Incorporation Of Ionic Liquid Research Articles

Constructing ether-rich and carboxylate hydrogen bonding sites in protic ionic liquids for efficient and simultaneous membrane separation of H2S and CO2 from CH4

Removing H2S and CO2 is of great significance for natural gas purification. With excellent gas affinity and tunable structure, ionic liquids (ILs) have been regarded as nontrivial candidates for fabricating polymer-based membranes. Herein, we firstly reported the incorporation of protic ILs (PILs) having ether-rich and carboxylate sites (ECPILs) into poly(ether-block-amide) (Pebax) matrix for efficient separation H2S and CO2 from CH4. Notably, the optimal permeability of H2S reaches up to 4310 Barrer (40 °C, 0.50 bar) in Pebax/ECPIL membranes, along with H2S CH4-1 and (H2S + CO2) CH4-1 selectivity of 97.7 and 112.3, respectively. These values are increased by 1125%, 160.8% and 145.9% compared to those in neat Pebax membrane. Additionally, the solubility and diffusion coefficients of the gases were measured, demonstrating that ECPIL can simultaneously strengthen the dissolution and diffusion of H2S and CO2, thus elevating the permeability and permselectivity. By using quantum chemical calculations and FT-IR spectroscopy, the highly reversible multi-site hydrogen bonding interaction between ECPILs and H2S was revealed, which is responsible for the fast permeation of H2S and good selectivity. Furthermore, H2S CO2-1 CH4-1 (3/3/94 mol%) ternary mixed gas can be efficiently and stably separated by Pebax/ECPIL membrane for at least 100 h. Overall, this work not only illustrates that PILs with ether-rich and carboxylate hydrogen bonding sites are outstanding materials for simultaneous removal of H2S and CO2, but may also provide a novel insight into the design of membrane materials for natural gas upgrading.

Two-Step Perovskite Solar Cells with > 25% Efficiency: Unveiling the Hidden Bottom Surface of Perovskite Layer.

While significant efforts in surface engineering have been devoted to the conversion process of lead iodide (PbI2) into perovskite and top surface engineering of perovskite layer with remarkable progress, the exploration of residual PbI2 clusters and the hidden bottom surface on perovskite layer have been limited. In this work, a new strategy involving 1-butyl-3-methylimidazolium acetate (BMIMAc) ionic liquid (IL) additives is developed and it is found that both the cations and the anions in ILs can interact with the perovskite components, thereby regulating the crystallization process and diminishing the residue PbI2 clusters as well as filling vacancies. The introduction of BMIMAc ILs induces the formation of a uniform porous PbI2 film, facilitating better penetration of the second-step organic salt and fostering a more extensive interaction between PbI2 and the organic salt. Surprisingly, the oversized residual PbI2 clusters at the bottom surface of the perovskite layer completely diminish. In addition, advanced depth analysis techniques including depth-resolved grazing-incidence wide-angle X-ray scattering (GIWAXS) and bottom thinning technology are employed for a comprehensive understanding of the reduction in residual PbI2. Leveraging effective PbI2 management and regulation of the perovskite crystallization process, the champion devices achieve a power conversion efficiency (PCE) of 25.06% with long-term stability.

Hybrid Hydrogen Bonding Strategy to Construct Instantaneous Self-Healing Highly Elastic Ionohydrogel for Multi-Functional Electronics.

Gels show great promise for applications in wearable electronics, biomedical devices, and energy storage systems due to their exceptional stretchability and adjustable electrical conductivity. However, the challenge lies in integrating multiple functions like elasticity, instantaneous self-healing, and a wide operating temperature range into a single gel. To address this issue, a hybrid hydrogen bonding strategy to construct gel with these desirable properties is proposed. The intricate network of hybrid strong weak hydrogen bonds within the polymer matrix enables these ionohydrogel to exhibit remarkable instantaneous self-healing, stretching up to five times their original length within seconds. Leveraging these properties, the incorporation of ionic liquids, water, and zinc salts into hybrid hydrogen bond crosslinked network enables conductivity and redox reaction, making it a versatile ionic skin for real-time monitoring of human movements and respiratory. Moreover, the ionohydrogel can be used as electrolyte in the assembly of a zinc-ion battery, ensuring a reliable power supply for wearable electronics, even in extreme conditions (-20°C and extreme deformations). This ionohydrogel electrolyte simplifies the diverse structural requirements of gels to meet the needs of various electronic applications, offering a new approach for multi-functional electronics.

