Advanced Cathode Materials Research Articles

Asymmetric supercapacitors assembled by hollow N, s co-doped carbon spheres decorated FeOOH and Co3S4 nanoparticles

Exploiting advanced anode and cathode materials with distinctive architectures and multi-component participation is of great significance to boosting the energy density of asymmetric supercapacitors. Herein, ultra-fine FeOOH nanoparticles are in situ grown on the hollow N, S co-doped carbon (HNSC) spheres using a facile solvothermal strategy and subsequent calcination process. Benefiting from the attractive hollow architecture and the synergistic effect between FeOOH and HNSC, the FeOOH/HNSC composite as anode for supercapacitors delivers an optimal capacity of 588.2C g−1 (1 A g−1) and remains 88.3 % of its initial value after 10,000 cycles at 15 A g−1 in 6 M KOH. Furthermore, the HNSC-supported Co3S4 nanoparticles are also prepared through a one-step solvothermal strategy. The obtained Co3S4/HNSC composite as cathode achieves a capacity of 420C g−1 (1 A g−1) and maintains a high retention of 95.3 % after 10,000 cycles at 15 A g−1. The constructed asymmetric supercapacitor using FeOOH/HNSC and Co3S4/HNSC as anode and cathode appears to possess a superior energy density of 82.3 Wh kg−1 at 821.6 W kg−1 with retention of 84.9 % after 10,000 cycles at 10 A g−1. These attainments demonstrate that constructing multi-component electrode materials with unique structures is an effective method to optimize the electrochemical characteristics of asymmetric supercapacitors.

Emerging trends and innovations in all-solid-state lithium batteries: A comprehensive review

All-solid-state lithium batteries, which utilize solid electrolytes, are regarded as the next generation of energy storage devices. Recent breakthroughs in this type of rechargeable battery have significantly accelerated their path towards becoming commercially viable. Nevertheless, the development of such devices is impeded by various obstacles, including limitations in ion transfer capability, interfacial hurdles, and chemical and electrochemical stability. This paper provides a comprehensive review of the latest advancements in all-solid-state lithium-based batteries. The main emphasis is on the fabrication techniques, novel solid electrolytes, and the application of advanced cathode and anode materials to expedite research and development in this field. Moreover, the feasibility of large-scale manufacturing of solid-state batteries has been evaluated. Finally, the most practical and effective approaches for the advancement of these batteries have been proposed and examined.

Insights into Tiny High‐Entropy Doping Promising Efficient Sodium Storage of Na3V2(PO4)2O2F toward Sodium‐Ion Batteries

AbstractBoth high operation voltage and theoretical capacity promise polyanion‐type fluorophosphate Na3V2(PO4)2O2F as a competitive cathode toward high‐energy‐density sodium‐ion batteries (SIBs). However, the intrinsic low kinetic characteristics seriously influence its high‐power property and service life. To well address this, a creative tiny high‐entropy (HE) doping methodology is purposefully developed to fabricate nanoscale Na3V1.94(Cr, Mn, Co, Ni, Cu)0.06(PO4)3O2F (NVPOF‐HE) as the advanced cathode materials for SIBs. The grain refinement effect induced by collaborative regulations from polyvinyl pyrrolidone and tiny HE heteroatomic doping is reasonably proposed for nanosizing particle dimension of NVPOF‐HE. Systematic experiments and theoretical calculations authenticate that the HE doping efficiently promotes the electronic/ionic transport and high‐voltage capacity contribution, and weakens the lattice expansion over Na+‐(de)intercalation processes. Thanks to the appealing virtues mentioned here, the nano NVPOF‐HE, compared to single‐ion/dual‐ion/triple‐ion doped cases, achieves even better Na+‐storage performance in terms of both high‐rate capacities and long‐term cycling stability. Furthermore, the NVPOF‐HE assembled full SIBs deliver a high materials‐level energy density of 463 Wh kg−1 and electrochemical stability of ≈93.8% capacity retention after 1000 cycles at 5 C rate. More essentially, the fundamental insights gained here provide a significant scientific and technological advancement in high‐performance and durable polyanionic cathodes toward next‐generation SIBs.

