Electrochemical Energy Storage Devices Research Articles

Single-Particle Imaging Reveals the Electrical Double-Layer Modulated Ion Dynamics at Crowded Interface.

The dynamics of ion transport at the interface is the critical factor for determining the performance of an electrochemical energy storage device. While practical applications are realized in concentrated electrolytes and nanopores, there is a limited understanding of their ion dynamic features. Herein, we studied the interfacial ion dynamics in room-temperature ionic liquids by transient single-particle imaging with microsecond-scale resolution. We observed slowed-down dynamics at lower potential while acceleration was observed at higher potential. Combined with simulation, we found that the microstructure evolution of the electric double layer (EDL) results in potential-dependent kinetics. Then, we established a correspondence between the ion dynamics and interfacial ion composition. Besides, the ordered ion orientation within EDL is also an essential factor for accelerating interfacial ion transport. These results inspire us with a new possibility to optimize electrochemical energy storage through the good control of the rational design of the interfacial ion structures.

Interpenetrated Structures for Enhancing Ion Diffusion Kinetics in Electrochemical Energy Storage Devices

HighlightsA new and compact device configuration was created with two interpenetrated, individually addressable electrodes, allowing precise control over the geometric features and interactions between the electrodes.The interpenetrated electrode design improves ion diffusion kinetics in electrochemical energy storage devices by shortening the ion diffusion length and reducing ion concentration inhomogeneity.The device with interpenetrated electrodes outperformed the traditional separate electrode configuration, enhancing both volumetric energy density and capacity retention rate.

All-in-All: Dead Lithium-Ion Battery to Active Lithium-Ion Capacitor.

Here, we have developed lithium-ion capacitors (LICs) with all the components, except the electrolyte solution, effectively recycled from the spent Lithium-ion batteries (LIBs). Hybrid capacitors, such as LICs, are potential breakthroughs in electrochemical energy storage devices, where most research is focused. These devices can simultaneously guarantee high energy and power by hybridizing battery-type and capacitive-type electrodes with two different reaction mechanisms. We have successfully upcycled the graphite, current collector, separator, etc., from the spent LIBs to fabricate a high-performance LIC. Our LIC consists of recovered graphite (RG) coated over recovered copper foil as an anode, recycled polypropylene as the separator, and reduced graphene oxide (rGO) synthesized from RG as the cathode. The RG half-cell exhibited an excellent specific capacity of 302 mAh g-1 even after 75 charge-discharge cycles with a coulombic efficiency of >99 %. The Li/rGO displayed remarkable cycling performance for over 1000 cycles with high stability and reversibility. Subsequently, the pre-lithiated RG (p-RG) electrode is paired with the rGO electrode under the balanced loading conditions to construct LIC, rGO/p-RG, delivering a maximum energy density of 185 Wh kg-1 with ultra-long durability of more than 10,000 cycles. The possibility of LIC under different climatic conditions is also explored, and its remarkable performance under various temperature conditions is worth mentioning.

Extrusion‐Based Additive Manufacturing of Carbonaceous and Non‐Carbonaceous Electrode Materials for Electrochemical Energy Storage Devices

Extrusion‐Based Additive Manufacturing of Carbonaceous and Non‐Carbonaceous Electrode Materials for Electrochemical Energy Storage Devices

Nitrogen and sulfur co-doped carbonized lignin nanotubes for supercapacitor applications

Carbon electrode material is crucial for the development of electric double-layered supercapacitor in clean energy storage and rechargeable aspects. Although lignin consists the promising biomass based carbon resource for containing higher carbon atom ratio than 60 %, it is still the difficult challenge to precisely tailoring the porous structure characteristics and surface property to facilitate the electrolyte penetration and rapid ion transportation. Herein, the lignin nanotubes (LNT) were successfully synthesized in a convenient molecular self-assembly way, which were subsequently carbonized and activated, with introduction of melamine as nitrogen doping agent, into hetero-atom doped lignin carbon nanotubes (LCNT) as electrode material for supercapacitor. The resultant LCNT exhibit excellent pore structure, and high degree of graphitization. At a current density of 0.5 A/g, the as high specific capacitance as 391.4 F/g was achieved. Furthermore, under symmetric double-layered capacitor electrode systems, the as prepared N, S co-doped LCNT electrode demonstrated a specific capacitance of 28.6 F/g at a high current density of 20 A/g, which presented a practically applicable energy storage efficiency. It has convincingly demonstrate the substantial potential of LCNT as biomass derived carbon materials for electrochemical energy storage devices, positioning them as a promising and competitive candidate for electrode materials.

