Entropymetry for detecting microcracks in high-nickel layered oxide cathodes.

Electric vehicles (EVs) are imposing ever-challenging standards on the lifetime and safety of lithium-ion batteries (LIBs); consequently, real-time nondestructive monitoring of battery cell degradation is highly desired. Unfortunately, high-nickel (Ni) layered oxides, the preferred LIB cathodes for EVs, undergo performance degradation originating from microcrack formation during cycling. Entropymetry is introduced as a real-time analytic tool for monitoring the evolution of microcracks in these cathodes along the state of charge. The entropy change of the layered cathode is associated with the lattice configuration and reflects the structural heterogeneity relevant to the evolution of these microcracks. The structural heterogeneity was correlated with peak broadening in in-situ X-ray diffractometry while varying the experimental conditions that affect crack formation such as the upper cutoff voltage during charging and the Ni-content of the active material. Entropymetry, proposed here as a nondestructive diagnostic tool, can contribute greatly to the safe and reliable operation of LIBs for EVs.

Interfacial Stabilization by Prelithiated Trithiocyanuric Acid as an Organic Additive in Sulfide-based All-Solid-State Lithium Metal Batteries.

Sulfide-based all-solid-state battery (ASSB) with a lithium metal anode (LMA) is a promising candidate to surpass conventional Li-ion batteries owing to their inherent safety against fire hazards and potential to achieve a higher energy density. However, the narrow electrochemical stability window and chemical reactivity of the sulfide solid electrolyte towards the LMA results in interfacial degradation and poor electrochemical performance. In this direction, we introduce an organic additive approach, that is the mixing of prelithiated trithiocyanuric acid, Li3TCA, with Li6PS5Cl, to establish a stable interface while preserving high ionic conductivity. Including 2.5 wt% Li3TCA alleviates the decomposition of the electrolyte on the lithium metal interface, decreasing the Li2S content in the solid-electrolyte interface (SEI) thus forming a more stable interface. In Li|Li symmetric cells this enables a rise in the critical current density from 1.0 to 1.9 mA cm-2 and stable cycling for over 750 hours at a high current density of 1.0 mA cm-2. This approach also enables Li|NbO-NCM811 full cell to operate more than 500 cycles at 0.3C.

Surface Overpotential as a Key Metric for the Discharge-Charge Reversibility of Aqueous Zinc-Ion Batteries.

Aqueous zinc-ion batteries (AZIBs) are receiving increasing attention for power-grid energy storage systems. Nevertheless, warranting long-term reversible operation is not trivial owing to uncontrolled interfacial phenomena related to zinc dendritic growth and parasitic reactions. Herein, the addition of hexamethylphosphoramide (HMPA) to the electrolyte revealed the surface overpotential (|ηs|) to be a key metric of the reversibility. HMPA adsorbs onto active sites on the zinc metal surface, raising the surface overpotential toward lowering the nucleation energy barrier and decreasing the critical size (rcrit) of nuclei. We also correlated the observed interface-to-bulk properties by the Wagner (Wa) dimensionless number. The controlled interface enables a Zn|V6O13 full cell to retain 75.97% capacity for 2000 cycles, with a capacity loss of only 1.5% after 72 h resting. Our study not only delivers AZIBs with unparalleled cycling and storage performance but also proposes surface overpotential as a key descriptor regarding the sustainability of AZIB cycling and storage.

Issues and Advances in Scaling up Sulfide-Based All-Solid-State Batteries.

