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Conductive metal-organic frameworks (c-MOFs) and ionic liquids (ILs) have emerged as auspicious combinations for high-performance supercapacitors. However, the nanoconfinement from c-MOFs and high viscosity of ILs slow down the charging process. This hindrance can, however, be resolved by adding solvent. Here, we performed constant-potential molecular simulations to scrutinize the solvent impact on charge storage and charging dynamics of MOF-IL-based supercapacitors. We find conditions for >100% enhancement in capacity and ~6 times increase in charging speed. These improvements were confirmed by synthesizing near-ideal c-MOFs and developing multiscale models linking molecular simulations to electrochemical measurements. Fundamentally, our findings elucidate that the solvent acts as an ionophobic agent to induce a substantial enhancement in charge storage, and as an ion traffic police to eliminate convoluted counterion and co-ion motion paths and create two distinct ion transport highways to accelerate charging dynamics. This work paves the way for the optimal design of MOF supercapacitors.

Constant-potential molecular dynamics (MD) simulations are indispensable for understanding the capacitance, structure, and dynamics of electrical double layers (EDLs) at the atomistic level. However, the classical constant-potential method, relying on the so-called 'floating charges' to keep electrode equipotential, overlooks quantum effects on the electrode and always underestimates EDL capacitance for typical electrochemical systems featuring metal electrodes in aqueous electrolytes. Here, we propose a universal theoretical framework as moment-tensor-based constant potential method (mCPM) to capture electronic structure variations with electric moments. For EDLs at Au(111) electrodes, mCPM-based MD reveals bell-shaped capacitance curves in magnitude and shape both quantitatively consistent with experiments. It further unveils the potential-dependent local electric fields, agreeing with experimental observations of redshift vibration of interfacial water under negative polarization and predicting a blueshift under positive polarization, and identifies geometry dependence of two time scales during EDL formation.

Referring video segmentation aims to segment the corresponding video object described by the language expression. To address this task, we first design a two-stream encoder to extract CNN-based visual features and transformer-based linguistic features hierarchically, and a vision-language mutual guidance (VLMG) module is inserted into the encoder multiple times to promote the hierarchical and progressive fusion of multi-modal features. Compared with the existing multi-modal fusion methods, this two-stream encoder takes into account the multi-granularity linguistic context, and realizes the deep interleaving between modalities with the help of VLGM. In order to promote the temporal alignment between frames, we further propose a language-guided multi-scale dynamic filtering (LMDF) module to strengthen the temporal coherence, which uses the language-guided spatial-temporal features to generate a set of position-specific dynamic filters to more flexibly and effectively update the feature of current frame. Extensive experiments on four datasets verify the effectiveness of the proposed model.

Recently, referring image segmentation has aroused widespread interest. Previous methods perform the multi-modal fusion between language and vision at the decoding side of the network. And, linguistic feature interacts with visual feature of each scale separately, which ignores the continuous guidance of language to multi-scale visual features. In this work, we propose an encoder fusion network (EFN), which transforms the visual encoder into a multi-modal feature learning network, and uses language to refine the multi-modal features progressively. Moreover, a co-attention mechanism is embedded in the EFN to realize the parallel update of multi-modal features, which can promote the consistent of the cross-modal information representation in the semantic space. Finally, we propose a boundary enhancement module (BEM) to make the network pay more attention to the fine structure. The experiment results on four benchmark datasets demonstrate that the proposed approach achieves the state-of-the-art performance under different evaluation metrics without any post-processing.

Asymmetric behaviors of capacitance and charging dynamics in the cathode and anode are general for nanoporous supercapacitors. Understanding this behavior is essential for the optimal design of supercapacitors. Herein, we perform constant-potential molecular dynamics simulations to reveal asymmetric features of porous supercapacitors and their effects on capacitance and charging dynamics. Our simulations show that, counterintuitively, charging dynamics can be fast in pores providing slow ion diffusion and vice versa. Unlike electrodes with single-size pores, multi-pore electrodes show overcharging and accelerated co-ion desorption, which can be attributed to the subtle interplay between the dynamics and charging mechanisms. We find that capacitance and charging dynamics correlate with how the ions respond to an applied cell voltage in the cathode and anode. We demonstrate that symmetrizing this response can help boost power density, which may find practical applications in supercapacitor optimization.

Whereas the majority of ions in the bulk of a solvent-free ionic liquid is bound into clusters, this is expected to change in the electrical double layer (EDL), in which the resulting electric field 'prefers' to interact with electrical monopoles-free, unclustered ions. The competition between the propensity of ions to stay in a clustered state and the reduction of the energy of ions in electric field in the free state determines the resulting portion of free ions in the EDL. We present a study of this effect, based on the simplest possible mean-field theory. 'Cracking' of ion clusters into individual ions in electric field is accompanied by the change of the dielectric response of ionic liquid which is different in clustered and unclustered states. The predictions of the theory are verified and further explored by specially performed molecular dynamics simulations. A particular finding of the theory is that the differential capacitance vs potential curve displays a bell shape despite low concentration of free charge carriers, because the dielectric response of bound ions reduces the threshold concentration of the bell- to camel-shape transition. Whereas qualitatively these findings make perfect sense, in reality the exact numbers and criteria might be different as the presented simple theory does not take into account overscreening and oscillating charge and electrostatic potential distributions near the electrode. This is why testing the theory with computer simulations is essential, but the latter basically reproduce the qualitative conclusions of the theory., Comment: 23 pages, 4 figures. Submitted to Energy & Environmental Materials

Humid hydrophobic ionic liquids, widely used as electrolytes, have narrowed electrochemical windows, because their water, absorbed on the electrode surface, gets involved in electrolysis. In this work, we performed molecular dynamics simulations to explore effects of adding Li-salt in humid ionic liquids on the water adsorbed on the electrode surface. Results reveal that most of water molecules are pushed away from both cathode and anode, by adding salt. The water remained on the electrode is almost bound with Li+, which has significantly lowered activity. The Li+-bonding and re-arrangement of the surface-adsorbed water both facilitate the inhibition of water electrolysis, and thus prevent the reduction of electrochemical windows of humid hydrophobic ionic liquids. This finding is testified by cyclic voltammetry measurements where salt-in-humid ionic liquids exhibit enhanced electrochemical windows. Our work provides the underlying mechanism and a simple but practical approach for protection of humid ionic liquids from performance degradation., Comment: 20 pages, 5 figures