Lyu Lulu, Hu Xu, Lee Suwon, Fan Wenqi, Kim Gilseob, Zhang Jiliang, Zhou Zhen, Kang Yong-Mook
Department of Materials Science and Engineering, Korea University, Seoul 02841, Republic of Korea.
School of Materials Science and Engineering, Institute of New Energy Material Chemistry, Renewable Energy Conversion and Storage Center (ReCast), Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300350, China.
J Am Chem Soc. 2024 Feb 21;146(7):4803-4813. doi: 10.1021/jacs.3c13111. Epub 2024 Feb 9.
The design of temperature-adaptive Zn-air batteries (ZABs) with long life spans and high energy efficiencies is challenging owing to sluggish oxygen reduction reaction (ORR) kinetics and an unstable Zn/electrolyte interface. Herein, a quasi-solid-state ZAB is designed by combining atomically dispersed Fe-N-C catalysts containing pyridinic N vacancies (FeNC-V) with a polarized organo-hydrogel electrolyte. First-principles calculation predicts that adjacent V sites effectively enhance the covalency of Fe-N moieties and moderately weaken *OH binding energies, significantly boosting the ORR kinetics and stability. Raman spectra reveal the dynamic evolution of *O and *OOH on the FeNC-V cathode in the aqueous ZAB, proving that the 4e associative mechanism is dominant. Moreover, the ethylene glycol-modulated organo-hydrogel electrolyte forms a zincophilic protective layer on the Zn anode surface and tailors the [Zn(HO)] solvation sheath, effectively guiding epitaxial deposition of Zn on the Zn (002) plane and suppressing side reactions. The assembled quasi-solid-state ZAB demonstrates a long life span of over 1076 h at 2 mA cm at -20 °C, outperforming most reported ZABs.
由于氧还原反应（ORR）动力学缓慢以及锌/电解质界面不稳定，设计具有长寿命和高能量效率的温度自适应锌空气电池（ZAB）具有挑战性。在此，通过将含有吡啶氮空位的原子分散Fe-N-C催化剂（FeNC-V）与极化有机水凝胶电解质相结合，设计了一种准固态ZAB。第一性原理计算预测，相邻的V位点有效地增强了Fe-N部分的共价性，并适度削弱了OH结合能，显著提高了ORR动力学和稳定性。拉曼光谱揭示了水性ZAB中FeNC-V阴极上O和*OOH的动态演变，证明4e缔合机制占主导地位。此外，乙二醇调制的有机水凝胶电解质在锌阳极表面形成亲锌保护层，并调整[Zn(HO)]溶剂化鞘，有效地引导锌在Zn(002)平面上的外延沉积并抑制副反应。组装的准固态ZAB在-20°C下2 mA cm时表现出超过1076 h的长寿命，优于大多数已报道的ZAB。
