RESUMEN

Zn metal is thermodynamically unstable in aqueous electrolytes, which induces dendrite growth and ongoing parasitic reactions at the interface during the plating process and even during shelf time, resulting in rapid battery failure and hindering the practical application of aqueous Zn ion batteries. In this work, glycine, a common multifunctional additive, is utilized to modulate the solvation shell structure and enhance the interfacial stability to guard the reversibility and stability of the Zn anode. Apart from partially replacing the original SO42- in the contact ion pair of Zn2+[H2O]5·OSO32- complexes to suppress the formation of Zn4(OH)6SO4·xH2O byproducts at the interface, glycine molecules can also form a water-poor electrical double layer on the zinc metal surface during resting and be further reduced to build in situ a ZnS-rich solid electrolyte interphase (SEI) layer during cycling, which further suppresses side reactions and the random growth of Zn dendrites in the whole process. As expected, the cycle life of the symmetrical cells reaches over 3200 h in glycine-containing electrolytes. In addition, the Zn//NVO full cell shows exceptional cycling stability for 3000 cycles at 5 A g-1. Given the low-cost superiority of glycine, the proposed strategy for interfacial chemistry modulation shows considerable potential in promoting the commercialization progress of aqueous batteries.

Asunto(s)

RESUMEN

Solid electrolyte interphase (SEI) formation and H2 O activity reduction in Water-in-Salt electrolytes (WiSE) with an enlarged stability window of 3.0 V have provided the feasibility of the high-energy-density aqueous Li-ion batteries. Here, we extend the cathodic potential of WiSE by rationally controlling intermolecular interaction and interphase chemistry with the introduction of trimethyl phosphate (TMP) into WiSE. The TMP not merely limits the H2 O activity via the strong interaction between TMP and H2 O but also contributes to the formation of reinforced SEI involving phosphate and LiF by manipulating the Li+ solvation structure. Thus, water-tolerance LiMn2 O4 (LMO)||Li4 Ti5 O12 (LTO) full cell with a P/N ratio of 1.14 can be assembled and achieve a long cycling life of 1000 times with high coulombic efficiency of >99.9 %. This work provides a promising insight into the cost-effective practical manufacture of LMO||LTO cells without rigorous moisture-free requirements.

RESUMEN

Proton is an ideal charge carrier for rechargeable batteries due to its small ionic radius, ultrafast diffusion kinetics and wide availability. However, in commonly used acid electrolytes, the co-interaction of polarized water and proton (namely hydronium) with electrode materials often causes electrode structural distortions. The hydronium adsorption on electrode surfaces also facilitates hydrogen evolution as an unwanted side reaction. Here, a "water-in-sugar" electrolyte with high concentration of glucose dissolved in acid to enable the naked proton intercalation, as well as an extended 3.9 V working potential window, is shown. A glucose-derived organic thin film is formed on electrode surface upon cycling. Molecular dynamics simulations reveal the significant decrease of free water in bulk electrolytes, while density functional theory calculations indicate that glucose preferentially binds to the electrode surface which can inhibit water adsorption. The scarcity of free water and the protective organic film work in synergy to suppress water interactions with the electrode surface, which enables the naked proton (de)intercalation. The "water-in-sugar" electrolyte significantly enhances a MoO3 electrode for stable cycling over 100 000 times. This facile electrolyte approach opens new avenues to aqueous electrochemistry and energy storage devices.

Asunto(s)

RESUMEN

The interfacial reactions in sodium-ion batteries (SIBs) are not well understood yet. The formation of a stable solid electrolyte interphase (SEI) in SIBs is still challenging due to the higher solubility of the SEI components compared to lithium analogues. This study therefore aims to shed light on the dissolution of SEI influenced by the electrolyte chemistry. By conducting electrochemical tests with extended open circuit pauses, and using surface spectroscopy, we determine the extent of self-discharge due to SEI dissolution. Instead of using a conventional separator, ß-alumina was used as sodium-conductive membrane to avoid crosstalk between the working and sodium-metal counter electrode. The relative capacity loss after a pause of 50 hours in the tested electrolyte systems ranges up to 30 %. The solubility of typical inorganic SEI species like NaF and Na2 CO3 was determined. The electrolytes were then saturated by those SEI species in order to oppose ageing due to the dissolution of the SEI.

RESUMEN

To understand how Li(+) interacts with individual carbonate molecules in nonaqueous electrolytes, we conducted natural abundance (17)O NMR measurements on electrolyte solutions of 1 M LiPF6 in a series of binary solvent mixtures of ethylene carbonate (EC) and dimethyl carbonate (DMC). It was observed that the largest changes in (17)O chemical shift occurred at the carbonyl oxygens of EC, firmly establishing that Li(+) strongly prefers EC over DMC in typical nonaqueous electrolytes, while mainly coordinating with carbonyl rather than ethereal oxygens. Further quantitative analysis of the displacements in (17)O chemical shifts renders a detailed Li(+)-solvation structure in these electrolyte solutions, revealing that maximum six EC molecules can coexist in the Li(+)-solvation sheath, while DMC association with Li(+) is more "noncommittal" but simultaneously prevalent. This discovery, while aligning well with previous fragmental knowledge about Li(+)-solvation, reveals for the first time a complete picture of Li(+) solvation structure in nonaqueous electrolytes.