Recent Advances in High-Entropy Layered Oxide Cathode Materials for Alkali Metal-Ion Batteries.

Since the electrochemical de/intercalation behavior is first detected in 1980, layered oxides have become the most promising cathode material for alkali metal-ion batteries (Li+/Na+/K+; AMIBs) owing to their facile synthesis and excellent theoretical capacities. However, the inherent drawbacks of unstable structural evolution and sluggish diffusion kinetics deteriorate their electrochemical performance, limiting further large-scale applications. To solve these issues, the novel and promising strategy of high entropy has been widely applied to layered oxide cathodes for AMIBs in recent years. Through multielement synergy and entropy stabilization effects, high-entropy layered oxides (HELOs) can achieve adjustable activity and enhanced stability. Herein, the basic concepts, design principles, and synthesis methods of HELO cathodes are introduced systematically. Notably, it explores in detail the improvements of the high-entropy strategy on the limitations of layered oxides, highlighting the latest advances in high-entropy layered cathode materials in the field of AMIBs. In addition, it introduces advanced characterization and theoretical calculations for HELOs and proposes potential future research directions and optimization strategies, providing inspiration for researchers to develop advanced HELO cathode materials in the areas of energy storage and conversion.

A tutorial review on solid oxide fuel cells: fundamentals, materials, and applications

AbstractSolid oxide fuel cells (SOFCs) are recognized as a clean energy source that, unlike internal combustion engines, produces no CO2 during operation when H2 is used as a fuel. They use a highly efficient chemical-to-electrical energy conversion process to convert oxygen and hydrogen into electricity and water. They can provide smaller-scale power for transportation (e.g., cars, buses, and ships) and be scaled up to provide long-term energy for an electrical grid, making SOFCs a promising, clean alternative to hydrocarbon combustion. Conventional SOFCs faced challenges of high operating temperatures, high cost, and poor durability. Research into advanced cathode, anode, electrolyte, and interconnect materials is providing more insight into the ideal structural and chemical properties that enable the commercialization of highly stable and efficient intermediate temperature (IT) SOFCs. In this paper, we discuss the functional properties of the cathode, anode, electrolyte, and interconnectors for IT-SOFCs. The performance of SOFCs depends not only on the materials used but also on the optimization of operating conditions to maximize efficiency. The voltaic, thermodynamic, and fuel efficiency of SOFCs is presented.

MXene Supported Electrodeposition Engineering of Layer Double Hydroxide for Alkaline Zinc Batteries

AbstractThe main challenges faced by aqueous rechargeable nickel‐zinc batteries are their comparatively low energy density and poor cycling stability, mainly due to the limited capacity and reversibility of existing Ni‐based cathodes. Moreover, the preparation procedures of these cathodes are complex and not easily scalable, which makes them less promising for large‐scale energy storage. Herein, we utilized MXene as a functional additive to effectively improve the electrodeposition preparation of NiCo layered double hydroxides (LDH). Benefiting from the improved interfacial contact between nickel foam (NF) and platting solution and the enhanced ionic conductivity of platting product based on MXene additives, the resulting binder‐free NiCo LDH electrode can achieve ultrahigh areal loading (~65 mg cm−2) with abundant active surface for redox reactions and maintained short transport pathway for ion diffusion and charge transfer. Furthermore, the as‐fabricated alkaline NiCo LDH‐based battery delivers high discharge capacity, up to 20.2 mAh cm−2 (311 mAh g−1), accompanied by remarkable rate performance (9.6 mAh cm−2 or 148 mAh g−1 at 120 mA cm−2). Due to the high structural and chemical stability of MXenes/LDH‐based electrode, excellent cycling life can also be achieved with 88.6 % capacity retention after 10000 cycles. In addition, ultrahigh areal energy density (31.2 mWh cm−2) and gravimetric energy density (465 Wh kg−1) can be simultaneously achieved. This work has inspired the design of advanced cathode materials to develop high‐performance aqueous zinc batteries.

Recent Advances in Cathode Materials with Core–Shell Structures and Concentration Gradients for Advanced Sodium‐Ion Batteries

Recent Advances in Cathode Materials with Core–Shell Structures and Concentration Gradients for Advanced Sodium‐Ion Batteries

Pore-Free Single-Crystalline Particles for Durable Na-Ion Battery Cathodes.

