Synthesis and electrochemical performances of Li4Ti4.95Al0.05O12/C as anode material for lithium-ion batteries

Spinel compounds Li₄Ti_5−xAl_xO₁₂/C (x=0, 0.05) were synthesized via solid state reaction in an Ar atmosphere, and the electrochemical properties were investigated by means of electronic conductivity, cyclic voltammetry, and charge-discharge tests at different discharge voltage ranges (0-2.5 V and 1-2.5 V). The results indicated that Al³⁺ doping of the compound did not affect the spinel structure but considerably improved the initial capacity and cycling performance, implying the spinel structure of Li₄Ti₅O₁₂ was more stable when Ti⁴⁺ was substituted by Al³⁺, and Al³⁺ doping was beneficial to the reversible intercalation and deintercalation of Li⁺. Al³⁺ doping improved the reversible capacity and cycling performance effectively especially when it was discharged to 0 V.     

Synthesis and electrochemical properties of Li4Ti5O12/C composite by the PVB rheological phase method

Spinel Li₄Ti₅O₁₂/C powders were synthesized successfully by a simple rheological phase method using polyvinylbutyral (PVB) as both template and carbon source. The structure and morphology characteristics of the composite were investigated by X-ray diffraction (XRD), field emission scanning electron microscopy and transmission electron microscopy. The XRD results showed that the composite had a good crystallinity. Its average particle size was about 2.1 μm with a narrow size distribution as a result of homogeneous mixing of the precursors. The in situ carbon coating produced by decomposition of PVB played an important role in improving electrical conductivity, thereby enhancing the rate capacity of Li₄Ti₅O₁₂ as anode material in Li-ion batteries. The Li₄Ti₅O₁₂/C composite, synthesized at 800 °C for 15 h under argon, containing 0.98 wt% of carbon, exhibited better electrochemical properties in comparison with the pristine Li₄Ti₅O₁₂, which could be attributed to the enhanced electrical conductive network of the carbon coating on the particle surface.     

High-rate Li4Ti5O12/C composites as anode for lithium-ion batteries

The Li₄Ti₅O₁₂/C composites were synthesized by a simple solid-state reaction at 800 °C for 12 h by using Super P® conductive carbon black as carbon source. X-ray diffraction analysis shows that the Li₄Ti₅O₁₂ with 0, 5, 7.5, and 10 wt% carbon shows similar patterns with cubic spinel structure. Scanning electron microscope shows that Li₄Ti₅O₁₂ aggregated seriously, but the aggregation was inhibited by the addition of Super P® carbon. The results indicate that the addition of 5 wt% carbon during sintering and a further 5 wt% carbon during slurry preparation shows the best rate capability of 110 mAh/g when the cells were charge/discharged at 10 C rate. The comparison of the charge–discharge curves shows that the higher rate improvement should further decrease the particle size of LTO or improve the conductivity of LTO itself.     

Electrostatic spray deposition of spinel Li4Ti5O12 thin films for rechargeable lithium batteries

Spinel Li₄Ti₅O₁₂ thin films are important for the fabrication of rechargeable lithium microbatteries. Porous thin films of Li₄Ti₅O₁₂ were prepared by electrostatic spray deposition (ESD) technique with lithium acetate and titanium butoxide as the precursors. The structures of these films were analyzed by scanning electron microscopy and X-ray diffraction. Coin-type cells with a liquid electrolyte were made with the Li₄Ti₅O₁₂ films against metallic lithium. Their electrochemical performance was investigated by means of galvanostatic cell cycling, cyclic voltammetry and Ac impedance spectroscopy. It was found that pure spinel phase of Li₄Ti₅O₁₂ was obtained. After annealing at the optimal temperature of 700 °C, the films can deliver a reversible specific capacity of about 150 mAh/g with excellent capacity retention after 70 cycles. Their electrochemical characteristics were quite comparable with those of the Li₄Ti₅O₁₂ laminate electrodes containing carbon black additive.     

