Ion Sieve Research Articles

Fabrication of N,C-H2TiO3 Ion Sieves for Rapid Adsorption of Lithium Using Rheological Phase Methods

Modifying β-H2TiO3 by elemental doping improves its adsorption capacity and shortens the equilibrium adsorption time, which is of positive significance for its industrial application.Herein, a novel N, C co-doped Li2TiO3 lithium ion sieve precursor N,C-Li2TiO3-3 (noted as N,C-LTO-3) was successfully prepared via the rheological phase method using urea as a vital raw material. Crystal structure of N,C-LTO-3 was characterized via XRD, XPS, FT-IR, and Raman. The morphology of N,C-LTO-3 was analysed by SEM and HR-TEM. The N,C-LTO-3 was pickled and obtained to N,C-H2TiO3-3, namely N,C-HTO-3. The equilibrium adsorption capacity (Qe) of N,C-HTO-3 was as high as 40.6mg⋅g-1 in LiOH solution of 100mg·L-1 at 293K. Ti4+ dissolution loss rate is below 0.5% in the fifth cycle. Adsorption isothermal curve, kinetics, and thermodynamic behaviour were fitted with the according equations. The exchange energy of N,C-HTO-3 for Li+ was calculated by density functional theory (DFT) to assess the feasibility of lithium absorption. Furthermore, N,C-HTO-3 exhibited high regeneration and selectivity for Li+ in lithium-containing brine, making N,C-HTO-3 an ideal candidate for Li+ extraction.

PVA-enhanced green synthesis of CMC-based lithium adsorption films

The titanium-based lithium ion sieve (HTO), renowned for its exceptional adsorption performance and cyclic stability, was utilized in addressing the global shortage of lithium resources. However, the recovery and reuse efficiency of HTO in powder form is relatively low, which limits its application in industrial fields. To address this issue, this study utilized carboxymethyl cellulose (CMC) as the principal matrix material, while polyvinyl alcohol (PVA) played a dual function as both matrix and crosslinker, negating the necessity for supplementary crosslinking materials. Employing water as the only solvent, HTO was embedded into the CMC-PVA blended film matrix. It was observed that augmenting the CMC content substantially elevates the adsorptive capability of the film. However, this enhancement comes at the cost of reduced mechanical robustness and diminished stability in solution. Consequently, by balancing the influence of adsorptive capacity and stability through fine-tuning the CMC-to-PVA ratio. Even when HTO powder is encapsulated within the film, the adsorption film retains the excellent adsorption properties of HTO, achieving an adsorption capacity for lithium of 29.21 mg g−1 within 12 h. This study provides an innovative pathway and ideas for the large-scale, low-cost production of sustainable lithium-ion adsorption materials.

Lysine-regulated turing structure membrane via interfacial polymerization for enhanced Li+/Mg2+ separation

The development of advanced membranes with precise ion selectivity is essential for efficient Li+/Mg2+ separation. In this study, we synthesized a novel Lys-TMC membrane via a nucleophilic addition reaction between Lysine and trimesoyl chloride (TMC), yielding in a negatively charged surface interconnected by amide bonds. We systematically investigated the effects of varying Lys:TMC ratios on the membrane’s chemical structure, surface morphology, and ion separation performance. Our results revealed that the degree of cross-linking increases initially with the Lysine content, reaching an optimum at a Lys:TMC ratio of 10:1, where the membrane exhibited prominent Turing patterns on its surface. These patterns were critical for achieving effective ion separation. In contrast, excessive Lysine led to spontaneous polymerization, resulting in irregular ‘stone-like’ structures and the loss of Turing patterns. The optimally cross-linked Lys-TMC membrane displayed superior Li+/Mg2+ separation performance, highlighting the crucial role of controlled cross-linking and Turing structure formation in enhancing ion selectivity. This work provides a mechanistic understanding of the relationship between Turing structure formation and ion sieving performance, offering a promising strategy for designing advanced separation membranes.

