacity retention over 10 000 cycles) and rate capability (109 mA h g-1 of discharge capacity at 6000 mA g-1 ). Comprehensive analyses reveal the essences of interfacial charge and bulk ions transfer. This finding opens new opportunities for the development of high-performance AZIBs.

Orthoquinone-Based Covalent Organic Frameworks with Ordered Channel Structures for Ultrahigh Performance Aqueous Zinc-Organic Batteries.

Elaborate molecular design on cathodes is of great importance for rechargeable aqueous zinc-organic batteries' performance elevation. Herein, we design a novel orthoquinone-based covalent organic framework with an ordered channel structures (BT-PTO COF) cathode for an ultrahigh performance aqueous zinc-organic battery. The ordered channel structure facilitates ions transfer and makes the COF follow a redox pseudocapacitance mechanism. Thus, it delivers a high reversible capacity of 225 mAh g-1 at 0.1 A g-1 and an exceptional long-term cyclability (retention rate 98.0 % at 5 A g-1 (≈18 C) after 10 000 cycles). Moreover, a co-insertion mechanism with Zn2+ first followed by two H+ is uncovered for the first time. Significantly, this co-insertion behaviour evolves to more H+ insertion routes at high current density and gives the COF ultra-fast kinetics thus it achieves unprecedented specific power of 184 kW kg-1 (COF) and a high energy density of 92.4 Wh kg-1 (COF) . Our work reports a superior organic material for zinc batteries and provides a design idea for future high-performance organic cathodes.

Optimize Lithium Deposition at Low Temperature by Weakly Solvating Power Solvent.

For lithium (Li) metal batteries, the decrease in operating temperature brings severe safety issues by more disordered Li deposition. Here, we demonstrate that the solvating power of solvent is closely related to the reversibility of the Li deposition/stripping process under low-temperature conditions. The electrolyte with weakly solvating power solvent shows lower desolvation energy, allowing for a uniform Li deposition morphology, as well as a high deposition/stripping efficiency (97.87 % at -40 °C). Based on a weakly solvating electrolyte, we further built a full cell by coupling the Li metal anode with a sulfurized polyacrylonitrile electrode at a low anode-to-cathode capacity ratio for steady cycling at -40 °C. Our results clarified the relationship between solvating power of solvent and Li deposition behavior at low temperatures.

Layered Ca0.28 MnO2 ·0.5H2 O as a High Performance Cathode for Aqueous Zinc-Ion Battery.

Aqueous zinc-ion batteries are promising candidates for grid-scale energy storage because of their intrinsic safety, low cost, and high energy intensity. However, lack of suitable cathode materials with both excellent rate performance and cycling stability hinders further practical application of aqueous zinc-ion batteries. Here, a nanoflake-self-assembled nanorod structure of Ca0.28 MnO2 ·0.5H2 O as Zn-insertion cathode material is designed. The Ca0.28 MnO2 ·0.5H2 O exhibits a reversible capacity of 298 mAh g-1 at 175 mA g-1 and long-term cycling stability over 5000 cycles with no obvious capacity fading, which indicates that the per-insertion of Ca ions and water can significantly improve reversible insertion/extraction stability of Zn2+ in Mn-based layered type material. Further, its charge storage mechanism, especially hydrogen ions, is elucidated. A comprehensive study suggests that the intercalation of hydrogen ions in the first discharge plat is controled by both pH value and type of anion of electrolyte. Further, it can stabilize the Ca0.28 MnO2 ·0.5H2 O cathode and facilitate the following insertion of Zn2+ in 1 m ZnSO4 /0.1 m MnSO4 electrolyte. This work can enlighten and promote the development of high-performance rechargeable aqueous zinc-ion batteries.

Aqueous Batteries Operated at -50 °C.

Insufficient ionic conductivity and freezing of the electrolyte are considered the main problems for electrochemical energy storage at low temperatures (low T). Here, an electrolyte with a freezing point lower than -130 °C is developed by using dimethyl sulfoxide (DMSO) as an additive with molar fraction of 0.3 to an aqueous solution of 2 m NaClO4 (2M-0.3 electrolyte). The 2M-0.3 electrolyte exhibits sufficient ionic conductivity of 0.11 mS cm-1 at -50 °C. The combination of spectroscopic investigations and molecular dynamics (MD) simulations reveal that hydrogen bonds are stably formed between DMSO and water molecules, facilitating the operation of the electrolyte at ultra-low T. Using DMSO as the electrolyte additive, the aqueous rechargeable alkali-ion batteries (AABs) can work well even at -50 °C. This work provides a simple and effective strategy to develop low T AABs.

