One‐Step Synthesis of 2‐Ethylhexylamine Pillared Vanadium Disulfide Nanoflowers with Ultralarge Interlayer Spacing for High‐Performance Magnesium Storage

Rechargeable magnesium batteries (RMBs) are attractive candidates for large‐scale energy storage owing to the high theoretical specific capacity, rich earth abundance, and good safety characteristics. However, the development of desirable cathode materials for RMBs is constrained by the high polarity and slow intercalation kinetics of Mg²⁺ ions. Herein, it is demonstrated that 2‐ethylhexylamine pillared vanadium disulfide nanoflowers (expanded VS₂) with enlarged interlayer distances exhibit greatly boosted electrochemical performance as a cathode material in RMBs. Through a one‐step solution‐phase synthesis and in situ 2‐ethylhexylamine intercalation process, VS₂ nanoflowers with ultralarge interlayer spacing are prepared. A series of ex situ characterizations verify that the cathode of expanded VS₂ nanoflowers undergoes a reversible intercalation reaction mechanism, followed by a conversion reaction mechanism. Electrochemical kinetics analysis reveal a relatively fast Mg‐ion diffusivity of expanded VS₂ nanoflowers in the order of 10^?11–10^?12 cm² s^?1, and the pseudocapacitive contribution is up to 64% for the total capacity at 1 mV s^?1. The expanded VS₂ nanoflowers show highly reversible discharge capacity (245 mAh g^?1 at 100 mA g^?1), good rate capability (103 mAh g^?1 at 2000 mA g^?1), and stable cycling performance (90 mAh g^?1 after 600 cycles at 1000 mA g^?1).     

CuS Microspheres with Tunable Interlayer Space and Micropore as a High‐Rate and Long‐Life Anode for Sodium‐Ion Batteries

Layered transition metal sulfides (LTMSs) have tremendous commercial potential in anode materials for sodium‐ion batteries (SIBs) in large‐scale energy storage application. However, it is a great challenge for most LTMS electrodes to have long cycling life and high‐rate capability due to their larger volume expansion and the formation of soluble polysulfide intermediates caused by the conversion reaction. Herein, layered CuS microspheres with tunable interlayer space and pore volumes are reported through a cost‐effective interaction method using a cationic surfactant of cetyltrimethyl ammonium bromide (CTAB). The CuS–CTAB microsphere as an anode for SIBs reveals a high reversible capacity of 684.6 mAh g^?1 at 0.1 A g^?1, and 312.5 mAh g^?1 at 10 A g^?1 after 1000 cycles with high capacity retention of 90.6%. The excellent electrochemical performance is attributed to the unique structure of this material, and a high pseudocapacitive contribution ensures its high‐rate performance. Moreover, in situ X‐ray diffraction is applied to investigate their sodium storage mechanism. It is found that the long chain CTAB in the CuS provides buffer space, traps polysulfides, and restrains the further growth of Cu particles during the conversion reaction process that ensure the long cycling stability and high reversibility of the electrode material.     

Hydrated Intercalation for High‐Performance Aqueous Zinc Ion Batteries

Aqueous zinc ion batteries (AZIBs) are steadily gaining attention based on their attractive merits regarding cost and safety. However, there are many obstacles to overcome, especially in terms of finding suitable cathode materials and elucidating their reaction mechanisms. Here, a mixed‐valence vanadium oxide, V₆O₁₃, that functions as a stable cathode material in mildly acidic aqueous electrolytes is reported. Paired with a zinc metal anode, this material exhibits performance metrics of 360 mAh g^?1 at 0.2 A g^?1, 92% capacity retention after 2000 cycles, and 145 mAh g^?1 at a current density of 24.0 A g^?1. A combination of experiments and density functional theory calculations suggests that hydrated intercalation, where water molecules are cointercalated with Zn ions upon discharge, accounts for the aforementioned electrochemical performance. This intercalation mechanism facilitates Zn ion diffusion throughout the host lattice and electrode–electrolyte interface via electrostatic shielding and concurrent structural stabilization. Through a correlation of experimental data and theoretical calculations, the promise of utilizing hydrated intercalation as a means to achieve high‐performance AZIBs is demonstrated.     

