Cathode For Rechargeable Batteries Research Articles

The Role of Carrier Ion‐Ligand Interaction on Intercalation Potentials and Phase Evolution of Berlin Green Cathodes in Rechargeable Batteries

AbstractIntercalation and deintercalation are fundamental processes in battery electrodes that involve the reversible addition and extraction of carrier ions such as lithium (Li) and sodium (Na) into a host framework made of transition metal (TM) ions and ligands. Although TM–ligand interactions are known to primarily determine intercalation potentials, a comprehensive understanding of their interactions involving the carrier ions still remains elusive. This study investigates the complex interactions between carrier ions (Li and Na) and the ligand in Berlin green (BG, Fe3+[Fe3+(CN)6]) cathodes to elucidate their effects on intercalation potentials and phase evolution. Comprehensive X‐ray characterizations and electrochemical analyses reveal that the strong carrier ion–ligand interaction, influenced by the type and concentration of carrier ions, can modify the electronic structure of Fe ions and affect the intercalated structure of BG cathodes, thereby tuning the intercalation potentials. Specifically, the enhanced covalent interaction of the Na–CN units compared with that of the Li–CN units induces rhombohedral distortion in the fully sodiated state and increases the working potential of high‐spin Fe ions. The findings highlight the critical role of carrier ion–ligand interactions in tuning the electrochemical properties of battery electrodes for the design of advanced battery systems.

Multicomponent hierarchical Cu-based advanced cathode for ultrahigh capacity rechargeable Cu-Zn battery

Rechargeable aqueous Zn-based batteries (RAZBs) have emerged as a practically attractive option for large-scale energy storage applications due to their cost-effectiveness, safety, eco-friendliness, and high theoretical capacity. Nonetheless, the application of RAZBs at the grid scale is restricted by the drawbacks of cathode that exhibit low capacities and poor durability. In this work, a multicomponent hierarchical Cu@CuO@Cu2O cathode with superior electrochemical energy storage performance has been successfully synthesized by a fairly simple calcination method. Benefiting from its large active area, fast ion diffusion channel, high conductivity, and synergetic effect between different components, the resulting Cu@CuO@Cu2O electrode exhibits ultrahigh specific capacity (40.2 mAh cm−2, 402 mAh cm−3 at 10 mA cm−2), excellent rate capability (24.8 mAh cm−2, 248 mAh cm−3 at 100 mA cm−2) and satisfactory cycling durability (71.5 % capacity retention after 3800 cycles). To our knowledge, such high areal/volumetric specific capacity ranks top among previously reported Cu-based electrode and other aqueous electrodes. Furthermore, the fabricated Cu@CuO@Cu2O//Zn battery achieves an extraordinary energy density of 24.5 mWh cm−2 and a remarkable cyclic capability of 91 % capacity retention after 3000 cycles, highlighting its potential for large-scale energy storage in RAZBs.

Anion vacancy engineering in carbon coating VS4 microspheres assembled by nanorod arrays for high-performance rechargeable Mg-Li hybrid batteries

Transition metal sulfides (TMSs) stand out as promising cathodes for rechargeable Mg-Li hybrid ion batteries (MLIBs) owing to their high theoretical capacity and rich redox chemistry. Nevertheless, it still faces great challenges involving the sluggish reaction kinetics and insufficient active sites, resulting in unsatisfactory stability and limited rate capability. And the role of anion vacancies on improving electrochemical properties of TMSs is still unclear. Herein, we have successfully designed an anion defect engineering strategy for the construction of carbon coating VS4 microspheres assembled by nanorod arrays (Sv-VS4@C-300) as the high-performance cathode for MLIBs. The systematic electrochemical tests together with theoretical calculations reveal that the sulfur vacancies simultaneously improve ion adsorption ability, facilitate charge transfer rate and boost reaction kinetics. Additionally, the open microsphere structure together with rich sulfur vacancies cooperatively provide more active sites and release the internal stress during cycling, thereby realizing the enhancement of capacity and structural stability. Consequently, these features enable Sv-VS4@C-300 with impressively high reversible capacity (485.1 mAh/g at 50 mA g−1) and exceptional long cycle lifespan (128.3 mAh/g at 2000 mA g−1 after 5000 cycles). This work implements an innovative strategy represented by anion vacancy engineering in the design of high-performance TMSs-based cathodes for rechargeable batteries.

