High-performance Cathode Materials Research Articles

Free-Standing Poly(vinyl benzoquinone)/Reduced Graphene Oxide Composite Films as a Cathode for Lithium-Ion Batteries.

Quinones with a rapid reduction-oxidation rate are promising high-capacity cathodes for lithium-ion batteries. However, the high solubility of quinone molecules in polar organic electrolytes results in low cycle stability, while their low electric conductivity causes low utilization of electrode materials. In this article, a new p-benzoquinone derivative, poly(vinyl benzoquinone) (PVBQ), is designed and synthesized, and a solution-based method of preparing free-standing PVBQ/reduced graphene oxide (RGO) composite films is developed. PVBQ has a high theoretical specific capacity (400 mA h g-1) because of its low dead moiety mass. In the produced composite films, PVBQ nanoparticles are uniformly dispersed on RGO sheets, which endows the composite films with high electric conductivity and inhibits the dissolution of PVBQ through strong adsorption. As a result, the composite films show a high active material utilization, high practical specific capacity, and excellent cycling stability. PVBQ in the composite membrane containing 60.2 wt % RGO deliver 244 mA h g-1 capacity after 200 charge-discharge cycles at a current density of 300 mA g-1. At a current density of 1500 mA g-1, the reversible specific capacity is still 170 mA h g-1. This work provides a high-performance cathode material for lithium-ion batteries, and the molecular structure and electrode structure design ideas are also instructive for developing other organic electrode materials.

A Novel 4-Fluorophenyl Isocyanate Additive Constructing Solid Cathodes-Electrolyte Interface for High-Performance Lithium-Ion Batteries.

Building a stable cathode-electrolyte interface (CEI) is crucial for achieving high-performance layered metal oxide cathode materials LiNixCoyMn1-x-yO2 (NCM). In this work, a novel 4-fluorobenzene isocyanate (4-FBC) electrolyte additive that contains isocyanate and benzene ring functional groups is proposed, which can form robust and homogeneous N-rich and benzene ring skeleton CEI film on the cathode surface, leading to significant improvement in the electrochemical performance of lithium-ion batteries. Taking LiNi0.5Co0.2Mn0.3O2 (NCM523) as an example, the NCM523/SiO@Graphite pouch full cells with electrolytes containing a mass fraction of 1% 4-FBC additives demonstrate improved capacity retention after 200 cycles, retaining capacity retention rates of 81.3%, which is much higher than that of 39.1% without additive. The improvement can be ascribed to the mitigation of electrolyte decomposition and inhibition of transition metal ions the dissolution from the cathode material due to the stable CEI film. Moreover, the electrochemical performance enhancement can also be achieved in high voltage and Ni-rich cathode materials, indicating the universality and effectiveness of this strategy for the practical applications of high energy density lithium-ion batteries.

Facilitating superior electrochemical efficacy and ultra rapid kinetic in Co/Ni-free layered oxides for sodium-ion batteries with phosphate-growing layer fast ion conductors

Co/Ni-free layered oxides have garnered significant interest due to their environmental friendliness and facile synthesis methodologies, while facing major challenges of inferior cycling stability and rate capability. Addressing these drawbacks necessitates the enhancement of the surface properties of Co/Ni-free layered oxides. This work introduces a Co/Ni-free layered oxide, Na0.67Mn0.65Fe0.3Al0.05O2 (NMFA), which has been subjected to phosphate-based surface engineering. This targeted surface modification aims to augment the specific surface area and establish a protective layer on NMFA. Such improvements are critical for expanding the effective electrochemical reaction zone, broadening sodium ion diffusion pathways, curtailing the P2-OP4 phase transition, and reducing the activation energy for interfacial charge transfer. This multifaceted surface treatment epitomizes the ingenious design and realization of advanced Co/Ni-free layered oxide cathode materials through straightforward processing techniques. Notably, the NMFA subjected to 3 %-AlPO4 surface modification demonstrated an initial discharge capacity of 189.1 mAh/g at 0.1C, maintaining its capacity after 500 cycles at 10C. Additionally, DFT calculations corroborate that such surface growth can bolster electrical conductivity, restrain oxygen liberation and foster sodium ion migration. This elucidates that the phosphate growth layer serves as the oxygen reservoir. Accordingly, this investigation propounds a promising avenue to circumvent the challenges confronting Co/Ni-free layered oxides, thus paving the way for the development of high-performance cathode materials.

