Lithium Titanium Oxide Research Articles

Experimental Investigation of Heat Dissipation of Lithium–Ion Cells and Its Correlation with Internal Resistance

Power loss is a limiting factor for batteries and individual cells. The resulting heat generation due to the power loss leads to reduced battery performance and, thus, lower efficiency. These losses are largely due to the internal resistance of the cells. Therefore, it is important to accurately determine the value of the internal resistance of lithium–ion cells. From the literature, it was found that there are three widely used internal resistance-measurement methods (current step method, direct-energy-loss method, and calorimeter measurement), with negligible research on their comparison demonstrating the most efficient method. Henceforth, to find the most optimal method, this research adopts all three methods on a variety of cell chemistries, including Lithium-ion Manganese Oxide (LMO), Lithium Iron Phosphate (LFP), Nickel Manganese Cobalt (NMC), and Lithium Titanium-Oxide (LTO) for different c-rates (1 C, 2 C, and 3 C), with a wide temperature range (from 0 °C to 40 °C).

Understanding the Non-Volatile Resistive Switching Behavior of Lithium Titanium Oxide during Spinel to Rock Salt Conversion for Neuromorphic Computing

Lithium based synaptic device research has been a growing new field in the last few years for enabling robust neuromorphic hardware systems. It can realize parallel analogue computation which is beyond the conventional von Neumann computing architecture which is slow, energy inefficient and expensive to execute complex tasks. In this study, we showcase the remarkable potential of Lithium Titanium Oxide (Li4Ti5O12) spinel, both computationally through Density of States (DoS) analysis using Density Functional Theory (DFT), and experimentally via direct current (DC) polarization investigation of electrochemically lithiated Li4Ti5O12 thin film, examining diverse states of discharge (SoD) in both in-plane and out-of-plane configurations. The observed conductivity jump spans up to six orders of magnitude, transitioning from the Li4Ti5O12 spinel phase to the fully lithiated Li7Ti5O12 rock salt phase. Raman Spectroscopy validates the transformation from the Li4Ti5O12 spinel phase to the Li7Ti5O12 rock salt phase. Moreover, the onset of increase in conductivity during this transformation is corroborated by changes in the oxidation state of Titanium (Ti), as explained with the help of X-Ray Photoelectron Spectroscopy. To actualize these findings, we engineered a three-terminal artificial synaptic device integrating Lithium Phosphorous Oxynitride (LiPON) solid-state electrolyte as the lithium ion source and conductor, while employing Lithium Titanium Oxide (Li4Ti5O12) spinel as the channel material. In device testing, we maintained a source-drain voltage (VSD) of 0.5 V, while sweeping the gate voltage (VG) from -3 V to 3 V, resulting in switching spanning up to 4 orders of magnitude, consistently replicable across multiple cycles. Widening the gate voltage window from ±3 V to ±7V induced an increase in conductance. Furthermore, non-volatile testing affirmed the sustained retention of the conductance state across all tested gate voltage windows, showcasing the device's stability over time. These compelling results portray a promising trajectory for the development of a robust synaptic device architecture reliant on lithium-based all solid-state materials, catalyzing the evolution of high-precision analogue neuromorphic computing systems.

Phase transitions limit lithium adsorption in titanium-based ion sieves

Hydrogen titanium oxide (HTO) is a promising material in extracting lithium ions from dilute sources such as geothermal or oil/gas brines. However, experiments show limited Li adsorption in HTO compared to its theoretical maximum capacity, where all H atoms in HTO are replaced by Li that forms lithium titanium oxide (LTO). Here, ab initio molecular dynamics (AIMD) simulations show clear evidence of phase transitions at specific Li adsorption in pure or doped HTO/LTO, which directly predict their experimental maximum capacity. Analysis of thermodynamic properties as well as layered crystal structures show distinct Li-poor to Li-rich phase transitions in the pure, Mo-doped, and Fe-doped HTO/LTO. In addition, it is observed a second phase transition in the Fe-doped HTO/LTO in the Li-poor phases that further constrains Li adsorption. To the best of my knowledge, this is the first study that accurately predict the experimental capacities in ion sieves from first principle. More importantly, this study puts spotlights on phase transitions as an important consideration in molecular engineering developments of functional separation materials, such as the high-performance lithium-ion sieves presented herein.

