Intercalation Host Research Articles

Triggering Reversible Intercalation-Conversion Combined Chemistry for High-Energy-Density Lithium Battery Cathodes.

Combining intercalation and conversion reactions maximizes the utilization of redox-active elements in electrodes, providing a means for overcoming the current capacity ceiling. However, integrating both mechanisms within a single electrode material presents significant challenges owing to their contrasting structural requirements. Intercalation requires a well-defined host structure for efficient lithium-ion diffusion, whereas conversion reactions entail structural reorganization, which can undermine intercalation capabilities. Based on the previous study that successfully demonstrated reversible intercalation-conversion chemistry in amorphous LiFeSO4F, this study aims to provide an in-depth understanding on how this can be enabled. Experimental and theoretical investigations of a model system based on tavorite-structured LiFeSO4F revealed that amorphization governs the activation and reversibility of the combined reactions. Enhanced reversibility is achieved through the facile migration of transition metals within the amorphous matrix. Unexpectedly, it is found that amorphization also narrowed the voltage gap between the intercalation and conversion reactions. This voltage-gap reduction is explained by the thermodynamic metastability of the amorphous phase. The applicability of the approach to other intercalation hosts is further demonstrated, showing that amorphization enables reversible intercalation and conversion. These findings suggest a new strategy that leverages the full potential of intercalation and conversion reactions, introducing new avenues for cathode design.

Competition for Ion Intercalation in Prussian Blue Analogues as Cathode Materials for Calcium Ion Batteries

With multivalent ion batteries being considered viable post‐lithium energy storage technologies, the last few years have seen increasing interest in intercalation type cathode materials for Ca‐ion batteries (CIBs). Prussian blue analogues (PBAs) display many positive attributes such as open structural framework, large interstitial sites, and versatile transition metal redox activity. The PBA cathodes reported for CIBs often contain K‐ion or Na‐ion due to the syntheses involving the use of potassium or sodium hexacyanoferrate. It has been long overlooked whether the presence of K‐ion or Na‐ion in pristine PBAs could affect the Ca‐ion storage in the PBAs when assessing their CIB performance. Through a combined experimental and computational investigation, this work reports that when K+/Na+ is present in the pristine PBAs, K/Na intercalation is preferred by the PBA structure over Ca intercalation even in the Ca cells. Ca‐ion intercalation can be increased when the K+/Na+ content in the pristine PBAs is reduced, shifting from a K or Na‐dominated intercalation process to a Ca/K or Ca/Na co‐intercalation process. This work consolidates that PBAs are an interesting and versatile intercalation host for several ions, but investigating PBAs as intercalation cathodes requires careful consideration of all ions present in the battery system.

Confining Conversion Chemistry in Intercalation Host for Aqueous Batteries

AbstractConversion‐type anode materials with high theoretical capacities play a pivotal role in developing future aqueous rechargeable batteries (ARBs). However, their sustainable applications have long been impeded by the poor cycling stability and sluggish redox kinetics. Here we show that confining conversion chemistry in intercalation host could overcome the above challenges. Using sodium titanates as a model intercalation host, an integrated layered anode material of iron oxide hydroxide‐pillared titanate (FeNTO) is demonstrated. The conversion reaction is spatially and kinetically confined within sub‐nano interlayer, enabling superlow redox polarization (ca. 4–6 times reduced), ultralong lifespan (up to 8700 cycles) and excellent rate performance. Notably, the charge compensation of interlayer via universal cation intercalation into host endows FeNTO with the capability of operating well in a broad range of aqueous electrolytes (Li+, Na+, K+, Mg2+, Ca2+, etc.). We further demonstrate the large‐scale synthesis of FeNTO thin film and powder, and rational design of quasi‐solid‐state high‐voltage ARB pouch cells powering wearable electronics against extreme mechanical abuse. This work demonstrates a powerful confinement means to access disruptive electrode materials for next‐generation energy devices.

Confining Conversion Chemistry in Intercalation Host for Aqueous Batteries.

