In the ongoing pursuit of sustainable and efficient energy storage, aqueous zinc-ion batteries have attracted significant interest due to their inherent safety profile, economic viability, and environmentally benign nature. Despite these advantages, the practical deployment of zinc metal anodes has been seriously impeded by persistent issues such as uncontrollable dendritic growth, aggressive hydrogen evolution side reactions, and the accumulation of harmful by-products. These phenomena are tightly interconnected, often reinforcing one another in a detrimental feedback loop that compromises battery longevity and safety. Specifically, the hydrogen evolution reaction (HER) triggers a localized pH spike at the electrolyte-electrode interface, accelerating zinc corrosion and promoting the formation of insulating by-products. Simultaneously, zinc dendrites can breach separators, causing catastrophic short circuits. Traditional mitigation strategies primarily involve physical barrier layers or tailored electrolytes, aiming to manage symptoms rather than address underlying mechanistic roots.
In a transformative departure from conventional approaches, an innovative interdisciplinary study harnesses principles from catalytic chemistry—namely the d-band center modulation strategy—to re-engineer the zinc electrode interface. This novel concept pivots on electronic structure manipulation, precisely altering the reaction kinetics governing zinc surface interactions. By introducing a carefully selected organic additive, the study achieves fine control over the electrode surface electronic properties, effectively suppressing side reactions at their source. This breakthrough marks a paradigm shift, moving beyond symptomatic treatments to fundamental kinetic regulation, significantly enhancing the cyclical longevity and operational safety of aqueous zinc batteries.
Catalytic science has long recognized the d-band center position as a critical descriptor of surface reactivity; it dictates the adsorption strength of reactant intermediates on metallic catalysts, thereby modulating reaction pathways and rates. Translating this concept to battery science, the authors identify the HER occurring on the zinc anode surface as an electrocatalytic event. This insight prompted the hypothesis that shifting the d-band center of surface zinc atoms could weaken the adsorption of hydrogen intermediates (H*), which are crucial to the HER mechanism. By effectively “applying the brakes” to these intermediates’ adsorption, the rate of hydrogen evolution can be suppressed, addressing a core challenge that has hampered the practical realization of durable aqueous zinc metal anodes.
To operationalize this concept, the research team screened a variety of organic molecules, ultimately pinpointing oxalic acid (OA) as an exemplary interface modulator. Leveraging first-principles computational methods, they demonstrated that OA molecules specifically adsorb onto zinc surfaces not merely by physical coverage but through inducing significant shifts in the zinc electronic structure. Quantitatively, the d-band center of surface zinc atoms shifts downward from -6.896 eV to -7.062 eV upon OA adsorption. This downward shift correlates with a decreased capability of zinc electrons to adsorb hydrogen intermediates, thus reducing both the thermodynamic drive and kinetic facilitation of HER. Computational adsorption energy simulations further corroborated this mechanism, illustrating how OA-modulated zinc surfaces favor hydrogen desorption, thereby impeding deleterious side reactions at a fundamental electronic level.
Beyond surface electronic modulation, this research sheds light on an equally critical effect of oxalic acid within the battery electrolyte’s bulk solution. Using a multidisciplinary toolkit—including Fourier-transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and molecular dynamics simulations—the team revealed that OA molecules interact strongly with zinc ions in solution, partially replacing water molecules within the primary solvation sheath around Zn²⁺. This modification has two key consequences: the first is a decreased coordination of water molecules directly to zinc ions, reducing their availability to participate in parasitic side reactions. The second involves weakening sulfate anion–zinc ion interactions, which in turn prevents the interfacial accumulation of insulating zinc hydroxide sulfate by-products. Together, these effects produce a synergistic “solvation editing,” complementing the surface electronic modulations to yield a stable and clean interphase conducive to uniform zinc plating and stripping.
The dual-functionality of oxalic acid—both as an electronic structure modulator at the electrode surface and a solvation structure editor in the electrolyte—represents a multifunctional strategy to synergistically suppress multiple degradation pathways in aqueous zinc batteries. This two-pronged approach stabilizes the electrodeposition environment, reducing dendrite nucleation and growth, curbing corrosive side reactions, and minimizing the formation of electrically insulating by-products. The resultant interface displays significantly improved chemical and mechanical stability, fostering homogeneous zinc dissolution and deposition that prolongs battery cycle life and operational safety.
Translating this molecular and interface design strategy into practical performance gains, the researchers conducted extensive electrochemical evaluations. Zinc-iodine (Zn||I₂) full cells incorporating the oxalic acid additive demonstrated remarkable cycle stability, maintaining 92.8% of their initial capacity even after 10,000 charge-discharge cycles—an unprecedented endurance metric for aqueous zinc metal batteries. Furthermore, the team showcased the scalability and robustness of their approach by assembling ampere-hour-scale pouch cells, which sustained stable electrochemical performance under mechanical deformation, such as bending. These demonstrations highlight the approach’s feasibility for real-world applications requiring flexible, safe, and long-lasting energy storage devices.
Reflecting on their innovative cross-disciplinary methodology, the authors emphasize the power of integrating catalytic theory insights to resolve vexing challenges in battery science. They state, “This work is a successful exploration of interdisciplinary cross-fertilization. It enlightens us that solving stubborn problems in the energy storage field sometimes requires drawing wisdom from adjacent disciplines. Catalysis theory provides us with a new lens through which to understand and design electrode/electrolyte interfaces.” Their success portends the broader potential of leveraging fundamental principles from heterogeneous catalysis and surface chemistry to design next-generation metal anode architectures.
Significantly, the strategy pioneered here transcends aqueous zinc systems. By demonstrating effective modulation of electrode surface electronic structures to regulate reaction kinetics, this approach lays groundwork for tackling interfacial challenges in other reactive metal anodes, including lithium, sodium, and aluminum. Each of these chemistries shares analogous issues with dendrite formation, hydrogen evolution (or equivalent side reactions), and interfacial instability. Thus, the catalysis-inspired paradigm offers a versatile toolkit for engineering safer, high-performance battery systems critical for future sustainable energy storage solutions.
This study represents a landmark advance in aqueous zinc battery technology, achieving low-cost and facile additive-based interfacial engineering that delivers exceptional electrochemical stability, safety, and practical applicability. More importantly, it exemplifies a new horizon for electrode design guided by precise electronic structure control, rather than purely empirical formulations. As global demands for durable, safe, and sustainable energy storage grow increasingly urgent, such pioneering interdisciplinary research that bridges theory to application will be a defining driver of future energy technology revolutions.
Subject of Research: Energy Storage, Aqueous Zinc-ion Batteries, Electrode Interface Engineering
Article Title: Catalysis-Inspired Electronic Structure Modulation Enables Durable and Safe Aqueous Zinc Metal Anodes
Web References: 10.1016/j.scib.2026.01.033
Image Credits: ©Science China Press
Keywords
Aqueous Zinc-Ion Battery, Zinc Metal Anode, Hydrogen Evolution Reaction, D-Band Center Modulation, Oxalic Acid Additive, Electrode Interface, Solvation Structure, Hydrogen Adsorption, Electrocatalysis, Cycle Stability, Energy Storage, Dendrite Suppression
