Current Lithium-ion Batteries Research Articles

Review of Progress in the Application of Polytetrafluoroethylene-Based Battery Separators.

Batteries have broad application prospects in the aerospace, military, automotive, and medical fields. The performance of the battery separator, a key component of rechargeable batteries, is inextricably linked to the quality of the batteries. The polytetrafluoroethylene (PTFE)-based membrane, in addition to PTFE's intrinsic properties of corrosion resistance and high temperature resistance, also possesses characteristics such as high porosity and high strength, making it an ideal substrate for the separator in current high-performance batteries, such as fuel cells (FC), all-vanadium redox liquid current batteries (VRBs), solid-state batteries (SSBs), and lithium-ion batteries (LIBs). This paper introduces the PTFE membrane's main preparation methods and application fields and outlines its advantages as a battery separator. It then comprehensively describes the status of PTFE-based battery separator applications, sums up the advantages and development prospects of PTFE-based battery separators, and looks forward to the important role and challenges PTFE-based battery separators will play in the future of rechargeable batteries and even in new energy equipment with even more harsh and complex electrolytes. In the future, PTFE-based battery separators will be used in rechargeable batteries and even in new energy devices with more severe and complex electrolytes, which will play an important role and challenge in providing a reference for the research on PTFE-based battery separators.

Investigating the environmental impacts of lithium-oxygen battery cathode production: A comprehensive assessment of the effects associated with oxygen cathode manufacturing

Lithium-oxygen batteries offer remarkably high energy density compared to current lithium-ion batteries. The key to their electrochemical performance lies in the processes occurring at the air cathode. However, the complexity of these reactions, coupled with the by-products generated during discharge, can make the reaction process slow or impede their efficiency. This study evaluates the environmental impact of high-efficiency lithium-oxygen batteries cathodes, including titanium oxide composites, graphene-based composites and activated carbon-based composites, through a life cycle assessment across 18 impact categories using a cradle-to-gate approach with a functional unit of 25 kWh. Results show that active material production was the largest contributor to environmental impact, particularly Global Warming Potential. Among the evaluated cathodes, reduced graphene oxide/α-mnaganese oxide/palladium (rGO/α-MnO2/Pd) demonstrated the highest environmental impact, with a global warming potential of 1130.71 kg carbon dioxide from active material production, due to its energy-intensive synthesis and the use of chemicals like sulfuric acid, sodium borohydride, hydrochloric acid, and hydrogen peroxide. Additionally, the rGO/α-MnO2/Pd cathode had the highest Human Toxicity Potential and Ozone Depletion Potential. Batteries with graphene-based cathodes achieved a specific capacity of 7500 mAh.g-1, underscoring their performance potential while highlighting the need for more sustainable cathode manufacturing methods. These findings emphasize the environmental considerations necessary for large-scale lithium-oxygen batteries implementation.

Study on the Commercial Metalized Plastic Current Collector PET-Cu and PP-Cu Toward High-Energy Lithium-Ion Battery.

Commercial metalized plastic current collector (MPCC) is receiving widespread attention from the business and academic communities, due to its properties of excellent electrical conductivity and low mass density. However, the application of MPCC on the side of copper is rarely studied. Herein, sandwich-like polyethylene terephthalate-based (PET) and polypropylene-based (PP) copper (Cu) current collectors via magnetron sputtering and electroplating are fabricated. Most importantly, the electrical performance, mechanical safety quality, and revealed the corresponding failure mechanism for the MPCC cells are first systematically evaluated. First, during the 45°C electrical cycling tests, PET-Cu CC (82.67%) and PP-Cu CC (82.32%) cells both have comparable capacity retention with the traditional Cu CC (Tra-Cu CC) cell (84.55%) after 500 cycles. The slight reduction in the cycling performance is induced by the crack of the Cu layer around the embedded SiO2 particle for PET-Cu CC cell and the detachment of Cu layer for PP-Cu CC cell. Second, during the nail-penetration test, MPCC cells maintain no fire and explosion for more than 5min, since the heat-shrinkable function of polymeric film can interrupt the continuous Joule heat released by internal short-circuit. This work provides important guidance for the large-scale application of MPCC in the field of lithium-ion batteries.

