High Cycle Life Research Articles

Sulfuric acid treatment to control the microcrystalline structure of starch-based hard carbon for sodium storage

By treating starch with different concentrations of sulfuric acid, we investigated the effect of cross-linked starch-based hard carbon on the performance of sodium-ion batteries (SIBs) at various concentrations. After treatment, the optimal sample exhibits a spherical microstructure, which can provide effective active sites and enhance structural stability, thereby achieving high capacity and long cycle life for SIB electrodes. In subsequent electrochemical tests, after 100 cycles at low current density of 0.1 A g−1, the capacity of H40 remains of 306 mA h g−1. And under the high current density of 1 A g−1, the capacity of H40 can still maintain of 228 mA h g−1, exhibiting a high capacity retention rate of 89 %, which is higher than other samples. This study provides a promising approach for the large-scale production of biomass-derived carbonaceous SIBs anodes.

Laser-formed nanoporous graphite anodes for enhanced lithium-ion battery performance

Lithium-ion batteries are pivotal in modern energy storage, commonly utilizing graphite anodes for their high theoretical capacity and long cycle life. However, graphite anodes face inherent limitations, such as restricted lithium-ion storage capacity and slow diffusion rates. Enhancing the porosity of graphite and increasing d-spacing in expanded graphite anodes have been explored to improve lithium-ion diffusion and intercalation. Recent advancements suggest that nanoscale modifications, such as utilizing nano-graphite and graphene, can further enhance performance. Laser processing has emerged as a promising technique for synthesizing and modifying graphite and graphene-related materials, offering control over surface defects and microstructure. Here, we demonstrate an industrially compatible one-step laser processing method to transform a nano-graphite and graphene mixture into a nanoporous matrix, significantly improving lithium-ion battery performance. The laser-processed anodes demonstrated significantly enhanced specific capacities at all charge rates, with improved relative performance at higher charge rates. Additionally, long-term cycling at 1 C showed that laser-processed cells outperformed their non-processed counterparts, with specific capacities of 323 and 241 mAh/g, respectively.

Solid‐State Revolution: Assessing the Potential of Solid Polymer Electrolytes in Lithium‐Ion Batteries

AbstractLithium‐ion batteries (LIBs) are crucial for achieving sustainable energy goals due to their high energy density and long cycle life. They dominate markets like consumer electronics, electric vehicles, and stationary energy storage systems. However, current LIBs use liquid electrolytes, which are toxic, flammable, and their liquid state does not resist dendrite growth, causing battery capacity decline and failure. Additionally, the limited availability of lithium and other metals makes liquid‐based LIBs less sustainable. On the other hand, solid polymer electrolytes (SPEs) offer a safer alternative as they are non‐volatile and can resist dendrite growth. However, ion transport in solids is much more restricted than in liquids, while imperfect solid‐solid interfaces contribute to interfacial resistance leading to lower ionic conductivity and increasing Ohmic losses or requiring battery operation at elevated temperatures. Chemical and mechanical degradation of these interfaces can also result in battery capacity fade, and poorer cyclic performance compared to liquid electrolytes. Understanding the ionic transport mechanisms in SPEs is critical for designing and optimizing the nanostructure of polymers and polymer/electrode interfaces to overcome these limitations. In this review, the fundamental mechanisms of ion transport in SPEs will first be explored. Various state‐of‐the‐art approaches for addressing the key challenges in SPEs and their solutions are then discussed. Furthermore, the current status of SPEs is analyzed to determine their potential for replacing liquid electrolytes in the future.

Architecting V2O5 with a Triune Crystal Water-Amorphous-Crystalline Feature for Robust Zinc-Ion Batteries.

