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.

No abstract

No abstract

High-voltage (>4.3 V) rechargeable lithium (Li) metal batteries (LMBs) face huge obstacles due to the high reactivity of Li metal with traditional electrolytes. Despite their good stability with Li metal, conventional ether-based electrolytes are typically used only in <4.0 V LMBs because of their limited oxidation stability. Here we report high-concentration ether electrolytes that can induce the formation of a unique cathode electrolyte interphase via the synergy between the salt and the ether solvent, which effectively stabilizes the catalytically active cathodes and preserves their structural integrity under high voltages. Eventually, LMBs can retain 92% capacity after 500 cycles at 4.3 V with very limited Li consumption. More importantly, such ether electrolytes enable stable battery cycling not only under voltages as high as 4.5 V but also on highly demanding Ni-rich layered cathodes. These findings significantly expand knowledge of ether electrolytes and provide new perspectives of electrolyte design for high-energy-density LMBs.

Aqueous rechargeable zinc–manganese dioxide batteries show great promise for large‐scale energy storage due to their use of environmentally friendly, abundant, and rechargeable Zn metal anodes and MnO2 cathodes. In the literature various intercalation and conversion reaction mechanisms in MnO2 have been reported, but it is not clear how these mechanisms can be simultaneously manipulated to improve the charge storage and transport properties. A systematical study to understand the charge storage mechanisms in a layered δ‐MnO2 cathode is reported. An electrolyte‐dependent reaction mechanism in δ‐MnO2 is identified. Nondiffusion controlled Zn2+ intercalation in bulky δ‐MnO2 and control of H+ conversion reaction pathways over a wide C‐rate charge–discharge range facilitate high rate performance of the δ‐MnO2 cathode without sacrificing the energy density in optimal electrolytes. The Zn‐δ‐MnO2 system delivers a discharge capacity of 136.9 mAh g−1 at 20 C and capacity retention of 93% over 4000 cycles with this joint charge storage mechanism. This study opens a new gateway for the design of high‐rate electrode materials by manipulating the effective redox reactions in electrode materials for rechargeable batteries.

The lithium (Li) metal battery (LMB) is one of the most promising candidates for next-generation energy storage systems. However, it is still a significant challenge to operate LMBs with high voltage cathodes under high rate conditions. In this work, an LMB using a nickel-rich layered cathode of LiNi 0.76 Mn 0.14 Co 0.10 O 2 (NMC76) and an optimized electrolyte [0.6 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) + 0.4 M lithium bis(oxalato)borate (LiBOB) + 0.05 M LiPF 6 dissolved in ethylene carbonate and ethyl methyl carbonate (EC:EMC, 4:6 by weight)] demonstratesexcellent stability at a high charge cutoff voltage of 4.5 V. Remarkably, these Li||NMC76 cells can deliver a high discharge capacity of >220 mAh g -1 (846 Wh kg -1 ) and retain more than 80% capacity after 1000 cycles at high charge/discharge current rates of 2C/2C (1C = 200 mA g -1 ). This excellent electrochemical performance can be attributed to the greatly enhanced structural/interfacial stability of both the Ni-rich NMC76 cathode material and the Li metal anode using the optimized electrolyte.

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...