High-performance Cathode Materials Research Articles

Freestanding Ammonium Vanadate Composite Cathodes with Lattice Self-Regulation and Ion Exchange for Long-Lasting Ca-Ion Batteries.

Calcium-ion batteries (CIBs) have emerged as a promising alternative for electrochemical energy storage. The lack of high-performance cathode materials severely limits the development of CIBs. Vanadium oxides are particularly attractive as cathode materials for CIBs, and preinsertion chemistry is often used to improve their calcium storage performance. However, the room temperature cycling lifespan of vanadium oxides in organic electrolytes still falls short of 1000 cycles. Here, based on preinsertion chemistry, the cycling life of vanadium oxides is further improved by integrated electrode and electrolyte engineering. Utilizing a tailored Ca electrolyte, the constructed freestanding (NH4)2V6O16·1.35H2O@graphene oxide@carbon nanotube (NHVO-H@GO@CNT) composite cathode achieves a 305 mAh g-1 high capacity and 10000 cycles record-long life. Additionally, for the first time, a Ca-ion hybrid capacitor full cell is assembled and delivers a capacity of 62.8 mAh g-1. The calcium storage mechanism of NHVO-H@GO@CNT based on a two-phase reaction and the exchange of NH4 + and Ca2+ during cycling are revealed. The lattice self-regulation of V─O layers is observed and the layered vanadium oxides with Ca2+ pillars formed by ion exchange exhibit higher capacity. This work provides novel strategies to enhance the calcium storage performance of vanadium oxides via integrated structural design of electrodes and electrolyte modification.

Modulating Valence Electrons and Na Occupancy in Layered Cathodes for High-Performance Na-Ion Batteries.

Na-ion batteries (NIBs) hold promise as a leading option for large-scale energy storage. However, their development faces challenges due to the lack of high-performance cathode materials. P2-type layered oxides are seen as potential cathode materials for NIBs due to higher structure stability, yet their commercialization is hindered by limited capacity and subpar phase transitions during Na extraction and insertion at high voltages. In this study, we introduce a new P2-type cathode material, Na0.76Ni0.23Li0.1Ti0.02Mn0.65O1.998F0.02 (NLTMOF), synthesized with ternary Li/Ti/F substitution. This modification of ternary Li/Ti/F substitution significantly tailors the electronic structures, increasing the number of valence electrons near the Fermi energy level. This facilitates the electronic conductivity and their involvement in charge compensation, thereby enhancing reversible capacity. Additionally, ternary doping synergistically adjusts the Na occupancy at the Na layer for favorable Na extraction without P2-O2 phase transitions even under a high voltage of 4.4 V, boosting cycling stability. As a result, NLTMOF demonstrates a reversible capacity of 110.0 and 132.2 mAh g-1 at 2-4.2 and 2-4.4 V, respectively, and maintains greatly enhanced cycling stability over long cycles. This study sheds light on the design of transition metal oxides for advanced cathode materials through the modulation of electronic structure and Na occupancy in cathode materials, thus promoting the development of NIBs.

CH3COOLi-assisted lithium source on the synthesis of high-performance single-crystal Ni-rich cathode material

CH3COOLi-assisted lithium source on the synthesis of high-performance single-crystal Ni-rich cathode material

A Feasible Dual Modification Strategy of Internal Anion Redox Chemistry and Surface Engineering on P2 Layer-Structured Cathodes in Sodium-Ion Batteries.

