Cathode Material Research Articles

Structural stability and enhanced electrochemical performance of Co-free Li-rich layered Mn-based Li1.2Mn0.6Ni0.2O2 cathodes via F doping at the O site of lithium-ion batteries

Li-rich Mn-based Co-free layered oxides (LLOs) are promising cathode materials for lithium-ion batteries (LIBs). However, they exhibit capacity loss and low initial Coulombic efficiency. Herein, an F-doped Li1.2Mn0.6Ni0.2O1.9F0.10 material has been prepared by the high-temperature solid-state method, with numerous oxygen vacancies on the surface to accelerate Li + transport. The electrochemical performance of Li1.2Mn0.6Ni0.2O1.9F0.10 considerably improved after the treatment. A high-capacity retention of 86.9 % after 100 charge/discharge cycles at 1C was achieved for Li1.2Mn0.6Ni0.2O1.9F0.10. Results revealed that F doping replaces part of O2−, forming more force between the TM-F bonds (compared to the TM-O bond), which inhibits the cation mixing phenomenon. The layered structure stability of the material is improved after F doping, and the migration energy barrier of Li+ is reduced, which promotes the migration of Li+, thereby improving the electrochemical performance of Li1.2Mn0.6Ni0.2O2.

Constructing Targeted Strong Nb4d-O2p-Li2s Configurations to Obtain Excellent Energy Density and Long Life for Li-Rich Cathodes.

The Li-rich Mn-based cathode materials (LMRs) deliver excellent energy density and exhibit low cost, which are considered as the most promising cathode materials for the next generation lithium-ion batteries. However, the irreversible redox reaction of the oxygen atoms directly leads to release oxygen and intensifies phase transformation. Besides, the local stress and strain will be generated due to the unit-cell volume difference between R-3m and C2/m phases, which continuously aggravates the collapse of secondary particles. Herein, the strong Nb4d-O2p-Li2s configurations at the Li1 sites of the TM-layer in the C2/m phase and secondary particles with the radial arrangement of refined primary particles are designed to inhibit oxygen release and relieve lattice stress by Nb2O5 treatment. Meanwhile, the preferential growth of the active {010} planes is presented to obtain an excellent transmission rate of Li+. As a result, the designed LMR delivers remarkable electrochemical properties with high discharge capacity and initial coulomb efficiency of 276 mAh g-1 and 85 % at 0.1 C, outstanding cycling retention rate of 81 % after 300 cycles. This novel crystal structure combining oxygen coordination regulation and micro-nano scale design provides inspiration for the design of high-performance LMRs.

Performance of carbon felt as cathodes in magnesium corrosion method to recover phosphate from swine wastewater

With the large-scale development of the livestock and poultry breeding industries, swine wastewater with high nitrogen and phosphorus concentrations has become an urgent problem. Given the continuous demand for phosphorus resources in industrial production, the study of phosphate recovery in phosphorus-rich wastewater is of great value for the sustainable utilization of phosphorus resources and for alleviating the eutrophication of aquatic ecosystems. In this study, a magnesium metal corrosion method was used to recover phosphorus resources from swine wastewater using carbon felt as the cathode instead of traditional cathode materials such as graphite and titanium plates. The effects of different cathode materials on the corrosion potential of magnesium metal plates were compared, and the effects of carbon felt as a cathode plate on the removal rate and pH of phosphate from wastewater were discussed. Additionally, the economic feasibility of phosphate recovery from swine wastewater was evaluated. The experimental results showed that the effect of carbon felt on the corrosion potential of the magnesium metal plate was more evident than that of the graphite and titanium plates (Ecorr = −1.74676). When carbon felt was used as the cathode plate, the most energy-saving reaction conditions were as follows: reaction time T = 30 min, ratio of wastewater volume to plate area V: S = 500 cm3:50 cm2, aeration rate Re = 8 L/min, stirring rate r = 400 rpm, phosphate recovery rate = 92.3%, and pH = 8.83. The economic feasibility assessment shows that the proposed method is $2.047 g-1 PO4-P without considering the reuse of carbon felt. Carbon felt has good stability and can be recycled eight times or more, and the proposed method achieves a more efficient phosphate recovery rate at a relatively low cost.

