Anion-Induced Uniform and Robust Cathode-Electrolyte Interphase for Layered Metal Oxide Cathodes of Sodium Ion Batteries.

Layer metal oxides demonstrate great commercial application potential in sodium-ion batteries, while their commercialization is extremely hampered by the unsatisfactory cycling performance caused by the irreversible phase transition and interfacial side reaction. Herein, trimethoxymethylsilane (TMSI) is introduced into electrolytes to construct an advanced cathode/electrolyte interphase by tuning the solvation structure of anions. It is found that due to the stronger interaction between ClO4- and TMSI than that of ClO4- and PC/FEC, the ClO4--TMSI complexes tend to accumulate on the surface of the cathode during the charging process, leading to the formation of a stable cathode/electrolyte interface (CEI). In addition, the Si species with excellent electronic insulation ability are distributed in the TMSI-derived CEI film, which is conducive to inhibiting the continuous side reaction of solvents and the growth of the CEI film. As a result, under a current density of 250 mA g-1, the capacity retention of the NaNi1/3Fe1/3Mn1/3O2 (NFM) cathode after 200 cycles in the TMSI-modified electrolyte is 74.4% in comparison to 51.5% of the bare electrolyte (1 M NaClO4/PC/5% FEC). Moreover, the NFM cathode shows better kinetics, with the specific discharge capacity increasing from 22 to 67 mAh g-1 at 300 mA g-1. It also demonstrates greatly improved rate capability, cycling stability, and Coulombic efficiency under various operating conditions, including high temperature (55 °C) and high cutoff voltage (2.0-4.3 V vs Na+/Na).

Commercially Viable Hybrid Li-Ion/Metal Batteries with High Energy Density Realized by Symbiotic Anode and Prelithiated Cathode.

The energy density of commercial lithium (Li) ion batteries with graphite anode is reaching the limit. It is believed that directly utilizing Li metal as anode without a host could enhance the battery's energy density to the maximum extent. However, the poor reversibility and infinite volume change of Li metal hinder the realistic implementation of Li metal in battery community. Herein, a commercially viable hybrid Li-ion/metal battery is realized by a coordinated strategy of symbiotic anode and prelithiated cathode. To be specific, a scalable template-removal method is developed to fabricate the porous graphite layer (PGL), which acts as a symbiotic host for Li ion intercalation and subsequent Li metal deposition due to the enhanced lithiophilicity and sufficient ion-conducting pathways. A continuous dissolution-deintercalation mechanism during delithiation process further ensures the elimination of dead Li. As a result, when the excess plating Li reaches 30%, the PGL could deliver an ultrahigh average Coulombic efficiency of 99.5% for 180 cycles with a capacity of 2.48 mAh cm-2 in traditional carbonate electrolyte. Meanwhile, an air-stable recrystallized lithium oxalate with high specific capacity (514.3 mAh g-1) and moderate operating potential (4.7-5.0 V) is introduced as a sacrificial cathode to compensate the initial loss and provide Li source for subsequent cycles. Based on the prelithiated cathode and initial Li-free symbiotic anode, under a practical-level 3 mAh capacity, the assembled hybrid Li-ion/metal full cell with a P/N ratio (capacity ratio of LiNi0.8Co0.1Mn0.1O2 to graphite) of 1.3 exhibits significantly improved capacity retention after 300 cycles, indicating its great potential for high-energy-density Li batteries.

In Situ Constructed Ionic-Electronic Dual-Conducting Scaffold with Reinforced Interface for High-Performance Sodium Metal Anodes.

The formation of severe dendritic sodium (Na) microstructure reduces the reversibility of anode and further hinders its practical implementation. In this work, an ionic-electronic dual-conducting (IEDC) scaffold composed of Na3 P and carbon nanotubes is in situ developed by a scalable strategy with subsequent alloying reaction, for realizing dendrite-free Na deposition under high current density and large areal capacity. The in situ formed Na3 P with high sodiophilicity not only sets up a hierarchically efficient ionic conducting network, but also participates in the construction of reinforced solid electrolyte interphase, while carbon nanotubes can assemble an electronic conducting framework. As a result, the multifunctional IEDC scaffold contributes to smooth Na plating and exceptionally reversible Na stripping. High average Coulombic efficiency of 99.8% after prolonged 1200 cycles at 3 mA cm-2 and small overpotential of 20 mV over 250 h (equals to 530 cycles) at high rate of 5 mA cm-2 are obtained. The high availability of Na in IEDC scaffold enables the impressive performance of full cell with limited Na, using Na3 V2 (PO4 )3 (NVP) cathode at practical level. More importantly, the as-developed anode-free full cell with IEDC||NVP configuration delivers a high capacity retention with long lifetime, indicating its great potential for practical Na metal batteries.