Characteristics of spherical-shaped Li4Ti5O12 anode powders prepared by spray pyrolysis

Spherical-shaped Li₄Ti₅O₁₂ anode powders with a mean size of 1.5 μm were prepared by spray pyrolysis. The precursor powders obtained by spray pyrolysis had no peaks of crystal structure of Li₄Ti₅O₁₂. The powders post-treated at temperatures of 800 and 900 °C had the single phase of spinel Li₄Ti₅O₁₂. The powders post-treated at a temperature of 1000 °C had main peaks of the Li₄Ti₅O₁₂ phase and small impurity peaks of Li₂Ti₃O₇. The spherical shape of the precursor powders was maintained after post-treatment at temperatures below 800 °C. The Brunauer-Emmett-Teller (BET) surface areas of the Li₄Ti₅O₁₂ anode powders post-treated at temperatures of 700, 800 and 900 °C were 4.9, 1.6 and 1.5 m²/g, respectively. The initial discharge capacities of Li₄Ti₅O₁₂ powders were changed from 108 to 175 mAh/g when the post-treatment temperatures were changed from 700 to 1000 °C. The maximum initial discharge capacity of the Li₄Ti₅O₁₂ powders was obtained at a post-treatment temperature of 800 °C, which had good cycle properties below current densities of 0.7 C.     

Recent development and application of Li4Ti5O12 as anode material of lithium ion battery

Lithium-ion batteries with both high power and high energy density are one of the promising power sources for electric devices, especially for electric vehicles (EV) and other portable electric devices. One of the challenges is to improve the safety and electrochemical performance of lithium ion batteries anode materials. Li₄Ti₅O₁₂ has been accepted as a novel anode material of power lithium ion battery instead of carbon because it can release lithium ions repeatedly for recharging and quickly for high current. However, Li₄Ti₅O₁₂ has an insulating character due to the electronic structure characterized by empty Ti 3d-states, and this might result in the insufficient applications of LTO at high current discharge rate before any materials modifications. This review focuses first on the present status of Li₄Ti₅O₁₂ including the synthesized method, doping, surface modification, application and theoretical calculation, then on its near future development.     

糠醇辅助的聚合凝胶法制备纳米Li4Ti5O12负极材料

以硝酸锂、钛酸正丁酯和糠醇为反应物,采用糠醇聚合凝胶法制备了纳米Li₄Ti₅O₁₂粉体．利用XRD、SEM和BET比表面测试对产物进行了表征,并研究了纳米Li₄Ti₅O₁₂粉体作为锂离子电池负极材料的电化学性能．在700℃或更高温度烧结时产物为纯相的尖晶石型．通过柠檬酸、聚乙烯吡咯烷酮、十六烷基三甲基溴化铵(CTAB)表面活性剂的加入能够减少产物颗粒的团聚程度,增大粉体的比表面积,提高其电化学性能．加入0.5 g CTAB、700℃烧结12 h的Li₄Ti₅O₁₂粉体展示出最高的比容量和最佳的循环性能,10 C下充电比容量高达156.7 mAh/g．     

Advanced electrochemical performances of Li4Ti5O12/Ag prepared by a facile synthesis route

Spinel Li₄Ti₅O₁₂ coated by highly dispersed nanosized Ag particles was synthesized via a facile and effective ultrasonic-assisted method in this paper. X-ray diffraction (XRD) results indicated that Ag was not doped into the lattice of spinel Li₄Ti₅O₁₂. The as-synthesized Li₄Ti₅O₁₂/Ag exhibited enhanced electronic conductivity and excellent electrochemical performances. Its electronic conductivity was increased about four times compared to that of the pristine Li₄Ti₅O₁₂. Even at 10 C rate, the as-synthesized Li₄Ti₅O₁₂/Ag could keep 86.5 % of the reversible capacity at 1 C rate and its reversible capacity was higher than 140 mAhg^?1 whereas those were 75.3 % and 118 mAhg^?1 for the pristine Li₄Ti₅O₁₂.     

Electrochemical properties of stacked-nanoflake Li4Ti5O12 spinel synthesized by a polymer-pyrolysis method

Stacked-nanoflake Li₄Ti₅O₁₂ spinel was synthesized via the pyrolysis of a Li–Ti copolymeric precursor formed by in situ polymerization of LiOH and [Ti(OC₄H₉)₄] and acrylic acid. XRD and SEM characterization shows that the powders calcined at 700 °C for 3 h was well-crystallized particles with submicron diameter. Charge–discharge measurement showed the Li₄Ti₅O₁₂ electrode had displayed excellent rate capability and delivered reversible capacity of 171, 158, 148, 138 and 99 mAh g⁻¹ at rates of 0.1C, 0.5C, 1C, 2C and 4C, respectively. The test electrode also showed excellent cyclability as the capacity retains 96.1% after 60 cycles between 0.5 and 2.5 V.     