Conversion-type anode materials with high theoretical capacities play a pivotal role in developing future aqueous rechargeable batteries (ARBs). However, their sustainable applications have long been impeded by the poor cycling stability and sluggish redox kinetics. Here we show that confining conversion chemistry in intercalation host could overcome the above challenges. Using sodium titanates as a model intercalation host, an integrated layered anode material of iron oxide hydroxide-pillared titanate (FeNTO) is demonstrated. The conversion reaction is spatially and kinetically confined within sub-nano interlayer, enabling superlow redox polarization (ca. 4-6 times reduced), ultralong lifespan (up to 8700 cycles) and excellent rate performance. Notably, the charge compensation of interlayer via universal cation intercalation into host endows FeNTO with the capability of operating well in a broad range of aqueous electrolytes (Li+, Na+, K+, Mg2+, Ca2+, etc.). We further demonstrate the large-scale synthesis of FeNTO thin film and powder, and rational design of quasi-solid-state high-voltage ARB pouch cells powering wearable electronics against extreme mechanical abuse. This work demonstrates a powerful confinement means to access disruptive electrode materials for next-generation energy devices.

Photo-rechargeable zinc-ion battery using highly ordered and vertically oriented C@VO2/ZnO microrod arrays

Development of photo-rechargeable batteries is a potential resolution for supplying off-grid solar power system in remote locations. Here, we present a photo-rechargeable zinc-ion battery (PRZIB) that can be directly recharged by the light without external photovoltaic cells and controllers. A highly ordered and vertically oriented ZnO microrod arrays (ZMRAs) were prepared using hydrothermal method in micron-scale patterned ZnO substrate defined by lithographic technology, which are used to incorporate with carbon encased vanadium oxide (C@VO2) nanocomposite to form a large specific surface area of three-dimensional network of C@VO2/ZnO heterojunction. PRZIB was assembled using C@VO2/ZMRAs structure as the photovoltaics as well as intercalation host for Zinc-ions, which demonstrates a photo-conversion efficiency of 3.3 % and gravimetric capacities of 286.0 mAh g−1 and 339.3 mAh g−1 at 500 mA g−1 in dark and light conditions. An excellent long-term cycling stability was achieved with a capacity retention of 88.79 % after 300 cycles at 1000 mA g−1 in dark condition. It is suggested that the distinctive morphologies and structure of C@VO2/ZMRAs provide effective strategies for enhancing photo-electrochemical redox reaction kinetics.

Controlling Structure and Morphology of MoS2 via Sulfur Precursor for Optimized Pseudocapacitive Lithium Intercalation Hosts

Molybdenum disulfide (MoS2)‐based electrode materials can exhibit a pseudocapacitive charge storage mechanism induced by nanosized dimension of the crystalline domains, which is why control over material structure via synthesis conditions is of significance. In this study, we investigate how the use of different sulfide precursors, specifically thiourea (TU), thioacetamide (TAA), and L‐cysteine (LC), during the hydrothermal synthesis of MoS2, affects its physicochemical, and consequently, electrochemical properties. The three materials obtained exhibit distinct morphologies, ranging from micron‐sized architectures (MoS2 TU), to nanosized flakes (MoS2 TAA and LC). While all three synthesized samples exhibit pseudocapacitive Li+ intercalation properties, the capacity retention of the latter two consisting of nanosized flakes is further improved at high cycling rates. The individual charge storage properties are analyzed by operando X‐ray diffraction, dilatometry, and 3D Bode analysis, revealing a correlation between the morphology, porosity, and the electrochemical intercalation behavior of the obtained electrode materials. The results demonstrate a facile strategy to control MoS2 structure and related functionality by choice of hydrothermal synthesis precursors.