Synergistic effect of Fe/Zr dual doping endows hydrophilic spinel-structured H4Ti5O12 ion sieves for efficient lithium extraction from liquid resources

The practical application of spinel-structured H4Ti5O12(HTO) lithium-ion sieves (LISs) is hampered by their poor adsorption properties and recyclability. Within this research, the surface properties and internal structure of lithium-ion sieve (LIS) materials were modulated by co-doping Fe and Zr metal ions to enhance their adsorption properties. The results show that Fe and Zr have been successfully introduced to the LIS lattice, increasing Li-O bond length of position 8a and O2− content. The synthesized H4Ti4.77Fe0.2Zr0.03O12 (HTFZO-II) LIS was made up of evenly distributed nanosheets layered on top of one another to create an open laminar structure, which possesses a hydrophilic surface (contact angle: 17.8°), a high surface area (95.89 m2/g), and hierarchical porous structure. Compared with the undoped HTO, the HTFZO-II LISs enjoy a high capacity for Li+ adsorption (28.72 mg/g), a strong cycling stability (Ti4+ dissolving loss: 0.12 %), and a fast reaching of the equilibrium in adsorption (adsorption equilibrium: 4 h). Theoretical calculation of DFT shows that Li(H2O)4+ on HTFZO-II and HTO dehydration were partially dehydrated into Li(H2O)+. The energy required for the dehydration of Li(H2O)4+ on HTFZO-II is lower than that on undoped HTO, indicating that metal ion doping modification was beneficial for the dehydration of hydrated lithium ions on the adsorbent surface, thereby accelerating the exchange reaction between H+ and dehydrated Li+ ions. This study reveals the key role of the synergistic effect of multi-element co-doping in enhancing the adsorption performance and structural stability of LISs.

Heterogeneous Covalent Organic Framework Membranes Mediated by Polycations for Efficient Ions Separation.

Precise ions sieving at angstrom-scale is gaining tremendous attention thanks to its significant impact at the water-energy nexus. Herein, a novel polycation-modulated interfacial polymerization (IP) strategy is developed to prepare a heterogeneously charged covalent organic frameworks (COFs) membrane. Cationic poly(diallyldimethylammonium chloride) (PDDA) regulates the growth and assembly of anionic COFs nanosheets, which thus provides a negative, smooth top surface and positive, rough bottom surface, indicating the presence of heterogeneously charged angstrom-scale channels through the membrane. Experiments and simulations are conducted to understand the facilitated ions transport behavior relative to specific interactions raised by heterogeneously charged channels and angstrom-scale steric hinderance as well, rendering the membrane with robust mono-/divalent cations sieving capabilities. The selectivity (61.6) of Li+ to Mg2+ in mixed saline under the continuous cross-flow filtration mode is superior to most of the reported nanofiltration membranes. This polycation-mediated interfacial polymerization strategy offers a compelling opportunity to develop versatile heterogeneously charged COF membranes for exquisite ion sieving.

Design of Quasi‐Metal–Organic Frameworks for Solid Polymer Electrolytes Enabling an Ultra‐Stable Interface with Li Metal Anode

AbstractSolid polymer electrolytes (SPEs) are crucial in the development of lithium metal batteries. Recently, metal–organic frameworks (MOFs) with open metal sites (OMSs) have shown promise as solid fillers to improve the performance of SPEs. However, the number of OMS‐containing MOFs is quite limited, comprising less than 5% of the total MOFs. When considering yield, cost, and processability, the commonly used OMS‐containing MOFs are no more than 10 types, causing great limitations. Herein, we reported a simple and universal methodology that converted OMS‐free MOFs to OMS‐rich quasi‐MOFs for developing high‐performance SPEs, and explored the underlying mechanism. The “OMS‐polymer” and “OMS‐ion” interactions were investigated in detail to elucidate the role of quasi‐MOFs on battery performance. It was found that quasi‐MOFs, functioning as ion sieves, can effectively regulate ion migration, thus promoting uniform Li deposition and enabling an ultra‐stable interface. As a result, the Li symmetric cell stably ran over 3000 h at 0.3 mA cm−2, while the full cell retained 85 % of its initial capacity after 1500 cycles at 1.0 C. Finally, universal testing was performed using other MOFs, confirming the generalizability and effectiveness of our design concept.