Boosting the anion redox reaction opens up a possibility of further capacity enhancement on transition-metal-ion redox-only layer-structured cathodes for sodium-ion batteries. To mitigate the deteriorating impact on the internal and surface structure of the cathode caused by the inevitable increase in the operation voltage, probing a solution to promote the bulk-phase crystal structure stability and surface chemistry environment to further facilitate the electrochemical performance enhancement is a key issue. A dual modification strategy of establishing an anion redox hybrid activation trigger agent inside the crystal structure in combination with surface oxide coating is successfully developed. P2-type layer structure cathode materials with Zn/Li (Na-O-Zn@Na-O-Li) anion redox hybrid triggers and a ZnO coating layer possess superior capacity and cycle performance, along with outstanding structural stability, decreased Mn-ion dissolution effect, and less crystal particle cracking during the cycling process. This study represents a facile modification solution to perform structure optimization and property enhancement toward high-performance layered structure cathode materials with anion redox features in sodium-ion batteries.

In Situ Constructed Spinel Layer Stabilized Upcycled LiCoO2 for High Performance Lithium-Ion Batteries.

With ever-increasing requirements for cathodes in the lithium-ion batteries market, an efficiency and eco-friendly upcycling regeneration strategy is imperative to meet the demand for high-performance cathode materials. Herein, a facile, direct and upcycling regeneration strategy is proposed to restore the failed LiCoO2 and enhance the stability at 4.6 V. Double effects combination of relithiation and outside surface reconstruction are simultaneously achieved via a facile solid-phase sintering method. The evolution process of the Li-supplement and grain-recrystallization is systematically investigated, and the high performance of the upcycled materials at high voltage is comprehensively demonstrated. Thanks to the favorable spinel LiCoxMn2-xO4 surface coating, the upcycled sample displays outstanding electrochemical performance, superior to the pristine cathode materials. Notably, the 1% surface-coated LiCoO2 achieves a high discharge-specific capacity of 207.9 mA h g-1 at 0.1 C and delivers excellent cyclability with 77.0% capacity retention after 300 cycles. Significantly, this in situ created spinel coating layer can be potentially utilized for recycling spent LiCoO2, thus providing a viable, promising recycling strategy insights into the upcycling of degraded cathodes.

Facile synthesis of V2O3@C nanoribbons by rapid cooling method for high-capacity zinc-ion batteries cathode

Aqueous zinc-ion batteries (ZIBs) have recently gained considerable attention due to their low price and great safety properties. However, the challenge of preparing high-performance cathode materials and developing low-cost, efficient preparation methods still demands urgent solutions. Herein, this paper proposes the use of a rapid cooling method to prepare V2O3@C cathode materials with excellent overall electrochemical performance for ZIBs. Utilizing low-cost ammonium metavanadate as the raw material and melamine as a binding agent, dispersed molecules facilitate the rapid creation of V-based nanoribbon precursors within just 1 h at a low temperature. After the annealing process, the obtained V2O3@C nanoribbons exhibit a unique structural architecture with a V2O3 covered by carbon, providing enhanced structural stability and electric conductivity. In contrast to the commercial V2O3 cathode, the V2O3@C cathode exhibits remarkably improved electrochemical characteristics, including enhanced specific capacity (41 % increase), extended cycle stability (capacity retention of 63 % after 15,000 cycles), and improved rate capability (53 % capacity retention at 10 A g−1). Additionally, the zinc storage mechanism of the V2O3@C cathode was systematically investigated. This facile synthesis method, coupled with the outstanding electrochemical performance, highlights the potential of V2O3@C cathode as a promising candidate for high-capacity cathodes in next-generation ZIBs.

Layered BaV6O16·3H2O@GO as a high performance cathode material for calcium ion batteries.

The lack of suitable cathode materials has hampered the further development of calcium-ion batteries (CIBs). A novel composite cathode material, namely BaV6O16·3H2O@GO, was fabricated, which delivers a high specific capacity of 285.72 mA h g-1 at 50 mA g-1 after 50 cycles and a long cycle life, benefiting from a large layer spacing and robust structure. This study provides guidance for the development of vanadium-based cathode materials for CIBs.

