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A stable anode-free all-solid-state battery (AF-ASSB) with sulfide-based solid-electrolyte (SE) (argyrodite Li

Laser processing is employed to fabricated zinc-ion battery (ZIB) anodes with state-of-the-art electrochemical performance from commercial zinc foils. Lasers are widely utilized for industrial surface finishing but have received minimal attention for zinc surface modification. Laser lithography patterned zinc foils “LLP@ZF” are hydrophilic, with an electrolyte contact angle of 0°. This is due to the concave-convex surface geometry that enhances wetting (periodic crests, ridges and valleys, roughness 16.5 times planar). During electrodeposition LLP@ZF's surface geometry generates a periodic electric field and associated current density distribution that suppresses tip growth (per continuum simulations). Per Density Functional Theory (DFT) its surface oxide is zincophilic, resulting in low nucleation barriers during plating (e.g. 3.8 mV at 1 mA cm−2). A combination of these attributes leads to stable dendrite-free plating/stripping behavior and low overpotentials at fast charge (e.g. 48.2 mV at 8 mA cm−2 in symmetric cell). Cycling is possible at an unprecedented areal capacity of 50 mA h cm−2, with 400 h stability at 1 mA cm−2. Moreover, exceptional aqueous zinc battery (AZB) performance is achieved, with MnO2-based cathode loading 10 mg cm−2 and corresponding anode capacity 7.6 mA h cm−2. A broad comparison with literature indicates that LLP@ZF symmetric cell and full battery performance are among most favorable.\ud \ud

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 LiPF6 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 Li2Se transformation, with the nanopores also providing a complementary fast ion diffusion path.

The shuttling of soluble lithium polysulfides (LiPS) and the sluggish Li-S conversion kinetics are two main barriers toward the practical application of lithium-sulfur batteries (LSBs). Herein, we propose the addition of copper selenide nanoparticles at the cathode to trap LiPS and accelerate the Li-S reaction kinetics. Using both computational and experimental results, we demonstrate the crystal phase and concentration of copper vacancies to control the electronic structure of the copper selenide, its affinity toward LiPS chemisorption, and its electrical conductivity. The adjustment of the defect density also allows for tuning the electrochemically active sites for the catalytic conversion of polysulfide. The optimized S/Cu1.8Se cathode efficiently promotes and stabilizes the sulfur electrochemistry, thus improving significantly the LSB performance, including an outstanding cyclability over 1000 cycles at 3 C with a capacity fading rate of just 0.029% per cycle, a superb rate capability up to 5 C, and a high areal capacity of 6.07 mAh cm-2 under high sulfur loading. Overall, the present work proposes a crystal phase and defect engineering strategy toward fast and durable sulfur electrochemistry, demonstrating great potential in developing practical LSBs., The authors thank the support from the projects ENE2016-77798-C4-3-R and NANOGEN (PID2020-116093RB-C43), funded by MCIN/AEI/10.13039/501100011033/and by “ERDF A way of making Europe”, by the “European Union”. D.Y., M.L., X.H., and C.Z. thank the China Scholarship Council for the scholarship support. ICN2 acknowledges the support from the Severo Ochoa Programme (MINECO, grant no. SEV-2017-0706). IREC and ICN2 are both funded by the CERCA Program/Generalitat de Catalunya. This project received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No. 823717-ESTEEM3. Calculations at UT Austin were supported by the Welch Foundation (F-1841) and the Texas Advanced Computing Center. Part of the present work has been performed in the framework of Universitat Autònoma de Barcelona Materials Science PhD program. J.L. is a Serra Húnter Fellow and is grateful to MICINN/FEDER RTI2018-093996-B-C31, GC 2017 SGR 128, and to the ICREA Academia program.