Vibrational mode of low-dimensional ionic liquid bismuth hybrid perovskite probed by FTIR and Raman Spectroscopy

Bismuth-based hybrid organic-inorganic perovskites (Bi-HOIPs) are developed as lead-free halide perovskites due to their low toxicity and good stability. In this study, the incorporation of ionic liquid (IL) cations in the Bi-HOIPs structure, namely 1-butyl-1-methylpyrrolidinium (BMP) and 1-(3-aminopropyl) imidazole (API), are investigated. Bi-based HOIPs are kept in ambient conditions (20–25 °C) to compare the structural differences in FTIR and Raman spectra between pristine and aged samples. The FTIR and Raman spectra of all aged samples are slightly shifted after being retrieved at the ambient conditions for four months (∼below 45 cm−1). Our work paves the way in developing Bi-based HOIPs for solar cells and photodetectors applications.

Enhanced Sensing and Electromagnetic Interference Shielding Performance of Hydrogels by the Incorporation of Ionic Liquids

Enhanced Sensing and Electromagnetic Interference Shielding Performance of Hydrogels by the Incorporation of Ionic Liquids

Boosting the Performance of PEDOT:PSS Based Electronics Via Ionic Liquids.

The conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) offers superior advantages in electronics due to its remarkable combination of high electrical conductivity, excellent biocompatibility, and mechanical flexibility, making it an ideal material among electronic skin, health monitoring, and energy harvesting and storage. Nevertheless, pristine PEDOT:PSS films exhibit limitations in terms of both low conductivity and stretchability; while, conventional processing techniques cannot enhance these properties simultaneously, facing the dilemma that highly conductive interconnected PEDOT:PSS domains are susceptible to tensile strain. Via modifying PEDOT:PSS with ionic liquids (ILs), not only a synergistic enhancement of the electrical and mechanical properties can be achieved but also the requirements for the printable bioelectronic are satisfied. In this comprehensive review, the task of providing a thorough examination of the mechanisms and applications of ILs as modifiers for PEDOT:PSS is undertaken. First, the theoretical mechanisms governing the interactions between ILs and PEDOT:PSS are discussed in detail. Then, the enhanced properties and the elucidation of the underlying mechanisms achieved through the incorporation of ILs are reviewed. Next, specific applications of ILs-modified PEDOT:PSS relevant to bioelectronic devices are presented. Last, there is a concise summary and a discussion regarding the opportunities and challenges in this exciting field.

Understanding Polymerized Ionic Liquids as Solid Polymer Electrolytes for Sodium Batteries.

Solid polymer electrolytes (SPEs) have emerged as promising candidates for sodium-based batteries due to their cost-effectiveness and excellent flexibility. However, achieving high ionic conductivity and desirable mechanical properties in SPEs remains a challenge. In this study, we investigated an AB diblock copolymer, PS-PEA(BuImTFSI), as a potential SPE for sodium batteries. We explored binary and ternary electrolyte systems by combining the polymer with salt and [C3mpyr][FSI] ionic liquid (IL) and analyzed their thermal and electrochemical properties. Differential scanning calorimetry revealed phase separation in the polymer systems. The addition of salt exhibited a plasticizing effect localized to the polyionic liquid (PIL) phase, resulting in an increased ionic conductivity in the binary electrolytes. Introducing the IL further enhanced the plasticizing effect, elevating the ionic conductivity in the ternary system. Spectroscopic analysis, for the first time, revealed that the incorporation of NaFSI and IL influences the conformation of TFSI- and weakens the interaction between TFSI- and the polymer. This establishes correlations between anions and Na+, ultimately enhancing the diffusivity of Na ions. The electrochemical properties of an optimized SPE in Na/Na symmetrical cells were investigated, showcasing stable Na plating/stripping at high current densities up to 0.7 mA cm-2, maintaining its integrity at 70 °C. Furthermore, we evaluated the performance of a Na|NaFePO4 cell cycled at different rates (C/10 and C/5) and temperatures (50 and 70 °C), revealing remarkable high-capacity retention and Coulombic efficiency. This study highlights the potential of solvent-free diblock copolymer electrolytes for high-performance sodium-based energy storage systems, contributing to advanced electrolyte materials.

