Utilization Of Active Material Research Articles

Free-Standing Poly(vinyl benzoquinone)/Reduced Graphene Oxide Composite Films as a Cathode for Lithium-Ion Batteries.

Quinones with a rapid reduction-oxidation rate are promising high-capacity cathodes for lithium-ion batteries. However, the high solubility of quinone molecules in polar organic electrolytes results in low cycle stability, while their low electric conductivity causes low utilization of electrode materials. In this article, a new p-benzoquinone derivative, poly(vinyl benzoquinone) (PVBQ), is designed and synthesized, and a solution-based method of preparing free-standing PVBQ/reduced graphene oxide (RGO) composite films is developed. PVBQ has a high theoretical specific capacity (400 mA h g-1) because of its low dead moiety mass. In the produced composite films, PVBQ nanoparticles are uniformly dispersed on RGO sheets, which endows the composite films with high electric conductivity and inhibits the dissolution of PVBQ through strong adsorption. As a result, the composite films show a high active material utilization, high practical specific capacity, and excellent cycling stability. PVBQ in the composite membrane containing 60.2 wt % RGO deliver 244 mA h g-1 capacity after 200 charge-discharge cycles at a current density of 300 mA g-1. At a current density of 1500 mA g-1, the reversible specific capacity is still 170 mA h g-1. This work provides a high-performance cathode material for lithium-ion batteries, and the molecular structure and electrode structure design ideas are also instructive for developing other organic electrode materials.

Chloride-Ion-Enriched Solid Electrolyte Interphase with Rapid Na+ Migration toward High-Performance Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) have emerged as potential alternatives to lithium-ion batteries (LIBs), particularly for large-scale applications. Alloy-type anode materials for sodium-ion batteries are esteemed as prospective candidate materials for sodium-ion anodes, owing to their elevated theoretical capacity, heightened utilization efficiency, and minimal production of insulating byproducts. However, the severe volume changes and sluggish ion diffusion kinetics can lead to irreversible particle fragmentation and reaggregation phenomena, ultimately resulting in electrode degradation. Additionally, repetitive volume changes can cause an unstable solid electrolyte interphase (SEI). This study presents the synthesis of chloride-ion-modulated bimetallic SnSb/C nanoparticle anode materials, highlighting the following advantages: (i) Designing a bimetallic SnSb alloy structure serves to buffer the structural stresses generated during sodium insertion/extraction processes, effectively mitigating particle fracture phenomena induced by electrode material expansion/contraction. (ii) Nanostructuring both alloy materials enables the full utilization of active materials and shortens diffusion pathways, thereby significantly enhancing the diffusion rate of sodium ions. (iii) Introducing a carbonaceous matrix serves to alleviate self-agglomeration phenomena of the material during charge/discharge cycles, enhancing the material's conductivity and structural stability. (iv) Utilizing chloride-ion interface modification to achieve a chloride-rich solid-electrolyte interphase (SEI) enhances battery performance.

Constructing Electron/Ion Conductive‐Enhanced Ultrahigh Loading LiFePO4 Electrodes Using Polytetrafluoroethylene and Carbon Nanotubes for High‐Performance Batteries

Thick electrodes represent an effective approach for augmenting energy density of batteries. However, their increased thickness invariably leads to longer electron and ion transport distance, limiting the utilization of active material and hindering practical application. Herein, an electron‐conducting‐enhanced and ion‐conducting‐enhanced strategy is presented for fabricating ultrahigh loading electrodes via constructing an interlaced 3D network. Carbon nanotubes (CNTs) serve as extended electron pathways. Different from the polyvinylidene fluoride binder which needs to be dissolved into molecules for preparing electrode, polytetrafluoroethylene (PTFE), however, exists as a separate phase inside the electrode, thus can become the extended pathways for electrolyte elongating due to its strong affinity to organic electrolyte. Note that based on the synergistic effect between CNT and PTFE, the latter can exhibit a form of long‐distance extension fibers rather than agglomeration. Finally, a LiFePO4 electrode with a record‐high loading of 141 mg cm−2 is successfully prepared. This electrode exhibits outstanding area capacity (20.7 mAh cm−2 at 0.2 C) and cycling stability with impressive energy density of 224 Wh kg−1 and 517 Wh L−1 in a full cell (graphite anode). The findings present a novel strategy for achieving high energy density in lithium‐ion batteries using existing material systems.

