Ultrahigh Rate Capability Research Articles

Small Molecule‐Assisted Thermal Radiation Synthesis of Super‐Sb Toward Ultrafast and Ultrastable Sodium Storage

AbstractNanostructure engineering of alloying‐type anodes is a key approach to achieving high electrochemical performance in sodium‐ion batteries (SIBs). Despite intensive efforts in traditional calcination methods, synthesizing high‐quality nanomaterials while maintaining ultrafine and homogeneous nanostructure under high temperature remains a key challenge. Herein, a one‐step small molecule‐assisted thermal radiation (MTR) method that fabricates ultrafine Sb nanoparticles with uniform dispersion across heteroatom‐doped carbon supports (Super‐Sb) is reported. This MTR method features the nonequilibrium synthetic conditions induced by ultrafast heating/cooling rate. Additionally, in situ, high‐temperature synchrotron X‐ray diffraction (SXRD) characterization of the MTR synthetic process demonstrates that the formation and stabilization of ultrasmall Sb nanoparticles can be ascribed to the simultaneous thermolysis of small‐molecule additives into defect‐rich carbon nanosheets. The as‐obtained Super‐Sb nanocomposite exhibits superior sodium‐ion storage performance in terms of ultralong cycling stability of 15 000 cycles at 20.0 A g−1 and ultrahigh rate capability of 152.8 mAh g−1 at 50.0 A g−1. Furthermore, in situ laboratory XRD and finite element analysis (FEA) demonstrate the structural advantages of the ultrafine nanoparticles in stress‐buffering effect. This study provides an effective strategy to manufacture high‐performance and high‐quality energy‐storage nanomaterials for advanced SIBs.

Single Atomic Cu-C3 Sites Catalyzed Interfacial Chemistry in Bi@C for Ultra-Stable and Ultrafast Sodium-Ion Batteries.

Regulating interfacial chemistry at electrode-electrolyte interface by designing catalytic electrode material is crucial and challenging for optimizing battery performance. Herein, a novel single atom Cu regulated Bi@C with Cu-C3 site (Bi@SA Cu-C) have been designed via the simple pyrolysis of metal-organic framework. Experimental investigations and theoretical calculations indicate the Cu-C3 sites accelerate the dissociation of P-F and C-O bonds in NaPF6-ether-based electrolyte and catalyze the formation of inorganic-rich and powerful solid electrolyte interphase. In addition, the Cu-C3 sites with delocalized electron around Cu trigger an uneven charge distribution and induce an in-plane local electric field, which facilitates the adsorption of Na+ and reduces the Na+ migration energy barrier. Consequently, the obtained Bi@SA Cu-C achieves a state-of-the-art reversible capacity, ultrahigh rate capability, and long-term cycling durability. The as-constructed full cell delivers a high capacity of 351 mAh g-1 corresponding to an energy density of 265 Wh kg-1. This work provides a new strategy to realize high-efficient sodium ion storage for alloy-based anode through constructing single-atom modulator integrated catalysis and promotion effect into one entity.

Facile assembly of solid-state on-chip planar micro-supercapacitors based on graphene quantum dots with overall electrochemical properties

To promote the rapid development of high-performance energy storage devices, graphene quantum dots (GQDs) have attracted extensive attention due to their excellent properties such as high electrical conductivity, high specific surface area, high mobility and good dispersion in various solvents. Here, the solid-state on-chip planar micro-supercapacitors (PMSCs) based on the GQDs were facilely assembled by liquid-air interface self-assembly, photolithography, oxygen plasma etching and gold sputtering. The fabricated PMSCs delivered an area capacitance of 2.83 µF cm−2, an energy density of 0.40 nWh cm−2 and a power density of 49.64 µW cm−2. The PMSCs allowed for operation at the scan rate up to 10,000 V s−1, indicating ultrahigh rate capability, and had the relaxation time constant of 197 µs, revealing excellent frequency response capability and the retention of initial specific capacitance of about 94% after 10,000 cycles at the scan rate of 500 V s−1, demonstrating good sustainable electrochemical stability. This work paves the way for new prospective applications of the GQDs in the portable-wearable micro-nano energy storage field.