ULPING-Based Titanium Oxide as a New Cathode Material for Zn-Ion Batteries

The need for alternative energy storage options beyond lithium-ion batteries is critical due to their high costs, resource scarcity, and environmental concerns. Zinc-ion batteries offer a promising solution, given zinc’s abundance, cost effectiveness, and safety, particularly its compatibility with non-flammable aqueous electrolytes. In this study, the potential of laser-ablation-based titanium oxide as a novel cathode material for zinc-ion batteries was investigated. The ultra-short laser pulses for in situ nanostructure generation (ULPING) technique was employed to generate nanostructured titanium oxide. This laser ablation process produced highly porous nanostructures, enhancing the electrochemical performance of the electrodes. Zinc and titanium oxide samples were evaluated using two-electrode and three-electrode setups, with cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic charge–discharge (GCD) techniques. Optimal cathode materials were identified in the Ti-5W (laser ablated twice) and Ti-10W (laser ablated ten times) samples, which demonstrated excellent charge capacity and energy density. The Ti-10W sample exhibited superior long-term performance due to its highly porous nanostructures, improving ion diffusion and electron transport. The potential of laser-ablated titanium oxide as a high-performance cathode material for zinc-ion batteries was highlighted, emphasizing the importance of further research to optimize laser parameters and enhance the stability and scalability of these electrodes.

Significant performance enhancement of Zn-ion hybrid supercapacitors based on microwave-assisted pyrolyzed active carbon via synergistic effect of NaHCO3 activation and CNT networks

Zinc-ion hybrid supercapacitors (ZIHSCs) represents a promising technological approach for large-scale energy storage with the combined advantages of supercapacitors and zinc-ion batteries. Unfortunately, it is still challengeable to quickly fabricate low-cost, high-performance carbonaceous cathode materials at relatively low temperature. To address such issues, herein, taking waste Eucommia ulmoides Oliver (EUO) wood as an example, we present a novel microwave-assisted carbonization (MWC) approach at relatively low temperature to quickly prepare active carbon, and we present a synergistic strategy to significantly enhance the electrochemical performance by introducing sodium bicarbonate activation (SA) and constructing conductive carbon nanotubes (CNT) networks. The MWC-SA@CNT hybrid exhibits outstanding specific capacitance of 344.2 F/g at 0.2 A/g within three-electrode system, much better than conventional high-temperature pyrolyzed AC, MWC carbon, and MWC-SA carbon. The superior performance of MWC-SA@CNT can be attributed to the synergistic effect of its large specific surface area of 1102.7 m2/g, high mesoporous percentage of 53.5%, and rich –OH and CO groups due to microwave-assisted carbonization and sodium bicarbonate activation, and rich electron transport paths due to the presence of CNT networks. Furthermore, ZIHSCs assembled by MWC-SA@CNT cathode could delivers impressive performance with excellent capacity (194.37 mA h/g at current density of 1 A/g), energy density (142.30 Wh/kg), and durability (capacitance retention rate of 97.65% after 5000 cycles). This work offers a rapid and low-temperature method for preparing wood-based active carbon with rich nanopores and strong conductivity to improve performance of Zinc ion storage.

Layered CrO2·nH2O as a cathode material for aqueous zinc-ion batteries: ab initio study.