One-step hydrothermal synthesis of vanadium dioxide/carbon core–shell composite with improved ammonium ion storage for aqueous ammonium-ion battery

Aqueous nonmetallic ion batteries have garnered significant interest due to their cost-effectiveness, environmental sustainability, and inherent safety features. Specifically, ammonium ion (NH4+) as a charge carrier has garnered more and more attention recently. However, one of the persistent challenges is enhancing the electrochemical properties of vanadium dioxide (VO2) with a tunnel structure, which serves as a highly efficient NH4+ (de)intercalation host material. Herein, a novel architecture, wherein carbon-coated VO2 nanobelts (VO2@C) with a core–shell structure are engineered to augment NH4+ storage capabilities of VO2. In detail, VO2@C is synthesized via the glucose reduction of vanadium pentoxide under hydrothermal conditions. Experimental results manifest that the introduction of the carbon layer on VO2 nanobelts can enhance mass transfer, ion transport and electrochemical kinetics, thereby culminating in the improved NH4+ storage efficiency. VO2@C core–shell composite exhibits a remarkable specific capacity of ∼300 mAh/g at 0.1 A/g, which is superior to that of VO2 (∼238 mAh/g) and various other electrode materials used for NH4+ storage. The NH4+ storage mechanism can be elucidated by the reversible NH4+ (de)intercalation within the tunnel of VO2, facilitated by the dynamic formation and dissociation of hydrogen bonds. Furthermore, when integrated into a full battery with polyaniline (PANI) cathode, the VO2@C//PANI full battery demonstrates robust electrochemical performances, including a specific capacity of ∼185 mAh·g−1 at 0.2 A·g−1, remarkable durability of 93 % retention after 1500 cycles, as well as high energy density of 58 Wh·kg−1 at 5354 W·kg−1. This work provides a pioneering approach to design and explore composite materials for efficient NH4+ storage, offering significant implications for future battery technology enhancements.

Modulating NH4+ in vanadium oxide framework for high-efficient aqueous NH4+ storage

Aqueous energy storage systems have garnered significant attention due to their inherent advantages, including low cost, high eco-sustainability, and enhanced safety profiles. Nonmetal ion as a charge carrier is a fascinated paradigm shift just recently. Vanadium-based materials for ammonium ion (NH4+) storage have received considerable interest and have been demonstrated to serve as highly efficient NH4+ (de)intercalation host materials. However, tuning their structure for enhanced NH4+ storage presents significant challenges. Herein, we report a strategy for the pre-intercalation of NH4+ in vanadium oxide framework to study on the influence of the amount of ammonium ions on their NH4+ storage properties. The results from the experiments and density functional theory (DFT) calculations demonstrate that the appropriate quantity of pre-inserted ammonium ions boosts the (de)intercalation of NH4+ and exhibits the superior electrochemical properties. Moreover, excessive pre-inserted ammonium ions in vanadium oxide framework occupy the active sites for storing NH4+, whereas insufficient pre-inserted ammonium ions in vanadium oxide framework do not support the interlayer space enough for rapid (de)intercalation of NH4+. All results elucidate that modulating NH4+ in vanadium oxide framework enables highly efficient aqueous ammonium ion storage for supercapacitors (SCs). At 0.5 A·g−1, the specific capacitance of 341F·g−1 (171 mAh·g−1) and stable cycle performance of nearly 100 % after 10,000 cycles are achieved. The assembled hybrid supercapacitor exhibits the capacitance with 330 mF·cm−2 at 1 mA·cm−2, and energy density with 13.7 Wh·kg−1 at 22.1 W·kg−1, complemented by commendable mechanical durability and energy output characteristics. The profound insights gleaned from this study illuminate the strategic modulation of NH4+ ions, unveiling the vast potential of vanadium-based materials for efficient NH4+ storage applications.