Distribution of relaxation times-based analysis of aging mechanisms and prediction of heating domain for alternating current pulse self-heating lithium-ion batteries

Lithium-ion batteries (LIBs)-based electric vehicles (EVs) often encounter challenges such as the reduction in endurance mileage and the increase in charging time at low temperatures. To address these issues, the alternating current (AC) pulse self-heating in LIBs emerges as a pivotal method to overcome performance limitations of EVs at low temperatures. However, employing AC pulsing with high amplitude and low frequency can potentially lead to battery degradation. In this study, the state transitions and aging causes of LIBs during the self-heating are meticulously examined using the distribution of relaxation times (DRT) method. The results reveal that at an AC frequency of 50 Hz or higher, even with amplitudes up to 12 C, there is no degradation for the battery used in this study. For aged LIBs, the significant rise in impedance of solid electrolyte interphase (SEI) due to lithium plating, is the main factor driving battery aging during AC self-heating. Subsequently, an electrochemical-thermal coupling (ETC) model grounded in the degradation mechanism has been developed and experimentally validated to accurately predict the optimal heating domain for self-heating. This approach holds significant implications for the rapid selection of self-heating parameters for facilitating efficient battery performance enhancement.

Development, characterization and validation of a novel physics-informed equivalent circuit model for silicon–graphite battery cells

The widespread deployment of electric vehicles (EVs), as well as the growing requirements both from manufacturers and consumers, necessitate an increase in energy density with regard to current lithium-ion batteries (LIBs). In this regard, one of the most promising alternatives is the addition of silicon to conventional graphite anodes, thus giving rise to energy-dense LIBs. However, this entails a significant increment in modeling, parameterization and computational complexities due to the interactions between both negative electrode materials. In this article, we present a novel physics-informed equivalent circuit model for cells with blended electrodes, which is able to provide accurate results with respect to a state-of-the-art electrochemical model, not only for the output voltage (≤25 mV RMS), but also internal states, namely active material particle surface concentrations (≤1.2 %) and current distribution (≤2.6 %) at a much lower computational cost. Furthermore, this formulation also allows for a notable simplification of model parameterization. Hence, we describe thorough static and dynamic parameterization processes from half-cell experimental data and impedance measurements. Finally, we validate the proposed model in constant-current as well as dynamic operation, highlighting the influence that the choice of hysteresis model has on the latter. We understand that the presented model is an interesting alternative for the modeling of cells with blended electrodes, and is also suitable for its implementation in Battery Management Systems (BMSs) in EVs.

High-Viscosity Phase Inversion Separators for Freestanding and Direct-on-Electrode Manufacturing in Lithium-Ion Batteries.

Separators play a critical role in lithium-ion batteries (LIBs) by facilitating lithium-ion (Li-ion) transport while enabling safe battery operation. However, commercial separators made from polypropylene (PP) or polyethylene (PE) impose a discrete processing step in current LIB manufacturing as they cannot be manufactured with the same slot-die coating process used to fabricate the electrodes. Moreover, commercial separators cannot accommodate newer manufacturing processes used to produce leading-edge microbatteries and flexible batteries with customized form factors. As a path toward rethinking LIB fabrication, we have developed a high-viscosity polymer composite separator slurry that enables the fabrication of both freestanding and direct-on-electrode films. A streamlined phase inversion process is used to impart porosity in cast separator films upon drying. To understand the impacts of material composition and rheology on phase inversion processing and separator performance, we investigated four different separator formulations. We used either diethylene glycol (DEG) or triethyl phosphate (TEP) as a nonsolvent, and either silica (SiO2) or alumina (Al2O3) as an inorganic additive in a polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) matrix. Through a down-selection process, we developed a TEP-SiO2 separator formulation that matched or outperformed a commercial Celgard 2325 (PP/PE/PP) separator and a Beyond Battery ceramic-coated PE (CC/PE/CC) separator under rate and cycle life tests in LiFePO4|Li4Ti5O12 (LFP|LTO) and LiNi0.5Mn0.3Co0.2O2|graphite (NMC-532|graphite) coin cells at C/10-1C rates. Our TEP-SiO2 slurry had a viscosity of 298 Pa s at a 1 s-1 shear rate and shear-thinning behavior. When deposited directly onto an LTO anode and cycled against an LFP cathode, the direct-on-electrode TEP-SiO2 separator increased the specific capacity by 58% and 304% at 2C rates relative to the PP/PE/PP and CC/PE/CC separators, respectively. Additionally, the freestanding TEP-SiO2 separator maintained dimensional stability when heated to 200 °C for 1 h and demonstrated a higher elastic modulus and hardness than the PP/PE/PP and CC/PE/CC separators when measured with nanoindentation.

