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At least 19 records

Fluorinated Rocksalt‐Polyanion Cathode for Lithium‐Ion Batteries

Integrated rocksalt‐polyanion cathodes (DRXPS) are promising candidates for next‐generation lithium‐ion battery cathode materials that combine high energy density, stable cycling performance, and reduced reliance on Co and Ni. In this work, we investigated Li 3 Mn 1.6 P 0.4 O 5.4 F 0.6 , a new DRXPS cathode with fluoride incorporation. A pure spinel phase was formed and a discharge capacity retention of 84% was achieved after 200 cycles between 1.5 and 4.8 V versus Li/Li + . In comparison, the similarly synthesized Li 3 Mn 1.6 Nb 0.4 O 5.4 F 0.6 , in which all P 5+ was substituted by Nb 5+ while maintaining the same stoichiometry for all other elements, crystallized in a disordered rocksalt structure, and exhibited inferior capacity retention and rate capability than the P 5+ counterpart. Our findings expand the compositional space of DRXPS to include F − , justify the viability of integrating polyanion groups in rocksalt‐type cathodes, and highlight the superiority of P 5+ as a cation charge compensator compared to the commonly used Nb 5+ . This work thereby advances the design of robust, high‐performance cathode materials for sustainable batteries.

36 MATERIALS SCIENCE↗

Demystifying In Situ Pyrolysis Chemistry for High-Performance Polyanionic Cathodes in Sodium-Ion Batteries

In this article, the carbon coating strategy has emerged as an indispensable approach to improve the conductivity of polyanionic cathodes. However, owing to the complex reaction process between precursors of carbon and cathode, establishing a unified screening principle for carbonaceous precursors remains a technical challenge. Herein, we reveal that carbonaceous precursor pyrolysis chemistry undeniably influences the formation process and performance of Na 3 V 2 (PO 4 ) 3 (NVP) cathodes from in situ insights. By investigating three types of carbonaceous precursors, it is found that O/H-containing functional groups can provide more bonding sites for cathode precursors and generate a reducing atmosphere by pyrolysis, which is beneficial to the formation of polyanionic materials and a uniform carbon coating layer. Conversely, excessive pyrolysis of functional groups leads to a significant amount of gas, which is detrimental to the compactness of the carbon layer. Furthermore, the substantial presence of residual heteroatoms diminishes graphitization. In this case, it is demonstrated that carbon dots (CDs) precursors with suitable functional groups can comprehensively enhance the Na+ migration rate, reversibility, and interface stability of the cathode material. As a result, the NVP/CDs cathode displays outstanding capacity retention, maintaining 92% after 10,000 cycles at a high rate of 50 C. Altogether, these findings provide a valuable benchmark for carbon source selection for polyanionic cathodes.

25 ENERGY STORAGE↗

Integrated rocksalt–polyanion cathodes with excess lithium and stabilized cycling

Co- and Ni-free disordered rocksalt cathodes utilize oxygen redox to increase the energy density of lithium-ion batteries, but it is challenging to achieve good cycle life at high voltages >4.5 V (versus Li/Li + ). Here, in this study, we report a family of Li-excess Mn-rich cathodes that integrates rocksalt- and polyanion-type structures. Following design rules for cation filling and ordering, we demonstrate the bulk incorporation of polyanion groups into the rocksalt lattice. This integration bridges the two primary families of lithium-ion battery cathodes—layered/spinel and phosphate oxides—dramatically enhancing the cycling stability of disordered rocksalt cathodes with 4.8 V upper cut-off voltage. The cathode exhibits high gravimetric energy densities above 1,100 Wh kg -1 and >70% retention over 100 cycles. This study opens up a broad compositional space for developing battery cathodes using earth-abundant elements such as Mn and Fe.