The O3-type Na[Ni1-x-yCoxMny]O2 cathodes have received significant attention in sodium-ion batteries (SIBs) due to their high energy density. However, challenges such as structural instability and interfacial instability against an electrolyte solution limit their practical use in SIBs. In this study, the single-crystalline O3-type Na[Ni0.6Co0.2Mn0.2]O2 (SC-NCM) cathode has been designed and synthesized to effectively relieve the degradation pathways of the polycrystalline O3-type Na[Ni0.6Co0.2Mn0.2]O2 (PC-NCM) cathode for SIBs. The mechanically robust SC-NCM due to the absence of pores in the particles enhances tolerance to particle cracking, resulting in stable cycling performance with a cycle retention of 73% over 350 cycles. Moreover, the proposed SC-NCM is synthesized using a simple and cost-effective molten-salt synthetic route without the complex quenching process typically associated with PC-NCM synthesis methods, showing good practical applicability. This study will provide an innovative direction for the development of advanced cathode materials for practical SIBs.

A Strategy to Mitigate Jahn Teller Effect of Mn-Rich NASICON Framework for Sodium-Ion Batteries.

Mn-based sodium superionic conductors have driven attention to the low-cost advanced cathode materials for sodium-ion batteries (SIBs). However, low-rate capability and unsatisfactory cyclic performance due to the Jahn teller effect of Mn3+ redox couple which occurs from the change in Mn-O bond length at the octahedral site of crystal structure during charge-discharge, eventually limiting their application. Herein, a disordered and sodium deficient NASICON Na4-xMn(FeVCrTi)0.25(PO4)3 (termed as Na4-xMn(HE)) is synthesized to mitigate this Jahn teller effect to achieve high rate and ultrastable cathode material. Interestingly, the as-prepared Na3.5Mn(HE) shows five reversible electron reactions (i.e., Ti3+/Ti4+, Fe2+/Fe3+, V3+/V4+, Mn2+/Mn3+, and Mn3+/Mn4+) and demonstrates 141mA h g-1 at 0.2 C with 80% capacity retention at 1 C after 500 cycles which is far superior to its counterparts binary Mn-based materials. The excellent cyclic performance is due to the remediation of the Jahn teller effect in sodium-deficient entropy-stabilized material. The structural reversibility, enhanced kinetics, and electronic properties are further studied in detail by in situ X-ray diffraction (XRD), ex situ X-ray photoelectron spectroscopy (XPS), and first principal calculations. Na3.5Mn(HE)//HC full cell delivered 89.7 mAh g-1 capacity at 0.2 C. This work sheds light on designing Mn-based cathodes with superior electrochemical performance for wide energy storage applications.

Rational design of amorphous vanadium pentoxide and hollow porous carbon spheres hybrid for superior zinc-ion battery

Aqueous zinc-ion batteries (AZIBs) are expected to be a promising large-scale energy storage system owing to their intrinsic safety and low cost. Nevertheless, the development of AZIBs is still plagued by the design and fabrication of advanced cathode materials. Herein, the amorphous vanadium pentoxide and hollow porous carbon spheres (AVO-HPCS) hybrid is elaborately designed as AZIBs cathode material by integrating vacuum drying and annealing strategy. Amorphous vanadium pentoxide provides abundant active sites and isotropic ion diffusion channels. Meanwhile, the hollow porous carbon sphere not only provides a stable conductive network, but also enhances the stability during charging/discharging process. Consequently, the AVO-HPCS exhibits a capacity of 474 mAh/g at 0.5 A/g and long-term cycle stability. Moreover, the corresponding reversible insertion/extraction mechanism is elucidated by ex-situ X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. Furthermore, the flexible pouch battery with AVO-HPCS cathode shows high comprehensive performance. Hence, this work provides insights into the development of advanced amorphous cathode materials for AZIBs.