The notorious collapse of the electrode structure and strong electrostatic interactions in aqueous zinc-ion batteries (AZIBs) limit the achievement of a long cycle life. Herein, by designing an ordered/disordered hybrid structure, we have effectively preserved the integrity of the V2O5·1.6H2O (VOH) electrode. Moreover, our approach facilitates the release of stress concentration contributed to by the amorphous component, alleviating the strong electrostatic interaction merited by crystal water and promoting the diffusion kinetics of Zn2+ assisted by the crystalline component. Noteworthy, the crystal water serves as an interlayer pillar significantly enhancing the structural stability of the electrode. As a result, our VOH electrode exhibits high electrochemical performance. It delivered 227.8 mAh g-1 at a higher current density of 2 A g-1, and a high cycle life of 1000 cycles with 95% capacity retention was achieved at a current density of 1 A g-1.

PV-fed multi-output buck converter-based renewable energy storage system with extended current control for lifetime extension of Li-ion batteries

Recently, there has been a visible intensification of research on increasing the cycle life of energy storage devices used in Photovoltaic (PV)-fed energy storage systems (ESS). Compared to existing battery technologies, Lithium-ion (Li-ion) batteries have advantages such as high energy density and high cycle life. However, many existing Hybrid energy storage system (HESS) suffers from the fact that Li-ion batteries have limited cycle life, calendar and cycle aging. Therefore, attention has shifted towards the charging techniques necessary to improve the service life of Li-ion batteries by increasing their cycle life and reducing capacity losses. One such approach is to charge the battery by gradually increasing it from a certain level, rather than starting the charging process directly with the maximum charging current. This study proposes Extended Current Control (ECC) to reduce battery capacity losses and extend service life in PV-fed HESSs. The maximum power point (MPP) of the PV module is provided by the Perturb and observe (P&O) algorithm via the supercapacitor (SC) converter, while ECC is performed via the battery converter. This approach requires less hardware, unlike optimization, rule, or filtering based techniques. Controlling the battery current over a large area protects the battery packs from high currents at the start of charge and reduces capacity losses by increasing cycle life. Compared to PV-fed ESS containing only battery packs, the proposed technique provides a 40 % improvement in battery charging current, an 8 % improvement in the converter duty ratio in reaching the MPP point, and a 31.69 % improvement in battery capacity fades.

In-situPreparation ofIron(II)-phthalocyanine@multi-walled-CNTs Nanocomposite for Quasi-solid-state Flexible Symmetric Supercapacitors with Long Cycling Life.

The construction of supercapacitor electrode materials with exceptional performance is the crucial to the commercialisation of flexible supercapacitors. Here, a novel in-situ precipitation technique was applied for constructing iron(II)-phthalocyanine (FePc) based nanocomposite as the electrode material in quasi-solid-state flexible supercapacitors. The highly redox-active FePc nanostructures were grown in the multi-walled-CNTs (MWCNTs) networks, which shows convenient electron/electrolyte ion transport pathways along with outstanding structural stability, leading to high energy storage and long cycling life. The electrode of FePc@MWCNTs delivered a higher specific capacity than that of individual MWCNTs and FePc. The quasi-solid-state symmetric flexible device that was constructed using FePc@MWCNTs electrode demonstrated impressive performance with a maximum energy density of 29.7 Wh kg-1 and a maximum power density of 4000 W kg-1. Moreover, the device demonstrated superior durability and flexibility, as evidenced by its exceptional cyclic stability (111.3%) even after 30000 cycles at 8 A g-1. These results reveal that the FePc@MWCNTs nanocomposite prepared by this simple in-situ precipitation method is promising as electrode material for next-generation flexible wearable power sources.

High-capacity, fast-charging and long-life magnesium/black phosphorous composite negative electrode for non-aqueous magnesium battery

Secondary non-aqueous magnesium-based batteries are a promising candidate for post-lithium-ion battery technologies. However, the uneven Mg plating behavior at the negative electrode leads to high overpotential and short cycle life. Here, to circumvent these issues, we report the preparation of a magnesium/black phosphorus (Mg@BP) composite and its use as a negative electrode for non-aqueous magnesium-based batteries. Via in situ and ex situ physicochemical measurements, we demonstrate that Mg ions are initially intercalated in black phosphorus two-dimensional structures, forming chemically stable MgxP intermediates. After the formation of the intermediates, Mg electrodeposition reaction became the predominant. When tested in the asymmetric coin cell configuration, the Mg@BP composite electrode allowed stable stripping/plating performances for 1600 h (800 cycles), a cumulative capacity of 3200 mAh cm−2, and a Coulombic efficiency of 99.98%. Assembly and testing of the Mg@BP | |nano-CuS coin cell enabled a discharge capacity of 398 mAh g−1 and an average cell discharge potential of about 1.15 V at a specific current of 560 mA g−1 with a low decay rate of 0.016% per cycle for 225 cycles at 25 °C.