Stable Dendrite-Free Room Temperature Sodium-Sulfur Batteries Enabled by a Novel Sodium Thiotellurate Interface.

The practical application of room-temperature sodium-sulfur (RT Na-S) batteries was severely hindered by inhomogeneous sodium deposition and notorious sodium polysulfides (NaPSs) shuttling. Herein, novel sodium thiotellurate (Na2TeS3) interfaces are constructed both on the cathode and anode for Na-S batteries to simultaneously address the Na dendritic growth and polysulfide shuttling. On the cathode side, a heterostructural sodium sulfide/sodium telluride embedded in a carbon matrix (Na2S/Na2Te@C) was rationally designed through a facile carbothermal reaction, where the Na2TeS3interface will be in-situ chemically obtained. Such an interface provides abundant electron/ion diffusion channels and ensures rich catalytic surfaces toward Na-S redox, which could significantly improve the utilization of active material and alleviate polysulfide shuttling in the cathode. On the anode side, the inevitable formation of soluble polytellurosulfides species will migrate on Na anode surface, finally constructing a compact and smooth solid-electrolyte Na2TeS3 interphase (SEI) layer. Such electrochemical formed Na2TeS3 interface can significantly enhance ionic transport and stabilize Na deposition, thus realizing dendrite-free Na-metal plating/stripping. Benefitting from these advantages, an anode-free cell fabricated with the Na2S/Na2Te@C cathode exhibits an ultrahigh initial discharge capacity of 634 mAh g-1 at 0.1 C, which could pave a new path to design high-performance cathodes for anode-free RT Na-S batteries.

Enhanced Discharge Capacity in Carbon Felt Electrodes for Aqueous Aluminium-Ion Half-Cells

