Tritium trapping by oxygen and lithium vacancies in Li4TiO4 from first-principles calculations

The Li₄TiO₄ ceramic is a promising solid-state tritium breeder material for the production of tritium fuel in the designs of fusion reactors. Tritium extraction efficiency is one of the key factors that determines the performance of the breeder material. Vacancies are known to trap tritium and adversely affect tritium extraction. Understandings of tritium-trapped defect configurations in Li₄TiO₄ are limited so far. In this work, the oxygen/lithium vacancy (V_O/Li) and the vacancy-tritium defect complex (V_O/Li + T) in Li₄TiO₄ are studied by first-principles density functional theory. The atomic configurations, formation energies and electronic structures of various charged defect species are obtained. We find that 2+ and 0 are the dominate charge states of V_O, 1- is the dominate charge state of V_Li, 1+ is the dominate charge state of the defect complex (V_O + T), and 0 is the dominate charge state of (V_Li + T). Tritium atoms trapped in V_O are bonded to Ti atoms, and those trapped in V_Li are bonded to O atoms.     

Structure and electrochemical behavior of lithium vanadate materials for lithium batteries

New vanadate compounds having the molecular structure Li_xMg_1−xV_2−xMo_xO₆ (0 ≤ x ≤ 1) were studied. Six samples were prepared by sol-gel process from precursor using the following ratios of x = 0, 0.2, 0.4, 0.6, 0.8 and 1, respectively. These samples were labeled S1, S2, S3, S4, S5 and S6. The final process of firing occurred at 750 °C for 18 h in air. The prepared materials were characterized by XRD, SEM, IR, electron spin resonance (ESR) and magnetic measurements. The morphologies of S1, S2, S5 and S6 are prismatic as they have monoclinic crystal structures. S3 and S4 differ in the crystal morphology from the other previous samples due to their triclinic crystal lattice structure. IR spectra revealed that the bond lengths of the vanadyl groups ν_VO, ν_{sy V-O} and σ_V-O increase in the same direction from S1 to S6. The data of the ESR explain the existence of V⁴⁺ beside V⁵⁺ in S1, S4 and S6 and also presence of Mo⁵⁺ with Mo⁶⁺ in S4 and S6. S4 exhibited better magnetic susceptibility and saturated magnetization than the other samples. The first specific discharge capacities of the samples were performed. S4 showed the maximum specific capacity of 265 mAh g⁻¹ in comparison with the other samples. Cyclic voltammogram of S4 exhibited the highest current intensity in comparison with the other samples. This sample showed two peaks at 0.53 and 1.3 V versus Li/Li⁺ characterizing double de-insertions of two lithium atoms from Li_1.6Mg_0.4V_1.4Mo_0.6O_6−x and Li_0.6Mg_0.4V_1.4Mo_0.6O₆, respectively. Also, two additional peaks were characterized for the oxidation of Mo⁵⁺ to Mo⁶⁺ and V⁴⁺ to V⁵⁺ at 3.5 and 4 V, respectively.     

Lithium ion diffusion in Li4+xTi5O12: From ab initio studies

Lithium ion dynamics in Li_4+xTi₅O₁₂ spinel are investigated from first principles calculations. The diffusion pathways are optimized and the energy barriers of lithium migration under four types of dilute defect extremes: Li_4+δTi₅O₁₂, Li_4−δTi₅O₁₂, Li_7+δTi₅O₁₂ and Li_7−δTi₅O₁₂ (δ ? 1) are calculated with the nudged elastic band method. Results show that lithium diffusion in the charged state (energy barriers are 1.0 and 0.7 eV for interstitial Li and Li vacancy diffusion, respectively) is much slower than in the discharged state (energy barriers are 0.13 and 0.35 eV for interstitial Li and Li vacancy diffusion, respectively). The diffusion coefficients are evaluated based on lattice gas model and hopping mechanism. The obtained results are compared with available experimental data within a two-phase co-existence framework.     

