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At least 91 records · Page 5

Ball Milling-Enabled Fe 2.4+ to Fe 3+ Redox Reaction in Prussian Blue Materials for Long-Life Aqueous Sodium-Ion Batteries

Aqueous Na-ion batteries using Prussian blue materials have inherent advantages on safety, material sustainability, and economic cost. However, it is challenging to obtain long term cycling stability because many redox reactions have poor intrinsic stability in water. In this report we demonstrate reversible Fe 2.4+ to Fe 3+ redox reaction of Prussian blue electrodes cycled in 17 m NaClO 4 water-in-salt electrolyte. The cubic phase c-Na 1.17 Fe[Fe(CN) 6 ]·0.35H 2 O) derived from monoclinic Prussian blue (m-Na 1.88 Fe[Fe(CN) 6 ]·0.7H 2 O) through ball milling delivers excellent cycling stability of >18,000 cycles with >90% capacity retention at 10C rate. The specific capacity is ~75 mAh/g and ~67 mAh/g at 1C and 10C rate, respectively. Systematic characterizations including electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy have verified the phase transition and iron oxidation state evolution, revealing the mechanism that enables the material’s high rate and long durability as the battery cathode.

25 ENERGY STORAGE↗

Weakly solvating ester electrolyte for high voltage sodium-ion batteries

Ethyl acetate (EA) was identified as a promising electrolyte solvent for sodium-ion batteries (SIBs), exhibiting low viscosity, cost-effectiveness, and low toxicity. Despite a significant portion of aggregation being linked to the weak solvation of Na + /EA as revealed by molecular dynamics (MD) simulations, pulsed-field gradient nuclear magnetic resonance (pfg-NMR) analysis identified a noteworthy Na+ diffusion coefficient of 3.95×10 -10 m 2 s -1 at 25°C in the presence of 1 m NaPF 6 salt. Employing fluoroethylene carbonate (FEC) as a film-forming additive to create electrode-electrolyte interphase, this electrolyte surprisingly made ~210 mAh Na 0.97 Ca 0.03 [Mn 0.39 Fe 0.31 Ni 0.22 Zn 0.08 ]O 2 (NCMFNZO)/hard carbon (HC) pouch cells achieve a lengthy cycling lifetime of 250 cycles with ~80 % capacity retention, cycled up to 4.0 V at 40°C. X-ray photoelectron spectroscopy (XPS) revealed increasing interphasial organic species over cycling, augmenting charge transfer resistance on both cathode and anode, particularly during fast charging or low temperatures (<10°C), promoting Na plating. Finally, gas chromatography-mass spectrometry combined with density functional theory identified CO 2 as the major gas generated from charged cathode/electrolyte interactions, exhibiting temperature/voltage dependence.

25 ENERGY STORAGE↗

Mechanically Robust Bismuth-Embedded Carbon Microspheres for Ultrafast Charging and Ultrastable Sodium-Ion Batteries

Advancements in the development of fast-charging and long-lasting microstructured alloying anodes with high volumetric capacities are essential for enhancing the operational efficiency of sodium-ion batteries (SIBs). These anodes, however, face challenges such as declined cyclability and rate capability, primarily due to mechanical degradation reduced by significant volumetric changes (over 252%) and slow kinetics of sodium-ion storage. Herein, we introduce a novel anode design featuring densely packed bismuth (Bi) embedded within highly conductive carbon microspheres to overcome the aforementioned challenges. Remarkably, the high loading Bi anode within carbon microspheres with a high tap density of 2.59 g cm -3 possesses significant mechanical strength exceeding 590 MPa and limits volume swelling of only 10.9% post-sodiation. This anode demonstrates a high volumetric capacity (908.3 mAh cm -3 ), ultrafast chargeability (200 A g -1 , full charge/discharge in just 5.5 s), and outstanding cyclability over 12,000 cycles and maintains exceptional cycling stability even at -30 °C. The full cell paired with a Na 3 V 2 (PO 4 ) 3 cathode retains over 80% capacity after 600 cycles at 36 C, demonstrating a remarkable rate capability of 126 C (full charge/discharge in 28.6 s). Our comprehensive experimental evaluations and chemo-mechanical simulations shed light on the mechanisms underpinning the anode's superior performance. In conclusion, this development marks a significant advancement in the design of durable and fast-charging anodes for high-performance SIBs.