Aqueous zinc-ion batteries are considered potential large-scale energy storage systems due to their low cost, environmentally friendly nature, and high safety. However, the development of high energy density cathode materials and uncertain reaction mechanisms remains a major challenge. In this work, the reaction mechanism, discharge voltage and diffusion properties of layered CrO2 as a cathode material for aqueous zinc-ion batteries were studied using first-principles calculations, and the effect of pre-intercalated structural water on the electrochemical performance of CrO2 electrodes is also discussed. The results show that CrO2 exhibits high average discharge voltages (2.65 V for H insertion (pH = 7) and 1.97 V for Zn insertion) and medium theoretical capacities (319 mA h g-1 (H and Zn)). The H intercalation voltage strongly depends on the pH value of the electrolyte. The H/Zn co-insertion mechanism occurs at low hydrogen concentrations (c(H) ≤ 0.125), where the initial insertion of H reduces the total amount of subsequent Zn insertion. For the substrate containing structured water (CrO2·nH2O, n ≥ 0.5), the average voltage of Zn insertion is significantly increased, while the average voltage of H slightly decreases. In addition, the pre-intercalated water strategy significantly improved the diffusion properties of H and Zn. This study shows that layered CrO2·nH2O is a promising cathode material for aqueous zinc-ion batteries, and also provides theoretical guidance for the development of high-performance cathode materials for aqueous zinc-ion batteries.

Oxygen-deficient NH4V4O10 cathode with Ag quantum dots and interlayer Ag+ towards high-performance aqueous zinc ion batteries

Herein, oxygen-deficient NH4V4O10 micro-flowers with loaded Ag quantum dots and pre-intercalated Ag+ (NVO-Ag) for aqueous zinc ion battery (AZIB) cathode materials were successfully synthesized by a one-step hydrothermal method. The reversible redox reaction between Ag+ and Ag quantum dots, and the abundant Zn2+ storage sites from oxygen vacancies provided capacity contributions for NVO-Ag. Meanwhile, the loaded Ag quantum dots, pre-intercalated Ag+ and introduced oxygen vacancies synergistically optimized the electronic structure and distribution of NVO-Ag, promoting the transport of electrons in NVO-Ag. The pre-intercalated Ag+ could also replace the NH4+ in the interlayer of NH4V4O10, weakening the repulsion between the interlayer NH4+ and Zn2+, which achieved rapid Zn2+ diffusion kinetics. Moreover, the abundant oxygen vacancies in NVO-Ag could alleviate the strong electrostatic interaction between Zn2+ and V-O framework, boosting the transmission of Zn2+ in NVO-Ag. Finally, the structural stability of NH4V4O10 micro-flowers was improved due to the high bonding strength between Ag+ and V-O layers. Benefiting from the above effects, NVO-Ag-100 achieved excellent capacity performance (387.2 mA h/g at 0.5 A/g), rate performance (178.9 mAh/g at 12 A/g) and cycle stability (91.7 % capacity retention after 1700 cycles at 8 A/g). This work provided effective ideas to achieve high-performance AZIB cathode materials.

Copper and nickel hexacyanoferrates/carbon nanotube nanocomposites thin films as high-performance light cathode materials for aqueous sodium-ion batteries

Aqueous rechargeable Na-ion batteries are gaining popularity as an attractive alternative for energy storage systems due to their low cost, wide range of raw material sources, non-flammability, and ultrahigh ionic conductivity. Currently, Because of their three-dimensional open structure, high specific capacity, and inexpensive cost, Prussian blue analogues are being investigated as electrode materials for electrochemistry. In this work, we present an innovative strategy to create novel two-component nanoarchitected thin films that exhibit exceptional performance as cathodes in aqueous sodium-ion batteries (SIBs). By leveraging the versatility of the liquid-liquid interfacial method, we have prepared two distinct transparent nanocomposite films composed of carbon nanotubes and either copper or nickel hexacyanoferrate nanoparticles. The results show that the NiHCF/CNT and CuHCF/CNT deliver a high specific capacity of 152 mA h g−1 and 135 mA h g−1, respectively, at a high current density of 1 A g−1. Moreover, the cells (rGO//NiHCF and rGO//CuHCF) show that the energy density of the battery can reach up to 7.75 Wh kg−1 at a power density of 27.92 W kg−1 for rGO//NiHCF/CNT, while rGO//CuHCF/CNT showed an energy density of 3.67 Wh kg−1 at a power density of 13.21 W kg−1. The results demonstrate that NiHCF/CNT and CuHCF/CNT nanocomposite films provide new insight into the design of high-performance PBA cathodes.