Unveiling the mechanisms behind high CO2 adsorption by the selection of suitable ionic liquids incorporated into a ZIF-8 metal organic framework: A computational approach

There is growing focus on the crucial task of effectively capturing carbon dioxide (CO2) from the atmosphere to mitigate environmental consequences. Metal-organic frameworks (MOFs) have been used to replace many conventional materials in gas separation, and the incorporation of ionic liquids (ILs) into porous MOFs has shown promise as a new technique for improving CO2 capture and separation. However, the driving force underlying the electronic modulation of MOF nanostructures and the mechanisms behind their high CO2 adsorption remain unclear. This study reports the effect of encapsulating different imidazolium ILs in porous ZIF-8, to clarify the adsorption mechanism of CO2 using density functional theory (DFT)-based approaches. For this purpose, a range of anions, including bis(trifluoromethylsulfonyl)imide [NTf2], methanesulfonate [MeSO3], and acetate [AC], were combined with the 1-ethyl-3-methylimidazolium [EMIM]+ cation. [EMIM]+-based ILs@ZIF-8 composites were computationally investigated to identify suitable materials for CO2 capture. First, the intermolecular and intramolecular interactions between [EMIM]+ and different anions were examined in detail, and their effects on CO2 adsorption were explored. Subsequently, the integration of these ILs into the ZIF-8 solid structure was studied to reveal how their interactions influenced the CO2 adsorption behavior. Our results demonstrate that the incorporation of ILs strongly affects the adsorption capability of CO2, which is highly dependent on the nature of the ILs inside the ZIF-8 framework. DFT simulations further confirmed that the incorporation of ILs into ZIF-8 led to superior CO2 capture compared to isolated ILs and pristine ZIF-8. This improvement was attributed to the mutual interactions between the ILs and ZIF-8, which effectively fine-tuned CO2 adsorption within the composite structure. This understanding may act as a general guide for gaining more insight into the interfacial interactions between ILs and ZIFs structures and how these molecular-level interactions can help predict the selection of ILs for CO2 adsorption and separation, thereby addressing environmental challenges with greater precision and effectiveness.

Exploring the compositional space of a metal–organic framework with ionic liquids to develop porous ionic conductors for enhanced signal and selectivity in VOC capacitive sensors

Incorporation of ionic liquids into ZIF-8 pores to obtain solid-ionic conductors that work as active layers in printed gas capacitive sensors to detect water and non-methane volatile organic vapours.

A comprehensive study on transport behaviour and physicochemical characteristics of PU/based 3-phase mixed matrix membranes: Effect of [HNMP][HSO4] ionic liquid and ZnO nanoparticles

The gas separation industry has witnessed a significant focus on mixed matrix membranes (MMMs) due to their exceptional potential, surpassing the performance of conventional polymeric membranes. This study aimed to develop and evaluate MMMs using polyurethane (PU) as the polymer matrix and zinc oxide (ZnO) and ionic liquids (ILs) as fillers. PU/ZnO, PU/IL, and PU/ZnO/IL MMMs were prepared utilizing the dry-phase inversion method, and their efficacy in separating CO2, CH4, and N2 gases was investigated under various conditions. A comprehensive characterization protocol using FTIR, FESEM, TGA, AFM, and tensile testing was employed for their thorough characterization. The membranes’ transport properties were assessed at different pressures and filler concentrations. Results showed that IL incorporation increased gas permeability by enhancing solubility, diffusion, ionic interactions, swelling, and accessible volume. Incorporating ZnO and IL particles in the PU matrix simultaneously improved transport properties, particularly selectivity. Robeson’s diagram analysis shows that the PU/0.5%ZnO/2%IL MMM performed best. Furthermore, molecular simulation methods, including Monte Carlo and molecular dynamics simulations, assessed adsorption isotherms and physicochemical properties such as free volume, density, and X-ray diffraction. Simulation outcomes were highly reliable with experimental results, affirming the results’ efficiency and validation. Overall, this study demonstrated the efficiency of using ZnO and IL in the MMMs, highlighting their potential in gas separation applications.