Cation/Anion Doping Strategy for Na4MnV(PO4)3 with High Energy Density and Long Cycling Life through Construction by Aspergillus niger.

Na4MnV(PO4)3 (NMVP) has gained attention for its high redox potential, good cycling stability, and competitive price but suffers from poor intrinsic electronic conductivity and Jahn-Teller effect from Mn3+. In this work, cation/anion doping strategy was used for Aspergillus niger-bioderived carbon-coated NMVP (NMVP/AN) to improve the structural stability and electrochemical performance, where Al3+ doping inhibited the dissolution of Mn and enhanced the Mn3+/Mn2+ redox pair activity; besides, F- doping not only weakens the Na2-O bond but also endows the hierarchical and porous structure of NMVP/AN, which led to a more rapid and fluid transfer of Na+. The elaborately designed Na3.9Mn0.9Al0.1V(PO4)3/AN (NMAVP/AN) exhibits 105.9 mA h g-1 at 0.5 C, and the as-prepared Na3.1MnV(PO3.7F0.3)3/AN (NMVPF/AN) delivers 104.1 mA h g-1 at 5 C. Further demonstration of the hard carbon//NMAVP/AN full cell manifests the good potential of Al3+-doped NMVP/AN for practical applications (100.6 mA h g-1 at 1 C). These findings open up the possibility of unlocking the high-performance Na superionic conductor (NASICON).

Compositional Engineering of Lithium Metal Anode for High-Performance Garnet-Type Solid-State Lithium Battery.

Garnet-type solid-state lithium batteries (SSLBs) possess excellent potential owing to their safety and high energy density. However, fundamental barriers are deficient cycling stability and poor rate capability. The main concern lies in generating voids at the Li|garnet interface during Li stripping, stemming from the sluggish diffusion of Li atoms inside the bulk Li metal. Herein, a composite anode (AN@Li) containing Li-Al alloy, Li3N, and LiNO2 is designed by introducing aluminum nitrate into molten Li. The lower interfacial formation energies exhibited by Li-Al alloy, Li3N, and LiNO2 with garnet solid-state electrolyte (SSE) enhance the wettability of AN@Li toward SSE. Meanwhile, it affords efficient conductive pathways that facilitate Li+ diffusion in the bulk anode (not just on the surface). Impressively, the resulting symmetric cell with AN@Li electrodes achieves high critical current density (1.95mA cm-2) and long cycle life (6000h at 0.3mA cm-2). The SSLB coupled with LiFePO4 cathode and AN@Li anode enables stable cycling for 200 cycles at a high rate of 1 C with a retention of 96% and exhibiting outstanding rate capability (145.9 mAh g-1 at 2 C). This work provides practical insights for producing high-performance lithium metal anode for advanced garnet-type SSLBs.

Recent Advances in the Application of Magnetite (Fe3O4) in Lithium-Ion Batteries: Synthesis, Electrochemical Performance, and Characterization Techniques.

With the promotion of portable energy storage devices and the popularization of electric vehicles, lithium-ion battery (LiB) technology plays a crucial role in modern energy storage systems. Over the past decade, the demands for LiBs have centered around high energy density and long cycle life. These parameters are often determined by the characteristics of the active materials in the electrodes. Given its high abundance, environmental friendliness, low cost and high capacity, magnetite (Fe3O4) emerges as a promising anode material. However, the practical application of Fe3O4 faces challenges, such as significant volume expansion during cycling. To overcome these obstacles and facilitate the commercialization of Fe3O4, a comprehensive understanding of its properties and behavior is essential. This review provides an overview of recent Fe3O4 research advances, focusing on its synthesis, factors influencing its electrochemical performance, and characterization techniques. By thoroughly understanding the characteristics of Fe3O4 in LiB applications, we can optimize its properties and enhance its performance, thereby paving the way for its widespread use in energy storage applications. Additionally, the review concludes with perspectives on promoting the commercialization of Fe3O4 in LiBs and future research directions.

