Performance Of Rechargeable Batteries Research Articles

Building Li–S batteries with enhanced temperature adaptability via a redox-active COF-based barrier-trapping electrocatalyst

Covalent organic frameworks (COFs) are promising materials for mitigating polysulfide shuttling in lithium-sulfur (Li–S) batteries, but enhancing their ability to convert polysulfides across a wide temperature range remains a challenge. Herein, we introduce a redox-active COF (RaCOF) that functions as both a physical barrier and a kinetic enhancer to improve the temperature adaptability of Li–S batteries. The RaCOF constructed from redox-active anthraquinone units accelerates polysulfide conversion kinetics through reversible C=O/C-OLi transformations within a voltage range of 1.7 to 2.8 V (vs. Li+/Li), optimizing sulfur redox reactions in ether-based electrolytes. Unlike conventional COFs, RaCOF provides bidentate trapping of polysulfides, increasing binding energy and facilitating more effective polysulfide management. In-situ XRD and ToF-SIMS analyses confirm that RaCOF enhances polysulfide adsorption and promotes the transformation of lithium sulfide (Li2S), leading to better sulfur cathode reutilization. Consequently, RaCOF-modified Li–S batteries demonstrate low self-discharge (4.0% decay over a 7-day rest), excellent wide-temperature performance (stable from −10 to +60 °C), and high-rate cycling stability (94% capacity retention over 500 cycles at 5.0 C). This work offers valuable insights for designing COF structures aimed at achieving temperature-adaptive performance in rechargeable batteries.

Unraveling the Dynamic Properties of New-Age Energy Materials Chemistry Using Advanced In Situ Transmission Electron Microscopy.

The field of energy storage and conversion materials has witnessed transformative advancements owing to the integration of advanced in situ characterization techniques. Among them, numerous real-time characterization techniques, especially in situ transmission electron microscopy (TEM)/scanning TEM (STEM) have tremendously increased the atomic-level understanding of the minute transition states in energy materials during electrochemical processes. Advanced forms of in situ/operando TEM and STEM microscopic techniques also provide incredible insights into material phenomena at the finest scale and aid to monitor phase transformations and degradation mechanisms in lithium-ion batteries. Notably, the solid-electrolyte interface (SEI) is one the most significant factors that associated with the performance of rechargeable batteries. The SEI critically controls the electrochemical reactions occur at the electrode-electrolyte interface. Intricate chemical reactions in energy materials interfaces can be effectively monitored using temperature-sensitive in situ STEM techniques, deciphering the reaction mechanisms prevailing in the degradation pathways of energy materials with nano- to micrometer-scale spatial resolution. Further, the advent of cryogenic (Cryo)-TEM has enhanced these studies by preserving the native state of sensitive materials. Cryo-TEM also allows the observation of metastable phases and reaction intermediates that are otherwise challenging to capture. Along with these sophisticated techniques, Focused ion beam (FIB) induction has also been instrumental in preparing site-specific cross-sectional samples, facilitating the high-resolution analysis of interfaces and layers within energy devices. The holistic integration of these advanced characterization techniques provides a comprehensive understanding of the dynamic changes in energy materials. This review highlights the recent progress in employing state-of-the-art characterization techniques such as in situ TEM, STEM, Cryo-TEM, and FIB for detailed investigation into the structural and chemical dynamics of energy storage and conversion materials.

Electron Spin Polarization in Rechargeable Batteries: Theoretical Foundation and Practical Applications

AbstractElectron spin polarization (ESP) refers to the alignment of electron spins in a specified direction, with burgeoning research underscoring its pivotal role in enhancing rechargeable batteries. This review delves into the theoretical underpinnings of ESP and its intricate connection to the performance of rechargeable batteries, elucidating its potential to augment charge/discharge efficiency, elevate energy density, and refine overall battery functionality. The review further encompasses an overview of experimental methodologies employed to probe ESP in rechargeable battery systems, spotlighting seminal discoveries from contemporary studies and evaluating the hurdles and prospects linked to its practical applications. The profound advantages of ESP for rechargeable batteries are underscored, suggesting that harnessing this phenomenon can empower researchers and engineers to develop batteries with superior energy storage capacities, swifter charging rates, and extended cycle lifespans. Such advancements can expedite the adoption of electric vehicles and the seamless integration of renewable energy sources into power grids, among other high‐energy‐demand applications. In conclusion, this review offers invaluable perspectives on rechargeable batteries through the lens of ESP, with the insights presented here expected to catalyze further research and innovation in the energy storage sector, thereby advancing the development of sustainable and efficient rechargeable battery technologies.