Intrinsic defects,Mo-related defects,and complexes in transition-metal carbide VC: A first-principles study

Intrinsic defects and Mo-related defects in vanadium carbide VC, as well as the defect complexes between vacancies and Mo defects were investigated by means of first-principles calculations within the framework of density functional theory. In addition, Mo diffusion in VC was also studied using LST/QST method. The formation energies of defects have clearly shown that except C vacancy (V_C) all other point defects are not energetic favorable compared to perfect VC. V_C can exist in the lattice forming nonstoichiometric carbide VC_x (x < 1), and also can stabilize the Mo-related defects (S_Mo-V, S_Mo-C, and T_Mo). Free Mo atoms have the strong tendency to enter the already formed V_V and occupy the lattice position of V atoms. Meanwhile, Mo atom in C lattice (S_Mo-C) and interstitial Mo (I_Mo) atom can also enter the V_V position stabilizing the lattice structure. S_Mo-C + V_V will transform into S_Mo-V + V_C and I_Mo + V_V will transform into S_Mo-V during optimization, and large binding energy makes Mo atom tend to exist in the interstitial position. From the perspective of energy, Mo atom tends to diffuse through the interstitial position.     

New anode materials of Li1+xV1?xO2 (0?≤?x?≤?0.1) for secondary lithium batteries: correlation between structures and properties

Li_1+x V_1−x O₂ (0 ≤ x ≤ 0.1) compounds were studied as the anode materials for a lithium-ion battery. The crystal and electronic structures of the prepared materials were correlated with electrical conductivities and electrochemical properties. The electrochemical behaviors were significantly dependent on the composition of Li_1+x V_1−x O₂, and these were resulted from the perturbation of the local electronic structure arising from the increase in lithium contents in Li_1+x V_1−x O₂ rather than from the slight distortion in the crystal structure. The electrical conductivities of Li_1+x V_1−x O₂ increased with the increase in lithium contents in the compounds. Li_1.1V_0.9O₂ and Li_1.075V_0.925O₂ samples exhibit the first discharge capacities of 250 and 241 mAh g⁻¹ at 0.2 C-rate, respectively.     

Li6V10O28, a novel cathode material for Li-ion battery

A novel cathode material, lithium decavanadate Li₆V₁₀O₂₈ with a large tunnel within the framework structure for lithium ion battery has been prepared by hydrothermal synthesis and annealing dehydration treatment. The structure and electrochemical properties of the sample have been investigated. The novel material shows good reversibility for Li⁺ insertion/extraction and long cycle life. High discharge capacity (132 mAh/g) is obtained at 0.2 mA/cm² discharge current and potential range between 2.0 and 4.2 V versus Li⁺/Li. AC impedance of the Li/Li₆V₁₀O₂₈ cell reveals that the cathode process is controlled mainly by Li⁺ diffusion in the active material. The novel material would be a promising cathode material for Li-ion batteries.     

A macaroni-like Li1.2V3O8 nanomaterial with high capacity for aqueous rechargeable lithium batteries

A macaroni-like Li_1.2V₃O₈ nanomaterial was directly prepared through a facile solution route using β-cyclodextrin (β-CD) as a template reagent. Its crystal structure was determined by the X-ray diffraction (XRD) pattern. From the scanning electron microscopy (SEM) and transmission electron microscopy (TEM) micrographs, we observed that the as-prepared Li_1.2V₃O₈ material consisted of the aggregated macaroni-like nanoparticles and showed a porous structure. The electrochemical properties of the as-prepared Li_1.2V₃O₈ in 1.0 M Li₂SO₄ aqueous electrolyte were studied through cyclic voltammograms and charge-discharge measurements. The results revealed that the as-prepared Li_1.2V₃O₈ could deliver the initial specific capacities of 189, 140, and 101 mAh g⁻¹ at 0.1, 0.5, and 1.0 C, respectively. It suggests that the as-prepared Li_1.2V₃O₈ should have an attractive future to be applied in aqueous rechargeable lithium battery (ARLB).     

Multi-electrochromism behavior and electrochromic mechanism of electrodeposited molybdenum doped vanadium pentoxide films

Molybdenum doped vanadium pentoxide (Mo doped V₂O₅) films are prepared by cathodic electrodeposition on indium tin oxide substrate from Mo doped V₂O₅ sol. As an anodic and cathodic coloration electrochromic material, the electrodeposited Mo doped V₂O₅ film presents a better cycling stability, reversibility and multi-electrochromic behavior (orange-yellow-green-blue) with an optical modulation of 60-90% in the spectral region 550-900 nm, which can be expected as a result of enhanced electron intervalence transfer between Mo⁶⁺ and V⁵⁺, V⁴⁺ states, in addition to V⁵⁺ and V⁴⁺ transition. The electrochromic mechanism of Mo doped V₂O₅ films is investigated with atomic force microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy. The surface roughness of the film increase at the different coloration states due to the increasing crystallinity degree. The change of the interlayer spacing for the host V₂O₅ and the change of the C and Li element states verify the insertion of organic solvent into the interlayer of the host V₂O₅ and some of the Li⁺ ions into the sites in the V-O layers. The electrochromic kinetics process indicates that the electrochromism of Mo doped V₂O₅ films can be considered as a reversible reduction/oxidation process accompanying the insertion/extraction of Li⁺ ions and electrons.     

