Intercalation Of Cations Research Articles

Single modular flow-electrode capacitive deionization using modified Prussian blue analogues as cation intercalation electrode for continuous water desalination.

Ion back-diffusion hinders the practical application of conventional flow-electrode capacitive deionization (FCDI) under long-term operational conditions. To address this challenge, the present study integrated cation intercalation deionization (CID) with FCDI. A novel PFCDI-CID system was developed by utilizing a modified Prussian blue analogues owing to their enhanced rheological and electrochemical properties. The PFCDI-CID system achieved a high charge efficiency of 89.77% and an energy-normalized removal salt of 0.69 mol kJ-1 in single-cycle (SC) mode with the flow electrodes mass fraction of 2% and a desalinized water chamber-to-concentrated saline water chamber ratio of 2:1. Furthermore, under continuous operation for 12 h in SC mode, the PFCDI-CID system maintained stable desalination performance within the first 2 h. Over an extended duration, the average charge efficiency of the PFCDI-CID system was maintained at 88.44%, with an average energy-normalized removal salt of 0.65 mol kJ-1. The mechanism revealed that the desalination process involving the Prussian blue analogues primarily involves Na+ intercalation, accompanied by a small amount of electro-sorption process. This system exhibits the characteristics of conventional FCDI while enabling desalination and concentration of simulated saline water during brine discharge, thereby mitigating the impact of ion back-diffusion and broadening the application scope of FCDI.

Spin-Phonon Coupling and Magnetic Transition in an Organic Molecule Intercalated Cr2Ge2Te6.

The manipulation of spin-phonon coupling in both formations and explorations of magnetism in two-dimensional van der Waals ferromagnetic semiconductors facilitates unprecedented prospects for spintronic devices. The interlayer engineering with spin-phonon coupling promises controllable magnetism via organic cation intercalation. Here, spectroscopic evidence reveals the intercalation effect on the intrinsic magnetic and electronic transitions in quasi-two-dimensional Cr2Ge2Te6 using tetrabutyl ammonium (TBA+) as the intercalant. The temperature evolution of Raman modes, Eg3 and Ag1, along with the magnetization measurements, unambiguously captures the enhancement of the ferromagnetic Curie temperature in the intercalated heterostructure. Moreover, the Eg4 mode highlights the increased effect of spin-phonon interaction in magnetic-order-induced lattice distortion. Combined with the first-principle calculations, we observed a substantial number of electrons transferred from TBA+ to Cr through the interface. The interplay between spin-phonon coupling and magnetic ordering in van der Waals magnets appeals for further understanding of the manipulation of magnetism in layered heterostructures.

Defect engineering and in-situ electrochemical oxidation promote lattice reconstruction of VO2 for boosting the energy storage of aqueous zinc-ion batteries

Finding a cathode with high capacity and rate performance is very important for the large-scale application of low-cost and safe aqueous zinc-ion batteries (AZIBs). In this work, VO2 containing oxygen rich vacancies (VO) was designed through fine regulation of the hydrothermal reaction, which was mainly due to the escape of crystalline water in the material. The rich oxygen vacancies in VO will adsorb water molecules in electrolyte and have redox reaction with water molecules, thus promoting the in-situ lattice reconstruction process. On the first charge of in-situ electrochemical oxidation process, VO undergoes a complete phase transition to an oxygen-deficient V2O5/V2O5·nH2O (O-VO), allowing subsequent (de)intercalation of zinc cations on the basis of the latter structure. The electrode thus has significant rate performance (376 mAh/g at 20 A/g). The energy density/power density at 20 A/g is 274 Wh kg−1/14550 W kg−1. This work provides fundamental insights into the formation of oxygen vacancies in materials, and for the first time combines defect engineering with in-situ electrochemical oxidation strategies, providing an innovative design strategy for constructing cathodes with high-rate capacity and high energy storage.