Combined sulfur and nitrogen (S ​= ​12.9 ​at.%, N ​= ​9.9 ​at.%) rich carbons are synthesized for potassium ion anode applications. The low-surface-area carbons (56 ​m2 ​g−1) have sulfur covalently bonded to the structure, with minimum unbound “free” sulfur. This allows for exceptional rate capability and stability: Capacities of 437, 234 and 72 mAh g−1 are achieved at 0.1, 1 and 10 ​A ​g−1, with 75% retention at 2 ​A ​g−1 after 3000 cycles. These are among the most favorable capacity-cyclability combinations reported in potassium ion battery carbon literature. As a proof of principle, the carbons are incorporated into a potassium ion capacitor with state-of-the-art energy and power (e.g. 110 ​W ​h ​kg−1 at 244 ​W ​kg −1). According to XPS analysis, the reaction of nitrogen with K+ is distinct from that of K+ with sulfur. The N and N–O moieties undergo a series of complex multi-voltage reactions that result in both reversible and irreversible changes to their structure. The K–S reactions involve a combination of reversible adsorption and reversible formation of sulfides, thiosulfate and sulfate. GITT and EIS analysis indicate that incorporation of S into the N-rich carbon increases the K+ solid-state diffusion coefficient by factors ranging from ~3 to 8, depending on the voltage. The diffusivities are asymmetric with charging vs. discharging, signifying distinct reaction pathways. The covalently bound sulfur also has a positive influence on the solid electrolyte interphase (SEI) formation, at early and at prolonged cycling.

We combined advanced TEM (HRTEM, HAADF, EELS) with solid-state (SS)MAS NMR and electroanalytical techniques (GITT, etc.) to understand the site-specific sodiation of selenium (Se) encapsulated in a nanoporous carbon host. The architecture employed is representative of a wide number of electrochemically stable and rate-capable Se-based sodium metal battery (SMB) cathodes. SSNMR demonstrates that during the first sodiation, the Se chains are progressively cut to form an amorphous mixture of polyselenides of varying lengths, with no evidence for discrete phase transitions during sodiation. It also shows that Se nearest the carbon pore surface is sodiated first, leading to the formation of a core-shell compositional profile. HRTEM indicates that the vast majority of the pore-confined Se is amorphous, with the only localized presence of nanocrystalline equilibrium Na

We report a bifunctional sodium metal battery (SMB) and lithium metal battery (LMB) cathode based on 63 wt.%SeS covalently bonded to a co-pyrolyzed polyacrylonitrile (PAN) host, termed “SeSPAN”. This dense, low surface area, fully-amorphous electrode offers a highly favorable combination of reversible capacity, rate capability, and cycling life: At a fast charging rate of 1 A g−1, the reversible capacities with Na and Li are 632 and 749 mAh g−1 (based on active SeS), with cycle 1 CE of 81% in both cases. At an ultra-fast charging rate of 4 A g−1 (∼5C) the reversible capacities with Na and Li are 453 and 604 mAh g−1. Li-SeSPAN degrades 3% at cycle 500, while with Na-SeSPAN degrades by 17% after 150 cycles at 0.5 A g−1. Both Na and Li cells display a uniquely low voltage hysteresis (210 and 200 mV at a current density of 0.2 A g−1), indicative of facile charge-discharge kinetics. Analysis of the post-cycled anodes shows negligible S or Se crossover, with neither species being detected in the Li-SEI after extended cycling.

An unstable solid electrolyte interphase (SEI) and accompanying Li metal dendrites are the key impediments to commercialization of high-energy lithium metal batteries (LMBs). We employ a strontium fluoride (SrF2) microsphere coated polypropylene (PP) separator to stabilize the SEI and to prevent dendrites from growing. This approach is tested with Li‖Cu half-cells, Li‖Li symmetrical cells, and Li‖NMC full LMBs, there being a major improvement in each case. The Li‖Cu cell with SrF2 maintains a stable coulombic efficiency (CE) of 80% after 100 cycles, when tested at 0.25 mA cm−2 to a capacity of 0.5 mA h cm−2. By comparison, the uncoated PP reference has a CE of 10% in cycle 60. The Li‖Li cell with SrF2 exhibits a markedly smaller voltage polarization and is able to stably cycle for approximately 340 h vs. the reference which begins to display severe voltage instability at 200 h. The Li‖NMC full LMB with SrF2 shows an initial discharge capacity of 173 mA h g−1, with 167 mA h g−1 (96.5%) being retained after 200 cycles at 200 mA g−1 (1C rate). The SrF2 containing LMB also has a substantially improved rate capability over the reference, the difference being drastic even at the highest testing rate of 20C. First-principles calculations based on DFT indicate that lithium ions prefer to adsorb onto the SrF2 surface, which should create a more uniform ion flux and reduce the propensity for dendrite nucleation. In parallel, the SrF2 spheres bind with the SEI layer, creating a tough in situ formed composite membrane that mechanically stabilizes a planar metal interface.