Unique Core-Shell Structured Polyaniline Nanofibers Toward Ultrahigh-Rate Flexible All-Solid-State Supercapacitor.

Promoting charge storage and fast charging capability simultaneously is a long-standing challenge for supercapacitors. A facile flowing seed polymerization is adopted to prepare polyaniline (PANI) nanofibers, in which phytic acid (PA) doped oligomers are first produced as the seeds for promoting the highly oriented growth of PANI nanofibers accompanying with the copolymerization of m-aminobenzene sulfonic acid (ASA) and aniline occurred on the surface of PANI nanofibers, as a result, unique core-shell structured PANI nanofibers are continuously fabricated. Benefitting from compact nanofiber structure, excellent dispersion, and self-doping effect, as-prepared PANI nanofibers exhibit a specific capacitance of 671.2 F g-1 at 2 A g-1 and ultrahigh rate capability of 93.1% from 2 to 100 A g-1. Then assembled all-solid-state supercapacitor can deliver the highest energy density of 28.3Wh kg-1 at a power density of 320.2W kg-1 with remarkable rate capability (81.2% from 1 to 20 A g-1), cycle stability (77.5% after 5000 cycles) as well as light weight and flexibility. It is highly desirable that the present green and scalable approach can be further applied to fabricate other unique core-shell structured PANI nanofibers with appealing potentials in energy storage devices.

Regulating the anion solvation and cathode-electrolyte interphase to improve the reversibility and kinetics of high-voltage dual-ion batteries

The development of high-voltage dual-ion batteries (DIBs) is greatly hindered by the structure degradation of graphite cathodes during the (de-)intercalation of bulky anions, the electrolyte oxidative decomposition at high voltages, and inadequate cathode-electrolyte interphase (CEI) protection. Here, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) is introduced as an electrolyte additive, which preferentially enters into the first shell structure of PF6− solvation, contributing to high oxidation stability of the electrolyte and formation of an inorganic LiF-rich CEI layer. This layer stabilizes the graphite structure and enhances the anion (de-)intercalation reversibility and transport kinetics. Consequently, the Li||graphite half cell with TTE in the electrolyte exhibits an ultrahigh rate capability (95.6 % at 30 C) and a remarkable capacity retention (67.6 % after 5000 cycles). The impressive performance is further demonstrated in the graphite||graphite full cell, showcasing exceptional cycle stability (91.9 % after 1000 cycles). This study underscores the significance of anionic solvent chemistry and CEI components on cathode materials for DIBs.

High-Performance All-Solid-State on-Chip Planar Micro-Supercapacitors Based on Aminated Graphene Quantum Dots by Photolithography

Rapid development of portable miniaturized electronic devices has put forward higher requirements for microenergy. Functionalized graphene quantum dots combine the properties of both functionalized graphene and quantum dots, and are expected to promote further development of high-performance energy storage devices. Here, all-solid-state on-chip planar micro-supercapacitors (PMSCs) were fabricated based on aminated graphene quantum dots by modified liquid-gas interface self-assembly and photolithography, with the electrode width/gap of 24 μm/8 μm. The electrochemical performance was analyzed by cyclic voltammetry (CV), galvanostatic charge-discharge (GCD), electrochemical impedance spectrometry and cycle stability in PVA/H2SO4 gel electrolyte. The results indicated that the fabricated PMSCs showed good capacitive response at the scan rates of 0.01 V s−1 to 10000 V s−1. The CV curves of the PMSCs displayed a typical pseudocapacitive feature at the scan rates of 0.01 V s−1 to 1 V s−1. The PMSCs had ultrahigh rate capability of up to 10000 V s−1, and the GCD curves were near triangle-shaped curves, demonstrating excellent electrochemical reversibility. The PMSCs showed ideal capacitive behavior at the low frequency region of the Nyquist plot. The Nyquist plot of the PMSCs showed a semicircle at the high frequency region. The relaxation time constant of the PMSCs were 3.59 μs, indicating that the PMSCs had fast frequency response. After 10000 charge-discharge cycles at the scan rate of 500 V s−1, the initial capacitance retention rate of the PMSCs were 99.17%, indicating that the PMSCs possessed good long-term electrochemical stability. This study provides an important reference for the application of functional graphene quantum dots in the field of the PMSCs.