Convergent Intercalation of Tetrahexyl Ammonium and Spiro-bipyrrolidinium Cations into Graphite Electrodes from Propylene Carbonate

Convergent Intercalation of Tetrahexyl Ammonium and Spiro-bipyrrolidinium Cations into Graphite Electrodes from Propylene Carbonate

Intercalation based synthesis of Chevrel phase superconductors

This work focuses on the superconducting and magnetic properties of Chevrel phase (CP) compounds (Cu2Mo6S8 and Ni2Mo6S8) processed via a novel self-propagating high-temperature synthesis (SHS) method involving ternary cation intercalation in MoS2 high-temperature polymorphs. Green pellets of the precursor materials sealed under vacuum and exposed to 1050 °C or 1200 °C rapidly transformed from a powder mixture into submicron CPs within minutes. X-ray diffraction analysis confirmed the presence of Cu2Mo6S8 CP (67%), and Ni2Mo6S8 (93%). This group has illustrated the first time CP were formed at low energy cost and full stoichiometry. Magnetization versus temperature data obtained for the samples under different field conditions confirmed the superconducting behavior of the Cu–CP at a critical temperature of 8.3 K. The Ni–CP behaved as a superparamagnetic at low temperature (4.2 K). The results of this work suggest that the novel SHS process offers a viable scalable synthesis route for the Chevrel family of compounds and that it is worth exploring the functional applications of the new compounds of this material system.

Fabrication of red-emitting perovskite LEDs by stabilizing their octahedral structure.

Light-emitting diodes (LEDs) based on metal halide perovskites (PeLEDs) with high colour quality and facile solution processing are promising candidates for full-colour and high-definition displays1-4. Despite the great success achieved in green PeLEDs with lead bromide perovskites5, it is still challenging to realize pure-red (620-650 nm) LEDs using iodine-based counterparts, as they are constrained by the low intrinsic bandgap6. Here we report efficient and colour-stable PeLEDs across the entire pure-red region, with a peak external quantum efficiency reaching 28.7% at 638 nm, enabled by incorporating a double-end anchored ligand molecule into pure-iodine perovskites. We demonstrate that a key function of the organic intercalating cation is to stabilize the lead iodine octahedron through coordination with exposed lead ions and enhanced hydrogen bonding with iodine. The molecule synergistically facilitates spectral modulation, promotes charge transfer between perovskite quantum wells and reduces iodine migration under electrical bias. We realize continuously tunable emission wavelengths for iodine-based perovskite films with suppressed energy loss due to the decrease in bond energy of lead iodine in ionic perovskites as the bandgap increases. Importantly, the resultant devices show outstanding spectral stability and a half-lifetime of more than 7,600 min at an initial luminance of 100 cd m-2.

Intercalation of quaternary ammonium cations as a key factor of electron storage in MoS2 thin films

Electrochemical intercalation of cations within two-dimensional transition metal dichalcogenides presents a promising route for tailoring their optoelectronic properties. We have now succeeded in modulating the optical properties of MoS2 thin films through electrochemical intercalation of quaternary ammonium cations. The spectroelectrochemical experiments conducted with varying sizes of the intercalant revealed the size-dependent stability of the intercalated MoS2 nanosheets. The observed absorption change of the exciton bands is reversible and arises from the storage of electrons in MoS2 nanosheets and the subsequent weakening of interlayer van der Waals interactions following cation intercalation. This structural change is evidenced by the emergence of A*1g out-of-plane Raman mode. Additionally, the photoelectron spectroscopy reveals the emergence of a lower binding energy component of Mo 3d and the shift in Fermi level to higher energies, confirming the presence of stored electrons in cation intercalated-MoS2. The underlying mechanism of intercalation-induced property modifications in MoS2 discussed in the present study is useful in developing strategies for energy conversion devices.

Two-Dimensional Lead Halide Perovskites with Spirocyclic Intercalating Cations

Two-Dimensional Lead Halide Perovskites with Spirocyclic Intercalating Cations

Two-Dimensional MoS2 Nanosheets Derived from Cathodic Exfoliation for Lithium Storage Applications.