Self-assembled 3D CoSe-based sulfur host enables high-efficient and durable electrocatalytic conversion of polysulfides for flexible lithium-sulfur batteries

Lithium-sulfur (Li-S) batteries are considered as promising candidates for next-generation energy storage systems. However, the commercial applications are severely limited by the sluggish kinetics and shuttling effect. Herein, we have designed an integrated free-standing functional CoSe-CNF-GO-MXene (CCGM) sulfur host with a “point-line-plane” 3D porous structure for Li-S batteries. The two-dimensional (2D) graphene, MXene and one-dimensional (1D) nanocellulose fibers combined with zero-dimensional (0D) transition metal selenide (CoSe) shows good electrical conductivity and enhanced catalytic performance, respectively. Additionally, the rationally designed porous structure (from 0D to 3D) demonstrates well-connected ion/electron transport channels, conferring the good kinetic performance. Electrochemical tests show that CoSe catalytic materials with moderate adsorption energies can catalyse both precipitation and dissolution processes of Li2S, enabling fast conversion kinetics. The density functional theory (DFT) calculations show that the synergistic effect of CoSe, Ti3C2Tx, and graphene can improve the chemisorption and catalytic performance. As a result, the 3D porous S@CCGM cathode exhibits a high initial discharge capacity of 1205.1 mAh g−1 at 0.2C and good long-term cycling performance with a low decay rate of 0.055 % per cycle at 1C. Furthermore, the gel electrolyte Li-S pouch cell successfully passes the 0–180° bending test, nailing test, and cutting test. Such design offers a new perspective for the commercialization of safe and flexible electrochemical energy-storage devices especially in Li-S batteries.

Graphene-supported MN4 single-atom catalysts for multifunctional electrocatalysis enabled by axial Fe tetramer coordination

Multifunctional electrocatalysts for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) are crucial for development of the key electrochemical energy storage and conversion devices, for which single-atom catalyst (SAC) has present great promises. Very recently, some experimental works showed that structurally well-defined ultra-small transition-metal clusters (such as Fe and Co tetramers, denoted as Fe4 and Co4, respectively), can efficiently modulate the catalytic behavior of SACs by axial coordination. Herein, taking the graphene-supported MN4 SACs as representatives, we theoretically explored the feasibility of realizing multifunctional SACs for ORR, OER and HER by this novel axial coordination engineering. Through extensive first-principles calculations, from 23 candidates, IrN4 decorated with Fe4 (IrN4/Fe4) is identified as the promising trifunctional catalyst with the theoretical overpotential of 0.43, 0.51 and 0.30 V for OER, ORR and HER, respectively. RhN4/Fe4 and CoN4/Fe4 are recognized as potential OER and ORR bifunctional catalysts. In addition, NiN4/Fe4 exhibits the best ORR activity with an overpotential of 0.30 V, far superior to the pristine NiN4 SAC (0.88 V). Electronic structure analyses reveal that the significantly enhanced ORR/OER activity can be ascribed to the orbital and charge redistribution of Ni/Ir active center, resulting from its electronic interaction with Fe4 cluster. This work could stimulate and guide the rational design of graphene-based multifunctional SACs realized by axial coordination of small TM clusters, and provide insights into the modulation mechanism.

Off-Stoichiometry of Sodium Iron Pyrophosphate as Cathode Materials for Sodium-Ion Batteries with Superior Cycling Stability.

As one of the important devices for large-scale electrochemical energy storage, sodium-ion batteries have received much attention due to the abundant resources of raw materials. However, whether it is a base station power source, an energy storage power station, or a start-stop power supply, long energy cycle life (more than 5000 cycles), high stability, and safety performance are application prerequisites. Regrettably, currently, few sodium-ion batteries can meet this requirement, mainly due to shortcomings in positive electrode performance. We report a sufficiently stable sodium-ion battery cathode material, Na2Fe0.95P2O7, that retains 97.5% capacity after 5000 charge/discharge cycles. The use of nonstoichiometry in the lattice enables simultaneous modification of the crystal and electronic structure, promoting Na2Fe0.95P2O7 to be extremely stable while still being able to achieve a capacity of 92 mAh g-1 and stable cycling at high temperatures up to 60 °C. Our results confirm the positive effect of nonstoichiometric ratios on the performance of Na2Fe0.95P2O7 and provide a reliable idea to promote the practical application of sodium-ion batteries.

