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Microporous polymers feature shape-persistent free volume elements (FVEs), which are permeated by small molecules and ions when used as membranes for chemical separations, water purification, fuel cells and batteries1-3. Identifying FVEs that have analyte specificity remains a challenge, owing to difficulties in generating polymers with sufficient diversity to enable screening of their properties. Here we describe a diversity-oriented synthetic strategy for microporous polymer membranes to identify candidates featuring FVEs that serve as solvation cages for lithium ions (Li+). This strategy includes diversification of bis(catechol) monomers by Mannich reactions to introduce Li+-coordinating functionality within FVEs, topology-enforcing polymerizations for networking FVEs into different pore architectures, and several on-polymer reactions for diversifying pore geometries and dielectric properties. The most promising candidate membranes featuring ion solvation cages exhibited both higher ionic conductivity and higher cation transference number than control membranes, in which FVEs were aspecific, indicating that conventional bounds for membrane permeability and selectivity for ion transport can be overcome4. These advantages are associated with enhanced Li+ partitioning from the electrolyte when cages are present, higher diffusion barriers for anions within pores, and network-enforced restrictions on Li+ coordination number compared to the bulk electrolyte, which reduces the effective mass of the working ion. Such membranes show promise as anode-stabilizing interlayers in high-voltage lithium metal batteries.
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In this work, we explain the origin and the mechanism responsible for the strong enhancement of the Raman signal of sulfur chains encapsulated by single-wall carbon nanotubes by running resonance Raman measurements in a wide range of excitation energies for two nanotube samples with different diameter distributions. The Raman signal associated with the vibrational modes of the sulfur chain is observed when it is confined by small-diameter metallic nanotubes. Moreover, a strong enhancement of the Raman signal is observed for excitation energies corresponding to the formation of excited nanotube-chain-hybrid electronic states. Our hypothesis was further tested by high pressure Raman measurements and confirmed by density functional theory calculations of the electronic density of states of hybrid systems formed by sulfur chains encapsulated by different types of single-wall carbon nanotubes.
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We report a nanocomposite coating for lithium metal protection, which consists of nanosized LiF particles embedded into a PEO polymer matrix. The composite offers a large LiF/PEO interface area throughout the coating, promoting an exceptionally high ionic conductivity of 0.97 mS cm-1 and high lithium-ion transference number of 0.77 at room temperature in contact with a carbonate-based liquid electrolyte. Both properties are key to realize uniform lithium plating and stripping and prevent lithium dendrite formation. Lithium metal electrodes coated with this protective coating enable stable lithium plating and stripping at 1 mA cm-2 for over 1000 h. A full cell with the coated lithium metal anode and an NMC622 cathode with an areal capacity of 1 mA h cm-2 shows much improved specific capacity and cycling stability. The cell exhibits a high initial capacity of 135 mA h g-1 and a capacity retention of 83% after 500 cycles at 1 mA cm-2. Even at a high current density of 3 mA cm-2, the full cell shows an initial capacity of 125 mA h g-1 and a capacity retention of 74% after 300 cycles.
RESUMO
Dendrite formation during electrodeposition while charging lithium metal batteries compromises their safety. Although high-shear-modulus (Gs) solid-ion conductors (SICs) have been prioritized to resolve the pressure-driven instabilities that lead to dendrite propagation and cell shorting, it is unclear whether these or alternatives are needed to guide uniform lithium electrodeposition, which is intrinsically density-driven. Here, we show that SICs can be designed within a universal chemomechanical paradigm to access either pressure-driven dendrite-blocking or density-driven dendrite-suppressing properties, but not both. This dichotomy reflects the competing influence of the SIC's mechanical properties and the partial molar volume of Li+ ([Formula: see text]) relative to those of the lithium anode (GLi and VLi) on plating outcomes. Within this paradigm, we explore SICs in a previously unrecognized dendrite-suppressing regime that are concomitantly 'soft', as is typical of polymer electrolytes, but feature an atypically low [Formula: see text] that is more reminiscent of 'hard' ceramics. Li plating (1 mA cm-2; T = 20 °C) mediated by these SICs is uniform, as revealed using synchrotron hard X-ray microtomography. As a result, cell cycle life is extended, even when assembled with thin Li anodes (~30 µm) and either high-voltage NMC-622 cathodes (1.44 mAh cm-2) or high-capacity sulfur cathodes (3.02 mAh cm-2).
