Recent Progress in the Applications of MXene-Based Materials in Multivalent Ion Batteries.

Multivalent-ion batteries have garnered significant attention as promising alternatives to traditional lithium-ion batteries due to their higher charge density and potential for sustainable energy storage solutions. Nevertheless, the slow diffusion of multivalent ions is the primary issue with electrode materials for multivalent-ion batteries. In this review, the suitability of MXene-based materials for multivalent-ion batteries applications is explored, focusing onions such as magnesium (Mg2+), aluminum (Al3+), zinc (Zn2+), and beyond. The unique structure of MXene offers large interlayer spacing and abundant surface functional groups that facilitates efficient ion intercalation and diffusion, making it an excellent candidate for multivalent-ion batteries electrodes with excellent specific capacity and power density. The latest advancements in MXene synthesis and engineering techniques to enhance its electrochemical performance have been summarized and discussed. With the versatility of MXenes and their ability to harness diverse multivalent ions, this review underscores the promising future of MXene-based materials in revolutionizing the landscape of multivalent-ion batteries.

Ion-Selective Transport Promotion Enabled by Angstrom-Scale Nanochannels in Dendrimer-Assembled Polyamide Nanofilm for Efficient Electrodialysis.

The ion permeability and selectivity of membranes are crucial in nanofluidic behavior, impacting industries ranging from traditional to advanced manufacturing. Herein, we demonstrate the engineering of ion-conductive membranes featuring angstrom-scale ion-transport channels by introducing ionic polyamidoamine (PAMAM) dendrimers for ion separation. The exterior quaternary ammonium-rich structure contributes to significant electrostatic charge exclusion due to enhanced local charge density; the interior protoplasmic channels of PAMAM dendrimer are assembled to provide additional degrees of free volume. This facilitates the monovalent ion transfer while maintaining continuity and efficient ion screening. The dendrimer-assembled hybrid membrane achieves high monovalent ion permeance of 2.81 mol m-2 h-1 (K+), reaching excellent mono/multivalent selectivity up to 20.1 (K+/Mg2+) and surpassing the permselectivities of state-of-the-art membranes. Both experimental results and simulating calculations suggest that the impressive ion selectivity arises from the significant disparity in transport energy barrier between mono/multivalent ions, induced by the "exterior-interior" synergistic effects of bifunctional membrane channels.

Tailor-Made Heterocharged Covalent Organic Framework Membrane for Efficient Ion Separation.

Pore size sieving, Donnan exclusion, and their combined effects seriously affect ion separation of membrane processes. However, traditional polymer-based membranes face some challenges in precisely controlling both charge distribution and pore size on the membrane surface, which hinders the ion separation performance, such as heavy metal ion removal. Herein, the heterocharged covalent organic framework (COF) membrane is reported by assembling two kinds of ionic COF nanosheets with opposite charges and different pore sizes. By manipulating the stacking quantity and sequence of two kinds of nanosheets, the impact of membrane surface charge and pore size on the separation performance of monovalent and multivalent ions is investigated. For the separation of anions, the effect of pore size sieving is dominant, while for the separation of cations, the effect of Donnan exclusion is dominant. The heterocharged TpEBr/TpPa-SO3H membrane with a positively charged upper layer and a negatively charged bottom layer exhibits excellent rejection of multivalent anions and cations (Ni2+, Cd2+, Cr2+, CrO4 2-, SeO3 2-, etc). The strategy provides not only high-performance COF membranes for ion separation but also an inspiration for the engineering of heterocharged membranes.

Freestanding Ammonium Vanadate Composite Cathodes with Lattice Self-Regulation and Ion Exchange for Long-Lasting Ca-Ion Batteries.

Calcium-ion batteries (CIBs) have emerged as a promising alternative for electrochemical energy storage. The lack of high-performance cathode materials severely limits the development of CIBs. Vanadium oxides are particularly attractive as cathode materials for CIBs, and preinsertion chemistry is often used to improve their calcium storage performance. However, the room temperature cycling lifespan of vanadium oxides in organic electrolytes still falls short of 1000 cycles. Here, based on preinsertion chemistry, the cycling life of vanadium oxides is further improved by integrated electrode and electrolyte engineering. Utilizing a tailored Ca electrolyte, the constructed freestanding (NH4)2V6O16·1.35H2O@graphene oxide@carbon nanotube (NHVO-H@GO@CNT) composite cathode achieves a 305 mAh g-1 high capacity and 10 000 cycles record-long life. Additionally, for the first time, a Ca-ion hybrid capacitor full cell is assembled and delivers a capacity of 62.8 mAh g-1. The calcium storage mechanism of NHVO-H@GO@CNT based on a two-phase reaction and the exchange of NH4 + and Ca2+ during cycling are revealed. The lattice self-regulation of V─O layers is observed and the layered vanadium oxides with Ca2+ pillars formed by ion exchange exhibit higher capacity. This work provides novel strategies to enhance the calcium storage performance of vanadium oxides via integrated structural design of electrodes and electrolyte modification.

