Cost-Effective Rechargeable Magnesium Battery Based on a Fluorinated Alkoxyaluminate Electrolyte and a Carbonyl Polymer Cathode.

Rechargeable magnesium batteries (RMBs) are one of the most promising "post-lithium" battery technologies, but the electrochemical performance is still far from expectation due to the sluggish reaction kinetics of divalent Mg2+ ions. Herein, we report a low-cost, high-performance Mg-organic battery based on the combination of a fluorinated alkoxyaluminate electrolyte and a carbonyl polymer cathode material. First, the one-pot synthesized Mg[Al(HFIP)4]2 (HFIP = hexafluoro-2-propanol) is proved superior to the Mg[B(HFIP)4]2 analogue in both Mg anode compatibility and electrochemical window, as the electrolyte salt in the G2-DME (G2 = diethylene glycol dimethyl ether; DME = 1,2-dimethoxyethane) mixture solvent. Second, a simple wet grinding method is proposed to effectively improve the dispersion uniformity of the poly(benzoquinone-pyrrole) (PBQPy) active material in the cathode. Third, the elaborate Mg-PBQPy battery exhibits superior electrochemical performance within 0.4-3.0 V, including a high reversible capacity of 197 mA h g-1, a high average discharge voltage of 1.6 V, and a high capacity retention of 71% after 500 cycles. Finally, based on various electrochemical analysis and ex situ characterization results, we propose a general microscopic structure evolution model to reveal the electrochemical behaviors of carbonyl polymer cathode in RMBs, including the swelling of polymer active material, trapping of Mg2+ ions, and reversible redox reaction.

Facile Synthesis of Diazaanthraquinone Dimers as High-Capacity Organic Cathode Materials for Rechargeable Lithium Batteries.

Organic cathode materials (OCMs) have tremendous potential to construct sustainable and highly efficient batteries beyond conventional Li-ion batteries. Thereinto, quinone/pyrazine hybrids show significant advantages in material availability, energy density, and cycling stability. Herein, we propose a facile method to synthesize quinone/pyrazine hybrids, i.e., the condensation reaction between ortho-diamine and bromoacetyl groups. Based on it, we have successfully synthesized three 1,4-diazaanthraquinone (DAAQ) dimers, including 2,2'-bi(1,4-diazaanthraquinone) (BDAAQ) with an exceptional theoretical capacity of 512 mAh g-1 based on the eight-electron reaction. It can be fully utilized in Li batteries in a wide voltage range of 0.8-3.8 V, at the cost of inferior cycling stability. In an optimal voltage range of 1.4-3.8 V, BDAAQ exhibits one of the best comprehensive electrochemical performances for small-molecule OCMs, including a high specific capacity of 366 mAh g-1, an average discharge voltage of 2.26 V, as well as a respectable capacity retention of 59% after 500 cycles. Moreover, the in-depth investigations reveal the redox reaction mechanisms based on C═O and C═N groups as well as the capacity fading mechanisms based on dissolution-redeposition behaviors. In brief, this work provides an instructive synthesis method and mechanism understanding of high-performance OCMs based on a quinone/pyrazine hybrid structure.

A Sustainable Dual Cross-Linked Cellulose Hydrogel Electrolyte for High-Performance Zinc-Metal Batteries.

Aqueous rechargeable Zn-metal batteries (ARZBs) are considered one of the most promising candidates for grid-scale energy storage. However, their widespread commercial application is largely plagued by three major challenges: The uncontrollable Zn dendrites, notorious parasitic side reactions, and sluggish Zn2+ ion transfer. To address these issues, we design a sustainable dual cross-linked cellulose hydrogel electrolyte, which has excellent mechanical strength to inhibit dendrite formation, high Zn2+ ions binding capacity to suppress side reaction, and abundant porous structure to facilitate Zn2+ ions migration. Consequently, the Zn||Zn cell with the hydrogel electrolyte can cycle stably for more than 400 h under a high current density of 10 mA cm-2. Moreover, the hydrogel electrolyte also enables the Zn||polyaniline cell to achieve high-rate and long-term cycling performance (> 2000 cycles at 2000 mA g-1). Remarkably, the hydrogel electrolyte is easily accessible and biodegradable, making the ARZBs attractive in terms of scalability and sustainability.

Amphoteric Cellulose-Based Double-Network Hydrogel Electrolyte Toward Ultra-Stable Zn Anode.

Zinc (Zn) metal anode suffers from uncontrollable Zn dendrites and parasitic side reactions at the interface, which restrict the practical application of aqueous rechargeable zinc batteries (ARZBs). Herein, an amphoteric cellulose-based double-network is introduced as hydrogel electrolyte to overcome these obstacles. On one hand, the amphoteric groups build anion/cation transport channels to regulate electro-deposition behavior on Zn (002) crystal plane enabled by homogenizing Zn2+ ions flux. On the other hand, the strong bonding between negatively charged carboxyl groups and Zn2+ ions promote the desolvation process of [Zn(H2 O)6 ]2+ to eliminate side reactions. Based on the above two functions, the hydrogel electrolyte enables an ultra-stable cycling with a cumulative capacity of 7 Ah cm-2 at 20 mA cm-2 /20 mAh cm-2 for Zn||Zn cell. This work provides significant concepts for developing hydrogel electrolytes to realize stable anode for high-performance ARZBs.

Constructing Extended π-Conjugated Molecules with o-Quinone Groups as High-Energy Organic Cathode Materials.

Although organic cathode materials with sustainability and structural designability have great potential for rechargeable lithium batteries, the dissolution issue presents a huge challenge to meet the demands of cycling stability and energy density simultaneously. Herein, we have designed and successfully synthesized two novel small-molecule organic cathode materials (SMOCMs) by the same innovative route, namely 7,14-diazabenzo[a]tetracene-5,6,8,13-tetraone (DABTTO) and 7,9,16,18-tetraazadibenzo[a,l]pentacene-5,6,8,14,15,17-hexaone (TADBPHO). The integrated p-quinone, o-quinone, and pyrazine groups provide these SMOCMs with attractive theoretical capacities of 473 and 568 mAh g-1 based on 6- and 10-electron reactions, respectively, which were almost fully utilized within 0.8-3.8 V vs Li+/Li. The extended aromatic nucleus of TADBPHO makes it much less soluble than DABTTO and thus able to achieve the highest level of cycling stability (66% @ 500th cycle) for SMOCMs in addition to the exceptional energy density (364 mAh g-1 × 2.56 V = 932 Wh kg-1) within 1.5-3.8 V. In addition to the excellent electrochemical performance, the redox reaction and capacity fading mechanisms have been also investigated in detail. The novel approach to construct extended π-conjugated molecules with o-quinone groups is enlightening for the development of high-energy and stable OCMs for future efficient and sustainable energy storage devices.