Pomegranate-like α-MoO3-x/C nanospheres as a stable and high-performance Li-ion intercalation host

Orthorhombic MoO3 (α-MoO3) is extensively investigated as a cathode material in Li-ion batteries with high capacity. However, suffering from the irreversible structural transformation and rapid capacity decline during discharge-charge process are still annoyed issues for α-MoO3 based electrodes. Herein, novel pomegranate-like oxygen-deficient α-MoO3/C (α-MoO3-x/C) nanospheres are prepared. The α-MoO3-x/C nanosphere is comprised of ultrafine α-MoO3-x subunits and porous graphitic carbon framework. Interlayer expansions caused by different contents of oxygen vacancies are realized in α-MoO3-x via a controllable oxidation process. When evaluated as the Li-ion intercalation host, the α-MoO3-x/C containing appropriate oxygen vacancies is found to be optimal with remarkable rate capability (230.0 mAh g−1 at 1 C, 54.5 mAh g−1 at 50 C) and long lifetime (69.6% retention after 3000 cycles at 10 C). Electrochemical test shows that the behavior of Li-ion intercalation in the intralayers of α-MoO3-x/C is suppressed effectively and becomes reversible. The structure evolutions during Li-ion intercalation/deintercalation process are investigated by ex situ X-ray diffraction, which reveals that α-MoO3-x/C undergoes lattice breathing rather than structural collapse compared with pure α-MoO3. Moreover, α-MoO3-x/C exhibits enhanced pseudocapacitance and improved Li-ion transport kinetics than pure α-MoO3. These unique features render α-MoO3-x/C an advanced intercalation host for Li-ions.

Charge Transport and Ion Kinetics in 1D TiS2 Structures are Dependent on the Introduction of Selenium Extrinsic Atoms.

Improving charge insertion into intercalation hosts is essential for crucial energy and memory technologies. The layered material TiS2 provides a promising template for study, but further development of this compound demands improvement to its ion kinetics. Here, we report the incorporation of Se atoms into TiS2 nanobelts to address barriers related to sluggish ion motion in the material. TiS1.8Se0.2 nanobelts are synthesized through a solid-state method, and structural and electrochemical characterizations reveal that solid solutions based on TiS1.8Se0.2 nanobelts display increased interlayer spacing and electrical conductivity compared to pure TiS2 nanobelts. Cyclic voltammetry and electrochemical impedance spectroscopy indicate that the capacitive behavior of the TiS2 electrode is improved upon Se incorporation, particularly at low depths of discharge in the materials. The presence of Se in the structure can be directly related to an increased pseudocapacitive contribution to electrode behavior at a low Li+ content in the material and thus to improved ion kinetics in the TiS1.8Se0.2 nanobelts.

Mg-rich disordered rocksalt oxide cathodes for Mg-ion batteries

The discovery of new transition metal (TM) oxide cathodes which can act as intercalation hosts for Mg2+ ions is critical for the development of high energy density Mg-ion batteries. In...

How machine learning can extend electroanalytical measurements beyond analytical interpretation.

Electroanalytical measurements are routinely used to estimate material properties exhibiting current and voltage signatures. Analysis of such measurements relies on analytical expressions of material properties to describe the experiments. The need for analytical expressions limits the experiments that can be used to measure properties as well as the properties that can be estimated from a given experiment. Such analytical relations are essentially solutions of the physics-based differential equations (with properties as coefficients) describing the material behavior under certain specific conditions. In recent years, a new machine learning-based approach has been gaining popularity wherein the differential equations are numerically solved to interpret the electroanalytical experiments in terms of corresponding material properties. Since the physics-based differential equations are solved, one can additionally estimate underlying fields, e.g., concentration profile, using such an approach. To exemplify the characteristics of such a machine learning assisted interpretation of electroanalytical measurements, we use data from the Hebb-Wagner test on a magnesium spinel intercalation host. As compared to the traditional analytical expression-based interpretation, the emerging approach decreases experimental efforts to characterize relevant material properties as well as provides field information that was previously inaccessible.

Strategies to alleviate distortive phase transformations in Li-ion intercalation reactions: an example with vanadium pentoxide.