ConspectusAll-solid-state batteries (ASSBs) are considered to be a next-generation energy storage concept that offers enhanced safety and potentially high energy density. The identification of solid electrolytes (SEs) with high ionic conductivity was the stepping-stone that enabled the recent surge in activity in this research area. Among the various types of SEs, including those based on oxides, sulfides, polymers, and hybrids thereof, sulfide-based SEs have gained discernible attention owing to their exceptional room temperature ionic conductivity comparable even to those of their liquid electrolyte counterparts. Moreover, the good deformability of sulfide SEs renders them suitable for reducing the interfacial resistance between particles, thereby obviating the need for high-temperature sintering. Nevertheless, sulfide-based ASSB technology still remains at the research stage without any manufacturing schemes having been established. This state of affairs originates from the complex challenges presented by various aspects of these SEs: their weak stability in air, questions surrounding the exact combination of slurry solvent and polymeric binder for solution-based electrode fabrication, their high interfacial resistance resulting from solid particle contacts, and limited scalability with respect to electrode fabrication and cell assembly. In this Account, we review recent developments in which these issues were addressed by starting with the materials and moving on to processing, focusing on new trials. As for enhancing the air stability of sulfide SEs, strengthening the metal-sulfur bond based on the hard-soft acid-base (HSAB) theory has yielded the most notable results, although the resulting sacrificed energy density and weakened anode interface stability would need to be resolved. Novel electrode fabrication techniques that endeavor to overcome the critical issues originating from the use of sulfide SEs are subsequently introduced. The wet chemical coating process can take advantage of the know-how and facilities inherited from the more established lithium-ion batteries (LIBs). However, the dilemmatic matter of contention relating to the polarity mismatch among the slurry solvent, SE, and binder requires attention. Recent solutions to these problems involved the exploration of various emerging concepts, such as polarity switching during electrode fabrication, fine polarity tuning by accurate grafting, and infiltration of the electrode voids by a solution of the SE. The process of using a dry film with a fibrous binder has also raised interest, motivated by lowering the manufacturing cost, maintaining the environment, and boosting the volumetric energy density. Finally, optimization of the cell assembly and operation is reviewed. In particular, the application of external pressure to each unit cell has been universally adopted both in the fabrication step and during cell operation to realize high cell performance. The effect of pressurization is discussed by correlating it with the interface stability and robust interparticle contacts. Based on the significant progress that has been made thus far, we aim to encourage the battery community to engage their wide-ranging expertise toward advancing sulfide-based ASSBs that are practically feasible.

Integrated Ring-Chain Design of a New Fluorinated Ether Solvent for High-Voltage Lithium-Metal Batteries.

Ether-based electrolytes offer promising features such as high lithium-ion solvation power and stable interface, yet their limited oxidation stability impedes application in high-voltage Li-metal batteries (LMBs). Whereas the fluorination of the ether backbone improves the oxidative stability, the resulting solvents lose their Li+ -solvation ability. Therefore, the rational molecular design of solvents is essential to combine high redox stability with good ionic conductivity. Here, we report the synthesis of a new high-voltage fluorinated ether solvent through integrated ring-chain molecular design, which can be used as a single solvent while retaining high-voltage stability. The controlled Li+ -solvation environment even at low-salt-concentration (1 M or 2 M) enables a uniform and compact Li anode and an outstanding cycling stability in the Li|NCM811 full cell (20 µm Li foil, N/P ratio of 4). These results show the impact of molecular design of electrolytes towards the utilization of LMBs.

Cationic Additive with a Rigid Solvation Shell for High-Performance Zinc Ion Batteries.

Despite substantial progresses, in aqueous zinc ion batteries (AZIBs), developing zinc metal anodes with long-term reliable cycling capabilities is nontrivial because of dendritic growth and related parasitic reactions on the zinc surface. Here, we exploit the tip-blocking effect of a scandium (Sc3+ ) additive in the electrolyte to induce uniform zinc deposition. Additional to the tri-valency of Sc3+ , the rigidity of its hydration shell effectively prevents zinc ions from concentrating at the surface tips, enabling highly stable cycling under challenging conditions. The shell rigidity, quantified by the rate constant of the exchange reaction (kex ), is established as a key descriptor for evaluating the tip-blocking effect of redox-inactive cations, explaining inconsistent results when only the valence state is considered. Moreover, the tip-blocking effect of Sc3+ is maintained in blends with organic solvents, allowing the zinc anode to cycle reliably even at -40 °C without corrosion.

Lithium-Conducting Self-Assembled Organic Nanotubes.