25 ENERGY STORAGE↗

A Perspective on Pathways Toward Commercial Sodium‐Ion Batteries

Lithium-ion batteries (LIBs) have been widely adopted in the automotive industry, with an annual global production exceeding 1000 GWh. Despite their success, the escalating demand for LIBs has created concerns on supply chain issues related to key elements, such as lithium, cobalt, and nickel. Sodium-ion batteries (SIBs) are emerging as a promising alternative due to the high abundance and low cost of sodium and other raw materials. Nevertheless, the commercialization of SIBs, particularly for grid storage and automotive applications, faces significant hurdles. This perspective article aims to identify the critical challenges in making SIBs viable from both chemical and techno-economic perspectives. First, a brief comparison of the materials chemistry, working mechanisms, and cost between mainstream LIB systems and prospective SIB systems is provided. The intrinsic challenges of SIBs regarding storage stability, capacity utilization, cycle stability, calendar life, and safe operation of cathode, electrolyte, and anode materials are discussed. Furthermore, issues related to the scalability of material production, materials engineering feasibility, and energy-dense electrode design and fabrication are illustrated. Finally, promising pathways are listed and discussed toward achieving high-energy-density, stable, cost-effective SIBs.

25 ENERGY STORAGE↗

Ameliorating the sodium storage performance of hard carbon anode through rational modulation of binder

Hard carbon anodes have emerged as promising candidates for sodium-ion batteries due to their inherent advantages. Nevertheless, the surface imperfections in these materials often culminate in irreversible electrolyte consumption, fostering the development of a heterogeneous and fragile solid electrolyte interface (SEI), thereby compromising the initial Coulombic efficiency (ICE). Here, drawing inspiration from the catalytic potential of C=O (carbonyl) bonds in directing preferential salt reduction, we introduce a novel strategy that leverages the modulation of the binder, a long-term overlooked pivotal components in the electrode process. Specifically, Polymethyl methacrylate (PMMA), abundant in C=O groups, is partially substituted for PVDF, ensuring robust adhesion of the electrode material to the current collector while preserving superior mechanical properties. The accurate combination of two binders with delightful compatibility in the state-of-art electrode process, can promote a uniform formation of the SEI on the hard carbon surface enriched in inorganic components, which can ensure long-term interfacial stability and suppresses excessive solvent decomposition and facilitates Na + transfer at the interface. Consequently, the initial Coulombic efficiency of the hard carbon anode with 70 %PMMA binder achieves 86 %, with prominent cycling stability (88 % capacity retention over 500 cycles) at a high current density of 1.2 A g −1 . When paired with high loading cathodes to assemble the pouch cell, it also demonstrates stable operational scenarios.

25 ENERGY STORAGE↗

Stable cycling of high-mass loaded MnO 2 electrodes for sodium-ion batteries

Achieving cost-effective, sustainable solutions for large-scale energy storage are critical for advancing the global clean energy transition. In view of the challenges posed by limited lithium reserves, low-cost sodium-ion batteries (SIBs) have emerged as a promising direction, especially for grid-level energy storage. Among the various battery electrode materials, manganese dioxide (MnO 2 ) stands out as a favorable choice for such large-scale applications due to its earth abundance, cost-effectiveness, and non-toxic nature. Although MnO 2 is known as a pseudocapacitive material with superior cycling stability in aqueous electrolytes, its dissolution in non-aqueous electrolytes has restricted its use in long-lifetime batteries. In this study, we address two issues which have limited the use of MnO 2 electrodes in non-aqueous electrolytes. First, using electrochemical quartz crystal microbalance measurements in combination with other electrochemical methods, we demonstrate that diglyme (bis(2-methoxyethyl) ether) electrolyte can achieve stable cycling of electrodeposited ε-MnO 2 . These results enable us to tackle a second objective, that is increasing the mass loading of the MnO 2 electrode, since achieving high areal energy density is a significant factor in reducing manufacturing costs. Using 3D printed graphene aerogel (GA) as a scaffold, our studies show that the electrodeposited MnO 2 /GA electrodes possess scalable properties with mass loadings from 20 to 80 mg cm −2 . The resulting electrodes exhibit areal energy densities as high as 4.4 mA h cm −2 at a current density of 10 mA cm −2 . The high mass loaded MnO 2 electrodes were incorporated as a cathode in a SIB which used TiO 2 as the anode. The SIB device exhibited excellent performance with power densities in excess of 70 mW cm −2 . These studies highlight the promise of MnO 2 electrodes for use in a low-cost technology for large-scale energy storage.