Tailoring d–p Orbital Hybridization to Decipher the Essential Effects of Heteroatom Substitution on Redox Kinetics

AbstractThe heteroatom substitution is considered as a promising strategy for boosting the redox kinetics of transition metal compounds in hybrid supercapacitors (HSCs) although the dissimilar metal identification and essential mechanism that dominate the kinetics remain unclear. It is presented that d‐p orbital hybridization between the metal and electrolyte ions can be utilized as a descriptor for understanding the redox kinetics. Herein, a series of Co, Fe and Cu heteroatoms are respectively introduced into Ni3Se4 cathodes, among them, only the moderate Co‐substituted Ni3Se4 can hold the optimal d‐p orbital hybridization resulted from the formed more unoccupied antibonding states π*. It inevitably enhances the interfacial charge transfer and ensures the balanced OH− adsorption‐desorption to accelerate the redox kinetics validated by the lowest reaction barrier (0.59 eV, matching well with the theoretical calculations). Coupling with the lower OH− diffusion energy barrier, the prepared cathode delivers ultrahigh rate capability (~68.7 % capacity retention even the current density increases by 200 times), and an assembled HSC also presents high energy/power density. This work establishes the principles for determining heteroatoms and deciphers the underlying effects of the heteroatom substitution on improving redox kinetics and the rate performance of battery‐type electrodes from a novel perspective of orbital‐scale manipulation.

Tailoring d-p Orbital Hybridization to Decipher the Essential Effects of Heteroatom Substitution on Redox Kinetics.

The heteroatom substitution is considered as a promising strategy for boosting the redox kinetics of transition metal compounds in hybrid supercapacitors (HSCs) although the dissimilar metal identification and essential mechanism that dominate the kinetics remain unclear. It is presented that d-p orbital hybridization between the metal and electrolyte ions can be utilized as a descriptor for understanding the redox kinetics. Herein, a series of Co, Fe and Cu heteroatoms are respectively introduced into Ni3Se4 cathodes, among them, only the moderate Co-substituted Ni3Se4 can hold the optimal d-p orbital hybridization resulted from the formed more unoccupied antibonding states π*. It inevitably enhances the interfacial charge transfer and ensures the balanced OH- adsorption-desorption to accelerate the redox kinetics validated by the lowest reaction barrier (0.59 eV, matching well with the theoretical calculations). Coupling with the lower OH- diffusion energy barrier, the prepared cathode delivers ultrahigh rate capability (~68.7 % capacity retention even the current density increases by 200 times), and an assembled HSC also presents high energy/power density. This work establishes the principles for determining heteroatoms and deciphers the underlying effects of the heteroatom substitution on improving redox kinetics and the rate performance of battery-type electrodes from a novel perspective of orbital-scale manipulation.

ZIF-derived "cocoon"-like in-situ Zn/N-doped carbon as high-capacity anodes for Li/Na-ion batteries

Owing to the unique structure and physicochemical properties, including high specific surface area, self-doped N atoms, open pore structure and good chemical stability, zeolitic imidazolate frameworks (ZIFs) and their derivatives have been widely used in the field of energy storage. Here, a new type of "cocoon"-like Zn/N doped ZIF-derived porous carbon (Zn@N-C-800) is synthesized as an anode for lithium-ion batteries (LIBs) and sodium ion batteries (SIBs) through a one-step carbonization process using a novel Zn-ZIF as the precursor. In Zn@N-C-800, the "cocoon"-like disordered carbon skeleton is conducive to electrolyte infiltration, while the Zn/N doping can provide additional active sites for ion storage. Benefiting from these unique structural characteristics, Zn@N-C-800 achieves excellent electrochemical performances as anode for both LIBs and SIBs: an ultrahigh rate capability of 352 mAh g−1 can be delivered at 12.8 A g−1 for LIBs; an outstanding long-term cycling stability (312 mAh g−1 at 1 A g−1 after 2000 cycles) can be achieved for SIBs. This paper provides new ideas for the design and preparation of high-performance anodes for LIBs and SIBs.