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

It is a major challenge to achieve fast charging and high reversible capacity in potassium ion storing carbons. Here, we synthesized sulfur-rich graphene nanoboxes (SGNs) by one-step chemical vapor deposition to deliver exceptional rate and cyclability performance as potassium ion battery and potassium ion capacitor (PIC) anodes. The SGN electrode exhibits a record reversible capacity of 516 mAh g-1 at 0.05 A g-1, record fast charge capacity of 223 mA h g-1 at 1 A g-1, and exceptional stability with 89% capacity retention after 1000 cycles. Additionally, the SGN-based PIC displays highly favorable Ragone chart characteristics: 112 Wh kg-1at 505 W kg-1 and 28 Wh kg-1 at 14618 W kg-1 with 92% capacity retention after 6000 cycles. X-ray photoelectron spectroscopy analysis illustrates a charge storage sequence based primarily on reversible ion binding at the structural-chemical defects in the carbon and the reversible formation of K-S-C and K2S compounds. Transmission electron microscopy analysis demonstrates reversible dilation of graphene due to ion intercalation, which is a secondary source of capacity at low voltage. This intercalation mechanism is shown to be stable even at cycle 1000. Galvanostatic intermittent titration technique analysis yields diffusion coefficients from 10-10 to 10-12 cm2 s-1, an order of magnitude higher than S-free carbons. The direct electroanalytic/analytic comparison indicates that chemically bound sulfur increases the number of reversible ion bonding sites, promotes reaction-controlled over diffusion-controlled kinetics, and stabilizes the solid electrolyte interphase. It is also demonstrated that the initial Coulombic efficiency can be significantly improved by switching from a standard carbonate-based electrolyte to an ether-based one.

Graphite is ubiquitous as the anode material in lithium-ion batteries, but offers relatively low volumetric capacity (330 to 430 mAh cm-3). By contrast, Tellurene (Te) is expected to alloy with alkali metals with high volumetric capacity (~2620 mAh cm-3), but to date there is no detailed study on its alloying behavior. In this work, we have investigated the alloying response of a range of alkali metals (A = Li, Na or K) with few-layer Te. In-situ transmission electron microscopy and density functional theory both indicate that Te alloys with alkali metals forming A2Te. However, the crystalline order of alloyed products varied significantly from single-crystal (for Li2Te) to polycrystalline (for Na2Te and K2Te). It is well established that typical alloying materials (e.g., silicon, tin, black phosphorous) lose their crystallinity when reacted with Li. The ability of Te to retain its crystallinity is therefore surprising. Nudged elastic band calculations and ab-initio molecular dynamics simulations reveal that compared to Na or K, the migration of Li is highly “isotropic” in Te, enabling its crystallinity to be preserved. Such isotropic Li transport is made possible by Te’s peculiar structure comprised of chiral chains bound by van der Waals forces. To evaluate the electrochemical performance of Te, we tested Te electrodes in half-cells vs Li/Na/K metal. While alloying with Na and K showed poor performance, with Li, the Te electrode exhibited a volumetric capacity of ~700 mAh cm-3, which is about two-times the practical capacity of commercial graphite. Such Te based batteries could play an important role in applications where high volumetric energy and power density are of paramount importance.