25 ENERGY STORAGE↗

Rinse-Free, Sodium-Efficient Synthesis of O3-Type Layered Oxide Materials Enabled by Acetate Precursors

Sodium-ion batteries (SIBs) are a sustainable alternative to lithium-ion systems for global electrification, with O3-type layered oxide cathodes offering high specific capacity and feasibility of scalable synthesis. Industrial co-precipitation synthesis of these cathodes typically uses transition metal sulfates, requiring extensive water rinsing to remove Na 2 SO 4 impurities, a process that consumes significant water and risks residual inactive phases if incomplete. Here, this work introduces a rinse-free, resource-efficient approach using metal acetate precursors. Residual sodium acetate in non-rinsed precursors decomposes during sintering to generate Na 2 CO 3 in situ, partially substituting an external sodium resource (e.g., NaOH and Na 2 CO 3 ) and reducing its consumption by ∼18–20%. Phase-pure O3-Na 1.0 Ni 1/3 Fe 1/3 Mn 1/3 O 2 (NFM111) cathodes synthesized via this method exhibit microstructure and electrochemical performance comparable to rinsed sulfate-derived counterparts, with initial capacities of 141 mAh g −1 at C/20 (7.5 mA g −1 ). By eliminating rinsing and minimizing sodium reagent use, this acetate-based route enhances sustainability and scalability of layered oxide production for SIBs.

acetate vs. sulfate↗

Comprehensively Strengthened Metal‐Oxygen Bonds for Reversible Anionic Redox Reaction

Introducing anionic redox in layered oxides is an effective approach to breaking the capacity limit of conventional cationic redox. However, the anionic redox reaction generally suffers from excessive oxidation of lattice oxygen to O 2 and O 2 release, resulting in local structural deterioration and rapid capacity/voltage decay. Here, a Na 0.71 Li 0.22 Al 0.05 Mn 0.73 O 2 (NLAM) cathode material is developed by introducing Al 3+ into the transition metal (TM) sites. Thanks to the strong Al–O bonding strength and small Al 3+ radius, the TMO 2 skeleton and the holistic TM–O bonds in NLAM are comprehensively strengthened, which inhibits the excessive lattice oxygen oxidation. The obtained NLAM exhibits a high reversible capacity of 194.4 mAh g —1 at 20 mA g —1 and decent cyclability with 98.6% capacity retention over 200 cycles at 200 mA g —1 . In situ characterizations reveal that the NLAM experiences phase transitions with an intermediate OP4 phase during the charge–discharge. Theoretical calculations further confirm that the Al substitution strategy is beneficial for improving the overlap between Mn 3d and O 2p orbitals. Importantly, this finding sheds light on the design of layered oxide cathodes with highly reversible anionic redox for sodium storage.

25 ENERGY STORAGE↗

Research Progress and Perspectives on Pre‐Sodiation Strategies for Sodium‐Ion Batteries

Sodium‐ion batteries (SIBs) with abundant elements have garnered significant attention from researches as a promise compensation to lithium‐ion batteries (LIBs). However, the large‐scale commercial application of SIBs is partially hindered by the limited initial coulombic efficiency (ICE) due to the irreversible formation of solid electrolyte interphase (SEI) and intercalation into the defects in the anode. Similar to pre‐lithiation techniques, pre‐sodiation approaches are considered to be one of the most direct and effective way to compensate for the loss of active sodium at the anode side of SIBs during the initial cycle. In this context, additional sodium ions are pre‐injected to the cathode/anode material by chemical/electrochemical methods, aiming to improve battery span life and energy density. Here, this review delves into the necessity and impact of pre‐sodiation techniques, compiling the latest research progress, for instance, self‐sacrificing cathode additives, over‐sodiated cathode materials, direct contact and solution chemical pre‐sodiation. Notably, the research mechanisms underlying solution chemical pre‐sodiation are highlighted. This comprehensive overview aims to foster a deeper understanding of the pre‐sodiation techniques and expects to provide guidance for realizing the commercial application of high energy density sodium‐ion batteries.