Diversifying the battery technology in use is an important step in ensuring a sustainable transition to a carbon neutral society, and reducing the emissions associated with lithium-ion cell manufacture. Aluminium is an attractive material for battery applications due to its high theoretical volumetric charge storage capacity of 8046 mA h cm−3 compared to lithium’s 2061 mAh cm-3 and relative abundance in the earth’s crust (1). Aqueous Al-ion batteries are one of many metal-ion systems being investigated utilising water as the electrolyte (2). Further, there are well-established mining, processing, and recycling routes for aluminium, with Li-ion battery recycling still in its infancy (3). Using aqueous electrolytes further provides improved safety as fire risk is reduced, and manufacturing costs are also reduced (4).The substrate on which the electrode material is applied impacts how it is utilised within an electrochemical system. The substrate provides both a shape to the electrode, as well as the material itself forming part of the system, and common substrates double as current collectors e.g. thin metal foils, but carbon polymers have also been explored as a substrate (5, 6). Carbon felt is a conductive substrate, with thin fibres of 5-10 μm diameter, providing a flexible porous structure and large surface area for the active material ‘ ink’ to adhere (0.4 m2 g-1 (7)) . Carbon based electrodes have been assessed in a non-aqueous Al-ion cathodes (8), with varying performance metrics based on the structure and make-up of the electrode, however, these were not investigated as a substrate for further electrode ink. In adding the ink to the carbon felt, the electrode becomes an effective 3D-matrix electrode.This poster explores the use of such 3D-matrix electrodes in order to increase the amount of active material utilised within the aq. Al-ion battery system (9) – a key requirement in reducing the environmental impacts of the battery overall (5), and a means for increasing the capacity of an individual electrode without increasing the overall volume. The cell described in (10) has a carbon-polymer electrode substrate, anatase TiO2 negative electrode and a copper hexacyanoferrate (CuHCF) positive electrode, with the electrolyte being 1 M AlCl3 + 1 M KCl. While the CuHCF redox reaction is partially understood, the negative electrode mechanism has not been fully elucidated. A theorised surface reaction, and pseudo-capacitance of the TiO2 electrode in the aq. Al-ion battery would benefit from an increased surface area of the electrode provided by the carbon felt. Therefore, a key factor in achieving the optimum utilisation of active material is not purely an increase of TiO2 in the electrode, but an increase in the surface area in contact with the electrolyte. Key findings presented show that the lower active material loadings result in a higher discharge capacity for both the positive and negative electrodes, with values reaching an order of magnitude higher than seen for the 2D electrodes studied in the past. For the TiO2 electrode, we see 205.0 mAh g-1 @978 mA g-1 (1.81 mg cm-2 active material loading) and for the CuHCF, 259 mA h g-1 @ 1256.8 mA g-1 (2.5 mg cm-2 active material loading). Elia GA, Kravchyk KV, Kovalenko MV, Chacón J, Holland A, Wills RGA. An overview and prospective on Al and Al-ion battery technologies. Journal of Power Sources. 2021;481:228870. Wu D, Li X, Liu X, Yi J, Acevedo-Peña P, Reguera E, et al. 2022 Roadmap on aqueous batteries. Journal of Physics: Energy. 2022;4(4):041501. Baum ZJ, Bird RE, Yu X, Ma J. Lithium-ion battery recycling─ overview of techniques and trends. ACS Publications; 2022. Chao D, Zhou W, Xie F, Ye C, Li H, Jaroniec M, et al. Roadmap for advanced aqueous batteries: From design of materials to applications. Science Advances. 2020;6:eaba4098. Melzack N. Advancing battery design based on environmental impacts using an aqueous Al-ion cell as a case study. Scientific Reports. 2022;12(1):8911. Holland A, Kimpton H, Cruden A, Wills R. CuHCF as an electrode material in an aqueous dual-ion Al3+/K+ ion battery. Energy Procedia. 2018 d;151:69-73. Sigracell. Speciality Graphites for Energy Storage. 2016. McKerracher RD, Holland A, Cruden A, Wills RGA. Comparison of carbon materials as cathodes for the aluminium-ion battery. Carbon. 2019;144:333-41. Holland A, McKerracher RD, Cruden A, Wills RGA. An aluminium battery operating with an aqueous electrolyte. Journal of Applied Electrochemistry. 2018;48(3):243-50. Melzack N, Wills R, Cruden A. Cleaner Energy Storage: Cradle-to-Gate Life Cycle Assessment of Aluminum-Ion Batteries With an Aqueous Electrolyte. Frontiers in Energy Research. 2021;9(290).

Evaluation of Electrochemical Techniques for Characterizing the Kinetics of Porous Insertion-Type Electrodes

The composite-type porous electrode remains the most commonly used electrode for a wide variety of electrochemical energy storage devices, including lithium-ion batteries, electrochemical capacitors, Li-S/Li-air batteries, and even all-solid-state batteries. This is due to its ease of manufacturability and ability to maintain a high electrochemical surface area with adequate ion and electron transport. Understanding porous electrode kinetics is essential to maximize the active material utilization at high rates. A variety of electrochemical techniques exist to characterize the kinetic behavior of porous electrodes. The most popular ones include electrochemical impedance spectroscopy, galvanostatic charge/discharge, galvanostatic intermittent titration technique, and cyclic voltammetry. The purpose of this work was to evaluate which of these four techniques provides the most relevant kinetic information for understanding porous electrode kinetics. To do this, we utilized porous electrodes composed of LiCoO2 as a model insertion-type material, and with varying thicknesses (10 - 40 µm). We find that GITT is an accessible and reliable method for obtaining the effective diffusion coefficient of the porous electrode. It yields consistent results, regardless of electrode thickness and component ratio. On the other hand, the cyclic voltammetry peak current behavior can be easily compromised, even at slow scan rates of 0.01 - 0.1 mV/s, and when using a high conducting domain ratio. When comparing the dQ/dV plot and cyclic voltammetry for observing peaks indicating phase transitions in the insertion material, the dQ/dV plot is less kinetically limited. We utilized the differential relaxation time (DRT) method to analyze electrochemical impedance spectroscopy data. Our findings demonstrate that as thickness increases, charge transfer resistance decreases, while diffusion resistance increases. This study provides a comprehensive evaluation on the differences between electrochemical methods to characterize the kinetics of composite porous electrodes.