Ti-doped O3-NaNi0.5Mn0.5O2 as high-performance cathode materials for sodium-ion batteries

With favorable electrochemical activity, NaNi0.5Mn0.5O2(NNMO) has been a key cathode material in sodium-ion batteries. However, the phase-transition irreversible and kinetics sluggish issues in NaNi0.5Mn0.5O2 greatly limit its application in sodium-ion batteries. Here, various Ti-doped O3-NaNi0.5Mn0.5-xTixO2 cathode materials were fabricated via solid-phase method. The extra Ti-doping treatment effectively stabilized the transition layer of metal and enlarged the Na layer spacing, as well as suppressed the Na+/vacancy ordering. In particular, the obtained O3-NaNi0.5Mn0.46Ti0.04O2 (NNMOTi-4) exhibits initial reversible capacity of 108.6 mAh g−1 at 0.1C and remarkable 65.2% capacity retention after 100 cycles at 1C. Accordingly, this work provides a facile Ti-doping strategy to regulate the structure and electrochemical performance of layered NaxTMO2 for sodium-ion batteries.

Enhancing the electrochemical activation kinetics of V2O3 for high-performance aqueous zinc-ion battery cathode materials

The discharge capacity and lifespan of zinc ion batteries currently remain impractical due to limitations in the cathode. Low-valence vanadium oxides are promising cathode material precursors that can be electrochemically converted into highly active hydrated amorphous oxides. However, the activation process itself suffers from structural instability or high local strain, due to the low electronic conductivity and the limited ion diffusion kinetics. To tackle this issue, herein, we synthesize porous carbon-coated nitrogen-doped V2O3 (p-NVO@C) microparticles utilizing a nitrogen-containing vanadium-based metal–organic framework (MOF) as the precursor. The uniform N doping and carbon coating improve the electronic conductivity of the active material particles. The carbon coating also traps the active material to reduce its dissolution loss; the high porosity of the p-NVO@C alleviates the stress from Zn2+-intercalation-induced expansion and shortens the ion transport paths. Moreover, first-principles calculations indicate that the doped N atoms in vanadium oxides generate a locally enhanced electric field, which accelerates the diffusion of Zn2+. Given the above advantages, the p-NVO@C particles demonstrate an outstanding specific capacity of 501 mAh/g at a current density of 0.2 A/g and a remarkable rate performance after the initial activation. The capacity retention rate remains as high as 95.7 % after 2000 cycles at a current density of 10 A/g. Ex-situ characterizations confirm the robust structural stability during phase transition cycles. This work provides an excellent solution to developing cathode materials for high-performance aqueous zinc ion batteries.

Carbon quantum dots/carbon-coated SnS2 as a high-performance potassium-ion battery cathode material

Carbon quantum dots/carbon-coated SnS2 as a high-performance potassium-ion battery cathode material

Al-doped flower-like VO2(B) microspheres as high-performance cathode materials for lithium-ion batteries

VO2(B), as a potential cathode material for lithium-ion batteries (LIBs), is attracting extensive attention from researchers because of its great superiority in terms of theoretical specific capacity, energy density, and cost. Nevertheless, VO2(B), leads to irreversible decay of specific capacity during cycling for reasons including structural stability and inferior electrical conductivity. In this work, the electrochemical performance of VO2(B) electrode materials are further enhanced via Al ion doping. The results reveal that the prepared Al-doped 3D flower-like VO2(B) microspheres exhibit a high initial discharge specific capacity (as high as 314.8 mAh/g at 0.1 A/g current density) at an Al doping amount of n(Al3+)/n(V5+) = 6.0 %. Moreover, it displays a first discharge specific capacity of up to 229.2 mAh/g at a current density of 1 A/g with the capacity retention rate of 90.0 % after 120 cycles. As a result, Al-doped 3D flower-like VO2(B) microspheres provide enormous commercialization potential as cathode materials for LIBs.