36 MATERIALS SCIENCE↗

Computational and experimental search for potential polyanionic K-ion cathode materials

Discovering high-energy cathode materials is critical to construct K-ion batteries for practical applications. Owing to the great success of layered oxides in Li- and Na-ion systems, K layered cathodes have also been investigated in recent years. However, the much larger size of K + compared to Li or Na introduces strong K + –K + interaction within the layer, which results in a sloped voltage profile thereby limiting the specific capacity and operating voltage. In contrast, polyanionic materials with a three-dimensional K + arrangement can effectively mitigate K + –K + interaction. In this work, ten K polyanionic compounds with theoretical capacity >100 mA h g –1 are screened from the Inorganic Crystal Structure Database as potential cathode materials for K-ion batteries. Among the ten proposed compounds, K 2 MnP 2 O 7 , K 2 Mn 2 P 2 O 7 F 2 , K 2 Fe 2 P 2 O 7 F 2 , and K 6 V 2 (PO 4 ) 4 with average voltage <4.5 V are synthesized and evaluated electrochemically. While the re-insertion of K into these compounds is not fully reversible, it may be related to the very high migration barrier that we compute for K ions. In addition, we show the successful synthesis of a series of K 3 V 3–x Cr x (PO 4 ) 4 (x = 0, 1, 2, 3) compounds. Among these, K 3 V 2 Cr(PO 4 ) 4 exhibits the largest reversible capacity, as revealed by the in situ investigation. Lastly, we find that the redox couples in many of these compounds sit at remarkably high potential, even higher than in equivalent Li compounds, which brings both opportunities and challenges in the future research of K polyanion cathodes.

25 ENERGY STORAGE↗

Counter-Intuitive Structural Instability Aroused by Transition Metal Migration in Polyanionic Sodium Ion Host

The structure of polyanionic materials is conventionally known to be free of transition metal migration and structurally stable when storing/releasing sodium ions. Herein, the observation of enhanced cycling stability of a typical polyanionic cathode, Na 3 VCr(PO 4 ) 3 (NVCP) at lower temperature (-15 degrees C vs 30 degrees C), triggers the exploration of its structural origins with a surprising finding that the migratable nature of vanadium in NVCP leads to detrimental structural degradation of the polyanionic host upon cycling. The correlation between long range and short range structural change associated with this atomic migration is established via a strong combination of various in situ/ex situ characterization tools, revealing the essential V-to-Na1 site migration. Such transition metal migration is effectively suppressed when V atoms are pinned to their original position in the lattice by lowering the temperature. More importantly and practically, a room temperature-based deep sodiation strategy is further developed to recover the structure. Overall, this work challenges the long-standing assumption of the stability of the polyanionic framework structure and calls for urgent attention to the structural understanding of the NVCP system as well as strategy development for property enhancement.

25 ENERGY STORAGE↗

A new high voltage alluaudite sodium battery insertion material

Large-scale stationary storage forms a key sector that can be economically served by sodium-ion batteries. In realizing practical sodium-ion batteries, discovery and development of novel cathodes is essential. In this spirit, alluaudite-type Na 2 Fe 2 (SO 4 ) 3 was reported in 2014 to have the highest Fe 3+ /Fe 2+ redox potential (~3.8 V vs. Na). This finding led to reports on various PO4 3– and SO4 2– based alluaudite compounds exhibiting high energy densities. In 2017, MoO 4 2– based alluaudite, Na 2.67 Mn 1.67 (MoO 4 ) 3 , was found as a 3.45 V cathode material. Exploring molybdenum chemistry further, this work reports alluaudite type Na 3.36 Co 1.32 (MoO 4 ) 3 (NCMo) as a novel versatile electroactive cathode for Li-ion and Na-ion batteries. It was synthesized by a wet solution-combustion route with a restricted annealing duration of 1 min at 600 °C. Calorimetric study revealed the formation enthalpy from component oxides (ΔH° f,ox = –575.49 ± 7.75 kJ/mol) to be highly exothermic. Unlike the sulfate class of alluaudites, this material is highly stable in air and moisture (ΔH ds = 537.42 ± 0.78 kJ/mol). Having an ionic conductivity of 6.065 × 10 –8 S/cm (at 50 °C), it offers a pseudo two-dimensional Na + migration pathway. Without any material optimization, NCMo was found to work as a high-voltage insertion cathode (ca. 4.0 V vs. Na/Na + and 4.1 V vs. Li/Li + ) in sync with theoretically predicted potential of 3.98 V (vs. Na/Na + ). Ex-situ X-ray diffraction and photoelectron spectroscopy studies revealed the occurrence of solid-solution redox mechanism solely involving Co 3+ /Co 2+ redox centre. Finally, it benchmarks Na 3.36 Co 1.32 (MoO 4 ) 3 as a novel electrochemically active Mo-based alluaudite-type polyanionic cathode insertion material.