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To suppress dendrite formation in lithium metal batteries, high cation transference number electrolytes that reduce electrode polarization are highly desirable, but rarely available using conventional liquid electrolytes. Here, we show that liquid electrolytes increase their cation transference numbers (e.g., â¼0.2 to >0.70) when confined to a structurally rigid polymer host whose pores are on a similar length scale (0.5-2 nm) as the Debye screening length in the electrolyte, which results in a diffuse electrolyte double layer at the polymer-electrolyte interface that retains counterions and reject co-ions from the electrolyte due to their larger size. Lithium anodes coated with â¼1 µm thick overlayers of the polymer host exhibit both a low area-specific resistance and clear dendrite-suppressing character, as evident from their performance in Li-Li and Li-Cu cells as well as in post-mortem analysis of the anode's morphology after cycling. High areal capacity Li-S cells (4.9 mg cm-2; 8.2 mAh cm-2) implementing these high transference number polymer-hosted liquid electrolytes were remarkably stable, considering â¼24 µm of lithium was electroreversibly deposited in each cycle at a C-rate of 0.2. We further identified a scalable manufacturing path for these polymer-coated lithium electrodes, which are drop-in components for lithium metal battery manufacturing.
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We demonstrate a new technique to produce lithium sulfide-carbon composite (Li2S-C) cathodes for lithium-sulfur batteries via aerosol spray pyrolysis (ASP) followed by sulfurization. Specifically, lithium carbonate-carbon (Li2CO3-C) composite nanoparticles are first synthesized via ASP from aqueous solutions of sucrose and lithium salts including nitrate (LiNO3), acetate (CH3COOLi), and Li2CO3, respectively. The obtained Li2CO3-C composites are subsequently converted to Li2S-C through sulfurization by reaction to H2S. Electrochemical characterizations show excellent overall capacity and cycle stability of the Li2S-C composites with relatively high areal loading of Li2S and low electrolyte/Li2S ratio. The Li2S-C nanocomposites also demonstrate clear structure-property relationships.
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We demonstrate an unusual electrochemical reaction of sulfur with lithium upon encapsulation in narrow-diameter (subnanometer) single-walled carbon nanotubes (SWNTs). Our study provides mechanistic insight on the synergistic effects of sulfur confinement and Li+ ion solvation properties that culminate in a new mechanism of these sub-nanoscale-enabled reactions (which cannot be solely attributed to the lithiation-delithiation of conventional sulfur). Two types of SWNTs with distinct diameters, produced by electric arc (EA-SWNTs, average diameter 1.55 nm) or high-pressure carbon monoxide (HiPco-SWNTs, average diameter 1.0 nm), are investigated with two comparable electrolyte systems based on tetraethylene glycol dimethyl ether (TEGDME) and 1,4,7,10,13-pentaoxacyclopentadecane (15-crown-5). Electrochemical analyses indicate that a conventional solution-phase Li-S reaction occurs in EA-SWNTs, which can be attributed to the smaller solvated [Li(TEGDME)]+ and [Li(15-crown-5)]+ ions within the EA-SWNT diameter. In stark contrast, the Li-S confined in narrower diameter HiPco-SWNTs exhibits unusual electrochemical behavior that can be attributed to a solid-state reaction enabled by the smaller HiPco-SWNT diameter compared to the size of solvated Li+ ions. Our results of the electrochemical analyses are corroborated and supported with various spectroscopic analyses including operando Raman, X-ray photoelectron spectroscopy, and first-principles calculations from density functional theory. Taken together, our findings demonstrate that the controlled solid-state lithiation-delithiation of sulfur and an enhanced electrochemical reactivity can be achieved by sub-nanoscale encapsulation and one-dimensional confinement in narrow-diameter SWNTs.