Enhanced Electrochemical Performance of Double Perovskites as Cathodes in Reversible Ceramic Electrochemical Cells through Nb Doping

Efficient and cost-effective generation of electricity and hydrogen holds promise through reversible protonic ceramic electrochemical cells (R-PCECs). However, the successful commercialization of R-PCECs depends on the advancement of air electrodes that are both highly active and durable. Here, we made an air electrode material with two phases of double perovskite and single perovskite by doping Nb into B-site of the traditional PrBaCo2O6 double perovskite. The coexistence of the mixed double perovskite and single perovskite phases demonstrates superior electrochemical performance and durability compared to pristine double perovskite and single perovskite materials when employed as cathode materials. X-ray photoelectron spectroscopy (XPS), synchrotron radiation X-ray absorption spectroscopy (XAS) and neutron diffraction analysis reveal that this enhancement is primarily attributed to the introduction of high-valence Nb5+, resulting in an increased number of oxygen vacancies and structural stability. The findings presented in this study contribute valuable insights into the design and development of advanced cathode materials for solid oxide fuel cells and electrolyzers, with the potential for applications in sustainable energy conversion and storage technologies.

A Redox-Active Iron-Organic Framework Cathodes for Sustainable Magnesium Metal Batteries.

Rechargeable magnesium metal batteries (RMBs) have shown promising prospects in sustainable energy storage due to the high crustal abundance, safety, and potentially large specific capacity of magnesium. However, their development is constrained by the lack of effective cathode materials that can achieve high capacity and stable magnesium storage at a practically reasonable rate. Herein, we construct a three-dimensional (3D) iron(III)-dihydroxy-benzoquinone (Fe2(DHBQ)3) metal-organic framework (MOF) material with dual redox centers of Fe3+ cations and DHBQ2- anions for reversible storage of Mg2+ in RMBs. Spectroscopic analysis and density functional theory (DFT) calculations reveal the redox chemistry of both Fe3+ ions and carbonyls from DHBQ ligands during electrochemical processes. Benefiting from the rational structure, the Fe2(DHBQ)3∥Mg cells exhibit a high reversible capacity of 395.3 mAh/g, large energy density of 463.5 Wh/kg, and high power density of 2456.0 W/kg. Moreover, the high electronic conductivity (8.35 × 10-5 S/cm) and favorable diffusion path of Mg2+ in Fe2(DHBQ)3 endow the cells with exceptional cycling stability and rate capability with a long life of 5000 cycles at 2000 mA/g. The dual redox-active MOF demonstrates a category of advanced cathode materials for high-performance RMBs.

MXene Supported Electrodeposition Engineering of Layer Double Hydroxide for Alkaline Zinc Batteries.

The main challenges faced by aqueous rechargeable nickel-zinc batteries are their comparatively low energy density and poor cycling stability, mainly due to the limited capacity and reversibility of existing Ni-based cathodes. Moreover, the preparation procedures of these cathodes are complex and not easily scalable, which makes them less promising for large-scale energy storage. Herein, we utilized MXene as a functional additive to effectively improve the electrodeposition preparation of NiCo layered double hydroxides (LDH). Benefiting from the improved interfacial contact between nickel foam (NF) and platting solution and the enhanced ionic conductivity of platting product based on MXene additives, the resulting binder-free NiCo LDH electrode can achieve ultrahigh areal loading (~65 mg cm-2) with abundant active surface for redox reactions and maintained short transport pathway for ion diffusion and charge transfer. Furthermore, the as-fabricated alkaline NiCo LDH-based battery delivers high discharge capacity, up to 20.2 mAh cm-2 (311 mAh g-1), accompanied by remarkable rate performance (9.6 mAh cm-2 or 148 mAh g-1 at 120 mA cm-2). Due to the high structural and chemical stability of MXenes/LDH-based electrode, excellent cycling life can also be achieved with 88.6 % capacity retention after 10000 cycles. In addition, ultrahigh areal energy density (31.2 mWh cm-2) and gravimetric energy density (465 Wh kg-1) can be simultaneously achieved. This work has inspired the design of advanced cathode materials to develop high-performance aqueous zinc batteries.