25 ENERGY STORAGE↗

Design of Sodium Chalcohalide Solid Electrolytes with Mixed Anions for All‐Solid‐State Sodium‐Ion Batteries

Solid-state sodium-ion batteries (SSNIBs) have emerged as a promising alternative to lithium-ion systems for grid-scale energy storage, owing to sodium's abundance and the improved safety of solid-state designs. Among various solid-state electrolytes (SSEs), halide-based Na + SSEs offer high electrochemical stability but are limited by low ionic conductivity and poor thermal stability. Herein, a novel class of sodium hafnium chalcohalide SSEs is reported with a dual-anion (S 2− /Cl − ) framework, with a high ionic conductivity of 4.5 × 10 −4 S cm −1 . The incorporation of sulfur enhances Na⁺ mobility by reducing the migration barrier through increased anion polarizability and expanded diffusion pathways. Additionally, S 2− contributes to stronger interatomic bonding, leading to higher cohesive energy density, improved thermal stability, and mechanical robustness. These SSEs exhibit minimal sulfur oxidation and excellent chemical/electrochemical interface stability with different cathode materials, such as O3-layered NaNi 1/3 Fe 1/3 Mn 1/3 O 2 , P2/O3 layered Na 0.85 Mn 0.5 Ni 0.4 Fe 0.1 O 2 , and Na 3 V 2 (PO 4 ) 3 cathodes. As a result, SSNIBs with P2/O3 layered Na 0.85 Mn 0.5 Ni 0.4 Fe 0.1 O 2 employing the sodium hafnium chalcohalide SSEs demonstrate outstanding cycling performance, achieving a capacity retention of 88.5% after 200 cycles at 0.1 C. This study establishes a new design strategy for high-performance SSEs, demonstrating that mixed-anion frameworks offer a viable route to overcome the intrinsic limitations of single-anion electrolytes in next-generation SSNIBs.

DFT calculation↗

Challenges and Prospects of Sodium‐Ion and Potassium‐Ion Batteries for Mass Production

The exponential growth of the lithium‐ion (LIB) market is causing a significant disparity between the supply chain and demand for its resources. In this regard, sodium‐ion and potassium‐ion batteries are promising alternatives to LIBs due to their low cost. However, the larger sizes of Na + and K + ions create challenges that prevent them from achieving energy densities comparable to LIBs while maintaining an acceptable cycle life. Here, in this perspective, the aim is to evaluate the status of Na‐ion and K‐ion batteries and the challenges associated with them on both fundamental and commercial levels. The focus is on the structural instability arising from phase transitions during cycling, intricate chemical degradation processes, and potential avenues for enhancing their performance with a specific goal of improving their viability for grid‐scale energy storage. Materials production and abundance limitations for the chemistries of the state‐of‐the‐art materials and account for critical parameters from both the perspective of researchers and investors are analyzed. This analysis aims to provide insights into the strategic trade‐offs required to effectively implement the technology in real‐world applications, such as grid‐scale storage and other areas. Furthermore, the utilization of metals with low or no supply‐chain problems as an important aspect of these trade‐offs is considered.

25 ENERGY STORAGE↗

Decoding Gas Evolution Pathways and Interfacial Chemistry in Layered Oxide Cathodes for Safer Sodium‐Ion Batteries

