Gate‐Induced Massive and Reversible Phase Transition of VO2 Channels Using Solid‐State Proton Electrolytes

The use of gate bias to control electronic phases in VO₂, an archetypical correlated oxide, offers a powerful method to probe their underlying physics, as well as for the potential to develop novel electronic devices. Up to date, purely electrostatic gating in 3‐terminal devices with correlated channel shows the limited electrostatic gating efficiency due to insufficiently induced carrier density and short electrostatic screening length. Here massive and reversible conductance modulation is shown in a VO₂ channel by applying gate bias V_G at low voltage by a solid‐state proton (H⁺) conductor. By using porous silica to modulate H⁺ concentration in VO₂, gate‐induced reversible insulator‐to‐metal (I‐to‐M) phase transition at low voltage, and unprecedented two‐step insulator‐to‐metal‐to‐insulator (I‐to‐M‐to‐I) phase transition at high voltage are shown. V_G strongly and efficiently injects H⁺ into the VO₂ channel without creating oxygen deficiencies; this H⁺‐induced electronic phase transition occurs by giant modulation (≈7%) of out‐of‐plane lattice parameters as a result of H⁺‐induced chemical expansion. The results clarify the role of H⁺ on the electronic state of the correlated phases, and demonstrate the potentials for electronic devices that use ionic/electronic coupling.     

Charge Storage Capability in Nanoarchitectures of V2O5/Chitosan/Poly(ethylene oxide) Produced Using the Layer‐by‐Layer Technique

The electrochemical and electrochromic properties of layer‐by‐layer nanoarchitectures of V₂O₅/chitosan and V₂O₅ alternated with a blend of poly(ethylene oxide) (PEO) and chitosan have been examined. Using a blend was important, since multilayers of PEO/V₂O₅ could not be built. The number of electrochemically active V₂O₅ sites was estimated to be around 3.4 × 10^–8 mol cm^–2 and 4.4 × 10^–8 mol cm^–2 for V₂O₅/chitosan and V₂O₅/blend, respectively, based on the UV‐vis absorbance attributed to the intervalence V⁴⁺→V⁵⁺ transfer. A pronounced effect from PEO was observed in the migration/diffusion process, according to cyclic voltammetry and impedance spectroscopy data. The charges injected were 3.29 mC cm^–2 and 8.02 mC cm^–2 for V₂O₅/chitosan and V₂O₅/blend, respectively, at 20 mV s^–1. For V₂O₅/blend, the chronopotentiometric curves show that x in Li_xV₂O₅ is about 1.77. Evidence of enhanced ionic transport was provided by the Fourier transform infrared (FTIR) spectrum, which indicated lithium complexation by PEO and formation of a larger amorphous phase of PEO within the V₂O₅ matrix. The importance of these results for the production of Li secondary microbatteries and electrochromic devices is discussed.     

A Family of High‐Performance Cathode Materials for Na‐ion Batteries,Na3(VO1−xPO4)2 F1+2x (0 ≤ x ≤ 1): Combined First‐Principles and Experimental Study

Room‐temperature Na‐ion batteries (NIBs) have recently attracted attention as potential alternatives to current Li‐ion batteries (LIBs). The natural abundance of sodium and the similarity between the electrochemical properties of NIBs and LIBs make NIBs well suited for applications requiring low cost and long‐term reliability. Here, the first successful synthesis of a series of Na₃(VO_1?x PO₄)₂F_1+2x (0 ≤ x ≤ 1) compounds as a new family of high‐performance cathode materials for NIBs is reported. The Na₃(VO_1?x PO₄)₂F_1+2x series can function as high‐performance cathodes for NIBs with high energy density and good cycle life, although the redox mechanism varies depending on the composition. The combined first‐principles calculations and experimental analysis reveal the detailed structural and electrochemical mechanisms of the various compositions in solid solutions of Na₃(VOPO₄)₂F and Na₃V₂(PO₄)₂F₃. The comparative data for the Na _y (VO_1?x PO₄)₂F_1+2x electrodes show a clear relationship among V³⁺/V⁴⁺/V⁵⁺ redox reactions, Na⁺?Na⁺ interactions, and Na⁺ intercalation mechanisms in NIBs. The new family of high‐energy cathode materials reported here is expected to spur the development of low‐cost, high‐performance NIBs.     