Challenges and Approaches to Designing High‐Energy Density Lithium‐Sulfur Pouch Cells

Lithium‐sulfur (Li‐S) batteries are of great interest as next‐generation energy storage devices in a wide variety of applications, due to their high specific capacity and the environmental abundance of sulfur. However, liquid electrolyte Li‐S technology faces several challenges such as polysulfide shuttling, anode corrosion and sluggish cathode kinetics. Practical deployment of Li‐S batteries requires evaluation in large‐format, high energy density pouch cells. Stringent operating conditions such as high sulfur loading and operating current, low electrolyte amount, and limited anode quantity are required for high energy density pouch cells, which further curtails the electrochemical performance and cycle life. This review aims to provide an understanding of the different failure mechanisms of large‐format Li‐S pouch cells and formulate key design parameters of Li‐S pouch cells that have high capacity, coulombic efficiency and long cycle life. Recent developments in Li‐S pouch cells are then discussed, focusing on cathode and electrolyte design for polysulfide immobilization, accelerated sulfur conversion kinetics, and Li anode protection. A review of advanced characterization techniques suitable for Li‐S pouch cell studies is also provided. Finally, viewpoints are offered on the remaining challenges and prospects to guide future research in scaling up Li‐S technology for real‐world applications.

Bamboo-templated MOF-67-derived carbon: A high-performance electrode for supercapacitors

Carbon-based supercapacitors are highly regarded for their high specific power and long cycle life. However, they often face the challenge of low specific energy and difficulty in simultaneously improving both specific energy and specific power. In this study, a high-performance composite electrode was prepared using the cross-section of bamboo as raw material, followed by KOH activation, in-situ growth of ZIF-67, and carbonization. The bamboo-derived porous carbon showed significant improvement in performance indicators such as specific capacitance and energy density. Electrochemical characterization in a three-electrode system showed that at a current density of 1 mA cm−2, our composite electrode material achieved a peak specific capacitance of 24.7 F cm−2. When assembled into a symmetric supercapacitor, it can provide an energy density of 1.00 mWh cm−2 at a power density of 2.49 mW cm−2. Notably, at a substantial current density of 30 mA cm−2, the electrode maintained a capacitance retention of 96.2 % after 10,000 cycles. These results not only highlight the potential of bamboo-derived porous carbon but also point to a broad avenue for the preparation of energy storage devices by combining MOFs with bamboo.

Electrochemical and structural properties of binder-free iron-based bifunctional catalyst for aqueous Zinc-Oxygen batteries

Global warming necessitates efficient new batteries, with Zn-O2 batteries standing out due to their high theoretical energy density, safety, and long cycle life, making them ideal for large-scale use. However, their industrial application faces challenges such as rapid energy density decline after initial cycles, limited cathode efficiency, and high overpotential between discharge and charge. This study focuses on synthesizing and characterizing ceramic iron compounds as catalysts for the cathode of Zn-O2 aqueous batteries. The findings revealed that obtained catalysts presented surface active areas beyond 220 m2/g after calcination at 800 °C, which removed organic templates. Various thermal treatments have been analysed to measure their impact on the final product. XRD, FTIR, and Raman spectroscopy confirmed sample nitridation, while SEM showed macro–meso-porosity. The electrochemical evaluation demonstrated a significant enhancement in the material's catalytic properties for ORR/OER in alkaline Zn-O2 batteries, surpassing 140 h of satable cyling with catalytic activity for ORR and OER. This improvement, coupled with optimized electrode design, resulted in a substantial increase in the batteries' operational life, achieving stable cycling for over 120 h.