Electrochemical Investigation of ZnS/NiO Nanocomposite based Symmetric Supercapattery

AbstractSupercapattery is an ideal energy storage device combining the features of supercapacitors and batteries, offers a high‐energy density as well as high‐power density with extended operational lifespan. In this work, zinc sulfide (ZnS) and zinc sulfide/nickel oxide (ZnS/NiO) nanocomposite was synthesized via chemical coprecipitation method and characterized using state‐of‐the‐art analytical tools. The ZnS/NiO electrode exhibited remarkable electrochemical performance as an electrode material than pure ZnS. The ZnS/NiO nanocomposite exhibited high crystallinity, and spherical nanoparticles with an average grain size of 20–40 nm having a homogeneous dispersion. The ZnS/NiO electrode exhibited an ultrahigh specific capacity of 1803.87 Cg−1 at a relatively low scan rate of 10 mVs−1 in a 1 M KOH solution from cyclic voltammetry and 393 Cg−1 at 16 Ag−1 from charge discharge measurements, and it showed exceptional cycling stability (98 % capacity retention after 1000 cycles). Furthermore, the ZnS/NiO symmetric supercapattery device exhibited 44.43 Fg−1 specific capacitance, 5.52 Wh kg−1 energy density, and 1600 Wkg−1 power density at current density of 0.8 Ag−1 in 1 M KOH solution from galvanostatic charge discharge. After 3000 cycles, the ZnS/NiO nanomaterial demonstrated promising cyclic stability of 95 %. The ZnS/NiO supercapattery nanocomposite might be considered as a potential hybrid electrode material for the future development of electrochemical energy storage devices.

Synergistic Advancements in Battery-Grade Energy Storage: AgCoS@MXene@AC Hybrid Electrode Material as an Enhanced Electrocatalyst for Oxygen Reduction Reaction

The extreme usage of fossil fuels and the rising conservation deterioration have made developing clean, renewable energy essential. Among the most promising methods for addressing the world’s energy dilemma are electrochemical energy storage devices (EES); batteries and supercapacitors (SCs) are two typical components in this class. Supercapacitors are incredibly impressive since they can store energy remarkably in seconds. In this work, we present a highly effective electrode material (AgCoS@MXene) for supercapattery device application that is produced hydrothermally. We examined the morphology and crystallinity of the synthesized materials using SEM and XRD studies. The synthesized compounds were subjected to a thorough electrochemical performance study employing a three-electrode configuration in a 1 M KOH electrolyte. AgCoS@MXene demonstrated an exceptional Qs of 943.22 C g−1 at a current density of 2.0 A g−1. We formed a supercapattery device (AgCoS@MXene//AC) with AgCoS@MXene as the positive electrode and activated carbon (AC) as the negative electrode. The supercapattery device was demonstrated to have a high specific capacity of 315.22 C g−1, a power density of 1275 W kg−1, and an energy density of 35.94 Wh kg−1. In addition, 5000 charging and discharging cycles were used to assess the device’s long-term longevity. The findings indicated that the device preserved nearly 82% of its initial capacity. Besides, the hybrid electrode is used for the electrocatalytic activity for the oxygen reduction reaction. These promising findings imply that AgCoS@MXene is a beneficial electrode material for upcoming energy storage devices to enhance the electrocatalytic activity for the oxygen reduction reaction.