Mesoporous MoS2 as a Transition Metal Dichalcogenide Exhibiting Pseudocapacitive Li and Na‐Ion Charge Storage

The ion insertion properties of MoS₂ continue to be of widespread interest for energy storage. While much of the current work on MoS₂ has been focused on the high capacity four‐electron reduction reaction, this process is prone to poor reversibility. Traditional ion intercalation reactions are highlighted and it is demonstrated that ordered mesoporous thin films of MoS₂ can be utilized as a pseudocapacitive energy storage material with a specific capacity of 173 mAh g^?1 for Li‐ions and 118 mAh g^?1 for Na‐ions at 1 mV s^?1. Utilizing synchrotron grazing incidence X‐ray diffraction techniques, fast electrochemical kinetics are correlated with the ordered porous structure and with an iso‐oriented crystal structure. When Li‐ions are utilized, the material can be charged and discharged in 20 seconds while still achieving a specific capacity of 140 mAh g^?1. Moreover, the nanoscale architecture of mesoporous MoS₂ retains this level of lithium capacity for 10 000 cycles. A detailed electrochemical kinetic analysis indicates that energy storage for both ions in MoS₂ is due to a pseudocapacitive mechanism.     

A Flexible Porous Carbon Nanofibers‐Selenium Cathode with Superior Electrochemical Performance for Both Li‐Se and Na‐Se Batteries

A flexible and free‐standing porous carbon nanofibers/selenium composite electrode (Se@PCNFs) is prepared by infiltrating Se into mesoporous carbon nanofibers (PCNFs). The porous carbon with optimized mesopores for accommodating Se can synergistically suppress the active material dissolution and provide mechanical stability needed for the film. The Se@PCNFs electrode exhibits exceptional electrochemical performance for both Li‐ion and Na‐ion storage. In the case of Li‐ion storage, it delivers a reversible capacity of 516 mAh g^?1 after 900 cycles without any capacity loss at 0.5 A g^?1. Se@PCNFs still delivers a reversible capacity of 306 mAh g^?1 at 4 A g^?1. While being used in Na‐Se batteries, the composite electrode maintains a reversible capacity of 520 mAh g^?1 after 80 cycles at 0.05 A g^?1 and a rate capability of 230 mAh g^?1 at 1 A g^?1. The high capacity, good cyclability, and rate capability are attributed to synergistic effects of the uniform distribution of Se in PCNFs and the 3D interconnected PCNFs framework, which could alleviate the shuttle reaction of polyselenides intermediates during cycling and maintain the perfect electrical conductivity throughout the electrode. By rational and delicate design, this type of self‐supported electrodes may hold great promise for the development of Li‐Se and Na‐Se batteries with high power and energy densities.     

Molecular Engineering of Monodisperse SnO2 Nanocrystals Anchored on Doped Graphene with High‐Performance Lithium/Sodium‐Storage Properties in Half/Full Cells

The fabrication of ultrasmall and high‐content SnO₂ nanocrystals anchored on doped graphene can endow SnO₂ with superior electrochemical properties. Herein, an effective strategy, involving molecular engineering of a layer‐by‐layer assembly technique, is proposed to homogeneously anchor SnO₂ nanocrystals on nitrogen/sulfur codoped graphene (NSGS), which serves as an advanced anode material in lithium/sodium‐ion batteries (LIBs/SIBs). Benefiting from novel design and specific structure, the optimized NSGS for LIBs displays high initial capacity (2123.9 mAh g^?1 at 0.1 A g^?1), long‐term cycling performance (only 0.8% loss after 500 cycles), and good rate capability (477.4 mAh g^?1 at 5 A g^?1). In addition, the optimized NSGS for SIBs also delivers high initial capacity (791.7 mAh g^?1 at 0.1 A g^?1) and high reversible capacity (180.2 mAh g^?1 after 500 cycles at 0.5 A g^?1). Meanwhile, based on the detailed analysis of phase transition and electrochemical reaction kinetics, the reaction mechanisms of NSGS in LIBs and SIBs as well as the distinction in LIBs/SIBs are clearly articulated. Notably, to further explore the practical application, Li/Na⁺ full cells are also assembled by coupling the optimized NSGS anode with LiCoO₂ and Na₃V₂(PO₄)₃/C cathodes, respectively.     