Electrochemical performance of ultra-high‑nickel layered oxide cathode synthesized using different lithium sources

Ultra-high‑nickel layered oxide cathodes are extensively explored in lithium-ion battery research owing to their high specific capacity. However, the rapid decline in discharge specific capacity considerably limits their long-term performance. The choice of lithium precursors is crucial in enhancing both the structural and cycle stability of these batteries, yet this aspect has not been adequately addressed in existing studies. In this study, Li2O, LiOH, and Li2CO3 were used as lithium precursors to synthesize LiNi0.92Co0.04Mn0.04O2 (NCM92) cathodes. We compare the structure and electrochemical properties of NCM92 cathode materials prepared with these three lithium precursors, examining a lithium residual layer on the surface of three NCM92 and thus inferring the varying amounts of Li incorporation into the bulk lattice. Our findings highlight the effect of lithium precursors on the rapid degradation of NCM92's discharge capacity. Notably, the NCM92–Li2O cathode demonstrates a higher discharge specific capacity and superior capacity retention after 100 cycles compared to cathodes synthesized with LiOH and Li2CO3. This study provides valuable insights and guidance for further research on ultra-high‑nickel layered oxide cathode materials.

Constructing Targeted Strong Nb4d−O2p−Li2s Configurations to Obtain Excellent Energy Density and Long Life for Li‐Rich Cathodes

AbstractThe Li‐rich Mn‐based cathode materials (LMRs) deliver excellent energy density and exhibit low cost, which are considered as the most promising cathode materials for the next generation lithium‐ion batteries. However, the irreversible redox reaction of the oxygen atoms directly leads to release oxygen and intensifies phase transformation. Besides, the local stress and strain will be generated due to the unit‐cell volume difference between R‐3m and C2/m phases, which continuously aggravates the collapse of secondary particles. Herein, the strong Nb4d−O2p−Li2s configurations at the Li1 sites of the TM‐layer in the C2/m phase and secondary particles with the radial arrangement of refined primary particles are designed to inhibit oxygen release and relieve lattice stress by Nb2O5 treatment. Meanwhile, the preferential growth of the active {010} planes is presented to obtain an excellent transmission rate of Li+. As a result, the designed LMR delivers remarkable electrochemical properties with high discharge capacity and initial coulomb efficiency of 276 mAh g−1 and 85 % at 0.1 C, outstanding cycling retention rate of 81 % after 300 cycles. This novel crystal structure combining oxygen coordination regulation and micro‐nano scale design provides inspiration for the design of high‐performance LMRs.

MnO2 nanowires modified reduced graphene oxide thick film cathode for aqueous zinc-ion prismatic battery

Aqueous zinc-ion batteries are an excellent alternative to lithium-ion batteries that can meet the energy requirements while also being safe and eco-friendly. However, developing a suitable cathode material with good energy density and high-rate capability is challenging. In this study, we developed an aqueous zinc-ion battery with a high surface area MnO2 nanowires modified reduced graphene oxide nanocomposite screen printed interdigitated array electrodes and a distinctive aqueous electrolyte comprising 1 M each of ZnSO4 and Na2SO4, 0.1 M MnSO4, and 0.8 mM sodium dodecyl sulfate. The charge-discharge curves reveal that the cathode material exhibits a high reversible storage capacity of 164 mAh g−1 at a current density of 50 mA g−1. The battery retained 99.59% of its Coulombic efficiency after 300 cycles when cycled at a high current rate of 300 mA g−1. The prismatic battery realized exhibited a calculated energy density of 505.5 Wh kg−1 which is higher than previously reported works. On account of the large energy density and high rate capability coupled with non-toxic components, low cost and facile fabrication method, the Zn||MnO2/rGO battery shows good promise for energy storage application.