Supramolecular polymers are compelling platforms for the design of stimuli-responsive materials with emergent functions. Here, we report the assembly of an amphiphilic nanotube for Li-ion conduction that exhibits high ionic conductivity, mechanical integrity, electrochemical stability, and solution processability. Imine condensation of a pyridine-containing diamine with a triethylene glycol functionalized isophthalaldehyde yields pore-functionalized macrocycles. Atomic force microscopy, scanning electron microscopy, and in solvo X-ray diffraction reveal that macrocycle protonation during their mild synthesis drives assembly into high-aspect ratio (>103) nanotubes with three interior triethylene glycol groups. Electrochemical impedance spectroscopy demonstrates that lithiated nanotubes are efficient Li+ conductors, with an activation energy of 0.42 eV and a peak room temperature conductivity of 3.91 ± 0.38 × 10-5 S cm-1. 7Li NMR and Raman spectroscopy show that lithiation occurs exclusively within the nanotube interior and implicates the glycol groups in facilitating efficient Li+ transduction. Linear sweep voltammetry and galvanostatic lithium plating-stripping tests reveal that this nanotube-based electrolyte is stable over a wide potential range and supports long-term cyclability. These findings demonstrate how the coupling of synthetic design and supramolecular structural control can yield high-performance ionic transporters that are amenable to device-relevant fabrication, as well as the technological potential of chemically designed self-assembled nanotubes.

Ionic Liquid Functionalized Gel Polymer Electrolytes for Stable Lithium Metal Batteries.

Metallic lithium (Li) is regarded as the ideal anode material in lithium-ion batteries due to its low electrochemical potential, highest theoretical energy density and low density. There are, however, still significant challenges to be addressed such as Li-dendrite growth and low interfacial stability, which impede the practical application of Li metal anodes. In order to circumvent these shortcomings, herein, we present a gel polymer electrolyte containing imidazolium ionic liquid end groups with a perfluorinated alkyl chain (F-IL) to achieve both high ionic conductivity and Li ion transference number by fundamentally altering the solubility of salt within the gel electrolyte through Lewis-acidic segments in the polymer backbone. Moreover, the presence of F-IL moieties decreased the binding affinity of Li cation towards the glycol chains, enabling a rapid transfer of Li cation within the gel network. These structural features enabled the immobilization of anions on the ionic liquid segments to alleviate the space-charge effect while promoting stronger anion coordination and weaker cation coordination in the Lewis-acidic polymers. Accordingly, we realized a high Li ion conductivity (9.16×10-3  S cm-1 ) and high Li ion transference number of 0.69 simultaneously, along with a good electrochemical stability up to 4.55 V, while effectively suppressing Li dendrite growth. Moreover, the gel polymer electrolyte exhibited stable cycling performance of the Li|Li symmetric cell of 9 mAh cm-2 for more than 1800 hours and retained 86.7 % of the original capacity after 250 cycles for lithium-sulfur (Li-S) full cell.

Fluorinated Aromatic Diluent for High-Performance Lithium Metal Batteries.

In lithium metal batteries, electrolytes containing a high concentration of salts have demonstrated promising cyclability, but their practicality with respect to the cost of materials is yet to be proved. Here we report a fluorinated aromatic compound, namely 1,2-difluorobenzene, for use as a diluent solvent in the electrolyte to realize the "high-concentration effect". The low energy level of the lowest unoccupied molecular orbital (LUMO), weak binding affinity for lithium ions, and high fluorine-donating power of 1,2-difluorobenzene jointly give rise to the high-concentration effect at a bulk salt concentration near 2 m, while modifying the composition of the solid-electrolyte-interphase (SEI) layer to be rich in lithium fluoride (LiF). The employment of triple salts to prevent corrosion of the aluminum current collector further improves cycling performance. This study offers a design principle for achieving a local high-concentration effect with reasonably low bulk concentrations of salts.

Switching between Local and Global Aromaticity in a Conjugated Macrocycle for High-Performance Organic Sodium-Ion Battery Anodes.