1T′‐ReS2 Confined in 2D‐Honeycombed Carbon Nanosheets as New Anode Materials for High‐Performance Sodium‐Ion Batteries

ReS₂ (rhenium disulfide) is a new transition‐metal dichalcogenide that exhibits 1T′ phase and extremely weak interlayer van der Waals interactions. This makes it promising as an anode material for sodium‐ion batteries. However, achieving both a high‐rate capability and a long‐life has remained a major research challenge. Here, a new composite is reported, in which both are realized for the first time. 1T′‐ReS₂ is confined through strong interfacial interaction in a 2D‐honeycombed carbon nanosheets that comprise an rGO inter‐layer and a N‐doped carbon coating‐layer (rGO@ReS₂@N‐C). The strong interfacial interaction between carbon and ReS₂ increases overall conductivity and decreases Na⁺ diffusion resistance, whilst the intended 2D‐honeycombed carbon protective layer maintains structural morphology and electrochemical activity during long‐term cycling. These findings are confirmed by advanced characterization techniques, electrochemical measurement, and density functional theory calculation. The new rGO@ReS₂@N‐C exhibits the greatest rate performance reported so far for ReS₂ of 231 mAh g^?1 at 10 A g^?1. Significantly, this is together with ultra‐stable long‐term cycling of 192 mAh g^?1 at 2 A g^?1 after 4000 cycles.     

Stable Carbon–Selenium Bonds for Enhanced Performance in Tremella‐Like 2D Chalcogenide Battery Anode

2D cobalt selenide based on conversion reaction has attracted much attention due to its open layered structure and high specific capacity. However, effectively suppressing the fast capacity fade caused by the irreversible Se dissolution and serious volume change during the cycling process is still a challenge. Herein, the concentration of dispersion liquid under supercritical conditions is tuned to induce the CoSe crystal to grow along the graphene oxide (GO), and finally obtain the Tremella‐like CoSe–reduced GO (rGO) hybrid. The nature of epitaxial growth leads to the formation of stable C? Se bonds, which maintain a favorable conductive connection between CoSe and rGO as well as enhance the mechanical strength of active materials to suppress Se dissolution and volume expansion during Na/Li intercalation and deintercalation. The unique microstructural merits of the hybrid result in superior sodium/lithium storage performance (400.8 mAh g^?1 at 1 A g^?1 after 100 cycles for sodium‐ion batteries and 769.6 mAh g^?1 at 2 A g^?1 after 500 cycles for lithium‐ion batteries). Moreover, the transmission X‐ray microscopy technique is first used to directly observe the Se segregation in cobalt selenide and it being suppressed by the C? Se bonds.     

Template‐Free Construction of Self‐Supported Sb Prisms with Stable Sodium Storage

Antimony (Sb) is a promising anode material for sodium‐ion batteries owing to its large capacity of 660 mAh g^?1. However, its practical application is restricted by the rapid capacity decay resulted from a large volume expansion up to 390% upon Na alloying. Herein, construction of a self‐supported Sb array that has enough space allowing for effective accommodation of the volume change is reported. The array of Sb prisms is directly grown on a Cu substrate via a template‐free electrodeposition, followed by mild heating to consolidate the structural integrity between Sb and Cu. The resulting 3D architecture endows the Sb array with excellent sodium storage performance, exhibiting a reversible capacity of 578 mAh g^?1 and retaining 531 mAh g^?1 over 100 cycles at 0.5 C. The potential of Sb array in sodium‐ion full cells by pairing it with a Na_0.67(Ni_0.23Mg_0.1Mn_0.67)O₂ cathode is further demonstrated. This full cell affords a specific energy of 197 Wh kg^?1 at 0.2 C and a specific power of 1280 W kg^?1 at 5 C. Considering its low cost and scale‐up capability, the template‐free route may find extensive applications in designing electrode architectures.     

Mn‐Rich P′2‐Na0.67[Ni0.1Fe0.1Mn0.8]O2 as High‐Energy‐Density and Long‐Life Cathode Material for Sodium‐Ion Batteries

Herein, P′2‐type Na_0.67[Ni_0.1Fe_0.1Mn_0.8]O₂ is introduced as a promising new cathode material for sodium‐ion batteries (SIBs) that exhibits remarkable structural stability during repetitive Na⁺ de/intercalation. The O? Ni? O? Mn? O? Fe? O bond in the octahedra of transition‐metal layers is used to suppress the elongation of the Mn? O bond and to improve the electrochemical activity, leading to the highly reversible Na storage mechanism. A high discharge capacity of ≈220 mAh g^?1 (≈605 Wh kg^?1) is delivered at 0.05 C (13 mAg^?1) with a high reversible capacity of ≈140 mAh g^?1 at 3 C and excellent capacity retention of 80% over 200 cycles. This performance is associated with the reversible P′2–OP4 phase transition and small volume change upon charge and discharge (≈3%). The nature of the sodium storage mechanism in a full cell paired with a hard carbon anode reveals an unexpectedly high energy density of ≈542 Wh kg^?1 at 0.2 C and good capacity retention of ≈81% for 500 cycles at 1 C (260 mAg^?1).     