The preparation of 2H-phase MoS2 thin nanosheets by electrochemical delamination remains a challenge, despite numerous efforts in this direction. In this work, by choosing appropriate intercalating cations for cathodic delamination, the insertion process was facilitated, leading to a higher degree of exfoliation while maintaining the original 2H-phase of the starting bulk MoS2 material. Specifically, trimethylalkylammonium cations were tested as electrolytes, outperforming their bulkier tetraalkylammonium counterparts, which have been the focus of past studies. The performance of novel electrochemically derived 2H-phase MoS2 nanosheets as electrode material for electrochemical energy storage in lithium-ion batteries was investigated. The lower thickness and thus higher flexibility of cathodically exfoliated MoS2 promoted better electrochemical performance compared to liquid-phase and ultrasonically assisted exfoliated MoS2, both in terms of capacity (447 vs. 371 mA·h·g-1 at 0.2 A·g-1) and rate capability (30% vs. 8% capacity retained when the current density was increased from 0.2 A·g-1 to 5 A·g-1), as well as cycle life (44% vs. 17% capacity retention at 0.2 A·g-1 after 580 cycles). Overall, the present work provides a convenient route for obtaining MoS2 thin nanosheets for their advantageous use as anode material for lithium storage.

Comparative Retention Analysis of Intercalated Cations Inside the Interlayer Gallery of Lamellar and Nonlamellar Graphene Oxide Membranes in Reverse Osmosis Process: A Molecular Dynamics Study.

Over the past decade, multilayered graphene oxide (GO) membranes have emerged as promising candidates for desalination applications. Despite their potential, a comprehensive understanding of separation mechanisms remains elusive due to the intricate morphology and structural arrangement of interlayer galleries. Moreover, a critical concern of multilayered GO membranes is their susceptibility to swelling within aqueous environments, which hinders their practical implementation. Therefore, this study introduces cation intercalation within GO laminates to elucidate the underlying factors governing swelling behavior and subsequently mitigate it. Moreover, this study performed nonequilibrium molecular dynamics simulations on the cation (Mg2+ or K+)-intercalated lamellar and nonlamellar GO membranes to understand the effect of the arrangement of GO sheets on the retention time of intercalated cations within GO layers, water permeance, and salt rejection mechanism in the reverse osmosis process using cation-intercalated GO membranes. Our results highlight that lamellar GO membranes exhibit higher water permeance, attributed to their well-defined interlayer gallery structure. On the other hand, nonlamellar GO membranes display superior salt rejection due to their complex interlayer gallery structure that impedes salt permeation. Moreover, the structural complexity of nonlamellar GO membranes contributes to greater stability by retention of the more intercalated cations for a longer time within the layers. Furthermore, it is observed that a higher percentage of Mg2+ cations remained inside the GO laminates as compared to K+ cations, hence resulting in the greater stability of the Mg2+-intercalated GO membrane in the aqueous environment.

Dual–ion symmetric hybrid supercapacitor built by vanadium oxide with expanded interlayers: The intercalation of cation–anion pair and reversible redox of anion excited by Al3+

The development of aluminum ion batteries (AIBs) is retarded by the low capacity of intercalation cathode and ineffective aluminum dissolution/deposition at Al anode. To solve the issues, benzoquinone(BQ)–preinserted hydrated vanadium oxide formulated as (BQ)0.04V2O5·0.87H2O (BQ-VO) with a large interlayer spacing of 13.3 Å was synthesized, which was used as both cathode and anode with Al(ClO4)3 acetonitrile (AN) electrolyte to fabricate a symmetric aluminum–ion supercapacitor. BQ-VO delivers a large capacity of ~152 mAh g−1 at 0.2 A g−1 in the range of 0–1.5 V, which is associated with the intercalation of ion (such as ClO4−, Al3+ or Al3+ − ClO4− pair) into BQ-VO and the reversible redox reaction of ClO4− ↔ Cl−, giving rise to a novel symmetric dual–ion hybrid supercapacitor. The reversible conversion of ClO4− ↔ Cl− is not observed in NaClO4 AN electrolyte, which is only excited by Al3+, leading to a continuous increasing capacity in the early stage of the cycling test. On the contrary, in the NaClO4 AN electrolyte, BQ-VO illustrates a surface-controlled capacitive performance with excellent cycling stability. Molecular dynamic (MD) simulations reveal that Al3+ and Na+ possess different solvation/anion sheaths, leading to different electrochemical performances of BQ-VO in the Al(ClO4)3 and NaClO4 electrolytes. The present work provides a routine to utilize the redox reaction of halide for energy storage.