Polyamide membranes with tannic acid-ZIF-8 for highly permeable and selective ion-ion separation

Highly permeable polyamide (PA) membranes with precise ion selection can be used for many energy-efficient chemical separations but are limited by membrane inefficiencies. Herein, polyphenol-mediated ZIF-8 nanoparticles with hydroxyl-rich hollow structure were synthesized by tannic acid tailored regulation. PA-based membranes with fast penetration, high retention, and precise Cl−/SO42− selection were then synthesized through spatially and temporally controlling interfacial polymerization with modified ZIF-8 nanoparticles (tZIF-8) as aqueous phase additives or as interlayers. The effects of the embedding position of tZIF-8 on the structure, morphology, physicochemical properties, and performance of PA-based membranes were explored through a sequence of characterization techniques. The results revealed that the PA-based membrane with tZIF-8 embedded in the PA layer could achieve a high water permeance of 24.8 L m−2 h−1 bar−1 with a high retention of 99.4 % Na2SO4 and a Cl−/SO42− selectivity of 141, which was superior to most state-of-the-art PA-based membranes. Comparatively, the Cl−/SO42− selection of the PA-based membrane with tZIF-8 embedded between the PA layer and the substrate was 136, while the water permeance was slightly enhanced to 28.2 L m−2 h−1 bar−1. Excitingly, the resulting membranes all exhibit superior antifouling properties and stability. Our facile strategy for tuning membrane microstructures provides new ideals into the development of highly permeable and excellently selective PA-based membranes for precise ion sieving.

Engineering of Covalent Organic Framework Nanosheet Membranes for Fast and Efficient Ion Sieving: Charge-Induced Cation Confined Transport.

Artificial membranes with ion-selective nanochannels for high-efficiency mono/divalent ion separation are of great significance in water desalination and lithium-ion extraction, but they remain a great challenge due to the slight physicochemical property differences of various ions. Here, the successful synthesis of two-dimensional TpEBr-based covalent organic framework (COF) nanosheets, and the stacking of them as consecutive membranes for efficient mono/divalent ion separation is reported. The obtained COF nanosheet membranes with intrinsic one-dimensional pores and abundant cationic sites display high permeation rates for monovalent cations (K+, Na+, Li+) of ≈0.1-0.3mol m-2 h-1, while the value of divalent cations (Ca2+, Mg2+) is two orders of magnitude lower, resulting in an ultrahigh mono/divalent cation separation selectivity up to 130.4, superior to the state-of-the-art ion sieving membranes. Molecular dynamics simulations further confirm that electrostatic interaction controls the confined transport of cations through the cationic COF nanopores, where multivalent cations face i) strong electrostatic repulsion and ii) steric transport hindrance since the large hydrated divalent cations are retarded due to a layer of strongly adsorbed chloride ions at the pore wall, while smaller monovalent cations can swiftly permeate through the nanopores.

Eliminating the effect of pH: Dual-matrix modulation adsorbent enables efficient lithium extraction from concentrated seawater

Lithium ion sieve adsorbents frequently extract liquid lithium resources due to their adsorption effect and cost advantages. However, the adsorption effect is significantly influenced by the ambient pH. The pH effects on the adsorption process can be categorized into two main areas: the competition adsorption of impurity ions and the difference in surface zeta potential. A dual-matrix modulation adsorbent was prepared, comprising a carrier matrix modified with zwitterionic quaternary ammonium bases and an adsorption matrix modified with carboxylation. The zwitterionic quaternary ammonium base groups were employed to mitigate the competitive adsorption of impurity ions by acid-base neutralization. Furthermore, the negative charge of carboxyl groups was employed to diminish the discrepancy in surface zeta potential. The adsorption effect of the ion sieve adsorbent under natural conditions appeared to be significantly enhanced by the dual-matrix modulation, with the saturated adsorption capacity (28 mg/g) and adsorption selectivity (α(Li+/Mg2+)=24.23) being 6.3 and 7.8 times higher than that of the manganese-based adsorbent (HMO) under the same conditions, respectively. Moreover, the adsorption effect was found to be consistent with HMO under alkaline conditions. The results demonstrate that by optimizing the adsorption conditions of the adsorbent, the detrimental impact of pH on the adsorption process of lithium ion sieves can be eliminated.