Core-shell carbon@Ni2(CO3)(OH)2 particles as advanced cathode materials for hybrid supercapacitor: The key role of carbon for enhanced electrochemical properties

Three-dimensional porous Ni2(CO3)(OH)2 compounds were grown on carbon nanopowder using a facile hydrothermal method for the production of core-shell carbon@Ni2(CO3)(OH)2 compounds. This work successfully overcame the shortcomings related to the low electrical conductivity and poor electrical stability caused by the presence of hollows in the Ni2(CO3)(OH)2 structure. The hollow spaces were filled with carbon powder, which acted as a seed material, yielding an ideal electrode material with a large specific surface area, high electrical conductivity, and good stability. A Ni2(CO3)(OH)2 electrode containing 50 mg of carbon powder could store more energy than a Ni2(CO3)(OH)2 electrode without carbon seed materials. The Ni2(CO3)(OH)2 electrode comprising 50 mg of carbon powder has a considerably high specific capacity (181.7 mAh g−1 at 3 A g−1) and excellent cycling stability (77.9 % capacity retention after 5000 cycles), which is 1.5 times higher than that of the Ni2(CO3)(OH)2 electrode without carbon powder. Moreover, an asymmetric supercapacitor using Ni2(CO3)(OH)2 containing 50 mg of carbon powder as the positive electrode and graphene as the negative electrode exhibits a high energy density of 34.2 Wh kg−1 and a power density of 176.1 W kg−1 at a current density of 2 A g−1. Using a combination of carbon and a Ni2(CO3)(OH)2 nanowire compound to increase the electrochemical property and specific surface area, respectively, a suitable synergistic effect can be obtained, which may pave the way for efficient electrode design for high-performance supercapacitors.

Synergistic structure engineering and electrochemical activation modulating vanadium oxide cathode toward superior zinc-ion storage

Aqueous zinc-ion batteries (ZIBs) have emerged as competitive systems for grid-scale energy storage due to their high safety and low cost. However, the lack of suitable high-performance cathode composites limits the practical progress of ZIBs. Herein, a novel cathode material, ammonium cation-inserted and oxygen vacancy co-modulated VO2 (named NVE), was firstly synthesized through the ethylene glycol (EG) sacrificial solvent-assisted structure transformation with the ammonium vanadate (named NV) as the precursor. The sacrificial solvent promotes the structural transformation of ammonium vanadate to NH4+-intercalated vanadium oxide and enhances the number of oxygen vacancies in the resulting material. Moreover, the electrochemical activation process was performed for in-situ construction of NH4+-inserted hydrated vanadium oxide (V2O5·nH2O) material. The electrochemical activation process with high anodic voltage enables multiple electron reactions, increasing the utilization of vanadium elements and achieving high capacity. Additionally, the formed hydrogen bonds between the V-O host and inserted NH4+ ions can enhance the structural integrity, while the oxygen vacancies decrease the interaction between the V-O host and inserted Zn2+ ions to boost ion diffusion. Consequently, the resulting activated cathode demonstrates higher capacity (441 mAh/g at 0.1 A/g), superior cycling durability (85.6 % retention over 4000 cycles), and exceptional rate capability (205 mAh/g at 20 A/g). Besides, the fabricated devices based on the activated NVE cathode show decent capacity and excellent flexible stability. Furthermore, the reversible electrochemical Zn2+ storage mechanism upon battery cycling was evaluated by several kinetic measurements and in/ex-situ characterizations. This work provides novel perspectives for the fabrication of advanced cathode materials for superior aqueous ZIBs.

An Active Strategy to Reduce Residual Alkali for High-Performance Layered Oxide Cathode Materials of Sodium-Ion Batteries.

Residual alkali is one of the biggest challenges for the commercialization of sodium-based layered transition metal oxide cathode materials since it can even inevitably appear during the production process. Herein, taking O3-type Na0.9Ni0.25Mn0.4Fe0.2Mg0.1Ti0.05O2 as an example, an active strategy is proposed to reduce residual alkali by slowing the cooling rate, which can be achieved in one-step preparation method. It is suggested that slow cooling can significantly enhance the internal uniformity of the material, facilitating the reintegration of Na+ into the bulk material during the calcination cooling phase, therefore substantially reducing residual alkali. The strategy can remarkably suppress the slurry gelation and gas evolution and enhance the structural stability. Compared to naturally cooled cathode materials, the capacity retention of the slowly cooled electrode material increases from 76.2% to 85.7% after 300 cycles at 1C. This work offers a versatile approach to the development of advanced cathode materials toward practical applications.

