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Titanium disulfide

Titanium disulfide (TiS₂) is an inorganic compound and a prototypical layered transition metal dichalcogenide (TMD) with the chemical formula TiS₂, appearing as a golden yellow crystalline powder that serves as a solid lubricant.^[1] It crystallizes in a CdI₂-type hexagonal lattice, featuring stacked S-Ti-S sandwich layers bound by weak van der Waals forces, which enable easy exfoliation into two-dimensional (2D) nanosheets.^[2] TiS₂ exhibits semimetallic conductivity in its bulk form, transitioning to semiconducting behavior in monolayers, with a tunable bandgap, high charge mobility, and theoretical lithium storage capacity of up to 239 mAh g⁻¹.^[3] Historically, it played a key role in the development of early lithium-ion batteries in the 1970s.^[4]

Structure

Crystal Structure

Titanium disulfide (TiS₂) is an inorganic layered transition metal dichalcogenide that adopts a cadmium iodide (CdI₂)-type structure.^[5] This layered arrangement places it within the family of transition metal dichalcogenides characterized by strong intralayer bonding and weak interlayer interactions.^[6] The crystal structure of TiS₂ belongs to the hexagonal crystal system with space group P-3m1 (No. 164).^[7] At room temperature, the lattice parameters are a = 3.407 Å and c = 5.695 Å.^[7] Within each layer, titanium atoms occupy octahedral holes in a close-packed hexagonal array of sulfur atoms, resulting in octahedral coordination where each Ti is surrounded by six S atoms.^[7] These TiS₆ octahedra share edges to form the S-Ti-S sandwich layers, with Ti-S bond lengths of 2.423 Å.^[8] The layers are stacked via weak van der Waals forces, leading to an interlayer S-S distance of approximately 3.49 Å and enabling facile cleavage along the basal planes.^[9] The predominant polytype is 1T-TiS₂, featuring octahedral coordination, though 2H and 3R variants can form under specific temperature or synthesis conditions.^[10]

Intercalation

Intercalation in titanium disulfide (TiS₂) involves the reversible insertion of guest species, such as alkali metal ions (e.g., Li⁺, Na⁺) or molecules (e.g., organic solvents like pyridine), into the weakly bound van der Waals gaps between its S-Ti-S layers. This process exploits the layered structure of TiS₂, enabling easy separation of the layers and accommodation of guests without disrupting the host lattice integrity. Upon insertion, the c-axis lattice parameter expands due to the increased interlayer spacing; for instance, it increases from 5.695 Å in pristine TiS₂ to approximately 5.98 Å for the Li₀.₅TiS₂ composition, reflecting a roughly 5% expansion at half occupancy.^[7] Intercalation forms ternary compounds such as LiₓTiS₂ (0 < x ≤ 1), where the lithium content determines the phase structure. For higher x values (typically x > 0.5), a stage 1 phase predominates, featuring a full monolayer of Li⁺ ions between every pair of TiS₂ layers. At lower x (e.g., x ≈ 0.25), a stage 2 phase emerges, characterized by bilayer spacing where intercalant layers alternate with empty van der Waals gaps, leading to a doubled c-axis parameter of about 11.5 Å. These staged configurations minimize electrostatic repulsion between guests while maximizing host utilization.^[11]^[7] The intercalation mechanism proceeds via diffusion of guest species primarily through edge planes of the layered crystals, as the van der Waals gaps are otherwise inaccessible in bulk material. Accompanying this insertion is electron transfer from the guest to the host, reducing Ti⁴⁺ cations to a mixed Ti³⁺/Ti⁴⁺ valence state and partially filling the d-band of titanium, which enhances the metallic conductivity of the semimetallic TiS₂. This charge transfer enhances electronic mobility, facilitating faster ion transport in the intercalated phases.^[12]^[13]^[14] Structurally, intercalation induces layer sliding or buckling as the TiS₂ sheets adjust to accommodate the guests, altering the stacking sequence (e.g., from 2H to 1T polytype in some cases) and optimizing ion-host interactions. The overall reaction for lithium intercalation can be represented as:

\text{TiS}_2 + x\text{Li}^+ + x\text{e}^- \rightarrow \text{Li}_x\text{TiS}_2

This electrochemical process preserves the octahedral coordination of Ti by S atoms while expanding the lattice anisotropically along the c-direction.^[15]^[14] The phenomenon of intercalation in TiS₂ was first explored in the 1970s for rechargeable battery applications, with pioneering work by M. Stanley Whittingham demonstrating its potential as a cathode material in lithium cells.^[16]