Robust ring insoluble naphthoquinone derivative cathode with high loading and long cycle life for aqueous zinc organic batteries

Robust ring insoluble naphthoquinone derivative cathode with high loading and long cycle life for aqueous zinc organic batteries

A High Current Density and Long Cycle Life Iron Chromium Redox Flow Battery Electrolyte

A High Current Density and Long Cycle Life Iron Chromium Redox Flow Battery Electrolyte

Protic Stabilization Engenders High Energy Density and Long Cycle Life in Polyaniline–Zinc Supercapacitors

The redox activities of polyaniline (PANI) are hindered by the instability of pernigraniline salt (PS) state which degrades into oligo‐aniline. In this work, the use of protic additives is examined to mitigate capacity fading and increase utilization of PANI in nonaqueous electrolytes. The protic additive propylene glycol, with its hydrogen‐bonding capabilities, stabilizes the PS PANI and promotes reversible redox reactions, facilitating high capacity and an extended cycle lifetime for applications in metal ion supercapacitors. The use of this protic nonaqueous electrolyte in a PANI–zinc device results in an energy density of 255 Wh kg−1 at a power density of 1.8 kW kg−1 and a robust cycle lifetime of 3,850 charge/discharge cycles. The PANI at a high current density of 6.5 mA cm−2 reaches a capacity of 257 mAh g−1, equivalent to 87% of the its theoretical capacity, showcasing the effectiveness of the protic additive in improving both capacity and cycle life in electrochemical supercapacitors.

The design of chemisorption and catalysis synergistic defender for efficient room temperature sodium-sulfur batteries

Room temperature sodium-sulfur (RT-Na/S) batteries are a promising candidate for large-scale energy storage systems owing to their low manufacturing cost and high energy density. However, the severe shuttle effects and sluggish reaction kinetics hinder their practical application. Here, a Fe3Se4 nanoparticle anchored three-dimensional nitrogen-doped porous carbon nanosheet was designed as a functional defender to inhibit the shuttle effect and achieve high sulfur utilization. The porous carbon nanosheet builds a fast platform for electron and ion transport and acts as a limiting barrier for polysulfide dissolution and shuttling. Additionally, Fe3Se4 nanoparticles are incorporated to enhance the chemical anchoring and catalytic activity of polysulfides. The ex-situ characterization revealed that the Fe sites can feed electrons to polysulfides, thus facilitating the conversion of long-chain polysulfides to Na2S, resulting in high sulfur availability (323 mAh/g at 2 A/g) and long-term cycle life (72 % capacity retention at 1 A/g for 500 cycles).

Mn2+-Modified Ammonium Vanadate as High Rate and Long Cycle Life Cathode for Aqueous Zinc Ion Batteries

Mn²⁺-Modified Ammonium Vanadate as High Rate and Long Cycle Life Cathode for Aqueous Zinc Ion Batteries

The significant enhancement of energy density by redox and molecular crowding synergistic effects for aqueous zinc-ion hybrid capacitors

Aqueous zinc-ion hybrid capacitors (ZHCs) combine the high energy density of metal-ion batteries with the advantages of fast charging and discharging, high power density and long cycle life of capacitors, and are considered to be one of the most promising next-generation energy storage devices. However, the low operating voltage of aqueous electrolyte and the capacity mismatch between the capacitive cathode and the zinc anode lead to the unsatisfactory energy density of ZHCs. To improve the energy output for ZHCs, we designed an active aqueous electrolyte with high working voltage window by utilizing molecular crowding effect of polyethylene glycol (PEG) and the effect between redox-active ions (3I−/I3−). This high-voltage active aqueous electrolyte exhibits a wide voltage window of 2.2 V by inhibiting the hydrogen evolution in HER. The specific capacity of optimal ZHCs is boosted to 469 F g1 by the additional psedocapacitance from ZnI2 redox additive. The energy density of ZHCs reaches 287.3 Wh kg−1 and the capacity retention remains at 91.6 % after 7000 cycles. These results indicate that the proposed high-voltage active aqueous electrolyte is not only facile and effective for ZHCs, but also can be applied to other aqueous device for high energy density and practical application.