K3 v2 (Po4 )3 /C as a New High-Voltage Cathode Material for Calcium-Ion Batteries with a Water-In-Salt Electrolyte.

Aqueous Ca-ion batteries (ACIBs) attract immense attention due to its high safety and the high abundance of calcium. However, the development of ACIBs is hindered by the lack of high voltage cathode materials to host the large radius and divalent Ca2+ . Herein, polyanionic phosphate K3 V2 (PO4 )3 /C (KVP/C) is provided as a new cathode material for ACIBs. Due to the robust structure of polyanion material and the wide electrochemical window of water-in-salt electrolyte, KVP/C delivers a high working voltage of 3.74 V versus Ca2+ /Ca with a specific capacity of 102.4 mAh g-1 and a long-life of 6000 cycles at 500 mA g-1 . Furthermore, the calcium storage mechanism of KVP/C is shown to be the coexistence of solid solution and two-phase reaction by in situ X-ray diffraction, ex situ transmission electron microscope, and X-ray photoelectron spectroscopy. Finally, an aqueous calcium-ion full cell, based on an organic compound as anode and KVP/C as cathode, is constructed and it shows good stability for 200 cycles and a specific capacity of 80.2 mAh g-1 . This work demonstrates that vanadium-based phosphate materials are promising high-voltage cathode materials for ACIBs and renew the prospects for ACIBs.

Potassium ion pre-intercalated MnO2 for aqueous multivalent ion batteries.

Manganese dioxide (MnO2), as a cathode material for multivalent ion (such as Mg2+ and Al3+) storage, is investigated due to its high initial capacity. However, during multivalent ion insertion/extraction, the crystal structure of MnO2 partially collapses, leading to fast capacity decay in few charge/discharge cycles. Here, through pre-intercalating potassium-ion (K+) into δ-MnO2, we synthesize a potassium ion pre-intercalated MnO2, K0.21MnO2·0.31H2O (KMO), as a reliable cathode material for multivalent ion batteries. The as-prepared KMO exhibits a high reversible capacity of 185 mAh/g at 1 A/g, with considerable rate performance and improved cycling stability in 1 mol/L MgSO4 electrolyte. In addition, we observe that aluminum-ion (Al3+) can also insert into a KMO cathode. This work provides a valid method for modification of manganese-based oxides for aqueous multivalent ion batteries.

First-Principles Dynamics Investigation of Germanium as an Anode Material in Multivalent-Ion Batteries.

Germanium, a promising electrode material for high-capacity lithium ion batteries (LIBs) anodes, attracted much attention because of its large capacity and remarkably fast charge/discharge kinetics. Multivalent-ion batteries are of interest as potential alternatives to LIBs because they have a higher energy density and are less prone to safety hazards. In this study, we probed the potential of amorphous Ge anodes for use in multivalent-ion batteries. Although alloying Al and Zn in Ge anodes is thermodynamically unstable, Mg and Ca alloys with Ge form stable compounds, Mg2.3Ge and Ca2.4Ge that exhibit higher capacities than those obtained by alloying Li, Na, or K with Ge, corresponding to 1697 and 1771 mA·h·g-1, respectively. Despite having a slightly lower capacity than Ca-Ge, Mg-Ge shows an approximately 150% smaller volume expansion ratio (231% vs. 389%) and three orders of magnitude higher ion diffusivity (3.0 × 10-8 vs. 1.1 × 10-11 cm2 s-1) than Ca-Ge. Furthermore, ion diffusion in Mg-Ge occurs at a rate comparable to that of monovalent ions, such as Li+, Na+, and K+. The outstanding performance of the Mg-Ge system may originate from the coordination number of the Ge host atoms and the smaller atomic size of Mg. Therefore, Ge anodes could be applied in multivalent-ion batteries using Mg2+ as the carrier ion because its properties can compete with or surpass monovalent ions. Here, we report that the maximum capacity, volume expansion ratio, and ion diffusivities of the alloying electrode materials can be understood using atomic-scale structural properties, such as the host-host and host-ion coordination numbers, as valuable indicators.