25 ENERGY STORAGE↗

Understanding High-Voltage Behavior of Sodium-Ion Battery Cathode Materials Using Synchrotron X-ray and Neutron Techniques: A Review

Despite substantial research efforts in developing high-voltage sodium-ion batteries (SIBs) as high-energy-density alternatives to complement lithium-ion-based energy storage technologies, the lifetime of high-voltage SIBs is still associated with many fundamental scientific questions. In particular, the structure phase transition, oxygen loss, and cathode–electrolyte interphase (CEI) decay are intensely discussed in the field. Synchrotron X-ray and neutron scattering characterization techniques offer unique capabilities for investigating the complex structure and dynamics of high-voltage cathode behavior. In this review, to accelerate the development of stable high-voltage SIBs, we provide a comprehensive and thorough overview of the use of synchrotron X-ray and neutron scattering in studying SIB cathode materials with an emphasis on high-voltage layered transition metal oxide cathodes. We then discuss these characterizations in relation to polyanion-type cathodes, Prussian blue analogues, and organic cathode materials. Finally, future directions of these techniques in high-voltage SIB research are proposed, including CEI studies for polyanion-type cathodes and the extension of neutron scattering techniques, as well as the integration of morphology and phase characterizations.

25 ENERGY STORAGE↗

Optimization of the compositions of polyanionic sodium-ion battery cathode NaFe 2-x V x (PO 4 )(SO 4 ) 2

Sodium (Na) super ionic conductor (NASICON) polyanionic compounds have recently attracted much attention from the battery community because of their electroactive properties and reasonably high ionic conductivities, leading to their use as a cathode in sodium-ion batteries. This article describes the compositional optimizations, crystallographic evaluations, and electrochemical behavior of a new mixed NASICON polyanionic compound, NaFe 2-x V x (PO 4 )(SO 4 ) 2 . By doping the characteristic Fe 3+ sites of the FeO 6 octahedrons with varying amounts of V 3+ , the electrochemical stability and charge transport in NaFe 2 (PO 4 )(SO 4 ) 2 were enhanced. The resulting best composition, with crystal structure NaFe 1.4 V 0.6 (PO 4 )(SO 4 ) 2 resolved through the Rietveld method, exhibited a stable capacity compared with the other synthesized compositions. In situ powder x-ray diffraction measurements, a single-phase intercalation/deintercalation mechanism of the NASICON structure in the measured sodium concentration window was observed with no impurity phase formation. Further electrochemical assessments revealed the interfacial charge transfer kinetics to be the rate-limiting step in the sodium concentration window. Also, the measured sodium-ion diffusivity values in the range of 6 × 10 -11 to 7 × 10 -11 cm 2 /s in the measured sodium concentration range. The results reported here highlight the potential of compositionally and morphologically optimized NaFe 1.4 V 0.6 (PO 4 )(SO 4 ) 2 with higher particle surface areas as a cathode material for high-performance sodium-ion batteries.