Partially Reduced Holey Graphene Oxide as High Performance Anode for Sodium‐Ion Batteries

The current Na⁺ storage performance of carbon‐based materials is still hindered by the sluggish Na⁺ ion transfer kinetics and low capacity. Graphene and its derivatives have been widely investigated as electrode materials in energy storage and conversion systems. However, as anode materials for sodium‐ion batteries (SIBs), the severe π–π restacking of graphene sheets usually results in compact structure with a small interlayer distance and a long ion transfer distance, thus leading to low capacity and poor rate capability. Herein, partially reduced holey graphene oxide is prepared by simple H₂O₂ treatment and subsequent low temperature reduction of graphene oxide, leading to large interlayer distance (0.434 nm), fast ion transport, and larger Na⁺ storage space. The partially remaining oxygenous groups can also contribute to the capacity by redox reaction. As anode material for SIBs, the optimized electrode delivers high reversible capacity, high rate capability (365 and 131 mAh g^?1 at 0.1 and 10 A g^?1, respectively), and good cycling performance (163 mAh g^?1 after 3000 cycles at a current density of 2 A g^?1), which is among the best reported performances for carbon‐based SIB anodes.     

Incorporating Solvate and Solid Electrolytes for All‐Solid‐State Li2S Batteries with High Capacity and Long Cycle Life

The development of all‐solid‐state lithium–sulfur batteries is hindered by the poor interfacial properties at solid electrolyte (SE)/electrode interfaces. The interface is modified by employing the highly concentrated solvate electrolyte, (MeCN)₂?LiTFSI:TTE, as an interlayer material at the electrolyte/electrode interfaces. The incorporation of an interlayer significantly improves the cycling performance of solid‐state Li₂S batteries compared to the bare counterpart, exhibiting a specific capacity of 760 mAh g^?1 at cycle 100 (330 mAh g^?1 for the bare cell). Electrochemical impedance spectroscopy shows that the interfacial resistance of the interlayer‐modified cell gradually decreases as a function of cycle number, while the impedance of the bare cell remains almost constant. Cross‐section scanning electron microscopy (SEM)/ energy dispersive X‐ray spectroscopy (EDS) measurements on the interlayer‐modified cell confirm the permeation of solvate into the cathode and the SE with electrochemical cycling, which is related to the decrease in cell impedance. In order to mimic the full permeation of the solvate across the entire cell, the solvate is directly mixed with the SE to form a “solvSEM” electrolyte. The hybrid Li₂S cell using a solvSEM electrolyte exhibits superior cycling performance compared to the solid‐state cells, in terms of Li₂S loading, Li₂S utilization, and cycling stability. The improved performance is due to the favorable ionic contact at the battery interfaces.     

Silica Restricting the Sulfur Volatilization of Nickel Sulfide for High‐Performance Lithium‐Ion Batteries

Nickel sulfides are regarded as promising anode materials for advanced rechargeable lithium‐ion batteries due to their high theoretical capacity. However, capacity fade arising from significant volume changes during operation greatly limits their practical applications. Herein, confined NiS_x@C yolk–shell microboxes are constructed to address volume changes and confine the active material in the internal void space. Having benefited from the yolk–shell structure design, the prepared NiS_x@C yolk–shell microboxes display excellent electrochemical performance in lithium‐ion batteries. Particularly, it delivers impressive cycle stability (460 mAh g^?1 after 2000 cycles at 1 A g^?1) and superior rate performance (225 mAh g^?1 at 20 A g^?1). Furthermore, the lithium storage mechanism is ascertained with in situ synchrotron high‐energy X‐ray diffractions and in situ electrochemical impedance spectra. This unique confined yolk–shell structure may open up new strategies to create other advanced electrode materials for high performance electrochemical storage systems.     