Br‐Doped Li4Ti5O12 and Composite TiO2 Anodes for Li‐ion Batteries: Synchrotron X‐Ray and in situ Neutron Diffraction Studies

Synchrotron X‐ray diffraction data were used to determine the phase purity and re‐evaluate the crystal‐structure of Li₄Ti₅O_12‐xBr_x electrode materials (where the synthetic chemical inputs are x = 0.05, 0.10 0.20, 0.30). A maximum of x′ = 0.12 Br, where x′ is the Rietveld‐refined value, can be substituted into the crystal structure with at least 2% rutile TiO₂ forming as a second phase. Higher Br concentrations induced the formation of a third, presumably Br‐rich, phase. These materials function as composite anodes that contain mixtures of TiO₂, Li₄Ti₅O_12‐xBr_x, and a Br‐rich third, unknown, phase. The minor quantities of the secondary phases in combination with Li₄Ti₅O_12‐xBr_x where x′ ～ 0.1 were found to correspond to the optimum in electrochemical properties, while larger quantities of the secondary phases contributed to the degradation of the performance. In situ neutron diffraction of a composite anatase TiO₂/Li₄Ti₅O₁₂ anode within a custom‐built battery was used to determine the electrochemical function of the TiO₂ component. The Li₄Ti₅O₁₂ component was found to be electrochemically active at lower voltages (1.5 V) relative to TiO₂ (1.7 V). This enabled Li insertion/extraction to be tuned through the choice of voltage range in both components of this composite or in the anatase TiO₂ phase only. The use of composite materials may facilitate the development of multi‐component electrodes where different active materials can be cycled in order to tune power output.     

On‐Demand Nanoscale Manipulations of Correlated Oxide Phases

Controlling material properties at the nanoscale is a critical enabler of high performance electronic and photonic devices. A prototypical material example is VO₂, where a structural phase transition in correlation with dramatic changes in resistivity, optical response, and thermal properties demonstrates particular technological importance. While the phase transition in VO₂ can be controlled at macroscopic scales, reliable and reversible nanoscale control of the material phases has remained elusive. Here, reconfigurable nanoscale manipulations of VO₂ from the pristine monoclinic semiconducting phase to either a stable monoclinic metallic phase, a metastable rutile metallic phase, or a layered insulating phase using an atomic force microscope is demonstrated at room temperature. The capability to directly write and erase arbitrary 2D patterns of different material phases with distinct optical and electrical properties builds a solid foundation for future reprogrammable multifunctional device engineering.     

Positive and Negative Pressure Regimes in Anisotropically Strained V2O3 Films

The metal-insulator phase transitions in V₂O₃ are considered archetypal manifestations of Mott physics. Despite decades of research, the effects of doping, pressure, and anisotropic strains on the transitions are still debated. To understand how these parameters control the transitions, anisotropically strained pure V₂O₃ films are explored with nearly the same contraction along the c-axis, but different degrees of ab-plane expansion. With small ab-plane expansion, the films behave similar to bulk V₂O₃ under hydrostatic pressure. However, with large ab-plane expansion, the films are driven into the “negative pressure” regime, similar to that of Cr-doped V₂O₃, exhibiting clear coexistence of paramagnetic insulator and paramagnetic metal phases between 180–500 K. This shows that c-axis contraction alone, or an increase in c/a ratio is insufficient for inducing “negative pressure” effects. Actually, c-axis contraction alone destabilizes the two insulating phases of V₂O₃, whereas a-axis expansion tends to stabilize them. The effects of strain are modeled using density functional theory providing good agreement with experimental results. The findings show that chemical pressure alone cannot account for the phase diagram of (V_1−xCr_x)₂O₃. This work enables to manipulate a Mott transition above room temperature, thereby expanding the opportunities for applications of V₂O₃ in novel electronics.     

Thermally grown vanadium oxide films and their electrical properties

A metal–insulator transition (MIT) occurring in vanadium oxide films prepared in different ways has been widely studied in many laboratories. It consists of a resistive change of various orders of magnitude taking place while traversing a temperature close to 67 °C. In this work the properties of VO_x films synthesized by thermal treatment of vanadium films which were vacuum-evaporated on an oxidized silicon substrate are shown. Such thermal oxidizing treatment was performed under atmospheric air at different temperatures during distinct times. Ellipsometry measurements allowed determining the thickness and optical constants of the layers after the oxidation process. From XRD, Raman and FTIR measurements, several phases with distinct oxygen content, V₂O₃, V₃O₅, VO₂ and V₂O₅, were found in the films, depending on the oxidation time and temperature. Current–temperature measurements across the films were carried out by using sandwich-type metal–insulator–metal structures. Unlike former studies on similar structures, no MIT was observed from these measurements. On the other hand, from room-temperature current–voltage measurements a well defined memristive behavior was found as a regular result in most of our structures. This memristive behavior is ascribed to the complex defect structure in the films, including the variable amount of oxygen vacancies in the lattice, rather than to the above-mentioned metal–insulator transition in vanadium oxide.     

