Enhancing Efficiency and Durability of Alkaline Zn-Co/Air Hybrid Batteries with Self-Reconstructed Co/Co2P Heterojunctions,Advanced Energy Materials

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Enhancing Efficiency and Durability of Alkaline Zn-Co/Air Hybrid Batteries with Self-Reconstructed Co/Co2P Heterojunctions
Advanced Energy Materials ( IF 24.4 ) Pub Date : 2024-08-29 , DOI: 10.1002/aenm.202402839
Zhuying Xu ₁ , Jie Chen ₁ , Tianyu Zhang ₂ , Haidan Lu ₁ , Lei Yan ₂ , Jiqiang Ning ₃ , Yong Hu _{1,

2}

Affiliation

Zn-Co/air hybrid batteries showcase enhanced energy efficiency, power density, and stability compared to Zn-air batteries. Nevertheless, it remains challenging to fabricate multi-functional cathode materials with fast reaction kinetics. Herein the synthesis of a wheat-like cathode composed of the “cereal-grains” of densely arranged Co/Co₂P heterostructures grown on the “central stems” of P/N codoped carbon nanofibers (denoted as Co/Co₂P@PNCF) is presented. The biomimetic nanostructures not only offer abundant exposed active sites to maximize accessibility but also establish efficient multi-channel networks for both electron transfer and O₂/OH⁻ diffusion. Furthermore, the active species of high-valent Co, resulting from self-reconstruction of the Co/Co₂P heterojunction during the first cycle, create efficient Co²⁺ ↔ Co⁴⁺ redox pairs and provide additional charging-discharging voltage plateaus. In situ Raman spectroscopy measurement combined with ex situ X-ray diffraction evidence supports the reversible process of Co^3+/4+O_x(OH)_y ↔ K_xCo^2+/3+O_y, leading to improved efficiency and durability of the battery. As a result, Zn-Co/air hybrid battery based on the Co/Co₂P@PNCF exhibits a remarkable power density (321 mW cm⁻²), ultralong cycle stability (700 h), and a large energy efficiency (62% at 20 mA cm⁻²).

中文翻译：

利用自重构 Co/Co2P 异质结提高碱性锌钴/空气混合电池的效率和耐用性

与锌空气电池相比，锌钴/空气混合电池具有更高的能源效率、功率密度和稳定性。然而，制造具有快速反应动力学的多功能正极材料仍然具有挑战性。本文合成了一种类小麦阴极，该阴极由生长在 P/N 共掺杂碳纳米纤维“中心茎”上的密集排列的 Co/Co ₂ P 异质结构“谷物”组成（表示为 Co/Co ₂ P@PNCF））提出。仿生纳米结构不仅提供丰富的暴露活性位点以最大限度地提高可及性，而且还为电子转移和O ₂ /OH ^-扩散建立有效的多通道网络。此外，在第一次循环期间由Co/Co ₂ P异质结的自重构产生的高价Co的活性物质，产生有效的Co ²⁺ ↔ Co ⁴⁺氧化还原对，并提供额外的充电-放电电压平台。原位拉曼光谱测量结合异位 X 射线衍射证据支持 Co ^3+/4+ O _x (OH) _y ↔ K _x Co ^2+/3+ O _y的可逆过程，从而提高了效率和耐用性电池。结果，基于Co/Co ₂ P@PNCF的Zn-Co/空气混合电池表现出显着的功率密度（321 mW cm ^-2 ）、超长循环稳定性（700 h）和高能量效率（62%）在20 mA cm ^-2 ）。

更新日期：2024-08-29

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