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A strategy for modifying the structure of solid-state electrolytes (SSEs) to reduce the cation diffusion activation energy is presented. Two heavily W-doped sodium thioantimonate SSEs, Na2.895 W0.3 Sb0.7 S4 and Na2.7 W0.3 Sb0.7 S4 are designed, both exhibiting exceptionally low activation energy and enhanced room temperature (RT) ionic conductivity; 0.09 eV, 24.2 mS/cm and 0.12 eV, 14.5 mS/cm. At -15 °C the Na2.895 W0.3 Sb0.7 S4 displays a total ionic conductivity of 5.5 mS/cm. The 30 % W content goes far beyond the 10-12 % reported in the prior studies, and results in novel pseudo-cubic or orthorhombic structures. Calculations reveal that these properties result from a combination of multiple diffusion mechanisms, including vacancy defects, strongly correlated modes and excessive Na-ions. An all-solid-state battery (ASSB) using Na2.895 W0.3 Sb0.7 S4 as the primary SSE and a sodium sulfide (Na2 S) cathode achieves a reversible capacity of 400 mAh g-1 .

In this work, the Na-K liquid alloy with a charge selective interfacial layer is developed to achieve an impressively long cycling life with small overpotential on a sodium super-ionic conductor solid-state electrolyte (NASICON SSE). With this unique multi-cation system as the platform, we further propose a unique model that contains a chemical decomposition domain and a kinetic decomposition domain for the interfacial stability model. Based on this model, two charge selection mechanisms are proposed with dynamic chemical kinetic equilibrium and electrochemical kinetics as the manners of control, respectively, and both are validated by the electrochemical measurements with microscopic and spectroscopic characterizations. This study provides an effective design for high-energy-density solid-state battery with alkali Na-K anode, but also presents a novel approach to understand the interfacial chemical processes that could inspire and guide future designs.

We report a new approach for nanosilicon-graphene hybrids with uniquely stable solid electrolyte interphase. Expanded graphite is gently exfoliated creating "defect-free" graphene that is non-catalytic towards electrolyte decomposition, simultaneously introducing high mass loading (48 wt. %) Si nanoparticles. Silane surface treatment creates epoxy chemical tethers, mechanically binding nano-Si to CMC binder through epoxy ring-opening reaction while stabilizing the Si surface chemistry. Epoxy-tethered silicon pristine-graphene hybrid "E-Si-pG" exhibits state-of-the-art performance in full battery opposing commercial mass loading (12 mg cm-2 ) LiCoO2 (LCO) cathode. At 0.4 C, with areal capacity of 1.62 mAh cm-2 and energy of 437 Wh kg-1 , achieving 1.32 mAh cm-2 , 340.4 Wh kg-1 at 1 C. After 150 cycles, it retains 1.25 mAh cm-2 , 306.5 Wh kg-1 . Sputter-down XPS demonstrates survival of surface C-Si-O-Si groups in E-Si-pG after repeated cycling. The discovered synergy between support defects, chemical-mechanical stabilization of Si surfaces, and SEI-related failure may become key LIB anode design rule.

This is the first report of molybdenum carbide-based electrocatalyst for sulfur-based sodium-metal batteries. MoC/Mo

This is the first report of a multifunctional separator for potassium-metal batteries (KMBs). Double-coated tape-cast micro-scale AlF3 on polypropylene (AlF3 @PP) yield state-of-the-art electrochemical performance: Symmetric cells are stable after 1,000 cycles (2,000 hours) at 0.5 mA cm-2 and 0.5 mAh cm-2 , with 0.042 V overpotential. Stability is maintained at 5.0 mA cm-2 for 600 cycles (14,400 minutes), with 0.138 V overpotential. Post-cycled plated surface is dendrite-free, while stripped surface contains smooth 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 the enhanced capacity retention (91% at 100 cycles versus 58%). AlF3 partially reacts with K to form an artificial SEI containing KF, AlF3 and Al2 O3 phases. 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 AlF3 and FSI- anions, as revealed through 19 F 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 AlF3 prevents Fe crossover and cycling-induced cathode pulverization. This article is protected by copyright. All rights reserved.