Materials Design and Mechanistic Understanding of Tellurium and Tellurium-Sulfur Cathodes for Rechargeable Batteries.

ConspectusThe market demand for lithium-ion batteries (LIBs) has been proliferating in wide applications, from portable electronics and electric vehicles to renewable energy storage, due to their advantages of high energy density and reliable life cycles. Currently, further development of LIBs is hindered by the limited specific/volumetric capacity and high cost of conventional intercalation-type cathode materials. In this context, sulfur (S) has gained intensive attention as a conversion-type cathode because of its abundance, low cost, and high theoretical capacity (1675 mAh g-1). However, the insulating nature of S causes severe issues of sluggish redox kinetics, low S utilization, and unsatisfactory practical capacity. So far, extensive efforts have been devoted to boosting Li-S redox kinetics and enhancing cycling stability by inhibiting the shuttle effect, including developing functional electrolyte additives, introducing redox catalysts, and tailoring the S cathode structure. Partially substituting S atoms in S8 rings with high-electrical-conductivity elements (e.g., selenium, 1 × 10-3 S m-1) at the molecular level proves to be an effective strategy for tackling the above-mentioned challenges in Li-S batteries. It is noteworthy that tellurium (Te), with remarkable electrical conductivity (2 × 102 S m-1) and high density (6.24 g cm-3), is a promising battery electrode material that can realize fast electron transport and deliver volumetric capacity comparable to that of S or Se. Additionally, Te-S molecular regulation is one facile strategy to reshape Li-S chemistry, accelerate redox kinetics, and manipulate the lithiation/delithiation behaviors. Te is an effective eutectic accelerator that prevents polysulfide dissolution in Li-S batteries under the dissolution-deposition mechanism. Meanwhile, the Li-Te electrochemistry can contribute to reversible capacity in Li-TexSy batteries through Te-Li2Te conversion and enhance the materials utilization of TexSy.This Account highlights state-of-the-art advancements in applying Te or TexSy as high-capacity cathodes for rechargeable batteries. First, battery configuration and reaction pathways in Li-Te batteries are discussed, followed by the introduction of cathode design strategies to improve cathode structure stability. The limitations of this Te-only cathode are outlined in terms of the abundance, cost, and energy density. Second, the role of Te in Li-S chemistry is clarified by the analysis of the crystal structure, electrochemical behaviors, solid electrolyte interphase composition, and energy profiles. Third, recent progresses on quasi-solid-state Li-Te batteries have been introduced, focusing on flexible gel polymer electrolytes with adjustable ionic conductivity. Afterward, advancements in interface engineering by the atomic layer deposition technique in metal-Te batteries are highlighted. Additionally, mechanistic analysis in emerging zinc-TexSy batteries with outstanding areal capacity is demonstrated. Finally, we provide insightful perspectives on the future directions of material design in Te-based energy storage technologies. This Account is expected to deepen the fundamental understanding of metal-Te/TexSy chemistry and offer inspiration for the further development of Te-based high-energy-density rechargeable batteries.

Roadmap for the Development of Transition Metal Oxide Cathodes for Rechargeable Zinc-Ion Batteries