Development of solid-state hybrid capacitor using carbon nanotube film as current collector

Structural energy-storage devices are receiving considerable attention because they can simultaneously store electrical energy and provide structural support, thereby offering high volumetric and gravimetric capacities. Although carbon fiber–based materials have been the most popular choice for current collectors, their conductivity and specific surface area are relatively low; this limits the ability to load other active materials on to the current collector. Carbon nanotube (CNT) fiber is a promising alternative for lightweight structural materials because it has a density of less than 1 g cm−3 as well as high strength and electrical conductivity. In this study, we produced a light, strong, and porous CNT film (CNTF) via direct spinning for use as a current collector. The CNTF exhibited a high specific strength compared with Al foil. We also created an activated carbon–lithium titanium oxide hybrid capacitor with the CNTF current collector, which achieved a capacity similar to that of a capacitor having an Al current collector. Furthermore, a planar pouch cell created using a solid polymer electrolyte achieved a capacity of 74.1 mAh g−1, which is comparable to that of coin cells. Thus, our findings highlight the feasibility of CNTF as a material for current collectors and provide a foundation to develop manufacturing processes for structural batteries.

Diffusion-Equation-Based Electrical Modeling for High-Power Lithium Titanium Oxide Batteries

Lithium titanium oxide (LTO) batteries offer superior performance compared to graphite-based anodes in terms of rapid charge/discharge capability and chemical stability, making them promising candidates for fast-charging and power-assist vehicle applications. However, commonly used battery models often struggle to accurately describe the current–voltage characteristics of LTO batteries, particularly before the charge/discharge cutoff conditions. In this work, a novel electrical model based on the solid-phase diffusion equation is proposed to capture the unique electrochemical phenomena arising from the diffusion mismatch between the positive and negative electrodes in high-power LTO batteries. The robustness of the proposed model is evaluated under various loading conditions, including constant current and dynamic current tests, and the results are compared against experimental data. The experimental results for LTO batteries exhibit remarkable alignment with the model estimation, demonstrating a maximum voltage error below 3%.

High-temperature all-solid-state batteries with LiBH4 as electrolyte – a case study exploring the performance of TiO2 nanorods, Li4Ti5O12 and graphite as active materials

Abstract The hexagonal high-temperature form of LiBH4 is known as a fast ion conductor. Here, we investigated its suitability as a solid electrolyte in high-temperature all-solid-state cells when combined with the following active materials: Li metal, graphite, lithium titanium oxide (Li4Ti5O12, LTO), and nanocrystalline rutile (TiO2). First results using lithium anodes and rutile nanorods as cathode material show that a cell constructed by simple cold-pressing operates at reversible discharge capacities in the order of 125 mA h g−1 at a C-rate of C/5 and at temperatures as high as 393 K. Besides TiO2, the compatibility of the LiBH4 with other active materials such as graphite and LTO was tested. We found evidence of possible interface instabilities that manifest through rare, yet still detrimental, self-charge processes that may be relevant for hydrogen storage applications. Moreover, we investigated the long-term cycling behavior of the cells assembled and demonstrate the successful employment of LiBH4 as an easily processable model solid electrolyte in practical test cells.

Laser Processing of Liquid Feedstock Plasma-Sprayed Lithium Titanium Oxide Solid-State-Battery Electrode

The astonishing safety and capacity characteristics of solid-state-batteries are encouraging researchers and companies to work on the manufacturing, development, and characterization of battery materials. In the present work, the effects of laser beam interaction with a liquid feedstock plasma-sprayed ceramic solid-state-battery (SSB) material coating were studied. Lithium Titanium Oxide (LTO) in the form of an aqueous suspension consisting of submicron powder particles was plasma-sprayed for the first time using a high-power axial III plasma torch on an aluminum substrate. The plasma-sprayed LTO coating suspension was subsequently post-processed using a fiber laser. The energy input of the laser beam on the surface of the deposited layer was the main variable. By varying the laser power and laser processing speed, the energy input values were varied, with values of 3.8 J/mm2, 9.6 J/mm2, 765.9 J/mm2, and 1914.6 J/mm2, and their effects on some key characteristics such as laser-processed zone dimensions and chemical composition were investigated. The results indicated that changing the laser beam parameter values has appreciable effects on the geometry, surface morphology, and elemental distribution of laser-processed zones; for instance, the highest energy inputs were 33% and 152%, respectively, higher than the lowest energy input.