Selective ion channel adsorbents facilitate efficient and low environmental impact extraction of liquid lithium resources

As lithium is the cornerstone of green energy development, it is crucial to realize a low environmental impact and efficient lithium extraction process. Ion-sieve adsorption is the most widely used method to extract liquid lithium resources, but this method is only efficient under alkaline conditions for H+ and Mg2+ competing adsorption. Conventional methods are often accompanied by the consumption of quantities of alkali, the generation of solid waste, and the acidification of liquid lithium resources. To address these issues, a selective ion-channel adsorbent was constructed. The composition comprises an ion sieve adsorbent and an organic carrier with a zwitterionic quaternary ammonium base group. This group storages OH-in situ, hinders H+ diffusion, slows down Mg2+ diffusion, and accelerates Li+ diffusion by relying on the difference in binding energies, which reduces the competing adsorption and avoids acidification and solid waste generation. The saturated adsorption capacity (21.38mg/g) and selectivity of the adsorbent are 4.7 and 24 times higher than that of conventional ion-sieve adsorbent under neutral conditions respectively. The dosage of alkali is 1/256 of the traditional method, the effluent remains neutral and no solid waste is generated. This study presents an environmental and effective adsorbent for lithium extraction.

Preparation, Characterization, and Adsorption Performance of H2TiO3 Lithium Ion Sieves with Homogeneous Nanoparticles: Kinetics, Thermodynamics, and Mechanism Analysis

AbstractLi2TiO3 precursor with layered structure is successfully prepared by template‐free method using anatase TiO2 and Li2CO3, followed by the treatment of dilute hydrochloric acid, which leads to obtaining H2TiO3 lithium ion sieve nanoparticles with uniform dispersion and small size. The adsorption performance and mechanism of the H2TiO3 are being studied. The experimental results show that the H2TiO3 lithium ion sieve has a large BET specific surface area (19.10 m2 g−1) and good thermal stability. At the same time, it also has a high adsorption rate and adsorption capacity (55.13 mg g−1) towards Li+ in solution due to its high dispersibility and uniformity of particle size, which can expose more adsorption sites in LiCl solution. The adsorption capacity of the H2TiO3 lithium ion sieve can reach 46.63 mg g−1, which achieves 84.58% of the equilibrium adsorption capacity. The equilibrium adsorption parameters follow the Langmuir model perfectly, demonstrating that Li+ undergoes monolayer adsorption. The results of thermodynamic and kinetic analysis show that the adsorption behavior of H2TiO3 is spontaneous and conforms to the pseudo‐second‐order kinetic model, indicating the adsorption process is controlled by chemosorption. In addition, after five adsorption/desorption cycles, the H2TiO3 lithium ion sieve still shows a high adsorption capacity of 46.15 mg g−1, and the dissolution loss of titanium is only 0.14%, which shows that the cycle stability is excellent. XPS and zeta potential analyses illustrate that the adsorption mechanism of Li+ on the H2TiO3 is an ion exchange reaction between Li+ and H+, combined with the electrostatic attraction of the adsorbent surface. Additionally, the adsorption performance of H2TiO3 lithium ion sieve in West Taijinaier Salt Lake brine was tested, and the adsorbent material proves itself is a perspective candidate for lithium extraction from aqueous lithium resources.

High-Current Water-Enabled Electricity Generation in Mushrooms via Synergistic Ion Sieving and Adsorption.