Sodium-ion batteries (SIBs) are attractive for the low cost and abundance of sodium. Yet, gas evolution—a critical challenge in SIBs—remains underexplored. Here, online electrochemical mass spectrometry is used to probe gas evolution in layered oxide cathodes with various compositions, cutoff voltages, dopants, and particle morphologies. Compared to LiNiO 2 (LNO), NaNiO 2 releases more gas, even at lower states of charge, due to the higher covalency of Ni─O bond caused by the more ionic Na─O bond through the inductive effect. Among Co, Mn, Al, and Mg, Mn and Mg doping suppress gas release most effectively by enhancing the metal-oxygen bond strength. NaNi 1/3 Fe 1/3 Mn 1/3 O 2 (NFM) cathodes synthesized via coprecipitation (CP-NFM) and solid-state routes exhibit distinct particle morphologies; CP-NFM exhibits more gas evolution, yet secondary particle morphology helps reduce it through differential cathode-electrolyte reactivity between inner and outer primary particles. Among Li, Ti, Mg, and Cu doping in NFM, Li has the largest effect, reducing gas levels comparable to LNO. Nuclear magnetic resonance and X-ray photoelectron spectroscopies reveal that electrolyte solvent decomposition mainly produces organic-rich cathode-electrolyte interphase (CEI) rather than soluble species. NaPF 6 salt further exacerbates cathode-electrolyte reactions, forming surface Na 2 O species. The findings provide actionable guidance for designing safer, durable SIBs.

25 ENERGY STORAGE↗

Regulating Cation Interactions for Zero–Strain and High–Voltage P2–type Na 2/3 Li 1/6 Co 1/6 Mn 2/3 O 2 Layered Oxide Cathodes of Sodium–Ion Batteries

Deep sodium extraction/insertion of sodium cathodes usually causes undesired Jahn–Teller distortion and phase transition, both of which will reduce structural stability and lead to poor long-cycle reliability. Here we report a zero-strain P2- Na 2/3 Li1/6Co 1/6 Mn 2/3 O 2 cathode, in which the lithium/cobalt substitution contributes to reinforcing the host structure by reducing the Mn 3+ /Mn 4+ redox, mitigating the Jahn–Teller distortion, and minimizing the lattice change. 94.5 % of Na + in the unit structure can be reversibly cycled with a charge cut-off voltage of 4.5 V (vs. Na + /Na). Impressively, a solid-solution reaction without phase transitions is realized upon deep sodium (de)intercalation, which poses a minimal volume deviation of 0.53 %. Finally, it attains a high discharge capacity of 178 mAh g –1 , a high energy density of 534 Wh kg –1 , and excellent capacity retention of 95.8 % at 1 C after 250 cycles.

25 ENERGY STORAGE↗

Fast oxygen redox enabled by flexible Al–O bonds in P2-type layered oxides for sodium batteries

Sodium-ion batteries (SIBs) exhibit significant potential for large-scale energy storage systems due to the abundance and low cost of sodium resources. Triggering lattice oxygen redox (LOR) in P2-type transition metal oxides is considered a promising approach to enhance energy density in SIB cathodes, providing high operating potential and substantial capacity. However, irreversible phase transitions associated with LOR, particularly from prisms (P-type stacking) to octahedrons (O-type stacking), lead to severe structural distortions and sluggish Na + diffusion kinetics. In this work, an Al-substitution strategy is proposed to suppress the formation of O-type stacking and instead promote the formation of a beneficial Z phase. Furthermore, the flexible Al-O bonds accommodate asymmetric variations in their occupied states during the sodiation process, mitigating local structural distortions through Al-O bond contraction. Stabilization of the local structure ensures the maintenance of a robust Na + diffusion pathway. As a result, the Al-substituted cathode achieves a low Na + diffusion barrier of 0.47 eV and delivers a capacity of 86 mAh/g even at a high current density of 1 A/g within 1.5–4.5 V, maintaining 62.5% capacity retention over 100 cycles.

36 MATERIALS SCIENCE↗

Discovery of a new phase transition and high-valent redox mechanism in Fe-substituted Na 2 Mn 3 O 7

Sodium-ion batteries are a promising lower-cost alternative to lithium-ion batteries, but further improvements in electrochemical performance are required. One strategy to increase capacity is to enable reversible high-valent cationic and anionic redox in layered cathode materials; however, this is typically accompanied by structural degradation. Here, in this study, we elucidate the mechanism by which Fe-doped Na 2 Mn 3 O 7 , featuring ordered transition metal-vacancies, achieves reversible high-valent redox. Using Mössbauer spectroscopy, soft X-ray absorption spectroscopy (XAS), and in-situ hard XAS, we demonstrate reversible high-valent cationic redox involving both Fe and Mn while in-situ Raman confirms the absence of local structural degradation associated with oxygen redox. Combining in-situ X-ray diffraction with theoretical calculations, we further identify a previously unreported global phase transition from the $\bar{P1}$ to the $P2_1/c$ space group during electrochemical cycling and develop a physical model describing this structural evolution. These results provide insights for structurally stable layered sodium transition metal oxide cathodes with reversible high-valent redox.