Properties

Physical Properties

Titanium disulfide (TiS₂) is a golden yellow crystalline solid (black in some impure forms) with a density of 3.22 g/cm³. It decomposes at approximately 600°C without undergoing melting, reflecting its thermal instability at elevated temperatures.^[17]^[18] TiS₂ exhibits anisotropic electrical properties characteristic of a semimetal, with high in-plane conductivity of approximately 10³ S/cm due to metallic behavior within the layers and much lower perpendicular conductivity of about 1 S/cm. The carrier density is on the order of 10²¹ cm⁻³, and Hall mobility reaches 200 cm²/V·s, contributing to its suitability for layered electronic applications. This anisotropy arises from the layered structure, where strong covalent bonding dominates in-plane transport while weak van der Waals interactions limit out-of-plane conduction.^[19]^[20] Optically, bulk TiS₂ is semimetallic with a small indirect band overlap of ~0.3 eV; in few-layer or monolayer forms, it exhibits an indirect band gap of ~0.9 eV and direct band gap of ~1.8 eV, enabling strong absorption in the visible range primarily through d-d transitions involving titanium d-orbitals. The refractive index ranges from 3.5 to 4.0, indicating significant light-matter interaction suitable for optoelectronic contexts.^[21]^[22] The thermal conductivity of TiS₂ is anisotropic, with in-plane values of ~6 W/m·K at 300 K and lower out-of-plane conduction due to phonon scattering at layer interfaces. At 300 K, the specific heat capacity is approximately 0.71 J/g·K (79 J/mol·K), consistent with its low atomic mass and vibrational modes in the layered lattice.^[23]^[24] TiS₂ is diamagnetic, with a magnetic susceptibility of χ = -9 × 10⁻⁶ emu/mol, arising from the absence of unpaired electrons in its filled d-band configuration. Mechanically, it displays strong in-plane stiffness with a Young's modulus of about 100 GPa, attributed to robust covalent Ti-S bonds within layers, while remaining brittle along the c-axis due to weak interlayer forces.^[25]^[26]

Chemical Properties

Titanium disulfide (TiS₂) is air-sensitive and undergoes slow oxidation in air at room temperature, forming titanium oxides over extended periods such as 46 days, with the process accelerating at elevated temperatures to yield primarily TiO₂ (rutile and anatase phases) along with sulfur loss.^[27] In moist air, it hydrolyzes gradually, producing hydrogen sulfide (H₂S) and titania (TiO₂).^[1] TiS₂ exhibits reactivity with strong acids, such as hydrochloric acid (HCl), generating toxic hydrogen sulfide gas and titanium species like TiCl₄.^[1] It is inert toward dilute bases under standard conditions. In water, TiS₂ decomposes slowly according to the reaction:

\text{TiS}_2 + 2\text{H}_2\text{O} \rightarrow \text{TiO}_2 + 2\text{H}_2\text{S}

This hydrolysis underscores its instability in aqueous environments.^[1] Thermodynamically, the standard enthalpy of formation (ΔH_f°) for TiS₂ is -462.1 ± 8.0 kJ/mol at 298.15 K, while the standard Gibbs free energy of formation (ΔG_f°) is -442 kJ/mol; these values indicate a stable compound under standard conditions.^[28] Its solubility product is negligible in non-oxidizing media, consistent with its practical insolubility in water.^[1] The Ti(IV) centers in TiS₂ are susceptible to reduction to lower oxidation states, enabling its use in electrochemical applications. The material operates within an electrochemical window of approximately 0–3 V versus Li/Li⁺, supporting reversible redox processes.^[29] Environmentally, TiS₂ displays low toxicity, with no significant bioaccumulation potential noted; however, handling precautions are essential due to the risk of H₂S release upon exposure to moisture or acids, which poses inhalation hazards.^[30]^[1]

High-Pressure Properties

High-pressure studies of titanium disulfide (TiS₂) have primarily utilized diamond anvil cell (DAC) techniques combined with synchrotron X-ray diffraction (XRD) to probe structural stability and phase behavior up to approximately 45 GPa. These experiments reveal that TiS₂ remains stable in its ambient trigonal (CdI₂-type) structure without decomposition up to at least 20 GPa, though a structural phase transformation begins at around 20.7 GPa, with the high-pressure phase requiring further characterization.^[31] Electronic properties under pressure show that bulk TiS₂ maintains its semimetallic character up to 20 GPa, with no observed structural or isostructural phase transition leading to a band gap opening or semiconductor behavior in this range. Instead, density functional theory (DFT) calculations and in situ transport measurements indicate persistent band overlap at the Fermi level, with the density of states at the Fermi energy slightly increasing from 0.66 states/eV at 5 GPa to 0.74 states/eV at 20 GPa. However, a notable change in electrical transport properties occurs around 15 GPa, marked by decreased resistivity and altered Hall coefficient slopes, potentially due to pressure-induced ionization of impurity levels enhancing metallic-like conduction.^[19] Compressibility of TiS₂ is characterized by a bulk modulus derived from Birch-Murnaghan equation-of-state fits to pressure-volume data. Experimental XRD yields an isothermal bulk modulus K_{0T} = 45.9 \pm 0.7 GPa with pressure derivative K'_{0T} = 9.5 \pm 0.3 for pressures below 17.8 GPa, reflecting moderate resistance to compression. DFT calculations corroborate this, reporting a zero-pressure bulk modulus of approximately 37.5 GPa via the Voigt-Reuss-Hill (VRH) approximation, with volume decreasing from 58.008 Å³ at 0 GPa to 42.318 Å³ at 20 GPa, corresponding to a ~27% reduction. The pressure-volume relation follows the third-order Birch-Murnaghan equation:

P(V) = \frac{3}{2} K_0 \left[ \left( \frac{V_0}{V} \right)^{7/3} - \left( \frac{V_0}{V} \right)^{5/3} \right] \left\{ 1 + \frac{3}{4} (K'_0 - 4) \left[ \left( \frac{V_0}{V} \right)^{2/3} - 1 \right] \right\}

where V_0 is the zero-pressure volume and K'_0 is the pressure derivative of the bulk modulus.^[31]^[32] Elastic properties exhibit pressure-dependent stiffening, with no phase instability up to 20 GPa according to DFT predictions. The VRH-averaged bulk modulus increases from 37.51 GPa at ambient pressure, while shear and Young's moduli follow similar upward trends, indicating enhanced mechanical resistance. Anisotropy is evident in the elastic constants, where C_{11} (in-plane) starts at 143.3 GPa and C_{33} (out-of-plane) at 36.0 GPa at 0 GPa, both rising with pressure but with greater relative stiffening along the c-axis, as C_{33} shows accelerated increase beyond 10 GPa. This suggests preferential compression and reinforcement perpendicular to the layers. No direct evidence of pressure-induced optical shifts, such as red-shift in the absorption edge, was identified in studies up to 20 GPa, though broader optoelectronic responses remain an area for further investigation.^[32] In 2D nanostructures, thermal conductivity can reduce to 1-2 W/m·K due to enhanced phonon scattering at boundaries.^[3]