Toward Practical Multivalent Ion Batteries with Quinone-Based Organic Cathodes.

Multivalent ion batteries have emerged as promising solutions to meet the future demands of energy storage applications, offering not only high energy density but also diverse socio-economic advantages. Among the various options for cathodes, quinone-based organic compounds have gained attention as suitable active materials for multivalent ion batteries due to their well-aligned ion channels, flexible structures, and competitive electrochemical performance. However, the charge carriers associated with anions that are often exploited in multivalent ion battery systems operate by way of a "non-rocking-chair" mechanism, which requires the use of an excess amount of electrolyte and results in a significant decrease in the energy density. In this review, by categorizing the various charge carriers exploited in previous studies on multivalent ion batteries, we summarize recently reported quinone-based organic cathodes for multivalent ion batteries and emphasize the importance of accurately identifying the charge carriers for calculating the energy density. We also propose potential future directions toward the practical realization of multivalent ion batteries, in link with their efficient energy storage applications.

Aromatic Organic Small-Molecule Material with (020) Crystal Plane Activation for Wide-Temperature and 68000 Cycle Aqueous Calcium-Ion Batteries.

Calcium-ion batteries are an emerging energy storage device owing to the low redox potential of Ca2+/Ca and the naturally abundant reserves of the Ca element. However, the high charge density and large radius of Ca2+ lead to a low calcium storage capacity or unsatisfactory cycling performance for most electrode materials. Herein, we report the organic crystal 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) as an anode material for aqueous calcium-ion batteries (ACIBs) in a water-in-salt electrolyte. PTCDI delivers a high discharge capacity of 131.8 mAh g-1, excellent rate performance (86.2 mAh g-1@10000 mA g-1), and an ultralong life of 68000 cycles (over 470 days) with a high capacity retention of 72.7%. The calcium storage mechanism of PTCDI is shown to be an enolization reaction by in situ attenuated total reflectance Fourier-transform infrared and ex situ X-ray photoelectron spectroscopy. The activation mechanism of PTCDI microribbon splitting along the (020) crystal plane is studied by in situ X-ray diffraction, 3D tomography reconstruction technologies, and ex situ transmission electron microscopy. In addition, the Ca2+ storage sites and diffusion pathways of PTCDI are studied by density functional theory calculations. Finally, by matching a high-voltage Prussian blue analogue cathode, the assembled aqueous calcium-ion full cells exhibit excellent wide-temperature operating capability (-20 to +50 °C) and an ultralong life of 30000 cycles. Further, an aqueous calcium-ion pouch cell is constructed and exhibits a long lifetime of over 500 cycles.

Novel Structural Motif To Promote Mg-Ion Mobility: Investigating ABO4 Zircons as Magnesium Intercalation Cathodes.

There is an increasing need for sustainable energy storage solutions as fossil fuels are replaced by renewable energy sources. Multivalent batteries, specifically Mg batteries, are one energy storage technology that researchers continue to develop with hopes to surpass the performance of Li-ion batteries. However, the limited energy density and transport properties of Mg cathodes remain critical challenges preventing the realization of high-performance multivalent batteries. In this work, ABO4 zircon materials (A = Y, Eu and B = V, Cr) are computationally and experimentally evaluated as Mg intercalation cathodes. Remarkably good Mg-ion transport properties were predicted and Mg-ion intercalation was experimentally verified in sol-gel synthesized zircon YVO4, EuVO4, and EuCrO4. Among them, EuVO4 exhibited the best electrochemical performance and demonstrated repeated reversible cycling. While we believe that the one-dimensional diffusion channels and redox-active species tetragonal coordination limit the value of many zircons as high-performance cathodes, their unique structural motif of overlapping polyhedra along the diffusion pathway appears instrumental for promoting good Mg-ion mobility. The motif results in a favorable "6-5-4" change in coordination that avoids unfavorable sites with lower coordination along the diffusion pathway and a structural design metric for future Mg cathode development.

Highly Reversible Intercalation of Calcium Ions in Layered Vanadium Compounds Enabled by Acetonitrile-Water Hybrid Electrolyte.