Modeling Metal Nitrides for Interface Design in Lithium-Sulfur Batteries with GPUs and CPUs

As current batteries reach their limits, finding new battery materials is crucial. Lithium-sulfur batteries are a promising next-generation technology but face three major issues: low active material utilization, cathode pulverization, and limited polysulfide conversion leading to anode corrosion. Nano-deposition of metal nitride (MNx, M = Ti, V, Zr, etc.) layers on the graphene sulfur cathodes could significantly improve conductivity and cycling performance. Nevertheless, the large number of potential metal candidates requires preliminary and efficient computational screening using density-functional theory (DFT). This modeling framework can be used to calculate many properties of the coatings and screen out poor candidates. Firstly, the surface-adsorption ability of metal nitride candidates for lithium polysulfide intermediates involved in the electrochemical cycle (Li2S, Li2S2, Li2S4, Li2S6, Li2S8, S8) must be greater than the adsorption by dioxolane and dimethyl ether electrolytes (>~0.99eV). Secondly, the electronic properties before and after adsorption must feature significant density of states near the Fermi level, as a possible indicator of good electrical conductivity. Lastly, the free-energy profiles for the sulfur reduction reaction (SRR) over the remaining candidates will be estimated to better understand the catalytic properties of the metals. Particular attention will be paid to the Li2S2 reduction to Li2S, the potential limiting step. The top catalyst candidates should allow for an exergonic reaction. Finally, this application serves as a case study for our modeling platform, and the relative merits of standard for CPUs and GPUs in terms of computation time and accuracy will be discussed. Careful analysis of binding energy results, densities of states, and energy profiles for the various metal candidates provides valuable insights into the design of experimentally viable lithium-sulfur batteries, as well as advanced interface design in the broader field of battery research.

Design and Characterization of Porous Electrodes for Redox Flow Batteries

The commercialization of redox flow batteries as large-scale energy storage systems depends on lowering the capital and operating costs which depend on achieving maximum power density. Optimizing electrode design parameters and flow field-electrode combinations is critical to minimize losses and maximize active material utilization. Modeling the current drawn from an electrode offers a means to interpret electrode structure based on the electrolyte distribution driven by internal design. However, direct imaging methods (such as in-situ fluorescence microscopy and X-ray tomography) and numerical methods for current to potential prediction (3D Lattice Boltzmann modeling) are specific to individual electrode structures and possess limited predictable value to obtain an ideal electrode design. In this work, we present an electrode impedance spectroscopy (EIS)-based approach for determining electrode design parameters and devise a general method for determination of effective diffusion layer thickness. Using COMSOL modeling we verified the development of slug flow behavior in highly randomized porous electrode systems, indicating that the mass transport properties are dictated by inter-fiber distance. An analytical model to predict current as a function of applied overpotential is presented which allows us to vary structural parameters of the porous electrodes to study the influence of surface area, inter-fiber distances and diffusion layer thickness on the RFB performance. This model is a highly flexible tool applicable to any electrochemical system using a porous electrode and identifies critical variables affecting electrode design to characterize optimal electrode structure to minimize mass transport losses and optimize operational parameters.