Quantum‐Chemical Studies on the Geometric and Electronic Structures of Bertholloide Cobalt Oxynitrides

We report electronic structure calculations using density‐functional theory (local density approximation (LDA) and generalized gradient approximation (GGA); plane waves and muffin‐tin orbitals; pseudopotentials and all‐electron approaches) on non‐stoichiometric CoN_xO_1–x oxynitride phases. The preference of the experimentally suggested zinc‐blende structure type over the rock‐salt type is confirmed and explained, on the basis of COHP (crystal orbital Hamilton population) chemical bonding analyses, by reduced Co–Co antibonding interactions in the ZnS structural alternative. A pressure‐induced phase transition into the NaCl type, however, is predicted at approximately 30 GPa. Supercell calculations touching upon the exact composition and local structure of CoN_xO_1–x provide evidence for a broad range of energetically metastable compositions with respect to the zinc‐blende‐type boundary phases CoN and CoO, especially for the more oxygen‐rich phases. All non‐stoichiometric compounds are predicted to be metallic materials which do not exhibit significant magnetic moments. Likewise, there is no indication for anionic ordering such that random anion arrangements are preferred.     

VOx@MoO3 Nanorod Composite for High‐Performance Supercapacitors

Vanadium oxide is a promising pseudocapacitive electrode, but their capacitance, especially at high current densities, requires improvement for practical applications. Herein, a VO_x@MoO₃ composite electrode is constructed through a facile electrochemical method. Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy demonstrate a modification on the chemical environment and electronic structure of VO_x upon the effective interaction with the thin layer of MoO₃. A careful investigation of the electrochemical impedance spectroscopy data reveals much enhanced power capability of the composite electrode. More charge storage sites will also be created at/near the heterogeneous interface. Due to those synergistic effects, the VO_x@MoO₃ electrode shows excellent electrochemical performance. It provides a high capacitance of 1980 mF cm⁻² at 2 mA cm⁻². Even at the high current density of 100 mA cm⁻², it still achieves 1166 mF cm⁻² capacitance, which doubles the sum of single electrodes. The MoO₃ layer also helps to prevent VO_x structure deformation, and 94% capacitance retention over 10 000 cycles is obtained for the composite electrode. This work demonstrates an effective strategy to induce interactions between heterogeneous components and enhance the electrochemical performance, which can also be applied to other pseudocapacitive electrode candidates.     

Broad Range Tuning of Phase Transition Property in VO2 Through Metal‐Ceramic Nanocomposite Design

Vanadium dioxide (VO₂) is a well‐studied Mott‐insulator because of the very abrupt physical property switching during its semiconductor‐to‐metal transition (SMT) around 341 K (68 °C). In this work, through novel oxide‐metal nanocomposite designs (i.e., Au:VO₂ and Pt:VO₂), a very broad range of SMT temperature tuning from ≈ 323.5 to ≈ 366.7 K has been achieved by varying the metallic secondary phase in the nanocomposites (i.e., Au:VO₂ and Pt:VO₂ thin films, respectively). More surprisingly, the SMT T_c can be further lowered to ≈ 301.8 K (near room temperature) by reducing the Au particle size from 11.7 to 1.7 nm. All the VO₂ nanocomposite thin films maintain superior phase transition performance, i.e., large transition amplitude, very sharp transition, and narrow width of thermal hysteresis. Correspondingly, a twofold variation of the complex dielectric function has been demonstrated in these metal‐VO₂ nanocomposites. The wide range physical property tuning is attributed to the band structure reconstruction at the metal‐VO₂ phase boundaries. This demonstration paved a novel approach for tuning the phase transition property of Mott‐insulating materials to near room temperature transition, which is important for sensors, electrical switches, smart windows, and actuators.     

