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Despite the continuous increase in capacity, lithium-ion intercalation batteries are approaching their performance limits. As a result, research is intensifying on next-generation battery technologies. The use of a lithium metal anode promises the highest theoretical energy density and enables use of lithium-free or novel high-energy cathodes. However, the lithium metal anode suffers from poor morphological stability and Coulombic efficiency during cycling, especially in liquid electrolytes. In contrast to solid electrolytes, liquid electrolytes have the advantage of high ionic conductivity and good wetting of the anode, despite the lithium metal volume change during cycling. Rapid capacity fade due to inhomogeneous deposition and dissolution of lithium is the main hindrance to the successful utilization of the lithium metal anode in combination with liquid electrolytes. In this perspective, we discuss how experimental and theoretical insights can provide possible pathways for reversible cycling of two-dimensional lithium metal. Therefore, we discuss improvements in the understanding of lithium metal nucleation, deposition, and stripping on the nanoscale. As the solid-electrolyte interphase (SEI) plays a key role in the lithium morphology, we discuss how the proper SEI design might allow stable cycling. We highlight recent advances in conventional and (localized) highly concentrated electrolytes in view of their respective SEIs. We also discuss artificial interphases and three-dimensional host frameworks, which show prospects of mitigating morphological instabilities and suppressing large shape change on the electrode level.

Cobalt is considered an essential element for layered cathode active materials supporting enhanced lithium‐ion conductivity and structural stability. Herein, we investigated the influence of Co concentration on the physicochemical properties and electrochemical performance of lithium‐rich layered oxides (LRLOs) with different Co content (Li1.2Ni0.2‐x/2Mn0.6‐x/2CoxO2, x=0, 0.04, and 0.08). Though the presence of Co grants structural stability to LRLOs, superior long‐term cycling stability is achieved with the Co‐free LRLO retaining 88.1 % of the initial specific capacity (vs. 75.9 % of Li1.2Ni0.16Mn0.56Co0.08O2) after 300 galvanostatic cycles at 250 mA g−1 (1 C). The chemical stability on the surface of LRLOs containing Co declines faster, indicating a higher bulk structural stability not being the primary determinant of the LRLOs' cycling performance. Ex‐situ investigations indicate that the superior cycling stability of Co‐free LRLO is obtained by reducing the Mn‐related redox at discharge, which contributes to the large degree of polarization and low energy efficiency. Finally, the full‐cell configured with the optimized LRLO as cathode and graphite anode delivers an energy density of 464 Wh kg−1 at C/10, and 74.4 % and 94.3 % of retention in discharge specific capacity and average voltage at the 1000th cycle, demonstrating the applicability of Co‐free LRLO for sustainable LIBs. [ABSTRACT FROM AUTHOR]

Sodium batteries are an attractive alternative for future energy storage as they can be produced with abundant and low-cost materials. Nonetheless, sodium-ion batteries (SIBs) are often composed of flammable and volatile carbonate-based liquid electrolytes. Polymer electrolytes have attracted significant attention as safer alternatives. Among polymer electrolytes, single-ion conductive polymer electrolytes (SIPEs) are considered particularly interesting because they can suppress dendrite growth, enabling high-performance (quasi)-solid-state sodium–(metal) batteries. In this work, a self-standing, flexible, quasi-solid-state SIPE is investigated, which is composed of sodium 4-styrene sulfonyl (trifluoromethanesulfonyl) imide (NaSTFSI), pentaerythritol tetrakis(3-mercaptopropionate) (PETMP) and pentaerythritol tetraacrylate (PET4A) blended with poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP). The SIPE membrane, including 50 wt% of molecular transporter, exhibits ionic conductivity of 1.4 × 10−5 S cm−1 and 1.3 × 10−4 S cm−1 at 20 °C and 90 °C, respectively, thermal stability up to 280 °C, electrochemical stability window up to 4.5 V vs. Na/Na+, and Na plating/stripping reversibility in symmetric Na‖Na cells. The manufactured SIPE implemented in Prussian White (PW)‖Na cells enables the delivery of 147 mA h g−1 of PW at 15 mA g−1 with a Coulombic efficiency of over 99%, which is comparable with the PW‖Na cells using liquid carbonate electrolyte, confirming the suitability of the designed SIPE for sodium–(metal) batteries. [ABSTRACT FROM AUTHOR]

In this study, the protic ionic liquid N,N-diethyl-3-sulfopropan-1-ammonium hydrogen methanedisulfonate is synthesized and characterized with the aim of elucidating its transport properties. A unique feature of this ionic liquid are the exchangeable acidic protons present on the anion and the cation, both of which contain low proton affinity sulfonic groups. The pronounced superionicity of this liquid, highlighted in the Walden-plot (ΔW > 0.8), indicates the decoupling of the conductivity from ionic diffusion. To explicate this enhanced proton mobility, the diffusion coefficients of the protons were measured by Pulsed-Field Gradient Spin-Echo NMR experiments at different temperatures. Below 373 K the diffusion coefficients of the cationic and anionic exchangeable protons are comparable with the ones of the other protons of the respective ions, indicating a vehicular transport mechanism. However, in the temperature range 383–413 K the diffusion coefficient of one of the exchangeable protons exceeds the diffusion of both ions by an unprecedented factor between 2 and 3. This temperature-induced switch in the proton transport mechanism is the result of a mixed-ion proton-transfer chain, as also supported by computational simulations. Both experimental and theoretical findings suggest the existence of a Grotthuss(-like) proton transport mechanism at high temperature in this system. [ABSTRACT FROM AUTHOR]

The EU's energy transition necessitates availability of green energy carriers with high volumetric energy densities for long‐term energy storage (ES) needs. A fully decarbonized scenario considering renewable energy availability is analyzed underpinning the need for such carriers. Considering the shortcomings of Power‐to‐X technologies in terms of efficiency and low volumetric density, Aluminum (Al) is identified as a potential alternative showing significantly high volumetric energy densities (23.5 kWh L−1). In this paper, an Al‐based long‐term ES concept is investigated, taking advantage of the inherent recycling of the active species (i.e., Al2O3 to Al) coupling decarbonized Hall–Héroult process with an Al‐steam oxidation for simultaneous hydrogen (H2) and heat generation. This work demonstrates an innovative lab‐scale fine Al powder‐steam oxidation process at ≈900 °C without use of catalysts or additives, exploiting alumina as inert material. Conducted SEM‐EDX analysis on oxidized Al provides supporting evidence in favor of employed oxidation pathway, hindering tendency of aluminum oxide (Al2O3) clumping and enabling direct use of oxides in the smelting process for fully recyclability. Moreover, outcomes of XRD analyses are presented to validate the measured total H2 yields. [ABSTRACT FROM AUTHOR]