Shear Thickening, Star-Shaped Polymer Electrolytes for Lithium-Ion Batteries.

The safety concerns associated with current lithium-ion batteries are a significant drawback. A short-circuit within the battery's internal components, such as those caused by a car accident, can lead to ignition or even explosion. To address this issue, a polymer shear thickening electrolyte, free from flammable solvents, has been developed. It comprises a star-shaped oligomer derived from a trimethylolpropane (TMP) core and polyether chains, along with the inclusion of 20 wt.% nanosilica. Notably, the star-shaped oligomer serves a dual function as both the solvent for the lithium salt and the continuous phase of the shear thickening fluid. The obtained electrolytes exhibit an ionic conductivity of the order of 10-6 S cm-1 at 20 °C and 10-4 S cm-1 at 80 °C, with a high Li+ transference number (t+ = 0.79). A nearly thirtyfold increase in viscosity to a value of 1187 Pa s at 25 °C and a critical shear rate of 2 s-1 were achieved. During impact, this electrolyte could enhance cell safety by preventing electrode short-circuiting.

Molecular Dynamics Study of Adhesion-Related Structural Properties for PVDF-HFP Polymer Binders

The current lithium-ion battery (LIB) market is expanding rapidly. Binders are essential to maintaining the high capacity and longevity of batteries. These binders can be classified into organic binders used for cathodes and aqueous binders used for anodes. Among them, Poly(vinylidene fluoride) (PVDF) binder is a representative organic binder that offers excellent electrochemical stability. To solve low adhesive force and weak mechanical strength of conventional PVDF binders, hexafluoropropylene (HFP) is added to improve these properties. However, the present poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) binders still show lower adhesive force than other polymeric binders, and therefore further research works are necessary.In this study, we employ classical molecular dynamics (MD) simulations to investigate the structural properties of the PVDF-HFP copolymers. To create realistic disordered PVDF-HFP polymers, we develop a computational scheme that can randomly arrange the angles and sequences of the constituent polymer chains. By varying the ratio of randomly arranged PVDF-HFP copolymers to 0/100, 5/95, 10/90, 15/85, and 20/80, we build a solution model that mimics the HFP concentration of PVDF-HFP (0–20%, Sigma Aldrich) used in the actual experiments. N-methyl-2-pyrrolidone (NMP) used as solvents. To create a large-scale model, we utilize the Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) and set parameters by using OPLS force field. This allows us to build a simulation model containing approximately 40,000 atoms consisting of 10 PVDF-HFP polymers and 1500 NMP monomers.After creating the simulation model, approximately eight steps of molecular dynamics simulation are performed by referring to the process of making the actual polymer film. In this process, NMP molecules are evaporated to produce a polymer film consisting only of PVDF-HFP polymers. Then we perform the adhesion analysis by applying forces to five polymer film models with different composition ratios in various conditions. Throughout these processes, we find the characteristic changes depending on the composition ratio. Finally, we will present the possible routes that can lead to the enhanced adhesive properties of PVDF-HFP, which is a key requirement to the development of high performance binders.