High Capacitance Porous Ruthenium Nitride Films with High Rate Capability for Micro-Supercapacitors.

The demand for high-performance energy storage devices to power Internet of Things applications has driven intensive research on micro-supercapacitors (MSCs). In this study, RuN films made by magnetron sputtering as an efficient electrode material for MSCs are investigated. The sputtering parameters are carefully studied in order to maximize film porosity while maintaining high electrical conductivity, enabling a fast charging process. Using a combination of advanced techniques, the relationships among the morphology, structure, and electrochemical properties of the RuN films are investigated. The films are shown to have a complex structure containing a mixture of crystallized Ru and RuN phases with an amorphous oxide layer. The combination of high electrical conductivity and pseudocapacitive charge storage properties enabled a 16µm-thick RuN film to achieve a capacitance value of 0.8Fcm-2 in 1m KOH with ultra-high rate capability.

In Situ Interphasial Engineering Enabling High‐Rate and Long‐Cycling Li Metal Batteries

AbstractThe practical implementation of Li metal anode has long been hindered by the significant challenges of notorious dendritic Li growth and severe interphase instability during repeated cycling. Herein, a highly lithiophilic NiSe‐modified host has rationally been constructed to stabilize Li metal by the facile mechanical rolling strategy. The in situ configurated high‐flux Li2Se‐enriched interphase layer can facilitate the fast interfacial charge transfer, high Li plating/stripping reversibility and homogeneous Li nucleation/growth. Consequently, the achieved modified Li metal demonstrates ultrahigh rate capability (10 mA cm−2) and ultralong‐term cycling stability (6600 cycles) with dendrite‐free Li deposition. The Li|LiFePO4 (LFP) cell exhibits an extraordinarily long lifespan cycling stability over 500 cycles with an ultra‐low decay rate of only ≈0.0092% per cycle at 1 C. Furthermore, the 4.5 V high‐voltage Li|LiCoO2 pouch cell with a high areal capacity (≈1.9 mAh cm−2) still reveals an impressively prolonged cyclability over 200 cycles even under the harsh test condition of low negative‐to‐positive‐capacity (N/P) ratio of ≈3.4 and lean electrolyte of ≈5.5 µL mAh−1. This work provides a facile and scalable strategy toward a highly stable Li metal anode for reliable practical usage.

Enhancing Rate Capability, Capacity, and Durability of Co‐Doped Germanium Phosphide Anodes for Li‐Ion Batteries

AbstractWhile germanium‐based anodes for Li‐ion batteries (LIBs) have potential to offer high energy density, their commercialization is impeded by low ionic and electronic conductivity and poor tolerance to volume change during cycling. Here a new quaternary CuGeSiP3 anode is reported to simultaneously overcome these limitations. Synthesized via ball milling process, CuGeSiP3 displays high ionic and electronic conductivity and excellent flexibility to accommodate volume change, attributed to increased structural entropy and reversible formation of favorable intermediates of both electronic and Li ion conductors, as confirmed by experimental measurements and theoretical calculations. When used as an LIB anode, CuGeSiP3 demonstrates large reversible capacity, high Coulombic efficiency, robust cycling stability, and high‐rate capability because it undergoes a reversible lithiation process that involves intercalation and conversion reaction. When composited with layered graphite, the electrode demonstrates exceptional cycling stability (1 261 mA h g−1 after 600 cycles at 400 mA g−1 and 861 mA h g−1 after 1 450 cycles at 20 00 mA g−1) and ultrahigh rate capability (448 mA h g−1 at 20 000 mA g−1). Further, the quaternary, pentanary, and hexanary cation‐disordered phosphides are also synthesized, all having similar Li‐storage superiority, implying the multiple co‐doping strategy is applicable to other material systems.