A new approach is employed to boost the electrochemical kinetics and stability of vanadium oxygen hydrate (VOH, V2O5·nH2O) employed for aqueous zinc-ion battery (ZIB) cathodes. The methodology is based on electrically conductive polyaniline (PANI) intercalated-exfoliated VOH, achieved by preintercalation of an aniline monomer and its in situ polymerization within the oxide interlayers. The resulting graphene-like PANI-VOH nanosheets possess a greatly boosted reaction-controlled contribution to the total charge storage capacity, resulting in more material undergoing the reversible V5+ to V3+ redox reaction. The PANI-VOH electrode obtains an impressive capacity of 323 mAh g-1 at 1 A g-1, and state-of-the-art cycling stability at 80% capacity retention after 800 cycles. Because of the facile redox kinetics, the PANI-VOH ZIB obtains uniquely promising specific energy-specific power combinations: an energy of 216 Wh kg-1 is achieved at 252 W kg-1, while 150 Wh kg-1 is achieved at 3900 W kg-1. Electrochemical impedance spectroscopy (EIS) and galvanostatic intermittent titration technique (GITT) analyses indicate that with PANI-VOH nanosheets, there is a simultaneous decrease in the charge transfer resistance and a boost in the diffusion coefficient of Zn2+ (by a factor of 10-100) vs the VOH baseline. The strategy of employing PANI for combined intercalation-exfoliation may provide a broadly applicable approach for improving the performance in a range of oxide-based energy storage materials.

The capacity-voltage fade phenomenon in lithium iron phosphate (LiFePO4) lithium ion battery cathodes is not understood. We provide its first atomic-scale description, employing advanced transmissi...

This review focuses on carbon-based sodium ion battery (NIB) negative electrodes, emphasizing the internal structure – Na storage mechanisms – electrochemical performance relations. We bring a unique vantage to the ever-expanding field of NIB anode literature: To quantify the critical emphasis on the structure – properties interdependence, we provide comprehensive data comparisons of representative published studies. This is accomplished through a series of “Master Plots”, which rather than focusing on an individual publication, combine the data by broad features first outlined in the taxonomy section. The advantage of such an approach is that it transcends the paper-to-paper differences in electrochemical performance in a given class of anodes, providing generalizable comparisons that are statistically significant. For instance, we manage to demonstrate that, while N-doped carbons have a slight advantage in terms of capacity, their rate performance at higher currents is unchanged over that of undoped carbons. To our knowledge such broad high-level data analysis has not been done in past reviews on either NIB or LIB carbon anodes. Furthermore, we also discuss a wide range of individual microstructures and chemistries, offering critical analysis when appropriate.

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.

We created Immense Surface Area Carbons (ISACs) by a novel heat treatment that stabilized the micelle structure in a biological based precursor prior to high temperature combined activation – pyrolysis. While displaying a morphology akin to that of commercial activated carbon, ISACs contain an unparalleled combination of electrochemically active surface area and pore volume (up to 4051 m2 g−1, total pore volume 2.60 cm3 g−1, 76% small mesopores). The carbons also possess the benefit of being quite pure (combined O and N: 2.6–4.1 at%), thus allowing for a capacitive response that is primarily EDLC. Tested at commercial mass loadings (∼10 mg cm−2) ISACs demonstrate exceptional specific capacitance values throughout the entire relevant current density regime, with superior rate capability primarily due to the large fraction of mesopores. In the optimized ISAC, the specific capacitance (Cg) is 540 F g−1 at 0.2 A g−1, 409 F g−1 at 1 A g−1 and 226 F g−1 at a very high current density of 300 A g−1 (∼0.15 second charge time). At intermediate and high currents, such capacitance values have not been previously reported for any carbon. Tested with a stable 1.8 V window in a 1 M Li2SO4 electrolyte, a symmetric supercapacitor cell yields a flat energy–power profile that is fully competitive with those of organic electrolyte systems: 29 W h kg−1 at 442 W kg−1 and 17 W h kg−1 at 3940 W kg−1. The cyclability of symmetric ISAC cells is also exceptional due to the minimization of faradaic reactions on the carbon surface, with 80% capacitance retention over 100 000 cycles in 1 M Li2SO4 and 75 000 cycles in 6 M KOH.