Intercalating polypyrrole tuning interlayer space of V2O5 for advanced aqueous zinc ion batteries

Aqueous zinc-ion batteries is considered as a promising system for large scale electrochemical energy storage system owing to their intrinsic safety, and low cost. Nevertheless, the industrialization process is slow due to the constraints of high-performance cathode materials. Adjusting the layered structure of V2O5 through metal ion or polymer intercalation can effectively improve low electron conductivity, vanadium dissolution, and slow ion transport kinetics. Herein, the conductive polymer polypyrrole-intercalated V2O5·H2O (PVOH) was successfully prepared via simple hydrothermal method and following interface polymerization reaction. Getting benefit from the insertion of polypyrrole, the prepared PVOH composite material achieves a V2O5 cathode with a more open structure, rich active sites, and greater stability, allowing for an expanded crystal plane spacing of 14.5 Å. Therefore, the PVOH electrode demonstrates a discharge capacity of 475 mAh g−1 and a cycling stability of 95% capacity retention after 2000 cycles. The intercalating conductive polymers strategy can become a new approach to improve the electrochemical behavior of vanadium oxide cathodes.

Research on the Performance Improvement Method for Lithium-Ion Battery in High-Power Application Scenarios

With the development of technology, high-power lithium-ion batteries are increasingly moving towards high-speed discharge, long-term continuous output, instantaneous high-rate discharge, and miniaturization, and are being gradually developed towards the fields of electric tools, port machinery and robotics. Improving the power performance of batteries can be achieved from multiple dimensions, such as electrochemical systems and battery design. In order to improve the power performance of lithium-ion batteries, this paper proposes design methods from the perspective of electrochemical systems, which include increasing the high-rate discharge capacity and low impedance of the battery. This article also studies the preparation of high-power lithium-ion batteries. This article aims to improve the rate performance of batteries by studying high-performance cathode materials, excellent conductive networks, and high-performance electrolytes. This article successfully screened high-performance cathode materials by comparing the effects of different particle sizes of cathode materials on electrode conductivity and battery internal resistance. By comparing the effects of electrolyte additives under pulse cycling, high-quality electrolyte additive materials were selected. By comparing the effects of different types, contents, and ratios of conductive agents on electrode conductivity, battery internal resistance, high-quality conductive agents, and appropriate ratios were selected. Finally, a 10 Ah cylindrical high-power lithium-ion battery with a specific energy of 110 Wh/kg, pulse discharge specific power of 11.3 kW/kg, an AC internal resistance of ≤0.7 m Ω, a 10C full capacity discharge cycle of over 1700, a 30C full capacity discharge cycle of over 500, and a continuous discharge capacity of 10C–30C, and a pulse discharge capacity of over 100C was prepared.

Three dimensional CuCo2S4@CNT as cathode for sustainable aluminum batteries

It is a challenging and meaningful subject that developing high-performance cathode materials for aluminum batteries（ABs）. In this work, a three dimensional CuCo2S4@CNT (CNT refers to carbon nanotube) material was designed for ABs. The three-dimensional structure is constructed by combining CuCo2S4 microspheres with CNT scaffolds. CuCo2S4 microspheres are constructed from ultrathin nanosheets and CuCo2S4 microspheres uniformly distribute in these three dimensional all-carbon CNT architectures. The CNT framework improves material conductivity and inhibits aggregation of CuCo2S4 particles, and also acts as a buffer, eliminating volume changes and providing more stable contacts between particles. Compared with the pristine CuCo2S4 electrode, the CuCo2S4@CNT electrode exhibits superior electrochemical performance. At a current density of 100 mA/g, CuCo2S4@CNT electrode still provides a reversible capacity of 128 mAh/g after 200 cycles. Meanwhile, the coulombic efficiency remains above 96 %.