Synthesis

Bulk Synthesis

Titanium disulfide (TiS₂) is commonly synthesized in bulk form through high-temperature solid-state reactions, primarily to produce macroscopic crystals or powders suitable for applications such as battery materials. The direct combination method involves mixing elemental titanium and sulfur powders in a stoichiometric ratio (Ti + 2S → TiS₂), sealing the mixture in a quartz ampoule under vacuum or inert gas, and heating to 600–800°C for several hours to days. This approach yields highly crystalline 2H-phase TiS₂ with uniform particle sizes and minimal agglomeration, often achieving high conversion rates exceeding 95% when excess sulfur is employed to suppress formation of titanium monosulfide (TiS) impurities.^[33]^[34] An alternative route for purer bulk samples utilizes titanium halides, such as the gas-phase reaction of titanium tetrachloride (TiCl₄) with hydrogen sulfide (H₂S) at 650–850°C: TiCl₄ + 2H₂S → TiS₂ + 4HCl. This method, conducted in a flow reactor under inert conditions, facilitates better control over stoichiometry and reduces metallic impurities compared to direct combination, producing fine powders with high phase purity. However, it requires careful handling of corrosive byproducts like HCl.^[33] For single-crystal growth, chemical vapor transport (CVT) is widely adopted, employing iodine (I₂) as a transport agent in a sealed quartz tube containing polycrystalline TiS₂ and excess titanium. The setup is placed in a temperature gradient furnace, typically with the source zone at 800–900°C and the growth zone at 700–800°C, enabling slow transport and crystallization over 7–14 days at rates around 0.1 mm/day to form platelet-like crystals up to several millimeters in size. This technique, refined in the 1970s, supports scalability for industrial production, particularly for lithium-ion battery cathodes following early demonstrations of TiS₂'s intercalation properties.^[33] Bulk synthesis of stoichiometric TiS₂ necessitates an inert atmosphere (e.g., argon or vacuum) throughout to prevent oxidation by trace oxygen or moisture, which can form titanium oxides and degrade material quality. Off-stoichiometric variants like TiS_{2-δ} are prevalent due to sulfur volatility at high temperatures, often requiring post-annealing in sulfur vapor to achieve precise composition. These methods trace back to initial syntheses in the 1960s, with significant advancements in the 1970s enabling large-scale production for energy storage.^[33]^[27]

Sol-Gel Methods

The sol-gel methods for titanium disulfide (TiS₂) synthesis provide solution-based routes that enhance material homogeneity and enable precise control over composition, contrasting with high-temperature bulk alternatives. These approaches typically involve the formation of molecular precursors through hydrolysis or thiolysis, followed by gelation and thermal decomposition to yield TiS₂ powders or films with uniform particle sizes. In the thio-sol-gel process, titanium(IV) thiolate precursors, such as [Ti(SBuᵗ)₄], serve as the metal source. These precursors react with H₂S at room temperature to generate a precipitate, which is then annealed under flowing H₂S at 600–800 °C to form crystalline TiS₂ via thermolysis, releasing organic byproducts. Powder X-ray diffraction confirms the hexagonal phase of TiS₂ at 800 °C, while lower temperatures like 600 °C yield mixtures with Ti-rich sulfides such as Ti₁.₂₅S₂.^[35] Conventional sol-gel synthesis employs titanium alkoxides, exemplified by titanium tetraisopropoxide [Ti(OᵢPr)₄], reacted with H₂S in an n-butylamine solvent at room temperature to produce an amorphous titanium alkoxy-sulfide gel. This intermediate undergoes pyrolysis at 800 °C in H₂S to achieve phase-pure hexagonal TiS₂, as demonstrated in a 2007 study that produced nanoparticles suitable for thin films and powders. At intermediate temperatures around 400–600 °C, the product remains largely amorphous and can be converted to crystalline TiS₂ with further heating. A key step in precursor preparation involves thiolysis:

\text{Ti(OR)}_4 + 4 \text{HSR} \rightarrow \text{Ti(SR)}_4 + 4 \text{ROH}

followed by thermolysis to TiS₂ under inert or sulfidizing conditions.^[36] These methods offer advantages including reaction initiation at ambient temperatures and final annealing below 900 °C—lower than many bulk syntheses requiring 600–900 °C—while achieving particle sizes of 10–100 nm for enhanced uniformity. However, challenges arise from potential sulfur loss during annealing, mitigated by maintaining an H₂S atmosphere to preserve the 1:2 Ti:S stoichiometry and prevent oxide impurities from trace moisture.^[36]