Lithium extraction from geothermal brines: Adsorption-desorption studies on 226Ra (228Ra) and 210Pb on lithium-titanium-oxides (LTO)

Extracting lithium from geothermal brines contributes to meet the growing demand for lithium-ion batteries and other energy applications. Deep geothermal brines of the Upper Rhine Graben (URG) contain up to 200 mg L−1 of lithium and a wide range of dissolved elements, including Th–U series radionuclides. This study presents data from a radiochemical monitoring conducted as part of pilot tests for lithium extraction at the Bruchsal geothermal site under site-specific thermodynamic conditions (T = 60 °C; p = 18 bar). The results show an uptake of the long-lived radionuclides 226Ra (228Ra) and 210Pb by the granulated lithium-titanium-oxide (LTO) sorbent employed. Increasing pH values favor the adsorption of the naturally occurring radionuclide, due to increasing negative charge of the LTO surface. The radioactive uptake of radium was found to be nearly in adsorption equilibrium state after 12 extraction cycles performed. In contrast, 210Pb is permanently removed from the Bruchsal brine by more than 96 % reflecting its high capability to approach the adsorbent surface during adsorption compared to the competing cations. Radioactive load of both radium and lead isotopes on the LTO adsorbent could be reduced using 0.5 M HCl as desorption agent. In this context, desorption percentages ranging from 50 to 100 % per extraction cycle were obtained.

N-doped lithium titanium oxide for high power Li-ion rechargeable batteries with excellent cyclability

Lithium titanate, Li4Ti5O12 (LTO) is being explored as an anode in Li-ion batteries owing to its minimal structural change during lithiation/delithiation and excellent capacity retention at higher current rates. However, the lack of stable cyclability at higher applied currents owing to low electronic conductivity, restricts its widespread applications. Solid state anionic doping represents a convenient strategy to improve the intrinsic electronic conductivity of the LTO material. Hence, a facile and scalable solid state‐inspired protocol has primarily been devised aimingthe large-scale production of nitrogen-doped LTO. The structural analysis demonstrates the diffusion of nitrogen into the lattice without damaging the intrinsic microstructure of LTO. The 2% nitrogen-doped LTO as a working electrode in Li-ion half-cell, displays enhancement in Li-storage capacity by 30%. Moreover, it exhibits excellent rate performance (131 mAhg−1 @ 5C) and ultra-long cycling stability upto 1000 cycles retaining 82 % capacity. Further, full cell study of N@LTO with LiCoO2 exhibits specific capacities of more than 155 mAh/g at a 0.05C rate. Overall, the enhancement in performance attributes to N doping which is likely to improve not only the electrical conductivity but also the ion transport capabilities. Hence the N@LTO will have potential in high power Li-ion batteries.

Structural, micro-structural, morphological, electrical spectroscopy and optical analysis of lithium-titanium oxide electronic material