(Invited) Electrolyte Design for Wide-Temperature Lithium Batteries

Improving the wide temperature performance of rechargeable batteries is vital to the operation of electronics and vehicles in extreme environments, where systems capable of higher energy, high-rate discharge and long cycling are in short supply. In this talk, we will show electrolyte designs to achieve high-energy density and stable cycling performance in wide temperature range, especially in extremely low-temperature environment. We will use a few examples, including ester- and ether-based electrolyte with different concentrations to showcase the critical role of solvation and desolvation in determining the charge-transfer kinetics at low-temperature. We will also discuss the role of solvation structure in shaping interfacial stability in different cathode and anode systems. These fundamental understanding may provide viable design strategies for high energy density and long-life batteries for both high and extremely low temperatures such as rechargeable Li metal batteries using both high-Ni oxide and sulfur cathodes.

Correlation Between Electrical Conductivity of Solid Electrolyte Interphase and Rechargeable Battery Performance Revealed by Cryo and In Situ TEM

Correlation Between Electrical Conductivity of Solid Electrolyte Interphase and Rechargeable Battery Performance Revealed by Cryo and In Situ TEM

Electrochemical performance of P4Se3 as high-capacity anode materials for monovalent and multivalent ion batteries

The increasing need for advanced anode materials with superior performance in rechargeable batteries has driven investigations into cutting-edge energy storage systems. This study delves into the potential of P4Se3 Molecular Cages (MCs) as innovative anode materials for both monovalent and multivalent ion batteries, including Na ion batteries (NIBs), Mg ion batteries (MIBs), Ca ion batteries (CIBs), Al ion batteries (AIBs), and Zn ion batteries (ZIBs) through a comprehensive Density Functional Theory (DFT) and molecular dynamics (MD) based investigations. The analyses encompass the electronic structure, structural stability, electrochemical performance, charge storage mechanisms, and redox properties to offer valuable insights into the potential of P4Se3 as an anode. The DFT calculations unveil critical aspects of adsorption, diffusion, and reaction kinetics in P4Se3 elucidating its potential as high-capacity and suitable anode material. The exothermic reactions between Na, Mg, Ca, Al, and Zn with host P4Se3 highlight its suitability for the intercalation process in monovalent and multivalent ion batteries. Furthermore, calculated storage capacities for NIB, MIB, CIB, AIB, and ZIB are found as 1484.84 mAhg−1, 519.69 mAhg−1, 1410.60 mAhg−1, 593.93 mAhg−1, and 74.24 mAhg−1 respectively. The voltage profiles indicate favorable open circuit voltages (OCV) of 0.31 V, 0.27 V, 0.55 V, and 3.3 V for NIB, MIB, CIB, and AIB respectively. The study employs climbing image nudged elastic band (Cl-NEB) simulations to compute diffusion barriers faced by monovalent and multivalent ions in the host structure. The calculated minimal diffusion barriers of 0.18 eV for NIB, 0.30 eV for MIB, 0.35 eV for CIB, 0.33 eV for AIB, and 0.71 eV for ZIB indicate fast charging capabilities due to efficient ion movement. Furthermore, the respective calculated values of diffusion coefficient are found as 5.27 × 10−10 m2/s, 5.27 × 10−9, 4.0 × 10−10 m2/s, 5.27 × 10−10 m2/s and 5.27 × 10−11 m2/s and respective values of ionic conductivity σ are found as 4.13 × 10−3 S/m, 14.57 × 10−2 S/m, 30.03 × 10−3 S/m, 16.65 × 10−3 S/m and 0.20 × 10−3 S/m for NIBs, MIBs, CIBs, AIBs and ZIBs. The findings of this study point out suitability of P4Se3 as anode material in monovalent and multivalent ion batteries.

Computational Investigation of LiF Formation at Graphite-Electrolyte Interfaces.

The performance of rechargeable batteries is strongly influenced by the solid-electrolyte interphase (SEI), and a comprehensive understanding of SEI formation from the atomic level is crucial for effective battery design. The dynamics of the electrode-electrolyte interface is important and needs to be considered when evaluating the mechanism of the SEI formation. Here, we employed ab initio molecular dynamics (AIMD) and density functional theory (DFT) calculations to examine interfacial behaviors and LiF formation. Through molecular dynamics and structure sampling, we successfully constructed an electrochemical stability diagram correlating the thermodynamic free energy with the potential, which is determined by the work function of electrode surfaces. DFT calculations revealed that LiF formation at the graphite-electrolyte interfaces occurs easily via the intermediate LiHF complex. Interestingly, LiF tends to be solvated by solvents rather than directly deposited onto electrode surfaces (e.g., the Au electrode), a phenomenon we identify as a critical determinant of the porous and uneven nature of the LiF layer observed on graphite electrodes. Our finding offers new mechanistic insights into LiF formation at graphite-electrolyte interfaces.

