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            Abstract A new concentrated ternary salt ether‐based electrolyte enables stable cycling of lithium metal battery (LMB) cells with high‐mass‐loading (13.8 mg cm−2, 2.5 mAh cm−2) NMC622 (LiNi0.6Co0.2Mn0.2O2) cathodes and 50 μm Li anodes. Termed “CETHER‐3,” this electrolyte is based on LiTFSI, LiDFOB, and LiBF4with 5 vol% fluorinated ethylene carbonate in 1,2‐dimethoxyethane. Commercial carbonate and state‐of‐the‐art binary salt ether electrolytes were also tested as baselines. With CETHER‐3, the electrochemical performance of the full‐cell battery is among the most favorably reported in terms of high‐voltage cycling stability. For example, LiNixMnyCo1–x–yO2(NMC)‐Li metal cells retain 80% capacity at 430 cycles with a 4.4 V cut‐off and 83% capacity at 100 cycles with a 4.5 V cut‐off (charge at C/5, discharge at C/2). According to simulation by density functional theory and molecular dynamics, this favorable performance is an outcome of enhanced coordination between Li+and the solvent/salt molecules. Combining advanced microscopy (high‐resolution transmission electron microscopy, scanning electron microscopy) and surface science (X‐ray photoelectron spectroscopy, time‐of‐fight secondary ion mass spectroscopy, Fourier‐transform infrared spectroscopy, Raman spectroscopy), it is demonstrated that a thinner and more stable cathode electrolyte interphase (CEI) and solid electrolyte interphase (SEI) are formed. The CEI is rich in lithium sulfide (Li2SO3), while the SEI is rich in Li3N and LiF. During cycling, the CEI/SEI suppresses both the deleterious transformation of the cathode R‐3m layered near‐surface structure into disordered rock salt and the growth of lithium metal dendrites.more » « less
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            Abstract This is the first report of a multifunctional separator for potassium‐metal batteries (KMBs). Double‐coated tape‐cast microscale AlF3on polypropylene (AlF3@PP) yields state‐of‐the‐art electrochemical performance: symmetric cells are stable after 1000 cycles (2000 h) at 0.5 mA cm−2and 0.5 mAh cm−2, with 0.042 V overpotential. Stability is maintained at 5.0 mA cm−2for 600 cycles (240 h), with 0.138 V overpotential. Postcycled plated surface is dendrite‐free, while stripped surface contains smooth solid electrolyte interphase (SEI). Conventional PP cells fail rapidly, with dendrites at plating, and “dead metal” and SEI clumps at stripping. Potassium hexacyanoferrate(III) cathode KMBs with AlF3@PP display enhanced capacity retention (91% at 100 cycles vs 58%). AlF3partially reacts with K to form an artificial SEI containing KF, AlF3, and Al2O3phases. The AlF3@PP promotes complete electrolyte wetting and enhances uptake, improves ion conductivity, and increases ion transference number. The higher of K+transference number is ascribed to the strong interaction between AlF3and FSI−anions, as revealed through19F NMR. The enhancement in wetting and performance is general, being demonstrated with ester‐ and ether‐based solvents, with K‐, Na‐, or Li‐ salts, and with different commercial separators. In full batteries, AlF3prevents Fe crossover and cycling‐induced cathode pulverization.more » « less
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            Abstract Anodes for lithium metal batteries, sodium metal batteries, and potassium metal batteries are susceptible to failure due to dendrite growth. This review details the structure–chemistry–performance relations in membranes that stabilize the anodes’ solid electrolyte interphase (SEI), allowing for stable electrochemical plating/stripping. Case studies involving Li, Na, and K are presented to illustrate key concepts. “Classical” versus “modern” understandings of the SEI are described, with an emphasis on the new structural insights obtained through novel analytical techniques, including in situ liquid‐secondary ion mass spectroscopy, titration gas chromatography, and tip‐enhanced Raman spectroscopy. This Review highlights diverse approaches for increasing SEI stability, either by inserting a secondary layer between the native SEI and the separator, or by combining the membrane with a native SEI to form a hybrid composite. Exciting and nonintuitive findings are discussed, such as that the metal anode roughness profoundly affects the SEI structure and stability, or that organic artificial SEI‐layers may be more effective than the native inorganic–organic SEIs. Emerging multifunctional architectures are presented, which serve a dual role as metal hosts and metal surface protection layers. Throughout the Review, fruitful future research directions and the critical areas where there is incomplete understanding are discussed.more » « less