Fluorination Promotes Lithium Salt Dissolution in Borate Esters for Lithium Metal Batteries

Lithium metal batteries promise higher energy densities than current lithium-ion batteries but require novel electrolytes to extend their cycle life. To promote electrolyte stability against lithium metal and improve the reversibility of lithium deposition/stripping, several electrolyte design strategies have been pursued. For example, high concentration electrolytes (HCEs) and localized high concentration electrolytes (LHCEs) produce solvation structure rich in salt aggregates and ion pairs, which can increase lithium metal cycling Coulombic efficiency to as high as 99.5%. Recently, molecular design of fluorinated ether solvents also leads to high lithium metal Coulombic efficiency of up to 99.9% in single-solvent-single-salt ~ 1 M electrolytes. In addition, fluorinated acetals, fluorinated carbonates, and fluorinated sulfonamides are also reported to enable efficient lithium metal cycling. Among those novel electrolytes, fluorinated solvents or diluents are frequently used because fluorinated moieties are known to yield LiF as a preferable component in solid electrolyte interphase (SEI). However, fluorinated groups are believed to weaken ion solvation as most fluorinated solvents show poorer solvation ability or lower ionic conductivity compared to their nonfluorinated counterparts. The trade-off between SEI passivation and ion solvation limits further optimization of fluorinated electrolytes.In this work, we synthesize tris(2-fluoroethyl) borate (TFEB) as a new fluorinated borate ester solvent. Interestingly, moderately fluorinated TFEB shows unexpectedly high lithium salt solubility (~1 M LiFSA) while the nonfluorinated triethyl borate (TEB) and heavily fluorinated tris(2,2,2-trifluoroethyl) borate (TTFEB) can hardly dissolve lithium salt. Through density functional theory (DFT) calculations and ab-initio molecular dynamics (AIMD) simulations, we show that the partially fluorinated -CH2F group in TFEB acts as primary coordination site that promotes lithium salt dissolution. The electrochemical property of TFEB electrolyte is then compared to the methoxy polyethyleneglycol borate esters reported in literature. Owing to the fluorinated solvent structure, TFEB electrolyte passivates lithium metal with LiF-rich SEI and supports compact lithium deposition morphology, high lithium metal Coulombic efficiency, and stable cycling of lithium metal/LiFePO4 cells. This work ushers in a new electrolyte design paradigm where partially fluorinated moieties enable salt dissolution and can serve as primary ion coordination sites for next-generation electrolytes. Figure 1

Unveiling the Origins of “Memory Effects” in Thick Electrodes through 2D XRF-XANES Mapping and Modeling

Making electrodes much thicker than the current commercial lithium-ion batteries is a promising approach to further increase the energy density of rechargeable batteries by reducing the weight/volume fraction of inactive components at the battery cell level. However, thick electrodes suffer inferior rate performance as non-uniform reaction develops within the electrode due to the increased ionic and electronic transport distances, which reduces the capacity utilization. In this work, we demonstrate yet another challenge faced by the application of thick electrodes (>100 µm), that is, they exhibit pronounced “memory effect” that is not seen in their thin electrode counterpart. While “memory effect” was initially observed in nickel-cadmium and nickel metal-hybrid batteries, which experience capacity reduction upon repeated shallow discharging, here we use the terminology to refer to the phenomenon that the (dis)charging performance of a lithium-ion battery depends on its cycling history. An example is illustrated in Figure 1, which shows the 2C discharge capacity of a 150μm-thick LiFePO4 electrode in a half cell when it starts from an initial state of charge (SoC) at 50%. Our experiment reveals that the discharge capacity has a strong dependence on how the electrode was first brought to the initial state. When it is charged to 50% SoC at 1.5C, the subsequent discharge capacity is 137% larger compared to when it is discharged to the same SoC at 1.5C. Similar phenomenon is also observed in another mainstream cathode NMC622. We show that such memory effect is caused by the reaction polarization present in the thick electrodes. To this end, 2D X-ray fluorescence (XRF) spectroscopy and Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) were employed to characterize the reaction distribution within the electrodes, and its correlation to the (dis)charging kinetics and OCV relaxation were investigated by electrochemical testing and pseudo-2D battery simulation. Our study highlights the issues created by the memory effect on the capacity prediction and SoC determination, which need to be addressed to develop a better battery management system for thick-electrode-based battery cells and packs. Figure 1