In this paper, we perform a thorough analysis into the electrical properties of high-purity, thick Li2TiO3 discs generated by the mixed oxide process, covering a wide range of frequencies and temperatures. Li2TiO3 samples are calcined and sintered at 920 °C and 940 °C. X-ray diffraction shows a monoclinic crystal structure with a space group of C2/c(15), matching JCPDS card (00-033-0831). The Scherrer and W-H plot methods provide consistent crystallite sizes of 51.23 and 49.34 nm. SEM and EDAX at room temperature reveal the material's structure and chemistry. The microstructure has well-defined porosity and homogeneous grain dispersion, with an average grain size of 2.82 µm. We studied frequencies from 1 kHz to 1 MHz and temperatures from 30 °C to 450 °C. Measure dielectric constant, tangent loss, and electrical conductivity. Above 350 °C, the dielectric constant increases significantly. Between 400 °C and 450 °C, electrical conductivity activation energy ranges from 0.431 to 0.624 eV. UV–Visible spectroscopy shows maximal absorption at 201 nm, indicating a band gap value of 3.78 eV. Its residual, saturation, and coercivity values were 0.00286 µc/cm2, 0.0267 µc/cm2, and 0.974 kV/cm, respectively, from the hysteresis loop. The UV spectrum shows Li2TiO3 absorbs most light at 201 nm and has a 3.82 eV band gap. Its composition and chemical processes are confirmed by FTIR peaks at various wavenumbers. Based on these results Li2TiO3 might have the potential applications in electronic devices such as capacitors, insulators, and electrochemical sensors as well as humidity and gas monitoring devices.

Lithium titanate battery system enables hybrid electric heavy-duty vehicles

Electrification plays an important role in the transformation of the global vehicle industry. Targeting the rapidly growing heavy-duty off-highway vehicles, we developed a battery system for hybrid-electric heavy-duty trucks based on lithium titanium oxide (LTO) batteries. With LTO as the anode and nickel manganese cobalt (NCM) as the cathode, comprehensive measurements of the battery cells and modules indicate that LTO batteries are uniquely suitable for applications requiring high-rate fast charging and discharging. An LTO battery system was constructed and implemented to realize the first advanced lithium-ion battery-based hybrid-electric heavy-duty vehicle, a hybrid-electric mining truck with vehicle mass 34 ton and maximum load 60 ton. Field operation tests of the hybrid-electric vehicle suggest that the performance of the LTO battery system meet the design expectations. After analyzing operation parameters of the hybrid-electric heavy-duty vehicle, we found 54.9 % fuel savings compared to conventional diesel-powered truck of the same mass and load.

Thickness-Controllable Electrode of Lithium Titanium Oxide Nanowire Sheets with Multiple Stacked Morphology for Ultrahigh Areal Capacity and Stability of Lithium-Ion Batteries

Thickness-Controllable Electrode of Lithium Titanium Oxide Nanowire Sheets with Multiple Stacked Morphology for Ultrahigh Areal Capacity and Stability of Lithium-Ion Batteries

Lithium extraction from geothermal brines in the Upper Rhine Graben: A case study of potential and current state of the art

Increasing demand for lithium is leading to a rising focus on alternative, non-conventional lithium sources. These include geothermal brines, among others. The geothermal brines of the Upper Rhine Graben are characterized by comparatively high lithium concentrations of up to 200 mg L−1. To exploit this untapped potential, various direct lithium extraction (DLE) techniques can be used including adsorption and ion exchange.Several laboratory experiments on lithium extraction using inorganic sorbents such as lithium‑manganese oxides (LMO), lithium‑titanium oxides (LTO) and lithium‑aluminum-layered double hydroxide chloride (LDH) have been conducted in the past. Based on the promising results, various research projects are currently working on the development and implementation of the first pilot plants on existing geothermal sites.Before lithium extraction from geothermal brines can be commercialized, not only the sustainability of the resource must be investigated, but also the DLE process must be adapted to the respective site conditions. Finally, improved sorbent performance will be the main driver for future cost reductions and enhanced economics in lithium extraction from geothermal brines.

Towards environmentally sustainable battery anode materials: Life cycle assessment of mixed niobium oxide (XNO™) and lithium‑titanium-oxide (LTO)