Novel chitosan-ionic liquid immobilized membranes for PEM fuel cells operating above the boiling point of water

Novel chitosan (CS) composite membranes modified with ionic liquids (ILs), namely, 1-Hexyl-3- methylimidazolium tricyanomethanide ([HMIM][TCM]), Diethylmethylammonium methanesulfonate ([DEMA][OMs]), were synthesized to be used as a polymer electrolyte membrane (PEM) in for PEM fuel cells. The ionic conductivities of the prepared membrane samples were evaluated using electrochemical impedance spectroscopy (EIS). The CS is one of the attractive choices of green and sustainable membrane materials in PEMs because of its chemical tunability and cost-effectiveness. The membranes were prepared by solution casting followed by a solvent evaporating procedure. The low proton conductivity of pristine CS biopolymer was enhanced by the incorporation of ILs in the membrane framework. Tensile testing confirmed the excellent membrane mechanical integrity. A significant enhancement in the membranes’ characteristics was observed upon the introduction of [DEMA][OMs] into its matrix. The experimental results showed enhanced proton conductivities of the prepared membranes along with enhanced flexibility. The proton conductivity of pristine CS membrane was increased from 8.4 × 10−4 to 1.25 × 10−2 S/cm and 1.1 × 10−2 S/cm when a 30 wt% [HMIM][TCM] and 100 wt% [DEMA][OMs] were added, respectively. Synergistic effects of amine and imidazolium-based ILs on the electrical, structural, water uptake, and thermal properties of CS-based biopolymer solid electrolyte membranes are reported for the first time in this work. The aforementioned characterization results demonstrate the potential of using these membranes in PEM fuel cells operating above the boiling point of water and at a lower cost. This work showed that there should be an optimization amount of the ILs content in the membrane to maintain its mechanical integrity.

Synthesis and properties of a novel ionic liquid copolymer shale inhibitor

AbstractAs oil reserves in shallow wells continue to deplete, the drilling industry must shift its focus toward extracting oil from deeper and more complex formations. Water‐based drilling fluid inhibitors are currently limited in their ability to withstand high temperatures. In the current work, for the first time, the application of 1‐vinyl‐3‐ethylimidazolium bromide salt‐allyl alcohol polyoxyethylene ether‐2‐acrylamide‐2‐methylpropanesulfonic acid (PIAA) as the shale inhibitor is reported. The incorporation of ionic liquids has made PIAA promising to be an effective shale inhibitor for high‐temperature‐tolerant water‐based drilling fluids. The high‐temperature resistance (300°C) of PIAA was verified through thermogravimetric test. Through mud ball, shale rolling recovery, and linear swelling experiments, we found that PIAA yielded the lowest swelling rate (27.3%) in the 24‐h linear swelling rate test, as compared to HMA‐15 (46.1%) and FA‐367 (31.2%). This confirmed the superior corrosion inhibition performance of PIAA. In addition, we investigated the inhibition mechanism using Zeta potential and other tests. Bentonite inhibition can be achieved through the coating of bentonite particles by PIAA, which effectively plugs shale pores, neutralizes negative charges on the surface of bentonite particles, and adsorbs them onto particle surfaces. Overall, PIAA has excellent high‐temperature resistance and inhibition properties.

Addressing the Stability Challenge of Perovskite Solar Cells: The Potential of Ionic Liquid Incorporation for Improved Device Durability

Perovskite solar cells (PSCs) have emerged as a promising technology for renewable energy generation due to their low cost and low carbon footprint compared to traditional silicon-based solar cells. However, some main challenges associated with PSCs lie ahead, namely their toxicity and lack of stability, particularly under factors such as light, temperature, oxygen, and humidity. We focus on the lack of stability of PSCs and the various ways it can be mitigated. We explore the use of vapor deposition methods, which can increase the crystallinity of the perovskite and thus improve stability and lifetime. Furthermore, we look into the potential of ionic liquids (ILs) as promising materials for improving the stability and performance of PSCs. ILs have advantageous physicochemical properties that make them suitable as an additive or interfacial layer in PSCs. They optimize the interface contact, improve energy level matching, suppress ion migration, and increase hydrophobicity, which inhibits the decomposition of the device in humid environments. ILs have also been used as precursors in the solution-based fabrication of perovskite thin films for PSC applications, assisting in the perovskite crystallization. Several studies have shown that the incorporation of ILs in PSCs can increase stability, lifetime, and efficiency. Overall, the existing research indicates that ILs hold great promise as materials for improving the stability and performance of PSCs, which could have significant implications for the development of low-cost, renewable energy technologies.