Synergistic Effect of Cation and Anion for Low-Temperature Aqueous Zinc-Ion Battery.

Although aqueous zinc-ion batteries have gained great development due to their many merits, the frozen aqueous electrolyte hinders their practical application at low temperature conditions. Here, the synergistic effect of cation and anion to break the hydrogen-bonds network of original water molecules is demonstrated by multi-perspective characterization. Then, an aqueous-salt hydrates deep eutectic solvent of 3.5 M Mg(ClO4)2 + 1 M Zn(ClO4)2 is proposed and displays an ultralow freezing point of - 121 °C. A high ionic conductivity of 1.41 mS cm-1 and low viscosity of 22.9 mPa s at - 70 °C imply a fast ions transport behavior of this electrolyte. With the benefits of the low-temperature electrolyte, the fabricated Zn||Pyrene-4,5,9,10-tetraone (PTO) and Zn||Phenazine (PNZ) batteries exhibit satisfactory low-temperature performance. For example, Zn||PTO battery shows a high discharge capacity of 101.5 mAh g-1 at 0.5 C (200 mA g-1) and 71 mAh g-1 at 3 C (1.2 A g-1) when the temperature drops to - 70 °C. This work provides an unique view to design anti-freezing aqueous electrolyte.

Bipolar Organic Polymer for High Performance Symmetric Aqueous Proton Battery.

Bipolar electroactive organic molecules receive an increasing research attention as electrode materials for rechargeable batteries due to their flexibility, controllability, and environmental friendliness. While its application for symmetric aqueous proton batteries is still in its infancy. Herein, a symmetric aqueous proton battery (APB) based on a bipolar poly(aminoanthraquinone) (PNAQ) is developed. The conductivity and solubility of PNAQ are significantly improved by introducing a polyaniline-like skeleton. It is demonstrated that the quinone-based moieties allow H+ reversible uptake/removal and the benzene ring-based units achieve HSO4 - adsorption/desorption. The fabricated symmetric APB exhibits a high discharge capacity of 85.3 mA h g-1 at 5 C and excellent rate performance (77 mA h g-1 at 100 C). The good rate performance benefits from capacitance-like ions diffusion mechanism. Furthermore, surprisingly, the system can also operate at -70 °C and shows superior electrochemical performance (60.4 mA h g-1 at -70 °C).

An Overcrowded Water-Ion Solvation Structure for a Robust Anode Interphase in Aqueous Lithium-Ion Batteries.

The water-in-salt electrolyte (WISE) features intimate interactions between a cation and anion, which induces the formation of an anion-derived solid electrolyte interphase (SEI) and expands the aqueous electrolyte voltage window to >3.0 V. Although further increasing the salt concentration (even to >60 molality (m)) can gradually improve water stability, issues about cost and practical feasibility are concerned. An alternative approach is to intensify ion-solvent interactions in the inner solvation structure by shielding off outward electrostatic attractions from nearby ions. Here, we design an "overcrowded" electrolyte using the non-polar, hydrogen-bonding 1,4-dioxane (DX) as an overcrowding agent, thereby achieving a robust LiF-enriched SEI and wide electrolyte operation window (3.7 V) with a low salt concentration (<2 m). As a result, the electrochemical performance of aqueous Li4Ti5O12/LiMn2O4 full cells can be substantially improved (88.5% capacity retention after 200 cycles, at 0.57 C). This study points out a promising strategy to develop low-cost and stable high-voltage aqueous batteries.

Functionalized Boron Nitride-Based Modification Layer as Ion Regulator Toward Stable Lithium Anode at High Current Densities.

It is difficult to achieve higher energy density with the existing system of lithium (Li)-ion batteries. As a powerful candidate, Li metal batteries are in the renaissance. Unfortunately, the uncontrolled growth process of Li dendrites has limited their actual application. Hence, inhibiting the formation and spread of Li dendrites has become an enormous challenge. Herein, a novel composite separator is developed with functionalized boron nitride nanosheet modification layer as a Li-ion regulator to regulate Li-ion fluxes. The composite separator contains abundant polar groups and nanoscale channels and could achieve uniform electrochemical deposition via the lithiophilic effect and shunting action. Under the synergy influence of the lithiophilic effect and shunting action, Li dendrites are effectively suppressed. As proof, the Li||Li symmetrical cells with composite separators can circulate steadily for a long time under high current densities (10 mA cm-2, 800 h). Moreover, the LiFePO4||Li full cells display excellent long cycling performance (82% retention after 800 cycles).