In this work, the performance and electrochemical charge/discharge behavior of Sn–Bi–Sb alloy films were examined, as well as pure Sn, Bi, and Sb films, as anodes for sodium ion batteries (SIBs). Alloying was utilized as an approach to modify the morphology and active phases in an effort to improve the cycling stability of elemental anodes of Sn or Sb, while maintaining a high capacity. The films were prepared via sputtering, which enabled study of a broad swath of compositional space. The cycling performance of the Sb-rich compositions surpassed that of all other alloys tested as anodes for SIBs. The best performing alloy had a composition of 10 at% Sn, 10 at% Bi, and 80 at% Sb (called Sn10Bi10Sb80, here), and maintained 99% of its maximum capacity during cycling (621 mA h g−1) after 100 cycles. Stability of these anodes dropped as the quantity of Sb decreased; to contrast, Sn20Bi20Sb60, Sn25Bi25Sb50 and Sn33Bi33Sb33 were increasingly less stable as anodes in SIBs as the molar quantity of Sb in the films dropped to 60%, 50%, and 33%, respectively. The Sn10Bi10Sb80 electrode was found to possess a single phase as-deposited microstructure of Sn and Bi in substitutional solid solution with the Sb lattice and the sodiation sequence was found to be significantly different from pure Sb. Numerous possible mechanisms for the improvement in capacity retention were discussed, where modification and material response to internal stresses by changes in the Sb chemical potential and solid solution strengthening were found to be the most likely.

Sulfur-rich carbons are minimally explored for potassium-ion batteries (KIBs). Here, a large amount of S (38 wt%) is chemically incorporated into a carbon host, creating sulfur-grafted hollow carbon spheres (SHCS) for KIB anodes. The SHCS architecture provides a combination of nanoscale (≈40 nm) diffusion distances and CS chemical bonding to minimize cycling capacity decay and Coulombic efficiency (CE) loss. The SHCS exhibit a reversible capacity of 581 mAh g-1 (at 0.025 A g-1 ), which is the highest reversible capacity reported for any carbon-based KIB anode. Electrochemical analysis of S-free carbon spheres baseline demonstrates that both the carbon matrix and the sulfur species are highly electrochemically active. SHCS also show excellent rate capability, achieving 202, 160, and 110 mAh g-1 at 1.5, 3, and 5 A g-1 , respectively. The electrode maintains 93% of the capacity from the 5th to 1000th cycle at 3 A g-1 , with steady-state CE being near 100%. Raman analysis indicates reversible breakage of CS and SS bonds upon potassiation to 0.01 V versus K/K+ . The galvanostatic intermittent titration technique (GITT) analysis provides voltage-dependent K+ diffusion coefficients that range from 10-10 to 10-12 cm2 s-1 upon potassiation and depotassiation, with approximately five times higher coefficient for the former.

We created a hybrid Na ion capacitor (NIC) with a unique architecture and exceptional energy–power characteristics. Both the anode and the cathode are based on peanut skin derived carbon nanosheets fabricated by simultaneous carbonization and activation or by carbonization alone. The tens of nanometer thick (down to 20 nm) – high surface area (up to 2070 m² g⁻¹) nanosheets possesses a disordered structure for copious reversible binding of Na at the carbon defects. They are also hierarchically micro–meso–macro porous, allowing facile ion transport at high rates both through the pore-filling electrolyte and in the solid-state. When employed as sodium ion battery anode, the carbon shows a tremendous reversible (desodiation) capacity of 461 mA h g⁻¹ at 100 mA g⁻¹ and excellent rate capability, e.g. 107 mA h g⁻¹ at 5 A g⁻¹. The optimized NIC device displays highly favorable Ragone chart placement, e.g. 112 and 45 W h kg⁻¹ at 67 and 12 000 W kg⁻¹, retaining 85% of its capacity after 3000 cycles.