Microstructural Analysis of Lithium-Ion Battery Cathode Carbon-Binder Domain across Processing Conditions

Improvement of lithium-ion battery (LIB) energy density and rate capability is necessary to increase adoption of electric vehicles (EVs) and curb transportation emissions. The cathode structure must support facile ion and electron transport, enabling rapid charging while maintaining near-theoretical capacity. Much investigation focuses on active material design for fast-charging cathodes, [1] but less is understood about the effect of electrode processing on carbon-binder domain (CBD) structure and its impact on rate capability. As conductive carbon facilitates electron transfer, slow Li+ diffusion through cathode micropores is rate-limiting and prevents full active material utilization at high charge rates. [2,3] However, efforts to improve Li+ diffusion, such as increasing porosity, introduce charge-transfer limitations. [4] Thus, cathode processing conditions and resulting microstructure must be carefully designed to optimize for both electronic and ionic conductivity. For example, an increase in coating shear rate and decrease in slurry solid content improves long-range electronic pathways [5,6] and calendaring strengthens active material-carbon contacts to reduce charge-transfer resistance. [2] However, the impact of processing variations on ionic transport pathways, which can be described by CBD porosity and tortuosity, is not well understood. Further, because the CBD is traditionally characterized as a single phase, the distinct influences of insulating binder and conductive carbon distributions on structure and performance are poorly defined.In this talk, I will discuss how electrode coating conditions impact pathways available to Li+ and electrons within the CBD with the goal of identifying optimal microstructures for efficient transport. We fabricate cathodes with varying solid content, coating shear rate, and degree of calendaring to explore disparate CBD microstructures. We use electrochemical impedance spectroscopy (EIS) with a symmetric cell & blocking electrolyte to determine cathode resistivity and tortuosity and plasma focused ion beam scanning electron microscopy (PFIB-SEM) to examine CBD morphology over a representative cathode volume (~80 x 80 x 50 µm3). We then use small-angle neutron scattering (SANS) with solvent contrast variation to distinguish between binder and carbon distributions and determine the surface area of each component within the CBD. Relationships between processing conditions, structural variations, and rate capability will be discussed, informing the design of the CBD for facile transport and improved fast charging performance. Further, reducing ionic transport limitations through intentional design of LIB cathodes will enable thicker electrodes to increase cell energy density.

Optimized Electrode/Electrolyte Interface Engineering for Dendrite‐Free Al Anode and Self‐Activated Graphite Cathode

AbstractRechargeable aluminum batteries (RABs) have garnered attention owing to their impressive theoretical capacity, outstanding safety features, and abundant Al reserves, thereby positioning them as a potential alternative and supplement to fixed energy storage. Nonetheless, RABs still suffer from issues, such as poor anode stability stemming from the corrosivity of the chloral aluminate ionic liquid electrolyte (ILs) and subpar wettability of the cathode. To address these issues, the proposed electrolyte interfacial engineering involves the nonionic surfactant (F127) as an interfacial optimizer in ILs, simultaneously modulating the anode–electrolyte and cathode–electrolyte interfaces. Systematic experiments and theoretical analyses validate that F127 preferentially adsorbs on the electrode surface, forming a dense and uniform adsorption layer. The F127 layer can effectively mitigate the corrosion of ILs on the Al anode and regulate the current density to achieve uniform Al deposition. Furthermore, F127 enhances the wettability between the cathode and ILs, preventing the collapse of the graphite structure and enhancing the active material's utilization. The Al//FG full battery assembled with F127 modifying ILs (F127‐0.5) is able to retain a specific capacity of 104.9 mAh g−1 after 1600 cycles, which is higher than ILs (69.0 mAh g−1). This electrolyte interface modification strategy holds considerable practical significance for achieving long‐lifespan and high‐capacity RABs.

A Small Electrolyte Drop Enables a Disruptive Semisolid High‐Energy Sulfur Battery Cell Design via an Argyrodite‐Based Sulfur Cathode in Combination with a Metallic Lithium Anode