The Dynamic Phase Transition Modulation of Ion‐Liquid Gating VO2 Thin Film: Formation,Diffusion, and Recovery of Oxygen Vacancies

Electrolyte gating with ionic liquids (IL) on correlated vanadium dioxide (VO₂) nanowires/beams is effective to modulate the metal‐insulator transition (MIT) behavior. While for macrosize VO₂ film, the gating treatment shows different phase modulation process and the intrinsic mechanism is still not clear, though the oxygen‐vacancy diffusion channel is always adopted for the explanation. Herein, the dynamic phase modulation of electrolyte gated VO₂ films is investigated and the oxygen vacancies formation, diffusion, and recovery at the IL/oxide interface are observed. As a relatively slow electrochemical reaction, the gating effect gradually permeates from surface to the inside of VO₂ film, along with an unsynchronized changes of integral electric, optical, and structure properties. First‐principles‐based theoretical calculation reveals that the oxygen vacancies can not only cause the structural deformations in monoclinic VO_2, but also account for the MIT transition by inducing polarization charges and thereby adjusting the d‐orbital occupancy. The findings not only clarify the oxygen vacancies statement of electrolyte gated VO₂ film, but also can be extended to other ionic liquid/oxide systems for better understanding of the surface electrochemical stability and electronic properties modulation.     

Nanostructured Vanadium Oxide Electrodes for Enhanced Lithium‐Ion Intercalation

This article summarizes our most recent studies on improved Li⁺‐intercalation properties in vanadium oxides by engineering the nanostructure and interlayer structure. The intercalation capacity and rate are enhanced by almost two orders of magnitude with appropriately fabricated nanostructures. Processing methods for single‐crystal V₂O₅ nanorod arrays, V₂O₅·n H₂O nanotube arrays, and Ni/V₂O₅·n H₂O core/shell nanocable arrays are presented; the morphologies, structures, and growth mechanisms of these nanostructures are discussed. Electrochemical analysis demonstrates that the intercalation properties of all three types of nanostructure exhibit significantly enhanced storage capacity and rate performance compared to the film electrode of vanadium pentoxide. Addition of TiO₂ to orthorhombic V₂O₅ is found to affect the crystallinity, microstructure, and possible interaction force between adjacent layers in V₂O₅, and subsequently leads to enhanced Li⁺‐intercalation properties in V₂O₅. The amount of water intercalated in V₂O₅ is found to have a significant influence on the interlayer spacing and electrochemical performance of V₂O₅·n H₂O. A systematic electrochemical study has demonstrated that the V₂O₅·0.3 H₂O film has the optimal water content and exhibits the best Li⁺‐intercalation performance.     

In Situ X‐Ray Diffraction Studies on Structural Changes of a P2 Layered Material during Electrochemical Desodiation/Sodiation

Sodium layered oxides with mixed transition metals have received significant attention as positive electrode candidates for sodium‐ion batteries because of their high reversible capacity. The phase transformations of layered compounds during electrochemical reactions are a pivotal feature for understanding the relationship between layered structures and electrochemical properties. A combination of in situ diffraction and ex situ X‐ray absorption spectroscopy reveals the phase transition mechanism for the ternary transition metal system (Fe–Mn–Co) with P2 stacking. In situ synchrotron X‐ray diffraction using a capillary‐based microbattery cell shows a structural change from P2 to O2 in P2–Na_0.7Fe_0.4Mn_0.4Co_0.2O₂ at the voltage plateau above 4.1 V on desodiation. The P2 structure is restored upon subsequent sodiation. The lattice parameter c in the O2 structure decreases significantly, resulting in a volumetric contraction of the lattice toward a fully charged state. Observations on the redox behavior of each transition metal in P2–Na_0.7Fe_0.4Mn_0.4Co_0.2O₂ using X‐ray absorption spectroscopy indicate that all transition metals are involved in the reduction/oxidation process.     

Charge Disproportionation and Voltage‐Induced Metal–Insulator Transitions Evidenced in β‐PbxV2O5 Nanowires

The roster of materials exhibiting metal–insulator transitions with sharply discontinuous switching of electrical conductivity close to room temperature remains rather sparse, despite the fundamental interest in the electronic instabilities manifested in such materials and the plethora of potential technological applications ranging from frequency‐agile metamaterials to electrochromic coatings and Mott field‐effect transistors. Here, unprecedented, pronounced metal‐insulator transitions induced by application of a voltage are demonstrated for nanowires of a vanadium oxide bronze with intercalated divalent cations, β‐Pb_xV₂O₅ (x ≈ 0.33). The induction of the phase transition through application of an electric field at room temperature makes this system particularly attractive and viable for technological applications. A mechanistic basis for the phase transition is proposed based on charge disproportionation evidenced at room temperature in near‐edge X‐ray absorption fine structure (NEXAFS) spectroscopy measurements, ab initio density functional theory calculations of the band structure, and electrical transport data, suggesting that transformation to the metallic state is induced by melting of specific charge localization and ordering motifs extant in these materials.     