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.

We report a directional flow-aided sonochemistry exfoliation technique that allows for unparalleled control of graphene structural order and chemical uniformity. Depending on the orientation of the shockwave relative to the flow-aligned graphite flakes, the resultant bilayer and trilayer graphene is nearly defect free (at-edge sonication graphene “AES-G”) or is highly defective (in-plane sonication graphene “IPS-G”). AES-G has a Raman G/D band intensity ratio of 14.3 and an XPS-derived O content of 1.3 at. %, while IPS-G has an IG/D of 1.6 and 6.2 at. % O. AES-G and IPS-G are then employed to understand the role of carbon support structure and chemistry in Na metal plating/stripping for sodium metal battery anodes. The presence of graphene defects and oxygen groups is highly deleterious: In a standard carbonate solution (1 M NaClO4, 1:1 EC–DEC, 5 vol % FEC), AES-G gives stable cycling at 2 mA/cm2 with 100% Coulombic efficiency (CE) (within instrument accuracy) and an area capacity of 1 mAh/cm2. Meanwhile ...

We employed an in situ electrochemical cell in the transmission electron microscope (TEM) together with ex situ time-of-flight, secondary-ion mass spectrometry (TOF-SIMS) depth profiling, and FIB-helium ion scanning microscope (HIM) imaging to detail the structural and compositional changes associated with Na/Na(+) charging/discharging of 50 and 100 nm thin films of Sb. TOF-SIMS on a partially sodiated 100 nm Sb film gives a Na signal that progressively decreases toward the current collector, indicating that sodiation does not proceed uniformly. This heterogeneity will lead to local volumetric expansion gradients that would in turn serve as a major source of intrinsic stress in the microstructure. In situ TEM shows time-dependent buckling and localized separation of the sodiated films from their TiN-Ge nanowire support, which is a mechanism of stress-relaxation. Localized horizontal fracture does not occur directly at the interface, but rather at a short distance away within the bulk of the Sb. HIM images of FIB cross sections taken from sodiated half-cells, electrically disconnected, and aged at room temperature, demonstrate nonuniform film swelling and the onset of analogous through-bulk separation. TOF-SIMS highlights time-dependent segregation of Na within the structure, both to the film-current collector interface and to the film surface where a solid electrolyte interphase (SEI) exists, agreeing with the electrochemical impedance results that show time-dependent increase of the films' charge transfer resistance. We propose that Na segregation serves as a secondary source of stress relief, which occurs over somewhat longer time scales.

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.

Germanium is a promising sodium ion battery (NIB, NAB, SIB) anode material that is held back by its extremely sluggish kinetics and poor cyclability. We are the first to demonstrate that activation by a single lithiation-delithiation cycle leads to a dramatic improvement in the practically achievable capacity, in rate capability, and in cycling stability of Ge nanowires (GeNWs) and Ge thin film (GeTF). TEM and TOF-SIMS analysis shows that without activation, the initially single crystal GeNWs are effectively Na inactive, while the 100 nm amorphous GeTF sodiates only partially and inhomogeneously. Activation with Li induces amorphization in GeNWs reducing the barrier for nucleation of the NaxGe phase(s) and accelerates solid-state diffusion that aids the performance of both GeNWs and GeTF. Low rate (0.1C) Li activation also introduces a dense distribution of nanopores that lead to further improvements in the rate capability, which is ascribed to the lowered solid-state diffusion distances caused by the effective thinning of the Ge walls and by an additional Na diffusion path via the pore surfaces. The resultant kinetics are promising. Tested at 0.15C (1C = 369 mA/g, i.e. Na/Ge 1:1) for 50 cycles the GeNWs and GeTF maintain a reversible (desodiation) capacity of 346 and 418 mAh/g, respectively. They also demonstrate a capacity of 355 and 360 mAh/g at 1C and 284 and 310 mAh/g at 4C. Even at a very high rate of 10C the GeTF delivers 169 mAh/g. Preliminary results demonstrate that Li activation is also effective in promoting cycling stability of Sb blanket films.