AbstractLithium–sulfur batteries with liquid electrolytes are discussed as the most promising post‐lithium‐ion‐battery technology in literature due to their high theoretical specific energy and first prototype cells delivering >470 Wh kg−1. Although several electrolyte and material concepts are developed that partially solve the issue of the so‐called shuttle mechanism, the most promising concept to genuinely confine sulfur species in the cathode is all‐solid‐state argyrodite–sulfur cathodes leading to almost theoretical active material utilization by maintaining reasonable sulfur loadings and electrolyte to sulfur ratios. However, this battery concept has so far not achieved reversible cycling against metallic lithium anodes as it requires high pressures for manufacturing, and ductile lithium metal creeps along the grain boundaries of the solid electrolyte particles leading to short cuts of the cells. Recent findings show that metallic lithium, however, can be stably cycled with dimethoxyethane/lithium‐bis(fluorosulfonyl)imide (DME/LiFSI)‐based electrolytes. Herein, for the first time, a semisolid concept is presented combining the benefits of an argyrodite‐based solid‐state cathode and a DME/LiFSI/hydrofluoroether‐based anolyte concept – in coin cells and first pouch cells. This disruptive approach enables projected specific energies higher than 600 Wh kg−1 at cell stack level.

Poly(ethylene) Oxide Electrolytes for All-Solid-State Lithium Batteries Using Microsized Silicon/Carbon Anodes with Enhanced Rate Capability and Cyclability.

Silicon (Si) has been widely studied as one of the promising anodes for lithium-ion batteries (LIBs) because of its ultrahigh theoretical specific capacity and low working voltage. However, the poor interfacial stability of silicon against conventional liquid electrolytes has largely impeded its practical use. Therefore, the combination of silicon-based anodes and solid electrolytes has attracted a great deal of attention in recent years. Here, we demonstrate three types of microsized porous silicon/carbon (Si/C) electrodes (i.e., pristine, prelithiated by liquid electrolyte, and preinfiltrated by polymer electrolyte) that are paired with poly(ethylene) oxide (PEO)-based electrolytes for all-solid-state lithium batteries (ASSLBs). We found that when compared with ionic conductivity, the mechanical stability of the PEO electrolyte dominates the electrochemical performance of ASSLBs using Si/C electrodes at elevated temperature. Additionally, both prelithiated and preinfiltrated Si/C electrodes show higher specific capacity in comparison to the pristine electrode, which is attributed to continuous lithium-ion conducting pathways within the electrode and thus improved utilization of active material. Moreover, owing to good interfacial lithium-ion transport in the electrode, a solid-state half-cell with preinfiltrated Si/C electrode and PEO-lithium bis (trifluoromethanesulfonyl)imide electrolyte delivers a specific capacity of ∼1,000 mAh g-1 after 100 cycles under 800 mA g-1 at 60 °C with average Coulombic efficiency >98.9%. This work provides a strategy for rationally designing the microstructure of silicon-based electrodes with solid electrolytes for high-performance all-solid-state lithium batteries.

Small-molecule organic electrode materials on carbon-coated aluminum foil for high-performance sodium-ion batteries

Organic molecular electrode materials are promising candidates in batteries. However, direct application of small molecule materials usually suffers from drastic capacity decay and inefficient utilization of active materials because of their high solubility in organic electrolytes and low electrical conductivity. Herein, a simple strategy is found to address the above issues through coating the small-molecule organic materials on a commercialized carbon-coated aluminum foil (CCAF) as the enhanced electrode. Both the experimental and calculation results confirm that the relatively rough carbon coating on the aluminum foil not only exhibits superior adsorption capacity of small-molecule organic electrode materials with a tight contact interface but also provides continuous electronic conduction channels for the facilitated charge transfer and accelerated reaction kinetics. In addition, the carbon coating also inhibits Al corrosion in electrochemical process. As a result, by using the tetrahydroxy quinone-fused aza-phenazine (THQAP) molecule as an example, the THQAP-CCAF electrode exhibits an excellent rate performance with a high capacity of 220 and 180 mAh g−1 at 0.1 and 2 A/g, respectively, and also a remarkable cyclability with a capacity retention of 77.3% even after 1700 cycles in sodium-ion batteries. These performances are much more superior than that of batteries with the THQAP on bare aluminum foil (THQAP-AF). This work provides a substantial step in the practical application of the small-molecule organic electrode materials for future sustainable batteries.

Oriented Structures for High Safety, Rate Capability, and Energy Density Lithium Metal Batteries.