Advanced Nanomaterial Synthesis

Advanced nanomaterial synthesis of titanium disulfide (TiS₂) has advanced significantly through vapor-phase and electrochemical techniques, enabling the production of thin films and nanostructures with precise control over phase, thickness, and composition. These methods, developed primarily post-2015, address limitations of traditional bulk synthesis by offering scalability, low-temperature processing, and compatibility with device fabrication substrates. Atomic layer deposition (ALD) utilizes tetrakis(dimethylamido)titanium (Ti(NMe₂)₄) and hydrogen sulfide (H₂S) precursors at temperatures of 100–200°C to deposit phase-controlled TiS₂ or TiS₃ films. A 2019 process achieves low-temperature deposition, yielding 1–10 nm thick layers with a growth rate of 0.5 Å per cycle, allowing selective formation of metallic TiS₂ or semiconducting TiS₃ by adjusting plasma exposure and temperature.^[37] Hybrid ALD/chemical vapor deposition (CVD) approaches employ tetrakis(dimethylamido)titanium and 1,2-ethanedithiol at 50 °C followed by annealing at 450 °C to grow two-dimensional (2D) TiS₂ films on silicon substrates. A 2022 study demonstrates scalable deposition through self-limiting growth cycles, providing atomic-level uniformity suitable for large-area applications. Recent in situ studies using synchrotron techniques have elucidated the mechanisms, revealing amorphous Ti-thiolate intermediates and annealing-induced crystallization into nanocrystalline TiS₂.^[22]^[38] Electrodeposition from deep eutectic solvents, such as choline chloride–urea, incorporates titanium and sulfur sources at 80 °C using potentiostatic conditions (-0.8 V vs. Pt) to form TiS₂ thin films. A 2020 method produces films optimized as hole transport layers with controlled stoichiometry and minimal defects.^[39] Solid-state reactions (SSR) at 400°C enable the synthesis of TiS₂ nanodiscs from elemental precursors under vacuum, offering advantages in precise thickness control for subsequent device integration. This approach ensures high crystallinity while avoiding solvent use.^[40] Recent advances emphasize greener, solvent-free strategies, such as molten salt-assisted vapor deposition and optimized electrochemical setups, which reduce energy consumption by up to 50% relative to bulk methods through lower operating temperatures and eliminated organic solvents. Sol-gel routes may serve as precursors in these hybrid processes for enhanced precursor delivery.^[3]

Nanostructures

Fullerene-like Forms

Inorganic fullerene-like (IF) TiS₂ structures consist of quasi-spherical nanoparticles, typically 20–100 nm in diameter, composed of nested, curved S-Ti-S shells that resemble the cage-like architecture of C₆₀ fullerenes. These structures feature folded layered sheets without dangling bonds and exhibit high folding angles of approximately 100°, enabling seamless closure of the molecular layers.^[41] The primary synthesis method involves a gas-phase reaction of TiCl₄ and H₂S precursors at around 900°C, yielding quasi-spherical nanoparticles with up to 100 concentric layers and an interlayer spacing of about 5.8 Å. Variants of this approach include arc discharge and laser ablation techniques, which produce similar closed-cage morphologies with yields of 10–20%. Discovered in the 1990s as part of broader efforts to create inorganic analogs of carbon fullerenes, recent characterizations using transmission electron microscopy (TEM) and scanning TEM (STEM) have provided detailed insights into their nested structure and folding mechanics.^[41]^[42] Raman spectroscopy reveals characteristic shifts to lower frequencies in IF-TiS₂ compared to bulk material, such as the A₁g mode at 330 cm⁻¹ versus 335 cm⁻¹ in bulk TiS₂, reflecting the strain from curvature in the folded layers. These nanoparticles demonstrate enhanced mechanical strength, with a compressive modulus approximately twice that of bulk TiS₂, arising from the robust, closed-cage design that distributes stress effectively. They also exhibit a low friction coefficient of 0.03, owing to a rolling mechanism that reduces shear during contact, thus providing superior lubricity over bulk TiS₂. Furthermore, IF-TiS₂ shows improved chemical stability, remaining inert to oxidation up to 500°C.^[41]

Nanotubes

Titanium disulfide (TiS₂) nanotubes are multi-walled cylindrical nanostructures consisting of scrolled or coaxial layers of TiS₂ sheets, forming open-ended tubes with typical outer diameters of approximately 20 nm, inner diameters of 10 nm, and lengths ranging from 2 to 5 µm. The interlayer spacing within these tubes is about 0.57 nm, matching the c-axis parameter of bulk 1T-TiS₂, and high-resolution transmission electron microscopy reveals parallel fringes indicative of the layered hexagonal structure. Structural defects, such as those altering atomic configuration and morphology to create convex or concave walls, play a key role in stabilizing the tubular form and influencing electronic properties, with defective tubes exhibiting metal-like conductivity compared to the semiconducting ideal structures.^[43]^[44] These nanotubes are synthesized via a low-temperature gas-phase reaction involving titanium tetrachloride (TiCl₄) and hydrogen sulfide (H₂S) at 450 °C, yielding the metastable 1T phase without templates or catalysts. An alternative route involves chemical transport reactions or solution-based methods to form open-ended multi-walled tubes from bulk precursors. The discovery of TiS₂ nanotubes for advanced applications dates to 2003, with subsequent 2004 studies demonstrating template-free exfoliation approaches using co-intercalants like MgCl₂ to enhance layer separation and tube formation from bulk TiS₂ powder. Recent investigations, including 2023 reports on Mg-ion variants, continue to explore optimized synthesis for battery cathodes, focusing on scalable gas or solution routes. As of 2024, heterostructures combining TiS₂ nanotubes with graphene oxide have shown enhanced electrochemical performance for energy storage.^[43]^[45] Compared to bulk TiS₂ (surface area ~1 m²/g), the nanotubes offer significantly higher surface area of approximately 25 m²/g, facilitating improved guest species interactions. They demonstrate enhanced Li intercalation, forming LiTiS₂ with a ~10.5% expansion along the c-axis and reversible capacities approaching the theoretical 239 mAh/g for LiTiS₂, due to the open-ended morphology enabling efficient ion diffusion.^[46]^[47] For Mg-ion batteries, the nanotubes provide high-capacity reversible intercalation (~0.49 Mg per TiS₂ unit in initial cycles), outperforming polycrystalline TiS₂, with good cycling stability attributed to the robust tubular architecture. These structures also exhibit reversible hydrogen storage up to 2.5 wt%, surpassing bulk materials. TiS₂ nanotubes show greater thermal robustness than analogous WS₂ tubes, maintaining integrity up to 600 °C, though specific photoluminescence data at 2.5 eV remains limited in early reports. Related fullerene-like forms share curved layer motifs but differ in their closed, spherical geometries.^[46]