Relationship between electrochemical behavior and Li/vacancy arrangement in ramsdellite type Li2+xTi3O7

The changes of Li⁺/vacancy arrangement in Li_2+xTi₃O₇ with a ramsdellite-type structure upon topo-electrochemical Li⁺ insertion were investigated by the entropy measurement of reaction combined with the Monte Carlo simulation. The experimental entropy measurement was conducted by potentiometric and calorimetrical methods. The obtained experimental data were in good accordance with simulated results.The results indicated that the ordered Li⁺/vacancy arrangement appeared at the compositions of x ∼ 0.45 and ∼1.20, where the observed entropy of reaction humped. The ordering of Li/vacancy were also indicated at the composition x ∼ 0.24 and 1.16 in Li_2+xTi₃O₇ by the Monte Carlo simulation which considers the most stable Li/vacancy arrangement in terms of Coulombic interaction. This substantial agreement between electrochemical behaviors and computational results confirmed that the formation of superstructure arising from Li/vacancy arrangement during the electrochemical reaction deeply related to the atomic level Coulombic interactions.     

Mechanism-based tuning of room-temperature ferromagnetism in Mn-doped β-Ga2O3 by annealing atmosphere

Mn-doped β-Ga₂O₃ (GMO) films with room-temperature ferromagnetism (RTFM) are synthesized by polymer-assisted deposition, and the effects of annealing atmosphere (air or pure O₂ gas) on their structures and physical properties are investigated. The characterizations show that the concentrations of vacancy defects and Mn dopants in various valence states and lattice constants of the samples are all modulated by the annealing atmosphere. Notably, the samples annealed in air (GMO–air) exhibit a saturation magnetization as strong as 170% times that of the samples annealed in pure O₂ gas (GMO–O₂), which can be quantitatively explained by oxygen vacancy (V_O)-controlled ferromagnetism due to bound magnetic polarons established between delocalized hydrogenic electrons of V_Os and local magnetic moments of Mn²⁺, Mn³⁺, and Mn⁴⁺ ions in the samples. Our results provide insights into mechanism-based tuning of RTFM in Ga₂O₃ and may be useful for design, fabrication, and application of related spintronic materials.     

Investigation of Native Point Defects and Nonstoichiometry Mechanisms of Two Yttrium Silicates by First‐Principles Calculations

First‐principles method is used to study the native point defects in Y₂SiO₅ and Y₂Si₂O₇ silicates. The calculated defect formulation energies show similar native point defect behaviors in Y₂SiO₅ and Y₂Si₂O₇: the oxygen Frenkel defect is predominant; and it is followed by the cation antisite and Schottky defects. The possible chemical potential range of each constituent is further considered in the calculation of defect formation energy. Oxygen interstitial (O_i) and oxygen vacancy (V_O) are the predominant native point defects under O‐rich and O‐poor condition, respectively. In addition, the mechanisms of accommodating composition deviations from stoichiometric Y₂SiO₅ and Y₂Si₂O₇ are investigated. For Y₂SiO₅, Y₂Si₂O₇ impurity may appear, together with the defects of Si_Y antisite, O_i interstitial, and/or V_Y vacancy when SiO₂ is excess; while Y_Si antisite appears together with Y_i interstitial and/or V_O vacancy in Y₂SiO₅ when Y₂O₃ is excess. For Y₂Si₂O₇, the main process is the formation of Si_Y antisite accompanied by O_i interstitial and/or V_Y vacancy when SiO₂ is excess; but Y₂SiO₅ impurity forms, together with Y_Si antisite, V_O vacancy, and/or Y_i interstitial in Y₂Si₂O₇ when Y₂O₃ is excess. We expect that the results are useful to control of processing conditions and further to optimization of performance of the two silicates.     

