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《Advanced Materials》 Professor Yuzhang Li & Professor Richard B. Kaner’s Research Teams Laser-Engraved Electrode Materials for Ultrafast Zinc-Ion Energy Storage

In May 2024, Professor Yuzhang Li and Professor Richard B. Kaner’s research teams published a paper titled “Laser-Scribed Battery Electrodes for Ultrafast Zinc-Ion Energy Storage” online in the journal Advanced Materials (impact factor > 20). This work synthesized a vanadium oxide nanocathode material on three-dimensional graphene through a simple laser-scribing technique, achieving excellent electrochemical performance, including high specific capacity, fast charge/discharge capability, and stable long-term cycling. The study also revealed the co-intercalation mechanism of hydrated hydrogen ions and zinc ions as the primary energy storage mechanism.

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Research summary and key highlights

Recently, the research team led by Professors Yuzhang Li and Richard B. Kaner from the University of California, Los Angeles (UCLA) published an article titled “Laser-Scribed Battery Electrodes for Ultrafast Zinc-Ion Energy Storage” in the internationally renowned journal Advanced Materials. In this work, a vanadium oxide nanocathode material was synthesized on three-dimensional graphene using a simple laser-scribing technique. The study observed that the vanadium oxide nanomaterial overcame slow reaction kinetics, enabling ultrafast Faradaic redox reactions on the electrode surface. Additionally, it revealed that the co-intercalation of hydrated hydrogen ions and zinc ions is the primary energy storage mechanism, with structural stability maintained during cycling (Figure 1). Consequently, this material exhibits excellent electrochemical performance, including high specific capacity, fast charge/discharge capabilities, and stable long-term cycling.

Figure 1: Structure and Fast-Charging Behavior of a Zinc-Ion Battery Using Laser-Scribed Vanadium Oxide as the Cathode Material

Background information

Lithium-ion batteries are the mainstream energy storage solution for electric vehicles and portable electronics. However, emerging applications such as grid-level storage and wearable devices require battery technologies that are safer and more resource-abundant. Aqueous zinc-ion batteries can meet these demands, but they lack a cathode material that can simultaneously achieve high specific capacity, fast charging, and excellent cycling stability. Although current research has made progress in rate performance, specific capacity, and cycling stability through the modification of nanostructures, the complex synthesis processes and high costs of nanomaterials remain a challenge. Therefore, there is a need for a high-performance zinc-ion battery cathode material that can be produced on a large scale.

Figure Analysis

Key Point 1: Chemical and Structural Characterization of Laser-Scribed Vanadium Oxide Cathode Material (Figure 2)

XRD and XPS confirm that the laser-scribed cathode material is a mixed-valence vanadium oxide. This mixed-valence compound enhances electronic conductivity through electron transitions between V⁴⁺ and V⁵⁺, and improves ionic conductivity through the formation of oxygen vacancies. SEM and TEM images show that the mixed-valence vanadium oxide nanoparticles are uniformly distributed on the layered, porous graphene oxide sheets, providing abundant active surface sites and additional diffusion pathways, which enable rapid kinetics of the electrochemical reactions.

Figure 2: Chemical and structural characterization of vanadium oxide cathode materials written by laser

Point 2: Electrochemical performance characterization of Zinc-ion batteries using vanadium oxide as a positive electrode material by laser writing (Figure 3)
In order to analyze the electrochemical reaction kinetics of the cathode material, the cyclic voltammetry curve (CV) was used to find that the electrochemical reaction during charge and discharge process is almost surface-controlled, and is not limited by the diffusion process. This rapid REDOX reaction at the surface provides an ideal way to store energy through battery-like REDOX reaction and capacitor-like charge and discharge rate, while achieving the high energy density and fast charge and discharge capability of the cathode material. Electrochemical magnification and cyclic testing further demonstrated that the zn-ion battery with laser writing vanadium oxide as the cathode material could achieve A high specific capacity of 553 mAh g-1 at 0.1 A g-1. Under the ultra-high current density of 100 A g-1, the battery can reach 264 mAh g-1 in 10 seconds, showing excellent magnifications performance; At the rate of 30 A g-1, the volume retention rate is still >90% after 3000 cycles.

Figure 3: Electrochemical performance characterization of Zinc-ion batteries using vanadium oxide as the cathode material

Point 3: Water and hydrogen ions H3O+ promote the co-insertion mechanism of Zn2+ (Figure 4)
In order to elucidate the fast charge storage mechanism on/near the material surface, this work first studies the chemical changes of the material during the cycle by using XPS and Raman spectroscopy, and proposes the co-insertion energy storage mechanism of hydrated hydrogen ions and zinc ions. TEM images after the cycle show that the lattice shrinkage caused by the insertion of zinc ions and the lattice expansion caused by the insertion of water and hydrogen ions cancel each other, and the lattice spacing of the positive electrode material remains basically unchanged during the cycle, which further verifies the co-insertion mechanism and explains the internal reason for maintaining the stability of the long cycle. At the same time, the specific capacity of the anode material in the anhydrous acetonitrile electrolyte is negligible, and this electrochemical behavior once again shows that H2O is crucial for the insertion of Zn2+.

Figure 4: Water and hydrogen ions H3O+ promote the co-insertion mechanism of Zn2+

Point 4: Practical application demonstration of zinc-ion battery with vanadium oxide as the positive electrode material by laser writing (Figure 5)
In practical applications, many parameters need to be considered, such as energy/power density, active material surface load, high and low temperature tolerance, mechanical stability, and fast charging performance. The zinc-ion battery with laser writing vanadium oxide as the positive electrode material can still achieve high energy and high power density when the face load is 4.5 mg cm-2 (2 mAh cm-2). Under high and low temperature test conditions (4-65 oC), it can work normally and its performance remains stable. In addition, when assembled into a flexible bag battery, it is able to cycle under flat, bent and twisted conditions, further demonstrating the mechanical stability of the material and its practical application potential in wearable devices.

Figure 5: Practical application demonstration of zinc-ion battery with vanadium oxide as positive electrode material written by laser

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