Continued efforts towards the decarbonization of the power sector through an uptake of renewable energy generation, namely solar and wind, play a key role in the fight against climate change. However, due to their variable nature, the simultaneous implementation of energy storage solutions capable of ensuring a reliable delivery of energy at any time of day is of the utmost importance. Aqueous rechargeable zinc-ion batteries (RZIBs) are a promising technology for this end. Offering several advantages over lithium-ion batteries in terms of cost, environmental impact, and material abundance, the investment in RZIB research continues to grow. However, the realization of commercial RZIBs is currently hindered by the lack of cathode materials with adequate performance for long-term storage solutions. This is the case for manganese (e.g., MnO2, Mn2O3, Mn3O4) and vanadium (e.g., V2O5, VO2) based oxides, which exhibit considerable capacity fade during realistic charge and discharge times. While simple transition metal oxides (MyOx, M=transition metal) are one of the most studied classes of materials for RZIB cathodes, a literature survey shows that there are still many unexplored redox active elements and redox pairs which may be employed in next-generation RZIBs. Therefore, to accelerate the discovery of these novel cathode systems, we mapped the theoretical Zn intercalation potential for simple oxides from 12 different transition metals using Density Functional Theory (DFT) calculated thermodynamic properties. The screened elements were chosen upon considering their commercial availability, toxicity, price, and existence of previously reported structures containing zinc. During the present analysis, the feasibility of Zn intercalation for each system was accounted for by analyzing the atomic arrangement in the charged and discharged phases. Experimentally obtained Pourbaix Diagrams were also used to probe the electrochemical stability of the cathodes in aqueous solution, with the possibility of electrolyte degradation (oxygen or hydrogen evolution reaction) and competing reactions (metal dissolution or solid phase change) also considered. Experimental validation of the computationally predicted potentials was also done for select materials. The result for the 35+ redox pairs evaluated in this study provides a clear roadmap for the future development of RZIBs cathodes.

Engineering Three-Dimensional Interconnected Pores with Plentiful Edge Sites via a Confined Space for Enhanced Oxygen Reduction.

N-Doped carbon sheets based on edge engineering provide more opportunities for improving oxygen reduction reaction (ORR) active sites. However, with regard to the correlation between porous structural configurations and performances, it remains underexplored. Herein, a silica-assisted localized etching method was employed to create two-dimensional mesoporous carbon materials with customizable pore structures, abundant edge sites, and nitrogen functionalities. The mesoporous carbon exhibited superior electrocatalytic performance for the ORR compared to that of a 20 wt % Pt/C catalyst, achieving a half-wave potential of 0.88 V versus RHE, situating them in the leading level of the reported carbon electrocatalysts. Experimental data suggest that the edge graphitic nitrogen sites played a crucial role in the ORR process. The three-dimensional interconnected pores provided a high density of active sites for the ORR and facilitated the efficient transport of electrons. These unique properties make the carbon sheets a promising candidate for highly efficient air cathodes in rechargeable Zn-air batteries.

Bilayered Vanadium Oxides Pillared by Strontium Ions and Water Molecules as Stable Cathodes for Rechargeable Zn-Metal Batteries.

Vanadium-based compounds have attracted significant attention as cathodes for aqueous zinc metal batteries (AZMBs) because of their remarkable advantages in specific capacities. However, their low diffusion coefficient for zinc ions and structural collapse problems lead to poor rate capability and cycle stability. In this work, bilayered Sr0.25V2O5·0.8H2O (SVOH) nanowires are first reported as a highly stable cathode material for rechargeable AZMBs. The synergistic pillaring effect of strontium ions and water molecules improves the structural stability and ion transport dynamics of vanadium-based compounds. Consequently, the SVOH cathode exhibits a high capacity of 325.6mAhg-1 at 50mAg-1, with a capacity retention rate of 72.6% relative to the maximum specific capacity at 3.0Ag-1 after 3000 cycles. Significantly, a unique single-nanowire device is utilized to demonstrate the excellent conductivity of the SVOH cathode directly. Additionally, the energy storage mechanism of zinc insertion and extraction is investigated using a variety of advanced in situ and ex situ analysis techniques. This method of ion intercalation to improve electrochemical performance will further promote the development of AZMBs in large-scale applications.

Disulfide bonded polyimide cathode of rechargeable magnesium batteries: Improved capacity via reversible break/formation of disulfide and sulfur-oxygen bonds

Rechargeable magnesium batteries are a potential selection for large-scale energy storage technologies, but development of cathode materials is the major difficulty at present. Organic polyimides are promising magnesium battery cathodes with the open and amorphous frameworks as well as enhanced charge delocalization. However, only two carbonyls are redox-active out of four for each imide unit, which largely limits the capacity. Herein, a new polyimide containing disulfide bond is fabricated and studied as cathode for rechargeable magnesium batteries. This polyimide shows a high capacity beyond the traditional two-electron principle. A mechanism study demonstrates that carbonyl enolization and disulfide bond break/formation occur in the redox process, leading to formation/break of sulfur-oxygen bond. This sulfur-oxygen bond enhances enolization and electron delocalization, resulting in an improved capacity. Further theoretical computation indicates a charge transfer within this sulfur-oxygen bond. The two-electron reduction state exhibits quite low HOMO and LUMO energy levels, which makes the disulfide bonded polyimide have a higher tendency to accept more electrons and a higher oxidation stability after reduction.