Vacancy-enhanced cycle life and electrochemical performance of lithium-rich layered oxide Li2RuO3

Vacancy plays an important role in charge/discharge processes of solid-state lithium batteries because the vacancy-induced charge carrier trap and transportation channels effectively facilitate the diffusion of Li ion. Although lithium-rich layered oxide Li₂TMO₃ is a promising electrode material, it's vacancy mechanism remains unclear. In particular, the role of vacancy in the cycle life and electrochemical performance of Li₂TMO₃ is unknown. Here, we report on the volume variation (ΔV), average open circuit voltage (V_oc) and electronic structure of Li₂RuO₃ layered oxide with various vacancies. Compared to Li_-va vacancy, O_-va (4.74 V) and Ru_-va (4.60 V) vacancies enhance the V_oc of Li₂RuO₃ (4.46 V) because O_-va and Ru_-va vacancies induced charge carrier traps improve the charge overlaps between the conduction band and valence band near the Fermi level. In particular, O_-va vacancy is more thermodynamically stable than that of the other vacancies. Whether the perfect vacancy or vacancies after Li extraction, the calculated ΔV of O_-va vacancy is smaller than that of the other vacancies. Therefore, we believe that O_-va vacancy can improve the cycle life and electrochemical performance of Li₂TMO₃ layered oxides lithium batteries.     

High rate capability and long-term cyclability of Li4Ti4.9V0.1O12 as anode material in lithium ion battery

Li₄Ti_4.9V_0.1O₁₂ nanometric powders were synthesized via a facile solid-state reaction method under inert atmosphere. XRD analyses demonstrated that the V-ions successfully entered the structure of cubic spinel-type Li₄Ti₅O₁₂ (LTO), reduced the lattice parameter and no impurities appeared. Compared with the pristine LTO, the electronic conductivity of Li₄Ti_4.9V_0.1O₁₂ powders is as high as 2.9 × 10⁻¹ S cm⁻¹, which should be attributed to the transformation of some Ti³⁺ from Ti⁴⁺ induced by the efficient V-ions doping and the deficient oxygen condition. Meanwhile, the results of XPS and EDS further proved the coexistence of V⁵⁺ and Ti³⁺ ions. This mixed Ti⁴⁺/Ti³⁺ ions can remarkably improve its cycle stability at high discharge–charge rates because of the enhancement of the electronic conductivity. The images of SEM showed that Li₄Ti_4.9V_0.1O₁₂ powders have smaller particles and narrower particle size distribution under 330 nm. And EIS indicates that Li₄Ti_4.9V_0.1O₁₂ has a faster lithium-ion diffusivity than LTO. Between 1.0 and 2.5 V, the electrochemical performance, especially at high rates, is excellent. The discharge capacities are as high as 166 mAh g⁻¹ at 0.5C and 117.3 mAh g⁻¹ at 5C. At the rate of 2C, it exhibits a long-term cyclability, retaining over 97.9% of its initial discharge capacity beyond 1713 cycles. These outstanding electrochemical performances should be ascribed to its nanometric particle size and high conductivity (both electron and lithium ion). Therefore, the as-prepared material is promising for such extensive applications as plug-in hybrid electric vehicles and electric vehicles.     

Structural characterization and electrochemical performance of lithium trivanadate synthesized by microwave sol-gel method

The Li_1+xV₃O₈ material was successfully synthesized at 450 °C in short sintering duration by microwave sol-gel route. X-ray diffraction suggests oxygen defects in the lattice. Based on Randles-Sevcik formula, cyclic voltammograms measurements were conducted to measure Li⁺ ion diffusion coefficient. The material exhibits high discharge capacity of 250 mA g⁻¹ at 0.2 mA/cm² after 30 cycles in the range of 2.0-4.0 V. Alternating current impedance tests show that the growth of the charge transfer resistance at 0.4 mA/cm² is more rapid than that of at 0.2 mA/cm² as the galvanostatical charge-discharge continues.     