Shielding Mn3+ Disproportionation with Graphitic Carbon-Interlayered Manganese Oxide Cathodes for Enhanced Aqueous Energy Storage System.

Manganese dioxide (MnO2) materials have recently garnered attention as prospective high-capacity cathodes, owing to their theoretical two-electron redox reaction in charge storage processes. However, their practical application in aqueous energy storage systems faces a formidable challenge: the disproportionation of Mn3+ ions, leading to a significant reduction in their capacity. To address this limitation, the study presents a novel graphitic carbon interlayer-engineered manganese oxide (CI-MnOx) characterized by an open structure and abundant defects. This innovative material serves several essential functions for efficient aqueous energy storage. First, a graphitic carbon layer coats the MnOx molecular interlayer, effectively inhibiting Mn3+ disproportionation and substantially enhancing electrode conductivity. Second, the phase variation within MnOx generates numerous crystal defects, vacancies, and active sites, optimizing electron-transfer capability. Third, the flexible carbon layer acts as a buffer, mitigating the volume expansion of MnOx during extended cycling. The synergistic effects of these features result in the CI-MnOx exhibiting an impressive high capacity of 272 mAh g-1 (1224 F g-1) at 0.25 A g-1. Notably, the CI-MnOx demonstrates zero capacity loss after 90000 cycles (≈3011h), an uncommon longevity for manganese oxide materials. Spectral characterizations reveal reversible cation intercalation and conversion reactions with multielectron transfer in a LiCl electrolyte.

UV to NIR Broadband Flexible Photodetector Based on Solution‐Processed MoS2/PDPP3T Inorganic–Organic Hybrid Heterostructures

AbstractMolybdenum disulfide (MoS2) is a 2D material with excellent electrical and optical properties, and developing a universal technology for the preparation of high‐performance MoS2‐based photodetector is extremely desirable. Here, a UV to NIR broadband flexible photodetector based on MoS2/(PDPP3T) inorganic–organic hybrid heterostructures is reported. In the experiment, high crystalline 2H‐phase few‐layer MoS2 nanoflakes are first prepared by optimized electrochemical intercalation of tetraheptylammonium cation (THA+) and ultrasound‐assisted exfoliation strategy. Thereafter, a narrow bandgap organic semiconductor PDPP3T is introduced to construct the MoS2/Poly(diketopyrrolopyrrolothiophrn) (PDPP3T) heterojunction. Experimental results reveal that the photodetector can have broadband photo response from 380 to 980 nm. Meanwhile, excellent responsivities and detectivity of 12.4 mA W−1, 2.2 × 1010 Jones at 380 nm and 0.1 mA W−1 and 5 × 108 Jones at 980 nm are achieved, which are ≈10 (UV band)/100 (NIR band) times high than that obtained on the pure MoS2‐based detector. Moreover, the flexibility of the device is investigated by conformal covering the device on a curved surface (R = 5 and 2.5 mm), it shows that the photo response remains almost the same as that measured on the planar substrate, indicating the possible application in the wearable electronics.

Anion–Cation Competition Chemistry for Comprehensive High‐Performance Prussian Blue Analogs Cathodes

AbstractThe extensively studied Prussian blue analogs (PBAs) in various batteries are limited by their low discharge capacity, or subpar rate etc., which are solely reliant on the cation (de)intercalation mechanism. In contrast to the currently predominant focus on cations, we report the overlooked anion‐cation competition chemistry (Cl−, K+, Zn2+) stimulated by high‐voltage scanning. With our designed anion‐cation combinations, the KFeMnHCF cathode battery delivers comprehensively superior discharge performance, including voltage plateau >2.0 V (vs. Zn/Zn2+), capacity >150 mAh g−1, rate capability with capacity maintenance above 96 % from 0.6 to 5 A g−1, and cyclic stability exceeding 3000 cycles. We further verify that such comprehensive improvement of electrochemical performance utilizing anion‐cation competition chemistry is universal for different types of PBAs. Our work would pave a new and efficient road towards the next‐generation high‐performance PBAs cathode batteries.