Carbonized wood fiber-supported S, N-codoped carbon layer-coated multinary metal sulfide nanoarchitecture for efficient oxygen evolution reaction at ampere-level current density

Multinary metal sulfides (MMSs) are highly suitable candidates for the application of electrocatalysis as they offer numerous parameters for optimizing the electronic structure and catalytic sites. Herein, a stable nanoarchitecture consisting of MMSs ((NiCoCrMnFe)Sx) nanoparticles embedded in S, N-codoped carbon (SNC) layers derived from metal organic framework (MOF) and supported on carbonized wood fibers (CWF) was fabricated by directly carbonization. Benefiting from this carbon-coated configuration, along with the synergistic effects within multinary metal systems, (NiCoCrMnFe)Sx@SNC/CWF delivers an exceptionally low overpotential of 260 mV at a high current density of 1000 mA cm−2, a small Tafel slope of 48.5 mV dec−1, and robust electrocatalytic stability. Furthermore, the (NiCoCrMnFe)Sx@SNC/CWF used as the cathode of rechargeable Zn-air batteries demonstrates higher power density and remarkable durability, surpassing that of commercial RuO2. Thus, we showcase the feasibility and advantages of employing highly efficient and durable MMSs materials for low-cost and sustainable energy conversion.

Recent Advances and Prospects of Chalcogenide Cathodes for Rechargeable Magnesium Batteries

AbstractRechargeable magnesium batteries (RMBs) have garnered considerable interest from researchers and industries owing to their abundant resources, cost‐effectiveness, impressive energy density, and safety features, positioning them as a compelling technology for sustainable energy. Chalcogenides, with their high electrochemical activity and low charge density, facilitate the diffusion and migration of Mg2+. “Soft” anionic lattices, such as S or Se, weaken the Coulombic attraction between the crystal structure and Mg2+, thereby promoting the accelerated diffusion and reversible intercalation of Mg2+. Consequently, they are highly regarded as promising cathode materials for RMBs. However, their real‐world implementation is hindered by challenges including low conductivity, formidable ion diffusion barriers, and insufficient cyclic stability. In this study, chalcogenides are categorized into intercalation‐ and conversion‐types based on the Mg2+ storage mechanism, providing a comprehensive examination and taxonomy of various modification approaches aimed at enhancing the electrochemical performance of chalcogenides. These approaches include intercalation engineering, phase engineering, defect engineering, doping effects, and nanostructure engineering. Furthermore, specific modification strategies for certain chalcogenide cathode materials are summarized and discussed. Finally, the key points of optimization strategies for chalcogenide cathode materials are summarized, along with the proposed future breakthrough directions.

Progress and Challenges of Vanadium Oxide Cathodes for Rechargeable Magnesium Batteries.

Among the challenges related to rechargeable magnesium batteries (RMBs) still not resolved are positive electrode materials with sufficient charge storage and rate capability as well as stability and raw material resources. Out of the materials proposed and studied so far, vanadium oxides stand out for these requirements, but significant further improvements are expected and required. They will be based on new materials and an improved understanding of their mode of operation. This report provides a critical review focused on this material, which is embedded in a brief overview on the general subject. It starts with the main strategic ways to design layered vanadium oxides cathodes for RMBs. Taking these examples in more detail, the typical issues and challenges often missed in broader overviews and reviews are discussed. In particular, issues related to the electrochemistry of intercalation processes in layered vanadium oxides; advantageous strategies for the development of vanadium oxide composite cathodes; their mechanism in aqueous, "wet", and dry non-aqueous aprotic systems; and the possibility of co-intercalation processes involving protons and magnesium ions are considered. The perspectives for future development of vanadium oxide-based cathode materials are finally discussed and summarized.