Lithium metal batteries (LMBs) have emerged in recent years as highly promising candidates for high-density energy storage systems. Despite their immense potential, mutual constraints arise when optimizing energy density, rate capability, and operational safety, which greatly hinder the commercialization of LMBs. The utilization of oriented structures in LMBs appears as a promising strategy to address three key performance barriers: 1) low efficiency of active material utilization at high surface loading, 2) easy formation of Li dendrites and damage to interfaces under high-rate cycling, and 3) low ionic conductivity of solid-state electrolytes in high safety LMBs. This review aims to holistically introduce the concept of oriented structures, provide criteria for quantifying the degree of orientation, and elucidate their systematic effects on the properties of materials and devices. Furthermore, a detailed categorization of oriented structures is proposed to offer more precise guidance for the design of LMBs. This review also provides a comprehensive summary of preparation techniques for oriented structures and delves into the mechanisms by which these can enhance the energy density, rate capability, and safety of LMBs. Finally, potential applications of oriented structures in LMBs and the crucial challenges that need to be addressed in this field are explored.

Synergistic restriction of polysulfides enabled by cobalt@carbon spheres embedded CNTs: A facile approach for constructing sulfur cathodes with high sulfur content

Despite the bright fortune of lithium-sulfur (Li-S) batteries as one of the next-generation energy storage systems owing to the ultrahigh theoretical energy density and earth-abundance of sulfur, crucial challenges including polysulfide shuttling and low sulfur content of sulfur cathodes need to be overcome before the commercial survival of sulfur cathodes. Herein, cobalt/carbon spheres embedded CNTs (Co-C-CNTs) are rationally designed as multifunctional hosts to synergistically address the drawbacks of sulfur cathodes. The host is synthesized by a facile pyrolysis using Co(OH)2 template and followed with the controllable etching process. The hierarchical porous structure owning high pore volume and surface area can buffer the volume change, physically confine polysulfides, and provide conductive networks. Besides, partially remained metallic cobalt nanoparticles are favorable for chemical adsorption and conversion of polysulfides, as validated by density functional theory simulations. With the combination of above merits, the S@Co-C-CNTs cathodes with a high sulfur content of 80 wt% present a superior initial capacity (1568 mAh g−1 at 0.1C) with ultrahigh 93.6% active material utilization, and excellent rate performance (649 mAh g−1 at 2C), providing feasible strategies for the optimization of cathodes in metal-sulfur batteries.

Tri-sulfur radical trapping in lithium–sulfur batteries

Lithium-sulfur (Li–S) batteries have emerged as a next-generation battery technology owing to their prospects of high capacity and energy density. They, however, suffer from rapid capacity decay due to the shuttling of reaction intermediate species: Li polysulfides (LiPSs). One of the more important and intriguing PSs is the tri-sulfur radical (S3•−), observed mainly in high-donor number (DN) solvent-based electrolytes. Although this radical has been proposed to be crucial to full active material (AM) utilization, there is currently no direct evidence of the impact of S3•− on cycling stability. To gain more insight into the role of the S3•−, we studied the use of radical traps in low and high DN solvent-based electrolytes by operando Raman spectroscopy. The traps were based on nitrone and iminium cation, and S3•− was indeed successfully trapped in ex situ analysis. However, it was the ionic liquid-based trap, specifically pyridinium, that effectively suppressed S3•− during battery operation. Overall, the PS formation was altered in the presence of the traps and we confirmed the impact of S3•− formation on the Li–S battery redox reactions and show how the trapping correlates with Li–S battery performance. Therefore, stabilization of the S3•− might be a path to improved Li–S batteries.

