Instability of electrolytes toward both highly reactive Li-metal anode and highvoltage cathodes has greatly impeded the development of Li-metal batteries. The authors designed an ether-based localized high-concentration electrolyte that can form stable interphases on both the Li anode and the Ni-rich NMC811 cathode to inhibit the undesired side reactions. This electrolyte enables a significantly enhanced battery performance under stringent practical conditions with a thin Limetal anode or Li-free anode, a high-loading cathode, and lean electrolyte.

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Exploratory synthesis in novel chemical spaces is the essence of solid-state chemistry. However, uncharted chemical spaces can be difficult to navigate, especially when materials synthesis is challenging. Nitrides represent one such space, where stringent synthesis constraints have limited the exploration of this important class of functional materials. Here, we employ a suite of computational materials discovery and informatics tools to construct a large stability map of the inorganic ternary metal nitrides. Our map clusters the ternary nitrides into chemical families with distinct stability and metastability, and highlights hundreds of promising new ternary nitride spaces for experimental investigation-from which we experimentally realized 7 new Zn-and Mg-based ternary nitrides. By extracting the mixed metallicity, ionicity, and covalency of solid-state bonding from the DFTcomputed electron density, we reveal the complex interplay between chemistry, composition, and electronic structure in governing large-scale stability trends in ternary nitride materials.

Functional electrolyte is the key to stabilize the highly reductive lithium (Li) metal anode and the high-voltage cathode for long-life, high-energy-density rechargeable Li metal batteries (LMBs). However, fundamental mechanisms on the interactions between reactive electrodes and electrolytes are still not well understood. Recently localized high-concentration electrolytes (LHCEs) are emerging as a promising electrolyte design strategy for LMBs. Here, we use LHCEs as an ideal platform to investigate the fundamental correlation between the reactive characteristics of the inner solvation sheath on electrode surfaces due to their unique solvation structures. The effects of a series of LHCEs with model electrolyte solvents (carbonate, sulfone, phosphate, and ether) on the stability of high-voltage LMBs are systematically studied. The stabilities of electrodes in different LHCEs indicate the intrinsic synergistic effects between the salt and the solvent when they coexist on electrode surfaces. Experimental and theoretical analyses reveal an intriguing general rule that the strong interactions between the salt and the solvent in the inner solvation sheath promote their intermolecular proton/charge transfer reactions, which dictates the properties of the electrode/electrolyte interphases and thus the battery performances.

IntroductionLithium (Li)-ion batteries (LIBs) have now been the indispensable power sources for portable electronic devices, electric vehicles, stationary or grid applications, etc. [1] However, further efforts on extending the cycle life, rate capability, energy density and working temperature range and improving the safety of LIBs are still facing significant challenges for their large-scale applications. Focusing on the increase in energy density of a battery, the possible approach is to use the high capacity electrode (cathode or anode) material and the high voltage cathode material. Ni-rich layered oxides LiNi x Mn y Co 1−x−y O 2 (NMC) with Ni content ≥80% (e.g., NMC811) are regarded as one of the most potential candidates to usher in the new stage of ultra-high energy density LIBs due to their increased specific capacities at higher voltages and the low cost with less Co content. However, the practical applications of these Ni-rich NMC cathode materials are greatly hindered by the poor cathode-electrolyte interface (CEI) layer formed on such cathode surface in the state-of-the-art electrolytes comprised of lithium hexafluorophosphate (LiPF 6 ) in carbonate solvents, especially at voltages higher than 4.3 V versus Li/Li + , [2] causing continuous electrolyte oxidative decomposition and other related side reactions such as transition metal dissolution from the cathode surface, thus leading to poor cycling stability, especially at elevated temperatures and high operating voltages. [3] Therefore, advanced electrolytes with better oxidative protection to Ni-rich NMC cathode materials, especially under high voltages are critically important for enabling application of Ni-rich NMCs in LIBs.Significant efforts have been made to develop novel electrolytes for high voltage cathode materials, mainly through using high anodic solvents to substitute carbonate solvents, the increase of salt concentration and the utilization of film-forming additives. Fan et al. developed an all-fluorinated electrolyte of 1 m LiPF 6 in fluoroethylene carbonate/3,3,3-fluoroethylmethyl carbonate/1,1,2,2-tetrafluoroethyl-2′,2′,2′-trifluoroethyl ether (FEC/FEMC/HFE, 2:6:2 by wt), which significantly enhanced the cycling stability of Li||NMC811 (2.7-4.4 V) and Li||LiCoPO 4 (3.5-5.0 V) in high voltages by effectively inhibiting electrolyte LiNi x Mn y Co 1−x−y O 2 (NMC) cathode materials with Ni ≥ 0.8 have attracted great interest for high energy-density lithium-ion batteries (LIBs) but their practical applications under high charge voltages (e.g., 4.4 V and above) still face significant challenges due to severe capacity fading by the unstable cathode/electrolyte interface. Here, an advanced electrolyte is developed that has a high oxidation potential over 4.9 V and enables NMC811-based LIBs to achieve excellent cycling stability in 2.5-4.4 V at room temperature and 60 °C, good rate capabilities under fast charging and discharging up to 3C rate (1C = 2.8 mA cm −2 ), and superior low-temperature discharge performance down to −30 °C with a ca...