25 ENERGY STORAGE↗

Chemical factors controlling the behaviour of oxide cathodes in batteries

Oxide cathodes enable high-energy lithium-ion and sodium-ion batteries, with their performances fundamentally governed by three interrelated chemical factors: electronic configuration, chemical bonding, and chemical reactivity. Here, we illustrate how these factors dictate the redox energy, structural stability, ionic and electronic transport, and interfacial behavior in both layered oxide and polyanion oxide cathodes. We discuss how crystal-field effects and octahedral-site stabilization energies influence cation migration, and how inductive effects tune bond covalency and operating voltages. We also explain how chemical bonding governs thermal stability, gas evolution, and first-cycle capacity loss, and how alignment of transition-metal redox band with the oxygen 2p band determines electrolyte reactivity. Comparison between lithium and sodium layered oxides further reveals how differences in Li-O and Na-O bond ionicity affect chemical reactivity. Finally, we outline strategies including compositional tuning, surface doping, and electrolyte optimization, and emphasize how high-throughput, data-driven approaches in guiding the design of next-generation oxide cathodes.

25 ENERGY STORAGE↗

Stable-Cycling Sustainable Na-Ion Batteries with Olivine Iron Phosphate Cathode in an Ether Electrolyte

Sustainable batteries using nontoxic, earth-abundant, and low-cost materials are key to decarbonization. Olivine NaFePO 4 fulfills these criteria, is attractive for Na-ion batteries, and can be derived from LiFePO 4 recycled from Li-ion battery wastes. Critical knowledge is needed for transforming LiFePO 4 to NaFePO 4 to enable such a sustainable, green engineering path toward high-performance Na-ion batteries. Herein, we report on the development of a stable-cycling, sustainable olivine iron phosphate-based Na-ion battery empowered by an improved understanding of materials transformation and electrolyte chemistry. First, we found that the conventional carbonate electrolyte with fluoroethylene carbonate additive causes an additional plateau (~2.4 V) at the end of the discharge process of the FePO 4 ||Na metal cell, leading to lower initial discharge capacity and voltage. This result shows that the voltage profile is influenced by not only intrinsic materials phase transformation during battery cycling but also the electrolyte additives and interphases formed. With the 1 M NaPF 6 diglyme electrolyte, we achieved an excellent capacity retention of 96% and 98% after 500 cycles at 1 and 5 C, respectively. Second, we chemically sodiated FePO 4 to form single-phase Na 0.9 FePO 4 . Na 0.9 FePO 4 ||hard carbon full cells demonstrated a remarkable capacity retention of ~84% at 3 and 5 C after 1000 cycles. The successful implementation of hard carbon, which can be derived from biomass waste, will further improve the sustainability of energy storage technologies. Our research demonstrates that electrolyte chemistry influences the voltage profile of phase-changing electrodes and provides effective electrolyte and full-cell design solutions for stable-cycling NaFePO 4 .

36 MATERIALS SCIENCE↗

Polyanion-type iron-based sulfate cathode materials: From fundamental research to industrialization

Sodium-ion batteries (SIBs) with the merits of abundant sodium resources and low cost are considered significant supplements to lithium-ion batteries in large-scale energy storage systems. Among the discovered cathode materials for SIBs, iron-based sulfate materials have attracted widespread attention due to their high operating voltage, superior structural stability, and high safety. Here, in this review, we summarize the research achievements of iron-based sulfate cathode materials in fundamental research, as well as provide a comprehensive overview of its industrialization progress for the first time. Meanwhile, effective modification strategies (including morphology design, hybridization with carbon materials, and construction of heterostructure) and further research directions to boost the sodium storage performance of iron-based sulfate cathode materials are also proposed. This review can provide valuable guidance for developing high-performance iron-based sulfate cathode materials for practical application.

cathode materials↗

Voltage Mining for (De)lithiation-Stabilized Cathodes and a Machine Learning Model for Li-Ion Cathode Voltage

Advances in lithium-metal anodes have inspired interest in discovery of Li-free cathodes, most of which are natively found in their charged state. This is in contrast to today's commercial lithium-ion battery cathodes, which are more stable in their discharged state. In this study, we combine calculated cathode voltage information from both categories of cathode materials, covering 5577 and 2423 total unique structure pairs, respectively. The resulting voltage distributions with respect to the redox pairs and anion types for both classes of compounds emphasize design principles for high-voltage cathodes, which favor later Period 4 transition metals in their higher oxidation states and more electronegative anions like fluorine or polyanion groups. Generally, cathodes that are found in their charged, delithiated state are shown to exhibit voltages lower than those that are most stable in their lithiated state, in agreement with thermodynamic expectations. Deviations from this trend are found to originate from different anion distributions between redox pairs. In addition, a machine learning model for voltage prediction based on chemical formulas is trained and shows state-of-the-art performance when compared to two established composition-based ML models for material properties predictions, Roost and CrabNet.