(Energy Technology Division Graduate Student Award sponsored by BioLogic) In-Situ, Non-Destructive, 3D Neutron Imaging of Lithium Plating Following Extreme Fast-Charging of Full-Cell Lithium-Ion Batteries

One of the primary challenges impeding extreme fast-charging (XFC) of current lithium-ion batteries (LIBs) for electric vehicles (EVs) within 10–15 minutes is the deposition of Li metal on graphite known as “Li plating”.1-2 After Li plates, it either re-intercalates into the graphite electrode or is stripped off during battery discharging to form “active Li”or becomes electronically disconnected resulting in “dead Li.” Previous studies have indicated that dead Li is the main contributor to the XFC-related capacity loss of LIBs. However, mechanistic understanding of the 3D morphological behavior and spatial heterogeneities of dead Li; and how they differ from those of plated and active Li during the XFC is not well understood.3-4 Here, we present an in-situ, non-destructive 3D characterization of the morphological behavior and spatial heterogeneities of plated, dead, and active Li on graphite electrodes in full-cell LIBs using high-resolution neutron micro-computed tomography. We performed neutron µCT5 (pixel size: ~ 5.74 µm; effective spatial resolution: ~10-15 µm) at the ICON beamline6 at the Swiss Spallation Neutron Source at the Paul Scherrer Institute. We imaged two batteries in the charged and discharged states: (1) after 4 cycles of 1C charging and (2) after 6 cycles of 6C charging.Our results show that Li plates at and around the edges of the graphite electrodes, indicating that graphite edges and the areas around these edges are the most susceptible to Li plating. However, certain edges and areas around these edges formed dead Li whereas others formed active Li, suggesting 3D spatial heterogeneities in the formation of dead and active Li at both 1C and 6C. Mainly, we discuss these heterogeneities at four regions: (1) near the Cu CC, (2) in the middle of the graphite electrode, (3) near the graphite-separator interface, and (4) in the separator. Specifically, we found that Li near the Cu CC remains active whereas most of the plated Li at the graphite-separator interface and in the separator becomes dead at both 1C and 6C.Morphologically, we observed porous nature of plated and dead Li at both 1C and 6C. Our 3D visualizations noticeably show nodules of varying densities of metallic Li. However, we observed different 3D behavior of Li plating at 1C and 6C. For example, tip-like Li deposits were seen laterally closer to the center of the graphite electrode, near the graphite-separator interface, and into the separator at 6C. In contrast, at 1C, no tip-like Li deposits were observed near the graphite-separator interface and into the separator. Based on our findings, we concluded that higher XFC-charging rate and cycling number (6 cycles of 6C charging) cause the formation of tip-like Li deposits as compared to the relatively slower XFC-charging rate and cycling number (4 cycles of 1C charging). We believe that insights derived from this work will guide the design of thick graphite electrodes with minimized-plating for fast-charged EVs.

(Battery Student Slam 8 Award Winner) Evaluating Electrodeposited Tin and Antimony-Based Anodes for Sodium-Ion Batteries

The widescale adaption of intermittent renewable energy sources, such as wind and solar, must be accompanied by a grid storage network to store energy when it is abundant and redistribute it as needed for on-demand use. Short-term storage in the form of rechargeable batteries is an attractive avenue for meeting these storage needs. The dominant technology in today’s market, the lithium-ion battery (LIB), is cost-prohibitive due to the need for rare-earth materials. Using the same working principle as LIBs, sodium-ion batteries (NIBs) utilize earth-abundant, low-cost sodium compounds instead of lithium compounds. Tin (Sn) and antimony (Sb) alone are promising anode materials for sodium-ion batteries with high theoretical capacities (847 and 660 mAh/g for Sn and Sb with Na, respectively) relative to current LIB anode chemistry (372 mAh/g) [1,2]. When combined, SnSb has shown to have increased stability relative to Sn or Sb alone [3]. Here, we synthesized Sn-Sb thin films with varied Sn and Sb atomic ratios by co-electrodeposition from a deep eutectic solvent by modifying solution stoichiometry and electrodeposition parameters. Using a combination of X-ray photoelectron spectroscopy (XPS), X-ray diffraction, and energy dispersive X-ray spectroscopy (EDS), phases and compositions of Sn-Sb synthesized by electrodeposition were identified. Once synthesized, we sought to determine the influence of morphology, surface chemistry, and composition on the capacity retention and rate capabilities of Sn and Sb-based anodes in NIBs. An optimized electrode composition was identified using a carbonate-based electrolyte, which resulted in stable capacity retention cycling at a rate of C/2 for 270 cycles.[1] W. T. Jing, C. C. Yang, and Q. Jiang, Journal of Materials Chemistry A, 8, 2913–2933 (2020).[2] S. Megahed and B. Scrosati, Journal of Power Sources, 51, 79–104 (1994).[3] W. P. Kalisvaart, H. Xie, B. C. Olsen, E. J. Luber, and J. M. Buriak, ACS Applied Energy Materials, 2, 5133–5139 (2019).