Nanodisks and Nanoclusters

Titanium disulfide (TiS₂) nanodisks are plate-like nanostructures characterized by their hexagonal platelet morphology, with typical thicknesses of a few layers (approximately 2-10 nm) and lateral dimensions ranging from 50 to 200 nm. These structures are synthesized primarily through solid-state reaction (SSR) methods or colloidal approaches involving surfactants. In a 2018 SSR process, TiS₂ nanodiscs were prepared by heating stoichiometric mixtures of titanium and sulfur powders at elevated temperatures under inert atmosphere, yielding crystalline nanodiscs confirmed by field-emission scanning electron microscopy (FESEM) images showing disc-like features. X-ray diffraction (XRD) analysis of these nanodiscs reveals prominent 00l reflections, indicative of the layered hexagonal structure (space group P-3m1) with a crystallite size around 23 nm. Alternatively, surfactant-assisted colloidal synthesis, such as dissolving TiCl₄ in oleylamine followed by addition of sulfur powder and heating to 300°C, produces single-layered nanodisks approximately 50 nm in diameter, which exhibit high dispersibility in nonpolar organic solvents like chloroform due to amine capping. These methods offer advantages in scalability and solvent compatibility compared to bulk synthesis, enabling facile integration into composite materials. As of 2025, hydrothermal synthesis has been reported for nanostructured TiS₂ suitable for NO₂ gas detection.^[48] TiS₂ nanoclusters, including three-dimensional aggregates and quantum dot-like particles with sizes of 1-5 nm, are obtained via colloidal routes that promote nucleation in confined environments. A common approach involves reverse micelle synthesis at room temperature, where TiCl₄ is solubilized in a tridodecylmethylammonium iodide (TDAI)/hexanol/octane mixture, followed by bubbling H₂S gas to form clusters extracted into acetonitrile. High-resolution transmission electron microscopy (HRTEM) confirms particle diameters of 3-5 nm, with some aggregation up to 6 nm. Microwave-assisted variants, though less documented for TiS₂ specifically, parallel these colloidal techniques by accelerating reaction kinetics for similar cluster formation, enhancing yield and uniformity. These nanoclusters demonstrate high dispersibility in polar and nonpolar solvents, attributed to surfactant stabilization, facilitating applications in optoelectronics. Key properties of TiS₂ nanodisks and nanoclusters stem from their reduced dimensionality. In nanodisks, the layered structure contributes to high specific capacitance values, such as approximately 200 F/g in aqueous KOH electrolytes, arising from efficient ion intercalation between sheets. For nanoclusters, quantum confinement effects significantly widen the band gap beyond the bulk indirect value of ~1 eV; for instance, 3 nm clusters exhibit an effective band gap of 3.46 eV due to blueshifts in absorption edges. Photoluminescence (PL) in these clusters is tunable, with emission peaks at 400-450 nm (corresponding to 2.76-3.1 eV) under excitations at 312-360 nm, enabling size-dependent control over optical response. Recent density functional theory (DFT) studies on doped TiS₂ nanostructures, including cluster-like motifs, reveal ferromagnetic coupling with magnetic moments up to 1.07 μ_B per unit, particularly in vanadium-substituted systems, highlighting potential for spintronic applications.

Applications

Energy Storage Devices

Titanium disulfide (TiS₂) has played a pivotal role in energy storage since the early development of rechargeable lithium-ion batteries, serving as a cathode material in the first such prototype demonstrated by M. Stanley Whittingham in 1973.^[49] The layered structure of TiS₂ enables reversible lithium intercalation, forming LixTiS₂ (0 ≤ x ≤ 1), with a theoretical specific capacity of 239 mAh/g based on one Li⁺ per TiS₂ unit.^[50] In practice, early Li-TiS₂ cells delivered capacities of approximately 150 mAh/g with a voltage plateau around 2.3 V versus Li/Li⁺, exhibiting good cycling stability over hundreds of cycles due to the minimal structural change during intercalation.^[51] The discharge reaction is represented as:

\text{Li}_x\text{TiS}_2 \rightarrow \text{TiS}_2 + x\text{Li}^+ + x\text{e}^-

Subsequent optimizations have pushed practical capacities to 150–200 mAh/g while maintaining stability over 500 cycles, though challenges like limited capacity beyond x=1 and electrolyte compatibility limited widespread adoption in favor of higher-voltage oxides.^[49] Recent advancements have revived interest in TiS₂ through nanostructuring, enhancing rate capability and power density. Nanocomposite TiS₂ cathodes in all-solid-state lithium batteries achieve power densities exceeding 1000 W/kg over 50 cycles, with a peak of ~1400 W/kg, attributed to improved ionic conductivity and reduced interfacial resistance in solid electrolytes.^[52] For sodium-ion and magnesium-ion variants, TiS₂ demonstrates viable performance as a conversion or intercalation host; in Na-ion batteries, it delivers a reversible capacity of 146 mAh/g at 0.1C with stability over 160 cycles,^[53] while in Mg-ion systems, it provides a stabilized capacity of 115 mAh/g in full cells.^[54] Recent studies (as of 2025) explore TiS₂ nanosheets for zinc-ion capacitors, achieving enhanced capacities.^[55] A key challenge in TiS₂-based lithium-sulfur hybrids is the polysulfide shuttle effect, which causes capacity fade; this is mitigated by nanostructuring, such as incorporating TiS₂ with carbon nanotubes to trap polysulfides and enhance conversion kinetics.^[56] In supercapacitors, nanostructured TiS₂, particularly nanodisks, exhibits pseudocapacitive behavior driven by sulfur redox and ion intercalation, achieving specific capacitances up to 250 F/g in 6 M KOH electrolyte at low scan rates.^[57] This performance stems from the material's high electrical conductivity and layered structure, enabling fast charge transfer, though long-term stability requires protective coatings to prevent oxidation.^[58]

Optoelectronics and Catalysis

Titanium disulfide (TiS₂) has emerged as a promising material in optoelectronics due to its tunable electronic properties and layered structure. Electrodeposited TiS₂ thin films, synthesized via ionic liquid methods at low temperatures, serve as inorganic hole transport layers (HTLs) in perovskite solar cells, offering p-type conductivity and high carrier mobility up to 14.4 cm² V⁻¹ s⁻¹.^[59] Additionally, water-soluble 2D TiS₂ has been used in interface engineering as an electron transport layer (ETL) in planar n-i-p perovskite solar cells, achieving a power conversion efficiency of 21.7% due to improved charge extraction and reduced recombination.^[60] Monolayer TiS₂ in the 1T phase exhibits an indirect bandgap of approximately 0.05 eV, facilitating its use in field-effect transistors (FETs) with high on/off current ratios around 10⁵, as demonstrated in TiS₂/MoS₂ metal-semiconductor FETs.^[61] In catalysis, layered TiS₂ structures, particularly those with sulfur vacancies, promote hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) by exposing active edge sites that lower the energy barrier for H₂ evolution. Nonstoichiometric TiS₂₋ₓ/NiS heterostructures display low HER overpotentials of 63 mV in alkaline media and 134 mV in acidic conditions at a current density of 10 mA cm⁻², outperforming pristine TiS₂ due to enhanced charge transfer and vacancy-induced active sites.^[62] For ORR, TiS₂ composites facilitate efficient four-electron pathways, though specific overpotentials remain higher than for HER, with ongoing efforts focusing on doping to improve selectivity and stability.^[3] Beyond optoelectronics and catalysis, inorganic fullerene-like (IF) TiS₂ nanoparticles enhance lubrication properties when dispersed in oils, reducing friction coefficients by up to 50% under boundary lubrication conditions through rolling mechanisms that minimize direct asperity contact. These nanoparticles have been applied in aerospace components since the early 2000s, providing durable solid lubrication in high-vacuum and extreme-temperature environments.^[63]^[64] In 2024, engineered monolayer TiS₂ doped with transition metals like cobalt induced ferromagnetic properties with magnetic moments around 0.8 μB per dopant atom, positioning it as a candidate for spintronic devices such as spin valves.^[61] TiS₂ thin films also excel in photodetectors, with horizontally aligned nanosheets achieving responsivities up to 1.17 × 10⁴ A W⁻¹ across broadband wavelengths (375–1050 nm) and fast response times of 0.3 s, leveraging the material's low bandgap for visible-to-infrared detection.^[65] TiS₂ benefits from its low cost and abundance as a transition metal dichalcogenide derived from readily available precursors, enabling scalable production for practical applications. However, challenges persist in humid environments, where amine-intercalated or pristine TiS₂ exhibits limited long-term stability due to oxidative decomposition and moisture-induced phase changes.^[17]^[66]