Recycled Cathodes in Rechargeable Aqueous Batteries as Ready-Made Electrodes for Oxygen Evolution Catalysis.

The development of a low-cost and efficient oxygen evolution reaction (OER) electrode is of critical importance for water electrolysis technologies. The general approach to achieving a high-efficiency OER electrode is to regulate catalytic material structures by synthetic control. Here we reported an orthogonal approach to obtaining the OER electrode without intentional design and synthesis, namely, recycling MnO2 cathodes from failed rechargeable aqueous batteries and investigating them as ready-made catalytic electrodes. The recycled MnO2 cathode showed very little Zn2+ storage capacity but surprisingly high OER activity with a low overpotential of 307 mV at 10 mA cm-2 and a small Tafel slope of 77.9 mV dec-1, comparable to the state-of-the-art RuO2 catalyst (310 mV, 86.9 mV dec-1). In situ electrochemical and theoretical studies jointly revealed that the accelerated OER kinetics of the recycled MnO2 electrode was attributed to the enlarged active surface area of MnO2 and optimized electronic structure of Mn sites. This work suggests failed battery cathodes as successful catalysis electrodes for sustainable energy development.

Dual-Salts Localized High-Concentration Electrolyte for Li- and Mn-Rich High-Voltage Cathodes in Lithium Metal Batteries.

Limited electrochemical stability windows of conventional carbonate-based electrolytes pose a challenge to support the Lithium (Li)- and manganese (Mn)-rich (LMR) high-voltage cathodes in rechargeable Li-metal batteries (LMBs). To address this issue, a novel localized high-concentration electrolyte (LHCE) composition incorporating LiPF6 and LiTFSI as dual-salts (D-LHCE), tailored for high-voltage (>4.6Vvs.Li) operation of LMR cathodes in LMBs is introduced. 7Li nuclear magnetic resonance and Raman spectroscopy revealed the characteristics of the solvation structure of D-LHCE. The addition of LiPF6 provides stable Al-current-collector passivation while the addition of LiTFSI improves the stability of D-LHCE by producing a more robust cathode-electrolyte interphase (CEI) on LMR cathode and solid-electrolyte interphase (SEI) on Li-metal anode. As a result, LMR/Li cell, using the D-LHCE, achieved 72.5% capacity retention after 300 cycles, a significant improvement compared to the conventional electrolyte (21.9% after 100 cycles). The stabilities of LMR CEI and Li-metal SEI are systematically analyzed through combined applications of electrochemical impedance spectroscopy and distribution of relaxation times techniques. The results present that D-LHCE concept represents an effective strategy for designing next-generation electrolytes for high-energy and high-voltage LMB cells.

Advanced K3V2(PO4)2O2F cathode for rechargeable potassium-ion batteries with high energy density

Potassium-ion batteries (PIBs) have emerged as promising candidates for cost-effective and sustainable energy-storage systems. Nevertheless, limited by the large K+ radius, PIBs have great difficulty in figuring out and designing suitable host materials. Herein, a suitable cathode material K3V2(PO4)2O2F (KVPOF) for PIBs has been carefully prepared. It exhibits a high specific capacity close to the theoretical value, 116.3 mAh/g at 20 mA/g within the voltage window of 2.0–4.5 V vs K+/K, corresponding to a de-/intercalation process of ∼2 mol K+ per formula unit. In addition, it presents an average operating voltage plateau of about 3.5 V, resulting in an energy density of about 410 Wh/kg. The crystal structure and phase transition are revealed by in situ x-ray diffraction, and the structure is found to be fully reversible during the de-/intercalation of K+. Furthermore, the potential of KVPOF cathode for applications at low temperatures was explored, and the full cell matched with graphite anode demonstrated fair electrochemical performance. The experimental results suggest the feasibility of using KVPOF as cathode material for rechargeable PIBs.