Conjugated Nitroxide Radical Polymer with Low Temperature Tolerance Potential for High-Performance Organic Polymer Cathode.

Low-temperature operation poses a significant challenge for current commercial rechargeable lithium-ion batteries (LIBs). Organic polymer electrode materials, exhibiting a nonintercalation redox mechanism, offer a viable solution to mitigate the decline in electrochemical performance at low temperatures in LIBs. Herein, a radical polymer P(DATPAPO-TPA) with a conjugated nitrogen-rich triphenylamine derivative as the backbone and high-density nitroxide pendants has been synthesized. Due to the large interstitial spaces between adjacent structural units and polymer chains, resulting from the significant torsion angle between the benzene rings in the P(DATPAPO-TPA) skeleton, ions could effectively transport. This structural feature demonstrated a notable discharge capacity of 143.3 mA h·g-1 and a high charge-discharge plateau at ∼3.75 V vs Li+/Li, outperforming most reported radical polymer cathode materials. In addition, its capacity retention could reach 83.1% after 2000 cycles at an ultrahigh current density of 50 C, showing excellent rate capability and promising cyclability. Also notable was P(DATPAPO-TPA)'s favorable low-temperature performance that maintains a high discharge capacity of 139.2 mA h·g-1 at 0 °C. The synthesized P(DATPAPO-TPA) is a tangible illustration of a viable design strategy for low-temperature electrode materials, thereby contributing to broadening applications for radical polymer electrode materials.

Investigating electrocatalytic properties of β12-borophene as a cathode material for an efficient lithium-oxygen battery: a first-principles study

Responding to the pressing need to mitigate climate change effects due to fossil fuel consumption, there is a collective push to transition towards renewable and clean energy sources. However, the effectiveness of this move depends on an efficient energy storage system that surpasses current lithium-ion battery technology. The lithium-oxygen battery, having significantly high theoretical specific capacity compared to other systems, has emerged as a promising solution. However, the issues of poor cathode electrode conductivity and slow kinetics during discharge product formation have limited its practical applications. In this work, the first principles-based density functional theory was used to investigate the electrocatalytic properties of β12-borophene as a cathode electrode material for a high-performance lithium-oxygen battery. The adsorption energy, charge density distributions, Gibbs free energy changes, and diffusion energy barriers of lithium superoxide (LiO2) on β12-borophene were calculated. Our findings revealed several important insights: The adsorption energy was found to be − 3.70 eV, suggesting a strong tendency for the LiO2 to remain anchored to the material during the discharging process. The dynamics in the charge density distributions between LiO2 and the β12-borophene substrate exhibited complex behavior. The analysis of the Gibbs free energy changes of the reactions yielded an overpotential of − 1.87 V, this moderate value suggests spontaneous reactions during the formation of the discharge products. Most interestingly, the density of states and band structure analysis suggested the preservation of metallic properties and improved electrical conductivity of the material after the adsorption of LiO2. Additionally, β12-borophene has a relatively low diffusion energy barrier of 1.08 eV, implying effortless diffusion of the LiO2 and an increase in the rate of discharging process. Ultimately, the predicted electronic properties of β12-borophene, make it a strong candidate as a cathode electrode material for an efficient lithium-oxygen battery.