25 ENERGY STORAGE↗

Biomimetic composite architecture achieves ultrahigh rate capability and cycling life of sodium ion battery cathodes

Sodium ion batteries are an emerging candidate to replace lithium ion batteries in large-scale electrical energy storage systems due to the abundance and widespread distribution of sodium. Despite the growing interest, the development of high-performance sodium cathode materials remains a challenge. In particular, polyanionic compounds are considered as a strong cathode candidate owing to their better cycling stability, a flatter voltage profile, and stronger thermal stability compared to other cathode materials. Here, we report the rational design of a biomimetic bone-inspired polyanionic Na3V2(PO4)3-reduced graphene oxide composite (BI-NVP) cathode that achieves ultrahigh rate charging and ultralong cycling life in a sodium ion battery. At a charging rate of 1 C, BI-NVP delivers 97% of its theoretical capacity and is able to retain a voltage plateau even at the ultra-high rate of 200 C. It also shows long cycling life with capacity retention of 91% after 10 000 cycles at 50 C. The sodium ion battery cells with a BI-NVP cathode and Na metal anode were able to deliver a maximum specific energy of 350 W h kg−1 and maximum specific power of 154 kW kg−1. In situ and postmortem analyses of cycled BI-NVP (including by Raman and XRD spectra) HRTEM, and STEM-EELS, indicate highly reversible dilation–contraction, negligible electrode pulverization, and a stable NVP-reduced graphene oxide layer interface. The results presented here provide a rational and biomimetic material design for the electrode architecture for ultrahigh power and ultralong cyclability of the sodium ion battery full cells when paired with a sodium metal anode.

25 ENERGY STORAGE↗

Li 5 VF 4 (SO 4 ) 2 : A Prototype High-Voltage Li-Ion Cathode.

A Li-rich polyanionic compound based on V 3+ with a previously unknown structure, Li 5 VF 4 (SO 4 ) 2 , has been developed as a high-voltage cathode material for Li-ion batteries. The solvothermal preparation of this material, crystal structure solution, and initial electrochemical characterization are presented. An analysis based on density functional theory electronic structure calculations suggests that a high voltage close to 5 V is required to extract two Li ions and to reach the oxidation state of V 5+ . However, the use of conventional carbonate-based electrolytes, which exhibit increasing degradation above a potential of 4.3 V, does not permit the full capacity of this compound to be achieved at this time.

25 ENERGY STORAGE↗

Developing low-cost rechargeable batteries: beyond traditional layered oxide cathodes for Li-ion and beyond Li-ion batteries

Here, the rising demand for energy storage systems, driven by the rapid adoption of electric vehicles and the global shift toward renewable energy, necessitates continuous efforts to lower the cost of current lithium-ion batteries (LIBs) and enhance the sustainability of existing battery chemistries. This feature article examines the key challenges associated with Ni- and Co-containing LIB cathodes and compares advancements in cathode development for non-traditional Li-ion and beyond Li-ion chemistries. First, a review of earth-abundant element containing disordered rock-salt cathodes is presented, with a discussion of key strategies such as compositional tuning and carbon coating to improve their electrochemical performance. Hurdles in developing oxide-based cathodes for Na- and K-ion batteries are also highlighted, followed by an in-depth overview of polyanion and Prussian blue cathodes for Na- and K-ion systems. Overall, this article provides a systematic perspective on the design of earth-abundant, low-cost, and sustainable cathode materials for both LIB and beyond LIB technologies.