3D printing of porous hollow nanosphere MoS2@NiS/rGO scaffolds empowering long-cycle sodium-ion batteries

Sodium-ion batteries (SIB), as one of the most appealing electrochemical energy storage devices in the field of energy storage, consistently require optimization for both capacity and long-term cycling performance. The amalgamation of diverse material modification techniques with up-and-coming 3D printing technology presents a promising yet relatively underexplored avenue. Herein, we report a composite material, MoS2@NiS/rGO, as the anode material for SIB, achieving high reversible capacity and outstanding long-term cycling performance, surpassing current reported levels. Through carefully designed anode electrode structure and component interface engineering, the material rate capability (with a capacity of 289.5 mAh g−1 at 0.1 A g−1 and 66.8 mAh g−1 at 5 A g−1) and cycling stability (maintaining a capacity of 131.3 mAh g−1 after 800 cycles at 1 A g−1) are significantly enhanced. The reasons for the improvement in electrochemical performance are elucidated through detailed electrochemical analysis. Encouragingly, we showcase the fabrication of a sodium-ion full battery entirely through 3D printing (3DP), achieving an area loading capacity as high as 8.23 mg cm−2 and retaining a capacity of 82.1 mAh g−1 after 240 cycles at 0.1 A g−1. This work underscores the pivotal significance of 3D-printed sodium-ion batteries in advancing the frontier of energy storage technology.

Insight Understanding of External Pressure on Lithium Plating in Commercial Lithium‐Ion Batteries

AbstractLithium‐ion batteries (LIBs), as efficient electrochemical energy storage devices, have been successfully commercialized. Lithium plating at anodes has been attracting increasing attention as batteries advance toward high energy density and large size, given its pivotal role in affecting the lifespan, safety, and fast‐charging performance of LIBs. Lithium plating mostly happens during fast charging or charging at low temperatures. However, external pressure is often overlooked as an essential factor that influences lithium plating in LIBs. This review analyzes and discusses the influence of external pressure on performance for commercial LIBs, with a particular focus on lithium plating. Recent advances in this topic, including experimental results and mechanism analyses, are reviewed. Lithium plating is explored by examining the influence of pressure on the internal morphology and electrochemical behavior of batteries. It is emphasized that external pressure affects performance through ion transport, electron transport, and their heterogeneities, thereby increasing the risk of lithium plating in batteries. Subsequently, the rationale for external pressure mitigating lithium plating is elucidated from the perspective of the morphology optimization inside LIBs. Overall, this review provides valuable insights into the role of external pressure on lithium plating in commercial LIBs, practically guiding their rational design and development.

Harnessing halides: Comparative study of oxide fullerene modifications for sodium ion secondary battery efficiency

The quest for secondary batteries drives ongoing research aimed at developing cost-effective and high-performance nanomaterials. While lithium-ion batteries initially offered high efficiency, however escalating demand has led to increased costs prompting exploration of other alternatives such as sodium (Na) ion batteries. Na resources are much more abundant and widely distributed globally compared to lithium. This study explores the potential of sodium ion battery by adopting a novel approach of incorporating endohedral halides into oxides fullerenes to enhance the voltage. We investigated the thermodynamic and electronic stabilities of Na/Na+ ions with both bare and halide-doped magnesium oxides (Mg12O12) and zinc oxides (Zn12O12) fullerenes to understand how encapsulated halide affects the structural and electrochemical properties. The bare oxide fullerenes exhibit cell voltages of 0.29 and −0.50 V in the presence of toluene solvent. Upon incorporation of various halide ions into oxides fullerenes, we obtained cell voltage in acceptable range for anode materials. Specifically, the variation in free energy experiences a remarkable improvement where the Cl−@Zn12O12 in toluene has the most appropriate cell voltage of 1.09 V in the presence of toluene solvent, among all halides adsorbed oxides nanocages. These findings provide valuable insights for the design of novel low-cost nanomaterials having better cell voltage. The endeavor additionally catalyzes further research work into the design of halide-encapsulated oxide-fullerene-based secondary batteries, intended for widespread applications in electrochemical energy storage devices. This comprehensive work serves as a detailed blueprint for experimentalists, facilitating the synthesis of such systems to address the future challenges posed by energy scarcity.

Monitoring the Behavior of Na Ions and Solid Electrolyte Interphase Formation at an Aluminum/Ionic Liquid Electrode/Electrolyte Interface via Operando Electrochemical X-ray Photoelectron Spectroscopy.