Optimizing interfacial modification for enhanced performance of Na3V2(PO4)3 cathode in sodium-ion batteries

A novel cathode material, Na3V2(PO4)3C@CNT (NVP/C@CNT), was designed and synthesized by a low-temperature solid-phase drying ball milling method. The nanoparticles are covered by an amorphous carbon layer, and simultaneously enveloped and embedded by carbon nanotubes on the surface. Consequently, a carbon network consisting of carbon nanotubes and amorphous carbon layers is formed in the material. Notably, no phase transition during the intercalation process of sodium ions, confirming the stable crystal structure, which ensures the stability and reversibility of the large-capacity cathode in the large-volume change. The addition of CNTs can regulate the size of NVP particles, increase the contact area between NVP and electrolyte, leading to an enhancement in the sodium ion diffusion coefficient. The NVP/C@CNT electrode exhibits a capacity of 114.5 mA h g−1 at 0.1 C. After 2650 cycles, the discharge capacity retention rate is 98.2 % at 10C. Even at 20 C, the discharge capacity is still 93.3 mA h g−1 after 2710 cycles, with a retention rate of 99.5 %. This work provides a feasible approach for the design of low-cost, long-life, high-performance cathode materials for sodium-ion batteries.

Fluorinated Hollow Porous Carbon Spheres as High-Performance Cathode Material for Primary Battery

Fluorinated carbon cathode materials have extremely high theoretical specific energy among known cathode materials of lithium primary batteries. Nevertheless, current fluorinated carbon cannot meet the performance demands of future applications due to the rate performance. This work innovatively applies hollow carbon spheres with a porous structure as carbon sources to prepare fluorinated hollow porous carbon spheres (FHPCS) with high energy density and power density. The porous structure provides more reaction sites for the fluorination process and also shortens the diffusion path of lithium ions during the discharge. Additionally, the hollow porous structure offers more interfacial contact areas and reduces volumetric expansion during discharge reactions. The Li/CFx primary battery has a maximum specific energy of 2007 Wh kg−1 and a maximum power density of 30,400 W kg−1 and can have a capacity retention rate of 80.8% at a current density of 16 A g−1. In addition, FHPCS also has the highest specific energy of 1999 Wh kg−1 and 1711 Wh kg−1 in Na/CFx and K/CFx primary batteries, respectively. The diffusion efficiency of an alkali metal ion is analyzed by the different discharge depths with electrochemical impedance spectroscopy and galvanostatic intermittent titration technique. This effort introduces a new high-performance fluorinated carbon featuring a hollow porous structure and puts forward an innovative approach to designing fluorinated carbon materials.

Mo-doped LiNi0.8Co0.1Mn0.1O2 cathode materials with improved performance for lithium ion batteries

The high nickel ternary LiNi[Formula: see text]Co[Formula: see text]Mn[Formula: see text]O2 (NCM811) cathode material has attracted much attention owing to its advantages of high capacity and low price. However, NCM811 suffers from surface side reactions and cation mixing, which results in an unstable crystal structure and lower Coulomb efficiency and capacity in lithium ion batteries. In this work, Mo-doped cathode material NCM811 is effectively synthesized by high-temperature solidification approach. The characterization results show that the doped NCM811 can form a coating layer on the surface, preventing electrolyte side reactions with the electrode. As the cathode for lithium ion batteries, the Mo-doped NCM811 electrode shows an initial discharge capacity of 185.21[Formula: see text]mAh/g and obtains 156.33[Formula: see text]mAh/g with a capacity retention of 84.5% after 100 cycles at 1C. This study provides a simple and reliable method of fabricating high-performance NCM811 cathode materials.