Bio-based hybrid nanocomposites as multifunctional sustainable materials for stone conservation

This study was aimed at developing a sustainable versatile bio-based epoxy-silica material to be potentially employed as hydrophobic and biocidal consolidating product in the field of stone conservation. For this purpose, two hybrid formulations containing 2,2,4,4-tetramethyl-1,3-cyclobutanediol diglycidylether (CBDO-DGE), a cycloaliphatic epoxy precursor derived from the arnica root, together with (3-glycidyloxypropyl)trimethoxysilane (GPTMS) and octyltriethoxysilane (OcTES) as silica-forming additives, were chosen as the basis of the multifunctional material to be finely adjusted and gain biocidal properties. With this goal in mind, different synthetic strategies based on ionic liquids (ILs), essential oils (EOs) and nanoparticles (NPs) doping have been employed. Specifically, dimethyloctadecyl[3(trimethoxysilyl)propyl]ammonium chloride (QAS), tetradecyl phosphonium chloride (QPS) and thymol, as well as cerium-TiO2 NPs and thymol-loaded SiO2 NPs were incorporated into the starting hybrid formulations, during the sol-gel process, to investigate their influence on the network formation. First, distribution studies by scanning electron microscopy/energy-dispersive X-ray (SEM-EDS) analysis were performed, whereas the suitability of each formulation to match the main requirements for a stone conservation material was evaluated in terms of thermostability, hydrophobicity and inhibition of the microbiological growth by a combination of TG-DTA, DSC, dynamic mechanical analysis (DMA), with contact angle and disk-diffusion measurements, respectively. Based on the data analysis, it was observed that the direct incorporation of ILs and EOs had an adverse effect on the ability of GPTMS to act as a coupling agent. This resulted in decreased thermal stability and a 50 % reduction in glass transition temperatures, along with the retention of hydrophilic behavior. In contrast, the inclusion of NPs did not significantly interfere with the hybrid network formation, and effectively maintained the thermo-mechanical and hydrophobic properties of the hybrids within satisfactory parameters. Consequently, both nanocomposite materials were further tested on stone samples by artificial ageing experiments under acidic atmosphere. In view of the results, the hybrid enriched with thymol-loaded SiO2 NPs demonstrate the most suitable thermo-mechanical and hydrophobic properties (Tonset, Tα and CA values of 276 °C, 54 °C and 100°, respectively), as well as a proper biocidal capability against bacteria. Furthermore, the developed material provided effective stone protection, resulting in a 92 % reduction in material loss, while preserving the substrate chromatic characteristics (ΔE 2.23). These findings suggest that the proposed treatment meets the first main requirements for stone conservation.

Nonlinear dynamics of ionic liquid enhanced soft composite membrane under electro-mechanical loading

The incorporation of ionic liquids (ILs) into dielectric elastomer composites has attracted significant interest due to their potential applications in soft actuators and optical devices. Their soft and hyperelastic nature make them a distinct dynamic. In this paper, nonlinear dynamics of IL enhanced soft composite (ILESC) dielectric membrane subjected to electro-mechanical loading is investigated. A mixed micromechanical model with the incorporation of an electric double layer (EDL) and Maxwell-Wagner-Sillars (MWS) polarization is developed to estimate mechanical and electrical properties of the ILESC. Governing equations are derived via an energy method with the framework of the hyperelastic membrane theory, Neo-Hookean constitutive model and the couple dielectric theory. These equations are discretized by Taylor series expansion (TSE) and differential quadrature (DQ) methods and are solved by incremental harmonic balance (IHB) method combined with arc-length technique. The developed model and results are verified by comparing to experimental data and previous results. The influence of volume fraction, shape and size of IL fillers, static and dynamic applied electric field and excitation amplitude on forced vibration and resonant response of the ILESC membrane are comprehensively analyzed. It is found that ILESC membrane with slender ellipsoidal ILs displays larger amplitude, lower peak amplitude frequency and more obvious softening behavior.

The Effect of Ionic Liquids Incorporation on the Self-healing Behavior of the Bitumen

The Effect of Ionic Liquids Incorporation on the Self-healing Behavior of the Bitumen

Different Approaches for the Preparation of Composite Ionic Liquid-Based Membranes for Proton Exchange Membrane Fuel Cell Applications—Recent Advancements