Covalent Encapsulation of Sulfur in a MOF‐Derived S,N‐Doped Porous Carbon Host Realized via the Vapor‐Infiltration Method Results in Enhanced Sodium–Sulfur Battery Performance

Practical applications of room temperature sodium–sulfur batteries are still inhibited by the poor conductivity and slow reaction kinetics of sulfur, and dissolution of intermediate polysulfides in the commonly used electrolytes. To address these issues, starting from a novel 3D Zn‐based metal–organic framework with 2,5‐thiophenedicarboxylic acid and 1,4‐bis(pyrid‐4‐yl) benzene as ligands, a S, N‐doped porous carbon host with 3D tubular holes for sulfur storage is fabricated. In contrast to the commonly used melt‐diffusion method to confine sulfur physically, a vapor‐infiltration method is utilized to achieve sulfur/carbon composite with covalent bonds, which can join electrochemical reaction without low voltage activation. A polydopamine derived N‐doped carbon layer is further coated on the composite to confine the high‐temperature‐induced gas‐phase sulfur inside the host. S and N dopants increase the polarity of the carbon host to restrict diffusion of sulfur, and its 3D porous structure provides a large storage area for sulfur. As a result, the obtained composite shows outstanding electrochemical performance with 467 mAh g^?1 (1262 mAh g^?1_(sulfur)) at 0.1 A g^?1, 270 mAh g^?1 (730 mAh g^?1_(sulfur)) after 1000 cycles at 1 A g^?1 and 201 mAh g^?1 (543 mAh g^?1_(sulfur)) at 5.0 A g^?1.     

Enhanced Potassium Ion Battery by Inducing Interlayer Anionic Ligands in MoS1.5Se0.5 Nanosheets with Exploration of the Mechanism

The strategy of inducing interlayer anionic ligands in 2D MoS_1.5Se_0.5 nanosheets is employed to consolidate the interlayer band gap and optimize the electronic structure for the potassium ion battery. It combines complementary advantages from two kinds of anionic ligands with high conductivity and good affinity with potassium ions. The potassium ion diffusion rate is accelerated as well by an optimized lower energy barrier for ion diffusion pathways, with the formation of highly reversible KMo₃Se₃ crystal other than K_0.4MoS₂/K₂MoS_4, which encounters a much slower electro/ion diffusion rate upon discharging. These advances deliver enhanced potassium storage properties with excellent cycling stability, with retained specific capacity of 531.6 mAh g^?1 at a current density of 200 mA g^?1 even after 1000 cycles, and high rate capability with specific capacity of 270.1 mAh g^?1 at 5 A g^?1. The insertion and conversion mechanism are also elucidated by a combination of density functional theory computations and in situ synchrotron measurements.     

Confined Fe2VO4⊂Nitrogen‐Doped Carbon Nanowires with Internal Void Space for High‐Rate and Ultrastable Potassium‐Ion Storage

Developing low‐cost, high‐capacity, high‐rate, and robust earth‐abundant electrode materials for energy storage is critical for the practical and scalable application of advanced battery technologies. Herein, the first example of synthesizing 1D peapod‐like bimetallic Fe₂VO₄ nanorods confined in N‐doped carbon porous nanowires with internal void space (Fe₂VO₄?NC nanopeapods) as a high‐capacity and stable anode material for potassium‐ion batteries (KIBs) is reported. The peapod‐like Fe₂VO₄?NC nanopeapod heterostructures with interior void space and external carbon shell efficiently prevent the aggregation of the active materials, facilitate fast transportation of electrons and ions, and accommodate volume variation during the cycling process, which substantially boosts the rate and cycling performance of Fe₂VO₄. The Fe₂VO₄?NC electrode exhibits high reversible specific depotassiation capacity of 380 mAh g^?1 at 100 mA g^?1 after 60 cycles and remarkable rate capability as well as long cycling stability with a high capacity of 196 mAh g^?1 at 4 A g^?1 after 2300 cycles. The first‐principles calculations reveal that Fe₂VO₄?NC nanopeapods have high ionic/electronic conductivity characteristics and low diffusion barriers for K⁺‐intercalation. This study opens up new way for investigating high‐capacity metal oxide as high‐rate and robust electrode materials for KIBs.     

Unlocking Few‐Layered Ternary Chalcogenides for High‐Performance Potassium‐Ion Storage

Potassium‐ion batteries (KIBs) have attracted increasing attention for grid‐scale energy storage due to the abundance of potassium resources, low cost, and competitive energy density. The key challenge for KIBs is to develop high‐performance electrode materials. However, the exploration of high‐capacity and ultrastable electrodes for KIBs remains challenging because of the sluggish diffusion kinetics of K⁺ ions during the charging/discharging processes. This study reports for the first time a facile ion‐intercalation‐mediated exfoliation method with Mg²⁺ cations and NO₃^– anions as ion assistants for the fabrication of expanded few‐layered ternary Ta₂NiSe₅ (EF‐TNS) flakes with interlayer spacing up to 1.1 nm and abundant Se sites (NiSe₄ tetrahedra/TaSe₆ octahedra clusters) for superior potassium‐ion storage. The EF‐TNS deliver a high capacity of 315 mAh g^–1, excellent rate capability (121 mAh g^–1 at a current density of 1000 mA g^–1), and ultrastable cycling performance (81.4% capacity retention after 1100 cycles). Detailed theoretical analysis via first‐principles calculations and experimental results elucidate that K⁺ ions intercalate through the expanded interlayers effectively and prefer to transport along zigzag pathways in layered Ta₂NiSe₅. This work provides a new avenue for designing novel ternary intercalation/pseudocapacitance‐type KIBs with high capacity, excellent rate capability, and superior long‐term cycling performance.     