Design and construction of V6O13/C nanorods as high-performance cathode material for aqueous zinc-ion batteries

As a candidate for commercial cathode material of aqueous zinc ion batteries (AZIBs), vanadium-based materials have attracted wide attention due to their unique layered structure and high specific capacity. However, the insertion/extraction process of Zn2+ can easily lead to the volume expansion of vanadium-based materials, resulting in battery failure. In addition, the inherent low conductivity and low diffusion kinetics of vanadium-based materials limiting their further development into high-performance cathode materials. Herein, a novel V6O13/N, O co-doped carbon (V6O13/C) nanorod electrode material has been successfully fabricated as a cathode for AZIBs. The N, O co-doped carbon can significantly improve the conductivity of materials and alleviate the volume change. The nanorod-like structure could enhance the structural stability during the Zn2+ insertion/extraction processes. Moreover, with N, O doped, the electrode can expose more reactive sites which is beneficial for promoting electrochemical processes. With the synergistic effort of the above optimization strategy, the as-obtained electrode delivers excellent long-term cycle stability of 151.7 mAh g−1 at 1 A g−1 after 1000 cycles.

Copper substituted manganese Prussian blue analogue composite nanostructures for efficient aqueous zinc-ion batteries

Aqueous zinc (Zn)-ion batteries (AZIBs) are considered a promising green energy storage alternative due to their large capacity, low cost, and exceptional safety. Prussian blue analogues (PBAs) with a robust three-dimensional structure and extensive ion channels are highly favorable for Zn2+ insertion/extraction, surpassing manganese (Mn) and vanadium oxides. Herein, copper (Cu) substituted Mn PBA (CuMn PBA) composite nanostructures are synthesized via a simple water-based co-precipitation technique using different concentrations of Cu and Mn sources. The partial substitution of Cu and the formation of Mn vacancies prevent Jahn-Teller distortions of MnN6 octahedra, extending the lifespan. The CuMn PBA-2 electrode exhibits a high discharge capacity of 175.14 mA h g−1 at 0.5 A g−1, superior rate capability of 89.08 mA h g−1 at 2.4 A g−1, and robust cycling stability, maintaining 73.15 mA h g−1 over 2000 cycles at 3 A g−1. Furthermore, the distinct structure provides numerous active sites and reduces volume volatility during cycling. The presence of Cu enhances electrode conductivity, thereby promoting a higher rate of Zn-ion diffusion between electrodes. The reversible intercalation and deintercalation of Zn2+ ions in the CuMn PBA-2 cathode are substantiated by ex-situ analysis methods. This work presents a novel approach for producing high-performance and stable PBA cathode materials for AZIBs.

Study on the influence of different manganese sources on the formation of P2/β Bi-phase cathode materials for sodium ion batteries

This work focuses on the effect of the of Mn3+/Mn4+ ratio in the reactants on the structure and electrochemical properties of NaMn0.9Cu0.1O2 cathode materials for sodium-ion batteries. By systematically varying the manganese valence states in the reactants, we observed a phase transition from the β-phase to the P2-phase with increasing Mn3+ concentrations in the reactants, contrary to the expected favorability of the β-phase at higher Mn3+ levels. This finding suggests a complex interplay between the valence states of the reactants and phase formation mechanisms, which needs further investigation. Additionally, electrochemical testing indicated that the phase composition significantly impacts the electrochemical performance of the material. Specifically, the M0 sample, possessing the optimal P2/β ratio, exhibited excellent electrochemical performances, achieving a high initial discharge capacity of 155.1 mA h g−1 and remains 88.1 % after 40 cycles. These results emphasize the importance of precursor selection and valence management in the development of high-performance cathode materials for sodium-ion batteries.