Overview of Inorganic Electrolytes for All-Solid-State Sodium Batteries.

All-solid-state sodium batteries (AS3B) emerged as a strong contender in the global electrochemical energy storage market as a replacement for current lithium-ion batteries (LIB) owing to their high abundance, low cost, high safety, high energy density, and long calendar life. Inorganic electrolytes (IEs) are highly preferred over the conventional liquid and solid polymer electrolytes for sodium-ion batteries (SIBs) due to their high ionic conductivity (∼10-2-10-4 S cm-1), wide potential window (∼5 V), and overall better battery performances. This review discusses the bird's eye view of the recent progress in inorganic electrolytes such as Na-β"-alumina, NASICON, sulfides, antipervoskites, borohydride-type electrolytes, etc. for AS3Bs. Current state-of-the-art inorganic electrolytes in correlation with their ionic conduction mechanism present challenges and interfacial characteristics that have been critically reviewed in this review. The current challenges associated with the present battery configuration are overlooked, and also the chemical and electrochemical stabilities are emphasized. The substantial solution based on ongoing electrolyte development and promising modification strategies are also suggested.

Oxygen-bridging Fe, Co dual-metal dimers boost reversible oxygen electrocatalysis for rechargeable Zn–air batteries

Rechargeable zinc-air batteries (ZABs) are regarded as a remarkably promising alternative to current lithium-ion batteries, addressing the requirements for large-scale high-energy storage. Nevertheless, the sluggish kinetics involving oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) hamper the widespread application of ZABs, necessitating the development of high-efficiency and durable bifunctional electrocatalysts. Here, we report oxygen atom-bridged Fe, Co dual-metal dimers (FeOCo-SAD), in which the active site Fe-O-Co-N6 moiety boosts exceptional reversible activity toward ORR and OER in alkaline electrolytes. Specifically, FeOCo-SAD achieves a half-wave potential (E1/2) of 0.87 V for ORR and an overpotential of 310 mV at a current density of 10 mA cm-2 for OER, with a potential gap (ΔE) of only 0.67 V. Meanwhile, FeOCo-SAD manifests high performance with a peak power density of 241.24 mW cm-2 in realistic rechargeable ZABs. Theoretical calculations demonstrate that the introduction of an oxygen bridge in the Fe, Co dimer induced charge spatial redistribution around Fe and Co atoms. This enhances the activation of oxygen and optimizes the adsorption/desorption dynamics of reaction intermediates. Consequently, energy barriers are effectively reduced, leading to a strong promotion of intrinsic activity toward ORR and OER. This work suggests that oxygen-bridging dual-metal dimers offer promising prospects for significantly enhancing the performance of reversible oxygen electrocatalysis and for creating innovative catalysts that exhibit synergistic effects and electronic states.

Solution-Based Suspension Synthesis of Li2S-P2S5 Glass-Ceramic Systems as Solid-State Electrolytes: A Brief Review of Current Research.

All-solid-state batteries are set to be the next generation of batteries offering improved performance and safety over current conventional lithium-ion batteries. Glass-ceramic Li2S-P2S5 solid-state sulfide electrolytes are promising contenders to achieve all-solid-state batteries with exceptional ionic conductivity on the order of 10-2 S cm-1. Solid-state processing techniques for synthesizing sulfide solid electrolytes are energetically and time consumptive. However, proposed solution processing techniques offer faster and lower temperature processes rendering them scalable. The chemistries that underly solution processing of sulfide solid electrolytes are still not well understood. This brief review highlights key aspects of current research into solution-based suspension synthesis processing techniques of Li2S-P2S5 sulfide solid electrolytes discussing precursor stoichiometries, solvent selectivity, reaction conditions, chemical impurities, and particle morphology with the intent of promoting further research into solution processing of sulfide solid-state electrolytes.