Rational design of α-MnO2@TiO2 composites for high-performance zinc ions batteries

Aqueous zinc ions batteries (AZIBs) have attracted widespread interest due to their remarkable energy density, non-toxicity, environmental friendliness and low cost. However, the application of MnO2 cathode materials for AZIBs is limited owing to the dissolution of Mn2+, structural collapse and intrinsic poor conductivity. Herein, α-MnO2@TiO2 composites were synthesized via simple hydrothermal and calcination approaches. Some smaller TiO2 were coated on the MnO2 nanorods to form the protective layer. The TiO2 protective layer not only prevents the dissolution of Mn2+ and structural collapse of MnO2, but also enhances the conductivity of the material due to the presence of Ti3+ defects, which increased electrode materials wettability, specific surface area and diffusion rate of Zn2+. In addition, the coating TiO2 causes surface adsorbed oxygen and surface binding defects in α-MnO2@TiO2, and increases surface reactivity and electrochemically active sites, which provides abundant channels and available insertion electrochemically active sites for H+/Zn2+ transport. As a result, α-MnO2@TiO2–2 delivers a high specific capacity of 182.90 mAh g−1 at 1 A g−1 after 600 cycles and outstanding rate capacity of 127.91 mAh g−1 at 5 A g−1. This work provides an idea for exploring high-performance cathode materials for AZIBs.

Constructing Quasi-Single Ion Conductors by a β-Cyclodextrin Polymer to Stabilize Zn Anode.

Aqueous Zn-ion batteries (AZIBs) are promising for the next-generation large-scale energy storage. However, the Zn anode remains facing challenges. Here, we report a cyclodextrin polymer (P-CD) to construct quasi-single ion conductor for coating and protecting Zn anodes. The P-CD coating layer inhibited the corrosion of Zn anode and prevented the side reaction of metal anodes. More important is that the cyclodextrin units enabled the trapping of anions through host-guest interactions and hydrogen bonds, forming a quasi-single ion conductor that elevated the Zn ion transference number (from 0.31 to 0.68), suppressed the formation of space charge regions and hence stabilized the plating/striping of Zn ions. As a result, the Zn//Zn symmetric cells coated with P-CD achieved a 70.6 times improvement in cycle life at high current densities of 10 mA cm-2 with 10 mAh cm-2. Importantly, the Zn//K1.1V3O8 (KVO) full-cells with high mass loading of cathode materials and low N/P ratio of 1.46 reached the capacity retention of 94.5 % after 1000 cycles at 10 A g-1; while the cell without coating failed only after 230 cycles. These results provide novel perspective into the control of solid-electrolyte interfaces for stabilizing Zn anode and offer a practical strategy to improve AZIBs.

Mitigating the Kinetic Hysteresis of Co‐Free Ni‐Rich Cathodes via Gradient Penetration of Nonmagnetic Silicon

AbstractCo‐free Ni‐rich layered oxides are considered a promising cathode material for next‐generation Li‐ion batteries due to their cost‐effectiveness and high capacity. However, they still suffer from the practical challenges of low discharge capacity and poor rate capability due to the hysteresis of Li‐ion diffusion kinetics. Herein, based on the regulation of the lattice magnetic frustration, the Li/Ni intermixing defects as the primary origin of kinetic hysteresis are radically addressed via the doping of the nonmagnetic Si element. Meanwhile, by adopting gradient penetration doping, a robust Si−O surface structure with reversible lattice oxygen evolution and low lattice strain is constructed on Co‐free Ni‐rich cathodes to suppress the formation of surface dense barrier layer. With the remarkably enhanced Li‐ion diffusion kinetics in atomic and electrode particle scales, the as‐obtained cathodes (LiNixMn1−xSi0.01O2, 0.6≤x≤0.9) achieve superior performance in discharge capacity, rate capability, and durability. This work highlights the coupling effect of magnetic structure and interfacial chemicals on Li‐ion transport properties, and the concept will inspire more researchers to conduct an intensive study.

Charge-Compensation-Driven Failure Mechanism of Ni Redox in Fe-Rich Ni/Fe/Mn-Based O3-Type Layered Oxide Sodium-Ion Cathodes.