Three solid electrolyte interphases of aqueous zinc batteries

With the increasing demand for enhanced safety performance of rechargeable batteries, water-based zinc-ion batteries have witnessed rapid development due to their exceptional safety characteristics. And, zinc batteries have been widely used in a diverse of various fields such as electric vehicles and electric bicycles. However, the dendrite issue and limited cycle life of the negative electrode pose significant challenges that hinder further advancements in this technology, which greatly limits the development of zinc batteries. For this reason, extensive research has been conducted on various solid electrolyte interphases related to the battery anode. By comprehensively understanding and comparing three materials of solid electrolyte interphase (SEI) utilizing similar controlled negative ion techniques, it can validate the accuracy of this theoretical approach. The utilization of these three materials results in a substantial improvement in battery performance compared to the original battery, particularly in terms of service life; however, each material also exhibits distinct advantages and drawbacks.

High-Entropy Oxides for Rechargeable Batteries.

High-entropy oxides (HEOs) have garnered significant attention within the realm of rechargeable batteries owing to their distinctive advantages, which encompass diverse structural attributes, customizable compositions, entropy-driven stabilization effects, and remarkable superionic conductivity. Despite the brilliance of HEOs in energy conversion and storage applications, there is still lacking a comprehensive review for both entry-level and experienced researchers, which succinctly encapsulates the present status and the challenges inherent to HEOs, spanning structural features, intrinsic properties, prevalent synthetic methodologies, and diversified applications in rechargeable batteries. Within this review, the endeavor is to distill the structural characteristics, ionic conductivity, and entropy stabilization effects, explore the practical applications of HEOs in the realm of rechargeable batteries (lithium-ion, sodium-ion, and lithium-sulfur batteries), including anode and cathode materials, electrolytes, and electrocatalysts. The review seeks to furnish an overview of the evolving landscape of HEOs-based cell component materials, shedding light on the progress made and the hurdles encountered, as well as serving as the guidance for HEOs compositions design and optimization strategy to enhance the reversible structural stability, electrical properties, and electrochemical performance of rechargeable batteries in the realm of energy storage and conversion.

Manipulating the corrosion homogeneity of aluminum anode toward long‐life rechargeable aluminum battery

AbstractAluminum metal batteries are considered to be promising secondary batteries due to their high theoretical specific capacity. However, metallic aluminum suffers from corrosion, pulverization, and crushing problems in nonaqueous electrolytes. Constructing a solid‐electrolyte interphase layer on the anode electrode has been confirmed to be the key to improving the cycling performance of rechargeable batteries. Herein, we demonstrate an Al metal anode with a physical protective layer achieved by a simple blade coating method. This modified Al metal anode demonstrates ultra‐low voltage hysteresis (~25 mV at 0.1 mA cm−2 and ~30 mV at 1 mA cm−2), and superior stability (630 h at 0.1 mA cm−2 and 580 h at 1 mA cm−2). When coupling this anode with flake graphite cathode, the assembled full cells exhibit superior cycling stability (92 mAh g−1 maintained after 740 cycles at 0.1 A g−1). The current work presents a promising approach to stabilize Al metal anodes for next‐generation rechargeable aluminum batteries.

Rational Design of High-Loading Electrodes with Superior Performances Toward Practical Application for Energy Storage Devices.

High-loading electrodes play a crucial role in designing practical high-energy batteries as they reduce the proportion of non-active materials, such as current separators, collectors, and battery packaging components. This design approach not only enhances battery performance but also facilitates faster processing and assembly, ultimately leading to reduced production costs. Despite the existing strategies to improve rechargeable battery performance, which mainly focus on novel electrode materials and high-performance electrolyte, most reported high electrochemical performances are achieved with low loading of active materials (<2mgcm-2). Such low loading, however, fails to meet application requirements. Moreover, when attempting to scale up the loading of active materials, significant challenges are identified, including sluggish ion diffusion and electron conduction kinetics, volume expansion, high reaction barriers, and limitations associated with conventional electrode preparation processes. Unfortunately, these issues are often overlooked. In this review, the mechanisms responsible for the decay in the electrochemical performance of high-loading electrodes are thoroughly discussed. Additionally, efficient solutions, such as doping and structural design, are summarized to address these challenges. Drawing from the current achievements, this review proposes future directions for development and identifies technological challenges that must be tackled to facilitate the commercialization of high-energy-density rechargeable batteries.

