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Spinel cathode materials (e.g., LiMn2O4 and LiNi0.5Mn1.5O4) with strongly bonded surface coatings are desirable for delivering improved electrochemical performance in long-term cycling. Here, we report that the introduction of bridging ions such as Fe and Co, which can diffuse into both the spinel cathode materials and Li3PO4, the latter is found to cover the spinel surface in the form of dense and uniform particles (∼2-3 nm). Detailed structural analysis of the surface reveals that the bridging ions diffuse into the 16c site of the spinel structure to form ion-doped spinel cathode materials, which contribute to the formation of strong bonds between the surface and Li3PO4, possibly via spinel-(surface bridging ions)-Li3PO4 bonds. The critical role of the surface bridging ions is further investigated by heating the as-formed Li3PO4-coated spinel cathode materials (with bridging ions) to high temperatures, resulting in further diffusion of bringing ions from the surface to the interior of the spinel materials and consequently depletion of the surface spinel-(surface bridging ions)-Li3PO4 bonds. This leads to the gradual growth of surface Li3PO4 particles (∼20 nm) and the exposure of the spinel surface.

Mixed silicon and carbon (Si–C) materials with high capacity are ideal candidates for the substitution of graphite or other carbon anodes in lithium-ion batteries. However, the low coulombic efficiency of the Si–C anode in the first cycle due to the formation of a solid electrolyte interphase and the consumption of active lithium have hindered its commercial applications. Here, we report using Li2S as a prelithiation material to compensate for the loss of active lithium in the first cycle and, consequently, to enhance the specific energy of lithium-ion batteries. The Si–C anode has an initial discharge specific capacity of ∼738 mA h g−1 and a charge specific capacity of ∼638 mA h g−1. The prelithiation material with a core–shell structure is prepared by mixing Li2S, Ketjenblack (KB) and poly(vinylpyrrolidone) (PVP) in anhydrous ethanol, which shows a high irreversible capacity of ∼1084 mA h g−1. The effect of the compensation of lost active lithium is verified via a LiFePO4 (Li2S)/Si–C full cell, which exhibits not only a high specific capacity but also a stable cycling performance. The specific energy of the LiFePO4 (Li2S)/Si–C full cell shows a remarkable increase compared to the LiFePO4/Si–C full cell, exhibiting ∼13.4%, ∼26.7%, ∼65.0% and ∼110.2% more specific energy after the 1st, 10th, 100th and 200th cycle, respectively.

The formation of Li dendrites is effectively inhibited by utilizing a small amount of polysulfide (1 to 2 mM Li2Sx, 2 ≤ x ≤ 8) in a conventional carbonate electrolyte to introduce a significant amount of polyethylene oxide (PEO)-like polymers into solid-electrolyte interphase (SEI) films. The polysulfide added likely acts as a catalyst rather than an additive, which is not consumed during repeated charging/discharging cycles. Thus the stability of Li-metal batteries during prolonged cycling is remarkably improved.

Batteries with lithium metal anodes are promising because of lithium’s high energy density. However, the growth of Li dendrites on the surface of the Li electrode in a liquid electrolyte during cycling reduces the safety and cycle performance of batteries, hindering their commercial application. In this work, we observe for the first time a smooth and dendrite-free Li deposition with a vertically grown, self-aligned, and highly compact columnar structure formed during cycling in a mixed carbonate–ether electrolyte. The stable microsized (∼10 μm in diameter and ∼20 μm in length) Li deposits are aligned in arrays on the surface of the Li electrode. The columnar Li deposits still exhibit a dendrite-free morphology and a compact structure after 200 cycles at a current density of 1 mA/cm2 and a 1.5 mAh/cm2 cycling capacity in a mixed carbonate–ether electrolyte. This work shows an optimiztic outlook for Li batteries with liquid electrolytes.

The high-voltage spinel LiNi0.5Mn1.5O4 cathode material suffers from the rapid degradation of electrochemical cycling performance at elevated temperatures, which prevents its successful commercialization. Herein, we show that coating the surface of this material with Ta2O5, which has high resistance against hydrofluoric acid (HF) attack, is an effective way to improve its electrochemical cycling performance. A Ta2O5-coated LiNi0.5Mn1.5O4 half-cell shows a capacity retention of ∼93% and a Coulombic efficiency of ∼98% after 100 cycles at 55 °C, compared to the corresponding values of ∼76% and ∼95% measured for the bare LiNi0.5Mn1.5O4 half-cell. The detailed structural analysis of the Ta2O5-coated LiNi0.5Mn1.5O4 shows that a small amount of Ta5+ ions diffuse into the 16c site on the cathode surface during the coating process, as directly observed by Cs corrected scanning transmission electron microscopy. The modification of the LiNi0.5Mn1.5O4 surface with Ta5+, together with the residual Ta2O5 coating, stabi...