In electrochemical energy storage devices, the interface between the electrode and the electrolyte plays a crucial role. A solid electrolyte interphase (SEI) is formed on the electrode surface due to spontaneous decomposition of the electrolyte, which in turn controls the dynamics of ion migration during charge and discharge cycles. However, the dynamic nature of the SEI means that its chemical structure evolves over time and as a function of the applied bias; thus, a true operando study is extremely valuable. X-ray photoelectron spectroscopy (XPS) is a widely used technique to understand the surface electronic and chemical properties, but the use of ultrahigh vacuum in standard instruments is a major hurdle for their utilization in measuring wet electrochemical processes. Herein, we introduce a 3-electrode electrochemical cell to probe the behavior of Na ions and the formation of SEI at the interface of an ionic liquid (IL) electrolyte and an aluminum electrode under operando conditions. A system containing 0.5 molar NaTFSI dissolved in the IL [BMIM][TFSI] was investigated using an Al working electrode and Pt counter and reference electrodes. By optimizing the scan rate of both XPS and cyclic voltammetry (CV) techniques, we captured the formation and evolution of SEI chemistry using real-time spectra acquisition techniques. A CV scan rate of 2 mVs-1 was coupled with XPS snapshot spectra collected at 10 s per core level. The technique demonstrated here provides a platform for the chemical analysis of materials beyond batteries.

Iron-Cobalt Phosphide Encapsulated in a N-Doped Carbon Framework as a Promising Low-Cost Oxygen Reduction Electrocatalyst for Zinc-Air Batteries.

The oxygen reduction reaction (ORR) plays a vital role in many next-generation electrochemical energy conversion and storage devices, motivating the search for low-cost ORR electrocatalysts possessing high activity and excellent durability. In this work, we demonstrate that iron-cobalt phosphide (FeCoP) nanoparticles encapsulated in a N-doped carbon framework (FeCoP@NC) represent a very promising catalyst for the ORR in alkaline media. The core-shell structured FeCoP@NC catalyst offered outstanding ORR activity with a half-wave potential (E1/2) of 0.86 V vs reversible hydrogen electrode (RHE) and excellent stability in a 0.1 M KOH electrolyte, outperforming commercial Pt/C and many recently reported noble-metal-free ORR electrocatalysts. The superiority of FeCoP@NC as an ORR electrocatalyst relative to Pt/C was further verified in prototype zinc-air batteries (ZABs), with the aqueous and flexible ZABs prepared using FeCoP@NC offering excellent stability, impressive open circuit voltages (1.56 and 1.44 V, respectively), and high maximum power densities (183.5 and 69.7 mW cm-2, respectively). Density functional theory calculations revealed that encapsulating FeCoP nanoparticles in N-doped carbon shells resulted in favorable electron penetration effects, which synergistically regulated the adsorption/desorption of ORR intermediates for optimal ORR performance while also boosting the electronic conductivity. Our findings offer valuable new insights for rational design of transition metal phosphide-based catalysts for the ORR and other electrochemical applications.

Ultrathin carbon film as ultrafast rechargeable cathode for hybrid sodium dual-ion capacitor

The development of electrochemical energy storage devices has a decisive impact on clean renewable energy. Herein, novel ultrafast rechargeable hybrid sodium dual-ion capacitors (HSDICs) were designed by using ultrathin carbon film (UCF) as the cathode material. The UCF is synthesized by a simple low temperature catalytic route followed by an acid leaching process. UCF owns a large adsorption interface and number of additional active sites, which is due to the nitrogen doping. In addition, there exists several short-range order carbons on the surface of UCF, which are beneficial for anionic storage. An ultrafast rechargeable remarkable performance, remarkable anion hybrid storage capability and outstanding structure stability is fully tapped employing UCF as cathode for HSDICs. The electrochemical performance of UCF in a half-cell system at the operating voltage between 1.0 and 4.8 V, achieving an admirable specific discharge capacity of 358.52 mAh·g−1 at 500 mA·g−1, and a high capacity retention ratio of 98.42% after cycling 2500 times at 1000 mA·g−1, respectively. Besides, with the support of ex-situ TEM and EDS mapping, the structural stability principle and anionic hybrid storage mechanism of UCF electrode are investigated in depth. In the full-cell system, HSDICs with the UCF as cathode and hard carbon as anode also presents a super-long cycle stability (80.62% capacity retention ratio after cycling 1300 times at 1000 mA·g−1).