Electric mobility has proven to be essential for the carbon neutrality of the transport sector. However, several studies have demonstrated the environmental costs linked to the supply of rechargeable batteries, which should not be overlooked. The supply of some elements has raised concerns, either because they are associated with environmental and social risks, or because they are considered critical raw materials due to their concentrated geographical supply. It is therefore important to look for innovative technologies capable of reducing the demand for traditional battery raw materials and technologies, but that also have lower environmental impacts linked to their supply. Niobium has been reported to improve the performance of battery components and could (partially) replace some traditional battery materials, but little is known about the environmental impacts of niobium-based battery materials. This study compares two commercial lithium-ion battery anode materials, namely lithium-titanate (LTO) and an innovative mixed niobium oxide anode material (ECA-302, a formulation of XNOTM). Life cycle assessment is employed to quantify the environmental impacts of both technologies, taking into account impacts on global warming potential (GWP), acidification, ozone depletion, photochemical ozone formation (POF) and the use of fossil resources. The impacts were quantified by mass (1 kg anode material) and functionality (1 kWh delivered/cycle life), using primary industrial data for ECA-302 and literature-adapted data for the LTO. Results show that ECA-302 performs better than LTO considering both the material mass and energy delivery per cycle levels. The GWP for the supply of the ECA-302 was 51% lower than the LTO, but the most remarkable differences were observed for POF, for which ECA-302 had an impact about 72% lower than LTO at the production stage and 77% lower at the energy delivery. The results also indicate that 20% less ECA-302 material is needed to deliver 1 kWh over the cycle life of the battery compared to LTO.

Ability of Li4Ti5O12 to suppress Li metal deposition under overpotential conditions confirmed by electrochemical surface plasmon resonance spectroscopy

Undesirable Li metal deposition on the negative electrode increases the risks associated with the use of Li-ion batteries. Generally, spinel-type lithium-titanium oxide Li4Ti5O12 (LTO)-based negative electrodes are well known as safe dendrite-free options, due to their higher working potential. However, the ability of LTO-based materials to prevent Li metal deposition has not been well confirmed under sudden overpotential application. This study examines the behavior of Li metal electrodeposition under various overpotential conditions for unloaded and LTO-loaded Cu electrodes. Electrochemical surface plasmon resonance spectroscopy (EC-SPR) is used as the optical diagnostic technique, owing to its sensitivity in detecting Li metal deposition. Li metal deposition is easily detected for the unloaded Cu electrode at overpotential of − 0.2 V (voltage) versus Li counter electrode (LiCE), whereas no Li metal deposition occurs for the LTO-loaded Cu electrode under the same overpotential. The safety of LTO is investigated by analyzing the reaction kinetics.

Effects of Butadiene Sulfone as an Electrolyte Additive on the Formation of Solid Electrolyte Interphase in Lithium-Ion Batteries Based on Li4Ti5O12 Anode Materials.

In this study, butadiene sulfone (BS) was selected as an efficient electrolyte additive to stabilize the solid electrolyte interface (SEI) film on the lithium titanium oxide (LTO) electrodes in Li-ion batteries (LIBs). It was found that the use of BS as an additive could accelerate the growth of stable SEI film on the LTO surface, leading to the improved electrochemical stability of LTO electrodes. It can be supported by the BS additive to effectively reduce the thickness of SEI film, and it significantly enhances the electron migration in the SEI film. Consequently, the LIB-based LTO anode in the electrolyte containing 0.5 wt.% BS showed a superior electrochemical performance to that in the absence of BS. This work provides a new prospect for an efficient electrolyte additive for next-generation LIBs-based LTO anodes, especially when discharged to low voltage.

Cation Distribution Effect on Structural and Electronic Properties of Oxygen Vacancy and Niobium Substituted Spinel Lithium Titanium Oxide Anode Material in Lithium-ion Batteries

We have presented the results of detailed studies of oxygen vacancy and niobium (Nb) substituted spinel Li4Ti5O12 (LTO) materials using first-principles method within the framework of the density functional theory (DFT). We have shown that the ground state of oxygen vacancy and Nb substituted LTO is paramagnetic (PM), and the Nb substitution is most stable on the 16d sites of both the Li and Ti ions. We have indicated that the Nb substitution in the 16d site of Li ion become the n-type metallic material. But the oxygen vacancy containing NbT i substituted LTO is changed from the p-type to the n-type, as increased a concentration of Nb ions.

Synthesis of High Specific Surface Lithium-Ion Sieve Templated by Bacterial Cellulose for Selective Adsorption of Li.