Chemical and electrochemical Li-ion insertion in transition metal oxides, either via a phase transformation reaction (ions insert into specific crystallographic sites of the host lattice) or a solid solution insertion (ions distribute uniformly throughout the host lattice), enables high energy density electrochemical energy storage. Many phase transformation cathode materials, that undergo two-phase reactions, exhibit high theoretical capacities arising from multi-electron redox reactions. However, challenges in distortive phase transformations and uncontrolled phase nucleation, propagation, segregation, and co-existence continue to limit the energy density, (dis)charging rate performances, and cycling stability of available phase transformation cathode materials. Vanadium pentoxide (V2O5), a classical layered intercalation host material with high theoretical capacity, undergoes irreversible structural changes and capacity fading when intercalating more than one lithium ion per V2O5 unit in its thermodynamically stable phase. Here, we review recent synthetic strategies to alter the V-O connectivity, thereby alleviating distortive phase transformations and promoting solid solution-based Li-ion insertion in V2O5. We also summarize several widely accessible and classical molecular-based analytical tools that can provide local structural dynamics and phase transformation mechanism information on the lithiation of V2O5, including single-crystal X-ray diffraction, infrared and Raman spectroscopy, electron paramagnetic resonance, and nuclear magnetic resonance spectroscopy.

Manganese-Based Tunnel and Layered Oxide Cathodes for Secondary Alkali-Ion Batteries

Designing new cathode materials remains crucial in developing (post) Li-ion batteries. Mn-based oxide cathodes have received wide attention due to their sustainable nature, low cost, elemental abundance, structural diversity/polymorphism, and rich oxidation states (2+ to 7+), offering tunable redox potential [1]. Here, we have investigated different oxide-based cathode insertion compounds for secondary metal-ion batteries.i) We have demonstrated tunnel-type sodium insertion material Na44MnO2(NMO) as an intercalation host for Li-ion and K-ion batteries. The solution combustion synthesized Na0.44MnO2 assuming an orthorhombic structure (space group Pbam), exhibited rod-like morphology. After electrochemical ion exchange from NMO, we obtained Na0.11K0.27MnO2 (NKMO) and Na0.18Li0.51MnO2 (NLMO) cathodes for K-ion batteries and Li-ion batteries, respectively [2]. These new compositions, NKMO and NLMO, showed excellent cycling stability with capacities of ∼74 and 141 mAh g–1 (first cycle, C/20 current rate). The underlying mechanistic features concerning charge storage and structural modifications in these cathode compositions were probed by combining ex-situ structural, spectroscopy, and electrochemical tools [3].ii) Using composite formation, we have tried to improve the P2-type layered material. Here, the stable Na7(Li1/18Mn1/18Ni3/18Fe2/18χ1/18)O2–xNa2MoO4 biphasic composite was synthesized using Mo doping. Overall, the redox chemistry was investigated using various spectroscopy techniques to prove the net capacity resulted from both cationic and anionic redox reactions [4]. Keywords: energy storage; batteries; cathode; manganese oxides; intercalation; doping

Understanding the Super-Theoretical Capacity Behavior of VO2 in Aqueous Zn Batteries.

VO2 material, as a promising intercalation host, is widely investigated not only in aqueous lithium-ion batteries, but also in aqueous zinc-ion batteries (AZIBs) owing to its stable tunnel-like framework and multivalence of vanadium. Different from lithium-ion storage, VO2 can provide higher capacity when storing zinc ions, even exceeding its theoretical capacity (323mAhg-1), but the specific reason for this unconventional performance in AZIBs is still unclear. The present study proposes a catalytic oxygen evolution reaction (OER) coupled with an interface oxidation mechanism of VO2 during the initial charging to a high voltage. This coupling induces a phase transformation of VO2 into a high oxidation state of V5O12∙6H2O, enabling a nearly two-electron reaction and providing additional zinc storage sites to achieve super-theoretical capacity. Furthermore, it is demonstrated that these vanadium oxide cathodes (V2O3, VO2, and V2O5) will all undergo phase change after the first charge or short cycle. Notably, water molecules participate in the final formation of layered vanadium-based hydrate, highlighting their crucial role as "pillars" for stabilizing the structure. This work significantly enhances the understanding of vanadium-based oxide cathodes.