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Insufficient relevant content. The provided text only includes a PubChem page identifier (Titanium disulfide | S2Ti | CID 61544) and a JavaScript requirement notice, with no substantive data on chemical formula, molecular weight, appearance, structure, properties, synthesis, or uses.
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TiS2 properties
Titanium disulfide appears as a golden yellow crystalline powder with metallic luster. The compound has a molar mass of 111.997 g/mol and a density of 3.22 g/ ...
[11]
Explaining Mysterious “Shoulder” Raman Band in TiS2 by ...
Oct 16, 2023 · The hexagonal, laminar structure has c = 5.6953 Å and a = 3.4073 Å with the interlayer S-S distance of 3.462(5) Å. 60. Amano, T.; Yamazaki, T ...
[12]
Phase relations and some electrical properties of compounds in TiS 2
Three polytypes, 1T, 2Ha, and 3R, are observed. The 1T-polytype is a high temperature phase, the 2Ha-polytype is a medium temperature phase, and the 3R ...
[13]
Structure determination of LixTiS2 by neutron diffraction
The crystal structures of the intercalation compounds of LixTiS2 are investigated by neutron diffraction for x = 0.12, 0.33, 0.67, and 1.0.
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Nondilute diffusion from first principles: Li diffusion in Li x TiS 2
Sep 26, 2008 · Li diffusion in intercalation compounds occurs by a vacancy mechanism, whereby individual Li ions hop into neighboring vacant sites.
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Magnetic investigation of the intercalation compounds Li x TiS 2
The metallic nature of these compounds originates from electron donation from Li to the TiS2 conduction band. The temperature-independent paramagnetism observed ...<|control11|><|separator|>
[16]
Lithium Diffusion Pathways in 3R-LixTiS2: A Combined Neutron ...
This work elucidates the pathways of lithium-ion diffusion in 3R-Li x TiS 2 and points out pitfalls in established experimental/computational methods.
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[PDF] Expanded lithiation of titanium disulfide: Reaction kinetics of multi ...
[15,16] Only intercalation process from TiS2 to LiTiS2 has been reported so far, TiS2 + xLi+ + e- → LixTiS2, 0 ≤ x ≤ 1,which pro- vides a capacity of 239 mAh/g ...
[18]
Intercalation chemistry and energy storage - ScienceDirect.com
The reaction between lithium and titanium disulfide is used to show the relationship between intercalation chemistry and electrochemical energy storage.Missing: 1970s | Show results with:1970s
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[PDF] First Principles Study of Structure and Lithium Storage in Inorganic ...
The maximum capacity was approximately 300 mAh/g for all studies. ... experimentally measured interlayer spacing in both bulk TiS2 and TiS2 nanotubes [35].
[20]
Titanium(IV) Sulfide (TiS2) Powder and Crystal - Ossila
90-day returnsSynthetic - Chemical Vapor Transport (CVT). Structure, Octahedral (1T). Electronic Properties, Semimetal, Diamagnetic. Melting Point, N/A. Color, Golden yellow.Missing: density | Show results with:density
[21]
Titanium Disulfide Powder (TiS2) - Stanford Advanced Materials
Titanium Disulfide Powder (TiS2) is primarily used in energy storage ... Appearance, Black Powder. Purity, 99.95%. Titanium Disulfide Powder (TiS2) from ...Missing: color | Show results with:color
[22]
Electrical properties of two-dimensional TiS2/V2O5 memristor with ...
Sep 24, 2025 · Considering that the decomposition temperature range of TiS2 is reported to be between 600 °C and 700 °C [47], it is inferred that both TiS2 ...
[23]
Electronic structure of TiS2 and its electric transport properties under ...
Mar 14, 2011 · ... band overlap of 0.5 eV. This value of band overlap agrees well with ... (Color online) (a) Calculated band structure of TiS2. View large ...INTRODUCTION · Band structure calculation · In situ Hall effect measurement...
[24]
Transport properties of V substituted TiS 2 - IOP Science
Transport properties of V substituted TiS2, C Levy-Clement, A Katty, A T ... The resistivity, Hall coefficient and magnetic susceptibility of pure and vanadium ...
[25]
Electronic and Optical Properties of TiS 2 Determined from ...
The optical properties of the material such as real and imaginary parts of dielectric constant (ε(ω)=ε1 (ω)+iε2 (ω)), refractive index n(ω), optical ...
[26]
Transition Metal Dichalcogenide TiS 2 Prepared by Hybrid Atomic ...
Dec 5, 2022 · Titanium Disulfide Coated Carbon Nanotube Hybrid Electrodes Enable High Energy Density Symmetric Pseudocapacitors. Adv. Mater. 2018, 30 ...
[27]
Thermoelectric properties of TiS2 mechanically alloyed compounds
... W): Toward Functionalization of the Conductive “Cu–S” Network. 2019, Advanced Energy Materials. Thermoelectric anisotropy and texture of intercalated TiS2.
[28]
Heat Capacities of Titanium Disulfide from 5.87 to 300.7 K
The heat capacity of tis2 was determined from 5.87 to 300.7 K by adiabatic calorimetry. The values at 298.5 K for cp deg, s deg (t)- s deg (o), ...
[29]
Magnetic and Electrical Properties of Cu, TiS2 - JPS Journals
We could not find any studies on magnetic property of. Cu,TiS2. In the present study, we prepare polycrystalline samples of Cu,TiS2, in which copper atoms are ...
[30]
Theoretical Study of the Mechanical Behavior of Individual TiS2 and MoS2 Nanotubes
### Mechanical Properties of TiS2 Nanotubes
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An in situ and ex situ TEM study into the oxidation of titanium (IV ...
Jul 10, 2017 · Titanium (IV) sulphide (TiS2) is a layered transition metal dichalcogenide, which we exfoliate using liquid phase exfoliation.
[32]
https://www.researchgate.net/publication/381916558_Elastic_Properties_of_TiS_2_Material_at_High_Pressure_Using_Pseudo-Potentials_Technique
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[PDF] Titanium Disulfide Coated Carbon Nanotube Hybrid Electrodes ...