Spinel lithium titanate (Li4Ti5O12) as novel anode material for room-temperature sodium-ion battery

This is the first time that a novel anode material, spinel Li₄Ti₅O₁₂ which is well known as a “zero-strain” anode material for lithium storage, has been introduced for sodium-ion battery. The Li₄Ti₅O₁₂ shows an average Na storage voltage of about 1.0 V and a reversible capacity of about 145 mAh/g, thereby making it a promising anode for sodium-ion battery. E_x-situ X-ray diffraction (XRD) is used to investigate the structure change in the Na insertion/deinsertion process. Based on this, a possible Na storage mechanism is proposed.     

Optical absorption and nuclear magnetic resonance in lithium titanium spinel doped by chromium

The optical absorption and nuclear magnetic resonance spectra of Li_{4 − x} Cr_3x Ti_{5 − 2x} O₁₂ (x = 0, 0.01, 0.02, 0.04) solid solutions have been investigated. It has been found that, in the Li₄Ti₅O₁₂ spinel, lithium ions migrate from tetrahedral to octahedral positions with increasing temperature. Doping of chromium to the spinel favors an increase in the fraction of tetrahedrally coordinated lithium and hinders diffusion.     

Electrical and electrochemical properties of carbon nanotube-based free standing LTO electrodes for current collector-free Li-ion batteries

The spinel lithium titanate oxide (Li₄Ti₅O₁₂, LTO) has been extensively studied as one of the most promising alternatives to carbon materials in energy conversion and storage devices, due to its high structural and thermal stability, rate capability, and excellent cycling stability. In this study, Li₄Ti₅O₁₂/multi-walled carbon nanotubes (LTO-MWCNTs) free-standing and flexible composite electrodes/buckypapers were prepared via tape casting technique and well compared with commercially available LTO. The structural, morphological, electrical and electrochemical properties of LTO-MWCNTs buckypaper as well as LTO were studied. The electrical conductivity of LTO-based buckypaper was found to be very high i. e, 4.4 × 10² Scm⁻¹ at room temperature. Further, the buckypaper prepared by synthesized LTO showed higher specific capacity (166 mAhg⁻¹) compared to commercially available LTO (137 mAhg⁻¹) at 0.2 C rate. The enhanced electrochemical performance of as-synthesized LTO-based buckypaper is mainly attributed to the higher electronic conductivity and homogeneous distribution of particles with its small size which facilitates large amount of active sites for lithium insertion and also short diffusion paths.     

Electrospinning preparation of one-dimensional Co<Superscript>2+</Superscript>-doped Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> nanofibers for high-performance lithium ion battery

One-dimensional Co²⁺-doped Li₄Ti₅O₁₂ nanofibers with a diameter of approximately 500 nm have been synthesized via a one-step controllable electrospinning method. The Co²⁺-doped Li₄Ti₅O₁₂ nanofibers were systematically characterized by XRD, ICP, TEM, SEM, BET, EDS mapping, and XPS. Based on the cubic spinel structure and one-dimensional effect of Li₄Ti₅O₁₂, Co²⁺-doped Li₄Ti₅O₁₂ nanofibers exhibit the enlarged lattice volume, reduced particle size and enhanced electrical conductivity. More importantly, Co²⁺-doped Li₄Ti₅O₁₂ nanofibers as a lithium ion battery anode electrode performs superior electrochemical performance than undoped Li₄Ti₅O₁₂ electrode in terms of electrochemical measurements. Particularly, the reversible capacity of Co²⁺-doped Li₄Ti₅O₁₂ electrode reaches up to 140.1 mAh g^?1 and still maintains 136.5 mAh g^?1 after 200 cycles at a current rate of 5 C. Therefore, one-dimensional Co²⁺-doped Li₄Ti₅O₁₂ nanofiber electrodes, showing high reversible capacity and remarkable recycling property, could be a potential candidate as an anode material.     

Synthesis and electrochemical performance of hole-rich Li4Ti5O12 anode material for lithium-ion secondary batteries

Hole-rich Li₄Ti₅O₁₂ composites are synthesized by spray drying using carbon nanotubes as additives in precursor solution, subsequently followed calcinated at high temperature in air. The structure, morphology, and texture of the as-prepared composites are characterized with XRD, Raman, BET and SEM techniques. The electrochemical properties of the as-prepared composites are investigated systematically by charge/discharge testing, cyclic voltammograms and AC impedance spectroscopy, respectively. In comparison with the pristine Li₄Ti₅O₁₂, the hole-rich Li₄Ti₅O₁₂ induced by carbon nanotubes exhibits superior electrochemical performance, especially at high rates. The obtained excellent electrochemical performances of should be attributed to the hole-rich structure of the materials, which offers more connection-area with the electrolyte, shorter diffusion-path length as well faster migration rate for both Li ions and electrons during the charge/discharge process.     