Comparative study of nudged elastic band and molecular dynamics methods for diffusion kinetics in solid-state electrolytes

Abstract Considerable efforts are being made to transition current lithium-ion and sodium-ion batteries towards the use of solid-state electrolytes. Computational methods, specifically nudged elastic band (NEB) and molecular dynamics (MD) methods, provide powerful tools for the design of solid-state electrolytes. The MD method is usually the choice for studying the materials involving complex multiple diffusion paths or having disordered structures. However, it relies on simulations at temperatures much higher than working temperature. This paper studies the reliability of the MD method using the system of Na diffusion in MgO as a benchmark. We carefully study the convergence behavior of the MD method and demonstrate that total effective simulation time of 12 ns can converge the calculated diffusion barrier to about 0.01 eV. The calculated diffusion barrier is 0.31 eV from both methods. The diffusion coefficients at room temperature are 4.3×10-9 and 2.2×10-9 cm2/s, respectively, from the NEB and MD methods. Our results justify the reliability of the MD method, even though high temperature simulations have to be employed to overcome the limitation on simulation time.

Double-Salts Super Concentrated Carbonate Electrolyte Boosting Electrochemical Performance of Ni-Rich LiNi0.90Co0.05Mn0.05O2 Lithium Metal Batteries.

Current lithium-ion batteries cannot meet the requirement of higher energy density with further large-scale application of electrical vehicles. Lithium metal batteries combined with Ni-rich layered oxides cathode are expected as the one of promising solutions, while the poor electrode and electrolyte interface impedes the commercial development of lithium metal batteries. A new double-salts super concentrated (DSSC) carbonate electrolyte is proposed to improve the electrochemical performance of LiNi0.90Co0.05Mn0.05O2 (NCM9055)||Li metal battery which exhibits stable cycling performance with the capacity retention of 93.04% and reversible capacity of 173.8 mAh g-1 after 100 cycles at 1 C, while cells with conventional 1m diluted electrolyte remains only 60.55% and capacity of 114.2 mAh g-1. The double salts synergistic effect in super concentrated electrolyte promotes the formation for more balanced stable cathode electrolyte interface (CEI) inorganic compounds of CFx, LiNOx, SOF2, Li2SO4, and less LiF by X-ray photoelectron spectroscopy (XPS)test, and the uniform 2-3nm rock-salt phase protection layer on the cathode surface by transmission electron microscope (TEM) characterization, improving the cycling performance of the Ni-rich NCM9055 layered oxide cathode. The DSSC electrolyte also can relief the Li dendrite growth on Li metal anode, as well as exhibit better flame retardance, promoting the application of more safety Ni-rich NCM9055||Li metal batteries.

Empowering the Potassium-Sulfur Battery with Commendable Reaction Kinetics and Capacity Output by Localized High-Concentration Electrolytes.

Potassium-sulfur (K-S) batteries are one of the promising high-energy-density candidates beyond current lithium-ion batteries. Nevertheless, in practice, the utilization of K-S batteries is largely hindered due to the dissolution and shuttle effect of the cathode redox intermediates and the scarcity of an effective anode protection layer in conventional electrolytes. Herein, electrolyte engineering is applied to formulate an ether-based localized high-concentration electrolyte (LHCE) for the first time in a K-S cell with the mitigated parasitic effect of polysulfide dissolution and shuttle and the tuned anode-electrolyte interface property. A nonsolvating and polysulfide-stable fluoroether is sieved as a cosolvent in such an LHCE, which possesses the ultralow polysulfides solubility due to less roaming solvents and thus alleviates the polysulfides shuttle effect. The anion-derived solid electrolyte interphase enriched in inorganic components is constructed due to the strengthened cation-anion interplay in the primary solvation sheath and highlighted with accelerated interfacial kinetics in a K-S cell. It is validated that the proposed LHCE unlocks the theoretical capacity of the K-S cell based on the conversion between S and K2S3. It is further revealed that the lifespan is limited to the anode corrosion with severe cosolvent degradation caused by limited solvating solvent compatibility with metallic K, and the inevitable byproduct accumulation at the S cathode. The K-S cell based on the designed LHCE could achieve a prolonged lifespan with a reversible capacity of 448 mA h/gs after 80 cycles with an elaborate cathode design. This work shines a light on the electrolyte design perspective for full utilization and an in-depth mechanistic understanding of high-energy-density K-S batteries.