High-stability room temperature ionic liquids: enabling efficient charge transfer in solid-state batteries by minimizing interfacial resistance

Currently, intensive research is underway to develop stable electrolyte systems that can significantly enhance the performance of rechargeable batteries. Recent advances in solid electrolytes have led to new types of promising systems owing to their high conductivity. This has generated considerable interest in the practical applications of safe batteries. Considering the safety concerns associated with rechargeable batteries, solid electrolytes have become indispensable for the advancement of next-generation battery technologies. However, the increased interfacial resistance at solid-solid interfaces has become a critical challenge. To address this problem, room-temperature ionic liquids (RTILs) have been investigated as functional materials for mitigating the interfacial resistance in solid-state batteries (SSBs). The special properties of RTILs, such as their non-volatility, non-flammability, and high safety characteristics, make them highly promising candidates for safe batteries. Various approaches have been explored for the effective utilization of ionic liquids in SSBs. This review provides a comprehensive discussion on the application of RTILs as electrolytes, considering their electrochemical properties and incorporation into composites to minimize resistance in SSBs.

Electron energy levels determining cathode electrolyte interphase formation

AbstractCathode electrolyte interphase (CEI) has a significant impact on the performance of rechargeable batteries and is gaining increasing attention. Understanding the fundamental and detailed CEI formation mechanism is of critical importance for battery chemistry. Herein, a diverse of characterization tools are utilized to comprehensively analyze the composition of the CEI layer as well as its formation mechanism by LiCoO2 (LCO) cathode. We reveal that CEI is mainly composed of the reduction products of electrolyte and it only parasitizes the degraded LCO surface which has transformed into a disordered spinel structure due to oxygen loss and lithium depletion. Based on the energy diagram and the chemical potential analysis, the CEI formation process has been well explained, and the proposed CEI formation mechanism is further experimentally validated. This work highlights that the CEI formation process is nearly identical to that of the anode‐electrolyte‐interphase, both of which are generated due to the electrolyte directly in contact with the low chemical potential electrode material. This work can deepen and refresh our understanding of CEI.

Interface Regulation via Electric Double Layer for Rechargeable Batteries.

Interphases, especially the electrochemically formed solid electrolyte interphase (SEI), are significantly important for cycling stability, reaction kinetics and safety of rechargeable batteries. The structure and composition of the electric double layer (EDL) greatly affect the formation of the SEI and the performance of electrodes. However, as far as we know, there is no review discussing the theme specifically. Herein, the recent substantial progress for EDL and its impact on the formation of SEI in rechargeable batteries are reviewed and discussed. Firstly, the specific adsorption of electrolyte components on electrodes' surface and the ionic solvation structure are introduced. Furthermore, various methods for controlling EDL in different electrode systems are described. Finally, the potential future advancements of the SEI through the manipulation of EDL are discussed, aiming to enhance the electrochemical performance of rechargeable batteries.

Direct in situ measurements of electrical properties of solid-electrolyte interphase on lithium metal anodes.

The solid-electrolyte interphase (SEI) critically governs the performance of rechargeable batteries. An ideal SEI is expected to be electrically insulative to prevent persistently parasitic reactions between the electrode and the electrolyte and ionically conductive to facilitate Faradaic reactions of the electrode. However, the true nature of the electrical properties of the SEI remains hitherto unclear due to the lack of a direct characterization method. Here we use in situ bias transmission electron microscopy to directly measure the electrical properties of SEIs formed on copper and lithium substrates. We reveal that SEIs show a voltage-dependent differential conductance. A higher rate of differential conductance induces a thicker SEI with an intricate topographic feature, leading to an inferior Coulombic efficiency and cycling stability in Li∣∣Cu and Li∣∣LiNi0.8Mn0.1Co0.1O2 cells. Our work provides insight into the targeted design of the SEI with desired characteristics towards better battery performance.

Dual photoelectrodes activate oxygen evolution and oxygen reduction reactions enabling a high-performance Zn-air battery and an efficient solar energy storage

Traditional Zn-air batteries (ZABs) require a large charge voltage but deliver a small discharge voltage due to their slow kinetics of oxygen evolution and reduction reaction (OER and ORR) on air electrodes. Herein, a novel photorechargeable Zn-air battery (PRZAB) is fabricated by two photoelectrodes to sandwich a Zn electrode, significantly promoting the kinetics of OER and ORR. As a result, the PRZAB achieves an ultra-low charge voltage of 0.63 V and a remarkably high discharge voltage of 1.64 V at a current density of 0.1 mA cm−2, leading to a considerable voltage gap of 1.01 V that the process of discharge exceeds charge to be realized in ZABs. Compared with the ZAB with a state-of-the-art Pt/C catalyst, the charge energy of the PRZAB is saved 184% and its output is enhanced by 18%. Finally, the overall solar-to-output energy conversion efficiency (SOEE) is estimated to be 1.38%. The work provides an innovative way to boost rechargeable battery performance and offers an efficient strategy to store and utilize solar energy.