Deciphering the Performance Enhancement, Cell Failure Mechanism, and Amelioration Strategy of Sodium Storage in Metal Chalcogenides-Based Andes.

Transition metal chalcogenides (TMCs) emerge as promising anode materials for sodium-ion batteries (SIBs), heralding a new era of energy storage solutions. Despite their potential, the mechanisms underlying their performance enhancement and susceptibility to failure in ether-based electrolytes remain elusive. This study delves into these aspects, employing CoS2 electrodes as a case in point to elucidate the phenomena. The investigation reveals that CoS2 undergoes a unique irreversible and progressive solid-liquid-solid phase transition from its native state to sodium polysulfides (NaPSs), and ultimately to a Cu1.8S/Co composite, accompanied by a gradual morphological transformation from microspheres to a stable 3D porous architecture. This reconstructed 3D porous structure is pivotal for its exceptional Na+ diffusion kinetics and resilience to cycling-induced stress, being the main reason for ultrastable cycling and ultrahigh rate capability. Nonetheless, the CoS2 electrode suffers from an inevitable cycle life termination due to the microshort-circuit induced by Na metal corrosion and separator degradation. Through a comparative analysis of various TMCs, a predictive framework linking electrode longevity is established to electrode potential and Gibbs free energy. Finally, the cell failure issue is significantly mitigated at a material level (graphene encapsulation) and cell level (polypropylene membrane incorporation) by alleviating the NaPSs shuttling and microshort-circuit.

Enhancing Conversion Kinetics through Electron Density Dual-Regulation of Catalysts and Sulfur toward Room-/Subzero-Temperature Na-S Batteries.

Room-temperature sodium-sulfur (RT Na/S) batteries have received increasing attention for the next generation of large-scale energy storage, yet they are hindered by the severe dissolution of polysulfides, sluggish redox kinetic, and incomplete conversion of sodium polysulfides (NaPSs). Herein, the study proposes a dual-modulating strategy of the electronic structure of electrocatalyst and sulfur to accelerate the conversion of NaPSs. The selenium-modulated ZnS nanocrystals with electron rearrangement in hierarchical structured spherical carbon (Se-ZnS/HSC) facilitate Na+ transport and catalyze the conversion between short-chain sulfur and Na2S. And the in situ introduced Se within S can enhance conductivity and form an S─Se bond, suppressing the "polysulfides shuttle". Accordingly, the S@Se-ZnS/HSC cathode exhibits a specific capacity of as high as 1302.5 mAh g-1 at 0.1 A g-1 and ultrahigh-rate capability (676.9 mAh g-1 at 5.0 A g-1). Even at -10 °C, this cathode still delivers a high reversible capacity of 401.2 mAh g-1 at 0.05 A g-1 and 94% of the original capacitance after 50 cycles. This work provides a novel design idea for high-performance Na/S batteries.

Ultrafast Metal-Free Microsupercapacitor Arrays Directly Store Instantaneous High-Voltage Electricity from Mechanical Energy Harvesters.

Harvesting renewable mechanical energy is envisioned as a promising and sustainable way for power generation. Many recent mechanical energy harvesters are able to produce instantaneous (pulsed) electricity with a high peak voltage of over 100 V. However, directly storing such irregular high-voltage pulse electricity remains a great challenge. The use of extra power management components can boost storage efficiency but increase system complexity. Here utilizing the conducting polymer PEDOT:PSS, high-rate metal-free micro-supercapacitor (MSC) arrays are successfully fabricated for direct high-efficiency storage of high-voltage pulse electricity. Within an area of 2.4 × 3.4cm2 on various paper substrates, large-scale MSC arrays (comprising up to 100 cells) can be printed to deliver a working voltage window of 160V at an ultrahigh scan rate up to 30V s-1. The ultrahigh rate capability enables the MSC arrays to quickly capture and efficiently store the high-voltage (≈150V) pulse electricity produced by a droplet-based electricity generator at a high efficiency of 62%, significantly higher than that (<2%) of the batteries or capacitors demonstrated in the literature. Moreover, the compact and metal-free features make these MSC arrays excellent candidates for sustainable high-performance energy storage in self-charging power systems.