XPS study of Li ion intercalation in V2O5 thin films prepared by thermal oxidation of vanadium metal

The intercalation and deintercalation mechanisms of lithium into V₂O₅ thin films prepared by thermal oxidation of vanadium metal have been studied by X-ray photoelectron spectroscopy (XPS) using a direct anaerobic and anhydrous transfer from the glove box (O₂ and H₂O < 1ppm), where the samples were electrochemically treated, to the XPS analysis chamber. Vanadium in the as-prepared oxide films is mostly (from 93 to 96% depending on samples) in a pentavalent state (V⁵⁺) with a stoichiometric O/V concentration ratio fitting that of V₂O₅. Four to seven percent of VO₂ is also observed. After the 1st and the 2nd intercalation steps at E = 3.3 and 2.8 V versus Li/Li⁺, respectively, the V2p core level spectra evidence a partial reduction to V⁴⁺ states with a remaining concentration of 73 and 56% of V⁵⁺, in agreement with the intercalation of about 1/2 mol of Li per V₂O₅ mol at each intercalation step. Intercalated lithium was observed at a binding energy of 56.1 eV for Li1s. Changes of the electronic structure of the V₂O₅ thin film after intercalation are evidenced by the observation, at a binding energy of 1.3 eV, of occupied V3d states (V⁴⁺) originally empty in the pristine film (V⁵⁺). The V2p and Li1s core level spectra show that the process of Li intercalation is partially irreversible. In the first cycle, 34 and 14% of the vanadium ions remain in the V⁴⁺ state after deintercalation at E = 3.4 and 3.8 V versus Li/Li⁺, respectively, indicating a partially irreversible process already after the 1st deintercalation. The analyses of C1s and O1s XP spectra show the formation of a solid-electrolyte interface (SEI). The analyzed surface layer includes lithium carbonate and Li-alkoxides.     

Electrochemical performance of the carbon coated Li3V2(PO4)3 cathode material synthesized by a sol-gel method

A carbon coated Li₃V₂(PO₄)₃ cathode material for lithium ion batteries was synthesized by a sol-gel method using V₂O₅, H₂O₂, NH₄H₂PO₄, LiOH and citric acid as starting materials, and its physicochemical properties were investigated using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) spectroscopy, scanning electron microscopy (SEM), energy dispersive analysis of X-ray (EDAX), transmission electron microscope (TEM), and electrochemical methods. The sample prepared displays a monoclinic structure with a space group of P2₁/n, and its surface is covered with a rough and porous carbon layer. In the voltage range of 3.0-4.3 V, the Li₃V₂(PO₄)₃ electrode displays a large reversible capacity, good rate capability and excellent cyclic stability at both 25 and 55 °C. The largest reversible capacity of 130 mAh g⁻¹ was obtained at 0.1C and 55 °C, nearly equivalent to the reversible cycling of two lithium ions per Li₃V₂(PO₄)₃ formula unit (133 mAh g⁻¹). It was found that the increase in total carbon content can improve the discharge performance of the Li₃V₂(PO₄)₃ electrode. In the voltage range of 3.0-4.8 V, the extraction and reinsertion of the third lithium ion in the carbon coated Li₃V₂(PO₄)₃ host are almost reversible, exhibiting a reversible capacity of 177 mAh g⁻¹ and good cyclic performance. The reasons for the excellent electrochemical performance of the carbon coated Li₃V₂(PO₄)₃ cathode material were also discussed.     

Synthesis,crystal structure,and characterization of Na2SrV4O12: A low-firing dielectric vanadate

In this work, cyclotetravanadate Na₂SrV₄O₁₂ was synthesized at a relatively low sintering temperature of ∼500°C using a solid-state reaction method. X-ray diffraction and a transmission electron microscope characterization featured a tetragonal structure that was built by a 3D frame of isolated tetracyclic (V₄O₁₂)⁴⁻. Dielectric measurements demonstrated strong dependence on frequency and temperature. A low relative permittivity of ε_r ∼ 8 ± 0.2 and a dielectric (loss tanδ) ∼ 0.4 ± 0.01 was achieved at a frequency of 10 kHz and room temperature. ac impedance and conductivity analysis revealed a thermally activated migration behavior of charge carriers with a short-range hopping feature. XPS analysis validated the existence of oxygen vacancy and reduction in vanadium (from V⁵⁺ to V⁴⁺), which gave rise to charged lattice defects. The migration or hopping of such charged defects was responsible for the observed electrical behaviors. Owing to the simple composition, inexpensive raw materials and low density (2.99 g/cm³) make Na₂SrV₄O₁₂ ceramic a potential candidate for lightweight devices and in photocatalytic degradation and all-solid-state ion batteries.     