Chemical and electrochemical synergistic weaving stable interface enabling longevous zinc plating/stripping process

Dendrites growth and hydrogen evolution reaction of Zn anode greatly hinder the practical application of aqueous zinc ion batteries. Interface engineering strategies have attracted immense interest in addressing these challenges. Herein, a chemical and electrochemical method is proposed to synergistically weave a stable interface by introducing AgNO3 additive in conventional aqueous ZnSO4 electrolyte. The formed compact Ag layer acts as zincophilic sites, which is beneficial for zinc ion nucleation and growth. Consequently, the cell cycled in 2 M ZnSO4 with 3 mM AgNO3 electrolyte exhibits much more stable electrochemical properties than its counterpart. To be specific, the Zn || Zn half cell using the electrolyte with 3 mM AgNO3 shows reversible Zn plating/stripping behavior over 1350 h at 5.0 mA cm−2 with an ultra-low potential hysteresis. Moreover, Zn || V2O5 full cell using the electrolyte with 3 mM AgNO3 exhibits glorious rate capability and more stable cycling performance, attributing to the inhibited zinc dendrites growth by the weaved interfacial layer. This work sheds new light on improving the electrochemical performance of rechargeable batteries.

Alloy-Type Lithium Anode Prepared by Laser Microcladding and Dealloying for Improved Cycling/Rate Performance.

Nanosized alloy-type materials (Si, Ge, Sn, etc.) present superior electrochemical performance in rechargeable batteries. However, they fail to guarantee cycling capacity and stability under high mass loading required by industrial applications due to low electric contact and adhesive strength, which has long been a challenge. This work proposes a rational design for an alloy-type anode via facile and versatile laser microcladding and dealloying. The proposed anode features a large-area porous network composed of continuous nano-ligaments, which consist of evenly distributed nanosized alloy-type material metallurgically bonded with conductive material. The fabrication of the structure is validated using Ge-Cu and Sn-Cu anodes, both exhibiting enhanced cycling stability at high areal capacity and rate performance in lithium-ion batteries. The enhancement is attributed to the structural features, which contribute to lithiation-delithiation stability and intact electron/Li ion transference path, as verified by in situ and ex situ transmission electron microscopy observations. More importantly, the critical solidification conditions of laser microcladding are provided by a multiphysics simulation, allowing for a thorough understanding of the structural formation mechanism. The study provides a possible approach to improve mass loading and performance of an alloy-type anode for practical application.

High-performance effective metal–organic frameworks for electrochemical applications

Metal–organic frameworks (MOFs) are a versatile category of porous coordination polymers which can be differentiated from other porous nanomaterials due to their fascinating properties such as adaptable surface chemistry, tuneable functionalities, and exceedingly large surface area and uniform/controllable pore size. This newly emerging family of materials with such extraordinary attributes has generated strong research interest, making pristine MOFs and MOF based hybrids a potential platform for a diverse range of applications. However, inferior electrical conductivities and poor chemical stabilities in aqueous solutions have narrowed MOF's application base. In this review article, recent advancement in the synthesis techniques of MOFs and the impact of various production parameters on their physical, chemical, and electrochemical characteristics have been discussed in detail. In addition, their electrochemical performance in rechargeable batteries, supercapacitors, fuel cells and electrochemical sensors has been discussed briefly. Furthermore, future research direction and anticipated challenges have also been reviewed.

Asynchronous-to-Synchronous Transition of Li Reactions in Solid-Solution Cathodes.

The composition dynamics regulate the accessible capacity and rate performance of rechargeable batteries. Heterogeneous Li reactions can lead to nonuniform electrochemical activities and amplify mechanical damage in the cell. Here, we employ operando optical microscopy as a laboratory tool to map the spatial composition heterogeneity in a solid-solution cathode for Li-ion batteries. The experiments are conducted at slow charging conditions to investigate the thermodynamic origins. We observe that the active particles charge asynchronously with reaction fronts propagating on the particle surfaces during the first charge, while subsequent (dis)charge cycles transition to a synchronous behavior for the same group of particles. Such transition is understood by computational modeling, which incorporates the dependence of Li diffusivity and interfacial reaction rate on the state of charge. The optical experiments and theoretical modeling provide insight into the reaction heterogeneity of porous electrodes and electrochemical conditioning for layered oxide cathodes.