Lohani, Harshita [Lawrence Berkeley National Labor↗

Engineering Na‐Rich P2‐Type Layered Oxides Through Li/Ti Dual Doping for Oxygen Redox Activation and Superior Structural Stability

Sodium layered oxides Na x MO 2 (x ≤ 1 and M = transition metal ions) have gained significant interest as sodium-ion battery (NIB) cathodes owing to their high operating voltages and potential for higher energy density compared with polyanion and Prussian blue–type cathodes. However, their practical applications are often hindered by the irreversible structural transitions leading to capacity fading during cycling. The nature and substitution of transition metal ions define the material properties and electrochemical performance. In this study, through comprehensive electrochemical characterization combined with multi-scale structural and spectroscopical analyses, we demonstrate the synergistic impacts of Lithium and Titanium doping, which not only increases overall capacity by boosting cation and anion cooperative redox contributions but also improves the rate capability and cycling stability. Specifically, Li + doping enhances the available sodium inventory for extraction, while Ti 4+ disrupts Na + /vacancy ordering at lower voltages (< 4 V) and mitigates the detrimental P2→OP4/O2 phase transition during cycling. The combined effect of Lithium and Titanium doping promotes more charge localization on Oxygen, which activates reversible lattice oxygen redox reactions at elevated voltages, contributing additional capacity beyond conventional cationic redox. This work provides crucial insights into the design of high-performance, high-capacity P2-type layered cathode materials for sodium-ion batteries.

36 MATERIALS SCIENCE↗

Polyanionic insertion hosts for aqueous rechargeable batteries

Safety concerns and costs of present-day lithium-ion batteries (LIBs) are prompting the development of alternate battery technologies with different types of electrolyte ( e.g. , solid-state, gel-polymer, aqueous, etc. ); notably, systems based on aqueous electrolytes have emerged as a promising alternative, especially for grid storage applications. The last decade has witnessed a considerable spike in the research carried out on aqueous batteries. However, the narrow operating voltage window of aqueous electrolytes and the structural instability of materials in aqueous media demand proper selection of cathode materials to achieve desirable energy density. Polyanionic materials can be an ideal choice as they are structurally more stable and exhibit tunable redox potentials. This class of materials is considered as a storehouse in which many materials can be realized by substituting different polyanionic subunits. Here, this review highlights some of the recent advances made in the polyanionic class of cathode materials for rechargeable aqueous batteries (Li-, Na- and Zn-ion batteries). The challenges facing the field, possible remedies to overcome them and future perspectives are also presented.

25 ENERGY STORAGE↗

A Polymer-Assisted Spinodal Decomposition Strategy toward Interconnected Porous Sodium Super Ionic Conductor-Structured Polyanion-Type Materials and Their Application as a High-Power Sodium-Ion Battery Cathode

A general polymer-assisted spinodal decomposition strategy is used to prepare hierarchically porous sodium super ionic conductor (NASICON)-structured polyanion-type materials (e.g., Na 3 V 2 (PO 4 ) 3 , Li 3 V 2 (PO 4 ) 3 , K 3 V 2 (PO 4 ) 3 , Na 4 MnV(PO 4 ) 3 , and Na 2 TiV(PO 4 ) 3 ) in a tetrahydrofuran/ethanol/H 2 O synthesis system. Depending on the boiling point of solvents, the selective evaporation of the solvents induces both macrophase separation via spinodal decomposition and mesophase separation via self-assembly of inorganic precursors and amphiphilic block copolymers, leading to the formation of hierarchically porous structures. We find that the resulting hierarchically porous Na 3 V 2 (PO 4 ) 3 possessing large specific surface area (≈77 m 2 g -1 ) and pore volume (≈0.272 cm 3 g -1 ) shows a high specific capacity of 117.6 mAh g -1 at 0.1 C achieving the theoretical value and a long cycling life with 77% capacity retention over 1000 cycles at 5 C. This method presented here can open a facile avenue to synthesize other hierarchically porous polyanion-type materials.

36 MATERIALS SCIENCE↗