Anion-Cation Competition Chemistry for Comprehensive High-Performance Prussian Blue Analogs Cathodes.

The extensively studied Prussian blue analogs (PBAs) in various batteries are limited by their low discharge capacity, or subpar rate etc., which are solely reliant on the cation (de)intercalation mechanism. In contrast to the currently predominant focus on cations, we report the overlooked anion-cation competition chemistry (Cl-, K+, Zn2+) stimulated by high-voltage scanning. With our designed anion-cation combinations, the KFeMnHCF cathode battery delivers comprehensively superior discharge performance, including voltage plateau >2.0 V (vs. Zn/Zn2+), capacity >150 mAh g-1, rate capability with capacity maintenance above 96 % from 0.6 to 5 A g-1, and cyclic stability exceeding 3000 cycles. We further verify that such comprehensive improvement of electrochemical performance utilizing anion-cation competition chemistry is universal for different types of PBAs. Our work would pave a new and efficient road towards the next-generation high-performance PBAs cathode batteries.

Dual-active centers of porous triazine frameworks for efficient Li storage

Integrating n-type and p-type redox-active centers into porous frameworks is an efficient approach to simultaneously mitigate the intrinsic problems of poor utility, low output voltage, and sluggish kinetics of organic electrodes for lithium ion batteries (LIBs). However, it is challenging to achieve an optimal utilization of the well-defined ordered porous structure and the multiple active centers due to the stacking structure of conventional covalent organic frameworks. Herein, we develop a post-modification approach to synthesize a bipolar pyrene-4,5,9,10-tetraone based porous covalent triazine frameworks (CTFs) for efficient dual-ion storage. The post-modification method successfully protects the active carbonyl groups under harsh conditions and effectively exposes the redox centers. The amorphous phase dominated CTFs enables excellent Li+ diffusion and high utilization of active sites, leading to ultrahigh specific capacity of 351 mAh/g at 0.2 A/g and impressive stability for 3000 cycles at 5.0 A/g. Moreover, the efficient dual-ion storage mechanism was confirmed by the in-depth investigation with ex situ FT-IR, and XPS study. Theoretical calculations also unveil the unique energy storage pathway using both p-doped and n-doped states for the intercalation of anions and cations. This work highlights the significance of the integrating strategy which allows the combination of dual-active-center with conjugated porous structure, broadening the avenues of organic electrode materials towards high-performance LIBs.

Revealing the role of calcium ion intercalation of hydrated vanadium oxides for aqueous zinc-ion batteries

Exploring suitable high-capacity V2O5-based cathode materials is essential for the rapid advancement of aqueous zinc ion batteries (ZIBs). However, the typical problem of slow Zn2+ diffusion kinetics has severely limited the feasibility of such materials. In this work, unique hydrated vanadates (CaVO, BaVO) were obtained by intercalation of Ca2+ or Ba2+ into hydrated vanadium pentoxide. In the CaVO//Zn and BaVO//Zn batteries systems, the former delivered up to a 489.8 mAh g−1 discharge specific capacity at 0.1 A g−1. Moreover, the remarkable energy density of 370.07 Wh kg−1 and favorable cycling stability yard outperform BaVO, pure V2O5, and many reported cathodes of similar ionic intercalation compounds. In addition, pseudocapacitance analysis, galvanostatic intermittent titration (GITT) tests, and Trasatti analysis revealed the high capacitance contribution and Zn2+ diffusion coefficient of CaVO, while an in-depth investigation based on EIS elucidated the reasons for the better electrochemical performance of CaVO. Notably, ex-situ XRD, XPS, and TEM tests further demonstrated the Zn2+ insertion/extraction and Zn-storage mechanism that occurred during the cycle in the CaVO//Zn battery system. This work provides new insights into the intercalation of similar divalent cations in vanadium oxides and offers new solutions for designing cathodes for high-capacity aqueous ZIBs.