Repeated cold rolling and folding is employed to fabricate a metallurgical composite of sodium-antimony-telluride Na2 (Sb2/6 Te3/6 Vac1/6 ) dispersed in electrochemically active sodium metal, termed "NST-Na." This new intermetallic has a vacancy-rich thermodynamically stable face-centered-cubic structure and enables state-of-the-art electrochemical performance in widely employed carbonate and ether electrolytes. NST-Na achieves 100% depth-of-discharge (DOD) in 1 m NaPF6 in G2, with 15 mAh cm-2 at 1 mA cm-2 and Coulombic efficiency (CE) of 99.4%, for 1000 h of plating/stripping. Sodium-metal batteries (SMBs) with NST-Na and Na3 V2 (PO4 )3 (NVP) or sulfur cathodes give significantly improved energy, cycling, and CE (>99%). An anode-free battery with NST collector and NVP obtains 0.23% capacity decay per cycle. Imaging and tomography using conventional and cryogenic microscopy (Cryo-EM) indicate that the sodium metal fills the open space inside the self-supporting sodiophilic NST skeleton, resulting in dense (pore-free and solid electrolyte interphase (SEI)-free) metal deposits with flat surfaces. The baseline Na deposit consists of filament-like dendrites and "dead metal", intermixed with pores and SEI. Density functional theory calculations show that the uniqueness of NST lies in the thermodynamic stability of the Na atoms (rather than clusters) on its surface that leads to planar wetting, and in its own stability that prevents decomposition during cycling.

This is the first report of successful potassium metal battery anode cycling with an aluminum-based rather than copper-based current collector. Dendrite-free plating/stripping is achieved through improved electrolyte wetting, employing an aluminum-powder-coated aluminum foil "Al@Al," without any modification of the support surface chemistry or electrolyte additives. The reservoir-free Al@Al half-cell is stable at 1000 cycles (1950 h) at 0.5 mA cm-2 , with 98.9% cycling Coulombic efficiency and 0.085 V overpotential. The pre-potassiated cell is stable through a wide current range, including 130 cycles (2600 min) at 3.0 mA cm-2 , with 0.178 V overpotential. Al@Al is fully wetted by a 4 m potassium bis(fluorosulfonyl)imide-dimethoxyethane electrolyte (θCA = 0°), producing a uniform solid electrolyte interphase (SEI) during the initial galvanostatic formation cycles. On planar aluminum foil with a nearly identical surface oxide, the electrolyte wets poorly (θCA = 52°). This correlates with coarse irregular SEI clumps at formation, 3D potassium islands with further SEI coarsening during plating/stripping, possibly dead potassium metal on stripped surfaces, and rapid failure. The electrochemical stability of Al@Al versus planar Al is not related to differences in potassiophilicity (nearly identical) as obtained from thermal wetting experiments. Planar Cu foils are also poorly electrolyte-wetted and become dendritic. The key fundamental takeaway is that the incomplete electrolyte wetting of collectors results in early onset of SEI instability and dendrites.

This is the first review on potassium-sulfur (K-S) batteries (KSBs), which are emerging metal battery (MB) systems. Since KSBs are quite new, there are fundamental questions regarding the electrochemistry of S-based cathode and of K metal anode, as well as the holistic aspects of full-cell performance. The manuscript begins with a critical discussion regarding the potassium-sulfur electrochemistry and on how it differs from the much better-known lithium-sulfur. Cathodes are discussed next, focusing on the role of sulfur structure, carbon host chemistry and porosity, and electrolytes in establishing the reversible potassium sulfide K2 Sn phase sequence, the parasitic polysulfide shuttle, pulverization-driven capacity fade, etc. Following is a discussion of solid-state electrolytes (SSEs), including of hybrid solid-liquid systems that show much promise. Potassium metal anodes are then critically reviewed, emphasizing electrolyte reactions to form stable versus unstable solid electrolyte interphase (SEI), covering the current understanding of potassium dendrites, and highlighting the deep-eutectic K-Na alloying approaches for room temperature liquid anodes. The manuscript concludes with K-S batteries, focusing on cell architectures and providing quantitative performance comparisons as master plots. Unanswered scientific/technological questions are identified, emerging research opportunities are discussed, and potential experimental and simulation-based studies that can unravel these unknowns are proposed.