Currently, the development of calcium-ion batteries (CIBs) is still in its infancy and greatly plagued by the absence of satisfactory cathode materials and compatible electrolytes. Herein, an acetonitrile-water hybrid electrolyte is first developed in CIB chemistry, in which, the strong lubricating and shielding effect of water solvent significantly boosts the swift transport of bulky Ca2+, thus contributing to large capacity storage of Ca2+ in layered vanadium oxides (Ca0.25V2O5·nH2O, CVO). Meanwhile, the acetonitrile component noticeably suppresses the dissolution of vanadium species during repeated Ca2+-ion uptake/release, endowing the CVO cathode with a robust cycle life. More importantly, spectral characterization and molecular dynamics simulation confirm that the water molecules are well stabilized by the mutual hydrogen bonding with acetonitrile molecules (O-H···N), endowing the aqueous hybrid electrolyte with high electrochemical stability. By using this aqueous hybrid electrolyte, the CVO electrode shows a high specific discharge capacity of 158.2 mAh g-1 at 0.2 A g-1, an appealing capacity of 104.6 mAh g-1 at a high rate of 5 A g-1, and a capacity retention of 95% after 2000 cycles at 1.0 A g-1, which is a record-high performance for CIBs reported so far. A mechanistic study exemplifies the reversible extraction of Ca2+ from the gap of VO polyhedral layers, which are accompanied by the reversible V-O and V-V skeleton change as well as reversible variation of layer spacing. This work constitutes a major advance in developing high-performance Ca-ion batteries.

Localized Ligands Assist Ultrafast Multivalent-Cation Intercalation Pseudocapacitance.

Rechargeable batteries based on multivalent cation (Mvn+ , n>1) carriers are considered potentially low-cost alternatives to lithium-ion batteries. However, the high charge-density Mvn+ carriers generally lead to sluggish kinetics and poor structural stability in cathode materials. Herein, we report an Mvn+ storage via intercalation pseudocapacitance mechanism in a 2D bivalve-like organic framework featured with localized ligands. By switching from conventional intercalation to localized ligand-assisted-intercalation pseudocapacitance, the organic cathode exhibits unprecedented fast kinetics with little structural change upon intercalation. It thus enables an excellent power density of 57 kW kg-1 over 20000 cycles for Ca2+ storage and a power density of 14 kW kg-1 with a long cycling life over 45000 cycles for Zn2+ storage. This work may provide a largely unexploited route toward constructing a local dynamic coordination microstructure for ultrafast Mvn+ storage.

Ultrastable Cu2+ Intercalation Chemistry Based on a Niobium Sulfide Nanosheet Cathode for Advanced Aqueous Storage Devices.

Exploring stable and durable cathodes for cost-effective reversible aqueous batteries is highly desirable for grid-scale energy storage applications, but significant challenges remain. Herein, we disclosed an ultrastable Cu2+ intercalation chemistry in mass-produced exfoliated NbS2 nanosheets to build ultralong lifespan aqueous batteries with cost advantages. Anisotropic interplanar expansion of NbS2 lattices balanced dynamic Cu2+ incorporation and the highly reversible redox reaction of Nb4+/Nb(4-δ)+ couple were illuminated by operando synchrotron X-ray diffraction and energy dispersive X-ray absorption spectroscopy, affording an extraordinary capacity of approximately 317 mAh g-1 at 1 A g-1 and a good stability of 92.2% capacity retention after 40000 cycles at 10 A g-1. Impressively, a budget NbS2||Fe hybrid ion cell involving an aqueous electrolyte/Fe-metal anode is established and provides a reliable energy supply of 225.4 Wh kg-1 at 750 W kg-1, providing insights for building advanced aqueous battery systems for large-scale applications.

Identification, measurement, and evaluation of blood concentrations of insulin glargine and insulin lispro by UPLC-MS-MS in a dead body suspected of insulin overdose.