Enhanced high-rate and long-cycle performance of Mg2+-Al3+ co-doped spinel LiMn2O4 cathode materials for Li-ion batteries

Spinel LiMn2O4 has the potential to be used as a cathode material in lithium-ion batteries because of its affordability, low toxicity, and excellent charge/discharge capability. However, severe capacity attenuation results from the degradation of its long-cycle and high-rate performance caused by the Jahn-Teller distortion and Mn dissolution. Herein, a simple solid-state combustion process is used to successfully prepare the Mg2+-Al3+ co-doped LiMn2O4 with truncated octahedral morphology. The Jahn-Teller distortion is inhibited by the stable Mn-O framework and the decreased lattice constant, which in turn lowers the dissolution of Mn. Moreover, Mg2+-Al3+ co-doped LiMn2O4 have lower activation energy and greater Li+ diffusion coefficient. As a result, the optimized LiMg0.03Al0.10Mn1.87O4 delivers satisfied initial capacity of 102.1 mAh‧g−1 with a capacity retention of 76.2 % after 1000 cycles at 10 C. Even at the ultra-high rate of 15 C and 20 C, Mg2+-Al3+ co-doped sample also remain desired structure stability and cycling performance, which remains 73.8 % of its original capacity after 1000 cycles at 20 C. This work provides a reference for developing high-performance and stability cathode materials for lithium-ion battery.

Fe, N Co-doped amine-functionalized MIL 101(Al)-derived mesoporous carbon-based catalysts as high-performance ORR cathode material for Zn-Air battery

The investigation of effective non-noble metal carbon catalysts for oxygen reduction reactions is of great significance importance in Zn-air batteries. Among them, carbon-based materials obtained from metal-organic frameworks (MOFs) demonstrate outstanding catalytic activity in ORR. However, most MOFs-derived catalysts are microporous, which results in poor mass transfer and low utilization of FeNX active sites. In this study, amine-functionalized MIL 101(Al) (NH2-MIL-101) precursors with mesoporous cage structure are synthesized. N-doped carbon carriers with mesoporou structures are prepared at various pyrolysis temperatures. Subsequently, the carbon materials are doped with Fe(phen)32+ complexes and pyrolyzed once more to fabricate highly efficient Fe-Phen-MIL101 catalyst with abundant FeN active sites. The obtained catalyst has a half-wave potential of 0.86 V, which is higher than that of the commercial Pt/C of 0.82 V. Notably, the assembled liquid Zn-air battery (ZAB) exhibits high power density of 120.6 mW cm−2, specific capacity of 725.17 mAh gZn−1, and remarkable cycling stability.

Cu/F Dual-Doping on the Ni–Mn Based Layered Oxide As Cathode Material for Sodium-Ion Batteries