A key advancement target for oxygen reduction reaction catalysts is to simultaneously improve both the electrochemical activity and durability. To this end, the efficacy of a new highly conductive support that comprises of a 0.5 nm titanium oxynitride film coated by atomic layer deposition onto an array of carbon nanotubes has been investigated. Support effects for pure platinum and for a platinum (50 at %)/nickel alloy have been considered. Oxynitride induces a downshift in the d-band center for pure platinum and fundamentally changes the platinum particle size and spatial distribution. This results in major enhancements in activity and corrosion stability relative to an identically synthesized catalyst without the interlayer. Conversely, oxynitride has a minimal effect on the electronic structure and microstructure, and therefore, on the catalytic performance of platinum-nickel. Calculations based on density functional theory add insight with regard to compositional segregation that occurs at the alloy catalyst-support interface.

Potassium (K) metal anodes suffer from a challenging problem of dendrite growth. Here, it is demonstrated that a tailored current collector will stabilize the metal plating-stripping behavior even with a conventional KPF6 -carbonate electrolyte. A 3D copper current collector is functionalized with partially reduced graphene oxide to create a potassiophilic surface, the electrode being denoted as rGO@3D-Cu. Potassiophilic versus potassiophobic experiments demonstrate that molten K fully wets rGO@3D-Cu after 6 s, but does not wet unfunctionalized 3D-Cu. Electrochemically, a unique synergy is achieved that is driven by interfacial tension and geometry: the adherent rGO underlayer promotes 2D layer-by-layer (Frank-van der Merwe) metal film growth at early stages of plating, while the tortuous 3D-Cu electrode reduces the current density and geometrically frustrates dendrites. The rGO@3D-Cu symmetric cells and half-cells achieve state-of-the-art plating and stripping performance. The symmetric rGO@3D-Cu cells exhibit stable cycling at 0.1-2 mA cm-2 , while baseline Cu prematurely fails when the current reaches 0.5 mA cm-2 . The half-cells cells of rGO@3D-Cu (no K reservoir) are stable at 0.5 mA cm-2 for 10 000 min (100 cycles), and at 1 mA cm-2 for 5000 min. The baseline 3D-Cu, planar rGO@Cu, and planar Cu foil fails after 5110, 3012, and 1410 min, respectively.

A hard carbon ion insertion anode gives much higher overpotential with K+ vs Na+. This significantly lowers the energy–power of symmetric hybrid potassium ion capacitors (KICs) vs sodium ion capacitors (NICs). However, high surface area, ion adsorption carbon works well with both K and Na, opening the possibility for high performance symmetric KICs. In article number 1802272, Mengqiang Wu, David Mitlin, and co‐workers provide a direct performance comparison of potassium ion capacitors versus the better‐known sodium ion capacitors.