Battery electronification: intracell actuation and thermal management

Electrochemical batteries – essential to vehicle electrification and renewable energy storage – have ever-present reaction interfaces that require compromise among power, energy, lifetime, and safety. Here we report a chip-in-cell battery by integrating an ultrathin foil heater and a microswitch into the layer-by-layer architecture of a battery cell to harness intracell actuation and mutual thermal management between the heat-generating switch and heat-absorbing battery materials. The result is a two-terminal, drop-in ready battery with no bulky heat sinks or heavy wiring needed for an external high-power switch. We demonstrate rapid self-heating (∼ 60 °C min−1), low energy consumption (0.138% °C−1 of battery energy), and excellent durability (> 2000 cycles) of the greatly simplified chip-in-cell structure. The battery electronification platform unveiled here opens doors to include integrated-circuit chips inside energy storage cells for sensing, control, actuating, and wireless communications such that performance, lifetime, and safety of electrochemical energy storage devices can be internally regulated.

Conductive Zinc-Based Metal–Organic Framework Nanorods as Cathodes for High-Performance Zn-Ion Capacitors

Zinc-ion capacitors (ZICs), combining the merits of both high-energy zinc-ion batteries and high-power supercapacitors, are known as high-potential electrochemical energy storage (EES) devices. However, the research on ZICs still faces many challenges because of the lack of appropriate cathode materials with robust crystal structures and rich channels for stable and fast Zn2+ ion transport. In this study, we synthesized a robust, conductive, two-dimensional metal–organic framework (MOF) material, zinc-benzenehexathiolate (Zn-BHT), and investigated its electrochemical performance for zinc storage. Zn2+ ions could insert into/extricate from the host structure with a high diffusion rate, enabling the Zn-BHT cathode to exhibit a surface-controlled charge storage mechanism. Due to its unique structure, Zn-BHT exhibited a good reversible discharge capacity approaching 90.4 mAh g−1 at 0.1 A g−1, as well as a desirable rate capability and good cycling performance. In addition, a ZIC device was fabricated using the Zn-BHT cathode and a polyaniline-derived porous carbon (PC) anode, which depicted a high working voltage of up to 1.8 V and a high energy density of ~37.2 Wh kg−1. This work shows that conductive MOFs are high-potential electrode materials for ZICs and provide new enlightenment for the development of electrode materials for EES devices.

The High-Performance Polymer Electrolytes Based on Agarose–Mg(ClO4)2 for Application in Electrochemical Energy Storage Devices

Electrochemical energy storage devices (EES) such as batteries and supercapacitors depend significantly on electrolytes, which have properties that significantly impact their energy capacity, rate performance, cyclability, and safety. Agarose–Mg(ClO4)2–based polymer electrolyte was prepared using the solution casting method by incorporating various amounts of Mg(ClO4)2 from 0 – 35 wt%. The presence of Mg(ClO4)2 as the dopant in agarose-matrix enhanced the ionic conductivity of the system from 1.796 × 10-8 S∙cm-1 to 6.247 × 10-4 S∙cm−1 in the composition of 30 wt% Mg(ClO4)2 due to the production of free ions. This system obeys the Arrhenius rule as it records the conductivity increment when temperature increases. This increment shows the amorphous nature of electrolytes, which XRD analyses by determining the crystallite size and degree of crystallinity of agarose–Mg(ClO4)2 polymer electrolyte. High ionic conductivity at room temperature has increased attention to this polymer electrolyte based on agarose–Mg(ClO4)2.

MOF‐Derived Porous Carbon for Zinc‐ion Hybrid Capacitors with Ultra‐High Energy Density and Long Cycling Life

AbstractZinc‐ion hybrid capacitors (ZHC) have been considered as emerging sustainable electrochemical energy storage devices. They integrate the benefits of high‐energy density of aqueous zinc ion battery (ZIB) with high‐power density of supercapacitor (SC). Metal‐organic frameworks (MOFs) have been widely used to design electrode materials for portable devices, especially in some energy storage fields because of their large specific surface area and adjustable pore structures. In this work, we prepare porous Mn3O4/C nanosheets with Mn‐BDC as a precursor. The assembled device delivers a specific capacitance of 155.3 mAh g−1 at a current of 3 A g−1 and keeps a retention rate of 97.7 % after 10,000 cycles. Moreover, it provides an energy density of 464.5 Wh kg−l at a power density of 100 W kg−1.