Unraveling high efficiency multi-step sodium storage and bidirectional redox kinetics synergy mechanism of cobalt-doping vanadium disulfide anode

Sodium-based storage devices based on conversion-type metal sulfide anodes have attracted great attention due to their multivalent ion redox reaction ability. However, they also suffer from sodium polysulfides (NaPSs) shuttling problems during the sluggish Na+ redox process, leading to “voltage failure” and rapid capacity decay. Herein, a metal cobalt-doping vanadium disulfide (Co-VS2) is proposed to simultaneously accelerate the electrochemical reaction of VS2 and enhance the bidirectional redox of soluble NaPSs. It is found that the strong adsorption of NaPSs by V-Co alloy nanoparticles formed in situ during the conversion reaction of Co-VS2 can effectively inhibit the dissolution and shuttle of NaPSs, and thermodynamically reduce the formation energy barrier of the reaction path to effectively drive the complete conversion reaction, while the metal transition of Co elements enhances reconversion kinetics to achieve high reversibility. Moreover, Co-VS2 also produce abundant sulfur vacancies and unsaturated sulfur edge defects, significantly improve ionic/electron diffusion kinetics. Therefore, the Co-VS2 anode exhibits ultrahigh rate capability (562 mA h g−1 at 5 A g−1), high initial coulombic efficiency (≈90%) and 12,000 ultralong cycle life with capacity retention of 90% in sodium-ion batteries (SIBs), as well as impressive energy/power density (118 Wh kg−1/31,250 W kg−1) and over 10,000 stable cycles in sodium-ion hybrid capacitors (SIHCs). Moreover, the pouch cell-type SIHC displays a high-energy density of 102 Wh kg−1 and exceed 600 stable cycles. This work deepens the understanding of the electrochemical reaction mechanism of conversion-type metal sulfide anodes and provides a valuable solution to the shuttling of NaPSs in SIBs and SIHCs.

Vascular tissue-derived hard carbon with ultra-high rate capability for sodium-ion storage

Vascular tissue helps quickly pass the nutrients and water through the plant. Inspiringly, the transport of electrolyte solutions within such biological tissue may also play an essential role in governing the high-current performance of sodium-ion storage. Herein, we report a facile and efficient approach to fabricate a vascular tissue-derived hard carbon (VHC) by an integrated procedure of leave stripping, carbonization and alkali/acid washing. By meticulously adjusting the pyrolysis temperatures, hierarchical microchannel carbon with abundant turbostratic nanodomains, suitable pore size and special surface functional groups can be obtained, enabling high specific capacity and excellent rate performances. It is believed that the vascular tissue-derived carbon can significantly shorten sodium ion transport paths and further enhance the storage performance on the surface and within the electrode materials, making it a promising candidate for sodium-ion batteries.

Synergistic Engineering of Carbon Nanotubes Threaded NiSe2/Co3Se4 Quantum Dots with Rich Se Vacancies for High‐Rate Nickel–Zinc Batteries