Regenerating the used LiFePO4 to high performance cathode via mechanochemical activation assisted V5+ doping

The wide usage of LiFePO₄ batteries makes their recovery and recycling urgent. Here, a novel, efficient and environmentally friendly recycling process has been developed to recover high performance LiFePO₄ nano composites from spent LiFePO₄ materials. The process comprises an intensive mechanochemical activation through mixing with precursor mixture and one-step solid state heat treatment. Spent LiFePO₄, V₂O₅, Li₂CO₃, and NH₄H₂PO₄ are mixed according to the molar ratio of 1-xLiFePO₄@xLi₃V₂(PO₄)₃ (x?=?0, 0.005, 0.01, 0.03 and 0.1). In the typical process, the decomposition of self-contained binder and the conductive carbon provide a reducing environment as well as an in-situ coating carbon source. The SEM, XRD and XPS results illustrate that V⁵⁺ is doped in the Fe²⁺ site when x?<?0.01, with co-existence of V⁵⁺ doping and Li₃V₂(PO₄)₃ when x?≥?0.03. Sole V⁵⁺ doping assisted in-situ carbon coating displays the best electrochemical performance. The optimized sample shows discharge capacities of 154.3?mA?h?g^?1 and 142.6?mA?h?g^?1 at 0.1 and 1?C rates, respectively, with a high capacity retention of nearly ～100% after 100 cycles. All results indicate that intensive mechanochemical activation assisted V⁵⁺ doping is a promising strategy for spent LiFePO₄ recycling.     

Synthesis and electrochemical performance of LiVOPO4–Li3V2(PO4)3 cathode materials for lithium ion batteries

Lithium-ion batteries (LIBs) present the advantages of long cycle life, high voltage, and energy density and are widely made in the field of energy storage. LiVOPO₄ (LVOP), a cathode material used in LIBs, has a high conceptual capacity of 159 mAh g⁻¹ and high operating voltage of 3.9 V. However, its low electrical conductivity and cycle performance limit its commercial applications. According to the X-ray diffraction results, orthogonal crystal LVOP and monoclinic crystal Li₃V₂(PO₄)₃ (LVP) coexisted in the synthesised composite material. The transmission electron microscopy results also indicated that the LVOP and LVP phases coexist, which were coated by carbon layer of about 2.5 nm. The discharge of LVOP–LVP composite material initially was 143.2 mAh g⁻¹, and that after 120 cycles was 132.2 mAh g⁻¹ (at 0.1 C and 3–4.5 V). Thus, the electronic conductivity and first discharge specific capacity of the material enhanced due to the introduction of fast ion conductor LVP into LVOP. Electrochemical performance improved because the introduction of LVP led to an increase in Li⁺ pervasion channels in the original material and the acceleration of the Li⁺ transmission speed.     

Preparation and characterization of three dimensionally ordered macroporous Li4Ti5O12 anode for lithium batteries

Three dimensionally ordered macroporous (3DOM) Li₄Ti₅O₁₂ membrane (80 μm thick) was prepared by a colloidal crystal templating process. Colloidal crystal consisting of monodisperse polystyrene particles (1 μm diameter) was used as the template for the preparation of macroporous Li₄Ti₅O₁₂. A precursor sol consisting of titanium isopropoxide and lithium acetate was impregnated into the void space of template, and it was calcined at various temperatures. A macroporous membrane of Li₄Ti₅O₁₂ with inverse-opal structure was successfully prepared at 800 °C. The interconnected pores with uniform size (0.8 μm) were clearly observed on the entire part of membrane. The electrochemical properties of the three dimensionally ordered Li₄Ti₅O₁₂ were characterized with cyclic voltammetry and galvanostatic charge and discharge in an organic electrolyte containing a lithium salt. The 3DOM Li₄Ti₅O₁₂ exhibited a discharge capacity of 160 mA h g⁻¹ at the electrode potential of 1.55 V versus Li/Li⁺ due to the solid state redox of Ti^3+/4+ accompanying with Li⁺ ion insertion and extraction. The discharge capacity was close to the theoretical capacity (167 mA h g⁻¹), which suggested that the Li⁺ ion insertion and extraction took place at the entire part of 3DOM Li₄Ti₅O₁₂ membrane. The 3DOM Li₄Ti₅O₁₂ electrode showed good cycle stability.