As demands for energy storage are ever-increasing, sodium ion batteries (SIB) have been widely conducted for superior electrochemical performance and reduction in cost compared to lithium ion batteries (LIBs), one of the most commonly used energy storage devices nowadays. Among all the parts in batteries, cathode materials play a crucial role with regard to performance. Here, layered transition metal oxides (LTMOs) (NaxTMO2, TM = Cu, Mn, Fe, Ti, Co, Cr, Ni, etc.) have kept catching researchers’ eyes due to their mature developments in commercial LIBs over decades.P2-type Ni/Mn-based LTMOs (such as Na0.67Ni0.33Mn0.67O2, NNMO) exhibit high theoretical specific capacity (~173 mAh g− 1) with environmentally friendly and cheap elements. However, they show limited stability upon charging over 4.2 V, directly restricting their energy density and lowering operating voltage. Besides, disadvantages such as poor rate performance and air/moisture sensitivity are remaining improvements for commercialization. Hence, our study mainly focuses on improvements for shortages of NNMO by applying a facile cation-and-anion co-doping strategy. Via transition metal Cu ion doping, the cycling stability of NNMO can be improved without sacrificing too much capacity, and the air stability can also be improved. In addition, F doping to replace oxygen can further enhance the structural stability and increase the rate performance by modifying interlayer spacing of the layered structure. A facile sol-gel method with heat treatment is used to synthesize cation-and-anion co-doped NNMO. The material characterization shows successful synthesis after cation and anion doping. In addition, the long cycle test shows that capacity retention increases from ~50% to ~90% over 100 cycles after Cu doping. The specific discharge capacity also increases from ~110 mAh/g to ~130 mAh/g at 0.1C with a slight increase in cycle retention from ~75% to ~77% after F doping. Also, the capacity at 20C could be maintained at ~50 mAh/g, around 45% of the initial capacity at 0.1C. The detailed charge storage mechanism will be studied by applying operando X-ray absorption spectroscopy and ex-situ X-ray photoelectron spectroscopy. As for the moisture sensitivity part, the XRD spectra indicate that no noticeable structural changes or impurity formation occurred after air exposure for one month, showing good air stability. Furthermore, operando XRD is conducted to confirm structural reversibility during charging and discharging.In summary, by applying a simple Cu/F co-doping strategy, Na0.67Ni0.13Cu0.20Mn0.67O2-xFx exhibits sufficient cycle stability for over 100 cycles as well as excellent rate capability even at a high current density of 20C, which proves itself a promising candidate as high-performance cathode material in SIBs. In addition, the cheap and environmentally friendly elemental usage (Ni, Mn and Cu) and air-stability enhancement also increase possibility of this material for large-scale energy storage application in industry.

Glassy Oxides as Positive Electrode Materials for Sustainable and High Energy Density Li-Ion and Na-Ion Batteries: First Attempts to Establish Relationships between Glass Compositions, Physicochemical Characterizations and Electrochemical Properties with Machine Learning and Design of Experiments Approaches

Today, rechargeable lithium-ion batteries (LIBs) represent one of the best alternatives to reduce our dependency on fossil fuels. LIBs are using cathode materials based on polycrystalline oxides or polyanionic compounds [1]. However, their performances can be limited by their crystalline structure when other compounds suffer from metallic dissolution and irreversible phase changes during cycling [2]. To overcome these key shortcomings, implementing glasses or glass-ceramics as cathode materials is an interesting approach [3]. Glasses have a structure composed of more free volume, and, in the literature that is mainly concerning glasses containing Vanadium transition metal, the glasses can so accept a large amount of lithium [4] and easily accommodate structural changes upon lithium ions extraction/insertion [5]. Furthermore, glass production is a scalable process and can be commercially easier to implement than most of synthesis processes of conventional cathode materials.The main objective targeted is to develop high capacity positive electrodes (up to 300mAh/g) for Li-ion batteries based on glassy oxides without critical transition metals such as Cobalt and Vanadium. The ambitious target is to exceed 1000Wh/kg at the active material level and so enable energy densities of 300-350 Wh/kg at the Li-Ion cell level. Additionally, the electrochemical behavior of some alkali-free glass compositions will be evaluated in sodium-ion configuration. The major scientific objective is to correlate the most relevant physicochemical properties of glass with the corresponding electrochemical performances using machine learning approaches or design of experiment methodology. For a better understanding of involved processes, three oxides glass families are studied as promising cathode materials for sustainable and high energy density lithium batteries. These oxides are composed of: i) a glass network-forming element (Si, B, P) leading to the 3 different families, ii) a transition metal (Mn, Fe, ...) and optionally iii) an alkali (Li, Na).The influence of the nature of the transition metal and the polyanionic group corresponding to the network-forming element (PO4, BO3, SiO4) on the electrical properties of the as-prepared glasses measured at different temperatures will be presented mainly for the lithiated compounds. For microstructural characterization, several techniques were coupled such as X-Ray Diffraction (XRD), SEM-EDX, DTA/TGA, Raman, IR and UV-Vis spectroscopies, Electrochemical Impedance Spectroscopy (EIS) and chronoamperometry.Finally, the electrochemical properties in terms of specific capacity, redox potentials, first cycle capacity loss, coulombic and energetic efficiencies of these materials were investigated in coin-cells vs lithium (or sodium) metal electrode. To understand the electrochemical processes involved in these materials at room temperature, SEM-EDX, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Mossbauër Spectroscopy for iron based compounds were coupled and performed on the as-prepared glasses and on ex-situ (after cycling) materials at different electrochemical states of charge.All the generated data and measurements were analyzed by machine learning approach and tools and in some cases compared with a more classical Design of Experiments (DOE) approach. For instance, figure 1 illustrates the contour diagram of first discharge capacities in the mixture diagram of phosphate glasses based on 3 different transition metal oxides. The final goal is to establish more precisely the relationships between the different glassy oxides structures and their electrochemical performances. First results of this important work of elaboration, characterization and data analysis will be presented here. This new study will bring significant elements to optimize both the glass composition and its elaboration conditions to obtain high performance cathode materials without critical materials.[1] Nitta, N. et al., Li-ion battery materials: present and future. Materials Today 18, 252–264 (2015).[2] Tesfamhret, Y. et al., On the Manganese Dissolution Process from LiMn2O4 Cathode Materials. ChemElectroChem 8, 1516–1523 (2021).[3] K. Kercher et al., « Mixed polyanion glass cathodes: Glass-state conversion reactions », J. Electrochem. Soc., vol. 163, no 2, p. A131-A137, 2016, doi: 10.1149/2.0381602jes [4] Afyon, S. et al., New High Capacity Cathode Materials for Rechargeable Li-ion Batteries. Scientific Reports 4, 7113 (2015).[5] Kindle, M. et al., Alternatives to Cobalt. ACS Sustainable Chemistry Engineering 9, 629–638 (2021). Figure 1