Dual Strategy of Morphology Optimization and Interlayer Expansion in VS2 Cathode Toward High-Performance Mg-Li Hybrid Ion Batteries.

Combining the merits of the dendrite-free formation of a Mg anode and the fast kinetics of Li ions, the Mg-Li hybrid ion batteries (MLIBs) are considered an ideal energy storage system. However, the lack of advanced cathode materials limits their further practical application. Herein, we report a dual strategy of morphology optimization and interlayer expansion for the construction of hierarchical flower-like VS2 architecture coated by N-doped amorphous carbon layers. This tailored hierarchical flower-like structure coupled with homogeneous N-doped amorphous carbon layers cooperatively provide more active sites and buffer volume changes, thus realizing the enhancement of capacity and structural stability. Moreover, the enlarged interlayer spacing caused by the cointercalation of polyvinylpyrrolidone and ammonium ions can effectively promote the charge transfer rate and facilitate the rapid ion diffusion, as further demonstrated by electrochemical results and theoretical calculations. These features endow the hierarchical flower-like VS2 cathode with superior specific energy density (644.4 Wh kg-1, average voltage of 1.2 V vs Mg2+/Mg) and excellent rate capability (181.1 mAh g-1 at 2000 mA g-1). Systematic ex situ characterization measurements are employed to reveal the ion storage mechanism, which confirms that Li+ storage plays a leading role in the capacity contribution of MLIBs. Our strategy is in favor of providing useful insights to design and construct MLIBs with high energy density and excellent rate performance.

V2O5 layered nanofiber as an advanced cathode material in lithium ion batteries

V2O5 layered nanofiber as an advanced cathode material in lithium ion batteries

Insights into Cation Migration and Intermixing in Advanced Cathode Materials for Lithium‐Ion Batteries

AbstractCathode materials are the core components of lithium‐ion batteries owing to the determination of the practical voltage and effective energy of the battery system. However, advanced cathodes have faced challenges related to cation migration and cation intermixing. In this review, the study summarizes the structural failure mechanisms due to the cation mixing of advanced cathodes, including Ni‐rich and Li‐rich layered cathodes, spinel, olivine, and disordered rock‐salt materials. This review starts by discussing the structural degradation mechanisms caused by cation intermixing in different cathodes, focusing on the electronic structure, crystal structure, and electrode structure. Furthermore, the optimization strategies for effective inhibition of cation migration and rational utilization of cation mixing are systematically encapsulated. Last but not least, the remaining challenges and proposed perspectives are highlighted for the future development of advanced cathodes. The accurate analysis of cation migration using advanced characterization, precise control of material synthesis, and multi‐dimensional synergistic modification will be the key research areas for cation migration in cathodes. This review provides a comprehensive understanding of cation migration and intermixing in advanced cathodes. The effective inhibition of cation migration and the rational utilization of cation intermixing will emerge as pivotal and controllable factors for the further development of advanced cathodes.

Recent Progress on Rechargeable Zn-X (X=S, Se, Te, I2, Br2) Batteries.

Recently, aqueous Zn-X (X=S, Se, Te, I2, Br2) batteries (ZXBs) have attracted extensive attention in large-scale energy storage techniques due to their ultrahigh theoretical capacity and environmental friendliness. To date, despite tremendous research efforts, achieving high energy density in ZXBs remains challenging and requires a synergy of multiple factors including cathode materials, reaction mechanisms, electrodes and electrolytes. In this review, we comprehensively summarize the various reaction conversion mechanism of zinc-sulfur (Zn-S) batteries, zinc-selenium (Zn-Se) batteries, zinc-tellurium (Zn-Te) batteries, zinc-iodine (Zn-I2) batteries, and zinc-bromine (Zn-Br2) batteries, along with recent important progress in the design and electrolyte of advanced cathode (S, Se, Te, I2, Br2) materials. Additionally, we investigate the fundamental questions of ZXBs and highlight the correlation between electrolyte design and battery performance. This review will stimulate an in-deep understanding of ZXBs and guide the design of conversion batteries.