Computational Investigation of MAX as Intercalation Host for Rechargeable Aluminum‐Ion Battery

AbstractLayered carbides and their analogs with MAX phase (general formula AMn+1Xn) have emerged as promising candidates for energy storage and conversion applications. One frontier for energy storage is using MAX as an Al‐ion intercalation electrode. Given that many MAXs have Al as the A sites, the structure can potentially serve as a stable host for Al intercalation. Here in this work, 425 ternary MAX Al‐ion battery electrodes are computationally enumerated. Specifically, first principal phase diagram calculations are performed on the combinatorial space of 17 types of typical transition metals, five types of anions (C, N, B, Si, and P), three types of stoichiometries (n = 1, 2, and 3) and two types of layered stackings (α and β). Among all the ternary MAX materials, 44 candidates show reasonable synthetic accessibility, and six with extraordinary performance are predicted to be promising Al‐ion battery electrodes. With the phase stability, and electrochemical performance (average voltage, theoretical capacity, energy density, and Al diffusion barrier), the work provides a comprehensive computational assessment of the great opportunities behind MAX‐based Al‐ion batteries.

Toggling Stereochemical Activity through Interstitial Positioning of Cations between 2D V2O5 Double Layers.

The 5/6s2 lone-pair electrons of p-block cations in their lower oxidation states are a versatile electronic and geometric structure motif that can underpin lattice anharmonicity and often engender electronic and structural instabilities that underpin the function of active elements in nonlinear optics, thermochromics, thermoelectrics, neuromorphic computing, and photocatalysis. In contrast to periodic solids where lone-pair-bearing cations are part of the structural framework, installing lone-pair-bearing cations in the interstitial sites of intercalation hosts provides a means of a systematically modulating electronic structure through the choice of the group and the period of the inserted cation while preserving the overall framework connectivity. The extent of stereochemical activity and the energy positioning of lone-pair-derived mid-gap states depend on the cation identity, stoichiometry, and strength of anion hybridization. V2O5 polymorphs are versatile insertion hosts that can accommodate a broad range of s-, p-, and d-block cations. However, the insertion of lone-pair-bearing cations remains largely underexplored. In this article, we examine the implications of varying the 6s2 cations situated in interlayer sites between condensed [V4O10]n double layers. Systematic modulations of lattice distortions, electronic structure, and magnetic ordering are observed with increasing strength of stereochemical activity from group 12 to group 14 cations. We compare and contrast p-block-layered MxV2O5 (M = Hg, Tl, and Pb) compounds and map the significance of local off-centering arising from the stereochemical activity of lone-pair cations to the emergence of filled antibonding lone-pair 6s2-O 2p-hybridized mid-gap states mediated by second-order Jahn-Teller distortions. Crystallographic studies of cation coordination environments and the resulting modulation of V-V interactions have been used in conjunction with variable-energy hard X-ray photoelectron spectroscopy measurements, first-principles electronic structure calculations, and crystal orbital Hamilton population analyses to decipher the origins of stereochemical activity. Magnetic susceptibility measurements reveal antiferromagnetic signatures for all the three compounds. However, the differences in V-V interactions significantly affect the energy balance of the superexchange interactions, resulting in an ordering temperature of 160 and 260 K for Hg0.5V2O5 and δ-Tl0.5V2O5, respectively, as compared to 7 K for δ-Pb0.5V2O5. In δ-Pb0.5V2O5, the strong stereochemical activity of electron lone pairs and the resulting electrostatic repulsions enforce superlattice ordering, which strongly modifies the electronic localization patterns along the [V4O10] slabs, resulting in disrupted magnetic ordering and an anomalously low ordering temperature. The results demonstrate a versatile strategy for toggling the stereochemical activity of electron lone pairs to modify the electronic structure near the Fermi level and to mediate superexchange interactions.