Aromatic organic compounds can be used as electrode materials in rechargeable batteries and are expected to advance the development of both anode and cathode materials for sodium-ion batteries (SIBs). However, most aromatic organic compounds assessed as anode materials in SIBs to date exhibit significant degradation issues under fast-charge/discharge conditions and unsatisfying long-term cycling performance. Now, a molecular design concept is presented for improving the stability of organic compounds for battery electrodes. The molecular design of the investigated compound, [2.2.2.2]paracyclophane-1,9,17,25-tetraene (PCT), can stabilize the neutral state by local aromaticity and the doubly reduced state by global aromaticity, resulting in an anode material with extraordinarily stable cycling performance and outstanding performance under fast-charge/discharge conditions, demonstrating an exciting new path for the development of electrode materials for SIBs and other types of batteries.

The emerging era of supramolecular polymeric binders in silicon anodes.

Silicon (Si) anode is among the most promising candidates for the next-generation high-capacity electrodes in Li-ion batteries owing to its unparalleled theoretical capacity (4200 mA h g-1 for Li4.4Si) that is approximately 10 times higher than that of commercialized graphitic anodes (372 mA h g-1 for LiC6). The battery community has witnessed substantial advances in research on new polymeric binders for silicon anodes mainly due to the shortcomings of conventional binders such as polyvinylidene difluoride (PVDF) to address problems caused by the massive volume change of Si (300%) upon (de)lithiation. Unlike conventional battery electrodes, polymeric binders have been shown to play an active role in silicon anodes to alleviate various capacity decay pathways. While the initial focus in binder research was primarily to maintain the electrode morphology, it has been recently shown that polymeric binders can in fact help to stabilize cracked Si microparticles along with the solid-electrolyte-interphase (SEI) layer, thus substantially improving the electrochemical performance. In this review article, we aim to provide an in-depth analysis and molecular-level design principles of polymeric binders for silicon anodes in terms of their chemical structure, superstructure, and supramolecular interactions to achieve good electrochemical performance. We further highlight that supramolecular chemistry offers practical tools to address challenging problems associated with emerging electrode materials in rechargeable batteries.

Lithium-Salt Mediated Synthesis of a Covalent Triazine Framework for Highly Stable Lithium Metal Batteries.

A new strategy for the synthesis of a covalent triazine framework (CTF-1) was introduced based on the cyclotrimerization reaction of 1,4-dicyanobenzene using lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) under ionothermal conditions. LiTFSI not only served as a catalyst, but also facilitated the in situ generation and homogeneous distribution of LiF particles across the framework. The hierarchical structure resulting upon integration of CTF-LiF onto an airlaid-paper (AP) offered unique features for lithium metal anodes, such as lithiophilicity from CTF, interface stabilization from LiF, and sufficient lithium storage space from AP. Based on this synergistic effect, the AP-CTF-LiF anode exhibited stable cycling performance even at a current density of 10 mA cm-2 .

Solution-Processed Metal Coating to Nonwoven Fabrics for Wearable Rechargeable Batteries.

Wearable rechargeable batteries require electrode platforms that can withstand various physical motions, such as bending, folding, and twisting. To this end, conductive textiles and paper have been highlighted, as their porous structures can accommodate the stress built during various physical motions. However, fabrics with plain weaves or knit structures have been mostly adopted without exploration of nonwoven counterparts. Also, the integration of conductive materials, such as carbon or metal nanomaterials, to achieve sufficient conductivity as current collectors is not well-aligned with large-scale processing in terms of cost and quality control. Here, the superiority of nonwoven fabrics is reported in electrochemical performance and bending capability compared to currently dominant woven counterparts, due to smooth morphology near the fiber intersections and the homogeneous distribution of fibers. Moreover, solution-processed electroless deposition of aluminum and nickel-copper composite is adopted for cathodes and anodes, respectively, demonstrating the large-scale feasibility of conductive nonwoven platforms for wearable rechargeable batteries.

Nanoscale Zirconium-Abundant Surface Layers on Lithium- and Manganese-Rich Layered Oxides for High-Rate Lithium-Ion Batteries.