Insulin preparations, which are drug treatments for diabetes, cause fatal hypoglycemia when an overdose is administered. Cases of homicide and suicide using these preparations have been reported and are of great forensic interest. However, there are few reports assessing the postmortem concentration of insulin preparations, and it is often difficult to determine the cause of death. In the present study, we report a case of a suspected insulin glargine and insulin lispro overdose for suicide. A woman in her 30s had a history of mental illness and diabetes. The day before her death, she reported to her boyfriend that she had taken large doses of insulin preparations and prescription drugs. An autopsy revealed no fatal injuries or lesions. Drug screening tests revealed several prescription drugs, none of which showed toxic concentrations. Analysis using LC-MS/MS detected insulin glargine in the peripheral and cardiac blood at 429 µU/mL and 1362 µU/mL, respectively, whereas insulin lispro was detected in both the peripheral and cardiac blood at levels below the lower limit of quantification (LLOQ; <50 µU/mL). The cause of death was considered likely to be hypoglycemia caused by an overdose of insulin glargine. Insulin glargine is rapidly metabolized after subcutaneous administration and is rarely detected in the blood when used at therapeutic doses. There are no other reports on the quantification of insulin glargine parent compounds in postmortem samples, and this case provides important data on postmortem blood concentrations of insulin glargine intoxication.

Initiating Reversible Aqueous Copper-Tellurium Conversion Reaction with High Volumetric Capacity through Electrolyte Engineering.

Pursuing conversion-type cathodes with high volumetric capacity that can be used in aqueous environments remains rewarding and challenging. Tellurium (Te) is a promising alternative electrode due to its intrinsic attractive electronic conductivity and high theoretical volumetric capacity yet still to be explored. Herein, the kinetically/thermodynamically co-dominat copper-tellurium (Cu-Te) alloying phase-conversion process and corresponding oxidation failure mechanism of tellurium are investigated using in situ synchrotron X-ray diffraction and comprehensive ex situ characterization techniques. By virtue of the fundamental insights into the tellurium electrode, facile and precise electrolyte engineering (solvated structure modulation or reductive antioxidant addition) is implemented to essentially tackle the dramatic capacity loss in tellurium, affording reversible aqueous Cu-Te conversion reaction with an unprecedented ultrahigh volumetric capacity of up to 3927 mAh cm-3 , a flat long discharge plateau (capacity proportion of ≈81%), and an extraordinary level of capacity retention of 80.4% over 2000 cycles at 20 A g-1 of which lifespan thousand-fold longer than Cu-Te conversion using CuSO4 -H2 O electrolyte. This work paves a significant avenue for expanding high-performance conversion-type cathodes toward energetic aqueous multivalent-ion batteries.

Deep Eutectic Solvent for Facile Synthesis of Mn3O4@N-Doped Carbon for Aqueous Multivalent-Based Supercapacitors: New Concept for Increasing Capacitance and Operating Voltage.

The capacitance and operating voltage of supercapacitors as well as their energy density have been increased by development of different materials and electrolytes. In this paper, two strategies, for the first time, were used to improve energy density: Mn3O4- and N-dual doped carbon electrode and aqueous mixture of multivalent ions as electrolyte. Mn3O4- and N-dual doped carbon was prepared by a novel and cost-effective procedure using deep eutectic solvent. XRD, XPS, and FTIR confirmed presence of Mn3O4 and nitrogen, while SEM and EDS elemental mapping showed micrometer-sized nanosheets with uniform distribution of C, O, N, and Mn atoms. Charge storage behavior of carbon was tested in aqueous multivalent-based electrolytes and their mixture (Ca2+-Al3+). Regarding both specific capacitance and workable voltage, the Ca2+-Al3+ mixed electrolyte was found as the best optimal solution. The calcium addition to the Al-electrolyte allows the higher operating voltage than in the case of individual Al(NO3)3 electrolyte while the addition of Al3+ ion in the Ca(NO3)2 electrolyte improves the multivalent-ion charge storage ability of carbon. As a result, the specific energy density of two-electrode Mn3O4@N-doped carbon//Al(NO3)2+Ca(NO3)2//Mn3O4@N-doped carbon supercapacitor (34 Wh kg-1 at 0.1 A g-1) overpasses the reported values obtained for Mn-based carbon supercapacitors using conventional aqueous electrolytes.

Extraordinarily Stable Aqueous Electrochromic Battery Based on Li4Ti5O12 and Hybrid Al3+/Zn2+ Electrolyte.