Femtojoule-Power-Consuming Synaptic Memtransistor Based on Mott Transition of Multiphasic Vanadium Oxides

To realize the potential of Mott transition of multiphasic vanadium oxides (VO_x) for memory applications, the development of VO_x memtransistors on SiO₂ wafer is introduced. Through electrical characterizations, the volatile memory behaviors of the VO_x memtransistors are observed in both two- and three-terminal measurements. Their capacitive memory and resistive switching mechanisms are strongly related to the mixed VO_x/SiO₂ interface (called VSiO_x). VSiO_x supports the Mott transition in VO_x at low bias voltages (<0.5 V), leading to the low power consumption of the memtransistor. Moreover, the fast switching time (≈35 ns) and tunable memory retention with the synaptic functions (potentiation and depression) of the memtransistors (by using the gate and drain biases) are demonstrated. Overall, the findings open up major opportunities for constructing ultrafast and femto-joule power-consuming neuromorphic devices.     

Effect of post-growth annealing on the structural,optical and electrical properties of V2O5 nanorods and its fabrication,characterization of V2O5/p-Si junction diode

We report the synthesis of V₂O₅ nanorods by utilizing simple wet chemical strategy with ammonia meta vanadate (NH₄VO₃) and polyethylene glycol (PEG) exploited as precursor and surfactant agent, respectively. The effect of post-annealing on structural, optical and electrical properties of V₂O₅ nanorods was characterized by XRD, HRSEM-EDX, TEM, FT-IR, UV (DRS), PL, TG–DTA and DC conductivity studies. The X-ray diffraction analysis revealed that the prepared sample annealed at 150 °C for 5 h which exhibited anorthic phase of V₅O₉ and annealed at 300–600 °C showed the anorthic phase change to orthorhombic phase of V₂O₅ due to the post-annealing effect. The surface morphology results indicated that increasing temperature caused a change from microrods to a nanorods shape in the morphology of V₂O₅. FT-IR spectrum confirmed that the presence of V₂O₅ functional groups and the formation of V–O bond. The optical band gap was found in the range 2.5–2.48 eV and observed to decreases with various annealed temperature. The DC electrical conductivity was studied as a function of temperature which indicated the semiconducting nature. Further, the potential of V₂O₅ nanostructures were grown on the p-Si substrate using the nebulizer spray technique. The junction properties of the V₂O₅/p-Si diode were evaluated by measuring current (I)–voltage (V) and AC characteristics.     

Phase Transitions in the BiVO<Subscript>4</Subscript>-<Emphasis Type="Italic">n</Emphasis>PbO (<Emphasis Type="Italic">n</Emphasis> = 1, 2) System: Structural–Electrical Properties Relationships

In a general survey of nPbO-BiVO₄ compounds, interesting phases corresponding to n = 1: PbBiVO₅, and n = 2: Pb₂BiVO₆ are described. A phase transition has been unambiguously characterized for PbBiVO₅. The crystal structures were solved from twinned crystals at room temperature (α phase, triclinic, S.G. P-1) and at 530°C (β phase, monoclinic, C2/m). Powder neutron diffraction experiments confirmed these settings and both room-temperature (RT) and high-temperature (HT) refinements corroborated space group choices, clearing up a literature controversy about the centrosymmetry of the α phase, and identifying structural modifications occurring under the α → β transition. Cationic substitutions for V were tested and PbBi(V_1−x M _x )O₅ (M = P) solid solutions identified. Pb₂BiVO₆ (n = 2) is a compound showing several successive structural transitions, i.e., α → β → δ. Structures of α and δ forms have been previously described from powder diffraction data (x-ray and neutron). In this work, we have refined these structures from single-crystal data, and the resolution of the intermediate β form, so far unsolved, was possible through a stabilization thermal cycle; its complete structural understanding required a 4D formalism. Two new polymorphic phases, α′ and δ′, were obtained by substituting Mn or P for V; their structures are closely related to, respectively, the α phase at room temperature, and the δ phase at 680°C. Electrical conductivities of all structurally characterized compositions were investigated, and correlations were drawn between their conduction properties and structural characteristics. Conductivity properties measured under variable O₂ partial pressures for Pb₂Bi(V_0.75P_0.25)O₆ were interpreted as a mixed ionic–electronic (p-type) conduction mechanism.     