The principle and amelioration of lithium plating in fast-charging lithium-ion batteries

Fast charging is restricted primarily by the risk of lithium (Li) plating, a side reaction that can lead to the rapid capacity decay and dendrite-induced thermal runaway of lithium-ion batteries (LIBs). Investigation on the intrinsic mechanism and the position of Li plating is crucial to improving the fast rechargeability and safety of LIBs. Herein, we investigate the Li plating behavior in porous electrodes under the restricted transport of Li+. Based on the theoretical model, it can be concluded that the Li plating on the anode-separator interface (ASI) is thermodynamically feasible and kinetically advantageous. Meanwhile, the prior deposition of metal Li on the ASI rather than the anode-current collector interface (ACI) is verified experimentally. In order to facilitate the transfer of Li+ among the electrode and improve the utilization of active materials without Li plating, a bilayer asymmetric anode composed of graphite and hard carbon (GH) is proposed. Experimental and simulation results suggest that the GH hybrid electrode homogenizes the lithiated-rate throughout the electrode and outperforms the pure graphite electrode in terms of the rate performance and inhibition of Li plating. This work provides new insights into the behavior of Li plating and the rational design of electrode structure.

Shear force effect of the dry process on cathode contact coverage in all-solid-state batteries

The state-of-the-art all-solid-state batteries have emerged as an alternative to the traditional flammable lithium-ion batteries, offering higher energy density and safety. Nevertheless, insufficient intimate contact at electrode-electrolyte surface limits their stability and electrochemical performance, hindering the commercialization of all-solid-state batteries. Herein, we conduct a systematic investigation into the effects of shear force in the dry electrode process by comparing binder-free hand-mixed pellets, wet-processed electrodes, and dry-processed electrodes. Through digitally processed images, we quantify a critical factor, ‘coverage’, the percentage of electrolyte-covered surface area of the active materials. The coverage of dry electrodes was significantly higher (67.2%) than those of pellets (30.6%) and wet electrodes (33.3%), enabling superior rate capability and cyclability. A physics-based electrochemical model highlights the effects of solid diffusion by elucidating the impact of coverage on active material utilization under various current densities. These results underscore the pivotal role of the electrode fabrication process, with the focus on the critical factor of coverage.

3D-printed channel-aligned core-sheath architecture with high sulfur loading for kinetics-enhanced Li–S battery

Sluggish kinetics in thick cathode with high sulfur (S) loading will lead to low active material utilization and fast capacity decay, thus hampering the practical applications of Li–S batteries. To tackle such issue, a slightly thickness-dependent cathode of activated carbon (AC)-S/single-walled carbon nanotube (SWNT)@SWNT with fast reaction kinetics is constructed via continuously printing core-sheath filaments. Such micro-filaments are composed of vertically aligned “thin AC-S/SWNT” in core layer and porous SWNT-strengthened shell layer, which constructs an appealing well-interconnected porous 3D architecture ensuring fast ion/electron/mass transport throughout the whole printed matrix, effectively expediting electrochemical kinetics even under a high S loading. Moreover, the SWNTs located in shell layer and intercalated in-between AC-S phase in core layer crosslink well for acting as the functional interlayer to suppress polysulfide shuttling, thereby enabling high S utilization. As a result, the 3D-printed thick AC-S/SWNT@SWNT cathode delivers outstanding gravimetric/areal capacity (752 mAh g−1/6.41 mAh cm−2 at 0.5C) and cycling performance under high S loading of 8.6 mg cm−2.

Operando Investigation on the Role of Densification and Chemo‐Mechanics on Solid‐State Cathodes

AbstractAll solid‐state batteries are desirable for a range of energy storage applications which require high energy density. Achieving a high energy density in a solid‐state battery requires the operation of an energy dense anode with a composite solid‐state cathode. Pores and/or voids within a solid state cathode are ion‐blocking and thus control over the concentration and distribution of pores in the initial electrode and cycled electrode is desirable. This study provides an understanding of the interplay between electrode microstructure and mechanics on active material utilization in solid state cathodes composed of NCM 811 and Li6PS5Cl. Decreasing the solid electrolyte particle size leads to greater active material‐electrolyte contact and less total deformation when exposed to an external load. Composite cathodes with greater compliance can potentially decrease strain between the active material and solid electrolyte, decrease delamination events and result in higher overall active material utilization and high capacity retention.