Polycarbonyl polymer with zincophilic sites as protective coating for highly reversible zinc metal anodes.

The Zn anode of aqueous zinc ion batteries (AZIBs) have suffered from a series of rampant side reactions such as dendrite growth and corrosion, which seriously affect the reversibility and stability of Zn anodes. Herein, a polycarbonyl polymer poly(1,4,5,8-naphthalene tetracarboxylic anhydride anthraquinone) imine (PNAQI) as the protective coating is synthesized through a simple solvothermal method with the raw materials of the equimolar 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA) and 2, 6-aminoanthraquinone (2,6-DAAQ). A series of characterizations such as contact angle measurement and ex-situ XRD analysis confirm that it can effectively prevent some side reactions. Moreover, CO on PNAQI can regulate the uniform distribution of zinc, thereby preventing the occurrence of zinc dendrites. Finally, the PNAQI@Zn//PNAQI@Zn symmetrical cell demonstrates a long cycle life exceeding 1000 h at current density of 1.0 mA cm-2 and a capacity of 1.0 mAh cm-2. The result significantly outperforms the cycling performance of the cell with bare zinc anode. Especially, the full battery of PNAQI@Zn//NH4V4O10 demonstrates an excellent capacity retention and prolonged cycle life (96.9 mAh/g after 1000 cycles at 1.0 A/g) compared to Zn//NH4V4O10. This work provides an effective, simple and low-cost solution for developing high-performance AZIBs.

Ultrahigh Nitrogen Content Carbon Nanosheets for High Stable Sodium Metal Anodes.

Sodium metal, with a high theoretical specific capacity of 1165 mAh g-1 , is the ultimate anode for sodium batteries, yet how to deal with the inhomogeneous and dendritic sodium deposition and the infinite relative dimension change of sodium metal anodes during sodium depositing/stripping is still challenging. Here, a facile fabricated sodiuphilic 2D N-doped carbon nanosheets (N-CSs) are proposed as sodium host material for sodium metal batteries (SMBs) to prevent dendrite formation and eliminate volume change during cycling. Revealing from combined in situ characterization analyses and theoretical simulations, the high nitrogen content and porous nanoscale interlayer gaps of the 2D N-CSs can not only concede dendrite-free sodium stripping/depositing but also accommodate the infinite relative dimension change. Furthermore, N-CSs can be easily process into N-CSs/Cu electrode via traditional commercial battery electrode coating equipment that pave the way for large-scale industrial applications. On account of the abundant nucleation sites and sufficient deposition space, N-CSs/Cu electrodes demonstrate a superior cycle stability of more than 1500 h at a current density of 2 mA cm-2 with a high coulomb efficiency of more than 99.9% and ultralow nucleation overpotential, which enable reversible and dendrites-free SMBs and shed light on further development of SMBs with even higher performance.

N, F-enriched inorganic/organic composite interphases to stabilize lithium metal anodes for long-life anode-free cells.

The practical application of lithium metal batteries is considered to be one of the most promising successors for lithium-ion batteries due to their ability to meet the high-energy storage demands of modern society. However, their application is still hindered by the unstable solid electrolyte interphase (SEI) and uncontrollable dendrite growth. In this study, we propose a robust composite SEI (C-SEI) that consists of a fluorine doped boron nitride (F-BN) inner layer and an organic polyvinyl alcohol (PVA) outer layer. Both theoretical calculations and experimental results demonstrate that the F-BN inner layer induces the formation of favourable components (LiF and Li3N) at the interface, promoting rapid ionic transport and inhibiting electrolyte decomposition. The PVA outer layer acts as a flexible buffer in the C-SEI, ensuring the structural integrity of the inorganic inner layer during lithium plating and stripping. The C-SEI modified lithium anode shows a dendrite-free performance and stable cycle over 1200 h, with an ultralow overpotential (15 mV) at 1 mA cm-2 in this study. This novel approach also enhances the stability of capacity retention rate by 62.3% after 100 cycles even in anode-free full cells (C-SEI@Cu||LFP). Our findings suggest a feasible strategy for addressing the instability inherent in SEI, showing great prospects for the practical application of lithium metal batteries.

Guiding Uniformly Distributed Li-Ion Flux by Lithiophilic Covalent Organic Framework Interlayers for High-Performance Lithium Metal Anodes.

Lithium (Li) metal anodes are regarded as prospective anode materials in next-generation secondary lithium batteries due to their ultrahigh theoretical capacities and ultralow potentials. However, inhomogeneous lithium deposition and uncontrollable growth of lithium dendrites always give rise to the low lithium utilization, rapid capacity fading, and poor cycling performance. Herein, we design the lithiophilic covalent organic frameworks (COFs) containing preorganized triazine rings and carbonyl groups as the multifunctional interlayer in lithium metal batteries (LMBs). Triazine rings rich in lone pair electrons can act as the donor attracting Li ions, and carbonyl groups serve as Li-anchoring sites effectively coordinating Li ions. These periodic arranged subunits significantly guide uniform Li ion flux distribution, guarantee smooth Li deposition and less lithium dendrite formation. Consequently, the symmetric batteries with COF interlayers exhibit an extraordinary cycling stability for more than 2450 and 1000 h with ultralow polarization voltage of about 12 and 14 mV at 0.5 and 1.0 mA cm-1. Coupling with sulfur (S) cathodes and LiFePO4 (LFP) cathodes, the full cells also demonstrate superb energy density achievement and rate performance. With introducing lithiophilic COFs interlayers, the Li-LFP batteries exhibit high capacity of 150 mAh g-1 and 86% capacity retention after 450 cycles at 0.5 C.

Concentrated LiODFB Electrolyte for Lithium Metal Batteries.

Nowadays, lithium (Li) metal batteries arouse widespread concerns due to its ultrahigh specific capacity (3,860 mAh g-1). However, the growth of Li dendrites has always limited their industrial development. In this paper, the use of concentrated electrolyte with lithium difluoro(oxalate)borate (LiODFB) salt in 1, 2-dimethoxyethane (DME) enables the good cycling of a Li metal anode at high Coulombic efficiency (up to 98.1%) without dendrite growth. Furthermore, a Li/Li cell can be cycled at 1 mA cm-2 for over 3,000 h. Besides, compared to conventional LiPF6-carbonate electrolyte, Li/LiFePO4 cells with 4 M LiODFB-DME exhibit superior electrochemical performances, especially at high temperature (65°C). These outstanding performances can be certified to the increased availability of Li+ concentration and the merits of LiODFB salt. We believe that the concentrated LiODFB electrolyte is help to enable practical applications for Li metal anode in rechargeable batteries.