Indium Alloy as Anodes for Rechargeable Calcium Ion Batteries at Room Temperature

Rechargeable multivalent ion batteries are poised to deliver the necessary breakthroughs in energy density and stability required for extended-range electric vehicles and large-scale grid energy storage. Calcium ion batteries are of interest owing to their high theoretical energy densities, natural abundance, and safety, yet are hindered by calcium’s strong interactions with non-aqueous electrolyte solutions and a general lack of suitable intercalation hosts. In order to realize the high voltage and theoretical capacity of a calcium-ion battery, replacement of the Ca metal anode with new electrode materials that can operate reversibly in conventional electrolyte systems is necessary, beginning with fundamental studies to identify novel intercalation or alloy-type hosts which can provide high-Ca content while avoiding considerable volume expansion and capacity loss. In this work, research into a novel indium anode as a host for Ca2+ ions in conventional electrolytes at room temperature is presented.

Exploring Unconventional Electrolytes to Tackle the Problem of Shuttling in Precipitation-Dissolution Battery Chemistries

A1-Triple I: Any galvanic cell functions by compartmentalizing, via the electron-blocking electrolyte, an exothermic chemical reaction into two redox half-reactions to force release of the reaction free energy as electrical energy. The conventional electrolyte is an ion-conductor shuttling the operative ions and preventing any other chemical exchange to maintain the integrity and reversibility of the electrodes. In overcoming the capacity ceiling of layered intercalation hosts, conversion reactions between low-cost chalcogens (sulfur, selenium, and oxygen) and alkali metals (lithium and sodium) have been investigated for decades. However, parasitic crossover of soluble polychalcogenides limit battery cycle life. We conceptualize that selective solute transport at the interface of partially miscible solvents can be utilized in designing organic electrolytes to suppress parasitic crossover in precipitation-dissolution battery chemistries. This talk will discuss successful concept-demonstration experiments and highlight intriguing physical phenomena within such electrolyte system under the dynamics of electrochemistry.

Effect of Stereochemically Active Electron Lone Pairs on Magnetic Ordering in Trivanadates.

Stereoactive electron lone pairs derived from filled 5/6s2 states of p-block cations are an intriguing electronic and geometric structure motif that have been exploited for diverse applications such as thermoelectrics, thermochromics, photocatalysis, and nonlinear optics. Layered trivanadates are dynamic intercalation hosts, where the insertion of cations can be used to tune electron correlation, charge localization, and magnetic ordering. However, the interaction of 5/6s2 stereoactive electron lone pairs with layered trivanadates remains unexplored. In this study, we contrast s- and p-block trivanadates and map off-centering in the coordination environment and reduction in symmetry arising from the stereochemical activity of lone pair cations to the emergence of filled antibonding lone-pair 6s2-O 2p hybridized states. The former is studied by high-resolution single-crystal X-ray diffraction studies of TlV3O8 and isostructural RbV3O8 to probe distinct differences in Tl and Rb coordination environments and the resulting modulation of V-V interactions in V3O8 slabs. The latter has been probed by variable-energy hard X-ray photoelectron spectroscopy (HAXPES) measurements, which manifest orbital-specific contributions from bonding and antibonding interactions of stereoactive Tl 6s2 electron lone pairs in TlV3O8. The spectroscopic assignment of valence band states to stereoactive lone pairs is further corroborated by first-principles electronic structure calculations, crystal orbital Hamilton population analyses, and electron localization function maps. The presence of the Tl 6s2 electron lone pair in TlV3O8 brings about the off-centering of Tl+ cations, which leads to anisotropy in Tl-O bonds. The off-centering of Tl ions weakens V-O bonds in one direction, which subsequently strengthens directional V-V coupling. Magnetic measurements reveal ferromagnetic signatures for both RbV3O8 and TlV3O8. However, the differences in V···V interactions significantly affect the energy balance of the superexchange interactions, resulting in an ordering temperature of 140 K for TlV3O8 as compared to 125 K for RbV3O8. The results demonstrate the distinctive effects of stereochemically active lone pairs in modifying electronic structure near the Fermi level and for mediating superexchange interactions.