Recycling of LiCoO2 from the cathode of a waste lithium battery via reduction in a molten salt

A new method for recycling and resynthesizing a lithium battery cathode material was developed. A LiCl-KCl molten salt was used as a medium. The raw materials were LiOH·H2O obtained by membrane electrolysis and Co2O3 obtained by carbothermal reduction, and the high-performance cathode material LiCoO2 was synthesized by molten salt method, and then placed into a battery for recycling. The specific reaction process and reaction kinetics for the LiCoO2 synthesis were studied by TG-DSC thermal analyses. The effects of different reaction conditions on the structure and morphology of the LiCoO2 were studied by XRD and SEM. The battery performance of the LiCoO2 was characterized with electrochemical analyses. The activation energies of the three endothermic reactions occurring in the synthetic process were calculated with the Kissinger method and were 34.212 kJ·mol−1, 168.53925 kJ·mol−1 and 221.26181 kJ·mol−1. The experimental battery prepared from a LiCoO2 sample calcined at 720 °C for 7 h showed first charge–discharge specific capacities of 150 mAh/g and 147 mAh/g, and the coulombic efficiency was 98%. The discharge specific capacity after 50 charge and discharge cycles was still 129 mAh/g. The battery showed good charge and discharge performance after rate cycling.

Recent Progress and Synthetic Methods for Single-crystalline Cathode in Lithium-ion Batteries

Ni-rich layered transition metal oxides have been regarded as the most feasible way for achieving high energy density of lithium-ion batteries. Conventional Ni-rich cathodes are composed of spherical secondary particles, consisting of numerous primary particles. Unfortunately, the grain boundaries in the polycrystalline structure are vulnerable to the pulverization, leading to microcracks during cycling. The newly exposed surface from the microcrack can induce undesirable side reactions with the electrolyte, which severely deteriorates the battery performance. On the other hand, single-crystalline Ni-rich cathodes have gained significant attention for industrial applications due to their robust mechanical strength, resulting from the elimination of grain boundaries. The improved mechanical properties of single-crystalline cathodes effectively mitigate the interfacial side reactions, thereby attaining superior structural, thermal, and electrochemical performance. Herein, we have introduced various synthetic methods of the single-crystalline cathode, encompassing not only high-temperature sintering and the molten-salt method for the Ni-rich cathode but also the other strategies for different single-crystalline cathode materials. This review aims to provide a comprehensive understanding of single-crystalline cathode synthesis, with implications for the development of high-performance cathode materials.

A new In Situ Oxidized 2D Layered MnBi2Te4 Cathode for High-Performance Aqueous Zinc-Ion Battery.

Recently, aqueous zinc ion batteries (AZIBs) with the superior theoretical capacity, high safety, low prices, and environmental protection, have emerged as a contender for advanced energy storage. However, challenges related to cathode materials, such as dissolution, instability, and structural collapse, have hindered the progress of AZIBs. Here, a novel AZIB is constructed using an oxidized 2D layered MnBi2Te4 cathode for the first time. The oxidized MnBi2Te4 cathode with large interlayer spacing and low energy barrier for zinc ion diffusion at 240°C, exhibited impressive characteristics, including a high reversibility capacity of 393.1mAhg-1 (0.4Ag-1), outstanding rate performance, and long cycle stability. Moreover, the corresponding aqueous button cell also exhibits excellent electrochemical performance. To demonstrate the application in practice in the realm of flexible wearable electronics, a quasi-solid-state micro ZIB (MZIB) is constructed and shows excellent flexibility and high-temperature stability (the capacity does not significantly degrade when the temperature reaches 100°C and the bending angle exceeds 150°). This research offers effective tactics for creating high-performance cathode materials for AZIBs.

Intermolecular Hydrogen Bonding Networks Stabilized Organic Supramolecular Cathode for Ultra-High Capacity and Ultra-Long Cycle Life Rechargeable Aluminum Batteries.

