Unveiling the Reaction Mystery Between Lithium Polysulfides and Lithium Metal Anode in Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are widely regarded as one of the most promising next-generation high-energy-density energy storage devices. However, soluble lithium polysulfides (LiPSs) corrode Li metal and deteriorate the cycling stability of Li-S batteries. Understanding the reaction mechanism between LiPSs and Li metal anode is imperative. Herein, the reaction rate and products of LiPSs with Li metal anode, the composition and structure of the as-generated solid electrolyte interphase (SEI), and the mechanism of lithium nitrate (LiNO3) additives for inhibiting the corrosion reactions are systematically unveiled. Concretely, LiPSs react with Li metal anode more rapidly than Li salt and generate a Li2S-rich SEI. The Li2S-rich SEI is highly reactive with LiPSs, which exacerbates the formation of dendritic Li and the continuous corrosion of active Li. LiNO3 functions dominantly by modulating the solvation structure of LiPSs and inherently reducing the reactivity of LiPSs, rather than the conventional understanding of LiNO3 participating in the formation of SEI. This work reveals the reaction mechanism between LiPSs and Li metal anode and inspires rational regulating of the solvation structure of LiPSs for stabilizing Li metal anode in Li-S batteries.

Molecular recognition effect enabled by novel crown ether as macrocyclic host towards highly reversible Zn anode.

Aqueous Zn2+ ion batteries present notable advantages, including high abundance, low toxicity, and intrinsic nonflammability. However, they exhibit severe irreversibility due to uncontrolled dendrite growth and corrosion reactions, which limit their practical applications. Inspired by their distinct molecular recognition characteristics, supramolecular crown ethers featuring interior cavity sizes identical to the diameter of Zn2+ ions were screened as macrocyclic hosts to optimize the Zn2+ coordination environment, facilitating the suppression of the reactivity of H2O molecules and inducing the in-situ formation of organic-inorganic hybrid dual-protective interphase. The in-situ assembled interphase confers the system with an "ion-sieving" effect to repel H2O molecules and facilitate rapid Zn2+ transport, enabling the suppression of side reactions and uniform deposition of Zn2+ ions. Consequently, we were able to achieve dendrite-free Zn2+ plating/stripping at 98.4% Coulombic efficiency for approximately 300 cycles in Zn||Cu cell, steady charge-discharge for 1360 h in Zn||Zn symmetric cell, and improved cyclability of 70% retention for 200 cycles in Zn||LMO full cell, outlining a promising strategy to challenge lithium-ion batteries in low-cost, and large-scale applications.

Reforming the Uniformity of Solid Electrolyte Interphase by Nanoscale Structure Regulation for Stable Lithium Metal Batteries.

The stability of high-energy-density lithium metal batteries depends on the uniformity of solid electrolyte interphase (SEI) on lithium metal anodes. Rationally improving SEI uniformity is hindered by poorly understanding the effect of structure and components of SEI on its uniformity. Herein, a bilayer structure of SEI formed by isosorbide dinitrate (ISDN) additives in localized high-concentration electrolytes was demonstrated to improve SEI uniformity. In the bilayer SEI, LiNx Oy generated by ISDN occupies top layer and LiF dominates bottom layer next to anode. The uniformity of lithium deposition is remarkably improved with the bilayer SEI, mitigating the consumption rate of active lithium and electrolytes. The cycle life of lithium metal batteries with bilayer SEI is three times as that with common anion-derived SEI under practical conditions. A prototype lithium metal pouch cell of 430 Wh kg-1 undergoes 173 cycles. This work demonstrates the effect of a reasonable structure of SEI on reforming SEI uniformity.

Electrolyte Design for Improving Mechanical Stability of Solid Electrolyte Interphase in Lithium-Sulfur Batteries.

Practical lithium-sulfur (Li-S) batteries are severely plagued by the instability of solid electrolyte interphase (SEI) formed in routine ether electrolytes. Herein, an electrolyte with 1,3,5-trioxane (TO) and 1,2-dimethoxyethane (DME) as co-solvents is proposed to construct a high-mechanical-stability SEI by enriching organic components in Li-S batteries. The high-mechanical-stability SEI works compatibly in Li-S batteries. TO with high polymerization capability can preferentially decompose and form organic-rich SEI, strengthening mechanical stability of SEI, which mitigates crack and regeneration of SEI and reduces the consumption rate of active Li, Li polysulfides, and electrolytes. Meanwhile, DME ensures high specific capacity of S cathodes. Accordingly, the lifespan of Li-S batteries increases from 75 cycles in routine ether electrolyte to 216 cycles in TO-based electrolyte. Furthermore, a 417 Wh kg-1 Li-S pouch cell undergoes 20 cycles. This work provides an emerging electrolyte design for practical Li-S batteries.

LiFSI and LiDFBOP Dual-Salt Electrolyte Reinforces the Solid Electrolyte Interphase on a Lithium Metal Anode.