Here we provide the first report on several compositions of ternary Sn-Ge-Sb thin film alloys for application as sodium ion battery (aka NIB, NaB or SIB) anodes, employing Sn50Ge50, Sb50Ge50, and pure Sn, Ge, Sb as baselines. Sn33Ge33Sb33, Sn50Ge25Sb25, Sn60Ge20Sb20, and Sn50Ge50 all demonstrate promising electrochemical behavior, with Sn50Ge25Sb25 being the best overall. This alloy has an initial reversible specific capacity of 833 mAhg-1 (at 85 mAg-1) and 662 mAhg-1 after 50 charge-discharge cycles. Sn50Ge25Sb25 also shows excellent rate capability, displaying a stable capacity of 381 mAhg-1 at a current density of 8500 mAg-1 (~10C). A survey of published literature indicates that 833 mAhg-1 is among the highest reversible capacities reported for a Sn-based NIB anode, while 381 mAhg-1 represents the optimum fast charge value. HRTEM shows that Sn50Ge25Sb25 is a composite of 10-15 nm Sn and Sn-Alloyed Ge nanocrystallites that are densely dispersed within an amorphous matrix. Comparing the microstructures of alloys where the capacity significantly exceeds the rule of mixtures prediction to those where it does not leads us to hypothesize that this new phenomenon originates from the Ge(Sn) that is able to sodiate beyond the 1:1 Na:Ge ratio reported for the pure element. Combined TOF-SIMS, EELS TEM, and FIB analysis demonstrates substantial Na segregation within the film near the current collector interface that is present as early as the second discharge, followed by cycling-induced delamination from the current collector. © Published 2014 by the American Chemical Society.

Scientific literature shows a substantial study-to-study variation in the electrochemical lithiation performance of “1-D” nanomaterials such as Si and Ge nanowires or nanotubes. In this study we varied the vapor–liquid–solid (VLS) growth temperature and time, resulting in nanowire arrays with distinct mass loadings, mean diameters and lengths, and thicknesses of the parasitic Ge films that are formed at the base of the array during growth. When all the results were compared, a key empirical trend to emerge was that increasing active material mass loading drastically degraded the electrochemical performance. For instance, GeNWs grown for 2 minutes at 320 °C (0.12 mg cm−2 mass loading, 34 nm mean nanowire diameter, 170 nm parasitic film thickness) had a reversible capacity of 1405 mA h g−1, a cycle 50 coulombic efficiency (CE) of 99.9%, a cycle 100 capacity retention of 98%, and delivered ∼1200 mA h g−1 at 5 C. In contrast, electrodes grown for 10 minutes at 360 °C (0.86 mg cm−2, 115 nm, 1410 nm) retained merely 5.6% of their initial capacity after 100 cycles, had a CE of 96%, and delivered ∼400 mA h g−1 at 5 C. Using TOF-SIMS we are the first to demonstrate marked segregation of Li to the current collector interface in planar Ge films that are 300 and 500 nm thick, but not in the 150 nm specimens. FIB analysis shows that the cycled higher mass loaded electrodes develop more SEI and interfacial cracks near the current collector. A comparison with the state-of-the-art scientific literature for a range of Ge-based nanostructures shows that our low mass loaded GeNWs are highly favorable in terms of the reversible capacity at cycle 1 and cycle 100, steady-state cycling CE and high-rate capability.

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.