For cathode materials of sodium-ion batteries, O3-type Ni/Fe/Mn-based (Na-NFM) layered oxides have garnered extensive attention because of high economic viability, environmental friendliness, and the potential for high energy density. Among them, Fe-rich compositions exhibit higher initial charge capacity and lower bill-of-material costs, while they fade rapidly and exhibit low initial coulombic efficiency, hindering their commercialization prospects. In this work, we investigate the failure of Fe-rich Na-NFM materials through X-ray absorption spectroscopy methods. The results reveal a combined failure mechanism that encompasses not only the conventional theory of Fe migration but also an abnormal Ni-redox deterioration, which has not yet been reported. More factors related to the failure of Fe-rich Na-NFM layered oxides are discussed in detail. These findings are expected to inspire targeted research efforts toward Fe-rich Na-NFM materials, thereby accelerating the practical application of sodium-ion batteries.

Constructing Quasi‐Single Ion Conductors by a β‐Cyclodextrin Polymer to Stabilize Zn Anode

AbstractAqueous Zn‐ion batteries (AZIBs) are promising for the next‐generation large‐scale energy storage. However, the Zn anode remains facing challenges. Here, we report a cyclodextrin polymer (P‐CD) to construct quasi‐single ion conductor for coating and protecting Zn anodes. The P‐CD coating layer inhibited the corrosion of Zn anode and prevented the side reaction of metal anodes. More important is that the cyclodextrin units enabled the trapping of anions through host–guest interactions and hydrogen bonds, forming a quasi‐single ion conductor that elevated the Zn ion transference number (from 0.31 to 0.68), suppressed the formation of space charge regions and hence stabilized the plating/striping of Zn ions. As a result, the Zn//Zn symmetric cells coated with P‐CD achieved a 70.6 times improvement in cycle life at high current densities of 10 mA cm−2 with 10 mAh cm−2. Importantly, the Zn//K1.1V3O8 (KVO) full‐cells with high mass loading of cathode materials and low N/P ratio of 1.46 reached the capacity retention of 94.5 % after 1000 cycles at 10 A g−1; while the cell without coating failed only after 230 cycles. These results provide novel perspective into the control of solid‐electrolyte interfaces for stabilizing Zn anode and offer a practical strategy to improve AZIBs.

Tailoring Cationic Cobalt Vacancies in Molybdenum-Cobalt Selenide Derived from POM@ZIF-67 for Enhanced Electrocatalysis in Lithium-Oxygen Batteries.

Slow reaction kinetics during redox reactions limits the utilization of the high theoretical energy density of lithium-oxygen batteries (LOBs). Vacancy engineering, a potential strategy for modulating active sites, is critical in the development of high performance catalysts. This study investigates cobalt vacancies in Mo-CoSe2 nanoparticles created by selenization of phosphomolybdic acid (POM) embedded into zeolitic imidazolate framework-67 (ZIF-67). The nanomaterial exhibits an outstanding electrochemical performance, characterized by high specific capacitance and excellent cycle durability. The LOBs with cobalt vacancies in the Mo-CoSe2 electrode material exhibit a discharge capacity of 21 836 mAh g-1 at a current density of 100 mA g-1 and exhibit stable cycling performance over 194 cycles at 300 mA g-1. Additionally, density functional theory (DFT) calculations suggest that the presence of cobalt vacancies increases the distance between the surface selenium atoms and the subsurface cobalt atoms. In addition, cobalt vacancies modify the electronic structure of the d-orbitals, lowering the energy barriers of the reaction and accelerating the reaction kinetics by improving the adsorption of the reactants. The research introduces a strategy for the rational design of efficient cathode materials in LOBs.

Achieving High Stability and Capacity in Micron-Sized Conversion-Type Iron Fluoride Li-Metal Batteries.