Construction of VS2/VOx Heterostructure via Hydrolysis-Oxidation Coupling Reaction with Superior Sodium Storage Properties

Heterostructure engineering is one of the most promising modification strategies for reinforcing Na⁺ storage of transition metal sulfides. Herein, based on the spontaneous hydrolysis-oxidation coupling reaction of transition metal sulfides in aqueous media, a VO_x layer is induced and formed on the surface of VS₂, realizing tight combination of VS₂ and VO_x at the nanoscale and constructing homologous VS₂/VO_x heterostructure. Benefiting from the built-in electric field at the heterointerfaces, high chemical stability of VO_x, and high electrical conductivity of VS₂, the obtained VS₂/VO_x electrode exhibits superior cycling stability and rate properties. In particular, the VS₂/VO_x anode shows a high capacity of 878.2 mAh g⁻¹ after 200 cycles at 0.2 A g⁻¹. It also exhibits long cycling life (721.6 mAh g⁻¹ capacity retained after 1000 cycles at 2 A g⁻¹) and ultrahigh rate property (up to 654.8 mAh g⁻¹ at 10 A g⁻¹). Density functional theory calculations show that the formation of heterostructures reduces the activation energy for Na⁺ migration and increases the electrical conductivity of the material, which accelerates the ion/electron transfer and improves the reaction kinetics of the VS₂/VO_x electrode.     

In-Situ Electrochemically Activated Surface Vanadium Valence in V2C MXene to Achieve High Capacity and Superior Rate Performance for Zn-Ion Batteries

Vanadium-based materials are fascinating potential cathodes for high energy density Zn-ion batteries (ZIBs), due to their high capacity arising from multi-electron redox chemistry. Most vanadium-based materials suffer from poor rate capability, however, owing to their low conductivity and large dimension. Here, we propose the application of V₂C MXene (V₂CT_x), a conductive 2D nanomaterial, for achieving high energy density ZIBs with superior rate capability. Through an initial charging activation, the valence of surface vanadium in V₂CT_x cathode is raised significantly from V²⁺/V³⁺ to V⁴⁺/V⁵⁺, forming a nanoscale vanadium oxide (VO_x) coating that effectively undergoes multi-electron reactions, whereas the inner V-C-V 2D multi-layers of V₂CT_x are intentionally preserved, providing abundant nanochannels with intrinsic high conductivity. Owing to the synergistic effects between the outer high-valence VO_x and inner conductive V-C-V, the activated V₂CT_x presents an ultrahigh rate performance, reaching 358 mAh g⁻¹ at 30 A g⁻¹, together with remarkable energy and power density (318 Wh kg⁻¹/22.5 kW kg⁻¹). The structural advantages of activated V₂CT_x are maintained after 2000 cycles, offering excellent stability with nearly 100% Coulombic efficiency. This work provides key insights into the design of high-performance cathode materials for advanced ZIBs.     

Reduced Surfactant Uptake in Three Dimensional Assemblies of VOx Nanotubes Improves Reversible Li+ Intercalation and Charge Capacity

The relationship between the nanoscale structure of vanadium pentoxide nanotubes and their ability to accommodate Li⁺ during intercalation/deintercalation is explored. The nanotubes are synthesized using two different precursors through a surfactant‐assisted templating method, resulting in standalone VO _x (vanadium oxide) nanotubes and also “nano‐urchin”. Under highly reducing conditions, where the interlaminar uptake of primary alkylamines is maximized, standalone nanotubes exhibit near‐perfect scrolled layers and long‐range structural order even at the molecular level. Under less reducing conditions, the degree of amine uptake is reduced due to a lower density of V⁴⁺ sites and less V₂O₅ is functionalized with adsorbed alkylammonium cations. This is typical of the nano‐urchin structure. High‐resolution TEM studies revealed the unique observation of nanometer‐scale nanocrystals of pristine unreacted V₂O₅ throughout the length of the nanotubes in the nano‐urchin. Electrochemical intercalation studies revealed that the very well ordered xerogel‐based nanotubes exhibit similar specific capacities (235 mA h g^?1) to Na⁺‐exchange nanorolls of VO_x (200 mA h g^?1). By comparison, the theoretical maximum value is reported to be 240 mA h g^?1. The VOTPP‐based nanotubes of the nano‐urchin 3D assemblies, however, exhibit useful charge capacities exceeding 437 mA h g^?1, which is a considerable advance for VO_x based nanomaterials and one of the highest known capacities for Li⁺ intercalated laminar vanadates.