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            Abstract Pore size distribution and surface chemistry of bio‐derived (milk) microporous dominated carbon “MDC” is synergistically tuned, allowing for promising carbon capture in a dry CO2atmosphere and in mixed H2O–CO2. The capture capacity is attributed to the synergy of a large total surface area with an ultramicroporous and microporous texture (e.g.,Stot1889 m2g−1,Smic1755 m2g−1,Sultra1393 m2g−1), and a high content of nitrogen and oxygen heteroatom moieties (e.g., 5 at% N, 10.5 at% O). Tailored two‐step low‐temperature pyrolysis‐chemical activation is employed to take advantage of the intrinsic properties of the precursor, allowing for this unusual textural properties‐heteroatoms combination. For example, tested at 1 bar and 295 or 273 K, MDCs adsorb up to 22.0 and 29.4 wt% CO2, respectively. MDCs are also tailored to be hydrophobic, with CO2/H2O adsorption selectivity even after prolonged cycling. Maximum working capacities of 10.8 wt% for pure CO2and 3.5 wt% for a flue gas simulant (15% CO2, 85% N2) are measured using temperature swing adsorption with dynamic purge gases, while being minimally affected by humid conditions. This work is directly aligned with the United Nation’s Sustainable Development Goal 13, take urgent action to combat climate change and its impacts.more » « less
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            Cobalt telluride anchored to nitrogen-rich carbon dodecahedra (CoTe@NCD) was synthesized by simultaneous pyrolysis-tellurium melt impregnation of ZIF-67 MOFs. The purely thermal method involved no secondary chemicals and no waste byproducts. The result is a microstructure consisting of nanoscale 86 wt% CoTe intermetallic nanoparticles contained within a thin N-rich carbon matrix. During electrochemical cycling, the 21 nm average diameter CoTe provides short diffusion paths for Na + /K + ions, which in conjunction with the electrically conducting carbon matrix allow for rapid potassiation or sodiation. As potassium ion battery (PIB and KIB) and sodium ion battery (NIB and SIB) anodes, CoTe@NCD demonstrates attractive reversible capacity, promising cycling stability, and state-of-the-art rate performance. For example, as a KIB anode, the CoTe@NCD electrode exhibits a reversible capacity of 380 mA h g −1 at 50 mA g −1 and a fast charge capacity of 136 mA h g −1 at 1000 mA g −1 . As a NIB anode, it also displays excellent rate capability achieving 620 mA h g −1 at 50 mA g −1 and 345 mA h g −1 at 1000 mA g −1 .more » « less
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            null (Ed.)Lithium metal–selenium (Li–Se) batteries offer high volumetric energy but are limited in their cycling life and fast charge characteristics. Here a facile approach is demonstrated to synthesize hierarchically porous hollow carbon spheres that host Se (Se@HHCS) and allow for state-of-the-art electrochemical performance in a standard carbonate electrolyte (1 M LiPF 6 in 1 : 1 EC : DEC). The Se@HHCS electrodes display among the most favorable fast charge and cycling behavior reported. For example, they deliver specific capacities of 442 and 357 mA h g −1 after 1500 and 2000 cycles at 5C and 10C, respectively. At 2C, Se@HHCS delivers 558 mA h g −1 after 500 cycles, with cycling coulombic efficiency of 99.9%. Post-mortem microstructural analysis indicates that the structures remain intact during extended cycling. Per GITT analysis, Se@HHCS possesses significantly higher diffusion coefficients in both lithiation and delithiation processes as compared to the baseline. The superior performance of Se@HHCS is directly linked to its macroscopic and nanoscale pore structure: the hollow carbon sphere morphology as well as the remnant open nanoporosity accommodates the 69% volume expansion of the Li to Li 2 Se transformation, with the nanopores also providing a complementary fast ion diffusion path.more » « less
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            null (Ed.)We present comprehensive first-principles density functional theory (DFT) analyses of the interfacial strength and bonding mechanisms between crystalline and amorphous selenium (Se) with graphene (Gr), a promising duo for energy storage applications. Comparative interface analyses are presented on amorphous silicon (Si) with graphene and crystalline Se with a conventional aluminum (Al) current collector. The interface strengths of monoclinic Se (0.43 J m–2) and amorphous Si with graphene (0.41 J m–2) are similar in magnitude. While both materials (c-Se, a-Si) are bonded loosely by van der Waals (vdW) forces over graphene, interfacial electron exchange is higher for a-Si/graphene. This is further elaborated by comparing the potential energy step and charge transfer (Δq) across the graphene interfaces. The interface strength of c-Se on a 3D Al current collector is higher (0.99 J m–2), suggesting a stronger adhesion. Amorphous Se with graphene has comparable interface strength (0.34 J m–2), but electron exchange in this system is slightly distinct from monoclinic Se. The electronic characteristics and bonding mechanisms are different for monoclinic and amorphous Se with graphene as they activate graphene via surface charge doping divergently. The implications of these interfacial physicochemical attributes on electrode performance have been discussed. Our findings highlight the complex electrochemical phenomena in Se interfaced with graphene, which may profoundly differ from their “free” counterparts.more » « less
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