Iron fluoride, a conversion-type cathode material with high energy density and low-cost iron, holds promise for Li-ion batteries but faces challenges in synthesis, conductivity, and cycling stability. This study addresses these issues by synthesizing micron-sized iron-fluoride using a simple solid-state synthesis. Despite a large particle size, a high capacity of 571mAhg-1 is achieved, which is attributed to the unique surface and internal pores within the iron-fluoride particles, which provided a large surface area. This is the first study to demonstrate the feasibility of using large iron fluoride particles to enhance the energy density of the electrode and achieve an iron fluoride full cell with high capacity. Also, the cause of the capacity fading is investigated. Electrode delamination from the current collector, which is the main cause of capacity fading in early cycles, is resolved using a carbon-coated aluminum (C/Al) current collector. Moreover,iron (Fe) dissolution and the deposition of dissolved Fe on the Li metal also contributed significantly to the degradation. Localized high-concentration electrolytes (LHCEs)suppress iron dissolution and Li dendrite growth, resulting in long-cycle stability for 300 cycles. This study provides insights into the further development of conversion-type metal fluorides across various compositions.

Progress and Prospects in Cathode Materials for Sodium-Ion Batteries: Synthesis, Characterization, and Engineering Aspects

Progress and Prospects in Cathode Materials for Sodium-Ion Batteries: Synthesis, Characterization, and Engineering Aspects

High rate capability performance of cobalt-free lithium-rich Li1.2Ni0.18Mn0.57Al0.05O2 cathode material synthesized via co-precipitation method

High rate capability performance of cobalt-free lithium-rich Li1.2Ni0.18Mn0.57Al0.05O2 cathode material synthesized via co-precipitation method

Interface Engineering Induced by Low Ru Doping in Ni/Co@NC Derived from Ni-ZIF-67 for Enhanced Electrocatalytic Overall Water Splitting.

Electrochemical water splitting is a promising approach for hydrogen evolution reactions (HER); however, the oxygen evolution reaction (OER) remains a major bottleneck due to its high energy requirements. High-performance electrocatalysts capable of facilitating HER, OER, and overall water splitting (OWS) are highly needed to improve OER kinetics. In this work, we synthesized a trimetallic heterostructure of Ru, Ni, and Co incorporated into N-doped carbon (denoted as Ru/Ni/Co@NC) by first synthesizing Ni/Co@NC from Ni-ZIF-67 polyhedrons via high-temperature carbonization, followed by Ru doping using the galvanic replacement method. Benefiting from increased active surface sites, modulated electronic structure, and enhanced interfacial synergistic effects, Ru/Ni/Co@NC exhibited exceptional electrocatalytic performance for both HER and OER processes. The optimized Ru/Ni/Co@NC catalyst, with a minimal Ru mass ratio of ∼2.07%, demonstrated significantly low overpotential values of 34 mV for HER and 174 mV for OER at a current density of 10 mA/cm2 with corresponding Tafel slope values of 33.42 and 34.39 mV/dec, respectively. Further, the optimized catalyst was loaded onto carbon paper and used as anode and cathode materials for alkaline water splitting. Interestingly, a low cell voltage of just 1.44 V was obtained. The enhanced electrolytic performance was further elaborated by density functional theory (DFT) calculations, which confirmed that Ru doping in Ni/Co introduced additional active sites for H*, enhancing adsorption/desorption abilities for HER (ΔGH* = -0.30 eV), lowering water dissociation barrier (ΔGb = 0.49 eV) and reducing the energy barrier for the rate-determining step of OER (O* → OOH*) to 1.62 eV in an alkaline environment. These findings reflect the significant potential of ZIF-67-based catalysts in energy conversion and storage applications.

Elucidating the diffusion and interaction mechanisms of Zn2+ and H+ in MnO2 for aqueous zinc-ion batteries: A DFT study

MnO2 is a promising cathode material for aqueous zinc-ion batteries (AZIBs) with potential applications in large-scale energy storage systems. However, its practical use is hindered by poor cyclic stability and slow diffusion kinetics. Despite considerable efforts, success has been limited due to an unclear understanding of the intrinsic properties of Zn2⁺ and proton (H⁺) insertion into MnO2. This study investigates the predominant phases of MnO2—α, β, δ, and γ—and elucidates their reaction mechanisms using first-principles computational methods based on density functional theory (DFT). Our research reveals that H⁺ ions exhibit a higher initial insertion voltage compared to Zn2⁺ ions, but their diffusion in MnO2 is significantly impeded by strong interactions with oxygen. Additionally, H⁺ insertion partially obstructs Zn2⁺ ion migration. Furthermore, the insertion of Zn2⁺/H⁺ and the adsorption of H⁺ on the MnO2 surface are intricately linked to the dissolution process of manganese. This work significantly enhances our fundamental understanding of MnO2 as a cathode material for AZIBs.