AbstractLimited by sluggish reaction kinetics, insufficient electrode utilization and severe volume deformation, designing nickel‐based materials with high capacity and rate capability is still a challenge. Herein, a carbon nanotubes threaded NiSe2/Co3Se4 quantum dots embedded in carbon nanospheres with rich Se vacancies both in NiSe2 and Co3Se4 is elaborately designed via MOF template method. The formation mechanism of the Se vacancies is elucidated for the first time, which is ascribed to the release of gas during the decomposition of organic ligand inhibits the ordered arrangement of atoms. The CNT‐V‐NiCoSe possesses many significant superiorities, such as sufficiently exposed active sites, high electrode utilization, favorable charge‐carrier migration, and relaxed structure deformation. Consequently, the CNT‐V‐NiCoSe electrode shows top‐level specific capacity (384 mAh g−1 at 1 A g−1), ultrahigh rate capability (209 mAh g−1 at 150 A g−1) and remarkable cycling durability. The CNT‐V‐NiCoSe//Zn battery achieves maximum energy density of 615.6 Wh kg−1 and maximum power density of 81.7 kW kg−1. Density functional theory calculations elucidate the Se vacancies improve the density of states at Fermi level, facilitates internal charge transfer, and enhances OH− adsorption ability. This study provides guidance for the preparation of high‐performance electrode materials with rich vacancies by template method.

High energy density biomass-derived activated carbon materials for sustainable energy storage

Biomass-derived activated carbons are promising materials for sustainable energy storage systems such as aqueous supercapacitors and Zn-ion capacitors due to their abundance, low cost, tunable porosity, and heteroatom-rich structures. Herein, we report biomass derived carbon materials fabrication via a two-step activation method. The activated carbons possess well-tuned pore structures and high heteroatom content, resulting in remarkable surface area, ultrahigh micropore volume, and good wettability. The symmetrical supercapacitors and aqueous Zn-ion capacitors were assembled using the produced activated carbons. The 2PA-6-800 supercapacitor delivers an ultrahigh rate capability (up to 10,000 mV s−1) and promising cycle life, retaining 66.3 % of its initial performance after 33,000 galvanostatic charge–discharge cycles. The assembled 2PA-6-800-based ZIC delivers a superior specific capacitance of 785.0 F g−1, a maximum energy density of 352.5 Wh kg−1, and a remarkable power density of 60.3 kW kg−1. The outstanding performance is attributed to the two-step activation method, high heteroatom content, and the structural integrity of the biomass derived AC to the ZIC device architecture. This work contributes to the design and development of high-performance, safe, and sustainable energy storage systems.

Insights into the Phase Purity and Storage Mechanism of Nonstoichiometric Na3.4Fe2.4(PO4)1.4P2O7 Cathode for High‐Mass‐Loading and High‐Power‐Density Sodium‐Ion Batteries

AbstractMixed‐anion‐group Fe‐based phosphate materials, such as Na4Fe3(PO4)2P2O7, have emerged as promising cathode materials for sodium‐ion batteries (SIBs). However, the synthesis of pure‐phase material has remained a challenge, and the phase evolution during sodium (de)intercalation is debating as well. Herein, a solid‐solution strategy is proposed to partition Na4Fe3(PO4)2P2O7 into 2NaFePO4 ⋅ Na2FeP2O7 from the angle of molecular composition. Via regulating the starting ratio of NaFePO4 and Na2FeP2O7 during the synthesis process, the nonstoichiometric pure‐phase material could be successfully synthesized within a narrow NaFePO4 content between 1.6 and 1.2. Furthermore, the proposed synthesis strategy demonstrates strong applicability that helps to address the impurity issue of Na4Co3(PO4)2P2O7 and nonstoichiometric Na3.4Co2.4(PO4)1.4P2O7 are evidenced to be the pure phase. The model Na3.4Fe2.4(PO4)1.4P2O7 cathode (the content of NaFePO4 equals 1.4) demonstrates exceptional sodium storage performances, including ultrahigh rate capability under 100 C and ultralong cycle life over 14000 cycles. Furthermore, combined measurements of ex situ nuclear magnetic resonance, in situ synchrotron radiation diffraction and X‐ray absorption spectroscopy clearly reveal a two‐phase transition during Na+ extraction/insertion, which provides a new insight into the ionic storage process for such kind of mixed‐anion‐group Fe‐based phosphate materials and pave the way for the development of high‐power sodium‐ion batteries.