36 MATERIALS SCIENCE↗

Understanding the Beneficial Role of Transition-Metal Layer Na + Substitution on the Structure and Electrochemical Properties of the P2-Layered Cathode Na 2+ x Ni 2– x /2 TeO 6

Layered Na x MO 2 sodium oxide positive electrode materials have experienced renewed interest owing to the current commercial attention on sodium-ion batteries. Although there are many attractive qualities of these materials, they suffer from serious shortcomings owing to Na + ordering and transition-metal layer gliding that cause a plethora of voltage plateaus during cycling. The P2-layered Na 2+x Ni 2–x/2 TeO 6 (0 ≤ x ≤ 0.5) system provides a framework for investigating the effect of dual Na + substitution into the sodium layer and the transition-metal layer of the structure and its effects on the electrochemical properties of the materials. A careful investigation into the synthesis and properties of these materials reveals that the sodium content used during material preparation has a drastic effect on the composition and electrochemical profile of these materials. The sodium substitution disrupts ordering within the transition-metal layer, thereby disrupting Na + ordering in the adjacent sodium layers. Beyond a critical sodium concentration, the layer stacking shifts, and all voltage plateaus of the P2-Na 2 Ni 2 TeO 6 material are no longer observed at 4.4 V versus Na + /Na. These results also question the common belief that additional sodium precursor is required when preparing layered sodium oxide cathodes, providing new guidelines for material synthesis and characterization.

36 MATERIALS SCIENCE↗

Stabilizing lattice oxygen redox in layered sodium transition metal oxide through spin singlet state

Abstract Reversible lattice oxygen redox reactions offer the potential to enhance energy density and lower battery cathode costs. However, their widespread adoption faces obstacles like substantial voltage hysteresis and poor stability. The current research addresses these challenges by achieving a non-hysteresis, long-term stable oxygen redox reaction in the P3-type Na 2/3 Cu 1/3 Mn 2/3 O 2 . Here we show this is accomplished by forming spin singlet states during charge and discharge. Detailed analysis, including in-situ X-ray diffraction, shows highly reversible structural changes during cycling. In addition, local CuO 6 Jahn-Teller distortions persist throughout, with dynamic Cu-O bond length variations. In-situ hard X-ray absorption and ex-situ soft X-ray absorption study, along with density function theory calculations, reveal two distinct charge compensation mechanisms at approximately 3.66 V and 3.99 V plateaus. Notably, we observe a Zhang-Rice-like singlet state during 3.99 V charging, offering an alternative charge compensation mechanism to stabilize the active oxygen redox reaction.

25 ENERGY STORAGE↗

A family of dual-anion-based sodium superionic conductors for all-solid-state sodium-ion batteries

The sodium (Na) superionic conductor is a key component that could revolutionize the energy density and safety of conventional Na-ion batteries. However, existing Na superionic conductors are primarily based on a single-anion framework, each presenting inherent advantages and disadvantages. Here we introduce a family of amorphous Na-ion conductors (Na 2 O 2 –MCl y , M = Hf, Zr and Ta) based on the dual-anion framework of oxychloride. Benefiting from a dual-anion chemistry and with the resulting distinctive structures, Na 2 O 2 –MCl y electrolytes exhibit room-temperature ionic conductivities up to 2.0 mS cm -1 , wide electrochemical stability windows and desirable mechanical properties. All-solid-state Na-ion batteries incorporating amorphous Na 2 O 2 –HfCl 4 electrolyte and a Na 0.85 Mn 0.5 Ni 0.4 Fe 0.1 O 2 cathode exhibit a superior rate capability and long-term cycle stability, with 78% capacity retention after 700 cycles under 0.2 C (1C = 120 mA g -1 ) at room temperature. The discoveries in this work could trigger a new wave of enthusiasm for exploring new superionic conductors beyond those based on a single-anion framework.

25 ENERGY STORAGE↗