Aqueous electrochromic battery (ECB) is a multifunctional technology that shows great potential in various applications including energy-saving buildings and wearable batteries with visible energy levels. However, owing to the mismatch between traditional electrochromic materials and the electrolyte, aqueous ECBs generally exhibit poor cycling stability which bottlenecks their practical commercialization. Herein, we present an ultrastable electrochromic system composed of lithium titanate (Li4Ti5O12, LTO) electrode and Al3+/Zn2+ hybrid electrolyte. The fully compatible system exhibits excellent redox reaction reversibility, thus leading to extremely high cycling stabilities in optical contrast (12 500 cycles with unnoticeable degradation) and energy storage (4000 cycles with 82.6% retention of capacity), superior electrochromic performances including high optical contrast (∼74.73%) and fast responses (4.35 s/7.65 s for bleaching/coloring), as well as excellent discharge areal capacity of 151.94 mAh m-2. The extraordinary cycling stability can be attributed to the robust [TiO6] octahedral frameworks which remain chemically active even upon the gradual substitution of Li+ with Al3+ in LTO over multiple operation cycles. The high-performance electrochromic system demonstrated here not only makes the commercialization of low-cost, high-safety aqueous-based electrochromic devices possible but also provides potential design guidance for LTO-related materials used in aqueous-based energy storage devices.

High-Energy Batteries: Beyond Lithium-Ion and Their Long Road to Commercialisation.

Rechargeable batteries of high energy density and overall performance are becoming a critically important technology in the rapidly changing society of the twenty-first century. While lithium-ion batteries have so far been the dominant choice, numerous emerging applications call for higher capacity, better safety and lower costs while maintaining sufficient cyclability. The design space for potentially better alternatives is extremely large, with numerous new chemistries and architectures being simultaneously explored. These include other insertion ions (e.g. sodium and numerous multivalent ions), conversion electrode materials (e.g. silicon, metallic anodes, halides and chalcogens) and aqueous and solid electrolytes. However, each of these potential "beyond lithium-ion" alternatives faces numerous challenges that often lead to very poor cyclability, especially at the commercial cell level, while lithium-ion batteries continue to improve in performance and decrease in cost. This review examines fundamental principles to rationalise these numerous developments, and in each case, a brief overview is given on the advantages, advances, remaining challenges preventing cell-level implementation and the state-of-the-art of the solutions to these challenges. Finally, research and development results obtained in academia are compared to emerging commercial examples, as a commentary on the current and near-future viability of these "beyond lithium-ion" alternatives.

Ether-Water Hybrid Electrolyte Contributing to Excellent Mg Ion Storage in Layered Sodium Vanadate.

Magnesium ion batteries have potential for large-scale energy storage. However, the high charge density of Mg2+ ions establishes a strong intercalation energy barrier in host materials, causing sluggish diffusion kinetics and structural degradation. Here, we report that the kinetic and dissolution issues connected to cathode materials can be resolved simultaneously using a tetraethylene glycol dimethyl ether (TEGDME)-water hybrid electrolyte. The lubricating and shielding effect of water solvent could boost the swift transport of Mg2+, contributing to a high diffusion coefficient within the sodium vanadate (NaV8O20·nH2O) cathode. Meanwhile, the organic TEGDME component can coordinate with water to diminish its activity, thus providing the hybrid electrolyte with a broad electrochemical window of 3.9 V. More importantly, the TEGDME preferentially amassed at the interface, leading to a robust cathode electrolyte interface layer that suppresses the dissolution of vanadium species. Consequently, the NaV8O20·nH2O cathode achieved a specific capacity of 351 mAh g-1 at 0.3 A g-1 and a long cycle life of 1000 cycles in this hybrid electrolyte. A mechanism study revealed the reversible interaction of Mg2+ during cycles. This organic water hybrid electrolyte is effective for overcoming the difficulty of multivalent ion storage.

Operando XAFS on Hydrated Calcium Vanadium Bronze Cathode for Aqueous Zn-ion Storage.

Multivalent ion storage and aqueous electrochemical systems continue to build interest for energy application. The Zn-ion system with 2 electron transfer and an ideal metal anode is a strong candidate but is still at the early stage of development. Using both in situ near-edge (XANES) and X-ray absorption fine structure spectroscopy, EXAFS, a nanostructured cathode material, Cax V2 O5 -H2 O (CVO), was probed at the V-K absorption edge. This operando study reveals the local electronic and geometric structure changes for CVO during galvanostatic cycling as the active material in an aqueous Zn-ion cell. The XANES data provides a fine resolution to track the evolution of the vanadium oxidative state and near-neighbor coordination sphere showing subtle shifts and delocalized charge. The Zn-ion influence on the V-K absorption edge is visualized using a difference technique called Δµ. Coupled with theoretical calculations and modelling, the extended region extracted local bonding information further confirms excellent electronic and structural reversibility of this vanadium oxide bronze in an aqueous Zn-ion electrochemical cell.