Metallic lithium (Li) has great potential as an anode material for high-energy-density batteries due to its high specific capacity. However, the uncontrollable dendritic lithium growth on the metallic lithium surface limits its practical application owing to the instability of the solid electrolyte interphase (SEI). A tailored SEI composition/structure can mitigate or inhibit the lithium dendrites' growth, thereby enhancing the cyclability of the Li-metal anode. In this work, excellent cycling stability of lithium metal anodes was achieved by utilizing a novel dual-salt electrolyte based on lithium bis(fluorosulfonyl) imide (LiFSI) and lithium difluorobis(oxalato) phosphate (LiDFBOP) in carbonate solvents. By combining surface/microstructural characterization and computations, we reveal that the preferential reduction of LiDFBOP occurs prior to LiFSI and carbonate solvents and its reduction products (Li2C2O4 and P-O species) bind to LiF, resulting in a favorable compact and protective SEI on the Li electrodes. It was found that the improved oxidative stability was accompanied by reduced corrosion of the current collector. A Li/Li symmetrical cell with a designed dual-salt electrolyte system exhibits stable polarization voltage over 1000 h of cycle time. In addition, the LiFSI-LiDFBOP advantage of this dual-salt electrolyte system enables the Li/LiFePO4 cells with significantly enhanced cycling stability. This work demonstrates that constructing a tailored SEI using a dual-salt electrolyte system is vital for improving the interfacial stability of lithium metal batteries.

Stabilized High-Voltage Cathodes via an F-Rich and Si-Containing Electrolyte Additive.

High-voltage cathodes provide a promising solution to the energy density limitation of currently commercialized lithium-ion batteries, but they are unstable in electrolytes during the charge/discharge process. To address this issue, we propose a novel electrolyte additive, pentafluorophenyltriethoxysilane (TPS), which is rich in elemental F and contains elemental Si. The effectiveness of TPS has been demonstrated by cycling a representative high-voltage cathode, LiNi0.5Mn1.5O4 (LNMO), in 1.0 M LiPF6-diethyl carbonate/ethylene carbonate/ethyl methyl carbonate (2/3/5 in weight). LNMO presents an increased capacity retention from 28 to 85% after 400 cycles at 1 C by applying 1 wt % TPS. Further electrochemical measurements combined with spectroscopic characterization and theoretical calculations indicate that TPS can not only construct a robust protective cathode electrolyte interphase via its oxidation during initial lithium desertion but also scavenge the detrimental hydrogen fluoride (HF) present in the electrolyte via its strong combination with the species HF, F-, and H+, highly stabilizing LNMO during the charge/discharge process. These features of TPS provide a new solution to the obstacle in the practical application of high-voltage cathodes not limited to LNMO.

Lithium Bis(oxalate)borate Reinforces the Interphase on Li-Metal Anodes.

Li metal provides an ideal anode for the highest energy density batteries, but its reactivity with electrolytes brings poor cycling stability. Electrolyte additives have been employed to effectively improve the cycling stability, often with the underlying mechanism poorly understood. In this work, applying lithium bis(oxalate)borate (LiBOB) as a chemical source for a dense and protective interphase, we investigate this issue with combined techniques of electrochemical/physical characterizations and theoretical calculations. It was revealed that the solid electrolyte interphase (SEI) formed by Li and the carbonate electrolyte is unstable and responsible for the fast deterioration of the Li anode. When LiBOB is present in the electrolyte, a reinforced SEI was formed, enabling significant improvement in cycling stability due to the preferential reduction of the BOB anion over the carbonate molecules and the strong combination of its reduction products with the species from the electrolyte reduction. The effectiveness of such new SEI chemistry on the Li anode supports excellent performance of a Li/LiFePO4 cell. This approach provides a pathway to rationally design an interphase on the Li anode so that high energy density batteries could be realized.

Simultaneously Regulating Lithium Ion Flux and Surface Activity for Dendrite-Free Lithium Metal Anodes.

Li dendrite growth due to uncontrolled Li plating/stripping processes has been a challenge for the application of Li metal anodes in high energy secondary batteries. A novel strategy is proposed in this work to address this issue, which is based on simultaneously regulating Li ion (Li+) flux and Li metal surface activity by a terpolymer cladding that orients the Li+ flux and mitigates the side reactions for Li plating/striping. This cladding provides the Li anode with dendrite-free surface morphology and enhanced electrochemical performances. Stable cycling of 800 and 1400 h is achieved for Li symmetric cells in carbonate-based and ether-based electrolytes, respectively. In addition, the asymmetric Li-LiFePO4 and Li-sulfur cells attain a prolonged cycle lifespan with reduced interfacial resistance after cycling. These performances might be further improved by more delicately designing the polymer structure and assembling the cladding, which might help fulfill the practical applications of Li anodes in high energy batteries.