Battery performance, such as the rate capability and cycle stability of lithium transition metal oxides, is strongly correlated with the surface properties of active particles. For lithium-rich layered oxides, transition metal segregation in the initial state and migration upon cycling leads to a significant structural rearrangement, which eventually degrades the electrode performance. Here, we show that a fine-tuning of surface chemistry on the particular crystal facet can facilitate ionic diffusion and thus improve the rate capability dramatically, delivering a specific capacity of ∼110 mAh g-1 at 30C. This high rate performance is realized by creating a nanoscale zirconium-abundant rock-salt-like surface phase epitaxially grown on the layered bulk. This surface layer is spontaneously formed on the Li+-diffusive crystallographic facets during the synthesis and is also durable upon electrochemical cycling. As a result, Li-ions can move rapidly through this nanoscale surface layer over hundreds of cycles. This study provides a promising new strategy for designing and preparing a high-performance lithium-rich layered oxide cathode material.

Delicate Structural Control of Si-SiOx-C Composite via High-Speed Spray Pyrolysis for Li-Ion Battery Anodes.

Despite the high theoretical capacity, silicon (Si) anodes in lithium-ion batteries have difficulty in meeting the commercial standards in various aspects. In particular, the huge volume change of Si makes it very challenging to simultaneously achieve high initial Coulombic efficiency (ICE) and long-term cycle life. Herein, we report spray pyrolysis to prepare Si-SiOx composite using an aqueous precursor solution containing Si nanoparticles, citric acid, and sodium hydroxide (NaOH). In the precursor solution, Si nanoparticles are etched by NaOH with the production of [SiO4]4-. During the dynamic course of spray pyrolysis, [SiO4]4- transforms to SiOx matrix and citric acid decomposes to carbon surface layer with the assistance of NaOH that serves as a decomposition catalyst. As a result, a Si-SiOx composite, in which Si nanodomains are homogeneously embedded in the SiOx matrix with carbon surface layer, is generated by a one-pot process with a residence time of only 3.5 s in a flow reactor. The optimal composite structure in terms of Si domain size and Si-to-O ratio exhibited excellent electrochemical performance, such as reversible capacity of 1561.9 mAh g-1 at 0.06C rate and ICE of 80.2% and 87.9% capacity retention after 100 cycles at 1C rate.

Unveiling anomalous CO2-to-N2 selectivity of graphene oxide.

When dry sorbents are considered for CO2 capture, selective uptake of CO2 over other gases is highly desirable. However, most dry sorbents suffer from selectivity drop upon temperature increase. Here, we report that graphene oxide (GO) exhibits high CO2-to-N2 selectivity, and the selectivity rises anomalously with temperature increase; CO2-to-N2 selectivity that starts at 192 at 273 K increases to an extraordinarily high value of 607 at 323 K. These high values and unusual trends in selectivity are attributed to a combined effect of CO2-philicity from the functional groups of GO and its relatively large macropores that are efficient at releasing N2. In-depth analysis using FT-IR reveals CO2-philic electrostatic interactions where CO2 serves as an electron donor and acceptor simultaneously; while CO2 can bind with electron-rich oxygen-containing groups of GO, the oxygen of CO2 can also bind with hydrogen-containing groups at the edges of GO. The current study with GO highlights a design principle for highly selective CO2 capture represented by CO2-philic electrostatic sites coupled with relatively large pores for efficient N2 release.

Role of intermediate phase for stable cycling of Na7V4(P2O7)4PO4 in sodium ion battery.