RESUMO
Combining theoretical and experimental approaches, we investigate the solvation properties of Li+ ions in a series of ether solvents (dimethoxyethane, diglyme, triglyme, tetraglyme, and 15-crown-5) and their subsequent effects on the solid-state lithium-sulfur reactions in subnano confinement. The ab initio and classical molecular dynamics (MD) simulations predict Li+ ion solvation structures within ether solvents in excellent agreement with experimental evidence from electrospray ionization-mass spectroscopy. An excellent correlation is also established between the Li+-solvation binding energies from the ab initio MD simulations and the lithiation overpotentials obtained from galvanostatic intermittent titration techniques (GITT). These findings convincingly indicate that a stronger solvation binding energy imposes a higher lithiation overpotential of sulfur in subnano confinement. The mechanistic understanding achieved at the electronic and atomistic level of how Li+-solvation dictates its electrochemical reactions with sulfur in subnano confinement provides invaluable guidance in designing future electrolytes and electrodes for Li-sulfur chemistry.
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We report the electrochemical intercalation-extraction of aluminum (Al) in the layered TiS2 and spinel-based cubic Cu0.31Ti2S4 as the potential cathode materials for rechargeable Al-ion batteries. The electrochemical characterizations demonstrate the feasibility of reversible Al intercalation in both titanium sulfides with layered TiS2 showing better properties. The crystallographic study sheds light on the possible Al intercalation sites in the titanium sulfides, while the results from galvanostatic intermittent titration indicate that the low Al3+ diffusion coefficients in the sulfide crystal structures are the primary obstacle to facile Al intercalation-extraction.
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Herein, facile synthesis of monodisperse silicon and carbon nanocomposite spheres (MSNSs) is achieved via a simple and scalable surface-protected magnesiothermic reduction with subsequent chemical vapor deposition (CVD) process. Li-ion batteries (LIBs) were fabricated to test the utility of MSNSs as an anode material. LIB anodes based on MSNSs demonstrate a high reversible capacity of 3207 mAh g-1, superior rate performance, and excellent cycling stability. Furthermore, the performance of full cell LIBs was evaluated by using MSNS anode and a LiCoO2 cathode with practical electrode loadings. The MSNS/LiCoO2 full cell demonstrates high gravimetric energy density in the order of 850 Wh L-1 with excellent cycling stability. This work shows a proof of concept of the use of monodisperse Si and C nanocomposite spheres toward practical lithium-ion battery applications.
RESUMO
We investigate the detailed effects and mechanisms of sub-nano confinement on lithium-sulfur (Li-S) electrochemical reactions in both ether-based and carbonate-based electrolytes. Our results demonstrate a clear correlation between the size of sulfur confinement and the resulting Li-S electrochemical mechanisms. In particular, when sulfur is confined within sub-nano pores, we observe identical lithium-sulfur electrochemical behavior, which is distinctly different from conventional Li-S reactions, in both ether and carbonate electrolytes. Taken together, our results highlight the critical importance of sub-nano confinement effects on controlling solid-state reactions in Li-S electrochemical systems.
RESUMO
Encapsulation of sulfur in HiPCO-SWNTs leads to large changes in the Raman spectra with the appearance of new peaks at 319, 395, and 715 cm(-1) which originate from the sulfur species within the SWNTs, while the high frequency SWNT bands (ν > 1200 cm(-1)) are decreased in intensity. The encapsulated species also shifts the near-IR interband electronic transitions to lower energy by more than 10%. These effects seem to originate with the van der Waals interaction of the confined sulfur species with the walls of the SWNTs which are not expected to be significant in the case of the previously studied large diameter SWNTs. We suggest that sulfur in the small diameter SWNTs exists as a helical polymeric sulfur chain that enters the SWNT interior in the form of S2 ((3)Σ(g)(-)) molecules which undergo polymerization to linear diradicals.