A hybrid ion capacitor (HIC) based on potassium ions (K+) is a new high‐power intermediate energy device that may occupy a unique position on the Ragone chart space. Here, a direct performance comparison of a potassium ion capacitor (KIC) versus the better‐known sodium ion capacitor is provided. Tests are performed with an asymmetric architecture based on bulk ion insertion, partially ordered, dense carbon anode (hard carbon, HC) opposing N‐ and O‐rich ion adsorption, high surface area, cathode (activated carbon, AC). A classical symmetric “supercapacitor‐like” configuration AC–AC is analyzed in parallel. For asymmetric K‐based HC–AC devices, there are significant high‐rate limitations associated with ion insertion into the anode, making it much inferior to Na‐based HC–AC devices. A much larger charge–discharge hysteresis (overpotential), more than an order of magnitude higher impedance R SEI, and much worse cyclability are observed. However, K‐based AC–AC devices obtained on‐par energy, power, and cyclability with their Na counterpart. Therefore, while KICs are extremely scientifically interesting, more work is needed to tailor the structure of “Na‐inherited” dense carbon anodes and electrolytes for satisfactory K ion insertion. Conversely, it should be possible to utilize many existing high surface area adsorption carbons for fast rate K application.

Lithium-rich Li[Li1/6 Fe1/6 Ni1/6 Mn1/2 ]O2 (0.4Li2 MnO3 -0.6LiFe1/3 Ni1/3 Mn1/3 O2 , LFNMO) is a new member of the xLi2 MnO3 ·(1 - x)LiMO2 family of high capacity-high voltage lithium-ion battery (LIB) cathodes. Unfortunately, it suffers from the severe degradation during cycling both in terms of reversible capacity and operating voltage. Here, the corresponding degradation occurring in LFNMO at an atomic scale has been documented for the first time, using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), as well as tracing the elemental crossover to the Li metal anode using X-ray photoelectron spectroscopy (XPS). It is also demonstrated that a cobalt phosphate surface treatment significantly boosts LFNMO cycling stability and rate capability. Due to cycling, the unmodified LFNMO undergoes extensive elemental dissolution (especially Mn) and O loss, forming Kirkendall-type voids. The associated structural degradation is from the as-synthesized R-3m layered structure to a disordered rock-salt phase. Prior to cycling, the cobalt phosphate coating is epitaxial, sharing the crystallography of the parent material. During cycling, a 2-3 nm thick disordered Co-rich rock-salt structure is formed as the outer shell, while the bulk material retains R-3m crystallography. These combined cathode-anode findings significantly advance the microstructural design principles for next-generation Li-rich cathode materials and coatings.

Energy density (energy per volume) is a key consideration for portable, automotive, and stationary battery applications. Selenium (Se) lithium and sodium metal cathodes are created that are monolithic and free-standing, and with record Se loading of 70 wt%. The carbon host is derived from nanocellulose, an abundant and sustainable forestry product. The composite is extremely dense (2.37 g cm−3), enabling theoretical volumetric capacity of 1120 mA h cm−3. Such architecture is fully distinct from previous Se–carbon nano- or micropowders, intrinsically offering up to 2× higher energy density. For Li storage, the cathode delivers reversible capacity of 1028 mA h cm−3 (620 mA h g−1) and 82% retention over 300 cycles. For Na storage, 848 mA h cm−3 (511 mA h g−1) is obtained with 98% retention after 150 cycles. The electrodes yield superb volumetric energy densities, being 1727 W h L−1 for Li–Se and 980 W h L−1 for Na–Se normalized by total composite mass and volume. Despite the low surface area, over 60% capacity is maintained as the current density is increased from 0.1 to 2 C (30 min charge) with Li or Na. Remarkably, the electrochemical kinetics with Li and Na are comparable, including the transition from interfacial to diffusional control.

Supercapacitors are attracting intense scientific attention as they can bridge the energy-power gap between commercial batteries and electrolytic capacitors. High-surface area activated carbon remains the electrode material of choice for commercial systems due to the inherently lower cost relative to the more exotic alternatives such as graphene, carbon nanotubes, or their hybrids. However, activated carbon possesses an inferior electrochemical performance relative to these more open and electrically conductive structures. This limits its feasibility as electrodes for future high-performance devices. In this concept paper we summarized two case studies of creating unique biomass-derived carbons by preserving the precursors’ intrinsic structure or transforming the precursor structure into graphene-like materials that actually demonstrate electrochemical performance on par with, or even better than, their much costlier alternatives.