A new composite material Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript>–SnO<Subscript>2</Subscript> for lithium-ion batteries

A new Li₄Ti₅O₁₂–SnO₂ composite anode material for lithium-ion batteries has been prepared by loading SnO₂ on Li₄Ti₅O₁₂ to obtain composite material with improved electrochemical performance relative to Li₄Ti₅O₁₂ and SnO₂. The composite material was characterized by X-ray diffraction and scanning electron microscopy. The results indicated that SnO₂ particles have encapsulated on the surface of the Li₄Ti₅O₁₂ uniformly and tightly. Electrochemical results indicated that the Li₄Ti₅O₁₂–SnO₂ composite material increases the reversible capacity of Li₄Ti₅O₁₂ and has good cycling reliability. At a current rate of 0.5 mA/cm², the material delivered a discharge capacity of 236 mAh/g after 16 cycles. It suggests the existence of synergistic interaction between Li₄Ti₅O₁₂ and SnO₂ and that the capacity of the composite is not a simple weighted sum of the capacities of the individual components. In the composite material, SnO₂ can act as a bridge between the spinel particles to reduce the interparticle resistance and as a good material for the Li intercalation/deintercalation. Thus, electrochemical performance of the Li₄Ti₅O₁₂ spinel can be improved by the surface modification with SnO₂, and the stability of Li₄Ti₅O₁₂ also serves to buffer the internal stress caused by the volume changes in lithium insertion and extraction reactions.     

Preparation and characteristics of Li4Ti5O12 with various dopants as anode electrode for hybrid supercapacitor

Spinel-Li₄Ti₅O₁₂ is successfully synthesized by a solid phase synthesis. The Li₄Ti₅O₁₂ powders with various dopants (Al³⁺, Cr³⁺, Mg²⁺) synthesized at 800 °C are in accordance with the Li₄Ti₅O₁₂ cubic spinel phase structure. The dopants are inserted into the lattice structure of Li₄Ti₅O₁₂ without causing any changes in structural characteristics. In order to study the effect on various dopants, the hybrid supercapacitor is prepared by using un-doped Li₄Ti₅O₁₂ and doped Li₄Ti₅O₁₂ in this work. The electrochemical performance of the hybrid supercapacitor is characterized by impedance spectroscopy and cycle performance. The results show Cr³⁺ and Mg²⁺ dopants enhance the conductivity of Li₄Ti₅O₁₂. Also, Al³⁺ substitution improves the reversible capacity and cycling stability of Li₄Ti₅O₁₂. It is found that effect of dopant on the electrochemical performance of Li₄Ti₅O₁₂ as electrode material for hybrid supercapacitor where the EDLC and the Li ion secondary battery coexist in one cell system.     

Preparation and electrochemical properties of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript>/Ti<Subscript>4</Subscript>O<Subscript>7</Subscript> composite for lithium-ion batteries

In order to improve the rate capability of Li₄Ti₅O₁₂, Ti₄O₇ powder was successfully fabricated by improved hydrogen reduction method, then a dual-phase composite Li₄Ti₅O₁₂/Ti₄O₇ has been synthesized as anode material for lithium-ion batteries. It is found that the Li₄Ti₅O₁₂/Ti₄O₇ composite shows higher reversible capacity and better rate capability compared to Li₄Ti₅O₁₂. According to the charge-discharge tests, the Li₄Ti₅O₁₂/Ti₄O₇ composite exhibits excellent rate capability of 172.3 mAh g^?1 at 0.2 C, which is close to the theoretical value of the spinel Li₄Ti₅O₁₂. More impressively, the reversible capacity of Li₄Ti₅O₁₂/Ti₄O₇ composite is 103.1 mAh g^?1 at the current density of 20 C after 100th cycles, and it maintains 84.8% of the initial discharge capacity, whereas that of the bare spinel Li₄Ti₅O₁₂ is only 22.3 mAh g^?1 with a capacity retention of 31.1%. The results indicate that Li₄Ti₅O₁₂/Ti₄O₇ composite could be a promising anode material with relative high capacity and good rate capability for lithium-ion batteries.     