A New Cathode for Rechargeable Magnesium Batteries

A New Cathode for Rechargeable Magnesium Batteries

Utilization of Delithiation-Induced Amorphous Oxide as a Cathode for Rechargeable Magnesium Batteries

Utilization of Delithiation-Induced Amorphous Oxide as a Cathode for Rechargeable Magnesium Batteries

Advanced Prussian Blue Cathodes for Rechargeable Li-Ion Batteries

Taking advantage of fact that the surface electrons of metallic nanoparticles (NPs) can be effectively released even at a low voltage bias, we demonstrate an improvement in the electrochemical performance of nanosized Prussian Blue (PB)-based secondary batteries through the incorporation of bare Ag or Ni NPs in the vicinity of the working PB NPs. It is found that the capacity for electrochemical energy storage of the 17 nm PB-based battery is significantly higher than the capacity of 10 nm PB-based, 35 nm PB-based or 46 nm PB-based batteries. There is a critical PB size for the highest electrochemical energy storage efficiency. The full specific capacity CF of the 17 nm PB-based battery stabilized to 62 mAh/g after 130 charge–discharge cycles at a working current of IW = 0.03 mA. The addition of 14 mass percent of Ag NPs in the vicinity of the PB NPs gave rise to a 32% increase in the stabilized CF. A 42% increase in the stabilized CF could be obtained with the addition of 14 mass percent of Ag NPs on the working electrode of the 35 nm PB-based battery. An enhancement in CF was also found for electrodes incorporating bare Ni NPs but the effect was smaller.

Electrode Behavior of Exfoliated Graphite Cathode for Aluminum Metal Anode Rechargeable Battery

Electrode Behavior of Exfoliated Graphite Cathode for Aluminum Metal Anode Rechargeable Battery

Carbonyl and imine conjugated frameworks for aqueous Organo-Aluminum batteries with high specific capacity and low dissolution

Carbonyl or imine-based compounds have received a great deal of attention due to their high specific capacity and designability as cathodes for aqueous rechargeable organo-aluminum batteries. However, the inherent low conductivity and high solubility of carbonyl and imine-based compounds severely affect the cycling stability of aluminum batteries. Therefore, it is urgent to find an organic cathodes material with low solubility and good cycling performance. In this work, dibenzo[a,c]dibenzo[5,6:7,8]quinoxalino[2,3-i]phenazine-10,21-dione (DDQP) were synthesized by simple dehydration condensation to form new imine covalent bonds, which led to the synthesis of imine-conjugated backbone structures with carbonyl, extended π-conjugation planes, and increased active sites, resulting in increased specific capacities. Its storage mechanism with Al(OTF)2+ has also been confirmed. This monovalent ion usually possesses a lower coulombic interaction, which leads to a reduced solubility of DDQP during redox processes and improves its cyclic stability. The specific capacity of DDQP is 252.22 mAh/g at a current density of 400 mA g−1. After cycling, the discharge specific capacity remains at 219 mAh/g. Surprisingly, the conductivity of the battery also is improved by this structure of multiple active sites. And it can be further confirmed by theoretical calculations that the synthesis of DDQP realigns the arrangement of the electron cloud, enhances the electron affinity, and reduces the energy gap. This study provides a new reference for improving the performance of aqueous organic aluminum batteries.

Poly(3-Methylthiophene)/Graphene Composite Cathode for Rechargeable Aluminum-Ion Batteries.

To reduce the dependence on traditional fossil energy, developing efficient energy storage systems is urgent. The reserves of aluminum resources in the earth's crust are extremely rich, which makes aluminum-ion batteries a promising competitor of new energy storage devices. Here, we report a poly(3-methylthiophene)/graphene (P3TH/Graphene) composite as the cathode of an aluminum-ion battery. The adjustment of polymer chain spacing by the methyl side chain provides a channel conducive to the transport of large-size AlCl4- complexes. The addition of electron donor groups also changes the electron delocalization characteristics of polymers and improves the specific capacity of the material. At the same time, the in situ composite of graphene can enhance the Π-Π interaction to form a favorable electronic transmission channel. At a current density of 200 mA g-1, the P3TH/Graphene composite showed a specific capacity of ∼150 mA g-1. The flexible structure of the polymer also guarantees the excellent rate capability of the composite.