Rechargeable aluminum batteries (RABs) are a promising candidate for large-scale energy storage, attributing to the abundant reserves, low cost, intrinsic safety, and high theoretical capacity of Al. However, the cathode materials reported thus far still face challenges such as limited capacity, sluggish kinetics, and undesirable cycle life. Herein, we propose an organic cathode benzo[i] benzo[6,7] quinoxalino [2,3-a] benzo [6,7] quinoxalino [2,3-c] phenazine-5,8,13,16,21,24-hexaone (BQQPH) for RABs. The six C=O and six C=N redox active sites in each molecule enable BQQPH to deliver a record ultra-high capacity of 413 mAh g-1 at 0.2 A g-1. Encouragingly, the intermolecular hydrogen bonding network and π-π stacking interactions endow BQQPH with robust structural stability and minimal solubility, enabling an ultra-long lifetime of 100,000 cycles. Moreover, the electron-withdrawing carbonyl group induces a reduction in the energy level of the lowest unoccupied molecular orbital and expands the π-conjugated system, which considerably enhances both the discharge voltage and redox kinetics of BQQPH. In-situ and ex-situ characterizations combined with theoretical calculations unveil that the charge storage mechanism is reversible coordination/dissociation of AlCl2+ with the N and O sites in BQQPH accompanied by 12-electron transfer. This work provides valuable insights into the design of high-performance organic cathode materials for RABs.

Achieving rapid sodiation/desodiation kinetics in NASICON-structured Na3MnTi(PO4)3 via Cr doping

Na3MnTi(PO4)3 is one of the most promising cathode candidates for sodium-ion batteries owing to its low cost, high operating voltage, and large reversible capacity. However, its electrochemical performance is significantly impeded by its deteriorative structure and sluggish Na+ diffusion kinetics. Herein, Cr-doping is introduced to tailor the structure of Na3MnTi(PO4)3, which helps to lengthen the Na2-O bond and expand the Na ion diffusion channels. X-ray diffraction, cyclic voltammetry, galvanostatic intermittent titration technique, and first principle calculations confirm the broadened diffusion channel for Na+ and facilitated Na+ diffusion rate after Cr-doping. As a result, the Na3.1MnTi0.9Cr0.1(PO4)3 electrode exhibits superior electrochemical performance with high discharge capacity (167.5 mAh g–1 at 0.1 C), outstanding rate capability (127.5 mAh g–1 at 10 C), and remarkable cyclability (70.56 % retention after 1400 cycles at 5 C). We believe that the results are useful for the design of high-performance NASICON-structured cathode materials for practical sodium-ion batteries.

Application of lattice expansion effect in SrCoO3 based cathodes by Ba doping with elevated electrochemical performances for low-temperature solid oxide fuel cells

Developing excellent-performance cathode materials is an inevitable and challenging obstacle in the process of developing practical solid oxide fuel cells, especially in low temperature range. In this paper, we introduce barium into the premium SrCoO3-based cathodes and research its consequent effect in the oxygen reduction reaction process. It is observed that the barium dopant could expand the lattice, produce more oxygen vacancies and at some extent reduce the thermal expansion coefficient of parent perovskite, which results from the expanded free space for oxygen migration and weakened Co–O bond by Ba doping. The polarization resistances of single cells with Sr1-xBaxCo0.8Sc0.1Nb0.05Ti0.05O3-δ cathodes (x = 0, 0.2 and 0.5, defined as SCSNTi, SB0.2CSNTi and SB0.5CSNTi, correspondingly) are 0.038, 0.025 and 0.016 Ω cm2 at 600 °C, respectively, and corresponding peak power density of 0.852, 1.054 and 1.217 W cm−2. The SB0.5CSNTi cathode is selected and it stably operates for 200 h at 550 °C. And it also exhibits excellent performance when CH4 is used as fuel and good stability for 100 h at 600 °C. First principle calculations prove that the Ba doping effectively reduces the oxygen vacancy formation energy and oxygen migration barrier. This work proves that the lattice expansion effect is an effective strategy for accelerating the oxygen exchange rate and designing high-performance cathode materials.