We demonstrate that peat moss, a wild plant that covers 3% of the earth's surface, serves as an ideal precursor to create sodium ion battery (NIB) anodes with some of the most attractive electrochemical properties ever reported for carbonaceous materials. By inheriting the unique cellular structure of peat moss leaves, the resultant materials are composed of three-dimensional macroporous interconnected networks of carbon nanosheets (as thin as 60 nm). The peat moss tissue is highly cross-linked, being rich in lignin and hemicellulose, suppressing the nucleation of equilibrium graphite even at 1100 C. Rather, the carbons form highly ordered pseudographitic arrays with substantially larger intergraphene spacing (0.388 nm) than graphite (c/2 = 0.3354 nm). XRD analysis demonstrates that this allows for significant Na intercalation to occur even below 0.2 V vs Na/Na+. By also incorporating a mild (300 C) air activation step, we introduce hierarchical micro- and mesoporosity that tremendously improves the high rate performance through facile electrolyte access and further reduced Na ion diffusion distances. The optimized structures (carbonization at 1100 C + activation) result in a stable cycling capacity of 298 mAh g-1 (after 10 cycles, 50 mA g-1), with ∼150 mAh g-1 of charge accumulating between 0.1 and 0.001 V with negligible voltage hysteresis in that region, nearly 100% cycling Coulombic efficiency, and superb cycling retention and high rate capacity (255 mAh g -1 at the 210th cycle, stable capacity of 203 mAh g-1 at 500 mA g-1). © 2013 American Chemical Society.

Hydrothermal carbonization followed by chemical activation is utilized to convert paper pulp mill sludge biowaste into high surface area (up to 2980 m2 g-1) carbons. This synthesis process employs an otherwise unusable byproduct of paper manufacturing that is generated in thousands of tons per year. The textural properties of the carbons are tunable by the activation process, yielding controlled levels of micro and mesoporosity. The electrochemical results for the optimized carbon are very promising. An organic electrolyte yields a maximum capacitance of 166 F g-1, and a Ragone curve with 30 W h kg-1 at 57 W kg-1 and 20 W h kg-1 at 5450 W kg-1. Two ionic liquid electrolytes result in maximum capacitances of 180-190 F g-1 with up to 62% retention between 2 and 200 mV s-1. The ionic liquids yielded energy density-power density combinations of 51 W h kg-1 at 375 W kg -1 and 26-31 W h kg-1 at 6760-7000 W kg-1. After 5000 plus charge-discharge cycles the capacitance retention is as high at 91%. The scan rate dependence of the surface area normalized capacitance highlights the rich interplay of the electrolyte ions with pores of various sizes. © 2013 Elsevier Ltd. All rights reserved.

We employed a polypyrrole hydrogel precursor to create a carbon framework that possesses both huge heteroatom content (13 wt% nitrogen and 11 wt% oxygen) and high surface area (945 m 2 g −1 ) that is equally divided between micropores and mesopores. A sodium ion capacitor (NIC, HIC) electrode fabricated from this N and O Functionalized Carbon (NOFC) has tremendous reversible capacity and rate capability, e.g. 437 mA h g −1 at 100 mA g −1 , and 185 mA h g −1 at 1600 mA g −1 . This is among the most favorable reported, and is due to copious nanoporosity that enables fast ion sorption at the many N and O moieties and graphene defects. The NOFC imbues a NIC device with energy–power characteristics that are not only state-of-the-art for Na hybrids, but also rival Li systems: Ragone chart placement is 111 W h kg −1 and 38 W h kg −1 at 67 W kg −1 and 14,550 W kg −1 , respectively, with 90% capacity retention at over 5000 charge/discharge cycles.

Titanium based molecular sieves, such as ETS-10, have the ability to exchange silver ions and subsequently support self assembly of stable silver nanoparticles when heated. We report that a high surface area sodium titanate (resembling ETS-2) displays a similar ability to self template silver nanoparticles on its surface. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show high concentrations of silver nanoparticles on the surface of this sodium titanate, formed by thermal reduction of exchanged silver cations. The nanoparticles range in size from 4 to 12 nm, centered at around 6 nm. In addition to SEM and TEM, XRD and surface area analysis were used to characterize the material. The results indicate that this sodium titanate has a high surface area (>263 m2/g), and high ion exchange capacity for silver (30+ wt%) making it an excellent substrate for the exchange and generation of uniform, high-density silver nanoparticles.