Understanding the Relation Between Intrinsic Parameters of Substituents and Physical‐Chemical Properties of NVP

AbstractNASICON‐type Na3V2(PO4)3 (NVP) is regarded as an intriguing cathode material choice for sodium ion batteries (SIBs) due to its cycling stability and relatively high capacity. However, its voltage and electronic conductivity still need to be improved for larger‐scale fast‐charging applications (e.g. electric vehicles and mobile phones). In this work, we investigate the influence of Vanadium (V) substitution by other environmentally friendly, cheap, and/or high‐valent transition metal (TM) elements on the electrochemical performance of NVP. Density functional theory calculation was used to study the volume change, voltage, conductivity, and redox mechanism during charge/discharge of different compositions. It is found that a substitution of 50% of V by Mn, Mo or W ions resulting in Na3VMn(PO4)3 (NVMnP), Na3VMo(PO4)3 (NVMoP), and Na3VW(PO4)3 (NVWP) significantly alters the cathode materials’ physical and chemical properties, notably decreasing the band gap. In particular, NVMnP has lesser than 1 eV theoretical band gap and provides a higher voltage, while NVWP a much lower voltage in comparison to NVP. This means that NVMnP and NVWP can be promising cathode and anode materials respectively. This work also establishes a relation between fundamental properties of substituents (i.e. ionization energy and ionic size) and the overall performance of NVP.

Design Double Layered Anode for Stably Introducing Lithium Source to Achieve Sulfur‐Carbon Full Batteries

AbstractLithium‐sulfur batteries offer high energy density but face great safety and cycle life challenges due to the use of Li metal anode. Replacing the Li metal anode with pre‐lithiated carbon anodes can thoroughly address cycling stability and safety issues. Directly contacting Li foil with graphite electrode is one of the most efficient and simple strategy to introduce a high content of lithium source into the sulfur‐carbon full batteries. However, the 100% lithiation of the graphite anode through the direct contact method generates excessive heat and stress heterogeneity, which leads to electrode structure cracking and electrochemical properties fading. This study implements a double‐layer anode to mitigate these issues. A thin layer of hard carbon placed between graphite and Cu foil limits heat generation and stress heterogeneity due to its structural and electrochemical stability. Additionally, differing from traditional electrochemical lithiation, this method gains better solid electrolyte interphase (SEI) for the graphite anode after several cycles. This research highlights the mass production potential of coupling high energy density lithium source‐free cathode materials with various lithium source‐free anodes for constructing long‐cycle and high‐safety rechargeable batteries.

High-Entropy Layered Oxide Cathode Materials with Moderated Interlayer Spacing and Enhanced Kinetics for Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) with low cost and environmentally friendly features have recently attracted significant attention for renewable energy storage. Sodium layer oxides stand out as a type of promising cathode material for SIBs owing to their high capacity, good rate performance, and high compatibility for manufacturing. However, the poor cycling stability of layer oxide cathodes due to structure distortion greatly impacts their practical applications. Herein, a high entropy doped Cu, Fe, and Mn-based layered oxide (HE-CFMO), Na0.95Li0.05Mg0.05Cu0.20Fe0.22Mn0.35Ti0.13O2 for high-performance SIBs, is designed. The HE-CFMO cathode possesses high-entropy transition metal (TM) layers with a homogeneous stress distribution, providing a moderated interlayer spacing to maintain the structure stability and enhance Na+ ion diffusion. In addition, Li doping in TM layers increases the Mn valence state, which effectively suppresses John-Teller effect, thus stabilizing the layered structure during cycling. Furthermore, the use of nontoxic and low-cost raw materials benefits future commercialization and reduces the risk of environmental pollution. As a result, the HE-CFMO cathode exhibits a super cycling performance with a 95% capacity retention after 300 cycles. This work provides a promising strategy to improve the structure stability and reaction kinetics of cathode materials for SIBs.