Feb 1, 2018 · Both TiS2 composite–VACNT and pristine VACNT electrodes exhibit a 3 V stable operation window, while other electrodes have either broad redox ...
[34]
[PDF] Material Safety Data Sheet - LTS Research Laboratories
Jul 27, 2016 · Titanium sulfide (TiS2) is for scientific research, with chemical formula TiS2, 100 wt.%, and CAS # 12039-13-3.
[35]
A high pressure x-ray diffraction study of titanium disulfide
Dec 10, 2008 · We observed a phase transformation of TiS2 beginning at about 20.7 GPa. The structure of the high pressure phase needs further identification.Missing: transitions | Show results with:transitions
[36]
(PDF) Elastic Properties of TiS 2 Material at High Pressure, Using ...
Jul 2, 2024 · Our study investigates the effect of pressure within the range of 0 to 20 GPa on elastic properties of titanium disulfide (TiS2) using density ...
[37]
https://pubs.acs.org/doi/10.1021/acs.chemmater.9b02895
[38]
Control of low dimensionality in flexible hybrid inorganic-organic ...
Oct 13, 2021 · We grew TiS2 single crystal using excess sulfur rather than conventional iodine as a transport agent to avoid impurities. The obtained TiS2 ...
[39]
https://link.springer.com/article/10.1557/adv.2020.412
[40]
https://doi.org/10.1063/1.5032456
[41]
Titanium Disulphide (TiS2) Dichalcogenide Thin Films as Inorganic ...
Dec 29, 2020 · In this work we demonstrate an ab initio facile inexpensive scalable synthesis of transition metal dichalcogenide (TiS2) by electrodeposition ...
[42]
https://www.researchgate.net/publication/233706455_Fullerene-like_Nanoparticles_of_Titanium_Disulfide
[43]
https://doi.org/10.1039/B300054K
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(PDF) Fullerene-like Nanoparticles of Titanium Disulfide
Aug 7, 2025 · It was found that adding 1-2% IF-TiS2 improves the behavior of lubricating oil substantially. The improved performance of the additive was ...
[45]
https://pubs.acs.org/doi/10.1021/acs.langmuir.4c02515
[46]
https://doi.org/10.1002/anie.200250573
[47]
https://www.sciencedirect.com/science/article/abs/pii/S1388248117301996
[48]
[PDF] Nobel Lecture in Chemistry 2019: The Origins of the Lithium Battery
All of today's lithi- um-ion batteries rely on the original intercalation concept used in titanium disulfide. There are still many scientific opportunities to ...
[49]
Fabrication and All Solid-State Battery Performance of TiS2 ...
Mar 4, 2016 · The electrochemical reaction is as follows: TiS2 + Li+ + e− ⇄ LiTiS2; moreover, the theoretical capacity is 239 mAh g−1.
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Electrical Energy Storage and Intercalation Chemistry - Science
The electrochemical reaction of layered titanium disulfide with lithium, forming lithium titanium disulfide, is the basis of a new battery system.
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TiS2 as an Advanced Conversion Electrode for Sodium‐Ion ...
Sep 15, 2018 · It delivers a reversible capacity of 146 mAh g−1 at 0.1 C (1 C = 239 mA h g−1) with a stable cycling performance over 160 cycles.24 Li and ...Missing: nanotubes | Show results with:nanotubes
[52]
Bifunctional TiS2/CNT as efficient polysulfide barrier to improve the ...
Aug 15, 2020 · The large specific surface area from the nanostructured TiS2 provides sufficient active sites to anchor polysulfide and therefore suppress its ...
[53]
(PDF) Synthesis of TiS2 nanodiscs for supercapacitor application
A mixture of titanium and sulphur powders are blended before being transferred and sealed into an ampoule under a vacuum. It is then calcined using muffle ...
[54]
[PDF] High Performance Pseudocapacitor Based on 2D Layered Metal ...
Feb 5, 2015 · Lithium intercalation into B-TiS2 leads to a c-axis lattice expansion to 6.17 Å and an a-axis lattice expansion to 3.43 Å, which are consistent ...<|control11|><|separator|>
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(PDF) Titanium Disulphide (TiS2) Dichalcogenide Thin Films as ...
Aug 6, 2025 · In this work we demonstrate an ab initio facile inexpensive scalable synthesis of transition metal dichalcogenide (TiS2) by electrodeposition ...
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21.7% efficiency achieved in planar n–i–p perovskite solar cells via ...
21.7% efficiency achieved in planar n–i–p perovskite solar cells via interface engineering with water-soluble 2D TiS2. P. Huang, Q. Chen, K. Zhang, L. Yuan, Y.
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Engineering the electronic and magnetic properties of monolayer TiS
Dec 1, 2024 · Cr impurity is the most suitable candidates for magnetizing 2D TiS2. ... gap of 0.76 eV. Fig. 1(b) displays the corresponding projected ...
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Sulfur-vacancy rich nonstoichiometric TiS2−x/NiS heterostructures ...
Aug 5, 2022 · As a HER electrocatalyst, it features the overpotentials of only 63 and 134 mV at a current density of 10 mA cm−2 in 1.0 M KOH and 0.5 M H2 ...Missing: cm2 | Show results with:cm2
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(PDF) Inorganic fullerene-like nanoparticles of TiS2 - ResearchGate
Aug 8, 2025 · Inorganic closed-cage nanoparticles of TiS2 were synthesized using gas-phase synthesis. The reported nanoparticles are perfectly spherical ...
[60]
Boundary lubrication: Influence of the size and structure of inorganic ...
Dec 15, 2014 · The use of Inorganic Fullerene-like (IF) nanoparticles in lubricants has proved extremely effective to reduce friction and wear under severe boundary ...Missing: TiS2 | Show results with:TiS2
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Development of ultra-sensitive broadband photodetector: a detailed ...
We report an ultra-sensitive broadband photodetector based on horizontally aligned titanium disulfide nanosheets (TNs).Missing: thin | Show results with:thin
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Long-Term Stability of TiS2–Alkylamine Hybrid Materials - PMC - NIH
In this paper, we show that amine-intercalated TiS 2 prepared by a simple mechanochemical process is prone to chemical decomposition through sulfur exsolution.