The stability of a battery is strongly dependent on the feature of solid electrolyte interphase (SEI). The electrical double layer forms prior to the formation of SEI at the interface between the Li metal anode and the electrolyte. The fundamental understanding on the regulation of the SEI structure and stability on Li surface through the structure of the electrical double layer is highly necessary for safe batteries. Herein, the interfacial chemistry of the SEI is correlated with the initial Li surface adsorption electrical double layer at the nanoscale through theoretical and experimental analysis. Under the premise of the constant solvation sheath structure of Li + in bulk electrolyte, a trace amount of lithium nitrate (LiNO 3 ) and copper fluoride (CuF 2 ) were employed in electrolytes to build robust electric double layer structures on a Li metal surface. The distinct results were achieved with the initial competitive adsorption of bis(fluorosulfonyl)imide ion (FSI − ), fluoride ion (F − ), and nitrate ion (NO 3 − ) in the inner Helmholtz plane. As a result, Cu−NO 3 − complexes are preferentially adsorbed and reduced to form the SEI. The modified Li metal electrode can achieve an average Coulombic efficiency of 99.5% over 500 cycles, enabling a long lifespan and high capacity retention of practical rechargeable batteries. The as-proposed mechanism bridges the gap between Li + solvation and the adsorption about the electrode interface formation in a working battery.
The intrinsic instability of organic electrolytes seriously impedes practical applications of high-capacity metal (Li, Na) anodes.I on-solvent complexes can even promote the decomposition of electrolytes on metal anodes. Herein, first-principles calculations were performed to investigate the origin of the reduced reductive stability of ionsolvent complexes.Both ester and ether electrolyte solvents are selected to interact with Li + ,N a + ,K + ,M g 2+ ,a nd Ca 2+ .T he LUMO energy levels of ion-ester complexes exhibit al inear relationship with the binding energy,r egulated by the ratio of carbon atomic orbital in the LUMO,w hile LUMOs of ionether complexes are composed by the metal atomic orbitals. This work shows why ion-solvent complexes can reduce the reductive stability of electrolytes,reveals different mechanisms for ester and ether electrolytes,a nd provides at heoretical understanding of the electrolyte-anode interfacial reactions and guidance to electrolyte and metal anode design.
Electrolyte solvation is a fundamental issue that regulates the lithium (Li) ion solvation sheath structure, the formation of cathode/anode−electrolyte interphase, and the plating/stripping behavior of Li ions in working Li batteries. Herein, we probe the cation‐solvent, cation‐anion, and solvent‐solvent interactions under both vacuum and electrolyte conditions through density functional theory calculations. The solvation effects can significantly weaken the aforementioned interactions in electrolytes as well as increase the Li−O/F distances in Li+‐containing complexes. The dissolution behaviour of Li salts in electrolytes was further explored and experimentally validated by dissolving lithium nitrate in different solvents. This work affords a mechanistic understanding of electrolyte microstructure and highlights the significant role of electrolyte solvation in regulating battery performance, affording fruitful insights into emerging electrolyte design for high‐performance batteries.
The intrinsic instability of organic electrolytes seriously impedes practical applications of high‐capacity metal (Li, Na) anodes. Ion–solvent complexes can even promote the decomposition of electrolytes on metal anodes. Herein, first‐principles calculations were performed to investigate the origin of the reduced reductive stability of ion–solvent complexes. Both ester and ether electrolyte solvents are selected to interact with Li+, Na+, K+, Mg2+, and Ca2+. The LUMO energy levels of ion–ester complexes exhibit a linear relationship with the binding energy, regulated by the ratio of carbon atomic orbital in the LUMO, while LUMOs of ion–ether complexes are composed by the metal atomic orbitals. This work shows why ion–solvent complexes can reduce the reductive stability of electrolytes, reveals different mechanisms for ester and ether electrolytes, and provides a theoretical understanding of the electrolyte–anode interfacial reactions and guidance to electrolyte and metal anode design.
Intervertebral disc degeneration (Idd) is an important cause of lower back pain, although the underlying mechanisms remain poorly understood. The present study aimed to examine the role of a circular RNA derived from tissue inhibitor of metallopeptidases 2 (circ-TIMP2) in degenerative nucleus pulposus (NP) tissues, and to validate its function in cultured human NP cells. Overexpression of miR-185-5p in NP cells markedly inhibited the enhanced extracellular matrix (EcM) catabolism induced by tumor necrosis factor-α (TNF-α) and interleukin-1β (IL-1β) treatment. Bioinformatics analysis demonstrated that matrix metalloproteinase 2 (MMP2) was a potential target of miR-185-5p. MMP2 protein expression levels were increased following treatment with TNF-α and IL-1β in NP cells compared with those in untreated cells, and this effect was attenuated by transfection with miR-185-5p. compared with normal NP tissues, Idd samples exhibited higher circ-TIMP2 expression levels. In addition, overexpression of circ-TIMP2 promoted EcM catabolism and suppressed EcM anabolism. Furthermore, circ-TIMP2 sequestered miR-185-5p, which may potentially upregulate the target genes associated with EcM degradation. In conclusion, the results of the present study revealed that circ-TIMP2 promoted TNF-αand IL-1β-induced NP cell imbalance between EcM anabolism and catabolism via miR-185-5p-MMP2 signaling. These findings provide a potential therapeutic option for the treatment of Idd.
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