Sodium ion batteries offer promising opportunities in emerging utility grid applications because of the low cost of raw materials, yet low energy density and limited cycle life remain critical drawbacks in their electrochemical operations. Herein, we report a vanadium-based ortho-diphosphate, Na7V4(P2O7)4PO4, or VODP, that significantly reduces all these drawbacks. Indeed, VODP exhibits single-valued voltage plateaus at 3.88 V vs. Na/Na(+) while retaining substantial capacity (>78%) over 1,000 cycles. Electronic structure calculations reveal that the remarkable single plateau and cycle life originate from an intermediate phase (a very shallow voltage step) that is similar both in the energy level and lattice parameters to those of fully intercalated and deintercalated states. We propose a theoretical scheme in which the reaction barrier that arises from lattice mismatches can be evaluated by using a simple energetic consideration, suggesting that the presence of intermediate phases is beneficial for cell kinetics by buffering the differences in lattice parameters between initial and final phases. We expect these insights into the role of intermediate phases found for VODP hold in general and thus provide a helpful guideline in the further understanding and design of battery materials.

Controlled Prelithiation of Silicon Monoxide for High Performance Lithium-Ion Rechargeable Full Cells.

Despite the recent considerable progress, the reversibility and cycle life of silicon anodes in lithium-ion batteries are yet to be improved further to meet the commercial standards. The current major industry, instead, adopts silicon monoxide (SiOx, x ≈ 1), as this phase can accommodate the volume change of embedded Si nanodomains via the silicon oxide matrix. However, the poor Coulombic efficiencies (CEs) in the early period of cycling limit the content of SiOx, usually below 10 wt % in a composite electrode with graphite. Here, we introduce a scalable but delicate prelithiation scheme based on electrical shorting with lithium metal foil. The accurate shorting time and voltage monitoring allow a fine-tuning on the degree of prelithiation without lithium plating, to a level that the CEs in the first three cycles reach 94.9%, 95.7%, and 97.2%. The excellent reversibility enables robust full-cell operations in pairing with an emerging nickel-rich layered cathode, Li[Ni0.8Co0.15Al0.05]O2, even at a commercial level of initial areal capacity of 2.4 mAh cm(-2), leading to a full cell energy density 1.5-times as high as that of graphite-LiCoO2 counterpart in terms of the active material weight.

5L-Scale Magnesio-Milling Reduction of Nanostructured SiO2 for High Capacity Silicon Anodes in Lithium-Ion Batteries.

Nanostructured silicon (Si) is useful in many applications and has typically been synthesized by bottom-up colloid-based solution processes or top-down gas phase reactions at high temperatures. These methods, however, suffer from toxic precursors, low yields, and impractical processing conditions (i.e., high pressure). The magnesiothermic reduction of silicon oxide (SiO2) has also been introduced as an alternative method. Here, we demonstrate the reduction of SiO2 by a simple milling process using a lab-scale planetary-ball mill and industry-scale attrition-mill. Moreover, an ignition point where the reduction begins was consistently observed for the milling processes, which could be used to accurately monitor and control the reaction. The complete conversion of rice husk SiO2 to high purity Si was demonstrated, taking advantage of the rice husk's uniform nanoporosity and global availability, using a 5L-scale attrition-mill. The resulting porous Si showed excellent performance as a Li-ion battery anode, retaining 82.8% of the initial capacity of 1466 mAh g-1 after 200 cycles.

Graphene Coating of Silicon Nanoparticles with CO2 -Enhanced Chemical Vapor Deposition.

Understanding the growth of graphene over Si species is becoming ever more important as the huge potential for the combination of these two materials becomes more apparent, not only for device fabrication but also in energy applications, particularly in Li-ion batteries. Thus, the drive for the direct fabrication of graphene over Si is crucial because indirect approaches, by their very nature, require processing steps that, in general, contaminate, damage, and are costly. In this work, the direct chemical vapor deposition growth of few-layer graphene over Si nanoparticles is systematically explored through experiment and theory with the use of a reducer, H2 or the use of a mild oxidant, CO2 combined with CH4 . Unlike the case of CH4 , with the use of CO2 as a mild oxidant in the reaction, the graphene layers form neatly over the surface and encapsulate the Si particles. SiC formation is also prevented. These structures show exceptionally good electrochemical performance as high capacity anodes for lithium-ion batteries. Density functional theory studies show the presence of CO2 not only prevents SiC formation but helps enhance the catalytic activity of the particles by maintaining an SiOx surface. In addition, CO2 can enhance graphitization.