Synthesis of spinel lithium titanate anodes incorporated with rutile titania nanocrystallites by spray drying followed by calcination

Lithium insertion into spinel Li₄Ti₅O₁₂ incorporated with rutile TiO₂ was investigated in order to clarify the redox mechanism responsible for the first plateau at 1.5 V vs. Li/Li⁺. Spherical Li₄Ti₅O₁₂ powders with an average diameter of 2-3 μm can be achieved by spray drying followed by sintering process. The Li/Ti molar ratio in the precursor is selected as the factor for preparing spinel Li₄Ti₅O₁₂ powders with different concentrations of rutile TiO₂. The specific capacity from the first plateau at 1.5 V contributes to the major portion in the overall capacity. The rutile TiO₂ in spinel Li₄Ti₅O₁₂ anodes tends to improve the specific capacity at the first plateau. This can be attributed to two possible reasons: (i) rutile TiO₂ provides an additional number of sites (i.e., oxygen octahedral vacancy in rutile TiO₂) for the Li insertion, and (ii) less amount of residual Li oxides results in high electronic conductivity. The Li₄Ti₅O₁₂ anodes display high rate capability with low irreversible capacity, indicating good reversibility of insertion/de-insertion of Li ions. The results presented in this work show unambiguously that the presence of rutile TiO₂ in spinel Li₄Ti₅O₁₂ has a positive effect on the performance promotion of Li₄Ti₅O₁₂ anodes.     

Titanium-modified Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> with a synergistic effect of surface modifying,bulk doping,and size reducing

In this work, a one-step solid-phase sintering process via TiO₂ and Li₂CO₃ under an argon atmosphere, with ultra-fine titanium powder as the modifying agent, was used to prepare a nano-sized Li₄Ti₅O₁₂/Ti composite (denoted as LTO–Ti) at 800 °C. The introduction of ultra-fine metal titanium powder played an important role. First, X-ray photoelectron spectroscopy demonstrates that Ti⁴⁺ was partially changed into Ti³⁺, through the reduction of the ultra-fine metal titanium powder. Second, X-ray diffraction revealed that the ultra-fine metal titanium powder did not react with the bulk structure of Li₄Ti₅O₁₂, while some pure titanium peaks could be seen. Additionally, the size of LTO–Ti particles could be significantly reduced from micro-scale to nano-scale. The structure and morphology of LTO–Ti were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, scanning electron microscopy, and transmission electron microscopy. Electrochemical tests showed a charge/discharge current of 0.5, 1, 5, and 10 C; the discharge capacity of the LTO–Ti electrode was 170, 161, 140, and 111 mAh g^?1. It is believed that the designed LTO–Ti composite makes full use of both components, thus offering a large contact area between the electrolyte and electrode, high electrical conductivity, and lithium-ion diffusion coefficient during electrochemical processes. Furthermore, ultra-fine titanium powder, as the modifying agent, is amenable to large-scale production.     

Structural and electrochemical study on Li(Li1/3Ti5/3)O4 anode material for lithium ion batteries

Chemical and electrochemical studies have shown that various titanium oxides can incorporate lithium in different ratios. Other compounds with a spinel-type structure and corresponding to the spinel oxides LiTi₂O₄ and Li₄Ti₅O₁₂ have been evaluated in rechargeable lithium cells with promising features. The spinel Li[Li_1/3Ti_5/3]O₄ [1–5] compound is a very appealing electrode material for lithium ion batteries. The lithium insertion-deinsertion process occurs with a minimal variation of the cubic unit cell and this assures high stability which may reflect into long cyclability. In addition, the diffusion coefficient of lithium is of the order of 10⁻⁸ cm²s⁻¹ [5] and this suggests fast kinetics which may reflect in high power capabilities. In this work we report a study on the kinetics and the structural properties of the Li[Li_1/3Ti_5/3]O₄ intercalation electrode carried out by: cyclic voltammetry, galvanostatic cycling and in-situ X-ray diffraction. The electrochemical characterization shows that the Li[Li_1/3Ti_5/3]O₄ electrode cycles around 1.56 V vs. Li with a capacity of the order of 130 mAhg⁻¹ which approaches the maximum value of 175 mAhg⁻¹ corresponding to the insertion of 1 equivalent per formula unit. The delivered capacity remains constant for hundred cycles confirming the stability of the host structure upon the repeated Li insertion-deinsertion process. This high structural stability has been confirmed by in situ Energy Dispersion X-ray analysis. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.