In recent years, with the development of batteries, ceramics, glass and other industries, the demand for lithium has increased rapidly. Due to the rich lithium resources in seawater and salt-lake brine, the question of how to selectively adsorb and separate lithium ions from such brine has attracted the attention and research of many scholars. The Li-ion sieve stands out from other methods thanks to its excellent special adsorption and separation performance. In this paper, mesoporous titanium dioxide and lithium hydroxide were prepared by hydrothermal reaction using bacterial cellulose as a biological template. After calcination at 600 °C, spinel lithium titanium oxide Li2TiO3 was formed. The precursor was eluted with HCl eluent to obtain H2TiO3. The lithium titanate were characterized by IR, SEM and X-ray diffraction. The adsorption properties of H2TiO3 were studied by adsorption pH, adsorption kinetics, adsorption isotherm and competitive adsorption. The results show that H2TiO3 has a single-layer chemical adsorption process, and has a good adsorption effect on lithium ions at pH 11.0, with a maximum adsorption capacity of 35.45 mg g-1. The lithium-ion sieve can selectively adsorb Li+, and its partition coefficient is 2242.548 mL g-1. It can be predicted that the lithium-ion sieve prepared by biological template will have broad application prospects.

Fast Charging Behaviour of High-Power Li-Ion Cell at Different Temperatures and Effect on Capacity and Internal Resistance

Lithium-Ion Batteries (LIBs), which have already proven to be a reliable power source in consumer electronics devices, are being considered a viable option for powering Electric Vehicles (EVs). Fast charging of EVs is one of the key challenges that is preventing a wide range of adoption of EVs. In this study, a lithium-ion cell with Lithium Titanium Oxide (LTO)-lithium Nickel Manganese Cobalt oxide (NMC) chemistry of 30 Ah has been used to study the fast charging capabilities at different temperatures and C-rates. Various parameters such as temperature rise, nominal and exponential capacity, and internal resistance have been studied for different C-rates (C/3, 1C, and 2C) and at different temperatures (25 °C, 40 °C, and -10 °C). The ΔV values along with the charge and discharge characteristics have been analyzed, and the experimental results are compared with the simulation results.

Structural, morphological, optical, electrical and dielectric features based on nanoceramic Li4Ti5O12 filler reinforced PEO/PVP blend for optoelectronic and energy storage devices

Polymer nanocomposite films had been fabricated by the solution casting process using the organic matrix of polyethylene oxide/polyvinylpyrrolidone (PEO/PVP: 50/50 wt%) blend and various filling levels of lithium titanium oxide nanoparticles (Li4Ti5O12 NPs). The TEM and XRD techniques indicated the phase purity of the cubic Li4Ti5O12 NPs with a crystallite size of about 69 nm. The FTIR spectra revealed that the complexation/miscibility between the PEO/PVP blend components were existed through the formation hydrogen bonding between the main functional groups of these polymers and also the loaded NPs fundamentally behaved as geometrical incarceration for the structure of PEO/PVP matrix, due to the formation of polymer-nanoparticles interactions. The SEM images indicated observable variations in the size of PEO spherulites, formed aggregations and pores of host matrix on 1 wt% Li4Ti5O12 NPs and additional 3 and 5 wt%. The optical features of nanocomposites such as optical energy band gap and refractive index were evaluated through the UV/vis. absorbance spectra, where the redshift for the main absorption edge of the filled films implied that Li4Ti5O12 NPs had been successfully embedded into the PEO/PVP matrix. The maximum refractive index and the lowest optical bandgap energy were obtained for the nanocomposite sample (5 wt%). The AC electrical conductivity σac and the dielectric response of the prepared samples were studied, where the loaded NPs increased the values of σac, dielectric loss, and dielectric constant of the PEO/PVP blend and the dielectric constant of the nanocomposite films decreased with increasing the applied frequency. The electrical modulus formalism (M*) and impedance formalism (Z*) were used to analyze the impedance data. The enhancements in the optical and electrical characteristics make these nanocomposite materials appropriate for many uses such as integral thin film capacitors, flexible nanodielectrics for organoelectronic devices, high power Li-ion batteries, optical band gap tuner and many optoelectronic devices.