Water-enabled electricity generation (WEG), which harvests energy from the natural water cycle, is a novel strategy for producing green electricity. Taking advantage of the ion sieving effect based on evaporation-induced water flows in charged nanopores, various WEG devices have been developed. Here, we report that a carbonized mushroom produces a record-high current output of up to 96.7 μA, which is attributed to a unique ion adsorption effect combined with an ion sieving effect. Specifically, the natural gradient potential from root to cap in a mushroom caused by tissue differentiation adsorbs different ions, enhancing the traditional ion sieving current. In synergy with the two effects, the mushroom can operate under a broad range of concentrations (0 to 0.6 mol L-1) and represents significant improvements in current, duration, and total charge transfer. These findings reveal the hidden talent of mushrooms as natural materials for WEG, providing inspiration for the development of high-performance WEG devices.

Polyamide nanofiltration membrane modified with defective covalent organic framework interlayer for selective ion sieving

Generally, thin-film composite (TFC) membranes prepared using piperazine (PIP) and trimesoyl chloride (TMC) exhibit good Na2SO4 rejection, but their MgCl2 rejection is not satisfactory. In this study, a defective covalent organic framework (COF) interlayer with residual unreacted amine groups was fabricated via interfacial polymerization (IP) by changing the catalyst concentration. Introduction of the COF layer into a polyamide (PA) separation membrane modified the pore size of the PA layer, thereby improving the rejection of divalent cations. The pore size of the PA layer decreased and the surface morphology of the membrane was converted from nodular to a hybrid morphology of “ridge-and-valleys’’ and nodules, indicating that the residual unreacted amine groups on the COF interlayer successfully reacted with the acyl chloride groups. The optimal membrane (PIP/COF-A/PES) exhibited high rejection of divalent ions (Na2SO4 of 98.3% and MgCl2 of 94.3%), and the membrane showed excellent capability for separating mono/divalent ions. Overall, a method of preparing nanofiltration membranes by modifying the PA layer to enhance the rejection of divalent cations was demonstrated.

Hydrophilic surface-modified titanium-based lithium ion sieve adsorbents for efficient lithium extraction

Titanium-based lithium ion sieve adsorbents (HTOs) are considered among the most promising materials for lithium extraction from aqueous sources. In this study, four surfactants—sodium dodecyl sulfate (SDS), cetyltrimethylammonium bromide (CTAB), hydroxypropyl cellulose (HPC), and tannic acid (TA)—were used to surface-etch HTOs, preparing adsorbents with enhanced hydrophilicity at the nanoscale. Correlation studies between the hydrophilicity of the HTO-X and their adsorption performance revealed that all HTO-X had lower contact angles than the unetched counterparts, indicating improved adsorption capacities. Notably, TA plays a synergistic role of “killing two birds with one stone”. The TA-etched HTO-T adsorbent exhibited the lowest contact angle (8.8°) and the highest specific surface area (62.10 m2/g). In a LiCl solution, HTO-T’s adsorption capacity for Li+ reached 33.61 mg/g, a 26 % increase over the unetched HTO adsorbent (26.56 mg/g). Simultaneously, HTO-T significantly reduces the adsorption time and enhances the adsorption efficiency during the surface diffusion phase. Additionally, HTO-T demonstrated remarkable selectivity for lithium ions, with separation factors α(Li/Na), α(Li/K), α(Li/Mg), and α(Li/Ca) of 397.13, 181.55, 1288.47, and 1345.19, respectively, showcasing an excellent separation effect. The adsorption mechanism indicates that Li+ adsorption by HTO-T primarily occurs through the disruption of O–H bonds and the formation of new O-Li bonds. This research presents an efficient strategy for the development of HTOs, demonstrating HTO-T as a potential adsorbent for lithium recovery from brine sources.

