Metallic WO2-Promoted CoWO4/WO2 Heterojunction with Intercalation-Mediated Catalysis for Lithium–Sulfur Batteries

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Metallic WO2-Promoted CoWO4/WO2 Heterojunction with Intercalation-Mediated Catalysis for Lithium–Sulfur Batteries
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Metallic WO2-Promoted CoWO4/WO2 Heterojunction with Intercalation-Mediated Catalysis for Lithium–Sulfur Batteries - Nano-Micro Letters

Lithium–sulfur (Li–S) batteries require efficient catalysts to accelerate polysulfide conversion and mitigate the shuttle effect. However, the rational design of catalysts remains challenging due to the lack of a systematic strategy that rationally optimizes electronic structures and mesoscale transport properties. In this work, we propose an autogenously transformed CoWO4/WO2 heterojunction catalyst, integrating a strong polysulfide-adsorbing intercalation catalyst with a metallic-phase promoter for enhanced activity. CoWO4 effectively captures polysulfides, while the CoWO4/WO2 interface facilitates their S–S bond activation on heterogenous catalytic sites. Benefiting from its directional intercalation channels, CoWO4 not only serves as a dynamic Li-ion reservoir but also provides continuous and direct pathways for rapid Li-ion transport. Such synergistic interactions across the heterojunction interfaces enhance the catalytic activity of the composite. As a result, the CoWO4/WO2 heterostructure demonstrates significantly enhanced catalytic performance, delivering a high capacity of 1262 mAh g−1 at 0.1 C. Furthermore, its rate capability and high sulfur loading performance are markedly improved, surpassing the limitations of its single-component counterparts. This study provides new insights into the catalytic mechanisms governing Li–S chemistry and offers a promising strategy for the rational design of high-performance Li–S battery catalysts.

A research team led by Professors Xiaoyan Zheng, Huigang Zhang, and Tao Yang has reported a significant advance in Nano-Micro Letters on catalyst design for lithium–sulfur (Li–S) batteries. Their work introduces a rationally engineered CoWO4/WO2 heterojunction that leverages intercalation-mediated catalysis and metallic conductivity to simultaneously accelerate polysulfide conversion and suppress the shuttle effect—two major challenges hindering practical Li–S batteries.

Why Heterojunction Catalysts Matter

  • Polysulfide Management: Li–S batteries suffer from the dissolution and migration of lithium polysulfides (LiPSs), which cause active material loss and poor cycling stability.
  • Catalytic Enhancement: Traditional catalysts often balance strong adsorption with limited conductivity or vice versa, leaving performance constrained.
  • Transport Dynamics: Efficient ion/electron pathways are critical for maintaining high sulfur utilization, especially under high rates and loadings.

Design Strategy of CoWO4/WO2

  • Strong Adsorption: CoWO4 provides robust chemisorption of LiPSs and weakens S–S bonds, lowering reaction barriers.
  • Metallic Conduction: The in situ–formed WO2 phase introduces metallic electron highways and donates electrons to CoWO4, enhancing catalytic activity.
  • Li-Ion Intercalation: Directional intercalation channels in CoWO4 act as Li-ion reservoirs, enabling fast ion diffusion and continuous transport.
  • Synergistic Interfaces: The heterointerface promotes charge redistribution, orbital interactions, and efficient Li–S bond activation.

Performance Highlights

  • High Capacity: The heterostructure achieves 1262 mAh g-1 at 0.1 C, outperforming single-component counterparts.
  • Rate Capability: Even at high current densities, the electrode maintains stable dual-plateau discharge profiles with low polarization.
  • Cycling Durability: At 1 mg cm-2 sulfur loading, the electrode shows a minimal decay rate of 0.038% per cycle over 1000 cycles. Under high loading (5 mg cm-2), it retains 79.1% capacity after 235 cycles.
  • Shuttle Suppression: In situ Raman and XRD confirm efficient polysulfide conversion with negligible shuttle effect.

Future Outlook

This study demonstrates how integrating adsorption, catalysis, and ion transport within a single heterojunction architecture can redefine Li–S battery design. The intercalation-mediated mechanism offers a blueprint for next-generation multifunctional catalysts, potentially enabling scalable, high-energy, and long-life Li–S systems. Beyond CoWO4/WO2, the approach provides a paradigm for constructing heterostructures that combine metallic promoters with ion-intercalating hosts, advancing practical energy storage solutions.

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Physical Sciences > Materials Science > Materials for Energy and Catalysis > Batteries
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  • Nano-Micro Letters Nano-Micro Letters

    Nano-Micro Letters is a peer-reviewed, international, interdisciplinary and open-access journal that focus on science, experiments, engineering, technologies and applications of nano- or microscale structure and system in physics, chemistry, biology, material science, and pharmacy.