(Invited) Redox Flow Batteries – Exploring Electrolyte Additives and Hybrid Organic/Inorganic Redox Pairs

Renewable energy sources are intermittent and thus require provision to store the energy when available using energy storage devices. These energy storage devices should be safe, efficient, and have a long life cycle for use in grid-scale energy storage systems. Lead-acid, Li-ion, and Redox Flow Batteries (RFBs) are examples of such energy storage devices. Among these energy storage systems, RFBs have unique advantages that make them attractive for large-scale energy storage applications, like a high cycle life of about 10,000 cycles.[1] The current generation of commercial RFBs use vanadium solution in different oxidation states as electrolytes (anolyte and catholyte), carbon-based electrodes and Nafion as the ion-exchange membrane. High cost, risk of electrolyte crossover, low volumetric energy density, and pumping losses limit the vanadium redox flow batteries (VRFBs).[2] Also, the Nafion membrane accounts for about 40% of the system's total cost.[3] To ensure high cycle life, the electrolytes must be stable (active material must remain dissolved in the supporting electrolyte), and vanadium ions should not crossover the Nafion membrane. The VRFBs tend to lose vanadium from electrolyte solutions due to the precipitation of V2O5 during charging, resulting in a significant loss of energy density. Additives help in maintaining the long-term stability of vanadium electrolytes. In this work, we have monitored the solubility and electrochemical characteristics of vanadium electrolyte solutions with V2O5 in the presence of different additives, namely HCl and MSA (methanesulfonic acid), for over three months.[4] The findings of this study provide insight into using these additives for VRFBs. Further research in RFBs has recently shifted towards redox-active aqueous-organic-based electrolytes consisting of Earth-abundant elements (C, H, O, N, S), accommodating the need for green, safe, and low-cost energy storage. We have studied the feasibility of using quinone-based organic electrolytes for RFBs. A proof-of-concept membrane-free two-compartment cell with an auxiliary electrode in each compartment was also demonstrated. In the conventional design, the hydrogen ions move through the Nafion membrane to balance charges but in the auxiliary electrode-based membrane-free setup, the auxiliary electrode in each compartment undergoes redox reactions opposite to the primary electrodes to balance charges.[5]References[1] Y.E. Durmus, H. Zhang, F. Baakes, G. Desmaizieres, H. Hayun, L. Yang, M. Kolek, V. Küpers, J. Janek, D. Mandler, S. Passerini, Y. Ein‐Eli, Side by Side Battery Technologies with Lithium‐Ion Based Batteries, Adv. Energy Mater. 10 (2020). https://doi.org/10.1002/aenm.202000089.[2] B. Turker, S. Arroyo Klein, E.M. Hammer, B. Lenz, L. Komsiyska, Modeling a vanadium redox flow battery system for large scale applications, Energy Convers. Manag. 66 (2013) 26–32. https://doi.org/10.1016/j.enconman.2012.09.009.[3] J. Ye, D. Yuan, M. Ding, Y. Long, T. Long, L. Sun, C. Jia, A cost-effective nafion/lignin composite membrane with low vanadium ion permeation for high performance vanadium redox flow battery, J. Power Sources. 482 (2021) 229023. https://doi.org/10.1016/j.jpowsour.2020.229023.[4] O.H. Nguyen, P. Iyapazham Vaigunda Suba, M. Shoaib, V. Thangadurai, Investigating the Electro-Kinetics and Long-Term Solubility of Vanadium Electrolyte in the Presence of Inorganic Additives, J. Electrochem. Soc. 170 (2023) 110523. https://doi.org/10.1149/1945-7111/ad0a75.[5] S.V. Venkatesan, K. Karan, S.R. Larter, V. Thangadurai, An auxiliary electrode mediated membrane-free redox electrochemical cell for energy storage, Sustain. Energy Fuels. 4 (2020) 2149–2152. https://doi.org/10.1039/c9se00734b.