High carrier mobility in organic cations intercalated multilayer MoS2

Two-dimensional semiconductors, such as MoS2, have demonstrated great potential applications in post-Moore electronic and optoelectronic devices, and organic cations intercalation has been widely utilized to modulate their physical properties. However, the correlation between the conductivity, carrier mobility, carrier density, and structure of organic cations intercalated MoS2 is still unclear. In this Letter, we systematically investigated the structural and electrical transport properties of pristine MoS2 and MoS2 intercalated with various organic cations such as tetradecyltrimethyl-ammonium, tetraheptyl-ammonium, and cetyltrimethyl-ammonium. Semimetal bismuth (Bi) was used as electrodes to make Ohmic contact with MoS2, and four-probe measurements were employed to obtain the intrinsic conductivity of MoS2. The intercalated organic cations greatly expand interlayer spacing and strongly dope MoS2 up to an electron concentration of 6.1 × 1013 cm−2 depending on the size and intercalation amount of organic cations. The severe electron doping constrains the out-of-plane A1g vibration mode and screens the Coulomb scattering, such that the intercalated MoS2 has enhanced Hall mobility of >50 cm2 V−1 s−1 at room temperature and even >1700 cm2 V−1 s−1 at 5 K. The intercalated MoS2 responds much faster than pristine MoS2 when functioning as a phototransistor. Our work provides insight for understanding the electrical transport properties of MoS2 and designing more efficient electronic and optoelectronic devices.

Surface functional modification of Nb2CTx MXene for high performance capacitive deionization

MXene, show a promising electrode material for capacitive deionization (CDI) due to their elevated conductivity and hydrophilic surface characteristics. Despite optimal electrochemical reaction conditions, MXene still exhibits unsatisfactory capacity. Enhancing capacitance in Nb2CTx MXene poses a key challenge, and addressing this involves leveraging pseudocapacitance through increased active site concentration. This study reports a method to notably improve the capacitance by incorporating cation intercalation and surface modification. After alkali treatment and thermal annealing, the obtained 400-KOH-Nb2C as a cathode in capacitive deionization, exhibiting notable salt adsorption capacity of 104.2 mg g−1 at 1.6 V and an efficient removal rate of 1.73 mg g−1 min−1, cyclic stability maintained over 200 cycles. This optimized electrochemical and desalination performance is due to the large interlayer spaces of Nb2CTx and the surface with lowest termination of -F and –OH group, promoting the delicate surface of Nb2CTx MXene and accelerating ion transport. Furthermore, the derivation of KNbO3 nanowires on 400-KOH-Nb2C surface further expands the layer spacing of MXene and enhances the active sites, and also acts as a protective layer to improve the stability of Nb2C, this effectively addressing challenges associated with desalination. This study offers a novel solution for improving Nb2CTx MXene electrochemical properties in CDI.

Switchable Charge Storage Mechanism via in Situ Activation of MXene Enables High Capacitance and Stability in Aqueous Electrolytes.

The need for reliable renewable energy storage devices has become increasingly important. However, the performance of current electrochemical energy storage devices is limited by either low energy or power densities and short lifespans. Herein, we report the synthesis and characterization of multilayer Ti4N3Tx MXene in various aqueous electrolytes. We demonstrate that Ti4N3Tx can be electrochemically activated through continuous cation intercalation over a 10 day period using cyclic voltammetry. A wide operating window of 2 V is maintained throughout activation. After activation, capacitance at 2 mV s-1 increases by 300%, 140%, and 500% in 1 M H2SO4, 1 M MgSO4, and 1 M KOH, respectively, while maintaining ∼600 F g-1 at 2 mV s-1 after 50000 cycles in 1 M H2SO4. This activation process is possibly attributed to the unique morphology of the multilayered material, allowing cation intercalation to increase access to redox-active sites between layers. This work adds to the growing repository of electrochemically stable MXenes reported for aqueous energy storage applications. These findings offer a reliable option for reliable energy storage devices with potential applications in large-scale grid storage and electric vehicles.