The use of ionic liquid-based membranes as polymer electrolyte membranes for fuel cell applications increases significantly due to the major features of ionic liquids (i.e., high thermal stability and ion conductivity, non-volatility, and non-flammability). In general, there are three major methods to introduce ionic liquids into the polymer membrane, such as incorporating ionic liquid into a polymer solution, impregnating the polymer with ionic liquid, and cross-linking. The incorporation of ionic liquids into a polymer solution is the most common method, owing to easy operation of process and quick membrane formation. However, the prepared composite membranes suffer from a reduction in mechanical stability and ionic liquid leakage. While mechanical stability may be enhanced by the membrane’s impregnation with ionic liquid, ionic liquid leaching is still the main drawback of this method. The presence of covalent bonds between ionic liquids and polymer chains during the cross-linking reaction can decrease the ionic liquid release. Cross-linked membranes reveal more stable proton conductivity, although a decrease in ionic mobility can be noticed. In the present work, the main approaches for ionic liquid introduction into the polymer film are presented in detail, and the recently obtained results (2019–2023) are discussed in correlation with the composite membrane structure. In addition, some promising new methods (i.e., layer-by-layer self-assembly, vacuum-assisted flocculation, spin coating, and freeze drying) are described.

Strain Regulation via Pseudo Halide‐Based Ionic Liquid toward Efficient and Stable α‐FAPbI3 Inverted Perovskite Solar Cells

AbstractInverted (p‐i‐n) perovskite solar cells have drawn great attention due to their outstanding stability and low‐temperature processibility. However, their power conversion efficiency (PCE) still lags behind conventional (n‐i‐p) devices mainly due to the lack of strategies to stabilize α‐FAPbI3 without changing the bandgap. In this work, a facile and effective strategy is reported to regulate the residual strain via pseudo halide‐based ionic liquids incorporation to stabilize α‐FAPbI3 perovskite in inverted perovskite solar cells (PVSCs). The employment of methylamine formate (MAFa) ionic liquid enables a homogenously stronger compressive strain to restrain the transition of shared‐corner PbI6 octahedron into shared‐face δ‐FAPbI3, as well as affecting the dynamic behavior of carriers and defects to achieve a record PCE (24.08%) among the reported inverted FAPbI3 perovskite solar cells up to now. In addition, the MAFa incorporation results in enhanced device stability, unencapsulated PVSC retains over 90% of its initial efficiency after stored in ambient environment (RH:30 ± 5%) for 1000 h. This work provides an efficient strategy to realize efficient and stable α‐FAPbI3 based inverted PVSCs to further catch up with the conventional ones.

Cooperative Proton and Li-ion Conduction in a 2D-layered MOF via Mechanical Insertion of Lithium Halides.

Ionic conduction in highly designable and porous metal-organic frameworks has been explored through the introduction of various ionic species (H+, OH-, Li+, etc.) using post-synthetic modification such as acid, salt, or ionic liquid incorporation. Here, we report on high ionic conductivity (σ > 10-2 S cm-1) in a two-dimensionally (2D)-layered Ti-dobdc (Ti2(Hdobdc)2(H2dobdc), H4dobdc: 2,5-dihydroxyterephthalic acid) via LiX (X= Cl, Br, I) intercalation using mechanical mixing. The anionic species in lithium halide strongly affect the ionic conductivity and durability of conductivity. Solid-state pulsed-field gradient nuclear magnetic resonance (PFG-NMR)verified the high mobility of H+ and Li+ ions in the temperature range of 300-400 K. In particular, the insertion of Li salts improved the H+ mobility above 373 K owing to strong binding with H2O. Furthermore, the continuous increase in Li+ mobility with temperature contributed to the retention of the overall high ionic conductivity at high temperatures.

Cooperative Proton and Li‐ion Conduction in a 2D‐Layered MOF via Mechanical Insertion of Lithium Halides

AbstractIonic conduction in highly designable and porous metal–organic frameworks has been explored through the introduction of various ionic species (H+, OH−, Li+, etc.) using post‐synthetic modification such as acid, salt, or ionic liquid incorporation. Here, we report on high ionic conductivity (σ>10−2 S cm−1) in a two‐dimensionally (2D)‐layered Ti‐dobdc (Ti2(Hdobdc)2(H2dobdc), H4dobdc: 2,5‐dihydroxyterephthalic acid) via LiX (X=Cl, Br, I) intercalation using mechanical mixing. The anionic species in lithium halide strongly affect the ionic conductivity and durability of conductivity. Solid‐state pulsed‐field gradient nuclear magnetic resonance (PFG NMR ) verified the high mobility of H+ and Li+ ions in the temperature range of 300–400 K. In particular, the insertion of Li salts improved the H+ mobility above 373 K owing to strong binding with H2O. Furthermore, the continuous increase in Li+ mobility with temperature contributed to the retention of the overall high ionic conductivity at high temperatures.