Preparation of highly hydrophilic cesium ion sieve and its performance in adsorbing Cs+

The unique properties of cesium compounds have garnered increasing attention, among which Cs2Ti6O13 shows great potential for applications. This paper synthesized Cs2Ti6O13(CTO-3) using a template-assisted solvothermal method with cesium carbonate as the cesium source and tetrabutyl titanate as the titanium source. Among them, F127 and hexadecylamine are used as template agents to modulate the surface morphology and hydrophilicity of the precursor. The cesium ion sieve H2Ti6O13 (HTO-3) synthesized after hydrochloric acid pickling has a large specific surface area and good hydrophilicity. This structure is conducive to the ion exchange between Cs+ and H+, resulting in a fast adsorption rate. It is completed within 2 h, and the adsorption capacity reaches 360 mg/g, which is significantly greater than that of the traditional high-temperature solid-phase method. The adsorption process of Cs+ on HTO-3 is more consistent with the pseudo-second-order kinetic equation model, and the adsorption process is chemical adsorption. HTO-3 exhibited good selectivity and cycle stability. At the fifth time of the adsorption-resolution cycle, the adsorption capacity was 87.1 % of the first time.

Synthesizing LiFePO4 by phosphate & iron recovered from sludge-incinerated ash and Li extracted from concentrated brines

Phosphorus (P) recovered from sludge-incinerated ash (SIA) could be applied to synthesize highly added-value products (FePO4 and LiFePO4) with in situ Fe in SIA. Indeed, LiFePO4 is a future of rechargeable batteries, which makes lithium (Li) highly needed. Alternatively, Li could also be extracted from concentrated brines to face a potential crisis of Li depletion on lands. Based on H3PO4 and Fe3+ co-extracted from the acidic leachate of SIA by tributyl phosphate (TBP), FePO4 (31.2 wt% Fe, 17.6 wt% P and the molar ratio of Fe/P = 0.98) was easily formed only adjusting pH of the stripping solution to 1.6. Interestingly, the organic phase from the first-stage co-extraction process of Fe3+ and H3PO4 could be utilized for Li-extraction from salt-lake brine, based on the TBP-FeCl3-kerosene system, and a good performance (78.7%) of Li-extraction and separation factors (β) (186.0–217.4) were obtained. Furthermore, the compounds with Li-extraction are complex, possibly LiFeCl4∙2TBP, in which Li+ could be stripped to form Li2CO3 by 4.0 M HCl (with a stripping rate up to 83%). Besides, Li2CO3 could also be obtained from desalinated brine by adsorption with manganese oxide ion sieve (HMO) and desorption with HCl. In the two cases, almost pure Li2CO3 products were obtained, up to 99.7 and 99.5 wt% Li2CO3 respectively, after further purification and concentration. Finally, recovered FePO4 and extracted Li2CO3 were synthesized for producing LiFePO4 that had a similar electrochemical property (69.5 and 77.8 mAh/g of the initial discharge capacity) to those synthesized from commercial raw materials.

Controlling the nano-channel configuration of hierarchical MoS2 framework membranes via covalent functionalization with amino acids for enhanced sieving ability

As the utilization of nanolaminates composed of two-dimensional (2D) materials has become promising candidates for precise molecule/ion separations, precisely controlling the size, chemistry and configuration of the intra-nanochannel is crucial for further development of membranes. Herein, we developed covalently functionalized MoS2 membranes with amino acids (AAs) pillars via polarized N-Mo bonding for substantially improving the selectivity and permeability towards high-concentration salts and micropollutants. The optimized Glycine-Proline configuration in tailorable nanochannels, combined with the steric hindrance imposed by the protruding AAs and the ion-confined partitioning of Pyrrole-N and Carboxyl-O functionalities, contribute to achieving selectivity of MgCl2/Na2SO4 up to 11.2 and 8.1 in single and binary solutions. Meanwhile, the synergy between the hierarchical network of water pathways and the decorated hydrophobic pyrrolidine rings effectively facilitates low-friction water transport across the confined nanochannels. Impressively, the improved HM-GP demonstrates rejection rates of 95.7% for 0.6 M NaCl with a water flux of 15.2 l m−2 h−1 bar−1 under osmosis-driven condition, and it maintains a high salt rejection of 93.2% with a water flux of 17.5 l m−2 h−1 in pressure-driven process. This work not only offers an efficient strategy for designing robust HM-GPs with great potential in sustainable water purification and ion sieving, but also provide valuable guidance for developing separation technologies based on 2D material membranes.