A High-Entropy Intergrowth Layered-Oxide Cathode with Enhanced Stability for Sodium-Ion Batteries.

Layered transition metal oxides are widely considered as ideal cathode materials for SIBs. However, the existing P2 and O3 structures possess specific issues, which limit their practical applications. To address these issues, this work designed a novel intergrowth layered oxide cathode with P2 and O3 phases by implementing Cu and Ti into the structure with the formation of high-entropy cathode materials with superior performance for SIBs. The electrochemical test results show that the optimized high-entropy cathode with the P2/O3 intergrowth structure possesses a high initial discharge capacity of 157.85 mAh g-1 at 0.1 C, an excellent rate performance of 84.41 mAh g-1 at 10 C, and long-term stability with capacity retention of 83.25 % after 500 cycles at 5 C. Furthermore, the analysis results of ex situ XRD and in situ XRD indicate that the adverse phase transition of P2-O2 under high voltage is effectively suppressed. This work indicates that the integration of high-entropy strategy with the two-phase intergrowth structure can effectively stabilize the layered structure, suppress the slipping of transition metal layers, and improve electrochemical performance, which provides a new approach for designing high-performance and practical layered transition metal oxide cathode materials for advanced SIBs.

Regulation of Electron Delocalization Region in 2D Heteroligand-Based Copper-Organic Framework to Enhance Charge Storage.

The rechargeable aqueous ammonium ion battery shows great potential in low-cost energy storage system because of its long life and environmental friendliness. However, most inorganic host materials used in ammonium ion batteries are still limited by slow diffusion kinetics. Herein, it is identified that a 2D heteroligand-based copper-organic framework featuring numerous ammonium ion adsorption site in the π-conjugated periodic skeleton supplies multiple accessible redox-active sites for high-performance ammonium storage. Benefitting from the effective regulation of electron delocalization by heteroligand and the inherent hydrogen bond cage mechanism between ammonium ions, the resultant full battery delivers a large specific energy density of 211.84Whkg-1, and it can be stably operated for 12000 cycles at 5Ag-1 for over 80 days. This explanatory understanding provides a new idea for the rational design of high-performance MOF-based ammonium ion battery cathode materials for efficient energy storage and conversion in the future.