Distinctive Supercapacitive Properties of Copper and Copper Oxide Nanocrystals Sharing a Similar Colloidal Synthetic Route

CuO and Cu₂O are non‐noble transition metal oxide supercapacitive materials with high theoretical specific capacitances above 1800 F g^?1. In this work, by adjusting organic additives of a colloidal system, Cu, Cu₂O, and CuO are grown in situ on nickel foam. CuO exhibits a specific capacitance of 1355 F g^?1 at 2 A g^?1 in 3 m KOH, a value well above those of Cu and Cu₂O (<500 F g^?1), and is superior to other known CuO electrodes. The CuO electrode exhibits 70% of its initial capacity, and the Columbic efficiency remains ≈100% after 7000 cycles at 4 A g^?1. Cu₂O exhibits the worst electrochemical performance, mainly due to the inactive barrier layer forming on the surface. This work provides an efficient synthetic platform for both comparable supercapacitive studies and cost‐effective electrochemical energy storage applications.     

Defect‐Rich Soft Carbon Porous Nanosheets for Fast and High‐Capacity Sodium‐Ion Storage

Soft carbon has attracted tremendous attention as an anode in rocking‐chair batteries owing to its exceptional properties including low‐cost, tunable interlayer distance, and favorable electronic conductivity. However, it fails to exhibit decent performance for sodium‐ion storage owing to difficulties in the formation of sodium intercalation compounds. Here, microporous soft carbon nanosheets are developed via a microwave induced exfoliation strategy from a conventional soft carbon compound obtained by pyrolysis of 3,4,9,10‐perylene tetracarboxylic dianhydride. The micropores and defects at the edges synergistically leads to enhanced kinetics and extra sodium‐ion storage sites, which contribute to the capacity increase from 134 to 232 mAh g^?1 and a superior rate capability of 103 mAh g^?1 at 1000 mA g^?1 for sodium‐ion storage. In addition, the capacitance‐dominated sodium‐ion storage mechanism is identified through the kinetics analysis. The in situ X‐ray diffraction analyses are used to reveal that sodium ions intercalate into graphitic layers for the first time. Furthermore, the as‐prepared nanosheets can also function as an outstanding anode for potassium‐ion storage (reversible capacity of 291 mAh g^?1) and dual‐ion full cell (cell‐level capacity of 61 mAh g^?1 and average working voltage of 4.2 V). These properties represent the potential of soft carbon for achieving high‐energy, high‐rate, and low‐cost energy storage systems.     

One‐Step In Situ Formation of N‐doped Carbon Nanosheet 3D Porous Networks/TiO2 Hybrids with Ultrafast Sodium Storage

In spite of the satisfactory advancement in preparing TiO₂‐based hybrid structures, most methods rely on additional template‐based multistep reactions for engineering the given structure. Herein, a unique self‐template and in situ recrystallization strategy is explored to synthesize uniform flowerlike multicompositional structures of nitrogen‐doped porous carbon nanosheet networks immobilizing TiO₂ nanoparticles (TiO₂∩NPCSs) via a self‐prepared single precursor and subsequent thermal treatment. Depending on the unique coordination ability of 2,4‐dihydroxybenzoic acid with metal ions under alkaline conditions to form a flowerlike network, a self‐produced single precursor can be achieved. Careful investigations of the self‐prepared precursor reveal a high practicability of the present synthetic scheme. Because of the novel structural and compositional features, these TiO₂∩NCSN flowers indicate superior sodium storage properties when evaluated as anodes for sodium‐ion batteries. Impressively, the TiO₂∩NCSN flowers deliver high reversible capacities of 152 mAh g^?1 at 2C for 3000 cycles and 114 mAh g^?1 at 10C for 10000 cycles, as well as an ultrahigh rate capability up to 50C with a capacity of 101 mAh g^?1. The facile method could stimulate further capability in precise construction of complex architectures with complicated compositions for different device applications.