Preparation of tungsten-doped Ti-based lithium ion sieves with excellent adsorption performance by hydrothermal method

Ti-based Li-ion sieve (H2TiO3, HTO), is attractive for adsorbing lithium from salt lakes. Nevertheless, the titanium dissolution and limited adsorption capacity affect the cycling stability and adsorption performance. In this work, an atom engineering technique was employed by doping tungsten (W) into layered HTO via a hydrothermal method. Through experiments and theoretical simulation, it was demonstrated that the doped W in HTO results in expanded interplanar spacing, increased surface adsorption energy, and excellent adsorption performance. The optimized HTO-W exhibits an Ti dissolution rate of 0.73 % (in 2 mol L−1 HCl for 12 h, 5.6 % that of pristine HTO) and adsorption capacity of 43.01 mg g−1 (in 425 mg L−1 LiCl solution at 30 °C, 1.4 times that of undoped HTO). Furthermore, the HTO-W reaches adsorption equilibrium in about 3 h with exceptional selectivity and stability. This work demonstrates an effective enhancement of lithium adsorption by W doping, providing new avenues for developing lithium adsorbents with high performance.

Ions Selectively Intrigued Ionologic Devices for Logic Operation

Capacitive analogues of semiconductor diodes (CAPodes) present a new avenue for energy-efficient and nature-inspired next-generation computing devices. Here, we disclose the generalized concept for bias-direction-adjustable n- and p-CAPodes based on selective ion sieving. Controllable-unidirectional ion flux is realized by blocking electrolyte ions from entering sub-nanometer pores. The resulting CAPodes exhibit charge-storage characteristics with a high rectification ratio (96.29 %). The enhancement of capacitance is attributed to the high surface area and porosity of an omnisorbing carbon as counter electrode. Furthermore, we demonstrate the use of an integrated device in a logic gate circuit architecture to implement logic operations (‘OR’, ‘AND’). This work demonstrates CAPodes as a generalized concept to achieve p-n and n-p analogue junctions based on selective ion electrosorption, provides a comprehensive understanding and highlights applications of ion-based diodes in ionologic architectures. Figure 1

Dynamical Janus Interface Design for Reversible and Fast-Charging Zinc-Iodine Battery under Extreme Operating Conditions.

Aqueous zinc (Zn) iodine (I2) batteries have emerged as viable alternatives to conventional metal-ion batteries. However, undesirable Zn deposition and irreversible iodine conversion during cycling have impeded their progress. To overcome these concerns, we report a dynamical interface design by cation chemistry that improves the reversibility of Zn deposition and four-electron iodine conversion. Due to this design, we demonstrate an excellent Zn-plating/-stripping behavior in Zn||Cu asymmetric cells over 1000 cycles with an average Coulombic efficiency (CE) of 99.95%. Moreover, the Zn||I2 full cells achieve a high-rate capability (217.1 mA h g-1 at 40 A g-1; C rate of 189.5C) at room temperature and enable stable cycling with a CE of more than 99% at -50 °C at a current density of 0.05 A g-1. In situ spectroscopic investigations and simulations reveal that introducing tetraethylammonium cations as ion sieves can dynamically modulate the electrode-electrolyte interface environment, forming the unique water-deficient and chloride ion (Cl-)-rich interface. Such Janus interface accounts for the suppression of side reactions, the prevention of ICl decomposition, and the enrichment of reactants, enhancing the reversibility of Zn-stripping/-plating and four-electron iodine chemistry. This fundamental understanding of the intrinsic interplay between the electrode-electrolyte interface and cations offers a rational standpoint for tuning the reversibility of iodine conversion.